611

CHAPTER 14
CHEMICAL KINETICS

PRACTICE EXAMPLES

1A (E) The rate of consumption for a reactant is expressed as the negative of the change in molarity
divided by the time interval. The rate of reaction is expressed as the rate of consumption of a
reactant or production of a product divided by its stoichiometric coefficient.
rate of consumption of A
| | ( )
5 1
A 0.3187 M 0.3629 M
1min
= = =8.93 10 M s
8.25min 60 s t

A

A

rate of reaction =rate of consumption of A2 =
5 1
5 1
8.93 10 M s
4.46 10 M s
2

=

1B (E) We use the rate of reaction of A to determine the rate of formation of B, noting from the
balanced equation that 3 moles of B form (+3 moles B) when 2 moles of A react (2 moles A).
(Recall that M means moles per liter.)
4 1
0.5522MA 0.5684MA 3moles B
rateof B formation= 1.62 10 M s
60s
2moles A
2.50min
1min

+
=

2A (M)
(a) The 2400-s tangent line intersects the 1200-s vertical line at 0.75 M and reaches 0 M at
3500 s. The slope of that tangent line is thus
4 1
0 M 0.75 M
slope= = 3.3 10 M s = instantaneous rate
3500 s 1200 s

of reaction
The instantaneous rate of
4 1
reaction=3.3 10 M s

.

(b)
| | | |
2 2 2 2
At 2400 s, H O =0.39 M. At 2450 s, H O =0.39 M+ rate t A
| |
4 1 1
2 2 2 2
At 2450 s, H O =0.39 M+ 3.3 10 mol H O L s 50s
=0.39 M 0.017 M =0.37 M

(



2B (M) With only the data of Table 14.2 we can use only the reaction rate during the first 400 s,
| |
4 1
2 2
H O / =15.0 10 M s t

A A , and the initial concentration,
| |
2 2
0
H O =2.32M.
We calculate the change in
| |
2 2
H O and add it to
| |
2 2
0
H O to determine
| |
2 2
100
H O .

| |
4 1
2 2 2 2
H O = rate of reaction of H O = 15.0 10 M s 100s= 0.15 M t

A A

| | | | | | ( )
2 2 2 2 2 2
100 0
H O = H O + H O =2.32 M+ 0.15 M =2.17 M A


This value differs from the value of 2.15 M determined in text Example 14-2b because
the text used the initial rate of reaction
( )
4 1
17.1 10 M s

, which is a bit faster than the average
rate over the first 400 seconds.
Chapter 14: Chemical Kinetics
612
3A (M) We write the equation for each rate, divide them into each other, and solve for n.
( )
( )
5 1
1 2 5
1
5 1
2 2 5
2
= N O =5.45 10 M s = 3.15 M
= N O =1.35 10 M s = 0.78 M
n n
n n
R k k
R k k

(
(


(
(




( )
( )
( )
5 1
2 5
1 1
5 1
2
2 5
2
N O 3.15 M
5.45 10 M s 3.15
= =4.04= = = = 4.04
1.35 10 M s 0.78
0.78 M N O
n n
n
n
n n
k k R
R
k k
(
(


(
(

| |
|

\ .

We kept an extra significant figure (4) to emphasize that the value of n =1. Thus, the reaction is
first-order in
2 5
N O .

3B (E) For the reaction, we know that | |
2
1
2
2 2 4
rate= HgCl C O k

(

. Here we will compare Expt. 4 to
Expt. 1 to find the rate.
( )
( )
2
1 2
2
2 2 4
4 4
2 2 5 1
1 2
1
2 2 4
HgCl C O
0.025 M 0.045 M
rate rate
= = =0.0214=
rate 1.8 10 Mmin
0.105 M 0.150 M
HgCl C O
k
k

(
(


(
(
(
(


(

The desired rate is
5 1 7 1
4
rate =0.0214 1.8 10 M min =3.9 10 Mmin

.

4A (E) We place the initial concentrations and the initial rates into the rate law and solve fork .
| | | | ( ) ( )
2 2
2 1
rate = A B =4.78 10 M s = 1.12 M 0.87 M k k



( )
2 1
2 2 1
2
4.78 10 M s
= =4.4 10 M s
1.12 M 0.87 M
k

4B (E) We know that
2
1 2
2 2 4
rate= HgCl C O k

(
(

(

and k =7.6 10
3 2 1

M min .
Thus, insertion of the starting concentrations and the k value into the rate law yields:
( ) ( )
1 2
3 2 1 7 1
Rate=7.6 10 M min 0.050 M 0.025 M =2.4 10 M min



5A (E) Here we substitute directly into the integrated rate law equation.
ln A ln A s s ln
t
kt = + = 3.02 10 325 + 2.80 = 0.982+1.030=0.048
0
3 1


b g
A e M
t
= =1.0
0.048


5B (M) This time we substitute the provided values into text Equation 14.13.
2 2 4 1
2 2
0
H O
1.49 M 0.443
ln = = 600 s=ln = 0.443 = =7.38 10 s
H O 2.32 M 600 s
t
kt k k
(
(

(
(

2 2 2 2
0
Now we choose H O =1.49 M, H O =0.62, =1800 s 600 s=1200 s
t
t
( (
( (


2 2 4 1
2 2
0
H O
0.62 M 0.88
ln = = 1200 s=ln = 0.88 = =7.3 10 s
H O 1.49 M 1200 s
t
kt k k
(
(

(
(

These two values agree within the limits of the experimental error and thus, the reaction is first-
order in [H
2
O
2
].
Chapter 14: Chemical Kinetics
613
6A (M) We can use the integrated rate equation to find the ratio of the final and initial
concentrations. This ratio equals the fraction of the initial concentration that remains at time t.
| |
| |
| |
| |
| |
3 1
0
0.443
0
0
A
ln = = 2.95 10 s 150 s= 0.443
A
A
= =0.642; 64.2%of A remains.
A
t
t
kt
e

6B (M) After two-thirds of the sample has decomposed, one-third of the sample remains.
Thus
2 2 2 2
0
H O = H O 3
t
( (
( (

, and we have

( )
2 2 2 2 4 1 0
2 2 2 2
0 0
3
4 1
H O H O 3
ln = =ln =ln 1/ 3 = 1.099= 7.30 10 s
H O H O
1.099 1 min
= =1.51 10 s =25.1 min
7.30 10 s 60 s
t
kt t
t
( (
( (

( (
( (

7A (M) At the end of one half-life the pressure of DTBP will have been halved, to 400 mmHg. At the
end of another half-life, at 160 min, the pressure of DTBP will have halved again, to 200 mmHg.
Thus, the pressure of DTBP at 125 min will be intermediate between the pressure at
80.0 min (400 mmHg) and that at 160 min (200 mmHg). To obtain an exact answer, first we
determine the value of the rate constant from the half-life.
( )
( )
1
1/2
DTBP
1
DTBP
0
0.693 0.693
= = =0.00866min
80.0min
ln = = 0.00866min 125min= 1.08
t
k
t
P
kt
P

( )
( )
( ) ( )
DTBP 1.08
DTBP
0
DTBP DTBP
0
= =0.340
=0.340 =0.340 800 mmHg=272 mmHg
t
t
P
e
P
P P

7B (M)
(a) We use partial pressures in place of concentrations in the integrated first-order rate
equation. Notice first that more than 30 half-lives have elapsed, and thus the ethylene oxide
pressure has declined to at most 0.5 =9 10
30
10
b g

of its initial value.


4 1 22.1 10 30 30
0 0
3600 s
ln = = 2.05 10 s 30.0 h = 22.1 = =2.4 10
1 h
P P
kt e
P P




10 10 7
30 0
=2.4 10 = 2.4 10 782 mmHg = 1.9 10 mmHg P P



Chapter 14: Chemical Kinetics
614
(b) P
ethylene oxide
initially 782 mmHg 1.9 10
7
mmHg (~0). Essentially all of the ethylene
oxide is converted to CH
4
and CO. Since pressure is proportional to moles, the final
pressure will be twice the initial pressure (1 mole gas 2 moles gas;
782 mmHg 1564 mmHg). The final pressure will be 1.56 10
3
mmHg.

8A (D) We first begin by looking for a constant rate, indicative of a zero-order reaction. If the rate is
constant, the concentration will decrease by the same quantity during the same time period. If we
choose a 25-s time period, we note that the concentration decreases ( ) 0.88 M 0.74 M = 0.14 M
during the first 25 s, ( ) 0.74 M 0.62 M = 0.12 M during the second 25 s,
( ) 0.62 M 0.52 M = 0.10 M during the third 25 s, and ( ) 0.52 M 0.44 M = 0.08 M during the
fourth 25-s period. This is hardly a constant rate and we thus conclude that the reaction is not
zero-order.

We next look for a constant half-life, indicative of a first-order reaction. The initial concentration
of 0.88 M decreases to one half of that value, 0.44 M, during the first 100 s, indicating a 100-s
half-life. The concentration halves again to 0.22 M in the second 100 s, another 100-s half-life.
Finally, we note that the concentration halves also from 0.62 M at 50 s to 0.31 M at 150 s, yet
another 100-s half-life. The rate is established as first-order. The rate constant is
k
t
=
0.693
=
0.693
100
=6.93 10
1/2
3 1
s
s

.
That the reaction is first-order is made apparent by the fact that the ln[B] vs time plot is a straight
line with slope =-k (k =6.85 10
3
s
1
).






















Plot of [B]
versus Time
0.15
0.25
0.35
0.45
0.55
0.65
0.75
0.85
0 100 200 300
Time(s)
[
B
]

(
M
)
Plot of ln([B]) versus
Time
-2
-1.8
-1.6
-1.4
-1.2
-1
-0.8
-0.6
-0.4
-0.2
0
0 200 400
Time(s)
l
n
(
[
B
]
)
Pl ot of 1/[B] versus
Ti me
1
2
3
4
5
6
7
0 100 200 300
Time (s)
1
/
[
B
]

(
M
-
1
)
Chapter 14: Chemical Kinetics
615
8B (D) We plot the data in three ways to determine the order. (1) A plot of [A] vs. time is linear if
the reaction is zero-order. (2) A plot of ln [A] vs. time will be linear if the reaction is first-order.
(3) A plot of 1/[A] vs. time will be linear if the reaction is second-order. It is obvious from the
plots below that the reaction is zero-order. The negative of the slope of the line equals
( )
3
= 0.083 M 0.250 M 18.00min=9.28 10 M/min k

(k =9.30 10
3
M/min using a
graphical approach).



















9A (M) First we compute the value of the rate constant at 75.0C with the Arrhenius equation. We
know that the activation energy is E
a
=1.06 10
5
J /mol, and that k =3.46 10
5 1

s at 298 K.
The temperature of
o
75.0 C=348.2 K.

ln ln
s
J / mol
J mol K K K
k
k
k E
R T T
a 2
1
2
5 1
1 2
5
1 1
=
3.46 10
=
1 1
=
1.06 10
8.3145
1
298.2
1
348.2
=6.14

F
H
G
I
K
J


F
H
G
I
K
J



5 1 +6.14 5 1 2 1
2
=3.46 10 s =3.46 10 s 4.6 10 =0.016 s k e



1/2
1
0.693 0.693
= = =43 s at 75 C
0.016 s
t
k



9B (M) We use the integrated rate equation to determine the rate constant, realizing that one-third
remains when two-thirds have decomposed.
( )
2 5 2 5
0
2 5 2 5
0 0
N O N O 3
1
ln =ln =ln = = 1.50 h = 1.099
N O N O 3
t
kt k
( (
( (

( (
( (

4 1
1.099 1 h
= =2.03 10 s
1.50 h 3600 s
k



Pl ot of [A]
versus Ti me
y =-0.00930x +0.2494
0.07
0.09
0.11
0.13
0.15
0.17
0.19
0.21
0.23
0.25
0 10 20
Time (min)
[
A
]

(
M
)
Pl ot of l n([A])
versus Ti me
-2.5
-2.3
-2.1
-1.9
-1.7
-1.5
0 10 20
Time (min)
l
n
(
[
A
]
)
Pl ot of 1/[A]
versus Ti me
4
5
6
7
8
9
10
11
12
0 10 20
Ti me (mi n)
1
/
[
A
]

(
M
-
1
)
Chapter 14: Chemical Kinetics
616
Now use the Arrhenius equation to determine the temperature at which the rate constant is 2.04
10
4
s
1
.
ln ln
s
s
J / mol
J mol K K
k
k
E
R T T T
a 2
1
4 1
5 1
1 2
5
1 1
2
=
2.04 10
3.46 10
=1.77=
1 1
=
1.06 10
8.3145
1
298
1

F
H
G
I
K
J


F
H
G
I
K
J



1
=
1
298
1.77 8.3145
1.06 10
=3.22 10 =311
2
1
5
3 1
2
T
T
K
K
K K

10A (M) The two steps of the mechanism must add, in a Hess's law fashion, to produce the overall
reaction.
2 2 2 2
Overall reaction: CO+NO CO +NO or CO+NO CO +NO

( ) ( )
3 2 2 2 2 3
Second step: NO +CO NO +CO or + NO +CO NO +CO

First step: 2 +
2 3
NO NO NO


If the first step is the slow step, then it will be the rate-determining step, and the rate of that step
will be the rate of the reaction, namely, rate of | |
2
1 2
reaction= NO k .

10B (M)
(1) The steps of the mechanism must add, in a Hess's law fashion, to produce the overall reaction.
This is done below. The two intermediates, NO F g
2 2
b g and F(g), are each produced in one step
and consumed in the next one.

Fast: ( ) ( ) ( )
2 2 2 2
NO g + F g NO F g

Slow: NO F g NO F g F g
2 2 2
+ b g b g b g
Fast: F g NO g NO F g b g b g b g +
2 2

Net: 2 + 2
2 2 2
NO g F g NO F g b g b g b g

(2) The proposed mechanism must agree with the rate law. We expect the rate-determining step
to determine the reaction rate:
| |
3 2 2
Rate= NO F k . To eliminate NO F
2 2
, we recognize that
the first elementary reaction is very fast and will have the same rate forward as
reverse:
| || | | |
1 2 2 2 2 2
= NO F = NO F =
f r
R k k R . We solve for the concentration of
intermediate:
| | | || |
2 2 1 2 2 2
NO F = NO F / k k . We now substitute this expression for NO F
2 2

into the rate equation: ( )| || |
1 3 2 2 2
Rate= / NO F k k k . Thus the predicted rate law agrees with
the experimental rate law.
Chapter 14: Chemical Kinetics
617

INTEGRATIVE EXAMPLE

A. (M)
(a) The time required for the fixed (c) process of souring is three times as long at 3 C refrigerator
temperature (276 K) as at 20 C room temperature (293 K).
4 a a a 2 1
1 2 1 2
1 1
4
a 4 1 4 1
/ 64 h 1 1 1 1
ln ln ln 1.10 ( 2.10 10 )
/ 3 64 h 293 K 276 K
1.10 1.10 8.3145 J mol K
4.4 10 J /mol 44 kJ /mol
2.10 10 K 2.10 10 K
E E E c t t
c t t R T T R R
R
E

= = = = = =

| |
| |
| |
\ .
\ .

= = = =


(b) Use the E
a
determined in part (a) to calculate the souring time at 40 C =313 K.
4
a 1 1
1 1
2 1 2
1.15 1
1
1 1 4.4 10 J /mol 1 1
ln 1.15 ln
8.3145 J mol K 313 K 293 K 64 h
0.317 0.317 64 h 20. h
64 h
E t t
t R T T
t
e t

| | | |
= = = =
| |
\ .
\ .
= = = =


B. (M) The species A
*
is a reactive intermediate. Lets deal with this species by using a steady state
approximation.
d[A
*
]/dt =0 =k
1
[A]
2
k
-1
[A
*
][A] k
2
[A
*
]. Solve for [A
*
]. k
-1
[A
*
][A] +k
2
[A
*
] =k
1
[A]
2


2
1
-1 2
k [A]
[A*] =
k [A] k +
The rate of reaction is: Rate =k
2
[A
*
] =
2
2 1
-1 2
k k [A]

k [A] k +

At low pressures ([A] ~0 and hence k
2
>>k
-1
[A]), the denominator becomes ~k
2
and the rate law is

2
2 2 1
1
2
k k [A]
Rate = = k [A]
k
Second-order with respect to [A]
At high pressures ([A] is large and k
-1
[A] >> K
2
), the denominator becomes ~k
-1
[A]

and the rate law
is

2
2 1 2 1
-1 -1
k k [A] k k [A]
Rate = =
k [A] k
First-order with respect to [A]


EXERCISES

Rates of Reactions
1. (M) 2A +B C +3D
[A]
t
A
A
=6.2 10
4
M s
1

(a) Rate =
1 [A]
2 t
A
A
=1/2(6.2 10
4
M s
1
) =3.1 10
4
M

s
1

(b) Rate of disappearance of B =
1 [A]
2 t
A
A
=1/2(6.2 10
4
M s
1
) =3.1 10
4
M

s
1

(c) Rate of appearance of D =
3 [A]
2 t
A
A
=3(6.2 10
4
M s
1
) =9.3 10
4
M

s
1

Chapter 14: Chemical Kinetics
618

2. (M) In each case, we draw the tangent line to the plotted curve.
(a) The slope of the line is
| |
2 2 4 1
H O
1.7 M 0.6 M
= = 9.2 10 M s
400 s 1600 s t

A


A


| |
2 2 4 1
H O
reaction rate= =9.2 10 M s
t

A

A


(b) Read the value where the horizontal line [H
2
O
2
] =0.50 M intersects the curve,
~ 2150 s or ~ 36 minutes

3. (E)
| | ( )
3 1
A 0.474 M 0.485 M
Rate= = =1.0 10 M s
82.4 s 71.5 s t

A

A


4. (M)
(a) Rate
A M M
min min
M min = =
0.1498 0.1565
1.00 0.00
=0.0067
1

A
A

t

Rate
A M M
min min
M min = =
0.1433 0.1498
2.00 1.00
=0.0065
1

A
A

t


(b) The rates are not equal because, in all except zero-order reactions, the rate depends on the
concentration of reactant. And, of course, as the reaction proceeds, reactant is consumed
and its concentration decreases, so the rate of the reaction decreases.

5. (M)
(a) A A A M M M = + =0.588 0.013 =0.575
i
A

(b) A A M M M =0.565 0.588 = 0.023
| |
| |
( )
2
0.023 M
= A = =1.0 min
A 2.2 10 M/min
time= + = 4.40+1.0 min=5.4min
t
t
t t

A
A A
A
A


6. (M) Initial concentrations are HgCl
2
=0.105 M and C O
2 4
2
=0.300

M.
The initial rate of the reaction is7.1 10
5 1

Mmin . Recall that the reaction is:
2
2 2 4 2 2 2
2 HgCl (aq)+C O (aq) 2 Cl (aq)+2 CO (g)+Hg Cl (aq)

.
The rate of reaction equals the rate of disappearance of C O
4
2
2

. Then, after 1 hour, assuming that
the rate is the same as the initial rate,

(a)

| |
2
5 2 4 2
2
2
2 4
mol C O 2 mol HgCl 60min
HgCl =0.105 M 7.1 10 1 h 0.096 M
L s 1 h 1 mol C O

| |
=
|

\ .


(b) C O M
mol
L min
h
min
h
M
4
2
2
5
=0.300 7.1 10 1
60
1
=0.296

F
H
G
I
K
J

Chapter 14: Chemical Kinetics
619
7. (M)
(a)
| | | |
| |
5 1
5 1 5
A C
Rate= = =1.76 10 M s
2
C
=2 1.76 10 M s =3.52 10 M/s
t t
t


A A

A A
A

A

(b)
A
A

A
A


A C
M s Assume this rate is constant
t t
=
2
= 1.76 10 .
5 1


| |
5 1
60 s
A =0.3580 M+ 1.76 10 M s 1.00min =0.357 M
1min

| |

|
\ .

(c)

| |
| |
5 1
2
5 5
A
= 1.76 10 M s
A
0.3500 M 0.3580 M
= = =4.5 10 s
1.76 10 M/s 1.76 10 M/s
t
t


A

A
A

A



8. (M)
(a)
| |
4
2 4 2 2 2
2
2 2
O
5.7 10 mol H O 1 mol O
=1.00 L soln =2.9 10 mol O /s
1 L soln s 2 mol H O
n
t

A


A

(b)
A
A


n
t
O mol O
s
s
min
mol O min
2 4 2 2
2
=2.9 10
60
1
=1.7 10 /
(c)
A
A

V
t
O mol O
min
mL O at STP
mol O
mL O at STP
min
2 2 2 2
2
2
2
=1.7 10
22,414
1
=
3.8 10


9. (M) Notice that, for every 1000 mmHg drop in the pressure of A(g), there will be a corresponding
2000 mmHg rise in the pressure of B(g) plus a 1000 mmHg rise in the pressure of C(g).

(a) We set up the calculation with three lines of information below the balanced equation: (1)
the initial conditions, (2) the changes that occur, which are related to each other by reaction
stoichiometry, and (3) the final conditions, which simply are initial conditions + changes.
A(g) 2B(g) + C(g)
Initial 1000. mmHg 0. mmHg 0. mmHg
Changes 1000. mmHg +2000. mmHg +1000. mmHg
Final 0. mmHg 2000. MmHg 1000. mmHg

Total final pressure mmHg mmHg mmHg mmHg =0. +2000. +1000. =3000.

(b) A(g) 2B(g) + C(g)
Initial 1000. mmHg 0. mmHg 0. mmHg
Changes 200. mmHg +400. mmHg +200. mmHg
Final 800 mmHg 400. mmHg 200. mmHg

Total pressure mmHg mmHg mmHg mmHg =800. +400. +200. =1400.

Chapter 14: Chemical Kinetics
620
10. (M)
(a) We will use the ideal gas law to determine N O
2 5
pressure

( )
2 5
2 5
1mol N O L atm
1.00g 0.08206 273 +65 K
108.0g mol K nRT 760 mmHg
P{N O } = = =13mmHg
V 15 L 1 atm
| |
|
\ .

(b) After 2.38 min, one half-life passes. The initial pressure of N O
2 5
decreases by half to 6.5
mmHg.
(c) From the balanced chemical equation, the reaction of 2 mol N O g
2 5
b g produces 4 mol
NO g
2
b g and 1 mol O g
2
b g . That is, the consumption of 2 mol of reactant gas produces 5
mol of product gas. When measured at the same temperature and confined to the same
volume, pressures will behave as amounts: the reaction of 2 mmHg of reactant produces 5
mmHg of product.
total 2 5 2 5
(product)
initially) reactant) (reactant)
(reactant)
( (
5 mmHg
=13 mmHg N O 6.5 mmHg N O + 6.5 mmHg
2 mmHg
P
| |
|
\ .
(13 6.5 16) mmHg 23mmHg = + =

Method of Initial Rates

11. (M)
(a) From Expt. 1 to Expt. 3, [A] is doubled, while [B] remains fixed. This causes the rate to
increases by a factor of
6.75 10
3.35 10
=2.01 2
4 1
4 1

~


M s
M s
.
Thus, the reaction is first-order with respect to A.
From Expt. 1 to Expt. 2, [B] doubles, while [A] remains fixed. This causes the rate to
increases by a factor of
1.35 10
3.35 10
=4.03 4
3 1
4 1

~


M s
M s
.
Thus, the reaction is second-order with respect to B.
(b) Overall reaction order = order with respect to A + order with respect to B =1 + 2 =3. The
reaction is third-order overall.
(c) Rate M s M M =3.35 10 = 0.185 0.133
4 1
2

kb gb g
k =
3.35 10
0.185 0.133
=0.102
4 1
2
2 1

M s
M M
M s
b gb g


12. (M) From Expt. 1 and Expt. 2 we see that [B] remains fixed while [A] triples. As a result, the
initial rate increases from 4.2 10
3

M/min to 1.3 10
2

M/min, that is, the initial reaction rate
triples. Therefore, the reaction is first-order in [A]. Between Expt. 2 and Expt. 3, we see that [A]
doubles, which would double the rate, and [B] doubles. As a consequence, the initial rate goes
from 1.3 10
2

M/min to 5.2 10
2

M/min, that is, the rate quadruples. Since an additional
doubling of the rate is due to the change in [B], the reaction is first-order in [B]. Now we
determine the value of the rate constant.
Chapter 14: Chemical Kinetics
621
Rate A B
Rate
A B
M min
M M
L mol min = = =
5.2 10 /
3.00 3.00
=5.8 10
1 1
2
3 1 1
k k

The rate law is Rate L mol min A B =5.8 10
3 1 1
1 1

c h
.

13. (M) From Experiment 1 to 2, [NO] remains constant while [Cl
2
] is doubled. At the same time the
initial rate of reaction is found to double. Thus, the reaction is first-order with respect to [Cl
2
],
since dividing reaction 2 by reaction 1 gives 2 =2
x
when x =1. From Experiment 1 to 3, [Cl
2
]
remains constant, while [NO] is doubled, resulting in a quadrupling of the initial rate of reaction.
Thus, the reaction must be second-order in [NO], since dividing reaction 3 by reaction 1 gives
4 =2
x
when x =2. Overall the reaction is third-order: Rate =k [NO]
2
[Cl
2
]. The rate constant
may be calculated from any one of the experiments. Using data from Exp. 1,

k =
5 1
2 2
2
Rate 2.27 10 M s
=
[NO] [Cl ] (0.0125 M) (0.0255M)

=5.70 M
2
s
1


14. (M)
(a) From Expt. 1 to Expt. 2, [B] remains constant at 1.40 M and [C] remains constant at
1.00 M, but [A] is halved 0.50 b g . At the same time the rate is halved 0.50 b g . Thus, the
reaction is first-order with respect to A, since 0.50 =0.50
x
whenx =1.
From Expt. 2 to Expt. 3, [A] remains constant at 0.70 M and [C] remains constant at
1.00 M, but [B] is halved 0.50 b g , from 1.40 M to 0.70 M. At the same time, the rate is
quartered 0.25 b g . Thus, the reaction is second-order with respect to B, since 0.50 =0.25
y

wheny =2.

From Expt. 1 to Expt. 4, [A] remains constant at 1.40 M and [B] remains constant at
1.40 M, but [C] is halved( ) 0.50 , from 1.00 M to 0.50 M. At the same time, the rate is
increased by a factor of 2.0.

4 3 2 2 1 1
1 1
Rate =16Rate =16 Rate =4Rate =4 Rate =2 Rate.
4 2
(

(



Thus, the order of the reaction with respect to C is 1, since 0.5 =2.0
z
when z = 1 .


(b)

( ) ( ) ( )
( ) ( ) ( )
1 2 1
1 2 1
5
1+2 1 2
1 2 1 1 2 1
1 1 1 1
1 1 1 2 2 2 4
1.40 M 1.40 M 1.00 M
rate = 0.70 M 0.70 M 0.50 M =
2 2 2
1 1
1.40 M 1.40 M 1.00 M =rate =rate = rate
2 2
k k
k

| | | | | |
| | |
\ . \ . \ .
| | | |
=
| |
\ . \ .

This is based on ( ) ( ) ( )
1 2 1
1
rate = 1.40 M 1.40 M 1.00 M k



Chapter 14: Chemical Kinetics
622
First-Order Reactions

15. (E)
(a) TRUE The rate of the reaction does decrease as more and more of B and C are formed,
but not because more and more of B and C are formed. Rather, the rate decreases
because the concentration of A must decrease to form more and more of B and
C.

(b) FALSE The time required for one half of substance A to reactthe half-lifeis
independent of the quantity of A present.

16. (E)
(a) FALSE For first-order reactions, a plot of ln [A] or log [A] vs. time yields a straight line.
A graph of [A] vs. time yields a curved line.
(b) TRUE The rate of formation of C is related to the rate of disappearance of A by the
stoichiometry of the reaction.

17. (M)
(a) Since the half-life is 180 s, after 900 s five half-lives have elapsed, and the original quantity
of A has been cut in half five times.
final quantity of A initial = 0.5
5
b g quantity of A initial =0.03125 quantity of A
About 3.13% of the original quantity of A remains unreacted after 900 s.
or
More generally, we would calculate the value of the rate constant, k, using

1
1/2
ln 2 0.693
= = =0.00385 s
180 s
k
t

Now ln(% unreacted) =-kt =-0.00385 s

-1
(900s) =-
3.465
(% unreacted) =0.0313 100% =3.13% of the original quantity.
(b) Rate A s M M/ s = =0.00385 0.50 =0.00193
1
k



18. (M)
(a) The reaction is first-order, thus
| |
| |
1
0
A
0.100 M 2.08
ln = =ln = 54min( ) = =0.0385min
A 0.800 M 54 min
t
kt k k

We may now determine the time required to achieve a concentration of 0.025 M

| |
| |
1
1
0
A
0.025 M 3.47
ln = =ln = 0.0385min ( ) = =90. min
A 0.800 M 0.0385min
t
kt t t

(b) Since we know the rate constant for this reaction (see above),
| |
1
1 4
Rate= A =0.0385min 0.025 M =9.6 10 k

M/min

Chapter 14: Chemical Kinetics
623
19. (M)
(a) The mass of A has decreased to one fourth of its original value, from 1.60 g to
0.40 g. Since
1
4
=
1
2
1
2
, we see that two half-lives have elapsed.
Thus, 2 =38
1/2
t min, or t
1/2
=19 min.
(b)
| |
| |
1 1
1/2
0
A
0.693
=0.693/ = =0.036min ln = = 0.036min 60min= 2.2
19min A
t
k t kt


| |
| |
| | | |
2.2
0
0
A
= e =0.11 or A = A =1.60 g A 0.11=0.18 g A
A
kt t
t
e



20. (M)
(a)
| |
| |
1
0
A
0.632 M 0.256
ln = =ln = 0.256 = =0.0160min
A 0.816 M 16.0min
t
kt k

(b)
1/2 1
0.693 0.693
= = =43.3 min
0.0160 min
t
k



(c) We need to solve the integrated rate equation to find the elapsed time.

| |
| |
1
0
A
0.235 M
ln = =ln = 1.245= 0.0160min
A 0.816 M
t
kt t

1
1.245
= =77.8min
0.0160min
t

(d) ln
A
A
0
=kt becomes
| |
| |
0
A
=
A
kt
e

which in turn becomes

| | | |
1
0
60min
A = A =0.816 M exp 0.0160min 2.5 h =0.816 0.0907=0.074 M
1 h
kt
e


| |
|
\ .


21. (M) We determine the value of the first-order rate constant and from that we can calculate the
half-life. If the reactant is 99% decomposed in 137 min, then only 1% (0.010) of the initial
concentration remains.
| |
| |
1
0
A
0.010 4.61
ln = =ln = 4.61= 137min = =0.0336min
A 1.000 137min
t
kt k k

t
k
1/2 1
=
0.0693
=
0.693
0.0336
=20.6
min
min

Chapter 14: Chemical Kinetics
624
22. (E) If 99% of the radioactivity of
32
P is lost, 1% (0.010) of that radioactivity remains. First we
compute the value of the rate constant from the half-life. k
t
=
0.693
=
0.693
14.3
=0.0485
1/2
1
d
d

Then we use the integrated rate equation to determine the elapsed time.
ln
A
A
ln
A
A d
ln days
t t
kt t
k
0 0
1
= =
1
=
1
0.0485
0.010
1.000
=95



23. (D)
(a)
0
0
35
[A]
100
ln
[A]
| |
|
|
|
\ .
=ln(0.35) =kt =(4.81 10
3
min
1
)t t =218 min.
Note: We did not need to know the initial concentration of acetoacetic acid to answer the
question.

(b) Lets assume that the reaction takes place in a 1.00L container.
10.0 g acetoacetic acid
1 mol acetoacetic acid
102.090 g acetoacetic acid
=0.09795 mol acetoacetic acid.
After 575 min. (~4 half lives, hence, we expect ~6.25% remains as a rough
approximation), use integrated form of the rate law to find [A]
t
=575 min.
0
[A]
ln
[A]
t
| |
|
\ .
=kt =(4.81 10
3
min
1
)(575 min) =2.766
0
[A]
[A]
t
=e
2.766
=0.06293 (~6.3% remains)
[A]
0.09795moles
t
=0.063 [A]
t
=6.2 10
3

moles.
[A]
reacted
=[A]
o
[A]
t
=(0.098 6.2 10
3
) moles =0.092 moles acetoacetic acid. The
stoichiometry is such that for every mole of acetoacetic acid consumed, one mole of CO
2

forms. Hence, we need to determine the volume of 0.0918 moles CO
2
at 24.5 C (297.65
K) and 748 torr (0.984 atm) by using the Ideal Gas law.
V =
L atm
0.0918mol 0.08206 297.65K
K mol
=
0.984atm
nRT
P
| |
|
\ .
=2.3 L CO
2


24. (M)
(a)
| |
| |
4 1
0
3
4 1
A
2.5 g
ln = =ln = 3.47= 6.2 10 s
A 80.0 g
3.47
= =5.6 10 s 93 min
6.2 10 s
t
kt t
t



~

We substituted masses for concentrations, because the same substance (with the same
molar mass) is present initially at time , t and because it is a closed system.

Chapter 14: Chemical Kinetics
625
(b) amount O g N O
mol N O
g N O
mol O
mol N O
mol O
2 2 5
2 5
2 5
2
2 5
2
=77.5
1
108.0
1
2
=0.359
2
2
L atm
0.359mol O 0.08206 (45 273) K
mol K
9.56L O
1atm
745mmHg
760mmHg
nRT
V
P
+
= = =

25. (D)
(a) If the reaction is first-order, we will obtain the same value of the rate constant from several
sets of data.

| |
| |
3 1
0
A
0.497 M 0.188
ln = =ln = 100 s= 0.188, = =1.88 10 s
A 0.600 M 100 s
t
kt k k



| |
| |
3 1
0
A
0.344 M 0.556
ln = =ln = 300 s= 0.556, = =1.85 10 s
A 0.600 M 300 s
t
kt k k




| |
| |
3 1
0
A
0.285 M 0.744
ln = =ln = 400 s= 0.744, = =1.86 10 s
A 0.600 M 400 s
t
kt k k




| |
| |
3 1
0
A
0.198 M 1.109
ln = =ln = 600 s= 1.109, = =1.85 10 s
A 0.600 M 600 s
t
kt k k




| |
| |
3 1
0
A
0.094 M 1.854
ln = =ln = 1000 s= 1.854, = =1.85 10 s
A 0.600 M 1000 s
t
kt k k


The virtual constancy of the rate constant throughout the time of the reaction confirms that
the reaction is first-order.
(b) For this part, we assume that the rate constant equals the average of the values obtained in
part (a).
k =
1.88+1.85+1.86+1.85
4
10 =1.86 10
3 1 3 1


s s
(c) We use the integrated first-order rate equation:
| | | | ( ) ( )
| |
3 1
750 0
1.40
750
A = A exp =0.600 M exp 1.86 10 s 750 s
A =0.600 M e =0.148 M
kt

26. (D)
(a) If the reaction is first-order, we will obtain the same value of the rate constant from several
sets of data.

0
264 mmHg
ln = =ln = 390 s= 0.167
312 mmHg
t
P
kt k
P
, k =
0.167
390
=4.28 10
4 1
s
s



0
224 mmHg
ln = =ln = 777 s= 0.331
312 mmHg
t
P
kt k
P
, k =
0.331
777
=4.26 10
4 1
s
s



0
187 mmHg
ln = =ln = 1195 s= 0.512
312 mmHg
t
P
kt k
P
, k =
0.512
1195
=4.28 10
4 1
s
s


Chapter 14: Chemical Kinetics
626

0
78.5 mmHg
ln = =ln = 3155 s= 1.38
312 mmHg
t
P
kt k
P
,
4 1
1.38
= =4.37 10 s
3155 s
k


The virtual constancy of the rate constant confirms that the reaction is first-order.

(b) For this part we assume the rate constant is the average of the values in part
(a):4.3 10
4 1

s .

(c) At 390 s, the pressure of dimethyl ether has dropped to 264 mmHg. Thus, an amount of
dimethyl ether equivalent to a pressure of 312 264 = mmHg mmHg b g 48 mmHg has
decomposed. For each 1 mmHg pressure of dimethyl ether that decomposes, 3 mmHg of
pressure from the products is produced. Thus, the increase in the pressure of the products is
3 48=144 mmHg. The total pressure at this point is 264 +144 =408 mmHg mmHg
mmHg. Below, this calculation is done in a more systematic fashion:

CH O g
3
2
b g b g CH g
4
b g + H g
2
b g + CO g b g
Initial 312 mmHg 0 mmHg 0 mmHg 0 mmHg
Changes 48 mmHg +48 mmHg +48 mmHg +48 mmHg
Final 264 mmHg 48 mmHg 48 mmHg 48 mmHg

P P P P P
total DME methane hydrogen CO
+
mmHg 48mmHg 48mmHg 48mmHg 408mmHg
= + +
264 = + + + =


(d) This question is solved in the same manner as part (c). The results are summarized below.

CH O g CH g H g CO g
Initial 312 mmHg 0mmHg 0mmHg 0mmHg
Changes mmHg mmHg mmHg +312 mmHg
Final mmHg mmHg mmHg mmHg
+
mmHg mmHg mmHg mmHg mmHg
total DME methane hydrogen CO
3
2
4 2
+
312 312 312
0 312 312 312
= + +
0 312 312 312 936
b g b g b g b g b g +
+ +
= + + + =
P P P P P

(e) We first determine P
DME
at 1000 s. ln s s
P
P
kt
1000
0
4 1
= = 4.3 10 1000 = 0.43


0.43 1000
1000
0
= =0.65 =312 mmHg 0.65=203 mmHg
P
e P
P

Then we use the same approach as was used for parts (c) and (d)

( ) ( ) ( ) ( ) ( )
3 4 2
2
total DME methane hydrogen CO
CH O g CH g + H g + CO g
Initial 312 mmHg 0 mmHg 0 mmHg 0 mmHg
Changes 109mmHg 109mmHg 109mmHg 109mmHg
Final 203 mmHg 109 mmHg 109 mmHg 109 mmHg
= + + +
=203 mmHg+109 mmHg+109 mmH
P P P P P

+ + +
g+109 mmHg=530. mmHg


Chapter 14: Chemical Kinetics
627
Reactions of Various Orders

27. (M)
(a) Set II is data from a zero-order reaction. We know this because the rate of set II is constant.
0.25 M/25 s M s =0.010
1
. Zero-order reactions have constant rates of reaction.
(b) A first-order reaction has a constant half-life. In set I, the first half-life is slightly less than
75 sec, since the concentration decreases by slightly more than half (from 1.00 M to 0.47 M)
in 75 s. Again, from 75 s to 150 s the concentration decreases from 0.47 M to 0.22 M, again
by slightly more than half, in a time of 75 s. Finally, two half-lives should see the
concentration decrease to one-fourth of its initial value. This, in fact, is what we see. From
100 s to 250 s, 150 s of elapsed time, the concentration decreases from 0.37 M to 0.08 M,
i.e., to slightly less than one-fourth of its initial value. Notice that we cannot make the same
statement of constancy of half-life for set III. The first half-life is 100 s, but it takes more
than 150 s (from 100 s to 250 s) for [A] to again decrease by half.
(c) For a second-order reaction,1/ 1/ =
0
A A
t
kt . For the initial 100 s in set III, we have
1 1 1
1 1
=1.0 L mol = 100 s, =0.010 L mol s
0.50 M 1.00 M
k k


For the initial 200 s, we have
1 1 1
1 1
=2.0 L mol = 200 s, =0.010 L mol s
0.33 M 1.00 M
k k


Since we obtain the same value of the rate constant using the equation for second-order
kinetics, set III must be second-order.

28. (E) For a zero-order reaction (set II), the slope equals the rate constant:
| |
= A / =1.00 M/100 s=0.0100 M/s k t A A

29. (M) Set I is the data for a first-order reaction; we can analyze those items of data to determine the
half-life. In the first 75 s, the concentration decreases by a bit more than half. This implies a half-
life slightly less than 75 s, perhaps 70 s. This is consistent with the other time periods noted in the
answer to Review Question 18 (b) and also to the fact that in the 150-s interval from 50 s to 200 s,
the concentration decreases from 0.61 M to 0.14 M, which is a bit more than a factor-of-four
decrease. The factor-of-four decrease, to one-fourth of the initial value, is what we would expect
for two successive half-lives. We can determine the half-life more accurately, by obtaining a
value of k from the relation | | | | ( )
0
ln A / A =
t
kt followed by t k
1/2
=0.693/ For instance,
ln(0.78/1.00) =-k (25 s);
k =9.94 10
-3
s
-1
. Thus, t
1/2
=0.693/9.94 10
-3
s
-1
=70 s.

30. (E) We can determine an approximate initial rate by using data from the first 25 s.
| |
1
A
0.80 M 1.00 M
Rate= = =0.0080 M s
25 s 0 s t

A


A


Chapter 14: Chemical Kinetics
628
31. (M) The approximate rate at 75 s can be taken as the rate over the time period from 50 s to 100 s.
(a) Rate
A M M
s s
M s
II
= =
0.00 0.50
100 50
=0.010
1

A
A

t


(b) Rate
A M M
s s
M s
I
= =
0.37 0.61
100 50
=0.0048
1

A
A

t


(c) Rate
A M M
s s
M s
III
= =
0.50 0.67
100 50
=0.0034
1

A
A

t

Alternatively we can use [A] at 75 s (the values given in the table) in the
relationshipRate A =k
m
, where m=0, 1, or 2.
(a) ( )
0
1 1
II
Rate =0.010 M s 0.25 mol/L =0.010 M s



(b)
1
1/2
Since 70s, 0.693/ 70s 0.0099s t k

= = =
1 1 1
I
Rate 0.0099 (0.47mol/L) 0.0047Ms s

= =

(c) ( )
2
1 1 1
III
Rate =0.010 L mol s 0.57 mol/L =0.0032 M s




32. (M) We can combine the approximate rates from Exercise 31, with the fact that 10 s have
elapsed, and the concentration at 100 s.
(a)
| |
II
A =0.00 M There is no reactant left after 100 s.

(b) A A s rate M s M s M
I
= 10 =0.37 10 0.0047 =0.32
100
1


b g c h


(c) A A s rate M s M s M
III
= 10 =0.50 10 0.0032 =0.47
100
1


b g c h


33. (E) Substitute the given values into the rate equation to obtain the rate of reaction.
Rate A B M min M M M min = = 0.0103 0.116 3.83 =1.39 10 /
2 0
1 1
2 0
4
k

c hb g b g

34. (M)
(a) A first-order reaction has a constant half-life. Thus, half of the initial concentration remains
after 30.0 minutes, and at the end of another half-life60.0 minutes totalhalf of the
concentration present at 30.0 minutes will have reacted: the concentration has decreased to
one-quarter of its initial value. Or, we could say that the reaction is 75% complete after two
half-lives60.0 minutes.

(b) A zero-order reaction proceeds at a constant rate. Thus, if the reaction is 50% complete in
30.0 minutes, in twice the time60.0 minutesthe reaction will be 100% complete. (And
in one-fifth the time6.0 minutesthe reaction will be 10% complete. Alternatively, we
can say that the rate of reaction is 10%/6.0 min.) Therefore, the time required for the
reaction to be 75%
60.0 min
complete=75% =45 min.
100%



Chapter 14: Chemical Kinetics
629
35. (M) For reaction: HI(g) 1/2 H
2
(g) + 1/2 I
2
(g) (700 K)

Time
(s)
[HI] (M) ln[HI] 1/[HI](M
1
)
0 1.00 0 1.00
100 0.90 0.105 1.11
200 0.81 0.211 1.235
300 0.74 0.301 1.35
400 0.68 0.386 1.47

From data above, a plot of 1/[HI] vs. t yields
a straight line. The reaction is second-order
in HI at 700 K. Rate =k[HI]
2
. The slope of
the line =k =0.00118 M
1
s
1

Plot of 1/[HI] vs time
y =0.00118x +0.997
1.00
1.20
1.40
1.60
0 250 500
Time(s)
1
/
[
H
I
]

(
M
-
1
)


36. (D)
(a) We can graph 1/[ArSO
2
H] vs. time and obtain a straight line. We can also graph [ArSO
2
H]
vs. time and ln([ArSO
2
H]) vs. time to demonstrate that they do not yield a straight line.
Only the plot of 1/[ArSO
2
H] versus time is shown.













The linearity of the line indicates that the reaction is second-order.

(b) We solve the rearranged integrated second-order rate law for the rate constant, using the
longest time interval.
1 1
=
1 1 1
=
0 0
A A A A
t t
kt
t
k
F
H
G
I
K
J

1 1
1 1 1
= =0.137 L mol min
300min 0.0196 M 0.100 M
k

| |

|
\ .


(c) We use the same equation as in part (b), but solved fort , rather thank .
| | | |
1 1
0
1 1 1 1 1 1
= = =73.0min
A A 0.137 L mol min 0.0500 M 0.100 M
t
t
k

| |
| |
|
|
|
\ .
\ .

Plot of 1/[ArSO
2
H] versus Time
y =0.137x +9.464
10
30
50
0 50 100 150 200 250 300
Time (min)
1
/
[
A
r
S
O
2
H
]

(
M
-
1
)
1
/
[
A
r
S
O
2
H
]

(
M
-
1
)

Plot of 1/[ArSO
2
H] versus Time
Chapter 14: Chemical Kinetics
630
(d) We use the same equation as in part (b), but solve fort , rather thank .
| | | |
1 1
0
1 1 1 1 1 1
= = =219min
A A 0.137 L mol min 0.0250 M 0.100 M
t
t
k

| |
| |
|
|
|
\ .
\ .


(e) We use the same equation as in part (b), but solve fort , rather thank .
| | | |
1 1
0
1 1 1 1 1 1
= = =136 min
A A 0.137 L mol min 0.0350 M 0.100 M
t
t
k

| |
| |
|
|
|
\ .
\ .


37. (M)
(a) Plot [A] vs t, ln[A] vs t, and 1/[A] vs t and see which yields a straight line.

y =-0.0050x +0.7150
R
2
=1.0000
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 150
Time(s)
[
A
]

(
m
o
l
/
L
)
y =-0.0191x
- 0.1092
R
2
=0.9192
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 150
Time(s)
l
n
[
A
]

y =0.1228x
- 0.9650
R
2
=0.7905
0
5
10
15
20
0 150
Time(s)
1
/
[
A
]


Clearly we can see that the reaction is zero-order in reactant A with a rate constant of 5.0 10
-3
.


(b) The half-life of this reaction is the time needed for one half of the initial [A] to react.
Thus,
| | A =0.715 M 2=0.358 A M and t
1/2 3
=
0.358
5.0 10
=72
M
M/ s

s.

Chapter 14: Chemical Kinetics
631
38. (D)
(a) We can either graph 1/
4 6
C H vs. time and obtain a straight line, or we can determine the
second-order rate constant from several data points. Then, if k indeed is a constant, the
reaction is demonstrated to be second-order. We shall use the second technique in this case.
First we do a bit of algebra.

1 1
=
1 1 1
=
0 0
A A A A
t t
kt
t
k
F
H
G
I
K
J

k =
1
12.18
1
0.0144
1
0.0169
=0.843
1 1
min M M
L mol min
F
H
G
I
K
J


k =
1
24.55
1
0.0124
1
0.0169
=0.875
1 1
min M M
L mol min
F
H
G
I
K
J


k =
1
42.50
1
0.0103
1
0.0169
=0.892
1 1
min M M
L mol min
F
H
G
I
K
J


k =
1
68.05
1
0.00845
1
0.0169
=0.870
1 1
min M M
L mol min
F
H
G
I
K
J


The fact that each calculation generates similar values for the rate constant indicates that
the reaction is second-order.
(b) The rate constant is the average of the values obtained in part (a).
1 1 1 1
0.843+0.875+0.892+0.870
= L mol min =0.87 L mol min
4
k



(c) We use the same equation as in part (a), but solve fort , rather thank .
| | | |
2
1 1
0
1 1 1 1 1 1
= = =2.0 10 min
A A 0.870 L mol min 0.00423 M 0.0169 M
t
t
k

| |
| |
|
|
|
\ .
\ .


(d) We use the same equation as in part (a), but solve fort , rather thank .
| | | |
2
1 1
0
1 1 1 1 1 1
= = =1.6 10 min
A A 0.870 L mol min 0.0050 M 0.0169 M
t
t
k

| |
| |
|
|
|
\ .
\ .


39. (E)
(a)
| | A
1.490 M 1.512 M
initial rate= = =+0.022 M/ min
1.0min 0.0min t
A


A


| | A
2.935 M 3.024 M
initial rate= = =+0.089 M/ min
1.0min 0.0min t
A


A


(b) When the initial concentration is doubled 2.0 b g , from 1.512 M to 3.024 M, the initial rate
quadruples 4.0 b g . Thus, the reaction is second-order in A (since 2.0 =4.0
x
when x =2).

Chapter 14: Chemical Kinetics
632
40. (M)
(a) Let us assess the possibilities. If the reaction is zero-order, its rate will be constant. During
the first 8 min, the rate is ( ) 0.60 M 0.80 M /8min=0.03 M/min . Then, during the first
24 min, the rate is ( ) 0.35 M 0.80 M /24min=0.019 M/min . Thus, the reaction is not
zero-order. If the reaction is first-order, it will have a constant half-life that is consistent
with its rate constant. The half-life can be assessed from the fact that 40 min elapse while
the concentration drops from 0.80 M to 0.20 M, that is, to one-fourth of its initial value.
Thus, 40 min equals two half-lives and
1/2
=20 min t .
This gives k t =0.693/ =0.693/ 20 =0.035
1/2
1
min min

. Also
kt k k
t
= =
0.35
0.80
=0.827= 24 =
0.827
24
=0.034
0
1


ln
A
A
ln
M
M
min
min
min
The constancy of the value of k indicates that the reaction is first-order.

(b) The value of the rate constant is k =0.034
1
min

.

(c) Reaction rate=
1
2
(rate of formation of B) =
1
k A First we need [A] at t =30. min
| |
| |
| |
| |
1 1.02
2
0 0
A A
ln = = 0.034min 30. min= 1.0 = =0.36
A A
kt e


A M M =0.36 0.80 =0.29
rate of formation of B min M M min =2 0.034 0.29 =2.0 10
1 2 1




41. (M) The half-life of the reaction depends on the concentration of A and, thus, this reaction cannot
be first-order. For a second-order reaction, the half-life varies inversely with the reaction rate:
t k
1/2
0
=1/ A
c h
ork t =1/
1/2
0
A
c h
. Let us attempt to verify the second-order nature of this
reaction by seeing if the rate constant is fixed.
1 1
1
= =0.020 L mol min
1.00 M 50 min
k

1 1
1
= =0.020 L mol min
2.00 M 25min
k

k =
1
0.50 100
=0.020
1 1
M min
L mol min

The constancy of the rate constant demonstrates that this reaction indeed is second-order. The rate
equation is Rate A =
2
k and k =0.020
1 1
L mol min

.

Chapter 14: Chemical Kinetics
633
42. (M)
(a) The half-life depends on the initial NH
3
and, thus, the reaction cannot be first-order. Let
us attempt to verify second-order kinetics.
1 1
3 1/2
0
1 1
= for a second-order reaction = =42 M min
NH 0.0031 M 7.6min
k k
t

(
(



1 1 1 1
1 1
= =180 M min = =865 M min
0.0015 M 3.7min 0.00068 M 1.7min
k k



The reaction is not second-order. But, if the reaction is zero-order, its rate will be constant.
| |
4 0
1/2
A / 2
0.0031 M 2
Rate= = =2.0 10 M/min
7.6min t

4
0.0015 M 2
Rate= =2.0 10 M/min
3.7 min

4
0.00068M 2
Rate = 2.0 10 M/ min
1.7 min

= Zero-order reaction

(b) The constancy of the rate indicates that the decomposition of ammonia under these
conditions is zero-order, and the rate constant is k =2.0 10
4

M/min.

43. (M) Zero-order: t
1/2
=
0
[A]
2k
Second-order: t
1/2
=
0
1
[A] k

A zero-order reaction has a half life that varies proportionally to [A]
0
, therefore, increasing [A]
0

increases the half-life for the reaction. A second-order reaction's half-life varies inversely
proportional to [A]
0
, that is, as [A]
0
increases, the half-life decreases. The reason for the
difference is that a zero-order reaction has a constant rate of reaction (independent of [A]
0
). The
larger the value of [A]
0
, the longer it will take to react. In a second-order reaction, the rate of
reaction increases as the square of the [A]
0
, hence, for high [A]
0
, the rate of reaction is large and
for very low [A]
0
, the rate of reaction is very slow. If we consider a bimolecular elementary
reaction, we can easily see that a reaction will not take place unless two molecules of reactants
collide. This is more likely when the [A]
0
is large than when it is small.

44. (M)
(a)
0
[A]
2k
=
0.693
k
Hence,
0
[A]
2
=0.693 or [A]
0
=1.39 M

(b)
0
0
[A] 1
2 [A] k k
= , Hence,
2
0
[A]
2
=1 or [A]
0
2
=2.00 M [A]
0
=1.414 M

(c)
o
0.693 1
[A] k k
= , Hence, 0.693 =
0
1
[A]
or [A]
0
=1.44 M

Chapter 14: Chemical Kinetics
634
Collision Theory; Activation Energy

45. (M)
(a) The rate of a reaction depends on at least two factors other than the frequency of collisions.
The first of these is whether each collision possesses sufficient energy to get over the
energy barrier to products. This depends on the activation energy of the reaction; the higher
it is, the smaller will be the fraction of successful collisions. The second factor is whether
the molecules in a given collision are properly oriented for a successful reaction. The more
complex the molecules are, or the more freedom of motion the molecules have, the smaller
will be the fraction of collisions that are correctly oriented.

(b) Although the collision frequency increases relatively slowly with temperature, the fraction
of those collisions that have sufficient energy to overcome the activation energy increases
much more rapidly. Therefore, the rate of reaction will increase dramatically with
temperature.

(c) The addition of a catalyst has the net effect of decreasing the activation energy of the
overall reaction, by enabling an alternative mechanism. The lower activation energy of the
alternative mechanism, (compared to the uncatalyzed mechanism), means that a larger
fraction of molecules have sufficient energy to react. Thus the rate increases, even though
the temperature does not.

46. (M)
(a) The activation energy for the reaction of hydrogen with oxygen is quite high, too high, in
fact, to be supplied by the energy ordinarily available in a mixture of the two gases at
ambient temperatures. However, the spark supplies a suitably concentrated form of energy
to initiate the reaction of at least a few molecules. Since the reaction is highly exothermic,
the reaction of these first few molecules supplies sufficient energy for yet other molecules
to react and the reaction proceeds to completion or to the elimination of the limiting
reactant.

(b) A larger spark simply means that a larger number of molecules react initially. But the
eventual course of the reaction remains the same, with the initial reaction producing enough
energy to initiate still more molecules, and so on.

47. (M)
(a) The products are 21 kJ /mol closer in energy to the energy activated complex than are the
reactants. Thus, the activation energy for the reverse reaction is
84 21 =63 . kJ / mol kJ / mol kJ / mol

Chapter 14: Chemical Kinetics
635
(b) The reaction profile for the reaction in Figure 14-10 is sketched below.



48. (M) In an endothermic reaction (right), E
a
must be larger than theAH for the reaction. For an
exothermic reaction (left), the magnitude of E
a
may be either larger or smaller than that of AH .
In other words, a small activation energy can be associated with a large decrease in the enthalpy,
or a large E
a
can be connected to a small decrease in enthalpy.



49. (E)
(a) There are two intermediates (B and C).

(b) There are three transition states (peaks/maxima) in the energy diagram.

(c) The fastest step has the smallest E
a
, hence, step 3 is the fastest step in the reaction with
step 2 a close second.

(d) Reactant A (step 1) has the highest E
a
, and therefore the slowest smallest constant

(e) Endothermic; energy is needed to go from A to B.

(f) Exothermic; energy is released moving from A to D.

reactants
products
H<0
reactants
products
H>0
Transiton State
E
a
(forward) =84 kJ
E
a
(reverse) =63 kJ
AH =+21 kJ
A +B
C +D
A
. . . .
B
Reactants
Products
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

(
k
J
)
Progress of Reaction
Chapter 14: Chemical Kinetics
636
50. (E)
(a) There are two intermediates (B and C).
(b) There are three transition states (peaks/maxima) in the energy diagram.
(c) The fastest step has the smallest E
a
, hence, step 2 is the fastest step in the reaction.
(d) Reactant A (step 1) has the highest E
a
, and therefore the slowest smallest constant
(e) Endothermic; energy is needed to go from A to B.
(f) Endothermic, energy is needed to go from A to D.

Effect of Temperature on Rates of Reaction

51. (M)
ln ln
L mol s
L mol s K K
k
k
E
R T T
E
R
a a 1
2 2 1
4 1 1
2 1 1
=
1 1
=
5.4 10
2.8 10
=
1
683
1
599

F
H
G
I
K
J

F
H
G
I
K
J





3.95 = 2.05 10
4
R E
a

E
R
a
=
3.95
2.05 10
=1.93 10 8.3145 =1.60 10 =160
4
4 1 1 1 5

K J mol K J / mol kJ / mol

52. (M)

3 1 1 5
1
2 1 1 1 1
2 2 1
1 1 5.0 10 L mol s 1.60 10 J /mol 1 1
ln = =ln =
683 K 2.8 10 L mol s 8.3145 J mol K
a
E k
k R T T T


| | | |

| |

\ .
\ .

4 5
4
1 1 1 1 1.72
1.72=1.92 10 = = 8.96 10
683 K 683 K 1.92 10 T T

| | | |

| |

\ . \ .

5 3 3
1
=8.96 10 +1.46 10 =1.55 10 =645 K T
T



53. (D)
(a) First we need to compute values of ln k and 1/ T . Then we plot the graph of ln k versus
1/T.
, C T

0 C 10 C 20 C 30 C
T , K 273 K 283 K 293 K 303 K
1/ ,
1
T K

0.00366 0.00353 0.00341 0.00330

1
, s k

5.6 10
6

3.2 10
5

1.6 10
4

7.6 10
4

ln k 12.09 10.35 8.74 7.18
Chapter 14: Chemical Kinetics
637












(b) The slope=E R
a
/ .
4
a 2
J 1 kJ kJ
= slope= 8.3145 1.35 10 K =112
mol K 1000 J mol
E R
(c) We apply the Arrhenius equation, with k =5.6 10
6 1

s at 0

C (273 K), k =? at 40C

(313 K), and E
a
=113 10
3
J /mol.
3
a
6 1 1 1
1 2
1 1 112 10 J /mol 1 1
ln = = =6.306
273 K 313 K 5.6 10 s 8.3145 J mol K
E k
R T T

| | | |

| |

\ .
\ .

6.306 6 1 3 1
6 1
=548= =548 5.6 10 s =3.07 10 s
5.6 10 s
k
e k

54. (D)
(a) Here we plot ln k vs.1/ T . The slope of the straight line equalsE R
a
/ . First we tabulate
the data to plot. (the plot is shown below).

, T C 15.83 32.02 59.75 90.61
T , K 288.98 305.17 332.90 363.76
1/ T , K
1
0.0034604 0.0032769 0.0030039 0.0027491
k , M
1
s
1
5.03 10
5

3.68 10
4

6.71 10
3

0.119
ln k 9.898 7.907 5.004 2.129











Plot of ln k versus 1/T
y =-13520x +37.4
-12.1
-11.1
-10.1
-9.1
-8.1
-7.1
0.00325 0.00345 0.00365
1/T (K
-1
)
l
n

k
Plot of ln k versus 1/T
y =-10890x +27.77
-12
-10
-8
-6
-4
-2
0
0.0027 0.0029 0.0031 0.0033 0.0035 1/T (K
-1
)
l
n

k
2
1/2
3 1
0.693 0.693
= = =2.3 10 s
3.07 10 s
t
k

Chapter 14: Chemical Kinetics

638
The slope of this graph K
a
= 1.09 10 = /
4
E R

( )
4 4
a
J J 1 kJ kJ
= 1.089 10 K 8.3145 = 9.054 10 =90.5
mol K mol 1000 J mol
E


(b) We calculate the activation energy with the Arrhenius equation using the two extreme data
points.
a a 2
5
1 1 2
1 1
4 1 4 a
a
4 1
0.119 1 1 1 1
ln =ln =+7.77= =
5.03 10 288.98 K 363.76 K
7.769 8.3145 J mol K
=7.1138 10 K = =9.08 10 J /mol
7.1138 10 K
E E k
k R T T R
E
E
R

| |
| |

| |

\ .
\ .

a
=91 E kJ /mol. The two E
a
values are in quite good agreement, within experimental limits.

(c) We apply the Arrhenius equation, with E
a
=9.080 10
4
J /mol,
k =5.03 10
5 1 1

M s at 15.83 C (288.98 K), and k =? at 100.0 C (373.2 K).

3
a
5 1 1 1 1
2
1
8.528 3
5 1 1 5 1 1
1 1 90.80 10 J /mol 1 1
ln = =
5.03 10 M s 8.3145 J mol K 288.98 K 373.2 K
ln =8.528 =5.05 10 =
5.03 10 M s 5.03 10 M s
E k
R T T
k k
e


| | | |

| |

\ .
\ .

3 5 1 1 1 1
=5.05 10 5.03 10 M s =0.254 M s k



55. (M) The half-life of a first-order reaction is inversely proportional to its rate constant:
k t =0.693/
1/2
. Thus we can apply a modified version of the Arrhenius equation to find E
a
.
(a)
( )
( ) ( )
1/2
a a 2 1
1 1/2 1 2
2
1 1 46.2min 1 1
ln =ln = =ln =
2.6min 298 K 102+273 K
t
E E k
k t R T T R
| |
| |

|
|
|
\ .
\ .

1 1
4 a
a
4 1
2.88 8.3145J mol K 1 kJ
2.88= 6.89 10 = =34.8 kJ /mol
6.89 10 K 1000 J
E
E
R

(b)
10.0
46.2
=
34.8 10
8.3145
1 1
298
= 1.53=4.19 10
1 1
298
3
1 1
3
ln
min
min
J / mol
J mol K

F
H
G
I
K
J

F
H
G
I
K
J

T T

4 3 o
3
1 1 1.53 1
= = 3.65 10 =2.99 10 =334 K =61 C
298 4.19 10
T
T T

| |

|

\ .


56. (M) The half-life of a first-order reaction is inversely proportional to its rate
constant: k t =0.693/
1/2
. Thus, we can apply a modified version of the Arrhenius equation.
(a)
( )
( ) ( )
1/2
a a 2 1
1 1/2 1 2
2
1 1 22.5 h 1 1
ln =ln = =ln =
1.5h 293 K 40+273 K
t
E E k
k t R T T R
| |
| |

|
|
|
\ .
\ .

1 1
4 a
a
4 1
2.71 8.3145J mol K 1 kJ
2.71= 2.18 10 , = =103 kJ /mol
2.18 10 K 1000 J
E
E
R

Chapter 14: Chemical Kinetics
639
(b) The relationship is k A E RT = / exp
a
b g
( )
3 1
1 1
13 1 13 1 40.9 5 1
103 10 J mol
8.3145 J mol K 273+30 K
=2.05 10 s exp =2.05 10 s 3.5 10 s k e

| |
=
|
\ .

57. (M)
(a) It is the change in the value of the rate constant that causes the reaction to go faster. Let k
1

be the rate constant at room temperature, 20 C

(293 K). Then, ten degrees higher (30 C

or 303 K), the rate constant
2 1
=2 k k .

4 1 a a 2 1
1 1 1 2
2 1 1 1 1
ln =ln =0.693= = =1.13 10 K
293 303 K
a
E E E k k
k k R T T R R

| |
| |

| |
\ .
\ .

E
a
J mol K
K
J / mol kJ / mol =
0.693 8.3145
1.13 10
=5.1 10 =51
1 1
4 1
4

(b) Since the activation energy for the depicted reaction (i.e., N
2
O +NO N
2
+NO
2
) is 209
kJ /mol, we would not expect this reaction to follow the rule of thumb.

58. (M) Under a pressure of 2.00 atm, the boiling point of water is approximately 121 C or 394 K.
Under a pressure of 1 atm, the boiling point of water is 100

C or 373 K. We assume an
activation energy of 5.1 10
4
J / mol and compute the ratio of the two rates.
ln
Rate
Rate
J / mol
J mol K K
2
1 1 2
4
1 1
=
1 1
=
5.1 10
8.3145
1
373
1
394
=0.88
E
R T T
a

F
H
G
I
K
J


F
H
G
I
K
J


0.88
2 1 1
Rate = Rate =2.4 Rate . e Cooking will occur 2.4 times faster in the pressure cooker.

Catalysis

59. (E)
(a) Although a catalyst is recovered unchanged from the reaction mixture, it does take part in
the reaction. Some catalysts actually slow down the rate of a reaction. Usually, however,
these negative catalysts are called inhibitors.

(b) The function of a catalyst is to change the mechanism of a reaction. The new mechanism is
one that has a different (lower) activation energy (and frequently a different A value), than
the original reaction.

60. (M) If the reaction is first-order, its half-life is 100 min, for in this time period [S] decreases from
1.00 M to 0.50 M, that is, by one half. This gives a rate constant of
k t =0.693/ =0.693/100 =0.00693
1/2
1
min min

.
The rate constant also can be determined from any two of the other sets of data.
| |
| |
1 0
A
1.00 M 0.357
=ln =ln =0.357= 60min = =0.00595min
A 0.70 M 60min
t
kt k k


This is not a very good agreement between the two k values, so the reaction is probably not first-
order in [A]. Let's try zero-order, where the rate should be constant.
Chapter 14: Chemical Kinetics
640
0.90 M 1.00 M 0.50 M 1.00 M
Rate= =0.0050 M/min Rate= =0.0050 M/min
20min 100min


0.20 M 0.90 M 0.50 M 0.90 M
Rate= =0.0050 M/min Rate= =0.0050 M/min
160min 20min 100min 20min




Thus, this reaction is zero-order with respect to [S].


61. (E) Both platinum and an enzyme have a metal center that acts as the active site. Generally
speaking, platinum is not dissolved in the reaction solution (heterogeneous), whereas enzymes are
generally soluble in the reaction media (homogeneous). The most important difference, however,
is one of specificity. Platinum is rather nonspecific, catalyzing many different reactions. An
enzyme, however, is quite specific, usually catalyzing only one reaction rather than all reactions
of a given class.

62. (E) In both the enzyme and the metal surface cases, the reaction occurs in a specialized location:
either within the enzyme pocket or on the surface of the catalyst. At high concentrations of
reactant, the limiting factor in determining the rate is not the concentration of reactant present but
how rapidly active sites become available for reaction to occur. Thus, the rate of the reaction
depends on either the quantity of enzyme present or the surface area of the catalyst, rather than on
how much reactant is present (i.e., the reaction is zero-order). At low concentrations or gas
pressures the reaction rate depends on how rapidly molecules can reach the available active sites.
Thus, the rate depends on concentration or pressure of reactant and is first-order.

63. (E) For the straight-line graph of Rate versus [Enzyme], an excess of substrate must be present.

64. (E) For human enzymes, we would expect the maximum in the curve to appear around 37C, i.e.,
normal body temperature (or possibly at slightly elevated temperatures to aid in the control of
diseases (37 - 41 C). At lower temperatures, the reaction rate of enzyme-activated reactions
decreases with decreasing temperature, following the Arrhenius equation. However, at higher
temperatures, these temperature sensitive biochemical processes become inhibited, probably by
temperature-induced structural modifications to the enzyme or the substrate, which prevent
formation of the enzyme-substrate complex.

Reaction Mechanisms

65. (E) The molecularity of an elementary process is the number of reactant molecules in the process.
This molecularity is equal to the order of the overall reaction only if the elementary process in
question is the slowest and, thus, the rate-determining step of the overall reaction. In addition, the
elementary process in question should be the only elementary step that influences the rate of the
reaction.

66. (E) If the type of molecule that is expressed in the rate law as being first-order collides with other
molecules that are present in much larger concentrations, the reaction will seem to depend only
on the amount of those types of molecules present in smaller concentration, since the larger
concentration will be essentially unchanged during the course of the reaction. Such a situation is
quite common, and has been given the name pseudo first-order. It is also possible to have
molecules which, do not participate directly in the reaction including product molecules
Chapter 14: Chemical Kinetics
641
strike the reactant molecules and impart to them sufficient energy to react. Finally, collisions of
the reactant molecules with the container walls may also impart adequate energy for reaction to
occur.

67. (M) The three elementary steps must sum to give the overall reaction. That is, the overall reaction
is the sum of step 1 + step 2 + step 3. Hence, step 2 =overall reaction step 1 step 3. Note that
all species in the equations below are gases.
Overall:
2 2 2 2 2 2
2 NO+2H N +2 H O 2 NO+2 H N +2 H O
First:
( ) 2 2 2 2
2 NO N O N O 2NO



Third ( )
2 2 2 2 2 2 2 2
N O+H N +H O or N +H O N O+H

The result is the second step, which is slow: H N O H O N O
2 2 2 2 2
+ +
The rate of this rate-determining step is: Rate = | | | |
2 2 2 2
H NO k
Since N O
2 2
does not appear in the overall reaction, we need to replace its concentration with the
concentrations of species that do appear in the overall reaction. To do this, recall that the first step
is rapid, with the forward reaction occurring at the same rate as the reverse reaction.
k k
1
2
1 2 2
= = = NO forward rate reverse rate N O

. This expression is solved for N O

2 2
,
which then is substituted into the rate equation for the overall reaction.
N O
NO
Rate H NO
2 2
1
2
1
2 1
1
2
2
= =
k
k
k k
k


The reaction is first-order in H
2
and second-order in [NO]. This result conforms to the
experimentally determined reaction order.

68. (M) Proposed mechanism:
1
-1
2
I (g) 2I(g)
k
k

Observed rate law:

2
2
2 I(g) +H (g) 2 HI(g)
k
Rate =k[I
2
][H
2
]
I
2
(g) +H
2
(g) 2 HI(g)
The first step is a fast equilibrium reaction and step 2 is slow. Thus, the predicted rate law is
Rate =k
2
[I]
2
[H
2
]. In the first step, set the rate in the forward direction for the equilibrium equal
to the rate in the reverse direction. Then solve for [I]
2
.

Rate
forward
=Rate
reverse
Use: Rate
forward
=k
1
[I
2
] and Rate
reverse
=k
-1
[I]
2


From this we see: k
1
[I
2
] =k
-1
[I]
2
. Rearranging (solving for [I]
2
)
[I]
2
=
1 2
-1
[I ] k
k
Substitute into Rate =k
2
[I]
2
[H
2
] =k
2
1 2
-1
[I ] k
k
[H
2
] =k
obs
[I
2
][H
2
]
Since the predicted rate law is the same as the experimental rate law, this mechanism is
plausible.


Chapter 14: Chemical Kinetics
642
69. (M) Proposed mechanism:
1
-1
2
Cl (g) 2Cl(g)
k
k

Observed rate law:

2
2 Cl(g) +2 NO(g) 2 NOCl(g)
k
Rate =k[Cl
2
][NO]
2
Cl
2
(g) +2NO(g) 2 NOCl(g)

The first step is a fast equilibrium reaction and step 2 is slow. Thus, the predicted rate law is
Rate =k
2
[Cl]
2
[NO]
2
In the first step, set the rate in the forward direction for the equilibrium equal
to the rate in the reverse direction. Then express [Cl]
2
in terms of k
1,
k
-1
and [Cl
2
]. This
mechanism is almost certainly not correct because it involves a tetra molecular second step.

Rate
forward
=Rate
reverse
Use: Rate
forward
=k
1
[Cl
2
] and Rate
reverse
=k
-1
[Cl]
2

From this we see: k
1
[Cl
2
] =k
-1
[Cl]
2
. Rearranging (solving for [Cl]
2
)
[Cl]
2
=
1 2
-1
[Cl ] k
k
Substitute into Rate =k
2
[Cl]
2
[NO]
2
=k
2
1 2
-1
[Cl ] k
k
[NO]
2
=k
obs
[Cl
2
][NO
2
]
2
There is another plausible mechanism.
1
-1
2
Cl (g) +NO(g) NOCl(g) +Cl(g)
k
k

1
-1
Cl(g) +NO(g) NOCl(g)
k
k

Cl
2
(g) +2NO(g) 2 NOCl(g)

Rate
forward
=Rate
reverse
Use: Rate
forward
=k
1
[Cl
2
][NO] and Rate
reverse
=k
-1
[Cl][NOCl]

From this we see: k
1
[Cl
2
][NO] =k
-1
[Cl][NOCl]. Rearranging (solving for [Cl])
[Cl] =
1 2
-1
k [Cl ][NO]
k [NOCl]
Substitute into Rate =k
2
[Cl][NO] =
2
2 1 2
-1
[Cl ][NO]
[NOCl]
k k
k

If [NOCl], the product is assumed to be constant (~0 M using method of initial rates), then
2 1
obs
-1
constant =k
[NOCl]
k k
k
= Hence, the predicted rate law is
2
2
[Cl ][NO]
obs
k which agrees with
the experimental rate law. Since the predicted rate law agrees with the experimental rate law,
both this and the previous mechanism are plausible, however, the first is dismissed as it has a
tetramolecular elementary reaction (extremely unlikely to have four molecules simultaneously
collide).

70. (M) A possible mechanism is: Step 1: ( )
3 2
O O + O fast

Step 2: ( )
3 2
3
O+ O 2 O slow
k

The overall rate is that of the slow step: Rate O O =
3 3
k . But O is a reaction intermediate, whose
concentration is difficult to determine. An expression for [O] can be found by assuming that the
forward and reverse fast steps proceed with equal speed.
| | | | | | | |
| |
1 3
1 2 1 3 2 2
2 2
O
Rate =Rate O = O O O =
O
k
k k
k
(
(


| |
| |
| |
2
1 3 3
3 1
3 3
2 2 2 2
O O
Rate= O =
O O
k
k k
k
k k
( (
( (


Then substitute this expression into the rate law for the reaction. This rate equation has the same
form as the experimentally determined rate law and thus the proposed mechanism is plausible.

Chapter 14: Chemical Kinetics
643
71. (M)
( )
( ) ( )
1
1
2
k
1 2 1 2
k
k
1 2 1 2
S S S :S
S :S S :S

-
-
+

( )
| || | ( ) ( )
| || | ( )( )
( ) | || |
( )
( )
| || |
1 2
1 1 2 1 1 2 2 1 2
1 1 2 1 2 1 2
1
1 2 1 2
1 2
2 1 1 2 1 2
2 1 2
1 2
d S :S
k S S k S :S k S :S
dt
k S S k k S :S
k
S :S S S
k k
k k S S d S :S
k S :S
dt k k
-
- -

=
= +
=
+

= =
+


72. (M)

( ) ( )
( ) ( )
1
1
2
k
3 3 2 2
2 k
k
3 2 3
2
CH CO(aq) +OH CH C O CH (aq) +H O (l)
CH C O CH (aq) + CH CO(aq) Prod

We note that CH
3
C(O)CH
2

is an intermediate species. Using the steady state approximation,

while its concentration is not known during the reaction, the rate of change of its concentration is
zero, except for the very beginning and towards the end of the reaction. Therefore,
( )
( ) ( ) | |
( ) ( )
3 2
1 3 1 3 2 2
2
2 3 2 3
2
d CH C O CH
k CH CO OH k CH C O CH H O
dt
k CH C O CH CH CO 0

(

( ( ( =

( ( =



Rearranging the above expression to solve for CH
3
C(O)CH
2

gives the following expression

( )
( )
| | ( )
1 3
2
3 2
1 2 2 3
2
k CH CO OH
CH C O CH
k H O k CH CO

( (

( =

( +



The rate of formation of product, therefore, is:
| |
( ) ( )
( )
( )
| | ( )
( )
| | ( )
2 3 2 3
2
1 3
2
2 3
2
1 2 2 3
2
2
2 1 3
2
1 2 2 3
2
d Prod
k CH C O CH CH CO
dt
k CH CO OH
k CH CO
k H O k CH CO
k k CH CO OH
k H O k CH CO

( ( =

( (

( =

( +

( (

=
( +


Chapter 14: Chemical Kinetics
644
INTEGRATIVE AND ADVANCED EXERCISES

73. (M) The data for the reaction starting with 1.00 M being first-order or second-order as well as that
for the first-order reaction using 2.00 M is shown below

Time
(min)
[A]
o
=1.00 M
(second order)
[A]
o
=1.00 M
(first order)
[A]
o
=2.00 M
(second order)
[A]
o
=2.00 M
(first order)
0 1.00 1.00 2.00 2.00
5 0.63 0.55 0.91 1.10

10
0.46 0.30 0.59 0.60
15 0.36 0.165 0.435 0.33
25 0.25 0.05 0.286 0.10

Clearly we can see that when [A]
o
=1.00 M, the first-order reaction concentrations will always be
lower than that for the second-order case (assumes magnitude of the rate constant is the same). If,
on the other hand, the concentration is above 1.00 M, the second-order reaction decreases faster
than the first-order reaction (remember that the half-life shortens for a second-order reaction as
the concentration increases, whereas for a first-order reaction, the half-life is constant).

From the data, it appears that the crossover occurs in the case where [A]
0
=2.00 M at just over 10
minutes.


1 1 0.12
Second-order at 11 minutes: (11 min) [A] =0.549 M
[A] 2 M min
0.12
First-order at 11 minutes: ln[A] ln(2) (11 min) [A] =0.534 M
min
| |
= +
|
\ .
| |
=
|
\ .

A quick check at 10.5 minutes reveals,
1 1 0.12(10.5 min)
Second-order at 10.5 minutes: [A] =0.568 M
[A] 2 M min
0.12(10.5 min)
First-order at 10.5 minutes: ln[A] ln(2) [A] =0.567 M
M min
= +
=

Hence, at approximately 10.5 minutes, these two plots will share a common point (point at which
the concentration versus time curves overlap).

74. (M)
(a) The concentration vs. time graph is not linear. Thus, the reaction is obviously not zero-order
(the rate is not constant with time). A quick look at various half lives for this reaction shows
the ~2.37 min (1.000 M to 0.5 M), ~2.32 min (0.800 M to 0.400 M), and ~2.38 min(0.400 M
to 0.200 M). Since the half-life is constant, the reaction is probably first-order.

(b) average
1
1/2
1/2
(2.37 2.32 2.38) 0.693 0.693
2.36 min 0.294min
3 t 2.36 min
t k

+ +
= = = = =
or perhaps better expressed as k =0.29 min
1
due to imprecision.
Chapter 14: Chemical Kinetics
645

(c) When M. 0.352 [A] min, .5 3 t = = Then, rate =k[A] =
1
0.294 min 0.352 M 0.103 M/min. =

(d)
[A] 0.1480 M 0.339 M
Slope Rate 0.0637 M/ min Rate 0.064 M/min.
6.00 min 3.00 min t
A
= = = = =
A


(e) Rate =k[A] =0.294 min
1
1.000 M =0.29
4
M/min.

75. (M) The reaction being investigated is:
- + 2+
4 2 2 2 2
2MnO (aq)+5H O (aq)+6H (aq) 2Mn (aq)+8H O(l)+5O (g)
We use the stoichiometric coefficients in this balanced reaction to determine [H
2
O
2
].

-
4 2 2
-
4
2 2
0.1000 mmol MnO 5 mmol H O
37.1 mL titrant
1 mL titrant 2 mmol MnO
[H O ] 1.86 M
5.00 mL

= =


76. (D) We assume in each case that 5.00 mL of reacting solution is titrated.
-
- 2 2 4
4 -
2 2 4
-
2 2 4
2.32 mmol H O 2 mmol MnO 1 mL titrant
volume MnO 5.00 mL
1 mL 5 mmol H O 0.1000 mmol MnO
20.0 2.32 M H O 46.4 mL 0.1000 M MnO titrant at 0 s
=
= =

At 200 s V
titrant
=20.0 2.01 M H
2
O
2
=40.2 mL
At 400 s V
titrant
=20.0 1.72 M H
2
O
2
=34.4 mL
At 600 s V
titrant
=20.0 1.49 M H
2
O
2
=29.8 mL
At 1200 s V
titrant
=20.0 0.98 M H
2
O
2
=19.
6
mL
At 1800 s V
titrant
=20.0 0.62 M H
2
O
2
=12.
4
mL
At 3000 s V
titrant
=20.0 0.25 M H
2
O
2
=5.0
0
mL

The graph of volume of titrant vs. elapsed time is given above. This graph is of approximately the
same shape as Figure 14-2, in which [H
2
O
2
] is plotted against time. In order to determine the rate,
the tangent line at 1400 s has been drawn on the graph. The intercepts of the tangent line are at 34
mL of titrant and 2800 s. From this information we determine the rate of the reaction.

-
4 2 2
-
4 4
0.1000 mol MnO 5 mol H O 34 mL 1 L
2800 s 1000 mL 1 L titrant 2 mol MnO
Rate 6.1 10 M/s
0.00500 L sample


= =
This is the same as the value of 6.1 10
4
obtained in Figure 14-2 for 1400 s. The discrepancy is
due, no doubt, to the coarse nature of our plot.

0
5.5
11
16.5
22
27.5
33
38.5
0 700 1400 2100 2800
Tangent line
Chapter 14: Chemical Kinetics
646
77. (M) First we compute the change in [H
2
O
2
]. This is then used to determine the amount, and
ultimately the volume, of oxygen evolved from the given quantity of solution. Assume the O
2
(g)
is dry.
3 2 2
2 2
2 2 2
2 2
2 2
[H O ] 60 s
[H O ] 1.7 10 M/s 1.00 min 0.102 M
1 min
0.102 mol H O 1 mol O
amount O 0.175 L soln 0.00892 mol O
1 L 2 mol H O
t
t

A | |
A = A = =
|
A
\ .
= =


2
2 2
L atm
0.00892 mol O 0.08206 (273 24) K
mol K
Volume O 0.22 L O
1 atm
757 mmHg
760 mmHg
nRT
P

= = =

78. (M) We know that rate has the units of M/s, and also that concentration has the units of M. The
generalized rate equation is
| |
0
Rate A k = . In terms of units, this becomes
M/s ={units of k} M
0
. Therefore
1
1 0
0
M/s
{Units of } M s
M
k

= =



79. (M)
(a) Comparing the third and the first lines of data, [I
-
] and [OH
-
]stay fixed, while [OCl

]
doubles. Also the rate for the third kinetics run is one half of the rate found for the first run.
Thus, the reaction is first-order in [OCl
-
]. Comparing the fourth and fifth lines, [OCl

] and
[I
-
] stay fixed, while [OH
-
] is halved. Also, the fifth run has a reaction rate that is twice that
of the fourth run. Thus, the reaction is minus first-order in [OH
-
]. Comparing the third and
second lines of data, [OCl
-
] and [OH
-
] stay fixed, while the [I
-
] doubles. Also, the second
run has a reaction rate that is double that found for the third run. Thus, the reaction is first-
order in [I
-
].

(b) The reaction is first-order in [OCl
-
] and [I
-
] and minus first-order in [OH
-
]. Thus, the overall
order =1 +1 1 =1. The reaction is first-order overall.

(c)
4
1
[OCl ][I ]
Rate
[OH ]
Rate [OH ] 4.8 10 M/s 1.00 M
using data from first run: 60. s
[OCl ][I ] 0.0040 M 0.0020 M
k

=

= =

80. (M) We first determine the number of moles of N
2
O produced. The partial pressure of N
2
O(g) in
the wet N
2
O is 756 mmHg 12.8 mmHg =743 mmHg.
O N mol 00207 . 0
K ) 15 273 ( K mol atm L 0.08206
L 0500 . 0
mmHg 760
atm 1
mmHg 743
O N amount
2
1 1
2
=
+

= =

RT
PV

Now we determine the change in [NH
2
NO
2
].
Chapter 14: Chemical Kinetics
647
2 2
2
2
2 2
1
2 2 final
1
0
1 mol NH NO
0.00207 mol N O
1 mol N O
[NH NO ] 0.0125 M
0.165 L soln
0.693
[NH NO ] 0.105 M0.0125 M 0.093 M 0.00563 min
123 min
[A] 1 1 0.093 M
ln ln 22 min elapsed t
[A] 0.00563 min 0.105 M
t
k
t
k

A = =
= = = =
= = = = ime


81. (D) We need to determine the partial pressure of ethylene oxide at each time in order to determine
the order of the reaction. First, we need the initial pressure of ethylene oxide. The pressure at
infinite time is the pressure that results when all of the ethylene oxide has decomposed. Because
two moles of product gas are produced for every mole of reactant gas, this infinite pressure is twice
the initial pressure of ethylene oxide. P
initial
=249.88 mmHg 2 =124.94 mmHg. Now, at each
time we have the following.
2 2 4
(CH ) O(g) CH (g) CO(g) +
Initial: 124.94 mmHg Changes: x mmHg +x mmHg +x mmHg Final: 124.94 +x mmHg
Thus, x =P
tot
124.94 and P
EtO
=124.94 x =124.94 (P
tot
124.94) =249.88 P
tot

Hence, we have, the following values for the partial pressure of ethylene oxide.

t, min 0 10 20 40 60 100 200
P
EtO
, mmHg 124.94 110.74 98.21 77.23 60.73 37.54 11.22
For the reaction to be zero-order, its rate will be constant.
The rate in the first 10 min is: mmHg/min 42 . 1
min 10
mmHg ) 94 . 124 74 . 110 (
Rate =

=
The rate in the first 40 min is: mmHg/min 19 . 1
min 40
mmHg ) 94 . 124 23 . 77 (
Rate =

=
We conclude from the non-constant rate that the reaction is not zero-order. For the reaction to be
first-order, its half-life must be constant. From 40 min to 100 mina period of 60 minthe partial
pressure of ethylene oxide is approximately halved, giving an approximate half-life of 60 min.
And, in the first 60 min, the partial pressure of ethylene oxide is approximately halved. Thus, the
reaction appears to be first-order. To verify this tentative conclusion, we use the integrated first-
order rate equation to calculate some values of the rate constant.
1
0
1 1
1 1 110.74 mmHg
ln ln 0.0121 min
10 min 124.94 mmHg
1 37.54 mmHg 1 60.73 mmHg
ln 0.0120 min ln 0.0120 min
100 min 124.94 mmHg 60 min 124.94 mmHg
P
k
t P
k k

= = =
= = = =

The constancy of the first-order rate constant suggests that the reaction is first-order.

82. (M) For this first-order reaction kt
P
P
t
=
0
ln Elapsed time is computed as:
0
ln
1
P
P
k
t
t
=
We first determine the pressure of DTBP when the total pressure equals 2100 mmHg.

Chapter 14: Chemical Kinetics
648

8 18 2 3 6 2 6
Reaction: C H O (g) 2C H O(g) C H (g) [Equation 15.16]
Initial: 800.0 mmHg
Changes: mmHg 2 mmHg mmHg
Final: (800.0 ) mmHg 2 mmHg
x x x
x x
+
+ +

8 18 2
2
2 3 1
0
mmHg
Total pressure (800.0 ) 2 800.0 2 2100.
650. mmHg {C H O (g)} 800. mmHg 650. mmHg 150. mmHg
1 1 150. mmHg
ln ln 19 min 1.9 10 min
8.7 10 min 800. mmHg
t
x
x x x x
x P
P
t
k P

= + + = + =
= = =
= = = =

83. (D) If we compare Experiment 1 with Experiment 2, we notice that [B] has been halved, and also
that the rate, expressed as A[A]/ t A , has been halved. This is most evident for the times 5 min,
10 min, and 20 min. In Experiment 1, [A] decreases from 1.000 10
3
M to 0.779 10
3
M in 5
min, while in Experiment 2 this same decrease in [A] requires 10 min. Likewise in Experiment 1,
[A] decreases from 1.000 10
3
M to 0.607 M10
3
in 10 min, while in Experiment 2 the same
decrease in [A] requires 20 min. This dependence of rate on the first power of concentration is
characteristic of a first-order reaction. This reaction is first-order in [B]. We now turn to the order
of the reaction with respect to [A]. A zero-order reaction will have a constant rate. Determine the
rate
After over the first minute: M/min 10 9 . 4
min 1
M 10 ) 000 . 1 951 . 0 (
Rate
5
3

=

=
After over the first five minutes: M/min 10 4 . 4
min 5
M 10 ) 000 . 1 779 . 0 (
Rate
5
3

=

=
After over the first twenty minutes: M/min 10 2 . 3
min 20
M 10 ) 000 . 1 368 . 0 (
Rate
5
3

=

=
This is not a very constant rate; we conclude that the reaction is not zero-order. There are no clear
half-lives in the data with which we could judge the reaction to be first-order. But we can
determine the value of the first-order rate constant for a few data.
1
0
1 1
1 [A] 1 0.951 mM
ln ln 0.0502 min
[A] 1 min 1.000 mM
1 0.607 mM 1 0.368 mM
ln 0.0499 min ln 0.0500 min
10 min 1.000 mM 20 min 1.000 mM
k
t
k k

= = =
= = = =

The constancy of the first-order rate constant indicates that the reaction indeed is first-order in [A].
(As a point of interest, notice that the concentrations chosen in this experiment are such that the
reaction is pseudo-zero-order in [B]. Here, then it is not necessary to consider the variation of [B]
with time as the reaction proceeds when determining the kinetic dependence on [A].)

Chapter 14: Chemical Kinetics
649
84. (M) In Exercise 79 we established the rate law for the iodine-hypochlorite ion reaction:
1
Rate [OCl ][I ][OH ] k

= . In the mechanism, the slow step gives the rate law;
3
Rate [I ][HOCl] k

= . We use the initial fast equilibrium step to substitute for [HOCl] in this rate
equation. We assume in this fast step that the forward rate equals the reverse rate.


1 2
1 2 1
1
[OCl ][H O]
[OCl ][H O] [HOCl][OH ] [HOCl]
[OH ]
k
k k
k

= =


1 2 2 1 2
2
1 1
[OCl ][H O] [H O][OCl ][I ] [OCl ][I ]
Rate [I ]
[OH ] [OH ] [OH ]
k k k
k k
k k

= = =

This is the same rate law that we established in Exercise 79. We have incorporated [H
2
O] in the
rate constant for the reaction because, in an aqueous solution, [H
2
O] remains effectively constant
during the course of the reaction. (The final fast step simply involves the neutralization of the acid
HOI by the base hydroxide ion, OH

.)

85. (M) It is more likely that the cis-isomer, compound (I), would be formed than the trans-isomer,
compound (II). The reason for this is that the reaction will involve the adsorption of both
CH
3
CCCH
3
and H
2
onto the surface of the catalyst. These two molecules will eventually be
adjacent to each other. At some point, one of the t bonds in the CC bond will break, the HH
bond will break, and two CH bonds will form. Since these two CH bonds form on the same side
of the carbon chain, compound (I) will be produced. In the sketches below, dotted lines ()
indicate bonds forming or breaking.


C C CH
3
CH
3
H H
C C CH
3
CH
3
H H

C C CH
3
CH
3
H H


86. (D) Hg
2
2+
+Tl
3+
2 Hg
2+
+Tl
+
2+ 3+
2
2+
[Hg ][Tl ]
Experimental rate law =k
[Hg ]

Possible mechanism: Hg
2
2+
+Tl
3+

1
1
k
k

Hg
2+
+HgTl
3+
(fast)
HgTl
3+
2
k

Hg
2+
+Tl
3+
(slow)
Hg
2
2+
+Tl
3+
2 Hg
2+
+Tl
+
Rate =k
2
[HgTl
3+
]

k
1
[Hg
2
2+
][Tl
3+
] =
-1
k [Hg
2+
][HgTl
3+
] rearrange
2+ 3+
3+ 1 2
2+
-1
[Hg ][Tl ]
[HgTl ] =
[Hg ]
k
k


Rate =k
2
[HgTl
3+
]
2+ 3+ 2+ 3+
2 1 2 2
obs 2+ 2+
-1
[Hg ][Tl ] [Hg ][Tl ]
= =
[Hg ] [Hg ]
k k
k
k


Chapter 14: Chemical Kinetics
650
87. (M)

3
formation disappearance formation decomposition
2
2 3 3 3 3 3
3
2
3 3 3 3
3
CCl
rate rate 0 so rate rate
t
[Cl(g)][CHCl ] [CCl ][[Cl(g)] and, simplifying, [CCl ] [CHCl ]
since rate [CCl ][Cl(g)] [CHCl ]
k
k k
k
k
k k
k
= + = =
= =
|
= =
\
2 3
[Cl(g)] [CHCl ][Cl(g)] k
|
=
|
.


1/2 1/2
1 1
2 overall 2 3 2
-1 -1
1/2 1/2
3
2 1
2 3
-1
We know: [Cl(g)] [Cl (g)] then rate = [CHCl ] [Cl (g)]
4.8 10
and the rate constant will be: (1.3 10 ) 0.015
3.6 10
k k
k
k k
k
k k k
k

| | | |
=
| |
\ . \ .
| | | |
= = =
| |

\ . \ .


88. (D)
t
o
3
3
0 t
[A] t
3 2 2
t o 0 [A]
2
t
d[A] d[A]
Rate= [A] - Rearrange: - t=
dt [A]
Integrateusing the limits time (0 to t) and concentration ([A] to [A] )
d[A] 1 1 1 1
- t= t ( (0))
[A] 2[A] 2[A]
1 1
Simplify: t
2[A] 2[
k k
k k k
k

| |
=
|
\ .
= +
} }
2 2 2
o t 0
1 1
Rearrange: t
A] 2[A] 2[A]
k = +

2 2
t o
o
12 12 t
12 2 2 2 2
o o o 0
12
1 1
Multiply through by 2 to give the integrated rate law: 2 t
[A] [A]
[A]
To derive the half life(t ) substitute t =t and [A] =
2
1 1 1 4
2 t Collect terms
[A] [A] [A] [A]
4 2
4
2 t
k
k
k
= +
= + = =
| |
|
\ .
=
12 12 2 2 2 2
o o o o
1 3 3
Solve for t t
[A] [A] [A] 2 [A] k
= =


89. (D) Consider the reaction: A +B products (first-order in A, first-order in B). The initial
concentration of each reactant can be defined as [A]
0
and [B]
0
Since the stoichiometry is 1:1, we
can define x as the concentration of reactant A and reactant B that is removed (a variable that
changes with time).

The [A]
t
=([A]
o
x) and [B]
t
=([B]
o
x).

Algebra note: [A]
o
x = (x [A]
o
) and [B]
o
x = (x [B]
o
).
Chapter 14: Chemical Kinetics
651
As well, the calculus requires that we use the absolute value of |x [A]
o
| and |x [B]
o
| when taking
the integral of the reciprocal of |x [A]
o
| and |x [B]
o
|
t t o o
o o
o o
Note: this i
d[A] d[B] dx dx
Rate=- =- = [A] [B] = ([A] -x)([B] -x) or =
([A] -x)([B] -x)
further ease integration:
1
([B] -[A] )
In order to solve this, partial fraction decomposition is required to
k k kdt
dt
dx
dt dt
=
o o
s aconstant
1 1
-
([A] -x) ([B] -x)
kdt =
| |
| |
|
|
|
\ .
\ .

o o
t
o o
From the point of view of integration, a further rearrangement is desirable (Seealgebra note above).
1 -1 -1
x -
([B] -[A] ) x-[A] x-[B]
d kdt =
| |
| |
|
|
|
\ .
\ .

o o
o o
o
o o o
o o
o o
1
Integrate both sides -ln - (-ln ) = t +C
([B] -[A] )
[A] -x and [B] -x Substitute and simplify
([B] -x) 1
ln = t +C DetermineC by setting =0
([B] -[A] ) [A] -x
x-[A] x-[B]
x-[A] = x-[B] =
k
k x
| |
(
|
\ .
| | | |
| |
\ . \ .
at t =0


o
o o o o o o o
o o
o o
([B] -x) 1 1 1
C= ln Hence: ln = t + ln
([B] -[A] ) ([B] -[A] ) ([A] -x) ([B] -[A] )
[B] [B]
[A] [A]
k
| | | | | | | |
| | | |
\ . \ . \ . \ .


o
o
o
o o o o
o o o
o
o o o o
o
o
o o
o
o
o
([B] -x)
ln = t +ln
([A] -x)
([B] -x)
([A] -x) ([B] -x) [A] ([B] -x)
ln -ln = t = ln =ln
([A] -x) [B] ([A] -x)
[B]
Multiply both sides by([B] -[A] ), hence, ([B] -[A] )
[A]
[B]
([B] -[A] )
[B]
[A]
[A]
k
k
| |
|
\ .
| |
|
| |
\ .
|
\ .
o t
o t
o t o t o o
[A] [B]
Set ln = t
[B] [A]

([A] -x)=[A] and ([B] -x)=[B] togive ([B] -[A] )

k
| |
|
\ .
| |
|
\ .


Chapter 14: Chemical Kinetics
652
90. (D) Let 250-2x equal the partial pressure of CO(g) and x be the partial pressure of CO
2
(g).

2
2CO CO C(s)
250-2 x x
+

P
tot
=P
CO
+P
CO2
=250 2x +x =250 x

P
tot
[torr]
Time
[sec]
P
CO2
P
CO
[torr]
250 0 0 250
238 398 12 226
224 1002 26 198
210 1801 40 170

The plots that follow show that the reaction appears to obey a second-order rate law.
Rate =k[CO]
2

R
2
=0.9867
170
180
190
200
210
220
230
240
250
0 1000 2000
time (S)
P
C
O

(
m
m
H
g
)

R
2
=0.9965
5.12
5.32
5.52
0 500 1000 1500 2000
time (S)
l
n

P
C
O

R
2
=1
0.004
0.005
0.006
0 1000 2000
time (S)
1
/
P
C
O

(
m
m
H
g
-
1
)


ZERO ORDER PLOT 1
st
ORDER PLOT 2
nd
ORDER PLOT







T P
CO
0 250
398 226
1002 198
1801 170
T lnP
CO
0 5.521461
398 5.420535
1002 5.288267
1801 5.135798
T 1/CO
0 0.004
398 0.004425
1002 0.005051
1801 0.005882
(Best
correlation
coefficient)
Chapter 14: Chemical Kinetics
653
91. (D) Let 100-4x equal the partial pressure of PH
3
(g), x be the partial pressure of P
4
(g)and 6x be the
partial pressure of H
2
(g)

3 4 2
4 PH (g) P ( ) 6 H (g)
100 4 6
g
x x x
+

P
tot
=P
PH
3
+P
P
4
+
P
H
2

=100 4 x + x +6x =100+3x


P
tot
[torr]
Time [sec] P
P
4

[torr] P
PH
3

[torr]
100 0 0 100
150 40 50/3 100-(4)(50/3)
167 80 67/3 100-(4)(67/3)
172 120 72/3 100-(4)(72/3)

The plots to follow show that the reaction appears to obey a first-order rate law.
Rate =k[PH
3
]
R
2
=0.8369
0
10
20
30
40
50
60
70
80
90
100
-50 50 150
time (S)
P
P
H
3

(
m
m
H
g
)

R
2
=0.9991
1.35
1.85
2.35
2.85
3.35
3.85
4.35
0 100 200
time (S)
l
n

P
P
H
3

ZERO ORDER PLOT 1
st
ORDER PLOT 2
nd
ORDER PLOT







T P
PH3
0 100
40 33.3
80 10.7
120 4
T lnP
PH3
0 4.61
40 3.51
80 2.37
120 1.39
T 1/P
PH3
0 0.010
40 0.030
80 0.093
120 0.250
R
2
=0.8652
0.010
0.060
0.110
0.160
0.210
0 50 100 150
ti me (S)
1
/
P
P
H
3
(
m
m
H
g
-
1
)
Chapter 14: Chemical Kinetics
654
92. (D) Consider the following equilibria.
( )
1 I
2
-1
k K
k
k
2
1 -1 2 1 -1 2
E +S ES E +P E +I EI
d[P]
Product production =k [ES] Use the steadystate approximation for [ES]
dt
d[ES]
=k [E][S] k [ES] k [ES] =k [E][S] [ES] k k = 0
dt
solve f

+


-1 2 1
M
1 -1 2 M
I
I
o
M I
k k k [E][S] [E][S]
or [ES] Keep in mind K = [ES] = =
k k k K
[E][I] [E][I]
Formation of EI: K = [EI] =
[EI] K
[E][S] [E][I]
[E ] =[E] +[ES] +[EI] =[E] + +
K K
| | +
|
+
\ .

o
o
M I
M I
[E ] [S] [I]
[E ] =[E] 1 + + Solve for [E] [E] =
K K
[S] [I]
1 + +
K K
| |
|
| |
\ .
|
\ .


o
M M
M M
M I
o o
M
M M
I I
[S]
[E ]
K
K [E][S]
From above: [ES] = [ES] = multiplication by affords
K K
[S] [I]
1 + +
K K
[E ][S] [E ][S]
[ES] = =
[I]K [I]
K +[S] + K 1 + +[S]
K K
d[P]
Remember
dt
| |
|
\ .
| |
|
\ .
| | | |
| |
\ . \ .
2 o
2
M
I
max
2 o max
M
I
k [E ][S]
=k [ES] =
[I]
K 1 + +[S]
K
V [S] d[P]
If we substitute k [E ] =V then =
dt
[I]
K 1 + +[S]
K
| |
|
\ .
| |
|
\ .

Thus, as [I] increases, the ratio
max
M
I
V [S]
[I]
K 1 + +[S]
K
| |
|
\ .
decreases;
i.e., the rate of product formation decreases as [I] increases.

Chapter 14: Chemical Kinetics
655
93. (D) In order to determine a value for K
M
, we need to rearrange the equation so that we may obtain
a linear plot and extract parameters from the slope and intercepts.

2 o M M
M 2 o 2 o 2 o
M
2 o 2 o
k [E ][S] K +[S] K 1 [S]
V = = = +
K +[S] V k [E ][S] k [E ][S] k [E ][S]
K 1 1
= + We need to have this in the form of y =mx+b
V k [E ][S] k [E ]
1 1
Plot on the y-axis and on the x-axis. See result below:
V [S]

x-intercept
=-1
y-intercept
=
K
M
k
2
[E
o
]
1
1
[S]
[V]
1
K
M
k
2
[
E
o
]
s
l
o
p
e

=


The plot of 1/V vs 1/[S] should yield a slope of
M
2 o
K
k [E ]
and a
y-intercept of
2 o
1
k [E ]
. The x-intercept =-1/K
M

2 o M
2 o 2 o 2 o M M
-k [E ] K 1 1 1 -1
0 = =
k [E ] [S] k [E ] [S] k [E ] K K
=

| |
|
\ .

To find the value of K
M
take the negative inverse of x-intercept.
To find k
2
, invert the y-intercept and divide by the [E
o
].


94. (M)
a) The first elementary step HOOBr O HBr
k1
2 + is rate-determining if the reaction obeys
reaction rate =k [HBr][O
2
] since the rate of this step is identical to that of the experimental rate
law.

b) No, mechanisms cannot be shown to be absolutely correct, only consistent with experimental
observations.

c) Yes; the sum of the elementary steps (3 HBr +O
2
HOBr +Br
2
+H
2
O) is not consistent with
the overall stoichiometry (since HOBr is not detected as a product) of the reaction and
therefore cannot be considered a valid mechanism.

95. (M)
(a) Both reactions are first-order, because they involve the decomposition of one molecule.

(b) k
2
is the slow reaction.

(c) To determine the concentration of the product, N
2
, we must first determine how much reactant
remains at the end of the given time period, from which we can calculate the amount of
reactant consumed and therefore the amount of product produced. Since this is a first-order
reaction, the concentration of the reactant, N
2
O after time t is determined as follows:
| | | |
| | ( ) ( )( )
( )
kt
t 0
1
2 2
0.1
A A e
N O 2.0M exp 25.7s 0.1s 0.153M N Oremaining

=
= =

Chapter 14: Chemical Kinetics
656
The amount of N
2
O consumed =2.0 M 0.153 M =1.847 M
2
2 2
1M N
[N ] 1.847M NO 0.9235M N
2M NO
= =
(d) The process is identical to step (c).
| | ( ) ( )( )
( )
1
2 2
0.1
N O 4.0M exp 18.2s 0.025s 2.538M N Oremaining

= =
The amount of N
2
O consumed =4.0 M 2.538 M =1.462 M
2
2 2
1M N O
[N O] 1.462M NO 0.731M N O
2M NO
= =


FEATURE PROBLEMS

96. (D)
(a) To determine the order of the reaction, we need C H N Cl
6 5 2
at each time. To determine
this value, note that 58.3 mL ( )
2
N g evolved corresponds to total depletion of C H N Cl
6 5 2
,
to C H N Cl M
6 5 2
=0.000 .
Thus, at any point in time, C H N Cl M volume N g
M C H N Cl
mL N g
6 5 2 2
6 5 2
2
=0.071
0.071
58.3

F
H
G
I
K
J
b g
b g

Consider 21 min: | |
( )
6 5 2
6 5 2 2
2
0.071 M C H N Cl
C H N Cl =0.071 M 44.3 mL N =0.017 M
58.3 mL N g
| |

|
|
\ .

The numbers in the following table are determined with this method.
Time, min 0 3 6 9 12 15 18 21 24 27 30
2
N
V , mL 0 10.8 19.3 26.3 32.4 37.3 41.3 44.3 46.5 48.4 50.4 58.3
| |
6 5 2
C H N Cl , mM 71 58 47 39 32 26 21 17 14 12 10 0
[The concentration is given in thousandths of a mole per liter (mM).]
(b)








time(min) 0 3 6 9 12 15 18 21 24 27 30
AT(min) 3 3 3 3 3 3 3 3 3 3
[C
6
H
5
N
2
Cl](mM) 71 58 47 39 32 26 21 17 14 12 10
A[C
6
H
5
N
2
Cl](mM) -13 -11 -8 -7 -6 -5 -4 -3 -2 -2
Reaction Rate (mM min
-1
) 4.3 3.7 2.7 2.3 2.0 1.7 1.3 1.0 0.7 0.7
Chapter 14: Chemical Kinetics
657
(c) The two graphs are drawn on the same axes.


(d) The rate of the reaction at t =21 min is the slope of the tangent line to the
C H N Cl
6 5 2
curve. The tangent line intercepts the vertical axis at about
C H N Cl mM
6 5 2
=39 and the horizontal axis at about 37 min
3
3 1 3 1
5
39 10 M
Reaction rate= =1.0 10 M min =1.1 10 M min
37 min

The agreement with the reported value is very good.

(e) The initial rate is the slope of the tangent line to the C H N Cl
6 5 2
curve at t =0. The
intercept with the vertical axis is 71 mM, of course. That with the horizontal axis is about
13 min.
3
3 1
71 10 M
Rate= =5.5 10 M min
13min

(f) The first-order rate law is
| |
6 5 2
Rate= C H N Cl k , which we solve for k:
| |
6 5 2
Rate
=
C H N Cl
k
3 1
1
0
3
5.5 10 M min
= =0.077 min
71 10 M
k

3 1
1
21
3
1.1 10 Mmin
= =0.065min
17 10 M
k

An average value would be a reasonable estimate: k
avg
min =0.071
1

(g) The estimated rate constant gives one value of the half-life:
t
k
1/2 1
=
0.693
=
0.693
0.071
=9.8
min
min

The first half-life occurs when
| |
6 5 2
C H N Cl drops from 0.071 M to 0.0355 M. This occurs
at about 10.5 min.

(h) The reaction should be three-fourths complete in two half-lives, or about 20 minutes.

Plot of [C
6
H
5
N
2
Cl] and V
N
versus time
0
20
40
60
0 5 10 15 20 25 30
ti me (min)
[C
6
H
5
N
2
Cl]
(m
M)
or
V
N
2
(m
L)
2
mL of N
2
[C
6
H
5
N
2
Cl]
[
C
6
H
5
N
2
C
l

(
m
M
)

o
r

V
N
2
(
m
L
)

Chapter 14: Chemical Kinetics
658

(i) The graph plots ln
| |
6 5 2
C H N Cl (in millimoles/L) vs. time in minutes.















The linearity of the graph demonstrates that the reaction is first-order.

(j)
( )
2 1 1
= slope= 6.61 10 min =0.0661min k


1/2
1
0.693
= =10.5min
0.0661min
t

, in good agreement with our previously determined values.

97. (D)
(a) In Experiments 1 & 2, [KI] is the same (0.20 M), while NH S O
4
2
2 8
b g is halved, from 0.20
M to 0.10 M. As a consequence, the time to produce a color change doubles (i.e., the rate is
halved). This indicates that reaction (a) is first-order in
2
2 8
S O

. Experiments 2 and 3
produce a similar conclusion. In Experiments 4 and 5, NH S O
4
2
2 8
b g is the same (0.20 M)
while [KI] is halved, from 0.10 to 0.050 M. As a consequence, the time to produce a color
change nearly doubles, that is, the rate is halved. This indicates that reaction (a) is also first-
order in I

. Reaction (a) is (1 + 1) second-order overall.

(b) The blue color appears when all the S O
3
2
2

has been consumed, for only then does reaction
(b) cease. The same amount of S O
3 2
2
is placed in each reaction mixture.
2
2 4 2 2 3 2 3
2 3
2 2 3
0.010 mol Na S O 1 mol S O 1 L
amount S O =10.0 mL =1.0 10 mol
1000 mL 1 L 1 mol Na S O

Through stoichiometry, we determine the amount of each reactant that reacts before this
amount of
2
2 3
S O

will be consumed.
Plot of ln[C
6
H
5
N
2
Cl] versus time
y =-0.0661x - 2.66
-4.75
-4.25
-3.75
-3.25
-2.75
0 10 20 30
Time (min)
l
n
[
C
6
H
5
N
2
C
l
]

Chapter 14: Chemical Kinetics
659
2
2 2 4 3 2 8
2 8 2 3 2
2 3 3
2 5
2 8
1 mol I 1 mol S O
amount S O 1.0 10 mol S O
2 mol S O 1 mol I
=5.0 10 mol S O




=

2 5 4
2 8 2
2 8
2 mol I
amount I =5.0 10 mol S O =1.0 10 mol I
1 mol S O

Note that we do not use 3 mol I

from equation (a) since one mole has not been

oxidized; it simply complexes with the product I
2
. The total volume of each solution
is( ) 25.0 mL +25.0 mL +10.0 mL +5.0 mL = 65.0 mL , or 0.0650 L.
The amount of
2
2 8
S O

that reacts in each case is 5.0 10
5

mol and thus
A

S O
mol
L
M
2 8
2
5
4
=
5.0 10
0.0650
= 7.7 10
Thus, Rate
S O
M
s
M s
8
1
2
2
4
5 1
= =
+7.7 10
21
=3.7 10
A
A

t


(c) For Experiment 2, Rate
S O
M
s
M s
2
2 8
2
4
5 1
= =
+7.7 10
42
=1.8 10
A
A

t

To determine the value of k , we need initial concentrations, as altered by dilution.
2
2 8
1 1
25.0 mL 25.0 mL
S O =0.20 M =0.077 M I =0.20M =0.077 M
65.0 mL total 65.0 mL

( (

Rate M s S O I M M
8
2
1
5 1
2
1 1
1 1
=3.7 10 = = 0.077 0.077

k kb g b g
5 1
3 1 1
3.7 10 M s
= =6.2 10 M s
0.077 M 0.077 M
k

2
2 8
2 2
25.0 mL 25.0 mL
S O =0.10 M =0.038 M I =0.20M =0.077 M
65.0 mL total 65.0 mL

( (


( ) ( )
1 1
1 1
5 1 2
2 2 8
Rate =1.8 10 M s = S O I = 0.038 M 0.077 M k k

( (


k =
1.8 10
0.038 0.077
=6.2 10
5 1
3 1 1

M s
M M
M s

(d) First we determine concentrations for Experiment 4.
2
2 8
4 4
25.0 mL 25.0 mL
S O =0.20 M =0.077 M I =0.10 =0.038 M
65.0 mL total 65.0 mL

( (


We have two expressions for Rate; let us equate them and solve for the rate constant.
( )( )
2
4
1 1 2 8
2
4 2 8
4 4
S O
+7.7 10 M
Rate = = = S O I = 0.077 M 0.038 M k k
t t

(
A


( (

A A

4 1 1
1 1
3
7.7 10 M 0.26 M 0.26 M
= = = =0.0014 M s
0.077 M 0.038 M 189 s
k k
t t

A A


Chapter 14: Chemical Kinetics
660
1 1
1 1 1 1
13 24
0.26 M 0.26 M
= =0.0030 M s = =0.0062 M s
88 s 42 s
k k




1
1 1
33
0.26 M
= =0.012 M s
21 s
k

(e) We plot ln k vs. 1/T The slope of the line= / E R
a
.















1 1 3
a
=+6135 K 8.3145 J mol K =51.0 10 J /mol =51.0kJ /mol E


The scatter of the data permits only a two significant figure result: 51 kJ /mol

(f) For the mechanism to agree with the reaction stoichiometry, the steps of the mechanism
must sum to the overall reaction, in the manner of Hess's law.
(slow) I +S O IS O
8 8
3

2
2
2

(fast) IS O SO I
8
3
4
2
2
+
2 +


(fast) I I I
+
2
+


(fast) I I I
3 2
+


(net) 3 + 2 +
2
I S O SO I
8
2
4
2
3




Each of the intermediates cancels: IS O
8
3
2

is produced in the first step and consumed in the
second, I
+
is produced in the second step and consumed in the third,
2
I is produced in the
third step and consumed in the fourth. The mechanism is consistent with the stoichiometry.
The rate of the slow step of the mechanism is
Rate S O I
8
2
1 1 2
1 1
=k


This is exactly the same as the experimental rate law. It is reasonable that the first step be
slow since it involves two negatively charged species coming together. We know that like
charges repel, and thus this should not be an easy or rapid process.
Plot of ln k versus 1/T
y =-6135x +16
-6
-5.5
-5
-4.5
-4
-3.5
0.00325 0.0034 0.00355 1/T (K
-1
)
l
n

k
Chapter 14: Chemical Kinetics
661

SELF-ASSESSMENT EXERCISES

98. (E)
(a) [A]
0
: Initial concentration of reactant A
(b) k: Reaction rate constant, which is the proportionality constant between reaction rate and
reactant concentration
(c) t
1/2
: Half-life of the reaction, the amount of time that the concentration of a certain reactant is
reduced by half
(d) Zero-order reaction: A reaction in which the rate is not dependent on the concentration of the
reactant
(e) Catalyst: A substance which speeds up the reaction by lowering the activation energy, but it
does not itself get consumed

99. (E)
(a) Method of initial rates: A study of the kinetics of the reaction by measuring the initial reaction
rates, used to determine the reaction order
(b) Activated complex: Species that exist in a transitory state between the reactants and the
products
(c) Reaction mechanism: Sequential elementary steps that show the conversion of reactant(s) to
final product(s)
(d) Heterogeneous Catalyst: A catalyst which is in a different physical phase than the reaction
medium
(e) Rate-determining step: A reaction which occurs more slowly than other reactions in a
mechanism and therefore usually controls the overall rate of the reaction

100. (E)
(a) First-order and second-order reactions: In a first-order reaction, the rate of the reaction
depends on the concentration of only one substrate and in a 1-to-1 manner (doubling the
concentration of the reactant doubles the rate of the reaction). In a second-order reaction, the
rate depends on two molecules reacting with each other at the elementary level.
(b) Rate law and integrated rate law: Rate law describes how the rate relates to the concentration
of the reactants and the overall rate of a reaction, whereas the integrated rate law expresses the
concentration of a reactant as a function of time
(c) Activation energy and enthalpy of reaction: Activation energy is the minimum energy
required for a particular reaction to take place, whereas enthalpy of reaction is the amount of
heat generated (or consumed) by a reaction when it happens
(d) Elementary process and overall reaction: Individual steps of a reaction mechanism, which
describes any molecular event that significantly alters a molecules energy or geometry or
produces a new molecule
(e) Enzyme and substrate: An enzyme is a protein that acts as a catalyst for a biological reaction.
A substrate is the reactant that is transformed in the reaction (in this context, by the enzyme).

101. (E) The answer is (c). The rate constant k is only dependent on temperature, not on the
concentration of the reactants

Chapter 14: Chemical Kinetics
662
102. (E) The answers are (b) and (e). Because half-life is 75 seconds, the quantity of reactant left at
two half-lives (75 +75 =150) equals one-half of the level at 75 seconds. Also, if the initial
concentration is doubled, after one half-life the remaining concentration would have to be twice
as much as the original concentration.

103. (E) The answer is (a). Half-life t

=13.9 min, k =ln 2/t

=0.050 min
-1
. Rate of a first-order
reaction is as follows:
| |
| | ( )( )
1 1
d A
k A 0.050min 0.40M 0.020 M min
dt

= = =

104. (E) The answer is (d). A second-order reaction is expressed as follows:
| |
| |
2
d A
k A
dt
=
If the rate of the reaction when [A] =0.50 is k(0.50)
2
=k(0.25). If [A] =0.25 M, then the rate is
k(0.0625), which is of the rate at [A] =0.50.

105. (M) The answer is (b). Going to slightly higher temperatures broadens the molecular speed
distribution, which in turn increases the fraction of molecules at the high kinetic energy range
(which are those sufficiently energetic to make a reaction happen).

106. (E) The answer is (c). Since the reaction at hand is described as an elementary one, the rate of the
reaction is k[A][B].

107. (E) We note that from the given data, the half-life of the reaction is 100 seconds (at t =0, [A] =
0.88 M/s, whereas at t =100, [A] =0.44 M/s). Therefore, the rate constant k is:
k =ln 2/100 s =0.00693 s
-1
. We can now calculate instantaneous rate of the reaction:
d[A]/dt =(0.00693 s
-1
)(0.44 M) =3.010
-3
Ms
-1


108. (M)
(a) For a first-order reaction,
( )
1
1/2
t 0
t 0
1
ln2 0.693
k 0.0231min
t 30
ln[A] ln[A] kt
ln 0.25 0 ln[A] ln[A]
t 60.0min
k 0.0231min

= = =
=

= = =


(b) For a zero-order reaction,
1
1/2
t 0
t 0
1
0.5 0.5
k 0.0167min
t 30
[A] [A] kt
[A] [A] 0.25 1.00
t 45.0min
k 0.0167min

= = =
=

= = =



Chapter 14: Chemical Kinetics
663
109. (M) The reaction is second-order, because the half-life doubles with each successive half-life
period.
110. (M)
(a) The initial rate =M/t =(1.204 M 1.180 M)/(1.0 min) =0.024 M/min
(b) In experiment 2, the initial concentration is twice that of experiment A. For a second-order
reaction:
Rate =k [A
exp 2
]
2
=k [2A
exp 1
]
2
=4 k [A
exp 1
]
2

This means that if the reaction is second order, its initial rate of experiment 2 will be 4 times that
of experiment 1 (that is, 4 times as many moles of A will be consumed in a given amount of
time). The initial rate is 40.024 M/min =0.096 M/s. Therefore, at 1 minute, [A] =2.408
0.0960 =2.312 M.
(c) The half-life of the reaction, obtained from experiment 1, is 35 minutes. If the reaction is
first-order, then k =ln 2/35 min =0.0198 min
-1
.
For a first-order reaction,
| | | |
| | ( ) ( )
kt
t 0
-1
35min
A A e
A 2.408 exp 0.0198 min 30min 1.33M

=
= =


111. (D) The overall stoichiometry of the reaction is determined by adding the two reactions with each
other: A +2B C +D
(a) Since I is made slowly but is used very quickly, its rate of formation is essentially zero. The
amount of I at any given time during the reaction can be expressed as follows:
| |
| || | | || |
| | | |
1 2
1
2
d I
0 k A B k B I
dt
k
I A
k
= =
=

Using the above expression for [I], we can now determine the overall reaction rate law:
| |
| || | | | | | | || |
1
2 2 1
2
d C
k
k I B k A B k A B
dt k
= = =
(b) Adding the two reactions given, we still get the same overall stoichiometry as part (a).
However, with the given proposed reaction mechanisms, the rate law for the product(s) is given
as follows:
Chapter 14: Chemical Kinetics
664
| |
| | | | | || |
| |
| |
| |
| |
| || |
| || |
| |
2
2
1 1 2 2
2
1
2
1 2
2
2 1
2 2
1 2
d B
k B k B k A B 0
dt
k B
B
k k A
Therefore,
d C k k A B
k A B
dt k k A

= =
=
+
= =
+

which does not agree with the observed reaction rate law.

112. (M) The answer is (b), first-order, because only in a first-order reaction is the half-life
independent of the concentration of the reacting species.
113. (E) The answer is (a), zero-order, because in a zero-order reaction the relationship between
concentration and time is: [A]
t
=kt +[A]
0

114. (M) The answer is (d). The relationship between rate constant (and thus rate) between two
reactions can be expressed as follows:

2
1 1 2
k Ea 1 1
exp
k R T T
| | | |
=
| |
|
\ . \ .

If T
2
is twice T
1
, the above expression gets modified as follows:
a
2
1 1 1
2 1
a 1 1
R
E
2 1
1 1
k Ea 1 1
ln
k R T 2T
k T 1 R
ln ,
E k 2T
k T 1
ln
k 2T
| | | |
=
| |
\ . \ .
| | | |
=
| |
\ . \ .
| |
=
|
\ .

a
a
R
E
2 1
1 1
R
E
1/2 2
1
For reasonably high temperatures,
k T 1
ln
k 2T 2
Therefore,
k
e 1.64
k
| |
= =
|
\ .
| |
= =
|
\ .

Chapter 14: Chemical Kinetics
665
115. (E) The answer is (c), remain the same. This is because for a zero-order reaction,
d[A]/dt =k[A]
0
=k. Therefore, the reaction rate is independent of the concentration of the
reactant.

116. (M) The overarching concept for this concept map is kinetics as a result of successful collision.
The subtopics are collision theory, molecular transition theory. Molecular speed and orientation
derive from collision theory. Transition complexes and partial bonds fall under the molecular
transition theory heading. Deriving from the collision theory is another major topic, the
Arrhenius relationship. The Arrhenius relationship encompasses the ideas of activation energy,
Arrhenius collision factor, and exponential relationship between temperature and rate constant.


666
CHAPTER 15
PRINCIPLES OF CHEMICAL EQUILIBRIUM

PRACTICE EXAMPLES

1A (E) The reaction is as follows:
2 2 4
2Cu (aq) Sn (aq) 2Cu (aq) Sn (aq)
+ + + +
+ +
Therefore, the equilibrium expression is as follows:

2
4
2
2 2
Cu Sn
K
Cu Sn
+ +
+ +
( (

=
( (


Rearranging and solving for Cu
2+
, the following expression is obtained:
( )
1/2
2
1/2
+ 4+
2
2+
2+
Cu Sn
Cu =
1.48 1.22 K Sn
x x x
x
| |
( (
| |

|
( = =
|

|
| (
\ .

\ .


1B (E) The reaction is as follows:
3 2 2 2
2
2Fe (aq) Hg (aq) 2Fe (aq) 2Hg (aq)
+ + + +
+ +
Therefore, the equilibrium expression is as follows:

( ) ( )
( ) ( )
2 2
2 2 2 2
6
2 2
3 2
2
Fe Hg
0.0025 0.0018
K 9.14 10
0.015 x
Fe Hg
+ +

+ +
( (

= = =
( (


Rearranging and solving for Hg
2
2+
, the following expression is obtained:
( ) ( )
( ) ( )
2 2
2 2 2 2
2
2 2 2
6
3
Fe Hg
0.0025 0.0018
Hg 0.009847 0.0098M
0.015 9.14 10
Fe K
+ +
+

+
( (

( = = = ~

(



2A (E) The example gives K
c
=5.810
5
for the reaction ( ) ( ) ( )
2 2 3
N g +3 H g 2 NH g

.
The reaction we are considering is one-third of this reaction. If we divide the reaction by
3, we should take the cube root of the equilibrium constant to obtain the value of the
equilibrium constant for the divided reaction:
3 5 2
3
c3 c
5.8 10 8.3 10 K K = = =

2B (E) First we reverse the given reaction to put NO g
2
b g on the reactant side. The new
equilibrium constant is the inverse of the given one.

( ) ( ) ( )
2
1
2 2 c 2
NO g NO g + O g ' =1/ (1.2 10 ) =0.0083 K

Then we double the reaction to obtain 2 moles of NO g
2
b g as reactant. The equilibrium
constant is then raised to the second power.

( ) ( ) ( ) ( )
2
5
2 2 c
2 NO g 2 NO g +O g = 0.00833 =6.9 10

Chapter15: Principles of Chemical Equilibrium
667

3A (E) We use the expression ( )
p c
=
gas
n
K K RT
A
. In this case, A n
gas
=3+1 2=2 and thus we
have

( ) ( )
2 2
9 6
p c
= =2.8 10 0.08314 298 =1.7 10 K K RT



3B (M) We begin by writing the K
p
expression. We then substitute
( ) / =[ ] = P n V RT concentration RT for each pressure. We collect terms to obtain an expression
relating K
c
and K
p
, into which we substitute to find the value of K
c
.
K
P P
P
RT RT
RT
RT K RT
p
2
2
2
2
2
2
2
2
2
2
2 2
2
2 c
H )} S
H S)}
H )
H S]
[H [S
[H S]
= = = =
{ ( { ( )}
{ (
([ ] ([S ] )
([ )
] ]
2

The same result can be obtained by using K K RT
n
p c
gas
= b g
A
, since A n
gas
=2+1 2=+1.
( )
2
p 4
c
1.2 10
= = =1.1 10
0.08314 1065+273
K
K
RT

But the reaction has been reversed and halved. Thus K
final
=
4
1 1
9091 95
1.1 10
c
K

= = =

4A (E) We remember that neither solids, such as Ca PO OH(s)
5 4 3
( ) , nor liquids, such as
2
H O(l) ,
appear in the equilibrium constant expression. Concentrations of products appear in the
numerator, those of reactants in the denominator. K
c
Ca HPO
H
=
2+
5
4
2
3
+
4

4B (E) First we write the balanced chemical equation for the reaction. Then we write the
equilibrium constant expressions, remembering that gases and solutes in aqueous solution
appear in the K
c
expression, but pure liquids and pure solids do not.

( ) ( ) ( ) ( )
2 3 4 2
3 Fe s +4 H O g FeO s +4 H g

K
P
P
K n K K
p c gas p c
H
H O
H
H O
Because = = =4 4=0, =
2
4
2
4
2
4
2
4
{ }
{ }
b g
b g
A

5A (M) We compute the value of Q
c
. Each concentration equals the mass m b g of the substance
divided by its molar mass (this quotient is the amount of the substance in moles) and further
divided by the volume of the container.

Chapter15: Principles of Chemical Equilibrium
668
| || |
| || |
2 2
2 2
c c
2
2
2 2
2
1 mol CO 1 mol H
1 44.0 g CO 2.0 g H
CO H 28.0 18.0
44.0 2.0
= =5.7 1.00=
1 mol H O 1 1 mol CO
CO H O 44.0 2.0
18.0 g H O 28.0 18.0 28.0 g CO
m m
V V
Q K
m m
V V

= = = >

(In evaluating the expression above, we cancelled the equal values of V , and we also
cancelled the equal values of m.) Because the value of Q
c
is larger than the value of K
c
,
the reaction will proceed to the left to reach a state of equilibrium. Thus, at equilibrium
there will be greater quantities of reactants, and smaller quantities of products than there
were initially.

5B (M) We compare the value of the reaction quotient,
p
Q , to that of
p
K .

3 2
p
5
{ (PCl )}{ (Cl )} 2.19 0.88
= = =0.098
{ (PCl } 19.7
P P
Q
P

( ) ( ) ( )
2 1 1 1
p c c
= = =0.0454 0.08206 (261 273) =1.99 K K RT K RT

+
Because Q K
c c
< , the net reaction will proceed to the right, forming products and consuming
reactants.

6A (E) O g
2
b g is a reactant. The equilibrium system will shift right, forming product in an
attempt to consume some of the added O
2
(g) reactant. Looked at in another way, O
2
is
increased above its equilibrium value by the addition of oxygen. This makes Q
c
smaller
than K
c
. (The O
2
is in the denominator of the expression.) And the system shifts right to
drive Q
c
back up to K
c
, at which point equilibrium will have been achieved.

6B (M)
(a) The position of an equilibrium mixture is affected only by changing the concentration
of substances that appear in the equilibrium constant expression, K
c
=
2
CO . Since
CaO(s) is a pure solid, its concentration does not appear in the equilibrium constant
expression and thus adding extra CaO(s) will have no direct effect on the position of
equilibrium.

(b) The addition of CO g
2
b g will increase CO
2
above its equilibrium value. The reaction
will shift left to alleviate this increase, causing some CaCO s
3
b g to form.

(c) Since CaCO
3
(s) is a pure solid like CaO(s), its concentration does not appear in the
equilibrium constant expression and thus the addition of any solid CaCO
3
to an
equilibrium mixture will not have an effect upon the position of equilibrium.

Chapter15: Principles of Chemical Equilibrium
669
7A (E) We know that a decrease in volume or an increase in pressure of an equilibrium mixture
of gases causes a net reaction in the direction producing the smaller number of moles of gas.
In the reaction in question, that direction is to the left: one mole of N O g
2 4
b g is formed when
two moles of NO g
2
b g combine. Thus, decreasing the cylinder volume would have the initial
effect of doubling both N O
2 4
and NO
2
. In order to reestablish equilibrium, some NO
2

will then be converted into N
2
O
4
. Note, however, that the NO
2
concentration will still
ultimately end up being higher than it was prior to pressurization.

7B (E) In the balanced chemical equation for the chemical reaction, A n
gas
=1+1 1+1 =0 b g b g .
As a consequence, a change in overall volume or total gas pressure will have no effect on the
position of equilibrium. In the equilibrium constant expression, the two partial pressures in
the numerator will be affected to exactly the same degree, as will the two partial pressures in
the denominator, and, as a result, Q
p
will continue to equal K
p
.

8A (E) The cited reaction is endothermic. Raising the temperature on an equilibrium mixture
favors the endothermic reaction. Thus, N O g
2 4
b g should decompose more completely at
higher temperatures and the amount of NO g
2
b g formed from a given amount of N O g
2 4
b g
will be greater at high temperatures than at low ones.

8B (E) The NH
3
(g) formation reaction is ( ) ( ) ( )
o
3 1
2 2 3 2 2
N g + H g NH g , = 46.11 kJ /mol. H A
This reaction is an exothermic reaction. Lowering temperature causes a shift in the direction
of this exothermic reaction to the right toward products. Thus, the equilibrium NH g
3
b g will
be greater at 100 C

.

9A (E) We write the expression for K
c
and then substitute expressions for molar concentrations.

2
2
4 2 2
c
2 2
2
0.22 0.11
[H ] [S ] 3.00 3.00
2.3 10
[H S]
2.78
3.00
K

| |
|
\ .
= = =
| |
|
\ .


9B (M) We write the equilibrium constant expression and solve for N O
2 4
.
| |
| |
| | ( )
2 2 2
2 2 3
c 2 4
3 3
2 4
NO NO 0.0236
=4.61 10 = N O = = =0.121 M
N O 4.61 10 4.61 10
K


(
(

Then we determine the mass of N O
2 4
present in 2.26 L.
N O mass L
mol N O
L
g N O
mol N O
g N O
2 4
2 4 2 4
2 4
2 4
=2.26
0.121
1
92.01
1
=25.2

Chapter15: Principles of Chemical Equilibrium
670
10A (M) We use the initial-change-equilibrium setup to establish the amount of each substance
at equilibrium. We then label each entry in the table in the order of its determination (1
st
,
2
nd
, 3
rd
, 4
th
, 5
th
), to better illustrate the technique. We know the initial amounts of all
substances (1
st
). There are no products at the start.
Because initial change equilibrium + = , the equilibrium amount (2
nd
) of ( )
2
Br g
enables us to determine change (3
rd
) for Br g
2
b g . We then use stoichiometry to write other
entries (4
th
) on the change line. And finally, we determine the remaining equilibrium
amounts (5
th
).

Reaction: ( ) ( ) ( )
2
2 NOBr g 2 NO g + Br g

Initial: 1.86 mol (1
st
) 0.00 mol (1
st
) 0.00 mol (1
st
)
Change: 0.164 mol (4
th
) +0.164 mol (4
th
) +0.082 mol (3
rd
)
Equil.: 1.70 mol (5
th
) 0.164 mol (5
th
) 0.082 mol (2
nd
)

2
2
4 2
c
2 2
0.164 0.082 mol
5.00 5.00
[NO] [Br ]
1.5 10
[NOBr]
1.70
5.00
K

| | | |
| |
\ . \ .
= = =
| |
|
\ .

Here,
gas
=2+1 2=+1. n A ( ) ( )
+1
4 3
p c
= =1.5 10 0.08314 298 =3.7 10 K K RT



10B (M) Use the amounts stated in the problem to determine the equilibrium concentration for
each substance.
Reaction: ( ) ( ) ( )
3 2 2
2 SO g 2 SO g + O g

Initial: 0 mol 0.100 mol 0.100 mol
Changes: +0.0916 mol 0.0916 mol 0.0916/ 2 mol
Equil.: 0.0916 mol 0.0084 mol 0.0542 mol
Concentrations:
0.0916 mol
1.52 L

0.0084
1.52
mol
L

0.0542
1.52
mol
L

Concentrations: 0.0603 M 0.0055 M 0.0357 M

We use these values to compute K
c
for the reaction and then the relationship
K K RT
n
p c
gas
= b g
A
(with
gas
=2+1 2=+1) n A to determine the value of K
p
.

| | | | ( ) ( )
( )
2 2
2 2 4
c 2 2
3
4
p
SO O 0.0055 0.0357
= = =3.0 10
0.0603 SO
=3.0 10 (0.08314 900) 0.022
K
K

(
(

Chapter15: Principles of Chemical Equilibrium
671
11A (M) The equilibrium constant expression is K P P
p
H O} CO = =0.231
2 2
{ { } at 100

C. From
the balanced chemical equation, we see that one mole of H O g
2
b g is formed for each mole of
CO g
2
b g produced. Consequently, P P { { } H O} CO
2 2
= and K P
p
CO =
2
2
{ } b g . We solve this
expression for
2
{CO }: P
2
2 2 p
{CO } ( {CO }) 0.231 0.481 atm. P P K = = = =

11B (M) The equation for the reaction is ( ) ( ) ( )
4 3 2 p
NH HS s NH g +H S g , =0.108 at 25 C. K

The two partial pressures do not have to be equal at equilibrium. The only instance in which
they must be equal is when the two gases come solely from the decomposition of NH HS s
4
b g .
In this case, some of the NH g
3
b g has come from another source. We can obtain the pressure
of H S g
2
b g by substitution into the equilibrium constant expression, since we are given the
equilibrium pressure of NH g
3
b g .
p 2 3 2 3 2
0.108
= {H S} {NH }=0.108= {H S} 0.500 atm NH {H S}= =0.216 atm
0.500
K P P P P
So, P
total
=
3
2
NH
H S
P P + =0.216 atm +0.500 atm =0.716 atm

12A (M) We set up this problem in the same manner that we have previously employed, namely
designating the equilibrium amount of HI as 2x . (Note that we have used the same
multipliers for x as the stoichiometric coefficients.)

Equation: ( ) ( ) ( )
2 2
H g + I g 2 HI g

Initial: 0.150 mol 0.200 mol 0 mol
Changes: x mol x mol +2x mol
Equil: 0.150 x b g mol 0.200 x b g mol 2x mol

( )
( )( )
2
2
c
2
2
15.0
= =50.2
0.150 0.200
0.150 0.200
15.0 15.0
x
x
K
x x
x x
| |
|
\ .
=

We substitute these terms into the equilibrium constant expression and solve for x.

4 = 0.150 0.200 50.2=50.2 0.0300 0.350 + =1.51 17.6 +50.2
2 2 2
x x x x x x x b gb g c h


2
0=46.2 17.6 +1.51 Now we use the quadratic equation to determine the value of . x x x

x
b b ac
a
=
4
2
=
17.6 (17.6) 4 46.2 1.51
2 46.2
=
17.6 5.54
92.4
=0.250 0.131
2 2

or

Chapter15: Principles of Chemical Equilibrium
672
The first root cannot be used because it would afford a negative amount of H
2
(namely,
0.150-0.250 =-0.100). Thus, we have 2 0.131=0.262 mol HI at equilibrium. We check
by substituting the amounts into the K
c
expression. (Notice that the volumes cancel.) The
slight disagreement in the two values (52 compared to 50.2) is the result of rounding error.

K
c
=
0.262
0.150 0.131 0.200 0.131
=
0.0686
0.019 0.069
=52
2
b g
b gb g


12B (D)
(a) The equation for the reaction is ( ) ( )
3
2 4 2 c
N O g 2 NO g and =4.61 10 K

at 25

C.
In the example, this reaction is conducted in a 0.372 L flask. The effect of moving the
mixture to the larger, 10.0 L container is that the reaction will be shifted to produce a
greater number of moles of gas. Thus, NO g
2
b g will be produced and N O g
2 4
b g will
dissociate. Consequently, the amount of N O
2 4
will decrease.

(b) The equilibrium constant expression, substituting 10.0 L for 0.372 L, follows.
K
x
x
x
x
c
2
2 4
NO
[N O
= =
F
H
G
I
K
J

=

[ ]
]
.
.
.
. ( . )
.
2
2
2
3
2
100
00240
100
4
100 00240
461 10
This can be solved with the quadratic equation, and the sensible result is x =0.0118
moles. We can attempt the method of successive approximations. First, assume that
x << 0.0240. We obtain:


3
3
4.61 10 10.0(0.0240 0)
4.61 10 2.50(0.0240 0) 0.0166
4
x

= = =

Clearly x is not much smaller than 0.0240. So, second, assume x ~ 0.0166. We obtain:
x = =

461 10 250 00240 00166 000925

3
. . ( . . ) .
This assumption is not valid either. So, third, assume x ~ 0.00925. We obtain:

3
4.61 10 2.50(0.0240 0.00925) 0.0130 x

= =
Notice that after each cycle the value we obtain for x gets closer to the value obtained
from the roots of the equation. The values from the next several cycles follow.

Cycle 4
th
5
th
6
th
7
th
8
th
9
th
10
th
11
th

x value 0.0112 0.0121 0.0117 0.0119 0.01181 0.01186 0.01183 0.01184

The amount of N O
2 4
at equilibrium is 0.0118 mol, less than the 0.0210 mol N O
2 4
at
equilibrium in the 0.372 L flask, as predicted.

Chapter15: Principles of Chemical Equilibrium
673
13A (M) Again we base our solution on the balanced chemical equation.
Equation: ( ) ( ) ( ) ( )
+ 2+ 3+
c
Ag aq + Fe aq Fe aq + Ag s =2.98 K

Initial: 0 M 0 M 1.20 M
Changes: +x M +x M x M
Equil: x M x M 1.20 x b g M

K
x
x
x x x x
c
Fe
Ag Fe
= =2.98=
1.20
2.98 =1.20 0=2.98 + 1.20
3+
+ 2+ 2
2 2

We use the quadratic formula to obtain a solution.

2 2
1.00 (1.00) +4 2.98 1.20 4 1.00 3.91
= = = =0.488 M or 0.824 M
2 2 2.98 5.96
b b ac
x
a

A negative root makes no physical sense. We obtain the equilibrium concentrations from x.

+ 2+ 3+
Ag = Fe =0.488 M Fe =1.20 0.488=0.71 M ( ( (



13B (M) We first calculate the value of Q
c
to determine the direction of the reaction.

Q K
c c
V Cr
V Cr
= =
0.150 0.150
0.0100 0.0100
=225 7.2 10 =
2+ 3+
3+ 2+
2

<

Because the reaction quotient has a smaller value than the equilibrium constant, a net
reaction to the right will occur. We now set up this solution as we have others, heretofore,
based on the balanced chemical equation.

( ) ( ) ( ) ( )
3+ 2+ 2+ 3+
V aq + Cr aq V aq + Cr aq

initial 0.0100 M 0.0100 M 0.150 M 0.150 M
changes x M x M +x M +x M
equil (0.0100 x)M (0.0100 x)M (0.150 +x)M (0.150 +x)M

K
x x
x x
x
x
c
V Cr
V Cr
= =
0.150+ 0.150+
0.0100 0.0100
=7.2 10 =
0.150+
0.0100
2+ 3+
3+ 2+
2
2
b g b g
b g b g

F
H
G
I
K
J

If we take the square root of both sides of this expression, we obtain
2
0.150
7.2 10 27
0.0100
x
x
+
= =

0.150 +x =0.27 27x which becomes 28 =0.12 x and yields 0.0043 M. Then the
equilibrium concentrations are: V Cr M M M
3+ 2+
= =0.0100 0.0043 =0.0057

V Cr M M M
2+ 3+
= =0.150 +0.0043 =0.154
Chapter15: Principles of Chemical Equilibrium
674

INTEGRATIVE EXAMPLE

A. (E) We will determine the concentration of F6P and the final enthalpy by adding the two
reactions:
6 12 6
6 12 6
C H O ATP G6P ADP
G6P F6P
C H O ATP ADP F6P
+ +
+ +

H
TOT
=19.74 kJ mol
-1
+2.84 kJ mol
-1
=16.9 kJ mol
-1


Since the overall reaction is obtained by adding the two individual reactions, then the overall
reaction equilibrium constant is the product of the two individual K values. That is,
1 2
K K K 1278 = =

The equilibrium concentrations of the reactants and products is determined as follows:

C
6
H
12
O
6
+ ATP

ADP + F6P
Initial 1.2010
-6
110
-4
110
-2
0
Change -x -x +x +x
Equil 1.2010
-6
-x 110
-4
-x 110
-2
+x x

| || |
| || |
( )( )
( )( )
6 12 6
2
2 2
10 4 2 6 4
ADP F6P
C H O ATP
1 10
1.0 10
1278
1.2 10 1.012 10 1.20 10 1 10
K
x x
x x
x x x x

=
+
+
= =
+


Expanding and rearranging the above equation yields the following second-order polynomial:
1277 x
2
0.1393 x +1.53410
-7
=0
Using the quadratic equation to solve for x, we obtain two roots: x =1.11310
-6
and
1.08010
-4
. Only the first one makes physical sense, because it is less than the initial value of
C
6
H
12
O
6
. Therefore, [F6P]
eq
=1.11310
-6
.

During a fever, the body generates heat. Since the net reaction above is exothermic,
Le Chtelier's principle would force the equilibrium to the left, reducing the amount of F6P
generated.

Chapter15: Principles of Chemical Equilibrium
675
B. (E)
(a) The ideal gas law can be used for this reaction, since we are relating vapor pressure and
concentration. Since K =3.310
-29
for decomposition of Br
2
to Br (very small), then it can be
ignored.
( )( )( )
1
0.100mol 0.08206L atm K 298.15K
nRT
V 8.47L
P 0.289atm

= = =

(b) At 1000 K, there is much more Br being generated from the decomposition of Br
2
.
However, K is still rather small, and this decomposition does not notably affect the volume
needed.

EXERCISES

Writing Equilibrium Constants Expressions

1. (E)
(a) ( ) ( ) ( )
| || |
| |
2 4
2 2 4 c
2
2
CO CF
2 COF g CO g +CF g K =
COF

(b) ( ) ( ) ( ) ( )
2+
+ 2+
c
2
+
Cu
Cu s +2 Ag aq Cu aq +2 Ag s K =
Ag
(

(

(c) ( ) ( ) ( ) ( )
2 2
2 3+
4
2 2 2+ 3+
2 8 4 c 2
2 2+
2 8
SO Fe
S O aq +2 Fe aq 2 SO aq +2 Fe aq =
S O Fe
K

( (

( (

2. (E)
(a) ( ) ( ) ( ) ( )
{ } { }
{ } { }
2 6
2 2
3 2 2 2 P 4 3
3 2
P N P H O
4 NH g +3 O g 2 N g +6 H O g =
P NH P O
K

(b) ( ) ( ) ( ) ( )
{ } { }
{ } { }
2 4
3 2
2 2 3 2 P 7 2
2 2
P NH P H O
7 H g +2 NO g 2 NH g +4 H O g =
P H P NO
K

(c) ( ) ( ) ( ) ( ) ( )
| |
3
2 2 3 c
2
CO
N g +Na CO s +4 C s 2 NaCN s +3 CO g =
N
K
(
(

3. (E)
(a)
| |
| | | |
2
2
c 2
2
NO
=
NO O
K (b) K
c
Zn
Ag
=
2+
+
2
(c) K
c
OH
CO
=
2
3
2

Chapter15: Principles of Chemical Equilibrium
676
4. (E)
(a) K
P
P
p
{CH }P{H S}
{CS }P{H
=
4 2
2
2 2
4
}
(b) K P
p
O =
2
1/2
l q (c) K P P
p
CO H O} =
2 2
{ } {

5. (E) In each case we write the equation for the formation reaction and then the equilibrium
constant expression, K
c
, for that reaction.
(a) ( ) ( ) ( )
| |
| | | |
1 1
2 2 c 2 2 1/2 1/2
2 2
HF
H g + F g HF g =
H F
K

(b) ( ) ( ) ( )
| |
| || |
2
3
2 2 3 c
3
2 2
NH
N g +3 H g 2 NH g =
N H
K

(c) ( ) ( ) ( )
2
2
2 2 2 c
2
2 2
[N O]
2 N g +O g 2 N O g =
[N ] [O ]
K

(d)
3 1
2 2 3 c 2 2 1/ 2 3/ 2
2 2
1
Cl (g)+ F (g) ClF (l)
[Cl ] [F ]
K =

6. (E) In each case we write the equation for the formation reaction and then the equilibrium
constant expression, K
p
, for that reaction.
(a) ( ) ( ) ( ) ( )
| |
2 2 2
NOCl
1 1 1
2 2 2 P 2 2 2 1/2 1/2 1/2
N O Cl
P
N g + O g + Cl g NOCl g =
P P P
K
( ( (

(b) ( ) ( ) ( ) ( )
2
2 2 2
2
ClNO
2 2 2 2 P
2
N O Cl
P
N g +2 O g + Cl g 2 ClNO g =
P P P
K
(

( ( (

(c) ( ) ( ) ( )
2 4
2 2
N H
2 2 2 4 P
2
N H
P
N g +2 H g N H g =
P P
K
( (

(d) ( ) ( ) ( ) ( )
2 2 2
1 1
2 2 2 4 P 2 2 1/2 2 1/2
N Cl
1
N g +2 H g + Cl g NH Cl s =
P P P
H
K
( ( (

7. (E) Since ( )
p c
=
g
n
K K RT
A
, it is also true that ( )
c p
=
g
n
K K RT
A
.
(a)
| |
( )
( 1)
2 2 -2 -1
c p
2 2
SO [Cl ]
= = =2.9 10 (0.08206 303) =0.0012
SO Cl
K K RT
+
(
(


(b)
| |
| |
( )
2
( 1)
2 4 5
c p 2
2
NO
= = =1.48 10 (0.08206 303) =5.55 10
NO [O ]
K K RT


(c)
| |
( )
3
0
2
c p p 3
2
H S
= = = =0.429
H
K K RT K
(
(



Chapter15: Principles of Chemical Equilibrium
677
8. (E) ( )
p c
=
g
n
K K RT
A
, with
1 1
=0.08206 L atm mol K R


(a)
2
+1 -3 1 2
p c
2 4
P{NO }
= (RT) =4.6110 (0.08206298) 0.113
P{N O }
K K = =
(b)
3
( 2) 2 3 2 2 2
p c
2
4
P{C H }P{H }
K (RT) (0.154)(0.08206 2000) 4.15 10
P{CH }
K
+
= = = =
(c)
4
( 2) 8 2 4 2 2
p c
2
2 4
P{H }P{CS }
K K (RT) (5.27 10 )(0.08206 973) 3.36 10
P{H S}P{CH }
+
= = = =

9. (E) The equilibrium reaction is ( ) ( )
2 2
H O l H O g

with An
gas
=+1. ( )
p c
=
g
n
K K RT
A
gives
( )
c p
=
g
n
K K RT
A
. K P
p 2
= {H O}=23.8 mmHg
1 atm
760 mmHg
=0 .0313
( )
1 p -3
c p
K
0.0313
= = = =1.28 10
RT 0.08206 298
K K RT

10. (E) The equilibrium rxn is ( ) ( )
6 6 6 6
C H l C H g

with An
gas
=+1. Using ( )
p c
=
g
n
K K RT
A
,
( ) ( )
3
p c 6 6
= =5.12 10 0.08206 298 =0.125 = {C H } K K RT P

6 6
760 mmHg
{C H }=0.125 atm =95.0 mmHg
1 atm
P

11. (E) Add one-half of the reversed 1
st
reaction with the 2
nd
reaction to obtain the desired
reaction.
( ) ( ) ( )
1 1
2 2 c 2 2
30
1
N g + O g NO g =
2.1 10
K

( ) ( ) ( )
1
2 c 2
NO g + Br g NOBr g =1.4 K

( ) ( ) ( ) ( )
16
1 1 1
2 2 2 c 2 2 2
30
1.4
net: N g + O g + Br g NOBr g = =9.7 10
2.1 10
K

12. (M) We combine the several given reactions to obtain the net reaction.
( ) ( )
( )
2 2 2 c
2
18
1
2 N O g 2 N g O (g) =
2.7 10
K

( ) ( )
( )
2 2 4 c 2
3
1
4 NO g 2 N O g =
4.6 10
K

( ) ( ) ( )
( )
( ) ( )
9 4
2 2 2 c
4
9
6
2 2 2 4 ( )
2 2
18 3
2N (g) +4O (g) 4NO (g) (4.1 10 )
4.1 10
net: 2 N O g +3 O g 2 N O g = =1.8 10
2.7 10 4.6 10
c Net
K
K

Chapter15: Principles of Chemical Equilibrium
678
13. (M) We combine the K
c
values to obtain the value of K
c
for the overall reaction, and then
convert this to a value for K
p
.
( ) ( ) ( ) ( ) ( )
2
2 2 2 c
2 CO g +2H g 2 CO g +2 H O g =1.4 K

( ) ( ) ( ) ( )
2
8
2
2 C graphite +O g 2 CO g = 1 10
c
K

( ) ( ) ( )
( )
2
2
1
4 CO g 2 C graphite +2 CO g =
0.64
c
K

net:
2 8 2
6
2 2 2 c(Net)
2
(1.4) (1 10 )
2H (g)+O (g) 2H O(g) 5 10
(0.64)
K

= =

( )
16
14
p c
5 10
= = = =5 10
0.08206 1200
n
c
K
K K RT
RT
A

14. (M) We combine the K
p
values to obtain the value of K
p
for the overall reaction, and then
convert this to a value for K
c
.
( ) ( ) ( )
2
2 2 p
2
1
2 NO Cl g 2 NOCl g +O g =
1.1 10
K
| |
|

\ .

( ) ( ) ( ) ( )
2
2 2 2 p
2 NO g + Cl g 2 NO Cl g = 0.3 K

( ) ( ) ( )
9 2
2 2 2 p
N g +2 O g 2 NO g =(1.0 10 ) K

net:
2 9 2
24
2 2 2 p(Net)
2 2
(0.3) (1.0 10 )
N (g) +O (g) +Cl (g) 2 NOCl(g) 7.4 10
(1.1 10 )
K

= =

( )
( ) ( )
24
p 22
p c c
2 3
7.4 10
= = = =2 10
0.08206 298
n
n
K
K K RT K
RT

A

A

15. (E)
2 2 2 3
CO (g) H O(l) H CO (aq) +
In terms of concentration, K =a(H
2
CO
3
)/a(CO
2
)
In terms of concentration and partial pressure,
| |
2
2 3
CO
H CO c
K
P P
=

16. (E)
2 2 3
2 Fe(s) 3 O (g) FeO (s) +
2 3
2
Fe O
Fe O
a
K
a a
=

. Since activity of solids and liquids is defined as 1, then the expression

simplifies to
2
O
1
K
a
=
Similarly, in terms of pressure and concentration,
( )
2
O
K 1 P / P =




Chapter15: Principles of Chemical Equilibrium
679
Experimental Determination of Equilibrium Constants

17. (M) First, we determine the concentration of PCl
5
and of Cl
2
present initially and at
equilibrium, respectively. Then we use the balanced equation to help us determine the
concentration of each species present at equilibrium.
| | | |
3 4
5 2
5 2
1.00 10 mol PCl 9.65 10 mol Cl
PCl = =0.00400 M Cl = =0.00386 M
0.250 L 0.250 L
initial equil



Equation: ( ) ( )
5 3 2
PCl g PCl (g) + Cl g

Initial: 0.00400M 0 M 0 M
Changes: xM +xM +xM
Equil: 0.00400M-xM xM xM 0.00386 M (from above)

At equilibrium, [Cl
2
] =[PCl
3
] =0.00386 M and [PCl
5
] =0.00400M xM =0.00014 M

| || |
| |
3 2
c
5
PCl Cl
(0.00386M)(0.00386M)
PCl 0.00014M
K = = =0.106

18. (M) First we determine the partial pressure of each gas.

( )
2
2
2
initial 2
1mol H 0.08206L atm
1.00gH 1670K
2.016gH mol K
{H g }= = 136atm
0.500L
nRT
P
V

=

( )
2
2
2
initial 2
1mol H S 0.08206L atm
1.06gH S 1670K
34.08gH S mol K
{H S g }= = 8.52atm
0.500L
nRT
P
V

=

( )
6
2
3
equil 2
0.08206L atm
8.00 10 mol S 1670K
mol K
{S g }= = 2.19 10 atm
0.500L
nRT
P
V

=
( ) ( ) ( )
2 2 2
Equation: 2 H g + S g 2 H S g
Initial : 136 atm 0 atm 8.52 atm
Changes: +0.00438atm 0.00219 atm 0.00438 atm
Equil : 136 atm 0.00219 atm 8.52 atm

( )
( )
( )
( )
2
2
2
p
2 2
2 2
{H S g } 8.52
= = =1.79
{H g } P{S (g)}
136 0.00219
P
K
P


Chapter15: Principles of Chemical Equilibrium
680
19. (M)
(a) K
c
5
3 2
5 5
3 3 2 2
PCl
PCl Cl
g PCl
L
mol PCl
g
g PCl
L
mol PCl
g
gCl
L
mol Cl
g
= =
0105
250
1
2082
0220
250
1
1373
212
250
1
709
263
L
N
M
O
Q
P
L
N
M
O
Q
P

F
H
G
I
K
J

F
H
G
I
K
J
=
.
. .
.
. .
.
. .
.
(b) K K RT
n
p c
= =26.3 0.08206 523 =0.613
1
b g b g
A


20. (M)
-3
initial
1 mol ICl
0.682 g ICl
162.36 g ICl
[ICl] = =6.7210 M
0.625 L


Reaction: 2 ICl(g)

I
2
(g) + Cl
2
(g)
Initial: 6.72 10
-3
M 0 M 0 M
Change -2x +x +x
Equilibrium 6.72 10
-3
M -2x x x


2
2
-4 2
2 equil
1 mol I
0.0383 g I
253.808 g I
[I ] = =2.4110 M
0.625L
=x

4 2
6
c 3 3 4
(2.41 10 )
9.31 10
(6.72 10 2 ) (6.72 10 2(2.41 10 ))
x x
K
x

= = =



21. (E)
( )
3 3
3
3 3
7
3 18
Fe Fe
K 9.1 10
H 1.0 10
Fe 9.1 10 M
+ +
+
+
( (

= =
(

( =



22. (E)
| |
3 3
3
9
3
NH (g) NH (g)
9 11
NH (g)
NH (aq)
5 10
K 57.5
P P
P 5 10 57.5 8.7 10

= =
= =



Chapter15: Principles of Chemical Equilibrium
681
Equilibrium Relationships

23. (M)
| | | | | |
2 2
3 3 2
c 2 2
3
2 2 2
SO SO SO
0.185 L 0.185
=281= = = =0.516
0.00247 mol SO 0.00247 281
SO O SO
K
(
( ( (
(
( ( (

24. (M)
| |
| |
2
2
c
2
2
0.37mol I
I
1 0.14
0.011 0.14 13L
1.00mol I
I 0.011
V
K V
V
V
| |
|
\ .
= = = = = =

25. (M)
(a) A possible equation for the oxidation of NH g
3
b g to NO g
2
b g follows.
( ) ( ) ( ) ( )
7 3
3 2 2 2 4 2
NH g + O g NO g + H O g

(b) We obtain
p
K for the reaction in part (a) by appropriately combining the values of
p
K given in the problem.
( ) ( ) ( ) ( )
19
5 3
3 2 2 4 2
NH g + O g NO g + H O g =2.11 10
p
K

( ) ( ) ( )
1
2 2 p 2
1
NO g + O g NO g =
0.524
K

( ) ( ) ( ) ( )
19
19
7 3
3 2 2 2 4 2
2.11 10
net: NH g + O g NO g + H O g = =4.03 10
0.524
p
K

26. (D)
(a) We first determine [H
2
] and [CH
4
] and then [C
2
H
2
]. [CH
4
] =[H
2
] =
0.10 mol
1.0 L
=0.10 M

| || |
| |
| |
3 2
2
2 2 2 c 4
c 2 2 2 3 3
4 2
C H H CH
0.154 0.10
= C H = = =1.54 M
0.10
CH H
K
K
( (
( (

In a 1.00 L container, each concentration numerically equals the molar quantities of
the substance.
2 2
2 2
2 2 4 2
1.54 mol C H
{C H }= =0.89
1.54 mol C H +0.10 mol CH +0.10 mol H
_

(b) The conversion of CH
4
(g) to C
2
H
2
(g) is favored at low pressures, since the conversion
reaction has a larger sum of the stoichiometric coefficients of gaseous products (4) than
of reactants (2).

(c) Initially, all concentrations are halved when the mixture is transferred to a flask that is
twice as large. To re-establish equilibrium, the system reacts to the right, forming more
moles of gas (to compensate for the drop in pressure). We base our solution on the
balanced chemical equation, in the manner we have used before.
Chapter15: Principles of Chemical Equilibrium
682
( ) ( ) ( )
4 2 2 2
Equation: 2 CH (g) C H (g) + 3 H
0.10mol 1.5mol 0.10mol
Initial:
2.00L 2.00L 2.00L
=0.050 M =0.75 M =0.050 M
Changes: 2 M + M +3 M
Equil: 0.050 2 M 0.0750+ M 0.050+3 M
x x x
x x x

| || | ( ) ( )
( )
3 3
2 2 2
c
2 2
4
C H H 0.050+3 0.750+
= = =0.154
0.050 2 CH
x x
K
x
(
(



We can solve this 4
th
-order equation by successive approximations.
First guess: x =0.010 M.


( ) ( ) ( )
( ) ( )
( ) ( )
( )
3 3
c
2 2
0.050+3 0.010 0.750+0.010 0.080 0.760
=0.010 = = =0.433 0.154
0.030 0.050 2 0.010
x Q >

( ) ( ) ( )
( ) ( )
( ) ( )
( )
3 3
c
2 2
0.050+3 0.020 0.750+0.020 0.110 0.770
=0.020 = = =10.2 0.154
0.010 0.050 2 0.020
x Q >

( ) ( ) ( )
( ) ( )
( ) ( )
( )
3 3
c
2 2
0.050+3 0.005 0.750+0.005 0.065 0.755
=0.005 = = =0.129 0.154
0.040 0.050 2 0.005
x Q <

( ) ( ) ( )
( ) ( )
( ) ( )
( )
3 3
c
2 2
0.050+3 0.006 0.750+0.006 0.068 0.756
=0.006 = = =0.165 0.154
0.038 0.050 2 0.006
x Q >

This is the maximum number of significant figures our system permits. We have
x =0.006 M.
| | | | | |
4 2 2 2
CH =0.038 M; C H =0.756 M; H =0.068 M
Because the container volume is 2.00 L, the molar amounts are double the values of
molarities.

2 2
2 2
0.756 mol C H
2.00 L =1.51 mol C H
1 L

4
4
0.038 mol CH
2.00 L =0.076 mol CH
1 L


2.00
0.068
1
=0.14
2
2
L
mol H
L
mol H

Thus, the increase in volume results in the production of some additional C
2
H
2
.

Chapter15: Principles of Chemical Equilibrium
683
27. (M)
(a)
| || |
| || |
{ } { }
{ }
2
2
c
2 2 2 2
CO H O
CO H O
V V
H CO H {CO }
V V
n n
K
n
n

= =

Since V is present in both the denominator and the numerator, it can be stricken from
the expression. This happens here because An
g
=0. Therefore, K
c
is independent of V.

(b) Note that K K
p c
= for this reaction, sinceAn
gas
=0.
K K
c p
mol CO mol H O
mol CO mol H
= =
0.224 0.224
0.276 0.276
=0.659
2
2 2

28. (M) For the reaction CO(g) +H
2
O(g)

CO
2
(g) +H
2
(g) the value of K
p
=23.2
The expression for Q
p
is
2 2
2
[CO ][H ]
[CO][H O]
. Consider each of the provided situations
(a)
2 2 2
CO H O H CO
P =P =P = P ; Q
p
=1 Not an equilibrium position
(b)
2 2
2
H CO
H O CO
P P
= = ;
P P
x Q
p
=x
2
If x = 23.2, this is an equilibrium position.
(c)
( ) ( )
2 2 2
CO H O CO H
P P = P P ; Q
p
=1 Not an equilibrium position
(d)
2 2
2
H CO
CO H O
P P
= = ;
P P
x Q
p
=x
2
If x = 23.2, this is an equilibrium position.


Direction and Extent of Chemical Change

29. (M) We compute the value of Q
c
for the given amounts of product and reactants.
Q
c
=
| |
| | | |
2
3
2
3
c 2 2
2 2
2 2
1.8mol SO
SO 7.2L
0.82 100
SO O
3.6mol SO 2.2mol O
7.2L 7.2L
K
| |
|
\ .
= = < =
| |
|
\ .

The mixture described cannot be maintained indefinitely. In fact, because Q K
c c
< , the
reaction will proceed to the right, that is, toward products, until equilibrium is established.
We do not know how long it will take to reach equilibrium.

Chapter15: Principles of Chemical Equilibrium
684
30. (M) We compute the value of Q
c
for the given amounts of product and reactants.
| |
| |
2
2
2
2 4 3
c c
2 4
2 4
0.0205mol NO
NO 5.25L
1.07 10 K 4.61 10
0.750mol N O
N O
5.25L
Q

| |
|
\ .
= = = < =
The mixture described cannot be maintained indefinitely. In fact, because Q
c
<K
c
, the
reaction will proceed to the right, that is, toward products, until equilibrium is established.
If E
a
is large, however, it may take some time to reach equilibrium.

31. (M)
(a) We determine the concentration of each species in the gaseous mixture, use these
concentrations to determine the value of the reaction quotient, and compare this value
of Q
c
with the value of K
c
.
| | | |
2 2
2 2
0.455 mol SO 0.183 mol O
SO = =0.239 M O = =0.0963 M
1.90 L 1.90 L

| |
| | ( )
( )
2 2
3 3
3
2 2
2 2
SO 0.299 0.568 mol SO
SO = =0.299 M = = =16.3
1.90 L
SO O 0.239 0.0963
c
Q
( (
( (


SinceQ K
c c
=16.3 2.8 10 =
2
= , this mixture is not at equilibrium.

(b) Since the value of Q
c
is smaller than that of K
c
, the reaction will proceed to the right,
forming product and consuming reactants to reach equilibrium.

32. (M) We compute the value of Q
c
. Each concentration equals the mass m b g of the substance
divided by its molar mass and further divided by the volume of the container.

| || |
| || |
2 2
2 2
c c
2
2
2 2
2
1 mol CO 1 mol H
44.0 g CO 2.0 g H 1
CO H 28.0 18.0
44.0 2.0
= =5.7 31.4(value of
1 mol H O 1
1 mol CO CO H O 44.0 2.0
28.0 18.0 18.0 g H O 28.0 g CO
)
m m
V V
Q K
m m
V V

= = = <

(In evaluating the expression above, we cancelled the equal values of V , along with, the
equal values of m.) Because the value of Q
c
is smaller than the value of K
c
, (a) the
reaction is not at equilibrium and (b) the reaction will proceed to the right (formation of
products) to reach a state of equilibrium.

Chapter15: Principles of Chemical Equilibrium
685
33. (M) The information for the calculation is organized around the chemical equation. Let
x =
2
mol H (or I
2
) that reacts. Then use stoichiometry to determine the amount of HI
formed, in terms of x , and finally solve for x .

Equation: H g
2
b g + I g
2
b g

2 HI g b g
Initial: 0.150 mol 0.150 mol 0.000 mol
Changes: x mol x mol +2x mol
Equil: 0.150 x 0.150 x 2x
| |
| || |
2
2
c
2 2
2
HI 3.25L
0.150 0.150
H I
3.25L 3.25L
x
K
x x
| |
|
\ .
= =

Then take the square root of both sides: K

x
x
c
= =

= 502
2
0150
709 .
.
.
1.06
2 =1.06 7.09 = =0.117 mol, amount HI =2 =2 0.117 mol =0.234 mol HI
9.09
x x x x
amount ( ) ( )
2 2 2 2
H = amount I = 0.150 mol = 0.150 0.117 mol =0.033 mol H (or I ) x

34. (M) We use the balanced chemical equation as a basis to organize the information
Equation: ( ) ( ) ( )
5 3 2
SbCl g SbCl g + Cl g

Initial:
0.00
2.50
0.280
2.50
0.160
2.50
mol
L
mol
L
mol
L

Initial: 0.000 M 0.112 M 0.0640 M
Changes: + M M M x x x
Equil: x x x M M M 0.112 0.0640 b g b g
| || | ( )( )
2
3 2
c
5
SbCl Cl 0.112 0.0640
0.00717 0.176 +
=0.025= = =
SbCl
x x
x x
K
x x
(
(




2 2
0.025 =0.00717 0.176 + 0.201 +0.00717=0 x x x x x
2
b b 4ac 0.201 0.0404 0.0287
= = =0.0464 or 0.155
2a 2
x



The second of the two values for x gives a negative value of
| | ( )
2
Cl = 0.091 M , and thus is
physically meaningless in our universe. Thus, concentrations and amounts follow.

| |
5 5 5
SbCl = =0.0464 M amount SbCl =2.50 L 0.0464 M =0.116 mol SbCl x

| |
3 3 3
SbCl =0.112 =0.066 M amount SbCl =2.50 L 0.066 M =0.17 mol SbCl x

| |
2 2 2
Cl =0.0640 =0.0176 M amount Cl =2.50 L 0.0176M =0.0440 mol Cl x

Chapter15: Principles of Chemical Equilibrium
686
35. (M) We use the chemical equation as a basis to organize the information provided about the
reaction, and then determine the final number of moles of ( )
2
Cl g present.

Equation: ( ) ( ) ( )
2 2
CO g + Cl g COCl g

Initial: 0.3500 mol 0.0000 mol 0.05500 mol
Changes: + mol + mol mol x x x
Equil.: ( ) ( ) 0.3500+ mol mol 0.05500 mol x x x

| |
| || |
2 3
c
2
(0.0550 )mol
COCl
3.050L
1.2 10
(0.3500 + )mol mol
CO Cl
3.050L 3.050 L
x
K
x x

= = =

3
1.2 10 0.05500
3.050 (0.3500 )
x
x x

=
+
Assumex << 0.0550 This produces the following expression.

3
4
2
3
1.2 10 0.05500 3.050 0.05500
= = =4.0 10 mol Cl
3.050 0.3500 0.3500 1.2 10
x
x

We use the first value we obtained,
4
4.0 10

(=0.00040), to arrive at a second value.

( )
( )
4
2
3
3.050 0.0550 0.00040
= =4.0 10 mol Cl
0.3500+0.00040 1.2 10
x

Because the value did not change on the second iteration, we have arrived at a solution.

36. (M) Compute the initial concentration of each species present. Then determine the equilibrium
concentrations of all species. Finally, compute the mass of CO
2
present at equilibrium.

| |
int
1.00 g 1 mol CO
CO = =0.0253 M
1.41 L 28.01 g CO

| |
2
2
int
2
1.00 g 1 mol H O
H O = =0.0394 M
1.41 L 18.02 g H O


| |
2
2
int
2
1.00 g 1 mol H
H = =0.352 M
1.41 L 2.016 g H


( ) ( ) ( ) ( )
( ) ( ) ( )
2 2 2
Equation: CO g + H O g CO g + H g
Initial : 0.0253 M 0.0394 M 0.0000 M 0.352 M
Changes: M M + M + M
Equil : 0.0253 M 0.0394 M M 0.352+ M
x x x x
x x x x




| || |
| || |
( )
( )( )
2
2 2
c
2
2
CO H 0.352+
0.352 +
= =23.2= =
CO H O 0.0253 0.0394 0.000997 0.0647 +
x x
x x
K
x x x x


2 2 2
0.0231 1.50 +23.2 =0.352 + 22.2 1.852 +0.0231=0 x x x x x x

Chapter15: Principles of Chemical Equilibrium

687

2
4 1.852 3.430 2.051
= = =0.0682 M, 0.0153 M
2 44.4
b b ac
x
a



The first value of x gives negative concentrations for reactants ([CO] =-0.0429 M and [H
2
O]
=-0.0288 M). Thus, x =0.0153 =
2
M CO . Now we can find the mass of CO
2
.

1.41
0.0153
1
44.01
1
=0.949
2 2
2
2
L
mol CO
L mixture
g CO
mol CO
g CO

37. (D) We base each of our solutions on the balanced chemical equation.

(a)
( ) ( ) ( )
( ) ( )
5 3 2
Equation: PCl g PCl g + Cl g
0.550 mol 0.550 mol 0 mol
Initial :
2.50 L 2.50 L 2.50 L
mol + mol + mol
Changes:
2.50 L 2.50 L 2.50 L
0.550 mol 0.550+ mol
mol
Equil :
2.50 L 2.50 L 2.50 L
x x x
x x
x

( )
2 2 3 2
c
5
0.550 mol
mol
[PCl ][Cl ] (0.550 )
2.50L 2.50L
3.8 10 3.8 10
(0.550 )mol
[PCl ] 2.50(0.550 )
2.50L
x
x
x x
K
x
x

+

+
= = = =

x x x x x
2 2
+0.550 =0.052 0.095 +0.645 0.052=0

2
4 0.645 0.416+0.208
= = =0.0725 mol, 0.717 mol
2 2
b b ac
x
a


The second answer gives a negative quantity. of Cl
2
, which makes no physical sense.
( )
5
PCl
n = 0.550 0.0725 =0.478 mol PCl
5
( )
3
PCl
n = 0.550+0.0725 =0.623 mol PCl
3


2
Cl
n = =0.0725 x mol Cl
2
(b) ( ) ( ) ( )
( ) ( )
5 3 2
Equation: PCl g PCl g + Cl g
0.610 mol
Initial : 0M 0M
2.50 L
+ mol mol + mol
Changes:
2.50 L 2.50 L 2.50 L
mol mol
0.610 mol
Equil :
2.50 L 2.50 L 2.50 L
x x x
x x
x

Chapter15: Principles of Chemical Equilibrium
688
| || |
3 2 2
c
5
2
2 2 2
( mol) ( mol)
PCl Cl
2.50L 2.50L
= =3.8 10
0.610 mol
PCl
2.50L
2.50 3.8 10 0.095 0.058 0.095 = +0.095 0.058=0
0.610
x x
K
x
x
x x x x
x

(
(

= =

2
4 0.095 0.0090+0.23
= = =0.20 mol, 0.29 mol
2 2
b b ac
x
a



amount PCl mol amount Cl
3 2
=0.20 = ; amount PCl mol
5
=0.610 0.20=0.41

38. (D)
(a) We use the balanced chemical equation as a basis to organize the information we have
about the reactants and products.


( ) ( ) ( )
2 2 4
Equation: 2 COF g CO g + CF g
0.145 mol 0.262 mol 0.074 mol
Initial:
5.00 L 5.00 L 5.00 L
Initial: 0.0290 M 0.0524 M 0.0148 M

And we now compute a value of Q
c
and compare it to the given value of
c
K .


| || | ( )( )
( )
2 4
c c
2 2
2
CO CF 0.0524 0.0148
= = =0.922 2.00=
0.0290 COF
Q K
(
(

<

Because
c
Q is not equal to
c
K , the mixture is not at equilibrium.

(b) Because
c
Q is smaller than
c
K , the reaction will shift right, that is, products will be
formed at the expense of COF
2
, to reach a state of equilibrium.

(c) We continue the organization of information about reactants and products.

( ) ( ) ( )
( ) ( ) ( )
2 2 4
Equation: 2 COF g CO g + CF g
Initial: 0.0290 M 0.0524 M 0.0148 M
Changes: 2 M + M + M
Equil: 0.0290 2 M 0.0524+ M 0.0148+ M
x x x
x x x

Chapter15: Principles of Chemical Equilibrium

689
| || | ( )( )
( )
2
2 4
c
2 2 2
2
CO CF 0.0524+ 0.0148+
0.000776+0.0672 +
= = =2.00=
0.000841 0.1160 +4
0.0290 2 COF
x x
x x
K
x x
x
(
(

0.00168 0.232 +8 =0.000776+0.0672 + 7 0.299 +0.000904=0
2 2 2
x x x x x x

x
b b ac
a
=
4
2
=
0.299 0.0894 0.0253
14
=0.0033 ,0.0394
2

M M

The second of these values for x (0.0394) gives a negative
| |( )
2
COF = 0.0498 M ,
clearly a nonsensical result. We now compute the concentration of each species at
equilibrium, and check to ensure that the equilibrium constant is satisfied.


| | ( )
2
COF =0.0290 2 =0.0290 2 0.0033 =0.0224 M x


| |
2
CO =0.0524+ =0.0524+0.0033=0.0557 M x


| |
4
CF =0.0148+ =0.0148+0.0033=0.0181 M x


| || |
( )
2 4
c
2 2
2
CO CF
0.0557 M 0.0181 M
= = =2.01
0.0224 M COF
K
(
(

The agreement of this value of K
c
with the cited value (2.00) indicates that this solution
is correct. Now we determine the number of moles of each species at equilibrium.

mol COF L M mol COF
2 2
=5.00 0.0224 =0.112

mol CO L M mol CO
2 2
=5.00 0.0557 =0.279

mol CF L M mol CF
4 4
=5.00 0.0181 =0.0905

But suppose we had incorrectly concluded, in part (b), that reactants would be formed
in reaching equilibrium. What result would we obtain? The set-up follows.

( ) ( ) ( )
( ) ( ) ( )
2 2 4
Equation: 2 COF g CO g + CF g
Initial : 0.0290M 0.0524 M 0.0148 M
Changes: +2 M M M
Equil : 0.0290+2 M 0.0524 M 0.0148 M
y y y
y y y

| || | ( )( )
( )
2
2 4
c
2 2 2
2
CO CF 0.0524 0.0148
0.000776 0.0672 +
= = =2.00=
0.000841+0.1160 +4
0.0290+2 COF
y y
y y
K
y y
y
(
(




0.00168+0.232 +8 =0.000776 0.0672 + 7 +0.299 +0.000904=0
2 2 2
y y y y y y

y
b b ac
a
=
4
2
=
0.299 0.0894 0.0253
14
= 0.0033 , 0.0394
2

M M

Chapter15: Principles of Chemical Equilibrium
690
The second of these values for x 0.0394 b g gives a negative
| |( )
2
COF = 0.0498 M ,
clearly a nonsensical result. We now compute the concentration of each species at
equilibrium, and check to ensure that the equilibrium constant is satisfied.


| | ( )
2
COF =0.0290+2 =0.0290+2 0.0033 =0.0224 M y

| |
2
CO =0.0524 =0.0524+0.0033=0.0557 M y


| |
4
CF =0.0148 =0.0148+0.0033=0.0181 M y

These are the same equilibrium concentrations that we obtained by making the correct
decision regarding the direction that the reaction would take. Thus, you can be assured
that, if you perform the algebra correctly, it will guide you even if you make the
incorrect decision about the direction of the reaction.

39. (D)
(a) We calculate the initial amount of each substance.

}
2 5
2 5 2 5 2 5
2 5
1 mol C H OH
{C H OH =17.2 g C H OH =0.373 mol C H OH
46.07 g C H OH
n

}
3 2
3 2 3 2 3 2
3 2
1 mol CH CO H
{CH CO H =23.8 g CH CO H =0.396 mol CH CO H
60.05 g CH CO H
n

3 2 2 5
3 2 2 5 3 2 2 5
3 2 2 5
3 2 2 5 3 2 2 5
1 mol CH CO C H
{CH CO C H }=48.6 g CH CO C H
88.11 g CH CO C H
{CH CO C H }=0.552 mol CH CO C H
n
n

{ }
2
2 2 2
2
1 mol H O
H O =71.2 g H O =3.95 mol H O
18.02 g H O
n

Since we would divide each amount by the total volume, and since there are the same
numbers of product and reactant stoichiometric coefficients, we can use moles rather
than concentrations in the
c
Q expression.

} { }
} { }
3 2 2 5 2
c c
2 5 3 2
{CH CO C H H O
0.552 mol 3.95 mol
= = =14.8 =4.0
{C H OH CH CO H 0.373 mol 0.396 mol
n n
Q K
n n

>

Since
c c
Q K > the reaction will shift to the left, forming reactants, as it attains
equilibrium.

(b)
2 5 3 2 3 2 2 5 2
Equation: C H OH + CH CO H CH CO C H + H O

Initial 0.373 mol 0.396 mol 0.552 mol 3.95 mol
Changes +x mol +x mol x mol x mol
Equil (0.373+x) mol (0.396+x) mol (0.552x) mol (3.95x) mol

Chapter15: Principles of Chemical Equilibrium
691
2
2
(0.552 )(3.95 ) 2.18 4.50
4.0
(0.373 )(0.396 ) 0.148 0.769
c
x x x x
K
x x x x
+
= = =
+ + + +


x x x x x x
2 2 2
4.50 +2.18=4 +3.08 +0.59 3 +7.58 1.59=0

2
4 7.58 57+19
= = =0.19 moles, 2.72 moles
2 6
b b ac
x
a



Negative amounts do not make physical sense. We compute the equilibrium amount of each
substance with x =0.19 moles.

}
2 5 2 5
{C H OH =0.373 mol +0.19 mol =0.56 mol C H OH n
2 5
2 5 2 5 2 5
2 5
46.07g C H OH
mass C H OH =0.56mol C H OH 26g C H OH
1 mol C H OH
=

}
3 2 3 2
{CH CO H =0.396 mol +0.19 mol =0.59 mol CH CO H n

3 2
3 2 3 2 3 2
3 2
60.05g CH CO H
mass CH CO H =0.59mol CH CO H 35g CH CO H
1 mol CH CO H
=

}
3 2 2 5 3 2 2 5
{CH CO C H =0.552 mol 0.19 mol =0.36 CH CO C H n

3 2 2 5
3 2 2 5 3 2 2 5 3 2 2 5
3 2 2 5
88.10g CH CO C H
mass CH CO C H =0.36mol CH CO C H 32g CH CO C H
1 mol CH CO C H
=

}
2 2
{H O =3.95 mol 0.19 mol =3.76 mol H O n


2
2 2 2
2
18.02g H O
mass H O =3.76mol H O 68g H O
1 mol H O
=

{ } { }
{ } { }
3 2 2 5 2
c
2 5 3 2
CH CO C H H O
0.36 mol 3.76 mol
To check = = =4.1
C H OH CH CO H 0.56 mol 0.59 mol
n n
K
n n

40. (M) The final volume of the mixture is 0.750 +2.25 =3.00 L L L . Then use the balanced
chemical equation to organize the data we have concerning the reaction. The reaction
should shift to the right, that is, form products in reaching a new equilibrium, since the
volume is greater.

( ) ( )
2 4 2
Equation: N O g 2 NO g
0.971 mol 0.0580 mol
Initial:
3.00 L 3.00 L
Initial: 0.324M 0.0193M
Changes: M 2 M
Equil : (0.324 )M (0.0193 2 )M
x x
x x
+
+

Chapter15: Principles of Chemical Equilibrium
692
| | ( )
2 2
2
2 3
c
2 4
NO 0.0193+2
0.000372+0.0772 +4
= = = =4.61 10
N O 0.324 0.324
x
x x
K
x x

(
(





0.000372+0.0772 +4 =0.00149 0.00461 4 +0.0818 0.00112=0
2 2
x x x x x

2
4 0.0818 0.00669+0.0179
= = =0.00938 M, 0.0298 M
2 8
b b ac
x
a



| | ( )
2
2 2
NO =0.0193+ 2 0.00938 =0.0381 M
amount NO =0.0381 M 3.00 L =0.114 mol NO

| |
2 4
2 4 2 4
N O =0.324 0.00938=0.3146 M
amount N O =0.3146 M 3.00 L =0.944 mol N O

41. (M) | |
2
init
0.186 mol
HCONH = =0.0861 M
2.16 L


( ) ( ) ( )
2 3
Equation: HCONH g NH g + CO g
Initial : 0.0861 M 0 M 0 M
Changes: M + M + M
Equil : (0.0861- )M M M
x x x
x x x

| || |
3 2 2
c
2
NH CO
= = =4.84 =0.417 4.84 0= +4.84 0.417
HCONH 0.0861
x x
K x x x x
x
(
(

2
4 4.84 23.4+1.67
= = =0.084 M, 4.92 M
2 2
b b ac
x
a



The negative concentration obviously is physically meaningless. We determine the total
concentration of all species, and then the total pressure with x =0.084.

| | | | | | | |
3 2
total = NH +CO +HCONH = + +0.0861 =0.0861+0.084=0.170 M x x x

1 1 1
tot
=0.170 mol L 0.08206 L atm mol K 400. K =5.58 atm P



42. (E) Compare
p
Q to
p
K . We assume that the added solids are of negligible volume so that the
initial partial pressures of CO
2
(g) and H
2
O(g) do not significantly change.
}
2 2
1 atm
{H O = 715 mmHg =0.941 atm H O
760 mmHg
P
| |

|
\ .

{ } { }
p 2 2
= CO H O =2.10 Q P P atm CO
2
0.941 atm
2
H O=1.98 0.23=
p
K >
Because Q
p
is larger than K
p
, the reaction will proceed left toward reactants to reach
equilibrium. Thus, the partial pressures of the two gases will decrease.

Chapter15: Principles of Chemical Equilibrium
693
43. (M)
We organize the solution around the balanced chemical equation.
( ) ( ) ( )
3+ 2+ 2
Equation: 2 Cr aq + Cd(s) 2 Cr aq Cd aq
Initial : 1.00 M 0 M 0 M
Changes: 2 M 2
Equil: (1.00 2 )M 2
x x x
x x x
+
+
+ +

( )
2
2+ 2+
2
,
c 2 2
3
Cr Cd
(2 ) ( )
= = =0.288 =0.257M
1.00 2
Cr
Via successiveapproximations one obtains
x x
K x
x
+
( (

(


Therefore, at equilibrium, [Cd
2+
] =0.257 M, [Cr
2+
] =0.514 M and [Cr
3+
] =0.486 M

Minimum mass of Cd(s) =0.350L 0.257 M 112.41 g/mol =10.1 g of Cd metal

44. (M) Again we base the set-up of the problem around the balanced chemical equation.
( ) ( ) ( ) ( )
3+ 2+ 2+
10
c
=3.2 10
Equation: Pb s +2 Cr aq Pb aq + 2 Cr aq
Initial: 0.100M 0M 0M
Changes: 2 M M 2 M
Equil : (0.100 2 )M M 2 M
K
x x x
x x x

+ +

2
10
2
(2 )
= =3.2 10
(0.100)
c
x x
K


3 2 10 12
4 (0.100) 3.2 10 3.2 10 x

= =
12
3
5
3.2 10
9.3 10 M
4
x

= = Assumption that 2 0.100 x << , is valid and thus

Pb M
2+ 5
= =9.3 10 x

, [Cr
2+
] =1.9 10
-4
M and [Cr
3+
] =0.100 M

45. (M) We are told in this question that the reaction SO
2
(g) +Cl
2
(g)

SO
2
Cl
2
(g) has
K
c
=4.0 at a certain temperature T. This means that at the temperature T, [SO
2
Cl
2
] =4.0
[Cl
2
] [SO
2
]. Careful scrutiny of the three diagrams reveals that sketch (b) is the best
representation because it contains numbers of SO
2
Cl
2,
SO
2
, and Cl
2
molecules that are
consistent with the K
c
for the reaction. In other words, sketch (b) is the best choice because it
contains 12 SO
2
Cl
2
molecules (per unit volume), 1 Cl
2
molecule (per unit volume) and 3 SO
2

molecules (per unit volume), which is the requisite number of each type of molecule needed
to generate the expected K
c
value for the reaction at temperature T.

46. (M) In this question we are told that the reaction 2 NO(g) +Br
2
(g)

2 NOBr(g) has
K
c
=3.0 at a certain temperature T. This means that at the temperature T, [NOBr]
2
=3.0
[Br
2
][NO]
2.
Sketch (c) is the most accurate representation because it contains 18 NOBr
molecules (per unit volume), 6 NO molecules (per unit volume), and 3 Br
2
molecules (per
unit volume), which is the requisite number of each type of molecule needed to generate the
expected K
c
value for the reaction at temperature T.

Chapter15: Principles of Chemical Equilibrium
694
47. (E)

| |
| |
( )
5
aconitate
K
citrate
4.0 10
Q 0.031
0.00128

= =

Since Q =K, the reaction is at equilibrium,

48. (E)
| || || |
| || |
( )( )( )
( )( )
2 red
ox
CO NAD oxoglut.
K
citrate NAD
0.00868 0.00132 0.00868
Q 0.00895
0.00128 0.00868
=
= =

Since Q <K, the reaction needs to proceed to the right (products).


Partial Pressure Equilibrium Constant, K
p


49. (M) The
I s
2
b g maintains the presence of I
2
in the flask until it has all vaporized. Thus, if
enough HI(g) is produced to completely consume the I s
2
b g , equilibrium will not be achieved.
2
1 atm
{H S}=747.6 mmHg =0.9837 atm
760 mmHg
P
Equation: ( ) ( ) ( ) ( )
2 2
H S g + I s 2 HI g + S s

Initial: 0.9837 atm 0 atm
Changes: x atm +2x atm
Equil: 0.9837 x b g atm 2x atm

( )
( )
2
2 2
5
2
2
{HI} 4
= = =1.34 10 =
{H S} 0.9837 0.9837
p
x
P x
K
P x

5
3
1.34 10 0.9837
= =1.82 10 atm
4
x

The assumption that 0.9837>> x is valid. Now we verify that sufficient I
2
(s) is present by
computing the mass of I
2
needed to produce the predicted pressure of HI(g). Initially, 1.85 g
I
2
is present (given).

3
2 2
2 2
1 1
2
1.82 10 atm 0.725 L 1 mol I 253.8 g I
mass I = =0.00613 g I
0.08206 L atm mol K 333 K 2 mol HI 1 mol I

( )
tot 2
tot
= {H S}+ {HI}= 0.9837 +2 =0.9837+ =0.9837+0.00182=0.9855 atm
=749.0mmHg
P P P x x x
P

Chapter15: Principles of Chemical Equilibrium
695

50. (M) We first determine the initial pressure of NH
3
.
( )
1 1
3
3
0.100 mol NH 0.08206 L atm mol K 298 K
{NH g }= = =0.948 atm
2.58 L
nRT
P
V



Equation: NH
4
HS(s)

NH
3
(g) + H
2
S(g)
Initial: 0.948 atm 0 atm
Changes: +x atm +x atm
Equil: ( ) 0.948+ atm x x atm

K P P x x x x x x
p 3 2
= {NH } {H S}=0.108= 0.948+ b g =0.948 + 0= +0.948 0.108
2 2

2
4 0.948 0.899+0.432
= = = 0.103 atm, 1.05 atm
2 2
b b ac
x
a



The negative root makes no physical sense. The total gas pressure is obtained as follows.
P P P x x x
tot
NH H S} atm = + = 0.948+ + =0.948+2 =0.948+2 0.103=1.154
3 2
{ } { b g

51. (M) We substitute the given equilibrium pressure into the equilibrium constant expression
and solve for the other equilibrium pressure.
( )
3 3
2 2
p 2 2
2
2
{O } {O }
= =28.5=
{CO }
0.0721 atm CO
P P
K
P

3 2
3 3
2 2 2
{O } {O } 28.5(0.0712atm) 0.529atm O P P = = =

total 2 2 2 2
= {CO }+ {O }=0.0721 atm CO +0.529 atm O =0.601 atm total P P P

52. (M) The composition of dry air is given in volume percent. Division of these percentages by
100 gives the volume fraction, which equals the mole fraction and also the partial pressure in
atmospheres, if the total pressure is 1.00 atm. Thus, we have
2
{O }=0.20946 P atm and
2
{CO }=0.00036 P atm. We substitute these two values into the expression for
p
Q .

( )
( )
3
3
2 4 2
p 2 2
2
2
0.20946 atm O {O }
= = =6.4 10 28.5=
{CO }
0.00036 atm CO
p
P
Q K
P
>

The value of
p
Q is much larger than the value of
p
K . Thus this reaction should be
spontaneous in the reverse direction until equilibrium is achieved. It will only be
spontaneous in the forward direction when the pressure of
2
O drops or that of
2
CO rises
(as would be the case in self-contained breathing devices).

Chapter15: Principles of Chemical Equilibrium
696
53. (M)
(a) We first determine the initial pressure of each gas.

P P
nRT
V
{ { } CO} Cl
mol L atm mol K K
L
atm = = =
1.00 0.08206 668
1.75
=31.3
2
1 1



Then we calculate equilibrium partial pressures, organizing our calculation around
the balanced chemical equation. We see that the equilibrium constant is not very large,
meaning that we must solve the polynomial exactly (or by successive approximations).
Equation CO(g) ( ) ( )
2 2
+ Cl g COCl g

K
p
=22.5
Initial: 31.3 atm 31.3 atm 0 atm
Changes:
x
atm
x
atm
+x
atm
Equil: 31.3 x
atm
31.3 x
atm
x
atm

2
p
2 2
2
2 2
2
{COCl }
22.5
{CO} {Cl } (31.3 ) (979.7 62.6 )
22.5(979.7 62.6 ) 22043 1408.5 22.5
22043 1409.5 22.5 0 (Solve by using the quadratic equation)
P x x
K
P P x x x
x x x x x x
x x
= = = =
+
+ = = + =
+ =


2 2
( 1409.5) ( 1409.5) 4(22.5)(22043) 4
= =
2 2(22.5)
1409.5 2818
= 30.14, 32.5(too large)
45
b b ac
x
a
x

=


2 2
{CO}= {Cl } =31.3 atm 30.14 atm =1.16atm {COCl }= 30.14 atm P P P

(b)
total 2 2
= {CO}+ {Cl }+ {COCl }=1.16 atm+1.16 atm+30.14 atm=32.46 atm P P P P

54. (M) We first find the value of K
p
for the reaction.

( ) ( ) ( )
6
2 2 c
2 NO g 2 NO g + O g , =1.8 10 at 184 C =457 K K

.

For this reactionA n
gas
=2+1 2=+1.

g
n
(RT)
p c
K K
A
= =1.8 10
-6
(0.08206 457)
1 +
=6.8 10
-5

To obtain the required reaction ( ) ( ) ( )
1
2 2 2
NO g + O g NO g

from the initial reaction,

that initial reaction must be reversed and then divided by two. Thus, in order to determine
the value of the equilibrium constant for the final reaction, the value of K
p
for the initial
reaction must be inverted, and the square root taken of the result.

2
p, final 5
1
1.2 10
6.8 10
K

= =

Chapter15: Principles of Chemical Equilibrium
697
Le Chtelier's Principle

55. (E) Continuous removal of the product, of course, has the effect of decreasing the
concentration of the products below their equilibrium values. Thus, the equilibrium system
is disturbed by removing the products and the system will attempt (in vain, as it turns out)
to re-establish the equilibrium by shifting toward the right, that is, to generate more
products.

56. (E) We notice that the density of the solid ice is smaller than is that of liquid water. This
means that the same mass of liquid water is present in a smaller volume than an equal mass
of ice. Thus, if pressure is placed on ice, attempting to force it into a smaller volume, the
ice will be transformed into the less-space-occupying water at 0 C

. Thus, at 0 C

under
pressure, H
2
O(s) will melt to form H
2
O(l). This behavior is not expected in most cases
because generally a solid is more dense than its liquid phase.

57. (M)
(a) This reaction is exothermic with A H
o
= 150. kJ . Thus, high temperatures favor the
reverse reaction (endothermic reaction). The amount of ( )
2
H g present at high
temperatures will be less than that present at low temperatures.

(b) H O g
2
b g is one of the reactants involved. Introducing more will cause the equilibrium
position to shift to the right, favoring products. The amount of ( )
2
H g will increase.

(c) Doubling the volume of the container will favor the side of the reaction with the
largest sum of gaseous stoichiometric coefficients. The sum of the stoichiometric
coefficients of gaseous species is the same (4) on both sides of this reaction.
Therefore, increasing the volume of the container will have no effect on the amount
of ( )
2
H g present at equilibrium.

(d) A catalyst merely speeds up the rate at which a reaction reaches the equilibrium position.
The addition of a catalyst has no effect on the amount of ( )
2
H g present at equilibrium.

58. (M)
(a) This reaction is endothermic, with AH
o
=+92.5 kJ . Thus, a higher temperature will
favor the forward reaction and increase the amount of HI(g) present at equilibrium.

(b) The introduction of more product will favor the reverse reaction and decrease the
amount of HI(g) present at equilibrium.

(c) The sum of the stoichiometric coefficients of gaseous products is larger than that for
gaseous reactants. Increasing the volume of the container will favor the forward
reaction and increase the amount of HI(g) present at equilibrium.

(d) A catalyst merely speeds up the rate at which a reaction reaches the equilibrium position.
The addition of a catalyst has no effect on the amount of HI(g) present at equilibrium.

Chapter15: Principles of Chemical Equilibrium
698
(e) The addition of an inert gas to the constant-volume reaction mixture will not change any
partial pressures. It will have no effect on the amount of HI(g) present at equilibrium.

59. (M)
(a) The formation of NO(g) from its elements is an endothermic reaction (AH
o
=+181
kJ /mol). Since the equilibrium position of endothermic reactions is shifted toward
products at higher temperatures, we expect more NO(g) to be formed from the
elements at higher temperatures.

(b) Reaction rates always are enhanced by higher temperatures, since a larger fraction of the
collisions will have an energy that surmounts the activation energy. This enhancement of
rates affects both the forward and the reverse reactions. Thus, the position of equilibrium is
reached more rapidly at higher temperatures than at lower temperatures.

60. (M) If the reaction is endothermic (AH >0), the forward reaction is favored at high
temperatures. If the reaction is exothermic (AH <0), the forward reaction is favored at
low temperatures.

(a) ( ) ( ) ( )
o o o o
f 5 f 3 f 2
= PCl g PCl g Cl g H H H H A A A A ( ( (


( )
o
(favored at low temperatures) = 374.9 kJ 287.0 kJ 0.00 kJ = 87.9 kJ /mol H A

(b) A A + A A H H H H H
o
f
o
2 f
o
f
o
2 f
o
2
H O(g ) (g) H S(g) =2 3 2 [ )] [S(rhombic ] [SO ] [ ] A
( ) ( ) ( ) ( )
o
o
=2 241.8 kJ +3 0.00 kJ 296.8 kJ 2 20.63 kJ
= 145.5 kJ /mol (favored at low temperatures)
H
H
A
A


(c) ( ) ( )
o o o
f f 2
=4 NOCl g +2 H O g H H H A A A ( (


( ) ( ) ( )
o o o
f 2 f 2 f
2 N g 3 O g 4 HCl g H H H A A A ( ( (




( ) ( ) ( ) ( ) ( )
o
o
(favored at higher temperatures)
4 51.71 kJ +2 241.8 kJ 2 0.00 kJ 3 0.00 kJ 4 92.31 kJ
+92.5 kJ/mol
=
=
H
H
A
A


61. (E) If the total pressure of a mixture of gases at equilibrium is doubled by compression, the
equilibrium will shift to the side with fewer moles of gas to counteract the increase in
pressure. Thus, if the pressure of an equilibrium mixture of N
2
(g), H
2
(g), and NH
3
(g) is
doubled, the reaction involving these three gases, i.e., N
2
(g) +3 H
2
(g)

2 NH
3
(g), will
proceed in the forward direction to produce a new equilibrium mixture that contains
additional ammonia and less molecular nitrogen and molecular hydrogen. In other words,
P{N
2
(g)} will have decreased when equilibrium is re-established. It is important to note,
however, that the final equilibrium partial pressure for the N
2
will, nevertheless, be higher
than its original partial pressure prior to the doubling of the total pressure.

Chapter15: Principles of Chemical Equilibrium
699
62. (M)
(a) Because AH
o
=0, the position of the equilibrium for this reaction will not be
affected by temperature. Since the equilibrium position is expressed by the value of
the equilibrium constant, we expect K
p
to be unaffected by, or to remain constant
with, temperature.

(b) From part (a), we know that the value of K
p
will not change when the temperature is
changed. The pressures of the gases, however, will change with temperature. (Recall
the ideal gas law: P nRT V = / .) In fact, all pressures will increase. The
stoichiometric coefficients in the reaction are such that at higher pressures the
formation of more reactant will be favored (the reactant side has fewer moles of gas).
Thus, the amount of D(g) will be smaller when equilibrium is reestablished at the
higher temperature for the cited reaction.

( ) ( ) ( ) ( )
1
A s B s +2 C g + D g
2

63. (M) Increasing the volume of an equilibrium mixture causes that mixture to shift toward
the side (reactants or products) where the sum of the stoichiometric coefficients of the
gaseous species is the larger. That is: shifts to the right if A > n
gas
0, shifts to the left
if An
gas
< 0, and does not shift if An
gas
=0.

(a) ( ) ( ) ( ) ( )
2 2 gas
C s + H O g CO g + H g , 0, shift right, toward products n A >

(b) ( ) ( ) ( ) ( ) ( )
2 3 2 gas
2
Ca OH s +CO g CaCO s +H O g , =0, n A

no shift, no change in
equilibrium position.

(c)
( ) ( ) ( ) ( )
3 2 2 gas
4 NH g +5 O g 4 NO g +6 H O g , 0, shifts right, towards products n A >

64. (M) The equilibrium position for a reaction that is exothermic shifts to the left (reactants
are favored) when the temperature is raised. For one that is endothermic, it shifts right
(products are favored) when the temperature is raised.
(a) ( ) ( ) ( )
1 1
2 2 2 2
NO g N g + O g = 90.2 kJ shifts left, % dissociation
o
H A +

(b) ( ) ( ) ( )
1
3 2 2 2
SO g SO g + O g =+98.9 kJ shifts right, %dissociation
o
H A |

(c) ( ) ( ) ( )
2 4 2 2
N H g N g +2 H g = 95.4 kJ shifts left, %dissociation
o
H A +

(d) ( ) ( ) ( )
2 2
COCl g CO g + Cl g =+108.3 kJ shifts right, %dissociation
o
H A |

65. (E)
(a) Hb:O
2
is reduced, because the reaction is exothermic and heat is like a product.
(b) No effect, because the equilibrium involves O
2
(aq). Eventually it will reduce the Hb:O
2

level because removing O
2
(g) from the atmosphere also reduces O
2
(aq) in the blood.
(c) Hb:O
2
level increases to use up the extra Hb.

Chapter15: Principles of Chemical Equilibrium
700
66. (E)
(a) CO
2
(g) increases as the equilibrium is pushed toward the reactant side
(b) Increase CO
2
(aq) levels, which then pushes the equilibrium to the product side
(c) It has no effect, but it helps establish the final equilibrium more quickly
(d) CO
2
increases, as the equilibrium shifts to the reactants

67. (E) The pressure on N
2
O
4
will initially increase as the crystal melts and then vaporizes, but
over time the new concentration decreases as the equilibrium is shifted toward NO
2
.

68. (E) If the equilibrium is shifted to the product side by increasing temperature, that means that
heat is a reactant (or being consumed). Therefore, HI decomposition is endothermic.

69. (E) Since H is >0, the reaction is endothermic. If we increase the temperature of the
reaction, we are adding heat to the reaction, which shifts the reaction toward the
decomposition of calcium carbonate. While the amount of calcium carbonate will decrease,
its concentration will remain the same because it is a solid.

70. (E) The amount of N
2
increases in the body. As the pressure on the body increases, the
equilibrium shifts from N
2
gas to N
2
(aq).


Integrative and Advanced Exercises

71. (E) In a reaction of the type I
2
(g)

2 I(g) the bond between two iodine atoms, the II
bond, must be broken. Since I
2
(g) is a stable molecule, this bond breaking process must be
endothermic. Hence, the reaction cited is an endothermic reaction. The equilibrium position
of endothermic reactions will be shifted toward products when the temperature is raised.

72. (M)
(a) In order to determine a value of K
c
, we first must find the CO
2
concentration in the gas phase.
Note, the total volume for the gas is 1.00 L (moles and molarity are numerically equal)

2
2
2 c
2
[CO (aq)] 1.00 atm 3.29 10 M
[CO ] 0.0409 M 0.804
L atm
[CO (g)] 0.0409 M
0.08206 298 K
mol K
n P
K
V RT

= = = = = = =

(b) It does not matter to which phase the radioactive
14
CO
2
is added. This is an example of
a Le Chteliers principle problem in which the stress is a change in concentration of the
reactant CO
2
(g). To find the new equilibrium concentrations, we must solve and I.C.E.
table. Since Q
c
<K
c
, the reaction shifts to the product, CO
2
(aq) side.

2 2
-3
Reaction: CO (g) CO (aq)
Initial: 0.0409 mol 3.29 10 mol
Stress +0.01000 mol
Changes: mol x

-3
mol
Equilibrium: (0.05090 ) mol 3.29 10 mol
x
x x +

Chapter15: Principles of Chemical Equilibrium
701
-3
-2
4 2
C 2
2
3.29 10 mol
[CO (aq)] 3.29 10 10
0.1000 L
0.804 7.43 10 mol CO
(0.05090 ) mol
[CO (g)] 0.05090
1.000 L
x
x
K x
x
x

+
+
= = = = =

Total moles of CO
2
in the aqueous phase (0.1000 L)(3.2910
-2
+7.4310
-3
) =4.03 10
-3
moles

Total moles of CO
2
in the gaseous phase (1.000 L)(5.09010
-2
7.4310
-4
) =5.0210
-2
moles
Total moles of CO
2
=5.0210
-2
moles +4.03 10
-3
moles =5.4210
-2
moles
There is continuous mixing of the
12
C and
14
C such that the isotopic ratios in the two phases is
the same. This ratio is given by the mole fraction of the two isotopes.
For
2
14
CO in either phase its mole fraction is
-2
0.01000 mol
100 18.45 %
5.419 10 mol
=

Moles of
2
14
CO in the gaseous phase =5.0210
-2
moles0.1845 =0.00926 moles
Moles of
2
14
CO in the aqueous phase =4.03 10
-3
moles0.1845 =0.000744 moles

73. (M) Dilution makes Q
c
larger than K
c
. Thus, the reaction mixture will shift left in order to
regain equilibrium. We organize our calculation around the balanced chemical equation.

2 3
Equation: Ag (aq) Fe (aq) Fe (aq) Ag(s) 2.98
Equil: 0.31 M 0.21 M 0.19 M
Dilution: 0.12 M 0.084 M
c
K
+ + +
+ + =

3
c 2
0.076 M
Changes: M M M
New equil: (0.12 ) M (0.084 ) M (0.076 ) M
[Fe ] 0.076
2.98 2.9
[Ag ][Fe ] (0.12 ) (0.084 )
x x x
x x x
x
K
x x
+
+ +

+ +
+ +

= = =
+ +
2 2
8 (0.12 ) (0.084 ) 0.076
0.076 0.030 0.61 2.98 2.98 1.61 0.046 0
x x x
x x x x x
+ + =
= + + + =


57 . 0 , 027 . 0
96 . 5
0.55 59 . 2 61 . 1
=
+
= x Note that the negative root makes no physical
sense; it gives M 49 . 0 57 . 0 084 . 0 ] Fe [
2
= =
+
.
Thus, the new equilibrium concentrations are

2
3
[Fe ] 0.084 0.027 0.111 M [Ag ] 0.12 0.027 0.15 M
[Fe ] 0.076- 0.027 0.049 M We can check our answer by substitution.
+ +
+
= + = = + =
= =


0.049 M
c = =2.94 2.98 (within precision limits)
0.111 M 0.15 M
K ~

74. (M) The percent dissociation should increase as the pressure is lowered, according to Le
Chteliers principle. Thus the total pressure in this instance should be more than in
Example 15-12, where the percent dissociation is 12.5%. The total pressure in Example
15-12 was computed starting from the total number of moles at equilibrium.
The total amount =(0.0240 0.00300) moles N
2
O
4
+ 2 0.00300 mol NO
2
=0.027 mol gas.

Chapter15: Principles of Chemical Equilibrium
702

-1 -1
total
0.0270mol 0.08206L atmK mol 298 K nRT
P = = =1.77atm (Example 15-12)
V 0.372 L


We base our solution on the balanced chemical equation. We designate the initial pressure
of N
2
O
4
as P. The change in P{N
2
O
4
}is given as 0.10 P atm. to represent the 10.0 %
dissociation.

2 4 2
Equation: N O (g) 2 NO (g)
Initial: P atm 0 atm
Changes: 0.10P atm +2(0.10P atm)
Equil: 0.90 P atm

0.20P atm



2 2
2
p
2 4
P{NO } (0.20P) 0.040P 0.113 0.90
K = = = =0.113 P= =2.54atm.
P{N O } 0.90P 0.90 0.040

Thus, the total pressure at equilibrium is 0.90 P +0.20 P and 1.10 P (where P =2.54 atm)
Therefore, total pressure at equilibrium =2.79 atm.

75. (M)
3 2 2
Equation: 2 SO (g) 2 SO (g) O (g) +

Initial: 1.00 atm 0atm 0 atm
Changes: 2 atm 2 atm atm
Equil: (1.00 2 )atm 2 atm atm
x x x
x x x
+ +

Because of the small value of the equilibrium constant, the reaction does not proceed very
far toward products in reaching equilibrium. Hence, we assume that x <<1.00 atm and
calculate an approximate value of x (small K problem).


2 2 3
5 2 2
2 2 2
3
{SO } {O } (2 ) 4
1.6 10 0.016 atm
{SO } (1.00 2 ) (1.00)
P
P P x x x
K x
P x

= = = ~ =

A second cycle may get closer to the true value of x.
atm 016 . 0
) 032 . 0 00 . 1 (
4
10 6 . 1
2
3
5
= =

~

x
x

Our initial value was sufficiently close. We now compute the total pressure at equilibrium.
atm 02 . 1 016 . 0 00 . 1 00 . 1 2 ) 2 00 . 1 ( } {O } SO { } SO {
2 2 3 total
= + = + = + + = + + = x x x x P P P P

76. (M) Let us start with one mole of air, and let 2x be the amount in moles of NO formed.

2 2
Equation: N (g) O (g) 2 NO(g)
Initial: 0.79 mol 0.21 mol 0 mol
Changes: mol mol 2 mol
Equil:
x x x
+
+

(0.79 )mol (0.21 )mol 2 mol x x x

Chapter15: Principles of Chemical Equilibrium
703
NO
2 2
2 2
{NO} 2 2
0.018
{N } {O } {NO} (0.79 ) (0.21 ) 2 1.00
0.0090 mol 0.79 0.78 mol N 0.21 0.20 mol O
2 0.018 mol NO
n x x
n n n x x x
x x x
x
_ = = = =
+ + + +
= = =
=

2
2 2 2
total 3
p
2 2
2 2 2 2
total total
{NO}
{NO} {NO} (0.018)
2.1 10
{N ) {O }
(N } {O } {N } {O } 0.78 0.20
n RT
V
P n
K
n RT n RT
P P n n
V V

| |
|
\ .
= = = = =

77. (D) We organize the data around the balanced chemical equation. Note that the reaction is
stoichimoetrically balanced.

(a)
2 2 3
Equation: 2 SO (g) O (g) 2 SO (g) +

M ) 2 (0.200 M M 2 : Equil
M 2 M M 2 : Changes
M 0.200 M 0.000 M 0.000 : right To
M 0.168 M 0.016 M 0.032 : Initial
x x x
x x x

+ +


In setting up this problem, we note that solving this question exactly involves finding
the roots for a cubic equation. Thus, we assumed that all of the reactants have been
converted to products. This gives the results in the line labeled To right. We then
reach equilibrium from this position by converting some of the product back into
reactants. Now, we substitute these expressions into the equilibrium constant
expression, and we solve this expression approximately by assuming that 0.200 2 << x .

033 . 0 or
4
) 200 . 0 (
10 8 . 2
) 2 (
) 2 200 . 0 (
] O [ ] SO [
] SO [
3
2
2
2
2
2
2
2
2
3
c
= ~ =

= = x
x x x
x
K

We then substitute this approximate value into the expression for K
c
.

025 . 0 10 8 . 2
4
) 066 . 0 200 . 0 (
2
3
2
c
= =

= x or
x
K

Let us try one more cycle. 027 . 0 or 10 8 . 2
4
) 050 . 0 200 . 0 (
2
3
2
c
= =

= x
x
K


L 10.0
mol 68 . 1

L 10.0
mol 0.16

L 10.0
mol 0.32
: Initial
mol 1.68 mol 0.16 mol 0.32 SO Add
mol 0.68 mol 0.16 mol 0.32 : Equil
3
Chapter15: Principles of Chemical Equilibrium
704
This gives the following concentrations and amounts of each species.

2 2 2
2 2 2
3 3 3
O mol 0.27 M 0.027 L 10.0 O amount M 0.027 ] [O
SO mol 0.54 M 0.054 L 10.0 SO amount M 0.054 0.027 2 ] [SO
SO mol 1.46 M 0.146 L 10.0 SO amount M 0.146 0.027) (2 0.200 ] [SO
= = =
= = = =
= = = =


(b)
2 2 3
Equation: 2 SO (g) O (g) 2 SO (g) +

M ) 2 (1.00 M M 2 : Equil
M 2 M M 2 : Changes
M 1.00 M 0.00 M 0.00 : right To
M 0.68 M 0.16 M 32 . 0 : 0.10
M 0.068 M 0.016 M 0.032 : Equil
L 10.0
mol 68 . 0

L 10.0
mol 16 . 0

L 10.0
mol 0.32
: Equil
mol 0.68 mol 0.16 mol 0.32 : Equil
x x x
x x x
V

+ +


Again, notice that an exact solution involves finding the roots of a cubic. So we have
taken the reaction 100% in the forward direction and then sent it back in the reverse
direction to a small extent to reach equilibrium. We now solve the K
c
expression for x,
obtaining first an approximate value by assuming 2x <<1.00.

096 . 0
4
) 00 . 1 (
10 8 . 2
) 2 (
) 2 00 . 1 (
] O [ ] SO [
] SO [
3
2
2
2
2
2
2
2
2
3
c
= ~ =

= = x or
x x x
x
K

We then use this approximate value of x to find a second approximation for x.

084 . 0 or 10 8 . 2
4
) 19 . 0 00 . 1 (
2
3
2
c
= =

= x
x
K

Another cycle gives 085 . 0 or 10 8 . 2
4
) 17 . 0 00 . 1 (
2
3
2
c
= =

= x
x
K
Then we compute the equilibrium concentrations and amounts.

3 3 3
2 2 2
2 2 2
[SO ] 1.00 (2 0.085) 0.83 M amount SO 1.00 L 0.83 M 0.83 mol SO
[SO ] 2 0.085 0.17 M amount SO 1.00 L 0.17 M 0.17 mol SO
[O ] 0.085 M amount O 1.00 L 0.085 M 0.085 mol O
= = = =
= = = =
= = =


78. (M)
( )
2
6 4 6 5 2
-3
co 2
Equation: HOC H COOH(g) C H OH(g) CO (g)
730mmHg 48.2 48.5 1 L
PV 760mmHg/atm 2 1000 mL
n 1.93 10 mol CO
RT 0.0821L atm/mol K 293K
+
| + | | | | |

| | |
\ .
| | = = =

| |
| |
\ .\ .

Chapter15: Principles of Chemical Equilibrium
705
2
-3
salicylic acid
Note that moles of CO moles phenol
0.300
2.17 10 mol salicylic acid
138 /
g
n
g mol
=
= =

2
6 5 2
c
6 4
1.93 mmol
[C H OH ] [CO (g)] 50.0 mL
K 0.310
(2.17 1.93) mmol
[HOC H COOH]
50.0 mL
| |
|
\ .
= = =

(2-1)
p c
L atm
K K (RT) (0.310) 0.08206 (473 K) 12.0
mol K
| |
= = =
|
\ .


79. (D)
(a) This reaction is exothermic and thus, conversion of synthesis gas to methane is favored at
lower temperatures. Since 2 ) 3 1 ( ) 1 1 (
gas
= + + = An , high pressure favors the products.

(b) The value of K
c
is a large number, meaning that almost all of the reactants are converted
to products (note that the reaction is stoichiometrically balanced). Thus, after we set up
the initial conditions we force the reaction to products and then allow the system to
reach equilibrium.


2 4 2
Equation: 3 H (g) CO(g) CH (g) H O(g)
3.00 mol 1.00 mol
Initial: 0M 0M
15.0 L 15.0 L
Initial: 0.200 M 0.0667 M 0 M 0M
To right: 0.000 M
+ +

0.000 M 0.0667 M 0.0667 M

Changes: 3 M M M M
Equil: 3 M M (0.0667 )M (0.0667 )M
x x x x
x x x x
+ +




2
4 2
c 3 3 2
2
2 2 2
2
[CH ][H O] (0.0667 ) 0.0667
190. 190.
[H ] [CO] (3 ) 27
190 27 0.0667 71.6 71.6 0.0667 0
4 1.00 1.00 19.1
0.0244 M
2 143
x x
K
x x x
x x x x x
b b ac
x
a

= = = =
= = + =
+
= = =

4 2
2
[CH ] [H O] 0.0667 0.0244 0.0423 M
[H ] 3 0.0244 0.0732 M
[CO] 0.0244 M
= = =
= =
=

We check our calculation by computing the value of the equilibrium constant.

187
0244 . 0 ) 0732 . 0 (
) 0423 . 0 (
CO] [ ] [H
O] H [ ] [CH
3
2
3
2
2 4
= = =
c
K


Chapter15: Principles of Chemical Equilibrium
706
Now we compute the amount in moles of each component present at equilibrium, and
finally the mole fraction of CH
4
.
4 2
amount CH amount H O 0.0423 M 15.0 L 0.635 mol = = =
2
amount H 0.0732 M 15.0 L 1.10 mol
amount CO 0.0244 M 15.0 L 0.366 mol
= =
= =



4
CH
0.635 mol
0.232
0.635 mol 0.635 mol 1.10 mol 0.366 mol
_ = =
+ + +


80. (M) We base our calculation on 1.00 mole of PCl
5
being present initially.

5 3 2
Equation: PCl (g) PCl (g) Cl (g)
Initial: 1.00 mol 0M 0M
Changes: mol mol mol
Equil: (1.00 ) mol mol mol
o o o
o o o
+
+ +

total
1.00 1.00 n o o o o = + + = +


5 3 2
Equation: PCl (g) PCl (g) Cl (g)
1.00
Mol fract.
1.00 1.00 1.00
o o o
o o o
+

+ + +

2
total 2 2
2 3 2 total 3 total total total
p 2
5 5 total
total
{Cl } {PCl } [ {Cl } ] [ {PCl } ] 1.00
1.00
{PCl } [ {PCl } ] (1.00 )(1.00 ) 1
P
1.00
P
P P P P P P
K
P P
o
_ _ o o o
o
_ o o o
o
| |
|
+
\ .
= = = = =

+
+


81. (M) We assume that the entire 5.00 g is N
2
O
4
and reach equilibrium from this starting point.
M 109 . 0
O N g 01 . 92
O N mol 1
L 0.500
g 00 . 5
] O N [
4 2
4 2
4 2
= =
i

Equation: N
2
O
4
(g)

2 NO
2
(g)
Initial: 0.109 0 M
Changes: x M +2x M
Equil: (0.0109 x) M 2x M

2 2
3 2 4 3 2
C
2 4
2
[NO ] (2 )
4.61 10 4 5.02 10 4.61 10
[N O ] 0.109
4 0.00461 0.000502 0
x
K x x
x
x x

= = = =

+ =


2 5 3
4 0.00461 2.13 10 8.03 10
0.0106M, 0.0118 M
2 8
b b ac
x
a

+
= = =
Chapter15: Principles of Chemical Equilibrium
707
2 4 2 4
2 2
2
(The method of successive approximationsyields 0.0106 after two iterations)
amount N O 0.500 L (0.109 0.0106) M 0.0492 mol N O
amount NO 0.500 L 2 0.0106 M 0.0106 mol NO
0.0106 mo
mol fraction NO
= =
= =
=
2
2 2 4
l NO
0.177
0.0106 mol NO 0.0492 mol N O
=
+


82. (M) We let P be the initial pressure in atmospheres of COCl
2
(g).
2 2
Equation: COCl (g) CO(g) Cl (g)
Initial: P 0M 0M
Changes:
Equil: P
x x x
x
+
+ +

Total pressure 3.00 atm P P P 3.00
x x
x x x x x = = + + = + =

2
2
p
2
2 2
2
P{COCl } P 3.00 3.00 2
P{CO}P{Cl }
K 0.0444
P(COCl } 3.00 2
0.133 0.0888 0.0888 0.133 0
4 0.0888 0.00789 0.532
0.323, 0.421
2 2
x x x x
x x
x
x x x x
b b ac
x
a
= = =

= = =

= + =
+
= = =


Since a negative pressure is physically meaningless, x =0.323 atm.
(The method of successive approximations yields x =0.323 after four iterations.)

2
2
{CO} {Cl } 0.323 atm
{COCl } 3.00 2 0.323 2.35 atm
P P
P
= =
= =

The mole fraction of each gas is its partial pressure divided by the total pressure. And the
contribution of each gas to the apparent molar mass of the mixture is the mole fraction of that
gas multiplied by the molar mass of that gas.


2 2
avg 2 2
tot tot tot
{Cl } {COCl } {CO}
{CO} {Cl } {COCl }
0.323 atm 0.323 atm 2.32 atm
28.01 g/mol 70.91g/mol 98.92g/mol
3.00 atm 3.00atm 3.00 atm
87.1 g/mol
P P P
M M M M
P P P
= + +
| |
| | | |
= + +
| | |
\ . \ .
\ .
=


Chapter15: Principles of Chemical Equilibrium
708
83. (M) Each mole fraction equals the partial pressure of the substance divided by the total
pressure. Thus
tot 3 3 tot 3 3
} NH { } NH { or / } NH { } NH { P P P P _ _ = =


2
tot
3
2 2
2
3
4
tot
2
tot
3
2 2
2
3
3
tot 2 tot 2
2
tot 3
3
2 2
2
3
p
) (
1
} {H } N {
} NH {

) (
) (
} {H } N {
} NH {
) } {H ( ) } N { (
) } NH { (
} H { } N {
} NH {
P
P
P
P P
P
P P
P
K
_ _
_
_ _
_
_ _
_
=
= = =


This is the expression we were asked to derive.

84. (D) Since the mole ratio of N
2
to H
2
is 1:3, } {N 3 } H {
2 2
_ _ = . Since P
tot
=1.00 atm, it follows.


56 . 1 0906 . 0 3
} {N
} {NH
} N {
} {NH
} {N } {N
} {NH
0906 . 0 3
0906 . 0 10 06 . 9
) 00 . 1 (
1
}) {N (3 } N {
} {NH
3
2
2
3
4
2
2
3
3
2 2
2
3 3
2
2 3
2 2
2
3
p
= = = =
= = =

_
_
_
_
_ _
_
_ _
_
K


We realize that } {N 3 } {N } {NH 00 . 1 } {H } {N } {NH
2 2 3 2 2 3
_ _ _ _ _ _ + + = = + +
This gives } {N 4 00 . 1 } {NH
2 3
_ _ = And we have


2
2
2
2
1.00 4 {N }
1.56 For ease of solving, we let {N }
{N }
x
_
_
_

= =

2 2
2
2
1.00 4
1.56 1.56 1.00 4 1.56 4 1.00 0
4 4.00 16.00 6.24
0.229, 2.794
2 3.12
x
x x x x
x
b b ac
x
a

= = + =
+
= = =


Thus 229 . 0 } {N
2
= _ Mole % NH
3
=(1.000 mol (4 0.229 mol)) 100% =8.4%

85. (M) Since the initial mole ratio is 2 H
2
S(g) to 1 CH
4
(g), the reactants remain in their
stoichiometric ratio when equilibrium is reached. Also, the products are formed in their
stoichiometric ratio.
3 3 4
4 2 4
2
3 4 2
2 4 2
4
4
2 2
1 mol CH
amount CH 9.54 10 mol H S 4.77 10 mol CH
2 mol H S
1 mol CS 1 mol S
amount CS 1.42 10 mol BaSO 7.10 10 mol CS
1 mol BaSO 2 mol S
4 mol
amount H 7.10 10 mol CS

= =
= =
=
3 2
2
2
3 3 4 3
2 4 2 2
3
H
2.84 10 mol H
1 mol CS
total amount 9.54 10 mol H S 4.77 10 mol CH 7.10 10 mol CS 2.84 10 mol H
17.86 10 mol

=
= + + +
=

The partial pressure of each gas equals its mole fraction times the total pressure.
Chapter15: Principles of Chemical Equilibrium
709

3
2
2 3
3
4
4 3
9.54 10 mol H S
{H S} 1.00 atm 0.534 atm
17.86 10 mol total
4.77 10 mol CH
{CH } 1.00 atm 0.267 atm
17.86 10 mol total
P
P

= =

= =

4
2
2 3
3
2
2 3
4 4
4 2 2
p 2 2
2 4
7.10 10 mol CS
{CS } 1.00 atm 0.0398 atm
17.86 10 mol total
2.84 10 mol H
{H } 1.00 atm 0.159 atm
17.86 10 mol total
{H } {CS } 0.159 0.0398
3.34 10
{H S} {CH } 0.534 0.267
P
P
P P
K
P P

= =

= =

= = =

86. (D)
81. We base our calculation on an I.C.E. table, after we first determine
the direction of the reaction by computing :

6
2
2 2
2
2
2 3
2 2 2 2
c
10 48 . 6
) 5000 . 0 ( ) 5000 . 0 (
) 03000 . 0 ( ) 03000 . 0 (
] Hg [ ] Fe [
] Hg [ ] [Fe

+ +
+ +
= = = Q

Because this value is smaller than K
c
, the reaction will shift to the right to reach equilibrium.
Since the value of the equilibrium constant for the forward reaction is quite small, let us
assume that the reaction initially shifts all the way to the left (line labeled to left:), and then
reacts back in the forward direction to reach a position of equilibrium.

3 2 2 2
2
Equation: 2 Fe (aq) Hg (aq) 2 Fe (aq) 2 Hg (aq)
Initial: 0.5000 M 0.5000 M 0.03000 M 0.03000 M
0.03000 M
+ + + +
+ +
+ +

0.0150 M 0.03000 M 0.03000 M

To left: 0.5300 M 0.5150 M 0 M 0 M
Changes: 2 M M x x


2 2 2 2 2 2 2 2
6
c 3 2 2 2
2
2 M 2 M
Equil: (0.5300 2 )M (0.5150 )M 2 M 2 M
[Fe ] [Hg ] (2 ) (2 ) 4 4
9.14 10
[Fe ] [Hg ] (0.5300 2 ) (0.5150 ) (0.530
x x
x x x x
x x x x
K
x x
+ +

+ +
+ +

= = = ~

2
0) 0.5150


Note that we have assumed that 5150 . 0 and 0.5300 2 < << x x

0170 . 0 10 26 . 8
4 4
(0.5150) (0.5300) 10 14 . 9
8
2 6
4
= =

x x
Our assumption, that 0.5300 0.0340) ( 2 << = x , is reasonably good.
3 2
2
2 2
[Fe ] 0.5300 2 0.0170 0.4960 M [Hg ] 0.5150 0.0170 0.4980
[Fe ] [Hg ] 2 0.0170 0.0340 M
+ +
+ +
= = = =
= = =


Chapter15: Principles of Chemical Equilibrium
710
c
2 2 2 2 2 2
6 6
c 3 2 2 2
2
We check by substituting into the K expression.
[Fe ] [Hg ] (0.0340) (0.0340)
9.14 10 K 11 10 Not a substantial difference.
[Fe ] [Hg ] (0.4960) 0.4980
+ +

+ +
= = = =


Mathematica (version 4.0, Wolfram Research, Champaign, IL) gives a root of 0.0163.

87. (D) Again we base our calculation on an I.C.E. table. In the course of solving the
Integrative Example, we found that we could obtain the desired equation by reversing
equation (2) and adding the result to equation (1)

2 4 2
2 2 2
4 2
(2) H O(g) CH (g) CO(g) 3 H (g) 1/190
(1) CO(g) H O(g) CO (g) H (g) 1.4
Equation:CH (g) 2 H O(g)
K
K
+ + =
+ + + =
+

2 2
CO (g) 4 H (g) 1.4/190 0.0074 K + = =

2 4 2
2 2 2
4 2
(2) H O(g) CH (g) CO(g) 3 H (g) 1/190
(1) CO(g) H O(g) CO (g) H (g) 1.4
Equation: CH (g) 2 H O(g)
K
K
+ + =
+ + + =
+

2 2
CO (g) 4 H (g) 1.4/190 0.0074
Initial: 0.100 mol 0.100 mol 0.100 mol 0.100 mol
0.025 mol 0.050 mol 0.025 mol 0.100 mol
T
K + = =
+ +

o left: 0.125 mol 0.150 mol 0.075 mol 0.000 mol

Concns: 0.0250 M 0.0300 M 0.015 M 0.000 M
Changes: M 2 mol x x mol 4 mol
Equil: (0.0250 ) M (0.0300 2 ) (0.015 ) M 4 mol
x x
x x x x
+ +
+


Notice that we have a fifth order polynomial to solve. Hence, we need to try to approximate
its final solution as closely as possible. The reaction favors the reactants because of the small
size of the equilibrium constant. Thus, we approach equilibrium from as far to the left as
possible.

M 014 . 0
256 0150 . 0
0.0074 (0.0300) 0.0250
(0.0300) 0250 . 0
) (4 0150 . 0
) 2 0300 . 0 ( ) 0250 . 0 (
) 4 )( 0150 . 0 (
O] H ][ CH [
] H ][ CO [
0074 . 0
4
2
2
4
2
4
2
2 4
4
2 2
c
=

~
~

+
= = =
x
x
x x
x x
K


Our assumption is terrible. We substitute to continue successive approximations.

4 4
2 2
(0.0150 0.014) (4 ) (0.029)(4 )
0.0074
(0.0250 0.014) (0.0300 2 0.014) (0.011)(0.002)
x x +
= =


Next, try x
2
=0.0026

4
2
(0.0150 0.0026)(4 )
0.074
(0.0250 0.0026) (0.0300 2 0.0026)
x +
=



Chapter15: Principles of Chemical Equilibrium
711
then, try x
3
=0.0123.

After 18 iterations, the x value converges to 0.0080.

Considering that the equilibrium constant is known to only two significant figures, this is a
pretty good result. Recall that the total volume is 5.00 L. We calculate amounts in moles.

4 4
2 2
2 2
2
CH (g) (0.0250 0.0080) 5.00 L 0.017 M 5.00 L 0.085 moles CH (g)
H O(g) (0.0300 2 0.0080) M 5.00 L 0.014 M 5.00 L 0.070 moles H O(g)
CO (g) (0.015 0.0080) M 5.00 L 0.023 M 5.00 L 0.12 mol CO
H (g) (4
= =
= =
+ = =

2
0.0080) M 5.00 L 0.032 M 5.00 L 0.16 mol H = =


88. (M) The initial mole fraction of C
2
H
2
is
i
0.88 _ = . We use molar amounts at equilibrium to
compute the equilibrium mole fraction of C
2
H
2
,
eq
_ . Because we have a 2.00-L container,
molar amounts are double the molar concentrations.


2 2
eq
2 2 4 2
(2 0.756) mol C H
0.877
(2 0.756) mol C H (2 0.038) mol CH (2 0.068) mol H
_

= =
+ +

Thus, there has been only a slight decrease in mole fraction.

89. (M)
(a) K
eq
=4.610
4

2 2
2 2
2
P{NOCl} (4.125)
=
P{NO} P{Cl } P{NO} (0.1125)

2
4
(4.125)
P{NO} = =0.0573atm
4.6 10 (0.1125)


(b) P
total
=P
NO
+P
Cl
2
+P
NOCl
=0.0573 atm +0.1125 atm +4.125 atm =4.295 atm

90. (M) We base our calculation on an I.C.E. table.

2 2 3
Reaction: N (g) + 3H (g) 2NH (g)
0.424mol 1.272mol 0mol
Initial:
10.0L 10.0L 10.0L
-3 mol +2 mol - mol
Change
10.0L 10.0L 10.0L
(1.272-3 )mol 2 mol (0.424- ) mol
Equilibrium
10.0L 10.0L 10.0L
x x x
x x x

Chapter15: Principles of Chemical Equilibrium
712
2
2
3
c 3 3
2 2
2 mol
10.0L [NH ]
K = =152=
[N ][H ]
(0.424- ) mol (1.272-3 )mol
10.0L 10.0L
x
x x
| |
|
\ .
| || |
| |
\ .\ .



( )
( ) ( ) ( )
( )
( )
( )
( )
2
c 3
2 2
c 4 4
3
100 2 mol
K =
(0.424- ) mol 3 0.424- ) mol
100 2 mol 2 mol
K = =152 =41.04 Take root of both sides
3 0.424- ) mol 0.424- ) mol
x
x x
x x
x x


( )
( )
2
2
2 2 2
3
2 mol
=6.41 6.41(0.424- ) = 2
0.424- ) mol
3.20(0.180 0.848 ) 3.20 2.71 0.576 3.20 3.71 0.576 0
Now solve using the quadratic equation: =0.1846 mol or 0.9756 mol (too large)
amount of NH 2
x
x x
x
x x x x x x x
x
+ = = + + =
=
2 2
2(0.1846mol) =0.369mol in 10.0 L or 0.0369 M
([H ] =0.0718 [ ] 0.0239 )
x
M and N M
=
=


91. (D)

2 3 c
2
n 3
p c
Equation: 2 H (g) CO(g) CH OH(g) K 14.5 at 483 K
L-atm
K K (RT) 14.5 0.08206 483K 9.23 10
mol-K

+ =
| |
= = =
|
\ .

2
CO
H
We know that mole percents equal pressure percents for ideal gases.
P 0.350 100 atm 35.0 atm
P 0.650 100 atm 65.0 atm
= =
= =

2 3
Equation: 2 H (g) CO(g) CH OH(g)
Initial: 65 atm 35 atm
Changes: 2P atm P atm P atm
Equi
+
+

3
2
2
3
CH OH
3
p
2
H
CO
CH OH
l: 65-2P 35-P P
P
P
K 9.23 10
(35.0 P)(65.0 2P) P P
By successive approximations, P 24.6 atm =P at equilibrium.

= = =

=


Mathematica (version 4.0, Wolfram Research, Champaign, IL) gives a root of 24.5.

Chapter15: Principles of Chemical Equilibrium
713

FEATURE PROBLEMS

92. (M) We first determine the amount in moles of acetic acid in the equilibrium mixture.
( )
( )
3 2 2
3 2
2
3 2
0.1000 mol Ba OH
2 mol CH CO H 1 L
amount CH CO H=28.85 mL
1000 mL 1 L 1 mol Ba OH
complete equilibrium mixture
=0.5770 mol CH CO H
0.01 of equilibrium mixture

| || |
| || |
3 2 2 5 2
c
2 5 3 2
0.423mol 0.423mol
CH CO C H H O
0.423 0.423
= 4.0
0.077mol 0.577mol
C H OH CH CO H 0.077 0.577
V V
K
V V

= = =

93. (D) In order to determine whether or not equilibrium has been established in each bulb, we
need to calculate the concentrations for all three species at the time of opening. The results
from these calculations are tabulated below and a typical calculation is given beneath this table.

Bulb
No.
Time
Bulb
Opened
(hours)
Initial
Amount
HI(g)
(in mmol)
Amount of I
2
(g)
and H
2
(g) at
Time of Opening
(in mmol)
Amount HI(g)
at Time of
Opening
(in mmol)
[HI]
(mM)
[I
2
] &
[H
2
]
(mM)
2
2 2
[HI]
] ][I [H

1 2 2.345 0.1572 2.03 5.08 0.393 0.00599
2 4 2.518 0.2093 2.10 5.25 0.523 0.00992
3 12 2.463 0.2423 1.98 4.95 0.606 0.0150
4 20 3.174 0.3113 2.55 6.38 0.778 0.0149
5 40 2.189 0.2151 1.76 4.40 0.538 0.0150

Consider, for instance, bulb #4 (opened after 20 hours).
Initial moles of HI(g) =0.406 g HI(g)
1 mole HI
127.9 g HI
=0.003174 mol HI(g) or 3.174 mmol
moles of I
2
(g) present in bulb when opened.
=0.04150 L Na
2
S
2
O
3

2 2 3
2 2 3
0.0150 mol Na S O
1 L Na S O

O S Na mol 2
I mol 1
3 2 2
2
=
-4
2
3.113 10 mol I

millimoles of I
2
(g) present in bulb when opened =
-4
2
3.113 10 mol I
moles of H
2
present in bulb when opened =moles of I
2
(g) present in bulb when opened.

HI reacted =3.113 10
-4
mol I
2

2
I mol 1
HI mole 2
=6.226 10
-4
mol HI (0.6226 mmol HI)
moles of HI(g) in bulb when opened=3.174 mmol HI 0.6226 mmol HI =2.55 mmol HI

Concentrations of HI, I
2
, and H
2

Chapter15: Principles of Chemical Equilibrium
714
[HI] =2.55 mmol HI 0.400 L =6.38 mM

[I
2
] =[H
2
] =0.3113 mmol 0.400 L =0.778 mM
Ratio:
2 2
2 2
[H ][I ] (0.778 mM)(0.778 mM)
[HI] (6.38 mM)
= =0.0149

As the time increases, the ratio
2
2 2
[HI]
] ][I [H
initially climbs sharply, but then plateaus at

0.0150 somewhere between 4 and 12 hours. Consequently, it seems quite reasonable to
conclude that the reaction 2HI(g)

H
2
(g) +I
2
(g) has a K
c
~0.015 at 623 K.

94. (D) We first need to determine the number of moles of ammonia that were present in the
sample of gas that left the reactor. This will be accomplished by using the data from the
titrations involving HCl(aq).

Original number of moles of HCl(aq) in the 20.00 mL sample

=0.01872 L of KOH
0.0523 mol KOH 1 mol HCl
1 L KOH 1 mol KOH


=9.7906 10
-4
moles of HCl
(initially)


Moles of unreacted HCl(aq)

=0.01542 L of KOH
0.0523 mol KOH 1 mol HCl
1 L KOH 1 mol KOH
=
8.0647 10
-4
moles of HCl
(unreacted)

Moles of HCl that reacted and /or moles of NH
3
present in the sample of reactor gas
=9.7906 10
-4
moles 8.0647 10
-4
moles =1.73 10
-4
mole of NH
3
(or HCl).

The remaining gas, which is a mixture of N
2
(g) and H
2
(g) gases, was found to occupy 1.82 L
at 273.2 K and 1.00 atm. Thus, the total number of moles of N
2
and H
2
can be found via the

ideal gas law:
2 2
H N
n
+
=
PV
RT
=
(1.00 atm)(1.82 L)
L atm
(0.08206 )(273.2 K)
K mol
=0.08118 moles of (N
2
+H
2
)

According to the stoichiometry for the reaction, 2 parts NH
3
decompose to give 3 parts H
2

and 1 part N
2
. Thus the non-reacting mixture must be 75% H
2
and 25% N
2
.

So, the number of moles of N
2
=0.25 0.08118 moles =0.0203 moles N
2
and the
number of moles of H
2
=0.75 0.08118 moles =0.0609 moles H
2
.

Chapter15: Principles of Chemical Equilibrium
715
Before we can calculate K
c
, we need to determine the volume that the NH
3
, N
2
, and H
2

molecules occupied in the reactor. Once again, the ideal gas law (PV = nRT) will be
employed. n
gas
=0.08118 moles (N
2
+H
2
) + 1.73 10
-4
moles NH
3
=0.08135 moles

V
gases
=
nRT
P
=
L atm
(0.08135 mol)( 0.08206 )(1174.2 K)
K mol
30.0 atm
=0.2613 L

So, K
c
=
-4
2
3 1
1.73 10 moles
0.2613 L
0.0609 moles 0.0203 moles
0.2613 L 0.2613 L
(
(

( (
( (

=4.46 10
-4

To calculate K
p
at 901 C, we need to employ the equation ( )
gas
n
p c gas
; 2 K K RT n
A
= A =

K
p
= 4.46 10
-4
[(0.08206 L atm K
-1
mol
-1
)] (1174.2 K)]
-2
=4.80 10
-8
at 901C for the
reaction N
2
(g) +3 H
2
(g)

2 NH
3
(g)

95. (M) For step 1, rate of the forward reaction =rate of the reverse reaction, so,

k
1
[I
2
] =k
-1
[I]
2
or
1
-1
k
k
=
] [I
[I]
2
2
=K
c
(step 1)
Like the first step, the rates for the forward and reverse reactions are equal in the second step
and thus,
k
2
[I]
2
[H
2
] =k
-2
[HI]
2
or
2
-2
k
k
=
2
2
2
[HI]
[I] [H ]
=K
c
(step 2)

Now we combine the two elementary steps to obtain the overall equation and its associated
equilibrium constant.
I
2
(g)

2 I(g) K
c
=
1
-1
k
k
=
] [I
[I]
2
2
(STEP 1)
and
H
2
(g) +2 I(g)

2 HI(g) K
c
=
2
-2
k
k
=
2
2
2
[HI]
[I] [H ]
(STEP 2)

H
2
(g) +I
2
(g)

2 HI(g) K
c(overall)
=K
c(step 1)
K
c(step 2)
K
c(overall)
=

1
-1
k
k

2 -
2
k
k
=
] [I
[I]
2
2

2
2
2
[HI]
[I] [H ]


K
c(overall)
=
1 2
-1 2
k k
k k

=
2
2 2
2
2
[I] [HI]
[I] [I ][H ]
=
2
2
2
[HI]
[I ][H ]

Chapter15: Principles of Chemical Equilibrium
716

96. (M) The equilibrium expressions for the two reactions are:
2
3 3
1 2
2 3 3
H HCO H CO
K ; K
H CO HCO
+ +

( ( ( (

= =
( (



First, start with [H
+
] =0.1 and [HCO
3

] =1. This means that [H

+
]/[HCO
3

] =0.1, which
means that [CO
3
2
] =10K
2
. By adding a small amount of H
2
CO
3
we shift [H
+
] by 0.1 and
[HCO
3

] by 0.1. This leads to [H

+
]/[HCO
3

] ~ 0.2, which means that [CO

3
2
] =5K
2
. Note that
[CO
3
2
] has decreased as a result of adding H
2
CO
3
to the solution.

97. (D) First, it is most important to get a general feel for the direction of the reaction by
determining the reaction quotient:

| |
| | | |
C(aq)
0.1
Q 10
A(aq) B(aq) 0.1 0.1
= = =


Since Q>>K, the reaction proceeds toward the reactants. Looking at the reaction in the
aqueous phase only, the equilibrium can be expressed as follows:


A(aq) + B(aq)

C(aq)
Initial 0.1 0.1 0.1
Change -x -x +x
Equil. 0.1 - x 0.1 - x 0.1 +x

We will do part (b) first, which assumes the absence of an organic layer for extraction:

( )
( )( )
0.1 x
K 0.01
0.1 x 0.1 x
+
= =



Expanding the above equation and using the quadratic formula, x =-0.0996. Therefore, the
concentration of C(aq) and equilibrium is 0.1 +(-0.0996) =410
-4
M.

If the organic layer is present for extraction, we can add the two equations together, as shown
below:

A(aq) + B(aq)

C(aq)
C(aq)

C(or)
A(aq) + B(aq)

C(or)

K =K
1
K
2
=0.1 15 =0.15.

Since the organic layer is present with the aqueous layer, and K
2
is large, we can expect that
the vast portion of C initially placed in the aqueous phase will go into the organic phase.
Chapter15: Principles of Chemical Equilibrium
717
Therefore, the initial [C] =0.1 can be assumed to be for C(or). The equilibrium can be
expressed as follows

A(aq) + B(aq)

C(or)
Initial 0.1 0.1 0.1
Change -x -x +x
Equil. 0.1 - x 0.1 - x 0.1 +x

We will do part (b) first, which assumes the absence of an organic layer for extraction:

( )
( )( )
0.1 x
K 0.15
0.1 x 0.1 x
+
= =



Expanding the above equation and using the quadratic formula, x =-0.0943. Therefore, the
concentration of C(or) and equilibrium is 0.1 +(-0.0943) =610
-4
M. This makes sense
because the K for the overall reaction is <1, which means that the reaction favors the
reactants.

SELF-ASSESSMENT EXERCISES

98. (E)
(a) K
p
: The equilibrium constant of a reaction where the pressures of gaseous reactants and
products are used instead of their concentrations
(b) Q
c
: The reaction quotient using the molarities of the reactants and products
(c) n
gas
: The difference between the number of moles (as determined from a balanced
reaction) of product and reactant gases

99. (E)
(a) Dynamic equilibrium: In a dynamic equilibrium (which is to say, real equilibrium), the
forward and reverse reactions happen, but at a constant rate
(b) Direction of net chemical change: In a reversible reaction, if the reaction quotient Q
c
>K
c
,
then the net reaction will go toward the reactants, and vice versa
(c) Le Chteliers principle: When a system at equilibrium is subjected to external change
(change in partial pressure of reactants/products, temperature or concentration), the
equilibrium shifts to a side to diminish the effects of that external change
(d) Effect of catalyst on equilibrium: A catalyst does not affect the final concentrations of the
reactants and products. However, since it speeds up the reaction, it allows for the
equilibrium concentrations to be established more quickly

100. (E)
(a) Reaction that goes to completion and reversible reaction: In a reversible reaction, the
products can revert back to the reactants in a dynamic equilibrium. In a reaction that goes
to completion, the formation of products is so highly favored that there is practically no
reverse reaction (or the reverse is practically impossible, such as a combustion reaction).
Chapter15: Principles of Chemical Equilibrium
718
(b) K
p
and K
c
: K
p
is the equilibrium constant using pressures of products and reactants, while
K
c
is the constant for reaction using concentrations.
(c) Reaction quotient (Q) and equilibrium constant expression (K): The reaction quotient Q is
the ratio of the concentrations of the reactants and products expressed in the same format
as the equilibrium expression. The equilibrium constant expression is the ratio of
concentrations at equilibrium.
(d) Homogeneous and heterogeneous reaction: In a homogeneous reaction, the reaction
happens within a single phase (either aqueous or gas). In a heterogeneous reaction, there
is more than one phase present in the reaction.

101. (E) The answer is (c). Because the limiting reagent is I
2
at one mole, the theoretical yield of
HI is 2 moles. However, because there is an established equilibrium, there is a small amount
of HI which will decompose to yield H
2
and I
2
. Therefore the total moles of HI created is
close, but less than 2.

102. (E) The answer is (d). The equilibrium expression is:
( )
( ) ( )
2
3
2
2 2
P SO
K 100
P SO P O
= =
If equilibrium is established, moles of SO
3
and SO
2
cancel out of the equilibrium expression.
Therefore, if K =100, the moles of O
2
have to be 0.01 to make K =100.

103. (E) The answer is (a). As the volume of the vessel is expanded (i.e., pressure is reduced), the
equilibrium shifts
toward
the side with more moles of gas.

104. (E) The answer is (b). At half the stoichiometric values, the equilibrium constant is K
1/2
. If
the equation is reversed, it is K
-1
. Therefore, the K =K
-1/2
=(1.810
-6
)
-1/2
=7.510
-2
.

105. (E) The answer is (a). We know that K
p
=K
c
(RT)
n
. Since n =(32) =1, K
p
=K
c
(RT).
Therefore, K
p
>K
c
.

106. (E) The answer is (c). Since the number of moles of gas of products is more than the
reactants, increasing the vessel volume will drive the equilibrium more toward the product
side. The other options: (a) has no effect, and (b) drives the equilibrium to the reactant side.

107. (E) The equilibrium expression is:
| |
| | | |
( )
( ) ( )
2 2
2 2
C 0.43
K 1.9
0.55 0.33 B A
= = =

108. (E)
(a) As more O
2
(a reactant) is added, more Cl
2
is produced.
(b) As HCl (a reactant) is removed, equilibrium shifts to the left and less Cl
2
is made.
(c) Since there are more moles of reactants, equilibrium shifts to the left and less Cl
2
is made.
(d) No change. However, the equilibrium is reached faster.
(e) Since the reaction is exothermic, increasing the temperature causes less Cl
2
to be made.
Chapter15: Principles of Chemical Equilibrium
719

109. (E) SO
2
(g) will be less than SO
2
(aq), because K >1, so the equilibrium lies to the product
side, SO
2
(aq).

110. (E) Since K >>1, there will be much more product than reactant

111. (M) The equilibrium expression for this reaction is:
| |
| | | |
2
3
2
2 2
SO
K 35.5
SO O
= =
(a) If [SO
3
]
eq
=[SO
2
]
eq
, then [O
2
] =1/35.5 =0.0282 M.
moles of O
2
=0.0282 2.05 L =0.0578 moles

(b) Plugging in the new concentration values into the equilibrium expression:
| |
| | | |
| |
| | | |
| |
2 2
3 2
2 2
2
2 2 2 2
SO 2 SO
4
K 35.5
O
SO O SO O

= = = =
[O
2
] =0.113 M

moles of O
2
=0.113 2.05 L =0.232 moles

112. (M) This concept map involves the various conditions that affect equilibrium of a reaction,
and those that dont. Under the category of conditions that do cause a change, there is
changing the partial pressure of gaseous products and reactants, which includes pressure and
vessel volume. The changes that do not affect partial pressure are changing the concentration
of reactants or products in an aqueous solution, through dilution or concentration. Changing
the temperature can affect both aqueous and gaseous reactions. Under the category of major
changes that dont affect anything is the addition of a non-reactive gas.

720
CHAPTER 16

ACIDS AND BASES


PRACTICE EXAMPLES

1A (E)
(a) In the forward direction, HF is the acid (proton donor; forms F

), and H
2
O is the base
(proton acceptor; forms H
3
O
+
). In the reverse direction, F

is the base (forms HF),

accepting a proton from H
3
O
+
, which is the acid (forms H
2
O).

(b) In the forward direction, HSO
4

is the acid (proton donor; forms SO

4
2
), and NH
3
is
the base (proton acceptor; forms NH
4
+
). In the reverse direction, SO
4
2
is the base
(forms HSO
4

), accepting a proton from NH

4
+
, which is the acid (forms NH
3
).

(c) In the forward direction, HCl is the acid (proton donor; forms Cl

), and C
2
H
3
O
2

is
the base (proton acceptor; forms HC
2
H
3
O
2
). In the reverse direction, Cl

is the base
(forms HCl), accepting a proton from HC
2
H
3
O
2
, which is the acid (forms C
2
H
3
O
2

).

1B (E) We know that the formulas of most acids begin with H. Thus, we identify HNO
2
and
HCO
3

as acids.

( ) ( ) ( )
( ) ( ) ( )
+
2 2 2 3
2 +
3 2 3 3
HNO aq +H O(l) NO aq +H O aq ;
HCO aq +H O(l) CO aq +H O aq

A negatively charged species will attract a positively charged proton and act as a base.
Thus PO
4
3
and HCO
3

can act as bases. We also know that PO

4
3
must be a base
because it cannot act as an acidit has no protons to donateand we know that all three
species have acid-base properties.

( ) ( ) ( )
( ) ( ) ( )
3 2
4 2 4
3 2 2 3 2 2
PO aq +H O(l) HPO aq +OH aq ;
HCO aq +H O(l) H CO (aq) CO H O aq +OH aq

Notice that HCO
3

is the amphiprotic species, acting as both an acid and a base.

2A (M) H O
3
+
is readily computed from pH: H O H O
pH
3
+
3
+ 2.85 3
=10 =10 =1.4 10

M.
OH

can be found in two ways: (1) fromK

w
H O OH =
3
+
, giving
14
12 w
3 +
3
1.0 10
OH = = =7.1 10
1.4 10 H O
K

(

(

M, or (2) frompH pOH + =14.00, giving
pOH pH =14.00 =14.00 2.85=11.15 , and then OH

(

pOH 11.15 12
=10 =10 =7.1 10

M.
Chapter 16: Acids and Bases
721
2B (M) H O
3
+
is computed from pH in each case: H O
pH
3
+
=10

H O M H O M
conc dil
3
+
.
2.50 3
3
+
.
3.10 4
=10 =3.2 10 =10 =7.9 10


All of the H O
3
+
in the dilute solution comes from the concentrated solution.
3 +
+ 3 + 3
3 3
3.2 10 mol H O
amount H O =1.00L conc. soln =3.2 10 mol H O
1 L conc. soln

Next we calculate the volume of the dilute solution.
3 +
3
4 +
3
1 L dilute soln
volume of dilute solution=3.2 10 mol H O =4.1 L dilute soln
7.9 10 mol H O

Thus, the volume of water to be added is =3.1 L.
Infinite dilution does not lead to infinitely small hydrogen ion concentrations. Since
dilution is done with water, the pH of an infinitely dilute solution will approach that of
pure water, namely pH =7.

3A (E) pH is computed directly from the equation below.
( )
+ +
3 3
H O , pH= log H O = log 0.0025 =2.60 ( (

.
We know that HI is a strong acid and, thus, is completely dissociated into H O
3
+
and I

.
The consequence is that I H O

= =0.0025
3
+
M. OH

is most readily computed from

pH:
pOH 11.40 12
pOH=14.00 pH=14.00 2.60=11.40; OH =10 =10 =4.0 10

(

M

3B (M) The number of moles of HCl(g) is calculated from the ideal gas law. Then H O
3
+
is
calculated, based on the fact that HCl(aq) is a strong acid (1 mol H O
3
+
is produced from
each mole of HCl).

+
3
+
3
1atm
747mmHg 0.535L
760mmHg
moles HCl(g) =
0.08206L atm
(26.5 273.2)K
mol K
moles HCl(g) 0.0214mol HCl(g) =0.0214mol H O when dissolved in water
[H O ] 0.0214mol pH =-log(0.0214) =1.670
| |

|
\ .
+
=
=


4A (E) pH is most readily determined frompOH logOH =

. Assume Mg OH b g
2
is a strong
base.
( ) ( )
( ) ( )
( )
2 2
2 2
9.63mg Mg OH 1mol Mg OH
1000mL 1g 2mol OH
OH =
100.0 mL soln 1 L 1000mg 58.32g Mg OH 1mol Mg OH
OH =0.00330M; pOH= log 0.00330 =2.481
pH=14.000 pOH=14.000 2.481=11.519

(

(



Chapter 16: Acids and Bases
722
4B (E) KOH is a strong base, which means that each mole of KOH that dissolves produces one
mole of dissolved OH aq

b g . First we calculate OH

and the pOH. We then use

pH pOH + =14.00 to determine pH.

OH
g KOH
g soln
mol KOH
g KOH
mol OH
mol KOH
g soln
mL soln
mL
L
M

=
3.00
100.00
1
56.11
1
1
1.0242
1
1000
1
=0.548
( ) pOH= log 0.548 =0.261 pH=14.000 pOH=14.000 0.261=13.739

5A (M) H O
pH
3
+ 4.18 5
=10 =10 =6.6 10

M.

Organize the solution using the balanced chemical equation.

Equation:
( )
2
HOCl aq + H O(l)

H O aq
3
+
b g + OCl aq

b g
Initial: 0.150 M

0 M ~ 0 M
Changes:
5
6.6 10 M

5
+6.6 10 M

5
+6.6 10 M

Equil: 0.150 M

5
6.6 10 M

5
6.6 10 M

| |
( )( )
5 5 +
3
8
6.6 10 6.6 10 H O OCl
= 2.9 10
HOCl 0.150
a
K

( (

= =

5B (M) First, we use pH to determine OH

. pOH pH =14.00 =14.00 10.08=3.92 .

OH
pOH
=10 =10 =1.2 10
3.92 4
M. We determine the initial concentration of cocaine
and then organize the solution around the balanced equation in the manner we have used
before.
17 21 4 17 21 4
17 21 4
17 21 4
0.17g C H O N 1mol C H O N 1000mL
[C H O N] = =0.0056M
100mL soln 1L 303.36g C H O N


Equation:
17 21 4 2
C H O N(aq) + H O(l)

C H O NH aq
17 21 4
+
b g + OH aq

b g
Initial: 0.0056 M

0 M 0 M ~
Changes:
4
1.2 10 M

4
+1.2 10 M

4
+1.2 10 M

Equil: 0.0055 M

4
1.2 10 M

4
1.2 10 M

K
b
= =

=

C H O NH OH
C H O N
17 21 4
+
17 21 4
4 4
6
1.2 10 1.2 10
00055
26 10
c hc h
.
.
Chapter 16: Acids and Bases
723
6A (M) Again we organize our solution around the balanced chemical equation.

Equation:
Initial:
2 2 2 2
HC H FO (aq) + H O(l)
0.100 M

H O
3
+
(aq) +
~ 0M
C H FO
2 2 2

(aq)
0 M
Changes: x M

+x M +x M
Equil: 0.100 x b g M

x M x M

( )
+
3 2 2 2
3
a
2 2 2
H O C H FO
= ; therefore, 2.6 10
0.100 HC H FO
x x
K
x

( (


=
(


We can use the 5% rule to ignore x in the denominator. Therefore, x =[H
3
O
+
] =0.016 M,
and pH =log (0.016) =1.8. Thus, the calculated pH is considerably lower than 2.89
(Example 16-6).

6B (M) We first determine the concentration of undissociated acid. We then use this value in
a set-up that is based on the balanced chemical equation.

9 7 4 9 7 4
9 7 4
0.500 g HC H O 1 mol HC H O 1
2aspirintablets =0.0171M
tablet 180.155gHC H O 0.325L

Equation:
Initial:
9 7 4
HC H O (aq) + H
2
O(l)
0.0171 M

H O
3
+
(aq) +
0 M
9 7 4
C H O (aq)

0 M
Changes: x M

+x M +x M
Equil: 0.0171 x b g M

x M x M

+
3 9 7 4
4
a
9 7 4
H O C H O
= =3.3 10 =
HC H O 0.0171
x x
K
x

(
(

( (

2 4 6
+3.3 10 5.64 10 =0 x

(find the physically reasonable roots of the quadratic equation)

4 7 5
3.3 10 1.1 10 2.3 10
0.0022M; pH log(0.0022) 2.66
2
x

+
= = = =

7A (M) Again we organize our solution around the balanced chemical equation.

Equation:
Initial:
Changes
2 2 2 2
HC H FO (aq) + H O(l)
0.015 M

x M

H
3
O
+
(aq) +
0M ~
+x M
C H FO
2 2 2

(aq)
0 M
+x M
Equil: 0.015 x b g M

x M x M

| |
( )( )
+
2
3 2 2 2
3
a
2 2 2
H O C H FO
= =2.6 10 =
HC H FO 0.015 0.015
x x
x
K
x

( (

~

x x = 0015 26 10 00062
2 3
= =

. . . M =[H O ]
3
+
Our assumption is invalid:

Chapter 16: Acids and Bases
724
0.0062 is not quite small enough compared to 0.015 for the 5% rule to hold. Thus we use
another cycle of successive approximations.

( )( )
( )( )
3 3 +
a 3
3 3 +
a 3
= =2.6 10 = (0.015 0.0062) 2.6 10 0.0048M =[H O ]
0.015 0.0062
= =2.6 10 = (0.015 0.0048) 2.6 10 0.0051M =[H O ]
0.015 0.0048
x x
K x
x x
K x


=

( )( )
3 3 +
a 3
= =2.6 10 = (0.015 0.0051) 2.6 10 0.0051M =[H O ]
0.015 0.0051
x x
K x

=

Two successive identical results indicate that we have the solution.

pH log H O log = = 0.0051 =2.29
3
+
b g . The quadratic equation gives the same result
(0.0051 M) as this method of successive approximations.

7B (M) First we find [C
5
H
11
N]. We then use this value as the starting base concentration in a
set-up based on the balanced chemical equation.
C H N
mg C H N
mL soln
mmol C H N
mg C H N
M
5 11
5 11 5 11
5 11
=
114
315
1
85.15
=0.00425
Equation:

Initial:
Changes:
Equil:
5 11 2
C H N(aq) + H O(l)
0.00425 M

M x

( ) 0.00425 M x

+
5 11
C H NH (aq) +
0 M
+ M x
M x
OH

(aq)
0 M ~
+ M x
M x

| |
+
5 11
3
b
5 11
C H NH OH
= =1.6 10 =
C H N 0.00425 0.00425
x x x x
K
x

( (


~

We assumed that 0.00425 x

x = = 00016 000425 00026 . . . M The assumption is not valid. Lets assume x ~ 00026 .
x = = 00016 000425 00026 00016 . ( . . ) . Lets try again, with x ~ 00016 .
x = = 00016 000425 00016 00021 . ( . . ) . Yet another try, with x ~ 00021 .
x = = 00016 000425 00021 00019 . ( . . ) . The last time, with x ~ 00019 .
0.0016(0.00425 0.0019) 0.0019M =[OH ] x

= =

3
pOH= log[H O ] log(0.0019) 2.72
+
= = pH pOH =14.00 =14.00 2.72=11.28
We could have solved the problem with the quadratic formula roots equation rather than by
successive approximations. The same answer is obtained. In fact, if we substitute
x =0.0019 into the K
b
expression, we obtain 0.0019 / 0.00425 0.0019 =1.5 10
2
3
b g b g


compared to K
b
=1.6 10
3

. The error is due to rounding, not to an incorrect value.
Using x =0.0020 gives a value of 1.8 10
3

, while using x =0.0018 gives 1.3 10
3

.

Chapter 16: Acids and Bases
725
8A (M) We organize the solution around the balanced chemical equation; a M is [HF]
initial
.
Equation:

Initial:
Changes:
Equil:
2
HF(aq) + H O(l)
M a

M x

( ) M a x

+
3
H O (aq)
0 M ~
+ M x
M x
+


F (aq)

0 M
+ M x
M x
| |
( )( )
+
2
3
4
a
H O F
= = =6.6 10
HF
x x
x
K
a x a

( (

~

x a = 66 10
4


.
For 0.20 M HF, a =0.20 M
4
= 0.20 6.6 10 0.011M x

=

0.011M
% dissoc= 100%=5.5%
0.20M

For 0.020 M HF, a =0.020 M x = 0020 66 10 00036
4
. . . =

M
We need another cycle of approximation: x = 0020 00036 66 10 00033
4
( . . ) . . =

M
Yet another cycle with x ~ 0.0033M : x = 0020 00033 66 10 00033
4
( . . ) . . =

M
0.0033M
% dissoc= 100%=17%
0.020M

As expected, the weak acid is more dissociated.

8B (E) Since both H O
3
+
and C H O
3 5 3

come from the same source in equimolar amounts,

their concentrations are equal. H O C H O M M
3
+
3 5 3
= =0.067 0.0284 =0.0019

K
a
H O C H O
HC H O
= =
0.0019 0.0019
0.0284 0.0019
=1.4 10
3
+
3 5 3
3 5 3
4

L
N
M
O
Q
P

b gb g


9A (M) For an aqueous solution of a diprotic acid, the concentration of the divalent anion is
very close to the second ionization constant:
2
6
2 a
OOCCH COO =2.0 10 M K

( ~

. We
organize around the chemical equation.

Equation:
Initial:
Change:
Equil:

( )
2 2
2
CH COOH (aq) +H O(l)
1.0 M

x M

(1.0 x) M

+
3
H O (aq)
0M ~
+ M x
M x
+


( )
2
2
HCH COO (aq)

0 M
+ M x
M x

2
3 2 3 2
2 2
[H O ][HCH (COO) ]
( )( )
1.4 10
[CH (COOH) ] 1.0 1.0
a
x x x
K
x
+

= = ~ =

3 2 +
3 2
1.4 10 3.7 10 M [H O ] [HOOCCH COO ] x

= = = = 1.0M x is a valid assumption.
Chapter 16: Acids and Bases
726
9B (M) We know
| |
2
a
doubly charged anion K ~ for a polyprotic acid. Thus,
2
5 2
a 2 4
=5.3 10 C O K

( ~

. From the pH,
+ pH 0.67
3
H O =10 =10 =0.21M

(

. We also
recognize that HC O H O
2 4 3
+
=

, since the second ionization occurs to only a very small

extent. We note as well that HC O
2 4

is produced by the ionization of H C O

2 2 4
. Each
mole of HC O
2 4

present results from the ionization of 1 mole of H C O

2 2 4
. Now we have
sufficient information to determine the
1
a
K .

1
+
3 2 4
2
a
2 2 4
H O HC O
0.21 0.21
= = =5.3 10
H C O 1.05 0.21
K

(
(

( (

10A (M) H SO
2 4
is a strong acid in its first ionization, and somewhat weak in its second, with
2
2
a
=1.1 10 =0.011 K

. Because of the strong first ionization step, this problem involves
determining concentrations in a solution that initially is 0.20 M H O
3
+
and 0.20 M HSO
4

.
We base the set-up on the balanced chemical equation.


Equation:
HSO aq H O
4 2
+

b g (l)

H O aq
3
+
b g
+
2-
4
SO (aq)
Initial: 0.20 M

0.20 M 0 M
Changes: M x

+ M x + M x
Equil:
( ) 0.20 M x

( ) 0.20+ M x
M x


( )
2
2 +
3 4
a
4
H O SO
0.20+
0.20
= = =0.011 , assuming that 0.20M.
0.20 0.20
HSO
=0.011M Try one cycle of approximation:
x x
x
K x
x
x

( (


~
(





0.011
0.20+0.011
0.20 0.011
=
0.21
0.19
=
0.19 0.011
0.21
=0.010 ~

b g
b g
x x
x M
The next cycle of approximation produces the same answer
2
4
0.010M = SO ,

(


+
3 4
H O =0.010+0.20M =0.21M, HSO =0.20 0.010M =0.19M

( (



10B (M) We know that H SO
2 4
is a strong acid in its first ionization, and a somewhat weak
acid in its second, with
2
2
a
=1.1 10 =0.011 K

. Because of the strong first ionization step,
the problem essentially reduces to determining concentrations in a solution that initially is
0.020 M H O
3
+
and 0.020 M HSO
4

. We base the set-up on the balanced chemical

equation. The result is solved using the quadratic equation.


Chapter 16: Acids and Bases
727
Equation:
HSO aq H O
4 2
+

b g (l)

H O aq
3
+
b g
+
SO aq
4
2
b g
Initial: 0.020 M

0.020 M 0 M
Changes: M x

+ M x + M x
Equil:
( ) 0.020 M x

( ) 0.020+ M x
M x

( )
2
2 +
3 4
2 4
a
4
H O SO
0.020+
= = =0.011 0.020 + =2.2 10 0.011
0.020
HSO
x x
K x x x
x

( (


(


+
4 3
HSO =0.020 0.0060=0.014 M H O =0.020+0.0060=0.026 M

( (



(The method of successive approximations converges to =0.006M x in 8 cycles.)

11A (E)
(a) CH NH NO
3 3
+
3

is the salt of the cation of a weak base. The cation,

+
3 3
CH NH , will
hydrolyze to form an acidic solution
( )
+ +
3 3 2 3 2 3
CH NH +H O CH NH +H O

, while
NO
3

, by virtue of being the conjugate base of a strong acid will not hydrolyze to a
detectable extent. The aqueous solutions of this compound will thus be acidic.

(b) NaI is the salt composed of the cation of a strong base and the anion of a strong
acid, neither of which hydrolyzes in water. Solutions of this compound will be pH
neutral.

(c) NaNO
2
is the salt composed of the cation of a strong base that will not hydrolyze in
water and the anion of a weak acid that will hydrolyze to form an alkaline solution
( ) 2 2 2
NO +H O HNO +OH

. Thus aqueous solutions of this compound will be

basic (alkaline).

11B (E) Even without referring to the K values for acids and bases, we can predict that the
reaction that produces H O
3
+
occurs to the greater extent. This, of course, is because the pH
is less than 7, thus acid hydrolysis must predominate.
We write the two reactions of H PO
2 4

with water, along with the values of their equilibrium

constants.
( ) ( ) ( )
2
+ 2 8
2 4 2 3 4 a
H PO aq +H O(l) H O aq +HPO aq =6.3 10 K

( ) ( ) ( )
1
14
12 w
2 4 2 3 4 b 3
a
1.0 10
H PO aq +H O(l) OH aq +H PO aq = = =1.4 10
7.1 10
K
K
K

As predicted, the acid ionization occurs to the greater extent.

2 2
4
0.031 0.00096+0.00088
+0.031 0.00022=0 = =0.0060M = SO
2
x x x


(

Chapter 16: Acids and Bases
728
12A (M) From the value of p
b
K we determine the value of K
b
and then K
a
for the cation.

cocaine
b
p
a
w
b
: =10 =10 =3.9 10 = =
1.0 10
3.9 10
=2.6 10
8.41 9
14
9
6
K K
K
K
K

codeine
b
p
a
w
b
: =10 =10 =1.1 10 = =
1.0 10
1.1 10
=9.1 10
7.95 8
14
8
7
K K
K
K
K

(This method may be a bit easier:
p p
a b a
K K K =14.00 =14.00 8.41=5.59, =10 =2.6 10
5.59 6


) The acid with the larger
K
a
will produce the higher H
+
, and that solution will have the lower pH. Thus, the
solution of codeine hydrochloride will have the higher pH (i.e., codeine hydrochloride is
the weaker acid).

12B (E) Both of the ions of NH CN aq
4
b g react with water in hydrolysis reactions.

( ) ( ) ( )
14
+ + 10 w
4 2 3 3 a
5
b
1.0 10
NH aq +H O(l) NH aq +H O aq = = =5.6 10
1.8 10
K
K
K

( ) ( ) ( )
14
5 w
2 b
10
a
1.0 10
CN aq +H O(l) HCN aq +OH aq = = =1.6 10
6.2 10
K
K
K

Since the value of the equilibrium constant for the hydrolysis reaction of cyanide ion is
larger than that for the hydrolysis of ammonium ion, the cyanide ion hydrolysis reaction
will proceed to a greater extent and thus the solution of NH CN aq
4
b g will be basic
(alkaline).

13A (M) NaF dissociates completely into sodium ions and fluoride ions. The released fluoride
ion hydrolyzes in aqueous solution to form hydroxide ion. The determination of the
equilibrium pH is organized around the balanced equation.

Equation:
Initial:
Changes:
Equil:

-
2
F (aq) + H O(l)
0.10 M

M x

( ) 0.10 M x

HF(aq)
0 M
+ M x
M x
+


OH

(aq)
0 M
+ M x
M x

14 2
11
4 -
1.0 10 [HF][OH ] ( )( )
1.5 10
6.6 10 [F ] (0.10 ) 0.10
w
b
a
K x x x
K
K x

= = = = = =



11 6 6
= 0.10 1.5 10 1.2 10 M=[OH ]; pOH= log(1.2 10 ) 5.92
pH =14.00 pOH =14.00 5.92 =8.08 (As expected, pH >7)
x

= =



Chapter 16: Acids and Bases
729
13B (M) The cyanide ion hydrolyzes in solution, as indicated in Practice Example 16-12B. As a
consequence of the hydrolysis, OH HCN

= . OH

can be found from the pH of the

solution, and then values are substituted into the K
b
expression for CN

, which is then
solved for CN

.

pOH=14.00 pH=14.00 10.38=3.62

| |
-pOH 3.62 4
OH =10 =10 =2.4 10 M = HCN
(

(



K
b
HCN OH
CN CN
CN M = =1.6 10 =
2.4 10
=
2.4 10
1.6 10
=3.6 10
5
4
2
4
2
5
3

c h c h


14A (M) First we draw the Lewis structures of the four acids. Lone pairs have been omitted
since we are interested only in the arrangements of atoms.

HClO
4
should be stronger than HNO
3
. Although Cl and N have similar electronegativities,
there are more terminal oxygen atoms attached to the chlorine in perchloric acid than to the
nitrogen in nitric acid. By virtue of having more terminal oxygens, perchloric acid, when
ionized, affords a more stable conjugate base. The more stable the anion, the more easily it is
formed and hence the stronger is the conjugate acid from which it is derived.CH FCOOH
2

will be a stronger acid than CH BrCOOH
2
because F is a more electronegative atom than Br.
The F atom withdraws additional electron density from the OH bond, making the bond
easier to break, which leads to increased acidity.

14B (M) First we draw the Lewis structures of the first two acids. Lone pairs are not depicted
since we are interested in the arrangements of atoms.

H PO
3 4
and H SO
2 3
both have one terminal oxygen atom, but S is more electronegative
than P. This suggests that
( )
1
2
2 3 a
H SO =1.3 10 K

should be a stronger acid than
( )
1
3
3 4 a
H PO =7.1 10 K

, and it is. The only difference between CCl CH COOH
3 2
and
CCl FCH COOH
2 2
is the replacement of Cl by F. Since F is more electronegative than Cl,
CCl CH COOH
3 2
should be a weaker acid than CCl FCH COOH
2 2
.
O N O
O
H O Cl O
O
H
O
O C C
O
F H
H
H
O C C
O
Br H
H
H
O P O
O
H H
O H
O S O
O
H H
Chapter 16: Acids and Bases
730
15A (M) We draw Lewis structures to help us decide.
(a) Clearly, BF
3
is an electron pair acceptor, a Lewis acid, and NH
3
is an electron pair
donor, a Lewis base.


(b) H O
2
certainly has electron pairs (lone pairs) to donate and thus it can be a Lewis
base. It is unlikely that the cation Cr
3+
has any accessible valence electrons that can
be donated to another atom, thus, it is the Lewis acid. The product of the reaction,
[Cr(H
2
O)
6
]
3+
, is described as a water adduct of Cr
3+
.

Cr
3+
(aq) + H
H
O 6
OH
2
OH
2
OH
2
OH
2
H
2
O
H
2
O
Cr
3+


15B (M) The Lewis structures of the six species follow.
Both the hydroxide ion and the chloride ion have lone pairs of electrons that can be
donated to electron-poor centers. These two are the electron pair donors, or the Lewis
bases. Al OH b g
3
and SnCl
4
have additional spaces in their structures to accept pairs of
electrons, which is what occurs when they form the complex anions [Al(OH)
4
]
-
and
[SnCl
6
]
2 -
. Thus, Al OH b g
3
and SnCl
4
are the Lewis acids in these reactions.








B F
F
F
N
H
H
H
+
B F
F
F
N
H
H
H O
H
H
Sn
Cl
Cl Cl
Cl
O H
+
Al O H O H
O
H
Al O H O H
O
H
O
H
-
Cl 2 Sn
Cl
Cl Cl
Cl
Cl
Cl
2-
2-
Chapter 16: Acids and Bases
731
INTEGRATIVE EXAMPLE


A. (D) To confirm the pH of rainwater, we have to calculate the concentration of CO
2
(aq) in
water and then use simple acid-base equilibrium to calculate pH.

Concentration of CO
2
in water at 1 atm pressure and 298 K is 1.45 g/L, or

2 2
2
2
1.45g CO 1mol CO
0.0329M CO
L 44.0g CO
=

Furthermore, if the atmosphere is 0.037% by volume CO
2
, then the mole fraction of CO
2
is
0.00037, and the partial pressure of CO
2
also becomes 0.00037 atm (because
2 2
CO CO atm
P P _ = )

From Henrys law, we know that concentration of a gas in a liquid is proportional to its
partial pressure.
2
CO
1 1
C(mol / L) H P , which can rearrange to solvefor H:
0.0329M
H 0.0329mol L atm
1atm

=
= =


Therefore, concentration of CO
2
(aq) in water under atmospheric pressures at 298 K is:

2
1 1 5
CO
C (mol / L) 0.0329mol L atm 0.00037atm =1.217 10 M

=

Using the equation for reaction of CO
2
with water:

CO
2
(aq) + 2 H
2
O (l)

H
3
O
+
(aq) +
3
HCO

(aq)
1.21710
-5
0 0
-x +x +x
1.21710
-5
x x X

( )
( )
2
7
a1
5
6
6
3
x
K 4.4 10
1.217 10 x
Using the quadratic formula, x =2.104 10 M
pH log H O log 2.104 10 5.68 5.7

+
= =

( = = = ~



We can, of course, continue to refine the value of [H
3
O
+
] further by considering the
dissociation of HCO
3

, but the change is too small to matter.

Chapter 16: Acids and Bases
732
B. (D)
(a) For the acids given, we determine values of m and n in the formula EO
m
(OH)
n
. HOCl or
Cl(OH) has m =0 and n =1. We expect K
a
~ 10
-7
or pK
a
~ 7, which is in good
agreement with the accepted pK
a
=7.52. HOClO or ClO(OH) has m =1 and n =1. We
expect K
a
~ 10
-2
or pK
a
~ 2, in good agreement with the pK
a
=1.92. HOClO
2
or
ClO
2
(OH) has m =2 and n =1. We expect K
a
to be large and in good agreement with
the accepted value of pK
a
=-3, K
a
=10
-pKa
=10
3
. HOClO
3
or ClO
3
(OH) has m =3 and
n =1. We expect K
a
to be very large and in good agreement with the accepted K
a
=-8,
pK
a
=-8, K
a
=10
-pKa
=10
8
which turns out to be the case.
(b) The formula H
3
AsO
4
can be rewritten as AsO(OH)
3
, which has m =1 and n =3. The
expected value is K
a
=10
-2
.

(c) The value of pK
a
=1.1 corresponds to K
a
=10
-pKa
=10
-1.1
=0.08, which indicates that
m =1. The following Lewis structure is consistent with this value of m.
O P
OH
H
OH


EXERCISES

Brnsted-Lowry Theory of Acids and Bases

1. (E)
(a) HNO
2
is an acid, a proton donor. Its conjugate base is NO
2

.

(b) OCl

is a base, a proton acceptor. Its conjugate acid is HOCl.

(c) NH
2

is a base, a proton acceptor. Its conjugate acid is NH

3
.

(d) NH
4
+
is an acid, a proton donor. Its conjugate base is NH
3
.

(e) CH NH
3 3
+
is an acid, a proton donor. Its conjugate base is CH NH
3 2
.

2. (E) We write the conjugate base as the first product of the equilibrium for which the acid is
the first reactant.

(a) ( ) ( ) ( )
+
3 2 3 3
HIO aq +H O(l) IO aq +H O aq

(b) ( ) ( ) ( )
+
6 5 2 6 5 3
C H COOH aq +H O(l) C H COO aq +H O aq

(c) ( ) ( ) ( )
2 3 +
4 2 4 3
HPO aq +H O(l) PO aq +H O aq

(d) ( ) ( ) ( )
+
2 5 3 2 2 5 2 3
C H NH aq +H O(l) C H NH aq +H O aq
+

Chapter 16: Acids and Bases
733

3. (E) The acids (proton donors) and bases (proton acceptors) are labeled below their
formulas. Remember that a proton, in Brnsted-Lowry acid-base theory, isH
+
.

(a)
+
2 3
HOBr(aq) + H O(l) H O (aq) + OBr (aq)
acid base acid base

(b)
2 +
4 2 3 4
HSO (aq) +H O(l) H O (aq) + SO (aq)
acid base acid base

(c)
2 2
HS (aq) + H O(l) H S(aq) + OH (aq)
base acid acid base

(d)
6 5 3 6 5 2 2
C H NH (aq) + OH (aq) C H NH (aq) + H O(l)
acid base base acid
+

4. (E) For each amphiprotic substance, we write both its acid and base hydrolysis reaction.
Even for the substances that are not usually considered amphiprotic, both reactions are
written, but one of them is labeled as unlikely. In some instances we have written an
oxygen as C to keep track of it through the reaction.
( )
2 +
2 3 2 2
H +H O +H O unlikely H +H O H +OH

C C C C



+ +
4 2 3 3 4
NH +H O NH +H O NH has no pairs that can be donated e
+

+ +
2 2 3 2 2 3
H +H O H +H O H +H O H +OH

C C C C



2 +
2 3 2 2
HS +H O S +H O HS +H O H S+OH



2 2 2 2
NO cannot act as an acid, (no protons) NO +H O HNO +OH

2 +
3 2 3 3 3 2 2 3
HCO +H O CO +H O HCO +H O H CO +OH




( )
+ +
2 3 2 2
unlikely HBr+H O H O +Br HBr+H O H Br +OH





5. (E) Answer (b), NH
3
, is correct. HC H O
2 3 2
will react most completely with the strongest
base.
3
NO

and Cl

are very weak bases. H O

2
is a weak base, but it is amphiprotic,
acting as an acid (donating protons), as in the presence of NH
3
. Thus, NH
3
must be the
strongest base and the most effective in deprotonating HC H O
2 3 2
.

6. (M) Lewis structures are given below each equation.
(a) ( )
+
3 4 2
2NH l NH +NH

+



2 H N H
H
H N H
H
H
H N H

+
Chapter 16: Acids and Bases
734
(b) ( )
+
2
2HF l H F +F

F
H
H F
F H F H +
+

(c) ( )
+
3 3 2 3
2CH OH l CH OH +CH O

(d) ( )
+
2 3 2 2 2 3 2 2 3 2
2HC H O l H C H O +C H O

(e)
2 4 3 4 4
2 H SO ( ) 2 H SO HSO l
+
+

7. (E) The principle we will follow here is that, in terms of their concentrations, the weaker
acid and the weaker base will predominate at equilibrium. The reason for this is that a
strong acid will do a good job of donating its protons and, having done so, its conjugate
base will be left behind. The preferred direction is:


strong acid + strong base weak (conjugate) base + weak (conjugate) acid


(a) The reaction will favor the forward direction because OH

(a strong base) > NH

3
(a
weak base) and
4 2
NH (relatively strong weak acid) H O (very weak acid)
+
> .


(b) The reaction will favor the reverse direction because HNO HSO
3 4
>

(a weak acid
in the second ionization) (acting as acids), and SO NO
4
2
3

> (acting as bases).


(c) The reaction will favor the reverse direction because HC H O CH OH
2 3 2 3
> (not
usually thought of as an acid) (acting as acids), and CH O C H O
3 2 3 2

> (acting as
bases).

2 H C O
H
H C O
H
H
+
H
H H
H
H C O
H
H
+
2 H C C
H
H C C
H
H
+
H
O O
O
+
H
O
H
H
H C C
H
H
O
O

S O
O
O H
O
H S O
O
O H
O
H + + S O
O
O H
O
S O
O
O H
O
H
H

+
Chapter 16: Acids and Bases
735
8. (M) The principle we follow here is that, in terms of their concentrations, the weaker acid
and the weaker base predominate at equilibrium. This is because a strong acid will do a
good job of donating its protons and, having done so, its conjugate base will remain in
solution. The preferred direction is:


strong acid + strong base weak (conjugate) base + weak (conjugate) acid


(a) The reaction will favor the forward direction because HC H O
2 3 2
(a moderate acid)
>

HCO
3
(a rather weak acid) (acting as acids) and CO C H O
3
2
2 3 2

> (acting as
bases).

(b) The reaction will favor the reverse direction because HClO
4
(a strong acid)
> HNO
2
(acting as acids), and NO ClO
2 4

> (acting as bases).

(c) The reaction will favor the forward direction, because
2 3 3
H CO HCO

> (acting as
acids) (because K K
1 2
> ) and CO HCO
3
2
3

> (acting as bases).

Strong Acids, Strong Bases, and pH

9. (M) All of the solutes are strong acids or strong bases.
(a)
+
+ 3
3 3
3
1mol H O
H O =0.00165M HNO 0.00165M
1mol HNO
( =


14
12 w
+
3
1.0 10
OH = = =6.1 10 M
0.00165M H O
K

(

(



(b) 1mol OH
OH =0.0087 M KOH 0.0087 M
1mol KOH

( =


14
+ 12 w
3
1.0 10
H O = = = 1.1 10 M
0.0087M
OH
K

(

(



(c)

( )
( )
2
2
2mol OH
OH =0.00213M Sr OH 0.00426M
1mol Sr OH

( =



14
+ 12 w
3
1.0 10
H O = = = 2.3 10 M
0.00426M
OH
K

(

(




(d)
+
+ 4 4 3
3
1mol H O
H O =5.8 10 M HI 5.8 10 M
1mol HI

( =



14
11 w
4 +
3
1.0 10
OH = = 1.7 10 M
5.8 10 M H O
K

( =

(



Chapter 16: Acids and Bases
736
10. (M) Again, all of the solutes are strong acids or strong bases.
(a)
( )
+
+ 3
3
1mol H O
H O =0.0045M HCl =0.0045M
1mol HCl
pH= log 0.0045 =2.35
(

(b)
( )
+
+ 4 4 3
3 3
3
4
1mol H O
H O =6.14 10 M HNO =6.14 10 M
1mol HNO
pH= log 6.14 10 =3.21

(




(c)
( )
1mol OH
OH =0.00683M NaOH =0.00683M
1mol NaOH
pOH= log 0.00683 =2.166 and pH=14.000 pOH=14.000 2.166=11.83

(




(d)
( )
( )
( )
3 3
2
2
3
2mol OH
OH =4.8 10 M Ba OH =9.6 10 M
1mol Ba OH
pOH= log 9.6 10 =2.02 pH=14.00 2.02=11.98

(




11. (E)
( ) ( )
( ) ( )
2 2
2 2
2 2
2 2
3.9 g Ba OH 8H O 1mol Ba OH 8H O
1000 mL 2 mol OH
OH =
100 mL soln 1L 315.5g Ba OH 8H O 1mol Ba OH 8H O
=0.25 M

(


( )
14
+ 14 w
3
14
1.0 10
H O = = =4.0 10 M
0.25 M OH OH
pH= log 4.0 10 =13.40
K

(

(



12. (M) The dissolved Ca OH b g
2
is completely dissociated into ions.
pOH pH =14.00 =14.00 12.35=1.65
pOH 1.65 2
OH =10 =10 =2.2 10 M OH =0.022 M OH

(



( ) ( )
( )
( )
( )
( )
2 2 2
2 2
2
2
1mol Ca OH 74.09g Ca OH 1000mgCa OH
0.022mol OH
solubility=
1L soln 2mol OH 1mol Ca OH 1gCa OH
8.1 10 mg Ca OH
=
1L soln

In 100 mL the solubility is
( )
( )
2
2
2
8.1 10 mg Ca OH
1L
100mL =81mg Ca OH
1000mL 1L soln

Chapter 16: Acids and Bases
737
13. (M) First we determine the moles of HCl, and then its concentration.

moles
3
1 1
1atm
751mmHg 0.205L
760mmHg
HCl = 8.34 10 mol HCl
0.08206L atmmol K 296K
PV
RT

| |

|
\ .
= =

+ 3
+ 3 3
3
1mol H O 8.34 10 mol HCl
H O = =1.96 10 M
4.25L soln 1mol HCl

(



14. (E) First determine the concentration of NaOH, then of OH

.

0.606mol NaOH 1mol OH
0.125L
1L 1mol NaOH
OH = =0.00505M
15.0L final solution

(



( ) pOH= log 0.00505M =2.297 pH=14.00 2.297=11.703

15. (E) First determine the amount of HCl, and then the volume of the concentrated solution
required.
amount HCl L
mol H O
L soln
mol HCl
mol H O
mol HCl =12.5
10
1
1
1
=0.099
2.10
3
+
3
+

solution
36.46g HCl 100.0g soln 1mL soln
=0.099mol HCl =8.5mL soln
1mol HCl 36.0g HCl 1.18g soln
V

16. (E) First we determine the amount of KOH, and then the volume of the concentrated solution
required.

pOH pH OH M
pOH
=14.00 =14.00 11.55=2.45 =10 =10 =0.0035
2.45




amount KOH L
M mol OH
L soln
mol KOH
mol OH
mol KOH =25.0
0.0035
1
1
1
=0.088

solution
56.11g KOH 100.0g soln 1mL soln
=0.088mol KOH =29mL soln
1mol KOH 15.0g KOH 1.14g soln
V

17. (E) The volume of HCl(aq) needed is determined by first finding the amount of NH aq
3
b g
present, and then realizing that acid and base react in a 1:1 molar ratio.

+
3 3
HCl
+
3 3
0.265mol NH 1mol H O 1mol HCl 1L acid
=1.25L base
1L base 1mol NH 6.15mol HCl 1mol H O
=0.0539L acid or 53.9 mL acid.
V


Chapter 16: Acids and Bases
738
18. (M) NH
3
and HCl react in a 1:1 molar ratio. According to Avogadros hypothesis, equal
volumes of gases at the same temperature and pressure contain equal numbers of moles.
Thus, the volume of H
2
(g) at 762 mmHg and 21.0

C that is equivalent to 28.2 L of H

2
(g)
at 742 mmHg and 25.0

Cwill be equal to the volume of NH

3
(g) needed for stoichiometric
neutralization.

( )
( )
( )
( )
( )
( )
( )
3
3
3 NH g
273.2+21.0 K 1L NH g
742mmHg
=28.2L HCl g =27.1L NH g
762mmHg 273.2+25.0 K 1L HCl g
V

Alternatively, we can solve the ideal gas equation for the amount of each gas, and then, by
equating these two expressions, we can find the volume of NH
3
needed.

n
R K
n
V
R K
{HCl}=
742 mmHg 28.2 L
{NH }
mmHg NH }
3
3

=

2982
762
2942 .
{
.


742 mmHg 28.2 L mmHg NH }
3

=

R K
V
R K 2982
762
2942 .
{
.
This yields
3 3
{NH } 27.1L NH (g) V =

19. (M) Here we determine the amounts of H O
3
+
and OH

and then the amount of the one

that is in excess. We express molar concentration in millimoles/milliliter, equivalent to
mol/L.

50.00
0.0155
1
1
1
=0.775
3
+
3
+
mL
mmol HI
mL soln
mmol H O
mmol HI
mmol H O

75.00
0.0106
1
1
1
=0.795 mL
mmol KOH
mL soln
mmol OH
mmol KOH
mmol OH

The net reaction is ( ) ( )
+
3 2
H O aq +OH aq 2H O(l)

.

There is an excess of OH

of (0.795 0.775= ) 0.020 mmol OH

.
Thus, this is a basic solution. The total solution volume is (50.00+75.00=) 125.00 mL.

( )
4 4
0.020mmol OH
OH = =1.6 10 M, pOH = log 1.6 10 =3.80, pH =10.20
125.00mL

(


20. (M) In each case, we need to determine the H O
3
+
or OH

of each solution being

mixed, and then the amount of H O
3
+
or OH

, so that we can determine the amount in

excess. We express molar concentration in millimoles/milliliter, equivalent to mol/L.

+ 2.12 3 + 3 +
3 3 3
H O =10 =7.6 10 M moles H O =25.00mL 7.6 10 M =0.19mmol H O

(


pOH OH M =14.00 12.65=1.35 =10 =4.5 10
1.35 2




amount OH mL M mmol OH

=25.00 4.5 10 =1.13
2


Chapter 16: Acids and Bases
739
There is excess OH

in the amount of 0.94 mmol (=1.13 mmol OH

0.19 mmol H
3
O
+
).

( )
2 2
0.94 mmol OH
25.00 mL +25.00 mL
OH = =1.88 10 M pOH = log 1.88 10 =1.73 pH=12.27

(




Weak Acids, Weak Bases, and pH

21. (M) We organize the solution around the balanced chemical equation.
Equation:
Initial:
Changes:
Equil:


2 2
HNO (aq) + H O(l)
0.143 M

M x

( ) 0.143 M x

+
3 2
H O (aq) + NO (aq)

0 M ~ 0 M
+ M x + M x
M x M x

+
2 2
3 2
4
a
2
4
H O NO
= 7.210 (if 0.143)
HNO 0.143 0.143
= 0.143 7.2 10 0.010M
x x
K x
x
x

(
(

( (

= =

=



We have assumed that 0.143 M x , an almost acceptable assumption. Another cycle of
approximations yields:

4 +
3
= (0.143 0.010) 7.2 10 0.0098M [H O ] pH log(0.0098) 2.01 x

= = = =
This is the same result as is determined with the quadratic formula roots equation.

22. (M) We organize the solution around the balanced chemical equation, and solve first for
OH

( )
+
2 5 2 2 2 5 3
Equation: C H NH (aq) + H O(l) OH (aq) + C H NH (aq)
Initial : 0.085 M 0 M 0 M
Changes: M + M + M
Equil : 0.085 M M M
x x x
x x x

+
2 2
2 5 3
4
b
2 5 2
OH C H NH
= = =4.3 10 assuming 0.085
C H NH 0.085 0.085
x x
K x
x

(
(

( (

~

x = 0085 43 10 00060
4
. . . =

M

We have assumed that 0.085 x M, an almost acceptable assumption. Another cycle of
approximations yields:

x = 0085 00060 43 10 00058
4
( . . ) . . ] =

M =[OH Yet another cycle produces:

Chapter 16: Acids and Bases
740
4
(0.085 0.0058) 4.3 10 0.0058M [OH ] pOH log(0.0058) 2.24 x

= = = = =

pH H O M
pH
=14.00 2.24=11.76 =10 =10 =1.7 10
3
+ 11.76 12




This is the same result as determined with the quadratic formula roots equation.

23. (M)
(a) The set-up is based on the balanced chemical equation.
Equation:
Initial:
Changes:
Equil:


8 7 2 2
HC H O (aq) + H O(l)
0.186 M

M x

( ) 0.186 M x

+
3
H O (aq) +
0 M ~
+ M x
M x
8 7 2
C H O (aq)

0 M
+ M x
M x

2
5 3 8 7 2
a
8 7 2
[H O ][C H O ]
4.9 10
[HC H O ] 0.186 0.186
x x x
K
x
+

= = = ~

x = 0186 49 10 00030
5
. . . ] [ = =

M =[H O C H O ]
3
+
8 7 2

0.0030 M is less than 5 % OF 0.186 M, thus, the approximation is valid.

(b) The set-up is based on the balanced chemical equation.


+
2 2
3 8 7 2
5 +
a 3
8 7 2
H O C H O
=4.9 10 = = =0.0024 M = H O
HC H O 0.121 0.121
x x
K x
x

(
(

( (

( ~

Assumption 0.121, x << is correct. pH log = 0.0024 =2.62 b g

24. (E)

| |
| |
3 5 2
initial
3 5 2
equilibrium
0.275mol 1000mL
HC H O = =0.440M
625mL 1L
HC H O =0.440M 0.00239M =0.438M
| || |
| |
\ .\ .

K
a
H O C H O
HC H O
= =
0.00239
0.438
=1.30 10
3
+
3 5 2
3 5 2
2
5

L
N
M
O
Q
P

b g


Equation:
8 7 2 2
HC H O (aq) + H O(l)

+
3
H O (aq) +
8 7 2
C H O (aq)
Initial: 0.121 M

~ 0M
0 M
Changes: M x

+ M x + M x
Equil:
( ) 0.121 M x

M x M x
Chapter 16: Acids and Bases
741
25. (M) We base our solution on the balanced chemical equation.
H O M
3
+ 1.56 2
=10 =2.8 10


( ) ( ) ( )
+
2 2 2 3
Equation: CH FCOOH aq + H O(l) CH FCOO aq + H O aq
Initial : 0.318 M 0 M 0 M
Changes: 0.028 M +0.028 M +0.028 M
Equil : 0.290 M 0.028 M 0.028 M

~

~

K
a
H O CH FCOO
CH FCOOH
= =
0.028 0.028
0.290
=2.7 10
3
+
2
2
3

b gb g


26. (M) HC H O
g
L
mol HC H O
g HC H O
M M
6 11 2
6 11 2
6 11 2
2
=
11
1
1
116.2
=9.5 10 =0.095



+ 2.94 3
3
equil
H O =10 =1.1 10 M =0.0011M

(



The stoichiometry of the reaction, written below, indicates that H O C H O
3
+
6 11 2
=



+
6 11 2 2 6 11 2 3
Equation: HC H O (aq) + H O(l) C H O (aq) + H O (aq)
Initial : 0.095M 0M 0M
Changes: 0.0011M +0.0011M +0.0011M
Equil : 0.094M 0.0011M 0.0011M

K
a
C H O H O
HC H O
= =
0.0011
0.094
=1.3 10
6 11 2 3
+
6 11 2
2
5

L
N
M
O
Q
P

b g


27. (M) Here we need to find the molarity S of the acid needed that yields
+ 2.85 3
3
H O =10 =1.4 10 M

(



Equation:
7 5 2 2
HC H O (aq) + H O(l)

+
3
H O (aq)
+
7 5 2
C H O (aq)

Initial: S

0 M 0 M
Changes: 0.0014 M

+0.0014M +0.0014M
Equil: S 0.0014M

0.0014 M 0.0014 M

K
S
S
a
H O C H O
HC H O
= =
0.0014
0.0014
=6.3 10 0.0014=
0.0014
6.3 10
=0.031
3
+
7 5 2
7 5 2
2
5
2
5

L
N
M
O
Q
P

b g b g


| |
7 5 2
=0.031+0.0014=0.032M = HC H O S

7 5 2 7 5 2
7 5 2
7 5 2
0.032mol HC H O 122.1g HC H O 1L
350.0mL =1.4 g HC H O
1000mL 1L soln 1mol HC H O


Chapter 16: Acids and Bases
742
28. (M) First we find OH

and then use the K

b
expression to find
| |
3 3
(CH ) N

pOH 2.88
pOH=14.00 pH=14.00 11.12=2.88 OH =10 =10 =0.0013M

(



| |
( )
| |
| |
2 +
3 3
5
b 3 3 3 3
equil
3 3 3 3
equil equil
(CH ) NH OH
0.0013
=6.3 10 = = (CH ) N =0.027 M (CH ) N
(CH ) N (CH ) N
K

( (

( )
( )
3
3
initial
3
3
initial
CH N =0.027 M(equil. concentration) +0.0013M(concentration ionized)
CH N =0.028M
(

(



29. (M) We use the balanced chemical equation, then solve using the quadratic formula.

( )
+
2 2 3 2
Equation: HClO (aq) + H O(l) H O (aq) + ClO (aq)
Initial : 0.55 M 0M 0M
Changes: M + M + M
Equil : 0.55 M M M
x x x
x x x

+
2
3 2
2 2
a
2
H O ClO
= = =1.1 10 =0.011 =0.0061 0.011
HClO 0.55
x
K x x
x

(
(

( (

x x
2
+0.011 0.0061=0
2
+
3
4 0.011 0.000121+0.0244
0.073 M H O
2 2
b b ac
x
a

( = = = =


The method of successive approximations converges to the same answer in four cycles.
pH log H O log pOH pH = = 0.073 =1.14 =14.00 =14.00 1.14=12.86
3
+
b g
pOH 12.86 13
OH =10 =10 =1.4 10 M

(


30. (M) Organize the solution around the balanced chemical equation, and solve first for
OH

.

( )
+
3 2 2 3 3
Equation: CH NH (aq) + H O(l) OH (aq) + CH NH (aq)
Initial : 0.386 M 0 M 0 M
Changes: M + M + M
Equil : 0.386 M M M
x x x
x x x

+
2 2
3 3
4
b
3 2
OH CH NH
= = =4.2 10 assuming 0.386
CH NH 0.386 0.386
x x
K x
x

(
(

( (

~

x = 0386 42 10 0013
4
. . . ] =

M =[OH pOH= log(0.013) =1.89

-


Chapter 16: Acids and Bases
743
+ pH 12.11 13
3
pH=14.00 1.89=12.11 H O =10 =10 =7.8 10 M

(



This is the same result as is determined with the quadratic equation roots formula.

31. (M)
| |
10 7 2 10 7 2 2
10 7 2
2 10 7 2
10 7 2
1g C H NH 1mol C H NH 1.00g H O 1000mL
C H NH =
590g H O 1mL 1L 143.2g C H NH
=0.012M C H NH




p 3.92 4
b
=10 =10 =1.2 10
b
K
K



Equation:
10 7 2 2
C H NH (aq) + H O(l)

OH (aq) +

10 7 3
C H NH (aq)
+
Initial: 0.012 M

0 M ~ 0 M
Changes: M x

+ M x + M x
Equil:
( ) 0.012 M x

M x M x

2 2
10 7 3
4
b
10 7 2
OH C H NH
= = =1.2 10
C H NH 0.012 0.012
x x
K
x
+

(
(

( (

~

assuming 0.012 x

x = 0012 12 10 00012
4
. . . =

This is an almost acceptable assumption. Another

approximation cycle gives:

x = 0012 00012 12 10 00011
4
( . . ) . . =

Yet another cycle seems necessary.

4
= (0.012 0.0011) 1.2 10 0.0011M [OH ] x

= =
The quadratic equation roots formula provides the same answer.

pOH logOH log pH pOH = = 0.0011 =2.96 =14.00 =11.04

b g

pH 11.04 12
3
H O 10 10 9.1 10 M
+
= = =


32. (M) The stoichiometry of the ionization reaction indicates that

p + 7.23 8
3 6 4 2 a
H O = OC H NO , =10 =10 =5.9 10
b
K
K

( (

and

H O M
3
+ 4.53 5
=10 =3.0 10

. We let S =the molar solubility of o -nitrophenol.

Equation:
6 4 2 2
HOC H NO (aq)+H O(l)

6 4 2
OC H NO (aq) +

+
3
H O (aq)
Initial: S

0 M 0 M ~
Changes:

5
3.0 10 M

5
+3.0 10 M

5
+3.0 10 M

Equil:
(
5
3.0 10 ) M S

5
3.0 10 M

5
3.0 10 M

Chapter 16: Acids and Bases
744
K
S
a
OC H NO H O
HOC H NO
=5.9 10 = =
3.0 10
3.0 10
8
6 4 2 3
+
6 5 2
5
2
5

L
N
M
O
Q
P

c h


S S

3.0 10 =
3.0 10
5.9 10
=1.5 10 =1.5 10 +3.0 10 =1.5 10
5
5
2
8
2 2 5 2
c h
M M M M
Hence,

solubility
mol HOC H NO
L soln
g HOC H NO
mol HOC H NO
g HOC H NO L soln =
1.5 10
1
139.1
1
=2.1 /
2
6 4 2 6 4 2
6 4 2
6 4 2

33. (M) Here we determine H O
3
+
which, because of the stoichiometry of the reaction,
equals
2 3 2
C H O .

(


+ pH 4.52 5
3 2 3 2
H O =10 =10 =3.0 10 M = C H O

( (


We solve forS , the concentration of HC H O
2 3 2
in the 0.750 L solution before it dissociates.

Equation:
2 3 2 2
HC H O (aq) + H O(l)

2 3 2
C H O (aq) +

+
3
H O (aq)
Initial: S M

0 M ~ 0M
Changes:


3.0 10
5
M

+3.0 10
5

M +3.0 10
5

M
Equil:
( )
5
3.0 10 M S

3.0 10
5

M 3.0 10
5

M

5 2
5 3 2 3 2
5
2 3 2
[H O ][C H O ] (3.0 10 )
1.8 10
[HC H O ] ( 3.0 10 )
a
K
S
+

= = =



3.0 10 =1.8 10 3.0 10 =9.0 10 =1.8 10 5.4 10
5
2
5 5 10 5 10


c h c h
S S

S =
9.0 10 +5.4 10
1.8 10
=8.0 10
10 10
5
5

M Now we determine the mass of vinegar needed.

5
2 3 2 2 3 2
2 3 2 2 3 2
8.0 10 mol HC H O 60.05g HC H O 100.0g vinegar
mass vinegar =0.750L
1L soln 1mol HC H O 5.7g HC H O
=0.063 g vinegar

34. (M) First we determine OH

which, because of the stoichiometry of the reaction,

equals NH
4
+
.

pOH 2.45 3
4
pOH =14.00 pH =14.00 11.55=2.45 OH =10 =10 =3.5 10 M = NH
+
( (



We solve forS , the concentration of NH
3
in the 0.625 L solution prior to dissociation.
Chapter 16: Acids and Bases
745

Equation:
3 2
NH ( ) + H O(l) aq

4
NH (aq) +
+
OH (aq)

Initial: S M

0 M 0 M ~
Changes: 0.0035 M

+0.0035 M +0.0035 M
Equil:
( ) 0.0035 M S

0.0035 M 0.0035 M

K
S
b
NH OH
NH
= =1.8 10 =
0.0035
0.0035
4
3
5
2
+
L
N
M
O
Q
P

b g
b g


( ) ( )
2
5 5 5 8
0.0035 =1.8 10 0.0035 =1.225 10 =1.8 10 6.3 10 S S



5 8
5
1.225 10 +6.3 10
= =0.68M
1.8 10
S

Now we determine the volume of household ammonia needed

3 3
ammonia
3 3
0.68mol NH 17.03g NH 100.0g soln 1mL soln
=0.625L soln
1L soln 1mol NH 6.8g NH 0.97g soln
V


35. (D)
(a) n
proplyamine
=
PV
RT
=
( )
( )( )
-1 -1
1 atm
316 Torr 0.275 L
760 Torr
0.08206 L atm K mol 298.15 K
| |

|
\ .
=4.67 10
3
mol propylamine

[propylamine] =
n
V
=
-3
4.67 10 moles
0.500 L

=9.35 10
3
M

K
b
=10
pK
b
=10
3.43
=3.7 10
4

CH
3
CH
2
CH
2
NH
2
(aq) +H
2
O(l)

CH
3
CH
2
CH
2
NH
3
+
(aq) + OH

(aq)
Initial 9.35 10
3
M

0 M ~ 0 M
Change x M

+x M +x M
Equil. (9.35 10
3
x) M

x M x M

K
b
=3.7 10
4
=
2
-3
9.35 10
x
x
or 3.5 10
6
3. 7 10
4
(x) =x
2


x
2
+3.7 10
4
x

3.5 10
6
=0


2
=1.1 10 mL household ammonia solution
Chapter 16: Acids and Bases
746
Find x with the roots formula:



-4 -4 2 -6
3.7 10 (3.7 10 ) 4(1)( 3.5 10 )
2(1)
x

=


Therefore x =1.695 10
3
M =[OH

] pOH =2.77 and pH =11.23

(b) [OH

] = 1.7 10
3
M =[NaOH] (MM
NaOH
=39.997 g mol
1
)

n
NaOH
=(C)(V) = 1.7 10
3
M 0.500 L =8.5 10
4
moles NaOH

mass of NaOH =(n)(MM
NaOH
) =8.5 10
4
mol NaOH 39.997 g NaOH/mol NaOH

mass of NaOH =0.034 g NaOH(34 mg of NaOH)


36. (M) K
b
=10
pK
b

=10
9.5
=3.2 10
10
MM
quinoline
=129.16 g mol
1


Solubility(25 C) =
0.6 g
100 mL


Molar solubility(25 C) =
0.6 g
100 mL

1 mol 1000 mL
129.16 g 1 L
=0.046 M (note: only 1 sig fig)

C
9
H
7
N(aq) +H
2
O(l)

C
9
H
7
NH
+
(aq) + OH

(aq)
Initial 0.046 M

0 M ~ 0 M
Change x M

+x M +x M
Equil. (0.046 x) M

x M x M

3.2 10
10
=
2
0.046
x
x
~
2
0.046
x
, x =3.8 10
6
M (x <<0.046, valid assumption)

Therefore, [OH

] =4 10
6
M pOH =5.4 and pH =8.6

37. (M) If the molarity of acetic acid is doubled, we expect a lower initial pH (more H
3
O
+
(aq)

in solution) and a lower percent ionization as a result of the increase in concentration. The
ratio between [H
3
O
+
] of concentration M and concentration 2 M is 2 1.4 ~ . Therefore,
(b), containing 14 H
3
O
+
symbols best represents the conditions (~(2)
1/2
times greater).

38. (M) If NH
3
is diluted to half its original molarity, we expect a lower pH (a lower [OH

]) and a
higher percent ionization in the diluted sample. The ratio between [OH

] of concentration M
and concentration 0.5 M is 0.5 0.71 ~ . Since the diagram represent M has 24 OH

symbols,
then diagram (c), containing 17 OH

symbols would be the correct choice.

Chapter 16: Acids and Bases
747
Percent Ionization

39. (M) Let us first compute the H O
3
+
in this solution.
Equation:
Initial:
Changes:
Equil:
3 5 2 2
HC H O (aq) + H O(l)
0.45 M

M x

( ) 0.45 M x

+
3 3 5 2
H O (aq) + C H O (aq)

0 M ~ 0 M ~
+ M x + M x
M x M x

+
2 2
3 3 5 2
4.89 5
a
3 5 2
H O C H O
= = =10 =1.3 10
HC H O 0.45 0.45
x x
K
x

(
(

( (

~

x =2.4 10
3

M; We have assumed that 0.45M x , an assumption that clearly is correct.

(a)
+
3
3
equil
3 5 2
initial
H O
2.4 10 M
= = =0.0053=degree
HC H O 0.45M
o

(
(

(

of ionization

(b) % = 100% 0.0053 100% 053% ionization = o = .


40. (M) For C
2
H
5
NH
2
(ethylamine), K
b
=4.3 10
4



C
2
H
5
NH
2
(aq) +H
2
O(l)

C
2
H
5
NH
3
+
(aq) + OH

(aq)
Initial 0.85 M

0 M ~ 0 M
Change x M

+x M +x M
Equil. (0.85 x) M

x M x M

4.3 10
4
=
2
(0.85 ) M
x
x
~
2
0.85 M
x
x =0.019 M (x <<0.85, thus a valid assumption)

Degree of ionization o =
0.019M
0.85 M
=0.022 Percent ionization =o 100% =2.2 %

41. (M) Let x be the initial concentration of NH
3
, hence, the amount dissociated is 0.042 x

NH
3
(aq) +H
2
O(l)
-5
a
=1.8 10 K

NH
4
+
(aq) + OH
-
(aq)
Initial x M

0 M ~ 0 M
Change 0.042x M

+0.042x M +0.042x M
Equil. (1x0.042x) M

0.042x M 0.042x M
=0.958 x

Chapter 16: Acids and Bases
748
| |
2
4
5
b
3
equil
NH OH
0.042
=1.8 10 = = =0.00184
NH [0.958 ]
x
K x
x
+

(
(

( (


| |
5
3
initial
1.8 10
NH = 0.00978 0.0098
0.00184
x M M

= = =

42. (M)
HC
3
H
5
O
2
(aq) +H
2
O(l)
-5
a
=1.3 10 K

C
3
H
5
O
2

(aq) + H
3
O
+
(aq)
Initial 0.100 M

0 M ~ 0 M
Change x M

+x M +x M
Equil. (0.100 x) M

x M x M

1.3 10
5
=
2
0.100 M
x
x
~
2
0.100
x
x =1.1 10
3
(x <<0.100, thus a valid assumption)
Percent ionization =
0.0011
0.100
100% =1.14 %
Next we need to find molarity of acetic acid that is 1.1% ionized

HC
2
H
3
O
2
(aq) + H
2
O(l)
-5
a
=1.8 10 K

C
2
H
3
O
2

(aq) + H
3
O
+
(aq)
Initial X M

0 M ~ 0 M
Change

100
4 1.1
X M

+
100
4 1.1
X M

+
100
4 1.1
X M
Equil.
X
100
4 1.1
X
=0.9886 X M

100
4 1.1
X M
=0.0114 M

100
4 1.1
X M
=0.0114 M
1.8 10
5
=
2
1.14
100
0.9886
X
X
| |
|
\ .
=1.3 10
4
(X); X =0.138 M
Consequently, approximately 0.14 moles of acetic acid must be dissolved in one liter of
water in order to have the same percent ionization as 0.100 M propionic acid.

43. (E) We would not expect these ionizations to be correct because the calculated degree of
ionization is based on the assumption that the [HC
2
H
3
O
2
]
initial
~[HC
2
H
3
O
2
]
initial

[HC
2
H
3
O
2
]
equil.,
which is invalid at the 13 and 42 percent levels of ionization seen here.

44. (M) HC
2
Cl
3
O
2
(trichloroacetic acid) pK
a
=0.52 K
a
=10
0.52
=0.30
For a 0.035 M solution, the assumption will not work (the concentration is too small and
K
a
is too large) Thus, we must solve the problem using the quadratic equation.

HC
2
Cl
3
O
2
(aq) +H
2
O(l)

C
2
Cl
3
O
2

(aq) + H
3
O
+
(aq)
Initial 0.035 M

0 M ~ 0 M
Change x M

+x M +x M
Equil. (0.035 x) M

x M x M
Chapter 16: Acids and Bases
749

0.30 =
2
0.035
x
x
or 0.0105 0.30(x) =x
2
or x
2
+0.30x 0.0105 =0 ; solve quadratic:



2
-0.30 (0.30) 4(1)(0.0105)
2(1)
x

=
Therefore x =0.032 M =[H
3
O
+
]

Degree of ionization o =
0.032 M
0.035 M
=0.91 Percent ionization =o 100% =91. %

Polyprotic Acids

45. (E) Because H
3
PO
4
is a weak acid, there is little HPO
4
2-
(produced in the 2
nd
ionization)
compared to the H
3
O
+
(produced in the 1
st
ionization). In turn, there is little PO
4
3-
(produced
in the 3
rd
ionization) compared to the HPO
4
2-
, and very little compared to the H
3
O
+
.

46. (E) The main estimate involves assuming that the mass percents can be expressed as 0.057
g of 75% H PO
3 4
per 100. mL of solution and 0.084 g of 75% H PO
3 4
per 100. mL of
solution. That is, that the density of the aqueous solution is essentially 1.00 g/mL. Based
on this assumption, the initial minimum and maximum concentrations of H PO
3 4
is:

3 4 3 4
3 4
3 4 3 4
3 4
75gH PO 1mol H PO
0.057gimpureH PO
100gimpureH PO 98.00gH PO
[H PO ] 0.0044M
1L
100mLsoln
1000mL

= =

3 4 3 4
3 4
3 4 3 4
3 4
75gH PO 1mol H PO
0.084gimpureH PO
100gimpureH PO 98.00gH PO
[H PO ] 0.0064M
1L
100mLsoln
1000mL

= =

Equation:
+
3 4 2 2 4 3
H PO (aq) + H O(l) H PO (aq) + H O (aq)

Initial: 0.0044 M

0 M ~ 0 M
Changes: x M

+x M +x M
Equil: (0.0044 x ) M

x M x M

1
+
2
2 4 3
3 2 5
a
3 4
H PO H O
= = =7.1 10 +0.0071 3.1 10 =0
H PO 0.0044
x
K x x
x

(
(

( (

2 5 4
3 +
3
4 0.0071 5.0 10 +1.2 10
= = =3.0 10 M = H O
2 2
b b ac
x
a

(



Chapter 16: Acids and Bases
750
The set-up for the second concentration is the same as for the first, with the exception that
0.0044 M is replaced by 0.0064 M.
1
+
2
2 4 3
3 2 5
a
3 4
H PO H O
= = =7.1 10 +0.0071 4.5 10 =0
H PO 0.0064
x
K x x
x

(
(

( (

2 5 4
3 +
3
4 0.0071 5.0 10 +1.8 10
= = =4.0 10 M = H O
2 2
b b ac
x
a

(



The two values of pH now are determined, representing the pH range in a cola drink.

( )
3
pH= log 3.0 10 =2.52

( )
3
pH= log 4. 10 =2.40

47. (D)
(a) Equation:
+
2 2 3
H S(aq) + H O(l) HS (aq) + H O (aq)

Initial: 0.075 M

0 M ~ 0 M
Changes: x M

+x M +x M
Equil: (0.075 x ) M

x M +x M

| |
1
2
+
2 2
3
7 5 +
a 3
2
5 2 19
a
HS H O
= =1.0 10 = =8.7 10 M = H O
H S 0.075 0.075
HS =8.7 10 M and S = =1 10 M
x x
K x
x
K

( (

( ~

( (



(b) The set-up for this problem is the same as for part (a), with 0.0050 M replacing 0.075
M as the initial value of H S
2
.

| |
1
+
2 2
3
7 5 +
a 3
2
HS H O
= =1.0 10 = =2.2 10 M = H O
H S 0.0050 0.0050
x x
K x
x

( (

( ~

2
5 2 19
a
HS =2.2 10 M and S = =1 10 M K

( (



(c) The set-up for this part is the same as for part (a), with 1.0 10
5

M replacing 0.075
M as the initial value of H S
2
. The solution differs in that we cannot
assumex <<1.0 10
5

. Solve the quadratic equation to find the desired equilibrium
concentrations.

| |
1
+
2
3
5
2
7
a
HS H O
H S 1.0 10
= =1.0 10 =
x
x
K

( (



2 7 12
1.0 10 1.0 10 0 x x

+ =


Chapter 16: Acids and Bases
751
( )
( )
7 14 12
1.0 10 1.0 10 4 1.0 10
=
2 1
x

+

2
7 + 7 2 19
3 a
=9.5 10 M = H O HS =9.5 10 M S = =1 10 M x K

( ( (



48. (M) For H CO
2 3 1
7
, =4.4 10 K

and K
2
11
=4.7 10



(a) The first acid ionization proceeds to a far greater extent than does the second and
determines the value of H O
3
+
.
Equation:
2 3 2
H CO (aq) + H O(l)
+
3
H O (aq)
+
3
HCO (aq)

Initial: 0.045 M

0 M ~ 0 M
Changes: x M

+x M +x M
Equil: 0.045 x b g M

x M x M

K
x
x
x
1
3
+
3
2 3
2
7
2
= =
0.045
=4.4 10
0.045
H O HCO
H CO

L
N
M
O
Q
P

~ x =1.4 10 =
4
3
+

M H O

(b) Since the second ionization occurs to only a limited extent,
4
3
HCO =1.4 10 M =0.00014 M

(




(c) We use the second ionization to determine CO
3
2
.
Equation:



Initial:
Changes:
Equil:
3 2
HCO (aq) + H O(l)

0.00014 M

M x

( ) 0.00014 M x

+
3
H O (aq) +
0.00014 M
+ M x
( ) 0.00014+ M x
2
3
CO (aq)

0 M
+ M x
M x
( ) ( )
2 +
3 3
11
2
3
H O CO
0.00014+ 0.00014
= = =4.7 10
0.00014 0.00014
HCO
x x x
K
x

( (

~
(


x =4.7 10 =
11
3
2

M CO
Again we assumed that 0.00014 x M, which clearly is the case. We also note that
our original assumption, that the second ionization is much less significant than the
first, also is a valid one. As an alternative to all of this, we could have recognized
that the concentration of the divalent anion equals the second ionization constant:
CO
3
2
2
=

K .

Chapter 16: Acids and Bases
752
49. (D) In all cases, of course, the first ionization of H SO
2 4
is complete, and establishes the
initial values of H O
3
+
and HSO
4

. Thus, we need only deal with the second ionization

in each case.
(a) Equation:
2 +
4 2 4 3
HSO (aq) + H O(l) SO (aq) + H O (aq)

Initial: 0.75 M

0 M 0.75 M
Changes: x M

+x M +x M
Equil: (0.75 x ) M

x M (0.75+x ) M
( )
2
2 +
4 3
2
a 4
4
SO H O
0.75+
0.75
= =0.011= =0.011 M = SO
0.75 0.75
HSO
x x
x
K x
x

( (

(
~

(



We have assumed that 0.75 x M, an assumption that clearly is correct.
+
4 3
HSO =0.75 0.011=0.74M H O =0.75+0.011=0.76M

( (



(b) The set-up for this part is similar to part (a), with the exception that 0.75 M is
replaced by 0.075 M.
2 4
2
+0.086 8.3 10 =0
4 0.086 0.0074+0.0033
= = =0.0087M
2 2
x x
b b ac
x
a

2
4
=0.0087M = SO x

(



+
4 3
HSO =0.075 0.0087=0.066M H O =0.075+0.0088M =0.084M

( (



(c) Again, the set-up is the same as for part (a), with the exception that 0.75 M is
replaced by 0.00075 M

2
2 2
4 3
a
2 6
4
0.011(0.00075 ) 0.00075 [SO ][H O ] (0.00075 )
0.011
0.00075 0.0118 8.3 10 0 [HSO ]
x x x x x
K
x x x
+

= + +
= = =
+ =

x
b b ac
a
=
4
2
=
0.0118 1.39 10 +3.3 10
2
=6.6 10
2 4 5
4

2 4 5
4 4
=6.6 10 M = SO HSO =0.00075 0.00066=9 10 M x

( (




+ 3 +
3 3
H O =0.00075+0.00066M =1.41 10 M H O

( (

is almost twice the initial
value of H SO
2 4
. Thus, the second ionization of H SO
2 4
is nearly complete in this
dilute solution.
( )
( )
2
2 +
4 3
2
a
4
SO H O
0.075+
= =0.011= 0.011 0.075 =0.075 +
0.075
HSO
x x
K x x x
x

( (


(

Chapter 16: Acids and Bases
753

50. (D) First we determine H O
3
+
, with the calculation based on the balanced chemical
equation.

Equation: ( ) ( ) ( ) ( ) ( )
+
2 2 2 3
4 4
HOOC CH COOH aq +H O(l) HOOC CH COO aq +H O aq

Initial: 0.10 M

0 M ~ 0 M
Changes: x M

+x M +x M
Equil: 0.10 x b g M

x M x M

K
x x
x
x
a
H O HOOC CH COO
HOOC CH COOH
1
= =3.9 10 =
0.10 0.10
3
+
2
4
2
4
5
2
b g

F
H
I
K

~

x = =

010 39 10 20 10
5 3
. . . ] M =[H O
3
+


We see that our simplifying assumption, that 0.10 x M, is indeed valid. Now we
consider the second ionization. We shall see that very little H O
3
+
is produced in this
ionization because of the small size of two numbers: K
a
2
and HOOC CH COO
2
4
b g

.
Again we base our calculation on the balanced chemical equation.

Equation: ( ) ( ) ( ) ( ) ( )
+
2 2 2 3
4 4
HOOC CH COO aq +H O(l) OOC CH COO aq +H O aq

Initial:
2.0 10
3

0 M
2.0 10
3

M
Changes: y M

+y M +y M
Equil: 0.0020 y b g M

y M 0.0020+y b g M

K
y y
y
y
a
H O OOC CH COO
HOOC CH COO
2
= =3.9 10 =
0.0020+
0.0020
0.0020
0.0020
3
+
2
4
2
4
6

F
H
I
K

~
b g
b g


6
2 4
3.9 10 M =[ OOC(CH ) COO ] y

=

Again, we see that our assumption, that 0.0020 y M, is valid. In addition, we also note
that virtually no H O
3
+
is created in this second ionization. The concentrations of all
species have been calculated above, with the exception of OH

.

( )
14
12 w
2
3 4 +
3
1.0 10
OH = = =5.0 10 M; HOOC CH COOH =0.10M
2.0 10 H O
K

( (

(



( ) ( )
+ 3 6
3 2 2
4 4
H O = HOOC CH COO =2.0 10 M; OOC CH COO =3.9 10 M

( ( (


Chapter 16: Acids and Bases
754

51. (M)
(a) Recall that a base is a proton acceptor, in this case, accepting H
+
fromH O
2
.
1
2
+
20 24 2 2 2 20 24 2 2 b
2+ +
20 24 2 2 2 20 24 2 2 2 b
First ionization: C H O N +H O C H O N H +OH p =6.0
Second ionization: C H O N H +H O C H O N H +OH p =9.8
K
K

(b)

1
3
20 24 2 2
6.0 6
b
1mol quinine
1.00gquinine
324.4gquinine
[C H O N ] 1.62 10 M
1L
1900 mL
1000mL
10 1 10 K

= =

= =


Because the OH
-
produced in (a) suppresses the reaction in (b) and since K
b1
>> K
b2
,
the solutions pH is determined almost entirely by the first base hydrolysis of the
first reaction. Once again, we set-up the I.C.E. table and solve for the [OH

] in this
case:
Equation:
+
20 24 2 2 2 20 24 2 2
C H O N (aq) + H O(l) C H O N H (aq) + OH (aq)

Initial: 0.00162 M

0 M ~ 0 M
Changes: x M

+x M +x M
Equil: 0.00162 x b g M

x M x M

1
+
2 2
20 24 2 2
6 5
b
20 24 2 2
C H O N H OH
= =1 10 = 4 10 M
C H O N 0.00162 0.00162
x x
K x
x

(
(

( (

~ ~

The assumption 0.00162 x , is valid.
( )
5
pOH = log 4 10 =4.4 pH =9.6

52. (M) Hydrazine is made up of two NH
2
units held together by a nitrogennitrogen single
bond:

H
N
H H
N
H

(a) N
2
H
4
(aq) +H
2
O(l)

N
2
H
5
+
(aq) +OH
-
(aq) K
b1
=10
-6.07
= 8.5 10
-7

(b) N
2
H
5
+
(aq) +H
2
O(l)

N
2
H
6
2+
(aq) +OH
-
(aq) K
b2
=10
-15.05
= 8.9 10
-16
Because the OH
-
produced in (a) suppresses the reaction in (b) and since K
b1
>> K
b2
,
the solutions pH is determined almost entirely by the first base hydrolysis reaction (a).
Thus we need only solve the I.C.E. table for the hydrolysis of N
2
H
4
in order to find the
[OH
-
]
equil
, which will ultimately provide us with the pH via the relationship
[OH
-
][H
3
O
+
] =1.00 10
-14
.

Chapter 16: Acids and Bases
755

Reaction:
N
2
H
4
(aq) + H
2
O(l)

N
2
H
5
+
(aq) + OH
-
(aq)
Initial: 0.245 M

0 M ~ 0 M
Changes: x M

+x M +x M
Equil: (0.245 x ) M

x M x M

1
+
2 2
2 5
7 4 -
b equil
2 4
14
+ 11 11
3 4
N H OH
= =8.5 10 = = =4.56 10 M =[OH ]
N H 0.245 0.245
1.0 10
Thus, [H O ] = =2.19 10 M pH =-log(2.19 10 ) =10.66
4.56 10
x x
K x
x

(
(

( (

53. (E) Protonated codeine hydrolyzes water according to the following reaction:
18 21 3 2 18 21 3 3
a
b a
C H O NH H O C H O N H O
pK 6.05
pK 14 pK 7.95
+ +
+ +
=
= =

54. (E) Protonated quinoline is, of course, an acid, which hydrolyzes water to give a
hydronium ion. The reaction is as follows:

( )
9 7 2 9 7 3
14
5 W
b 10
a
5
b
C H NH H O C H N H O
K 1 10
K 1.6 10
K 6.3 10
pK log 1.6 10 4.8
+ +

+ +

= = =

= =

55. (E) The species that hydrolyze are the cations of weak bases, namely, NH
4
+
and
C H NH
6 5 3
+
, and the anions of weak acids, namely, NO
2

and C H O
7 5 2

.

(a) ( ) ( ) ( ) ( ) ( )
+ +
4 3 2 3 3 3
NH aq +NO aq +H O(l) NH aq +NO aq +H O aq

(b) ( ) ( ) ( ) ( ) ( )
+ +
2 2 2
Na aq +NO aq +H O(l) Na aq +HNO aq +OH aq

(c) ( ) ( ) ( ) ( ) ( )
+ +
7 5 2 2 7 5 2
K aq +C H O aq +H O(l) K aq +HC H O aq +OH aq

(d) ( ) ( ) ( ) ( )
+ +
2
K aq +Cl aq +Na aq +I aq +H O(l) no reaction



(e) ( ) ( ) ( ) ( ) ( )
+ +
6 5 3 2 6 5 2 3
C H NH aq +Cl aq +H O(l) C H NH aq +Cl aq +H O aq

Chapter 16: Acids and Bases
756
56. (E) Recall that, for a conjugate weak acidweak base pair, K K K
a b w
=
(a)
14
6 + w
a 5 5
9
b
1.0 10
= = =6.7 10 for C H NH
1.5 10
K
K
K

(b)
14
11 w
b 2
4
a
1.0 10
= = 5.6 10 for CHO
1.8 10
K
K
K

(c)
14
4 w
b 6 5
10
a
1.0 10
= = 1.0 10 forC H O
1.0 10
K
K
K

57. (E)
(a) Because it is composed of the cation of a strong base, and the anion of a strong acid,
KCl forms a neutral solution (i.e., no hydrolysis occurs).

(b) KF forms an alkaline (basic) solution. The fluoride ion, being the conjugate base of
a relatively strong weak acid, undergoes hydrolysis, while potassium ion, the weakly
polarizing cation of a strong base, does not react with water.

2
F (aq)+H O(l) HF(aq)+OH (aq)

(c) NaNO
3
forms a neutral solution, being composed of a weakly polarizing cation and
anionic conjugate base of a strong acid. No hydrolysis occurs.

(d) Ca OCl b g
2
forms an alkaline (basic) solution, being composed of a weakly polarizing
cation and the anion of a weak acid Thus, only the hypochlorite ion hydrolyzes.

2
OCl (aq)+H O(l) HOCl(aq)+OH (aq)

(e) NH NO
4 2
forms an acidic solution. The salt is composed of the cation of a weak base
and the anion of a weak acid. The ammonium ion hydrolyzes:

( )
+ + 10
4 2 3 3 a
NH (aq)+H O(l) NH aq +H O (aq) =5.6 10 K

as does the nitrite ion:

11
2 2 2 b
NO (aq)+H O(l) HNO (aq)+OH (aq) =1.4 10 K

Since NH
4
+
is a stronger acid than NO
2

is a base (as shown by the relative sizes of

the K values), the solution will be acidic. The ionization constants were computed
from data in Table 16-3 and with the relationshipK K K
w a b
= .

For NH For NO
a b 4
+
14
5
10
2
14
4
11
, =
1.0 10
1.8 10
=5.6 10 , =
1.0 10
7.2 10
=1.4 10 K K

5 4
b 3 a 2
Where1.8 10 = of NH and 7.2 10 = of HNO K K


Chapter 16: Acids and Bases
757
58. (E) Our list in order of increasing pH is also in order of decreasing acidity. First we look
for the strong acids; there is justHNO
3
. Next we look for the weak acids; there is only
one, HC H O
2 3 2
. Next in order of decreasing acidity come salts with cations from weak
bases and anions from strong acids; NH ClO
4 4
is in this category. Then come salts in
which both ions hydrolyze to the same degree; NH C H O
4 2 3 2
is an example, forming a pH-
neutral solution. Next are salts that have the cation of a strong base and the anion of a
weak acid; NaNO
2
is in this category. Then come weak bases, of which NH aq
3
b g is an
example. And finally, we terminate the list with strong bases: NaOH is the only one.
Thus, in order of increasing pH of their 0.010 M aqueous solutions, the solutes are:
HNO HC H O NH ClO NH C H O NaNO NH NaOH
3 2 3 2 4 4 4 2 3 2 2 3
< < < < < <

59. (M) NaOCl dissociates completely in aqueous solution intoNa aq
+
b g , which does not
hydrolyze, and OCl
-
(aq), which undergoes base hydrolysis. We determine [OH
-
] in a 0.089 M
solution of OCl

, finding the value of the hydrolysis constant from the ionization constant of
HOCl, K
a
=2.9 10
8

.

( )

2
Equation: OCl (aq) + H O(l) HOCl(aq) + OH (aq)
Initial : 0.089M 0M 0M
Changes: M + M + M
Equil : 0.089 M M M
x x x
x x x

~

K
K
K
x
x
x
b
w
a
HOCl OH
OCl
= =
1.0 10
2.9 10
=3.4 10 = =
0.089 0.089
14
8
7
2 2

4
1.7 10 M 0.089, the assumption is valid.

<<

( )
4 4
=1.7 10 M = OH ; pOH= log 1.7 10 =3.77, pH=14.00 3.77=10.23 x

(



60. (M) dissociates completely in aqueous solution intoNH aq
4
+
b g , which hydrolyzes,
andCl aq

b g , which does not. We determine H O

3
+
in a 0.123 M solution of NH
4
+
, finding
the value of the hydrolysis constant from the ionization constant of
3
NH ,
5
b
=1.8 10 K

.

( )
+ +
4 2 3 3
Equation: NH (aq) + H O(l) NH (aq) H O (aq)
Initial : 0.123M 0M 0M
Changes: M + M + M
Equil : 0.123 M M M
x x x
x x x
+
~

K
K
K
x
x
x
b
w
a
3
NH H O
NH
= =
1.0 10
1.8 10
=5.6 10 =
0123 0123
14
5
10 3
4
2 2

+
+
[ ][ ]
[ ] . .


Chapter 16: Acids and Bases
758
6
8.3 10 M <<0.123, the assumption is valid

( )
6 + 6
3
=8.3 10 M = H O ; pH= log 8.3 10 =5.08 x

(



61. (M) KC H O
6 7 2
dissociates completely in aqueous solution into K aq),
+
( which does not
hydrolyze, and the ion C H O (aq)
6 7 2

, which undergoes base hydrolysis. We determine

OH

in 0.37 M KC H O
6 7 2
solution using an I.C.E. table.
Note:
p 4.77 5
a
=10 =10 =1.7 10
K
K



( )
6 7 2 2 6 7 2
Equation: C H O (aq) + H O(l) HC H O (aq) + OH (aq)
Initial : 0.37M 0M 0M
Changes: M + M + M
Equil : 0.37 M M M
x x x
x x x

~

K
K
K
x
x
x
b
w
a
6 7 2
6 7
HC H O ][OH
C H O
= =

= = =

10 10
17 10
59 10
037 037
14
5
10
2
2 2
.
.
.
[ ]
[ ] . .


( )
5 5
=1.5 10 M = OH , pOH= log 1.5 10 =4.82, pH=14.00 4.82=9.18 x

(



62. (M)
( )

+ +
5 5 2 5 5 3
Equation: C H NH (aq) + H O(l) C H N(aq) + H O (aq)
Initial : 0.0482M 0M 0M
Changes: M + M + M
Equil : 0.0482 M M M
x x x
x x x
~

| |
+
14 2 2
5 5 3
6 w
a 9 +
b 5 5
C H N H O
1.0 10
= = =6.7 10 = =
1.5 10 0.0482 0.0482 C H NH
K x x
K
K x

~
(



4
5.7 10 M <<0.0482 M, the assumption is valid

( )
4 + 4
3
=5.7 10 M = H O , pH= log 5.7 10 =3.24 x

(



63. (M)
(a)
2
2 + 8
3 2 3 3 a a ,Sulfurous
HSO +H O H O +SO = =6.2 10 K K

1
14
13 w
3 2 2 3 b
2
a ,Sulfurous
1.0 10
HSO +H O OH +H SO = = =7.7 10
1.3 10
K
K
K

SinceK K
a b
> , solutions of HSO
3

are acidic.


Chapter 16: Acids and Bases
759
(b)
2
+ 2 19
2 3 a a ,Hydrosulfuric
HS +H O H O +S = =1 10 K K

1
14
7 w
2 2 b 7
a ,Hydrosulfuric
1.0 10
HS +H O OH +H S = = =1.0 10
1.0 10
K
K
K

SinceK K
a b
< , solutions of HS

are alkaline, or basic.

(c)
3
2 3 + 13
4 2 3 4 a a ,Phosphoric
HPO +H O H O +PO = =4.2 10 K K

2
14
2 7 w
4 2 2 4 b 8
a ,Phosphoric
1.0 10
HPO +H O OH +H PO = = =1.6 10
6.3 10
K
K
K

SinceK K
a b
< , solutions of HPO
4
2
are alkaline, or basic.

64. (M) pH=8.65 (basic). We need a salt made up of a weakly polarizing cation and an
anion of a weak acid, which will hydrolyze to produce a basic solution. The salt (c) KNO
2

satisfies these requirements. (a)NH Cl
4
is the salt of the cation of a weak base and the anion
of a strong acid, and should form an acidic solution. (b) KHSO
4
and (d) NaNO
3
have
weakly polarizing cations and anions of strong acids; they form pH-neutral solutions.
pOH OH M =14.00 8.65=5.35 =10 =4.5 10
5.35 6




( )
2 2 2
6 6 6
6 6 6
Equation: NO (aq) + H O(l) HNO (aq) + OH (aq)
Initial: 0M 0M
Changes: 4.5 10 M +4.5 10 M +4.5 10 M
Equil: 4.5 10 M 4.5 10 M 4.5 10 M
S
S



~

K
K
K S
b
w
a
HNO OH
NO
= =
1.0 10
7.2 10
=1.4 10 = =
4.5 10
4.5 10
14
4
11
2
2
6
2
6

c h

( )
| |
2
6
6 6
2 11
4.5 10
4.5 10 = =1.4M =1.4M +4.5 10 =1.4M = KNO
1.4 10
S S

Molecular Structure and Acid-Base Behavior

65. (M)
(a) HClO
3
should be a stronger acid than isHClO
2
. In each acid there is an H O Cl
grouping. The remaining oxygen atoms are bonded directly to Cl as terminal O
atoms. Thus, there are two terminal O atoms in HClO
3
and only one inHClO
2
.
For oxoacids of the same element, the one with the higher number of terminal
oxygen atoms is the stronger. With more oxygen atoms, the negative charge on the
conjugate base is more effectively spread out, which affords greater stability.
HClO
3
:
1
2
a
=5 10 K and HClO
2
: K
a
=1.1 10
2

.

Chapter 16: Acids and Bases
760
(b) HNO
2
and H CO
2 3
each have one terminal oxygen atom. The difference? N is more
electronegative than C, which makes
( )
4
2 a
HNO =7.2 10 K

, a stronger acid than
H
2
CO
3

( )
1
7
a
=4.4 10 K

.

(c) H PO
3 4
and H SiO
2 3
have the same number (one) of terminal oxygen atoms.
They differ in P being more electronegative than Si, which makes
3 4
H PO
( )
1
3
a
=7.1 10 K

a stronger acid than
( )
1
10
2 3 a
H SiO =1.7 10 K

.

66. (E) CCl COOH
3
is a stronger acid than CH COOH
3
because in CCl COOH
3
there are
electronegative (electro-withdrawing) Cl atoms bonded to the carbon atom adjacent to the
COOH group. The electron-withdrawing Cl atoms further polarize the OH bond and
enhance the stability of the conjugate base, resulting in a stronger acid.

67. (E)
(a) HI is the stronger acid because the HI bond length is longer than the HBr
bond length and, as a result, HI is easier to cleave.

(b) HOClO is a stronger acid than HOBr because
(i) there is a terminal O in HOClO but not in HOBr
(ii) Cl is more electronegative than Br.

(c) H CCH CCl COOH
3 2 2
is a stronger acid than I CCH CH COOH
3 2 2
both because Cl is
more electronegative than is I and because the Cl atoms are closer to the acidic
hydrogen in the COOH group and thus can exert a stronger e

withdrawing effect on
the OH bond than can the more distant I atoms.


68. (M) The weakest of the five acids isCH CH COOH
3 2
. The reasoning is as follows. HBr is a
strong acid, stronger than the carboxylic acids. A carboxylic acidsuch as CH ClCOOH
2

and CH FCH COOH
2 2
with a strongly electronegative atom attached to the hydrocarbon
chain will be stronger than one in which no such group is present. But the I atom is so
weakly electronegative that it barely influences the acid strength. Acid strengths of some
of these acids (as values of p
a
K ) follow. (Larger values of p
a
K indicate weaker acids.)
Strength: ( ) ( )
3 2 3 2 2 2
CH CH COOH 4.89 CI COOH CH FCH COOH CH ClCOOH HBr 8.72 < < < <

69. (E) The largest K
b
(most basic) belongs to (c) CH
3
CH
2
CH
2
NH
2
(hydrocarbon chains have
the lowest electronegativity). The smallest K
b
(least basic) is that of (a) o-chloroaniline
(the nitrogen lone pair is

delocalized (spread out over the ring), hence, less available to
accept a proton (i.e., it is a poorer Brnsted base)).

70. (E) The most basic species is (c) CH
3
O

(methoxide ion). Methanol is the weakest acid,

thus its anion is the strongest base. Most acidic: (b) ortho-chlorophenol. In fact, it is the
only acidic compound shown.
Chapter 16: Acids and Bases
761

Lewis Theory of Acids and Bases

71. (E)
(a) acid is CO
2
and base is H
2
O
O C O +
H
O
H
O
C
O
O H
+
O
H
H
H

(b) acid is BF
3
and base is H
2
O
F
B
F F
+
H
O
H
F
B
F F
H
O
H

(c) acid is H
2
O and base is O
2


O O
2-
+
H
O
H
O H 2

(d) acid is SO
3
and base is S
2

S S
2-
+
O
S
O O
O
S
O O
S
2-

72. (E)
(a) SOI
2
is the acid, and BaSO
3
the base.
(b)

3
HgCl is the acid, Cl

the base.

73. (E) A Lewis base is an electron pair donor, while a Lewis acid is an electron pair acceptor.
We draw Lewis structures to assist our interpretation.

(a)

O H


The lone pairs on oxygen can readily be donated;
this is a Lewis base.

(b)
H C C B
H H
H H
C C H
H
H
H
H
C H
2
C H
3
The incomplete octet of B provides a site for
acceptance of an electron pair, this is a Lewis acid.
Chapter 16: Acids and Bases
762
(c)
H N C H
H H
H

The incomplete octet of B provides a site for
acceptance of an electron pair, this is a Lewis acid.

74. (M) A Lewis base is an electron pair donor, while a Lewis acid is an electron pair acceptor.
We draw Lewis structures to assist our interpretation.

(a) According to the following Lewis structures, SO
3
appears to be the electron pair
acceptor (the Lewis acid), and H O
2
is the electron pair donor (the Lewis base).
(Note that an additional sulfur-to-oxygen bond is formed upon successful attachment
of water to SO
3
.)







(b) The Zn metal center in Zn OH b g
2
accepts a pair of electrons. Thus, Zn OH b g
2
is a
Lewis acid. OH

donates the pair of electrons that form the covalent bond.

Therefore, OH

is a Lewis base. We have assumed here that Zn has sufficient

covalent character to form coordinate covalent bonds with hydroxide ions.
O H
O H Zn O H Zn O O
O
O
H H
H
H
2 +
2-


75. (M) (a)
O H
+
B O H O H
O
H
B O H O H
O
H
O
H
-



Acid: e

pair acceptor
Base: e

pair donor

O S
O
H O H +
O
O S
O
O
H O H
Base: e

pair donor Acid: e

pair acceptor
Chapter 16: Acids and Bases
763
(b)
H H N
H H
N
H
O
H
H H O
H
H
H H N
H H
N
The actual Lewis acid is H
+
, which is supplied by H
3
O
+


(c)
H
C H
H
C
H
H
O C
H
H
C
H
H
H
Base: electron pair donor Acid: electron pair acceptor
F
F B F
F
F F
H
C H
H
C
H
H
C
H
H
C
H
H
H
B
O


76. (E) The C in a CO
2
molecule can accept a pair of electrons. Thus, CO
2
is the Lewis acid.
The hydroxide anion is the Lewis base as it has pairs of electrons it can donate.
O C O
+
O H
O C O
O H
-
acid base


77. (E)
2 3
I (aq) I (aq) I (aq)

+

I I I
Lewis acid
(e
-
pair acceptor)
Lewis base
(e
-
pair donor)
I I I


78. (E)
(a)
Lewis acid
(e
-
pair acceptor)
Lewis base
(e
-
pair donor)
H F
Sb
F
F
F
F
F
Sb
F
F
F
F
F
F
H



(b)
Lewis acid
(e
-
pair acceptor)
Lewis base
(e
-
pair donor)
H F B F
F
F
B F
F
F
F
H


Chapter 16: Acids and Bases
764
79. (E)

H O H O S O O S
O
O
H
H
O S
O
O
H
H
Lewis base
(e
-
pair donor)
Lewis acid
(e
-
pair acceptor)



80. (E)
H
N
H
H 2 Ag
+
H
N H
H
H N
H
H
Ag
+
electron pair donor electron pair acceptor ammonia aduct



INTEGRATIVE AND ADVANCED EXERCISES

81. (E) We use (ac) to represent the fact that a species is dissolved in acetic acid.
(a)
2 3 2 2 3 2 2 3 2 2 3 2
C H O (ac) HC H O (l) HC H O (l) C H O (ac)

+ +

C
2
H
3
O
2

is a base in acetic acid.

(b)
2 2 3 2 3 2 3 2
H O(ac) HC H O ( ) H O (ac) C H O (ac) l
+
+ +

Since H
2
O is a weaker acid than HC
2
H
3
O
2
in aqueous solution, it will also be weaker in
acetic acid. Thus H
2
O will accept a proton from the solvent acetic acid, making H
2
O a
base in acetic acid.

(c)
2 3 2 2 3 2 2 2 3 2 2 3 2
HC H O (l) HC H O ( ) H C H O (ac) C H O (aq) l
+
+ +

Acetic acid can act as an acid or a base in acetic acid.

(d)
4 2 3 2 4 2 2 3 2
HClO (ac) HC H O (l) ClO (ac) H C H O (ac)

+ +

Since HClO
4
is a stronger acid than HC
2
H
3
O
2
in aqueous solution, it will also be
stronger in acetic acid. Thus, HClO
4
will donate a proton to the solvent acetic acid,
making HClO
4
an acid in acetic acid.

82. (E) Sr(OH)
2
(sat'd)

Sr
2+
(aq) +2 OH
-
(aq)
-0.88
pOH 14 pH=14-13.12 0.88
[OH ] 10 0.132 M

= =
= =

ammoniaadduct
Chapter 16: Acids and Bases
765

3
dilute
3
3
10.0 ml concentrate
[OH ] 0.132M ( ) 5.28 10 M
250.0 mL total
(10.0 ml ) (5.28 10 M)
[HCl] 2.10 10 M
25.1 mL

= =

= =


83. (M)
(a) H
2
SO
4
is a diprotic acid. A pH of 2 assumes no second ionization step and the second
ionization step alone would produce a pH of less than 2, so it is not matched.
(b) pH 4.6 matched; ammonium salts hydrolyze to form solutions with pH <7.
(c) KI should be nearly neutral (pH 7.0) in solution since it is the salt of a strong acid (HI)
and a strong base (KOH). Thus it is not matched.
(d) pH of this solution is not matched as it's a weak base. A 0.002 M solution of KOH has a
pH of about 11.3. A 0.0020 M methylamine solution would be lower (~10.9).
(e) pH of this solution is matched, since a 1.0 M hypochlorite salt hydrolyzes to form a
solution of ~pH 10.8.
(f) pH of this solution is not matched. Phenol is a very weak acid (pH >5).
(g) pH of this solution is 4.3. It is close, but not matched.
(h) pH of this solution is 2.1, matched as it's a strong organic acid.
(i) pH of this solution is 2.5, it is close, but not matched.

84. (M) We let [H
3
O
+
]
a
=0.500 [H
3
O
+
]
i
pH =log[H
3
O
+
]
i

pH
a
=log[H
3
O
+
]
a
=log(0.500 [H
3
O
+
]
i
) =log [H
3
O
+
]
i
log (0.500) =pH
i
+0.301
The truth of the statement has been demonstrated. Remember, however, that the extent of
ionization of weak acids and weak bases in water increases as these solutions become more
and more dilute. Finally, there are some solutions whose pH doesnt change with dilution,
such as NaCl(aq), which has pH =7.0 at all concentrations.


85. (M) Since a strong acid is completely ionized, increasing its concentration has the effect of
increasing [H
3
O
+
] by an equal degree. In the case of a weak acid, however, the solution of
the K
a
expression gives the following equation (if we can assume that [H
3
O
+
] is negligible
compared to the original concentration of the undissociated acid, [HA]). x
2
=K
a
[HA] (where
x =[H
3
O
+
]), or ] HA [
a
K x = . Thus, if [HA] is doubled, [H
3
O
+
] increases by 2 .


86. (E) H
2
O(l) +H
2
O(l) H
3
O
+
(aq)

+OH
-
(aq) AH
o
=(-230.0 kJ mol) (-285.8 kJ mol
-1
)
=55.8 kJ
Since AH
o
is positive, the value of K
eq
is larger at higher temperatures. Therefore, the ionic
products increase with increasing temperature. Le Ch teliers principle or the Vant Hoff
equation would show this to be true.


Chapter 16: Acids and Bases
766
87. (M) First we assume that molarity and molality are numerically equal in this dilute aqueous
solution. Then compute the molality that creates the observed freezing point, with K
f
=1.86
C/m for water.


f
0.096 C
0.052 concentration 0.052 M
1.86 C/
f
T
m m
K m
A
= = = =

This is the total concentration of all species in solution, ions as well as molecules. We base
our remaining calculation on the balanced chemical equation.


4 5 2 2 4 5 2 3
Equation: HC H O (aq) H O C H O (aq) H O (aq)
Initial: 0.0500 M 0 M 0 M
Changes: M M M
Equil: (0.0500 )
x x x
x
+
+ +
+ +

M M M x x


6 6
2
5 4 5 2 3 6
a
4 5 2 6
Total conc. 0.051 M (0.0500 ) M M M 0.0500 M M 0.001 M
[C H O ][H O ] (0.001 )
5 10
[HC H O ] 0.0500 0.0500 0.001
x x x x x
x x
K
x
+

= = + + = + =

= = = =



88. (D) [H
3
O
+
] =10
pH
=10
5.50
=3.2 10
6
M
(a) To produce this acidic solution we could not use 15 M NH
3
(aq), because aqueous
solutions of NH
3
have pH values greater than 7 owing to the fact that NH
3
is a weak
base.
(b)
6
5 3
HCl
3
3.2 10 mol H O 1 mol HCl 1 L soln
V 100.0 mL 2.7 10 mL 12 M HCl soln
1 L 12 mol HCl 1 mol H O
+

= =
(very unlikely, since this small a volume is hard to measure)

(c) K
a
=5.6 10
10
for NH
4
+
(aq)
4 2 3 3
6 6 6
6
Equation: NH (aq) H O(l) NH (aq) H O (aq)
Initial: M 0 M 0 M
Changes: 3.2 10 M 3.2 10 M 3.2 10 M
Equil: ( 3.2 10 ) M
c
c
+ +

+ +
~
+ +

( )
6 6
6 6
10 3 3
a
6
4
3.2 10 M 3.2 10 M
[NH ][H O ] (3.2 10 )(3.2 10 )
5.6 10
[NH ] 3.2 10
K
c

+

+


= = =


Chapter 16: Acids and Bases
767
Cl NH g 096 . 0
Cl NH mol 1
Cl NH g 49 . 53
NH mol 1
Cl NH mol 1
mL 1000
NH mol 0.018
mL 100.0 mass Cl NH
M 018 . 0 ] [NH M 10 8 . 1
10 6 . 5
) 10 2 . 3 (
10 2 . 3
4
4
4
4
4 4
4
4
2
10
2 6
6
= =
= =

=
+
+
+

c
This would be an easy mass to measure on a laboratory three decimal place balance.

(d) The set-up is similar to that for NH
4
Cl.
2 3 2 2 2 3 2 3
6 6
Equation: HC H O (aq) H O (l) C H O (aq) H O (aq)
Initial: M 0 M 0 M
Changes: 3.2 10 M 3.2 10 M
c
+

+ +
~
+

6
6 6 6
3.2 10 M
Equil: ( 3.2 10 ) M 3.2 10 M 3.2 10 M c

+



6 6
5 2 3 2 3
a 6
2 3 2
6 2
6 7 6
2 3 2 5
6
2 3 2
2 3 2
[C H O ][H O ] (3.2 10 )(3.2 10 )
K 1.8 10
[HC H O ] 3.2 10
(3.2 10 )
3.2 10 5.7 10 [HC H O ] 3.8 10
1.8 10
3.8 10 mol HC H O 60.
HC H O mass 100.0 mL
1000 mL
c
c c
+

= = =

= = = =

=
2 3 2
2 3 2
5
2 3 2
05 g HC H O
1 mol HC H O
2.3 10 g HC H O (an almost impossibly small mass to measure
using conventional laboratory scales)

=

89. (M)
(a) 1.0 10
-5
M HCN:
HCN(aq) + H
2
O(l)
10
6.2 10
a
K

=

H
3
O
+
(aq) + CN
-
(aq)
Initial: 1.0 10
-5
M 1.0 10
-7
M 0 M
Change: x +x +x
Equilibrium: (1.0 10
-5
-x) M (1.0 10
-7
+x) M x


7
10 15 10 7 2
5
2 7 15
7 7 2 15
7
(1.0 10 )
6.2 10 6.2 10 6.2 10 1.0 10
(1.0 10 )
1.006 10 6.2 10 0
1.006 10 (1.006 10 ) 4(1)( 6.2 10 )
1.44 10
2(1)
x x
x x x
x
x
x

+
= = +

+ =

= =

Final pH =-log[H
3
O
+
] =-log(1.0 10
-7
+ 1.44 10
-7
) =6.61


Chapter 16: Acids and Bases
768
(b) 1.0 10
-5
M C
6
H
5
NH
2
:
C
6
H
5
NH
2
(aq) + H
2
O(l)
10
7.4 10
a
K

=

OH
-
(aq) + C
6
H
5
NH
3
+
(aq)
Initial: 1.0 10
-5
M 1.0 10
-7
M 0 M
Change: x +x +x
Equilibrium: (1.0 10
-5
x) M (1.0 10
-7
+x) M x


7
10 15 10 7 2
5
2 7 15
7 7 2 15
8
(1.0 10 )
7.4 10 7.4 10 7.4 10 1.0 10
(1.0 10 )
1.0074 10 7.4 10 0
1.0074 10 (1.0074 10 ) 4(1)( 7.4 10 )
4.93 10 M
2(1)
x x
x x x
x
x
x

+
= = +

+ =

= =

Final pOH =-log[OH
-
] =-log(1.0 10
-8
+ 4.93 10
-7
) =6.83 Final pH =7.17

90. (D)
(a) For a weak acid, we begin with the ionization constant expression for the weak acid, HA.
2 2 2
3
a
[H O ][A ] [H ] [H ] [H ]
[HA] [HA] M [H ] M
K
+ + + +
+
= = = ~

The first modification results from realizing that [H
+
] =[A

]. The second modification

is based on the fact that the equilibrium [HA] equals the initial [HA] minus the amount
that dissociates. And the third modification is an approximation, assuming that the
amount of dissociated weak acid is small compared to the original amount of HA in
solution. Now we take the logarithm of both sides of the equation.
M M
c
K log ] [H log 2 log ] [H log
] H [
log log
2
2
a
= = =
+ +
+

1 1
a a a 2 2
2 log [H ] log log 2 pH p log pH p log K M K M K M
+
= = =
For a weak base, we begin with the ionization constant expression for a weak base, B.
M M
K
2 2 2
b
] OH [
] OH [
] OH [
[B]
] OH [
[B]
] OH ][ BH [

+
~

= = =
The first modification results from realizing that [OH

] =[BH
+
]. The second
modification is based on the fact that the equilibrium [B] equals the initial [B] minus
the amount that dissociates. And the third modification is an approximation, assuming
that the amount of dissociated weak base is small compared to the original amount of B
in solution. Now we take the logarithm of both sides of the equation.
2
2
b
1 1
b b b 2 2
1 1
b 2 2
[OH ]
log K log log [OH ] log M 2 log [OH ] log M
M
2 log [OH ] log K log M 2 pOH pK log M pOH pK logM
pH 14.00 pOH 14.00 pK log M

= = =
= = =
= = +


The anion of a relatively strong weak acid is a weak base. Thus, the derivation is the
same as that for a weak base, immediately above, with the exception of the value for
K
b
. We now obtain an expression for pK
b
.
Chapter 16: Acids and Bases
769

a w b a w b
a w
a
w
b
a
w
b
p p p log log log
log log log log
K K K K K K
K K
K
K
K
K
K
K
= = + =
= = =

Substitution of this expression for pK
b
into the expression above gives the following result.
M K K log p p 14.00 pH
2
1
a 2
1
w 2
1
+ + =
(b) 0.10 M HC
2
H
3
O
2
pH =0.500 4.74 0.500 log 0.10 =2.87

2 3 2 2 2 3 2 3
Equation: HC H O (aq) H O(l) C H O (aq) H O (aq)
Initial: 0.10 M 0 M 0 M
Changes: M M M
Equil: (0.1
x x x
+
+ +
~
+ +

0 ) M M M x x x


2
5 3 2 3 2
a
2 3 2
5 3 3
[H O ][C H O ]
1.8 10
[HC H O ] 0.10 0.10
0.10 1.8 10 1.3 10 M, pH log(1.3 10 ) 2.89
x x x
K
x
x
+

= = = ~

= = = =


. pH 14.00 0.500 4.74 0.500 log 0.10 11.13 = + =
3
0 10 M NH

3 2 4
Equation: NH (aq) H O(l) NH (aq) OH (aq)
Initial: 0.10 M 0 M 0 M
Changes: M M M
Equil: (0.10 ) M
x x x
x
+
+ +
~
+ +

M M x x

2
5 5 3 4
b
3
3
[NH ][OH ]
1.8 10 0.10 1.8 10 1.3 10 M
[NH ] 0.10 0.10
pOH log(1.3 10 ) 2.89 pH 14.00 2.89 11.11
x x x
K x
x
+

= = = ~ = =

= = = =


3
. pH 14.00 0.500 14.00 0.500 4.74 0.500 log 0.10 8.87 = + + =
2 2
0 10 M NaC H O

2 3 2 2 2 3 2
Equation: C H O (aq) H O(l) HC H O (aq) OH (aq)
Initial: 0.10 M 0 M 0 M
Changes: M M M
Equil: (0.10 )
x x x
x

+ +
~
+ +

14 2
2 3 2
a
5
2 3 2
14
6 6
5
M M M
[OH ][HC H O ] 1.0 10
0.10 0.10 [C H O ] 1.8 10
0.10 1.0 10
7.5 10 M pOH log(7.5 10 ) 5.12
1.8 10
pH 14.00 5.12 8.88
x x
x x x
K
x
x

= = = ~


= = = =

= =

Chapter 16: Acids and Bases
770

91. (D)
(a) We know
eq
eq eq 3
a
[HA]
] A [ ] O H [
+
= K ,
i
[HA]
] A [
eq

= o and finally % ionized =o 100%.

Let us see how far we can get with no assumptions. Recall first what we mean by [HA]
eq
.
eq eq eq eq
] [A HA] [ [HA] or ] A [ HA] [ ] HA [

+ = =
i i

We substitute this expression into the expression for o.
eq eq
eq
] [ [HA]
] [

+
=
A
A
o
We solve both the o and the K
eq
expressions for [HA]
eq
, equate the results, and solve for o.
_
3
eq eq eq
a
_
3
a
[H O ][A ] [A ] [A ]
[HA] [A ] [HA] [A ] [HA]
[H O ][A ] [A ](1 )
R
1
R 1 R 1 (1 R)
1 R
K
K
o o
o
o
o
o o o o o o
+

+

= = + =

= =
= + = = + =
+

Momentarily, for ease in writing, we have let
pH) p (
pK
pH
a
3
10
10
10 O] [H
R

+
= = =
K
K

Once we realize that 100o =% ionized, we note that we have proven the cited formula.
Notice that no approximations were made during the course of this derivation.

(b) Formic acid has pK
a
=3.74. Thus 10
(pKpH)
=10
(3.742.50)
=10
1.24
=17.4
% 43 . 5
17.4 1
100
ionization % =
+
=

(c) [H
3
O
+
] =10
2.85
=1.4 10
3
M % 93 . 0 % 100
M 150 . 0
M 10 1.4
ionization %
3
=

=


5 88 . 4
a
pH) p ( pH) p (
pH) p (
10 3 . 1 10 88 . 4 03 . 2 85 . 2 03 . 2 pH p pH p 03 . 2
107 10 108
93 . 0
100
10 1
10 1
100
93 . 0

= = = + = + = =
= = = +
+
=
K K K
K K
K


92. (M) We note that, as the hydrocarbon chain between the two COOH groups increases in
length, the two values of pK
a
get closer together. The reason for this is that the ionized
COOH group, COO

, is negatively charged. When the two COOH groups are close together,
the negative charge on the molecule, arising from the first ionization, inhibits the second
ionization, producing a large difference between the two ionization constants. But as the
hydrocarbon chain lengthens, the effect of this negative COO
-
group on the second
ionization becomes less pronounced, due to the increasing separation between the two
carbonyl groups, and the values of the two ionization constants are more alike.

Chapter 16: Acids and Bases
771
93. (M) Consider only the 1
st
dissociation.
-5
6.2 10
2 4 4 4 2 3 4 4 4
Equation: H C H O (aq) H O(l) H O (aq) HC H O (aq)
Initial: 0.100 M 0 M 0 M
Changes: M x

+
+ +
~

M M
Equil: (0.100 ) M M M
x x
x x x
+ +


( )
2
5
a
6.2 10 0.00246M
0.100
Solve using the quadratic equation. Hence pH = log 0.00246 =2.61
x
K x
x

= = =

Consider only the 2
nd
dissociation.
-5
2.3 10
2
4 4 4 2 3 4 4 4
Equation: HC H O (aq) H O(l) H O (aq) C H O (aq)
Initial: 0.0975 M 0.00246 M

+
+ +

0 M
Changes: M M M
Equil: (0.0975 ) M 0.00246 + M M
x x x
x x x
+ +


6
a
(0.00246 ) (0.00246)
2.3 10
0.0975 0.0975
0.000091M or 0.000088M (solve quadratic) Hence pH 2.59
Thus, the pH is virually identical, hence, we need only consider the 1st ionization.
x x x
K
x
x x

+
= = =

= = ~

94. (M) To have the same freezing point, the two solutions must have the same total
concentration of all particles of soluteions and molecules. We first determine the
concentrations of all solute species in 0.150 M HC
2
H
2
ClO
2
, K
a
=1.4 10
3


2 2 2 2 3 2 2 2
Equation: HC H ClO (aq) H O(l) H O (aq) C H ClO (aq)
Initial: 0.150 M 0 M 0 M
Changes: M M x x
+
+ +
~
+

M
Equil: (0.150 ) M M M
x
x x x
+
+


3 3 2 2 2
a
2 2 2
2 4 3 2 3 4
2 3 6 4
[H O ][C H ClO ]
1.4 10
[HC H ClO ] 0.150
2.1 10 1.4 10 1.4 10 2.1 10 0
4 1.4 10 2.0 10 8.4 10
0.014 M
2 2
x x
K
x
x x x x
b b ac
x
a
+

= = =

= + =
+
= = =

total concentration =(0.150 x) +x + x =0.150 +x =0.150 +0.014 =0.164 M
Now we determine the [HC
2
H
3
O
2
] that has this total concentration.
Chapter 16: Acids and Bases
772

2 3 2 2 3 2 3 2
Equation: HC H O (aq) H O(l) H O (aq) C H O ( )
Initial: M 0 M 0 M
Changes: M
aq
z
y
+
+ +
~

5 3 2 3 2
a
2 3 2
M M
Equil: ( ) M M M
[H O ][C H O ]
1.8 10
[HC H O ]
y y
z y y y
y y
K
z y
+

+ +

= = =

We also know that the total concentration of all solute species is 0.164 M.
5
2
10 8 . 1
2 164 . 0
164 . 0 164 . 0

=

= = + = + +
y
y
y z y z y y y z
We assume that
3 6 5 2
10 7 . 1 10 0 . 3 10 8 . 1 164 . 0 0.164 2

= = = << y y y
The assumption is valid: 0.164 0034 . 0 2 << = y
Thus, [HC
2
H
3
O
2
] =z =0.164 y =0.164 0.0017 =0.162 M
2 3 2
2 3 2
2 3 2 2 3 2
2 3 2
O H HC g 73 . 9
O H HC mol 1
O H HC g 05 . 60
soln L 1
O H HC mol 0.162
L 000 . 1 O H HC mass = =

95. (M) The first ionization of H
2
SO
4
makes the major contribution to the acidity of the
solution.
Then the following two ionizations, both of which are repressed because of the presence of
H
3
O
+
in the solution, must be solved simultaneously.

- 2
4 2 4 3
Equation: HSO (aq) H O(l) SO (aq) H O ( )
Initial: 0.68 M 0 M 0.68 M
Changes: M M
aq
x x
+
+ +

M
Equil: (0.68 ) M M (0.68 )M
x
x x x
+
+



x
x x
K

+
= = =

+
68 . 0
) 68 . 0 (
011 . 0
] HSO [
] ][SO O H [
4
2
4 3
2


Let us solve this expression for x. 0.011 (0.68 x) =0.68x + x
2
=0.0075 0.011x


2
2
4 0.69 0.48 0.030
0.69 0.0075 0 0.01 M
2 2
b b ac
x x x
a
+
+ = = = =

Chapter 16: Acids and Bases
773
This gives [H
3
O
+
] =0.68 +0.01 =0.69 M. Now we solve the second equilibrium.


2 2 2 3
Equation: HCHO (aq) H O( ) CHO (aq) H O ( )
Initial: 1.5 M 0 M 0.69 M
Changes: M
l aq
x
+
+ +

4 3 2
a
2
M M
Equil: (1.5 ) M M (0.69 ) M
[H O ][CHO ] (0.69 ) 0.69
1.8 10
[HCHO ] 1.5 1.5
x x
x x x
x x x
K
x
+

+ +
+
+
= = = ~

4
3.9 10 M x

=


We see that the second acid does not significantly affect the [H
3
O
+
], for which a final value is
now obtained. [H
3
O
+
] =0.69 M, pH =log(0.69) =0.16

96. (D)
( )
( )
1
2 1
1 1 1 1
1 1 1 1
2 2
1
1
1 1
2 2
2
2
2 2
2
1/2
2
2
1
2
[ ][ ] [ ] [ ]
Let [ ]
[ ] [ ] [ ]
[ ][ ] [ ] [ ]
Let [ ] 2
[ ] [ ] [ ]
[ ]
[ ] [ ]
[ ]
2 [ ] 2 [ ] 2 2
HA
HA HA
HA HA HA HA
HA HA HA HA
H A H H
HA M K
HA H HA M
H A H H
HA M K K
HA H HA M
H
K H K M H K M K M
M
H
K H K M H K M K M
M
+ + +
+
+ + +
+
+
+ +
+
+ +
= = ~ =

= = = ~ =

= = = =
= = = =
/2

( ) ( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
1 1
1 1
1 1 1 1
1 1
1/2 1/2
10
1/2 1/2
1/2 1/2
[ ] 2 (takethenegativelog of bothsides)
log([ ] ) log log 2
1 1
pH log log log log2
2 2
1 1
pH log log2 log
2 2
overall HA HA
overall HA HA
HA HA HA HA
HA HA
H K M K M
H K M K M
K M K M K M K M
K M K M K
+
+
= +
= +
= =
= + =
( ) ( )
( ) ( )
1 1
1 1
2
1 1
pH 3 3
2 2
HA HA
HA HA
M K M
K M MK
+
= =


Chapter 16: Acids and Bases
774
97. (M) HSbF
6
H
+
+ SbF
6
-
Sb
F
F
F
F
F
F
H
+
Sb has 6 sp
3
d
2
hybrid orbitals
F has 2p orbital
The six bonds are all sigma bonds
o (Sb
sp3d2
- F
2p
)

HBF
4
H
+
+ BF
4
-

B
F
F
F
H
+
B has 4 sp
3
hybrid orbitals
F has 2p orbital
The four bonds are all sigma bonds
o (B
sp3
- F
2p
)
F

98. (M) The structure of H
3
PO
3
is shown on the right.
The two ionizable protons are bound to oxygen.

99. (M)
(a) H
2
SO
3
>HF >N
2
H
5
+
>CH
3
NH
3
+
>H
2
O
(b) OH

>CH
3
NH
2
>N
2
H
4
>F

>HSO
3

(c) (i) to the right and (ii) to the left.
F uses one of its 2p orbitals
Sb uses all six of its sp
3
d
2
hybrid orbitals
F uses one of its 2p orbitals
B uses all four of its sp
3
hybrid orbitals
H H
H
O O P
O

Chapter 16: Acids and Bases
775
FEATURE PROBLEMS

100. (D)
(a) From the combustion analysis we can determine the empirical formula. Note that the
mass of oxygen is determined by difference.
2
2
2 2
1mol CO 1mol C
amount C =1.599g CO =0.03633mol C
44.01g CO 1mol CO
12.011g C
mass of C =0.03633mol C =0.4364g C
1mol C

2
2
2 2
1mol H O 2mol H
amount H =0.327g H O =0.03629mol H
18.02g H O 1mol H O
1.008g H
mass of H =0.03629mol H =0.03658g H
1mol H

amount O g sample g C g H
mol O
g O
mol O =1.054 0.4364 0.03568
1
16.00
=0.0364 b g
There are equal moles of the three elements. The empirical formula is CHO.
The freezing-point depression data are used to determine the molar mass.
A
A

T K m m
T
K m
m
f f
f
f
C
C
= = =
0.82
3.90 /
=0.21

1kg 0.21mol solute
amount of solute=25.10g solvent =0.0053mol
1000g 1kg solvent

M =
0.615
0.0053
=1.2 10
2
g solute
mol solute
g/mol
The formula mass of the empirical formula is: 12.0 +1.0 +16.0 =29.0 g C g H g O g/ mol
Thus, there are four empirical units in a molecule, the molecular formula isC H O
4 4 4
,
and the molar mass is 116.1 g/mol.

(b) Here we determine the mass of maleic acid that reacts with one mol OH

,
mass 0.4250 gmaleic acid
58.03g/mol OH
1L 0.2152mol KOH
mol OH
34.03mL base
1000 mL 1L base

= =


This means that one mole of maleic acid (116.1 g/mol) reacts with two moles of
hydroxide ion. Maleic acid is a diprotic acid: H C H O
2 4 2 4
.

(c) Maleic acid has twoCOOH groups joined together by a bridging C
2
H
2
group. A
plausible Lewis structure is shown below:
C
O
C
H
C
H
C O H O H
O

Chapter 16: Acids and Bases
776
(d) We first determine
+ pH 1.80
3
H O =10 =10 =0.016 M

(

and then the initial
concentration of acid.
( )
2
initial
0.215g 1000mL 1mol
CHCOOH = =0.0370M
50.00mL 1L 116.1g
(


We use the first ionization to determine the value of
1
a
K
( ) ( )
+
2 3
2 2
Equation: CHCOOH (aq) + H O(l) H CHCOO (aq) + H O (aq)
Initial: 0.0370M 0M 0 M
Changes: 0.016M +0.016M +0.016M
Equil: 0.021M 0.016M 0.016M

( )
( )
( )( )
+
3
2
2
a
2
H CHCOO H O
0.016 0.016
= = =1.2 10
0.021 CHCOOH
K

(
(

( (


K
a
2
could be determined if we had some way to measure the total concentration of all
ions in solution, or if we could determine ( )
2
2
a
2
CHCOO K

(
=



(e) Practically all the H O
3
+
arises from the first ionization.
( ) ( )
( )
+
2 3
2 2
Equation: CHCOOH (aq)+ H O(l) H CHCOO (aq)+ H O (aq)
Initial: 0.0500M 0 M 0M
Changes: M + M + M
Equil: 0.0500 M M M
x x x
x x x

2
2 2 3
2
2 2
[H(CHCOO) ][H O ]
1.2 10
[(CHCOOH) ] 0.0500
0.00060 0.012 0.012 0.00060 0
a
x
K
x
x x x x
+

= = =

= + =

2
+
3
4 0.012 0.00014+0.0024
= = =0.019 M = H O
2 2
b b ac
x
a

(


pH log = 0.019 =1.72 b g

Chapter 16: Acids and Bases
777
101. (D)
(a)

2 2
4
1
2 2
4
2
2 2
4
3
2 2
4.2 10 0.00102
0.00250 0.00250
4.2 10 0.000788
0.00250 0.00102 0.00148
4.2 10 0.000848
0.00250 0.000788 0.00171
4.
0.00250 0.000848 0.00165
x x
x
x
x x
x
x x
x
x x

4
4
2 2
4
5
2 2
4
6
4
6
2 10 0.000833
4.2 10 0.000837
0.00250 0.000833 0.00167
4.2 10 0.000836
0.00250 0.000837 0.00166
0.000836 or 8.4 10 ,
x
x x
x
x x
x
x

which is the same as the value obtained using the quadratic equation.

(b) We organize the solution around the balanced chemical equation, as we have done before.
+
2 2 2 3
Equation: HClO (aq) +H O(l) ClO (aq) + H O (aq)
Initial: 0.500M 0M 0 M
Changes: M + M + M
Equil: M M M
x x x
x x x

+
2 2
2 3
2
a
2
ClO H O
= = =1.1 10
HClO 0.500 0.500
x x
K
x

(
(

( (

~

Assuming 0.500 M x ,
2 2
= 0.500 1.1 10 0.074M Not significantly smaller than 0.500 M. x x

= =
2
2
2
Assume 0.074 (0.500 0.0774) 1.1 10 0.068M Try once more.
Assume 0.068 (0.500 0.068) 1.1 10 0.069M One more time.
Assume 0.069 (0.500 0.069) 1.1 10 0.069M Final result!
x x
x x
x x

= = =
= = =
= = =


( )
+ +
3 3
H O =0.069M, pH= log H O = log 0.069 =1.16 ( (



Chapter 16: Acids and Bases
778
102. (D)
(a) Here, two equilibria must be satisfied simultaneously. The common variable,
H O
3
+
=z .
( )
+
2 3 2 2 2 3 2 3
+
3 2 3 2
5
a
2 3 2
Equation: HC H O (aq) + H O(l) C H O (aq) + H O (aq)
Initial: 0.315M 0 M 0 M
Changes: + M + M + M
Equil: 0.315 M M M
H O C H O
= = =1.8 10
HC H O 0.315
x x z
x x z
xz
K
x

(
(

~

( (

+
2 2 2 3
+
3 2
4
a
2
Equation: HCHO (aq) + H O(l) CHO (aq) + H O (aq)
Initial: 0.250 M 0M 0M
Changes: M + M + M
Equil: (0.250 )M M M
H O CHO
= = =1.8 10
HCHO 0.250
y y z
y y z
yz
K
y

(
(

( (

In this system, there are three variables, x y = , =
2 3 2 2
C H O CHO

, and z =
3
+
H O .
These three variables also represent the concentrations of the only charged species in
the reaction, and thus x y z + = . We solve the two K
a
expressions for x and y. (Before
we do so, however, we take advantage of the fact that x and y are quite small:
x << 0.315 and y << 0.250.) Then we substitute these results into the expression for z ,
and solve to obtain a value of that variable.
( ) ( )
5 6 4 5
6 5
=1.8 10 0.315 =5.7 10 =1.8 10 0.250 =4.5 10
5.7 10 4.5 10
= =
xz yz
x y
z z





6 5 5
5 3 +
3
5.7 10 4.5 10 5.07 10
= + = + = = 5.07 10 =7.1 10 M=[H O ] z x y z
z z z




pH log = 7.1 10 =2.15
3


c h
We see that our assumptions about the sizes of x and y
must
be valid, since each of them is smaller than z . (Remember that x y z + = .)

(b) We first determine the initial concentration of each solute.
| |
5 3 2
3 b
3
1mol NH 12.5g NH
NH = =1.96M =1.8 10
0.375L soln 17.03g NH
K


| |
4 3 2 3 2
3 2 b
3 2
1.55g CH NH 1mol CH NH
CH NH = =0.133M =4.2 10
0.375L soln 31.06g CH NH
K


Now we solve simultaneously two equilibria, which have a common variable, OH

=z .
Chapter 16: Acids and Bases
779
( ) ( ) ( )
( )
+
3 2 4
+
4
5
b
3
Equation: NH aq + H O NH aq + OH aq
Initial: 1.96 M 0 M 0M
Changes: M + M + M
Equil: 1.96 M M M
NH OH
= =1.8 10 =
NH 1.96 1.96
x x z
x x z
xz xz
K
x

(
(

~


( (

~

( ) ( ) ( )
+
3 2 2 3 3
+
3 3
4
b
3 2
Eqn: CH NH aq + H O(l) CH NH aq + OH aq
Initial: 0.133M 0M 0M
Changes: M M M
Equil: (0.133 )M M M
CH NH OH
= =4.2 10 = =
CH NH 0.133 0.133
y y z
y y z
yz yz
K
y

(
(

~
+ +

( (

In this system, there are three variables, x y = , =
4
+
3 3
+
NH CH NH , and z =OH

.
These three variables also represent the concentrations of the only charged species in
solution in substantial concentration, and thus x y z + = . We solve the two K
b
expressions
for x andy . Then we substitute these results into the expression for z , and solve to obtain
the value of that variable.

5 5 5 5
5 5
=1.96 1.8 10 =3.53 10 =0.133 4.2 10 =5.59 10
3.53 10 5.59 10
= =
xz yz
x y
z z






5 5 5
2 5
3.53 10 5.59 10 9.12 10
= + = + = =9.12 10 z x y z
z z z

( )
3 3
=9.5 10 M = OH pOH= log 9.5 10 =2.02 pH=14.00 2.02=11.98 z

(



We see that our assumptions about x and y (that x << 1.96 M and y << 0.133 M) must be
valid, since each of them is smaller than z . (Remember that x y z + = .)

(c) In 1.0 M NH CN
4
there are the following species: NH aq NH aq CN aq
4
+
3
, , b g b g b g

, HCN(aq),
H O aq
3
+
b g , and OH aq

b g . These species are related by the following six equations.

( )
14
14 +
w 3
+
3
1.0 10
1 =1.0 10 = H O OH OH =
H O
K

( ( (

(


2 =6.2 10 =
10
3
+
b g K
a
H O CN
HCN

3 =1.8 10 =
5
4
+
3
b g K
b
NH OH
NH

L
N
M
O
Q
P

Chapter 16: Acids and Bases
780
( ) | | | |
+ +
3 4 3 4
4 NH + NH =1.0M NH =1.0 NH ( (


( ) | | | | 5 HCN + CN =1.0M HCN =1.0 CN

( (


( )
+ + +
4 3 4
6 NH + H O = CN + OH or NH CN

( ( ( ( ( ( ~



Equation (6) is the result of charge balance, that there must be the same quantity of
positive and negative charge in the solution. The approximation is the result of
remembering that not much H O
3
+
or OH

will be formed as the result of hydrolysis of

ions. Substitute equation (4) into equation (3), and equation (5) into equation (2).

3 =1.8 10 =
1.0
2 =4.0 10 =
1.0
5
4
+
4
+
10
3
+
b g b g K K
b a
NH OH
NH
H O CN
CN

Now substitute equation (6) into equation 2 b g , and equation (1) into equation 3 b g .
2 =6.2 10 =
1.0
3
1.8 10
1.0 10
=
1.0
10
3
+
4
+
4
+
5
14
4
+
3
+
4
+
b g b g
e j
K
a
H O NH
NH
NH
H O NH

Now we solve both of these equations for NH
4
+
.
2:6.2 10 6.2 10 = =
6.2 10
6.2 10 +
10 10
4
+
3
+
4
+
4
+
10
10
3
+
b g

NH H O NH NH
H O

3:1.8 10 1.8 10 = =
1.8 10
1.00+1.8 10
9
3
+ 9
3
+
4
+
4
+
4
+
9
3
+
9
3
+
b g

H O H O NH NH NH
H O
H O

We equate the two results and solve for
H O
3
+
.
6.2 10
6.2 10 +
=
1.8 10
1.00+1.8 10
10
10
3
+
9
3
+
9
3
+

H O
H O
H O


6.2 10 +1.1 =1.1 +1.8 10 6.2 10 =1.8 10
10
3
+
3
+ 9
3
+
2
10 9
3
+
2


H O H O H O H O
H O M pH log
3
+
10
9
10 10
=
62 10
18 10
59 10 = 5.9 10 =9.23
.
.
.

c h

+ a w
3 a w b
b
Note that H O = or pH=0.500(p p p )
K K
K K K
K

( +


Chapter 16: Acids and Bases
781

SELF-ASSESSMENT EXERCISES

103. (E)
(a) K
W
: Dissociation constant of water, which is defined as [H
3
O
+
][OH]
(b) pH: A logarithmic scale of expressing acidity of a solution (H
3
O
+
); it is defined as
-log [H
3
O
+
]
(c) pKa: A logarithmic scale expressing the strength of an acid (which is how much an acid
dissociates in water at equilibrium); it is defined as log K
a

(d) Hydrolysis: A reaction involving ionization of water
(e) Lewis acid: A compound or species that accepts electrons

104. (E)
(a) Conjugate base: A base that is derived by removing an abstractable proton from the acid
(b) Percent ionization of acid/base: The ratio between the conjugate of the acid or base
under study and the acid/base itself times 100
(c) Self-ionization: A reaction involving ionization of two molecules of water to give
[H
3
O
+
] and [OH]
(d) Amphiprotic behavior: A substance acting as either an acid or a base

105. (E)
(a) BrnsteadLowry acid and base: A BrnstedLowry acid is a substance that when
placed in water will cause the formation of hydronium ion by donating a proton to
water. The base is one that abstracts a proton from water and results in a hydroxyl ion.
(b) [H
3
O
+
] and pH: [H
3
O
+
] is the molar concentration of hydronium ion in water, whereas
pH is the log [H
3
O
+
]
(c) K
a
for NH
4
+
and K
b
for NH
3
: K
b
of NH
3
is the equilibrium constant for hydrolysis of
water with NH
3
to generate NH
4
+
and OH. K
a
of NH
4
+
is for deprotonation of NH
4
+

with water to give NH
3
and OH.
(d) Leveling effect and electron-withdrawing effect: The leveling effect is the result of
reaction of water with any acid or base such that no acid or base can exist in water that
are more acidic than H
3
O
+
or more basic than OH. The electron-withdrawing effect is
the tendency for a central atom with high electronegativity in an oxoacid to withdraw
electrons from the OH bond.

106. (E) The answer is (a), HCO
3

, because it can donate a proton to water to become CO

3
2
, or
it can be protonated to give H
2
CO
3
(i.e., CO
2
(aq)).

107. (E) The answer is (c). CH
3
CH
2
COOH is a weak acid, so the concentration of H
3
O
+
ions it
will generate upon dissociation in water will be significantly less than 0.1 M. Therefore, its
pH will be higher the 0.10 M HBr, which dissociates completely in water to give 0.10 M
H
3
O
+
.

108. (E) The answer is (d). CH
3
NH
2
is a weak base.

Chapter 16: Acids and Bases
782
109. (M) The answer is (e) because CO
3
2-
is the strongest base and it drives the dissociation of
acetic acid furthest.

110. (M) The answer is (c). H
2
SO
4
dissociation is nearly complete for the first proton, giving a
[H
3
O
+
] =0.10 M (pH =1). The second dissociation is not complete. Therefore, (c) is the
only choice that makes sense.

111. (M) The answer is (b). You can write down the stepwise equations for dissociation of
H
2
SO
3
and then the dissociation of HSO
3
and calculate the equilibrium concentration of
each species. However, you can determine the answer without detailed calculations. The
two dissociation equations are given below:

Eq.1
2 3 2 3 3
H SO H O HSO H O
+
+ +
K
a1
=1.310
-2
Eq.2
2
3 2 3 3
HSO H O SO H O
+
+ +
K
a2
=6.310
-8


For the first equation, the equilibrium concentrations, of HSO
3
and H
3
O
+
are the same.
They become the initial concentration values for the second dissociation reaction. Since
K
a2
is 6.310
-8
(which is small), the equilibrium concentrations of HSO
3
and H
3
O
+
wont
change significantly. So, the equation simplifies as follows:
( )
2- + 2- +
3 3 3 3
8
a2
-
3
SO H O SO H O +
K 6.8 10 =
HSO -
x
x

( ( ( (
/

= =
(
/

-
3
HSO (

8 2-
a2 3
K =6.8 10 SO

( =



112. (E) Since both the acid and the base in this reaction are strong, they dissociate completely.
The pH is determined as follows:

mol H
3
O
+
: 0.248 M HNO
3
0.02480 L =0.00615 mol
mol OH: 0.394 M KOH 0.01540 L =0.00607 mol


Final: 0.00615 0.00607 =8.0010
-5
mol H
3
O
+
( )
( )
5
3
8.00 10 mol
H O 0.00200 M
0.02480L +0.01540 L
pH log 0.00200 2.70

+

( = =

= =


113. (M) Since pH =3.25, the [H
3
O
+
] =10
-3.25
=5.6210
-4
M. Using the reaction below, we
can determine the equilibrium concentrations of other species

HC
2
H
3
O
2
+ H
2
O

C
2
H
3
O
2
+ H
3
O
+
Initial C 0 0
Change -x +x +x
Equil. C - x x x
Chapter 16: Acids and Bases
783

Since x =5.6210
-4
M, the equilibrium expression becomes
| |
( )( )
( )
4 4
3 2 3 2
5
a
4
2 3 2
5.62 10 M 5.62 10 M H O C H O
K 1.8 10
HC H O C 5.62 10 M
+

( (

= = =



Solving C gives a concentration of 0.0181 M.

Since concentrated acetic acid is 35% by weight and the density is 1.044 g/mL, the
concentration of acetic acid is:

35g HAc 1.044g Conc. HAc 1mol HAc
6.084M HAc
100g Conc. HAc sol'n 0.001L sol'n 60.06 g HAc
=

Therefore, volume of concentrated solution required to make 12.5 L of 0.0181 M HAc
solution is:

( ) ( )
( )( )
dilute conc.
conc
M V M V
0.0181M 12500mL
V 37.2mL
6.084M
=
= =


114. (M) Table 16.3 has the K
a
value for chloroacetic acid, HC
2
H
2
ClO
2
. K
a
=1.410
-3
. The
solution is made of the chloroacetate salt, which hydrolyzes water according to the
following reaction:

C
2
H
2
ClO
2
+ H
2
O

HC
2
H
2
ClO
2
+ OH

Initial 2.05 0 0
Change -x +x +x
Equil. 2.05 x x x


14
12 W
b 3
a
K 1.0 10
K 7.14 10
K 1.4 10

= = =

| |
( )
-
2 2 2
2 2 2
12
- -6
-6
HC H ClO OH
C H ClO
7.14 10
2.05
Solvingthe above simplified expression for x, we get x = OH =3.82610
pH=14-pOH=14- -log 3.82610 =8.58
b
K
x x
x

(

=
(

/
(

(




Chapter 16: Acids and Bases
784
115. (M) 0.10 M HI <0.05 M H
2
SO
4
<0.05 M HC
2
H
2
ClO
2
<0.50 M HC
2
H
3
O
2
<0.50 M
NH
4
Cl <1.0 M NaBr <0.05 M KC
2
H
3
O
2
<0.05 M NH
3
<0.06 M NaOH <0.05 M
Ba(OH)
2


116. (M) Since pH =5 pOH, pH must be significantly larger than pOH, which means that the
solution is basic. The pH can be determined by solving two simultaneous equations:
pH 5pOH 0
pH +pOH =14
=

pOH =2.333
pH =14 2.33 =11.67.
Therefore, [H
3
O
+
] =2.1410
-12
M (and [OH] =4.6710
-3
M)

The solute must be NH
3
, because it is the only basic species (the other two are acidic and
neutral, respectively). Since the K
b
of NH
3
is 1.810
-5
, the concentration of NH
3
can be
determined as follows:

| |
( )( )
3 3 - +
4
5
b
3
4.67 10 4.67 10 OH NH
K = 1.8 10
NH
1.2 M
x
x

( (

= =
=



117. (M) The answer is (a). If HC
3
H
5
O
2
is 0.42% ionized for a 0.80 M solution, then the
concentration of the acid at equilibrium is (0.800.0042) =0.00336. The equilibrium
expression for the dissociation of HC
3
H
5
O
2
is:

| |
( )( )
( )
3 3 5 2
5
a
3 5 2
H O C H O
0.00336 0.00336
K 1.42 10
HC H O 0.800 0.00336
+

( (

= = =

118. (E) The answer is (b), because H
2
PO
4
is a result of addition of one proton to the base
HPO
4
2-
.

119. (M) The answer is (d). This is because, in the second equation, HNO
2
will give its proton
to ClO (rather than HClO giving its proton to NO
2
), which means that HNO
2
is a
stronger acid than HClO. Also, in the first equation, ClO is not a strong enough base to
abstract a proton from water, which means that HClO is in turn a stronger acid than H
2
O.

120. (M) The dominant species in the solution is ClO
2
. Therefore, determine its concentration
and ionization constant first:

2 2
2
2
3.00 mol CaClO 2mol ClO
ClO =2.40 M
2.50L 1mol CaClO

( =


14
13 W
b 2
a
K 1.0 10
K 9.1 10
K 1.1 10

= = =

Chapter 16: Acids and Bases
785

The reaction and the dissociation of ClO
2
is as follows:

ClO
2
+ H
2
O

HClO
2
+ OH

Initial 2.40 0 0
Change -x +x +x
Equil. 2.40 x x x

( )
-
2
-
2
13
- -6
-6
HClO OH
ClO
9.1 10
2.40
Solvingthe above simplified expression for x, we get x = OH =1.47810 .
pH=14-pOH=14- -log 1.47810 =8.2
b
K
x x
x

( (

=
(

/
(

(



121. (M) Section 16-8 discusses the effects of structure on acid/base behavior. The major
subtopics are effects of structure on binary acids, oxo acids, organic acids, and amine
bases. For binary acids, acidity can be discussed in terms of electronegativity of the main
atom, bond length, and heterolytic bond dissociation energy. For oxo acids, the main
things affecting acidity are the electronegativity of the central atom and number of oxygen
atoms surrounding the central atom. For organic acids, the main topic is the electron-
withdrawing capability of constituent groups attached to the carboxyl unit. For amines, the
basicity is discussed in terms of electron withdrawing or donating groups attached to the
nitrogen in the amine, and the number of resonance structures possible for the base
molecule.
786
CHAPTER 17

ADDITIONAL ASPECTS OF ACIDBASE EQUILIBRIA

PRACTICE EXAMPLES

1A (D) Organize the solution around the balanced chemical equation, as we have done before.


+
2 3
Equation: HF(aq) H O(l) H O (aq) F (aq)
Initial: 0.500M 0M 0M
Changes: M + M + M
Equil: (0.500 )M M M
x x x
x x x

+ +
~

K
x x
x
x
a
3
+
H O F
HF]
= =

= ~

[ ][ ]
[
( ) ( )
.
.
. 0500
66 10
0500
4
2
assuming 0.500 x


x = =

0500 66 10 0018
4
. . . M One further cycle of approximations gives:


4 +
3
(0.500 0.018) 6.6 10 0.018M [H O ] x

= = =


Thus, [HF] =0.500M 0.018M 0.482M =

Recognize that 0.100 M HCl means
+
3
initial
H O 0.100M ( =

, since HCl is a strong acid.

+
2 3
Equation: HF(aq) + H O(l) H O (aq) +F (aq)
Initial: 0.500M 0.100M 0 M
Changes: M + M + M
Equil: (0.500 )M (0.100+)M M
x x x
x x x

K
x x
x
x
a
3
+
H O F ]
[HF]
+
= =

= ~

[ ][ ( )( . )
.
.
.
.
0100
0500
66 10
0100
0500
4
assuming x 0.100

4
3
6.6 10 0.500
= =3.3 10 M = F The assumption is valid.
0.100
x

(



| |
HF =0.500M 0.003M =0.497M
[H
3
O
+
] =0.100 M +x =0.100 M +0.003 M =0.103 M

Chapter 17: Additional Aspects of AcidBase Equilibria
787
1B (M) From Example 17-6 in the text, we know that [ ] [ ] . H O C H O M
3
+
2 3 2
= =

13 10
3
in
0.100 M HC H O
2 3 2
. We base our calculation, as usual, on the balanced chemical
equation. The concentration of H O
3
+
from the added HCl is represented by x.
+
2 3 2 2 3 2 3 2
Equation: HC H O (aq) +H O(l) H O (aq) + C H O (aq)
Initial: 0.100M 0M 0M
Changes: 0.00010M +0.00010M +0.00010M
From HCl: + M
Equil: 0.100 M (0.00010 )M 0.00010M
x
x

~

+

K
x
a
3
+
2 3 2
2 3 2
H O C H O
HC H O ]
(0.00010+
=
000010
0100
18 10
5
[ ][ ]
[
) .
.
.

= =

5
1.8 10 0.100
0.00010 0.018M 0.018M 0.00010M 0.018M
0.00010
x x

+ = = = =

+
3
+
3
12 M HCl
0.018 mol H O 1mol HCl 1L soln 1000 mL 1drop
1.00L 30.drops
1L 1mol H O 12 mol HCl 1L 0.050 mL
= V =
Since 30. drops corresponds to 1.5 mL of 12 M solution, we see that the volume of solution
does indeed remain approximately 1.00 L after addition of the 12 M HCl.

2A (M) We again organize the solution around the balanced chemical equation.

( ) ( ) ( )
+
2 2 2 3
Equation: HCHO aq + H O(l) CHO aq +H O aq
Initial: 0.100M 0.150M 0M
Changes: M + M + M
Equil: (0.100 )M (0.150 + ) M M
x x x
x x x

4 2 3
2
[CHO ][H O ] (0.150+ )( ) 0.150
1.8 10
[HCHO ] 0.100 0.100
a
x x x
K
x
+

= = = ~

assuming 0.100 x

4
4 +
3
2
0.100 1.8 10
= =1.2 10 M = H O , <<0.100, thus our assumptionis valid
0.150
CHO =0.150M+0.00012M =0.150M
x x

(

(



Chapter 17: Additional Aspects of AcidBase Equilibria
788
2B (M) This time, a solid sample of a weak base is being added to a solution of its
conjugate acid. We let x represent the concentration of acetate ion from the added
sodium acetate. Notice that sodium acetate is a strong electrolyte, thus, it completely
dissociates in aqueous solution. H O M M
pH
3
+ 5.00 5
=10 =10 =1.0 10 =0.000010


( ) ( ) ( )
+
2 3 2 2 2 3 2 3
Equation: HC H O aq + H O(l) C H O aq + H O aq
Initial: 0.100M 0M 0M
Changes: 0.000010M +0.000010M +0.000010M
From NaAc: + M
Equil: 0.100M (0.000010+ )M 0.000010M
x
x

( )
+
3 2 3 2
5
a
2 3 2
H O C H O
0.000010 0.000010+
= = =1.8 10
HC H O 0.100
x
K

(
(

( (



5
1.8 10 0.100
0.000010+ 0.18M 0.18M 0.000010M =0.18M
0.000010
x x

= = =

2 3 2 2 3 2 2 3 2
2 3 2
2 3 2 2 3 2
2 3 2
0.18mol C H O 1mol NaC H O 82.03g NaC H O
mass of NaC H O =1.00L
1L 1mol NaC H O 1mol C H O
=15gNaC H O

3A (M) A strong acid dissociates essentially completely, and effectively is a source of
+
3 2 3 2
H O . NaC H O also dissociates completely in solution. The hydronium ion and the acetate
ion react to form acetic acid:
3 2 3 2 2 3 2 2
H O (aq) C H O (aq) HC H O (aq) H O(l)
+
+ +

All that is necessary to form a buffer is to have approximately equal amounts of a weak
acid and its conjugate base together in solution. This will be achieved if we add an
amount of HCl equal to approximately half the original amount of acetate ion.

3B (M) HCl dissociates essentially completely in water and serves as a source of hydronium
ion. This reacts with ammonia to form ammonium ion:
( ) ( ) ( )
+
+
3 3 4 2
NH aq +H O aq NH aq +H O(l)

.
Because a buffer contains approximately equal amounts of a weak base (NH
3
) and its
conjugate acid (NH
4
+
), to prepare a buffer we simply add an amount of HCl equal to
approximately half the amount of NH
3
(aq) initially present.

Chapter 17: Additional Aspects of AcidBase Equilibria
789
4A (M) We first find the formate ion concentration, remembering that NaCHO
2
is a strong
electrolyte, existing in solution as Na aq
+
b g and ( )
2
CHO aq

.

2 2 2
2
2 2
23.1gNaCHO 1000 mL 1mol NaCHO 1mol CHO
[CHO ] 0.679M
500.0 mL soln 1L 68.01g NaCHO 1 mol NaCHO

= =

As usual, the solution to the problem is organized around the balanced chemical equation.
( ) ( ) ( )
+
2 2 2 3
Equation: HCHO aq + H O(l) CHO aq +H O aq
Initial: 0.432M 0.679M 0M
Changes: M + M + M
Equil: (0.432 ) M (0.679+ ) M M
x x x
x x x

( )
+
4
3 2
4
a
2
H O CHO
0.679+
0.679 0.432 1.8 10
= = =1.8 10 =
HCHO 0.432 0.432 0.679
x x
x
K x
x

(
(

( (


~

This gives
+ 4
3
H O =1.14 10 M

(

. The assumption that 0.432 x is clearly correct.
( )
4
3
pH log H O log 1.14 10 3.94 3.9
+
( = = = ~




4B (M) The concentrations of the components in the 100.0 mL of buffer solution are found
via the dilution factor. Remember that NaC H O
2 3 2
is a strong electrolyte, existing in
solution as
Na aq
+
b g and C H O aq
2 3 2

b g .

2 3 2 2 3 2
63.0 mL 37.0mL
[HC H O ] 0.200 M 0.126 M [C H O ] 0.200 M 0.0740M
100.0 mL 100.0mL

= = = =

As usual, the solution to the problem is organized around the balanced chemical equation.
Equation: ( ) ( ) ( )
+
2 3 2 2 2 3 2 3
HC H O aq + H O(l) C H O aq + H O aq

Initial: 0.126 M 0.0740 M 0 M ~
Changes: x M x + M x + M
Equil: ( . ) 0126 x M 0.0740+x b g M x M



+
5 3 2 3 2
a
2 3 2
[H O ][C H O ] (0.0740 ) 0.0740
1.8 10
[HC H O ] 0.126 0.126
x x x
K
x

+
= = = ~

x =

=

18 10 0126
00740
31 10
5
5
. .
.
. ] M =[H O
3
+
; pH= H O
3
+
= =

log[ ] log . . 31 10 451

5


Note that the assumption is valid: 0.0740 0.126. x <
Thus, x is neglected when added or subtracted

Chapter 17: Additional Aspects of AcidBase Equilibria
790
5A (M) We know the initial concentration of NH
3
in the buffer solution and can use the pH
to find the equilibrium [OH
-
]. The rest of the solution is organized around the balanced
chemical equation. Our first goal is to determine the initial concentration of
4
NH
+
.

pOH=14.00 pH=14.00 OH M
pOH
= = = =

900 500 10 10 10 10
500 5
. . [ ] .
.


Equation: ( ) ( ) ( )
+
3 2 4
NH aq + H O(l) NH aq + OH aq

Initial: 0.35 M x M 0 M ~
Changes:
5
1.0 10 M

5
1.0 10 M

+
5
1.0 10 M

+
Equil:
5
(0.35 1.0 10 )M

( . ) x +

10 10
5
M 10 10
5
.

M


5 5 5
5 4
b
5
3
[NH ][OH ] ( 1.0 10 )(1.0 10 ) 1.0 10
1.8 10
[NH ] 0.35 1.0 10 0.35
x x
K
+

+
= = = =



5
5 +
4 5
0.35 1.8 10
Assume 1.0 10 = =0.63M =initial NH concentration
1.0 10
x x

( )
( ) ( )
( )
+
4 4 4 4
4 2 2
4 4
2
+
4 4 4
2
1mol NH SO 132.1g NH SO
0.63mol NH
mass NH SO =0.500L
1L soln 1mol NH SO 2mol NH


Mass of (NH
4
)
2
SO
4
=21 g

5B (M) The solution is composed of 33.05 g NaC
2
H
3
O
2

-
3 H
2
O dissolved in 300.0 mL of 0.250 M
HCl. NaC
2
H
3
O
2
-
3 H
2
O , a strong electrolyte, exists in solution as Na
+
(aq) and C
2
H
3
O
2
-
(aq)
ions. First we calculate the number of moles of NaC
2
H
3
O
2
-
3 H
2
O, which, based on the 1:1
stoichiometry, is also equal to the number of moles of C
2
HO
-
that are released into solution.
From this we can calculate the initial [C
2
H
3
O
2
-
] assuming the solution's volume remains at
300. mL.

moles of
2 3 2
NaC H O
-
3 H
2
O (and moles of C
2
H
3
O
2
-
)
=
2 3 2 2
2 3 2 2 2 3 2
2 3 2 2
2 3 2 2
33.05g NaC H O 3H O
0.243molesNaC H O 3H O molesC H O
1 mole NaC H O 3H O
136.08 g NaC H O 3H O

-
-
-
-
= =
2 3 2
2 3 2
0.243mol C H O
[C H O ] 0.810
0.300 L soln
M

= =
(Note: [HCl] is assumed to remain unchanged at 0.250 M)
We organize this information around the balanced chemical equation, as before. We
recognize that virtually all of the HCl has been hydrolyzed and that hydronium ion will
react to produce the much weaker acetic acid.
Chapter 17: Additional Aspects of AcidBase Equilibria
791
Equation:
2 3 2 2
HC H O (aq) +H O(l)

2 3 2
C H O (aq)

+ H O (aq)
3
+

Initial: 0 M 0.810 M 0.250 M
Form HAc: +0.250 M 0.250 M 0.250 M
0.250 M 0.560 M 0 M ~
Changes: x M +x M +x M
Equil: (0.250 x) M (0.560 +x) M +x M
+
5 3 2 3 2
a
2 3 2
[H O ][C H O ] (0.560 ) 0.560
1.8 10
[HC H O ] 0.250 0.250
x x x
K
x

+
= = = ~

5
6 +
3
1.8 10 0.250
8.0 10 M =[H O ]
0.560
x

= =
(The approximation was valid since x << both 0.250 and 0.560 )
+ 6
3
pH = log[H O ] log8.0 10 5.09 5.1

= = ~

6A (D)
(a) For formic acid, p
a
K = =

log( . ) . . 18 10 374
4
The Henderson-Hasselbalch equation
provides the pH of the original buffer solution:
pH=p
[CHO
HCHO
a
2
2
K + = + =

log
]
[ ]
. log
.
.
. 374
0350
0550
354
(b) The added acid can be considered completely reacted with the formate ion to produce
formic acid. Each mole/L of added acid consumes 1 M of formate ion and forms 1 M of
formic acid:
+
2 3 2 2
CHO +H O HCHO +H O (aq) (aq) (aq) (l).

K
neut
=K
b
/K
w

5600. Thus,
2
CHO 0.350 M 0.0050 M =0.345 M

= (

and
| |
2
HCHO =0.550M+0.0050M =0.555M. By using the Henderson-Hasselbalch
equation
2
a
2
[CHO ] 0.345
pH=p +log =3.74+log =3.53
[HCHO ] 0.555
K

(c) Added base reacts completely with formic acid producing, an equivalent amount of
formate ion. This continues until all of the formic acid is consumed.
Each 1 mole of added base consumes 1 mol of formic acid and forms 1 mol of
formate ion:
2 2 2
HCHO +OH CHO +H O

. K
neut
=K
a
/K
w
1.8 10
10
. Thus,
2
CHO =0.350M +0.0050 M =0.355 M

(


| | ( )
2
HCHO = 0.550 0.0050 M =0.545M . With the Henderson-Hasselbalch equation
we find
2
a
2
CHO
0.355
pH =p +log =3.74+log =3.55
HCHO 0.545
K

(
(

(



Chapter 17: Additional Aspects of AcidBase Equilibria
792
6B (D) The buffer cited has the same concentration as weak acid and its anion, as does the
buffer of Example 17-6. Our goal is to reach pH=5.03 or
+ pH 5.03 6
3
H O =10 =10 =9.3 10 M

(

. Adding strong acid H O
3
+
c h
, of course, produces
HC H O
2 3 2
at the expense of C H O
2 3 2

. Thus, adding H
+
drives the reaction to the left.
Again, we use the data around the balanced chemical equation.
Equation: ( )
2 3 2 2
HC H O aq + H O(l)

C H O aq
2 3 2

b g + H O aq
3
+
b g
Initial: 0.250 M 0.560 M
6
8.0 10

M
Add acid: +y M
Form HAc: +y M y M y M
0.250+y b g M 0.560 y b g M ~ 0 M
Changes: x M x + M x + M
Equil: 0.250+y x b g M 0.560 + y x b g M 9.3 10
6

M
+ 6 6
5 3 2 3 2
a
2 3 2
[H O ][C H O ] 9.3 10 (0.560 ) 9.3 10 (0.560 )
1.8 10
[HC H O ] 0.250 0.250
(Assume that is negligible compared to )
y x y
K
y x y
x y

+
= = = ~
+ +

1.8 10 0.250+
9.3 10
=0.484+1.94 =0.560 =
0.560 0.484
1.94+1.00
=0.026
5
6

y
y y y
b g
M
Notice that our assumption is valid: ( ) ( ) 0.250+ =0.276 0.560 =0.534 x y y < .
( )
3
+
3 3
+
3
HNO 3
1mL HNO aq 0.026 mmol H O
1mL buffer 6.0 mmol H O
300.0 mL buffer =1.3mL of 6.0M HNO V =
Instead of the algebraic solution, we could have used the Henderson-Hasselbalch
equation, since the final pH falls within one pH unit of the p
a
K of acetic acid. We let z
indicate the increase in HC H O
2 3 2
, and also the decrease in C H O
2 3 2

pH p log
C H O
HC H O
log
a
= + =4.74+
0.560
0.250+
=5.03
0.560
0.250+
=10 =1.95
2 3 2
2 3 2
5.03 4.74
K
z
z
z
z

L
N
M
O
Q
P

0.560 =1.95 0.250+ =0.488+1.95 =
0.560 0.488
1.95+1.00
=0.024

z z z z b g M
This is, and should be, almost exactly the same as the value of y we obtained by the
I.C.E. table method. The slight difference is due to imprecision arising from rounding
errors.

7A (D)
(a) The initial pH is the pH of 0.150 M HCl, which we obtain from H O
3
+
of that
strong acid solution.
[H O
mol HCl
1L soln
mol H O
mol HCl
M,
3
+ 3
+
]
.
. = =
0150 1
1
0150

pH= [H O
3
+
= = log ] log( . ) . 0150 0824

Chapter 17: Additional Aspects of AcidBase Equilibria
793
(b) To determine H O
3
+
and then pH at the 50.0% point, we need the volume of the
solution and the amount of H O
3
+
left unreacted. First we calculate the amount of
hydronium ion present and then the volume of base solution needed for its
complete neutralization.
amount H O mL
mmol HCl
mL soln
mmol H O
mmol HCl
mmol H O
3
+ 3
+
3
+
=25.00
0.150
1
1
1
=3.75

+
acid 3
+
3
1mmol OH 1mmol NaOH 1mL titrant
=3.75mmol H O
1mmol H O 1mmol OH 0.250mmol NaOH
15.0mL titrant
V

=


At the 50.0% point, half of the H
3
O
+
(1.88 mmol H O
3
+
) will remain unreacted and
only half (7.50 mL titrant) of the titrant solution will be added. From this information,
and the original 25.00-mL volume of the solution, we calculate H O
3
+
and then pH.


( )
+ 3
3
1.88mmol H O left
H O = =0.0578M
25.00mL original +7.50mL titrant
pH= log 0.0578 =1.238
+
(

(c) Since this is the titration of a strong acid by a strong base, at the equivalence
point, thepH=7.00. This is because the only ions of appreciable concentration in
the equivalence point solution are Na
+
(aq) and Cl
-
(aq), and neither of these
species undergoes detectable hydrolysis reactions.
(d) Beyond the equivalence point, the solution pH is determined almost entirely by
the concentration of excess OH
-
(aq) ions. The volume of the solution is
40.00mL +1.00mL =41.00 mL. The amount of hydroxide ion in the excess
titrant is calculated and used to determine OH

, from which pH is computed.

0.250mmol NaOH
amountof OH =1.00mL =0.250mmol OH
1mL
0.250mmol OH
OH = =0.006098M
41.00mL

(



( ) pOH = log 0.006098 =2.215; pH =14.00 2.215=11.785
7B (D)
(a) The initial pH is simply the pH of 0.00812 MBa OH b g
2
, which we obtain from
OH

for the solution.

OH
mol Ba OH
L soln
mol OH
mol Ba OH

=
0.00812
1
2
1
=0.01624
2
2
b g
b g
M
( ) pOH= log OH = log 0.0162 =1.790; pH=14.00 pOH=14.00 1.790=12.21

(



Chapter 17: Additional Aspects of AcidBase Equilibria
794

(b) To determine OH

and then pH at the 50.0% point, we need the volume of the

solution and the amount of OH

unreacted. First we calculate the amount of

hydroxide ion present and then the volume of acid solution needed for its complete
neutralization.

( )
( )
2
2
0.00812mmol Ba OH
2mmol OH
amount OH =50.00mL =0.812mmol OH
1mL soln 1mmol Ba OH

+
3
acid +
3
1mmol H O 1mmol HCl 1mL titrant
=0.812mmol OH =32.48mL titrant
0.0250mmol HCl 1mmol OH 1mmol H O
V

At the 50.0 % point, half (0.406 mmol OH

) will remain unreacted and only half

(16.24 mL titrant) of the titrant solution will be added. From this information, and
the original 50.00-mL volume of the solution, we calculate OH

and then pH.

OH
mmol OH left
mL original mL titrant
M

=
0.406
50.00 +16.24
=0.00613
( ) pOH= log 0.00613 =2.213; pH=14.00 pOH=11.79


(c) Since this is the titration of a strong base by a strong acid, at the equivalence
point,pH =7.00. The solution at this point is neutral because the dominant ionic
species in solution, namely Ba
2+
(aq) and Cl
-
(aq), do not react with water to a
detectable extent.

8A (D)
(a) Initial pH is just that of 0.150 M HF (p log
a
K = 6.6 10 =3.18
4


c h
).
[Initial solution contains
0.150mmol HF
20.00 mL
1mL
=3.00 mmol HF]

( ) ( ) ( )
+
2 3
Equation: HF aq + H O(l) H O aq + F aq
Initial : 0.150M 0M 0M
Changes: M + M + M
Equil: (0.150 ) M M M
x x x
x x x

| |
+ -
2
3
4
a
H O F
= = =6.6 10
HF 0.150 0.150
x x x
K
x

( (


~

4 3
0.150 6.6 10 9.9 10 M x

= =
( ) 0.05 0.150 x > . The assumption is invalid. After a second cycle of
approximation,
+ 3
3
H O =9.6 10 M

(

;
( )
3
pH= log 9.6 10 =2.02

Chapter 17: Additional Aspects of AcidBase Equilibria
795
(b) When the titration is 25.0% complete, there are (0.253.00=) 0.75 mmol F

for every
3.00 mmol HF that were present initially. Therefore, (3.00-0.75=) 2.25 mmol HF
remain untitrated. We designate the solution volume (the volume holding these
3.00 mmol total) as V and use the Henderson-Hasselbalch equation to find the
pH.
pH p log
F
HF
log
mmol
mmol
a
= + =3.18+
0.75 /
2.25 /
=2.70 K
V
V

(c) At the midpoint of the titration of a weak base, pH =pK
a
=3.18.
(d) At the endpoint of the titration, the pH of the solution is determined by the
conjugate base hydrolysis reaction. We calculate the amount of anion and the
volume of solution in order to calculate its initial concentration.

0.150 mmol HF 1mmol F
amount F =20.00 mL =3.00mmol F
1 mL soln 1 mmol HF

1mmol OH 1mL titrant
volume titrant =3.00mmol HF =12.0mL titrant
1mmol HF 0.250mmol OH

3.00mmol F
F = =0.0938M
20.00mL original volume+12.0mL titrant

(


We organize the solution of the hydrolysis problem around its balanced equation.

( ) ( ) ( )
( )
2
Equation: F aq + H O(l) HF aq + OH aq
Initial: 0.0938M 0M 0M
Changes: M + M + M
Equil : 0.0938 M M M
x x x
x x x

~

| |
14 2
11 w
b 4
a
HF OH
1.0 10
= = = =1.5 10 =
6.6 10 0.0938 0.0938 F
K x x x
K
K x

(


~
(



11 6
0.0934 1.5 10 1.2 10 M =[OH ] x

= =
The assumption is valid (x 0.0934).

( )
6
pOH = log 1.2 10 =5.92; pH =14.00 pOH =14.00 5.92=8.08

8B (D)
(a) The initial pH is simply that of 0.106 MNH
3
.
Equation: ( ) ( ) ( )
+
3 2 4
NH aq + H O(l) NH aq + OH aq

Initial: 0.106 M 0 M ~ 0 M
Changes: x M +x M +x M
Equil: 0.106 x b g M x M x M
Chapter 17: Additional Aspects of AcidBase Equilibria
796


+
2
4
b
3
NH OH
= =
NH 0.106 0.106
x x x
K
x

(
(

( (

=1.8 10
5

4 3
0.106 1.8 10 1.4 10 M x

= = =[OH
-
]
The assumption is valid (x <<0.106).
( ) pOH = log 0.0014 =2.85 pH =14.00 pOH =14.00 2.85 =11.15
(b) When the titration is 25.0% complete, there are 25.0 mmol NH
4
+
for every 100.0
mmol of NH
3
that were present initially (i.e., there are 1.33 mmol of NH
4
+
in
solution), 3.98 mmol NH
3
remain untitrated. We designate the solution volume
(the volume holding these 5.30 mmol total) as V and use the basic version of the
Henderson-Hasselbalch equation to find the pH.
+
4
b
3
1.33mmol
NH
pOH =p +log =4.74+log =4.26
3.98mmol
NH
V
K
V
(
(

(



pH =14.00 4.26=9.74

(c) At the midpoint of the titration of a weak base,
b
pOH =p =4.74 and pH =9.26 K

(d) At the endpoint of the titration, the pH is determined by the conjugate acid
hydrolysis reaction. We calculate the amount of that cation and the volume of the
solution in order to determine its initial concentration.


+
3 4 +
4
3
+
+
4 4
0.106mmol NH 1mmol NH
amount NH =50.00mL
1mL soln 1mmol NH
amount NH =5.30mmol NH




+
3
titrant 3
+
3 3
1mmol H O 1mL titrant
=5.30mmol NH =23.6mL titrant
1mmol NH 0.225mmol H O
V


+
+
4
4
5.30mmol NH
NH = =0.0720M
50.00mL original volume+23.6mL titrant
(




We organize the solution of the hydrolysis problem around its balanced chemical
equation.

Equation: ( ) ( ) ( )
+ +
4 2 3 3
NH aq + H O(l) NH aq + H O aq

Initial: 0.0720 M 0 M ~ 0 M
Changes: x M +x M +x M
Equil: 0.0720 x b g M x M x M

Chapter 17: Additional Aspects of AcidBase Equilibria
797
K
K
K
x x
x
x
b
w
b
NH H O
NH
= = =
1.0 10
1.8 10
=5.6 10 =
0.0720 0.0720
3 3
+
4
+
14
5
10
2

10 6 +
3
0.0720 5.6 10 6.3 10 M=[H O ]
The assumption is valid ( <<0.0720).
x
x

= =


pH log = 6.3 10 =5.20
6


c h


9A (M) The acidity of the solution is principally the result of the hydrolysis of the carbonate
ion, which is considered first.

Equation: ( ) ( ) ( )
2
3 2 3
CO aq + H O(l) HCO aq + OH aq

Initial: 1.0 M 0 M ~ 0 M
Changes: x M +x M +x M
Equil: 1.0 x b g M x M x M

14 2
3
4 w
b 11 2
a 3 3
HCO OH
1.0 10
= = =2.1 10 =
4.7 10 1.0 1.0 (HCO ) CO
K x x x
K
x K

( (


= ~
(


4 2
1.0 2.1 10 1.5 10 M 0.015 M [OH ] The assumption is valid ( 1.0 ). x x M

= = = = <<
Now we consider the hydrolysis of the bicarbonate ion.

Equation: ( ) ( ) ( )
3 2 2 3
HCO aq + H O(l) H CO aq + OH aq

Initial: 0.015 M 0 M 0.015 M
Changes: y M +y M +y M
Equil: 0.015 y b g M y M 0.015+y b g M

K
K
K
y y
x
y
y
b
w
a
H CO
H CO OH
HCO
= =
1.0 10
4.4 10
=2.3 10 = =
0.015+
0.015
0.015
0.015
=
2 3
14
7
8
2 3
3
F
H
I
K

~
b g


The assumption is valid (y <<0.015) and y = =2.3 10
2 3
8
H CO

M. Clearly, the
second hydrolysis makes a negligible contribution to the acidity of the solution. For the
entire solution, then

pOH logOH log pH = = 0.015 =1.82 =14.00 1.82=12.18

b g

9B (M) The acidity of the solution is principally the result of hydrolysis of the sulfite ion.
Equation: ( ) ( ) ( )
2
3 2 3
SO aq + H O(l) HSO aq + OH aq

Initial: 0.500 M 0 M ~ 0 M
Changes: x M +x M +x M
Equil: 0.500 x b g M x M x M

Chapter 17: Additional Aspects of AcidBase Equilibria
798
14 2
3
7
b
8 2
3 a 3
HSO OH
1.0 10
= = =1.6 10
6.2 10 [SO ] 0.500 0.500 HSO
w
K x x x
K
x K

( (


= = ~



7 4
0.500 1.6 10 2.8 10 M =0.00028 M =[OH ]
The assumption is valid ( <<0.500).
x
x

= =


Next we consider the hydrolysis of the bisulfite ion.

Equation: ( ) ( ) ( )
3 2 2 3
HSO aq + H O(l) H SO aq + OH aq

Initial: 0.00028 M 0 M 0.00028 M
Changes: y M +y M +y M
Equil: 0.00028 y b g M y M 0.00028+y b g M

| |
( )
14
13 w
b 2
a 2 3
2 3
13
b
3
1.0 10
= = =7.7 10
H SO 1.3 10
H SO OH
0.00028+
0.00028
=7.7 10 = = =
0.00028 0.00028
HSO
K
K
K
y y
y
K y
y

(

~
(



The assumption is valid (y <<0.00028) and
| |
13
2 3
= H SO =7.7 10 y

M. Clearly, the
second hydrolysis makes a negligible contribution to the acidity of the solution. For the
entire solution, then
pOH logOH log pH = = 0.00028 =3.55 =14.00 3.55=10.45

b g


INTEGRATIVE EXAMPLE

A. (D)

From the given information, the following can be calculated:
pH of the solution =2.716 therefore, [H
+
] =1.9210
-3


pH at the halfway point =pK
a

pH =4.602 =pK
a

pK
a
=-log K
a
therefore Ka =2.5010
-5




f
f f
f
FP =0C + T
T =-i K
T -1 1.86 C/ molality
m
m
A
A
A =

Chapter 17: Additional Aspects of AcidBase Equilibria
799
molality =
#moles solute #moles solute
=
kg solvent 0.500 kg - 0.00750 kg


To determine the number of moles of solute, convert 7.50 g of unknown acid to moles by
using its molar mass. The molar mass can be calculated as follows:

pH =2.716 [H
+
] =1.9210
-3



+ -
HA H + A
Initial
7.50 g
MM
0.500 L
0 0
Change x x x
Equilibrium
3
7.50 g
MM
1.92 10
0.500 L

| |
|

|
|
\ .
1.9210
-3
1.9210
-3



+ -
-5
3 2
-5
3
[H ][A ]
2.50 10 =
[HA]
(1.92 10 )
2.50 10
7.50
MM
1.92 10
0.500
MM =100.4 g/mol

=
| |
|

|
\ .



1 mol
#moles of solute =7.50 g 0.0747 mol
100.4 g
=

Molality =
#moles solute 0.0747 mol
= 0.152
Kg solvent 0.500 Kg - 0.00750 Kg
m =


f f

f
f
f
T =-i K
T -1 1.86 C/ 0.152
T -0.283 C
FP =0C + T =0C 0.283 C = 0.283 C
m
m m
A
A =
A =
A

Chapter 17: Additional Aspects of AcidBase Equilibria
800
B. (M) By looking at the titration curve provided, one can deduce that the titrant was a strong acid.
The pH before titrant was added was basic, which means that the substance that was titrated was
a base. The pH at the end of the titration after excess titrant was added was acidic, which means
that the titrant was an acid.

Based on the titration curve provided, the equivalence point is at approximately 50 mL of
titrant added. At the halfway point, of approximately 25 mL, the pH =pK
a
. A pH ~8 is
obtained by extrapolation a the halfway point.
pH =8 =pK
a

K
a
=10
-8
=1 10
-8

K
b
=K
w
/K
a
=1 10
-6


~50 mL of 0.2 M strong acid (110
-2
mol) was needed to reach the equivalence point. This
means that the unknown contained 110
-2
mol of weak base. The molar mass of the unknown
can be determined as follows:


2
0.800 g
80 g/mol
1 10 mol

EXERCISES

The Common-Ion Effect

1. (M)
(a) Note that HI is a strong acid and thus the initial H O HI M
3
+
= =0.0892


+
3 5 2 2 3 5 2 3
Equation: HC H O + H O C H O + H O

Initial : 0.275 M 0M 0.0892M
Changes: M x + M + M x x
( ) Equil : 0.275 M x M x ( ) 0.0892+ M x


( )
+
2
3 5 3
5 5
a
3 5 2
C H O H O
0.0892+
0.0892
= =1.3 10 = 4.0 10 M
HC H O 0.275 0.275
x x
x
K x
x

(
(

( (

~ =

The assumption that 0.0892 x M is correct. H O M
3
+
=0.0892

(b) OH
H O
M
w

= =
1.0 10
0.0892
=1.1 10
3
+
14
13
K


(c)
5
3 5 2
C H O = =4.0 10 M x

(




Chapter 17: Additional Aspects of AcidBase Equilibria
801
(d) | |
int
I = HI =0.0892M

(



2. (M)
(a) The NH Cl
4
dissociates completely, and thus,
+
4
int int
NH = Cl =0.102M

( (


Equation:
3 2 4
NH (aq) + H O(l) NH (aq) + OH (aq)
+

Initial: 0.164 M 0.102 M ~ 0 M
Changes: x M +x M +x M
Equil: 0.164 x b gM 0.102+x b gM x M


( )
+
4
5 5
b
3
NH OH
0.102+
0.102
= = =1.8 10 ; =2.9 10 M
NH 0.164 0.164
x x
x
K x
x

(
(

( (

~

Assumed 0.102 M x , a clearly valid assumption. OH M

= =2.9 10
5
x

(b)
4
NH =0.102+ =0.102M x
+
(


(c) Cl M

=0.102
(d) H O M
3
+
14
5
10
=
1.0 10
2.9 10
=3.4 10

3. (M)
(a) We first determine the pH of 0.100 M HNO
2
.

( )
+
2 2 2 3
Equation HNO (aq) + H O(l) NO (aq) + H O (aq)
Initial : 0.100 M 0M 0M
Changes: M + M + M
Equil : 0.100 M M M
x x x
x x x

+
2
2 3
4
a
2
NO H O
= =7.2 10 =
HNO 0.100
x
K
x

(
(

( (

Via the quadratic equation roots formula or via successive approximations,
3 +
3
=8.1 10 M = H O x

(

.
Thus
( )
3
pH= log 8.1 10 =2.09

When 0.100 mol NaNO
2
is added to 1.00 L of a 0.100 M HNO
2
, a solution with
NO M HNO
2 2
=0.100 =

is produced. The answer obtained with the Henderson-

Hasselbalch equation, is pH p log
a
= = 7.2 10 =3.14
4
K

c h
. Thus, the addition has
caused a pH change of 1.05 units.

Chapter 17: Additional Aspects of AcidBase Equilibria
802
(b) NaNO
3
contributes nitrate ion, NO
3

, to the solution. Since, however, there is no

molecularHNO aq
3
b g in equilibrium with hydrogen and nitrate ions, there is no
equilibrium to be shifted by the addition of nitrate ions. The [H
3
O
+
] and the pH are thus
unaffected by the addition of NaNO
3
to a solution of nitric acid. The pH changes are not
the same because there is an equilibrium system to be shifted in the first solution, whereas
there is no equilibrium, just a change in total ionic strength, for the second solution.

4. (M) The explanation for the different result is that each of these solutions has acetate
ion present, C H O
2 3 2

, which is produced in the ionization of acetic acid. The presence

of this ion suppresses the ionization of acetic acid, thus minimizing the increase in
H O
3
+
. All three solutions are buffer solutions and their pH can be found with the aid
of the Henderson-Hasselbalch equation.

(a)
pH p log
C H O
HC H O
log H O M
a
= + =4.74+
0.10
1.0
=3.74 =10 =1.8 10
2 3 2
2 3 2
3
+ 3.74 4
K

% . ionization
H O
HC H O
M
M
= 100%
1.8 10
1.0
100% 0018%
3
2 3 2
4
+

=

=


(b)
2 3 2
a
2 3 2
+ 4.74 5
3
C H O
0.10
pH=p +log =4.74+log =4.74
HC H O 0.10
H O =10 =1.8 10 M
K

(
(


(

(



% . ionization
H O
HC H O
M
M
= 100%
1.8 10
0.10
100% 0018%
3
2 3 2
5
+

=

=


(c)
2 3 2
a
2 3 2
+ 5.74 6
3
C H O
0.10
pH=p +log =4.74+log =5.74
HC H O 0.010
H O =10 =1.8 10 M
K

(
(


(

(



% . ionization
H O
HC H O
M
M
= 100%
1.8 10
0.010
100% 0018%
3
2 3 2
6
+

=

=

5. (M)
(a) The strong acid HCl suppresses the ionization of the weak acid HOCl to such an
extent that a negligible concentration of H O
3
+
is contributed to the solution by
HOCl. Thus, H O HCl M
3
+
= =0.035

Chapter 17: Additional Aspects of AcidBase Equilibria
803
(b) This is a buffer solution. Consequently, we can use the Henderson-Hasselbalch
equation to determine its pH.
( )
4
a
p = log 7.2 10 =3.14; K




2
a
2
NO
0.100M
pH =p +log =3.14+log =3.40
HNO 0.0550M
K

(
(

(



H O M
3
+ 3.40 4
=10 =4.0 10


(c) This also is a buffer solution, as we see by an analysis of the reaction between the
components.
Equation: ( ) ( ) ( )
2 3 2
fromHCl fromNaC H O
+
3 2 3 2 2 3 2 2
H O aq, +C H O aq, HC H O aq +H O(l)

In soln: 0.0525 M 0.0768 M 0 M
Produce HAc: 0.0525 0.0525 +0.0525 M M M
Initial: ~ 0M 0.0243 M 0.0525 M
Now the Henderson-Hasselbalch equation can be used to find the pH.
p log
a
K = 1.8 10 =4.74
5


c h



2 3 2
a
2 3 2
C H O
0.0243M
pH =p +log =4.74+log =4.41
HC H O 0.0525M
K

(
(

(




+ 4.41 5
3
H O =10 =3.9 10 M

(



6. (M)
(a) Neither Ba aq
2+
b g nor Cl aq

b g hydrolyzes to a measurable extent and hence they

have no effect on the solution pH. Consequently, OH

is determined entirely
by the Ba OH b g
2
solute.


( )
( )
2
2
0.0062 mol Ba OH
2mol OH
OH = =0.012M
1 L soln 1mol Ba OH

(



(b) We use the Henderson-Hasselbalch equation to find the pH for this buffer
solution.
( )
( )
+
+ +
4
4 4 4 a 4
2
4 4
2
2 mol NH
NH =0.315M NH SO =0.630M p =9.26for NH .
1 mol NH SO
K
(





| |
3
a
+
4
NH
0.486M
pH=p +log =9.26+log =9.15 pOH=14.00 9.15=4.85
0.630M
NH
K
(



OH M

=10 =1.4 10
4.85 5


Chapter 17: Additional Aspects of AcidBase Equilibria
804
(c) This solution also is a buffer, as analysis of the reaction between its components shows.
Equation: ( ) ( )
( )
4 4 3 2
aq, fromNH Cl aq, fromNaOH NH +OH NH aq + H O(l)
+

In soln: 0.264 M 0.196 M 0 M
Form NH
3
: 0.196 M 0.196 M +0.196 M
Initial: 0.068 M ~ 0M 0.196 M


| |
3
a
+
4
NH
0.196M
pH=p +log =9.26+log =9.72 pOH=14.00 9.72=4.28
0.068M NH
K
(
(



Buffer Solutions

7. (M) H O M
3
+ 4.06 5
=10 =8.7 10

. We let
2
int
= CHO S

(



( ) ( ) ( )
( )
+
2 2 2 3
5 5 5
5 5
Equation: HCHO aq + H O(l) CHO aq + H O aq
Initial : 0.366M M 0M
Changes: 8.7 10 M +8.7 10 M +8.7 10 M
Equil : 0.366M +8.7 10 M 8.7 10 M
S
S

K
S
S
a
H O CHO
HCHO
= =1.8 10 =
+8.7 10 8.7 10
0.366
8.7 10
0.366
3
+
2
2
4
5 5
5

L
N
M
O
Q
P

~

c h
; =0.76 M S

To determineS , we assumed
5
8.7 10 M S

, which is clearly a valid
assumption. Or, we could have used the Henderson-Hasselbalch equation (see
below). p log
a
K = 1.8 10 =3.74
4


c h


2 2
2
2 2
CHO CHO
4.06=3.74+log ; =2.1; CHO =2.1 0.366=0.77M
HCHO HCHO

( (
( (

( (

(




The difference in the two answers is due simply to rounding.

8. (E) We use the Henderson-Hasselbalch equation to find the required [NH
3
].
p log
b
K = 1.8 10 =4.74
5


c h


p p pH log
NH
NH
a b
K K =14.00 =14.00 4.74=9.26 =9.12=9.26+
3
4
+


| |
| |
+ 3 0.14
3 4
+
4
NH
=10 =0.72 NH =0.72 NH =0.72 0.732M =0.53M
NH

(


(



Chapter 17: Additional Aspects of AcidBase Equilibria
805
9. (M)
(a) Equation: ( )
+
7 5 2 2 7 5 2 3
HC H O aq + H O(l) C H O (aq) + H O (aq)

Initial: 0.012 M 0.033 M ~ 0 M
Changes: x M +x M +x M
Equil: ( ) 0.012 M x 0.033+x b gM x M


( )
+
3 7 5 2
5 5
a
7 5 2
H O C H O
0.033+
0.033
= =6.3 10 = =2.3 10 M
HC H O 0.012 0.012
x x
x
K x
x

(
(

( (

~

To determine the value of x , we assumed 0.012 x M, which is an assumption
that clearly is correct.
H O M pH log
3
+ 5 5
=2.3 10 = 2.3 10 =4.64

c h


(b)
( )
( ) ( )
3 2 4
Equation: NH aq + H O(l) NH (aq) +OH (aq)
Initial : 0.408 M 0.153 M 0 M
Changes: M + M + M
Equil : 0.408 M 0.153+ M M
x x x
x x x
+
~

K
x x
x
x
x
b
NH OH
NH
M = =1.8 10 =
0.153+
0.408
0.153
0.408
=4.8 10
4
+
3
5 5

L
N
M
O
Q
P

~
b g


To determine the value of x , we assumed 0.153 x , which clearly is a valid
assumption.

( )
5 5
OH =4.8 10 M; pOH= log 4.8 10 =4.32; pH=14.00 4.32=9.68

(



10. (M) Since the mixture is a buffer, we can use the Henderson-Hasselbalch equation to
determine K
a
of lactic acid.

3 5 3 3 5 3 3 5 3
3 5 3
3 5 3 3 5 3
1.00 g NaC H O 1 mol NaC H O 1 mol C H O 1000 mL
C H O = =0.0892 M
100.0 mL soln 1 L soln 112.1 g NaC H O 1 mol NaC H O

(


3 5 3
a a a
3 5 3
C H O
0.0892 M
pH=4.11=p +log =p +log =p +0.251
HC H O 0.0500 M
K K K

(
(

(


3.86 4
a a
p =4.11 0.251=3.86; =10 =1.4 10 K K



11. (M)
(a) 0.100 M NaCl is not a buffer solution. Neither ion reacts with water to a
detectable extent.
(b) 0.100 M NaCl0.100 M NH Cl
4
is not a buffer solution. Although a weak acid,
NH
4
+
, is present, its conjugate base, NH
3
, is not.

Chapter 17: Additional Aspects of AcidBase Equilibria
806
(c) 0.100 M CH NH
3 2
and 0.150 M CH NH Cl
3
+
3

is a buffer solution. Both the weak
base, CH NH
3 2
, and its conjugate acid, CH NH
3
+
3
, are present in approximately
equal concentrations.
(d) 0.100 M HCl0.050 M NaNO
2
is not a buffer solution. All the NO
2

has
converted to HNO
2
and thus the solution is a mixture of a strong acid and a weak
acid.
(e) 0.100 M HCl0.200 M NaC H O
2 3 2
is a buffer solution. All of the HCl reacts
with half of the C H O
2 2 3

to form a solution with 0.100 M HC H O
2 3 2
, a weak acid,
and 0.100 M C H O
2 2 3

, its conjugate base.

(f) 0.100 M HC H O
2 3 2
and 0.125 M NaC H O
3 5 2
is not a buffer in the strict sense
because it does not contain a weak acid and its conjugate base, but rather the
conjugate base of another weak acid. These two weak acids (acetic,
K
a
=1.8 10
5

, and propionic, K
a
=1.35 10
5

) have approximately the same
strength, however, this solution would resist changes in its pH on the addition of
strong acid or strong base, consequently, it could be argued that this system
should also be called a buffer.
12. (M)
(a) Reaction with added acid:
2 +
4 3 2 4 2
HPO +H O H PO +H O


Reaction with added base: H PO OH HPO H O
2 4 4
2
2
+ +



(b) We assume initially that the buffer has equal concentrations of the two ions,
H PO HPO
2 4 4
2
=



2
2
4
a
2 4
HPO
pH =p +log =7.20+0.00=7.20(pH at which the buffer is most effective).
H PO
K

(

(


(c)
2
4
2 4
HPO
0.150M
pH =7.20+log =7.20+log =7.20+0.48=7.68
0.050M
H PO

(

(




13. (M)
+ +
6 5 3 6 5 3
+
6 5 3
6 +
6 5 3
1mol C H NH Cl 1mol C H NH 1 g
moles of solute=1.15mg
1000mg 129.6 g 1mol C H NH Cl
=8.87 10 mol C H NH

C H NH
mol C H NH
L soln
M
6 5 3
+
6
6 5 3
+
6
=
8.87 10
3.18
=2.79 10

Equation: ( ) ( ) ( )
+
6 5 2 2 6 5 3
C H NH aq + H O(l) C H NH aq + OH aq

Initial: 0.105 M 2.79 10
6

M ~ 0 M
Changes: x M +x M +x M
Equil: 0.105 x b gM 2.79 10 +
6

x
c h
M x M

Chapter 17: Additional Aspects of AcidBase Equilibria
807
K
x x
x
b
C H NH OH
C H NH
= =7.4 10 =
2.79 10 +
0.105
6 5 3
+
6 5 2
10
6
L
N
M
O
Q
P

c h


( ) ( )
10 6 11 10 6 2
7.4 10 0.105 = 2.79 10 + ; 7.8 10 7.4 10 =2.79 10 + x x x x x x



( )
2 6 10 11 2 6 11
+ 2.79 10 +7.4 10 7.8 10 =0; +2.79 10 7.8 10 0 x x x x

=

x
b b ac
a
=
4
2
=
2.79 10 7.78 10 +3.1 10
2
=7.5 10 =
2 6 12 10
6




M OH

pOH log pH = 7.5 10 =5.12 =14.00 5.12=8.88
6

c h


14. (M) We determine the concentration of the cation of the weak base.

+ +
6 5 3 6 5 3
+
+
6 5 3
6 5 3
1 mmol C H NH Cl 1 mmol C H NH
8.50 g
129.6 g 1 mmol C H NH Cl
[C H NH ] 0.0874 M
1 L
750 mL
1000 mL

= =

In order to be an effective buffer, each concentration must exceed the ionization
constant K
b
=7.4 10
10

c h
by a factor of at least 100, which clearly is true. Also, the
ratio of the two concentrations must fall between 0.1 and 10:
C H NH
C H NH
M
M
6 5 3
+
6 5 2
=
0.0874
0.215
=0.407
L
N
M
O
Q
P
.
Since both criteria are met, this solution will be an effective buffer.

15. (M)
(a) First use the Henderson-Hasselbalch equation.
( )
5
b
p = log 1.8 10 =4.74, K


a
p =14.00 4.74=9.26 K to determine NH
4
+
in the buffer solution.

| | | | | |
3 3 3
+ + +
4 4 4
a
NH NH NH
NH NH NH
pH =9.45=p +log =9.26+log ; log =9.45 9.26=+0.19 K
( ( (



| | | |
3 3 0.19 +
4
+
4
NH NH
0.258M
=10 =1.55 NH = = =0.17M
1.55 1.55 NH
(
(

(



We now assume that the volume of the solution does not change significantly when
the solid is added.
( )
( )
+
4 4
4 2
4 4 + 2
4
1mol NH SO
1 L soln 0.17 mol NH
mass NH SO =425mL
1000mL 1 L soln 2mol NH


( )
( )
( )
4 4
2
4 4
2
4 4
2
132.1 g NH SO
=4.8g NH SO
1mol NH SO


Chapter 17: Additional Aspects of AcidBase Equilibria
808
(b) We can use the Henderson-Hasselbalch equation to determine the ratio of
concentrations of cation and weak base in the altered solution.


| | | | | |
3 3 3
a
+ + +
4 4 4
NH NH NH
pH =9.30=p +log =9.26+log log =9.30 9.26=+0.04
NH NH NH
K
( ( (



| |
3 0.04
+
4
NH
0.258
=10 =1.1= 0.19 1.1 0.258 0.062
0.17 M+ M NH
x x M
x
(
(

+ = =

The reason we decided to add x to the denominator follows. (Notice we cannot
remove a component.) A pH of 9.30 is more acidic than a pH of 9.45 and
therefore the conjugate acids NH
4
+
d i
concentration must increase. Additionally,
mathematics tells us that for the concentration ratio to decrease from 1.55 to 1.1,
its denominator must increase. We solve this expression for x to find a value of
0.062 M. We need to add NH
4
+
to increase its concentration by 0.062 M in 100
mL of solution.


( )
( ) ( )
( )
( )
+
4 4 4 4
4 2 2
4 4
2 +
4 4 4 2
4 4
2
1mol NH SO 132.1g NH SO
0.062mol NH
NH SO mass =0.100L
1 L 1mol NH SO 2mol NH
=0.41g NH SO Hence,we needto add 0.4 g

16. (M)
(a)
7 5 2
7 5 2
HC H O 7 5 2 7 5 2
7 5 2
1mol HC H O
=2.00 g HC H O =0.0164mol HC H O
122.1g HC H O
n

7 5 2
7 5 2 7 5 2
7 5 2
C H O
7 5 2 7 5 2
7 5 2
1mol NaC H O 1mol C H O
=2.00 g NaC H O
144.1g NaC H O 1mol NaC H O
=0.0139mol C H O
n

( )
7 5 2
5 7 5 2
a
7 5 2 7 5 2
C H O
0.0139mol C H O /0.7500L
pH =p +log = log 6.3 10 +log
HC H O 0.0164mol HC H O /0.7500L
=4.20 0.0718=4.13
K

(
(

(



(b) To lower the pH of this buffer solution, that is, to make it more acidic, benzoic acid
must be added. The quantity is determined as follows. We use moles rather than
concentrations because all components are present in the same volume of solution.

4.00=4.20+
0.0139 0.0139
= 0.20
7 5 2
7 5 2
7 5 2
7 5 2
log
mol C H O
mol HC H O
log
mol C H O
mol HC H O

x x



0.20 7 5 2
7 5 2
7 5 2
0.0139mol C H O 0.0139
=10 =0.63 = =0.022mol HC H O (required)
mol HC H O 0.63
x
x

Chapter 17: Additional Aspects of AcidBase Equilibria
809

7 5 2
7 5 2 7 5 2 7 5 2
7 5 2 7 5 2
HC H O thatmustbeadded=amountrequired amount already in solution
HC H O thatmustbeadded=0.022mol HC H O 0.0164mol HC H O
HC H O thatmustbeadded=0.006mol HC H O

added mass HC H O mol HC H O
g HC H O
mol HC H O
g HC H O
7 5 2 7 5 2
7 5 2
7 5 2
7 5 2
=0.006
122.1
1
=0.7


17. (M) The added HCl will react with the ammonia, and the pH of the buffer solution will
decrease. The original buffer solution has
| |
3
NH =0.258 M and
4
NH =0.17 M
+
(

.
We first calculate the [HCl] in solution, reduced from 12 M because of dilution. [HCl]
added M
mL
mL
M =12
0.55
100.6
=0.066 We then determine p
a
K for ammonium ion:

p log p
b a
K K = 1.8 10 =4.74 =14.00 4.74=9.26
5

c h


Equation: ( ) ( ) ( ) ( )
+ +
3 3 4 2
NH aq + H O aq NH aq +H O l

Buffer: 0.258 M 0 M 0.17 M
Added: +0.066 M
Changes: 0.066 0.066 +0.066 M M M
Final: 0.192 M 0 M 0.24 M
pH p log
NH
NH
log
a
4
+
= + =9.26+
0.192
0.24
=9.16
3
K
L
N
M
O
Q
P


18. (M) The added NH
3
will react with the benzoic acid, and the pH of the buffer solution
will increase. Original buffer solution has [C
7
H
5
O
2

] =0.0139 mol C
7
H
5
O
2

/0.750 L =
0.0185 M and
| |
7 5 2 7 5 2
HC H O =0.0164mol HC H O /0.7500L =0.0219M. We first
calculate the NH
3
in solution, reduced from 15 M because of dilution.

| |
3
0.35mL
NH added=15M =0.0070M
750.35mL

For benzoic acid, p log
a
K = 6.3 10 =4.20
5


c h


Equation: ( ) ( ) ( ) ( )
+
3 7 5 2 7 5 2 4
NH aq + HC H O aq NH aq + C H O aq

Buffer: 0 M 0.0219 M 0 M 0.0185 M
Added: 0.0070 M
Changes: 0.0070M 0.0070M +0.0070 M +0.0070M
Final: 0.000 M 0.0149 M 0.0070 M 0.0255 M

7 5 2
a
7 5 2
C H O
0.0255
pH=p +log =4.20+log =4.43
HC H O 0.0149
K

(
(

(



Chapter 17: Additional Aspects of AcidBase Equilibria
810
19. (M) The p s
a
K of the acids help us choose the one to be used in the buffer. It is the acid
with a p
a
K within 1.00 pH unit of 3.50 that will do the trick. p
a
K =3.74 for
HCHO p
a 2
, =4.74 K for HC H O
2 3 2
, and
1
p =2.15
a
K for H PO
3 4
. Thus, we choose
HCHO
2
and NaCHO
2
to prepare a buffer with pH=3.50. The Henderson-Hasselbalch
equation is used to determine the relative amount of each component present in the buffer
solution.

2 2
2 2
2
0.24
2
CHO CHO
pH=3.50=3.74+log log =3.50 3.74= 0.24
HCHO HCHO
CHO
=10 =0.58
HCHO

( (
( (

(
(

( (


(



This ratio of concentrations is also the ratio of the number of moles of each component
in the buffer solution, since both concentrations are a number of moles in a certain
volume, and the volumes are the same (the two solutes are in the same solution). This
ratio also is the ratio of the volumes of the two solutions, since both solutions being
mixed contain the same concentration of solute. If we assume 100. mL of acid solution,
acid
=100. mL V . Then the volume of salt solution is
salt 2
=0.58 100. mL =58 mL 0.100 M NaCHO V

20. (D) We can lower the pH of the 0.250 M HC H O M C H O
2 3 2 2 3 2
0.560

buffer
solution by increasing HC H O
2 3 2
or lowering C H O
2 3 2

. Small volumes of NaCl

solutions will have no effect, and the addition of NaOH(aq) or NaC H O aq
2 3 2
b g will
raise the pH. The addition of 0.150 M HCl will raise HC H O
2 3 2
and lower C H O
2 3 2

through the reaction
+
3 2 3 2 2 3 2 2
H O (aq) +C H O (aq) HC H O (aq) +H O(l)

and bring
about the desired lowering of the pH. We first use the Henderson-Hasselbalch equation
to determine the ratio of the concentrations of acetate ion and acetic acid.
pH log
C H O
HC H O
=5.00=4.74+
2 3 2
2 3 2

L
N
M
O
Q
P


2 3 2 2 3 2
0.26
2 3 2 2 3 2
C H O C H O
log =5.00 4.74=0.26; =10 =1.8
HC H O HC H O

( (
( (

( (


Now we compute the amount of each component in the original buffer solution.

amount of C H O mL
mmol C H O
mL soln
mmol C H O
2 3 2
2 3 2
2 3 2
=300.
0.560
1
=168

2 3 2
2 3 2 2 3 2
0.250mmol HC H O
amount of HC H O =300. mL =75.0mmol HC H O
1mL soln


Chapter 17: Additional Aspects of AcidBase Equilibria
811
Now let x represent the amount of H O
3
+
added in mmol.

( )
168
1.8= ; 168 =1.8 75+ =135+1.8 168 135=2.8
75.0+
x
x x x x
x

+
3
168 135
x= =12mmol H O
2.7

+
3
+
3
1mmol HCl 1mL soln
Volume of 0.150 M HCl =12mmol H O
0.150mmol HCl 1mmol H O
=80mL 0.150M HCl solution



21. (M)
(a) The pH of the buffer is determined via the Henderson-Hasselbalch equation.

pH p log
C H O
HC H O
log
M
M
a
= + =4.89+
0.100
0.100
=4.89
3 5 2
3 5 2
K

L
N
M
O
Q
P


The effective pH range is the same for every propionate buffer: from pH=3.89
to pH=5.89, one pH unit on either side of p
a
K for propionic acid, which is 4.89.

(b) To each liter of 0.100 M HC H O M NaC H O
3 5 2 3 5 2
0.100 we can add 0.100
mol OH

before all of the HC H O

3 5 2
is consumed, and we can add 0.100 mol
H O
3
+
before all of the C H O
3 5 2

is consumed. The buffer capacity thus is 100.

millimoles (0.100 mol) of acid or base per liter of buffer solution.

22. (M)
(a) The solution will be an effective buffer one pH uniton either side of the p
a
K of
methylammonium ion,
4
3 3 b
CH NH , =4.2 10 K
+
for methylamine,
p log
b
K = 4.2 10 =3.38
4


c h
. For methylammonium cation,
p
a
K =14.00 3.38=10.62 . Thus, this buffer will be effective from a pH of 9.62 to
a pH of 11.62.
(b) The capacity of the buffer is reached when all of the weak base or all of the
conjugate acid has been neutralized by the added strong acid or strong base.
Because their concentrations are the same, the number of moles of base is equal to
the number of moles of conjugate acid in the same volume of solution.

3 2 3 3
0.0500mmol
amount of weakbase=125 mL =6.25mmol CH NH or CH NH
1mL
+

Thus, the buffer capacity is 6.25 millimoles of acid or base per 125 mL buffer solution.

Chapter 17: Additional Aspects of AcidBase Equilibria
812
23. (M)
(a) The pH of this buffer solution is determined with the Henderson-Hasselbalch equation.

( )
2
4
a
2
CHO
8.5mmol/75.0mL
pH=p +log = log 1.8 10 +log
HCHO 15.5mmol/75.0mL
=3.74 0.26=3.48
K

(
(

(

[Note: the solution is not a good buffer, as CHO
2
1
=1.1 10

, which is only ~
600 times K
a
]

(b) Amount of added OH mmol Ba OH
mmol OH
mmol Ba OH
mmol OH

=0.25
2
1
=0.50
2
2
b g
b g

The OH

added reacts with the formic acid and produces formate ion.

2 2 2
Equation: HCHO (aq) + OH (aq) CHO (aq) + H O(l)
Buffer: 15.5mmol 0M 8.5mmol
Add base: +0.50mmol
React: 0.50mmol 0.50mmol +0.50mmol
Final: 15.0mmol 0mmol 9.0mmol

~

( )
2
4
a
2
CHO
9.0mmol/75.0mL
pH=p +log = log 1.8 10 +log
HCHO 15.0mmol/75.0mL
=3.74 0.22=3.52
K

(
(

(

(c) Amount of added
+
+ + 3
3 3
12 mmol HCl 1 mmol H O
H O =1.05 mL acid =13 mmol H O
1 mL acid 1 mmol HCl

The
3
H O
+
added reacts with the formate ion and produces formic acid.

+
2 3 2 2
Equation: CHO (aq) + H O (aq) HCHO (aq) +H O(l)
Buffer : 8.5mmol 0mmol 15.5mmol
Add acid: 13mmol
React: 8.5mmol 8.5mmol +8.5mmol
Final : 0mmol 4.5mmol 24.0mmol

~
+

The buffer's capacity has been exceeded. The pH of the solution is determined by
the excess strong acid present.
( )
+
3
4.5mmol
H O = =0.059M; pH= log 0.059 =1.23
75.0mL +1.05mL
(


Chapter 17: Additional Aspects of AcidBase Equilibria
813
24. (D) For NH p log
b 3
5
, = 1.8 10 K

c h
For NH p p
4 a b
+
, =14.00 =14.00 4.74=9.26 K K

(a)
| |
3 3
3
3
1.68g NH 1 mol NH
NH = =0.197 M
0.500 L 17.03g NH


( ) ( )
( ) ( )
4 4 4 4
4 2 2
4
4 4 4 4
2 2
4.05g NH SO 1 mol NH SO
2mol NH
NH = =0.123M
0.500L 132.1g NH SO 1mol NH SO
+
+
(



pH p log
NH
NH
log
M
M
a
= + =9.26+
0.197
0.123
=9.46
3
4
K
+ L
N
M
O
Q
P


(b) The OH aq

b g reacts with the NH aq

4
+
b g to produce an equivalent amount of NH aq
3
b g .
OH
g NaOH
L
mol NaOH
g NaOH
mol OH
mol NaOH
M

i
=
0.88
0.500
1
40.00
1
1
=0.044


( ) ( ) ( )
4 3 2
Equation: NH aq + OH aq NH aq + H O(l)
Initial : 0.123M 0M 0.197M
Add NaOH: 0.044M
React: 0.044M 0.044M +0.044M
Final : 0.079M 0.0000M 0.241M
+
~
+

pH p log
NH
NH
log
M
M
a
= + =9.26+
0.241
0.079
=9.74
3
4
K
+ L
N
M
O
Q
P



(c)
( ) ( ) ( )
( ) ( )
+
3 3 4 2
9
Equation: NH aq + H O aq NH aq + H O(l)
Initial : 0.197M 0M 0.123M
Add HCl : + M
React: M M + M
Final : 0.197 M 1 10 M 0 0.123+ M
x
x x x
x x
+

~

~

pH p log
NH
NH
log
M
M
a
=9.00= + =9.26+
0.197
0.123+
3
4
K
x
x
+ L
N
M
O
Q
P
b g
b g

log
M
M
M
M
0.197
0.123+
=9.00 9.26= 0.26
0.197
0.123+
=10 =0.55
0.26

x
x
x
x
b g
b g
b g
b g

0.197 =0.550.123+ =0.068+0.55 1.55 =0.197 0.068=0.129 x x x x b g

x =
0.129
1.55
=0.0832M

+
3
+
3
0.0832 mol H O 1mol HCl 1000mL HCl
volume HCl =0.500L =3.5mL
1L soln 1mol H O 12 mol HCl

Chapter 17: Additional Aspects of AcidBase Equilibria
814
25. (D)
(a) We use the Henderson-Hasselbalch equation to determine the pH of the solution.
The total solution volume is


( )
5
a b
36.00mL +64.00mL =100.00mL. p =14.00 p =14.00 +log 1.8 10 =9.26 K K



NH
mL M NH
mL
mmol NH
mL
M
3
3 3
=
36.00 0.200
100.00
=
7.20
100.0
=0.0720

NH
mL M NH
mL
mmol NH
mL
M
4
4 4
=
64.00 0.200
100.00
=
12.8
100.0
=0.128
+
+ +

3
a
4
[NH ] 0.0720 M
pH=p log 9.26 log 9.01 9.00
0.128M [NH ]
K
+
+ = + = ~

(b) The solution has OH M

=10 =1.0 10
4.99 5

The Henderson-Hasselbalch equation depends on the assumption that:

| |
5
3 4
NH 1.8 10 M NH
+
(

If the solution is diluted to 1.00 L, NH M
3
3
=7.20 10

, and

NH M
4
2
=1.28 10
+
. These concentrations are consistent with the assumption.

However, if the solution is diluted to 1000. L, NH M
3
6
=7.2 10

, and
NH M
3
5
=1.28 10

, and these two concentrations are not consistent with the
assumption. Thus, in 1000. L of solution, the given quantities of NH
3
and NH
4
+

will not produce a solution with pH=9.00. With sufficient dilution, the solution
will become indistinguishable from pure water (i.e.; its pH will equal 7.00).


(c) The 0.20 mL of added 1.00 M HCl does not significantly affect the volume of the
solution, but it does add 0.20 1.00 =0.20
3
+
mL M HCl mmol H O . This added
H O
3
+
reacts with NH
3
, decreasing its amount from 7.20 mmol NH
3
to 7.00
mmol NH
3
, and increasing the amount of NH
4
+
from 12.8 mmol NH
4
+
to 13.0
mmol NH
4
+
, as the reaction: NH H O NH H O
3 3
+
4 2
+ +
+


pH log
mmol NH mL
mmol NH mL
=9.26+
7.00 /100.20
13.0 /100.20
=8.99
3
4
+


(d) We see in the calculation of part (c) that the total volume of the solution does not
affect the pOH of the solution, at least as long as the Henderson-Hasselbalch
equation is obeyed. We let x represent the number of millimoles of H O
3
+
added,
Chapter 17: Additional Aspects of AcidBase Equilibria
815
through 1.00 M HCl. This increases the amount of NH
4
+
and decreases the
amount of NH
3
, through the reaction NH H O NH H O
3 3
+
4 2
+ +
+


7.20 7.20
pH=8.90=9.26+log ; log =8.90 9.26= 0.36
12.8+ 12.8+
x x
x x


Inverting, we have:

( )
0.36
12.8+
=10 =2.29; 12.8+ =2.29 7.20 =16.5 2.29
7.20
x
x x x
x

+
3
16.5 12.8
= =1.1 mmol H O
1.00+2.29
x



vol
+
3
+
3
1mmol HCl 1mL soln
1.00M HCl =1.1mmol H O =1.1mL 1.00M HCl
1mmol H O 1.00mmol HCl


26. (D)
(a)

2 3 2 2 3 2 2 3 2
2 3 2 2 3 2
2 3 2 2 3 2
12.0g NaC H O 1mol NaC H O 1mol C H O
C H O = =0.488M C H O
0.300L soln 82.03g NaC H O 1mol NaC H O

(




+
2 3 2 2 2 3 2 3
2 3 2
+
3
Equation: HC H O +H O C H O + H O
Initial : 0M 0M 0.200M
Add C H O 0M 0.488M 0M
Consume H O +0.200M 0.200M 0.200M
Buffer : 0.200M 0.288M 0M

+

~

Then use the Henderson-Hasselbalch equation to find the pH.


pH p log
C H O
HC H O
log
M
M
a
= + =4.74+
0.288
0.200
=4.74+0.16=4.90
2 3 2
2 3 2
K

L
N
M
O
Q
P


(b) We first calculate the initial OH

due to the added Ba OH b g

2
.

OH
g Ba OH
L
mol Ba OH
g Ba OH
mol OH
mol Ba OH
M

=
1.00
0.300
1
171.3
2
1
=0.0389
2 2
2 2
b g b g
b g b g


Then HC H O
2 3 2
is consumed in the neutralization reaction shown directly below.

Equation:
2 3 2 2 3 2 2
HC H O + OH C H O + H O

Initial: 0.200 M 0.0389 M 0.288 M
Consume OH

: -0.0389 M -0.0389 M +0.0389 M

Buffer: 0.161 M ~0M 0.327 M


Chapter 17: Additional Aspects of AcidBase Equilibria
816
Then use the Henderson-Hasselbalch equation.

pH p log
C H O
HC H O
log
M
M
a
= + =4.74+
0.327
0.161
=4.74+0.31=5.05
2 3 2
2 3 2
K

L
N
M
O
Q
P


(c) Ba OH b g
2
can be added up until all of the HC H O
2 3 2
is consumed.

Ba OH HC H O Ba C H O H O b g b g
2
2 3 2 2 3 2
2
2
+2 +2


( )
( )
( )
( ) ( )
( )
( )
( )
2 3 2 2
2 2
2 3 2
2
2 2 2
2
1mol Ba OH
0.200mol HC H O
moles of Ba OH =0.300L =0.0300mol Ba OH
1L soln 2mol HC H O
171.3g Ba OH
mass of Ba OH =0.0300mol Ba OH =5.14g Ba OH
1mol Ba OH

(d) 0.36 g Ba OH b g
2
is too much for the buffer to handle and it is the excess of OH
-

originating from the Ba(OH)
2
that determines the pOH of the solution.

OH
g Ba OH
L soln
mol Ba OH
g Ba OH
mol OH
mol Ba OH
M OH

=
0.36
0.300
1
171.3
2
1
=1.4 10
2 2
2 2
2
b g b g
b g b g


pOH log pH = 1.4 10 =1.85 =14.00 1.85=12.15
2

c h


AcidBase Indicators

27. (E)
(a) The pH color change range is 1.00 pH unit on either side of p
Hln
K . If the pH color
change range is below pH=7.00, the indicator changes color in acidic solution. If
it is above pH=7.00, the indicator changes color in alkaline solution. If pH=7.00
falls within the pH color change range, the indicator changes color near the neutral
point.

Indicator
HIn
K
HIn
pK pH Color Change Range Changes Color in?
Bromphenol blue 1.4 10
4

3.85 2.9 (yellow) to 4.9 (blue) acidic solution
Bromcresol green 2.1 10
5

4.68 3.7 (yellow) to 5.7 (blue) acidic solution
Bromthymol blue 7.9 10
8

7.10 6.1 (yellow) to 8.1 (blue) neutral solution
2,4-Dinitrophenol 1.3 10
4

3.89 2.9 (colorless) to 4.9 (yellow) acidic solution
Chlorophenol red 1.0 10
6

6.00 5.0 (yellow) to 7.0 (red) acidic solution
Thymolphthalein 1.0 10
10

10.00 9.0 (colorless) to 11.0 (blue) basic solution


(b) If bromcresol green is green, the pH is between 3.7 and 5.7, probably about pH=4.7.
If chlorophenol red is orange, the pH is between 5.0 and 7.0, probably about pH=6.0.

Chapter 17: Additional Aspects of AcidBase Equilibria
817

28. (M) We first determine the pH of each solution, and then use the answer in Exercise
27 (a) to predict the color of the indicator. (The weakly acidic or basic character of the
indicator does not affect the pH of the solution, since very little indicator is added.)

(a) ( )
+
+ 3
3
1 mol H O
H O =0.100 M HCl =0.100 M; pH= log 0.100 M =1.000
1 mol HCl
(


2,4-dinitrophenol is colorless.

(b) Solutions of NaCl(aq) are pH neutral, with pH=7.000. Chlorphenol red assumes
its neutral color in such a solution; the solution is red/orange.

(c) Equation:
+
3 2 4
NH (aq) + H O(l) NH (aq) + OH (aq)

Initial: 1.00 M 0 M ~ 0 M
Changes: x M +x M +x M
Equil: ( ) 1.00 M x x M x M

K
x
x
x
x
b
NH OH
NH
M OH = =1.8 10 =
1.00 1.00
=4.2 10 =
4
+
3
5
2 2
3

L
N
M
O
Q
P

~
(x <<1.00 M, thus the approximation was valid).

pOH log pH = 4.2 10 =2.38 =14.00 2.38=11.62
3

c h


Thus, thymolphthalein assumes its blue color in solutions with pH 11.62 > .

(d) From Figure 17-8, seawater has pH=7.00 to 8.50. Bromcresol green solution is
blue.


29. (M)
(a) In an AcidBase titration, the pH of the solution changes sharply at a definite pH
that is known prior to titration. (This pH change occurs during the addition of a
very small volume of titrant.) Determining the pH of a solution, on the other hand,
is more difficult because the pH of the solution is not known precisely in
advance. Since each indicator only serves to fix the pH over a quite small region,
often less than 2.0 pH units, several indicatorscarefully chosen to span the
entire range of 14 pH unitsmust be employed to narrow the pH to 1 pH unit
or possibly lower.

(b) An indicator is, after all, a weak acid. Its addition to a solution will affect the
acidity of that solution. Thus, one adds only enough indicator to show a color
change and not enough to affect solution acidity.

Chapter 17: Additional Aspects of AcidBase Equilibria
818
30. (E)
(a) We use an equation similar to the Henderson-Hasselbalch equation to determine the
relative concentrations of HIn, and its anion, In

, in this solution.

| | | | | |
HIn
In In In
pH=p +log ; 4.55=4.95+log ; log =4.55 4.95= 0.40
HIn HIn HIn
K

( ( (



| |
0.40
In
40
=10 =0.40= =40 0.40 = =29% In and 71%HIn
HIn 100 1.40
x
x x x
x

(b) When the indicator is in a solution whose pH equals its p
a
K (4.95), the ratio
In HIn

/ =1.00. And yet, at the midpoint of its color change range (about
pH=5.3), the ratio In

/[HIn] is greater than 1.00. Even though HIn In <

at
this midpoint, the contribution of HIn to establishing the color of the solution is
about the same as the contribution of In

. This must mean that HIn (red) is more

strongly colored than In

(yellow).
31. (E)
(a) 0.10 M KOH is an alkaline solution and phenol red will display its basic color in
such a solution; the solution will be red.

(b) 0.10 M HC H O
2 3 2
is an acidic solution, although that of a weak acid, and phenol
red will display its acidic color in such a solution; the solution will be yellow.

(c) 0.10 M NH NO
4 3
is an acidic solution due to the hydrolysis of the ammonium ion.
Phenol red will display its acidic color, that is, yellow, in this solution.

(d) 0.10 M HBr is an acidic solution, the aqueous solution of a strong acid. Phenol red
will display its acidic color in this solution; the solution will be yellow.

(e) 0.10 M NaCN is an alkaline solution because of the hydrolysis of the cyanide ion.
Phenol red will display its basic color, red, in this solution.

(f) An equimolar acetic acidpotassium acetate buffer has pH p
a
= =4.74 K for acetic
acid. In this solution phenol red will display its acid color, namely, yellow.
32. (M)
(a) pH log = 0.205 =0.688 b g The indicator is red in this solution.

(b) The total volume of the solution is 600.0 mL. We compute the amount of each
solute.
amount H O mL M mmol H O
3
+
3
+
=350.0 0.205 =71.8
amount NO mL M mmol NO
2 2
=250.0 0.500 =125


H O
mmol
mL
M NO
mmol
mL
M
3
+
2
=
71.8
600.0
=0.120 =
125
600.0
=0.208

The H O
3
+
and
2
NO

react to produce a buffer solution in which
HNO M
2
=0.120 and NO M
2
=0.208 0.120=0.088

. We use the
Chapter 17: Additional Aspects of AcidBase Equilibria
819
Henderson-Hasselbalch equation to determine the pH of this solution.
p log
a
K = 7.2 10 =3.14
4


c h


2
a
2
NO
0.088M
pH =p +log =3.14+log =3.01
HNO 0.120M
K

(
(

(

The indicator is yellow in this
solution.

(c) The total volume of the solution is 750. mL. We compute the amount and then the
concentration of each solute. Amount OH mL M mmol OH

=150 0.100 =15.0
This OH

reacts with HNO

2
in the buffer solution to neutralize some of it and leave
56.8 mmol (=71.8 15.0 ) unneutralized.
HNO
mmol
mL
M NO
mmol
mL
M
2 2
=
56.8
750.
=0.0757 =
125+15
750.
=0.187

b g

We use the Henderson-Hasselbalch equation to determine the pH of this solution.
pH p log
NO
HNO
log
M
M
a
= + =3.14+
0.187
0.0757
=3.53
2
2
K

L
N
M
O
Q
P

The indicator is yellow in this solution.

(d) We determine the OH

due to the added Ba OH b g

2
.
OH
g Ba OH
L
mol Ba OH
g Ba OH
mol OH
mol Ba OH
M

=
5.00
0.750
1
171.34
2
1
=0.0778
2 2
2 2
b g b g
b g b g

This is sufficient OH

to react with the existing HNO

2
and leave an excess

( ) OH =0.0778M 0.0757M =0.0021M. pOH= log 0.0021 =2.68.
pH=14.00 2.68=11.32 The indicator is blue in this solution.

33. (M) Moles of HCl =C V =0.04050 M 0.01000 L =4.050 10
4
moles
Moles of Ba(OH)
2
at endpoint =C V =0.01120 M 0.01790 L =2.005 10
4
moles.
Moles of HCl that react with Ba(OH)
2
=2 moles Ba(OH)
2
Moles of HCl in excess 4.050 10
4
moles 4.010 10
4
moles =4.05 10
6
moles
Total volume at the equivalence point =(10.00 mL +17.90 mL) =27.90 mL

[HCl]
excess
=
6
4.05 10 mole HCl
0.02790 L

=1.45 10
4
M; pH =log(1.45 10
4
) =3.84

(a) The approximate pK
HIn
=3.84 (generally +1 pH unit)

(b) This is a relatively good indicator (with ~ 1 % of the equivalence point volume),
however, pK
Hin
is not very close to the theoretical pH at the equivalence point
(pH =7.000) For very accurate work, a better indicator is needed (i.e.,
bromthymol blue (pK
Hin
=7.1). Note: 2,4-dinitrophenol works relatively well
here because the pH near the equivalence point of a strong acid/strong base
Chapter 17: Additional Aspects of AcidBase Equilibria
820
titration rises very sharply (~ 6 pH units for an addition of only 2 drops (0.10
mL)).

34. Solution (a): 100.0 mL of 0.100 M HCl, [H
3
O
+
] =0.100 M and pH =1.000 (yellow)
Solution (b): 150 mL of 0.100 M NaC
2
H
3
O
2

K
a
of HC
2
H
3
O
3
=1.8 10
5
K
b
of C
2
H
3
O
2

=5.6 10
10

C
2
H
3
O
2

(aq) + H
2
O(l)
-10
b
=5.6 10 K

HC
2
H
3
O
2
(aq) + OH

(aq)
Initial 0.100 M 0 M ~0 M
Change
x
+x +x
Equil. 0.100 x x x

Assume x is small: 5.6 10
11
=x
2
; x =7.48 10
6
M (assumption valid by inspection)
[OH

] =x =7.48 10
6
M, pOH =5.13 and pH =8.87 (green-blue)
Mixture of solution (a) and (b). Total volume =250.0 mL
n
HCl
=C V =0.1000 L 0.100 M =0.0100 mol HCl
n
C
2
H
3
O
2
=C V =0.1500 L 0.100 M =0.0150 mol C
2
H
3
O
2

HCl is the limiting reagent. Assume 100% reaction.
Therefore, 0.0050 mole C
2
H
3
O
2

is left unreacted, and 0.0100 moles of HC

2
H
3
O
2
form.

[C
2
H
3
O
2

] =
n
V
=
0.0050 mol
0.250 L
=0.020 M [HC
2
H
3
O
2
] =
n
V
=
0.0100 mol
0.250 L
=0.0400 M
HC
2
H
3
O
2
(aq) + H
2
O(l)
-5
a
=1.8 10 K

C
2
H
3
O
2

(aq) + H
3
O
+
(aq)
Initial 0.0400 M 0.020 M ~0 M
Change
x
+x +x
Equil. 0.0400 x 0.020 +x x

1.8 10
-5
=
(0.020 )
0.0400
x x
x
+

~
(0.020)
0.0400
x
x =3.6 10
5


(proof 0.18 % <5%, the assumption was valid)
[H
3
O
+
] =3.6 10
5
pH =4.44 Color of thymol blue at various pHs:


1.2 2.8 8.0 9.8
Red Orange Yellow Green Blue
pH pH pH pH
Solution (a)
RED
Solution (b)
GREEN
Solution (c)
YELLOW
Chapter 17: Additional Aspects of AcidBase Equilibria
821
Neutralization Reactions

35. (E) The reaction (to second equiv. pt.) is: ( ) ( ) ( )
3 4 2 4 2
H PO aq +2KOH aq K HPO aq +2H O(l) .
The molarity of the H PO
3 4
solution is determined in the following manner.

3 4
3 4
3 4
1mmol H PO 0.2420mmol KOH
31.15mL KOHsoln
1mL KOHsoln 2mmol KOH
H PO molarity= =0.1508M
25.00mL H PO soln



36. (E) The reaction (first to second equiv. pt.) is:

( ) ( ) ( )
2 4 2 4 2
NaH PO aq +NaOH aq Na HPO aq +H O(l) . The molarity of the H PO
3 4


solution is determined in the following manner.

H PO molarity
mL NaOHsoln
0.1885mmol NaOH
1mL NaOHsoln
mmol H PO
mmol NaOH
mL H PO soln
M
3 4
3 4
3 4
=
1867
1
1
20.00
=0.1760
.


37. (M) Here we must determine the amount of H O
3
+
or OH

in each solution, and the

amount of excess reagent.
amount H O mL
mmol H SO
mL soln
mmol H O
mmol H SO
mmol H O
3
+ 2 4 3
+
2 4
3
+
=50.00
0.0150
1
2
1
=1.50
(assuming complete ionization of H
2
SO
4
and HSO
4

in the presence of OH

)

amount
0.0385 mmol NaOH 1mmol OH
OH =50.00mL =1.93 mmol OH
1mL soln 1mmol NaOH

Result: ( ) ( )
+
3 2
Titration reaction: OH aq + H O aq 2H O(l)
Initial amounts: 1.93mmol 1.50mmol
After reaction: 0.43mmol 0mmol

( )
3
3
0.43mmol OH
OH = =4.3 10 M
100.0mL soln
pOH = log 4.3 10 =2.37 pH =14.00 2.37=11.63

(




Chapter 17: Additional Aspects of AcidBase Equilibria
822
38. (M) Here we must determine the amount of solute in each solution, followed by the amount of
excess reagent.

H O M
3
+ 2.50
=10 =0.0032

mmol HCl mL
mmol H O
mL soln
mmol HCl
mmol H O
mmol HCl =100.0
0.0032
1
1
1
=0.32
3
+
3
+



3.00 3
pOH=14.00 11.00=3.00 OH =10 =1.0 10 M

(


mmol NaOH mL
mmol OH
mL soln
mmol NaOH
mmol OH
mmol NaOH =100.0
0.0010
1
1
1
=0.10

Result:

( ) ( ) ( )
2
Titration reaction: NaOH aq + HCl aq NaCl aq + H O(l)
Initial amounts: 0.10mmol 0.32mmol 0mmol
After reaction: 0.00mmol 0.22mmol 0.10mmol

+
+ 3 3
3
1mmol H O 0.22mmol HCl
H O = =1.1 10 M
200.0mL soln 1mmol HCl

(


( )
3
pH= log 1.1 10 =2.96

Titration Curves

39. (M) First we calculate the amount of HCl. The relevant titration reaction is

( ) ( ) ( )
2
HCl aq + KOH aq KCl aq + H O(l)

+
3
0.160 mmol HCl
amount HCl =25.00 mL =4.00 mmol HCl =4.00 mmol H O present
1 mL soln


Then, in each case, we calculate the amount of OH

that has been added, determine

which ion, OH aq

b g or H O aq
3
+
b g , is in excess, compute the concentration of that ion,
and determine the pH.
(a) amount
+
3
0.242 mmol OH
OH =10.00 mL =2.42 mmol OH ; H O
1 mL soln

is in excess.

[H O ]
mmol H O mmol OH
mmol H O
1 mmol OH
mL originally+10.00 mL titrant
M
3
+
3
3
+
=
4.00 242
1
2500
=0.0451
+

F
H
G
I
K
J
.
.


pH log = 0.0451 =1.346 b g


Chapter 17: Additional Aspects of AcidBase Equilibria
823
(b) amount
+
3
0.242 mmol OH
OH =15.00 mL =3.63 mmol OH ; H O
1 mL soln

is in excess.

[H O ]
mmol H O mmol OH
mmol H O
1 mmol OH
mL originally+15.00 mL titrant
M
3
+
3
3
+
=
4.00 363
1
2500
=0.00925
+

F
H
G
I
K
J
.
.


pH log = 0.00925 =2.034 b g

40. (M) The relevant titration reaction is ( ) ( ) ( )
2
KOH aq + HCl aq KCl aq + H O(l)

mmol of
0.275 mmol KOH
KOH=20.00 mL =5.50 mmol KOH
1 mL soln


(a) The total volume of the solution is =20.00 mL +15.00 mL =35.00 mL V


0.350 mmol HCl
mmol HCl =15.00 mL =5.25 mmol HCl
1 mL soln


( )
-
- -
1mmol OH
mmol excess OH = 5.50mmol KOH-5.25mmol HCl =0.25mmol OH
1mmol KOH



( )
0.25mmol OH
OH = =0.0071M pOH = log 0.0071 =2.15
35.00mL soln
pH =14.00 2.15=11.85

(b) The total volume of solution is V =20.00 +20.00 =40.00 mL mL mL


0.350mmol HCl
mmol HCl =20.00mL =7.00mmol HCl
1mL soln


( )
+
+ 3
3
1mmol H O
mmol excess H O =7.00mmol HCl 5.50mmol KOH
1mmol HCl

=1.50
3
+
mmol H O

H O
mmol H O
mL
M pH log
3
+ 3
+
=
1.50
40.00
=0.0375 = 0.0375 =1.426 b g

41. (M) The relevant titration reaction is ( ) ( ) ( )
2 2 2
HNO aq + NaOH aq NaNO aq + H O(l)
2
2 2
0.132 mmol HNO
amount HNO =25.00 mL =3.30 mmol HNO
1 mL soln



Chapter 17: Additional Aspects of AcidBase Equilibria
824
(a) The volume of the solution is 25.00 +10.00 =35.00 mL mL mL

amount NaOH mL
mmol NaOH
mL soln
mmol NaOH =10.00
0.116
1
=1.16

1.16 mmol NaNO
2
are formed in this reaction and there is an excess of (3.30 mmol
2 2
HNO 1.16mmol NaOH) =2.14mmol HNO . We can use the
Henderson-Hasselbalch equation to determine the pH of the solution.

p log
a
K = 7.2 10 =3.14
4


c h


pH p log
NO
HNO
log
mmol NO mL
mmol HNO mL
a
= + =3.14+
1.16 / 35.00
2.14 / 35.00
=2.87
2
2
2
2
K

L
N
M
O
Q
P

(b) The volume of the solution is 25.00 +20.00 =45.00 mL mL mL

amount NaOH mL
mmol NaOH
mL soln
mmol NaOH =20.00
0.116
1
=2.32

2.32 mmol NaNO
2
are formed in this reaction and there is an excess of
(3.30 mmol
2
HNO 2.32 mmol NaOH=) 0.98 mmol HNO
2
.

pH p log
NO
HNO
log
mmol NO mL
mmol HNO mL
a
= + =3.14+
2.32 / 45.00
0.98 / 45.00
=3.51
2
2
2
2
K

L
N
M
O
Q
P

42. (M) In this case the titration reaction is NH aq HCl aq NH Cl aq H O l
3 4 2
+ + b g b g b g b g

amount NH mL
mmol NH
mL soln
mmol NH
3
3
3
=20.00
0.318
1
=6.36
(a) The volume of the solution is 20.00 +10.00 =30.00 mL mL mL
amount HCl mL
mmol NaOH
mL soln
mmol HCl =10.00
0.475
1
=4.75
4.75 mmol NH Cl
4
is formed in this reaction and there is an excess of (6.36 mmol
NH
3
4.75 mmol HCl =) 1.61 mmol NH
3
. We can use the Henderson-
Hasselbalch equation to determine the pH of the solution.


( )
5
b a b
p = log 1.8 10 =4.74; p =14.00 p =14.00 4.74=9.26 K K K

pH p log
NH
NH
log
mmol NH mL
mmol NH mL
a
= + =9.26+
1.61 / 30.00
4.75 / 30.00
=8.79
3
4
+
3
4
+
K
(b) The volume of the solution is 20.00 +15.00 =35.00 mL mL mL

amount HCl mL
mmol NaOH
mL soln
mmol HCl =15.00
0.475
1
=7.13

Chapter 17: Additional Aspects of AcidBase Equilibria
825
6.36 mmol NH Cl
4
is formed in this reaction and there is an excess of (7.13 mmol
HCl 6.36 mmol NH
3
=) 0.77 mmol HCl; this excess HCl determines the pH of
the solution.

( )
+
+ 3
3
1mmol H O 0.77mmol HCl
H O = =0.022M pH= log 0.022 =1.66
35.00mL soln 1mmol HCl
(



43. (E) In each case, the volume of acid and its molarity are the same. Thus, the amount of
acid is the same in each case. The volume of titrant needed to reach the equivalence point
will also be the same in both cases, since the titrant has the same concentration in each
case, and it is the same amount of base that reacts with a given amount (in moles) of acid.
Realize that, as the titration of a weak acid proceeds, the weak acid will ionize,
replenishing the H O
3
+
in solution. This will occur until all of the weak acid has ionized
and all of the released H
+
has subsequently reacted with the strong base. At the
equivalence point in the titration of a strong acid with a strong base, the solution contains
ions that do not hydrolyze. But the equivalence point solution of the titration of a weak
acid with a strong base contains the anion of a weak acid, which will hydrolyze to
produce a basic (alkaline) solution. (Dont forget, however, that the inert cation of a
strong base is also present.)

44. (E)
(a) This equivalence point solution is the result of the titration of a weak acid with a
strong base. The CO
3
2
in this solution, through its hydrolysis, will form an
alkaline, or basic solution. The other ionic species in solution, Na
+
, will not
hydrolyze. Thus, pH >7.0.

(b) This is the titration of a strong acid with a weak base. The NH
4
+
present in the
equivalence point solution hydrolyzes to form an acidic solution. Cl

does not
hydrolyze. Thus, pH <7.0.

(c) This is the titration of a strong acid with a strong base. Two ions are present in the
solution at the equivalence point, namely, K
+
and Cl

, neither of which
hydrolyzes. Thus the solution will have a pH of 7.00.

45. (D)
(a) Initial OH M OH pOH log pH

=0.100 = 0.100 =1.000 =13.00 b g
Since this is the titration of a strong base with a strong acid, KI is the solute
present at the equivalence point, and since KI is a neutral salt, the pH=7.00. The
titration reaction is:

( ) ( ) ( )
2
KOH aq +HI aq KI aq +H O(l)

HI
0.100mmol KOH soln 1mmol HI 1mL HI soln
=25.0mL KOH soln
1mL soln 1mmol KOH 0.200mmol HI
=12.5mL HI soln
V


Chapter 17: Additional Aspects of AcidBase Equilibria
826
Initial amount of KOH present mL KOH soln M mmol KOH =25.0 0.100 =2.50
At the 40% titration point: 5.00 0.200 =1.00 mL HI soln M HI mmol HI
excess KOH mmol KOH mmol HI mmol KOH =2.50 1.00 =1.50


( )
1.50mmol KOH 1mmol OH
OH = =0.0500M pOH= log 0.0500 =1.30
30.0mL total 1mmol KOH
pH=14.00 1.30=12.70

At the 80% titration point: 10.00 0.200 =2.00 mL HI soln M HI mmol HI
excess KOH mmol KOH mmol HI mmol KOH =2.50 2.00 =0.50


( )
0.50mmol KOH 1mmol OH
OH = =0.0143M pOH= log 0.0143 =1.84
35.0mL total 1mmol KOH
pH=14.00 1.84=12.16

At the 110% titration point:13.75 0.200 =2.75 mL HI soln M HI mmol HI
excess HI =2.75mmol HI 2.50mmol HI =0.25mmol HI


+ 3
3
1mmol H O 0.25mmol HI
[H O ] 0.0064M; pH= log(0.0064) 2.19
38.8mL total 1mmol HI
+
= = =

Since the pH changes very rapidly at the equivalence point, from about pH=10
to about pH=4, most of the indicators in Figure 17-8 can be used. The main
exceptions are alizarin yellow R, bromphenol blue, thymol blue (in its acid range),
and methyl violet.

(b) Initial pH:
Since this is the titration of a weak base with a strong acid, NH
4
Cl is the solute
present at the equivalence point, and since NH
4
+
is a slightly acidic cation, the pH
should be slightly lower than 7. The titration reaction is:


( ) ( ) ( )
( )
+
3 2 4
Equation: NH aq +H O(l) NH aq + OH aq
Initial : 1.00M 0M 0M
Changes: M + M + M
Equil : 1.00 M M M
x x x
x x x

+
4
5
b
3
NH OH
= =1.8 10
NH
K

(
(

( (


2 2
=
1.00 1.00
x x
x
~

(x <<1.0, thus the approximation is valid)


( )
3 3
=4.2 10 M = OH , pOH= log 4.2 10 =2.38,
pH=14.00 2.38=11.62=initial pH
x

(

3 4 2
: NH +HCl NH Cl +H O Volume of titrant

Chapter 17: Additional Aspects of AcidBase Equilibria
827


3
HCl
3
1.00mmol NH 1mmol HCl 1mL HCl soln
=10.0mL =40.0mL HCl soln
1mL soln 1mmol NH 0.250mmol HCl
V


pH at equivalence point: The total solution volume at the equivalence point is
( ) 10.0+40.0 mL =50.0mL

Also at the equivalence point, all of the NH
3
has reacted to form NH
4
+
. It is this
NH
4
+
that hydrolyzes to determine the pH of the solution.

NH
mL
1.00mmol NH
mLsoln
mmol NH
mmol NH
mL total solution
M
3 4
+
3
4
+
=
100
1
1
1
50.0
=0.200
.



( ) ( ) ( )
( )
+ +
4 2 3 3
Equation: NH aq +H O(l) NH aq +H O aq
Initial : 0.200M 0M 0M
Changes: M + M + M
Equil : 0.200 M M M
x x x
x x x
~

| |
+
14 2 2
3 3
w
a
5
b 3
NH H O
1.0 10
= = = =
1.8 10 NH 0.200 0.200
K x x
K
K x

(
(

(

~


(x <<0.200, thus the approximation is valid)


( )
5 + 5 5
3
=1.1 10 M; H O =1.1 10 M; pH= log 1.1 10 =4.96 x

(



Of the indicators in Figure 17-8, one that has the pH of the equivalence point
within its pH color change range is methyl red (yellow at pH=6.2 and red at
pH=4.5); Bromcresol green would be another choice. At the 50% titration point,
NH NH
3 4
+
= and pOH pK pH
b
= =4.74 =14.00 4.74=9.26

The titration curves for parts (a) and (b) follow.

Chapter 17: Additional Aspects of AcidBase Equilibria
828

46. (M)
(a) This part simply involves calculating the pH of a 0.275 MNH
3
solution.
( ) ( ) ( )
+
3 2 4
Equation: NH aq + H O(l) NH aq + OH aq
Initial: 0.275M 0M 0M
Changes: M + M + M
Equil: (0.275 )M M M
x x x
x x x

K
x
x
x
x
b
NH OH
NH
M OH = =1.8 10 =
0.275 0.275
=2.2 10 =
4
+
3
5
2 2
3

L
N
M
O
Q
P

~
(x <<0.275, thus the approximation is valid)
( )
3
pOH = log 2.2 10 =2.66 pH =11.34

(b) This is the volume of titrant needed to reach the equivalence point.
The relevant titration reaction is NH aq HI aq NH I aq
3 4
+ b g b g b g

( )
3
HI 3
3 3
HI
0.275mmol NH 1mmol HI 1mL HI soln
=20.00mL NH aq
1mL NH soln 1mmol NH 0.325mmol HI
=16.9mL HI soln
V
V



(c) The pOH at the half-equivalence point of the titration of a weak base with a strong
acid is equal to the p
b
K of the weak base.
b
pOH=p =4.74; pH=14.00 4.74=9.26 K

(d) NH
4
+
is formed during the titration, and its hydrolysis determines the pH of the
solution. Total volume of solution=20.00mL +16.9mL =36.9mL

( )
+
+ +
3 4
4 3 4
3 3
0.275mmol NH 1mmol NH
mmol NH =20.00mL NH aq =5.50mmol NH
1mL NH soln 1mmol NH

NH
mmol NH
mL soln
M
4
+
4
+
=
5.50
36.9
=0.149

( ) ( ) ( )
+ +
4 2 3 3
Equation: NH aq + H O(l) NH aq + H O aq
Initial: 0.149M 0M 0M
Changes: M + M + M
Equil: (0.149 )M M M
x x x
x x x
~

Chapter 17: Additional Aspects of AcidBase Equilibria
829
| |
( )
+
14 2 2
3 3
w
a
5 +
b
4
6 + 6
3
NH H O
1.0 10
= = = =
0.149 0.149 1.8 10 NH
( <<0.149, thus the approximation is valid)
=9.1 10 M = H O pH = log 9.1 10 =5.04
K x x
K
K x
x
x

~
(

(



47. (M) A pH greater than 7.00 in the titration of a strong base with a strong acid means that
the base is not completely titrated. A pH less than 7.00 means that excess acid has been
added.

(a) We can determine OH

of the solution from the pH. OH

is also the quotient

of the amount of hydroxide ion in excess divided by the volume of the solution:
20.00 mL base +x mL added acid.

pOH pH OH M
pOH
=14.00 =14.00 12.55=1.45 =10 =10 =0.035
1.45




+
3
0.175mmol OH 0.200mmol H O
20.00mL base mL acid
1mL base 1mL acid
[OH ] 0.035M
20.00mL + mL
x
x

= =
| | | |
| |
\ . \ .


3.50 0.200 =0.70+0.035 ; 3.50 0.70=0.035 +0.200 ; 2.80=0.235 x x x x x
x =
2.80
0.235
=11.9 . mL acid added

(b) The set-up here is the same as for part (a).

pOH pH OH M
pOH
=14.00 =14.00 10.80=3.20 =10 =10 =0.00063
3.20



+
3
0.200mmol H O 0.175mmol OH
20.00mL base mL acid
1mL base 1mL acid
[OH ]
20.00mL + mL
mmol
[OH ] 0.00063 =0.00063M
mL
x
x

| | | |

| |
\ . \ .
=
=

3.50 0.200 =0.0126+0.00063 ; 3.50 0.0126=0.00063 +0.200 ; 3.49=0.201 x x x x x
3.49
= =17.4mL acid added. This is close to the equivalence point at 17.5 mL.
0.201
x


Chapter 17: Additional Aspects of AcidBase Equilibria
830
(c) Here the acid is in excess, so we reverse the set-up of part (a). We are just slightly
beyond the equivalence point. This is close to the mirror image of part (b).
H O M
pH
3
+ 4.25
=10 =10 =0.000056



[ ]
.
H O =
mLacid
0.200mmol H O
mLacid
mL base
0.175mmol OH
1mL base
20.00mL+ mL
M
3
+
3
+
x
x

F
H
G
I
K
J

F
H
G
I
K
J

1
2000
=5.6 10
5

5 5
0.200 3.50=0.0011+5.6 10 ; 3.50+0.0011= 5.6 10 +0.200 ;
3.50=0.200
x x x x
x




3.50
= =17.5mL acid added, which is the equivalence point for this titration.
0.200
x
48. (D) In the titration of a weak acid with a strong base, the middle range of the titration,
with the pH within one unit of p
a
K (=4.74 for acetic acid), is known as the buffer
region. The Henderson-Hasselbalch equation can be used to determine the ratio of weak
acid and anion concentrations. The amount of weak acid then is used in these
calculations to determine the amount of base to be added.

(a)
2 3 2
2 3 2 2 3 2
a
2 3 2 2 3 2
2 3 2 2 3 2
0.89
2 3 2 2 3 2
2 3 2
HC H O
C H O C H O
pH =p +log =3.85=4.74+log
HC H O HC H O
C H O C H O
log =3.85 4.74 =10 =0.13;
HC H O HC H O
0.100mmol HC H O
=25.00mL =2.50mmol
1mL acid
K
n

( (
( (

( (
( (

( (

( (



Since acetate ion and acetic acid are in the same solution, we can use their
amounts in millimoles in place of their concentrations. The amount of acetate ion
is the amount created by the addition of strong base, one millimole of acetate ion
for each millimole of strong based added. The amount of acetic acid is reduced by
the same number of millimoles. HC H O OH C H O H O
2 3 2 2 3 2 2
+ +



013
1
1 0200
250 0200
3
.
.
. .
=


F
H
G
I
K
J
=

x
x
x
x
mL base
0.200mmol OH
mL base
mmol C H O
mmol OH
2.50mmol HC H O mL base
0.200mmol OH
mL base
2 3 2
2 2

0.200 =0.132.50 0.200 =0.33 0.026 0.33=0.200 +0.026 =0.226 x x x x x x b g

0.33
= =1.5mL of base
0.226
x

Chapter 17: Additional Aspects of AcidBase Equilibria
831
(b) This is the same set-up as part (a), except for a different ratio of concentrations.
pH log
C H O
HC H O
log
C H O
HC H O
=5.25=4.74+ =5.25 4.74=0.51
2 3 2
2 3 2
2 3 2
2 3 2

L
N
M
O
Q
P

L
N
M
O
Q
P



C H O
HC H O
2 3 2
2 3 2
0.51
=10 =3.2 3.2=
0.200
2.50 0.200

L
N
M
O
Q
P

x
x

0.200 =3.2 2.50 0.200 =8.0 0.64 8.0=0.200 +0.64 =0.84 x x x x x x b g

8.0
= =9.5mL base. This is close to the equivalence point, which is reached
0.84
by adding 12.5 mL of base.
x


(c) This is after the equivalence point, where the pH is determined by the excess added
base.
pOH pH OH M
pOH
=14.00 =14.00 11.10=2.90 =10 =10 =0.0013
2.90




OH M
mL
0.200mmol OH
mL base
mL mL mL

=0.0013 =
1
+12.50 +25.00
=
0.200
37.50+
x
x
x
x b g


0.200 =0.001337.50+ =0.049+0.0013 =
0.049
0.200 0.0013
=0.25 x x x x b g

mL excess
Total base added=12.5mL to equivalence point+0.25 mL excess=12.8 mL

49. (D) For each of the titrations, the pH at the half-equivalence point equals the pK
a
of the acid.
The initial pH is that of 0.1000 M weak acid:
2
a 3
[H O ]
0.1000
x
K x
x
+
= =

x must be found using the quadratic formula roots equation unless the approximation is
valid.
One method of determining if the approximation will be valid is to consider the ratio C
a
/K
a
. If
the value of C
a
/K
a
is greater than 1000, the assumption should be valid, however, if the value of
C
a
/K
a
is less than 1000, the quadratic should be solved exactly (i.e., the 5% rule will not be
satisfied).

The pH at the equivalence point is that of 0.05000 M anion of the weak acid, for which
the OH

is determined as follows.
2
w w
b
a a
= = 0.05000 [OH ]
0.05000
K K x
K x
K K

~ =
We can determine the pH at the quarter and three quarter of the equivalence point by
using the Henderson-Hasselbalch equation (effectively +0.48 pH unit added to the
pK
a
).

Chapter 17: Additional Aspects of AcidBase Equilibria
832
And finally, when 0.100 mL of base has been added beyond the equivalence point, the
pH is determined by the excess added base, as follows (for all three titrations).

OH
mL
0.1000mmol NaOH
1mL NaOH soln
mmol OH
mmol NaOH
mL soln total
M

=
0100
1
1
20.1
=4.98 10
4
.


pOH log pH = 4.98 10 =3.303 =14.000 3.303=10.697
4

c h


(a) C
a
/K
a
=14.3; thus, the approximation is not valid and the full quadratic equation
must be solved.

Initial: From the roots equation x =
3
[H O ] 0.023M
+
= pH=1.63
Half equivalence point: pH =pK
a
=2.15
pH at quarter equivalence point =2.15 - 0.48 =1.67
pH at three quarter equivalence point =2.15 +0.48 =2.63
Equiv: x =
14
7
3
1.0 10
OH = 0.05000 2.7 10
7.0 10

( =



pOH 6.57
pH 14.00 6.57 7.43
=
= =

Indicator: bromthymol blue, yellow at pH=6.2 and blue at pH=7.8

(b) C
a
/K
a
=333; thus, the approximation is not valid and the full quadratic equation
must be solved.

Initial: From the roots equation x =
3
[H O ] 0.0053M
+
= pH=2.28
Half equivalence point: pH =pK
a
=3.52
pH at quarter equivalence point =3.52 - 0.48 =3.04
pH at three quarter equivalence point =3.52 +0.48 =4.00
Equiv: x =
14
6
4
1.0 10
OH = 0.05000 1.3 10
3.0 10

( =



pOH
pH=14.00
=
=
589
589 811
.
. .

Indicator: thymol blue, yellow at pH=8.0 and blue at pH=9.6

(c) C
a
/K
a
=510
6
; thus, the approximation is valid..

Initial: [ ] . . . H O M
3
+
= = 01000 20 10 0000045
8
pH=4.35
pH at quarter equivalence point =4.35 - 0.48 =3.87
pH at three quarter equivalence point =4.35 +0.48 =4.83
Half equivalence point: pH =pK
a
=7.70

Equiv: x = OH

= =
10 10
2.0 10
0.0500 16 10
14
8
4
.
.

pOH
pH
=
= =
380
1400 380 1020
.
. . .

Chapter 17: Additional Aspects of AcidBase Equilibria
833

Indicator: alizarin yellow R, yellow at pH=10.0 and violet at pH=12.0
The three titration curves are drawn with respect to the same axes in the diagram below.
0
2
4
6
8
10
12
0 2 4 6 8 10 12
Volume of 0.10 M NaOH added (mL)
p
H


50. (D) For each of the titrations, the pOH at the half-equivalence point equals the p
b
K of
the base. The initial pOH is that of 0.1000 M weak base, determined as follows.
2
b a
; 0.1000 [OH ]
0.1000
x
K x K
x

= ~ =

if C
b
/K
b
>1000. For those cases
where this is not the case, the approximation is invalid and the complete quadratic
equation must be solved. The pH at the equivalence point is that of 0.05000 M cation of
the weak base, for which the H O
3
+
is determined as follows.
2
+ w w
a 3
b b
0.05000 [H O ]
0.05000
K K x
K x
K K
= = = =

And finally, when 0.100 mL of acid has been added beyond the equivalence point, the
pH for all three titrations is determined by the excess added acid, as follows.

+
3
+ 4
3
1mmol H O 0.1000mmol HCl
0.100mL HCl
1mL HCl soln 1mmol HCl
H O = =4.98 10 M
20.1 mL soln total


(



pH log = 4.98 10 =3.303
4


c h


(a) C
b
/K
b
=100; thus, the approximation is not valid and the full quadratic equation must be solved.

Initial: From the roots equation x =0.0095. Therefore,
[OH ] 0.0095M pOH=2.02 pH=11.98

=

Half-equiv: pOH log pH = 1 10 =3.0 =11.0
3


c h


Equiv: x =
14
+ 7
3
3
1.0 10
[H O ] 0.05000 7 10 pH =6.2
1 10

= =

Chapter 17: Additional Aspects of AcidBase Equilibria
834
Indicator: methyl red, yellow at pH=6.3 and red at pH=4.5

(b) C
b
/K
b
=33,000; thus, the approximation is valid.

Initial:
6 4
[OH ] 0.1000 3 10 5.5 10 M pOH=3.3 pH=10.7

= =

Half-equiv:
( )
6
pOH = log 3 10 =5.5 pH =14 pOH pH =8.5

Equiv: x =
14
+ 5 5
3
6
1.0 10
[H O ] 0.05000 1 10 pH -log(1 10 ) =5.0
3 10

= =

Indicator: methyl red, yellow at pH=6.3 and red at pH=4.5

(c) C
b
/K
b
=1.410
6
; thus, the approximation is valid.

Initial: [OH M pOH=4.1 pH=9.9

= = ] . 01000 7 10 8 10
8 5


Half-equiv:
( )
8
pOH = log 7 10 =7.2 pH =14 pOH pH =6.8

Equiv: x =
14
+ 5
3 8
1.0 10
[H O ] 0.05000 8.5 10 pH=4.1
7 10

= =

Indicator: bromcresol green, blue at pH=5.5 and yellow at pH=4.0
The titration curves are drawn with respect to the same axes in the diagram below.




51. (D) 25.00 mL of 0.100 M NaOH is titrated with 0.100 M HCl

(i) Initial pOH for 0.100 M NaOH: [OH

] =0.100 M, pOH =1.000 or pH =13.000

(ii) After addition of 24 mL: [NaOH] =0.100 M
25.00 mL
49.00 mL
=0.0510 M
[HCl] =0.100 M
24.00 mL
49.00 mL
=0.0490 M
Chapter 17: Additional Aspects of AcidBase Equilibria
835
NaOH is in excess by 0.0020 M =[OH

] pOH =2.70

(iii) At the equivalence point (25.00 mL), the pOH should be 7.000 and pH =7.000

(iv) After addition of 26 mL: [NaOH] =0.100M
25.00
51.00
=0.0490 M
[HCl] =0.100 M
26.00 mL
51.00 mL
=0.0510 M
HCl is in excess by 0.0020 M =[H
3
O
+
] pH =2.70 or pOH =11.30

(v) After addition of 33.00 mL HCl( xs) [NaOH] =0.100 M
25.00 mL
58.00 mL
=0.0431 M
[HCl] =0.100 M
33.00 mL
58.00 mL
=0.0569 M [HCl]
excess
=0.0138 M pH =1.860, pOH =12.140

The graphs look to be mirror images of one another. In reality, one must reflect about a
horizontal line centered at pH or pOH =7 to obtain the other curve.



52. (D) 25.00 mL of 0.100 M NH
3
is titrated with 0.100 M HCl K
a
=
w
b
K
K
=
14
5
1 10
1.8 10

=5.6 10
10
(i) For initial pOH, use I.C.E.(initial, change, equilibrium) table.
NH
3
(aq) + H
2
O(l)
-5
b
K =1.8 10

NH
4
+
(aq) + OH

(aq)
Initial 0.100 M 0 M 0 M
Change
x
+x +x
Equil. 0.100 x x x
1.8 10
5
=
2
0.100
x
x
~
2
0.100
x
(Assume x ~0) x =1.3 10
3

(x <5% of 0.100, thus, the assumption is valid).
Hence, x =[OH

] =1.3 10
3
pOH =2.89, pH =11.11

(ii) After 2 mL of HCl is added: [HCl] =0.100 M
2.00 mL
27.00 mL
=0.00741 M (after
dilution)
[NH
3
] =0.100 M
25.00 mL
27.00 mL
=0.0926 M (after dilution)

0.100 M NaOH(25.00 mL) + 0.100 M HCl
0
2
4
6
8
10
12
14
0 10 20 30 40 50 60
Volume of HCl (mL)
p
O
H
0.100 M NaOH(25.00 mL) + 0.100 M HCl
0
2
4
6
8
10
12
14
0 10 20 30 40 50 60
Vol ume of HCl (mL)
p
H
Chapter 17: Additional Aspects of AcidBase Equilibria
836
The equilibrium constant for the neutralization reaction is large (K
neut
=K
b
/K
w
=
1.910
5
) and thus the reaction goes to nearly 100% completion. Assume that the
limiting reagent is used up (100% reaction in the reverse direction) and re-establish
the equilibrium by a shift in the forward direction. Here H
3
O
+
(HCl) is the limiting
reagent.

NH
4
+
(aq) +H
2
O(l)
-10
a
=5.6 10 K

NH
3
(aq) + H
3
O
+
(aq)
Initial 0 M 0.0926 M 0.00741 M
Change +x x = 0.00741 x

x
100% rxn 0.00741 0.0852 0
Change
y
re-establish equilibrium +y +y
Equil 0.00741y 0.0852 +y y

5.6 10
10
=
(0.0852 )
(0.00741 )
y y
y
+

=
(0.0852)
(0.00741)
y
(set y ~0) y =4.8 10
11

(the approximation is clearly valid)
y =[H
3
O
+
] =4.8 10
11
; pH =10.32 and pOH =3.68

(iii) pH at 1/2 equivalence point =pK
a
=log 5.6 10
10
=9.25 and pOH =4.75

(iv) After addition of 24 mL of HCl:
[HCl] =0.100 M
24.00 mL
49.00 mL
=0.0490 M; [NH
3
] =0.100 M
25.00 mL
49.00 mL
=0.0510 M

The equilibrium constant for the neutralization reaction is large (see above), and thus
the reaction goes to nearly 100% completion. Assume that the limiting reagent is
used up (100% reaction in the reverse direction) and re-establish the equilibrium in
the reverse direction. Here H
3
O
+
(HCl) is the limiting reagent.
NH
4
+
(aq) +H
2
O(l)
-10
a
=5.6 10 K

NH
3
(aq) +H
3
O
+
(aq)
Initial 0 M 0.0541 M 0.0490 M
Change +x x = 0.0490 x

x
100% rxn 0.0490 0.0020 0
Change
y
re-establish equilibrium +y +y
Equil 0.0490y 0.0020 +y y

5.6 10
10
=
(0.0020 )
(0.0490 )
y y
y
+

=
(0.0020)
(0.0490)
y
(Assume y ~0) y =1.3 10
8
(valid)
y =[H
3
O
+
] = 1.3 10
8
; pH =7.89 and pOH =6.11
(v) Equiv. point: 100% reaction of NH
3
NH
4
+
: [NH
4
+
] =0.100
25.00 mL
50.00 mL
=0.0500 M
NH
4
+
(aq) + H
2
O(l)
-10
a
=5.6 10 K

NH
3
(aq) + H
3
O
+
(aq)
Initial 0.0500 M 0 M ~0 M
Change
x
+x +x
Equil 0.0500x x x

Chapter 17: Additional Aspects of AcidBase Equilibria
837
5.6 10
10
=
2
(0.0500 )
x
x
=
2
0.0500
x
(Assume x ~0) x =5.3 10
6


(the approximation is clearly valid)
x =[H
3
O
+
] =5.3 10
6
; pH =5.28 and pOH =8.72


(vi) After addition of 26 mL of HCl, HCl is in excess. The pH and pOH should be the
same as those in Exercise 51. pH =2.70 and pOH =11.30


(vii) After addition of 33 mL of HCl, HCl is in excess. The pH and pOH should be the
same as those in Exercise 51. pH =1.860 and pOH =12.140. This time the curves
are not mirror images of one another, but rather they are related through a
reflection in a horizontal line centered at pH or pOH =7.

0.100 M NH3 (25mL) + 0.100 HCl
0
2
4
6
8
10
12
14
0 10 20 30 40 50
Volume of HCl (mL)
p
O
H

0.100 M NH3 (25mL) + 0.100 HCl
0
2
4
6
8
10
12
14
0 10 20 30 40 50
Volume of HCl (mL)
p
H


Salts of Polyprotic Acids

53. (E) We expect a solution of Na S
2
to be alkaline, or basic. This alkalinity is created by the
hydrolysis of the sulfide ion, the anion of a very weak acid ( K
2
19
=1 10

forH S
2
).
( ) ( ) ( )
2
2
S aq +H O(l) HS aq +OH aq

54. (E) We expect the pH of a solution of sodium dihydrogen citrate, NaH Cit
2
, to be acidic
because the p
a
K values of first and second ionization constants of polyprotic acids are
reasonably large. The pH of a solution of the salt is the average of pK
1
andpK
2
. For citric
acid, in fact, this average is( ) 3.13+4.77 2=3.95 . Thus, NaH
2
Cit affords acidic
solutions.

55. (M)
(a) ( ) ( ) ( ) ( )
2
3 4 3 2 4 3
H PO aq +CO aq H PO aq +HCO aq

( ) ( ) ( ) ( )
2 2
2 4 3 4 3
H PO aq +CO aq HPO aq +HCO aq

( ) ( ) ( )
2 3
4 4 2
HPO aq +OH aq PO aq +H O(l)

Chapter 17: Additional Aspects of AcidBase Equilibria
838
(b) The pH values of 1.00 M solutions of the three ions are;
1.0 M OH

pH=14.00 1.0 M CO
3
2
pH=12.16 1.0 M PO
4
3
pH=13.15
Thus, we see that CO
3
2
is not a strong enough base to remove the third proton
fromH PO
3 4
. As an alternative method of solving this problem, we can compute
the equilibrium constants of the reactions of carbonate ion withH PO
3 4
, H
2
PO
4
-

and HPO
4
2-
.
3
2 8 3 4 1
3 4 3 2 4 3
11
2 3 2
{H PO } 7.1 10
H PO +CO H PO +HCO 1.5 10
{H CO } 4.7 10
a
a
K
K
K

= = =

8
2 2 3 3 4 2
2 4 3 4 3
11
2 3 2
{H PO } 6.3 10
H PO +CO HPO +HCO 1.3 10
{H CO } 4.7 10
a
a
K
K
K

= = =

13
2 2 3 3 3 4 3
4 3 4 3
11
2 3 2
{H PO } 4.2 10
HPO +CO PO +HCO 8.9 10
{H CO } 4.7 10
a
a
K
K
K

= = =

Since the equilibrium constant for the third reaction is much smaller than 1.00, we
conclude that it proceeds to the right to only a negligible extent and thus is not a
practical method of producingPO
4
3
. The other two reactions have large
equilibrium constants, and products are expected to strongly predominate. They
have the advantage of involving an inexpensive base and, even if they do not go to
completion, they will be drawn to completion by reaction with OH

in the last step

of the process.

56. (M) We expect CO
3
2-
to hydrolyze and the hydrolysis products to determine the pH of
the solution.

Equation:
3 2
HCO (aq) H O(l)

2 3
"H CO "(aq) +
OH aq)

(
Initial 1.00 M 0 M ~ 0 M
Changes: x M +x M +x M
Equil: (1.00 x) M x M x M
| |
( ) ( )
14 2
2 3
8 w
b 7
1
3
H CO OH
1.00 10
= = =2.3 10 = =
4.4 10 1.00 1.00
HCO
x x K x
K
K x

~
(



(C
b
/K
b
=a very large number; thus, the approximation is valid).
x = = =

100 23 10 15 10
8 4
. . . [ ] M OH ; pOH= =

log( . ) . 15 10 382
4
pH=10.18

For ( ) 1.00MNaOH, OH =1.00 pOH= log 1.00 =0.00 pH=14.00

(



Both 1.00
3
M NaHCO and 1.00 M NaOH have an equal capacity to neutralize acids
since one mole of each neutralizes one mole of strong acid.
( ) ( ) ( )
+ +
3 2
NaOH aq +H O aq Na aq +2H O(l)

Chapter 17: Additional Aspects of AcidBase Equilibria
839
( ) ( ) ( ) ( )
+ +
3 3 2 2
NaHCO aq +H O aq Na aq +CO g +2H O(l) .

But on a per gram basis, the one with the smaller molar mass is the more effective.
Because the molar mass of NaOH is 40.0 g/mol, while that of NaHCO
3
is 84.0 g/mol,
NaOH(s) is more than twice as effective as NaHCO
3
(s) on a per gram basis. NaHCO
3
is
preferred in laboratories for safety and expense reasons. NaOH is not a good choice
because it can cause severe burns. NaHCO
3
, baking soda, by comparison, is relatively
non-hazardous. It also is much cheaper than NaOH.


57. (M) Malonic acid has the formula H
2
C
3
H
2
O
4
MM =104.06 g/mol
Moles of H
2
C
3
H
2
O
4
=19.5 g
1 mol
104.06 g
=0.187 mol
Concentration of H
2
C
3
H
2
O
4
=
moles
V
=
0.187 moles
0.250 L
=0.748 M
The second proton that can dissociate has a negligible effect on pH (
2
a
K is very small).
Thus the pH is determined almost entirely by the first proton loss.
H
2
A(aq) + H
2
O(l)

HA

(aq) + H
3
O
+
(aq)
Initial 0.748 M 0 M 0 M
Change
x
+x +x
Equil 0.748x x x

So, x =
2
= ;
0.748
a
x
K
x
pH =1.47, therefore, [H
3
O
+
] =0.034 M =x ,

1
a
K =
2
(0.034)
0.748 0.034
=1.6 10
3

(1.5 10
3
in tables, difference owing to ionization of the second proton)
HA
-
(aq) + H
2
O(l)

A
2
(aq) + H
3
O
+
(aq)
Initial 0.300 M 0 M 0 M
Change
x
+x +x
Equil 0.300x x x
pH =4.26, therefore, [H
3
O
+
] =5.5 10
5
M =x,
2
a
K =
5 2
5
(5.5 10 )
0.300 5.5 10

=1.0 10
8

58. (M) Ortho-phthalic acid.
1
a
K =1.1 10
3
,
2
a
K =3.9 10
6

(a) We have a solution of HA.
HA

(aq) + H
2
O(l)

A
2
(aq) + H
3
O
+
(aq)
Initial 0.350 M 0 M ~0 M
Change
x
+x +x
Equil 0.350x x x

Chapter 17: Additional Aspects of AcidBase Equilibria
840
3.9 10
6
=
2 2
0.350 0.350
x x
x
, x =1.2 10
3

(x 0.350, thus, the approximation is valid)
x =[H
3
O
+
] =1.2 10
3
, pH =2.92

(b) 36.35 g of potassium ortho-phthalate (MM =242.314 g mol
1
)
moles of potassium ortho-phthalate =36.35 g
1 mol
242.314 g
=0.150 mol in 1 L

A
2
(aq) + H
2
O(l)

HA

(aq) + OH

(aq)
Initial 0.150 M 0 M 0 M
Change
x
+x +x
Equil 0.150 x x x


2
2
14 2 2
9 w
6 b,A
a
1.0 10
2.6 10
0.150 0.150 3.9 10
K x x
K
K x

= = = = ~



5
2.0 10 x

= (x <<0.150, so the approximation is valid) =[OH

]
pOH =log 2.010
5
=4.70; pH =9.30

General AcidBase Equilibria

59. (E)
(a) Ba OH b g
2
is a strong base.
2.12
pOH =14.00 11.88=2.12 OH =10 =0.0076 M

(


Ba OH
mol OH
L
mol Ba OH
mol OH
M b g
b g
2
2
=
0.0076
1
1
2
=0.0038

(b)
2 3 2
a
2 3 2 2 3 2
C H O
0.294M
pH=4.52=p +log =4.74+log
HC H O HC H O
K

( (
( (

(




2 3 2
0.294M
log =4.52 4.74
HC H O
(
(


0.22
2 3 2
0.294M
=10 =0.60
HC H O

(
(




| |
2 3 2
0.294M
HC H O = =0.49M
0.60


Chapter 17: Additional Aspects of AcidBase Equilibria
841
60. (M)
(a) pOH OH M =14.00 8.95=5.05 =10 =8.9 10
5.05 6



Equation:
6 5 2 2
C H NH (aq) H O(l) +

C H NH (aq)
6 5 3
+

+
OH aq)

(
Initial x M 0 M ~ 0 M
Changes:


89 10
6
. M

+

89 10
6
. M

+

89 10
6
. M
Equil:
( . ) x

89 10
6
M

89 10
6
.

M

89 10
6
.

M

K
x
b
C H NH OH
C H NH
= =7.4 10 =
8.9 10
8.9 10
6 5 3
+
6 5 2
10
6
2
6

L
N
M
O
Q
P

c h


x x

8.9 10 =
8.9 10
7.4 10
=0.11 =0.11 =
6
6
2
10
c h
M M molarity of aniline

(b) H O M
3
+ 5.12 6
=10 =7.6 10


Equation:
+
4 2
NH (aq) H O(l) +

NH (aq)
3

+
H O aq)
3
+
(
Initial x M 0 M ~ 0 M
Changes:


76 10
6
. M

+

76 10
6
. M

+

76 10
6
. M
Equil:
( . ) x

76 10
6
M

76 10
6
.

M

76 10
6
.

M

K
K
K x
a
w
b
NH H O
NH
for NH
= = =
1.0 10
1.8 10
=5.6 10 =
7.6 10
7.6 10
3 3
+
4
+
3
14
5
10
6
2
6

c h

x x

7.6 10 =
7.6 10
5.6 10
=0.10 = = =0.10
6
6
2
10 4
+
4
c h
M NH NH Cl M

61. (M)
(a) A solution can be prepared with equal concentrations of weak acid and conjugate
base (it would be a buffer, with a buffer ratio of 1.00, where the pH =pK
a
=9.26).
Clearly, this solution can be prepared, however, it would not have a pH of 6.07.

(b) These solutes can be added to the same solution, but the final solution will have an
appreciable HC H O
2 3 2
because of the reaction of H O aq
3
+
b g with C H O aq
2 3 2

b g

Equation:
H O (aq)
3
+

+
C H O (aq)
2 3 2

2 3 2 2
HC H O (aq) +H O(l)
Initial 0.058 M 0.10 M 0 M
Changes: 0.058 M 0.058 M +0.058 M
Equil: 0.000 M 0.04 M 0.058 M
Of course, some H O
3
+
will exist in the final solution, but not equivalent to 0.058 M HI.
Chapter 17: Additional Aspects of AcidBase Equilibria
842
(c) Both 0.10 M KNO
2
and 0.25 M KNO
3
can exist together. Some hydrolysis of the
NO aq
2

b g ion will occur, formingHNO aq

2
b g and OH
-
(aq).

(d) Ba OH b g
2
is a strong base and will react as much as possible with the weak
conjugate acidNH
4
+
, to formNH aq
3
b g .We will end up with a solution
of BaCl aq NH aq
2 3
, b g b g , and unreactedNH Cl aq
4
b g .

(e) This will be a benzoic acidbenzoate ion buffer solution. Since the two
components have the same concentration, the buffer solution will have
pH p log
a
= = 6.3 10 =4.20
5
K

c h
. This solution can indeed exist.

(f) The first three components contain no ions that will hydrolyze. But C H O
2 3 2

is
the anion of a weak acid and will hydrolyze to form a slightly basic solution.
Since pH=6.4 is an acidic solution, the solution described cannot exist.

62. (M)
(a) When H O
3
+
and HC H O
2 3 2
are high and C H O
2 3 2

is very low, a common

+
3
ion H O has been added to a solution of acetic acid, suppressing its ionization.

(b) When C H O
2 3 2

is high and H O
3
+
and HC H O
2 3 2
are very low, we are
dealing with a solution of acetate ion, which hydrolyzes to produce a small
concentration of HC H O
2 3 2
.

(c) When HC H O
2 3 2
is high and both H O
3
+
and C H O
2 3 2

are low, the

solution is an acetic acid solution, in which the solute is partially ionized.

(d) When both HC H O
2 3 2
and C H O
2 3 2

are high while H O

3
+
is low, the
solution is a buffer solution, in which the presence of acetate ion suppresses the
ionization of acetic acid.


INTEGRATIVE AND EXERCISES


63. (M)
(a) O(l) H (aq) SO Na NaOH(aq) (aq) NaHSO
2 4 2 4
+ +


O(l) H aq) ( SO (aq) OH aq) ( HSO
2
2
4

4
+ +

(b) We first determine the mass of NaHSO
4
.
4
4
4
4
4
NaHSO g 988 . 0
NaHSO mol 1
NaHSO g 06 . 120
NaOH mol 1
NaHSO mol 1
L 1
NaOH mol 225 . 0
mL 1000
L 1
mL 56 . 36 NaHSO mass
=
=
Chapter 17: Additional Aspects of AcidBase Equilibria
843

4
1.016 g sample 0.988 g NaHSO
% NaCl 100% 2.8% NaCl
1.016 g sample
= =
(c) At the endpoint of this titration the solution is one of predominantly SO
4
2
, from
which the pH is determined by hydrolysis. Since K
a
for HSO
4

is relatively large (1.1

10
2
), base hydrolysis of SO
4
2
should not occur to a very great extent. The pH of a
neutralized solution should be very nearly 7, and most of the indicators represented
in Figure 17-8 would be suitable. A more exact solution follows.

2
2- 4 4 4
4
4 4
1 mol SO
0.988 g NaHSO 1 mol NaHSO
[SO ] 0.225 M
0.03656 L 120.06 g NaHSO 1 mol NaHSO

= =


2 -
4 2 4
Equation: SO (aq) H O(l) HSO (aq) OH (aq)
Initial: 0.225 M 0 M 0 M
Changes: M M M
Equil: (0.225 )M M M
x x x
x x x

+ +
~
+ +

225 . 0 225 . 0
10 1 . 9
10 1 . 1
10 0 . 1
] SO [
] OH [ ] [HSO
2
13
2
14
w
4

4
b
2
2
x
x
x x
K
K
K
a
~

= =

= = =

13 7
7
[OH ] 9.1 10 0.225 4.5 10 M
(the approximation was valid since <<0.225 M)
pOH log(4.5 10 ) 6.35 pH 14.00 6.35 7.65
x

= =
= = = =


Thus, either bromthymol blue (pH color change range from pH =6.1 to pH =7.9) or
phenol red (pH color change range from pH =6.4 to pH =8.0) would be a suitable
indicator, since either changes color at pH =7.65.

64. (D) The original solution contains
3 5 2
3 5 2
0.100 mmol HC H O
250.0 mL 25.0 mmol HC H O
1 mL soln
=


5
a
p log(1.35 10 ) 4.87 K

= = We let V be the volume added to the solution, in mL.


(a) Since we add V mL of HCl solution (and each mL adds 1.00 mmol H
3
O
+
to the
solution), we have added V mmol H
3
O
+
to the solution. Now the final [H
3
O
+
] =10
1.00

=0.100 M.

3
3
mmol H O
[H O ] 0.100 M
(250.0 ) mL
25.0
25.0 0.100 , therefore, 27.8 mL added
0.900
V
V
V V V
+
+
= =
+
= + = =


Now, we check our assumptions. The total solution volume is 250.0 mL+27.8 mL =
277.8 mL There are 25.0 mmol HC
2
H
3
O
2
present before equilibrium is established,
and 27.8 mmol H
3
O
+
also.

Chapter 17: Additional Aspects of AcidBase Equilibria
844
2 3 2 3
25.0 mmol 27.8 mmol
[HC H O ] 0.0900 M [H O ] 0.100 M
277.8 mL 277.8 mL
+
= = = =

3 5 2 2 3 5 3
2
3 3 5 5 2
a
3 5 2
Equation: HC H O ( ) H O(l) C H O ( ) H O ( )
Initial: 0.0900 M 0 M 0.100 M
Changes: - M M M
Equil: (0.08999 M M (0.100 x)M
[H O ][C H O ]
(0.100 ) 0.10
1.35 10
[HC H O ] 0.0900
aq aq aq
x x x
x) x
x x
K
x
+
+

+ +

+ +
+
+
= = = ~

5
0
1.22 10 M
0.0900
x
x

=


The assumption used in solving this equilibrium situation, that x <<0.0900
clearly is correct. In addition, the tacit assumption that virtually all of the H
3
O
+

comes from the HCl also is correct.

(b) The pH desired is within 1.00 pH unit of the pK
a
. We use the Henderson-
Hasselbalch equation to find the required buffer ratio.

- - -
- - -
-

A A A
a a a
HA HA HA
0.87 A A A
A
HA HA
3 5 2
soln 3 5
2
3 5
2
/ V
[A ]
pH p p log P log 4.00 4.87 log
[HA] / V
log 0.87 10 0.13 3.3
25.00
1 mmol NaC H O 1 mL
V 3.3 mmol C H O
1 mmol C H O
n n n
K K K
n n n
n n n
n
n n

= + = + = + = = +
= = = = =
=
3 5 2
soln
3.3 mL added
1.00 mmol NaC H O
=


We have assumed that all of the C
3
H
5
O
2

is obtained from the NaC

3
H
5
O
2
solution,
since the addition of that ion in the solution should suppress the ionization of
HC
3
H
5
O
2
.

(c) We let V be the final volume of the solution.

3 5 2 2 3 5 3
2
Equation: HC H O ( ) H O(l) C H O ( ) H O ( )
Initial: 25.0/ 0 M 0 M
Changes: M M M
Equil: (25.0/ M M M
aq aq aq
V
x/V x/V x/V
V x/V) x/V x/V
+
+ +
~
+ +

0 . 25
/
/ / 0 . 25
) / (
10 35 . 1
] O H HC [
] O H C [ ] O H [
2 2
5
2 5 3
2
5 3 3
a
V x
V x V
V x
K ~

= = =

+


When V =250.0 mL, x =0.29 mmol H
3
O
+
M 10 2 . 1
mL 250.0
mmol 29 . 0
] O H [
3
3
+
= =

pH =log(1.2 10
3
) =2.92
An increase of 0.15 pH unit gives pH =2.92 +0.15 =3.07
Chapter 17: Additional Aspects of AcidBase Equilibria
845
[H
3
O
+
] =10
3.07
=8.5 10
4
M This is the value of x/V. Now solve for V.

4 2 4 2
5 4
4 5
2
(8.5 10 ) (8.5 10 )
1.3 10 25.0/ 8.5 10 0.056
25.0/ 8.5 10 1.3 10
25.0
25.0/ 0.056 0.00085 0.057 4.4 10 mL
0.057
V
V
V V




= = =

= + = = =

On the other hand, if we had used [H
3
O
+
] =1.16 10
3
M (rather than
1.2 10
3
M), we would obtain V =4.8 10
2
mL. The answer to the problem thus
is sensitive to the last significant figure that is retained. We obtain V =4.6 10
2

mL, requiring the addition of 2.1 10
2
mL of H
2
O.

Another possibility is to recognize that [H
3
O
+
]
a a
K C = for a weak acid with
ionization constant K
a
and initial concentration C
a
if the approximation is valid.

If C
a
is changed to C
a
/2, [H
3
O
+
]
a
2 2.
a
K C = Since, pH =log [H
3
O
+
], the
change in pH given by:
15 . 0 30103 . 0 5 . 0 2 log 5 . 0 2 log 2 log pH
2 / 1
= = = = = A .
This corresponds to doubling the solution volume, that is, to adding 250 mL water.
Diluted by half with water, [H
3
O
+
] goes down and pH rises, then (pH
1
pH
2
) <0.

65. (E) Carbonic acid is unstable in aqueous solution, decomposing to CO
2
(aq) and H
2
O.
The CO
2
(aq), in turn, escapes from the solution, to a degree determined in large part
by the partial pressure of CO
2
(g) in the atmosphere.
H
2
CO
3
(aq) H
2
O(l) +CO
2
(aq) CO
2
(g) +H
2
O(l)

Thus, a solution of carbonic acid in the laboratory soon will reach a low [H
2
CO
3
], since
the partial pressure of CO
2
(g) in the atmosphere is quite low. Thus, such a solution
would be unreliable as a buffer. In the body, however, the [H
2
CO
3
] is regulated in part
by the process of respiration. Respiration rates increase when it is necessary to decrease
[H
2
CO
3
] and respiration rates decrease when it is necessary to increase [H
2
CO
3
].

66. (E)
(a) At a pH =2.00, in Figure 17-9 the pH is changing gradually with added NaOH. There
would be no sudden change in color with the addition of a small volume of NaOH.

(b) At pH =2.0 in Figure 17-9, approximately 20.5 mL have been added. Since,
equivalence required the addition of 25.0 mL, there are 4.5 mL left to add.

Therefore,
4.5
% HCl unneutralized 100% 18%
25.0
= =


Chapter 17: Additional Aspects of AcidBase Equilibria
846
67. (D) Let us begin the derivation with the definition of [H
3
O
+
].

3
3
amount of excess H O
[H O ]
volume of titrant volume of solution being titrated
Let volume of acid ( solution being titrated) volume of base (titrant)
molarity of a
a b
a
V V
M
+
+
=
+
= =
=
3
cid molarity of base
[H O ]
b
a a b b
a b
M
V M V M
V V
+
=

=
+


Now we solve this equation for V
b

b
a a
b
b
a a
b
a a b b b a b b a a
M
M V
V
M
M V
V
M V M V V V M V M V
+

=
+

=
= + + =

+
+
+ + +
pH
pH
3
3
3 3 3
10
) 10 (
] O H [
]) O H [ (
]) O H [ ( ) ] O H ([ ) ( ] O H [


(a)
pH 2.00 2
20.00 mL (0.1500 0.010)
10 10 1.0 10 M 25.45 mL
0.010 0.1000
b
V


= = = =
+


(b)
pH 3.50 4
20.00 mL (0.1500 0.0003)
10 10 3.2 10 M 29.85 mL
0.0003 0.1000
b
V


= = = =
+


(c)
pH 5.00 5
20.00 mL (0.1500 0.00001)
10 10 1.0 10 M 30.00 mL
0.00001 0.1000
b
V


= = = =
+


Beyond the equivalence point, the situation is different.

b a
a a b b
V V
M V M V
+

= =
olume solution v total
OH excess of amount
] OH [

Solve this equation for V
b
. [OH

](V
a
+V
b
) =V
b
M
b
V
a
M
a

] OH [
) ] OH ([
]) OH [ ( ) ] OH ([

+
= = +
b
a a
b b b a a
M
M V
V M V M V

(d)
pOH 14.00 pH 3.50
[OH ] 10 10 10 0.00032 M;
0.00032 0.1500
20.00 mL 30.16 mL
0.1000 0.00032
b
V
+
= = = =
+ | |
= =
|

\ .


(e)
pOH 14.00 pH 2.00
[OH ] 10 10 10 0.010 M;
0.010 0.1500
20.00 mL 35.56 mL
0.1000 0.010
b
V
+
= = = =
+ | |
= =
|

\ .

The initial pH =log(0.150) =0.824. The titration curve is sketched below.
Chapter 17: Additional Aspects of AcidBase Equilibria
847
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
25 30 35
Volume NaOH (ml)
p
H



68. (D)
(a) The expressions that we obtained in Exercise 67 were for an acid being titrated by a
base. For this titration, we need to switch the a and b subscripts and exchange [OH

]
and [H
3
O
+
].


] O H [
] O H [
: point e equivalenc After the
] OH [
] OH [
: point e equivalenc the Before
3
3
+
+

+
=
+

=
a
b
b a
a
b
b a
M
M
V V
M
M
V V



1.00 1
2.00 2
pH 13.00 pOH 14.00 13.00 1.00 [OH ] 10 1.0 10 0.10 M
0.250 0.10
25.00 mL 9.38 mL
0.10 0.300
pH 12.00 pOH 14.00 12.00 2.00 [OH ] 10 1.0 10 0.010 M
0.250 0.010
25.00 mL
0.0
a
a
V
V


= = = = = =

= =
+
= = = = = =

= 19.4 mL
10 0.300
=
+


4.00 4
4.00 4
3
pH 10.00 pOH 14.00 10.00 4.00 [OH ] 10 1.0 10 0.00010 M
0.250 0.00010
25.00 mL 20.8 mL
0.00010 0.300
pH 4.00 [H O ] 10 1.0 10 0.00010 M
0.00010 0.250
25.00 20.
0.300 0.00010
a
a
V
V

+
= = = = = =

= =
+
= = = =
+
= =

3.00 3
3
8 mL
pH 3.00 [H O ] 10 1.0 10 0.0010 M
0.0010 0.250
25.00 21.0 mL
0.300 0.0010
a
V
+
= = = =
+
= =

Chapter 17: Additional Aspects of AcidBase Equilibria
848

(b) Our expression does not include the equilibrium constant, K
a
. But K
a
is not needed
after the equivalence point. pOH =14.00 11.50 =2.50 [OH

] =10
2.50
=3.2 10
3

=0.0032 M

mL 1 . 14
0032 . 0 0500 . 0
0.0032) (0.0100 mL 00 . 50
] O [
]) O [ (
=

+
=

+
=

H M
H M V
V
b
a a
b


Let us use the Henderson-Hasselbalch equation as a basis to derive an expression that
incorporates K
a
. Note that because the numerator and denominator of that expression
are concentrations of substances present in the same volume of solution, those
concentrations can be replaced by numbers of moles.
Amount of anion =V
b
M
b
since the added OH

reacts 1:1 with the weak acid.

Amount of acid =V
a
M
a
V
b
M
b
the acid left unreacted


b b a a
b b
M V M V
M V
K K

+ = + =

log p
HA] [
] [A
log p pH
a a


Rearrange and solve for V
b

b b a a
b b
M V M V
M V

=
pK pH
10

) 10 1 (
10
10 ) (
pK pH
pK pH
pK pH

+
= =
b
a a
b b b b b a a
M
M V
V M V M V M V
pH pK 4.50 4.20
pH pK 5.50 4.20
50.00 mL 0.0100 M 2.0
pH 4.50, 10 10 2.0 6.7 mL
0.0500(1 2.0)
50.00 mL 0.0100 M 20
pH 5.50, 10 10 20. 9.5 mL
0.0500(1 20.)
b
b
V
V



= = = = =
+

= = = = =
+


69. (M)
(a) We concentrate on the ratio of concentrations of which the logarithm is taken.


eq
eq
[conjugate base]
equil. amount conj. base initial amt. weak acid
[weak acid] equil. amount weak acid (1 ) initial amt. weak acid 1
f f
f f

= = =


The first transformation is the result of realizing that the volume in which the weak acid
and its conjugate base are dissolved is the same volume, and therefore the ratio of
equilibrium amounts is the same as the ratio of concentrations. The second
transformation is the result of realizing, for instance, that if 0.40 of the weak acid has
been titrated, 0.40 of the original amount of weak acid now is in the form of its
conjugate base, and 0.60 of that amount remains as weak acid. Equation 17.2 then is:
pH =pK
a
+log (f /(1 f ))
(b) We use the equation just derived.
( )
0.27
pH 10.00 log 9.56
1 0.23
= + =

Chapter 17: Additional Aspects of AcidBase Equilibria
849
70. (M)
(a)
0.20
2
2 2 2
2- 2- 2-
4 4 4
- - -
4 4 4
[HPO ] [HPO ] [HPO ]
pH p log 7.20 log 7.40 10 1.6
[H PO ] [H PO ] [H PO ]
a
K
+
= + = + = = =
(b) In order for the solution to be isotonic, it must have the same concentration of ions
as does the isotonic NaCl solution.
M 31 . 0
NaCl mol 1
ions mol 2
NaCl g 44 . 58
NaCl mol 1
soln L 1
NaCl g 9.2
ions] [ = =
Thus, 1.00 L of the buffer must contain 0.31 moles of ions. The two solutes that are
used to formulate the buffer both ionize: KH
2
PO
4
produces 2 mol of ions (K
+
and
H
2
PO
4

) per mole of solute, while

O H 12 HPO Na
2 4 2

produces 3 mol of ions (2 Na
+

and HPO
4
2
) per mole of solute. We let x =amount of KH
2
PO
4
and y =amount of
O H 12 HPO Na
2 4 2
.
2 4 2 4 2
1.6 or 1.6 2 3 0.31 2 3(1.6 ) 6.8
0.31
0.046 mol KH PO 1.6 0.046 0.074 mol Na HPO 12 H O
6.8
y
y x x y x x x
x
x y
= = + = = + =
= = = =

2 4
2 4 2 4 2 4
2 4
136.08 g KH PO
mass KH PO 0.046 mol KH PO 6.3 g KH PO
1 mol KH PO
= =
2 4 2
2 4 2 2 4 2
2 4 2
2 4 2
358.1 g Na HPO 12H O
mass of Na HPO 12H O 0.074 mol Na HPO 12H O
1 mol Na HPO 12H O
26 g Na HPO 12H O

=

71. (M) A solution of NH
4
Cl should be acidic, hence, we should add an alkaline solution to
make it pH neutral. We base our calculation on the ionization equation for NH
3
(aq), and
assume that little NH
4
+
(aq) is transformed to NH
3
(aq) because of the inhibition of that
reaction by the added NH
3
(aq), and because the added volume of NH
3
(aq) does not
significantly alter the V
total
.

3 2 4
7
7
5 4
b
3
Equation: NH (aq) H O(l) NH (aq) OH (aq)
Initial: M 0.500 M 1.0 10 M
[NH ][OH ] (0.500 M)(1.0 10 M)
1.8 10
[NH ] M
(0.500 M)(1.0 10
M
x
K
x
x
+

+ +

= = =

7
3
3
5
3
3
3
M)
2.8 10 M [NH ]
1.8 10 M
2.8 10 mol NH 1 L conc. soln 1 drop
V 500 mL =2.8 drops 3 drops
1 L final soln 10.0 mol NH 0.05 mL

= =

= ~


Chapter 17: Additional Aspects of AcidBase Equilibria
850
72. (D)
(a) In order to sketch the titration curve, we need the pH at the following points.
i ) Initial point. That is the pH of 0.0100 M p-nitrophenol, which we represent by
the general formula for an indicator that also is a weak acid, HIn.

2 3
Equation: HIn(aq) H O(l) H O (aq) In (aq)
Initial: 0.0100 M 0 M 0 M
Changes: M M M
Equil: (0.0100 ) M M M
x x x
x x x
+
+ +
~
+ +

2
7.15 8 3
HIn
5
a a
8 5 5
3
[H O ] [In ]
10 7.1 10
[HIn] 0.0100 0.0100
/ 1 10 ; thus, the approximation is valid
[H O ] 0.0100 7.1 10 2.7 10 M pH log(2.7 10 ) 4.57
x x x
K
x
C K
+

+

= = = = ~

=
= = = =

ii) At the half-equivalence point, the pH =pK
HIn
=7.15
iii) At the equiv point, pH is that of In

. n
In
=25.00 mL 0.0100 M =0.250 mmol In


titrant
3
1 mmol NaOH 1 mL titrant
V =0.25 mmol HIn 12.5 mL titrant
1 mmol HIn 0.0200 mmol NaOH
0.25 mmol In
[In ] 6.67 10 M 0.00667 M
25.00 mL 12.5 mL

=
= = =
+

2
Equation: In (aq) H O(l) HIn(aq) OH (aq)
Initial: 0.00667 M 0 M 0 M
Changes: M M M
Equil: (0.00667 ) M M M
x x x
x x x

+ +
~
+ +

4
7 w
b 8
a
[HIn][OH ] 1.0 10
1.4 10
[In ] 7.1 10 0.00667 0.00667
K x x x x
K
K x

= = = = ~ =


(C
a
/K
a
=1.410
5
; thus, the approximation is valid)
7 5
5
[OH ] 0.00667 1.4 10 3.1 10
pOH log(3.1 10 ) 4.51; therefore, pH 14.00 pOH 9.49

= =
= = = =

iv) Beyond the equivalence point, the pH is determined by the amount of excess OH
in solution. After 13.0 mL of 0.0200 M NaOH is added, 0.50 mL is in excess, and
the total volume is 38.0 mL.
10.42 pH 3.58 pOH M 10 63 . 2
mL 0 . 38
M 0.0200 mL 50 . 0
] OH [
4
= = =

=


After 14.0 mL of 0.0200 M NaOH is added, 1.50 mL is in excess, and Vtotal =
39.0 mL.
10.89 pH 3.11 pOH M 10 69 . 7
mL 0 . 39
M 0.0200 mL 50 . 1
] OH [
4
= = =

=


v) In the buffer region, the pH is determined with the use of the Henderson-
Hasselbalch equation.
Chapter 17: Additional Aspects of AcidBase Equilibria
851
0.10 0.90
At 0.10, pH 7.15 log 6.20 At 0.90, pH 7.15 log 8.10
0.90 0.10
f f = = + = = = + =
f =0.10 occurs with 0.10 12.5 mL =1.25 mL added titrant; f =0.90 with 11.25
mL added. The titration curve plotted from these points follows.

4
5
6
7
8
9
10
11
12
0 5 10 15 20
Volume NaOH (ml)
pH

(b) The pH color change range of the indicator is shown on the titration curve.

(c) The equivalence point of the titration occurs at a pH of 9.49, far above the pH at which
p-nitrophenol has turned yellow. In fact, the color of the indicator changes gradually during the
course of the titration, making it unsuitable as an indicator for this titration.
Possible indicators are as follows.
Phenolphthalein: pH color change range from colorless at pH =8.0 to red at pH =10.0
Thymol blue: pH color change range from yellow at pH =8.0 to blue at pH =9.8
Thymolphthalein: pH color change range from colorless at 9 pH ~ to blue at 11 pH ~
The red tint of phenolphthalein will appear orange in the titrated p-nitrophenol
solution. The blue of thymol blue or thymolphthalein will appear green in the titrated
p-nitrophenol solution, producing a somewhat better yellow end point than the orange
phenolphthalein endpoint.

73. (M)
(a) Equation (1) is the reverse of the equation for the autoionization of water. Thus, its
equilibrium constant is simply the inverse of Kw.

14
14
w
10 00 . 1
10 0 . 1
1 1
=

= =

K
K

Equation (2) is the reverse of the hydrolysis reaction for NH4+. Thus, its equilibrium
constant is simply the inverse of the acid ionization constant for NH4+, Ka =
5.6 10-10

9
10
a
10 8 . 1
10 6 . 5
1 1
' =

= =

K
K


Chapter 17: Additional Aspects of AcidBase Equilibria
852
(b) The extremely large size of each equilibrium constant indicates that each reaction goes
essentially to completion. In fact, a general rule of thumb suggests that a reaction is considered
essentially complete if Keq >1000 for the reaction.

74. (D) The initial pH is that of 0.100 M HC
2
H
3
O
2
.
2 3 2 2 2 3 2 3
Equation: HC H O (aq) H O(l) C H O (aq) H O (aq)
Initial: 0.100 M 0 M 0 M
Changes: M M M
Equil:
x x x
+
+ +
~
+ +

2
5 3 2 3 2
a
2 3 2
(0.100 ) M M M
[H O ][C H O ]
1.8 10
[HC H O ] 0.100 0.100
x x x
x x x
K
x
+

= = = ~

(C
a
/K
a
=5.510
3
; thus, the approximation is valid)
5 3 3
3
[H O ] 0.100 1.8 10 1.3 10 M pH log(1.3 10 ) 2.89
+
= = = =

At the equivalence point, we have a solution of NH
4
C
2
H
3
O
2
which has a pH =7.00, because
both NH
4
+
and C
2
H
3
O
2

hydrolyze to an equivalent extent, since

) (NH ) O H HC (
3 b 2 3 2 a
K K ~ and their hydrolysis constants also are virtually equal.
Total volume of titrant =10.00 mL, since both acid and base have the same concentrations.

At the half equivalence point, which occurs when 5.00 mL of titrant have been added,
pH =pK
a
=4.74. When the solution has been 90% titrated, 9.00 mL of 0.100 M NH
3

has been added. We use the Henderson-Hasselbalch equation to find the pH after 90% of
the acid has been titrated
69 . 5
1
9
log 74 . 4
] O H HC [
] O H [C
log p pH
2 3 2
2 3 2
a
= + = + =

K
When the solution is 110% titrated, 11.00 mL of 0.100 M NH
3
have been added.
amount NH
3
added =11.00 mL 0.100 M =1.10 mmol NH
3

amount NH
4
+
produced =amount HC
2
H
3
O
2
consumed =1.00 mmol NH
4
+

amount NH
3
unreacted =1.10 mmol NH
3
1.00 mmol NH
4
+
=0.10 mmol NH
3

We use the Henderson-Hasselbalch equation to determine the pH of the solution.
8.26 pH 74 . 5
NH mmol 10 . 0
NH mmol 1.00
log 74 . 4
] NH [
] [NH
log p pOH
3
4
3
4
b
= = + = + =
+ +
K
When the solution is 150% titrated, 15.00 mL of 0.100 M NH
3
have been added.
amount NH
3
added =15.00 mL 0.100 M =1.50 mmol NH
3

amount NH
4
+
produced =amount HC
2
H
3
O
2
consumed =1.00 mmol NH
4
+

amount NH
3
unreacted =1.50 mmol NH
3
1.00 mmol NH
4
+
=0.50 mmol NH
3

8.96 pH 04 . 5
NH mmol 50 . 0
NH mmol 1.00
log 74 . 4
] NH [
] [NH
log p pOH
3
4
3
4
b
= = + = + =
+ +
K
The titration curve based on these points is sketched next. We note that the equivalence
point is not particularly sharp and thus, satisfactory results are not obtained from acetic
acidammonia titrations.

Chapter 17: Additional Aspects of AcidBase Equilibria
853














75. (D) C
6
H
5
NH
3
+
is a weak acid, whose acid ionization constant is determined from
K
b
(C
6
H
5
NH
2
) =7.4 10
10
.
85 . 4 pK and 10 4 . 1
10 4 . 7
10 0 . 1
a
5
10
14
a
= =

K . We first determine the initial pH.

6 5 3 2 6 5 2 3
Equation: C H NH (aq) H O(l) C H NH (aq) H O (aq)
Initial: 0.0500 M 0 M 0 M
Changes: M M M
Equil: (0.0500 ) M M M
x x x
x x x
+ +
+ +
~
+ +

2
5 6 5 2 3
a
6 5 3
3
a a
5 4 4
3
[C H NH ] [H O ]
1.4 10
0.0500 0.0500 [C H NH ]
(Since / =3.610 ; thus, the approximation is valid)
[H O ] 0.0500 1.4 10 8.4 10 M pH log (8.4 10 ) 3.08
x x x
K
x
C K
+

+
+

= = = ~

= = = =



At the equivalence point, we have a solution of C
6
H
5
NH
2
(aq). Now find the volume of
titrant.

6 5 3
6 5 3
6 5 2 6 5 2
6 5 2
6 5 2
0.0500 mmol C H NH 1 mmol NaOH 1 mL titrant
V 10.00 mL 5.00 mL
1 mL 1 mmol C H NH 0.100 mmol NaOH
amount C H NH 10.00 mL 0.0500 M 0.500 mmol C H NH
0.500 mmol C H NH
[C H NH ] 0.03
10.00 mL 5.00 mL
+
+
= =
= =
= =
+
33 M

0
1
2
3
4
5
6
7
8
9
10
0 2 4 6 8 10 12 14 16
Volume of NH3 (mL)
p
H
Chapter 17: Additional Aspects of AcidBase Equilibria
854
6 5 2 2 6 5 3
Equation: C H NH (aq) H O(l) C H NH (aq) OH (aq)
Initial: 0.0333 M 0 M 0 M
Changes: M M M
Equil: (0.033
x x x
+
+ +
~
+ +

2
10 6 5 3
b
6 5 2
b b
10
3 ) M M M
[C H NH ][OH ]
7.4 10
[C H NH ] 0.0333 0.0333
( / =very large number; thus, the approximation is valid)
[OH ] 0.0333 7.4 10 5.
x x x
x x x
K
x
C K
+

= = = ~

= =
6
0 10 pOH 5.30 pH 8.70

= =


At the half equivalence point, when 5.00 mL of 0.1000 M NaOH has been added,
pH =pKa =4.85. At points in the buffer region, we use the expression derived in Exercise
69.

After 4.50 mL of titrant has been added, f =0.90, pH =4.85 +
0.90
log
0.10
=5.80
After 4.75 mL of titrant has been added, f =0.95, pH =4.85 +
0.95
log
0.05
=6.13

After the equivalence point has been reached, with 5.00 mL of titrant added, the pH of the
solution is determined by the amount of excess OH

that has been added.

At 105% titrated,
0.25 mL 0.100 M
[OH ] 0.0016 M pOH 2.80 pH 11.20
15.25 mL

= = = =
At 120% titrated,
1.00 mL 0.100 M
[OH ] 0.00625 M pOH 2.20 pH 11.80
16.00 mL

= = = =

Of course, one could sketch a suitable titration curve by calculating fewer points. Below is
the titration curve.
2
4
6
8
10
12
0 5
Volume NaOH (ml)
p
H

Chapter 17: Additional Aspects of AcidBase Equilibria
855

76. In order for a diprotic acid to be titrated to two distinct equivalence points, the acid must
initially start out with two undissociated protons and the K
a
values for the first and second
protons must differ by >1000. This certainly is not the case for H
2
SO
4
, which is a strong
acid (first proton is 100% dissociated). Effectively, this situation is very similar to the
titration of a monoprotic acid that has added strong acid (i.e., HCl or HNO
3
). With the
leveling effect of water, K
a1
=1 and K
a2
=0.011, there is a difference of only 100 between
K
a1
and K
a2
for H
2
SO
4
.

77. (D) For both titration curves, we assume 10.00 mL of solution is being titrated and the
concentration of the solute is 1.00 M, the same as the concentration of the titrant. Thus,
10.00 mL of titrant is required in each case. (You may be able to sketch titration curves
based on fewer calculated points. Your titration curve will look slightly different if you
make different initial assumptions.)

(a) The initial pH is that of a solution of HCO
3

(aq). This is an anion that can ionize to

CO
3
2
(aq) or be hydrolyzed to H
2
CO
3
(aq). Thus,
34 . 8 ) 33 . 10 35 . 6 ( ) p p ( pH
2
1
2
1
= + = + =
2 1
a a
K K

The final pH is that of 0.500 M H
2
CO
3
(aq). All of the NaOH(aq) has been
neutralized, as well as all of the HCO
3

(aq), by the added HCl(aq).

2 3 2 3 3
Equation: H CO (aq) H O(l) HCO (aq) H O (aq)
Initial: 0.500 M 0 M 0 M
Changes: M M M
Equil
x x x
+
+ +
~
+ +

2
7 3 3
b
2 3
6
a a
: (0.500 ) M M M
[HCO ][H O ]
4.43 10
[H CO ] 0.500 0.500
( / =1.110 ; thus, the approximation is valid)
[OH ] 0.500 4.4
x x x
x x x
K
x
C K
+

= = = ~

=
7 4
10 4.7 10 M pH 3.33

= =


During the course of the titration, the pH is determined by the Henderson-
Hasselbalch equation, with the numerator being the percent of bicarbonate ion
remaining, and as the denominator being the percent of bicarbonate ion that has been
transformed to H
2
CO
3
.

90% titrated: pH =6.35 +log 40 . 5
% 90
% 10
= 10% titrated: pH =6.35 + log 30 . 7
% 10
% 90
=

95% titrated: pH =6.35 +log 07 . 5
% 95
% 5
= 5% titrated: pH =6.35 +log 63 . 7
% 5
% 95
=
After the equivalence point, the pH is determined by the excess H
3
O
+
.
1.61 pH 024 . 0
mL 5 . 20
M 1.00 mL 50 . 0
] O [H titrated, 105% At
3
= =

=
+

Chapter 17: Additional Aspects of AcidBase Equilibria
856
1.04 pH M 091 . 0
mL 0 . 22
M 1.00 mL 00 . 2
] O [H titrated, 120% At
3
= =

=
+

The titration curve derived from these data is sketched below.

0
1
2
3
4
5
6
7
8
9
0 2 4 6 8 10 12
Volume 1.00 M HCl
p
H

(b) The final pH of the first step of the titration is that of a solution of HCO
3

(aq). This
is an anion that can be ionized to CO
3
2
(aq) or hydrolyzed to H
2
CO
3
(aq). Thus,
1 2
1 1
a a 2 2
pH (pK pK ) (6.35 10.33) 8.34 = + = + = . The initial pH is that of 1.000 M
CO
3
2
(aq), which pH is the result of the hydrolysis of the anion.

2
3 2 3
3
b 2
3
Equation: CO (aq) H O(l) HCO (aq) OH (aq)
Initial: 1.000 M 0 M 0 M
Changes: M M M
Equil: (1.000 ) M M M
[HCO ][OH ]
[CO
x x x
x x x
K


+ +
~
+ +

=

2
14 2
4 w
11
4 2
1.0 10
2.1 10
] 4.7 10 1.000 1.000
[OH ] 1.000 2.1 10 1.4 10 M pOH 1.85 pH 12.15
a
K x x x
K x

= = = = ~

= = = =


During the course of the first step of the titration, the pH is determined by the
Henderson-Hasselbalch equation, modified as in Exercise 69, but using as the
numerator the percent of carbonate ion remaining, and as the denominator the
percent of carbonate ion that has been transformed to HCO
3

.

10% 90%
90% titrated: pH 10.33 log 9.38 10% titrated: pH 10.33 log 11.28
90% 10%
5% 95%
95% titrated: pH 10.33 log 9.05 5% titrated: pH 10.33 log 11.61
95% 5%
= + = = + =
= + = = + =


During the course of the second step of the titration, the values of pH are precisely as
they are for the titration of NaHCO
3
, except the titrant volume is 10.00 mL more (the
volume needed to reach the first equivalence point). The solution at the second
Chapter 17: Additional Aspects of AcidBase Equilibria
857
equivalence point is 0.333 M H
2
CO
3
, for which the set-up is similar to that for 0.500 M
H
2
CO
3
.
3.42 pH M 10 8 . 3 10 4 . 4 333 . 0 ] O [H
4 7
3
= = =
+

After the equivalence point, the pH is determined by the excess H
3
O
+
.
3
3
0.50 mL 1.00 M
At 105% titrated, [H O ] 0.0164 M pH 1.8
30.5 mL
2.00 mL 1.00 M
At 120% titrated, [H O ] 0.0625 M pH 1.20
32.0 mL
+
+

= = =

= = =


The titration curve from these data is sketched below.

0
2
4
6
8
10
12
-3 2 7 12 17 22
Volume 1.00 M HCl, mL
p
H


(c)
3
HCl 3
3 3
1 mol NaHCO 1 mol HCl 1000 mL
V 1.00 g NaHCO
84.01 g NaHCO 1 mol NaHCO 0.100 mol HCl
=
HCl M 0.100 mL 119 =

(d)
2 3
HCl 2 3
2 3 2 3
1 mol Na CO 2 mol HCl 1000 mL
V 1.00 g Na CO
105.99 g Na CO 1 mol Na CO 0.100 mol HCl
=
HCl M 0.100 mL 189 =

(e) The phenolphthalein endpoint occurs at pH =8.00 and signifies that the NaOH has
been neutralized, and that Na
2
CO
3
has been half neutralized. The methyl orange
endpoint occurs at about pH =3.3 and is the result of the second equivalence point
of Na
2
CO
3
. The mass of Na
2
CO
3
can be determined as follows:

Chapter 17: Additional Aspects of AcidBase Equilibria
858
3 2 3
2 3
3
2 3
2 3
2 3
2 3 2 3
1 mol HCO 1 mol Na CO 1 L 0.1000 mol HCl
mass Na CO 0.78 mL
1000 mL 1 L soln 1 mol HCl 1 mol HCO
105.99 g Na CO
0.0083 g Na CO
1 mol Na CO
0.0083g
% Na CO 100 8.3% Na CO by mass
0.1000g

=
=
= =


78. (M) We shall represent piperazine as Pip in what follows. The cation resulting from the
first ionization is HPiP
+
, and that resulting from the second ionization is H
2
Pip
2+
.
(a) [Pip] =

4 10 2 2 4 10 2 2

4 10 2 2
1.00g C H N 6H O 1mol C H N 6H O
0.0515
0.100L 194.22g C H N 6H O
M =
2
Equation: (aq) H O(l) H (aq) OH (aq)
Initial: 0.0515 M 0 M 0 M
Changes: M M M
Equil: (0.0515 ) M M
Pip Pip
x x x
x x
+
+ +
~
+ +

M x

C
a
/K
a
=858; thus, the approximation is not valid. The full quadratic equation must be
solved.
1
4.22 5
b
3
[H ][OH ]
10 6.0 10
[ ] 0.0515
From the roots of the equation, =[OH ] 1.7 10 M pOH 2.77 pH 11.23
Pip x x
K
Pip x
x
+

= = = =

= = =


(b) At the half-equivalence point of the first step in the titration, pOH =pK
b1
=4.22
pH =14.00 pOH =14.00 4.22 =9.78

(c) Volume of HCl =100. mL
0.0515mmol Pip 1mmol HCl 1mL titrant
=10.3mL
1mL 1mmol Pip 0.500mmol HCl


(d) At the first equivalence point we have a solution of HPip
+
. This ion can react as a base
with H
2
O to form H
2
Pip
2+
or it can react as an acid with water, forming Pip (i.e. HPip
+

is amphoteric). The solutions pH is determined as follows (base hydrolysis
predominates):
pOH = (pK
b1
+pK
b2
) = (4.22 +8.67) =6.45, hence pH =14.00 6.45 =7.55

(e) The pOH at the half-equivalence point in the second step of the titration equals pK
b2
.
pOH =pK
b2
=8.67 pH =14.00 8.67 =5.33

(f) The volume needed to reach the second equivalence point is twice the volume
needed to reach the first equivalence point, that is 2 10.3 mL =20.6 mL.

(g) The pH at the second equivalence point is determined by the hydrolysis of the
H
2
Pip
2+
cation, of which there is 5.15 mmol in solution, resulting from the reaction
Chapter 17: Additional Aspects of AcidBase Equilibria
859
of HPip
+
with HCl. The total solution volume is 100. mL +20.6 mL =120.6 mL
[H
2
Pip
2+
] =
2
8.67 9
5.15
0.0427 10 2.1 10
120.6
b
mmol
M K
mL

= = =

2+
2 2 3
Equation: H Pip (aq) H O(l) HPip (aq) H O (aq)
Initial: 0.0427 M 0 M 0 M
Changes: M M M
Equil: (0.0427 ) M
x x x
x
+ +
+ +
~
+ +

2
14 2
6 3
a 9 2+
2
6 4
3
M M
[HPip ][H O ] 1.00 10
4.8 10
2.1 10 [H Pip ] 0.0427 0.0427
[H O ] 0.0427 4.8 10 4.5 10 M pH 3.347
w
b
x x
K x x x
K
K x
x
+ +

+

= = = = = ~

= = = =

(x <<0.0427; thus, the approximation is valid).
79. (M) Consider the two equilibria shown below.
H
2
PO
4
-
(aq) +H
2
O(l)

HPO
4
2-
(aq) +H
3
O
+
(aq) K
a2
=
2- +
4 3
-
2 4
[HPO ][H O ]
[H PO ]

H
2
PO
4
-
(aq) +H
2
O(l)

H
3
PO
4
(aq) +OH
-
(aq) K
b
=K
w
/K
a1
=
-
3 4
-
2 4
[H PO ][OH ]
[H PO ]

All of the phosphorus containing species must add up to the initial molarity M.
Hence, mass balance: [HPO
4
2-
] +[H
2
PO
4
-
] +[H
3
PO
4
] =M
charge balance: [H
3
O
+
] +[Na
+
] =[H
2
PO
4
-
] +2[HPO
4
2-
]
Note: [Na
+
] for a solution of NaH
2
PO
4
=M

Thus, [H
3
O
+
] +[Na
+
] =[H
2
PO
4
-
] +2[HPO
4
2-
] =[H
3
O
+
] +M (substitute mass balance equation)
[H
3
O
+
] +[HPO
4
2-
] +[H
2
PO
4
-
] +[H
3
PO
4
] =[H
2
PO
4
-
] +2[HPO
4
2-
] (cancel terms)
[H
3
O
+
] =[HPO
4
2-
] - [H
3
PO
4
]
(Note: [HPO
4
2-
] =initial [H
3
O
+
] and [H
3
PO
4
] =initial [OH
-
])
Thus: [H
3
O
+
]
equil
=[H
3
O
+
]
initial
|OH

]
initial
(excess H
3
O
+
reacts with OH
-
to formH
2
O)

Rearrange the expression for K
a2
to solve for [HPO
4
2-
], and the expression for K
b
to solve
for [H
3
PO
4
].
- -
+ 2- a2 2 4 b 2 4
3 4 3 4
+ -
3
K [H PO ] K [H PO ]
[H O ] =[HPO ] - [H PO ] =
[H O ] [OH ]

- w
2 4 - - + -
+ a2 2 4 1 a2 2 4 3 2 4
3
+ +
w
a1 3 3
+
3
K
[H PO ]
K [H PO ] K [H PO ] [H O ][H PO ]
[H O ]
K
K [H O ] [H O ]
[H O ]
a
K
= =

Multiply through by [H
3
O
+
] K
a1
and solve for [H
3
O
+
].
Chapter 17: Additional Aspects of AcidBase Equilibria
860
+ + - + + -
a1 3 3 a1 a2 2 4 3 3 2 4
+ 2 - + 2 -
a1 3 a1 a2 2 4 3 2 4
+ 2 + 2 - - + 2 -
a1 3 3 2 4 a1 a2 2 4 3 a1 2 4
+ 2 + 2 - -
a1 3 3 2 4 a1 a2 2 4
K [H O ][H O ] K K [H PO ] [H O ][H O ][H PO ]
K [H O ] K K [H PO ] [H O ] [H PO ]
K [H O ] [H O ] [H PO ] K K [H PO ] =[H O ] (K [H PO ])
K [H O ] [H O ] [H PO ] K K [H PO ] =
=
=
+ = +
+ =
+ 2 -
3 a1 2 4
-
+ 2 - - a1 a2 2 4
3 2 4 a1 2 4
-
a1 2 4
[H O ] (K [H PO ])
K K [H PO ]
[H O ] = For moderate concentrations of [H PO ], K <<[H PO ]
(K [H PO ])
+
+

-
+ 2 a1 a2 2 4
3 a1 a2 -
2 4
+ 2 + 12
3 a1 a2 3 a1 a2 a1 a2
K K [H PO ]
This simplifies our expression to: [H O ] = =K K
[H PO ]
Take the square root of both sides: [H O ] =K K [H O ] = K K (K K )
Take the -log of both sides and simplif
=
( )
+ 12
3 a1 a2 a1 a2 a1 a2
+ +
3 a1 a2 3 a1 a1 a2 a2
+
3 a1 a2 a1
y:
-log[H O ] = log(K K ) 12 log(K K ) 12(logK +logK )
-log[H O ] 12( logK logK ) Use -log[H O ] =pH and logK pK logK pK
Hence, -log[H O ] = 12( logK logK ) becomes pH =12(pK
= =
= = =
+
a2
+pK ) (Equation 17.5)
Equation 17.6 can be similarly answered.


80. (D) H
2
PO
4

can react with H

2
O by both ionization and hydrolysis.

- 2
2 4 2 4 3
H PO (aq) H O(l) HPO (aq) H O (aq)
+
+ +

2- 3
4 2 4 3
HPO (aq) H O(l) PO (aq) H O (aq)
+
+ +

The solution cannot have a large concentration of both H
3
O
+
and OH

(cannot be
simultaneously an acidic and a basic solution). Since the solution is acidic, some of the
H
3
O
+
produced in the first reaction reacts with virtually all of the OH

produced in the
second. In the first reaction [H
3
O
+
] =[HPO
4
2
] and in the second reaction [OH

] =
[H
3
PO
4
]. Thus, following the neutralization of OH

by H
3
O
+
, we have the following.

2 2 1
2
1
- w
2 4 - -
-
2 4 2 4 2- - b 2 4
3 4 2 4
w
3 3
3
-
-
2 4
3 2 4
3
3
1
3
Then multiply through by [H O ]
and solve for [H O ].
[H PO ]
[H PO ] [H PO ]
[H PO ]
[H O ] [HPO ] [H PO ]
[H O ] [OH ] [H O ]
[H O ]
[H PO ]
[H O ][H PO ]

[H O ]
a a a
a
a
a
K
K
K K K
K
K
K
K
+
+ +
+
+
+
+
+
= = =
=


1 2
1 1 2
1
-
2 4
2 - 2 -
3 2 4 3 2 4 3
-
2 4
[H PO ]
[H O ] [H PO ] [H O ] [H PO ] [H O ]
[ [H PO ]
a a
a a a
a
K K
K K K
K
+ + +
= =
+


But, for a moderate [H
2
PO
-
4
], from Table 16-6,
1
a
K =7.1 10
3
<[H
2
PO
-
4
] and thus
] PO H [ ] PO H [
4 2 4 2
1

~ +
a
K . Then we have the following expressions for [H
3
O
+
] and pH.

Chapter 17: Additional Aspects of AcidBase Equilibria
861
1 2
1 2 1 2 1 2
1 2
3
1/2
1 1
3 2 2
1
2
[H O ]
pH log[H O ] log( ) [ log( )] ( log log )
pH (p p )
+
+
=
= = = =
= +
a a
a a a a a a
a a
K K
K K K K K K
K K


Notice that we assumed K
a
<[H
2
PO
4

]. This assumption is not valid in quite dilute

solutions because K
a
=0.0071.

81. (D)
(a) A buffer solution is able to react with small amounts of added acid or base. When strong acid is
added, it reacts with formate ion.

O H (aq) HCHO (aq) O H aq) ( CHO
2 2 3 2
+ +
+


Added strong base reacts with acetic acid.

(aq) O H C O(l) H (aq) OH (aq) O H HC
2 3 2 2 2 3 2

+ +


Therefore neither added strong acid nor added strong base alters the pH of the solution very much.
Mixtures of this type are referred to as buffer solutions.

(b) We begin with the two ionization reactions.


2 2 2 3
HCHO (aq) H O(l) CHO (aq) H O (aq)
+
+ +

2 3 2 2 2 3 2 3
HC H O (aq) H O(l) C H O (aq) H O (aq)
+
+ +

3 2 3 2 2
[Na ] 0.250 [OH ] 0 [H O ] [C H O ] [CHO ] x y z
+ +
= ~ = = =

y = = + =

150 . 0 ] O H C [ 150 . 0 ] O H [HC ] O H C [ ] O H HC [ 150 . 0
2 3 2 2 3 2 2 3 2 2 3 2

z = = + =

250 . 0 ] CHO [ 250 . 0 ] [HCHO ] CHO [ ] HCHO [ 250 . 0
2 2 2 2


] OH [ ] CHO [ ] O H C [ ] O [H ] Na [
2 2 3 2 3
+ +
+ + = + (electroneutrality)
z y x + = + = +

] CHO [ ] O H C [ 250 . 0
2 2 3 2
(1)


y
y x
K

= = =

+
150 . 0
10 8 . 1
] O H [HC
] O H C ][ O H [
5
A
2 3 2
2 3 2 3
(2)


z
z x
K

= = =

+
250 . 0
10 8 . 1
] [HCHO
] ][CHO O [H
4
F
2
2 3
(3)

There now are three equations(1), (2), and (3)in three unknownsx, y, and z.
We solve equations (2) and (3), respectively, for y and z in terms of x.

Chapter 17: Additional Aspects of AcidBase Equilibria
862

x K
K
z xz K z K
x K
K
y xy K y K
+
= =
+
= =
F
F
F F
A
A
A A
250 . 0
250 . 0
150 . 0
150 . 0


Then we substitute these expressions into equation (1) and solve for x.



4.40 pH
] O [H M 10 0 . 4
2
10 6 . 7 10 2 . 5 10 2 . 7
10 9 . 1 10 2 . 7 0 600 . 0 400 . 0
) 00 . 1 600 . 0 ( 60 . 1 ) (
) ( 250 . 0 ) ( 150 . 0 ) ( ) ( 250 . 0
250 . 0 since 250 . 0
250 . 0 150 . 0
250 . 0
3
5
9 11 6
9 6 2
F A A
2
F A F A
2
F A F A
A F F A A F
F
F
A
A
=
= =
+
=
+ = = +
+ + = + + +
+ + + = + +
<< ~
+
+
+
= +
+


x
x x K K x K x
K K x K K x x K K K K
x K K x K K x K x K
x
x K
K
x K
K
x

(c) Adding 1.00 L of 0.100 M HCl to 1.00 L of buffer of course dilutes the
concentrations of all components by a factor of 2. Thus, [Na
+
] =0.125 M; total
acetate concentration =0.0750 M; total formate concentration =0.125 M. Also, a
new ion is added to the solution, namely, [Cl

] =0.0500 M.

z y x = = = = ~ =
+ +
] [CHO ] O H [C M 0500 . 0 ] [Cl ] O [H 0 ] [OH 125 . 0 ] Na [
2 2 3 2 3

y = = + =

0750 . 0 ] O H [C 0750 . 0 ] O H [HC ] O H C [ ] O H [HC 0750 . 0
2 3 2 2 3 2 2 3 2 2 3 2

z = = + =

125 . 0 ] CHO [ 125 . 0 ] [HCHO ] CHO [ ] HCHO [ 125 . 0
2 2 2 2


] [Cl ] [CHO ] OH [ ] O H C [ ] O [H ] Na [
2 2 3 2 3
+ +
+ + + = + (electroneutrality)

z y x z y x + = + + + + = + + = +

0.075 0500 . 0 0 ] Cl [ ] CHO [ ] O H C [ 125 . 0
2 2 3 2



y
y x
K

= = =

+
0750 . 0
10 8 . 1
] O H HC [
] O H C ][ O [H
5
A
2 3 2
2 3 2 3



4 3 2
F
2
[H O ][CHO ]
1.8 10
[HCHO ] 0.125
x z
K
z
+

= = =

Again, we solve the last two equations for y and z in terms of x.


A
A A
A
F
F F
F
0.0750
0.0750
0.125
0.125
K
K y K xy y
K x
K
K z K xz z
K x
= =
+
= =
+


Chapter 17: Additional Aspects of AcidBase Equilibria
863
Then we substitute these expressions into equation (1) and solve for x.

A F
A F
F A A F F A
2
A F A F A F F A
2 2 4
F A F
0.0750 K 0.125 K
0.0750 x 0.0750 since x 0.0750
K x K x
0.0750 (K x) (K x) 0.0750 K (K x) 0.125 K (K x)
K K (K K )x x 2.67 K K x(1.67 K 1.00 K )
x 0.67 K x 1.67 K K 0 x 1.2 10 x 5

+ = + ~ <<
+ +
+ + = + + +
+ + + = + +
= =
9
4 8 8
4
3
.4 10
1.2 10 1.4 10 2.2 10
x 1.55 10 M [H O ]
2
pH 3.81 3.8

+
= = =
= ~


As expected, the addition of HCl(aq), a strong acid, caused the pH to drop. The
decrease in pH was relatively small, nonetheless, because the H
3
O
+
(aq) was
converted to the much weaker acid HCHO
2
via the neutralization reaction:

CHO
2
-
(aq) +H
3
O
+
(aq) HCHO
2
(aq) +H
2
O(l) (buffering action)

82. (M) First we find the pH at the equivalence point:

-
3 3 2
3
CH CH(OH)COOH(aq) OH ( ) CH CH(OH)COO (aq) H O(l)
1 mmol 1 mmol 1 mmol
The concentration of the salt is 1 10 mol/0.1 L =0.01 M
The lactate anion undergoes hydrolysis
aq

+ +

-
3 2 3
thus:
CH CH(OH)COO ( ) H O(l) CH CH(OH)COOH(aq) OH ( )
Initial 0.01 M 0 M 0 M
Change + +
Equilibrium (0.01 ) M
Where
aq aq
x x x
x x x
x

+ +
~

-
is the [hydrolyzed lactate ion], as well as that of the [OH ] produced by hydrolysis

14
11 3 w
- 3.86
3 a
2 2
11 - 7
[CH CH(OH)COOH][OH ] K 1.0 10
K for the above reaction 7.2 10
[CH CH(OH)COO ] K 10
so 7.2 10 and [OH ] 8.49 10 M
0.01 0.01
0.01, thus, the assumption is valid
log (8.49
x x
x
x
x
pOH

= = = =
~ = = =

7
10 ) 6.07 14 14.00 6.07 7.93 M pH pOH

= = = =


(a) Bromthymol blue or phenol red would be good indicators for this titration since they change
color over this pH range.


Chapter 17: Additional Aspects of AcidBase Equilibria
864
(b) The H
2
PO
4

/HPO
4
2-
system would be suitable because the pK
a
for the acid (namely, H
2
PO
4

) is
close to the equivalence point pH of 7.93. An acetate buffer would be too acidic, an ammonia
buffer too basic.

(c)
- 2 8
4 4
2 2 3 a2
H PO H O H O HPO K 6.3 10
+
+ + =

2 8
4
a2
- 7.93
4
2 3
K [HPO ] 6.3 10
Solving for 5.4 (buffer ratio required)
[H PO ] [H O ] 10

+

= = =

83. (M)
2
3
2
2 2 2 3 a
2 2
[H O ][HO ]
H O (aq) H O(l) H O (aq) HO (aq) K
[H O ]
+
+
+ + =

Data taken from experiments 1 and 2:
( )
2 2
2 2
2
2 2
( )
3
(14.9
3
[H O ] [HO ] 0.259 M (6.78) (0.00357 M) [HO ] 0.259 M
[HO ] 0.235 M [H O ] (6.78)(0.00357 M) 0.0242 M
[H O ] 10
log 0.250 - 0.235) M NaOH log(0.015 M NaOH) =1.824
[H O ] 10

+
+
+ = + =
= = =
=
=
=
pKw pOH
4 1.824) 14
14
2
13 3
a
2 2
a
7.7 10
[H O ][HO ] (7.7 10 M)(0.235 M)
K 7.4 10
[H O ] (0.0242 M)
pK 12.14

+

= = =
=


From data taken from experiments 1 and 3:
2 2
2 2
2
[H O ] [HO ] 0.123 M (6.78)(0.00198 M) [HO ] 0.123 M
[HO ] 0.1096 M

+ = + =
=

2 2
( )
3
[H O ] (6.78)(0.00198 M) 0.0134 M
[H O ] 10 , pOH =-log[(0.125- 0.1096 ) M NaOH] 1.81
pKw pOH +
= =
= =


(14.94 1.81) 14
3
14
2
13 3
2 2
13
[H O ] 10 7.41 10
[H O ][HO ] (7.41 10 M)(0.1096M)
6.06 10
[H O ] (0.0134 M)
p =-log (6.06 10 ) =12.22
Average value for p =12.17
+
+

= =

= = =

a
a
a
K
K
K


Chapter 17: Additional Aspects of AcidBase Equilibria
865
84. (D) Let's consider some of the important processes occurring in the solution.

2 -13
4
2 2 4 (1) a2
14
2 3 7
4 4
2 3 (2) b 8
4
2 3 3 (3) a
(1) HPO (aq) H O(l) H PO (aq) OH (aq) = 4.2 10
1.0 10
(2) HPO (aq) H O(l) H O (aq) PO (aq) = 1.6 10
6.3 10
1.0
(3) NH (aq) H O(l) H O (aq) NH (aq) =

+ +
+ + =

+ + = =

+ + =

K K
K K
K K
14
10
5
- 4
4
2 3 (4) 5
10
5.6 10
1.8 10
1
(4) NH (aq) OH (aq) H O(l) NH (aq) 5.6 10
1.8 10

+ + = =

K

- 2
4 4
2 -
4 4 4
2 3
May have interaction between NH and OH formed from the hydrolysis of HPO .
NH (aq) HPO (aq) H PO (aq) NH (aq)
Initial 0.10M 0.10M 0 M 0 M
Change
Equil
x x x x
+
+
+ +
+ +

4
. 0.100 0.100
(where is the molar concentration of NH that hydrolyzes)
x x x x
x
+



7 4 3
(2) (4)
(1.6 10 ) (5.6 10 ) 9.0 10 K K K

= = =

- 2
4
3 3 2 3
2 2
4 4
[H PO ] [NH ] [ ]
9.0 10 and 8.7 10 M
[NH ] [HPO ] [0.10- ]

+
= = = =
x
K x
x


2 3
4
8
a - 3
4
2
4
3
Finding the pH of this buffer system:
[HPO ] 0.100-8.7 10 M
pH p log log(6.3 10 ) log 8.2
[H PO ] 8.7 10 M
As expected, we get the same result using the NH /NH buffer system.
K

+
| |
= + = + =
|

\ .


85. Consider the two weak acids and the equilibrium for water (autodissociation)

+ - + -
+ - 3 3
2 3 HA
HA
+ - + -
+ - 3 3
2 3 HB
HB
+ - + -
2 2 3 w 3
[H O ][A ] [H O ][A ]
HA(aq) +H O(l) H O (aq) +A (aq) K = [HA]=
[HA] K
[H O ][B ] [H O ][B ]
HB(aq) +H O(l) H O (aq) +B (aq) K = [HB]=
[HB] K
H O(l) +H O(l) H O (aq) +OH (aq) K =[H O ][OH ] [O

- w
+
3
K
H ] =
[H O ]


Chapter 17: Additional Aspects of AcidBase Equilibria
866
+ - +
- - - 3 3
initial
HA HA
- initial
+
3
HA
[H O ][A ] [H O ]
Mass Balance: [HA] =[HA]+[A ] = +[A ] =[A ] +1
K K
[HA]
From which: [A ] =
[H O ]
+1
K
| |
|
\ .
| |
|
\ .


+ - +
- - - 3 3
initial
HB HB
- initial
+
3
HB
[H O ][B ] [H O ]
[HB] =[HB] +[B ] = +[B ] =[B ] +1
K K
[HB]
From which: [B ] =
[H O ]
+1
K
| |
|
\ .
| |
|
\ .



+ - - -
3
+ initial initial w
3 + + +
3 3 3
HA HB
Charge Balance: [H O ] =[A ] +[B ] +[OH ] (substitute above expressions)
[HA] [HB] K
[H O ] =
[H O ] [H O ] [H O ]
+1 +1
K K
+ +
| | | |
| |
\ . \ .


86. (D) We are told that the solution is 0.050 M in acetic acid (Ka =1.8 10-5) and 0.010 M in phenyl
acetic acid (Ka =4.9 10-5). Because the Ka values are close, both equilibria must be satisfied
simultaneously. Note: [H3O+] is common to both equilibria (assume z is the concentration of
[H3O+]).

Reaction: HC2H3O2(aq) + H2O(l)

C2H3O2-(aq) + H3O+(aq)
Initial: 0.050 M 0 M 0 M
Change: -x M +x M +z M
Equilibrium (0.050 x)M x M z M
+ - 5
5 3 2 3 2
a
2 3 2
[H O ][C H O ] 1.8 10 (0.050 )
For acetic acid: K = 1.8 10 or
[HC H O ] (0.050 )
x xz
x
x z

= = =

Reaction: HC8H7O2(aq) + H2O(l)

C8H7O2-(aq) +
H3O+(aq)
Initial: 0.010 M 0 M 0 M
Change: -y M +y M +z M
Equilibrium (0.010 y)M y M z M

+ -
5 3 8 7 2
a
8 7 2
5
[H O ][C H O ]
For phenylacetic acid: K = 4.9 10
[HC H O ] (0.010 )
4.9 10 (0.010 )
or
yz
y
y
y
z

= =

=


Chapter 17: Additional Aspects of AcidBase Equilibria
867
There are now three variables: x =[C2H3O2- ], y =[C8H7O2- ], and z =[H3O+]
These are the only charged species, hence, x +y =z.
(This equation neglects contribution from the [H3O+] from water.)
Next we substitute in the values of x and y from the rearranged Ka expressions above.

x +y =z =
5
1.8 10 (0.050 ) x
z

+
5
4.9 10 (0.010 ) y
z

Since these are weak acids, we can simplify this expression by assuming that x <<0.050 and y <<
0.010.

z =
5
1.8 10 (0.050)
z

+
5
4.9 10 (0.010)
z

Simplify even further by multiplying through by z.

z2 =9.010-7 + 4.910-7 =1.4 10-6

z =1.1810-3 =[H3O+] From which we find that x =7.6 10-4 and y =4.210-4
(as a quick check, we do see that x +y =z).

We finish up by checking to see if the approximation is valid (5% rule)..

4 4
7.6 10 4.2 10
For : 100% 1.5% For : 100% 4.2%
0.050 0.010
x y


= =


Since both are less than 5%, we can be assured that the assumption is valid.
The pH of the solution =-log(1.1810-3) =2.93.
(If we simply plug the appropriate values into the equation developed in the previous question we
get the exact answer 2.933715 (via the method of successive approximations), but the final answers
can only be reported to 2 significant figures. Hence the best we can do is say that the pH is
expected to be 2.93 (which is the same level of precision as that for the result obtained following
the 5% rule).

87. (D)
(a) By using dilution, there are an infinite number of ways of preparing the pH =7.79
buffer. We will consider a method that does not use dilution.

Let TRIS =weak base and TRISH
+
be the conjugate acid.

pKb =5.91, pKa =14 pKb =8.09 Use the Henderson Hasselbalch equation.

pH =pKa +log (TRIS/TRISH
+
) =7.79 =8.09+log (TRIS/TRISH
+
)

log (TRIS/TRISH
+
) =7.79 8.09 =-0.30 Take antilog of both sides

(TRIS/TRISH
+
) =10-0.30 =0.50; Therefore, nTRIS =0.50(nTRISH
+
)
Chapter 17: Additional Aspects of AcidBase Equilibria
868
Since there is no guidance given on the capacity of the buffer, we will choose an arbitrary
starting point. We start with 1.00 L of 0.200 M TRIS (0.200 moles). We need to convert 2/3 of
this to the corresponding acid (TRISH
+
) using 10.0 M HCl, in order for the TRIS/TRISH
+
ratio
to be 0.5. In all, we need (2/3)0.200 mol of HCl, or a total of 0.133 moles of HCl.

Volume of HCl required =0.133 mol 10.0 mol/L =0.0133 L or 13.3 mL.

This would give a total volume of 1013.3 mL, which is almost a liter (within 1.3%).
If we wish to make up exactly one liter, we should only use 987 mL of 0.200 M TRIS.
This would require 13.2 mL of HCl, resulting in a final volume of 1.0002 L.

Lets do a quick double check of our calculations.
nHCl =0.0132 L10.0 M =0.132 mol =nTRISH
+

nTRIS =ninitial nreacted =0.200 M0.987 L 0.132 mol =0.0654 mol
pH =pKa +log (TRIS/TRISH
+
) =8.09+log (0.0654 mol/0.132 mol) = 7.785

We have prepared the desired buffer (realize that this is just one way of preparing the buffer).

(b) To 500 mL of the buffer prepared above, is added 0.030 mol H
3
O
+
.
In the 500 mL of solution we have 0.132 mol 2 mol TRISH
+
=0.0660 mol TRISH
+

and 0.0654 mol 2 mol TRIS =0.0327 mol TRIS (we will assume no change in
volume).

HCl will completely react ( 100%) with TRIS, converting it to TRISH
+
.
After complete reaction, there will be no excess HCl, 0.0327 mol 0.0300 mol =
0.0027 mol TRIS and 0.0660 mol +0.0300 mol =0.0960 mol TRISH
+
.

By employing the Henderson Hasselbalch equation, we can estimate the pH of the
resulting solution:

pH =pK
a
+log (TRIS/TRISH
+
) =8.09 +log (0.0027 mol/0.0960 mol) = 6.54

This represents a pH change of 1.25 units. The buffer is nearly exhausted owing to
the fact that almost all of the TRIS has been converted to TRISH
+
. Generally, a pH
change of 1 unit suggests that the capacity of the buffer has been pretty much
completely expended. This is the case here.

(Alternatively, you may solve this question using an I.C.E. table).

(c) Addition of 20.0 mL of 10.0 M HCl will complete exhaust the buffer (in part (b) we saw
that addition of 3 mL of HCl used up most of the TRIS in solution). The buffer may be
regenerated by adding 20.0 mL of 10.0 M NaOH. The buffer will be only slightly
diluted after the addition of HCl and NaOH (500 mL 540 mL). Through the slow and
careful addition of NaOH, one can regenerate the pH =7.79 buffer in this way (if a pH
meter is used to monitor the addition).

Chapter 17: Additional Aspects of AcidBase Equilibria
869

88. (M)
(a) The formula given needs to be rearranged to isolate , as shown below.
a
3
a
3
a
a a
pH
a 3 a
1
pH pK log 1
H O
1
pH pKa log log 1
K
H O
1
1
K
K K
=
10 K H O K
o
o
o
o
+
+
+
| |
=
|
\ .
| |
(
| |

| = =
|
|
\ .
\ .
(

=
=
+ ( +


Now, use the given K
a
(6.310
-8
) and calculate for a range of pH values.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
o

(b) When pH =pK
a
, =0.5 or 50%.

(c) At a pH of 6.0,
8
a
pH 6.0 8
a
K 6.3 10
= 0.059
10 K 10 6.3 10
o

= =
+ +
or 5.9%.

(c)
Chapter 17: Additional Aspects of AcidBase Equilibria
870

89. (D)
(a) We start by writing the equilibrium expression for all reactions:

( )
( )
2
1
2
CO aq
K
CO g
(

=
(



2 2
2 3
K Ca CO
+
( ( =


3
3
2
3 3
HCO
K
H O CO

+
(

=
( (


( )
2
4
3 3
CO aq
K
HCO H O
+
(

=
( (



First, we have to express [H
3
O
+
] using the available expressions:

( )
( ) ( )
3
3
2
3 3
2
3
4 3
2
3 2 2
3
2 2
3 3 4 3 3 4 3
HCO
H O
K CO
CO aq
H O
K HCO
HCO CO aq CO aq
H O
K CO K HCO K K CO

+

(

( =

(

(

( =

(

(
( (

( = =

( ( (



From the expression for K
1
, we know that [CO
2
(aq)] =K
1
[CO
2
(g)]. Therefore,

( ) 2
1 2
3
2
3 4 3
K CO g
H O
K K CO
+

(

( =

(


Now, the expression for K
2
can be plugged into the above expression as follows:
( ) ( )
( )
2
2
1 2 1 2
3
2
2 3 4 3 4 3
2
1 2
3
2 3 4
K CO g Ca K CO g
H O
K K K K K CO
K CO g Ca
H O
K K K
+
+

+
+
( ( (

( = =

(

( (

( =




(b) The K values for the reactions are as follows:
K
1
=0.8317 (given in the problem)
K
2
=K
sp
(CaCO
3
) =2.810
-9

K
3
=1/Kaof HCO
3

=1/(4.710
-11
) =2.1310
10

K
4
=1/Ka of H
2
CO
3
=1/(4.410
-7
) =2.2710
6


| |
6
5 2 2 2
2
2
280 10 L CO 1mol CO mol CO
CO (g) 1.145 10
L air 24.45L CO L air

= =
Chapter 17: Additional Aspects of AcidBase Equilibria
871
( ) ( )( )( )
( )( )( )
5 3 2
1 2
3
9 10 6
2 3 4
8
0.8317 1.145 10 10.24 10 K CO g Ca
H O
K K K 2.8 10 2.13 10 2.27 10
2.684 10 M
+
+

( (

( = =


=


( )
8
pH log 2.684 10 7.57

= =

90. (M) To determine pH, we must first determine what is the final charge balance of the solution
without adding any H
3
O
+
or OH ions. As such, we have to calculate the number of moles of each
ion (assume 1 L):

Moles of Na
+
: 23.0 g Na
+
(1 mol/23.0 g) =1.00 mol Na
+

Moles of Ca
2+
: 10.0 g Ca
2+
(1 mol/40.0 g) =0.250 mol Ca
2+

Moles of CO
3
2-
: 40.02 g CO
3
2-
(1 mol/60.01 g) =0.670 mol CO
3
2-
Moles of SO
4
2-
: 9.6 g SO
4
2-
(1 mol/96.056 g) =0.100 mol

Looking at the list of ions and consulting the solubility guide, we note that Ca
2+
will precipitate
with both SO
4
2-
and CO
3
2-
. Since both of these anions have a 2 charge, it doesnt matter with
which anion the precipitation occurs (in reality, it does a little, but the effects are small compared to
the effects of adding H
3
O
+
or OH ions).

Moles of anions left =(0.670 +0.100) 0.250 =0.520 moles

Since we have 0.520 moles of 2 ions, we must have 1.04 moles of 1+ions to balance. However,
we only have 1 mole of Na
+
. The difference in charge is:
1.04(-) 1.0(+) =0.04(-) moles of ions

To balance, we need 0.04 moles of H
3
O
+
. The pH =log (0.04) =1.40.

91. (M)
(a) We note that the pH is 5.0. Therefore,
5.0 5
3
H O 10 1.0 10 M
+
( = =


( )
( )( )( )
( )
2 5 5
a 3
3
2 2
5 5
a 3
2.0 10 1.8 10 1.0 10 C K H O
4.6 10
1.8 10 1.0 10 K H O
|
+

+
(

= = =
+ ( +



(b)
( ) ( )
( ) ( )
A A
3 3
dC d pH d pH dC
d pH 1.0 10 4.6 10 0.22
pH 5 0.22 4.78
| |

~ ~
= =
= =


(c) At an acetic acid concentration of 0.1 M, C is also 0.1, because C is the total concentration of
the acetic acid and acetate. The maximum buffer index (2.5010
-2
) happens at a pH of 4.75,
Chapter 17: Additional Aspects of AcidBase Equilibria
872
where [HAc] =[Ac

]. The minima are located at pH values of 8.87 (which correspond to pH of a

solution of 0.1 M acetic acid and 0.1 M acetate, respectively).
0.0E+00
5.0E-03
1.0E-02
1.5E-02
2.0E-02
2.5E-02
3.0E-02
0 1 2 3 4 5 6 7 8 9
pH

FEATURE PROBLEMS

92. (D)
(a) The two curves cross the point at which half of the total acetate is present as
acetic acid and half is present as acetate ion. This is the half equivalence point in a
titration, wherepH p
a
= =4.74 K .

(b) For carbonic acid, there are three carbonate containing species: H CO
2 3
which
predominates at low pH,
3
HCO

, and CO
3
2
, which predominates in alkaline
solution. The points of intersection should occur at the half-equivalence points in
each step-wise titration: at pH p log
a
= = 4.4 10 =6.36
1
7
K

c h
and at
pH p log
a
= = 4.7 10 =10.33
2
11
K

c h
. The following graph was computer-
calculated (and then drawn) from these equations. f in each instance represents
the fraction of the species whose formula is in parentheses.

( )
( )
( )
1 1 2
2 +
+
2
+
2
+
1
2
+ +
2
1 2 2
1
=1+ +
H A H
H
H
1
= +1+
HA H
H H
1
= + +1
A

(
(


(

(

( (

K K K
f
K
K f
K K K f

Chapter 17: Additional Aspects of AcidBase Equilibria
873


(c) For phosphoric acid, there are four phosphate containing species: H PO
3 4
under acidic
conditions, H PO HPO
4 2 4
2
,

, and PO
4
3
, which predominates in alkaline solution. The points
of intersection should occur at pH p log = = 7.1 10 =2.15,
1
3
K
a


c h

pH p log = = 6.3 10 =7.20
2
8
K
a


c h
, andpH p log = = 4.2 10 =12.38
3
13
K
a


c h
, a quite alkaline
solution. The graph that follows was computer-calculated and drawn.


f (H
3
PO
4
)
f (H
2
PO
4
-
)
f (HPO
4
2-
)
f (PO
4
3-
)




( )
( )
( )
2 3
3
2
3
f H CO
f HCO
f CO

( )
( )
( )
( )
3 4
2 4
2
4
3
4
f H PO
f H PO
f HPO
f PO

Chapter 17: Additional Aspects of AcidBase Equilibria
874
93. (D)
(a) This is exactly the same titration curve we would obtain for the titration of 25.00 mL of
0.200 M HCl with 0.200 M NaOH, because the acid species being titrated is H O
3
+
. Both acids
are strong acids and have ionized completely before titration begins. The initial pH is that of
0.200 M H
3
O
+
=[HCl] +[HNO
3
]; ( ) pH= log 0.200 =0.70. At the equivalence point,
pH=7.000. We treat this problem as we would for the titration of a single strong acid with a
strong base.
0
2
4
6
8
10
12
14
0 5 10 15 20 25
Vol ume of 0.200 M NaOH (ml )
p
H


(b) In Figure 17-9, we note that the equivalence point of the titration of a strong acid occurs at
pH=7.00, but that the strong acid is essentially completely neutralized at pH =4. In Figure 17-
13, we see that the first equivalence point of H PO
3 4
occurs at about pH =4.6. Thus, the first
equivalence point represents the complete neutralization of HCl and the neutralization of
H PO
3 4
to H PO
2 4

. Then, the second equivalence point represents the neutralization of

H PO
2 4

to HPO
4
2
. To reach the first equivalence point requires about 20.0 mL of 0.216 M
NaOH, while to reach the second one requires a total of 30.0 mL of 0.216 M NaOH, or an
additional 10.0 mL of base beyond the first equivalence point. The equations for the two
titration reactions are as follows.

To the first equivalence point:
3 4 2 4 2
NaOH+H PO NaH PO +H O


2
NaOH+HCl NaCl +H O


To the second equivalence point:
2 4 2 4 2
NaOH+NaH PO Na HPO +H O


There is a third equivalence point, not shown in the figure, which would require an additional
10.0 mL of base to reach. Its titration reaction is represented by the following equation.

To the third equivalence point:
2 4 3 4 2
NaOH+Na HPO Na PO +H O


Chapter 17: Additional Aspects of AcidBase Equilibria
875
We determine the molar concentration of
H PO
3 4
and then of HCl. Notice that only 10.0 mL of
the NaOH needed to reach the first equivalence point reacts with the HCl(aq); the rest reacts
with
H PO
3 4
.

3 4
3 4
0.216 mmol NaOH 1mmol H PO
(30.0 20.0) mL NaOH(aq)
1mL NaOH soln 1mmol NaOH
0.216 M H PO
10.00 mL acid soln

=


0.216 mmol NaOH 1mmol HCl
(20.0 10.0) mL NaOH(aq)
1mL NaOH soln 1mmol NaOH
0.216 M HCl
10.00 mL acid soln

=


(c) We start with a phosphoric acid-dihydrogen phosphate buffer solution and titrate until all of
theH PO
3 4
is consumed. We begin with

10.00
0.0400
1
=0.400
3 4
3 4
mL
mmol H PO
mL
mmol H PO
and the diprotic anion,

2
2 4
2 4
0.0150mmol H PO
10.00mL =0.150mmol H PO
1mL

. The volume of 0.0200 M

NaOH needed is:
3 4
3 4
1 mmol NaOH 1mL NaOH
0.400 mmol H PO =20.00 mL
1 mmol H PO 0.0200 mmol NaOH

To reach the first equivalence point. The pH value of points during this titration are computed
with the Henderson-Hasselbalch equation.

( )
2 4
3
1
3 4
H PO
0.0150
Initially: pH=p +log = log 7.1 10 +log =2.15 0.43=1.72
H PO 0.0400

(
(

(

K
0.150+0.100
At 5.00mL : pH=2.15+log =2.15 0.08 2.07
0.400 0.100
=

0.150 0.200
At 10.0 mL, pH=2.15 log 2.15 0.24 2.39
0.400 0.200
+
+ = + =

0.150 0.300
At 15.0mL, pH=2.15 log 2.15 0.65 2.80
0.400 0.300
+
+ = + =

This is the first equivalence point, a solution of 30.00 mL (=10.00 mL originally +20.00 mL
titrant), containing 0.400 mmol
2 4
H PO

from the titration and the 0.150 mmol
2
2 4
H PO


originally present.
This is a solution with
Chapter 17: Additional Aspects of AcidBase Equilibria
876

2 4
2 4
(0.400+0.150) mmol H PO
H PO = =0.0183 M
30.00mL

(

, which has

( ) ( ) ( )
( )
8
1 2
1
pH= p +p =0.50 2.15 log 6.3 10 =0.50 2.15+7.20 =4.68
2
K K



To reach the second equivalence point means titrating 0.550 mmol H PO
2 4

, which
requires an additional volume of titrant given by

2 4
2 4
1 mmol NaOH 1mL NaOH
0.550 mmol H PO =27.5 mL
0.0200mmol NaOH 1 mmol H PO

.

To determine pH during this titration, we divide the region into five equal portions
of 5.5 mL and use the Henderson-Hasselbalch equation.

( )
( )
( )
2
2
4
4
2
2 4 2 4
At 20.0+5.5 mL,
HPO
0.20 0.550 mmol HPO formed
pH=p +log =7.20+log
0.80 0.550 mmol H PO remaining H PO
pH=7.20 0.60=6.60
K

(


(

( )
0.40 0.550
At 20.0+11.0 mL =31.0mL, pH=7.20+log =7.02
0.60 0.550

At 36.5 mL, pH=7.38 At 42.0mL, pH=7.80

The pH at the second equivalence point is given by

pH p p log =
1
2
+ =0.50 7.20 4.2 10 =0.50 7.20+12.38 =9.79
2 3
13
K K b g c h e j
b g

.

Another 27.50 mL of 0.020 M NaOH would be required to reach the third
equivalence point. pH values at each of four equally spaced volumes of 5.50 mL
additional 0.0200 M NaOH are computed as before, assuming the Henderson-
Hasselbalch equation is valid.

( )
3
4
3
2
4
PO
0.20 0.550
At 47.50+5.50 mL =53.00mL, pH=p +log =12.38+log
0.80 0.550
HPO
=12.38 0.60=11.78
K

(


(

Chapter 17: Additional Aspects of AcidBase Equilibria
877

At 58.50 mL, pH=12.20 At 64.50mL, pH=12.56 At 70.00mL, pH=12.98
But at infinite dilution with 0.0200 M NaOH, the pH =12.30, so this point cant be
reached.

At the last equivalence point, the solution will contain 0.550 mmol PO
4
3
in a total of
10.00+20.00+27.50+27.50mL =85.00 mL of solution, with

3
4
0.550mmol
PO = =0.00647
85.00mL

(

M. But we can never reach this point, because the

pH of the 0.0200 M NaOH titrant is 12.30. Moreover, the titrant is diluted by its
addition to the solution. Thus, our titration will cease sometime shortly after the
second equivalence point. We never will see the third equivalence point, largely
because the titrant is too dilute. Our results are plotted below.



Chapter 17: Additional Aspects of AcidBase Equilibria
878
94. (D) p
1
a
K =2.34;
1
a
K =4.6 10
3
and p
2
a
K =9.69;
2
a
K =2.0 10
10

(a) Since the K
a
values are so different, we can treat alanine (H
2
A
+
) as a monoprotic acid
with
1
a
K =4.6 10
3
. Hence:


H
2
A
+
(aq) + H
2
O(l)

HA(aq) + H
3
O
+
(aq)
Initial 0.500 M 0 M ~ 0 M
Change x M +x M +x M
Equilibrium (0.500 x) M x M x M



1
a
K =
+
3
+
2
[HA][H O ]
[H A ]
=
( )( )
(0.500 )
x x
x
=4.6 10
3
~
2
0.500
x

x =0.048 M =[H
3
O
+
] (x =0.0457, solving the quadratic equation)

pH =log[H
3
O
+
] =log(0.046) =1.34


(b) At the first half-neutralization point a buffer made up of H
2
A
+
/HA is formed, where
[H
2
A
+
] =[HA]. The Henderson-Hasselbalch equation gives pH =pK
a
=2.34.

(c) At the first equivalence point, all of the H
2
A
+
(aq) is converted to HA(aq).
HA(aq) is involved in both
1
a
K and
2
a
K , so both ionizations must be considered.

If we assume that the solution is converted to 100% HA, we must consider two
reactions. HA may act as a weak acid (HAA

+H
+
) or HA may act as a base
(HA +H
+
H
2
A
+
). See the following diagram.

Some HA
unreacted
+ A
- H
3
O
+
HA
reacts as
a base
Some HA
reacts as
an acid
H
2
A
+
100 %
HA
amphoteric nature
(reactions occur)
H
A
a
s
a
c
id
H
A
a
s b
ase


Using the diagram above, we see that the following relations must hold true.
[A

] =[H
3
O
+
] +[H
2
A
+
]

2
a
K =
+
3
[A ][H O ]
[HA]

or [A

] =
2
a
+
3
[HA]
[H O ]
K
&
1
a
K =
+
3
+
2
[HA][H O ]
[H A ]
or [H
2
A
+
] =
1
+
3
a
[H O ][HA]
K


Substitute for [A

] and [H
2
A
+
] in [A

] =[H
3
O
+
] +[H
2
A
+
]

Chapter 17: Additional Aspects of AcidBase Equilibria
879
2
a
+
3
[HA]
[H O ]
K
=[H
3
O
+
] +
1
+
3
a
[H O ][HA]
K
(multiply both sides by
1
a
K [H
3
O
+
])

1 2
a a
[HA] K K =
1
a
K [H
3
O
+
][H
3
O
+
] +
+ +
3 3
[H O ][H O ][HA]

1 2
a
[HA]
a
K K =[H
3
O
+
]
2
(
1
a
K +[HA])

[H
3
O
+
]
2
=
1 2
1
a a
a
[HA]
( +[HA])
K K
K
Usually, [HA]
1
a
K (Here, 0.500 4.6 10
3
)

Make the assumption that
1
a
K +[HA] ~ [HA]
[H
3
O
+
]
2
=
1 2
a a
[HA]
[HA]
K K
=
1 2
a a
K K Take log of both sides

log[H
3
O
+
]
2
=2log [H
3
O
+
] =2(pH) =log
1 2
a a
K K

=log
1
a
K log
2
a
K =p
1
a
K +p
2
a
K

2(pH) =p
1
a
K +p
2
a
K

pH =
1 2
a a
p +p
2
K K
=
2.34 +9.69
2
=6.02

(d) Half-way between the first and second equivalence points, half of the HA(aq) is
converted to A

(aq). We have a HA/A

buffer solution where [HA] =[A

]. The
Henderson-Hasselbalch equation yields pH =p
2
a
K =9.69.

(e) At the second equivalence point, all of the H
2
A
+
(aq) is converted to A

(aq). We can
treat this simply as a weak base in water having:
K
b
=
2
w
a
K
K
=
14
10
1 10
2.0 10

=5.0 10
5

Note: There has been a 1:3 dilution, hence the [A

] =0.500 M
1 V
3 V
=0.167 M
A

(aq) + H
2
O(l)

HA(aq) + OH

(aq)
Initial 0.167 M 0 M ~ 0 M
Change x M +x M +x M
Equilibrium (0.167 x) M x M x M

K
b
=
[HA][OH ]
[A ]

=
( )( )
(0.167 )
x x
x
=5.0 10
5
~
2
0.167
x


x =0.0029 M =[OH

]; pOH =log[OH

] =2.54;

pH =14.00 pOH =14.00 2.54 =11.46

Chapter 17: Additional Aspects of AcidBase Equilibria
880
(f) All of the points required in (f) can be obtained using the Henderson-Hasselbalch
equation (the chart below shows that the buffer ratio for each point is within the
acceptable range (0.25 to 4.0))

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0 110.0
mL NaOH
%H
2
A
+
%HA
%A
-
0 0 0 0 0 0 0 20 40 60 80 100
0 20 40 60 80 100 80 60 40 20 0 0
100 100 80 60 40 20 0 0 0 0 0 0
buffer
ratio
=
base
acid
0 4.0 0.25 0.67 1.5 1.5 0.67 0.25 4.0 888
May use Henderson-Hasselbalchequation May use Henderson-Hasselbalch equation


(i) After 10.0 mL

Here we will show how to obtain the answer using both the Henderson-Hasselbalch
equation and setting up the I. C. E. (Initial, Change, Equilibrium) table. The results
will differ within accepted experimental limitation of the experiment (+0.01 pH units)
n
H
2
A
+ =(CV) =(0.500 M)(0.0500 L) =0.0250 moles H
2
A

n
OH
- =(CV) =(0.500 M)(0.0100 L) =0.00500 moles OH

V
total
=(50.0 +10.0) mL =60.0 mL or 0.0600 L
[H
2
A
+
] =
+
2
H A
total
0.0250mol
= =0.417M
0.0600L
n
V
[OH

] =
OH
total
0.00500mol
= =0.0833M
0.0600L
n
V

K
eq
for titration reaction =
b(HA)
1
K
=
1
w
a
1
K
K
| |
|
|
\ .
=
1
3
a 11
14
w
4.6 10
4.6 10
1.00 10
K
K

= =

H
2
A
+
(aq) + OH

(aq)

HA(aq) + H
2
O(l)
Initial: 0.417 M 0.0833 M 0 M
100% rxn: -0.0833 -0.0833 M +0.0833 M
New initial: 0.334 M 0 M 0.0833 M
Change: +x M +x M x M
Equilibrium: ~0.334 M x M ~0.0833 M

4.6 10
11
=
(0.0833)
(0.334)( ) x
; x =
11
(0.0833)
(0.334)(4.6 10 )
=5.4 10
13
(valid assumption)

x =5.4 1013 =[OH]; pOH =log(5.4 1013) =12.27;
pH =14.00 pOH =14.00 12.27 =1.73
Alternative method using the Henderson-Hasselbalch equation:

Chapter 17: Additional Aspects of AcidBase Equilibria
881
(i) After 10.0 mL, 20% of H2A+reacts, forming the conjugate base HA.
Hence the buffer solution is 80% H2A+(acid) and 20% HA (base).

pH =
1
a
pK
+log
base
acid
= 2.34 +log
20.0
80.0
=2.34 +(0.602) =1.74 (within +0.01)

For the remainder of the calculations we will employ the Henderson-Hasselbalch equation
with the understanding that using the method that employs the I.C.E. table gives the same
result within the limitation of the data.

(ii) After 20.0 mL, 40% of H
2
A
+
reacts, forming the conjugate base HA.
Hence the buffer solution is 60% H
2
A
+
(acid) and 40% HA (base).

pH =
1
a
pK
+log
base
acid
= 2.34 +log
40.0
60.0
=2.34 +(0.176) =2.16


(iii) After 30.0 mL, 60% of H
2
A
+
reacts, forming the conjugate base HA.
Hence the buffer solution is 40% H
2
A
+
(acid) and 60% HA (base).

pH =
1
a
pK
+log
base
acid
= 2.34 +log
60.0
40.0
=2.34 +(+0.176) =2.52

(iv) After 40.0 mL, 80% of H
2
A
+
reacts, forming the conjugate base HA.
Hence the buffer solution is 20% H
2
A
+
(acid) and 80% HA (base).
pH =
1
a
pK +log
base
acid
= 2.34 +log
80.0
20.0
=2.34 +(0.602) =2.94

(v) After 50 mL, all of the H
2
A
+
(aq) has reacted, and we begin with essentially 100%
HA(aq), which is a weak acid. Addition of base results in the formation of the
conjugate base (buffer system) A

(aq). We employ a similar solution, however,

now we must use p
2
a
K =9.69.

(vi) After 60.0 mL, 20% of HA reacts, forming the conjugate base A

.
Hence the buffer solution is 80% HA

(acid) and 20% A

(base)
pH =
2
a
pK +log
base
acid
= 9.69 +log
20.0
80.0
=9.69 +(0.602) =9.09

(vii) After 70.0 mL, 40% of HA reacts, forming the conjugate base A

.
Hence the buffer solution is 60% HA

(acid) and 40% A

(base).
pH =
2
a
pK +log
base
acid
= 9.69 +log
40.0
60.0
=9.69 +(0.176) =9.51


Chapter 17: Additional Aspects of AcidBase Equilibria
882
(viii) After 80.0 mL, 60% of HA reacts, forming the conjugate base A

.
Hence the buffer solution is 40% HA

(acid) and 60% A

(base).
pH =
2
a
pK +log
base
acid
= 9.69 +log
60.0
40.0
=9.69 +(+0.176) =9.87
(ix) After 90.0 mL, 80% of HA reacts, forming the conjugate base A

.
Hence the buffer solution is 20% HA

(acid) and 80% A

(base).
pH =
2
a
pK +log
base
acid
= 9.69 +log
80.0
20.0
=9.69 +(0.602) =10.29
(x) After the addition of 110.0 mL, NaOH is in excess. (10.0 mL of 0.500 M NaOH is in excess,
or, 0.00500 moles of NaOH remains unreacted). The pH of a solution that has NaOH in
excess is determined by the [OH

] that is in excess.
(For a diprotic acid, this occurs after the second equivalence point.)
[OH

]
excess
=
OH
total
0.00500mol
= =0.0312 M
0.1600L
n
V

5 ; pOH =log(0.03125) =1.51

pH =14.00 pOH =14.00 1.51 =12.49

(g) A sketch of the titration curve for the 0.500 M solution of alanine hydrochloride,
with some significant points labeled on the plot, is shown below.

Plot of pH versus Volume of NaOH Added
0
2
4
6
8
10
12
14
0 20 40 60 80 100 120
NaOH volume (mL)
p
H
isoelectric point
pH = pK
a1
pH = pK
a2
NaOH
in excess
H
2
A
+
/HA
buffer region
HA/A
-
buffer region








Chapter 17: Additional Aspects of AcidBase Equilibria
883

SELF-ASSESSMENT EXERCISES

95. (E)
(a) mmol: millimoles, or 110
-3
mol
(b) HIn: An indicator, which is a weak acid
(c) Equivalence point of a titration: When the moles of titrant equals the moles of the substance
being titrated
(d) Titration curve: A curve of pH of the solution being titrated versus the pH of the titrating
solution

96. (E)
(a) The common-ion effect: A process by which ionization of a compound is suppressed by having
present one of the product ions (from another source) in the solution
(b) use of buffer to maintain constant pH: A buffer is a solution of a weak acid and its conjugate
base, and it resists large changes in pH when small amounts of an acid or base are added.
(c) determination of pK
a
from titration curve: At the half-way point (when half of the species being
titrated is consumed, the concentration of that species and its conjugate is the same, and the
equilibrium expression simplifies to pK
a
=pH
(d) measurement of pH with an indicator: An approximate method of measuring the pH, where the
color of an ionizable organic dye changes based on the pH

97. (E)
(a) Buffer capacity and buffer range: Buffer capacity is a measure of how much acid or base can be
added to the buffer without an appreciable change in the pH, and is determined by the
concentration of the weak acid and conjugate base in the buffer solution. The buffer range,
however, refers to the range over which a buffer effectively neutralizes added acids and bases
and maintains a fairly constant pH.
(b) Hydrolysis and neutralization: Hydrolysis is reaction of an acid or base with water molecules,
which causes water to split into hydronium and hydroxide ions. Neutralization is the reaction of
H
3
O
+
and OH

together to make water.

(c) First and second equivalence points in the titration of a weak diprotic acid: First equivalence
point is when the first proton of a weak diprotic acid is completely abstracted and the resulting
acid salt and base have been consumed and neither is in excess. Second equivalence point is the
equivalence point at which all protons are abstracted from the acid and what remains is the (2-)
anion.
(d) Equivalence point of a titration and end point of an indicator: Equivalence point of a titration is
when the moles of titrant added are the same as the moles of acid or base in the solution being
titrated. The endpoint of an indicator is when the indicator changes color because of abstraction
or gain of a proton, and is ideally as close as possible to the pH of the equivalence point.

Chapter 17: Additional Aspects of AcidBase Equilibria
884
98. (E)
(a) HCHO
2
+OH CHO
2
+H
2
O
CHO
2
+H
3
O
+
HCHO
2
+H
2
O

(b) C
6
H
5
NH
3
+
+OH C
6
H
5
NH
2
+H
2
O
C
6
H
5
NH
2
+H
3
O
+
C
6
H
5
NH
3
+
+H
2
O

(c) H
2
PO
4
+OH HPO
4
2-
+H
2
O
HPO
4
2-
+H
3
O
+
H
2
PO
4
+H
2
O

99. (M)
(a) The pH at theequivalence point is 7. Use bromthymol blue.
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H


(b) The pH at the equivalence point is ~5.3 for a 0.1 M solution. Use methyl red.

0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H

Chapter 17: Additional Aspects of AcidBase Equilibria
885

(c) The pH at the equivalence point is ~8.7 for a 0.1 M solution. Use phenolphthalein, because it
just begins to get from clear to pink around the equivalence point.

0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H


(d) The pH for the first equivalence point (NaH
2
PO
4

to Na
2
HPO
4
2
) for a 0.1 M solution is right
around ~7, so use bromthymol blue.
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Vol of Titrant (mL)
p
H


Chapter 17: Additional Aspects of AcidBase Equilibria
886
100. (D)
(a) This is the initial equilibrium before any base has reacted with the acid. The reaction that
dominates, along with changes in concentration, is shown below:

HC
7
H
5
O
2
+ H
2
O

C
7
H
5
O
2
+ H
3
O
+
0.0100 0 0
- x +x +x
0.0100 x x x

| |
( )( )
( )
+ -
3 7 5 2
7 5 2
-5
4
+ 4
3
H O C H O
HC H O
6.3 10
0.0100-
Solvingfor x using the quadratic formula, =7.63 10 M.
pH = log H O log 7.63 10 3.12
a
K
x x
x
x

( (

=
=

( = =



(b) In this case, we titrate the base with 0.00625 L of Ba(OH)
2
. Therefore, we have to calculate the
final moles of the base and the total volume to determine the concentration.
( )
( )
4
7 5 2 7 5 2
4
2
2
mol HC H O 0.02500L 0.0100M HC H O 2.5 10 mol
2mol OH
mol OH 0.00625L 0.0100M Ba OH =1.25 10 mol
1mol Ba OH

= =
=

Since the amount of OH is half of the initial amount of HC
7
H
5
O
2
, the moles of HC
7
H
5
O
2
and
C
7
H
5
O
2
are equal. Therefore, K
a
=[H
3
O
+
], and pH =log(6.310
-5
) =4.20.

(c) At the equivalence point, there is initially no HC
7
H
5
O
2
. The equilibrium is dominated by
C
7
H
5
O
2
hydrolyzing water. The concentration of C
7
H
5
O
2
is:
Total moles of HC
7
H
5
O
2
=2.510
-4
mol as shown previously. At the equivalence point, the
moles of acid equal moles of OH.
( )
( )
4 4 2
2
1mol Ba OH
mol Ba OH 2.5 10 mol OH 1.25 10 mol
2 mol OH

= =
Vol of Ba(OH)
2
=1.2510
-4
mol / 0.0100 M =0.0125 L

Total volume of the solution at the equivalence point is the sum of the initial volume plus the
volume of Ba(OH)
2
added. That is,

V
TOT
=0.02500 L +0.0125 L =0.0375 L

Therefore, the concentration of C
7
H
5
O
2
=2.510
-4
/0.0375 L =0.00667 M.
Chapter 17: Additional Aspects of AcidBase Equilibria
887

C
7
H
5
O
2
+ H
2
O

HC
7
H
5
O
2
+ OH

0.00667 0 0
-x +x +x
0.00667 x x x

Since this is a base reaction,
( )
4 5 10
b w a
K K K 1.00 10 6.3 10 1.587 10 .

= = =
| |
( )( )
( )
-
7 5 2
b
-
7 5 2
10
6
6
OH HC H O
K =
C H O
1.59 10
0.00667
solvingfor (by simplifying the formula above) yields =1.03 10 M.
pH =14 pOH 14 log 1.03 10 14 6.00 8.00
x x
x
x x

(

(

=

(
= = =



(d) In this part, we have an excess of a strong base. As such, we have to determine how much
excess base there is and what is the final volume of the solution.
( )
( )
( )
2
2
4
mol Ba OH
2mol OH
mol OH 0.01500L 0.0100
L 1mol Ba OH
3.000 10 mol OH

=
=


4 4
7 5 2
5
Excessmol OH mol HC H O mol OH 3.000 10 2.500 10
5.000 10 mol

= =
=

( )
( )
5
5.0 10 mol
OH 0.00125M
0.02500L+0.01500L
pH =14 pOH 14 log 0.00125 14 2.903 11.1

( = =

= = = (



101. (E) The answer is (c); because of the common ion-effect, the presence of HCO
2
will repress
ionization of formic acid.

102. (E) The answer is (d), because NaHCO
3
is a weak base and will react with protons in water, shifting
the formic acid ionization equilibrium to the right.
103. (E) The answer is (b), raise the pH. NH
4
+
is an acid, and to be converted to its conjugate base, it
must react with a base to abstract its proton.

104. (E) The answer is (b), because at that point, the number of moles of weak base remaining is the
same as its conjugate acid, and the equilibrium expression simplifies to K
a
=[H
3
O
+
].

Chapter 17: Additional Aspects of AcidBase Equilibria
888
105. (M) The base, C
2
H
5
NH
2
, is reacted with HClO
4
. The reaction is:

2 5 2 4 2 5 3 4
C H NH HClO C H NH ClO
+
+ +

Assuming a volume of 1 L for each solution,

| |
2 5 2
1.49 mol 1.001 mol 0.489 mol
C H NH 0.2445M
2L 2L
= = =
2 5 3
1.001 mol
C H NH 0.5005M
2L
+
( = =


| |
( )( )
( )
( )
2 5 3
4
2 5 2
4
4
C H NH OH
0.5005 +
4.3 10
C H NH 0.2445
2.10 10
pOH log 2.10 10 3.68
pH 14 3.68 10.32
+

( (

= =

=
= =
= =
x x
x
x

106. (D) We assume that all of Ca(HSe)
2
dissociates in water. The concentration of HSe

is therefore:

( )
( )
2
2
2mol HSe
0.5M Ca HSe 1.0M HSe
1mol Ca HSe

=
We note that HSe

is amphoteric; that is, it can act either as an acid or a base. The acid reaction of
HSe

and the concentration of [H

3
O
+
] generated, are as follows:

HSe

+H
2
O Se
2
+H
3
O
+


( )( )
( )
2
3
11
11 6
Se H O
1.00 10
1.00 HSe
= 1.00 10 3.16 10
+

( (

= =
(

=
x x
x
x


The basic reaction of HSe

and the concentration of [OH

] generated, are as follows:

HSe

+H
2
O H
2
Se +OH

K
b
=1.0010
-14
/1.310
-4
=7.6910
-11


| |
( )( )
( )
2
11
11 6
H Se OH
7.69 10
1.00 HSe
= 7.69 10 8.77 10

(

= =
(

=
x x
x
x


Chapter 17: Additional Aspects of AcidBase Equilibria
889
Therefore, we have [H
3
O
+
] =3.1610
-6
and [OH

] =8.7710
-6
. Since these two react to give H
2
O,
the result is 8.7710
-6
3.1610
-6
=5.6110
-6
M [OH

]. The pH of the solution is:

pH =14 pOH =14 5.25 =8.75


107. (E) The answer is (a). The solution system described is a buffer, and will resist large changes in
pH. Adding KOH should raise the pH slightly.

108. (E) The answer is (b), because HSO
3
is a much stronger acid (K
a
=1.310
-2
) than H
2
PO
4

(K
a
=6.310
-8
).

109. (E) The answer is (b). The pK
a
of the acid is 9, which puts it squarely in the middle of the 810 pH
range for the equivalence point.

110. (E)
(a) NaHCO
3
titrated with NaOH: pH >7, because HCO
3
is itself slightly basic, and is being
titrated with NaOH to yield CO
3
2-
at the equivalence point, which is even more basic.
(b) HCl titrated with NH
3
: pH <7, because the resulting NH
4
+
at the equivalence point is acidic.
(c) KOH titrated with HI: pH =7, because a strong base is being titrated by a strong acid, and the
resulting anions and cations are all non-basic and non-acidic.

111. (M) The concepts that define Sections 17-2, 17-3, and 17-4 are buffers, indicators, and titrations.
For buffers, after definition, there are a number of concepts, such as composition, application, the
equilibrium expression (the Henderson-Hasselbalch equation is a subtopic of the equilibrium
expression). Under composition, there are other subtopics such as buffer range and capacity. For
indicators, after defining it, there are subtopics such as equilibrium expression and usage. With
titration, topics such as form (weak acid titrated by strong base, and weak base titrated by strong
acid), the titration curve, and the equivalence point. Look at these sections to find inter-related
terminology and other concepts.
890
CHAPTER 18

SOLUBILITY AND COMPLEX-ION EQUILIBRIA

PRACTICE EXAMPLES

1A (E) In each case, we first write the balanced equation for the solubility equilibrium and then
the equilibrium constant expression for that equilibrium, the K
sp
expression:
(a) ( ) ( ) ( )
2 2+
3 3
MgCO s Mg aq +CO aq

K
sp
=[Mg
2+
][CO
3
2
]

(b) ( ) ( ) ( )
3 +
3 4 4
Ag PO s 3Ag aq +PO aq

K
sp
=[Ag
+
]
3
[PO
4
3
]

1B (E)
(a) Provided the [OH

] is not too high, the hydrogen phosphate ion is not expected to ionize
in aqueous solution to a significant extent because of the quite small values for the
second and third ionization constants of phosphoric acid.
( ) ( ) ( )
2 2+
4 4
CaHPO s Ca aq +HPO aq

(b) The solubility product constant is written in the manner of a K
c
expression:
K
sp
=[Ca
2+
][HPO
4
2
] =1. 10
7

2A (M) We calculate the solubility of silver cyanate, s , as a molarity. We then use the solubility
equation to (1) relate the concentrations of the ions and (2) write the K
sp
expression.

4
7 mg AgOCN 1000mL 1g 1mol AgOCN
= =5 10 moles/L
100mL 1L 1000mg 149.9g AgOCN
s



( ) ( ) ( )
+
Equation: AgOCN s Ag aq +OCN aq

Solubility Product : s s

( ) ( ) ( )
2
+ 2 4 7
sp
= Ag OCN = = = 5 10 =3 10 K s s s

( (



2B (E) We calculate the solubility of lithium phosphate, s , as a molarity. We then use the
solubility equation to (1) relate the concentrations of the ions and (2) write the K
sp
expression.
3 4 3 4
3 4
0.034g Li PO 1mol Li PO 1000mL
= =0.0029 moles/L
100mL soln 1L 115.79g Li PO
s

Equation: ( ) ( ) ( )
3 +
3 4 4
Li PO s 3Li aq +PO aq

Solubility Product: (3 s)
3
s


( ) ( )
3
3 3 +
sp 4
= Li PO = 3 = K s s

( (

4 4 9
27 27(0.0029) 1.9 10 s

= =

Chapter 18: Solubility and Complex-Ion Equilibria
891
3A (E) We use the solubility equilibrium to write the K
sp
expression, which we then solve to
obtain the molar solubility, s , of Cu
3
(AsO
4
)
2
.
( ) ( ) ( )
2+
3 4 2 4
Cu (AsO ) . s 3 Cu aq +2 AsO aq

( ) ( )
3 2
3 2
2+ 5 36
sp 4
= AsO = 3 2 =108 =7.6 10 K Cu s s s

( (



Solubility :
36
8
5
7.6 10
3.7 10 M
108
s

= =

3B (E) First we determine the solubility of BaSO
4
, and then find the mass dissolved.

( ) ( ) ( )
2 2+
4 4
BaSO aq Ba aq +SO aq

K s
sp
Ba SO = =
2+
4
2 2


The last relationship is true because Ba SO
2+
4
2
=

in a solution produced by dissolving
BaSO
4
in pure water. Thus,
10 5
sp
s= K 1.1 10 1.05 10 M.

= =

5
4 4
4 4
4
1.05 10 mmol BaSO 233.39mg BaSO
mass BaSO =225 mL =0.55mg BaSO
1 mL satd soln 1mmol BaSO

4A (M) For PbI Pb I
sp 2
2+
2
9
, = =7.1 10 K

. The solubility equilibrium is the basis of the
calculation.

Equation:
PbI s
2
b g

Pb aq
2+
b g
+
2I aq

b g
Initial: 0.10 M 0 M
Changes: +s M +2s M
Equil: (0.10 +s) M 2s M

K s s s
sp
Pb I = =7.1 10 = 0.10+ 2 0.40
2+
2
9
2
2
~ b gb g s =

=

71 10
040
13 10
9
4
.
.
. M
(assumption 0.10 s is valid)
This value of s is the solubility of PbI
2
in 0.10 MPb NO aq
3
2
b g b g .

4B (E) We find pOH from the given pH:

pOH =14.00 8.20 =5.80; [OH

] =10
-pOH
=10
-5.80
=1.610
-6
M.
We assume that pOH remains constant, and use the K
sp
expression forFeOH
3
b g .
( )
( )
38
3 3
3+ 38 3+ 6 3+ 21
sp 3
6
4 10
= Fe OH =4 10 = Fe 1.6 10 Fe = =9.8 10 M
1.6 10
K

( ( ( (



Therefore, the molar solubility of Fe(OH)
3
is 9.810
21
M.
The dissolved FeOH b g
3
does not significantly affect OH

.

Chapter 18: Solubility and Complex-Ion Equilibria
892
5A (M) First determine I

as altered by dilution. We then compute Q

sp
and compare it withK
sp
.

4
0.05mL 0.20mmol KI 1mmol I
3drops
1drop 1mL 1mmol KI
I = =3 10 M
100.0mL soln

(



( )( )
+ 4 6
sp
= Ag I = 0.010 3 10 =3 10 Q

( (

17
sp sp
8.5 10 = Thus, precipitation should occur. Q K

>

5B (M) We first use the solubility product constant expression for PbI
2
to determine the I

needed in solution to just form a precipitate when Pb
2+
=0.010 M. We assume that the
volume of solution added is small and that Pb
2+
remains at 0.010 M throughout.

K
sp
Pb I I I M = =7.1 10 = 0.010 =
71 10
0010
=8.4 10
2+
2
9
2
9
4

b g
.
.


We determine the volume of 0.20 M KI needed.
volume of KI aq mL
mmol I
mL
mmol KI
mmol I
mL KI aq
mmol KI
drop
mL
drops drops
b g
b g
=100.0
8.4 10
1
1
1
1
0.20
1
0.050
=8.4 =9
4

Since one additional drop is needed, 10 drops will be required. This is an insignificant volume
compared to the original solution, so Pb
2+
remains constant.

6A (E) Here we must find the maximum Ca
2+
that can coexist with OH =0.040M.

(


( )
( )
6
2
2
6 2+ 2+ 2+ 3
sp 2
5.5 10
=5.5 10 = Ca OH = Ca 0.040 ; Ca = =3.4 10 M
0.040
K

( ( ( (


For precipitation to be considered complete, Ca
2+
should be less than 0.1% of its original
value. 3.4 10
3

M is 34% of 0.010 M and therefore precipitation of Ca OH b g
2
is not complete
under these conditions.

6B (E) We begin by finding Mg
2+
that corresponds to1 /
2+
g Mg L .
2+ 2+
2+ 8
6 2+
1 g Mg 1 g 1mol Mg
Mg = =4 10 M
1L soln 10 g 24.3g Mg

(


Now we use the K
sp
expression for Mg OH b g
2
to determine OH

.
K
sp
Mg OH OH =1.8 10 = = 4 10
11 2+
2
8
2


c h
OH M

= =
18 10
4 10
0.02
11
8
.


Chapter 18: Solubility and Complex-Ion Equilibria
893
7A (M) Let us first determine Ag
+
when AgCl(s) just begins to precipitate. At this point,
Q
sp
and K
sp
are equal.

K Q
sp sp
Ag Cl Ag M =1.8 10 = = = 0.115
10 + +


Ag M
+
10
9
=
1.8 10
0.115
=1.6 10

Now let us determine the maximumBr

that can coexist with this Ag

+
.

K
sp
Ag Br M Br =5.0 10 = =1.6 10
13 + 9


; Br M

=
5.0 10
1.6 10
=3.1 10
13
9
4


The remaining bromide ion has precipitated as AgBr(s) with the addition of AgNO aq
3
b g .

Percent of
4
final
initial
[Br ] 3.1 10 M
Br remaining 100% 100% 0.12%
[Br ] 0.264M

= = =

7B (M) Since the ions have the same charge and the same concentrations, we look for two K
sp

values for the salt with the same anion that are as far apart as possible. The K
sp
values for the
carbonates are very close, while those for the sulfates and fluorides are quite different.
However, the difference in the K
sp
values is greatest for the chromates; K
sp
for
( )
10
4
BaCrO 1.2 10

is so much smaller than K

sp
for
( )
5
4
SrCrO 2.2 10 ,

4
BaCrO will
precipitate first and
4
SrCrO will begin to precipitate when
2
4
CrO

(

has the value:


5
2 sp 4
4
2+
2.2 10
CrO = = =2.2 10 M
0.10 Sr
K

(


(

.

At this point
2+
Ba (

is found as follows.


10
sp 2+ 7
4 2
4
1.2 10
Ba = = =5.5 10 M
2.2 10
CrO
K

(

(

;


[Ba
2+
] has dropped to 0.00055% of its initial value and therefore is considered to be
completely precipitated, before
4
SrCrO begins to precipitate. The two ions are thus effectively
separated as chromates. The best precipitating agent is a group 1 chromate salt.

8A (M) First determine OH

resulting from the hydrolysis of acetate ion.

Equation:
( )
-
2 3 2 2
C H O aq + H O(l)

HC H O aq
2 3 2
b g
+
OH aq

b g
Initial: 0.10 M 0 M
~ 0M
Changes: x M
+x M

+x M
Equil: 0.10 x b g M
x M

x M

Chapter 18: Solubility and Complex-Ion Equilibria
894
| |
14 2
2 3 2
10
b 5
2 3 2
HC H O OH
1.0 10
5.6 10 =
1.8 10 0.10 0.10
C H O
x x x
K
x

(


= = = ~
(


x = = =

[ ] . . . OH M 010 56 10 75 10
10 6
(the assumption 0.10 x was valid)
Now compute the value of the ion product in this solution and compare it with the value of
K
sp
for Mg OH b g
2
.

Q K
sp sp
Mg OH M M Mg OH = = 0.010 7.5 10 =5.6 10 1.8 10 =
2+
2
6
2
13 11
2

b gc h b g <
Because Q
sp
is smaller than K
sp
, this solution is unsaturated and precipitation of Mg OH s b g b g
2

will not occur.

8B (M) Here we can use the HendersonHasselbalch equation to determine the pH of the buffer.
pH p log
C H O
HC H O
log log
M
M
a
= + = 1.8 10 +
0.250
0.150
=4.74+0.22=4.96
2 3 2
2 3 2
5
K

L
N
M
O
Q
P

c h


pOH pH OH M
pOH 9
=14.00 =14.00 4.96=9.04 =10 =10 =9.1 10
.04 10





Now we determine Q
sp
to see if precipitation will occur.

( )( )
3 3
3+ 10 30
sp
38
sp sp 3
= Fe OH = 0.013M 9.1 10 =9.8 10
4 10 = ; Thus, Fe(OH) precipitation should occur.
Q
Q K

( (

>


9A (M) Determine OH

, and then the pH necessary to prevent the precipitation of Mn OH b g

2
.

( )
2 2
13 2+
sp
=1.9 10 = Mn OH = 0.0050M OH K

( ( (

13
6
1.9 10
OH = 6.2 10 M
0.0050

( =



pOH log = 6.2 10 =5.21
6


c h
pH=14.00 5.21=8.79

We will use this pH in the HendersonHasselbalch equation to determine
+
4
NH .
(



b
p =4.74 K for NH
3
.
| |
( )
3
a
+ +
4 4
NH
0.025M
pH=p +log =8.79= 14.00 4.74 +log
NH NH
K
( (



( )
+
4
0.025M
log =8.79 14.00 4.74 = 0.47
NH

(


0.47
+
4
0.025
=10 =0.34
NH

(



+
4
0.025
NH = =0.074M
0.34
(



Chapter 18: Solubility and Complex-Ion Equilibria
895
9B (M) First we must calculate the [H
3
O
+
] in the buffer solution that is being employed to
dissolve the magnesium hydroxide:
NH
3
(aq) + H
2
O(l)

NH
4
+
(aq) + OH

(aq) ; K
b
=1.8 10
5



5 4
b
3
14 2
5 10
3 2 5
[NH ][OH ] [0.100M][OH ]
1.8 10
[NH ] [0.250M]
1.00 10 M
[OH ] 4.5 10 M; [H O ] 2.2 10 M
4.5 10 M
+

= = =

= = =

K

Now we can employ Equation 18.4 to calculate the molar solubility of Mg(OH)
2
in the buffer
solution; molar solubility Mg(OH)
2
=[Mg
2+
]
equil
Mg(OH)
2
(s) + 2 H
3
O
+
(aq)
17
K =1.8 10

Mg
2+
(aq) + 4H
2
O(l) ;
Equilibrium 2.2 10
10
x


2
17 3 2
equil 2 10 2
3
-3
2
[Mg ]
K 1.8 10 8.7 10 M [Mg ]
[H O ] [2.2 10 M]
So, themolar solubility for Mg(OH) =8.7 10 M.
+
+
+
= = = = =

x
x


10A (M)
(a) In solution are Cu aq SO aq Na aq
2+
4
2 +
, , b g b g b g

, and ( ) OH aq .

( ) ( ) ( ) ( )
2+
2
Cu aq +2OH aq Cu OH s

(b) In the solution above, Cu OH s b g b g
2
is Cu aq
2+
b g :
( ) ( ) ( ) ( )
2+
2
Cu OH s Cu aq +2OH aq

This Cu aq
2+
b g reacts with the added NH aq
3
b g :
( ) ( ) ( ) ( )
2+
2+
3 3
4
Cu aq +4 NH aq Cu NH aq (

The overall result is: ( ) ( ) ( ) ( ) ( ) ( )
2+
3 3
2 4
Cu OH s +4NH aq Cu NH aq +2OH aq

(c) HNO aq
3
b g (a strong acid), forms H O aq
3
+
b g , which reacts with OH aq

b g and NH aq
3
b g .

( ) ( )
+
3 2
OH aq +H O aq 2H O(l);

( ) ( ) ( )
+ +
3 3 4 2
NH aq +H O aq NH aq +H O(l)

As NH aq
3
b g is consumed, the reaction below shifts to the left.
( ) ( ) ( ) ( ) ( ) ( )
2+
3 3
2 4
Cu OH s +4NH aq Cu NH aq +2OH aq

But as OH aq

b g is consumed, the dissociation reactions shift to the side with the

dissolved ions: ( ) ( ) ( ) ( )
2+
2
Cu OH s Cu aq +2OH aq

The species in solution at the end of all this are
Chapter 18: Solubility and Complex-Ion Equilibria
896
( ) ( ) ( ) ( ) ( ) ( )
2+ + + + 2
3 4 3 4
Cu aq , NO aq , NH aq , excess H O aq , Na aq , andSO aq


(probably HSO
4

(aq) as well).

10B (M)
(a) In solution are Zn (aq), SO aq),
2+
4
2
( and NH (aq),
3

( ) ( ) ( ) ( )
2+
2+
3 3
4
Zn aq +4NH aq Zn NH aq (

(b) HNO aq
3
b g , a strong acid, produces H O aq
3
+
b g , which reacts with NH aq
3
b g .
( ) ( ) ( )
+ +
3 3 4 2
NH aq +H O aq NH aq +H O(l) As NH aq
3
b g is consumed, the tetrammine
complex ion is destroyed.
( ) ( ) ( ) ( ) ( ) ( )
2+ 2+
+ +
3 3 2 4
4 4
Zn NH aq +4H O aq Zn H O aq +4NH aq ( (

(c) NaOH(aq) is a strong base that produces OH aq

b g , forming a hydroxide precipitate.

( ) ( ) ( ) ( ) ( ) ( )
2+
2 2
4 2
Zn H O aq +2OH aq Zn OH s +4H O l

Another possibility is a reversal of the reaction of part (b).
( ) ( ) ( ) ( ) ( ) ( ) ( )
2+ 2+
+
2 4 3 2
4 4
Zn H O aq +4NH aq +4OH aq Zn NH aq +8H O l

( (

(d) The precipitate dissolves in excess base.
( ) ( ) ( ) ( ) ( )
2
2 4
Zn OH s +2OH aq Zn OH aq

11A (M) We first determine Ag
+
in a solution that is 0.100 M Ag
+
(aq) (from AgNO
3
) and
0.225 M NH aq
3
b g . Because of the large value of K
f
=1.6 10
7
, we start by having the
reagents form as much complex ion as possible, and approach equilibrium from this point.
Equation: Ag aq
+
b g + 2
3
NH aq b g

Ag NH aq
3
2
+
b g b g
In soln 0.100 M 0.225 M 0 M
Form complex 0.100 M 0.200 M +0.100 M
Initial 0 M 0.025 M 0.100 M
Changes +x M +2x M x M
Equil x M (0.025 +x) M (0.100 x) M
K
f
Ag NH
Ag NH
=1.6 10 =
7
3
2
+
+
3
2

L
N
M
O
Q
P
b g
( ) ( )
2 2
0.100 0.100
=
0.025+2 0.025
x
x x x

~

x =
0.100
0.025 1.6 10
=1.0 10 = =
2
7
5 +
b g


M Ag concentrationof free silver ion
(x <<0.025 M, so the approximation was valid)
The Cl

is diluted:
initial
final initial
final
1.00mL
Cl = Cl =3.50M 1500=0.00233M
1,500mL

( (


Chapter 18: Solubility and Complex-Ion Equilibria
897
Finally we compare Q
sp
with K
sp
to determine if precipitation of AgCl(s) will occur.
Q K
sp sp
Ag Cl M M = =1.0 10 0.00233 =2.3 10 1.8 10 =
+ 5 8 10
>
c hb g
Because the value of the Q
sp
is larger than the value of the K
sp
, precipitation of AgCl(s) should
occur.

11B (M) We organize the solution around the balanced equation of the formation reaction.
Equation: Pb aq
2+
b g + EDTA aq
4
b g

PbEDTA aq
2
b g
Initial 0.100 M 0.250 M 0 M
Form Complex: 0.100 M (0.250 0.100) M 0.100 M
Equil x M 0.150+x b g M 0.100 x b g M

| |
( )
2
18
f
2+ 4
19
18
PbEDTA
0.100 0.100
= =2 10 =
0.150+ 0.150 Pb EDTA
0.100
= =3 10 M ( <<0.100 M, thus the approximation was valid.)
0.150 2 10

(


~
( (

x
K
x x x
x x


We calculate Q
sp
and compare it to K
sp
to determine if precipitation will occur.
( )( )
2
2
2+ 19 21
sp
= Pb I = 3 10 M 0.10M =3 10 Q

( (

.
9
sp sp
7.1 10 = Q K

< Thus precipitation will not occur.

12A (M) We first determine the maximum concentration of free
+
Ag .
+ 10
sp
= Ag Cl =1.8 10 K

( (

Ag
+
10
8
=
1.8 10
0.0075
=2.4 10

M.
This is so small that we assume that all the Ag
+
in solution is present as complex ion:
Ag NH
3
2
+
=0.13 b g M. We use K
f
to determine the concentration of free NH
3
.

K
f
Ag NH
Ag NH
M
NH
= =1.6 10 =
0.13
2.4 10
3
2
+
+
3
2
7
8
3
2
b g
L
N
M
O
Q
P

L
N
M
O
Q
P

NH M.
3 8 7
=
013
24 10 16 10
=0.58
.
. .

If we combine this with the ammonia present in the complex ion, the total ammonia
concentration is 0.58 +2 0.13 =0.84 M M M b g . Thus, the minimum concentration of
ammonia necessary to keep AgCl(s) from forming is 0.84 M.

Chapter 18: Solubility and Complex-Ion Equilibria
898
12B (M) We use the solubility product constant expression to determine the maximum Ag
+

that can be present in 0.010 M Cl

without precipitation occurring.

( )
10
10 + + + 8
sp
1.8 10
=1.8 10 = Ag Cl = Ag 0.010M Ag = =1.8 10 M
0.010
K

( ( ( (


This is also the concentration of free silver ion in the K
f
expression. Because of the large
value of K
f
, practically all of the silver ion in solution is present as the complex ion,
[Ag(S
2
O
3
)
2
]
3
]. We solve the expression for [S
2
O
3
2
] and then add the [S
2
O
3
2
] tied up in
the complex ion.
( )
3
2 3
2
13
f 2 2
2 2 + 8
2 3 2 3
Ag S O
0.10 M
1.7 10
Ag S O 1.8 10 M S O
K

(
(

(

= = =
( ( (




2 2 4
2 3 2 3
8 13
0.10
S O = =5.7 10 M =concentration of free S O
1.8 10 1.7 10

(





( )
( )
2
3
2 4 2 3
2 3 2 3
3 2
2 3
2
2mol S O
total S O =5.7 10 M+0.10M Ag S O
1mol Ag S O
=0.20 M+0.00057M =0.20M

(
(

( (



13A (M) We must combine the two equilibrium expressions, for K
f
and for K
sp
, to find K
overall
.

( ) ( ) ( ) ( )
3+
3
Fe OH s Fe aq +3OH aq

K
sp
=4 10
38

( ) ( ) ( ) ( )
3
2 3+
2 4 2 4
3
Fe aq +3C O aq Fe C O aq

K
f
=2 10
20


( ) ( ) ( ) ( ) ( ) ( )
3
2
2 4 2 4
3 3
Fe OH s +3C O aq Fe C O aq +3OH aq

18
overall
=8 10 K


Initial 0.100 M 0 M ~ 0M
Changes 3x M +x M +3x M
Equil 0.100 3 x b g M M x 3x M

( ) | |
( )( )
( ) ( )
3 overall
3
3
3
4
2 4 3 18
3 3
2
2 4
Fe C O
3 27
0.100 3 0.100
OH
= =8 10
C O
=

~
( (

(

x x x
x
K

(3x <<0.100 M, thus the approximation was valid.)

x =

=

( . ) 0100 8 10
27
4 10
3 18 4
6
M The assumption is valid.
Thus the solubility of FeOH b g
3
in 0.100 M C O
2 4
2
is 4 10
6

M.

Chapter 18: Solubility and Complex-Ion Equilibria
899
13B (M) In Example 18-13 we saw that the expression for the solubility, s , of a silver halide in an
aqueous ammonia solution, where NH
3
is the concentration of aqueous ammonia, is given
by:
2
sp f sp f
3 3
=
NH 2 [NH ] 2
s s
K K or K K
s s
(
(

| |
=
|
|

\ .


For all scenarios, the
| |
3
NH stays fixed at 0.1000 M and
7
f
is always 1.6 10 K .
We see that s will decrease as does K
sp
. The relevant values are:

( ) ( ) ( )
10 13 17
sp sp sp
AgCl =1.8 10 , AgBr =5.0 10 , AgI =8.5 10 K K K

.
Thus, the order of decreasing solubility must be: AgI >AgBr >AgCl.

14A (M) For FeS, we know that K
spa
=6 10
2
; for Ag S
spa 2
30
, =6 10 K

.

We compute the value of Q
spa
in each case, with H S M
2
=0.10 and H O M
3
+
=0.30 .

( )
2
spa spa
2
0.020 0.10
For FeS, = =0.022 6 10 =
0.30
Q K

<
Thus, precipitation of FeS should not occur.
( )
( )
2
4
2 spa 2
30
spa spa 2
0.010 0.10
For Ag S, = =1.1 10
0.30
6 10 = ; thus, precipitation of Ag S shouldoccur.

>
Q
Q K


14B (M) The H O
3
+
needed to just form a precipitate can be obtained by direct substitution of the
provided concentrations into the K
spa
expression. When that expression is satisfied, a
precipitate will just form.
| | ( )( )
2+ 2+
2 2
2 +
spa 3 2 2 2
+ +
3 3
Fe H S 0.015MFe 0.10MH S
0.015 0.10
= =6 10 = , H O = =0.002M
6 10
H O H O
K

(

(

( (


pH log H O log = = 0.002 =2.7
3
+
b g
Chapter 18: Solubility and Complex-Ion Equilibria
900


INTEGRATIVE EXAMPLES

A. (D) To determine the amount of Ca(NO
3
)
2
needed, one has to calculate the amount of Ca
2+
that
will result in only 1.0010
-12
M of PO
4
3-

( )
( ) ( )
2+ 3-
3 4 4
2
3 2
sp
Ca PO 3Ca +2PO
3 2 =

K s s


Using the commonion effect, we will try to determine what concentration of Ca
2+
ions forces
the equilibrium in the lake to have only 1.0010
-12
M of phosphate, noting that (2s) is the
equilibrium concentration of phosphate.

( )
2 3
32 2 12
1.30 10 Ca 1.00 10
+
( =


Solving for [Ca
2+
] yields a concentration of 0.00235 M.

The volume of the lake: V =300 m 150 m 5 m =225000 m
3
or 2.2510
8
L.

Mass of Ca(NO
3
)
2
is determined as follows:
( )
( ) ( )
( )
( )
2
3 3 8 2 2
3 2 2
3
2
6
3
2
1 mol Ca NO 164.1g Ca NO
0.00235mol Ca
massCa NO 2.25 10 L
L 1mol Ca 1 mol Ca NO
87 10 g Ca NO
+
+
=
=

B. (M) The reaction of AgNO
3
and Na
2
SO
4
is as follows:

( )
( )
3 2 4 3 2 4
2 2 4
2 4 3
3
3
3 2 4
2 4
2AgNO Na SO 2NaNO Ag SO
1mol Ag SO
mol Ag SO 0.350L 0.200 M AgNO 3.5 10 mol
2mol AgNO
2mol NaNO
mol NaNO 0.250L 0.240 M Na SO 0.12mol
1mol Na SO

+ +
= =
= =

Ag
2
SO
4
is the precipitate. Since it is also the limiting reagent, there are 3.510
-2
moles of
Ag
2
SO
4
produced.

The reaction of Ag
2
SO
4
with Na
2
S
2
O
3
is as follows:

( )
2 2 3 2 4 2 4 2 2 3
2 2 3 2 2 3
Na S O Ag SO Na SO Ag S O
mol Na S O 0.400L 0.500 M Na S O =0.200 mol
+ +
=


Ag
2
SO
4
is the limiting reagent, so no Ag
2
SO
4
precipitate is left.


Chapter 18: Solubility and Complex-Ion Equilibria
901

EXERCISES

K
sp
and Solubility

1. (E)
(a) ( ) ( ) ( )
2 +
2 4 4
Ag SO s 2Ag aq +SO aq

2
2 +
sp 4
= Ag SO K

( (



(b) ( ) ( ) ( ) ( )
2+
3 3
2
Ra IO s Ra aq +2IO aq

2
2+
sp 3
= Ra IO K

( (



(c) ( ) ( ) ( ) ( )
3 2+
3 4 4
2
Ni PO s 3Ni aq +2PO aq

2 3
3 2+
sp 4
= Ni PO K

( (



(d) ( ) ( ) ( )
2+ 2
2 3 2 3
PuO CO s PuO aq +CO aq

2+ 2
sp 2 3
= PuO CO K

( (



2. (E)
(a) ( ) ( ) ( ) ( )
3
3+ 3+
sp
3
= Fe OH Fe OH s Fe aq +3OH aq K

( (

(b) ( ) ( ) ( )
+ +
sp
= BiO OH BiOOH s BiO aq +OH aq K

( (

(c) ( ) ( ) ( )
2
2+ 2+
sp 2 2 2 2
= Hg I Hg I s Hg aq +2I aq K

( (

(d) ( ) ( ) ( ) ( )
2 3
3 3 2+ 2+
sp 4 3 4 4
2
= Pb AsO Pb AsO s 3Pb aq +2AsO aq K

( (

3. (E)
(a) ( ) ( ) ( )
3+
3
CrF s Cr aq +3F aq

3
3+ 11
sp
= Cr F =6.6 10 K

( (


(b) ( ) ( ) ( ) ( )
2 3+
2 2 4 2 4
3
Au C O s 2Au aq +3C O aq

3 2
2 3+ 10
sp 2 4
= Au C O =1 10 K

( (


(c) ( ) ( ) ( ) ( )
3 2+
3 4 4
2
Cd PO s 3Cd aq +2PO aq

K
sp
Cd PO = =2.1 10
2+
3
4
3
2
33

(d) ( ) ( ) ( )
2+
2
SrF s Sr aq +2F aq

K
sp
Sr F = =2.5 10
2+
2
9


4. (E) Let s =solubility of each compound in moles of compound per liter of solution.

(a) K s s s
sp
Ba CrO = = = =1.2 10
2+
4
2 2 10
b gb g s =1.1 10
5

M
(b) K s s s
sp
Pb Br = = 2 =4 =4.0 10
2+
2
2
3 5
b gb g s =2.2 10
2

M
(c) K s s s
sp
Ce F = = 3 =27 =8 10
3+
3
3
4 16
b gb g s =7 10
5

M
(d) K s s s
sp
Mg AsO = = 3 2 =108 =2.1 10
2+
3
4
3
2
3 2
5 20
b g b g s =4.5 10
5

M

Chapter 18: Solubility and Complex-Ion Equilibria
902
5. (E) We use the value of K
sp
for each compound in determining the molar solubility in a
saturated solution. In each case, s represents the molar solubility of the compound.
( )( )
+ 2 16 8
sp
AgCN = Ag CN = = =1.2 10 =1.1 10 M K s s s s

( (


( )( )
+ 2 8 4
3 sp 3
AgIO = Ag IO = = =3.0 10 =1.7 10 M K s s s s

( (


( )( )
+ 2 17 9
sp
AgI = Ag I = = =8.5 10 =9.2 10 M K s s s s

( (


( )( )
+ 2 4 2
2 sp 2
AgNO = Ag NO = = =6.0 10 =2.4 10 M K s s s s

( (


( ) ( )
2
2
+ 2 3 5 2
2 4 sp 4
Ag SO = Ag SO = 2 =4 =1.4 10 =1.5 10 M K s s s s

( (


Thus, in order of increasing molar solubility, from smallest to largest:

AgI AgCN AgIO Ag SO AgNO < < < <
3 2 4 2


6. (E) We use the value of K
sp
for each compound in determining Mg
2+
in its saturated
solution. In each case, s represents the molar solubility of the compound.

(a) MgCO Mg CO
sp 3
2+
3
2 2 8
= = = =3.5 10 K s s s

b gb g
s =1.9 10 =1.9 10
4 2+ 4


M Mg M
(b) MgF Mg F
sp 2
2+
2
2
3 8
= = 2 =4 =3.7 10 K s s s

b gb g
s =2.1 10 =2.1 10
3 2+ 3


M Mg M
(c) ( ) ( )
2 3
3 2 3 2+ 5 25
3 4 2 sp 4
Mg (PO ) = Mg PO = 3 2 =108 =2.1 10 K s s s

( (


6 2+ 5
=4.5 10 M Mg =1.4 10 M s

(


Thus a saturated solution of MgF
2
has the highest Mg
2+
.
7. (M) We determine F

in saturated CaF
2
, and from that value the concentration of F
-
in ppm.

For CaF Ca F M
sp 2
2+
2
2
3 9 3
= = 2 =4 =5.3 10 =1.1 10 K s s s s

b gb g

The solubility in ppm is the number of grams of CaF
2
in 10
6
g of solution. We assume a
solution density of 1.00g/mL.

3
6 2
2
1mL 1Lsoln 1.1 10 mol CaF
mass of F 10 gsoln
1.00gsoln 1000mL 1Lsoln
2mol F 19.0gF
42gF
1mol CaF 1mol F

=
=


This is 42 times more concentrated than the optimum concentration of fluoride ion for
fluoridation. CaF
2
is, in fact, more soluble than is necessary. Its uncontrolled use might lead to
excessive F

in solution.

Chapter 18: Solubility and Complex-Ion Equilibria
903
8. (E) We determine OH

in a saturated solution. From this OH

we determine the pH.

K s s
sp
BiO OH M OH BiO = =4 10 = =2 10 = =
+ 10 2 5 +


pOH log pH = 2 10 =4.7 =9.3
5


c h


9. (M) We first assume that the volume of the solution does not change appreciably when its
temperature is lowered. Then we determine the mass of Mg C H O
16 31 2
2
b g dissolved in each
solution, recognizing that the molar solubility of Mg C H O
16 31 2
2
b g equals the cube root of one
fourth of its solubility product constant, since it is the only solute in the solution.
K s s K
sp sp
= = 4 4
3 3
/

3 3
12 4 12 5
At50 C: = 4.8 10 / 4 1.1 10 M; At25 C: = 3.3 10 / 4 9.4 10 M s s

= =

amount of Mg C H O
16 31 2
2
b g (50C)
( )
4
16 31 2 4 2
1.1 10 mol Mg C H O
=0.965L =1.1 10 mol
1L soln

amount of Mg C H O
16 31 2
2
b g (25C)
( )
5
16 31 2 4 2
9.4 10 mol Mg C H O
=0.965L =0.91 10 mol
1L soln

( )
( )
( )
( )
16 31 2
2
16 31 2 4 2
16 31 2
2
mass of Mg C H O precipitated:
535.15g Mg C H O
1000mg
=1.1 0.91 10 mol =11mg
1mol Mg C H O 1g

10. (M) We first assume that the volume of the solution does not change appreciably when its
temperature is lowered. Then we determine the mass of CaC O
2 4
dissolved in each solution,
recognizing that the molar solubility of CaC O
2 4
equals the square root of its solubility product
constant, since it is the only solute in the solution.
At
8 4 9 5
95 C = 1.2 10 1.1 10 M; At 13 C: 2.7 10 5.2 10 M s s

= = =
mass of
2 4
CaC O (95 C)
4
2 4 2 4
2 4
2 4
1.1 10 mol CaC O 128.1g CaC O
=0.725 L =0.010g CaC O
1L soln 1mol CaC O

mass of
2 4
CaC O (13 C)
5
4 2 4
2 4
2 4
5.2 10 mol PbSO 128.1g CaC O
=0.725 L =0.0048g CaC O
1L soln 1mol CaC O

mass of ( )
2 4
1000mg
CaC O precipitated= 0.010g 0.0048g =5.2mg
1g


Chapter 18: Solubility and Complex-Ion Equilibria
904
11. (M) First we determine I

in the saturated solution.

K s s s s
sp
Pb I M = =7.1 10 = 2 =4 =1.2 10
2+
2
9
2
3 3
b gb g
The AgNO
3
reacts with the I

in this saturated solution in the titration.

Ag aq I aq AgI s
+
+ b g b g b g

We determine the amount of Ag

+
needed for this titration, and
then AgNO
3
in the titrant.
moles Ag L
mol PbI
L soln
mol I
mol PbI
mol Ag
mol I
mol Ag
+
3
2
2
+
5 +
=0.02500
1.2 10
1
2
1
1
1
=6.0 10

AgNO molarity
mol Ag
L soln
mol AgNO
mol Ag
M
3
5 +
3
+
3
=
6.0 10
0.0133
1
1
=4.5 10

12. (M) We first determine C O
2 4
2
=

s, the solubility of the saturated solution.

C O
mL
0.00134mmol KMnO
mL soln
mmol C O
2 mmol MnO
mL
M Ca
4 2 4
4
2 4
2
2
5 2+
=
48
1
5
250.0
=6.4 10 = =

.
s
K s s s
sp
Ca C O = = = = 6.4 10 =4.1 10
2+
2 4
2 2 5
2
9
b gb g c h


13. (M) We first use the ideal gas law to determine the moles of H S
2
gas used.
n
PV
RT
= =

F
H
G
I
K
J

F
H
G
I
K
J
+
=


748 304
008206 23 273
123 10
1 1
3
mmHg
1atm
760mmHg
mL
1L
1000mL
L atmmol K K
moles
.
. ( )
.
If we assume that all the H S
2
is consumed in forming Ag S
2
, we can compute the Ag
+
in
the AgBrO
3
solution. This assumption is valid if the equilibrium constant for the cited reaction
is large, which is the case, as shown below:

( ) ( ) ( ) ( )
+
2 2
2Ag aq +HS aq +OH aq Ag S s +H O(l)

2
19
31
a sp
51
1.0 10
/ = 3.8 10
2.6 10
K K

( ) ( ) ( )
+
2 2 3
H S aq +H O(l) HS aq +H O aq

7
1
=1.0 10 K



( ) ( )
+
2 3
2H O(l) H O aq +OH aq

14
w
=1.0 10 K



( ) ( ) ( ) ( )
2
+ +
2 2 2 3
10
a sp 1 w
31 7 14
overall
2Ag aq +H S aq +2H O(l) Ag S s +2H O aq
=3.8 10 =( / )( )( ) (3.8 10 )(1.0 10 )(1.0 10 ) K K K K K

=

Ag
mol H S
mL soln
mL
L soln
mol Ag
mol H S
M
+
3
2
+
2
3
=
1.23 10
338
1000
1
2
1
=7.28 10

Then, for
( )
2
+ 3 5
3 sp 3
AgBrO , = Ag BrO = 7.28 10 =5.30 10 K

( (



Chapter 18: Solubility and Complex-Ion Equilibria
905
14. (M) The titration reaction is ( ) ( ) ( ) ( )
2 2
2
Ca OH aq +2HCl aq CaCl aq +2H O(l)

2
1L 0.1032mol HCl 1mol OH
10.7 mL HCl
1000mL 1L 1mol HCl
OH 0.0221M
1L
50.00mL Ca(OH) soln
1000mL

( = =

In a saturated solution of ( )
2+
2
Ca OH , Ca = OH 2

( (


( )( )
2
2
2+ 6
sp
= Ca OH = 0.0221 2 0.0221 =5.40 10 K

( (

(5.5 10
6

in Appendix D).

The Common-Ion Effect

15. (E) We let s =molar solubility of Mg OH b g
2
in moles solute per liter of solution.
(a) K s s s
sp
Mg OH = = 2 =4 =1.8 10
2+
2
2
3 11
b gb g s =1.7 10
4

M
(b) ( ) ( ) ( ) ( )
2+
2
Equation: Mg OH s Mg aq + 2OH aq

Initial : 0.0862M 0M ~
Changes: + M +2 M s s
( ) Equil : 0.0862+ M 2 M s s
( ) ( ) ( ) ( )
2 2
11 2 6
sp
= 0.0862+ 2 =1.8 10 0.0862 2 =0.34 =7.3 10 M K s s s s s

~
(s <<0.0802 M, thus, the approximation was valid.)

(c) OH KOH M

= =0.0355
( ) ( ) ( ) ( )
2+
2
Equation: Mg OH s Mg aq + 2OH aq

Initial : 0M 0.0355M
Changes: + M +2 M s s
( ) Equil : M 0.0355+2 M s s
( )( ) ( )( )
2 2
11 8
sp
= 0.0355+2 =1.8 10 0.0355 =0.0013 =1.4 10 M K s s s s s

~
16. (E) The solubility equilibrium is ( ) ( ) ( )
2 2+
3 3
CaCO s Ca aq +CO aq

(a) The addition of Na CO aq
2 3
b g produces CO aq
3
2
b g in solution. This common ion
suppresses the dissolution of CaCO s
3
b g .

(b) HCl(aq) is a strong acid that reacts with carbonate ion:
( ) ( ) ( )
2 +
3 3 2 2
CO aq +2H O aq CO g +3H O(l)

.
This decreases CO
3
2
in the solution, allowing more CaCO s
3
b g to dissolve.

Chapter 18: Solubility and Complex-Ion Equilibria
906
(c) HSO aq
4

b g is a moderately weak acid. It is strong enough to protonate appreciable

concentrations of carbonate ion, thereby decreasing CO
3
2
and enhancing the solubility
of CaCO s
3
b g , as the value of K
c
indicates.

( ) ( ) ( ) ( )
2 2
4 3 4 3
HSO aq +CO aq SO aq +HCO aq

8 a 4
11
a 3
(HSO ) 0.011
2.3 10
4.7 10 (HCO )
c
K
K
K

= = =

17. (E) The presence of KI in a solution produces a significant I

in the solution. Not as much AgI

can dissolve in such a solution as in pure water, since the ion product, Ag I
+
, cannot exceed
the value of
sp
K (i.e., the I
-
from the KI that dissolves represses the dissociation of AgI(s). In
similar fashion, AgNO
3
produces a significant Ag
+
in solution, again influencing the value of
the ion product; not as much AgI can dissolve as in pure water.


18. (E) If the solution contains KNO
3
, more AgI will end up dissolving than in pure water, because
the activity of each ion will be less than its molarity. On an ionic level, the reason is that ion
pairs, such as Ag
+
NO
3

(aq) and K
+
I

(aq) form in the solution, preventing Ag

+
and I

ions from
coming together and precipitating.


19. (E) Equation: ( ) ( ) ( )
+ 2
2 4 4
Ag SO s 2Ag aq + SO aq

Original: 0 M 0.150 M
Add solid: +2x M +x M
Equil: 2x M ( ) 0.150+ M x

( ) ( ) ( ) ( )
+ 3
2 2
2 2 + 3 5
sp 4
2 = Ag =9.7 10 M; =0.00485
= Ag SO = 2 0.150+ = 9.7 10 0.150+0.00485 =1.5 10
x x M
K x x

(

( (



20. (M) Equation: ( ) ( ) ( )
2 2+
4 4
CaSO s Ca aq + SO aq .

Soln: 0 M 0.0025 M
( )
4
Add CaSO s +x M +x M
Equil: x M ( ) 0.0025+ M x
If we use the approximation that x <<0.0025, we find x =0.0036. Clearly, x is larger than
0.0025 and thus the approximation is not valid. The quadratic equation must be solved.
( )
2 2+
4
6 2
sp
2 6
Ca SO = =9.1 10 = 0.0025+ =0.0025 +
+0.0025 9.1 10 =0
K x x x x
x x

( (




Chapter 18: Solubility and Complex-Ion Equilibria
907
x
b b ac
a
=
4
2
=
0.0025 6.3 10 +3.6 10
2
=2.0 10 =
2 6 5
3
4

M CaSO
3
4 4
4 4
4
2.0 10 mol CaSO 136.1g CaSO
mass CaSO =0.1000L =0.027 g CaSO
1 L soln 1mol CaSO

21. (M) For PbI Pb I
sp 2
9 2+
2
, =7.1 10 = K



In a solution where
4 2 4
2
1.5 10 mol PbI is dissolved, Pb 1.5 10 M
+
( =

, and
I Pb

=2 =3.0 10
2+ 4
M

Equation: ( ) ( ) ( )
2+
2
PbI s Pb aq + 2I aq

Initial:
4
1.5 10 M

4
3.0 10 M

Add lead(II): +x M
Equil: ( ) 0.00015+ M x 0.00030 M

( )( )
2
9
sp
=7.1 10 = 0.00015+ 0.00030 K x

;( ) 0.00015+ =0.079 x ;
2+
=0.079 M = Pb x (



22. (M) For PbI Pb I
sp 2
9 2+
2
, =7.1 10 = K




In a solution where
5 2 5
2
1.5 10 mol PbI /L is dissolved, Pb 1.5 10 M
+
( =

, and
I Pb

=2 =3.0 10
2+ 5
M
Equation: ( ) ( ) ( )
2+
2
PbI s Pb aq + 2I aq

Initial: 1.5 10 3.0 10
5 5


M M
Add KI: +x M
Equil:
5 5
1.5 10 M (3.0 10 ) M x

+

K
sp
=7.1 10
-9
=(1.5 10
-5
) (3.0 10
-5
+x)
2

(3.0 10
-5
+x) =(7.1 10
-9
1.5 10
-5
)
1/2
x =(2.2 10
-2
) (3.0 10
-5
) =2.1 10
-2
M =[I
-
]
23. (D) For
2
2 12 +
2 4 sp 4
Ag CrO , =1.1 10 = Ag CrO K

( (


In a
8 2 8
2 4 4
5.0 10 M solution of Ag CrO , CrO =5.0 10 M

(

and Ag
+ 7
=1.0 10

M
Equation: ( ) ( ) ( )
2 +
2 4 4
Ag CrO s 2Ag aq + CrO aq

Initial: 1.0 10 5.0 10
7 8


M M
Add chromate: +x M
Equil: 1.0 10 5.0 10 +
7 8


M M x
c h

( ) ( )
2
12 7 8
sp
=1.1 10 =1.0 10 5.0 10 + ; K x


( )
8 2
5.0 10 + =1.1 10 x

2
4
= CrO

(

.
Chapter 18: Solubility and Complex-Ion Equilibria
908
This is an impossibly high concentration to reach. Thus, we cannot lower the solubility of
Ag CrO
2 4
to
8
5.0 10 M

with CrO
4
2
as the common ion. Lets consider using Ag
+
as the
common ion.
Equation: ( ) ( ) ( )
2 +
2 4 4
Ag CrO s 2Ag aq + CrO aq

Initial:
7
1.0 10 M

8
5.0 10 M

Add silver(I) ion: +x M
Equil:
( )
7
1.0 10 + M x

8
5.0 10 M

( ) ( ) ( )
-12
2
-12 -8 -7 -3
sp
-8
1.1 10
=1.1 10 = 1.0 + 5.0 10 1.0 10 + = =4.7 10
5.0 10
K x x

x =4.7 10 1.0 10 =4.7 10 =
3 7 3


M I ; this is an easy-to-reach concentration. Thus,
the solubility can be lowered to 5.010
-8
M by carefully adding Ag
+
(aq).

24. (M) Even though BaCO
3
is more soluble than
4
BaSO , it will still precipitate when 0.50 M
Na CO aq
2 3
b g is added to a saturated solution of
4
BaSO because there is a sufficient Ba
2+

in such a solution for the ion product Ba CO
2+
3
2
to exceed the value of K
sp
for the compound.
An example will demonstrate this phenomenon. Let us assume that the two solutions being mixed
are of equal volume and, to make the situation even more unfavorable, that the saturated
BaSO
4
solution is not in contact with solid
4
BaSO , meaning that it does not maintain its
saturation when it is diluted. First we determine Ba
2+
in saturated
4
BaSO (aq) .
K s s
sp
Ba SO M = =1.1 10 = = 11 10 10 10
2+
4
2 10 2 10 5
= . .
Mixing solutions of equal volumes means that the concentrations of solutes not common to the
two solutions are halved by dilution.
5 2+
2+ 6 4
4
1 1.0 10 mol BaSO 1mol Ba
Ba = =5.0 10 M
2 1L 1mol BaSO

(


2
2
2 3 3
3
2 3
0.50 mol Na CO 1mol CO 1
CO = =0.25M
2 1L 1mol Na CO

(



( )( )
2 2+ 6 6 9
sp 3 3 sp 3
{BaCO }= Ba CO = 5.0 10 0.25 =1.3 10 5.0 10 = {BaCO } Q K

( ( >


Thus, precipitation of BaCO
3
indeed should occur under the conditions described.
25. (E)
2+ 2+
2+ 3
6 2+
115g Ca 1mol Ca 1000g soln
Ca = =2.87 10 M
10 g soln 40.08g Ca 1L soln

(



( )
2 2
2+ 9 3 3
sp
Ca F = =5.3 10 = 2.87 10 F F =1.4 10 M K

( ( ( (


3
6
1.4 10 mol F 19.00g F 1L soln
ppm F = 10 g soln=27 ppm
1L soln 1mol F 1000g

Chapter 18: Solubility and Complex-Ion Equilibria
909
26. (M) We first calculate the Ag
+
and the Cl

in the saturated solution.

K s s s s
sp
Ag Cl M Ag Cl = =1.8 10 = = =1.3 10 = =
+ 10 2 5 +
b gb g
Both of these concentrations are marginally diluted by the addition of 1 mL of NaCl(aq)

Ag Cl M
mL
mL mL
M
+ 5 5
= =1.3 10
100.0
100.0 +1.0
=1.3 10


The Cl

in the NaCl(aq) also is diluted.

3
1.0mL
Cl =1.0M =9.9 10 M
100.0mL +1.0mL

(


Let us use this Cl

to determine the Ag
+
that can exist in this solution.
( )
10
+ 10 + 3 + 8
3
1.8 10
Ag Cl =1.8 10 = Ag 9.9 10 M Ag = =1.8 10 M
9.9 10

( ( ( (



We compute the amount of AgCl in this final solution, and in the initial solution.

mmol AgCl final mL
mol Ag
L soln
mmol AgCl
mmol Ag
mmol AgCl =101.0
1.8 10
1
1
1
=1.8 10
8 +
+
6

mmol AgCl
5 +
3
+
1.3 10 mol Ag 1mmol AgCl
initial =100.0mL =1.3 10 mmol AgCl
1L soln 1mmol Ag

The difference between these two amounts is the amount of AgCl that precipitates. Next we
compute its mass.
( )
3 6
143.3mg AgCl
mass AgCl =1.3 10 1.8 10 mmol AgCl =0.19mg
1mmol AgCl


We conclude that the precipitate will not be visible to the unaided eye, since its mass is less
than 1 mg.

Criteria for Precipitation from Solution

27. (E) We first determine Mg
2+
, and then the value of Q
sp
in order to compare it to the value of
sp
. K We express molarity in millimoles per milliliter, entirely equivalent to moles per liter.

2+
2+ 4 2 2 2
2 2 2
22.5mgMgCl 1mmol MgCl 6H O 1mmol Mg
[Mg ] 3.41 10 M
325mLsoln 203.3mgMgCl 6H O 1mmol MgCl

= =

2+ 2 4 2 7 8
sp sp
[Mg ][F ] (3.41 10 )(0.035) 4.2 10 3.7 10 Q K

= = = > =
Thus, precipitation of MgF s
2
b g should occur from this solution.

28. (E) The solutions mutually dilute each other.

3
155mL
Cl =0.016M =6.2 10 M
155mL +245mL

(



2+
245mL
Pb =0.175M =0.107 M
245mL +155mL
(



Chapter 18: Solubility and Complex-Ion Equilibria
910
Then we compute the value of the ion product and compare it to the solubility product constant
value.

( )( )
2 2
2+ 3 6 5
sp sp
= Pb Cl = 0.107 6.2 10 =4.1 10 1.6 10 = Q K

( ( <



Thus, precipitation of PbCl s
2
b g will not occur from these mixed solutions.

29. (E) We determine the OH

needed to just initiate precipitation of Cd(OH)

2
.

K
sp
Cd OH M OH OH M = =2.5 10 = 0.0055 =
25 10
0.0055
=2.1 10
2+
2
14
2
14
6

b g
.


pOH log pH = 2.1 10 =5.68 =14.00 5.68=8.32
6

c h


Thus, Cd OH b g
2
will precipitate from a solution with pH 8.32. >

30. (E) We determine the OH

needed to just initiate precipitation of Cr(OH)

3
.

3+ 3 31 3
sp
[Cr ][OH ] 6.3 10 (0.086M) [OH ] K

= = = ;
31
10
6.3 10
[OH ] 1.9 10 M
0.086

= =

pOH log pH = 1.9 10 =9.72 =14.00 9.72=4.28
10

c h


Thus,Cr OH b g
3
will precipitate from a solution with pH >4.28.

31. (D)
(a) First we determine Cl

due to the added NaCl.

6
0.10mg NaCl 1g 1mol NaCl 1mol Cl
Cl = =1.7 10 M
1.0L soln 1000mg 58.4g NaCl 1mol NaCl

(



Then we determine the value of the ion product and compare it to the solubility product
constant value.

( )( )
+ 6 7 10
sp sp
= Ag Cl = 0.10 1.7 10 =1.7 10 1.8 10 = for AgCl Q K

( ( >



Thus, precipitation of AgCl(s) should occur.


(b) The KBr(aq) is diluted on mixing, but the Ag
+
and Cl

are barely affected by

dilution.

Br M
mL
mL mL
M

=0.10
0.05
0.05 +250
=2 10
5


Now we determine Ag
+
in a saturated AgCl solution.

K s s s s
sp
Ag Cl M = = = =1.8 10 =1.3 10
+ 2 10 5
b gb g
Chapter 18: Solubility and Complex-Ion Equilibria
911

Then we determine the value of the ion product for AgBr and compare it to the solubility
product constant value.

| | ( )( )
+ 5 5 10 13
sp sp
= Ag Br =1.3 10 2 10 =3 10 5.0 10 = for AgBr Q K

( >



Thus, precipitation of AgBr(s) should occur.

(c) The hydroxide ion is diluted by mixing the two solutions.

7
0.05mL
OH =0.0150M =2.5 10 M
0.05mL +3000mL

(



But the Mg
2+
does not change significantly.

2+ 2+
2+ 5
2.0mg Mg 1g 1mol Mg
Mg = =8.2 10 M
1.0L soln 1000mg 24.3g Mg

(



Then we determine the value of the ion product and compare it to the solubility product
constant value.

( ) ( )
2 2
2+ 7 5 18
sp
= Mg OH = 2.5 10 8.2 10 =5.1 10 Q

( (



( )
11
sp sp
2
1.8 10 = for Mg OH Q K

< Thus, no precipitate forms.

32. First we determine the moles of H
2
produced during the electrolysis, then determine [OH

].
2 2
1 1
1atm
752mmHg 0.652L
760mmHg
moles H = = =0.0267mol H
0.08206L atm mol K 295K
PV
RT

OH
0.0267 mol H
mol OH
mol H
L sample
M
2
2

=
2
1
0.315
=0.170

( )( )
2
2
2+ 3 11
sp sp
= Mg OH = 0.185 0.170 =5.35 10 1.8 10 = Q K

( ( >



Thus, yes, precipitation of Mg OH s b g b g
2
should occur during the electrolysis.

33. (D) First we must calculate the initial [H
2
C
2
O
4
] upon dissolution of the solid acid:
[H
2
C
2
O
4
]
initial
=1.50 g H
2
C
2
O
4
2 2 4
2 2 4
1 mol H C O 1
=0.0833 M
90.036 g H C O 0.200 L

(We assume the volume of the solution stays at 0.200 L.)
Next we need to determine the [C
2
O
4
2-
] in solution after the hydrolysis reaction between oxalic
acid and water reaches equilibrium. To accomplish this we will need to solve two I.C.E. tables:
Chapter 18: Solubility and Complex-Ion Equilibria
912
Table 1: H
2
C
2
O
4
(aq) + H
2
O(l)
2
a1
5.2 10 K

=

HC
2
O
4
-
(aq) + H
3
O
+
(aq)
Initial: 0.0833 M 0 M 0 M
Change: x +x M +x M
Equilibrium: 0.0833 x M x M x M

Since C
a
/K
a
=1.6, the approximation cannot be used, and thus the full quadratic equation must
be solved: x
2
/(0.0833 x) =5.210
-2
; x
2
+5.210
-2
x 4.3310
-3

-2 -3
-
2 4 3
-5.210 2.710 +0.0173
= =0.045 M =[HC O ] [H O ]
2
x x
+

~
Now we can solve the I.C.E. table for the second proton loss:
Table 2: HC
2
O
4
-
(aq) + H
2
O(l)
5
a1
5.4 10 K

=

C
2
O
4
2-
(aq) + H
3
O
+
(aq)
Initial: 0.045 M 0 M 0.045 M
Change: y +y M +y M
Equilibrium: (0.045 y) M y M (0.045+y) M

Since C
a
/K
a
=833, the approximation may not be valid and we yet again should solve the full
quadratic equation:
-5
(0.045 )
=5.4 10
(0.045 )
y y
y
+

; y
2
+0.045y =2.4310
-6
5.410
-5
y
-3 -6
-5 2-
2 4
-0.045 2.0310 +9.7210
= =8.2 10 M =[C O ]
2
y y

Now we can calculate the Q
sp
for the calcium oxalate system:
Q
sp
=[Ca
2+
]
initial
[ C
2
O
4
2-
]
initial
=(0.150)(8.210
-5
) =1.210
-5
>1.3 10
-9
(K
sp
for CaC
2
O
4
)
Thus, CaC
2
O
4
should precipitate from this solution.

34. (D) The solutions mutually dilute each other. We first determine the solubility of each
compound in its saturated solution and then its concentration after dilution.

( )
5 3
2
2 2 + 5 3 2
sp 4
1.4 10
= Ag SO =1.4 10 = 2 =4 = 1.5 10 M
4
K s s s s

( ( =



2 +
4
100.0mL
SO =0.015M =0.0043M Ag =0.0086M
100.0mL +250.0mL

( (


K s s s
sp
2+
4
2
Pb CrO = = = =

[ ][ ] . ( )( ) 28 10
13 2
s = =

28 10 53 10
13 7
. . M

2 2+ 7 7
4
250.0mL
Pb = CrO =5.3 10 =3.8 10 M
250.0mL +100.0mL

( (



From the balanced chemical equation, we see that the two possible precipitates are PbSO
4
and
2 4
Ag CrO . (Neither PbCrO
4
nor Ag SO
2 4
can precipitate because they have been diluted
below their saturated concentrations.)
4 2 4 4 2 4
PbCrO +Ag SO PbSO +Ag CrO

Thus, we compute the value of
sp
Q for each of these compounds and compare those values
with the solubility constant product value.

Chapter 18: Solubility and Complex-Ion Equilibria
913
( )( )
2 2+ 7 9 8
sp 4 sp 4
= Pb SO = 3.8 10 0.0043 =1.6 10 1.6 10 = for PbSO Q K

( ( <



Thus, PbSO (s)
4
will not precipitate.

( ) ( )
2
2 2 + 7 11 12
sp 4 sp 2 4
= Ag CrO = 0.0086 3.8 10 =2.8 10 1.1 10 = for Ag CrO Q K

( ( >



Thus, Ag CrO s
2 4
b g should precipitate.

Completeness of Precipitation

35. (M) First determine that a precipitate forms. The solutions mutually dilute each other.

CrO M
mL
mL mL
M
4
2
=0.350
200.0
200.0 +200.0
=0.175

Ag M
mL
mL mL
M
+
=0.0100
200.0
200.0 +200.0
=0.00500

We determine the value of the ion product and compare it to the solubility product constant
value.

( ) ( )
2
2 2 + 6 12
sp 4 sp 2 4
= Ag CrO = 0.00500 0.175 =4.4 10 1.1 10 = for Ag CrO Q K

( ( >



Ag CrO
2 4
should precipitate.

Now, we assume that as much solid forms as possible, and then we approach equilibrium by
dissolving that solid in a solution that contains the ion in excess.

( ) ( ) ( )
+ 2
2 4 4
12
1.1 10
Equation: Ag CrO s 2Ag aq + CrO aq

Orig. soln: 0.00500M 0.175M
Form solid: 0.00500M 0.00250M
Not at equilibrium 0 M 0.173 M
Changes: +2 M x + M x
( ) Equil : 2 M 0.173+ M x x

( ) ( ) ( )( )
2
2 12 2
4
Ag CrO 1.1 10 2 0.173 4 0.173
sp
K x x x
+
+
( ( = = = + ~



( )
12 6 + 6
= 1.1 10 4 0.173 =1.3 10 M Ag =2 =2.6 10 M x x

(


%Ag
+
unprecipitated =

=

26 10
100% 0052%
6
.
.
M final
0.00500M initial
unprecipitated
36. (M) [Ag
+
]
diluted
=0.0208 M
175 mL
425 mL
=0.008565 M
[CrO
4
2
]
diluted
=0.0380 M
250 mL
425 mL
=0.02235 M
2
2 6
sp 4 sp
Ag CrO 1.6 10 Q K
+
( ( = = >


Chapter 18: Solubility and Complex-Ion Equilibria
914
Because Q
sp
>K
sp
, then more Ag
2
Cr
2
O
4
precipitates out. Assume that the limiting reagent is
used up (100% reaction in the reverse direction) and re-establish the equilibrium in the reverse
direction. Here Ag
+
is the limiting reagent.
Ag
2
CrO
4
(s)
-12
sp
(Ag CrO )
2 4
=1.1 10 K

2 Ag
+
(aq) + CrO
4
2
(aq)
Initial 0.008565 M 0.02235 M
Change x = 0.00428 M 2x
x
100% rxn 0 0.0181
Change re-establish equil +2y +y
Equil (assume y ~ 0) 2y 0.0181 +y

1.1 10
12
=(2y)
2
(0.0181+y) ~ (2y)
2
(0.0181) y =3.9 10
6
M
y <<0.0181, so this assumption is valid.
2y =[Ag
+
] =7.8 10
6
M after precipitation is complete.
% [Ag
+
]
unprecipitated
=
6
7.8 10
0.00856

100% =0.091% (precipitation is essentially quantitative)

37. (M) We first use the solubility product constant expression to determine Pb
2+
in a solution
with 0.100 M Cl .

( )
( )
5
2
2
2+ 5 2+ 2+ 3
sp 2
1.6 10
= Pb Cl =1.6 10 = Pb 0.100 Pb = =1.6 10 M
0.100
K

( ( ( (


Thus, % unprecipitated
3
1.6 10 M
100% 2.5%
0.065M

= =
Now, we want to determine what [Cl
-
] must be maintained to keep
2+
final
[Pb ] 1%; =
2+ 4
initial
[Pb ] 0.010 0.065M =6.5 10 M

=
K
sp
Pb Cl Cl Cl M = =1.6 10 = 6.5 10 =
6 10
6.5 10
=0.16
2+
2
5 4
2
5
4

c h


38. (M) Lets start by assuming that the concentration of Pb
2+
in the untreated wine is no higher
than 1.5 10
4
M (this assumption is not unreasonable.) As long as the Pb
2+
concentration is
less than 1.5 10
4
M, then the final sulfate ion concentration in the CaSO
4
treated wine
should be virtually the same as the sulfate ion concentration in a saturated solution of CaSO
4

formed by dissolving solid CaSO
4
in pure water ( i.e., with [Pb
2+
] less than or equal to 1.5
10
4
M, the [SO
4
2
] will not drop significantly below that for a saturated solution, ~ 3.0 10
3

M.) Thus, the addition of CaSO
4
to the wine would result in the precipitation of solid PbSO
4
,
which would continue until the concentration of Pb
2+
was equal to the K
sp
for PbSO
4
divided
by the concentration of dissolved sulfate ion, i.e.,
[Pb
2+
]
max
=1.6 10
8
M
2
/3.0 10
3
M =5.3 10
6
M.

Chapter 18: Solubility and Complex-Ion Equilibria
915
Fractional Precipitation

39. (M) First, assemble all of the data. K
sp
for Ca(OH)
2
=5.510
-6
, K
sp
for Mg(OH)
2
=1.810
-11


2+ 2+
2+
2+
440 g Ca 1 mol Ca 1 kg seawater 1.03 kg seawater
[Ca ] 0.0113 M
1000 kg seawater 1000 g seawater 1 L seawater 40.078 g Ca
= =
[Mg
2+
] =0.059 M, obtained from Example 18-6. [OH
-
] =0.0020 M (maintained)

(a) Q
sp
=[Ca
2+
][OH
-
]
2
=(0.0113)( 0.0020)
2
=4.510
-8
Q
sp
<K
sp
no precipitate forms.

(b) For the separation to be complete, >>99.9 % of the Mg
2+
must be removed before Ca
2+
begins to precipitate. We have already shown that Ca
2+
will not precipitate if the [OH
-
] =
0.0020 M and is maintained at this level. Let us determine how much of the 0.059 M
Mg
2+
will still be in solution when [OH
-
] =0.0020 M.
K
sp
=[Mg
2+
][OH
-
]
2
=(x)( 0.0020)
2
= 1.810
-11
x =4.510
-6
M
The percent Mg
2+
ion left in solution =
6
4.5 10
100% =0.0076 %
0.059

This means that 100% - 0.0076 % Mg =99.992 % has precipitated.
Clearly, the magnesium ion has been separated from the calcium ion (i.e., >>99.9% of the
Mg
2+
ions have precipitated and virtually all of the Ca
2+
ions are still in solution.)

40. (D)
(a) 0.10 M NaCl will not work at all, since both BaCl
2
and CaCl
2
are soluble in water.


(b) K
sp
=1.1 10
10

for BaSO
4
and K
sp
=9.1 10
6

for CaSO
4
. Since these values differ by
more than 1000, 0.05 M Na SO
2 4
would effectively separate Ba
2+
from Ca
2+
.

We first compute SO
4
2
when BaSO
4
begins to precipitate.

( )
10
2 2 2 2+ 10 9
4 4 4
1.1 10
Ba SO = 0.050 SO =1.1 10 ; SO = =2.2 10 M
0.050

( ( ( (



And then we calculate SO
4
2
when Ba
2+
has decreased to 0.1% of its initial value,
that is, to 5.0 10
5

M.

( )
10
2 2 2 2+ 5 10 6
4 4 4
5
1.1 10
Ba SO = 5.0 10 SO =1.1 10 ; SO = =2.2 10 M
5.0 10

( ( ( (




And finally, SO
4
2
when CaSO
4
begins to precipitate.

( )
6
2 2 2 2+ 6 4
4 4 4
9.1 10
Ca SO = 0.050 SO =9.1 10 ; SO = =1.8 10 M
0.050

( ( ( (


Chapter 18: Solubility and Complex-Ion Equilibria
916
(c) Now, K
sp
=5 10
3

for Ba OH b g
2
and K
sp
=5.5 10
6

for ( )
2
Ca OH . The fact that these
two K
sp
values differ by almost a factor of 1000 does not tell the entire story, because
OH

is squared in both K
sp
expressions. We compute OH

when Ca OH b g
2
begins
to precipitate.

Ca OH OH OH M
2+
2
6
2
6
2
=5.5 10 = 0.050 =
55 10
0050
=1.0 10

b g
.
.

Precipitation will not proceed, as we only have 0.001 M NaOH, which has
OH

=1 10
3
M.

(d) K
sp
=5.1 10
9

for BaCO
3
and K
sp
=2.8 10
9

for
3
CaCO . Since these two values
differ by less than a factor of 2, 0.50 M Na CO
2 3
would not effectively separate Ba
2+

from
2+
Ca .

41. (M)
(a) Here we need to determine I

when AgI just begins to precipitate, and I

when
PbI
2
just begins to precipitate.

K
sp
Ag I I I M = =8.5 10 = 0.10 =8.5 10
+ 17 16
b g

( )
9
2 2
2+ 9 4
sp
7.1 10
= Pb I =7.1 10 = 0.10 I I =2.7 10 M
0.10
K

( ( ( ( =



Since 8.5 10
16

M is less than 2.7 10
4

M, AgI will precipitate before PbI
2
.


(b)
4
I must be equal to 2.7 10 M

(

before the second cation,
2+
Pb , begins to precipitate.

(c) K
sp
Ag I Ag Ag M = =8.5 10 = 2.7 10 =3.1 10
+ 17 + 4 + 13

c h


(d) Since Ag
+
has decreased to much less than 0.1% of its initial value before any PbI
2

begins to precipitate, we conclude that Ag
+
and Pb
2+
can be separated by precipitation
with iodide ion.

42. (D) Normally we would worry about the mutual dilution of the two solutions, but the values
of the solubility product constants are so small that only a very small volume of 0.50 M
Pb NO
3
2
b g solution needs to be added, as we shall see.

(a) Since the two anions are present at the same concentration and they have the same type
of formula (one anion per cation), the one forming the compound with the smallest K
sp

value will precipitate first. Thus, CrO
4
2
is the first anion to precipitate.


Chapter 18: Solubility and Complex-Ion Equilibria
917
(b) At the point where SO
4
2
begins to precipitate, we have

( )
8
2 2+ 8 2+ 2+ 6
sp 4
1.6 10
= Pb SO =1.6 10 = Pb 0.010M ; Pb = =1.6 10 M
0.010
K

( ( ( (


Now we can test our original assumption, that only a very small volume of 0.50 M
Pb NO
3
2
b g solution has been added. We assume that we have 1.00 L of the original
solution, the one with the two anions dissolved in it, and compute the volume of 0.50 M
Pb NO
3
2
b g that has to be added to achieve Pb
2+ 6
=1.6 10

M.

( )
( )
6 2+ 2+
3
2
added 2+
3
2
5 2+ 2+
added
1mol Pb NO
1.6 10 mol Pb 1L Pb soln
=1.00L
1L soln 1mol Pb 0.50mol Pb NO
=3.2 10 L Pb soln=0.0032mL Pb soln
V
V

This is less than one drop (0.05 mL) of the Pb
2+
solution, clearly a very small volume.


(c) The two anions are effectively separated if Pb
2+
has not reached 1.6 10
6

M when
CrO
4
2
is reduced to 0.1% of its original value, that is, to
2 3 5
4
0.010 10 M =1.0 10 M = CrO

(



K
sp
Pb CrO Pb = =2.8 10 = 1.0 10
2+
4
2 13 2+ 5

c h

13
2+ 8
5
2.8 10
Pb = =2.8 10 M
1.0 10

(



Thus, the two anions can be effectively separated by fractional precipitation.

43. (M) First, lets assemble all of the data. K
sp
for AgCl =1.810
-10
K
sp
for AgI =8.510
-17
[Ag
+
] =2.00 M [Cl
-
] =0.0100 M [I
-
] =0.250 M

(a) AgI(s) will be the first to precipitate by virtue of the fact that the K
sp
value for AgI is
about 2 million times smaller than that for AgCl.

(b) AgCl(s) will begin to precipitate when the Q
sp
for AgCl(s) >K
sp
for AgCl(s)
.
The
concentration of Ag
+
required is: K
sp
=[Ag
+
][Cl
-
] =1.810
-10
=(0.0100)(x) x =
1.810
-8
M
Using this data, we can determine the remaining concentration of I
-
using the K
sp
.
K
sp
=[Ag
+
][I
-
] =8.510
-17
=(x)( 1.810
-8
) x =4.710
-9
M

(c) In part (b) we saw that the [I
-
] drops from 0.250 M 4.710
-9
M. Only a small
percentage of the ion remains in solution.
9
4.7 10
100% =0.0000019 %
0.250

This means that 99.999998% of the I
-
ion has been precipitated before any of the Cl
-
ion
has precipitated. Clearly, the fractional separation of Cl
-
from I
-
is feasible.

Chapter 18: Solubility and Complex-Ion Equilibria
918
44. (M)
(a) We first determine the Ag
+
needed to initiate precipitation of each compound.
( )
sp
10
+ 10 + + 10
1.8 10
AgCl : = Ag Cl =1.8 10 = Ag 0.250 ; Ag = =7.2 10 M
0.250
K

( ( ( (



( )
sp
13
+ 13 + + 10
5.0 10
AgBr: = Ag Br =5.0 10 = Ag 0.0022 ; Ag = =2.3 10 M
0.0022
K

( ( ( (




Thus, Br

precipitates first, as AgBr, because it requires a lower Ag

+
.

(b) Ag
+ 10
=7.2 10

M when chloride ion, the second anion, begins to precipitate.
(c) Cl

and Br

cannot be separated by this fractional precipitation. Ag

+
will have to
rise to 1000 times its initial value, to 2.3 10
7

M, before AgBr is completely precipitated.
But as soon as Ag
+
reaches 7.2 10
10

M, AgCl will begin to precipitate.

Solubility and pH

45. (E) In each case we indicate whether the compound is more soluble in water. We write the net
ionic equation for the reaction in which the solid dissolves in acid. Substances are more
soluble in acid if either (1) an acid-base reaction occurs or (2) a gas is produced, since escape
of the gas from the reaction mixture causes the reaction to shift to the right.

Same: KCl (K
+
and Cl
-
do not react appreciably with H
2
O)
Acid: ( ) ( ) ( ) ( )
+ 2+
3 2 2
MgCO s +2H aq Mg aq +H O(l)+CO g
Acid: ( ) ( ) ( ) ( )
+ 2+
2
FeS s +2H aq Fe aq +H S g
Acid: ( ) ( ) ( ) ( )
+ 2+
2
2
Ca OH s +2H aq Ca aq +2H O(l)
Water: C H COOH
6 5
is less soluble in acid, because of the H O
3
+
common ion.

46. (E) In each case we indicate whether the compound is more soluble in base than in water. We
write the net ionic equation for the reaction in which the solid dissolves in base. Substances are
soluble in base if either (1) acid-base reaction occurs [as in (b)] or (2) a gas is produced, since
escape of the gas from the reaction mixture causes the reaction to shift to the right.
Water: BaSO
4
is less soluble in base, hydrolysis of SO
4
2
will be repressed.

Base: ( ) ( ) ( )
2
2 2 4 2 4 2
H C O s +2OH aq C O aq +2H O(l)



Water: FeOH b g
3
is less soluble in base because of the OH

common ion.

Same: NaNO
3
(neither Na
+
nor NO
3
-
react with H
2
O to a measurable extent).

Water: MnS is less soluble in base because hydrolysis of S
2
will be repressed.

Chapter 18: Solubility and Complex-Ion Equilibria
919
47. (E) We determine Mg
2+
in the solution.

Mg
g Mg OH
L soln
mol Mg OH
g Mg OH
mol Mg
mol Mg OH
M
2+ 2 2
2
2+
2
=
0.65
1
1
58.3
1
1
=0.011
b g b g
b g b g


Then we determine OH

in the solution, and its pH.

( )
2 2
2 11
sp
Mg OH 1.8 10 0.011 OH K
+
( ( ( = = =

;
11
5
1.8 10
OH 4.0 10 M
0.011

( = =



( )
5
pOH= log 4.0 10 =4.40 pH=14.00 4.40=9.60

48. (M) First we determine the [Mg
2+
] and [NH
3
] that result from dilution to a total volume of
0.500 L.
| |
2+ initial initial
3
final final
0.150 L 0.350 L
Mg =0.100M =0.0300M; NH =0.150M =0.105M
0.500 L 0.500 L
(



Then determine the OH

that will allow Mg

2+
=0.0300 M in this solution.

( )
11
2 2
11 2+ 5
sp
1.8 10
1.8 10 = Mg OH = 0.0300 OH ; OH = =2.4 10 M
0.0300
K

= ( ( ( (



This OH

is maintained by the
+
3 4
NH / NH buffer; since it is a buffer, we can use the
HendersonHasselbalch equation to find the [NH
4
+
].
( )
| | | |
3 3 5
a
+ +
4 4
NH NH
pH=14.00 pOH=14.00+log 2.4 10 =9.38=p +log =9.26+log
NH NH
K

( (


3 3 + +0.12 3
4
+ +
4 4
NH NH
0.105 M NH
log =9.38 9.26=+0.12; =10 =1.3; NH = =0.081M
1.3
NH NH
( (

(

( (



( )
( ) ( )
( )
+
4 4 4 4
4 2 2
4 4 + 2
4 4 4 2
1mol NH SO 132.1g NH SO
0.081mol NH
mass NH SO =0.500 L =2.7 g
L soln 1mol NH SO 2 mol NH

49. (M)
(a) Here we calculate OH

needed for precipitation.

( )
3+ 3 33 3
sp
3 33
11 11

[Al ][OH ] 1.3 10 (0.075M)[OH ]
1.3 10
[OH ] 2.6 10 pOH= log 2.6 10 =10.59
0.075
pH=14.00 10.59=3.41
K

= = =

= =

Chapter 18: Solubility and Complex-Ion Equilibria
920
(b) We can use the HendersonHasselbalch equation to determine C H O
2 3 2

.

pH p log
C H O
HC H O
log
C H O
M
a
=3.41= + =4.74+
1.00
2 3 2
2 3 2
2 3 2
K

L
N
M
O
Q
P

2 3 2 2 3 2
1.33
2 3 2
C H O C H O
log =3.41 4.74= 1.33; =10 =0.047; C H O =0.047M
1.00M 1.00M


( (

(


This situation does not quite obey the guideline that the ratio of concentrations must fall
in the range 0.10 to 10.0, but the resulting error is a small one in this circumstance.
2 3 2 2 3 2 2 3 2
2 3 2
2 3 2 2 3 2
2 3 2
0.047mol C H O 1mol NaC H O 82.03g NaC H O
mass NaC H O =0.2500L
1L soln 1mol NaC H O 1mol C H O
0.96 g NaC H O

=


50. (D)
(a) Since HI is a strong acid,
3 3 3
I =1.05 10 M+1.05 10 M =2.10 10 M.

(


We determine the value of the ion product and compare it to the solubility product
constant value.
( )( )
2 2
2+ 3 3 9 9
sp sp 2
= Pb I =1.1 10 2.10 10 =4.9 10 7.1 10 = for PbI Q K

( ( <



Thus a precipitate of PbI
2
will not form under these conditions.


(b) We compute the OH

needed for precipitation.

( )
2 2
2 11
sp
Mg OH 1.8 10 0.0150 OH K
+
( ( (

= = = ;
11
5
1.8 10
OH 3.5 10 M
0.0150

(


= =

Then we compute OH

in this solution, resulting from the ionization of NH

3
.

| |
3
4
3
0.05 10 L
NH =6.00M =1.2 10 M
2.50L

Even though NH
3
is a weak base, the OH

produced from theNH

3
hydrolysis reaction
will approximate 4 10
5

M (3.85 if you solve the quadratic) in this very dilute solution.
(Recall that degree of ionization is high in dilute solution.) And since OH

=3.5 10
5

M is needed for precipitation to occur, we conclude that Mg OH b g
2
will precipitate from
this solution (note: not much of a precipitate is expected).

(c) 0.010 M HC H O
2 3 2
and 0.010 M NaC H O
2 3 2
is a buffer solution with pH p
a
= K of
acetic acid (the acid and its anion are present in equal concentrations.) From this, we
determine the OH

.

Chapter 18: Solubility and Complex-Ion Equilibria
921
pH pOH OH =4.74 =14.00 4.74=9.26 =10 =5.5 10
9.26 10




( )( ) ( )
3 3
3+ 10 30 33
sp
3
= Al OH = 0.010 5.5 10 =1.7 10 1.3 10 = of Al OH Q K

( ( >



Thus, Al OH s b g b g
3
should precipitate from this solution.

Complex-Ion Equilibria

51. (E) Lead(II) ion forms a complex ion with chloride ion. It forms no such complex ion with
nitrate ion. The formation of this complex ion decreases the concentrations of free Pb aq
2+
b g
and free Cl aq

b g . Thus, PbCl
2
will dissolve in the HCl(aq) up until the value of the solubility
product is exceeded. ( ) ( ) | | ( )
2+
3
Pb aq +3Cl aq PbCl aq

52. (E) ( ) ( ) ( ) ( )
2+
2+ 8
3 3 f
4
Zn aq +4NH aq Zn NH aq =4.1 10 K (

NH aq
3
b g will be least effective in reducing the concentration of the complex ion. In fact, the
addition of NH aq
3
b g will increase the concentration of the complex ion by favoring a shift of
the equilibrium to the right. NH aq
4
+
b g will have a similar effect, but not as direct. NH aq
3
b g is
formed by the hydrolysis of NH aq
4
+
b g and, thus, increasing NH
4
+
will eventually increase
NH aq
3
b g : ( ) ( ) ( )
+ +
4 2 3 3
NH aq +H O(l) NH aq +H O aq .

The addition of HCl(aq) will

cause the greatest decrease in the concentration of the complex ion. HCl(aq) will react with
NH aq
3
b g to decrease its concentration (by forming NH
4
+
) and this will cause the complex ion
equilibrium reaction to shift left toward free aqueous ammonia and Zn
2+
(aq).

53. (E) We substitute the given concentrations directly into the K
f
expression to calculate K
f
.

3
30 4
f + 4 32 4
[[Cu(CN) ] 0.0500
2.0 10
[Cu ][CN ] (6.1 10 )(0.80)
K

= = =

54. (M) The solution to this problem is organized around the balanced chemical equation. Free
NH
3
is 6.0 M at equilibrium. The size of the equilibrium constant indicates that most
copper(II) is present as the complex ion at equilibrium.

Equation:
( ) ( )
2+
3
Cu aq +4NH aq

Cu NH aq
3
4
2+
b g b g
Initial: 0.10 M 6.00 M 0 M
Change(100 % rxn): 0.10 M 0.40 M +0.10 M
Completion: 0 M 5.60 M 0.10 M
Changes: +x M +4x M x M
Equil: x M 5.60 +4x M 0.10 x b g M

Chapter 18: Solubility and Complex-Ion Equilibria
922
Lets assume (5.60 +4x) M 5.60 M and (0.10 x) M 0.10 M
( )
( )
2+
3
4
13
f
4 4 4
2+
3
Cu NH
0.10 0.10 0.10
= =1.1 10
983.4 (5.60)
5.60 4 Cu NH
x
K
x x
x x
(
(

(
(

(

= ~ ~
(



18 2
13
0.10
9.2 10 M Cu ( <<0.10, thus the approximation was valid)
983.4 (1.1 10 )
x x
+
( = = =




55. (M) We first find the concentration of free metal ion. Then we determine the value of Q
sp
for
the precipitation reaction, and compare its value with the value of K
sp
to determine whether
precipitation should occur.
Equation:
Ag aq
+
+ b g
( )
2
2 3
2S O aq

AgS O aq
2 3
2
3
b g b g

Initial: 0 M 0.76 M 0.048 M
Changes: +x M +2x M x M
Equil: x M
( ) 0.76+2 M x

( ) 0.048 M x

( )
( )
3
2 3
2
2
2 +
2 3
13
f 2 2
Ag S O
Ag S O
0.048 0.048
= =1.7 10 =
(0.76)
0.76+2
x
K
x
x x

(
(


~
( (

;
15 +
=4.9 10 M = Ag x

(


(x << 0.048 M, thus the approximation was valid.)
( )( )
+ 15 15 17
sp sp
= Ag I = 4.9 10 2.0 =9.8 10 8.5 10 = Q K

( ( >

.
Because
sp sp
Q K > , precipitation of AgI(s) should occur.

56. (M) We need to determine OH

in this solution, and also the free Cu

2+
.
| |
3
a
+
4
NH
0.10M
pH=p +log =9.26+log =9.26 pOH=14.00 9.26=4.74
0.10M
NH
K
(


4.74 5
OH =10 =1.8 10 M

(

( ) ( ) ( ) ( )
2+
2+
3 3
4
Cu aq +4NH aq Cu NH aq (

( )
2+
3
4
4 13 4 2+ 4 2+
3
13 2+ 11
f
Cu NH
0.015 0.015
1.1 10 0.10 Cu 0.10 Cu NH
= =1.1 10 = ; Cu = =1.4 10 M K

(
(


(
(


(

( (



Now we determine the value of
sp
Q and compare it with the value of K
sp
for Cu OH b g
2
.
( ) ( ) ( )
2 2
2+ 11 5 21 20
sp sp
2
Cu OH 1.410 1.810 ) = = = 4.510 < 2.210 ( for Cu OH

( (

Q K
Precipitation of Cu OH s b g b g
2
from this solution should not occur.

Chapter 18: Solubility and Complex-Ion Equilibria
923
57. (M) We first compute the free Ag
+
in the original solution. The size of the complex ion
formation equilibrium constant indicates that the reaction lies far to the right, so we form as
much complex ion as possible stoichiometrically.

Equation:
Ag aq
+
+ b g 2
3
NH aq b g

Ag NH aq
3
2
+
b g b g
In soln: 0.10 M 1.00 M 0 M
Form complex: 0.10 M 0.20 M +0.10 M
0 M 0.80 M 0.10 M
Changes: +x M +2x M x M
Equil: x M 0.80+2x b g M 0.10 x b g M
( )
( ) ( ) ( )
+
3
2
7 9
f 2 2 2 2
7 +
3
Ag NH
0.10 0.10 0.10
=1.6 10 = = = =9.8 10 M
0.80+2 0.80 1.6 10 0.80 Ag NH
x
K x
x x x
(
(

(
(
(

(

.
(x << 0.80 M, thus the approximation was valid.)

Thus,
+ 9
Ag =9.8 10 M.

(

We next determine the I

that can coexist in this solution

without precipitation.
( )
17
+ 17 9 9
sp
9
8.5 10
= Ag I =8.5 10 = 9.8 10 I ; I = =8.7 10 M
9.8 10
K

( ( ( (



Finally, we determine the mass of KI needed to produce this I

9
6
8.7 10 mol I 1mol KI 166.0g KI
mass KI =1.00L soln =1.4 10 g KI
1L soln 1mol I 1mol KI

58. (M) First we determine Ag
+
that can exist with this Cl

. We know that Cl

will be
unchanged because precipitation will not be allowed to occur.
10
+ 10 + + 9
sp
1.8 10
= Ag Cl =1.8 10 = Ag 0.100M; Ag = =1.8 10 M
0.100
K

( ( ( (


We now consider the complex ion equilibrium. If the complex ions final concentration is x ,
then the decrease in NH
3
is 2x , because 2 mol NH
3
react to form each mole of complex
ion, as follows. ( ) ( ) ( ) ( )
+
+
3 3
2
Ag aq +2NH aq Ag NH aq (

We can solve the K

f

expression for x.
K
x
x
f
Ag NH
Ag NH
=1.6 10 = =
1.8 10 1.00 2
7
3
2
+
+
3
2
9
2

L
N
M
O
Q
P

b g
b g

x x x x x x =1.6 10 1.8 10 1.00 2 =0.0291.00 4.00 +4.00 =0.029 0.12 +0.12
7 9
2
2 2

c hc hb g c h
2
0=0.029 1.12 +0.12 We use the quadratic formula roots equation to solve for . x x x
2 2
1.12 (1.12) 4 0.029 0.12 4 1.12 1.114
= = = =9.3, 0.025
2 2 0.12 0.24
b b ac
x
a

Chapter 18: Solubility and Complex-Ion Equilibria
924

Thus, we can add 0.025 mol AgNO
3
(~4.4 g AgNO
3
) to this solution before we see a
precipitate of AgCl(s) form.

Precipitation and Solubilities of Metal Sulfides


59. (M) We know that K
spa
=3 10
7
for MnS and K
spa
=6 10
2
for FeS. The metal sulfide will
begin to precipitate when Q K
spa spa
= . Let us determine the H O
3
+
just necessary to form each
precipitate. We assume that the solution is saturated with
| |
2 2
H S, H S =0.10 M.


2 2
+ 5 2 2
spa 3
+ 2 7
3 spa
[M ][H S] [M ][H S] (0.10M)(0.10M)
[H O ] 1.8 10 M for MnS
[H O ] 3 10
K
K
+ +

= = = =

+ 3
3 2
(0.10M)(0.10M)
H O = 4.1 10 M for FeS
6 10

(

=

Thus, if the [H
3
O
+
] is maintained just a bit higher than
5
1.8 10 M

, FeS will precipitate and

Mn aq
2+
b g will remain in solution. To determine if the separation is complete, we see whether
Fe
2+
has decreased to 0.1% or less of its original value when the solution is held at the
aforementioned acidity. Let
+ 5
3
H O =2.0 10 M

(

and calculate Fe
2+
.

| | ( )
( )
( )( )
2
2+ 2+ 2 5
2
2 2
5 +
3
2 2+ 6
spa
Fe H S Fe 0.10 M 6 10 2.0 10
0.10
2.0 10 M H O
= =6 10 = ; Fe = =2.4 10 M K

( (

(

(


( )
6
2+
2.4 10 M
%Fe aq remaining= 100%=0.0024% Separation is complete.
0.10M

60. (M) Since the cation concentrations are identical, the value of Q
spa
is the same for each one. It
is this value of Q
spa
that we compare with K
spa
to determine if precipitation occurs.

| |
( )
2+
2
1
spa 2 2
+
3
M H S
0.05M 0.10M
= = =5 10
0.010M
H O
Q
(



(



If Q K
spa spa
> , precipitation of the metal sulfide should occur. But, if Q K
spa spa
< , precipitation
will not occur.
For CuS, K Q
spa spa
=6 10 =5 10
16 1

< Precipitation of CuS(s) should occur.

For HgS, K Q
spa spa
=2 10 =5 10
32 1

< Precipitation of HgS(s) should occur.

For MnS, K Q
spa spa
=3 10 =5 10
7 1
> Precipitation of MnS(s) will not occur.

Chapter 18: Solubility and Complex-Ion Equilibria
925
61. (M)
(a) We can calculate H O
3
+
in the buffer with the HendersonHasselbalch equation.

2 3 2
+ 4.52 5
a 3
2 3 2
C H O
0.15M
pH =p +log =4.74+log =4.52 H O =10 =3.0 10 M
HC H O 0.25M
K

(
(


(

(


We use this information to calculate a value of Q
spa
for MnS in this solution and then
comparison of Q
spa
with K
spa
will allow us to decide if a precipitate will form.

| |
( )( )
( )
2+
2
7 7
spa spa 2 2
+ 5
3
Mn H S
0.15 0.10
= = =1.7 10 3 10 = for MnS
H O 3.0 10
Q K

(

<
(


Thus, precipitation of MnS(s) will not occur.
(b) We need to change H O
3
+
so that
( )( ) ( )
7 + + 5
spa 3 3 2 7
+
3
0.15 0.10 (0.15) 0.10
=3 10 = ; H O = [H O ] =2.2 10 M pH =4.66
3 10
H O
Q

(

(


This is a more basic solution, which we can produce by increasing the basic component
of the buffer solution, namely, the acetate ion. We can find out the necessary acetate ion
concentration with the HendersonHasselbalch equation.
2 3 2 2 3 2
a
2 3 2
2 3 2
[C H O ] [C H O ]
pH p log 4.66 4.74 log
[HC H O ] 0.25M
[C H O ]
log 4.66 4.74 0.08
0.25M
K

= + = = +
= =

2 3 2
0.08
2 3 2
C H O
=10 =0.83 C H O =0.83 0.25M =0.21M
0.25M

(

(



62. (M)
(a) CuS is in the hydrogen sulfide group of qualitative analysis. Its precipitation occurs
when 0.3 M HCl is saturated with
2
H S. It will certainly precipitate from a (non-acidic)
saturated solution of H
2
S which has a much higher S
2
.
( ) ( ) ( ) ( )
2+ +
2
Cu aq +H S satd aq CuS s +2H aq
This reaction proceeds to an essentially quantitative extent in the forward direction.
(b) MgS is soluble, according to the solubility rules listed in Chapter 5.
( ) ( )
0.3M HCl 2+
2
Mg aq +H S satd aq no reaction

(c) As in part (a), PbS is in the qualitative analysis hydrogen sulfide group, which
precipitates from a 0.3 M HCl solution saturated with
2
H S. Therefore, PbS does not
dissolve appreciably in 0.3 M HCl. ( ) ( ) PbS s +HCl 0.3M no reaction
Chapter 18: Solubility and Complex-Ion Equilibria
926
(d) Since ZnS(s) does not precipitate in the hydrogen sulfide group, we conclude that it is
soluble in acidic solution.
( ) ( ) ( ) ( ) ( )
3 3 2
2
ZnS s +2HNO aq Zn NO aq +H S g

Qualitative Cation Analysis

63. (E) The purpose of adding hot water is to separate Pb
2+
from AgCl and
2 2
Hg Cl . Thus, the
most important consequence would be the absence of a valid test for the presence or absence
of
2+
Pb . In addition, if we add NH
3
first, PbCl
2
may form ( )
2
Pb OH . If Pb OH b g
2
does
form, it will be present with Hg Cl
2 2
in the solid, although Pb OH b g
2
will not darken with
added
3
NH . Thus, we might falsely conclude that Ag
+
is present.

64. (M) For ( )
2+
2
PbCl aq , 2 Pb = Cl

( (

where s =molar solubility of PbCl
2
.
Thus
2+
= Pb s (

.
3
2+ 2 2 3 5 5 2 2+
sp
[Pb ][Cl ] ( )(2 ) 4 1.6 10 ; 1.6 10 4 1.6 10 M =[Pb ] K s s s s

= = = = = =
Both Pb
2+
and CrO
4
2
are diluted by mixing the two solutions.
2 2+
4
1.00mL 0.05mL
Pb =0.016M =0.015M CrO =1.0M =0.048M
1.05mL 1.05mL

( (


( )( )
2 2+ 4 13
sp 4 sp
= Pb CrO = 0.015M 0.048M =7.2 10 2.8 10 = Q K

( ( >


Thus, precipitation should occur from the solution described.

65. (E)
(a) Ag
+
and/or Hg
2
2+
are probably present. Both of these cations form chloride precipitates
from acidic solutions of chloride ion.
(b) We cannot tell whether Mg
2+
is present or not. Both MgS and MgCl
2
are water soluble.

(c) Pb
2+
possibly is absent; it is the only cation of those given which forms a precipitate in
an acidic solution that is treated with
2
H S, and no sulfide precipitate was formed.

(d) We cannot tell whether Fe
2+
is present. FeS will not precipitate from an acidic solution that
is treated with
2
H S; the solution must be alkaline for a FeS precipitate to form.

(a) and (c) are the valid conclusions.

66. (E)
(a) ( ) ( ) ( )
2+
2
Pb aq +2Cl aq PbCl s

(b) ( ) ( ) ( ) ( ) ( )
2
2 4
Zn OH s +2OH aq Zn OH aq

(


(c) ( ) ( ) ( ) ( ) ( ) ( )
3+
+ 3+
3 2 2
3 6
Fe OH s +3H O aq Fe aq +6H O(l) or Fe H O aq (


Chapter 18: Solubility and Complex-Ion Equilibria
927
(d) ( ) ( ) ( ) ( )
2+ +
2
Cu aq +H S aq CuS s +2H aq


INTEGRATIVE AND ADVANCED EXERCISES

67. (M) We determine s, the solubility of CaSO
4
in a saturated solution, and then the concentration of
CaSO
4
in ppm in this saturated solution, assuming that the solutions density is 1.00 g/mL.
2 2 2 6 3
sp 4
6 2 4 4
4
4
[Ca ][SO ] ( )( ) 9.1 10 3.0 10 M
0.0030 mol CaSO 136.1 g CaSO 1 mL 1 L soln
ppm CaSO 10 g soln 4.1 10 ppm
1.00 g 1000 mL 1 L soln 1 mol CaSO
K s s s s
+
= = = = =
= =
Now we determine the volume of solution remaining after we evaporate the 131 ppm CaSO
4

down to a saturated solution (assuming that both solutions have a density of 1.00 g/mL.)
mL 10 2 . 3
g 1.00
mL 1
CaSO g 10 1 . 4
soln d sat' g 10
CaSO g 131 soln d sat' volume
5
4
2
6
4
=

=
Thus, we must evaporate 6.8 10
5
mL of the original 1.000 10
6
mL of solution, or 68% of the
water sample.

68. (M)
(a) First we compute the molar solubility, s, of CaHPO
4
2H
2
O.

3 4 2 4 2
4 2
2 2 2 3 2 6
sp 4
0.32 g CaHPO 2H O 1 mol CaHPO 2H O
1.9 10 M
1 L soln 172.1 g CaHPO 2H O
[Ca ][HPO ] ( )( ) (1.9 10 ) 3.6 10
Thus the values are not quite consistent.

+

= =

= = = = =
s
K s s s

(b) The value of K
sp
given in the problem is consistent with a smaller value of the molar
solubility. The reason is that not all of the solute ends up in solution as HPO
4
2
ions.
HPO
4
2
can act as either an acid or a base in water (see below), but it is base hydrolysis that
predominates.
.
2 3 13
4 2 3 4 3
HPO (aq) H O(l) H O (aq) PO (aq) 4.2 10
+
+ + =

a
K
2 7 w
4 2 2 4 b
2
HPO (aq) H O(l) OH (aq) H PO (aq) 1.6 10
K
K
K

+ + = =

69. (M) The solutions mutually dilute each other and, because the volumes are equal, the
concentrations are halved in the final solution: [Ca
2+
] =0.00625 M, [SO
4
2
] =0.00760 M. We
cannot assume that either concentration remains constant during the precipitation. Instead, we
assume that precipitation proceeds until all of one reagent is used up. Equilibrium is reached
from that point.
Chapter 18: Solubility and Complex-Ion Equilibria
928
2 2 6
4 4 sp
2 2
sp 4
Equation: CaSO (s) Ca (aq) SO (aq) 9.1 10
In soln 0.00625 M 0.00760 M [Ca ][SO ]
Form ppt
+
+
+ =
=

K
K
sp
sp
0.00625 M 0.00625 M ( )(0.00135 )
Not at equil 0 M 0.00135 M 0.00135
Changes
= +
~

K x x
K x
6
3
9.1 10
M M 6.7 10 M
0.00135
Equil: M (0.00135 ) M {not a reasonable assumption!}

+ + = =
+
x x x
x x

Solving the quadratic 0 =x
2
+(1.3510
-2
)x 9.110
-6
yields x =2.410
-3
.

-3
2+ final
initial
2.410 M
% unprecipitated Ca = 100% = 38% unprecipitated
0.00625 M

70. (M) If equal volumes are mixed, each concentration is reduced to one-half of its initial value.
We assume that all of the limiting ion forms a precipitate, and then equilibrium is achieved by
the reaction proceeding in the forward direction to a small extent.

2 2
3 3
Equation: BaCO (s) Ba (aq) CO (aq)
Orig. soln: 0.00050 M 0.0010 M
Form ppt: 0 M
+
+

0.0005 M
Changes: M M
Equil: M (0.0005 )M
x x
x x
+ +
+


2 2 9
sp 3
9
5 2+ -4 -5
[Ba ][CO ] 5.1 10 ( )(0.0005 ) 0.0005
5.1 10
1 10 M The [Ba ] decreases from 5 10 M to 1 10 M.
0.0005
+

= = = + ~

= =
K x x x
x

(x < 0.0005 M, thus the approximation was valid.)
% 2 % 100
M 10 5
M 10 1
ated unprecipit %
4
5
=

Thus, 98% of the Ba

2+
is precipitated as BaCO
3
(s).

71. (M) The pH of the buffer establishes [H
3
O
+
] =10
pH
=10
3.00
=1.0 10
3
M.
Now we combine the two equilibrium expressions, and solve the resulting expression for the
molar solubility of Pb(N
3
)
2
in the buffer solution.
Chapter 18: Solubility and Complex-Ion Equilibria
929
2 9
3 2 3 sp
2 9
a
2
3 2 3 3
3 3 3 2 5 2
Pb(N ) (s) Pb (aq) 2 N (aq) 2.5 10
1/ 2.8 10
Pb(N ) (s) 2 H O (aq) Pb (aq) 2 HN (aq
1
2 H O (aq) 2 N (aq) 2 HN (aq) 2 H O(l)
(1.9 10 )
+
+ +
+

+ =
= =
+ +
+ +

K
K
2
2 sp a
2
3 2 3 3 2
) 2 H O (l) 7.0

Pb(N ) (s) 2 H O (aq) Pb (aq) 2 HN (aq) 2 H O (l)
Buffer: 0.0010 M 0 M 0 M
Dissolving: (buffer) M 2 M
(1/ )
+ +
+ = =
+ + +

+ +

K K K
x x
2 2 2 2
3
3 2 3
2 2
3
Equilibrium: 0.0010 M M 2 M
[Pb ][HN ] ( ) (2 ) 7.0(0.0010)
7.0 4 7.0 (0.0010) 0.012 M
[H O ] (0.0010) 4
+
+

= = = = = =
x x
x x
K x x

Thus, the molar solubility of Pb(N
3
)
2
in a pH =3.00 buffer is 0.012 M.

72. (M) We first determine the equilibrium constant of the suggested reaction.
2
2 4 3 2
Mg(OH) (s) 2 NH (aq) Mg (aq) 2 NH (aq) 2 H O(l)
Initial: 1.00 M 0 M 0 M
Changes: 2 M M 2 M
Equil: (1.00 2 ) M M 2
x x x
x x
+ +
+ + +

+ +

2 2 11 2 3
sp
3
2 5 2 2 2 2
b 4
3
M
[Mg ][NH ] 1.8 10 (2 ) 4
0.056
(1.8 10 ) [NH ] (1.00 2 ) 1.00
0.056
0.24 M
4
x
K
x x x
K
K x
x
+
+

= = = = = ~

= =

Take this as a first approximation and cycle through again. 2x =0.48

M 16 . 0
4
) 48 . 0 (1.00 056 . 0
056 . 0
) 48 . 0 00 . 1 (
4
3
2
2
3
=

= =

~ x
x
K

Yet another cycle gives a somewhat more consistent value. 2x =0.32

M 19 . 0
4
) 38 . 0 (1.00 056 . 0
056 . 0
) 32 . 0 00 . 1 (
4
3
2
2
3
=

= =

~ x
x
K

Another cycle gives more consistency. 2x =0.38
2 11
2 sp
2 5 2
4 3 2 b
Mg(OH) (s) Mg (aq) 2 OH (aq) 1.8 10
2 NH (aq) 2 OH (aq) 2 NH (aq) 2 H O(l) 1/ 1/(1.8 10 )
K
K
+
+
+ =
+ + =

Chapter 18: Solubility and Complex-Ion Equilibria

930

] [Mg M 18 . 0
4
) 38 . 0 (1.00 056 . 0
056 . 0
) 38 . 0 00 . 1 (
4
2
3
2
2
3
+
= =

= =

~ x
x
K

The molar solubility of Mg(OH)
2
in a 1.00 M NH
4
Cl solution is 0.18 M.

73. (D) First we determine the value of the equilibrium constant for the cited reaction.
( )
2 2 9
3 3 sp
2 11
3 3 2 3 2
2
3 3 3 2 sp 2
CaCO (s) Ca (aq) CO (aq) 2.8 10
H O (aq) CO (aq) H O(l) HCO (aq) 1/ 1/ 4.7 10
CaCO (aq) H O (aq) Ca (aq) HCO (aq) H O(l) 1/
2.8 10
a
overall a
overall
K
K
K K K
K
+
+
+ +
+ =
+ + =
+ + + =

9
11
60
4.7 10

2
3 3 3 2
pH
Equation: CaCO (s) H O (aq) Ca (aq) HCO (aq) H O(l)
Initial: 10 0 M 0 M
Change: ( ) M M
Equil:
+ +

+ + +

+ +

buffer x x
pH
10 M M

x x

In the above set-up, we have assumed that the pH of the solution did not change because of the
dissolving of the CaCO
3
(s). That is, we have treated the rainwater as if it were a buffer solution.

(a) ] [Ca M 10 1 10 3 60
10 3
. 60
] O H [
] HCO ][ Ca [
2 2 6
6
2
3
3
2
+
+
+
= = =

= = = x
x
K

2 2
5 2 2 3
5
3
[Ca ][HCO ]
60. 60 6.3 10 6.1 10 M [Ca ]
[H O ] 6.3 10
x
K x
+

+
+
= = = = = =

(b)

74. We use the Henderson-Hasselbalch equation to determine [H
3
O
+
] in this solution, and then use the
K
sp
expression for MnS to determine [Mn
2+
] that can exist in this solution without precipitation
occurring.
Chapter 18: Solubility and Complex-Ion Equilibria
931

2 3 2
a
2 3 2
5.44 6
3
2 7
3 2 2 spa
2
2
[C H O ] 0.500 M
pH p log 4.74 log 4.74 0.70 5.44
[HC H O ] 0.100 M
[H O ] 10 3.6 10 M
MnS(s) 2 H O (aq) Mn (aq) H S(aq) 2 H O(l) 3 10
Note that [H S] [Mn ] , the molar solubility of
K
K
s

+
+ +
+
= + = + = + =
= =
+ + + =
= =

2 2
7 2
spa
2 6 2
3
2
2
MnS.
[Mn ][H S]
3 10 0.02 M
[H O ] (3.6 10 M)
0.02 mol Mn 1 mol MnS 87 g MnS
mass MnS/L 2 g MnS/L
1 L soln 1 mol MnS 1 mol Mn
s
K s
+
+
+
+
= = = =

= =


75. (M)
(a) The precipitate is likely Ca
3
(PO
4
)
2
. Let us determine the %Ca of this compound (by mass)

aq) ( H 2 s) ( ) PO ( Ca aq) ( HPO 2 aq) ( Ca 3
Ca % 763 . 38 % 100
) PO ( Ca g 18 . 310
Ca g 40.078 3
Ca %
2 4 3
2
4
2
2 4 3
+ +
+ +
=

=

(b) aq) ( CO H O(l) H g) ( CO : g) ( CO are bubbles The
3 2 2 2 2
+

2
2 3 3
2+ -
3 2 3 3
Ca (aq) H CO (aq) CaCO (s) 2 H (aq) precipitation
CaCO (s) +H CO (aq) Ca (aq) +2 HCO (aq) redissolving
+ +
+ +

76. (D)
(a) A solution of CO
2
(aq) has [CO
3
2-
] =K
a
[H
2
CO
3
] =5.6 10
-11
. Since K
sp
=2.8 10
-9
for
CaCO
3
, the [Ca
2+
] needed to form a precipitate from this solution can be computed.

-9
sp 2+
2- -11
3
2.810
[Ca ] = = =50.M
[CO ] 5.610
K

This is too high to reach by dissolving CaCl
2
in solution. The reason why the technique works
is because the OH
-
(aq) produced by Ca(OH)
2
neutralizes some of the HCO
3
-
(aq) from the
ionization of CO
2
(aq), thereby increasing the [CO
3
2-
] above a value of 5.6 10
-11
.

(b) The equation for redissolving can be obtained by combining several equations.
Chapter 18: Solubility and Complex-Ion Equilibria
932
2+ 2- -9
3 3 sp
2- + -
3 3 3 2 -11
a2
- + -7
2 2 3 3 a1
2+ -
3 2 2 3
CaCO (s) Ca (aq) +CO (aq) =2.810
1 1
CO (aq) +H O (aq) HCO (aq) +H O(l) =
5.610
CO (aq)+2H O(l) HCO (aq) +H O (aq) =4.210
CaCO (s) +CO (aq)+H O(l) Ca (aq) +2HCO (aq)

K
K
K
K
sp a1
a2

=
K K
K


2+ - 2 -9 -7
-5 3
-11
2
[Ca ][HCO ] (2.810 )(4.210 )
= =2.110 =
5.610 [CO ]
K
If CaCO
3
is precipitated from 0.005 M Ca
2+
(aq) and then redissolved, [Ca
2+
] =0.005 M and
[HCO
3
2-
] =20.005 M = 0.010 M. We use these values in the above expression to compute
[CO
2
].

2+ - 2 2
3
2
-5 -5
[Ca ][HCO ] (0.005)(0.010)
[CO ]= = =0.02 M
2.110 2.110

We repeat the calculation for saturated Ca(OH)
2
, in which [OH
-
] =2 [Ca
2+
], after first
determining [Ca
2+
] in this solution.
K
sp
=[Ca
2+
][OH
-
]
2
=4 [Ca
2+
] =5.510
-6
[Ca
2+
]
6
3
5.5 10
4

=0.011
M
2+ - 2 2
3
2
-5 -5
[Ca ][HCO ] (0.011)(0.022)
[CO ]= = =0.25 M
2.110 2.110

Thus, to redissolve the CaCO
3
requires that [CO
2
] =0.25 M if the solution initially is saturated
Ca(OH)
2
, but only 0.02 M CO
2
if the solution initially is 0.005 M Ca(OH)
2
(aq).
A handbook lists the solubility of CO
2
as 0.034 M. Clearly the CaCO
3
produced cannot
redissolve if the solution was initially saturated with Ca(OH)
2
(aq).

77. (M)
(a)

2 2 -10
4
4 sp
2 2-
3
3 -9
2- 2
3 4
4 3
sp
BaSO (s) Ba (aq) SO (aq) 1.1 10
1
Ba (aq) CO (aq) BaCO (s) =
5.1 10
1.1
Sum BaSO (s) +CO (aq) BaCO (s) + SO (aq)
1


+
+

+ =
+

overall
K
K
K
-10
-9
10
0.0216
5.1 10
Initial 3 M 0
Equil. (3- )M
(where is the carbonate use

~
x x
x d up in the reaction)

2-
4
2-
3
[SO ]
0.0216 and 0.063 Since 0.063 M 0.050 M, the response is yes.
[CO ] 3
= = = = >

x
K x
x

Chapter 18: Solubility and Complex-Ion Equilibria
933

-10 2
sp
2-
3 2 3 sp -12
2-
3 2 3 overall
+ -
2AgCl(s) 2Ag (aq) +2 Cl (aq) =(1.8 10 )
1
+
2 Ag (aq) +CO (aq) Ag CO (s) 1/ =
8.5 10
-
Sum 2AgCl(s) +CO (aq) Ag CO (s) + 2 Cl (aq)

(b)

K
K
K
-10 2
-9
-12
(1.8 10 )
= =3.8 10
8.5 10
Initial 3 M 0 M
Equil. (3- )M 2
(where is the carbona

~
x x
x te used up in the reaction)

2 2
-9 -5
overall 2-
3
-5
-
[Cl ] (2 )
= = =3.8 10 and =5.3 10 M
[CO ] 3-
Since 2 , (2(5.35 10 M)) , <<0.050 M, theresponse is no.

x
K x
x
x


2+ -
2 sp
2+ 2-
3 3 sp -8
-8
MgF (s) Mg (aq) 2 F (aq) 3.7 10
1
Mg (aq) CO (aq) MgCO (s) 1/
3.5 10
sum
+ =
+ =

(c)

K
K
-8
2- -
2 3 3 overall -8
3.7 10
MgF (s) CO (aq) MgCO (s) 2 F (aq) 1.1
3.5 10
initial 3 M 0 M
equil. (

+ + = =

K
2 2
overall 2-
3
3- )M 2
(where is the carbonate used up in the reaction)
[F ] (2 )
1.1 and 0.769M
[CO ] 3
Since 2 , (2(0.769M)) 0.

= = = =

>
x x
x
x
K x
x
x 050 M, the response is yes.


78. (D) For ease of calculation, let us assume that 100 mL, that is, 0.100 L of solution, is to be
titrated. We also assume that [Ag
+
] =0.10 M in the titrant. In order to precipitate 99.9% of the
Br

as AgBr, the following volume of titrant must be added.

0.010 mmol Br 1 mmol Ag 1 mL titrant
volume titrant 0.999 100 mL 9.99 mL
1 mL sample 1 mmol Br 0.10 mmol Ag
+
+
= =
We compute [Ag
+
] when precipitation is complete.

M 10 0 . 5
M 01 . 0 001 . 0
10 0 . 5
] [Br
] Ag [
8
13
sp

+
=

= =
f
K

Thus, during the course of the precipitation of AgBr, while 9.99 mL of titrant is added, [Ag
+
]
increases from zero to 5.0 10
8
M. [Ag
+
] increases from 5.0 10
8
M to 1.0 10
5
M from
the point where AgBr is completely precipitated to the point where Ag
2
CrO
4
begins to
precipitate. Let us assume, for the purpose of making an initial estimate, that this increase in
[Ag
+
] occurs while the total volume of the solution is 110 mL (the original 100 mL plus 10 mL
Chapter 18: Solubility and Complex-Ion Equilibria
934
of titrant needed to precipitate all the AgBr.) The amount of Ag
+
added during this increase is
the difference between the amount present just after AgBr is completely precipitated and the
amount present when Ag
2
CrO
4
begins to precipitate.

titrant mL 10 1 . 1
Ag mmol 10 . 0
titrant mL 1
Ag mmol 10 1.1 titrant added volume
Ag mmol 10 1 . 1
soln mL 1
Ag mmol 10 5.0
mL 110
soln mL 1
Ag mmol 10 1.0
mL 110 added Ag amount
2 3
3
8 5

+
+
+
+ +
+
= =
=

=

We see that the total volume of solution remains essentially constant. Note that [Ag
+
] has
increased by more than two powers of ten while the volume of solution increased a very small
degree; this is indeed a very rapid rise in [Ag
+
], as stated.

79. (D) The chemistry of aluminum is complex, however, we can make the following assumptions.
Consider the following reactions at various pH:
pH >7 Al(OH)
3
(s) +OH
-

overall
=1.43
sp f
K K K =

Al(OH)
4
-
(aq)
pH <7 Al(OH)
3
(s)
33
sp
=1.3 10 K

Al
3+
(aq) +3 OH
-


For the solubilities in basic solutions, consider the following equilibrium at pH =13.00 and 11.00.
At pH =13.00: Al(OH)
3
(s) + OH
-

=1.43
ov f sp
K K K =

Al(OH)
4
-
(aq)
Initial : 0.10 0
Change: x +x
Equilibrium: 0.10 x x
K
f
=1.43 = (buffered at pH =13.00)
0.10 0.10
x x
x
~

x =0.143 M
At pH =11.00: K
f
=1.43 = (buffered at pH =11)
0.0010 0.0010
x x
x
~

x =0.00143 M
Thus, in these two calculations we see that the formation of the aluminate ion [Al(OH)
4

] is
favored at high pH values. Note that the concentration of aluminum(III) increases by a factor of
one-hundred when the pH is increased from 11.00 to 13.00, and it will increase further still
above pH 13. Now consider the solubility equilibrium established at pH =3.00, 4.00, and 5.00.
These correspond to [OH

] =1.0 10
11
M, 1.0 10
10
M, and 1.0 10
9
M, respectively.
Al(OH)
3
(s)
33
sp
=1.3 10 K

Al
3+
(aq) +3 OH

(aq)

At these pH values, [Al
3+
] in saturated aqueous solutions of Al(OH)
3
are

[Al
3+
] =1.3 10
33
/(1.0 10
11
)
3
=1.3 M at pH =3.00

Chapter 18: Solubility and Complex-Ion Equilibria
935
[Al
3+
] =1.3 10
33
/(1.0 10
10
)
3
=1.3 10
3
M at pH =4.00

[Al
3+
] =1.3 10
33
/(1.0 10
9
)
3
=1.3 10
6
M at pH =5.00

These three calculations show that in strongly acidic solutions the concentration of
aluminum(III) can be very high and is certainly not limited by the precipitation of Al(OH)
3
(s).
However, this solubility decreases rapidly as the pH increases beyond pH 4.
At neutral pH 7, a number of equilibria would need to be considered simultaneously, including
the self-ionization of water itself. However, the results of just these five calculations do
indicate that concentration of aluminum(III) increases at both low and high pH values, with a
very low concentration at intermediate pH values around pH 7, thus aluminum(III)
concentration as a function of pH is a U-shaped (or V-shaped) curve.

80. (M) We combine the solubility product expression for AgCN(s) with the formation expression
for [Ag(NH
3
)
2
]
+
(aq).

sp
7
3 3 2 f
3 3 2 overall sp f
3 2
overall
Solubility: AgCN(s) Ag (aq) CN (aq) ?
Formation: Ag (aq) 2NH (aq) [Ag(NH ) ] (aq) 1.6 10
Net reaction: AgCN(s) 2 NH (aq) [Ag(NH ) ] CN (aq)
[[Ag(NH ) ] ][CN
+
+ + +
+
+
+ =
+ =
+ + =
=

K
K
K K K
K
6 2
9 7
sp 2 2
3
9
16
sp 7
] (8.8 10 )
1.9 10 1.6 10
[NH ] (0.200)
1.9 10
1.2 10
1.6 10

+

= = =

= =

K
K

Because of the extremely low solubility of AgCN in the solution, we assumed that [NH
3
] was
not altered by the formation of the complex ion.


81. We combine the solubility product constant expression for CdCO
3
(s) with the formation
expression for [CdI
4
]
2
(aq).
2 2 12
3 3 sp
2 2
4 f
2 2
3 4 3
Solubility: CdCO (s) Cd (aq) CO (aq) 5.2 10
Formation: Cd (aq) 4 I (aq) [CdI ] (aq) ?
Net reaction: CdCO (s) 4 I (aq) [CdI ] (aq) CO
K
K
+
+

+ =
+ =
+ +

overall sp f
(aq) K K K =

2 2 3 2
6 12 4 3
overall f 4 4
6
5
f 12
[[CdI ] ][CO ] (1.2 10 )
1.4 10 5.2 10
[I ] (1.00)
1.4 10
2.7 10
5.2 10

= = = =

= =

K K
K

Chapter 18: Solubility and Complex-Ion Equilibria
936
Because of the low solubility of CdCO3 in this solution, we assumed that [I] was not
appreciably lowered by the formation of the complex ion.

82. (M) We first determine [Pb
2+
] in this solution, which has [Cl
-
] =0.10 M.
M 10 6 . 1
) 10 . 0 (
10 6 . 1
] [Cl
] Pb [ ] Cl ][ Pb [ 10 6 . 1
3
2
5
2
sp 2 2 2 5
sp

+ +
=

= = = =
K
K
Then we use this value of [Pb
2+
] in the K
f
expression to determine [[PbCl
3
]

].

M 10 8 . 3 10 6 . 1 24 ] ] PbCl [[
10 6 . 1
] ] PbCl [[
) 10 . 0 )( 10 6 . 1 (
] ] PbCl [[
24
] Cl ][ Pb [
] ] PbCl [[
5 6
3
6
3
3 3
3
3 2
3
f

= =

=

= = = K

The solubility of PbCl
2
in 0.10 M HCl is the following sum.
solubility =[Pb
2+
] +[[PbCl
3
]

] =1.6 10
3
M +3.8 10
5
M =1.6 10
3
M
83. (M) Two of the three relationships needed to answer this question are the two solubility product
expressions. 1.6 10
8
=[Pb
2+
][SO
4
2
] 4.0 10
7
=[Pb
2+
][S
2
O
3
2
]
The third expression required is the electroneutrality equation, which states that the total
positive charge concentration must equal the total negative charge concentration:
[Pb
2+
] =[SO
4
2
] +[S
2
O
3
2
], provided [H
3
O
+
] =[OH
-
].
Or, put another way, there is one Pb
2+
ion in solution for each SO
4
2
ion and for each S
2
O
3
2
ion.
We solve each of the first two expressions for the concentration of each anion, substitute these
expressions into the electroneutrality expression, and then solve for [Pb
2+
].

8 7 8 7
2 2 2
4 2 3 2 2 2 2
2 2 8 7 7 2 7 4
1.6 10 4.0 10 1.6 10 4.0 10
[SO ] [S O ] [Pb ]
[Pb ] [Pb ] [Pb ] [Pb ]
[Pb ] 1.6 10 4.0 10 4.2 10 [Pb ] 4.2 10 6.5 10 M

+
+ + + +
+ +

= = = +
= + = = =


84. (D) The chemical equations are:

2 2
2 2
PbCl (s) Pb (aq) 2 Cl (aq) and PbBr (s) Pb (aq) 2 Br (aq)
+ +
+ +




The two solubility constant expressions, [Pb
2+
][Cl

]
2
=1.6 10
5
, [Pb
2+
][Br

]
2
=4.0 10
5
and
the condition of electroneutrality, 2 [Pb
2+
] =[Cl

] +[Br

], must be solved simultaneously to

determine [Pb
2+
]. (Rearranging the electroneutrality relationship, one obtains:
] Br [ ] Cl [ ] Pb [
2
1
2
1
2 +
+ = .) First we solve each of the solubility constant expressions for the
concentration of the anion. Then we substitute these values into the electroneutrality expression
and solve the resulting equation for [Pb
2+
].

M 10 0 . 3 ] Pb [ 10 7 . 2 ] Pb [ 10 2 . 5 ] Pb [
10 03 . 1 10 3 . 6 10 0 . 4 10 0 . 4 10 6 . 1 ] Pb [ 2
] Pb [
10 0 . 4
] Pb [
10 6 . 1
] Pb [ 2
] Pb [
10 0 . 4
] Br [
] Pb [
10 6 . 1
] Cl [
2 2 5 3 2 3 3 2
2 3 3 5 5 3 2
2
5
2
5
2
2
5
2
5
+ + +
+
+

+
+

= = =
= + = + =

=

Chapter 18: Solubility and Complex-Ion Equilibria
937

85. (D) (a) First let us determine if there is sufficient Ag
2
SO
4
to produce a saturated solution, in
which [Ag
+
] =2 [SO
4
2
].
M 0535 . 0
SO Ag mol 1
SO mol 1
SO Ag g 8 . 311
SO Ag mol 1
L 150 . 0
SO Ag g 50 . 2
] [SO
M 015 . 0
4
10 4 . 1
] SO [ ] SO [ 4 ] SO [ ] Ag [ 10 4 . 1
4 2
2
4
4 2
4 2 4 2
2
4
3
5
2
4
3 2
4
2
4
2 5
sp
= =
=

= = = =

+
K


Thus, there is more than enough Ag
2
SO
4
present to form a saturated solution. Let us now see if
AgCl or BaSO
4
will precipitate under these circumstances. [SO
4
2
] =0.015 M and [Ag
+
] =0.030
M.
Q =[Ag
+
][Cl

] =0.030 0.050 =1.5 10

3
>1.8 10
10
=K
sp
, thus AgCl should precipitate.
Q =[Ba
2+
][SO
4
2
] =0.025 0.015 =3.8 10
4
>1.1 10
10
=K
sp
, thus BaSO
4
should precipitate.
Thus, the net ionic equation for the reaction that will occur is as follows.
AgCl(s) 2 s) ( BaSO aq) ( Cl 2 aq) ( Ba s) ( SO Ag
4
2
4 2
+ + +
+

(b) Let us first determine if any Ag
2
SO
4
(s) remains or if it is all converted to BaSO
4
(s) and
AgCl(s). Thus, we have to solve a limiting reagent problem.

2
3 2
2
4 2
3
4 2
4 2
4 2 4 2
aCl mol 10 75 . 3
soln L 1
BaCl mol 0.025
L 150 . 0 BaCl amount
SO Ag mol 10 02 . 8
SO Ag g 8 . 311
SO Ag mol 1
SO Ag g 50 . 2 SO Ag amount
B = =
= =

Since the two reactants combine in a 1 mole to 1 mole stoichiometric ratio, BaCl
2
is the limiting
reagent. Since there must be some Ag
2
SO
4
present and because Ag
2
SO
4
is so much more soluble
than either BaSO
4
or AgCl, we assume that [Ag
+
] and [SO
4
2
] are determined by the solubility of
Ag
2
SO
4
. They will have the same values as in a saturated solution of Ag
2
SO
4
.
[SO
4
2
] =0.015 M [Ag
+
] =0.030 M
We use these values and the appropriate K
sp
values to determine [Ba
2+
] and [Cl

].
M 10 0 . 6
030 . 0
10 8 . 1
] [Cl M 10 3 . 7
015 . 0
10 1 . 1
] Ba [
9
10
9
10
2

+
=

= =

=

Since BaCl
2
is the limiting reagent, we can use its amount to determine the masses of
BaSO
4
and AgCl.
AgCl g 07 . 1
AgCl mol 1
AgCl g 3 . 143
BaCl mol 1
AgCl mol 2
BaCl mol 0.00375 AgCl mass
BaSO g 875 . 0
BaSO mol 1
BaSO g 4 . 233
BaCl mol 1
BaSO mol 1
BaCl mol 00375 . 0 BaSO mass
2
2
4
4
4
2
4
2 4
= =
= =


Chapter 18: Solubility and Complex-Ion Equilibria
938
The mass of unreacted Ag
2
SO
4
is determined from the initial amount and the amount that
reacts with BaCl
2
.

2 4 2 4
2 4 2 4 2
2 2 4
2 4 2 4
1 mol Ag SO 311.8 g Ag SO
mass Ag SO 0.00802 mol Ag SO 0.00375 mol BaCl
1 mol BaCl 1 mol Ag SO
mass Ag SO 1.33 g Ag SO unreacted
| |
=
|
\ .
=


Of course, there is some Ag
2
SO
4
dissolved in solution. We compute its mass.
2 4 2 4
2 4
2 4
2 4 2 4
0.0150 mol Ag SO 311.8 g Ag SO
mass dissolved Ag SO 0.150 L 0.702 g dissolved
1 L soln 1 mol Ag SO
mass Ag SO (s) 1.33 g 0.702 g 0.63 g Ag SO (s)
= =
= =



86. (M) To determine how much NaF must be added, determine what the solubility of BaF
2
is
considering that the final concentration of F

must be 0.030 M.
K
sp
=110
-6.

BaF
2
(s)

Ba
2+
(aq) + 2F

(aq)
0 0
+s +2s
s 2s (0.030 M)

( )( ) ( )
2
6. 4
sp
1 10 0.030 9.0 10 ; Therefore, 0.0011M K s s s

= = = = .
Since s is 0.0011 M, the F

contribution from BaF

2
considering the common ion effect exerted
by NaF is 0.0022 M. Therefore, the total number of moles of NaF in a 1 L solution required is
therefore 0.0278 moles.

To determine how much BaF
2
precipitates, we must first determine what the value of s is for a
saturated solution in absence of the common ion effect. That is,
( )( )
2
6. 3
sp
1 10 2 4 ; Therefore, 0.0063M K s s s s

= = = = .

Since in absence of the common ion effect from NaF the solubility of BaF
2
is 0.0063 M, and
with NaF the solubility is 0.0011, the difference between the two (0.0063 0.0011 =
0.0052 M) has to be precipitated. The mass of the precipitate is therefore:

2 2
2
2
0.0052mol BaF 175.3 g BaF
mass of BaF 0.91g
1L solution 1 mol BaF
= =
Chapter 18: Solubility and Complex-Ion Equilibria
939

FEATURE PROBLEMS

87. (M) Ca SO
2+
4
2
=

in the saturated solution. Let us first determine the amount of H O
3
+
in
the 100.0 mL diluted effluent. ( ) ( ) ( )
+ +
3 2
H O aq +NaOH aq 2H O(l)+Na aq
( )
+
+ 3
3
+
3
1mmol H O 8.25mL base 0.0105mmol NaOH
mmol H O =100.0mL
10.00mL sample 1mL base 1mmol NaOH
=0.866 mmol H O aq


Now we determine Ca
2+
in the original 25.00 mL sample, remembering that 2
3
+
H O were
produced for each
2+
Ca .
2
+
3
2+ 3
1mmol Ca
0.866mmol H O (aq)
2mmol H O
Ca = =0.0173M
25.00mL
+
+

(



( )
2
2+ 2 4 6
sp 4 4
= Ca SO = 0.0173 =3.0 10 ; the for CaSO is 9.1 10 in Appendix D.

( (

sp
K K
88. (D)
(a) We assume that there is little of each ion present in solution at equilibrium (that this is a
simple stoichiometric calculation). This is true because the K value for the titration
reaction is very large. K
titration
=1/K
sp(AgCl)
=5.6 10
9
. We stop the titration when just
enough silver ion has been added. ( ) ( ) ( )
+
Ag aq +Cl aq AgCl s

+
3
29.5mg Cl 1mmol Cl 1mmol Ag 1mL
=100.0mL
1000mL 35.45mg Cl 1mmol Cl 0.01000mmol AgNO
=8.32mL
V





(b) We first calculate the concentration of each ion as the consequence of dilution. Then we
determine the [Ag
+
] from the value of K
sp
.
+ 4
8.32mL added
initial Ag =0.01000M =7.68 10 M
108.3mL final volume

(


4
1mmol Cl
29.5 mg Cl
100.0mL taken 35.45mgCl
initial Cl = =7.68 10 M
1000mL 108.3mL final volume

(



The slight excess of each ion will precipitate until the solubility constant is satisfied.
Ag Cl M
sp
+ 10 5
= = 18 10 13 10

= = K . .

(c) If we want Ag CrO
2 4
to appear just when AgCl has completed precipitation,

+ 5
Ag =1.3 10 M

(

. We determine CrO
4
2
from the K
sp
expression.
Chapter 18: Solubility and Complex-Ion Equilibria
940
( )
( )
12
2
5
2 2
+ 2 12 5 2 2
sp 4 4 4
1.1 10
1.3 10
= Ag CrO =1.1 10 =1.3 10 CrO ; CrO = =0.0065M K

( ( ( (

(d) If CrO
4
2
were greater than the answer just computed for part (c), Ag CrO
2 4
would
appear before all Cl

had precipitated, leading to a false early endpoint. We would

calculate a falsely low Cl

for the original solution.

If CrO
4
2
were less than computed in part 3, Ag CrO
2 4
would appear somewhat after
all Cl

had precipitated, leading one to conclude there was more Cl

in solution than
actually was the case.

(e) If it was Ag
+
that was being titrated, it would react immediately with the CrO
4
2
in the
sample, forming a red-orange precipitate. This precipitate would not likely dissolve, and
thus, very little if any AgCl would form. There would be no visual indication of the
endpoint.

89. (D)
(a) We need to calculate the Mg
2+
in a solution that is saturated with Mg(OH)
2
.
( )( )
2
2
11 2+ 3
sp
=1.8 10 = Mg OH = 2 =4 K s s s

( (



11 3
4 2+
1.8 10
= 1.7 10 M =[Mg ]
4
s

=

(b) Even though water has been added to the original solution, it remains saturated (it is in
equilibrium with the undissolved solid ( )
2
Mg OH ).
2+ 4
Mg =1.7 10 M.

(



(c) Although HCl(aq) reacts with OH ,

it will not react with

2+
Mg . The solution is simply
a more dilute solution of Mg
2+
.
( )
2+ 4 5
100.0mL initial volume
Mg =1.7 10 M =2.8 10 M
100.0+500. mL final volume

(



(d) In this instance, we have a dual dilution to a 275.0 mL total volume, followed by a
common-ion scenario.

4 2+ 2+
2+
1.7 10 mmol Mg 0.065 mmol Mg
25.00 mL 250.0 mL
1mL 1mL
initial Mg =
275.0 mL total volume
0.059M

+
=
| | | |
| |
\ . \ .
(



4 2+
2+
5
1.7 10 mmol Mg 2mmol OH
25.00mL
1mL 1mmol Mg
initial OH = 3.1 10 M
275.0mL total volume

( =



Chapter 18: Solubility and Complex-Ion Equilibria
941
Lets see if precipitation occurs.
Q K
sp sp
Mg OH = = 0.059 3.1 10 =5.7 10 1.8 10 =
2+
2
5
2
11 11
> b gc h


Thus, precipitation does occur, but very little precipitate forms. If OH

goes down by
5
1.4 10 M

(which means that Mg

2+
drops by 0.7 10
5

M), then
OH M

=1.7 10
5
and

( )
2+ 5
Mg = 0.059M 0.7 10 M =0.059M

(

, then Q K
sp sp
< and precipitation will
stop. Thus,
2+
Mg =0.059M (

.

(e) Again we have a dual dilution, now to a 200.0 mL final volume, followed by a common-
ion scenario.
4 2+
2+ 5
1.7 10 mmol Mg
50.00mL
1mL
initial Mg = 4.3 10 M
200.0mL total volume

( =




150.0mLinitial volume
initial OH =0.150M 0.113M
200.0mL total volume

( =



Now it is evident that precipitation will occur. Next we determine the Mg
2+
that can
exist in solution with 0.113 M OH .

It is clear that Mg
2+
will drop dramatically to
satisfy the K
sp
expression but the larger value of OH

will scarcely be affected.

( )
( )
2
2
2+ 11 2+
sp
11
2+ 9
2
= Mg OH =1.8 10 = Mg 0.0113M
1.8 10
Mg = =1.4 10 M
0.113
K

( ( (

(


Chapter 18: Solubility and Complex-Ion Equilibria
942

SELF-ASSESSMENT EXERCISES

90. (E)
(a) K
sp
: The solubility product constant, which is the constant for the equilibrium established
between a solid solute and its ions in a saturated solution
(b) K
f
: The formation constant of a complex ion, which is the equilibrium constant describing
the formation of a complex ion from a central ion (typically a metal cation) and the ligands
that attach to it
(c) Q
sp
: The ion product, which is the product of concentrations of the constituent ions of a
compound, and is used to determine if they meet the precipitation criteria or not.
(d) Complex ion: A polyatomic cation or anion composed of a central metal ion to which other
groups (molecules or ions) called ligands are coordinated/attached to.


91. (E)
(a) Common-ion effect in solubility equilibrium: Where the solubility of a sparingly soluble
compound is suppressed by the presence of a quantity (often large) of one of the
compounds ions from another source
(b) Fractional precipitation: A technique in which two or more ions in solution, each capable
of being precipitated by the same reagent, are separated by the proper use of that reagent:
One ion is precipitated, while the other(s) remains in solution.
(c) Ion-pair formation: Pair of ions held loosely together by electrostatic interactions in water
(d) Qualitative cation analysis: A qualitative method that is used to identify various the cations
present in a solution by stepwise addition of various anions in order to selectively
precipitate out various cations in steps.

92. (E)
(a) Solubility and solubility product constant: Solubility is the number of moles of a
precipitate dissolved in a certain mass of water (or some other solvent.) The solubility
product constant is the constant for the equilibrium established between a solid solute and
its ions in a saturated solution.
(b) Commonion effect and salt effect: The common ion effect is a consequence of Le
Chteliers principle, where the equilibrium concentration of all ions resulting from the
dissolution of a sparingly soluble precipitate is reduced because a large amount of one (or
more) of the ions from another source is present. The salt effect is the presence of a large
quantity of ions from a very soluble salt which slightly increases the solubility of a
sparingly soluble precipitate.
(c) Ion pair and ion product: An ion pair comprises two oppositely charged ions held together
by electrostatic forces. The ion product (Q
sp
) is the product of concentrations of the
constituent ions of a compound, and is used to determine if they meet the precipitation
criteria or not.

Chapter 18: Solubility and Complex-Ion Equilibria
943
93. (E) The answer is (d). See the reasoning below.
(a) Wrong, because the stoichiometry is wrong
(b) Wrong, because K
sp
=[Pb
2+
][I
-
]
2

(c) Wrong, because [Pb
2+
] =K
sp
/[ I
-
]
2

(d) Correct because of the [Pb
2+
]:2[I
-
] stoichiometry

94. (E) The answer is (a). ( )
2 2
4 4
BaSO s Ba SO
+
+ . If Na
2
SO
4
is added, the commonion effect
forces the equilibrium to the left and reduces [Ba
2+
].

95. (E) The answer is (c). Choices (b) and (d) reduce solubility because of the commonion effect.
In the case of choice (c), the diverse non-commonion effect or the salt effect causes more
Ag
2
CrO
4
to dissolve.

96. (E) The answer is (b). The sulfate salt of Cu is soluble, whereas the Pb salt is insoluble.

97. (M) The answers are (c) and (d). Adding NH
3
causes the solution to become basic (adding
OH

). Mg, Fe, Cu, and Al all have insoluble hydroxides. However, only Cu can form a
complex ion with NH
3
, which is soluble. In the case of (NH
4
)
2
SO
4
, it is slightly acidic and
dissolved readily in a base.

98. (M) The answer is (a). CaCO
3
is slightly basic, so it is more soluble in an acid. The only
option for an acid given is NH
4
Cl.

99. (M) The answer is (c). Referring to Figure 18-7, it is seen that ammonia is added to an
aqueous H
2
S solution to precipitate more metal ions. Since ammonia is a base, increasing the
pH should cause more precipitation.

100. (M)
(a) H
2
C
2
O
4
is a moderately strong acid, so it is more soluble in a basic solution.
(b) MgCO
3
is slightly basic, so it is more soluble in an acidic solution.
(c) CdS is more soluble in acidic solutions, but the solubility is still so small that it is
essentially insoluble even in acidic solutions.
(d) KCl is a neutral salt, and therefore its solubility is independent of pH.
(e) NaNO
3
is a neutral salt, and therefore its solubility is independent of pH.
(f) Ca(OH)
2
, a strong base, is more soluble in an acidic solution.

101. (E) The answer is NH
3
. NaOH(aq) precipitates both, and HCl(aq) precipitates neither.
Mg(OH)
2
precipitates from an NH
3
(aq) solution but forms the soluble complex
Cu(NH
3
)
4
(OH)
2
.

102. (D) Al(OH)
3
will precipitate. To demonstrate this, the pH of the acetate buffer needs to be
determined first, from which the OH

can be determined. The OH

concentration can be used

to calculate Q
sp
, which can then be compared to K
sp
to see if any Al(OH)
3
will precipitate. This
is shown below:

Chapter 18: Solubility and Complex-Ion Equilibria
944
| |
( )
( )
5
a
14 pH 10
Ac
0.35 M
pH pK log log 1.8 10 log 4.65
HAc 0.45 M
[OH ] 10 4.467 10 M

(

= + = + =
= =

( )
( )( )
3+
3
3
sp
3
10 29
sp
sp sp
Al OH Al +3OH
( )(3 )
0.275 4.467 10 2.45 10
, therefore there will be precipitation.

=
= =
>

-
Q s s
Q
Q K


103. (E) The answer is (b). Based on solubility rules, Cu
3
(PO
4
)
2
is the only species that is sparingly
soluble in water.

104. (M) The answer is (d). The abbreviated work shown for each part calculates the molar
solubility (s) for all the salts. They all follow the basic outlined below:

( ) ( )
x y
x y
sp
M A xM +yA
K x s y s
andwe solve for s.
=

(a)
2
2
MgF Mg 2F
+
+
8 2 3
3
3.7 10 s (2s) 4s
s 2.1 10 M

= =
=


(c) ( )
2 3
3 4 4
2
Mg PO 3Mg 2PO
+
+
( ) ( )
3 2
25 5
6
1 10 3s 2s 108s
s 3.9 10 M

= =
=


(b)
2 2
3 3
MgCO Mg CO
+
+
8
4
3.5 10 s s
s 1.9 10 M

=
=


(d)
3
3 4 4
Li PO 3Li PO
+
+
( )
3
9 4
3
3.2 10 3s s 27s
s 3.3 10 M

= =
=




105. (E) The answer is (b). This is due to the salt effect. The more moles of salt there are
available, the greater the solubility. For (b), there are 0.300 moles of ions (30.100 M Na
2
S
2-
O
3
).

106. (E) It will decrease the amount of precipitate. Since all salts of NO
3

are highly soluble and

Ag
+
and Hg
2+
salts of I

are not, anything that forms a soluble complex ion with Ag

+
and Hg
2+

will reduce the amount of those ions available for precipitation with I

and therefore will

reduce the amount of precipitate.

Chapter 18: Solubility and Complex-Ion Equilibria
945
107. (M) No precipitate will form. To demonstrate this, one has to calculate [Ag
+
], and then, using
[I

], determine the Q
sp
and compare it to K
sp
of AgI.

Since K
f
is for the formation of the complex ion Ag(CN)
2
, its inverse is for the dissociation of
Ag(CN)
2
to Ag
+
and CN.
18 19
dis f
1 15.6 10 1.786 10

= = = K K

The dissociation of Ag(CN)
2
is as follows:
( )
+ -
2
19
dis
Ag CN (aq) Ag +2CN
(1.05 )
1.786 10
(0.012 )

+
/
= =

x x
K
x

We can simplify the calculations by noting that x is very small in relation to [Ag
+
] and [CN].
Therefore, x =1.7010
-19
M.

Dissociation of AgI is as follows:
( )( )
+ -
19 19
sp
AgI Ag +I
1.7 10 2.0 3.4 10

= =

Q

Since Q
sp
<K
sp
, no precipitate will form.


108. (M) In both cases, the dissolution reaction is similar to reaction (18.5), for which K =K
f
K
sp
.
This is an exceedingly small quantity for (a) but large for (b). CuCO
3
is soluble in NH
3
(aq) and
CuS(s) is not.

109. (M) In this chapter, the concept of solubility of sparingly soluble precipitates is the overarching
concept. Deriving from this overall concept is the dissociation constant for the precipitate, K
sp

and molar solubility. Also emanating from the solubility concept are factors that affect
solubility: the common ioneffect, the salt effect, the effects of pH on solubility, and formation
of complex ions. Take a look at the subsection headings and problems for more refining of the
general and specific concepts.

946
CHAPTER 19

SPONTANEOUS CHANGE:
ENTROPY AND GIBBS ENERGY

PRACTICE EXAMPLES

1A (E) In general, A > S 0 if A > n
gas
0. This is because gases are very dispersed compared to
liquids or solids; (gases possess large entropies). Recall that An
gas
is the difference
between the sum of the stoichiometric coefficients of the gaseous products and a similar
sum for the reactants.


(a) An
gas
=2+0 2+1 ( )=1. One mole of gas is consumed here. We predict AS < 0.


(b) A n
gas
=1+0 0=+1. Since one mole of gas is produced, we predict A > S 0.


1B (E) (a) The outcome is uncertain in the reaction between ZnS(s) and Ag
2
O s ( ). We have
used An
gas
to estimate the sign of entropy change. There is no gas involved in this
reaction and thus our prediction is uncertain.



(b) In the chlor-alkali process the entropy increases because two moles of gas have
formed where none were originally present (An
gas
= (1+1+ 0) (0+ 0) = 2



2A (E) For a vaporization, A A A

G H T S
vap vap vap
=0= . Thus, A A

S H T
vap vap vap
= / .


We substitute the given values. AS
vap

=
AH
vap

T
vap
=
20.2kJ mol
1
29.79+273.15 ( ) K
=83.0J mol
1
K
1



2B (E) For a phase change, A A A

G H T S
tr tr tr
=0= . Thus, A A

H T S
tr tr
= . We substitute in the
given values. AH
tr

=TAS
tr

= 95.5+273.2 ( ) K 1.09J mol

1
K
1
=402J/mol


3A (M) The entropy change for the reaction is expressed in terms of the standard entropies of
the reagents.


( ) ( ) ( )
3 2 2
1 1 1 1 1 1 1 1
=2 NH g N g 3 H g
=2 192.5J mol K 191.6J mol K 3 130.7J mol K = 198.7J mol K
S S S S

A ( ( (






Thus to form one mole of NH
3
g ( ), the standard entropy change is

99.4
1 1
J mol K

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
947
3B (M) The entropy change for the reaction is expressed in terms of the standard entropies of
the reagents.

AS
o
=S
o
NO g ( )

+S
o
NO
2
g ( )

S
o
N
2
O
3
g ( )

( )
( )
1 1 1 1 1 1
2 3
1 1
2 3
138.5J mol K =210.8J mol K +240.1J mol K N O g
=450.9J mol K N O g
S
S


(

(

( )
1 1 1 1 1
2 3
N O g =450.9J mol K 138.5J mol K =312.4J mol K S

(

4A (E) (a) Because An
gas
=2 1+3 ( )=2 for the synthesis of ammonia, we would predict
AS < 0 for the reaction. We already know that AH < 0. Thus, the reaction falls into
case 2, namely, a reaction that is spontaneous at low temperatures and non-
spontaneous at high temperatures.

(b) For the formation of ethylene An
gas
=1 2+0 ( )=1 and thus AS < 0. We are given
that A > H 0 and, thus, this reaction corresponds to case 4, namely, a reaction that is
non-spontaneous at all temperatures.

4B (E) (a) Because An
gas
=+1 for the decomposition of calcium carbonate, we would predict
A > S 0 for the reaction, favoring the reaction at high temperatures. High
temperatures also favor this endothermic

AH
o
> 0
( )
reaction.

(b) The roasting of ZnS(s) has A n
gas
=2 3= 1 and, thus, AS < 0. We are given that
AH < 0; thus, this reaction corresponds to case 2, namely, a reaction that is
spontaneous at low temperatures, and non-spontaneous at high ones.

5A (E) The expression A A A G H T S

= is used with T =298.15K .

AG
o
=AH
o
TAS
o
=1648kJ 298.15K 549.3J K
1
( )
1kJ /1000J ( )
=1648kJ +163.8kJ =1484kJ


5B (M) We just need to substitute values from Appendix D into the supplied expression.


( ) ( ) ( )
f 2 f f 2
1 1 1 1
=2 NO g 2 NO g O g
=2 51.31kJ mol 2 86.55kJ mol 0.00kJ mol = 70.48kJ mol
G G G G


A A A A ( ( (

6A (M) Pressures of gases and molarities of solutes in aqueous solution appear in
thermodynamic equilibrium constant expressions. Pure solids and liquids (including
solvents) do not appear.

(a)

K =
P
SiCl
4
P
Cl
2
2
= K
p
(b) K =
HOCl

H
+

Cl

P
Cl
2


p
= K K for (a) because all terms in the K expression are gas pressures.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
948
6B (M) We need the balanced chemical equation in order to write the equilibrium constant
expression. We start by translating names into formulas.
PbS s ( )+HNO
3
aq ( )Pb NO
3
( )
2
aq ( )+S s ( )+NO g ( )
The equation then is balanced with the ion-electron method.


( ) ( ) ( )
( ) ( ) ( )
2+
+
3 2
oxidation: {PbS s Pb aq +S s +2e } 3
reduction:{NO aq +4H aq +3e NO g +2H O(l) } 2

( ) ( ) ( ) ( ) ( ) ( )
+ 2+
3 2
net ionic: 3 PbS s +2NO aq +8H aq 3Pb aq +3S s +2NO g +4H O(l)

In writing the thermodynamic equilibrium constant, recall that
neither pure solids (PbS(s) and S(s)) nor pure liquids ( )
2
H O(l)
appear in the thermodynamic equilibrium constant expression. Note
also that we have written H
+
aq ( ) here for brevity even though we
understand that H
3
O
+
aq ( ) is the acidic species in aqueous solution.
K =
[Pb
2+
]
3
p
NO
2
[NO
3

]
2
[H
+
]
8



7A (M) Since the reaction is taking place at 298.15 K, we can use standard free energies of
formation to calculate the standard free energy change for the reaction:

2 4 2
N O (g) 2NO (g)
( ) ( )
f 2 f 2 4
=2 NO g N O g 2 51.31 kJ /mol 97.89kJ /mol 4.73kJ G G G A A A = = + ( (




AG
o
rxn
=+4.73 kJ . Thus, the forward reaction is non-spontaneous as written at 298.15 K.

7B (M) In order to answer this question we must calculate the reaction quotient and compare
it to the K
p
value for the reaction:


2
2 4 2 p
(0.5)
N O (g) 2NO (g) 0.5
0.5
0.5bar 0.5bar
Q = =

AG
o
rxn
=+4.73 kJ =RTlnK
p
; 4.73 kJ /mol =(8.3145 10
3
kJ /Kmol)(298.15 K)lnK
p


Therefore, K
p
= 0.148. Since Q
p
is greater than K
p
, we can conclude that the reverse
reaction will proceed spontaneously, i.e. NO
2
will spontaneously convert into N
2
O
4
.

8A (D) We first determine the value of AG

and then set = ln G RT K A

to determine K .
( ) ( )
+
f f f
Ag aq + [I (aq)] AgI s
[(77.11 51.57) ( 66.19)] kJ /mol 91.73
G G G G

( A = A A A (

= = +



Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
949
1 1
37.00 17
91.73kJ / mol 1000J
ln 37.00
1kJ 8.3145J mol K 298.15K
e 8.5 10
G
K
RT
K


A
= = =

= =

This is precisely equal to the value for the K
sp
of AgI listed in Appendix D.
8B (D) We begin by translating names into formulas.
MnO
2
s ( )+HCl aq ( )Mn
2+
aq ( )+Cl
2
aq ( ) Then we produce a balanced net ionic
equation with the ion-electron method.

( ) ( )
( ) ( ) ( )
2
+ 2+
2 2
oxidation: 2 Cl aq Cl g +2e
reduction: MnO s +4H aq +2e Mn aq +2H O(l)

( ) ( ) ( ) ( ) ( )
+ 2+
2 2 2
net ionic: MnO s +4H aq +2Cl aq Mn aq +Cl g +2H O(l)

Next we determine the value of AG

for the reaction and then the value of K.

( ) ( ) ( )
( ) ( ) ( )
( )
( ) ( )
2+
f f 2 f 2
+
f 2 f f
= Mn aq + Cl g +2 H O l
MnO s 4 H aq 2 Cl aq
= 228.1kJ +0.0kJ +2 237.1kJ
465.1kJ 4 0.0kJ 2 131.2kJ =+25.2kJ
G G G G
G G G


( A A A A ( (

( ( A A A (

3 1
10.2 5
-1 1
( 25.2 10 J mol )
ln 10.17 e 4 10
8.3145J mol K 298.15
G
K K
RT K

+ A
= = = = =

Because the value of K is so much smaller than unity, we do not expect an appreciable
forward reaction.

9A (M) We set equal the two expressions for AG

and solve for the absolute temperature.

( )
= = ln = ln = ln G H T S RT K H T S RT K T S R K A A A A A A



( )
o 3
o 1 1
114.1 10 J /mol
= = =607K
ln 146.4 8.3145 ln 150 J mol K
H
T
S R K

A
A (



9B (D) We expect the value of the equilibrium constant to increase as the temperature
decreases since this is an exothermic reaction and exothermic reactions will have a larger
equilibrium constant (shift right to form more products), as the temperature decreases.
Thus, we expect K to be larger than 1000, which is its value at 4.3 10
2
K.
(a) The value of the equilibrium constant at 25

C is obtained directly from the value of

AG
o
, since that value is also for 25

C. Note:
( )
o o o
= = 77.1kJ /mol 298.15K 0.1213kJ /mol K = 40.9kJ /mol G H T S A A A
3 1
+16.5 7
1 1
( 40.9 10 J mol )
ln 16.5 e 1.5 10
8.3145J mol K 298.15K
G
K K
RT

A
= = = = =

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
950
(b) First, we solve for AG
o
at 75 =348

C K
o o o
3
kJ 1000J J
= = 77.1 348.15K 121.3
mol 1kJ mol K
= 34.87 10 J /mol
G H T S
| | | |
A A A
| |
\ . \ .


Then we use this value to obtain the value of the equilibrium constant, as in part (a).
3 1
+12.05 5
-1 1
( 34.87 10 J mol )
ln 12.05 e 1.7 10
8.3145J mol K 348.15K
G
K K
RT

A
= = = = =

As expected, K for this exothermic reaction decreases with increasing temperature.

10A (M) We use the value of K
p
=9.1 10
2
at 800 K and A H
o
J / mol = 1.8 10
5
, for the
appropriate terms, in the van't Hoff equation.
2 5
2 1 1 5
5.8 10 1.8 10 J /mol 1 1 1 1 9.66 8.3145
ln = = 9.66; =
9.1 10 8.3145J mol K 800K K 800 1.8 10 T T

| |

|

\ .


3 4 4
1/ =1.25 10 4.5 10 =8.0 10 =1240K 970 C T T

~



This temperature is an estimate because it is an extrapolated point beyond the range of the
data supplied.

10B (M) The temperature we are considering is 235 =508

C K. We substitute the value of

K
p
=9.1 10
2
at 800 K andA H
o
= 1.8 10
5
J /mol, for the appropriate terms, in the van't
Hoff equation.
6
5
p p +15. 6
.6 2 1 1 2
1.8 10 J /mol 1 1
ln = =+15 ; =e =6 10
9.1 10 8.3145J mol K 800K 508K 9.1 10
K K

| |

|

\ .

6 2 9
p
=6 10 9.1 10 =5 10 K


INTEGRATIVE EXAMPLE
11A (D) The value of AG
o
can be calculated by finding the value of the equilibrium constant K
p

at 25
o
C. The equilibrium constant for the reaction is simply given by K
p
= p{N
2
O
5
(g)}.
The vapor pressure of N
2
O
5
(g) can be determined from the Clausius-Clapeyron eqution,
which is a specialized version of the vant Hoff equation.
Stepwise approach:
We first determine the value of AH
sub
.
ln
p
2
p
1
=
AH
sub
R
1
T
1

1
T
2
|
\

|
.
|
ln
760 mmHg
100 mmHg
=
AH
sub
8.314Jmol
-1
K
-1
1
7.5+ 273.15

1
32.4+ 273.15
|
\

|
.
|
AH
sub
=
2.028
3.4910
5
= 5.8110
4
J/mol
Using the same formula, we can now calculate the vapor pressure of N
2
O
5
at 25
o
C.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
951
ln
p
3
100 mmHg
=
5.8110
4
J/mol
8.314Jmol
-1
K
-1
1
280.7

1
298.2
|
\

|
.
|
= 1.46
p
3
100 mmHg
= e
1.46
= 4.31
p
3
= 4.31100mmHg
1 atm
760 mmHg
= 0.567atm= K
p
AG
o
= RT lnK
p
= (8.31410
3
kJmol
-1
K
-1
298.15K)ln(0.567) = 1.42kJ/mol

Conversion pathway approach:
ln
p
2
p
1
=
AH
sub
R
1
T
1

1
T
2
|
\

|
.
|
AH
sub
=
Rln
p
2
p
1
1
T
1

1
T
2
|
\

|
.
|
AH
sub
=
8.314Jmol
-1
K
-1
ln
760mmHg
100mmHg
1
7.5+ 273.15

1
32.4+ 273.15
|
\

|
.
|
=
2.028
3.4910
5
Jmol
-1
= 5.8110
4
Jmol
-1

ln
p
3
p
1
=
AH
sub
R
1
T
1

1
T
2
|
\

|
.
|
p
3
= p
1
e
AH
sub
R
1
T
1

1
T
2
|
\

|
.
|
p
3
= 100mmHg e
5.8110
4
Jmol
-1
8.314JK
-1
mol
-1
1
280.7

1
298.2
|
\

|
.
|
K
-1
= 431mmHg
1atm
760mmHg
= 0.567atm= K
p
AG
o
= RT lnK
p
= (8.31410
3
kJmol
-1
K
-1
298.15K)ln(0.567) = 1.42kJ/mol


11B (D) The standard entropy change for the reaction (AS
o
) can be calculated from the known
values of AH
o
and AG
o
.
Stepwise approach:
AG
o
= AH
o
TAS
o
AS
o
=
AH
o
AG
o
T
=
454.8kJmol
-1
(323.1kJmol
-1
)
298.15K
= 441.7JK
-1
mol
-1
Plausible chemical reaction for the production of ethylene glycol can also be written as:
2C(s)+3H
2
(g)+O
2
(g) CH
2
OHCH
2
OH(l)
Since AS
o
= {S
products
o
} {S
reac tants
o
}

it follows that:
AS
rxn
o
= S
o
(CH
2
OHCH
2
OH(l))[2 S
o
(C(s))+ 3 S
o
(H
2
(g))+ S
o
(O
2
(g))]
441.7JK
-1
mol
-1
= S
o
(CH
2
OHCH
2
OH(l))[2 5.74JK
-1
mol
-1
+ 3130.7JK
-1
mol
-1
+ 205.1JK
-1
mol
-1
]
S
o
(CH
2
OHCH
2
OH(l)) = 441.7JK
-1
mol
-1
+ 608.68JK
-1
mol
-1
= 167JK
-1
mol
-1

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
952
Conversion pathway approach:
AG
o
= AH
o
TAS
o
AS
o
=
AH
o
AG
o
T
=
454.8kJmol
-1
(323.1kJmol
-1
)
298.15K
= 441.7JK
-1
mol
-1
441.7JK
-1
mol
-1
= S
o
(CH
2
OHCH
2
OH(l))[2 5.74JK
-1
mol
-1
+ 3130.7JK
-1
mol
-1
+ 205.1JK
-1
mol
-1
]
S
o
(CH
2
OHCH
2
OH(l)) = 441.7JK
-1
mol
-1
+ 608.68JK
-1
mol
-1
= 167JK
-1
mol
-1


EXERCISES


Spontaneous Change and Entropy

1. (E) (a) The freezing of ethanol involves a decrease in the entropy of the system. There is
a reduction in mobility and in the number of forms in which their energy can be
stored when they leave the solution and arrange themselves into a crystalline state.

(b) The sublimation of dry ice involves converting a solid that has little mobility into a
highly dispersed vapor which has a number of ways in which energy can be stored
(rotational, translational). Thus, the entropy of the system increases substantially.

(c) The burning of rocket fuel involves converting a liquid fuel into the highly dispersed
mixture of the gaseous combustion products. The entropy of the system increases
substantially.

2. (E) Although there is a substantial change in entropy involved in (a) changing H O
2
(1iq., 1
atm) to H O
2
(g, 1 atm), it is not as large as (c) converting the liquid to a gas at 10 mmHg.
The gas is more dispersed, (less ordered), at lower pressures. In (b), if we start with a solid
and convert it to a gas at the lower pressure, the entropy change should be even larger,
since a solid is more ordered (concentrated) than a liquid. Thus, in order of increasingAS ,
the processes are: (a) <(c) <(b).
3. (E) The first law of thermodynamics states that energy is neither created nor destroyed (thus,
The energy of the universe is constant). A consequence of the second law of
thermodynamics is that entropy of the universe increases for all spontaneous, that is, naturally
occurring, processes (and therefore, the entropy of the universe increases toward a
maximum).

4. (E) When pollutants are produced they are usually dispersed throughout the environment.
These pollutants thus start in a relatively compact form and end up dispersed throughout a
large volume mixed with many other substances. The pollutants are highly dispersed, thus,
they have a high entropy. Returning them to their original compact form requires reducing
this entropy, which is a highly non-spontaneous process. If we have had enough foresight to
retain these pollutants in a reasonably compact form, such as disposing of them in a secure
landfill, rather than dispersing them in the atmosphere or in rivers and seas, the task of
permanently removing them from the environment, and perhaps even converting them to
useful forms, would be considerably easier.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
953
5. (E) (a) Increase in entropy because a gas has been created from a liquid, a condensed
phase.

(b) Decrease in entropy as a condensed phase, a solid, is created from a solid and a gas.

(c) For this reaction we cannot be certain of the entropy change. Even though the number
of moles of gas produced is the same as the number that reacted, we cannot conclude
that the entropy change is zero because not all gases have the same molar entropy.

(d) 2H
2
S g ( )+3O
2
g ( )2H
2
O g ( )+2SO
2
g ( ) Decrease in entropy since five moles of
gas with high entropy become only four moles of gas, with about the same quantity
of entropy per mole.

6. (E) (a) At 75

C, 1 mol H O
2
(g, 1 atm) has a greater entropy than 1 mol H O
2
(1iq., 1
atm) since a gas is much more dispersed than a liquid.

(b)
1mol Fe
50.0g Fe =0.896
55.8 g Fe
mol Fe has a higher entropy than 0.80 mol Fe, both (s)
at 1 atm and 5

C, because entropy is an extensive property that depends on the

amount of substance present.

(c) 1 mol Br
2
(1iq., 1 atm, 8

C) has a higher entropy than 1 mol Br

2
(s, 1atm, 8

C)
because solids are more ordered (concentrated) substances than are liquids, and
furthermore, the liquid is at a higher temperature.

(d) 0.312 mol SO
2
(g, 0.110 atm, 32.5

C) has a higher entropy than 0.284 mol O

2
(g,
15.0 atm, 22.3

C) for at least three reasons. First, entropy is an extensive property

that depends on the amount of substance present (more moles of SO
2
than O
2
). Second,
entropy increases with temperature (temperature of SO
2
is greater than that for O
2
.
Third, entropy is greater at lower pressures (the O
2
has a much higher pressure).
Furthermore, entropy generally is higher per mole for more complicated molecules.

7. (E) (a) Negative; A liquid (moderate entropy) combines with a solid to form another
solid.

(b) Positive; One mole of high entropy gas forms where no gas was present before.

(c) Positive; One mole of high entropy gas forms where no gas was present before.

(d) Uncertain; The number of moles of gaseous products is the same as the number of
moles of gaseous reactants.

(e) Negative; Two moles of gas (and a solid) combine to form just one mole of gas.

8. (M) The entropy of formation of a compound would be the difference between the absolute
entropy of one mole of the compound and the sum of the absolute entropies of the
appropriate amounts of the elements constituting the compound, with each species in its
most stable form.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
954
Stepwise approach:
It seems as though CS
2
1 ( ) would have the highest molar entropy of formation of the
compounds listed, since it is the only substance whose formation does not involve the
consumption of high entropy gaseous reactants. This prediction can be checked by
determining AS
f
o
values from the data in Appendix D:

(a) ( ) ( ) ( )
2 4
C graphite +2H g CH g

AS
f
o
CH
4
g
( )

=S
o
CH
4
g
( )

S
o
C graphite
( )

2S
o
H
2
g
( )

=186.3J mol
1
K
1
5.74J mol
1
K
1
2130.7J mol
1
K
1
=80.8J mol
1
K
1


(b) ( ) ( ) ( ) ( )
1
2 2 3 2 2
2C graphite +3H g + O g CH CH OH l
( ) ( ) ( ) ( ) ( )
o o o o o
3 2 3 2 2 2 f
1 1 1 1 1 1 1 1 1
2
1 1
1
CH CH OH l = CH CH OH l 2 C graphite 3 H g O g
2
=160.7J mol K 2 5.74J mol K 3 130.7J mol K 205.1J mol K
= 345.4J mol K
S S S S S


( ( ( ( (

A

(c) ( ) ( ) ( )
2
C graphite +2S rhombic CS l
( ) ( ) ( ) ( )
o o o
f 2 2
1 1 1 1 1 1
1 1
CS l = CS l C graphite 2 S rhombic
=151.3J mol K 5.74J mol K 2 31.80J mol K
=82.0J mol K
S S S S

A ( ( ( (


Conversion pathway approach:
CS
2
would have the highest molar entropy of formation of the compounds listed, because
it is the only substance whose formation does not involve the consumption of high
entropy gaseous reactants.
(a) ( ) ( ) ( )
2 4
C graphite +2H g CH g


AS
f
o
CH
4
g
( )

=186.3J mol
1
K
1
5.74J mol
1
K
1
2130.7J mol
1
K
1
= 80.8J mol
1
K
1

(b) ( ) ( ) ( ) ( )
1
2 2 3 2 2
2C graphite +3H g + O g CH CH OH l


AS
f
o
CH
3
CH
2
OH l
()

=(160.7 25.74 3130.7

1
2
205.1)J mol
1
K
1
=345.4J mol
1
K
1

(c) ( ) ( ) ( )
2
C graphite +2S rhombic CS l


AS
f

CS
2
l
()

=151.3J mol
1
K
1
5.74J mol
1
K
1
2 31.80J mol
1
K
1
=82.0J mol
1
K
1

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
955
Phase Transitions

9. (M) (a)

vap f 2 f 2
[H O(g)] [H O(l)] 241.8kJ /mol ( 285.8kJ /mol)
44.0kJ /mol
H H H

A = A A =
= +


( ) ( )
o o 1 1 1 1
vap 2 2
1 1
= H O g H O l =188.8 J mol K 69.91J mol K
=118.9J mol K
S S S


A ( (


There is an alternate, but incorrect, method of obtainingA

S
vap
.

3
vap 1 1
vap
44.0 10 J /mol
= = =148 J mol K
298.15K
H
S
T

A

A

This method is invalid because the temperature in the denominator of the equation
must be the temperature at which the liquid-vapor transition is at equilibrium. Liquid
water and water vapor at 1 atm pressure (standard state, indicated by

) are in
equilibrium only at 100 =373

C K.

(b) The reason why A

H
vap
is different at 25

C from its value at 100

C has to do with
the heat required to bring the reactants and products down to 298 K from 373 K. The
specific heat of liquid water is higher than the heat capacity of steam. Thus, more
heat is given off by lowering the temperature of the liquid water from 100

C to
25

C than is given off by lowering the temperature of the same amount of steam.
Another way to think of this is that hydrogen bonding is more disrupted in water at
100

C than at 25

C (because the molecules are in rapidthermalmotion), and

hence, there is not as much energy needed to convert liquid to vapor (thus
vap
H

A has
a smaller value at 100

C. The reason why A

S
vap
has a larger value at 25

C than at
100

C has to do with dispersion. A vapor at 1 atm pressure (the case at both

temperatures) has about the same entropy. On the other hand, liquid water is more
disordered (better able to disperse energy) at higher temperatures since more of the
hydrogen bonds are disrupted by thermal motion. (The hydrogen bonds are totally
disrupted in the two vapors).

10. (M) In this problem we are given standard enthalpies of the formation (AH
f
o
) of liquid
and gas pentane at 298.15 K and asked to estimate the normal boiling point of
pentane, AG
vap
o
and furthermore comment on the significance of the sign of AG
vap
o
.
The general strategy in solving this problem is to first determine AH
vap
o
from the
known enthalpies of formation. Troutons rule can then be used to determine the
normal boiling point of pentane. Lastly, AG
vap,298K
o
can be calculated using
A A A

G H T S
vap vap vap
= .

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
956
Stepwise approach:
Calculate AH
vap
o
from the known values of AH
f
o
(part a):
C
5
H
12
(l)

C
5
H
12
(g)
AH
f
o
-173.5 kJ mol
-1
-146.9 kJ mol
-1

AH
vap
o
= 146.9 (173.5)kJmol
-1
= 26.6kJmol
-1

Determine normal boiling point using Troutons rule (part a):
AS
vap
o
=
AH
vap
o
T
nbp
= 87Jmol
-1
K
-1

T
nbp
=
AH
vap
o
AS
vap
o
=
26.6kJmol
1
87kJK
1
mol
1
1000
= 306K
T
nbp
= 32.9
o
C
Use A A A

G H T S
vap vap vap
= to calculate AG
vap,298K

(part b):
A A A

G H T S
vap vap vap
=

AG
vap,298K

= 26.6kJmol
-1
298.15K
87kJmol
-1
K
-1
1000
AG
vap,298K

= 0.66kJmol
-1

Comment on the value of AG
vap,298K

(part c):
The positive value of A

G
vap
indicates that normal boiling (having a vapor pressure
of 1.00 atm) for pentane should be non-spontaneous (will not occur) at 298. The
vapor pressure of pentane at 298 K should be less than 1.00 atm.
Conversion pathway approach:
C
5
H
12
(l)

C
5
H
12
(g)
AH
f
o
-173.5 kJ mol
-1
-146.9 kJ mol
-1

AH
vap
o
= 146.9 (173.5)kJmol
-1
= 26.6kJmol
-1

AS
vap
o
=
AH
vap
o
T
nbp
= 87Jmol
-1
K
-1
T
nbp
=
AH
vap
o
AS
vap
o
=
26.6kJmol
-1
87kJK
-1
mol
-1
1000
= 306K
AG
vap

=AH
vap

TAS
vap

= 26.6kJmol
-1
298.15K
87kJmol
-1
K
-1
1000
= 0.66kJmol
-1


11. (M) Trouton's rule is obeyed most closely by liquids that do not have a high degree of
order within the liquid. In both HF and CH OH
3
, hydrogen bonds create considerable order
within the liquid. In C H CH
6 5 3
, the only attractive forces are non-directional London
forces, which have no preferred orientation as hydrogen bonds do. Thus, of the three
choices, liquid C H CH
6 5 3
would most closely follow Troutons rule.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
957
12. (E)
vap f 2 f 2
[Br (g)] [Br (l)] 30.91kJ /mol 0.00 kJ /mol =30.91kJ /mol H H H

A = A A ~

3
vap vap 1 1 2
vap vap 1 1
vap vap
30.91 10 J /mol
= 87 J mol K or = =3.5 10 K
87J mol K
H H
S T
T S



A A

A ~ ~
A


The accepted value of the boiling point of bromine is
2
58.8C=332 K =3.32 10 K

.
Thus, our estimate is in reasonable agreement with the measured value.

13. (M) The liquid water-gaseous water equilibrium
2 2
H O (l, 0.50 atm) H O (g, 0.50 atm)
can only be established at one temperature, namely the boiling point for water under 0.50
atm external pressure. We can estimate the boiling point for water under 0.50 atm external
pressure by using the Clausius-Clapeyron equation:

ln
2
1
P
P
=
vap
o
H
R
A
1 2
1 1
T T
| |

|
\ .


We know that at 373 K, the pressure of water vapor is 1.00 atm. Let's make P
1
=1.00
atm, P
2
=0.50 atm and T
1
=373 K. Thus, the boiling point under 0.50 atm pressure is T
2
.
To find T
2
we simply insert the appropriate information into the Clausius-Clapeyron
equation and solve for T
2
:

ln
0.50 atm
1.00 atm
=
1
3 1 1
40.7 kJ mol
8.3145 10 kJ K mol

2
1 1
373 K T
| |

|
\ .


-1.416 10
4
K =
2
1 1
373 K T
| |

|
\ .


Solving for T
2
we find a temperature of 354 K or 81C. Consequently, to achieve an
equilibrium between gaseous and liquid water under 0.50 atm pressure, the temperature
must be set at 354 K.

14. (M) Figure 12-19 (phase diagram for carbon dioxide) shows that at 60C and under 1
atm of external pressure, carbon dioxide exists as a gas. In other words, neither solid nor
liquid CO
2
can exist at this temperature and pressure. Clearly, of the three phases,
gaseous CO
2
must be the most stable and, hence, have the lowest free energy when T =
60 C and P
ext
=1.00 atm.

Gibbs Energy and Spontaneous Change

15. (E) Answer (b) is correct. BrBr bonds are broken in this reaction, meaning that it is
endothermic, with A > H 0. Since the number of moles of gas increases during the
reaction, A > S 0. And, because A A A G H T S = , this reaction is non-spontaneous
(A > G 0) at low temperatures where the AH term predominates and spontaneous
(AG < 0) at high temperatures where the T S A term predominates.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
958
16. (E) Answer (d) is correct. A reaction that proceeds only through electrolysis is a reaction
that is non-spontaneous. Such a reaction has A > G 0.

17. (E) (a) AH
o
< 0and AS
o
< 0 (sinceAn
gas
< 0) for this reaction. Thus, this reaction is case
2 of Table 19-1. It is spontaneous at low temperatures and non-spontaneous at high
temperatures.

(b) We are unable to predict the sign of AS
o
for this reaction, sinceAn
gas
=0. Thus, no
strong prediction as to the temperature behavior of this reaction can be made. Since
AH
o
>0, we can, however, conclude that the reaction will be non-spontaneous at low
temperatures.

(c) A > H
o
0and A > S
o
0 (since
gas
0 n A > ) for this reaction. This is case 3 of Table 19-1.
It is non-spontaneous at low temperatures, but spontaneous at high temperatures.
18. (E) (a) A > H
o
0and AS
o
< 0 (sinceAn
gas
< 0) for this reaction. This is case 4 of Table
19-1. It is non-spontaneous at all temperatures.

(b) AH
o
< 0and A > S
o
0 (sinceA > n
gas
0) for this reaction. This is case 1 of Table 19-1.
It is spontaneous at all temperatures.

(c) AH
o
< 0and AS
o
< 0 (sinceAn
gas
< 0) for this reaction. This is case 2 of Table 19-1.
It is spontaneous at low temperatures and non-spontaneous at high temperatures.

19. (E) First of all, the process is clearly spontaneous, and thereforeAG < 0. In addition, the
gases are more dispersed when they are at a lower pressure and thereforeA > S 0. We also
conclude thatAH =0because the gases are ideal and thus there are no forces of attraction
or repulsion between them.

20. (E) Because an ideal solution forms spontaneously,AG < 0. Also, the molecules of solvent
and solute that are mixed together in the solution are in a more dispersed state than the
separated solvent and solute. Therefore,A > S 0. However, in an ideal solution, the
attractive forces between solvent and solute molecules equal those forces between solvent
molecules and those between solute molecules. Thus, AH =0. There is no net energy of
interaction.

21. (M) (a) An exothermic reaction (one that gives off heat) may not occur spontaneously if,
at the same time, the system becomes more ordered (concentrated) that is,AS
o
< 0.
This is particularly true at a high temperature, where the T S A term dominates the
AG expression. An example of such a process is freezing water (clearly exothermic
because the reverse process, melting ice, is endothermic), which is not spontaneous
at temperatures above0

C.

(b) A reaction in which A > S 0 need not be spontaneous if that process also is
endothermic. This is particularly true at low temperatures, where the AH term
dominates the AG expression. An example is the vaporization of water (clearly an
endothermic process, one that requires heat, and one that produces a gas, soA > S 0),
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
959
which is not spontaneous at low temperatures, that is, below100

C (assuming P
ext
=
1.00 atm).

22. (M) In this problem we are asked to explain whether the reaction AB(g)A(g)+B(g) is
always going to be spontaneous at high rather than low temperatures. In order to answer
this question, we need to determine the signs of AH , AS and consequently AG. Recall
that AG = AH TAS .
Stepwise approach:
Determine the sign of AS:
We are generating two moles of gas from one mole. The randomness of the system
increases and AS must be greater than zero.
Determine the sign of AH:
In this reaction, we are breaking A-B bond. Bond breaking requires energy, so the reaction
must be endothermic. Therefore, AH is also greater than zero.
Use AG = AH TAS to determine the sign of AG:
AG = AH TAS . Since AH is positive and AS is positive there will be a temperature at
which TAS will become greater than AH . The reaction will be favored at high
temperatures and disfavored at low temperatures.
Conversion pathway approach:
AS for the reaction is greater than zero because we are generating two moles of gas from
one mole. AH for the reaction is also greater than zero because we are breaking A-B
(bond breaking requires energy). Because AG = AH TAS , there will be a temperature at
which TAS will become greater than AH . The reaction will be favored at high
temperatures and disfavored at low temperatures.


Standard Gibbs Energy Change

23.

(M) AH
o
=AH
f

NH
4
Cl s
( )

AH
f

NH
3
g
( )

AH
f

HCl g
( )

= 314.4kJ/mol (46.11kJ/mol 92.31kJ/mol) = 176.0kJ/mol

AG
o
= AG
f

NH
4
Cl s
( )

AG
f

NH
3
g
( )

AG
f

HCl g
( )

= 202.9kJ/mol (16.48kJ/mol 95.30kJ/mol) = 91.1kJ/mol

AG
o
=AH
o
T AS
o
AS
o
=
AH
o
AG
o
T
=
176.0kJ/mol + 91.1kJ/mol
298K

1000J
1kJ
= 285J mol
1


24. (M) (a)
( ) ( ) ( )
( )
o
f 2 6 f 2 2 f 2
= C H g C H g 2 H g
= 32.82kJ /mol 209.2kJ /mol 2 0.00kJ /mol = 242.0kJ /mol
G G G G

A A A A ( ( (




(b)
AG
o
=2AG
f

SO
2
g ( )

+AG
f

O
2
g ( )

2AG
f

SO
3
g ( )

=2 300.2kJ/mol ( )+0.00kJ/mol 2 371.1kJ/mol ( )=+141.8kJ/mol

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
960

(c)
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
o
f f 2 f 3 4 f 2
=3 Fe s +4 H O g FeO s 4 H g
=3 0.00kJ /mol +4 228.6kJ /mol 1015kJ /mol 4 0.00kJ /mol =101kJ /mol
G G G G G

A A A A A ( ( ( (




(d)
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
o 3+ +
f f 2 f f
=2 Al aq +3 H g 2 Al s 6 H aq
=2 485kJ /mol +3 0.00kJ /mol 2 0.00kJ /mol 6 0.00kJ /mol = 970. kJ /mol
G G G G G

( ( A A A A A ( (



25. (M) (a)
( ) ( ) ( )
( ) ( )
o o o o
3 3 2
=2 POCl 1 2 PCl g O g
=2 222.4J /K 2 311.7J /K 205.1J /K = 383.7J /K
S S S S A ( ( (



( )( )
o o o 3 3
= = 620.2 10 J 298K 383.7 J /K = 506 10 J = 506kJ G H T S A A A

(b) The reaction proceeds spontaneously in the forward direction when reactants and
products are in their standard states, because the value of AG
o
is less than zero.

26. (M) (a) ( ) | | ( ) | | ( ) ( ) ( ) | |
( ) ( ) ( ) ( )
o o o o + o o
2 2 2
= Br l +2 HNO aq 2 H aq 2 Br aq 2 NO g
=152.2 J /K +2 135.6 J /K 2 0 J /K 2 82.4 J /K 2 240.1J /K = 221.6 J /K
S S S S S S

A

( (



( )( )
o o o 3 3
= = 61.6 10 J 298K 221.6J /K =+4.4 10 J =+4.4kJ G H T S A A A

(b) The reaction does not proceed spontaneously in the forward direction when reactants and
products are in their standard states, because the value of AG
o
is greater than zero.

27. (M) We combine the reactions in the same way as for any Hess's law calculations.
(a) N
2
O g ( )N
2
g ( )+
1
2
O
2
g ( ) AG
o
=
1
2
+208.4kJ ( )=104.2kJ
N
2
g ( )+2O
2
g ( )2NO
2
g ( ) AG
o
=+102.6kJ
Net: N
2
O g ( )+
3
2
O
2
g ( )2NO
2
g ( ) AG
o
=104.2+102.6=1.6 kJ
This reaction reaches an equilibrium condition, with significant amounts of all
species being present. This conclusion is based on the relatively small absolute
value of AG
o
.

(b) 2N
2
g ( )+6H
2
g ( )4NH
3
g ( ) AG
o
=2 33.0kJ ( )=66.0kJ
4NH
3
g ( )+5O
2
g ( )4NO g ( )+6H
2
O l ( ) AG
o
=1010.5 kJ
4NO g ( )2N
2
g ( )+2O
2
g ( ) AG
o
=2 +173.1kJ ( )=346.2kJ
Net: 6H
2
g ( )+3O
2
g ( )6H
2
O l ( ) AG
o
=66.0kJ 1010.5kJ 346.2kJ =1422.7kJ
This reaction is three times the desired reaction, which therefore has
o
= 1422.7kJ 3= 474.3 G A kJ .
The large negativeAG
o
value indicates that this reaction will go to completion at 25

C.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
961
(c) 4NH
3
g ( )+5O
2
g ( )4NO g ( )+6H
2
O l ( ) AG
o
=1010.5kJ
4NO g ( )2N
2
g ( )+2O
2
g ( ) AG
o
=2 +173.1kJ ( )=346.2kJ
( ) ( ) ( )
o
2 2 2
2N g +O g 2N O g =+208.4kJ G A

( ) ( ) ( ) ( )
o
3 2 2 2
4NH g +4O g 2N O g +6H O l = 1010.5kJ 346.2kJ +208.4kJ
= 1148.3kJ
G A

This reaction is twice the desired reaction, which, therefore, has AG
o
=-574.2 kJ .
The very large negative value of theAG
o
for this reaction indicates that it will go to
completion.
28. (M) We combine the reactions in the same way as for any Hess's law calculations.

(a) COS g ( )+2CO
2
g ( )SO
2
g ( )+3CO g ( ) AG
o
= 246.4kJ ( )=+246.6kJ
2CO g ( )+2H
2
O g ( )2CO
2
g ( )+2H
2
g ( ) AG
o
=2 28.6kJ ( )=57.2kJ

COS g ( )+2H
2
O g ( )SO
2
g ( )+CO g ( )+2H
2
g ( ) AG
o
=+246.6 57.2=+189.4kJ

This reaction is spontaneous in the reverse direction, because of the large positive
value of AG
o


(b) COS g ( )+2CO
2
g ( )SO
2
g ( )+3CO g ( ) AG
o
= 246.4kJ ( )=+246.6kJ
3CO g ( )+3H
2
O g ( )3CO
2
g ( )+3H
2
g ( ) AG
o
=3 28.6kJ ( )=85.8kJ
COS g ( )+3H
2
O g ( )CO
2
g ( )+SO
2
g ( )+3H
2
g ( ) AG
o
=+246.6 85.8=+160.8kJ
This reaction is spontaneous in the reverse direction, because of the large positive value
of AG
o
.

(c) ( ) ( ) ( ) ( ) ( )
o
2 2
COS g +H g CO g +H S g = +1.4 kJ G A
( ) ( ) ( ) ( )
o
2 2 2
CO g +H O g CO g +H g = 28.6kJ = 28.6kJ G A
COS g ( )+H
2
O g ( )CO
2
g ( )+H
2
S g ( ) AG
o
=1.4kJ 28.6kJ =30.0kJ
The negative value of theAG
o
for this reaction indicates that it is spontaneous in the
forward direction.


29. (D) The combustion reaction is :C
6
H
6
l ( )+
15
2
O
2
g ( )6CO
2
g ( )+3H
2
O g or l ( )

(a)
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
o
15
f 2 f 2 f 6 6 f 2 2
15
2
=6 CO g +3 H O l C H l O g
=6 394.4kJ +3 237.1kJ +124.5kJ 0.00kJ = 3202kJ
G G G G G

A A A A A ( ( ( (





(b)

( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
o
15
f 2 f 2 f 6 6 f 2 2
15
2
=6 CO g +3 H O g C H l O g
=6 394.4kJ +3 228.6kJ +124.5kJ 0.00kJ = 3177kJ
G G G G G

A A A A A ( ( ( (




Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
962
We could determine the difference between the two values of AG
o
by noting the
difference between the two products: 3H
2
O l ( )3H
2
O g ( )and determining the
value of AG
o
for this difference:
( ) ( ) ( )
o
f 2 f 2
=3 H O g 3 H O l =3 228.6 237.1 kJ =25.5kJ G G G

A A A ( ( (



30. (M) We wish to find the value of the AH
o
for the given reaction: F
2
g ( )2F(g)
( ) ( ) ( ) ( )
o o o 1 1 1
2
=2 F g F g =2 158.8 J K 202.8 J K =+114.8 J K S S S

A ( (


( )
o o o 3
= + =123.9 10 J + 298K 114.8J /K =158.1kJ /mole of bonds H G T S A A A
The value in Table 10.3 is 159 kJ /mol, which is in quite good agreement with the value
found here.
31. (M) (a) AS
rxn
=ES
products
- ES
reactants

= [1 mol 301.2 J K
1
mol
1
+2 mol 188.8 J K
1
mol
1
] [2 mol 247.4 J K
1
mol
1

+1 mol 238.5 J K
1
mol
1
] =54.5 J K
1
AS
rxn
==0.0545 kJ K
1

(b) AH
rxn
=E(bonds broken in reactants (kJ /mol)) E(bonds broken in products(kJ / mol))
=[4 mol (389 kJ mol
1
)
N-H
+4 mol (222 kJ mol
1
)
O-F
]
[4 mol (301 kJ mol
1
)
N-F
+4 mol (464 kJ mol
1
)
O-H
]
AH
rxn
=616 kJ
(c) AG
rxn
=AH
rxn
TAS
rxn
= 616 kJ 298 K(0.0545 kJ K
1
) =600 kJ
Since the AG
rxn
is negative, the reaction is spontaneous, and hence feasible
(at 25 C ). Because both the entropy and enthalpy changes are negative, this
reaction will be more highly favored at low temperatures (i.e., the reaction is
enthalpy driven)

32. (D) In this problem we are asked to find AG at 298 K for the decomposition of
ammonium nitrate to yield dinitrogen oxide gas and liquid water. Furthermore, we are
asked to determine whether the decomposition will be favored at temperatures above or
below 298 K. In order to answer these questions, we first need the balanced chemical
equation for the process. From the data in Appendix D, we can determine AH
rxn
and
AS
rxn
. Both quantities will be required to determine AG
rxn
(AG
rxn
=AH
rxn
-TAS
rxn
).
Finally the magnitude of AG
rxn
as a function of temperature can be judged depending on
the values of AH
rxn
and AS
rxn
.
Stepwise approach:
First we need the balanced chemical equation for the process:
NH
4
NO
3
(s)
A
N
2
O(g) +2H
2
O(l)
Now we can determine AH
rxn
by utilizing AH
f
o
values provided in Appendix D:
NH
4
NO
3
(s)
A
N
2
O(g) + 2H
2
O(l)
AH
f
o
-365.6 kJ mol
-1
82.05 kJ mol
-1
-285.6 kJ mol
-1

AH
rxn
=EAH
f

products
EAH
f

reactants
AH
rxn
=[2 mol(285.8 kJ mol
1
)

+1 mol(82.05 kJ mol
1
)] [1 mol (365.6 kJ
mol
1
)]
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
963
AH
rxn
=124.0 kJ
Similarly, AS
rxn
can be calculated utilizing S values provided in Appendix D
NH
4
NO
3
(s)
A
N
2
O(g) + 2H
2
O(l)
S
o
15.1 J mol
-1
K
-1
219.9 J mol
-1
K
-1
69.91 J mol
-1
K
-1

AS
rxn
=ES
products
ES
reactants
AS
rxn
=[2 mol 69.91 J K
1
mol
1
+1 mol 219.9 J K
1
mol
1
] [1 mol 151.1 J
K
1
mol
1
]
AS
rxn
=208.6 J K
1
=0.2086 kJ K
1
To find AG
rxn
we can either utilize AG
f
values provided in Appendix D or AG
rxn
=AH
rxn
-
TAS
rxn
:
AG
rxn
=AH
rxn
-TAS
rxn
=-124.0 kJ 298.15 K0.2086 kJ K
-1

AG
rxn
=-186.1 kJ
Magnitude of AG
rxn
as a function of temperature can be judged depending on the values of
AH
rxn
and AS
rxn
:

Since AH
rxn
is negative and AS
rxn
is positive, the decomposition of ammonium nitrate is
spontaneous at all temperatures. However, as the temperature increases, the TAS term gets
larger and as a result, the decomposition reaction shift towards producing more products.
Consequently, we can say that the reaction is more highly favored above 298 K (it will also
be faster at higher temperatures)
Conversion pathway approach:
From the balanced chemical equation for the process
NH
4
NO
3
(s)
A
N
2
O(g) +2H
2
O(l)
we can determine AH
rxn
and AS
rxn
by utilizing AH
f
o
and S values provided in Appendix
D:
AH
rxn
=[2 mol(285.8 kJ mol
1
)

+1 mol(82.05 kJ mol
1
)] [1 mol (365.6 kJ mol
1
)]
AH
rxn
=124.0 kJ
AS
rxn
=[2 mol 69.91 J K
1
mol
1
+1 mol 219.9 J K
1
mol
1
] [1 mol 151.1 J
K
1
mol
1
]
AS
rxn
=208.6 J K
1
=0.2086 kJ K
1
AG
rxn
=AH
rxn
-TAS
rxn
=-124.0 kJ 298.15 K0.2086 kJ K
-1

AG
rxn
=-186.1 kJ
Since AH
rxn
is negative and AS
rxn
is positive, the decomposition of ammonium nitrate is
spontaneous at all temperatures. However, as the temperature increases, the TAS term gets
larger and as a result, the decomposition reaction shift towards producing more products.
The reaction is highly favored above 298 K (it will also be faster).


The Thermodynamic Equilibrium Constant

33. (E) In all three cases, K K
eq p
= because only gases, pure solids, and pure liquids are present
in the chemical equations. There are no factors for solids and liquids in K
eq
expressions,
and gases appear as partial pressures in atmospheres. That makes K
eq
the same as K
p
for
these three reactions.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
964
We now recall thatK
p
=K
c
RT ( )
An
. Hence, in these three cases we have:
(a) ( ) ( ) ( ) ( ) ( )
1
2 2 3 gas p c
2SO g +O g 2SO g ; =2 2+1 = 1; = = n K K K RT

A

(b) ( ) ( ) ( ) ( )
1 1 1 1
2 2 gas p c 2 2 2 2
HI g H g + I g ; =1 + =0; = = n K K K A

(c)
( ) ( ) ( ) ( )
( ) ( )
4 3 3 2 2
2
gas p c
NH HCO s NH g +CO g +H O l ;
=2 0 =+2 = = n K K K RT A



34. (M) (a)
( )
( )
4
2
4
2
{H g }
=
{H O g }
P
K
P


(b) Terms for both solids, Fe(s) and Fe
3
O
4
s ( ), are properly excluded from the
thermodynamic equilibrium constant expression. (Actually, each solid has an activity
of 1.00.) Thus, the equilibrium partial pressures of both H
2
g ( ) and H
2
O g ( ) do not
depend on the amounts of the two solids present, as long as some of each solid is
present. One way to understand this is that any chemical reaction occurs on the
surface of the solids, and thus is unaffected by the amount present.
(c) We can produce H
2
g ( ) from H
2
O g ( ) without regard to the proportions of Fe(s) and
Fe
3
O
4
s ( ) with the qualification, that there must always be some Fe(s) present for the
production of H
2
g ( ) to continue.

35. (M) In this problem we are asked to determine the equilibrium constant and the change in
Gibbs free energy for the reaction between carbon monoxide and hydrogen to yield
methanol. The equilibrium concentrations of each reagent at 483K were provided. We
proceed by first determining the equilibrium constant. Gibbs free energy can be
calculated using AG
o
= RT lnK .
Stepwise approach:
First determine the equilibrium constant for the reaction at 483K:

2 3
CO(g)+2H (g) CH OH(g)
K =
[CH
3
OH(g)]
[CO(g)][H
2
(g)]
=
0.00892
0.0911 0.0822
2
= 14.5
Now use AG
o
= RT lnK to calculate the change in Gibbs free energy at 483 K:
AG
o
= RT lnK

AG
o
= 8.314 483 ln(14.5)Jmol
-1
= 1.110
4
Jmol
-1
AG
o
= 11kJmol
-1

Conversion pathway approach:
K =
[CH
3
OH(g)]
[CO(g)][H
2
(g)]
=
0.00892
0.0911 0.0822
2
= 14.5
AG
o
= RT lnK = 8.314 483 ln(14.5)Jmol
-1
= 1.110
4
Jmol
-1
AG
o
= 11kJmol
-1

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
965
36. (M) Gibbs free energy for the reaction (AG
o
= AH
o
TAS
o
) can be calculated using AH
f
o

and S
o
values for CO(g), H
2
(g) and CH
3
OH(g) from Appendix D.
AH
o
= AH
f
o
(CH
3
OH(g))[AH
f
o
(CO(g))+ 2AH
f
o
(H
2
(g)]
AH
o
= 200.7kJmol
-1
(110.5kJmol
-1
+ 0kJmol
-1
) = 90.2kJmol
-1

AS
o
= S
o
(CH
3
OH(g))[S
o
(CO(g))+ 2S
o
(H
2
(g)]
AS
o
= 239.8JK
1
mol
-1
(197.7JK
1
mol
-1
+ 2130.7JK
1
mol
-1
) = 219.3JK
-1
mol
-1

AG
o
= 90.2kJmol
-1

483K (219.3)kJK
-1
mol
-1
1000
= 15.7kJmol
-1

Equilibrium constant for the reaction can be calculated using AG
o
= RT lnK
lnK =
AG
o
RT
lnK =
15.71000Jmol
1
8.314JK
1
mol
1
483K
= 3.9 K = e
3.9
= 2.010
2

The values are different because in this case, the calculated K is the thermodynamic
equilibrium constant that represents the reactants and products in their standard states. In
Exercise 35, the reactants and products were not in their standard states.


Relationships Involving AG, AG
o
, Q and K

37. (M)
( ) ( ) ( )
( ) ( ) ( )
( )( )
o
f f 2 f 2
3 1 1
p p
=2 NO g N O g 0.5 O g
=2 86.55kJ /mol 104.2kJ /mol 0.5 0.00kJ /mol =68.9kJ /mol
= ln = 8.3145 10 kJ mol K 298K ln
G G G G
RT K K


A A A A ( ( (




p
3 1 1
68.9kJ /mol
ln = = 27.8
8.3145 10 kJ mol K 298K
K




27.8 13
p
=e =8 10 K



38. (M) (a) ( ) ( ) ( )
( ) ( ) ( )
o
f 2 5 f 2 4 f 2
=2 N O g 2 N O g O g
=2 115.1kJ /mol 2 97.89kJ /mol 0.00kJ /mol =34.4kJ /mol
G G G G

A A A A ( ( (



(b)

o 3
o
p p 1 1
13.9 7
p
34.4 10 J /mol
= ln ln = = = 13.9
8.3145 J mol K 298K
=e =9 10
G
G RT K K
RT
K


A
A

39. (M) We first balance each chemical equation, then calculate the value of AG
o
with data
from Appendix D, and finally calculate the value of K
eq
with the use of A G RT K
o
ln = .
(a) ( ) ( ) ( ) ( )
2 2 2
4HCl g +O g 2H O g +2Cl s
( ) ( ) ( ) ( )
o
f 2 f 2 f f 2
=2 H O g +2 Cl g 4 HCl g O g
kJ kJ kJ kJ kJ
=2 228.6 +2 0 4 95.30 0 = 76.0
mol mol mol mol mol
G G G G G

A A A A A ( ( ( (

| | | |

| |
\ . \ .

o 3
+30.7 13
1 1
+76.0 10 J /mol
ln = = =+30.7 =e =2 10
8.3145J mol K 298K
G
K K
RT

A

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
966
(b) ( ) ( ) ( ) ( )
2 3 2 3 4 2
3Fe O s +H g 2FeO s +H O g

( ) ( ) ( ) ( )
( ) ( )
o
f 3 4 f 2 f 2 3 f 2
=2 FeO s + H O g 3 FeO s H g
=2 1015kJ /mol 228.6kJ /mol 3 742.2kJ /mol 0.00kJ /mol
= 32kJ /mol
G G G G G

A A A A A ( ( ( (

o 3
+13 5
1 1
32 10 J /mol
ln = = =13; =e =4 10
8.3145J mol K 298K
G
K K
RT

A

(c) ( ) ( ) ( )
+ 2
4 2 4
2Ag aq +SO aq Ag SO s

AG
o
=AG
f

Ag
2
SO
4
s ( )

2AG
f

Ag
+
aq ( )

AG
f

SO
4
2
aq ( )

=618.4kJ/mol 2 77.11kJ/mol 744.5kJ/mol ( )=28.1kJ/mol

o 3
+11.3 4
1 1
28.1 10 J /mol
ln = = =11.3; =e =8 10
8.3145J mol K 298K
G
K K
RT

A

40. (E)
( ) ( ) ( ) ( )
o o o o o
2 2 2
1 1 1 1 1 1 1 1
1 1
= {CO g }+ {H g } {CO g } {H O g }
=213.7J mol K +130.7 J mol K 197.7 J mol K 188.8J mol K
= 42.1J mol K
S S S S S


A

41. (M) In this problem we need to determine in which direction the reaction
( ) ( ) ( )
2 2 3
2SO g +O g 2SO g is spontaneous when the partial pressure of SO
2
, O
2
, and
SO
3
are 1.010
-4
, 0.20 and 0.10 atm, respectively. We proceed by first determining the
standard free energy change for the reaction (AG
o
) using tabulated data in Appendix D.
Change in Gibbs free energy for the reaction (AG) is then calculated by employing the
equation
o
ln
p
G G RT Q A = A + , where Q
p
is the reaction quotient. Based on the sign of
AG, we can determine in which direction is the reaction spontaneous.
Stepwise approach:
First determine AG
o
for the reaction using data in Appendix D:
( ) ( ) ( )
2 2 3
2SO g +O g 2SO g

AG
o
=2AG
f
o
SO
3
g
( )

2AG
f
o
SO
2
g
( )

AG
f
o
O
2
g
( )

AG
o
= 2 (371.1 kJ/mol) 2 (300.2 kJ/mol) 0.0 kJ/mol

AG
o
= 141.8kJ
Calculate AG by employing the equation
o
ln
p
G G RT Q A = A + , where Q
p
is the reaction
quotient:

o
ln
p
G G RT Q A = A +

( )
( ) ( )
2
3
p
2
2 2
{SO g }
=
{O g } {SO g }
P
Q
P P

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
967

( )
( )( )
2
6
p 2
4
0.10 atm
= 5.0 10
0.20 atm 1.0 10 atm
Q

G A =141.8 kJ +(8.3145 10
3
kJ /Kmol )(298 K)ln(5.0 10
6
)
G A =141.8 kJ +38.2 kJ =104 kJ .
Examine the sign of AG to decide in which direction is the reaction spontaneous:
Since G A is negative, the reaction is spontaneous in the forward direction.
Conversion pathway approach:

AG
o
=2AG
f
o
SO
3
g
( )

2AG
f
o
SO
2
g
( )

AG
f
o
O
2
g
( )

AG
o
= 2 (371.1 kJ/mol) 2 (300.2 kJ/mol) 0.0 kJ/mol=-141.8kJ


o
ln
p
G G RT Q A = A +


Q
p
=
P{SO
3
g
( )
}
2
P{O
2
g
( )
}P{SO
2
g
( )
}
2
=
0.10 atm
( )
2
0.20 atm
( )
1.010
4
atm
( )
2
= 5.010
6

G A =141.8 kJ +(8.3145 10
3
kJ /Kmol )(298 K)ln(5.0 10
6
)=-104 kJ .
Since G A is negative, the reaction is spontaneous in the forward direction.

42. (M) We begin by calculating the standard free energy change for the reaction:
( ) ( ) ( )
2 2
H g +Cl g 2HCl g

( ) ( ) ( )
f f 2 f 2
=2 HCl g Cl g H g
2 ( 95.30 kJ /mol) 0.0 kJ /mol 0.0 kJ /mol 190.6kJ
G G G G A A A A ( ( (

= =



Now we can calculate G A by employing the equation
o
ln
p
G G RT Q A = A + , where

( )
( ) ( )
2
p
2 2
{HCl g }
=
{H g } {Cl g }
P
Q
P P
;
( )
( )( )
2
p
0.5 atm
= 1
0.5 atm 0.5 atm
Q =

G A =190.6 kJ +(8.3145 10
3
kJ /Kmol )(298 K)ln(1)
G A =190.6 kJ +0 kJ =190.6 kJ .

Since G A is negative, the reaction is spontaneous in the forward direction.

43. (M) In order to determine the direction in which the reaction is spontaneous, we need to
calculate the non-standard free energy change for the reaction. To accomplish this, we will
employ the equation
o
ln
c
G G RT Q A = A + , where


( ) ( )
( )
+
3 3 2
c
3 2
[H O aq ] [CH CO aq ]
=
[CH CO H aq ]
Q

;
( )
2
3
5
c
1.0 10 M
= 1.0 10
(0.10 M)
Q

=

G A =27.07 kJ +(8.3145 10
3
kJ /Kmol )(298 K)ln(1.0 10
5
)
G A =27.07 kJ +(28.53 kJ ) =1.46 kJ .

Since G A is negative, the reaction is spontaneous in the forward direction.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
968
44. (M) As was the case for exercise 39, we need to calculate the non-standard free energy
change for the reaction. Once again, we will employ the equation
o
ln G G RT Q A = A + , but
this time

( ) ( )
( )
+
4
c
3
[NH aq ] [OH aq ]
=
[NH aq ]
Q

;
( )
2
3
5
c
1.0 10 M
= 1.0 10
(0.10 M)
Q

=
G A =29.05 kJ +(8.3145 10
3
kJ /Kmol)(298 K)ln(1.0 10
5
)
G A =29.05 kJ +(28.53 kJ ) =0.52 kJ .
Since G A is positive, the reaction is spontaneous in the reverse direction.

45. (E) The relationship AS
o
=(AG
o
AH
o
)/T (Equation (b)) is incorrect. Rearranging this
equation to put AG
o
on one side by itself gives AG
o
=AH
o
+TAS
o
. This equation is not
valid. The TAS
o
term should be subtracted from the AH
o
term, not added to it.

46. (E) The AG
o
value is a powerful thermodynamic parameter because it can be used to
determine the equilibrium constant for the reaction at each and every chemically
reasonable temperature via the equation AG
o
=RT ln K.

47. (M) (a) To determine K
p
we need the equilibrium partial pressures. In the ideal gas law,
each partial pressure is defined byP nRT V = / . Because R, T, and V are the same for
each gas, and because there are the same number of partial pressure factors in the
numerator as in the denominator of the K
p
expression, we can use the ratio of amounts
to determineK
p
.

{ } { }
{ } { }
{ } { }
{ } { }
2 2 2
p
2 2 2 2 2 2
CO(g) H O(g) CO(g) H O(g) 0.224mol CO 0.224mol H O
= = = =0.659
CO (g) H (g) CO (g) H (g) 0.276mol CO 0.276mol H
P P n n
K
P P n n

(b)

( )
o 1 1
1000K p
3
= ln = 8.3145J mol K 1000. K ln 0.659
=3.467 10 J /mol =3.467 kJ /mol
G RT K

A

(c)
2
p p
2 2
0.0340mol CO 0.0650mol H O
= =0.31 0.659=
0.0750mol CO 0.095mol H
Q K

<

Since Q
p
is smaller than K
p
, the reaction will proceed to the right, forming products,
to attain equilibrium, i.e., AG =0.

48. (M) (a) We know thatK
p
=K
c
RT ( )
An
. For the reaction ( ) ( ) ( )
2 2 3
2SO g +O g 2SO g ,
( )
gas
=2 2+1 = 1 n A , and therefore a value of K
p
can be obtained.


K
p
=K
c
RT
( )
1
=
2.810
2
0.08206L atm
mol K
1000K
= 3.41= K
We recognize that
p
= K K since all of the substances involved in the reaction are
gases. We can now evaluateAG
o
.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
969

( )
o 4
eq
8.3145J
= ln = 1000K ln 3.41 = 1.02 10 J /mol = 10.2kJ /mol
mol K
G RT K A
(b) We can evaluate Q
c
for this situation and compare the value with that of K
c
=2.8 10
2
to
determine the direction of the reaction to reach equilibrium.
2
3
2
2 3
c c 2 2
2 2
2 2
0.72mol SO
2.50L [SO ]
45 2.8 10
[SO ] [O ]
0.40mol SO 0.18mol O
2.50L 2.50L
Q K
| |
|
\ .
= = = < =
| | | |

| |
\ . \ .

Since Q
c
is smaller than K
c
the reaction will shift right, producing sulfur trioxide
and consuming sulfur dioxide and molecular oxygen, until the two values are equal.

49. (M) (a)
c
= K K

( )( )
o 3 1 1
eq
= ln = 8.3145 10 kJ mol K 445+273 K ln 50.2= 23.4kJ G RT K

A
(b) ( ) ( )
g
n 1/2
13 13
p c
= = =1.7 10 0.0821 298 =8.4 10 K K K RT
A


( )( ) ( )
o 3 1 1 13
p
o
= ln = 8.3145 10 kJ mol K 298K ln 8.4 10
=+68.9kJ /mol
G RT K
G

A
A

(c) ( ) ( )
+1
3
p c
= = =4.61 10 0.08206 298 =0.113
n
K K K RT
A


AG
o
=RT lnK
p
= 8.314510
3
kJ mol
1
K
1
( )
298K ( )ln 0.113 ( )=+5.40kJ/mol
(d)
6
c
= =9.14 10 K K



( )( ) ( )
o 3 1 1 6
c
o
= ln = 8.3145 10 kJ mol K 298K ln 9.14 10
=+28.7 kJ /mol
G RT K
G

A
A

50. (M) (a) The first equation involves the formation of one mole of Mg
2+
aq ( ) from
Mg OH ( )
2
s ( ) and ( )
+
2H aq , while the second equation involves the formation of
only half-a-mole of Mg
2+
aq ( ). We would expect a free energy change of half the
size if only half as much product is formed.

(b) The value of K for the first reaction is the square of the value of K for the second
reaction. The equilibrium constant expressions are related in the same fashion.


K
1
=
Mg
2+

H
+

2
=
Mg
2+

1/2
H
+

|
\

|
.
|
|
2
= K
2
( )
2


(c) The equilibrium solubilities will be the same regardless which expression is used.
The equilibrium conditions (solubilities in this instance) are the same no matter how
we choose to express them in an equilibrium constant expression.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
970
51. (E)
( )( ) ( )
o 3 1 1 11
p
= ln = 8.3145 10 kJ mol K 298K ln 6.5 10 = 67.4kJ /mol G RT K

A
( ) ( ) ( )
2 2
CO g +Cl g COCl g
o
= 67.4kJ /mol G A
( ) ( ) ( )
1
2 2
C graphite + O g CO g
f
= 137.2kJ /mol G

A

( ) ( ) ( ) ( )
1
2 2 2 2
C graphite + O g +Cl g COCl g
f
= 204.6kJ /mol G

A
A

G
f
of COCl
2
g ( ) given in Appendix D is 204.6 kJ /mol, thus the agreement is excellent.

52. (M) In each case, we first determine the value of AG
o
for the solubility reaction. From
that, we calculate the value of the equilibrium constant,
sp
K , for the solubility reaction.
(a) ( ) ( ) ( )
+
AgBr s Ag aq +Br aq

( ) ( ) ( )
( )
o +
f f f
= Ag aq + Br aq AgBr s
=77.11kJ /mol 104.0kJ /mol 96.90kJ /mol =+70.0kJ /mol
G G G G

( ( A A A A (



3 o
28.2 13
sp
1 1
70.0 10 J /mol
ln = = = 28.2; =e =6 10
8.3145J mol K 298.15K
G
K K
RT


A

(b) ( ) ( ) ( )
2+ 2
4 4
CaSO s Ca aq +SO aq

( ) ( ) ( )
( )
o o 2 o o 2+
f f 4 f 4
= Ca aq + SO aq CaSO s
= 553.6kJ /mol 744.5kJ /mol 1332kJ /mol =+34kJ /mol
G G G G

( ( A A A A (



3 o
14 7
sp
1 1
34 10 J /mol
ln = = = 14; =e =8 10
8.3145J mol K 298.15K
G
K K
RT


A

(c) ( ) ( ) ( ) ( )
3+
3
Fe OH s Fe aq +3OH aq

AG
o
=AG
f

Fe
3+
aq ( )

+3AG
f

OH

aq ( )

AG
f

Fe OH ( )
3
s ( )

=4.7kJ/mol +3 157.2kJ/mol ( ) 696.5kJ/mol ( )=+220.2kJ/mol

3 o
88.83 39
sp
1 1
220.2 10 J /mol
ln = = = 88.83 =e =2.6 10
8.3145J mol K 298.15K
G
K K
RT


A

53. (M)(a) We can determine the equilibrium partial pressure from the value of the equilibrium
constant.

o 3
o
p p
1 1
58.54 10 J /mol
= ln ln = = = 23.63
8.3145J mol K 298.15K
G
G RT K K
RT

A
A

( ) ( ) ( )
2
1/2 23.63 11 11 21
p 2 2
= {O g } =e =5.5 10 {O g }= 5.5 10 =3.0 10 atm K P P



(b) Lavoisier did two things to increase the quantity of oxygen that he obtained. First, he ran
the reaction at a high temperature, which favors the products (i.e., the side with
molecular oxygen.) Second, the molecular oxygen was removed immediately after it was
formed, which causes the equilibrium to shift to the right continuously (the shift towards
products as result of the removal of the O
2
is an example of Le Chtelier's principle).
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
971

54. (D) (a) We determine the values of AH
o
and AS
o
from the data in Appendix D, and then
the value of AG
o
at 25 =298

C K.
( ) ( ) ( ) ( )
( ) ( ) ( )
o
f 3 f 2 f 2 f 2
= CH OH g + H O g CO g 3 H g
= 200.7kJ /mol + 241.8kJ /mol 393.5kJ /mol 3 0.00kJ /mol = 49.0kJ /mol
H H H H H

A A A A A ( ( ( (



( ) ( ) ( ) ( )
o o o o o
3 2 2 2
1 1 1 1
= CH OH g + H O g CO g 3 H g
=(239.8+188.8 213.7 3 130.7)J mol K = 177.2J mol K
S S S S S

A ( ( ( (



( )
o o o 1 1
= = 49.0kJ /mol 298K 0.1772kJ mol K =+3.81kJ /mol G H T S

A A A
Because the value of AG
o
is positive, this reaction does not proceed in the forward
direction at 25

C.

(b) Because the value of AH
o
is negative and that of AS
o
is negative, the reaction is non-
spontaneous at high temperatures, if reactants and products are in their standard states.
The reaction will proceed slightly in the forward direction, however, to produce an
equilibrium mixture with small quantities of ( )
3
CH OH g and H
2
O g ( ). Also, because
the forward reaction is exothermic, this reaction is favored by lowering the
temperature. That is, the value of K increases with decreasing temperature.

(c)
( )
o o o 1 1
500K
3
p
= = 49.0kJ /mol 500.K 0.1772kJ mol K =39.6kJ /mol
=39.6 10 J /mol = ln
G H T S
RT K

A A A


3
9.53 5
p p
1 1
39.6 10 J /mol
ln 9.53; e 7.3 10
8.3145J mol K 500. K
G
K K
RT


A
= = = = =

(d) Reaction: CO
2
g ( )+ 3H
2
g ( )

CH
3
OH g ( ) +H
2
O g ( )
Initial: 1.00 atm 1.00 atm 0 atm 0 atm
Changes: x atm 3x atm +x atm +x atm
Equil: (1.00 x ) atm 1.00 3x ( ) atm x atm x atm
{ } { }
{ } { } ( )( )
3 2 5 2
p 3 3
2 2
CH OH H O
=7.3 10 = =
CO H 1.00 1.00 3
P P
x x
K x
P P x x

~


{ }
5 3
3
7.3 10 8.5 10 atm P CH OH x

= = = Our assumption, that 3 1.00 x atm, is valid.

AG
o
and K

as Function of Temperature

55 (M)(a)
( ) ( ) ( ) ( )
o o o o o
2 3 2 2 3
J J J J J
K mol K mol K mol K mol K mol
= Na CO s + H O l + CO g 2 NaHCO s
=135.0 +69.91 +213.7 2 101.7 = 215.2
S S S S S A ( ( ( (

| |
+
|
\ .


Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
972
(b)
( ) ( ) ( ) ( )
o
f 2 3 f 2 f 2 f 3
kJ kJ kJ kJ kJ
mol mol mol mol mol
= Na CO s + H O l + CO g 2 NaHCO s
= 1131 285.8 393.5 2 950.8 =+91
H H H H H

A A A A A ( ( ( (

| |

|
\ .


(c)
( )( )
o o o 3 1 1
= =91kJ /mol 298K 215.2 10 kJ mol K
=91kJ /mol 64.13kJ /mol =27 kJ /mol
G H T S

A A A

(d)
3 o
o
1 1
27 10 J /mol
= ln ln = = = 10.9
8.3145J mol K 298K
G
G RT K K
RT

A
A

K =e
10.9
=210
5


56. (M) (a)

( ) ( ) ( ) ( ) ( )
3 2 2 2 3
o o o o o o
o
o
CH CH OH g H O g CO g H g CH OH g
J J J J J
K mol K mol K mol K mol K mol
J
K mol
= + 2
=282.7 +188.8 197.7 2 130.7 239.8
= 227.4
S S S S S S
S
S
( ( ( ( (

| |
|
\ .
A
A
A



( ) | | ( ) ( ) ( ) | | ( ) | |
3 2 2 3 2
o
f f f f f
o
o
CH CH OH g H g CH OH g H O g CO g
kJ kJ kJ kJ kJ
mol mol mol mol mol
kJ
mol
= + 2
= 235.1 241.8 110.5 2 0.00 200.7
= 165.7
H H H H H H
H
H

( (

| | | | | |
| | |
\ . \ . \ .
A A A A A A
A
A


( )
o 3
kJ kJ kJ kJ kJ
mol K mol mol mol mol
= 165.7 298K 227.4 10 = 165.4 +67.8 = 97.9 G

| |
|
|
\ .
A


(b) AH
o
< 0for this reaction. Thus it is favored at low temperatures. Also, because
A n
gas
=+2 4= 2, which is less than zero, the reaction is favored at high pressures.

(c) First we assume that neither AS
o
nor AH
o
varies significantly with temperature. Then
we compute a value for AG
o
at 750 K. From this value of AG
o
, we compute a value
for K
p
.


AG
o
=AH
o
TAS
o
=165.7kJ/mol 750.K
( )
227.410
3
kJ mol
1
K
1
( )
=165.7kJ/mol +170.6kJ/mol =+4.9kJ/mol =RT lnK
p



lnK
p
=
AG
o
RT
=
4.
9
10
3
J/mol
8.3145J mol
1
K
1
750.K
=0.79 K
p
=e
0.79
=0.5

57. (E) In this problem we are asked to determine the temperature for the reaction between
iron(III) oxide and carbon monoxide to yield iron and carbon dioxide given AG
o
, AH
o
,
and AS
o
. We proceed by rearranging AG
o
=AH
o
TAS
o
in order to express the
temperature as a function of AG
o
, AH
o
, and AS
o
.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
973
Stepwise approach:
Rearrange

AG
o
=AH
o
TAS
o
in order to express T as a function of AG
o
, AH
o
, and AS
o
:


AG
o
=AH
o
TAS
o
TAS
o
=AH
o
AG
o
T=
AH
o
AG
o
AS
o

Calculate T:


T =
24.810
3
J 45.510
3
J
( )
15.2J/K
=1.3610
3
K
Conversion pathway approach:


AG
o
=AH
o
TAS
o
T =
AH
o
AG
o
AS
o
=
24.810
3
J 45.510
3
J
( )
15.2J/K
=1.3610
3
K

58. (E) We use the van't Hoff equation with
o 5
1
= 1.8 10 J /mol, =800 H T A . K,

T
2
=100. =373

C K, andK
1
2
=9.1 10 .

ln
K
2
K
1
=
AH
o
R
1
T
1

1
T
2
|
\

|
.
|
=
1.810
5
J/mol
8.3145J mol
1
K
1
1
800K

1
373K
|
\

|
.
|
=31

( )( )
31 13 13 2 16 2 2
2
2
1
=e =2.9 10 = = 2.9 10 9.1 10 =3 10
9.1 10
K K
K
K

59. (M) We first determine the value of AG
o
at 400 C

, from the values of AH

o
and AS
o
,
which are calculated from information listed in Appendix D.
( ) ( ) ( )
( ) ( ) ( )
o
f 3 f 2 f 2
2
=2 NH g N g 3 H g
=2 46.11kJ /mol 0.00kJ /mol 3 0.00 kJ /mol = 92.22kJ /mol N
H H H H

A A A A ( ( (




( ) ( ) ( )
( ) ( ) ( )
o o o o
3 2 2
1 1 1 1 1 1 1 1
=2 NH g N g 3 H g
=2 192.5J mol K 191.6J mol K 3 130.7J mol K = 198.7J mol K
S S S S

A ( ( (




( )
o o o 1 1
p
= = 92.22kJ /mol 673K 0.1987kJ mol K
=+41.51kJ /mol = ln
G H T S
RT K

A A A

o 3
7.42 4
p p
1 1
41.51 10 J /mol
ln = = = 7.42; =e =6.0 10
8.3145J mol K 673K
G
K K
RT


A

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
974
60. (M) (a)

( ) ( ) ( ) ( )
( ) ( )
o
f 2 f 2 f f 2
= CO g + H g CO g H O g
= 393.5kJ /mol 0.00kJ /mol 110.5kJ /mol 241.8kJ /mol = 41.2kJ /mol
H H H H H

A A A A A ( ( ( (





( ) ( ) ( ) ( )
o o o o o
2 2 2
1 1 1 1 1 1 1 1
1 1
= CO g + H g CO g H O g
=213.7J mol K +130.7J mol K 197.7J mol K 188.8J mol K
= 42.1J mol K
S S S S S


A ( ( ( (

AG
o
= AH
o
TAS
o
= 41.2kJ/mol 298.15K (42.110
3
)kJ/molK
AG
o
= 41.2kJ/mol +12.6kJ/mol = 28.6kJ/mol


(b)
AG
o
=AH
o
T AS
o
=41.2kJ/mol 875K ( ) 42.110
3
kJ mol
1
K
1
( )
=41.2kJ/mol +36.8kJ/mol =4.4kJ/mol =RT lnK
p

o 3
+0.60
p p
1 1
4.4 10 J /mol
ln = = =+0.60 =e =1.8
8.3145J mol K 875K
G
K K
RT

A

61. (M) We assume that both AH
o
and AS
o
are constant with temperature.
AH
o
=2AH
f

SO
3
g ( )

2AH
f

SO
2
g ( )

AH
f

O
2
g ( )

=2 395.7kJ/mol ( ) 2 296.8kJ/mol ( ) 0.00kJ/mol ( )=197.8kJ/mol

( ) ( ) ( )
( ) ( ) ( )
o o o o
3 2 2
1 1 1 1 1 1
1 1
=2 SO g 2 SO g O g
=2 256.8J mol K 2 248.2J mol K 205.1J mol K
= 187.9J mol K
S S S S


A ( ( (

o
o o o o o
o
= = ln = ln =
ln
H
G H T S RT K H T S RT K T
S R K
A
A A A A A
A

( )
3
1 1 1 1 6
197.8 10 J /mol
= 650K
187.9J mol K 8.3145J mol K ln 1.0 10
T


~


This value compares very favorably with the value of T =6.37 10
2
that was obtained in
Example 19-10.

62. (E) We use the van't Hoff equation to determine the value of
o
(448 C =721K H A

and
350 C =623K)

.
ln
K
1
K
2
=
AH
o
R
1
T
2

1
T
1
|
\

|
.
|
=ln
50.0
66.9
=0.291=
AH
o
R
1
623

1
721
|
\

|
.
|
=
AH
o
R
2.210
4
( )

o
3
4 -1
o 3 -1 -1 3 -1 -1
0.291
= = 1.3 10 K;
2.2 10 K
= 1.3 10 K 8.3145 J K mol = 11 10 J mol = 11kJ mol
H
R
H

A


Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
975
63. (M) (a)
o 3
2
1 1
1 1 2
1 1 57.2 10 J /mol 1 1
ln = = = 2.11
8.3145J mol K 298K 273K
K H
K R T T

| | | | A

| |
\ . \ .


2.11 2
2
1
=e =0.121 =0.121 0.113=0.014at 273K
K
K
K

(b) ln
K
2
K
1
=
AH
o
R
1
T
1

1
T
2
|
\

|
.
|
=
57.210
3
J/mol
8.3145J mol
1
K
1
1
T
1

1
298K
|
\

|
.
|
=ln
0.113
1.00
=2.180
1
T
1

1
298K
|
\

|
.
|
=
2.180 8.3145
57.210
3
K
1
=3.1710
4
K
1

4 3 4 3 1
1
1
1 1
= 3.17 10 =3.36 10 3.17 10 =3.04 10 K ; =329K
298
T
T



64. (D) First we calculate AG
o
at 298 K to obtain a value for K
eq
at that temperature.
( ) ( ) ( )
( ) ( )
o
f 2 f f 2
=2 NO g 2 NO g O g
=2 51.31kJ /mol 2 86.55kJ /mol 0.00kJ /mol = 70.48kJ /mol
G G G G

A A A A ( ( (



3
28.43 12
70.48 10 J /mol K
ln 28.43 e 2.2 10
8.3145J
298.15 K
mol K
G
K K
RT
A
= = = = =

Now we calculate AH
o
for the reaction, which then will be inserted into the van't Hoff equation.
AH
o
=2AH
f

NO
2
g ( )

2AH
f

NO g ( )

AH
f

O
2
g ( )

=2 33.18kJ/mol ( ) 2 90.25kJ/mol ( ) 0.00kJ/mol =114.14kJ/mol

o 3
2
1 1
1 1 2
1 1 114.14 10 J /mol 1 1
ln = = = 9.26
8.3145J mol K 298K 373K
K H
K R T T

| | | | A

| |
\ . \ .

9.26 5 5 12 8 2
2
1
=e =9.5 10 ; =9.5 10 2.2 10 =2.1 10
K
K
K


Another way to find K at 100 C is to compute AH
o
114.14kJ/mol ( ) from AH
f
o
values
and
( )
o 1 1
146.5J mol K S

A from S
o
values. Then determine AG
o
(59.5 kJ /mol), and
find K
p
with the expression A G RT K
o
p
ln = . Not surprisingly, we obtain the same
result,
8
p
=2.2 10 K .

65. (M) First, the van't Hoff equation is used to obtain a value of AH
o
. 200 =473

C K and
260 =533

C K .
o 11 o
2
8 1 1
1 1 2
1 1 2.15 10 1 1
ln = =ln =6.156=
4.56 10 8.3145J mol K 533K 473K
K H H
K R T T

| | | | A A

| |

\ . \ .

6.156= 2.9 10 =
6.156
2.9 10
= 2.1 10 = 2.1 10
5
5
5 2
A A

H H
o o
J / mol kJ / mol
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
976
Another route to AH
o
is the combination of standard enthalpies of formation.
( ) ( ) ( ) ( )
2 4 2
CO g +3H g CH g +H O g
( ) ( ) ( ) ( )
( )
o
f 4 f 2 f f 2
= CH g + H O g CO g 3 H g
= 74.81kJ /mol 241.8 kJ /mol 110.5 3 0.00kJ /mol = 206.1kJ /mol
H H H H H

A A A A A ( ( ( (




Within the precision of the data supplied, the results are in good agreement.

66. (D) (a)
t,

C
T , K
1/ ,
1
T K

K
p
ln
p
K

30. 303
3.30 10
3

1.66 10
5

11.006

50. 323
3.10 10
3

3.90 10
4

7.849

70. 343
2.92 10
3

6.27 10
3

5.072

100. 373
2.68 10
3

2.31 10
1

1.465















The slope of this graph is A H R
o
/ = 1.54 10
4
K

( )( )
o 1 1 4 3
= 8.3145 J mol K 1.54 10 K =128 10 J /mol =128kJ /mol H

A

(b) When the total pressure is 2.00 atm, and both gases have been produced from NaHCO
3
s ( ),

( ) ( )
2 2
{H O g }= {CO g }=1.00 atm P P

( ) ( ) ( )( )
p 2 2
= {H O g } {CO g }=1.00 1.00 =1.00 K P P

Thus, lnK
p
=ln 1.00 ( )=0.000. The corresponds to
3 1
1/ =2.59 10 K T

;
=386 K T .
We can compute the same temperature from the van't Hoff equation.

Plot of ln(K
p
) versus 1/T
y = -15402.12x + 39.83
-12
-10
-8
-6
-4
-2
0
0.0026 0.0029 0.0032
1/T(K-1)
l
n

K
p
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
977
ln
K
2
K
1
=
AH
o
R
1
T
1

1
T
2
|
\

|
.
|
=
12810
3
J/mol
8.3145J mol
1
K
1
1
T
1

1
303K
|
\

|
.
|
=ln
1.6610
5
1.00
=11.006


1
T
1

1
303K
|
\

|
.
|
=
11.006 8.3145
12810
3
K
1
=7.1510
4
K
1


4 3 4 3 1
1
1
1 1
= 7.15 10 =3.30 10 7.15 10 =2.59 10 K ; =386K
303
T
T



This temperature agrees well with the result obtained from the graph.

Coupled Reactions

67. (E) (a) We compute AG
o
for the given reaction in the following manner


( ) ( ) ( ) ( )
( ) ( )
o
f 4 f 2 f 2 f 2
= TiCl l + O g TiO s 2 Cl g
= 804.2kJ /mol +0.00kJ /mol 944.7kJ /mol 2 0.00kJ /mol
=+140.5kJ /mol
H H H H H

A A A A A ( ( ( (




( ) ( ) ( ) ( )
( ) ( )
1 1 1 1 1 1
o o o o o
4 2 2 2
1 1
1 1
J mol K J mol K J mol K
= TiCl l + O g TiO s 2 Cl g
=252.3 +205.1J mol K 50.33 2 223.1
= 39.1J mol K
S S S S S


A ( ( ( (

( )( )
o o o 3 1 1
= =+140.5kJ /mol 298K 39.1 10 kJ mol K
=+140.5kJ /mol +11.6kJ /mol =+152.1kJ /mol
G H T S

A A A


Thus the reaction is non-spontaneous at25

C. (we also could have used values of AG

f
o

to calculateAG
o
).

(b) For the cited reaction, AG
o
=2AG
f

CO
2
g ( )

2AG
f

CO g ( )

AG
f

O
2
g ( )

AG
o
=2 394.4kJ/mol ( ) 2 137.2kJ/mol ( ) 0.00kJ/mol =514.4kJ/mol

Then we couple the two reactions.

( ) ( ) ( ) ( )
2 2 4 2
TiO s +2Cl g TiCl l +O g
o
=+152.1kJ /mol G A

( ) ( ) ( )
2 2
2CO g +O g 2CO g
o
= 514.4kJ /mol G A
_________________________________________________________________
( ) ( ) ( ) ( ) ( )
o
2 2 4 2
TiO s +2Cl g +2CO g TiCl l +2CO g ; = 362.3 kJ /mol G A

The coupled reaction has AG
o
< 0, and, therefore, is spontaneous.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
978
68. (E) If AG
o
< 0 for the sum of coupled reactions, the reduction of the oxide with carbon is
spontaneous.

(a) ( ) ( ) ( )
1
2 2
NiO s Ni s + O g
o
=+115kJ G A
( ) ( ) ( )
1
2 2
C s + O g CO g
o
= 250kJ G A

( ) ( ) ( ) ( ) Net: NiO +C s Ni s +CO g s
o
=+115kJ 250kJ = 135kJ G A
Therefore the coupled reaction is spontaneous

(b) ( ) ( ) ( )
1
2 2
MnO s Mn s + O g
o
=+280kJ G A
( ) ( ) ( )
1
2 2
C s + O g CO g
o
= 250kJ G A

( ) ( ) ( ) ( ) Net: MnO s +C s Mn s +CO g
o
=+280kJ 250kJ =+30kJ G A
Therefore the coupled reaction is non-spontaneous

(c) ( ) ( ) ( )
2 2
TiO s Ti s +O g
o
=+630kJ G A
( ) ( ) ( )
2
2C s +O g 2CO g ( )
o
=2 250 kJ = 500 kJ G A

( ) ( ) ( ) ( )
2
Net: TiO s +2C s Ti s +2CO g
o
=+630kJ 500kJ =+130kJ G A
Therefore the coupled reaction is non-spontaneous

69. (E) In this problem we need to determine if the phosphorylation of arginine with ATP is a
spontaneous reaction. We proceed by coupling the two given reactions in order to
calculate AG
t
o
for the overall reaction. The sign of AG
t
o
can then be used to determine
whether the reaction is spontaneous or not.
Stepwise approach:
First determine AG
t
o
for the coupled reaction:

ATP+H
2
O ADP+P AG
t
o
= 31.5kJmol
-1
arginine+P phosphorarginine+H
2
O AG
t
o
= 33.2kJmol
-1


___________________________________________

ATP+arginine phosphorarginine+ADP
AG
o
= (31.5+ 33.2)kJmol
-1
= 1.7kJmol
-1

Examine the sign of AG
t
o
:
AG
t
o
> 0. Therefore, the reaction is not spontaneous.
Conversion pathway approach:
AG
t
o
for the coupled reaction is:

ATP+arginine phosphorarginine+ADP
AG
o
= (31.5+ 33.2)kJmol
-1
= 1.7kJmol
-1

Since AG
t
o
> 0, the reaction is not spontaneous.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
979
70. (E) By coupling the two reactions, we obtain:

Glu
-
+NH
4
+
Gln+H
2
O AG
t
o
= 14.8kJmol
-1
ATP+H
2
O ADP+P AG
t
o
= 31.5kJmol
-1

_________________________________________
Glu
-
+NH
4
+
+ATP Gln+ADP+P AG
o
= (14.8 31.5)kJmol
-1
= 16.7kJmol
-1

Therefore, the reaction is spontaneous.


INTEGRATIVE AND ADVANCED EXERCISES


71. (M) (a) The normal boiling point of mercury is that temperature at which the mercury
vapor pressure is 1.00 atm, or where the equilibrium constant for the vaporization
equilibrium reaction has a numerical value of 1.00. This is also the temperature where
0 = AG , since
eq
lnK RT G = A and 0 ) 00 . 1 ( ln = .
Hg(l) Hg(g)
1 1 1 1 1 1
f f
K mol J 0 . 99 K mol J 02 . 76 K mol J 0 . 175 )] Hg(l [ )] Hg(g [
kJ /mol 32 . 61 kJ /mol 00 . 0 kJ /mol 32 . 61 )] Hg(l [ )] Hg(g [

= = = A
= = A A = A
S S S
H H H
1 1 3
K mol J 0 . 99 J /mol 10 32 . 61 0

= A A = T S T H
K 619
K mol J 0 . 99
J /mol 10 32 . 61
1 1
3
=

=

T

(b) The vapor pressure in atmospheres is the value of the equilibrium constant, which is
related to the value of the free energy change for formation of Hg vapor.

eq f
ln kJ /mol 82 . 31 ] Hg(g) [ K RT G = = A

3
1 1
31.82 10 J /mol
ln 12.84
8.3145J mol K 298.15K
K


= =

12.84 6
e 2.65 10 atm K

= =
Therefore, the vapor pressure of Hg at 25C is 2.6510
-6
atm.

72. (M) (a) TRUE; It is the change in free energy for a process in which
reactants and products are all in their standard states (regardless of
whatever states might be mentioned in the statement of the problem).
When liquid and gaseous water are each at 1 atm at 100 C (the normal
boiling point), they are in equilibrium, so that AG =AG =0 is only true
when the difference of the standard free energies of products and reactants
is zero. A reaction with AG =0 would be at equilibrium when products
and reactants were all present under standard state conditions and the
pressure of H
2
O(g) =2.0 atm is not the standard pressure for H
2
O(g).

(b) FALSE; . 0 = AG The system is not at equilibrium.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
980
(c) FALSE; AG can have only one value at any given temperature, and that is the
value corresponding to all reactants and products in their standard states,
so at the normal boiling point AG =0 [as was also the case in answering
part (a)]. Water will not vaporize spontaneously under standard conditions
to produce water vapor with a pressure of 2 atmospheres.

(d) TRUE; . 0 > AG The process of transforming water to vapor at 2.0 atm pressure
at 100C is not a spontaneous process; the condensation (reverse) process
is spontaneous. (i.e. for the system to reach equilibrium, some H
2
O(l)
must form)
73. (D) ] BrCl(g) [ ] (g) Cl [ ] (g) Br [
f 2 f 2
1
2 f 2
1
A A + A + = A G G G G

p 2
1
2
1
ln kJ /mol 54 . 2 ) kJ /mol 98 . 0 ( ) kJ /mol 00 . 0 ( ) kJ /mol 11 . 3 ( K RT = + = + + =

02 . 1
K 15 . 298 K mol J 3145 . 8
J /mol 10 54 . 2
ln
1 1
3
p
=

=
A
=

T R
G
K
1.02
p
e 0.361 K

= =

For ease of solving the problem, we double the reaction, which squares the value of the
equilibrium constant. 130 . 0 ) 357 . 0 (
2
eq
= = K

2 2
Reaction: 2BrCl(g) Br (g) Cl (g)
Initial: 1.00mol 0mol 0mol
Changes: 2 mol mol mol
Equil: (1.00 2 )mol mol mol
x x x
x x x
+
+ +

x x
x
x
x
x
n
n n
V RT n
V RT n V RT n
P
P P
K
722 . 0 361 . 0 361 . 0
2 00 . 1
) 361 . 0 (
) 2 00 . 1 (
} BrCl(g) {
} (g) Cl { } (g) Br {
] / } BrCl(g) { [
] / } (g) Cl { [ ] / )} (g Br { [
} BrCl(g) {
} (g) Cl { } (g) Br {

2
2
2
2
2 2
2
2 2
2
2 2
p
= =

=
= = =

BrCl mol 580 . 0 2 00 . 1 Cl mol 210 . 0 Br mol 210 . 0
722 . 1
361 . 0
2 2
= = = = x x

74. (M) First we determine the value of K
p
for the dissociation reaction. If I
2
(g) is 50% dissociated,
then for every mole of undissociated I
2
(g), one mole of I
2
(g) has dissociated, producing two
moles of I(g). Thus, the partial pressure of I(g) is twice the partial pressure of I
2
(g)
(
2
I (g) 2I(g) ).
atm 333 . 0 3 2 atm 00 . 1
) (g I (g) I (g) I (g) I ) I(g (g) I total
2 2 2 2 2
= = + = + = = P P P P P P P
293 . 0 ln 34 . 1
333 . 0
) 667 . 0 (
p
2
) (g I
2
I(g)
p
2
= = = = K
P
P
K
1 1 1 1 1 1
2
2 f f
K mol J 9 . 100 K mol J 7 . 260 K mol J 8 . 180 2 ] (g) I [ ] I(g) [ 2 S
kJ /mol 2 . 151 kJ /mol 44 . 62 kJ /mol 8 . 106 2 ] (g) I [ ] I(g) [ 2

= = = A
= = A A = A
S S
H H H

Now we equate two expressions for AG and solve for T.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
981
AG = AH T AS = RT lnK
p
= 151.210
3
100.9T = 8.3145 T 0.293
151.210
3
= 100.9T 2.44T = 98.4T T =
151.210
3
98.5
= 1535K ~1.510
3
K

75. (M) (a) The oxide with the most positive (least negative) value of
f
AG is the one that
most readily decomposes to the free metal and O
2
(g), since the decomposition is the
reverse of the formation reaction. Thus the oxide that decomposes most readily is
Ag
2
O(s).

(b) The decomposition reaction is (g) O Ag(s) 4 ) O(s Ag 2
2 2
+ For this reaction
(g) O p
2
P K = . Thus, we need to find the temperature where 00 . 1
p
= K .Since
p
lnK RT G = A and 0 ) 00 . 1 ( ln = , we wish to know the temperature where 0 = AG .
Note also that the decomposition is the reverse of the formation reaction. Thus, the
following values are valid for the decomposition reaction at 298 K.
kJ /mol 20 . 11 G kJ /mol 05 . 31 + = A + = AH
We use these values to determine the value of AS for the reaction.
1 1
3 3
K mol J 6 . 66
K 298
J /mol 10 20 . 11 J /mol 10 05 . 31

+ =

= A
A A
= A A A = A A A = A
S
T
G H
S G H S T S T H G

Now we determine the value of T where 0 = AG .
C 193 K 466
K mol J 6 . 66
J /mol 0 . 0 J /mol 10 05 . 31
1 1
3
= =
+

=
A
A A
=

S
G H
T

76. (M) At 127 C =400 K, the two phases are in equilibrium, meaning that
] (red) (yellow) [ ] (red) (yellow) [ 0
f f
A A = A A = = A S S T H H S T H G
rxn rxn rxn


J /mol 10 20 . 7 yellow) ( K 400 J /mol 10 5 . 2
] K mol J 180 yellow) ( [ K 400 J 10 )] 4 . 105 ( 9 . 102 [
4 3
1 1 3
+ =
=

S
S


1 1
3 4
K mol J 186
K 400
J /mol ) 10 5 . 2 10 20 . 7 (
) yellow (

=
+
= S
Then we compute the value of the entropy of formation of the yellow form at 298 K.
1 1 1 1
f 2 2
[HgI ] [Hg(l)] [I (s)] [186 76.02 116.1] J mol K 6J mol K S S S S

A = = =
Now we can determine the value of the free energy of formation for the yellow form.

f f f
kJ J 1kJ kJ
102.9 [298K ( 6 ) ] 101.1
mol K mol 1000J mol
G H T S A = A A = =

77. (M) First we need a value for the equilibrium constant. 1% conversion means that 0.99 mol
N
2
(g) are present at equilibrium for every 1.00 mole present initially.

2 2
2
2 2
NO(g)
p
N (g) O (g) 2 2 2 2
[ {NO(g)}RT/V] {NO(g)}

[ {N (g)}RT/V][ {O (g)}RT/V] {N (g)} {O (g)}
P
n n
K K
P P n n n n
= = = =

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
982

2 2
Reaction: N (g) O (g) 2NO(g)
Initial: 1.00mol 1.00mol 0mol
Changes(1% rxn): 0.010mol 0.010mol 0.020mol
Equil: 0.99mol 0.99mol 0.020mol
+
+

2
4
(0.020)
4.1 10
(0.99)(0.99)
K

= =

The cited reaction is twice the formation reaction of NO(g), and thus


f
2 2
-1 -1 -1 -1 -1 -1 -1
-1 -1 -
H =2 H [NO(g)] =2 90.25kJ /mol =180.50kJ /mol
S =2S[NO(g)] - S[N (g)] - S[O (g)]
=2(210.7J mol K)-191.5J mol K -205.0J mol K =24.9J mol K
G =-RTlnK =-8.31447J K mol (T)ln(4.1 10
A A
A
A
4
-1 -1
-1 -1 3
) =64.85(T)
G = H-T S =64.85(T) =180.5kJ /mol -(T)24.9J mol K
180.5 10J /mol =64.85(T) +(T)24.9J mol K =89.75(T) T =2.01 10 K
A A A



78. (E) Sr(IO
3
)
2
(s)

Sr
2+
(aq) +2 IO
3
-
(aq)

AG =(2 mol(-128.0 kJ /mol) +(1 mol -500.5 kJ /mol)) (1 mol -855.1 kJ /mol) =-0.4 kJ

AG =-RTlnK =-8.31447 J K
-1
mol
-1
(298.15 K)ln K =-0.4 kJ =-400 J

ln K =0.16 and K =1.175 =[Sr
2+
][IO
3
-
]
2
Let x =solubility of Sr(IO
3
)
2

[Sr
2+
][IO
3
-
]
2
=1.175 =x(2x)
2
=4x
3
x = 0.665 M for a saturated solution of Sr(IO
3
)
2
.


79. (M) P
H2O
=75 torr or 0.0987 atm. K =(P
H2O
)
2
=(0.0987)
2
=9.74 10
-3

AG =(2 mol(-228.6 kJ /mol) +(1 mol)-918.1 kJ /mol) (1 mol)-1400.0 kJ /mol =309.0 kJ

AH =(2 mol(-241.8 kJ /mol) +(1 mol)-1085.8.1 kJ /mol) (1 mol)-1684.3 kJ /mol =114.9 kJ

AS =(2 mol(188.J /K mol) +(1 mol146.J /K mol) +(1 mol)221.3.J /K mol =302.3 J /K mol

-1 -1 -3
eq
-1 -1 -1
-1 o
G =-RTlnK =-8.3145J mol K T ln(9.74 10 ) =38.5(T)
G =38.5(T) = H-T S =114,900J mol - (T) 302.3J K mol
114,900=340.8K (T) Hence: T =337K =64 C
A
A A A

80. (D) (a)
3
1 1
131 10 J /mol
ln ln 52.8
8.3145J mol K 298.15K
G
G RT K K
RT

A
A = = = =

52.8 23 21
760mmHg
e 1.2 10 atm 8.9 10 mmHg
1atm
K

= = =

Since the system cannot produce a vacuum lower than 10
9
mmHg, this partial pressure
of CO
2
(g) won't be detected in the system.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
983
(b) Since we have the value of AG for the decomposition reaction at a specified
temperature (298.15 K), and we need AH and
AS
for this same reaction to
determine (g)} P{CO
2
as a function of temperature, obtaining either AH or
AS
will
enable us to determine the other.

(c) ] (s) [CaCO ] (g) CO [ )] CaO(s [
3 f 2 f f
A A + A = A H H H H
kJ /mol 178 ) kJ /mol 1207 ( kJ /mol 5 . 393 kJ /mol 1 . 635 + = =


H G
G H T S T S H G S
T
A A
A = A A A = A A A =


2 1 1
178 kJ /mol 131 kJ /mol 1000 J
1.6 10 J mol K
298. K 1 kJ
S

A = =


9 12
1 atm
1.0 10 mmHg 1.3 10
760 mmHg
K

= =


eq
lnK RT S T H G = A A = A ln H T S RT K A = A


3
2
2 1 1 1 1 12
178 10 J /mol
4.6 10 K
1.6 10 J mol K 8.3145J mol K ln(1.3 10 ) ln
H
T
S R K

= =

A
=
A


81. (D) ] (g) PCl [ ] (g) Cl [ )] (g PCl [
5 f 2 f 3 f
A A + A = A H H H H


3 2 5
-1 -1 -1 -1 -1 -1 -1 -1
287.0 kJ /mol 0.00 kJ /mol ( 374.9 kJ /mol) 87.9 kJ /mol
[PCl (g)] [Cl (g)] [PCl (g)]
311.8 J mol K +223.1 J mol K 364.6 J mol K =+170.3 J mol K
S S S S
= + =
A = +
=



1 1 3
K mol J 3 . 170 K 500 J /mol 10 9 . 87

= A A = A S T H G

AG
3
p
2.8 10 J /mol ln RT K = =


0.67
p p
1 1
2.8 10 J /mol
ln 0.67 e 0.51
8.3145J mol K 500K
G
K K
RT
3

A
= = = = =

atm 74 . 2
L 50 . 1
K 500 K mol atm L 08206 . 0 mol 100 . 0
] PCl [
1 1
5
=

= =

V
nRT
P
i



5 3 2
Reaction: PCl (g) PCl (g) Cl (g)
Initial: 2.74atm 0 atm 0 atm
Changes: atm atm atm
Equil: (2.74 )atm atm atm
x x x
x x x
+
+ +

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
984
3 2
p
5
2 2
[PCl ] [Cl ]
0.51
[PCl ] 2.74
0.51(2.74 ) 1.4 0.51 0.51 1.4 0
P P x x
K
P x
x x x x x

= = =

= = + =

2
4 0.51 0.26 5.6
0.96atm, 1.47atm
2 2
b b ac
x
a
+
= = =
atm 70 . 3 96 . 0 74 . 2 74 . 2 ) 74 . 2 (
2 3 5
Cl PCl PCl total
= + = + = + + = + + = x x x x P P P P

82. (M) The value of AH determined in Exercise 64 is kJ /mol 128 + = AH . We use any one of
the values of
eq p
K K = to determine a value of AG . At 30 C =303 K,
J /mol 10 77 . 2 ) 10 66 . 1 ln( ) K 303 )( K mol J 3145 . 8 ( ln
4 5 1 1
eq
+ = = = A

K RT G
Now we determine AS . A A = A S T H G

1 1
4 3
K mol J 331
K 303
J /mol 10 77 . 2 J /mol 10 128

+ =

=
A A
= A
T
G H
S
By using the appropriate S values in Appendix D, we calculate
1 1
K mol J 334

+ = AS .

83. (M) In this problem we are asked to estimate the temperature at which the vapor pressure of
cyclohexane is 100 mmHg. We begin by using Troutons rule to determine the value of
vap
H A for cyclohexane. The temperature at which the vapor pressure is 100.00 mmHg can
then be determined using ClausiusClapeyron equation.
Stepwise approach:
Use Troutons rule to find the value of
vap
H A :
J /mol 10 31 K mol J 87 K 9 . 353
3 1 1
vap nbp vap
= = A = A

S T H
Next, use ClausiusClapeyron equation to find the required temperature:

ln
P
2
P
1
=
AH
vap
R
1
T
1

1
T
2
|
\

|
.
|
= ln
100mmHg
760mmHg
=
3110
3
J/mol
8.3145J mol
1
K
1
1
353.9K

1
T
|
\

|
.
|
= 2.028
1
353.9

1
T
=
2.028 8.3145
3110
3
= 5.410
4
=
2.82610
3

1
T
1
T
= 3.3710
3
K
1
T = 297K = 24C


Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
985
Conversion pathway approach:

ln
P
2
P
1
=
AH
vap
R
1
T
1

1
T
2
|
\

|
.
|
=
T
nbp
AS
vap
R
1
T
1

1
T
2
|
\

|
.
|
1
T
1

1
T
2
|
\

|
.
|
=
R
T
nbp
AS
vap
ln
P
2
P
1

1
T
2
=
1
T
1

R
T
nbp
AS
vap
ln
P
2
P
1
1
T
2
=
1
353.9K

8.314JK
-1
mol
-1
353.9K 87JK
-1
mol
-1
ln
100mmHg
760mmHg
= 3.3710
3
T
2
= 297K=24
o
C


92. (M)(a) 2Ag(s) +
1
2
O
2
(g) Ag
2
O
AG
f
o
= AG
f
o
(Ag
2
O(s))-{2AG
f
o
(Ag(s)) +
1
2
AG
f
o
(O
2
)}
AG
f
o
= -11.2 kJ-{2(0) +
1
2
(0)}= 11.2 kJ Ag
2
O is thermodynamically stable at 25
o
C



(b) Assuming AH
o
, AS
o
are constant from 25-200
o
C (not so, but a reasonable assumption !)
AS
o
= S
o
(Ag
2
O)-{2 S
o
(Ag(s)) +
1
2
S
o
(O
2
)}= 121.3 (2(42.6) +
1
2
(205.1)) = 66.5 J/K
AG
o
= 31.0 kJ
(473 K)(-66.5 J/K)
1000 J/kJ
= AH
o
TAS
o
= +0.45 kJ
thermodynamically unstable at 200
o
C


85. (M) AG =0 since the system is at equilibrium. As well, AG =0 because this process is
under standard conditions. Since AG =AH - TAS =0. =AH =TAS

=273.15 K21.99 J
K
-1
mol
-1
=6.007 kJ mol
-1
. Since we are dealing with 2 moles of ice melting, the
values of AH and AS are doubled. Hence, AH =12.01 kJ and AS =43.98 J K
-1
.
Note: The densities are not necessary for the calculations required for this question.

86. (D) First we determine the value of K
p
that corresponds to 15% dissociation. We represent
the initial pressure of phosgene as x atm.


2 2
Reaction: COCl (g) CO(g) Cl (g)
Initial : atm 0 atm 0 atm
Changes: 0.15 atm 0.15 atm 0.15 atm
Equil: 0.85 atm 0.15 atm 0.15 atm
x
x x x
x x x
+
+ +

84.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
986


atm 870 . 0
15 . 1
00 . 1
atm 00 . 1 atm 15 . 1 atm 15 . 0 atm 15 . 0 atm 85 . 0
total
= = = = + + = x x x x x P

0230 . 0
870 . 0 85 . 0
) 870 . 0 15 . 0 (
2
COCl
Cl CO
p
2
2
=

= =
P
P P
K

Next we find the value of AH for the decomposition reaction.

) 10 18 . 1 (
0 . 373
1
668
1
71 . 15
10 44 . 4
10 7 . 6
ln
1 1
ln
3
2
9
1 2 2
1

A
= |
.
|

\
|

A
= =

=
|
|
.
|

\
|

A
=
R
H
R
H
T T R
H
K
K


4
3
10 33 . 1
10 18 . 1
71 . 15
=


=
A

R
H
,
kJ /mol 111 J /mol 10 111 3145 . 8 10 33 . 1
3 4
= = = AH
And finally we find the temperature at which K =0.0230.


C 374 K 647
10 546 . 1
1 1
10 497 . 1 10 93 . 4
10 111
3145 . 8 658 . 0 1
668
1
658 . 0
1
K 668
1
K mol J 3145 . 8
J /mol 10 111
0444 . 0
0230 . 0
ln
1 1
ln
3 3 5
3
1 1
3
1 2 2
1
= =
= = =

=
=
|
|
.
|

\
|

= =
|
|
.
|

\
|

A
=


T
T T T
T T T R
H
K
K


87. (D) First we write the solubility reaction for AgBr. Then we calculate values of AH and
AS for the reaction:
2
eq sp
AgBr(s) Ag (aq) Br (aq) [Ag ][Br ] K K s
+ +
+ = = =
AgBr(s)] [ ] (aq) Br [ )] (aq Ag [
f f f
A A + A = A
+
H H H H
kJ /mol 4 . 84 ) kJ /mol 4 . 100 ( kJ /mol 6 . 121 kJ /mol 6 . 105 + = + =
] AgBr(s) [ ] (aq) Br [ ] (aq) Ag [ + = A
+
S S S S

1 1 1 1 1 1 1 1
K mol J 0 . 48 K mol J 1 . 107 K mol J 4 . 82 K mol J 68 . 72

+ = + + =
These values are then used to determine the value of AG for the solubility reaction, and the
standard free energy change, in turn, is used to obtain the value of K.

3 1 1 1 3
3
21.4 10 2 5
sp
84.4 10 J mol (100 273)K 48.0J mol K 66.5 10 J /mol
66. 10
ln 21.4 e 5.0 10 s
8.3145J
373K
mol K
G H T S
G
K K K
RT


A = A A = + =
A
= = = = = = =

And now we compute the solubility of AgBr in mg/L.
AgBr/L mg 2 . 4
g 1
mg 1000
AgBr mol 1
AgBr g 187.77
10 0 . 5
10
= =

s

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
987
88. (M) S
298.15
=S
274.68
+AS
fusion
+AS
heating

S
298.15
= 67.15 J K
-
mol
-1
+
-1
12,660 J mol
274.68 K
+ ( )
298.15
2
274.68
J J
97.78 +0.0586 274.68
mol K mol K
T
}

S
298.15
= 67.15 J K
-1
mol
-1
+46.09 J K
-1
mol
-1
+8.07 J K
-1
mol
-1
=121.3 J K
-1
mol
-1


89. (M) S

=S
solid
+AS
fusion
+AS
heating
+AS
vaporization
+AS
pressure change

S

=128.82 J K
-1
mol
-1
+
-1
9866 J mol
278.68 K
+
298.15
278.68
J
134.0
mol K
T
dT
}
+
-1
33,850 J mol
298.15 K

+8.3145 J K
-1
mol
-1

95.13 torr
ln
760 torr
| |
|
\ .

S

=128.82 J K
-1
mol
-1
+35.40 J K
-1
mol
-1
+9.05 J K
-1
mol
-1
+113.5 J K
-1
mol
-1
+(-17.28 J K
-1
mol
-1
)
S

= 269.53 J K
-1
mol
-1


90. (D) Start by labeling the particles A, B and C. Now arrange the particles among the states.
One possibility includes A, B, and C occupying one energy state (c=0,1,2 or 3). This counts as
one microstate. Another possibility is two of the particles occupying one energy state with the
remaining one being in a different state. This possibility includes a total of three microstates.
The final set of combinations is one with each particle being in different energy state. This
combination includes a total of six microstates. Therefore, the total number of microstates in the
system is 10. See pictorial representation on the following page illustrating the three different
cases.
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
988
c=0
c=1
c=2
c=3
A B C
c=0
c=1
c=2
c=3
A B
C
1 microstate
c=0
c=1
c=2
c=3
A
B
C
1 microstate
c=0
c=1
c=2
c=3
B
A
C
1 microstate
1 microstate
3 microstates
c=0
c=1
c=2
c=3
A
B
C
1 microstate
c=0
c=1
c=2
c=3
1 microstate
c=0
c=1
c=2
c=3
1 microstate
c=0
c=1
c=2
c=3
1 microstate
c=0
c=1
c=2
c=3
1 microstate
c=0
c=1
c=2
c=3
1 microstate
6 microstates
B
A
C
C
A
B
A
C
B
B
C
A
C
B
A
All particles are in a single
energy level ( i.e. c=0)
Two particles are in one energy level (i.e. c=0) and the remaining
particle is in a different level (i.e. c=2)
All particles are in different energy levels (i.e. c=0, 1 and 2)


91. (M) (a) In the solid as the temperature increases, so do the translational, rotational, and
vibrational degrees of freedom. In the liquid, most of the vibrational degrees of freedom are
saturated and only translational and rotational degrees of freedom can increase. In the gas phase,
all degrees of freedom are saturated. (b) The increase in translation and rotation on going from
solid to liquid is much less than on going from liquid to gas. This is where most of the change in
entropy is derived.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
989
92. (D) Because KNO
3
is a strong electrolyte, its solution reaction will be:

3 2 3
( ) ( ) ( ) KNO s H O K aq NO aq
+
+ +
This reaction can be considered to be at equilibrium when the solid is in contact with a
saturated solution, i.e. the conditions when crystallization begins. The solubility, s, of the
salt, in moles per liter, can be calculated from the amount of salt weighted out and the
volume of the solution. The equilibrium constant K for the reaction will be:
K=[K
+
(aq)][NO
3
-
(aq)]=(s)(s)=s
2

In the case of 25.0 mL solution at 340 K, the equilibrium constant K is:

n(KNO
3
) =
m
M
=
20.2g
101.103gmol
1
= 0.200mol s=
n
V
=
0.200mol
0.0250L
= 8.0molL
-1
K = s
2
= 8
2
= 64

The equilibrium constant K can be used to calculate AG for the reaction using AG=-RTlnK:
AG = 8.314JK
-1
mol
-1
340K ln64= 12kJmol
-1

The values for K and AG at all other temperatures are summarized in the table below.

Volume (mL) T/(K) 1/T (K
-1
) s (molL
-1
) K lnK AG (kJ mol
-1
)
25.0 340 0.00294 8.0 64 4.2 -12
29.2 329 0.00304 6.9 48 3.9 -11
33.4 320 0.00312 6.0 36 3.6 -9.6
37.6 313 0.00320 5.3 28 3.3 -8.6
41.8 310 0.00322 4.8 23 3.1 -8.0
46.0 306 0.00327 4.3 18.5 2.9 -7.4
51.0 303 0.00330 3.9 15 2.7 -6.8

The plot of lnK v.s. 1/T provides AH (slope=-AH/R) and AS (y-intercept=AS/R) for the
reaction:
2.5
3
3.5
4
4.5
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
y =16.468 - 4145.7x R=0.99156
l
n

K
1/T (K
-1
)

AH = slope R = 4145.7 8.314JK
-1
mol
-1
= 34.5kJmol
1
AS = y intercept R = 16.468 8.314JK
-1
mol
-1
= 136.9JK
-1
mol
-1

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
990
AH for the crystallization process is -35.4 kJ mol
-1
. It is negative as expected because
crystallization is an exothermic process. Furthermore, the positive value for AS shows that
crystallization is a process that decreases the entropy of a system.


FEATURE PROBLEMS

93. (M) (a) The first method involves combining the values of AG
f
o
. The second uses

A A A G H T S
o o o
=

( ) ( )
( )
o
f 2 f 2
= H O g H O l
= 228.572kJ /mol 237.129kJ /mol =+8.557kJ /mol
G G G

A A A ( (




( ) ( )
( )
o
f 2 f 2
= H O g H O l
= 241.818kJ /mol 285.830kJ /mol =+44.012kJ /mol
H H H

A A A ( (




( ) ( )
o o o
2 2
1 1 1 1 1 1
= H O g H O l
=188.825J mol K 69.91J mol K =+118.92J mol K
S S S

A ( (

o o o
3 1 1
=
=44.012kJ /mol 298.15K 118.92 10 kJ mol K =+8.556kJ /mol
G H T S

A A A



(b) We use the average value:
o 3
=+8.558 10 J /mol = ln G RT K A
3.452
1 1
8558J /mol
ln = = 3.452; =e =0.0317 bar
8.3145J mol K 298.15K
K K

(c)
2
1atm 760mmHg
{H O}=0.0317bar =23.8mmHg
1.01325bar 1atm
P

(d)
1 1
8590J /mol
ln = = 3.465
8.3145J mol K 298.15K
K

;
3.465
7
=e =0.0312 atm K

;
2
760mmHg
{H O}=0.0313atm =23.8mmHg
1atm
P
94. (D) (a) When we combine two reactions and obtain the overall value of AG
o
, we subtract
the value on the plot of the reaction that becomes a reduction from the value on the
plot of the reaction that is an oxidation. Thus, to reduce ZnO with elemental Mg, we
subtract the values on the line labeled 2 + 2
2
Zn O ZnO from those on the line
labeled 2 + 2
2
Mg O MgO . The result for the overall AG
o
will always be
negative because every point on the zinc line is above the corresponding point on
the magnesium line

(b) In contrast, the carbon line is only below the zinc line at temperatures above about
1000

C. Thus, only at these elevated temperatures can ZnO be reduced by carbon.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
991
(c) The decomposition of zinc oxide to its elements is the reverse of the plotted reaction,
the value of AG
o
for the decomposition becomes negative, and the reaction becomes
spontaneous, where the value of AG
o
for the plotted reaction becomes positive. This
occurs above about 1850

C.

(d) The carbon line has a negative slope, indicating that carbon monoxide becomes
more stable as temperature rises. The point where CO(g) would become less stable
than 2C(s) and O
2
(g) looks to be below 1000

C (by extrapolating the line to lower

temperatures). Based on this plot, it is not possible to decompose CO(g) to C(s) and
O
2
g ( ) in a spontaneous reaction.

(e)












Reaction 1
2 CO(g) +O
2
(g) 2 CO
2
(g)

Reaction 2
C(s) +O
2
(g) CO
2
(g)

Reaction 3
2 C(s) +O
2
(g) 2 CO(g)

All three lines are straight-line plots of AG vs. T following the equation AG =AH

TAS.

The general equation for a straight line is given below with the slightly modified
Gibbs Free-Energy equation as a reference: AG =

AST + AH (here AH assumed
constant)

y =mx +b (m =AS =slope of the line)

Thus, the slope of each line multiplied by minus one is equal to the AS for the oxide
formation reaction. It is hardly surprising, therefore, that the slopes for these lines
differ so markedly because these three reactions have quite different AS values (AS
for Reaction 1 =-173 J K
1
, AS for Reaction 2 =2.86 J K
1
, AS for Reaction 3
=178.8 J K
1
)

(f) Since other metal oxides apparently have positive slopes similar to Mg and Zn, we
can conclude that in general, the stability of metal oxides decreases as the
temperature increases. Put another way, the decomposition of metal oxides to their
elements becomes more spontaneous as the temperature is increased. By contrast,
the two reactions involving elemental carbon, namely Reaction 2 and Reaction 3,
have negative slopes, indicating that the formation of CO
2
(g) and CO(g) from
graphite becomes more favorable as the temperature rises. This means that the AG
for the reduction of metal oxides by carbon becomes more and more negative with
-700
-600
-500
-400
-300
-200
-100
0
0 500 1000 1500 2000
Temperature (C)
S
t
a
n
d
a
r
d

F
r
e
e

E
n
e
r
g
y

C
h
a
n
g
e

(
k
J
)
3
1
2
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
992
increasing temperature. Moreover, there must exist a threshold temperature for each
metal oxide above which the reaction with carbon will occur spontaneously. Carbon
would appear to be an excellent reducing agent, therefore, because it will reduce
virtually any metal oxide to its corresponding metal as long as the temperature
chosen for the reaction is higher than the threshold temperature (the threshold
temperature is commonly referred to as the transition temperature).

Consider for instance the reaction of MgO(s) with graphite to give CO
2
(g) and Mg metal:
2 MgO(s) +C(s) 2 Mg(s) +CO
2
(g) AS
rxn
=219.4 J /K and AH
rxn
=809.9 kJ
T
transition
=
o
rxn
o
rxn
H
S
A
A
=
1
809.9 kJ
0.2194 kJ K

=3691 K =T
threshold
Consequently, above 3691 K, carbon will spontaneously reduce MgO to Mg metal.

95. (D) (a) With a 36% efficiency and a condenser temperature (T
l
) of 41 C =314 K,

h 1
h
efficiency 100% 36%
T T
T

= =
h
h
314
0.36
T
T

= ;
T
h
=(0.36 T
h
) +314 K; 0.64 T
h
=314 K; T
h
=4.9 10
2
K

(b) The overall efficiency of the power plant is affected by factors other than the
thermodynamic efficiency. For example, a portion of the heat of combustion of the
fuel is lost to parts of the surroundings other than the steam boiler; there are
frictional losses of energy in moving parts in the engine; and so on. To compensate
for these losses, the thermodynamic efficiency must be greater than 36%. To obtain
this higher thermodynamic efficiency, T
h
must be greater than 4.9 10
2
K.

(c) The steam pressure we are seeking is the vapor pressure of water at 4.9 10
2
K. We
also know that the vapor pressure of water at 373 K (100 C) is 1 atm. The enthalpy of
vaporization of water at 298 K is AH =AH
f
[H
2
O(g) AH
f
[H
2
O(l)] =241.8 kJ /mol
(285.8 kJ /mol) =44.0 kJ /mol. Although the enthalpy of vaporization is somewhat
temperature dependent, we will assume that this value holds from 298 K to 4.9 10
2

K, and make appropriate substitutions into the Clausius-Clapeyron equation.


( )
1
3 3 3 2
3 1
44.0 kJ mol 1 1
ln = =5.29 10 2.68 10 2.04 10
1atm 8.3145 10 kJ mol 373K 490K
P



| | | |

| |

\ . \ .

2
ln =3.39
1atm
P | |
|
\ .
;

P
2
1 atm
|
\

|
.
|
=29.7; P
2
~ 30 atm
The answer cannot be given with greater certainty because of the weakness of the
assumption of a constant H
vapn
.

(d) It is not possible to devise a heat engine with 100% efficiency or greater. For 100%
efficiency, T
l
=0 K, which is unattainable. To have an efficiency greater than 100 %
would require a negative T
l
, which is also unattainable.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
993
96. (D) (a) Under biological standard conditions:
ADP
3
+HPO
4
2
+H
+
ATP
4
+H
2
O AG
o'
=32.4 kJ /mol
If all of the energy of combustion of 1 mole of glucose is employed in the
conversion of ADP to ATP, then the maximum number of moles ATP produced is

1
1
2870 kJ mol
Maximum number = 88.6 moles ATP
32.4 kJ mol

=

(b) In an actual cell the number of ATP moles produced is 38, so that the efficiency is:

number of ATP's actually produced 38
Efficiency = 0.43
Maximum number of ATP's that can be produced 88.6
= =
Thus, the cells efficiency is about 43%.

(c) The previously calculated efficiency is based upon the biological standard state. We
now calculate the Gibbs energies involved under the actual conditions in the cell. To
do this we require the relationship between AG and AG
'
for the two coupled
reactions. For the combustion of glucose we have

AG = AG
o
'
+ RT ln
a
CO
2
6
a
H
2
O
6
a
glu
a
O
2
6
|
\

|
.
|
|

For the conversion of ADP to ATP we have

AG = AG
o
'
+ RT ln
a
ATP
a
H
2
O
a
ADP
a
P
i
H
+

/ 10
7
( )
|
\

|
.
|
|


Using the concentrations and pressures provided we can calculate the Gibbs energy
for the combustion of glucose under biological conditions. First, we need to replace
the activities by the appropriate effective concentrations. That is,

AG = AG
o
'
+ RT ln
p / p
o
( )
CO
2
6
a
H
2
O
6
glu

/ glu

o
p / p
o
( )
O
2
6
|
\

|
.
|
|
|

using
2
H O
1 a ~ for a dilute solution we obtain
( )
| | ( )
6
6
6
0.050 bar/1 bar 1
ln
glu /1 0.132 bar/1 bar
G G RT
| |

'
A = A + |
|

\ .

The concentration of glucose is given in mg/mL and this has to be converted to
molarity as follows:
1
1
1.0 mg g 1000 mL 1
[glu] = 0.00555 mol L
mL 1000 mg L 180.16 g mol

= ,

where the molar mass of glucose is 180.16 g mol
1
.
Assuming a temperature of 37
o
C for a biological system we have, for one mole of
glucose:
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
994
( )
( )
6
6
3 1
6
0.050 1
2870 10 J 8.314J K 310K ln
0.00555/1 0.132
G

| |

A = + |
|

\ .


AG = 287010
3
J + 8.314JK
1
310K ln
2.95410
3
0.00555
|
\

|
.
|

( )
3 1
2870 10 J 8.314J K 310K ln 0.5323 G

A = +

( )
3 1
2870 10 J 8.314J K 310K 0.6305 G

A = +

AG = 287010
3
J 1.62510
3
J
AG = 287210
3
J


In a similar manner we calculate the Gibbs free energy change for the conversion of
ADP to ATP:

AG = AG
o
'
+ RT ln
ATP | |/11
ADP | |/1 P
i
| |
/1 ( H
+

/10
7
)
|
\

|
.
|


3 1
7 7
0.0001
32.4 10 J 8.314J K 310K ln
0.0001 0.0001 (10 /10 )
G


| |
A = +
|

\ .


( )
3 1 4
32.4 10 J 8.314J K 310K ln 10 G

A = +

( )
3 1 3 3 3
32.4 10 J 8.314J K 310K 9.2103) 32.4 10 J 23.738 10 J 56.2 10 J G

A = + = + =

(d) The efficiency under biological conditions is

number of ATP's actually produced 38
Efficiency = 0.744
Maximum number of ATP's that can be produced 2872/56.2
= =

Thus, the cells efficiency is about 74%.

The theoretical efficiency of the diesel engine is:

h 1
h
1923 873
Efficiency 100% 100% 55%
1923
T T
T

= = =
Thus, the diesels actual efficiency is 0.78 55 % =43 %.
The cells efficiency is 74% whereas that of the diesel engine is only 43 %. Why is
there such a large discrepancy? The diesel engine supplies heat to the surroundings,
which is at a lower temperature than the engine. This dissipation of energy raises the
temperature of the surroundings and the entropy of the surroundings. A cell operates
under isothermal conditions and the energy not utilized goes only towards changing
the entropy of the cells surroundings. The cell is more efficient since it does not
heat the surroundings.

Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
995
97. (E) (a) In this case CO can exist in two states, therefore, W=2. There are N of these
states in the crystal, and so we have
S = k ln2
N
= 1.38110
23
JK
-1
6.02210
23
mol
-1
ln2= 5.8JK
-1
mol
-1

(b) For water, W=3/2, which leads to
S = k ln(
3
2
)
N
= 1.38110
23
JK
-1
6.02210
23
mol
-1
ln1.5= 3.4JK
-1
mol
-1


SELF-ASSESSMENT EXERCISES

98. (E) (a) AS
univ
or total entropy contains contributions from the entropy change of the
system (AS
sys
) and the surroundings (AS
surr
). According to the second law of
thermodynamics, AS
univ
is always greater then zero.
(b) AG
f
o
or standard free energy of formation is the free energy change for a reaction in
which a substances in its standard state is formed from its elements in their reference
forms in their standard states.
(c) For a hypothetical chemical reaction

aA+bBcC+dD, the equilibrium constant K is

defined as K =
[C]
c
[D]
d
[A]
a
[B]
b
.

99. (E) (a) Absolute molar entropy is the entropy at zero-point energy (lowest possible
energy state) and it is equal to zero.
(b) Coupled reactions are spontaneous reactions (AG<0) that are obtained by pairing
reactions with positive AG with the reactions with negative AG.
(c) Troutons rule states that for many liquids at their normal boiling points, the standard
molar entropy of vaporization has a value of approximately 87 J mol
-1
K
-1
.
(d) Equilibrium constant K for a certain chemical reaction can be evaluated using either
AG
f
o
or AH
f
o
in conjunction with S
o
(which are often tabulated). The relationship used
to calculate K is AG
o
= RT lnK .

100. (E) (a) A spontaneous process is a process that occurs in a system left to itself; once
started, no external action form outsize the system is necessary to make the process
continue. A nonspontaneous process is a process that will not occur unless some external
action is continuously applied.
(b) Second law of thermodynamics states that the entropy of universe is always greater
than zero or in other words that all spontaneous processes produce an increase in the
entropy of the universe. The third law of thermodynamics states that the entropy of
perfect pure crystal at 0K is zero.
(c) AG is the Gibbs free energy defined as AG=AH-TAS. AG
0
is the standard free energy
change.

101. (E) Second law of thermodynamics states that all spontaneous processes produce an
increase in the entropy of the universe. In other words, AS
univ
= AS
sys
+ AS
surr
> 0.
Therefore, the correct answer is (d).
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
996

102. (E) The Gibbs free energy is a function of AH, AS and temperature T. It cannot be used
to determine how much heat is absorbed from the surroundings or how much work the
system does on the surroundings. Furthermore, it also cannot be used to determine the
proportion of the heat evolved in an exothermic reaction that can be converted to various
forms of work. Since Gibbs free energy is related to the equilibrium constant of a
chemical reaction (AG = RT lnK ) its value can be used to access the net direction in
which the reaction occurs to reach equilibrium. Therefore, the correct answer is (c).

103. (M) In order to answer this question, we must first determine whether the entropy
change for the given reaction is positive or negative. The reaction produces three moles
of gas from two moles, therefore there is an increase in randomness of the system, i.e.
entropy change for the reaction is positive. Gibbs free energy is a function of enthalpy,
entropy and temperature (AG = AH TAS ). Since AH < 0 and AS > 0, this reaction
will be spontaneous at any temperature. The correct answer is (a).
104. (M) Recall that AG
o
= RT lnK . If AG
o
= 0, then it follows that AG
o
= RT lnK = 0.
Solving for K yields: lnK = 0 K = e
0
= 1. Therefore, the correct answer is (b).

105. (E) In this reaction, the number of moles of reactants equals the number of moles of
products. Therefore, K is equal to K
p
and K
c
. The correct answers are (a) and (d).

106. (M) (a) The two lines will intersect at the normal melting point of I
2
(s) which is 113.6

o
C. (b) AG
o
for this process must be equal to zero because solid and liquid are at
equilibrium and also in their standard states.

107. (M) (a) No reaction is expected because of the decrease in entropy and the expectation
that the reaction is endothermic. As a check with data from Appendix D, AG
o
=326.4
kJ mol
-1
for the reaction as written-a very large value. (b) Based on the increase in
entropy, the forward reaction should occur, at least to some extent. For this reaction
AG
o
=75.21 kJ mol
-1
. (c) AS is probably small, and AH is probably also small (one Cl-Cl
bond and one Br-Br bonds are broken and two Br-Cl bonds are formed). AG
o
should be
small and the forward reaction should occur to a significant extent. For this reaction
AG
o
=-5.07 kJ mol
-1
.

108. (M) (a) Entropy change must be accessed for the system and its surroundings (AS
univ
),
not just for the system alone. (b) Equilibrium constant can be calculated from
AG
o
(AG
o
= RT lnK ), and K permits equilibrium calculations for nonstandard
conditions.

109. (D) (a) First we need to determine AH
vap
o
which is simply equal to:
AH
vap
o
= AH
f
o
[(C
5
H
10
(g)] AH
f
o
[(C
5
H
10
(l)] = 77.2kJ/mol (105.9kJ/mol) = 28.7kJ/mol . Now
we use Troutons rule to calculate the boiling point of cyclopentane:
Chapter 19: Spontaneous Change: Entropy and Gibbs Energy
997

AS
vap
o
=
AH
vap
o
T
bp
= 87Jmol
-1
K
-1
T
bp
=
AH
vap
o
87Jmol
-1
K
-1
=
28.71000Jmol
-1
87Jmol
-1
K
-1
= 330K
T
bp
= 330K 273.15K = 57
o
C

(b) If we assume that AH
vap
o
and AS
vap
o
are independent of T we can calculate AG
vap
o
:
AG
vap,298K
o
= AH
vap
o
TAS
vap
o
= 28.7kJmol
-1
298.15K
87
1000
kJK
-1
mol
-1
= 2.8kJmol
-1

(c) Because AG
vap,298K
o
>0, the vapor pressure is less than 1 atm at 298 K, consistent with
T
bp
=57
o
C.

110. (M) (a) We can use the data from Appendix D to determine the change in enthalpy and
entropy for the reaction:

AH
o
= AH
f
o
(N
2
O(g))+ 2AH
f
o
(H
2
O(l)) AH
f
o
(NH
4
NO
3
(s))
AH
o
= 82.05kJmol
-1
+ 2 (285.8kJmol
-1
) (365.6kJmol
-1
) = 124kJmol
-1
AS
o
= S
o
(N
2
O(g))+ 2S
o
(H
2
O(l)) S
o
(NH
4
NO
3
(s))
AS
o
= 219.9JK
-1
mol
-1
+ 2 69.91JK
-1
mol
-1
151.1JK
-1
mol
-1
= 208.6JK
-1
mol
-1

(b) From the values of AH
o
and AS
o
determined in part (a) we can calculate AG
o
at
298K:

AG
o
= AH
o
TAS
o
AG
o
= 124kJmol
-1
298K
208.6kJmol
-1
K
-1
1000
= 186.1kJmol
-1

Alternatively, AG
o
can also be calculated directly using AG
f
o
values tabulated in
Appendix D.
(c) The equilibrium constant for the reaction is calculated using AG
o
= RT lnK :

AG
o
= RT lnK 186.11000Jmol
-1
= 8.314JK
-1
mol
-1
298K lnK
186100Jmol
-1
= 2477.6lnK lnK = 75.1 K = e
75.1
= 4.110
32

(d) The reaction has AH
o
< 0 and AS
o
> 0. Because AG
o
= AH
o
TAS
o
, the reaction
will be spontaneous at all temperatures.

111. (M) Recall from exercise 104 that AG
o
= 0 when K=1. Therefore, we are looking for
the diagram with smallest change in Gibbs free energy between the products and the
reactants. The correct answer is diagram (a). Notice that diagrams (b) and (c) represent
chemical reactions with small and large values of equilibrium constants, respectively.

112. (M) Carbon dioxide is a gas at room temperature. The melting point of carbon dioxide is
expected to be very low. At room temperature and normal atmospheric pressure this
process is spontaneous. The entropy of the universe if positive.

998
CHAPTER 20

ELECTROCHEMISTRY

PRACTICE EXAMPLES

1A (E) The conventions state that the anode material is written first, and the cathode material is written
last.
Anode, oxidation: Sc s ( )Sc
3+
aq ( )+3e

Cathode, reduction: ( ) ( )
+
{Ag aq +e Ag s } 3

___________________________________
Net reaction Sc s ( )+3Ag
+
aq ( )Sc
3+
aq ( )+3Ag s ( )

1B (E) Oxidation of Al(s) at the anode: Al s ( )Al
3+
aq ( )+3e

Reduction of Ag
+
aq ( ) at the cathode: Ag
+
aq ( )+e

Ag s ( )
________________
Overall reaction in cell: Al s ( )+3Ag
+
aq ( )Al
3+
aq ( )+3Ag s ( ) Diagram:
3+ +
Al(s)|Al (aq)||Ag (aq)|Ag(s)

2A (E) Anode, oxidation: Sn s ( )Sn
2+
aq ( )+2e

Cathode, reduction: {Ag
+
aq ( )+1e Ag(s)} 2
___________________________________________
Overall reaction in cell: Sn(s)+ 2Ag
+
(aq) Sn
2+
(aq)+ 2Ag(s)
2B (E) Anode, oxidation: {In s ( ) In
3+
aq ( )+3e

} 2
Cathode, reduction: {Cd
2+
aq ( )+ 2e Cd(s)} 3
___________________________________________
Overall reaction in cell: 2In(s)+ 3Cd
2+
(aq)2In
3+
(aq)+ 3Cd(s)

3A (M) We obtain the two balanced half-equations and the half-cell potentials from Table 20-1.

Oxidation: ( ) ( )
2+ 3+
{Fe aq Fe aq +e } 2

o
= 0.771V E
Reduction: ( ) ( )
2
Cl g +2e 2Cl aq


o
=+1.358V E
Net: ( ) ( ) ( ) ( )
2+ 3+
2
2Fe aq +Cl g 2Fe aq +2Cl aq

;
o
cell
=+1.358V 0.771V =+0.587V E

3B (M) Since we need to refer to Table 20-1, in any event, it is perhaps a bit easier to locate the
two balanced half-equations in the table. There is only one half-equation involving both
Fe
2+
aq ( ) and Fe
3+
aq ( ) ions. It is reversed and written as an oxidation below. The half-
equation involving MnO
4

aq ( ) is also written below. [Actually, we need to know that in

acidic solution Mn
2+
aq ( ) is the principal reduction product of MnO
4

aq ( ).]

Oxidation: ( ) ( )
2+ 3+
{Fe aq Fe aq +e } 5

o
= 0.771V E
Reduction: ( ) ( ) ( )
+ 2+
4 2
MnO aq +8H aq +5e Mn aq +4H O(l)


o
=+1.51V E
Net: ( ) ( ) ( ) ( ) ( )
2+ + 2+ 3+
4 2
MnO aq +5Fe aq +8H aq Mn aq +5Fe aq +4H O(l)

a
n
o
d
e
c
a
t
h
o
d
e
e
-
salt bridge
NO
3
-
Ag
+
K
+
Al
3+
Al
Ag
Chapter 20: Electrochemistry
999
E
cell
o
V V V =+1.51 0.771 =+0.74

4A (M) We write down the oxidation half-equation following the method of Chapter 5, and
obtain the reduction half-equation from Table 20-1, along with the reduction half-cell
potential.

Oxidation:
+
2 2 4 2
{H C O (aq) 2CO (aq) 2H (aq) 2e } 3

+ +
2 2 2 4
{CO /H C O } E


Reduction: ( ) ( ) ( )
2 + 3+
2 7 2
Cr O aq +14H aq +6e 2Cr aq +7H O(l)


o
=+1.33V E
Net: ( ) ( ) ( ) ( ) ( )
2 + 3+
2 7 2 2 4 2 2
Cr O aq +8H aq +3H C O aq 2Cr aq +7H O(l)+6CO g

o o
2 2 2 4 cell
=+1.81V =+1.33V {CO /H C O }; E E
o
2 2 2 4
{CO /H C O }=1.33V 1.81V = 0.48V E

4B (M) The 2
nd
half-reaction must have O
2
g ( ) as reactant and
2
H O(l) as product.
Oxidation:
2+ 3+
{Cr (aq) Cr (aq) e } 4

+ +
3 2
{Cr /Cr } E
+ +

Reduction: ( ) ( )
+
2 2
O g +4H aq +4e 2H O(l)

o
=+1.229V E
______________________________________
Net: ( ) ( ) ( )
+ 2+ 3+
2 2
O g +4H aq 4Cr (aq) 2H O(l)+4Cr aq +
o o 3 2
cell
1.653V 1.229V E {Cr /Cr } E
+ +
= + = + ;
o 3 2
{Cr /Cr } 1.229V 1.653V 0.424V E
+ +
= =

5A (M) First we write down the two half-equations, obtain the half-cell potential for each, and
then calculate E
cell
o
. From that value, we determine AG
o

Oxidation: ( ) ( )
3+
{Al s Al aq +3e } 2

o
=+1.676V E
Reduction: ( ) ( )
2
{Br l +2e 2Br aq } 3


o
=+1.065V E
____________________________
Net: ( ) ( ) ( ) ( )
3+ o
2 cell
2Al s +3Br l 2Al aq +6Br aq =1.676V +1.065V =2.741V E

o o 6
cell
96,485 C
= = 6mol e 2.741V = 1.587 10 J = 1587kJ
1mol e
G nFE

A

5B (M) First we write down the two half-equations, one of which is the reduction equation from
the previous example. The other is the oxidation that occurs in the standard hydrogen
electrode.
Oxidation: ( ) ( )
+
2
2H g 4H aq +4e

Reduction: ( ) ( )
+
2 2
O g +4H aq +4e 2H O(l)

Net: ( ) ( ) ( )
2 2 2
2H g +O g 2H O l =4 in this reaction. n
This net reaction is simply twice the formation reaction for
2
H O(l) and, therefore,
( ) ( )
o o 3 o
f 2 cell
=2 H O l =2 237.1 kJ = 474.2 10 J = G G nFE A A (


( )
3
o
o o
cell
474.2 10 J
= = 1.229V
96,485C
4mol e
mol e
G
E E
nF

A
= + =

, as we might expect.

6A (M) Cu(s) will displace metal ions of a metal less active than copper. Silver ion is one
example.
Chapter 20: Electrochemistry
1000
Oxidation: ( ) ( )
2+ o
Cu s Cu aq +2e = 0.340V E

(from Table 20.1)

Reduction: ( ) ( )
+ o
{Ag aq +e Ag s } 2 =+0.800V E

Net: ( ) ( ) ( ) ( )
+ 2+ o
cell
2Ag aq +Cu s Cu aq +2Ag s = 0.340V +0.800V =+0.460V E

6B (M) We determine the value for the hypothetical reaction's cell potential.
Oxidation: ( ) ( )
+
{Na s Na aq +e } 2

o
=+2.713V E
Reduction: ( ) ( )
2+
Mg aq +2e Mg s

o
= 2.356V E
Net: ( ) ( ) ( ) ( )
2+ +
2Na s +Mg aq 2Na aq +Mg s
o
cell
=2.713V 2.356 V =+0.357V E
The method is not feasible because another reaction occurs that has a more positive cell
potential, i.e., Na(s) reacts with water to form H
2
g ( ) and NaOH(aq):
Oxidation: ( ) ( )
+
{Na s Na aq +e } 2

o
=+2.713V E
Reduction:

2H
2
O+2e
-
H
2
(g)+2OH
-
(aq) E
o
=-0.828V
E
cell
o
V V V =2.713 0.828 =+1.885 .

7A (M) The oxidation is that of SO
4
2
to S
2
O
8
2
, the reduction is that of O
2
to H
2
O.

Oxidation: ( ) ( )
2 2 o
4 2 8
{2SO aq S O aq +2e } 2 = 2.01V E


Reduction: ( ) ( )
+ o
2 2
O g +4H aq +4e 2H O(l) =+1.229V E

________________
Net: ( ) ( ) ( ) ( )
2 2 +
2 4 2 8 2
O g +4H aq +2SO aq S O aq +2H O(l)

E
cell
=-0.78 V
Because the standard cell potential is negative, we conclude that this cell reaction is
nonspontaneous under standard conditions. This would not be a feasible method of producing
peroxodisulfate ion.

7B (M) (1) The oxidation is that of Sn
2+
aq ( ) to Sn
4+
aq ( ); the reduction is that of O
2
to
H
2
O.
Oxidation: {Sn
2+
aq ( )Sn
4+
aq ( )+2e

}2 E
o
=0.154V
Reduction: ( ) ( )
+ o
2 2
O g +4H aq +4e 2H O(l) =+1.229V E

___________
Net: ( ) ( ) ( ) ( )
+ 2+ 4+
2 2
O g +4H aq +2Sn aq 2Sn aq +2H O(l)
o
cell
=+1.075V E

Since the standard cell potential is positive, this cell reaction is spontaneous under
standard conditions.

(2) The oxidation is that of Sn(s) to Sn
2+
aq ( ); the reduction is still that of O
2
to H
2
O.
Oxidation: {Sn s ( )Sn
2+
aq ( )+2e

} 2 E
o
=+0.137V
Reduction: ( ) ( )
+ o
2 2
O g +4H aq +4e 2H O(l) =+1.229V E

_______________
Net: ( ) ( ) ( ) ( )
+ 2+
2 2
O g +4H aq +2Sn s 2Sn aq +2H O(l)
o
cell
=0.137V +1.229V =+1.366V E
Chapter 20: Electrochemistry
1001
The standard cell potential for this reaction is more positive than that for situation (1).
Thus, reaction (2) should occur preferentially. Also, if Sn
4+
aq ( ) is formed, it should
react with Sn(s) to form Sn
2+
aq ( ).
Oxidation: Sn s ( )Sn
2+
aq ( )+2e

E
o
=+0.137V
Reduction: ( ) ( )
4+ 2+ o
Sn aq +2e Sn aq =+0.154V E

___________________________________
Net: Sn
4+
aq ( )+Sn s ( )2Sn
2+
aq ( ) E
cell
o
=+0.137V +0.154V =+0.291V

8A (M) For the reaction 2Al s ( )+3Cu
2+
aq ( )2Al
3+
aq ( )+3Cu s ( ) we know

n =6 and
E
cell
o
V =+2.013 . We calculate the value of K
eq
.
o
o 470 204 cell
cell eq eq eq
0.0257 6 (+2.013)
= ln ; ln = = =470; =e =10
0.0257 0.0257
nE
E K K K
n

The huge size of the equilibrium constant indicates that this reaction indeed will go to
essentially 100% to completion.

8B (M) We first determine the value of E
cell
o
from the half-cell potentials.
Oxidation: ( ) ( )
2+
Sn s Sn aq +2e

o
=+0.137V E
Reduction: ( ) ( )
2+
Pb aq +2e Pb s

o
= 0.125V E
_________________________________
Net: ( ) ( ) ( ) ( )
2+ 2+
Pb aq +Sn s Pb s +Sn aq
o
cell
=+0.137V 0.125V =+0.012V E
o
o 0.93 cell
cell eq eq eq
0.0257 2 (+0.012)
= ln ln = = =0.93 =e =2.5
0.0257 0.0257
nE
E K K K
n

The equilibrium constant's small size (0.001 <K <1000) indicates that this reaction will not
go to completion.

9A (M) We first need to determine the standard cell voltage and the cell reaction.
Oxidation: ( ) ( )
3+
{Al s Al aq +3e } 2

o
=+1.676V E
Reduction: ( ) ( )
4+ 2+
{Sn aq +2e Sn aq } 3

o
=+0.154V E
_________________________
Net: ( ) ( ) ( ) ( )
4+ 3+ 2+
2Al s +3Sn aq 2Al aq +3Sn aq
o
cell
=+1.676V +0.154V =+1.830V E

Note that

n =6. We now set up and substitute into the Nernst equation.
E
cell
=E
cell
o

0.0592
n
log
Al
3+

2
Sn
2+

3
Sn
4+

3
=+1.830
0.0592
6
log
0.36M ( )
2
0.54M ( )
3
0.086M ( )
3
=+1.830V 0.0149V =+1.815V


9B (M) We first need to determine the standard cell voltage and the cell reaction.
Oxidation: ( ) ( )
2
2Cl 1.0 M Cl 1 atm +2e


o
= 1.358V E
Reduction: ( ) ( ) ( )
+ 2+
2 2
PbO s +4H aq +2e Pb aq +2H O(l)

o
=+1.455V E
__________________________________________
Chapter 20: Electrochemistry
1002
Net: ( ) ( ) ( ) ( ) ( )
+ 2+
2 2 2
PbO s +4H 0.10 M +2Cl 1.0 M Cl 1 atm +Pb 0.050 M +2H O(l)

E
cell
o
V V V = 1.358 +1.455 =+0.097 Note that n =2. Substitute values into the Nernst
equation.
( )( )
( ) ( )
2+
2
o
cell cell 4 2 4 2
+
P{Cl } Pb
1.0atm 0.050M
0.0592 0.0592
= log =+0.097 log
2
0.10M 1.0M
H Cl
=+0.097 V 0.080V =+0.017V
E E
n

(


( (

10A (M) The cell reaction is ( ) ( ) ( ) ( )
3+ 2+ 2+
2Fe 0.35 M +Cu s 2Fe 0.25 M +Cu 0.15 M with

n =2and E
cell
o
V V V = 0.337 +0.771 =0.434 Next, substitute this voltage and the
concentrations into the Nernst equation.
( ) ( )
( )
2
2 2+ 2+
o
cell cell 2 2
3+
Fe Cu
0.25 0.15
0.0592 0.0592
= log =0.434 log =0.434 0.033
2
0.35
Fe
E E
n
( (

(

+
cell
=+0.467V E Thus the reaction is spontaneous under standard conditions as written.
10B (M) The reaction is not spontaneous under standard conditions in either direction when
E
cell
V =0.000 . We use the standard cell potential from Example 20-10.


E
cell
=E
cell
o

0.0592
n
log
Ag
+

2
Hg
2+

; 0.000V =0.054V
0.0592
2
log
Ag
+

2
Hg
2+

log
Ag
+

2
Hg
2+

=
0.054 2
0.0592
=1.82;
Ag
+

2
Hg
2+

=10
1.82
=0.0150


11A (M) In this concentration cell E
cell
o
V =0.000 because the same reaction occurs at anode and
cathode, only the concentrations of the ions differ.
+
Ag =0.100 M (

in the cathode
compartment. The anode compartment contains a saturated solution of AgCl(aq).

K s
sp
Ag Cl =1.8 10 = =
10 + 2

;
10 5
1.8 10 1.3 10 M s

= =

Now we apply the Nernst equation. The cell reaction is

Ag
+
0.100M ( )Ag
+
1.310
5
M
( )


E
cell
log
M
M
V =0.000
0.0592
1
1.3 10
0.100
=+0.23
5

11B (D) Because the electrodes in this cell are identical, the standard electrode potentials are
numerically equal and subtracting one from the other leads to the value
o
cell
=0.000V. E
However, because the ion concentrations differ, there is a potential difference between the
Chapter 20: Electrochemistry
1003
two half cells (non-zero nonstandard voltage for the cell).
2+
Pb =0.100 M (

in the cathode
compartment, while the anode compartment contains a saturated solution of PbI
2
.
We use the Nernst equation (with n =2) to determine Pb
2+
in the saturated solution.

cell
0.0592 M M 2 0.0567
=+0.0567 V =0.000 log ; log = = 1.92
2 0.100M 0.100M 0.0592
x x
E

1.92 2+
anode
M
=10 =0.012; Pb = M =0.012 0.100M =0.0012M;
0.100M
I =2 0.0012M 0.0024 M
x
x

(

( =



K
sp
= Pb
2+

2
= 0.0012 ( ) 0.0024 ( )
2
=6.910
9
compared with 7.1 10
9

in Appendix
D

12A (M) From Table 20-1 we choose one oxidations and one reductions reaction so as to get the
least negative cell voltage. This will be the most likely pair of -reactions to occur.
Oxidation: ( ) ( )
2
2I aq I s +2e


o
= 0.535V E
( ) ( )
+
2 2
2H O(l) O g +4H aq +4e

o
= 1.229V E
Reduction: ( ) ( )
+
K aq +e K s

o
= 2.924V E
( ) ( )
2 2
2H O(l)+2e H g +2OH aq


o
= 0.828V E
The least negative standard cell potential 0.535V 0.828V =1.363V ( ) occurs when I
2
s ( ) is
produced by oxidation at the anode, and H
2
g ( ) is produced by reduction at the cathode.

12B (M) We obtain from Table 20-1 all the possible oxidations and reductions and choose one of each
to get the least negative cell voltage. That pair is the most likely pair of half-reactions to occur.

Oxidation: ( ) ( )
+ o
2 2
2H O(l) O g +4H aq +4e = 1.229V E

Ag s ( )Ag
+
aq ( )+e

E
o
=0.800V
[We cannot further oxidize NO
3

aq ( ) or Ag
+
aq ( ).]
Reduction: ( ) ( )
+ o
Ag aq +e Ag s =+0.800V E

( ) ( )
o
2 2
2H O(l)+2e H g +2OH aq = 0.828V E


Thus, we expect to form silver metal at the cathode and Ag
+
aq ( ) at the anode.

13A (M) The half-cell equation is Cu
2+
aq ( )+2e

Cu s ( ), indicating that two moles of

electrons are required for each mole of copper deposited. Current is measured in amperes, or
coulombs per second. We convert the mass of copper to coulombs of electrons needed for the
reduction and the time in hours to seconds.
Chapter 20: Electrochemistry
1004

Current =
12.3gCu
1molCu
63.55gCu

2mole

1molCu

96,485C
1mole

5.50h
60min
1h

60s
1min
=
3.73510
4
C
1.9810
4
s
= 1.89 amperes

13B (D) We first determine the moles of O
2
g ( ) produced with the ideal gas equation.
( )
2 2
1atm
738mmHg 2.62L
760mmHg
molesO (g) 0.104 mol O
0.08206L atm
26.2 273.2 K
mol K
| |

|
\ .
= =
+

Then we determine the time needed to produce this amount of O
2
.
elapsed time mol O
mol e
mol O
C
mol e
s
C
h
s
h =0.104
4
1
96,485
1
1
2.13
1
3600
=5.23
2
2

INTEGRATIVE EXAMPLE
14A (D) In this problem we are asked to determine E
o
for the reduction of CO
2
(g) to C
3
H
8
(g) in
an acidic solution. We proceed by first determining AG
o
for the reaction using tabulated
values for AG
f
o
in Appendix D. Next, E
cell
o
for the reaction can be determined using
AG
o
= zFE
cell
o
. Given reaction can be separated into reduction and oxidation. Since we are
in acidic medium, the reduction half-cell potential can be found in Table 20.1. Lastly, the
oxidation half-cell potential can be calculated using
E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell).
Stepwise approach
First determine AG
o
for the reaction using tabulated values for AG
f
o
in Appendix D:
C
3
H
8
(g) + 5O
2
(g) 3CO
2
(g) + 4H
2
O(l)
AG
f
o
-23.3 kJ /mol 0 kJ /mol -394.4 kJ /mol -237.1 kJ /mol

AG
o
= 3 AG
f
o
(CO
2
(g))+ 4 AG
f
o
(H
2
O(l))[AG
f
o
(C
3
H
8
(g))+ 5 AG
f
o
(O
2
(g))]
AG
o
= 3 (394.4)+ 4 (237.1)[23.3+ 5 0]kJ/mol
AG
o
= 2108kJ/mol

In order to calculate E
cell
o
for the reaction using AG
o
= zFE
cell
o
, z must be first determined.
We proceed by separating the given reaction into oxidation and reduction:
Reduction: 5{O
2
(g)+4H
+
(aq)+4e
-
2H
2
O(l)} E
o
=+1.229 V
Oxidation: C
3
H
8
(g) +6H
2
O(l) 3CO
2
(g) +20H
+
+20e
-
E
o
=xV
_____________________________________________________
Overall: C
3
H
8
(g) +5O
2
(g) 3CO
2
(g) +4H
2
O(l) E
o
=+1.229 V-xV
Since z=20, E
cell
o
can now be calculated using AG
o
= zFE
cell
o
:
Chapter 20: Electrochemistry
1005

AG
o
= zFE
cell
o
21081000J/mol = 20mol e
-

96485C
1mol e
-
E
cell
o
E
cell
o
=
21081000
20 96485
V = 1.092V

Finally,E
o
(reduction half-cell)can be calculated using
E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell):
1.092 V =1.229 V E
o
(oxidation half-cell) V
E
o
(oxidation half-cell)=1.229 V 1.092 V =0.137 V
Therefore, E
o
for the reduction of CO
2
(g) to C
3
H
8
(g) in an acidic medium is 0.137 V.
Conversion pathway approach:
Reduction: 5{O
2
(g)+4H
+
(aq)+4e
-
2H
2
O(l)} E
o
=+1.229 V
Oxidation: C
3
H
8
(g) +6H
2
O(l) 3CO
2
(g) +20H
+
+20e
-
E
o
=x V
_____________________________________________________
Overall: C
3
H
8
(g) + 5O
2
(g) 3CO
2
(g) + 4H
2
O(l) E
o
=+1.229 V-x V
AG
f
o
-23.3 kJ /mol 0 kJ /mol -394.4 kJ /mol -237.1 kJ /mol

AG
o
= 3 AG
f
o
(CO
2
(g))+ 4 AG
f
o
(H
2
O(l))[AG
f
o
(C
3
H
8
(g))+ 5 AG
f
o
(O
2
(g))]
AG
o
= 3 (394.4)+ 4 (237.1)[23.3+ 5 0]kJ/mol
AG
o
= 2108kJ/mol


AG
o
= zFE
cell
o
21081000J/mol = 20mol e
-

96485C
1mol e
-
E
cell
o
E
cell
o
=
21081000
20 96485
V = 1.092V

1.092 V =1.229 V E
o
(oxidation half-cell) V
E
o
(oxidation half-cell)=1.229 V 1.092 V =0.137 V

14B (D) This is a multi component problem dealing with a flow battery in which oxidation
occurs at an aluminum anode and reduction at a carbon-air cathode. Al
3+
produced at the
anode is complexed with OH
-
anions from NaOH(aq) to form [Al(OH)
4
]
-
.
Stepwise approach:
Part (a): The flow battery consists of aluminum anode where oxidation occurs and the formed
Al
3+
cations are complexes with OH
-
anions to form [Al(OH)
4
]
-
. The plausible half-reaction
for the oxidation is:
Oxidation: Al(s) +4OH
-
(aq) [Al(OH)
4
]
-
+3e
-

The cathode, on the other hand consists of carbon and air. The plausible half-reaction for the
reduction involves the conversion of O
2
and water to form OH
-
anions (basic medium):
Reduction: O
2
(g) +2H
2
O(l) +4e
-
4OH
-
(aq)
Combining the oxidation and reduction half-reactions we obtain overall reaction for the
process:
Oxidation: {Al(s) +4OH
-
(aq) [Al(OH)
4
]
-
+3e
-
}4
Chapter 20: Electrochemistry
1006

Reduction: {O
2
(g) +2H
2
O(l) +4e
-
4OH
-
(aq)} 3
____________________________________________
Overall: 4Al(s) +4OH
-
(aq) +3O
2
(g) +6H
2
O(l) 4[Al(OH)
4
]
-
(aq)
Part(b): In order to find E
o
for the reduction, use the known value for E
cell
o
as well as E
o
for
the reduction half-reaction from Table 20.1:

E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell)
E
cell
o
= +0.401V E
o
(oxidation half-cell) = +2.73V
E
o
(oxidation half-cell) = +0.401V 2.73V = 2.329V

Part (c): From the given value for E
cell
o
(+2.73V) first calculate AG
o
using AG
o
= zFE
cell
o

(notice that z=12 from part (a) above):

AG
o
= zFE
cell
o
= 12mol e
-

96485C
1mol e
-
2.73V
AG
o
= 3161kJ/mol

Given the overall reaction (part (a)) and AG
f
o
for OH
-
(aq) anions and H
2
O(l), we can
calculate the Gibbs energy of formation of the aluminate ion, [Al(OH)
4
]
-
:
Overall reaction: 4Al(s) + 4OH
-
(aq) + 3O
2
(g) + 6H
2
O(l) 4[Al(OH)
4
]
-
(aq)
AG
f
o
0 kJ /mol -157 kJ /mol 0 kJ /mol -237.2 kJ /mol x

AG
o
= 4 x [4 0+ 4 (157)+ 3 0+ 6 (237.2)kJ/mol = 3161kJ/mol
4x = 3161 2051.2= 5212.2kJ/mol
x = 1303kJ/mol

Therefore, AG
f
o
([Al(OH)
4
]

) = 1303kJ/mol
Part(d): First calculate the number of moles of electrons:

number of mol e

= current(C / s) time(s)
1mol e
-
96485C
number of mol e

= 4.00h
60min
1h

60s
1min
10.0
C
s

1mol e
-
96485C
number of mol e

= 1.49mol e
-

Now, use the oxidation half-reaction to determine the mass of Al(s) consumed:
mass(Al) = 1.49mol e
-

1mol Al
3mol e
-

26.98g Al
1mol Al
= 13.4g
Conversion pathway approach:
Part (a):
Oxidation: {Al(s) +4OH
-
(aq) [Al(OH)
4
]
-
+3e
-
}4

Reduction: {O
2
(g) +2H
2
O(l) +4e
-
4OH
-
(aq)} 3
____________________________________________
Overall: 4Al(s) +4OH
-
(aq) +3O
2
(g) +6H
2
O(l) 4[Al(OH)
4
]
-
(aq)
Part (b):
Chapter 20: Electrochemistry
1007

E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell)
E
cell
o
= +0.401V E
o
(oxidation half-cell) = +2.73V
E
o
(oxidation half-cell) = +0.401V 2.73V = 2.329V

Part (c):

AG
o
= zFE
cell
o
= 12mol e
-

96485C
1mol e
-
2.73V
AG
o
= 3161kJ/mol

Overall reaction: 4Al(s) + 4OH
-
(aq) + 3O
2
(g) + 6H
2
O(l) 4[Al(OH)
4
]
-
(aq)
AG
f
o
0 kJ /mol -157 kJ /mol 0 kJ /mol -237.2 kJ /mol x

AG
o
= 4 x [4 0+ 4 (157)+ 3 0+ 6 (237.2)kJ/mol = 3161kJ/mol
4x = 3161 2051.2= 5212.2kJ/mol
x = AG
f
o
([Al(OH)
4
]

) = 1303kJ/mol

Part (d):

number of mol e

= current(C / s) time(s)
1mol e
-
96485C
number of mol e

= 4.00h
60min
1h

60s
1min
10.0
C
s

1mol e
-
96485C
number of mol e

= 1.49mol e
-

mass(Al) = 1.49mol e
-

1mol Al
3mol e
-

26.98g Al
1mol Al
= 13.4g


EXERCISES

Standard Electrode Potential

1. (E) (a) If the metal dissolves in HNO
3
, it has a reduction potential that is smaller than
( ) ( )
{ }
o
3
NO aq /NO g =0.956V E

. If it also does not dissolve in HCl, it has a
reduction potential that is larger than ( ) ( ) { }
o +
2
H aq /H g =0.000V E . If it displaces
Ag
+
aq ( ) from solution, then it has a reduction potential that is smaller than
( ) ( ) { }
o +
Ag aq /Ag s =0.800V E . But if it does not displace Cu
2+
aq ( ) from solution,
then its reduction potential is larger than
( ) ( ) { }
o 2+ o
Cu aq /Cu s =0.340V Thus, 0.340V 0.800V E E < <

(b) If the metal dissolves in HCl, it has a reduction potential that is smaller than
( ) ( ) { }
o +
2
H aq /H g =0.000V E . If it does not displace Zn
2+
aq ( ) from solution, its
reduction potential is larger than ( ) ( ) { }
o 2+
Zn aq /Zn s = 0.763V E . If it also does not
displace Fe
2+
aq ( ) from solution, its reduction potential is larger than
Chapter 20: Electrochemistry
1008
( ) ( ) { }
o 2+
Fe aq /Fe s = 0.440V E . 0.440 0.000 V V
o
< < E

2. (E) We would place a strip of solid indium metal into each of the metal ion solutions and see
if the dissolved metal plates out on the indium strip. Similarly, strips of all the other metals
would be immersed in a solution of In
3+
to see if indium metal plates out. Eventually, we
will find one metal whose ions are displaced by indium and another metal that displaces
indium from solution, which are adjacent to each other in Table 20-1. The standard
electrode potential for the In/In
3+
(aq) pair will lie between the standard reduction potentials
for these two metals. This technique will work only if indium metal does not react with
water, that is, if the standard reduction potential of In
3+
aq ( )/ In s ( ) is greater than about
1.8 V . The inaccuracy inherent in this technique is due to overpotentials, which can be as
much as 0.200 V. Its imprecision is limited by the closeness of the reduction potentials for
the two bracketing metals

3. (M) We separate the given equation into its two half-equations. One of them is the reduction
of nitrate ion in acidic solution, whose standard half-cell potential we retrieve from Table 20-1
and use to solve the problem.

Oxidation:
2
4
{Pt(s) 4Cl (aq) [PtCl ] (aq) 2e } 3

+ + ;
o 2
4
{[PtCl ] (aq)/Pt(s)} E


Reduction: ( ) ( ) ( )
+
3 2
{NO aq +4H aq +3e NO g +2H O(l)} 2

;
o
=+0.956V E
Net: 3Pt s ( )+2NO
3

aq ( )+8H
+
aq ( )+12Cl

aq ( )3 PtCl
4
| |
2
aq ( )+2NO g ( )+6H
2
O l ( )
o o 2
cell 4
0.201V 0.956V {[PtCl ] (aq)/Pt(s)} E E

= = +
o 2
4
{[PtCl ] (aq)/Pt(s)} 0.956V 0.201V 0.755V E

= = +

4. (M) In this problem, we are dealing with the electrochemical reaction involving the oxidation
of Na(in Hg) to Na
+
(aq) and the reduction of Cl
2
(s) to Cl
-
(aq). Given that E
cell
o
= 3.20V , we
are asked to find E
o
for the reduction of Na
+
to Na(in Hg). We proceed by separating the
given equation into its two half-equations. One of them is the reduction of Cl (g)
2
to Cl (aq)

whose standard half-cell potential we obtain from Table 20-1 and use to solve the problem.
Stepwise approach:
Separate the given equation into two half-equations:
Oxidation:{Na(inHg) Na (aq) e } 2
+
+ {Na (aq)/ Na(inHg)} E
+

Reduction:
2
Cl (g) 2e 2Cl (aq)

+ 1.358V E = +

Net:
2
2Na(in Hg) Cl (g) 2Na (aq) 2Cl (aq)
+
+ +
cell
3.20V E

=
Use E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell) to solve for
E
o
(oxidation half-cell):

E
cell
o
= 3.20V=+1.385V E
o
{Na
+
(aq) / Na(inHg)}
{Na (aq)/ Na(in Hg)} 1.358V 3.20V 1.84V E
+
= =

Conversion pathway approach:
Oxidation:{Na(inHg) Na (aq) e } 2
+
+ {Na (aq)/ Na(inHg)} E
+

Chapter 20: Electrochemistry
1009
Reduction:
2
Cl (g) 2e 2Cl (aq)

+ 1.358V E = +

Net:
2
2Na(in Hg) Cl (g) 2Na (aq) 2Cl (aq)
+
+ +
cell
3.20V E

=
3.20V = 1.358 E
o
{Na
+
(aq) / Na(in Hg)}
E
o
{Na
+
(aq) / Na(in Hg)}= 1.358V 3.20V = 1.84V


5. (M) We divide the net cell equation into two half-equations.

Oxidation: ( ) ( ) ( )
4
{Al s +4OH aq [Al(OH) ] aq +3e } 4

;
o
4
{[Al(OH) ] (aq)/Al(s)} E


Reduction: ( ) ( )
2 2
{O g +2H O(l)+4e 4OH aq } 3

;
o
=+0.401V E
Net: ( ) ( ) ( ) ( )
2 2 4
4Al s +3O g +6H O(l) +4OH aq 4[Al(OH) ] aq


o
cell
=2.71V E
o o
cell 4
=2.71V=+0.401V {[Al(OH) ] (aq)/Al(s)} E E


o
4
{[Al(OH) ] (aq)/Al(s)}=0.401V 2.71V = 2.31V E



6. (M) We divide the net cell equation into two half-equations.

Oxidation: ( ) ( ) ( )
+
4 2 2
CH g +2H O(l) CO g +8H aq +8e

( ) ( ) { }
o
2 4
CO g /CH g E
Reduction: ( ) ( )
+
2 2
{O g +4H aq +4e 2H O(l)} 2

o
=+1.229V E
Net: ( ) ( ) ( )
4 2 2 2
CH g +2 O g CO g +2H O(l)
o
cell
=1.06V E
( ) ( ) { }
( ) ( ) { }
o o
cell 2 4
o
2 4
1.06V 1.229V CO g /CH g
CO g /CH g 1.229V 1.06V 0.17V
E E
E
= = +
= = +


7. (M) (a) We need standard reduction potentials for the given half-reactions from Table 10.1:
Ag
+
(aq)+e
-
Ag(s) E
o
=+0.800 V
Zn
2+
(aq)+2e
-
Zn(s) E
o
=-0.763 V
Cu
2+
(aq)+2e
-
Cu(s) E
o
=+0.340 V
Al
3+
(aq)+3e
-
Al(s) E
o
=-1.676 V
Therefore, the largest positive cell potential will be obtained for the reaction involving the
oxidation of Al(s) to Al
3+
(aq) and the reduction of Ag
+
(aq) to Ag(s):
Al(s) +3Ag
+
(aq) 3Ag(s)+Al
3+
(aq) E
cell
o
= +1.676V + 0.800V = 2.476V
Ag is the anode and Al is the cathode.
(b) Reverse to the above, the cell with the smallest positive cell potential will be obtained for
the reaction involving the oxidation of Zn(s) to Zn
2+
(aq) (anode) and the reduction of Cu
+2
(aq)
to Cu(s) (cathode):
Zn(s) +Cu
2+
(aq) Cu(s)+Zn
2+
(aq) E
cell
o
= 0.763V + 0.340V = 1.103V

8. (M) (a) The largest positive cell potential will be obtained for the reaction:
Zn(s) +4NH
3
(aq) +2VO
2+
(aq) +4H
+
(aq) [Zn(NH
3
)
4
]
2+
(aq)+2V
3+
(aq)+2H
2
O(l)
E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell) = 0.340V (1.015V) = 1.355V
Zn is the anode and VO
2+
is the cathode.
Chapter 20: Electrochemistry
1010
(b) Reverse to the above, the cell with the smallest positive cell potential will be obtained for the
reaction involving the oxidation of Ti
2+
(aq) to Ti
3+
(aq) (anode) and the reduction of Sn
+2
(aq) to
Sn(s) (cathode):
2Ti
2+
(aq) +Sn
2+
(aq) 2Ti
3+
(aq)+Sn(aq)
E
cell
o
= E
o
(reduction half-cell) E
o
(oxidation half-cell) = 0.14V (0.37V) = 0.23V

Predicting Oxidation-Reduction Reactions

9. (E) (a) Ni
2+
, (b) Cd.

10. (E) (a) potassium, (b) barium.

11. (M) (a) Oxidation: ( ) ( )
2+
Sn s Sn aq +2e

o
=+0.137 V E
Reduction: ( ) ( )
2+
Pb aq +2e Pb s

o
= 0.125V E
________________________________
Net: ( ) ( ) ( ) ( )
2+ 2+
Sn s +Pb aq Sn aq +Pb s
o
cell
=+0.012V Spontaneous E

(b) Oxidation: ( ) ( )
2
2I aq I s +2e


o
= 0.535V E
Reduction: ( ) ( )
2+
Cu aq +2e Cu s

o
=+0.340V E
________________________
Net: ( ) ( ) ( ) ( )
2+
2
2I aq +Cu aq Cu s +I s

o
cell
= 0.195V Nonspontaneous E

(c) Oxidation: ( ) ( )
+
2 2
{2H O(l) O g +4H aq +4e } 3

o
= 1.229V E
Reduction: ( ) ( )
+
3 2
{NO (aq)+4H aq +3e NO g +2H O(l)} 4


o
=+0.956V E
_______________________ _
Net: ( ) ( ) ( ) ( )
+
3 2 2
4NO aq + 4H aq 3O g +4NO g +2H O(l)

o
cell
= 0.273V E
Nonspontaneous

(d) Oxidation: ( ) ( ) ( )
2
Cl aq + 2OH aq OCl aq +H O(l) +2e


o
= 0.890V E
Reduction: ( ) ( ) ( )
3 2 2
O g +H O(l) +2 e O g +2OH aq


o
=+1.246V E
Net: ( ) ( ) ( ) ( )
3 2
Cl aq + O g OCl aq + O g

(basic solution)
o
cell
=+0.356V E
Spontaneous

12. (M) It is more difficult to oxidize Hg(l) to Hg
2
2+
0.797V ( ) than it is to reduce H
+
to H
2

(0.000 V); Hg(l) will not dissolve in 1 M HCl. The standard reduction of nitrate ion to NO(g)
in acidic solution is strongly spontaneous in acidic media (+0.956V ). This can help overcome
the reluctance of Hg to be oxidized. Hg(l) will react with and dissolve in the HNO
3
aq ( ).

13. (M) (a) Oxidation: ( ) ( )
2+
Mg s Mg aq +2 e

o
=+2.356V E
Reduction: ( ) ( )
2+
Pb aq +2 e Pb s

o
= 0.125V E
_____________________________________
Net: ( ) ( ) ( ) ( )
2+ 2+
Mg s +Pb aq Mg aq +Pb s
o
cell
= +2.231V E
Chapter 20: Electrochemistry
1011
This reaction occurs to a significant extent.

(b) Oxidation: ( ) ( )
2+
Sn s Sn aq +2e

o
=+0.137V E
Reduction: ( ) ( )
+
2
2H aq H g
o
=0.000V E
________________________________________
Net: ( ) ( ) ( ) ( )
+ 2+
2
Sn s + 2H aq Sn aq + H g
o
cell
=+0.137V E
This reaction will occur to a significant extent.


(c) Oxidation: ( ) ( )
2+ 4+
Sn aq Sn aq +2e

o
= 0.154V E
Reduction: ( ) ( ) ( )
2 +
4 2 2
SO aq +4H aq +2e SO g +2H O(l)


o
=+0.17V E
________________________
Net: ( ) ( ) ( ) ( ) ( )
2 2+ + 4+
4 2 2
Sn aq +SO aq +4H aq Sn aq +SO g +2H O(l)

o
cell
=+0.02V E
This reaction will occur, but not to a large extent.

(d) Oxidation: ( ) ( ) ( )
+
2 2 2
{H O aq O g +2H aq +2e } 5

o
= 0.695V E
Reduction: ( ) ( ) ( )
- + - 2+
4 2
{MnO aq +8H aq +5e Mn aq +4H O(l)} 2
o
=+1.51V E
Net: ( ) ( ) ( ) ( ) ( )
-
+ 2+
2 2 4 2 2
5H O aq +2MnO aq +6H aq 5O g +2Mn aq +8H O(l)
o
cell
=+0.82V E
This reaction will occur to a significant extent.

(e) Oxidation: ( ) ( )
o
2
2Br aq Br aq +2e = 1.065V E


Reduction: ( ) ( )
o
2
I s +2e 2I aq =+0.535V E


__________________________________
Net: ( ) ( ) ( ) ( )
o
2 2 cell
2Br aq +I s Br aq +2I aq = 0.530V E


This reaction will not occur to a significant extent.

14. (M) In this problem we are asked to determine whether the electrochemical reaction between
Co(s) and Ni
2+
(aq) to yield Co
2+
(aq) +Ni(s) will proceed to completion based on the known
E
cell
o
value. This question can be answered by simply determining the equilibrium constant.
Stepwise approach
First comment on the value of E
cell
o
:
The relatively small positive value of E
cell
o
for the reaction indicates that the reaction will
proceed in the forward direction, but will stop short of completion. A much larger positive
value of E
cell
o
would be necessary before we would conclude that the reaction goes to
completion.
Calculate the equilibrium constant for the reaction using E
cell
o
=
0.0257
n
ln K
eq
:


E
cell
o
=
0.0257
n
ln K
eq
ln K
eq
=
n E
cell
o
0.0257
=
2 0.02
0.0257
= 2

2
eq
e 7 K = =
Comment on the value of K
eq
:
Chapter 20: Electrochemistry
1012
K
eq
is small. A value of 1000 or more is needed before we can describe the reaction as one
that goes to completion.
Conversion pathway approach:


E
cell
o
=
0.0257
n
ln K
eq
ln K
eq
=
n E
cell
o
0.0257
K
eq
= e
n E
cell
o
0.0257
= e
20.02
0.0257
= 7

K
eq
is too small. The reaction does not go to completion.
15. (M) If E
cell
o
is positive, the reaction will occur. For the reduction of Cr
2
O
7
2
to Cr
3+
aq ( ):
( ) ( ) ( )
2 + 3+ o
2 7 2
Cr O aq +14H aq +6e 2Cr aq +7H O(l) =+1.33V E


If the oxidation has E
o
smaller (more negative) than 1.33V, the oxidation will not occur.

(a) ( ) ( )
2+ 4+ o
Sn aq Sn aq +2e = 0.154V E

Hence, Sn
2+
aq ( ) can be oxidized to Sn
4+
aq ( ) by Cr
2
O
7
2
aq ( ).

(b) ( ) ( ) ( )
+ o
2 2 3
I s +6H O(l) 2IO aq +12H aq +10e = 1.20V E


I
2
s ( ) can be oxidized to IO
3

aq ( ) by Cr
2
O
7
2
aq ( ).

(c) ( ) ( ) ( )
2+ + o
2 4
Mn aq +4H O(l) MnO aq +8H aq +5e = 1.51V E


Mn
2+
aq ( ) cannot be oxidized to MnO
4

aq ( ) by Cr
2
O
7
2
aq ( ).

16. (M) In order to reduce Eu
3+
to Eu
2+
, a stronger reducing agent than Eu
2+
is required. From
the list given, Al(s) and H
2
C
2
O
4
(aq) are stronger reducing agents. This is determined by
looking at the reduction potentials (-1.676 V for Al
3+
/Al(s) and -0.49 V for CO
2
,
H
+
/H
2
C
2
O
4
(aq)), are more negative than -0.43 V). Co(s), H
2
O
2
and Ag(s) are not strong
enough reducing agents for this process. A quick look at their reduction potentials shows
that they all have more positive reduction potentials than that for Eu
3+
to Eu
2+
(-0.277 V for
Co
2+
/Co(s), +0.695 V for O
2
, H
+
/H
2
O
2
(aq) and +0.800 V for Ag
+
/Ag(s).

17. (M) (a) Oxidation: ( ) ( )
+
{Ag s Ag aq +e } 3

o
= 0.800V E
Reduction: ( ) ( ) ( )
+
3 2
NO aq +4H aq +3e NO g +2H O(l)


o
=+0.956V E
______________ _____________
Net:
( ) ( ) ( ) ( ) ( )
+ +
3 2
3Ag s +NO aq +4H aq 3Ag aq +NO g +2H O(l)

o
cell
=+0.156V E
Ag(s) reacts with HNO
3
aq ( ) to form a solution of AgNO
3
aq ( ).
(b) Oxidation: ( ) ( )
2+
Zn s Zn aq +2e

o
=+0.763V E
Reduction: ( ) ( )
+
2
2H aq +2e H g

o
=0.000V E
Net: ( ) ( ) ( ) ( )
+ 2+
2
Zn s +2H aq Zn aq +H g
o
cell
=+0.763V E
Zn(s) reacts with HI(aq) to form a solution of ( )
2
ZnI aq .

Chapter 20: Electrochemistry
1013
(c) Oxidation: ( ) ( )
3+
Au s Au aq +3e

o
= 1.52V E
Reduction: ( ) ( ) ( )
+
3 2
NO aq +4H aq +3e NO g +2H O(l)


o
=+0.956V E
Net: ( ) ( ) ( ) ( ) ( )
+ 3+
3 2
Au s +NO aq +4H aq Au aq +NO g +2H O(l)

;
o
cell
= 0.56V E
Au(s) does not react with 1.00 M HNO
3
aq ( ).

18. (M) In each case, we determine whether E
cell
o
is greater than zero; if so, the reaction will
occur.
(a) Oxidation: ( ) ( )
2+
Fe s Fe aq +2e

o
0.440V E =
Reduction: ( ) ( )
2+
Zn aq +2e Zn s

o
= 0.763V E
Net: ( ) ( ) ( ) ( )
2+ 2+
Fe s +Zn aq Fe aq +Zn s
o
cell
0.323V E =
The reaction is not spontaneous under standard conditions as written

(b) Oxidation: ( ) ( )
2
{2Cl aq Cl g +2e } 5


o
= 1.358V E
Reduction: ( ) ( ) ( )
+ 2+
4 2
{MnO aq +8H aq +5e Mn aq +4H O(l)}2

;
o
=1.51V E
Net: ( ) ( ) ( ) ( ) ( )
+ 2+
4 2 2
10Cl aq +2MnO aq +16H aq 5Cl g +2Mn aq +8H O(l)


o
cell
=+0.15V E . The reaction is spontaneous under standard conditions as written.

(c) Oxidation: ( ) ( )
+
{Ag s Ag aq +e } 2

o
= 0.800V E
Reduction: ( ) ( )
+
2
2H aq +2e H g

o
=+0.000V E
Net: ( ) ( ) ( ) ( )
+ +
2
2Ag s +2H aq 2Ag aq +H g
o
cell
= 0.800V E
The reaction is not spontaneous under standard conditions as written.

(d) Oxidation: ( ) ( )
2
{2Cl aq Cl g +2e } 2


o
= 1.358V E
Reduction: ( ) ( )
+
2 2
O g +4H aq +4e 2H O(l)

o
=+1.229V E
_______________________________________
Net: ( ) ( ) ( ) ( )
+
2 2 2
4Cl aq +4H aq +O g 2Cl g +2H O(l)

o
cell
= 0.129V E
The reaction is not spontaneous under standard conditions as written.

Galvanic Cells

19. (M) (a) Oxidation: ( ) ( )
3+
{Al s Al aq +3e } 2

o
=+1.676V E
Reduction: ( ) ( )
2+
{Sn aq +2e Sn s } 3

o
= 0.137 V E
____________________________
Net: ( ) ( ) ( ) ( )
2+ 3+
2Al s +3Sn aq 2Al aq +3Sn s
o
cell
=+1.539V E
(b) Oxidation: ( ) ( )
2+ 3+
Fe aq Fe aq +e

o
= 0.771V E
Reduction: ( ) ( )
+
Ag aq +e Ag s

o
=+0.800V E
____________________
Net: ( ) ( ) ( ) ( )
2+ + 3+
Fe aq +Ag aq Fe aq +Ag s
o
cell
=+0.029V E
(c) Oxidation: {Cr(s)Cr
2+
(aq)+2e
-
} 3 E
o
=+0.90V
Chapter 20: Electrochemistry
1014
Reduction: {Au
3+
(aq)+3e
-
Au(s)} 2 E
o
=1.52V
____________________
Net: 3Cr(s)+2Au
3+
(aq)3Cr
2+
(aq)+2Au(s) E
cell
o
=2.42V
(d) Oxidation: 2H
2
O(l)O
2
(g)+4H
+
(aq)+4e
-
E
o
=1.229V
Reduction: O
2
(g)+2H
2
O(l)+4e
-
4OH
-
(aq) E
o
=+0.401V
____________________
Net: H
2
O(l)H
+
(aq)+OH
-
(aq) E
cell
o
=0.828V


20. (M) In this problem we are asked to write the half-reactions, balanced chemical equation
and determine E
cell
o
for a series of electrochemical cells.
(a) Stepwise approach
First write the oxidation and reduction half-reactions and find E
o
values from
Appendix D:
Oxidation: Cu(s) Cu
2+
(aq)+2e
-
E
o
=0.340V
Reduction:

Cu
+
(aq)+e
-
Cu(s) E
o
=+0.520V
In order to obtain balanced net equation, the reduction half-reaction needs to be
multiplied by 2:


2Cu
+
(aq)+2e
-
2Cu(s)
Add the two half-reactions to obtain the net reaction:
Cu(s) Cu
2+
(aq)+2e
-



2Cu
+
(aq)+2e
-
2Cu(s)
____________________
Net:

2Cu
+
(aq) Cu
2+
(aq)+Cu(s)
Determine E
cell
o
:


E
cell
o
=-0.340V+0.520V=+0.18V
Conversion pathway approach:
Oxidation: Cu(s) Cu
2+
(aq)+2e
-
E
o
=0.340V
Reduction:

{Cu
+
(aq)+e
-
Cu(s)} 2 E
o
=+0.520V
___________
Net:

2Cu
+
(aq) Cu
2+
(aq)+Cu(s) E
cell
o
= +0.18V
Follow the same methodology for parts (b), (c), and (d).
(b) Oxidation:

Ag(s)+I
-
(aq) AgI(s)+e
-
E
o
=+0.152V
Reduction:

AgCl(s)+e
-
Ag(s)+Cl
-
(aq) E
o
=+0.2223V
____________________
Net:

AgCl(s)+I
-
(aq) AgI(s)+Cl
-
(aq) E
cell
o
=+0.3743V
(c) Oxidation:

{Ce
3+
(aq) Ce
4+
(aq)+e
-
} 2

E
o
=1.76V
Reduction:

I
2
(s)+2e
-
2I
-
(aq)

E
o
=+0.535V
____________________
Net:

2Ce
3+
(aq)+I
2
(s) 2Ce
4+
(aq)+2I
-
(aq)

E
cell
o
=-1.225V
Chapter 20: Electrochemistry
1015


(d) Oxidation:

{U(s) U
3+
(aq)+3e
-
} 2

E
o
=+1.66V
Reduction: {V
2+
(aq)+2e
-
V(s)} 3

E
o
=1.13V
____________________
Net:

2U(s)+3V
2+
(aq) 2U
3+
(aq)+3V(s)

E
cell
o
=+0.53V

21. (M) In each case, we determine whether E
cell
o
is greater than zero; if so, the reaction will
occur.
(a) Oxidation: ( )
2
H (g) 2H +2e aq
+

o
0.000V E =
Reduction: ( )
2
F (g) +2e 2F aq


o
=2.866V E
Net:
+ -
2 2
H (g) +F (g) 2 H (aq) +2 F (aq)
o
cell
2.866V E = +
The reaction is spontaneous under standard conditions as written

(b) Oxidation:
2+
Cu(s) Cu (aq) +2e

o
= 0.340V E
Reduction:
2+
Ba (aq) +2e Ba(s)

; E
o
=2.92V
Net:
2+ 2+
Cu(s) +Ba (aq) Cu (aq) +Ba(s)
o
cell
= 3.26 V E .
The reaction is not spontaneous under standard conditions as written.

(c) Oxidation:
{ }
2+ 3+
Fe (aq) Fe (aq) +e 2

o
= 0.771 V E
Reduction:
2+
Fe (aq) + 2e Fe(s)

o
= 0.440 V E
Net:
2+ 3+
3 Fe (aq) Fe(s) +2 Fe (aq)
o
cell
= 1.211 V E
The reaction is not spontaneous as written.

(d) Oxidation:
-
2 2
2 Hg(l) +2 Cl Hg Cl (s) +2 e

o
= (0.2676)V E
Reduction:
-
2 2 2
2 HgCl (aq) +2 e Hg Cl (s) +2 Cl (aq)

o
=+0.63V E

Net:
2 2 2
2 Hg(l) +2 HgCl (aq) 2 Hg Cl (s)
o
cell
= 0.36V E +
(divide by 2 to get
2 2 2
Hg(l) +HgCl (aq) Hg Cl (s) )
The reaction is spontaneous under standard conditions as written.
Chapter 20: Electrochemistry
1016
22. (M) (a)

e
-
salt bridge
a n o d e
c a t h o d e
Cu
Cu
2+
Pt
Fe
3+
Fe
2+

Anode, oxidation: ( ) ( )
2+
Cu s Cu aq +2e

o
= 0.340V E
Cathode, reduction: ( ) ( )
3+ 2+
{Fe aq +e Fe aq } 2

;
o
=+0.771V E

Net: ( ) ( ) ( ) ( )
3+ 2+ 2+
Cu s +2Fe aq Cu aq +2Fe aq
o
cell
=+0.431V E
(b)

e
-
salt bridge
a n o d e
c a t h o d e
Al
Al
3+
Pb
Pb
2+

Anode, oxidation: ( ) ( )
3+
{Al s Al aq +3e } 2

o
=+1.676V E
Cathode, reduction: ( ) ( )
2+
{Pb aq +2e Pb s } 3

;
o
= 0.125V E
Net: ( ) ( ) ( ) ( )
2+ 3+
2Al s +3Pb aq 2Al aq +3Pb s
o
cell
=+1.551V E
(c)

e
-
salt bridge
a n o d e
c a t h o d e
Pt
H
2
O
Pt
Cl
-
Cl
2
(g)
H
+
O
2
(g)

Anode, oxidation: ( ) ( )
+
2 2
2H O(l) O g +4H aq +4e

o
= 1.229V E
Cathode, reduction: ( ) ( )
2
{Cl g +2e 2Cl aq } 2


o
=+1.358V E
Chapter 20: Electrochemistry
1017
Net: ( ) ( ) ( ) ( )
+
2 2 2
2H O(l)+2Cl g O g +4H aq +4Cl aq

o
cell
=+0.129V E

(d)

e
-
salt bridge
a n o d e
c a t h o d e
Zn Pt
HNO
3
NO(g) Zn
+2

Anode, oxidation: ( ) ( )
2+
{Zn s Zn aq +2e } 3

o
=+0.763V E
Cathode, reduction: ( ) ( ) ( )
+
3 2
{NO aq +4H aq +3e NO g +2H O(l)} 2

;
o
=+0.956V E
Net:
( ) ( ) ( ) ( ) ( )
+ 2+ o
3 2 cell
3Zn s +2NO aq +8H aq 3Zn aq +2NO g +4H O(l) =+1.719V E

23. (M) In each case, we determine whether E
cell
o
is greater than zero; if so, the reaction will
occur.
(a) Oxidation:

Ag(s) Ag
+
(aq)+e
-
E
o
= 0.800V
Reduction:

Fe
3+
(aq)+e
-
Fe
2+
(aq) E
o
=+0.771V
Net:

Ag(s)+Fe
3+
(aq) Ag
+
(aq)+Fe
2+
(aq) E
cell
o
= 0.029V
The reaction is not spontaneous under standard conditions as written.

(b) Oxidation:

Sn(s) Sn
2+
(aq)+2e
-
E
o
= +0.137V
Reduction:

Sn
4+
(aq)+2e
-
Sn
+2
(aq) E
o
=+0.154V
Net:

Sn(s)+Sn
4+
(aq) 2Sn
2+
(aq) E
cell
o
= +0.291V
The reaction is spontaneous under standard conditions as written.
(c) Oxidation:

2Br
-
(aq) Br
2
(l)+2e
-
E
o
= 1.065V
Reduction:

2Hg
2+
(aq)+2e
-
Hg
2
+
(aq) E
o
=+0.630V
Net:

2Br
-
(aq)+2Hg
2+
(aq) Br
2
(l)+Hg
2
+
E
cell
o
= 0.435V
The reaction is not spontaneous under standard conditions as written.
(d) Oxidation:

{NO
3
-
(aq)+2H
+
(aq)+e
-
NO
2
(g)+H
2
O(l)} 2 E
o
= 2.326V
Reduction:

Zn(s) Zn
2+
(aq)+2e
-
E
o
=+1.563V
Net:

2NO
3
-
(aq)+4H
+
(aq)+Zn(s) 2NO
2
(g)+2H
2
O(l)+Zn
2+
(aq)

E
cell
o
= 0.435V
The reaction is not spontaneous under standard conditions as written.


Chapter 20: Electrochemistry
1018
24. (M) (a) Fe s ( )Fe
2+
aq ( )Cl

aq ( )Cl
2
g ( )Pt s ( )
Oxidation: ( ) ( )
2+
Fe s Fe aq +2e

o
=+0.440V E
Reduction: ( ) ( )
2
Cl g +2e 2Cl aq


o
=+1.358V E
Net: ( ) ( ) ( ) ( )
2+
2
Fe s +Cl g Fe aq +2Cl aq

o
cell
=+1.798 V E
(b) ( ) ( ) ( ) ( )
2+
Zn s Zn aq Ag aq Ag s
+

Oxidation: ( ) ( )
2+
Zn s Zn aq +2e

o
=+0.763V E
Reduction: ( ) ( )
+
{Ag aq +e Ag s } 2

o
=+0.800V E
Net: ( ) ( ) ( ) ( )
+ 2+
Zn s +2Ag aq Zn aq +2Ag s
o
cell
=+1.563V E
(c) Pt s ( )Cu
+
aq ( ),Cu
2+
aq ( )Cu
+
aq ( )Cu s ( )
Oxidation: ( ) ( )
+ 2+
Cu aq Cu aq +e

o
= 0.159V E
Reduction: ( ) ( )
+
Cu aq +e Cu s

o
=+0.520V E
Net: ( ) ( ) ( )
+ 2+
2Cu aq Cu aq +Cu s
o
cell
=+0.361V E
(d) Mg s ( )Mg
2+
aq ( )Br

aq ( )Br
2
l ( )Pt s ( )
Oxidation: ( ) ( )
2+
Mg s Mg aq +2e

o
=+2.356V E
Reduction: ( ) ( )
2
Br l +2e 2Br aq


o
=+1.065V E
Net: ( ) ( ) ( ) ( )
2+
2
Mg s +Br l Mg aq +2Br aq

o
cell
=+3.421V E

Pt
Fe
Cl
-
salt bridge
e
-
c
a
t
h
o
d
e
a
n
o
d
e
Cl
2
(g)
34(a)
Fe
2+

34(b)
a
n
o
d
e
c
a
t
h
o
d
e
e
-
salt bridge
Zn
2+
Zn
Ag
Ag
+


34(c)
a
n
o
d
e
c
a
t
h
o
d
e
e
-
salt bridge
Cu
+
Cu
2+
Cu
+
Cu
Pt

34(d)
a
n
o
d
e
c
a
t
h
o
d
e
e
-
salt bridge
Mg
2+
Mg
Pt
Br
2
Br
-

24(a) 24(b)
24(c) 24(d)
Chapter 20: Electrochemistry
1019
A
o
G ,
o
cell
E , and K

25. (M) (a) Oxidation: ( ) ( )
3+
{Al s Al aq +3e } 2

o
=+1.676V E
Reduction: ( ) ( )
2+
{Cu aq +2e Cu s } 3

o
=+0.337V E
______________________
Net: ( ) ( ) ( ) ( )
2+ 3+
2Al s +3Cu aq 2Al aq +3Cu s
o
cell
=+2.013V E
( )( )( )
o o
cell
o 6 3
= = 6 mol e 96,485C/mol e 2.013V
= 1.165 10 J = 1.165 10 kJ
G nFE
G

A
A


(b) Oxidation: ( ) ( )
2
{2I aq I s +2e } 2


o
= 0.535V E
Reduction: ( ) ( )
+
2 2
O g +4H aq +4e 2H O(l)

o
=+1.229V E
_________________________________________
Net: ( ) ( ) ( ) ( )
+
2 2 2
4I aq +O g +4H aq 2I s +2H O(l)

o
cell
=+0.694V E
( )( )( )
o o 5
cell
= = 4 mol e 96,485C/mol e 0.694V = 2.68 10 J = 268kJ G nFE

A

(c) Oxidation: ( ) ( )
+
{Ag s Ag aq +e } 6

o
= 0.800V E
Reduction: ( ) ( ) ( )
2 + 3+
2 7 2
Cr O aq +14H aq +6e 2Cr aq +7H O(l)


o
=+1.33V E

Net: ( ) ( ) ( ) ( ) ( )
2 + + 3+
2 7 2
6Ag s +Cr O aq +14H aq 6Ag aq +2Cr aq +7H O(l)

E
cell
o
= 0.800V +1.33V =+0.53V

( )( )( )
o o 5 2
cell
= = 6mol e 96,485C/mol e 0.53V = 3.1 10 J = 3.1 10 kJ G nFE

A
26. (M) In this problem we need to write the equilibrium constant expression for a set of redox
reactions and determine the value of K at 25
o
C. We proceed by calculating E
cell
o
from
standard electrode reduction potentials (Table 20.1). Then we use the expression

AG
o
=nFE
cell
o
=RTlnK to calculate K.
(a)
Stepwise approach:
Determine E
cell
o
from standard electrode reduction potentials (Table 20.1):
Oxidation:

Ni(s) Ni
2+
(aq)+2e
-
E
o
= 0.257 V
Reduction:

{V
3+
(aq)+e
-
V
2+
(aq)} 2 E
o
= 0.255 V
_________________________
Net:

Ni(s)+2V
3+
(aq) Ni
2+
(aq)+2V
2+
(aq) E
cell
o
=0.003V

Use the expression

AG
o
=nFE
cell
o
=RTlnK to calculate K:
Chapter 20: Electrochemistry
1020

AG
o
=nFE
cell
o
=RTlnK;
AG
o
= 2mole

96485
C
mol
0.003V = 578.9J
AG
o
= RT lnK 578.9J = 8.314JK
1
mol
1
298.15K lnK
lnK = 0.233 K = e
0.233
= 1.26
K = 1.26=
Ni
2+

V
2+

2
V
3+

2

Conversion pathway approach:
Determine E
cell
o
from standard electrode reduction potentials (Table 20.1):
Oxidation: Ni(s) Ni
2+
(aq)+2e
-
E
o
= 0.257 V
Reduction:

{V
3+
(aq)+e
-
V
2+
(aq)} 2 E
o
= 0.255 V
_________________________
Net:

Ni(s)+2V
3+
(aq) Ni
2+
(aq)+2V
2+
(aq) E
cell
o
=0.003V

AG
o
=nFE
cell
o
=RTlnK lnK
eq
=
nFE
cell
o
RT
=
n 96485Cmol
1
8.314JK
1
mol
1
298.15K
E
cell
o
lnK
eq
=
n
0.0257
E
cell
o
=
2 mol e

0.003V
0.0257
= 0.233




K
eq
= e
0.233
= 1.26=
Ni
2+

V
2+

2
V
3+

2

Similar methodology can be used for parts (b) and (c)
(b) Oxidation: 2Cl

aq ( )Cl
2
g ( )+2e

E
o
V = 1.358
Reduction: ( ) ( ) ( )
+ 2+
2 2
MnO s +4H aq +2e Mn aq +2H O(l)

o
=+1.23V E
Net: ( ) ( ) ( ) ( ) ( )
+ 2+ o
2 2 2 cell
2Cl aq +MnO s +4H aq Mn aq +Cl g +2H O(l) = 0.13V E

( )
( )
2+
2
10.1 5
eq 1 eq 2 4
+
Mn {Cl g }
2mol e 0.13V
ln = = 10. ; =e =4 10 =
0.0257
Cl H
P
K K

(



( (


(c) Oxidation: ( ) ( )
2 2
4OH aq O g +2H O(l)+4e


o
= 0.401V E
Reduction:
2
{OCl (aq)+H O(l)+2e Cl (aq)+2OH } 2


o
0.890V E = +

Net:
2
2OCI (aq) 2CI (aq) O (g)

+
o
cell
0.489V E = +
ln
{ }
2
2
76.1 33
eq eq 2
Cl P O (g)
4mol e (0.489V)
76.1 e 1 10
0.0257
OCl
K K

(

= = = = =
(


27. (M) First calculate E
cell
o
from standard electrode reduction potentials (Table 20.1). Then use

AG
o
=nFE
cell
o
=RTlnK to determine AG
o
and K.
Chapter 20: Electrochemistry
1021
(a)
Oxidation: {Ce
3+
(aq) Ce
4+
(aq)+ e

} 5 E
o
=1.61V
Reduction:

MnO
4
-
(aq)+8H
+
(aq)+5e
-
Mn
2+
(aq)+4H
2
O(l) E
o
=+1.51V
Net:MnO
4
-
(aq)+8H
+
(aq)+5Ce
3+
(aq)Mn
2+
(aq)+4H
2
O(l)+5Ce
4+
(aq) E
cell
o
= 0.100V
(b)


AG
o
=nFE
cell
o
=RTlnK;
AG
o
= 5 96485
C
mol
(0.100V) = 48.24kJmol
-1

(c)


AG
o
= RT lnK 48.241000Jmol
-1
= 8.314JK
-1
mol
-1
298.15K lnK
lnK = 19.46 K = e
19.46
= 3.510
9


(d) Since K is very small the reaction will not go to completion.

28. (M) First calculate E
cell
o
from standard electrode reduction potentials (Table 20.1). Then use

AG
o
=nFE
cell
o
=RTlnK to determine AG
o
and K.
(a) Oxidation:Pb
2+
(aq)Pb
4+
(aq)+2e
-
E
o
= 0.180V
Reduction:Sn
4+
(aq)+2e
-
Sn
2+
(aq) E
o
= +0.154V

Net:Pb
2+
(aq)+Sn
4+
(aq)Pb
4+
(aq)+Sn
2+
(aq) E
cell
o
= 0.026V
(b)

AG
o
=nFE
cell
o
=RTlnK AG
o
= 2 96485
C
mol
(0.026) = 5017Jmol
-1

(c)

AG
o
= RT lnK 5017Jmol
-1
= 8.314JK
-1
mol
-1
298.15K lnK
lnK = 2.02 K = e
2.02
= 0.132

(d) The value of K is small and the reaction does not go to completion.

29. (M) (a) A negative value of E
cell
o
(0.0050V ) indicates that
o o
cell
= G nFE A is positive
which in turn indicates that K
eq
is less than one K
eq
<1.00
( )
; A G RT K
o
eq
ln = .

K
eq
Cu Sn
Cu Sn
=
2+
2
2+
+
2
4+


Thus, when all concentrations are the same, the ion product, Q, equals 1.00. From the
negative standard cell potential, it is clear that K
eq
must be (slightly) less than one.
Therefore, all the concentrations cannot be 0.500 M at the same time.

(b) In order to establish equilibrium, that is, to have the ion product become less than 1.00,
and equal the equilibrium constant, the concentrations of the products must decrease
and those of the reactants must increase. A net reaction to the left (towards the
reactants) will occur.
Chapter 20: Electrochemistry
1022

30. (D) (a) First we must calculate the value of the equilibrium constant from the standard
cell potential.


E
cell
o
=
0.0257
n
ln K
eq
; ln K
eq
=
nE
cell
o
0.0257
=
2mol e

(0.017)V
0.0257
=1.32
K
eq
=e
1.32
=0.266

To determine if the described solution is possible, we compare
K
eq
with Q. Now

K
eq
=
BrO
3
-

Ce
4+

2
H
+

2
BrO
4
-

Ce
3+

2
. Thus, when
BrO
4
-

= Ce
4+

= 0.675M, BrO
3
-

= Ce
3+

= 0.600M and pH=1 ( H

+

=0.1M
the ion product, Q =
0.600 0.675
2
0.1
2
0.675 0.600
2
=112.5> 0.266=K
eq
. Therefore, the
described situation can occur

(b) In order to establish equilibrium, that is, to have the ion product (112.5) become equal
to 0.266, the equilibrium constant, the concentrations of the reactants must increase and
those of the products must decrease. Thus, a net reaction to the left (formation of
reactants) will occur.

31. (M) Cell reaction: Zn s ( )+Ag
2
O s ( )ZnO s ( )+2Ag s ( ). We assume that the cell operates at
298 K.

( ) ( ) ( ) ( )
( ) ( )
o o o o o
f f f f 2
o
cell
= ZnO s +2 Ag s Zn s Ag O s
= 318.3 kJ /mol +2 0.00 kJ /mol 0.00 kJ /mol 11.20 kJ /mol
= 307.1 kJ /mol =
G G G G G
nFE
A A A A A ( ( ( (




o 3
o
cell
307.1 10 J /mol
= = =1.591V
2 mol e /mol rxn 96,485C/mol e
G
E
nF

A

32. (M) From equation (20.15) we know n =12 and the overall cell reaction. First we must
compute value of AG
o
.
o o 6 3
cell
96485 C
= = 12 mol e 2.71V = 3.14 10 J = 3.14 10 kJ
1mol e
G n FE

A
Then we will use this value, the balanced equation and values of AG
f
o
to calculate
( )
o
f
4
Al OH G

A (

.
( ) ( ) ( ) ( ) ( )
2 2
4
4Al s +3O g +6H O(l)+4OH aq 4 Al OH aq

(


( ) | | ( ) ( ) ( ) ( )
o o o o o o
f f f 2 f 2 f
4
=4 Al OH 4 [Al s ] 3 [O g ] 6 [H O l ] 4 [OH aq ] G G G G G G

A A A A A A
Chapter 20: Electrochemistry
1023
( ) | | ( ) ( )
( ) | |
3 o
f
4
o
f
4
3.14 10 kJ =4 Al OH 4 0.00 kJ 3 0.00 kJ 6 237.1kJ 4 157.2
=4 Al OH +2051.4 kJ
G
G

A
A

( ) | | ( )
o
f
4
3 3
Al OH = 3.14 10 kJ 2051.4kJ 4= 1.30 10 kJ /mol G

A
33. (D) From the data provided we can construct the following Latimer diagram.
Latimer diagrams are used to calculate the standard potentials of non-adjacent half-cell
couples. Our objective in this question is to calculate the voltage differential between IrO
2

and iridium metal (Ir), which are separated in the diagram by Ir
3+
. The process basically
involves adding two half-reactions to obtain a third half-reaction. The potentials for the two
half-reactions cannot, however, simply be added to get the target half-cell voltage because
the electrons are not cancelled in the process of adding the two half-reactions. Instead, to
find E
1/2 cell
for the target half-reaction, we must use free energy changes, which are additive.
To begin, we will balance the relevant half-reactions in acidic solution:

4 H
+
(aq) +IrO
2
(s) +e

Ir
3+
(aq) +2 H
2
O(l) E
1/2red(a)
=0.223 V
Ir
3+
(aq)+3 e

Ir(s) E
1/2red(b)
=1.156V

4 H
+
(aq) +IrO
2
(s) +4e

2 H
2
O(l) +Ir(s) E
1/2red(c)
=?
E
1/2red(c)
= E
1/2red(a)
+E
1/2red(b)
but AG
(a)
+AG
(b)
= AG
(c)
and AG =nFE
4F(E
1/2red(c)
) =1F(E
1/2red(a)
) + 3F(E
1/2red(b)
)
4F(E
1/2red(c)
) =1F(0.223) + 3F(1.156)
E
1/2red(c)
=
1 (0.223) 3 (1.156)
4
F F
F
+

=
1(0.223) 3(1.156)
4
+

=0.923 V
In other words, E
(c)
is the weighted average of E
(a)
and E
(b)


34. (D) This question will be answered in a manner similar to that used to solve 31.
Let's get underway by writing down the appropriate Latimer diagram:
This time we want to calculate the standard voltage change for the 1 e

reduction of MoO
2
to
Mo
3+
. Once again, we must balance the half-cell reactions in acidic solution:

H
2
MoO
4
(aq) +2 e

+2 H
+
(aq) MoO
2
(s) +2 H
2
O(l) E
1/2red(a)
=0.646 V
MoO
2
(s) +4 H
+
(aq) +1 e

Mo
3+
(aq) +2 H
2
O(l) E
1/2red(b)
=? V

H
2
MoO
4
(aq) +3 e

+6 H
+
(aq) Mo
3+
(aq) +4 H
2
O(l) E
1/2red(c)
=0.428 V

So, 3F(E
1/2red(c)
) =2F(E
1/2red(a)
) + 1F(E
1/2red(b)
)
3F(0.428 V) =2F(0.646) + 1F(E
1/2red(b)
)
1FE
1/2red(b)
=3F(0.428 V) +2F(0.646)
IrO
2
(IV)
Ir
3+
(III)
Ir
(0)
(Acidic conditions)
0.223 V 1.156V
H
2
MoO
4
(VI)
MoO
2
(IV)
Mo
3+
(III)
(Acidic conditions)
0.646 V
? V
0.428 V
Chapter 20: Electrochemistry
1024
E
1/2red(c)
=
3 (0.428 V) 2 (0.646)
1
F F
F
+

=1.284 V 1.292 V = 0.008 V

Concentration Dependence of E
cell
the Nernst Equation

35. (M) In this problem we are asked to determine the concentration of [Ag
+
] ions in
electrochemical cell that is not under standard conditions. We proceed by first determining
E
cell
o
. Using the Nerst equation and the known value of E, we can then calculate the
concentration of [Ag
+
].
Stepwise approach:
First, determine E
cell
o
:
Oxidation: ( ) ( )
2+
Zn s Zn aq +2e

o
=+0.763V E
Reduction: ( ) ( )
+
{Ag aq +e Ag s } 2

o
=+0.800V E
Net: ( ) ( ) ( ) ( )
+ 2+ o
cell
Zn s +2Ag aq Zn aq +2Ag s =+1.563V E
Use the Nerst equation and the known value of E to solve for [Ag]
+
:
2+
o
cell
2 2
+
Zn
1.00 0.0592 0.0592
= log =+1.563V log =+1.250V
2
Ag
E E
n x
(


(


2
1.00M 2 (1.250 1.563)
log 10.6
0.0592 x

= = ;
11 6
2.5 10 5 10 M x

= =
Therefore, [Ag
+
] =5 10
-6
M
Conversion pathway approach:
Oxidation: ( ) ( )
2+
Zn s Zn aq +2e

o
=+0.763V E
Reduction: ( ) ( )
+
{Ag aq +e Ag s } 2

o
=+0.800V E
Net: ( ) ( ) ( ) ( )
+ 2+ o
cell
Zn s +2Ag aq Zn aq +2Ag s =+1.563V E


E=E
cell
o

0.0592
n
log
Zn
2+

Ag
+

2
log
Zn
2+

Ag
+

2
=
n
0.0592
(E E
cell
o
)
Ag
+

2
=
Zn
2+

10

n
0.0592
(E E
cell
o
)
Ag
+

=
Zn
2+

10

n
0.0592
(E E
cell
o
)
Ag
+

=
1.00
10

2
0.0592
(1.2501.563)
= 510
6

36. (M) In each case, we employ the equation
cell
=0.0592pH E .
(a)
cell
=0.0592pH=0.0592 5.25=0.311V E

(b) pH =log 0.0103 ( )=1.987 E
cell
=0.0592pH =0.05921.987=0.118V

Chapter 20: Electrochemistry
1025
(c) K
a
=
H
+

C
2
H
3
O
2

HC
2
H
3
O
2

(
=1.810
5
=
x
2
0.158 x
~
x
2
0.158


5 3
0.158 1.8 10 1.7 10 M x

= =
pH log(1.7 10 ) 2.77
3
= =

cell
=0.0592pH=0.0592 2.77=0.164V E

37. (M) We first calculate E
cell
o
for each reaction and then use the Nernst equation to calculate
E
cell
.
(a) Oxidation: ( ) ( )
3+
{Al s Al 0.18M +3e } 2

o
=+1.676V E
Reduction: ( ) ( )
2+
{Fe 0.85M +2e Fe s } 3

o
= 0.440V E
Net: ( ) ( ) ( ) ( )
2+ 3+
2Al s +3Fe 0.85 M 2Al 0.18 M +3Fe s
o
cell
=+1.236V E

( )
( )
2
2 3+
o
cell cell
3 3
2+
Al
0.18
0.0592 0.0592
= log =1.236V log 1.249V
6
0.85
Fe
E E
n
(

=
(



(b) Oxidation: ( ) ( )
+
{Ag s Ag 0.34M +e } 2

o
= 0.800V E
Reduction: ( ) ( )
2
Cl 0.55atm +2e 2Cl 0.098M


o
=+1.358V E
Net: ( ) ( ) ( ) ( )
+
2
Cl 0.55atm +2Ag s 2Cl 0.098M +2Ag 0.34M

;
o
cell
=+0.558V E
( )
( ) ( )
2 2
+ 2 2
2
o
cell cell
Cl Ag
0.34 0.098 0.0592 0.0592
{Cl g } 2 0.55
= = log =+0.558 log =+0.638V
n P
E E

( (


38. (M) (a) Oxidation: ( ) ( )
2+
Mn s Mn 0.40M +2e

o
=+1.18V E
Reduction: ( ) ( )
3+ 2+
{Cr 0.35M +1e Cr 0.25M } 2

o
= 0.424V E
Net: ( ) ( ) ( ) ( )
3+ 2+ 2+
2Cr 0.35M +Mn s 2Cr 0.25M +Mn 0.40M
o
cell
=+0.76V E

( ) ( )
( )
2
2 2+ 2+
o
cell cell
2 2
3+
Cr Mn
0.25 0.40
0.0592 0.0592
= log =+0.76V log =+0.78V
2
0.35
Cr
E E
n
( (


(



(b) Oxidation:
( ) ( )
2+
{Mg s Mg 0.016M +2e } 3

o
=+2.356V E
Reduction:{

Al OH
( )
4

0.25M
( )
+3e

4OH

0.042M
( )
+Al s
( )
} 2;
o
= 2.310V E
___________
Net:
( ) ( ) ( ) ( ) ( ) ( )
4
2
3Mg s +2[Al OH ] 0.25M 3Mg 0.016M +8OH 0.042M +2Al s
+
;

o
cell
=+0.046V E
Chapter 20: Electrochemistry
1026

E
cell
=E
cell
o

0.0592
6
log
Mg
2+

3
OH

8
Al OH ( )
4

2
=+0.046
0.0592
6
log
0.016 ( )
3
0.042 ( )
8
0.25 ( )
2
=0.046V +0.150V =0.196V


39. (M) All these observations can be understood in terms of the procedure we use to balance
half-equations: the ionelectron method.

(a) The reactions for which E depends on pH are those that contain either H
+
aq ( ) or
OH

aq ( ) in the balanced half-equation. These reactions involve oxoacids and

oxoanions whose central atom changes oxidation state.

(b) H
+
aq ( )will inevitably be on the left side of the reduction of an oxoanion because
reduction is accompanied by not only a decrease in oxidation state, but also by the loss
of oxygen atoms, as in
3 2
ClO CIO

,
2
4 2
SO SO

, and
3
NO NO

. These
oxygen atoms appear on the right-hand side as H O
2
molecules. The hydrogens that are
added to the right-hand side with the water molecules are then balanced with H
+
aq ( )
on the left-hand side.

(c) If a half-reaction with H
+
aq ( ) ions present is transferred to basic solution, it may be
re-balanced by adding to each side OH

aq ( ) ions equal in number to the H

+
aq ( )
originally present. This results in
2
H O(l) on the side that had H
+
aq ( ) ions (the left
side in this case) and OH

aq ( ) ions on the other side (the right side.)

40. (M) Oxidation: ( ) ( )
2
2Cl aq Cl g +2e


o
= 1.358V E
Reduction: ( ) ( ) ( )
+ 2+
2 2
PbO s +4H aq +2e Pb aq +2H O(l)

o
=+1.455V E
Net: ( ) ( ) ( ) ( ) ( )
+ 2+
2 2 2
PbO s +4H aq +2Cl aq Pb aq +2H O(l)+Cl g

;
o
cell
=+0.097 V E
We derive an expression for E
cell
that depends on just the changing H
+
.

2
o 2
cell cell 4 2 4 2
+
0.0592 P{Cl }[Pb ] (1.00atm)(1.00M)
= log =+0.097 0.0296log
2 [H ] [Cl ] [H ] (1.00)
0.097 4 0.0296log[H ] 0.097 0.118log[H ] 0.097 0.118pH
E E
+
+ +
+

= + + = + + = +


(a) E
cell
=+0.097+0.118 log 6.0 ( )=+0.189V
Forward reaction is spontaneous under standard conditions

(b) E
cell
=+0.097+0.118 log 1.2 ( )=+0.106V
Forward reaction is spontaneous under standard conditions
Chapter 20: Electrochemistry
1027

(c) E
cell
V =+0.097 0.118 4.25= 0.405
Forward reaction is nonspontaneous under standard conditions

The reaction is spontaneous in strongly acidic solutions (very low pH), but is
nonspontaneous under standard conditions in basic, neutral, and weakly acidic solutions.

41. (M) Oxidation: ( ) ( )
2+
Zn s Zn aq 2e

+
o
=+0.763V E
Reduction: ( ) ( )
2+
Cu aq +2e Cu s

o
=+0.337V E
Net: ( ) ( ) ( ) ( )
2+ 2+
Zn s +Cu aq Cu s +Zn aq
o
cell
=+1.100V E

(a) We set E =0.000V , Zn M
2+
=1.00 , and solve for Cu
2+
in the Nernst equation.

2+
o
cell cell
2+ 2+
Zn
0.0592 1.0M
= log ; 0.000=1.100 0.0296log
2 Cu Cu
E E
(


( (



2+ 37.2 38
2+
1.0M 0.000 1.100
log = =37.2; Cu =10 =6 10 M
0.0296 Cu

(

(



(b) If we work the problem the other way, by assuming initial concentrations of
2+
Cu =1.0M
initial
(

and
2+
Zn =0.0M
initial
(

, we obtain
2+ 38
Cu =6 10 M
final

(

and
2+
Zn =1.0M
final
(

. Thus, we would conclude that this reaction goes to completion.

42. (M) Oxidation: ( ) ( )
2+ o
Sn s Sn aq +2e =+0.137 V E

Reduction: Pb
2+
aq ( )+2e

Pb s ( ) E
o
=0.125V
Net: Sn s ( )+Pb
2+
aq ( )Sn
2+
aq ( )+Pb s ( ) E
cell
o
=+0.012V
Now we wish to find out if Pb
2+
aq ( ) will be completely displaced, that is, will Pb
2+
reach
0.0010 M, if Sn
2+
is fixed at 1.00 M? We use the Nernst equation to determine if the cell
voltage still is positive under these conditions.
E E
cell cell
o
log
Sn
Pb
log V =
0.0592
2
=+0.012
0.0592
2
1.00
0.0010
=+0.012 0.089= 0.077
2+
2+

The negative cell potential tells us that this reaction will not go to completion under the conditions
stated. The reaction stops being spontaneous when E
cell
=0. We can work this the another way as
well: assume that Pb
2+

=1.0 x ( ) M and calculate Sn M

2+
=x at equilibrium, that is,
whereE
cell
=0. E E
x
x
cell cell
o
log
Sn
Pb
log =0.00=
0.0592
2
=+0.012
0.0592
2 1.0
2+
2+

Chapter 20: Electrochemistry
1028
log
x
1.0 x
=
2 0.012
0.0592
=0.41 x =10
0.41
1.0 x ( )=2.6 2.6x x =
2.6
3.6
=0.72M
We would expect the final Sn
2+
to equal 1.0 M (or at least 0.999 M) if the reaction went to
completion. Instead it equals 0.72 M and consequently, the reaction fails to go to completion.

43. (M) (a) The two half-equations and the cell equation are given below. E
cell
o
V =0.000
Oxidation:
H
2
g ( )2H
+
0.65M KOH ( )+2e

Reduction:
2H
+
1.0M ( )+2e

H
2
g ( )
Net:
2H
+
1.0M ( )2H
+
0.65M KOH ( )

14 2
+ 14 w
base
1.00 10 M
H = = =1.5 10 M
0.65 M
OH
K

(

(


E
cell
=E
cell
o

0.0592
2
log
H
+

base
2
H
+

acid
2
=0.000
0.0592
2
log
1.510
14
( )
2
1.0 ( )
2
=+0.818V
(b) For the reduction of
2
H O(l) to H
2
g ( ) in basic solution,
( ) ( )
2 2
2H O(l)+2e 2H g +2OH aq

, E
o
V = 0.828 . This reduction is the
reverse of the reaction that occurs in the anode of the cell described, with one small
difference: in the standard half-cell, [OH

] =1.00 M, while in the anode half-cell in

the case at hand, [OH

] =0.65 M. Or, viewed in another way, in 1.00 M KOH, [H

+
]
is smaller still than in 0.65 M KOH. The forward reaction (dilution of H
+
) should be
even more spontaneous, (i.e. a more positive voltage will be created), with 1.00 M
KOH than with 0.65 M KOH. We expect that E
cell
o
(1.000 M NaOH) should be a
little larger than E
cell
(0.65 M NaOH), which, is in fact, the case.
44. (M) (a) Because NH
3
aq ( ) is a weaker base than KOH(aq), [OH

] will be smaller than in

the previous problem. Therefore the [H
+
] will be higher. Its logarithm will be less
negative, and the cell voltage will be less positive. Or, viewed as in Exercise 41(b), the
difference in [H
+
] between 1.0 M H
+
and 0.65 M KOH is greater than the difference in
[H
+
] between 1.0 M H
+
and 0.65 M NH
3
. The forward reaction is less spontaneous
and
cell
E is less positive.

Reaction:

Initial:
Changes:
Equil:
( )
3 2
NH aq +H O(l)
0.65M
x M
0.65 x ( ) M

( )
+
4
NH aq +
0M
+x M
x M
OH

aq ( )
~ 0M
+x M
x M

+
2
4
5
3
NH OH
= =1.8 10 =
NH 0.65 0.65
b
x x x
K
x

(
(

( (


~

14
5 3 + 12
3
3
1.00 10
= OH = 0.65 1.8 10 3.4 10 M; [H O ] 2.9 10 M
3.4 10
x

( = = =



(b)
Chapter 20: Electrochemistry
1029
E E
cell cell
o base
2
acid
2
H ]
H ]
V =
0.0592
2
0000
00592
2
29 10
10
0683
12 2
2
=

= +
+
+

log
[
[
.
.
log
( . )
( . )
.

45. (M) First we need to find Ag
+
in a saturated solution of
2 4
Ag CrO .
K
sp
= Ag
+

2
CrO
4
2

= 2s ( )
2
s ( )=4s
3
=1.110
12
s =
1.110
12
4
3
= 6.510
5
M
The cell diagrammed is a concentration cell, for which E
cell
o
V =0.000 , n =1,
+ 4
anode
Ag =2 =1.3 10 M s

(


Cell reaction: Ag s ( )+Ag
+
0.125M ( )Ag s ( )+Ag
+
1.310
4
M
( )

E E
cell cell
o
log
M
M
V V =
0.0592
1
1.3 10
0.125
=0.000+0.177 =0.177
4

46. (M) First we need to determine Ag
+
in the saturated solution of Ag PO
3 4
.
The cell diagrammed is a concentration cell, for which
o
cell
=0.000V, =1 E n .
Cell reaction: Ag s ( )+Ag
+
0.140M ( )Ag s ( )+Ag
+
x M ( )
o
cell cell
0.0592 M M 0.180
=0.180V = log ; log = = 3.04
1 0.140M 0.140M 0.0592
x x
E E

3.04 4 4 +
anode
M =0.140M 10 =0.140M 9.1 10 =1.3 10 M = Ag x

(


( ) ( ) ( ) ( )
3 3
3
+ 3 4 4 17
sp 4
= Ag PO = 3 =1.3 10 1.3 10 3 =9.5 10 K s s

( (



47. (D) (a) Oxidation: ( ) ( )
2+ o
Sn s Sn 0.075M +2e =+0.137 V E

Reduction: Pb
2+
0.600M ( )+2e

Pb s ( ) E
o
=0.125V
_____
Net: ( ) ( ) ( ) ( )
2+ 2+ o
cell
Sn s +Pb 0.600M Pb s +Sn 0.075M ; =+0.012V E

2+
o
cell cell
2+
Sn
0.0592 0.075
= log =0.012 0.0296log =0.012+0.027=0.039V
2 0.600
Pb
E E
(


(



(b) As the reaction proceeds, [Sn
2+
] increases while [Pb
2+
] decreases. These changes cause
the driving force behind the reaction to steadily decrease with the passage of time.
This decline in driving force is manifested as a decrease in E
cell
with time.

(c) When Pb M M M
2+
=0.500 =0.600 0.100 , Sn M M
2+
=0.075 +0.100 , because
the stoichiometry of the reaction is 1:1 for Sn
2+
and Pb
2+
.

2+
o
cell cell
2+
Sn
0.0592 0.175
= log =0.012 0.0296log =0.012+0.013=0.025V
2 0.500 Pb
E E
(


(


Chapter 20: Electrochemistry
1030
Reaction:
Sn(s) + ( )
2+
Pb aq ( ) Pb s + Sn
2+
aq ( )
Initial: 0.600 M
0.075 M
Changes:
x M
+x M
Final:
( ) 0.600 M x

( ) 0.075+ M x

E E
x
x
cell cell
o
log
Sn
Pb
log =
0.0592
2
=0.020=0.012 0.0296
0.075+
0.600
2+
2+

0.27 cell
0.012 0.075+ 0.020 0.012 0.075+
log = = = 0.27; =10 =0.54
0.600 0.0296 0.0296 0.600
E x x
x x

( )
0.324 0.075
0.075+ =0.54 0.600 =0.324 0.54 ; = =0.162M
1.54
x x x x


Sn M
2+
=0.075+0.162=0.237

(e) Here we use the expression developed in part (d).
log
cell
0.075+
0.600
=
0.012
0.0296
=
0.000 0.012
0.0296
=+0.41
x
x
E

( )
+0.41
0.075+
=10 =2.6; 0.075+ =2.6 0.600 =1.6 2.6
0.600
x
x x x
x

1.6 0.075
= =0.42M
3.6
x


2+ 2+
Sn =0.075+0.42=0.50M; Pb =0.600 0.42=0.18M ( (



48. (D) (a) Oxidation: ( ) ( )
+
Ag s Ag 0.015M +e

o
= 0.800V E
Reduction: ( ) ( )
3+ 2+
Fe 0.055M +e Fe 0.045 M

o
=+0.771V E
Net: ( ) ( ) ( ) ( )
3+ + 2+
Ag s +Fe 0.055M Ag 0.015M +Fe 0.045M
o
cell
= 0.029V E

+ 2+
o
cell cell
3+
Ag Fe
0.0592 0.015 0.045
= log = 0.029 0.0592log
1 0.055 Fe
= 0.029V +0.113V =+0.084V
E E
( (



(

(b) As the reaction proceeds, Ag
+
and Fe
2+
will increase, while Fe
3+
decrease. These
changes cause the driving force behind the reaction to steadily decrease with the passage
of time. This decline in driving force is manifested as a decrease in E
cell
with time.

(c) When Ag M M M
+
=0.020 =0.015 +0.005 , Fe M M M
2+
=0.045 +0.005 =0.050 and
Fe M M M
3+
=0.055 0.005 =0.500 , because, by the stoichiometry of the reaction, a mole
of Fe
2+
is produced and a mole of Fe
3+
is consumed for every mole of Ag
+
produced.
(d)
Chapter 20: Electrochemistry
1031

E E
cell cell
o
log
Ag Fe
Fe
log
V V V
=
0.0592
1
= 0.029 0.0592
0.020 0.050
0.050
= 0.029 +0.101 =+0.072
+ 2+
3+

Reaction: Ag s ( )+
( )
3+
Fe 0.055M



Ag
+
0.015M ( )+ Fe
2+
0.045M ( )
Initial: 0.055 M 0.015 M 0.045 M
Changes: M x + M x + M x
Final:
( ) 0.055 M x ( ) 0.015+ M x ( ) 0.045+ M x
E
cell
=E
cell
o

0.0592
1
log
Ag
+

Fe
2+

Fe
3+

=0.029 0.0592log
0.015+x ( ) 0.045+x ( )
0.055 x ( )

log
0.015+x ( ) 0.045+x ( )
0.055 x ( )
=
E
cell
+0.029
0.0592
=
0.010+0.029
0.0592
=0.66

0.015+x ( ) 0.045+x ( )
0.055 x ( )
=10
0.66
=0.22
0.00068+0.060x +x
2
=0.22 0.055 x ( )=0.012 0.22x x
2
+0.28x 0.011=0
x
b b ac
a
=
4
2
=
0.28 (0.28) +4 0.011
2
=0.035
2 2

M
Ag M M M
+
=0.015 +0.035 =0.050
Fe M M M
2+
=0.045 +0.035 =0.080
Fe M M M
3+
=0.055 0.035 =0.020
(e) We use the expression that was developed in part (d).

log
0.015+x ( ) 0.045+x ( )
0.055 x ( )
=
E
cell
+0.029
0.0592
=
0.000+0.029
0.0592
=0.49


0.015+x ( ) 0.045+x ( )
0.055 x ( )
=10
0.49
=0.32
0.00068+0.060x +x
2
=0.32 0.055 x ( )=0.018 0.32x x
2
+0.38x 0.017=0

x
b b ac
a
=
4
2
=
0.38 (0.38) +4 0.017
2
=0.040
2 2

M

Ag M M M
+
=0.015 +0.040 =0.055

Fe M M M
2+
=0.045 +0.040 =0.085

Fe M M M
3+
=0.055 0.040 =0.015

(d)
Chapter 20: Electrochemistry
1032
49. (M) First we will need to come up with a balanced equation for the overall redox reaction.
Clearly, the reaction must involve the oxidation of Cl

(aq) and the reduction of Cr

2
O
7
2
(aq):

14 H
+
(aq) +Cr
2
O
7
2
(aq) +6 e

2 Cr
3+
(aq) +7 H
2
O(l) E
1/2red
=1.33 V
{Cl

(aq) 1/2 Cl
2
(g) +1 e

} 6 E
1/2ox
=1.358 V
_____________________________________________
14 H
+
(aq) +Cr
2
O
7
2
(aq) +6 Cl

(aq) 2 Cr
3+
(aq) +7 H
2
O(l) +3 Cl
2
(g) E
cell
=0.03 V


A negative cell potential means, the oxidation of Cl

(aq) to Cl
2
(g) by Cr
2
O
7
2
(aq) at standard
conditions will not occur spontaneously. We could obtain some Cl
2
(g) from this reaction by
driving it to the product side with an external voltage. In other words, the reverse reaction is
the spontaneous reaction at standard conditions and if we want to produce some Cl
2
(g) from
the system, we must push the non-spontaneous reaction in its forward direction with an
external voltage, (i.e., a DC power source). Since E
cell
is only slightly negative, we could
also drive the reaction by removing products as they are formed and replenishing reactants as
they are consumed.

50. (D) We proceed by first deriving a balanced equation for the reaction occurring in the cell:
Oxidation: Fe(s)Fe
2+
(aq)+2e
-

Reduction: {Fe
3+
(aq)+e
-
Fe
2+
(aq)} 2

Net: Fe(s)+2Fe
3+
(aq)3Fe
2+
(aq)

(a) AG
o
and the equilibrium constant K
eq
can be calculated using

AG
o
=nFE
cell
o
= RT lnK
eq
:

AG
o
=nFE
cell
o
=2 96485Cmol
-1
1.21V = 233.5kJmol
-1
AG
o
= RT lnK = 8.314JK
-1
mol
-1
298.15K lnK = 233.51000Jmol
-1
lnK = 94.2 K = e
94.2
= 8.110
40

(b) Before calculating voltage using the Nernst equation, we need to re-write the net reaction
to take into account concentration gradient for Fe
2+
(aq):
Oxidation: Fe(s)Fe
2+
(aq,1.010
3
M)+2e
-

Reduction: {Fe
3+
(aq,1.010
3
M)+e
-
Fe
2+
(aq,0.10M)} 2

Net: Fe(s)+2Fe
3+
(aq,1.010
-3
)Fe
2+
(aq,1.010
-3
M)+2Fe
2+
(aq,0.10M)
Therefore,
Q =
1.010
3
(0.10)
2
(1.010
3
)
2
= 10
Now, we can apply the Nerst equation to calculate the voltage:

E
cell
= E
cell
o

0.0592
n
log Q
( )
=1.21 V
0.0592
2
log10= 1.18 V

(c) From parts (a) and (b) we can conclude that the reaction between Fe(s) and Fe
3+
(aq) is
spontaneous. The reverse reaction (i.e. disproportionation of Fe
2+
(aq)) must therefore be
nonspontaneous.

50.
Chapter 20: Electrochemistry
1033
Batteries and Fuel Cells

51. (M) Stepwise approach:
(a) The cell diagram begins with the anode and ends with the cathode.
Cell diagram: Cr s ( )|Cr
2+
aq ( ),Cr
3+
aq ( )||Fe
2+
aq ( ),Fe
3+
aq ( )|Fe s ( )

(b) Oxidation: ( ) ( )
2+ 3+
Cr aq Cr aq +e

o
=+0.424V E
Reduction: ( ) ( )
3+ 2+
Fe aq +e Fe aq

o
=+0.771V E
Net: ( ) ( ) ( ) ( )
2+ 3+ 3+ 2+
Cr aq +Fe aq Cr aq +Fe aq
o
cell
=+1.195V E
Conversion pathway approach:
Cr s ( )|Cr
2+
aq ( ),Cr
3+
aq ( )||Fe
2+
aq ( ),Fe
3+
aq ( )|Fe s ( )

o
=+0.424V E
o
=+0.771V E


E
cell
o
=+0.424V + 0.771V = +1.195V
52. (M) (a) Oxidation: ( ) ( )
2+ o
Zn s Zn aq +2e =+0.763V E

Reduction: ( ) ( ) ( )
2 2 2 3
2MnO s +H O(l)+2e Mn O s +2OH aq


Acid-base: ( ) ( ) ( ) ( )
+
4 3 2
{NH aq +OH aq NH g +H O l } 2

Complex: Zn
2+
aq ( )+2NH
3
aq ( )+2Cl

aq ( ) Zn NH
3
( )
2

Cl
2
s ( )
___________________________________________________
Net:
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
+
2 4 2 3 2 3 2
2
Zn s +2MnO s +2NH aq +2Cl aq Mn O s +H O l +[Zn NH ]Cl s

(b)
( )( )( )
o o 5
cell
= = 2mol e 96485C/mol e 1.55V = 2.99 10 J /mol G nFE

A
This is the standard free energy change for the entire reaction, which is composed of
the four reactions in part (a). We can determine the values of AG
o
for the acid-base
and complex formation reactions by employing the appropriate data from Appendix D
and pK
f
= 4.81 (the negative log of the K
f
for [Zn(NH
3
)
2
]
2+
).


( )( ) ( )
2
2 o 1 1 5 4
a b b
= ln = 8.3145J mol K 298.15K ln 1.8 10 =5.417 10 J /mol G RT K

A

( )( ) ( )
o 1 4.81 4
cmplx
= ln = 8.3145J mol K 298.15K ln 10 = 2.746 10 J /mol
f
G RT K

A
o o o o
total redox a b cmplx redox total a b cmplx
5 4 4 5
Then = + + =
= 2.99 10 J /mol 5.417 10 +2.746 10 J /mol = 3.26 10 J /mol
o o o o
G G G G G G G G

A A A A A A A A



Thus, the voltage of the redox reactions alone is
E
o
J
mol e C mol e
V =
3.26 10
2 96485 /
=1.69
5



{ }
o
2 2 3
1.69V =+0.763V + MnO /Mn O E
{ }
o
2 2 3
MnO /Mn O =1.69V 0.763V =+0.93V E

The electrode potentials were calculated by using equilibrium constants from Appendix D.
These calculations do not take into account the cells own internal resistance to the flow of
electrons, which makes the actual voltage developed by the electrodes less than the
theoretical values derived from equilibrium constants. Also because the solid species
Chapter 20: Electrochemistry
1034
(other than Zn) do not appear as compact rods, but rather are dispersed in a paste, and
since very little water is present in the cell, the activities for the various species involved
in the electrochemical reactions will deviate markedly from unity. As a result, the
equilibrium constants for the reactions taking place in the cell will be substantially
different from those provided in Appendix D, which apply only to dilute solutions and
reactions involving solid reactants and products that posses small surface areas. The
actual electrode voltages, therefore, will end up being different from those calculated here.

53. (M) (a) Cell reaction: 2H
2
g ( )+O
2
g ( )2H
2
O l ( )
( ) ( )
o o
f 2
=2 H O l =2 237.1 kJ /mol = 474.2 kJ /mol
rxn
G G A A (



o 3
o
cell
474.2 10 J /mol
= = =1.229V
4mol e 96485C/mol e
G
E
nF

A

(b) Anode, oxidation: ( ) ( )
2+
{Zn s Zn aq +2e } 2

o
=+0.763V E
Cathode, reduction: ( ) ( )
+
2 2
O g +4H aq +4e 2H O(l)

o
=+1.229V E
Net: ( ) ( ) ( ) ( )
+ 2+
2 2
2Zn s +O g +4H aq 2Zn aq +2H O(l)
o
cell
=+1.992V E

(c) Anode, oxidation: ( ) ( )
2+
Mg s Mg aq +2e

o
=+2.356V E
Cathode, reduction: ( ) ( )
2
I s +2e 2I aq


o
=+0.535V E
Net: ( ) ( ) ( ) ( )
2+
2
Mg s +I s Mg aq +2I aq

o
cell
=+2.891V E

54. (M) (a) Oxidation: Zn(s)

Zn
2+
(aq) +2 e

Precipitation: Zn
2+
(aq) +2 OH

(aq)

Zn(OH)
2
(s)
Reduction: 2 MnO
2
(s) +H
2
)(l) +2 e

Mn
2
O
3
(s) +2 OH

(aq)
__
Net : Zn(s) +2 MnO
2
(s) +H
2
O(l) +2 OH

(aq)

Mn
2
O
3
(s) +Zn(OH)
2
(s)

(b) In 50, we determined that the standard voltage for the reduction reaction is +0.93 V (n
=2 e

). To convert this voltage to an equilibrium constant (at 25 C) use:

o
red
2(0.93)
log 31.4
0.0592 0.0592
nE
K = = =
;
31.42 31
red
10 3 10 K = =

and for Zn(s)

Zn
2+
(aq) +2 e

(E =0.763 V and n =2 e

)

o
ox
2(0.763)
log 25.8
0.0592 0.0592
nE
K = = = ;
25.78 25
ox
10 6 10 K = =

AG
total
=AG
precipitation
+AG
oxidation
+AG
reduction

AG
total
=RT ln
2
sp, Zn(OH)
1
K

+ (RT lnK
ox
) + (RT lnK
red
)
Chapter 20: Electrochemistry
1035
AG
total
=RT (ln
2
sp, Zn(OH)
1
K

+ lnK
ox
+ lnK
red
)
AG
total
=0.0083145
kJ
K mol
(298 K) (ln
17
1
1.2 10

+ ln(6.0 10
25
) + ln(2.6 10
31
))
AG
total
=423 kJ =nFE
total

Hence, E
total
=E
cell
=
3
1
423 10 J
(2mol)(96485 C mol )

=2.19 V

55. (M) Aluminum-Air Battery: 2 Al(s) +3/2 O
2
(g) Al
2
O
3
(s)
Zinc-Air Battery: Zn(s) + O
2
(g) ZnO(s)
Iron-Air Battery Fe(s) + O
2
(g) FeO(s)
Calculate the quantity of charge transferred when 1.00 g of metal is consumed in each cell.

Aluminum-Air Cell:
4
1 mol Al(s) 3 mol e 96,485C
1.00 g Al(s) 1.07 10 C
26.98 g Al(s) 1 mol Al(s) 1 mol e

=


Zinc-Air Cell:
3
1 mol Zn(s) 2 mol e 96,485 C
1.00 g Zn(s) 2.95 10 C
65.39 g Zn(s) 1 mol Zn(s) 1 mol e

=


Iron-Air Cell:
3
1 mol Fe(s) 2 mol e 96,485 C
1.00 g Fe(s) 3.46 10 C
55.847 g Fe(s) 1 mol Fe(s) 1 mol e

=


As expected, aluminum has the greatest quantity of charge transferred per unit mass
(1.00 g) of metal oxidized. This is because aluminum has the smallest molar mass and forms
the most highly charged cation (3+for aluminum vs 2+for Zn and Fe).

56. (M) (a) A voltaic cell with a voltage of 0.1000 V would be possible by using two half-
cells whose standard reduction potentials differ by approximately 0.10 V, such as the
following pair.
Oxidation:
( ) ( ) ( )
2 3+ +
7 2 2
2Cr aq +7H O(l) Cr O aq +14H aq +6e


o
= 1.33V E
Reduction:
( ) ( ) ( )
+ 2+
2 2
{PbO s +4H aq +2e Pb aq +2H O(l)} 3

o
=+1.455V E
______________________________
Net: ( ) ( ) ( ) ( ) ( )
2- 3+ 2+ +
2 2 2 7
2Cr aq +3PbO s +H O(l) Cr O aq +3Pb aq +2H aq
o
cell
=0.125V E
The voltage can be adjusted to 0.1000 V by a suitable alteration of the concentrations.
Pb
2+
or H
+
could be increased or Cr
3+
could be decreased, or any combination
of the three of these.

(b) To produce a cell with a voltage of 2.500 V requires that one start with two half-cells
whose reduction potentials differ by about that much. An interesting pair follows.

Oxidation: ( ) ( )
3+
Al s Al aq +3e

o
=+1.676V E
Chapter 20: Electrochemistry
1036
Reduction: ( ) ( )
+
{Ag aq +e Ag s } 3

o
=+0.800V E
___________________________
Net: ( ) ( ) ( ) ( )
+ 3+
Al s +3Ag aq Al aq +3Ag s
o
cell
=+2.476V E

Again, the desired voltage can be obtained by adjusting the concentrations. In this case
increasing Ag
+
and/or decreasing Al
3+
would do the trick.

(c) Since no known pair of half-cells has a potential difference larger than about 6 volts,
we conclude that producing a single cell with a potential of 10.00 V is currently
impossible. It is possible, however, to join several cells together into a battery that
delivers a voltage of 10.00 V. For instance, four of the cells from part (b) would deliver
~10.0 V at the instant of hook-up.
57. (M) Oxidation (anode): Li(s)Li
+
(aq)+e
-
E
o
= +3.040V
Reduction (cathode): MnO
2
(s)+2H
2
O(l)+e
-
Mn(OH)
3
(s)+OH
-
(aq) E
o
= 0.20V
________________________________________________________________________________________________________
Net:MnO
2
(s)+2H
2
O(l)+Li(s)Mn(OH)
3
(s)+OH
-
(aq)+Li
+
(aq) E
cell
o
= 2.84V
Cell diagram: Li(s),Li
+
(aq) KOH(satd) MnO
2
(s),Mn(OH)
3
(s)
58. (M) (a) Oxidation (anode): Zn(s)Zn
+2
(aq)+2e
-
E
o
= +0.763V
Reduction (cathode): Br
2
(l)+2e
-
2Br
-
(aq) E
o
= +1.065V
________________________________________________________________________________________________________
Net: Zn(s)+Br
2
(l)Zn
2+
(aq)+2Br
-
(aq) E
cell
o
= 1.828V
(b) Oxidation (anode): {Li(s)Li
+
(aq)+e
-
} 2 E
o
= +3.040V
Reduction (cathode): F
2
(g)+2e
-
2F
-
(aq) E
o
= +2.866V
________________________________________________________________________________________________________
Net: 2Li(s)+F
2
(g)2Li
+
(aq)+2F
-
(aq) E
cell
o
= 4.868V

Electrochemical Mechanism of Corrosion

59. (M) (a) Because copper is a less active metal than is iron (i.e. a weaker reducing agent),
this situation would be similar to that of an iron or steel can plated with a tin coating
that has been scratched. Oxidation of iron metal to Fe
2+
(aq) should be enhanced in the
body of the nail (blue precipitate), and hydroxide ion should be produced in the vicinity
of the copper wire (pink color), which serves as the cathode.

(b) Because a scratch tears the iron and exposes fresh metal, it is more susceptible to
corrosion. We expect blue precipitate in the vicinity of the scratch.

(c) Zinc should protect the iron nail from corrosion. There should be almost no blue
precipitate; the zinc corrodes instead. The pink color of OH

should continue to form.

60. (M) The oxidation process involved at the anode reaction, is the formation of Fe
2+
(aq). This
occurs far below the water line. The reduction process involved at the cathode, is the formation
of OH

aq ( ) from O
2
(g). It is logical that this reaction would occur at or near the water line
close to the atmosphere (which contains O
2
). This reduction reaction requires O
2
(g) from the
atmosphere and H
2
O(l) from the water. The oxidation reaction, on the other hand simply
Chapter 20: Electrochemistry
1037
requires iron from the pipe together with an aqueous solution into which the Fe
2+
aq ( ) can
disperse and not build up to such a high concentration that corrosion is inhibited.

Anode, oxidation: Fe s ( )Fe
2+
aq ( )+2e

Cathode, reduction: ( ) ( )
2 2
O g +2H O(l)+4e 4OH aq



61. (M)During the process of corrosion, the metal that corrodes loses electrons. Thus, the metal
in these instances behaves as an anode and, hence, can be viewed as bearing a latent negative
polarity. One way in which we could retard oxidation of the metal would be to convert it
into a cathode. Once transformed into a cathode, the metal would develop a positive charge
and no longer release electrons (or oxidize). This change in polarity can be accomplished by
hooking up the metal to an inert electrode in the ground and then applying a voltage across
the two metals in such a way that the inert electrode becomes the anode and the metal that
needs protecting becomes the cathode. This way, any oxidation that occurs will take place at
the negatively charged inert electrode rather than the positively charged metal electrode.

62. (M) As soon as the iron and copper came into direct contact, an electrochemical cell was
created, in which the more powerfully reducing metal (Fe) was oxidized. In this way, the
iron behaved as a sacrificial anode, protecting the copper from corrosion. The two half-
reactions and the net cell reaction are shown below:

Anode (oxidation) Fe(s) Fe
2+
(aq) +2 e

E =0.440 V
Cathode (reduction)
Cu
2+
(aq) +2 e

Cu(s) E =0.337 V

Net: Fe(s) +Cu
2+
(aq) Fe
2+
(aq) +Cu(s) E
cell
=0.777 V

Note that because of the presence of iron and its electrical contact with the copper, any
copper that does corrode is reduced back to the metal.

Electrolysis Reactions

63. (M) Here we start by calculating the total amount of charge passed and the number of moles
of electrons transferred.
60s 2.15C 1mol e
mol e =75min =0.10mol e
1min 1s 96485C

(a) mass Zn mol e
mol Zn
mol e
mol Zn
mol Zn
g Zn
mol Zn
g Zn =0.10
1
2
1
1
65.39
1
=3.3
2+
2+

(b)
3+
3+
1mol Al 1mol Al 26.98g Al
mass Al =0.10mol e =0.90 g Al
3mol e 1mol Al 1mol Al

(c) mass Ag mol e
mol Ag
mol e
mol Ag
mol Ag
g Ag
mol Ag
g Ag =0.10
1
1
1
1
107.9
1
=11
+
+

Chapter 20: Electrochemistry
1038
(d)
2+
2+
1mol Ni 1mol Ni 58.69g Ni
mass Ni =0.10mol e =2.9 g Ni
2mol e 1mol Ni 1mol Ni

64. (M) We proceed by first writing down the net electrochemical reaction. The number of
moles of hydrogen produced in the reaction can be calculated from the reaction
stoichiometry. Lastly, the volume of hydrogen can be determined using ideal gas law.
Stepwise approach:
The two half reactions follow: Cu
2+
aq ( )+2e

Cu s ( ) and 2H
+
aq ( )+2e

H
2
g ( )
Thus, two moles of electrons are needed to produce each mole of Cu(s) and two moles of
electrons are needed to produce each mole of H
2
g ( ). With this information, we can
compute the moles of H
2
g ( ) that will be produced.
( )
( )
( )
2
2 2
1mol H g
1mol Cu 2mol e
mol H g =3.28g Cu =0.0516mol H g
63.55g Cu 1mol Cu 2mol e

Then we use the ideal gas equation to find the volume of H
2
g ( ).
Volume of H (g)
0.0516mol H
0.08206Latm
mol K
(273.2 28.2)K
763 mmHg
1atm
760 mmHg
1.27 L
2
2
=
+

=
This answer assumes the H
2
g ( ) is not collected over water, and that the H
2
(g) formed is the
only gas present in the container (i.e. no water vapor present)
Conversion pathway approach:
Cu
2+
aq ( )+2e

Cu s ( ) and 2H
+
aq ( )+2e

H
2
g ( )
( )
( )
( )
2
2 2
1mol H g
1mol Cu 2mol e
mol H g =3.28g Cu =0.0516mol H g
63.55g Cu 1mol Cu 2mol e

V(H
2
(g)) =
0.0516mol H
2

0.08206L atm
mol K
(273.2+ 28.2)K
763 mmHg
1atm
760 mmHg
= 1.27L

65. (M) Here we must determine the standard cell voltage of each chemical reaction. Those
chemical reactions that have a negative voltage are the ones that require electrolysis.

(a) Oxidation: ( ) ( )
+
2 2
2H O(l) 4H aq +O g +4e

o
= 1.229V E
Reduction: ( ) ( )
+
2
{2H aq +2e H g } 2

o
=0.000V E
Net: ( ) ( )
2 2 2
2H O(l) 2H g +O g
o
cell
= 1.229V E
This reaction requires electrolysis, with an applied voltage greater than+1.229V.

(b) Oxidation: ( ) ( )
2+
Zn s Zn aq +2e

o
=+0.763V E
Reduction: ( ) ( )
2+
Fe aq +2e Fe s

o
= 0.440V E
Chapter 20: Electrochemistry
1039
Net: ( ) ( ) ( ) ( )
2+ 2+
Zn s +Fe aq Fe s +Zn aq
o
cell
=+0.323V E
This is a spontaneous reaction under standard conditions.

(c) Oxidation: {Fe
2+
aq ( )Fe
3+
aq ( )+e

} 2 E
o
=0.771V
Reduction: ( ) ( )
o
2
I s +2e 2I aq =+0.535V E


Net: 2Fe
2+
aq ( )+I
2
s ( )2Fe
3+
aq ( )+2I

aq ( ) E
cell
o
=0.236V
This reaction requires electrolysis, with an applied voltage greater than +0.236V .

(d) Oxidation: ( ) ( )
2+ o
Cu s Cu aq +2e = 0.337V E

Reduction: ( ) ( )
4+ 2+ o
{Sn aq +2e Sn aq } 2 =+0.154V E

Net: Cu s ( )+Sn
4+
aq ( )Cu
2+
aq ( )+Sn
2+
aq ( ) E
cell
o
=0.183V
This reaction requires electrolysis, with an applied voltage greater than +0.183V.

66. (M) (a) Because oxidation occurs at the anode, we know that the product cannot be H
2

(H
2
is produced from the reduction of H O
2
), SO
2
, (which is a reduction product of
SO
4
2
), or SO
3
(which is produced from SO
4
2
without a change of oxidation state;
it is the dehydration product of H SO
2 4
). It is, in fact O
2
that forms at the anode.
The oxidation of water at the anode produces the O
2
(g).

(b) Reduction should occur at the cathode. The possible species that can be reduced are
H O
2
to H
2
g ( ), K
+
aq ( ) to K s ( ), and SO
4
2
aq ( ) to perhaps SO
2
g ( ). Because
potassium is a highly active metal, it will not be produced in aqueous solution. In order
for SO
4
2
aq ( ) to be reduced, it would have to migrate to the negatively charged
cathode, which is not very probable since like charges repel each other. Thus, H
2
g ( )
is produced at the cathode.

(c) At the anode: ( ) ( )
+
2 2
2H O(l) 4H aq +O g +4e

o
= 1.229V E
At the cathode: ( ) ( )
+
2
{2H aq +2e H g } 2

o
=0.000V E
Net cell reaction: ( ) ( )
2 2 2
2H O(l) 2H g +O g
o
cell
= 1.229V E
A voltage greater than 1.229 V is required. Because of the high overpotential required
for the formation of gases, we expect that a higher voltage will be necessary.

67. (M) (a) The two gases that are produced are H
2
g ( ) and O
2
g ( ).
(b) At the anode: ( ) ( )
+
2 2
2H O(l) 4H aq +O g +4e

o
= 1.229V E
At the cathode: ( ) ( )
+
2
{2H aq +2e H g } 2

o
=0.000V E
Net cell reaction: ( ) ( )
2 2 2
2H O(l) 2H g +O g
o
cell
= 1.229V E

68. (M) The electrolysis of Na
2
SO
4
aq ( ) produces molecular oxygen at the anode.
( ) { }
o
2 2
O g /H O = 1.229V E . The other possible product is S
2
O
8
2
aq ( ). It is however,
Chapter 20: Electrochemistry
1040
unlikely to form because it has a considerably less favorable half-cell potential.
( ) ( )
{ }
2 2 o
2 8 4
S O aq /SO aq = 2.01V E

.
H
2
g ( ) is formed at the cathode.
mol O h
s
h
C
s
mol e
C
mol O
mol e
mol O
2
2
2
=3.75
3600
1
2.83
1
1
96485
1
4
=0.0990

The vapor pressure of water at 25

C, from Table 12-2, is 23.8 mmHg.

1 1
2
0.0990mol 0.08206L atmmol K 298K
2.56L O (g)
1atm
(742 23.8) mmHg
760mmHg
nRT
V
P


= = =



69. (M) (a) Zn
2+
aq ( )+2e

Zn s ( )

65.39g Zn 60s 1.87C 1mol e 1mol Zn
mass of Zn=42.5min =1.62 g Zn
1min 1s 96,485C 1mol Zn 2mol e

(b) 2I

aq ( )I
2
s ( )+2e

2
2
2 2
1mol I
2mol e 1s 1min 96,485 C
time needed=2.79gI =20.2min
253.8gI 1mol I 1.75C 60s 1mol e

70. (M) (a) Cu
2+
aq ( )+2e

Cu s ( )

2+
2+
2+
2.68C 1mol e 1mol Cu 1000mmol
mmol Cu consumed=282s
1s 96,485C 1mol 2mol e
=3.92mmol Cu

decrease in Cu
mmol Cu
mL
M
2+
2+
=
3.92
425
=0.00922
final Cu M M M
2+
=0.366 0.00922 =0.357

(b) ( )
+ +
mmol Ag consumed=255mL 0.196M 0.175M =5.36mmol Ag


time needed=5.36mmol Ag
+

1mol Ag
+
1000mmol Ag
+

1mol e

1mol Ag
+

96485C
1mol e

1s
1.84C
=281 s~ 2.810
2
s



71. (M) (a) charge g Ag
mol Ag
g Ag
mol e
mol Ag
C
mol e
C =1.206
1
107.87
1
1
96,485
1
=1079

(b) current
C
s
A =
1079
1412
=0.7642


Chapter 20: Electrochemistry
1041
72. (D) (a) Anode, oxidation: ( ) ( )
+
2 2
2H O(l) 4H aq +4e +O g

o
= 1.229V E
Cathode, reduction: ( ) ( )
+
{Ag aq +e Ag s } 4

o
=+0.800V E
Net: ( ) ( ) ( ) ( )
+ +
2 2
2H O(l)+4Ag aq 4H aq +O g +4Ag s
o
cell
= 0.429V E

(b) ( )
1mol Ag 1mol e 96,485C
charge= 25.8639 25.0782 g Ag =702.8C
107.87g Ag 1mol Ag 1mol e

current
C
h
h
s
A =
702.8
2.00
1
3600
=0.0976

(c) The gas is molecular oxygen.



2
2 2
1mol O 1 mol e L atm
702.8C 0.08206 (23+273) K
96485 C mol K 4mol e
1atm
755mmHg
760mmHg
1000mL
0.0445L O 44.5mL of O
1L
nRT
V
P

| |

|
\ .
= =

= =


73. (D) (a) The electrochemical reaction is:
Anode (oxidation): {Ag(s)Ag
+
(aq)+e
-
(aq)} 2 E
o
= 0.800V
Cathode (reduction): Cu
2+
(aq)+2e
-
Cu(s) E
o
= +0.340V
___________________________________________________________________________________________________
Net: 2Ag(s)+Cu
2+
(aq)Cu(s)+2Ag
+
(aq) E
cell
o
= 0.46V
Therefore, copper should plate out first.
(b) current =
charge
2.50hmin

1h
3600s
=0.75A charge= 6750C
mass=6750 C
1 mole
-
96485 C

1mol Cu
2 mol e
-

63.546 g Cu
1 mol Cu
=2.22 g Cu
(c) The total mass of the metal is 3.50 g out of which 2.22g is copper. Therefore, the mass
of silver in the sample is 3.50g-2.22g=1.28g or (1.28/3.50)x100=37%.

74. (D) First, calculate the number of moles of electrons involved in the electrolysis:
1.20C / s 32.0min
60sec
1min

1mole e
-
96485C
= 0.0239mol e
-

From the known mass of platinum, determine the number of moles:
2.12gPt
1mol Pt
195.078gPt
= 0.0109molPt
Determine the number of electrons transferred:

0.0239 mol e
-
0.0109 mol Pt
= 2.19
Chapter 20: Electrochemistry
1042
Therefore, 2.19 is shared between Pt
2+
and Pt
x+
. Since we know the mole ratio between
Pt
2+
and Pt
x+
, we can calculate x:
2.19=0.90(+2) +0.10 (x).
2.19= 1.80+ 0.10 x x ~ 4
(a) The oxidation state of the contaminant is +4.


INTEGRATIVE AND ADVANCED EXERCISES

75. (M)
3 2
2
Oxidation: V H O VO 2 H e
a
E
+ + +
+ + +
o
3 2 o
2 cell
o
a
Reduction: Ag e Ag(s) 0.800 V
Net: V H O Ag VO 2 H Ag(s) 0.439 V
0.439 V 0.800 V 0
a
E
E
E E
+
+ + + +
+ = +
+ + + + =
= + = .800 V 0.439 V 0.361 V =


2 3 o
2 3 o
2
2 2 3
2
Oxidation: V V e
Reduction: VO 2 H e V H O 0.361 V
Net: V VO 2 H 2 V H O
b
E
E
+ +
+ + +
+ + + +
+
+ + + = +
+ + +
o
cell
o o
3 2 o
0.616 V
0.616 V 0.361 V 0.361 V 0.616 V 0.255 V
Thus, for the cited reaction: V V = 0.255 V
b b
E
E E
e E
+ +
= +
= + = =
+


76. (M)The cell reaction for discharging a lead storage battery is equation (20.24).
O(l) H 2 (s) PbSO (aq) HSO 2 aq) ( H 2 s) ( PbO Pb(s)
2 4 4 2
+ + + +
+

The half-reactions with which this equation was derived indicates that two moles of electrons
are transferred for every two moles of sulfate ion consumed. We first compute the amount of
H
2
SO
4
initially present and then the amount of H
2
SO
4
consumed.
M 63 . 4
L 50 . 1
mol 56 . 0 mol 50 . 7
] SO [H final
SO H mol 0.56
SO mol 1
SO H mol 1
e mol 2
SO mol 2
C 96485
e mol 1
s 1
C 50 . 2
h 1
s 3600
h 6.0 consumed SO H amount
SO H mol 50 . 7
soln L 1
SO H mol 5.00
L 50 . 1 SO H amount initial
4 2
4 2
2
4
4 2
2
4
4 2
4 2
4 2
4 2
=

=
=
=
= =

77. (M) The cell reaction is (g) Cl (g) H (aq) OH 2 O(l) H 2 (aq) Cl 2
2 2 2
+ + +


We first determine the charge transferred per 1000 kg Cl
2
.
9 2
2
2 2
1 mol Cl 1000 g 2 mol e 96,485 C
charge 1000 kg Cl 2.72 10 C
1 kg 70.90 g Cl 1 mol Cl 1 mol e

= =
Chapter 20: Electrochemistry
1043
(a) kJ 10 38 . 9
J 1000
kJ 1
C V 1
J 1
C 10 2.72 V 3.45 energy
6 9
=

=
(b) kWh 10 61 . 2
h W 1000
kWh 1
s 3600
h 1
J 1
s W 1
J 10 9.38 energy
3 9
=

=

78. (D) We determine the equilibrium constant for the reaction.

3+ 2+ 2+
cell
Net: Fe(s) +2 Cr (aq) Fe (aq) +2 Cr (aq) E =+0.016 V


AG
o
= nFE
cell
o
= RT lnK lnK =
nFE
cell
o
RT

3 . 3 e 2 . 1
K 298 K mol J 8.3145
V 016 . 0 e Coul/mol 96485 e mol 2
ln
1..2
1 - 1 -
_ _
= = =

= K K

3 2 2
Reaction: Fe(s) 2Cr (aq) Fe (aq) 2Cr (aq)
Initial : 1.00 M 0 M 0 M
Changes : 2 M M 2 M
Equil: (
x x x
+ + +
+ +
+ +

2 2 2 2
3 2 2
1.00 2 )M M 2 M
[Fe ][Cr ] (2 )
3.3
[Cr ] (1.00 2 )
x x x
x x
K
x
+ +
+
= = =

Let us simply substitute values of x into this cubic equation to find a solution. Notice that x
cannot be larger than 0.50, (values >0.5 will result in a negative value for the denominator.

3 . 3 8 . 3
) 76 . 0 00 . 1 (
(0.76) 38 . 0
38 . 0 3 . 3 0 . 3
) 74 . 0 00 . 1 (
(0.74) 37 . 0
37 . 0
3.3 9 . 1
) 70 . 0 00 . 1 (
(0.70) 35 . 0
35 . 0 3.3 4 . 6
) 80 . 0 00 . 1 (
(0.80) 40 . 0
40 . 0
2
2
2
2
2
2
2
2
> =

= = < =

= =
> =

= = > =

= =
K x K x
K x K x


Thus, we conclude that x =0.37 M =[Fe
2+
].

79. (D) First we calculate the standard cell potential.

2 3 o
o
2 3 o
cell
Oxidation: Fe (aq) Fe (aq) e 0.771 V
Reduction: Ag (aq) e Ag(s) 0.800 V
Net: Fe (aq) Ag (aq) Fe (aq) Ag(s) 0.029 V
E
E
E
+ +
+
+ + +
+ =
+ = +
+ + =

Next, we use the given concentrations to calculate the cell voltage with the Nernst equation.

3
o
cell cell
2
0.0592 [Fe ] 0.0050
log 0.029 0.0592 log 0.029 0.018 0.047 V
1 0.0050 2.0 [Fe ][Ag ]
E E
+
+ +
= = = + =

The reaction will continue to move in the forward direction until concentrations of reactants
decrease and those of products increase a bit more. At equilibrium, E
cell
=0, and we have the
following.
V 424 . 0 2 (aq)} Cr e aq) ( Cr { : Reduction
V 440 . 0 2e (aq) Fe Fe(s) : Oxidation
2 _ 3
_
= +
+ = +
+ +
+ 2
E
E
Chapter 20: Electrochemistry
1044

3 3
o
cell 2 2
2 3
0.0592 [Fe ] [Fe ] 0.029
log 0.029 log 0.49
1 [Fe ][Ag ] [Fe ][Ag ] 0.0592
Reaction: Fe (aq) Ag (aq) Fe (aq) Ag(s)
Initial: 0.0050 M 2.0 M
E
+ +
+ + + +
+ + +
= = = =
+ +
3
0.49
2
0.0050 M
Changes: M M M
Equil: (0.0050 ) M (2.0 - ) M (0.0050 ) M
[Fe ] 0.0050
10 3.1
[Fe ][Ag ] (0.0050 )(2.0 )
x x x
x x x
x
x x
+
+ +

+
+
+
= = =

0.0050
2.0(0.0050 )
0.026
6.2(0.0050 ) 0.0050 0.031 6.2 7.2 0.026 0.0036 M
7.2
x
x
x x x x x
+
~

= + = = = =

Note that the assumption that 2.0 << x is valid. [Fe
2+
] =0.0050 M 0.0036 M =0.0014 M

80. (D) We first note that we are dealing with a concentration cell, one in which the standard
oxidation reaction is the reverse of the standard reduction reaction, and consequently its
standard cell potential is precisely zero volts. For this cell, the Nernst equation permits us to
determine the ratio of the two silver ion concentrations.
cell
1.45
0.0592 [Ag (satd AgI)]
0.000 V log 0.0860 V
1 [Ag (satd AgCl, M Cl )]
[Ag (satd AgI)] 0.0860 [Ag (satd AgI)]
log 1.45 10
0.0592 [Ag (satd AgCl, M Cl )] [Ag (satd AgCl, M Cl )]
E
x
x x
+
+
+ +

+ +
= =

= = = = 0.035


We can determine the numerator concentration from the solubility product expression for AgI(s)

9 17 2 17
sp
10 2 . 9 10 5 . 8 10 5 . 8 ] I ][ Ag [
+
= = = = = s s K M
This permits the determination of the concentration in the denominator.
M 10 6 . 2
035 . 0
10 2 . 9
)] Cl M AgCl, (satd Ag [
7
9

+
=

= x
We now can determine the value of x. Note: Cl

arises from two sources, one being the dissolved

AgCl.

] [Cl M 10 9 . 6
10 6 . 2
10 8 . 6 10 8 . 1

10 6 . 2 10 8 . 6 ) 10 6 . 2 )( 10 6 . 2 ( 10 8 . 1 ] Cl ][ Ag [
4
7
14 10
7 14 7 7 10
sp

+
= =

=
+ = + = = =
x
x x K


81. (M) The Faraday constant can be evaluated by measuring the electric charge needed to
produce a certain quantity of chemical change. For instance, lets imagine that an electric
circuit contains the half-reaction
2
Cu (aq) 2 e Cu(s)
+
+ . The electrode on which the
solid copper plates out is weighed before and after the passage of electric current. The mass
gain is the mass of copper reduced, which then is converted into the moles of copper
reduced. The number of moles of electrons involved in the reduction then is computed from
the stoichiometry for the reduction half-reaction. In addition, the amperage is measured
during the reduction, and the time is recorded. For simplicity, we assume the amperage is
constant. Then the total charge (in coulombs) equals the current (in amperes, that is,
Chapter 20: Electrochemistry
1045
coulombs per second) multiplied by the time (in seconds). The ratio of the total charge (in
coulombs) required by the reduction divided by the amount (in moles) of electrons is the
Faraday constant. To determine the Avogadro constant, one uses the charge of the electron,
1.602 10
19
C and the Faraday constant in the following calculation.


mole
electrons
10 023 . 6
C 10 602 . 1
electron 1
electrons mol 1
C 485 , 96
23
19
A
=

=

N

82. (M) In this problem we are asked to determine AG
f
o
for N
2
H
4
(aq) using the electrochemical
data for hydrazine fuel cell. We first determine the value of
o
G A for the cell reaction, a
reaction in which n =4. AG
f
o
can then be determined using data in Appendix D.
Stewise approach:
Calculate
o
G A for the cell reaction (n=4):
AG
o
= n FE
cell
o
4 mol e
-

96,485 C
1 mol e

1.559 V = 6.01710
5
J = 601.7 kJ
Using the data in Appendix D, determine AG
f
o
for hydrazine (N
2
H
4
):

-601.7 kJ = AG
o
f
[N
2
(g)]+ 2 AG
o
f
[H
2
O(l)] AG
o
f
[N
2
H
4
(aq)] AG
o
f
[O
2
(g)]
= 0.00 kJ + 2 ( 237.2 kJ) AG
o
f
[N
2
H
4
(aq)] 0.00 kJ
AG
o
f
[N
2
H
4
(aq)] = 2 ( 237.2 kJ) + 601.7 kJ = +127.3 kJ

Conversion pathway approach:
AG
o
= n FE
cell
o
4 mol e
-

96,485 C
1 mol e

1.559 V = 6.01710
5
J = 601.7 kJ

-601.7 kJ = AG
o
f
[N
2
(g)]+ 2 AG
o
f
[H
2
O(l)] AG
o
f
[N
2
H
4
(aq)] AG
o
f
[O
2
(g)]
= 0.00 kJ + 2 ( 237.2 kJ) AG
o
f
[N
2
H
4
(aq)] 0.00 kJ
AG
o
f
[N
2
H
4
(aq)] = 2 ( 237.2 kJ) + 601.7 kJ = +127.3 kJ


83. (M) In general, we shall assume that both ions are present initially at concentrations of 1.00 M.
Then we shall compute the concentration of the more easily reduced ion when its reduction
potential has reached the point at which the other cation starts being reduced by electrolysis. In
performing this calculation we use the Nernst equation, but modified for use with a half-
reaction. We find that, in general, the greater the difference in E values for two reduction
half-reactions, the more effective the separation.

(a) In this case, no calculation is necessary. If the electrolysis takes place in aqueous solution,
H
2
(g) rather than K(s) will be produced at the cathode. Cu
2+
can be separated from K
+
by
electrolysis.

(b)
2 o o
Cu (aq) 2 e Cu(s) 0.340 V Ag (aq) e Ag(s) 0.800 V E E
+ +
+ = + + = +
Ag
+
will be reduced first. Now we ask what [Ag
+
] will be when E =+0.337 V.
77 . 7
0592 . 0
340 . 0 800 . 0
] Ag [
1
log
] Ag [
1
log
1
0592 . 0
V 0.800 V 337 . 0 + =

= =
+ +

Chapter 20: Electrochemistry
1046
[Ag
+
] =1.7 10
8
M. Separation of the two cations is essentially complete.

(c)
2 o 2 o
Pb (aq) 2 e Pb(s) 0.125 V Sn (aq) 2 e Sn(s) 0.137 V E E
+ +
+ = + =
Pb
2+
will be reduced first. We now ask what [Pb
2+
] will be when E =0.137 V.
2 2
0.0592 1 1 2(0.137 0.125)
0.137 V 0.125 V log log 0.41
2 0.0592 [Pb ] [Pb ]
+ +

= = =
[Pb
2+
] =10
0.41
=0.39 M Separation of Pb
2+
from Sn
2+
is not complete.

84. (D) The efficiency value for a fuel cell will be greater than 1.00 for any exothermic reaction
( 0
o
< AH ) that has AG that is more negative than its
o
H A value. Since
o o o
S T H G A A = A , this
means that the value of
o
S A must be positive. Moreover, for this to be the case, An
gas
is usually
greater than zero. Let us consider the situation that might lead to this type of reaction. The
combustion of carbon-hydrogen-oxygen compounds leads to the formation of H
2
O(l) and
CO
2
(g). Since most of the oxygen in these compounds comes from O
2
(g) (some is present in
the C-H-O compound), there is a balance in the number of moles of gas producedCO
2
(g)
and those consumedO
2
(g)which is offset in a negative direction by the H
2
O(l) produced.
Thus, the combustion of these types of compounds will only have a positive value of
gas
n A if
the number of oxygens in the formula of the compound is more than twice the number of
hydrogens. By comparison, the decomposition of NOCl(g), an oxychloride of nitrogen, does
produce more moles of gas than it consumes. Let us investigate this decomposition reaction.

278 . 1
kJ /mol 71 . 51
kJ /mol 08 . 66

kJ /mol 08 . 66 kJ /mol 08 . 66 kJ /mol) 0.00 kJ /mol 0.00 kJ /mol (0.00 0.500
NOCl(g)] [ (g)] Cl [ (g)] O [ (g)] N [ G
kJ /mol 71 . 51 kJ /mol 71 . 51 kJ /mol) 0.00 kJ /mol 0.00 kJ /mol (0.00 0.500
NOCl(g)] [ (g)] Cl [ (g)] O [ (g)] N [
(g) Cl g) ( O (g) N NOCl(g)
o
o
f
o
2
f
o
2
1
2
f
o
2
1
2
f
o
2
1
o
f
o
2
f
o
2
1
2
f
o
2
1
2
f
o
2
1
o
2 2
1
2 2
1
2 2
1
=

=
A
A
=
= + + =
A A + A + A = A
= + + =
A A + A + A = A
+ +
H
G
G G G G
H H H H H
c


Yet another simple reaction that meets the requirement that
o o
H G A < A is the combustion of
graphite: g) ( CO g) ( O ) C(graphite
2 2
+ We see from Appendix D that
kJ /mol 4 . 394 g)] ( CO [
2
o
f
= AG is more negative than kJ /mol 5 . 393 g)] ( CO [
2
o
f
= AH . (This
reaction is accompanied by an increase in entropy; AS =213.7-5.74-205.1 =2.86 J /K, c =1.002.)

o o
H G A < A is true of the reaction in which CO(g) is formed from the elements. From
Appendix D, kJ /mol 5 . 110 CO(g)} {
o
f
= AH , and kJ /mol 2 . 137 g)} ( CO {
o
f
= AG , producing c
=(137.2/110.5) =1.242.

Note that any reaction that has c >1.00 will be spontaneous under standard conditions at all
temperatures. (There, of course, is another category, namely, an endothermic reaction that has
0
o
< AS . This type of reaction is nonspontaneous under standard conditions at all temperatures. As
such it consumes energy while it is running, which is clearly not a desirable result for a fuel cell.)

Chapter 20: Electrochemistry
1047
85. (M) We first write the two half-equations and then calculate a value of
o
G A from
thermochemical data. This value then is used to determine the standard cell potential.

_
3 2 2 2
_
2 2
3 2 2 2 2
Oxidation: CH CH OH(g) 3 H O(l) 2CO ( ) 12 H (aq) 12 e
Reduction: {O (g) 4H (aq) 4e 2H O(l)} 3
Overall: CH CH OH(g) 3 O (g) 3H O(l) 2CO ( )
g
g
+
+
+ + +
+ +
+ +

Thus, 12 n =

(a) g)] ( O [ 3 OH(g)] CH CH [ O(l)] H [ G 3 g)] ( CO [ 2
2
o
f 2 3
o
f 2
o
f 2
o
f
o
G G G G A A A + A = A
2( 394.4 kJ /mol) 3( 237.1 kJ /mol) ( 168.5 kJ /mol) 3(0.00 kJ /mol) 1331.6 kJ /mol = + =

3
cell
1331.6 10 J /mol
1.1501 V
12 mol e 96,485 C/mol e
G
E
n F

A
= = = +

(b) V 1501 . 1 )] OH(g CH /CH ) g ( CO [ O] (g)/H O [
2 3 2 2 2 cell
= =

E E E

V 079 . 0 1501 . 1 1.229 OH(g)] CH CH / ) g ( [CO
OH(g)] CH CH / ) g ( CO [ V 1.229
2 3 2
2 3 2
+ = =
=
E
E


86. (M) First we determine the change in the amount of H
+
in each compartment.

2 2 2
Oxidation: 2H O(l) O ( ) 4H (aq) 4e Reduction: 2H (aq) 2e H (g)
60s 1.25C 1mol e 1mol H
amountH 212min 0.165mol H
1min 1s 96,485C 1mol e
g
+ +
+
+ +

+ + +
A = =


Before electrolysis, there is 0.500 mol H
2
PO
4

and 0.500 mol HPO

4
2
in each compartment. The
electrolysis adds 0.165 mol H
+
to the anode compartment, which has the effect of transforming
0.165 mol HPO
4
2
into 0.165 mol H
2
PO
4

, giving a total of 0.335 mol HPO

4
2
(0.500 mol 0.165
mol) and 0.665 mol H
2
PO
4

(0.500 mol +0.165 mol). We can use the Henderson-Hasselbalch

equation to determine the pH of the solution in the anode compartment.

90 . 6
L 500 . 0 / PO H mol 665 . 0
L 500 . 0 / HPO mol 335 . 0
log 20 . 7
] PO H [
] HPO [
log p pH
4 2
2
4
4 2
2
4
2
= + = + =


a
K

Again we use the Henderson-Hasselbalch equation in the cathode compartment. After electrolysis
there is 0.665 mol HPO
4
2
and 0.335 mol H
2
PO
4

. Again we use the Henderson-Hasselbalch

equation.

50 . 7
L 500 . 0 / PO H mol 335 . 0
L 500 . 0 / HPO mol 665 . 0
log 20 . 7
] PO H [
] HPO [
log p pH
4 2
2
4
4 2
2
4
2
= + = + =

a
K



87. (M) We first determine the change in the amount of M
2+
ion in each compartment.


AM
2+
=10.00h
3600 s
1 h

0.500 C
1 s

1mol e
-
96485 C

1mol M
2+
2mol e
-
=0.0933 mol M
2+

This change in amount is the increase in the amount of Cu
2+
and the decrease in the amount of
Zn
2+
. We can also calculate the change in each of the concentrations.
Chapter 20: Electrochemistry
1048

2 2
2 2
0.0933mol Cu 0.0933mol Zn
[Cu ] 0.933M [Zn ] 0.933M
0.1000L 0.1000 L
+ +
+ +
+
A = = + A = =
Then the concentrations of the two ions are determined.

2 2
[Cu ] 1.000M 0.933M 1.933M [Zn ] 1.000M 0.933M 0.067 M
+ +
= + = = =
Now we run the cell as a voltaic cell, first determining the value of E
cell
.

2
2
2
cell
Oxidation : Zn(s) Zn (aq) 2 e 0.763 V
Reduction : Cu (aq) 2 e Cu(s) 0.340 V
Net: Zn(s) Cu (aq) Cu(s) 1.103 V
E
E
E
+
+
+
+ = +
+ = +
+ = +

Then we use the Nernst equation to determine the voltage of this cell.

2
cell cell
2
0.067 M 0.0592 [Zn ] 0.0592
log 1.103 log 1.103 0.043 1.146V
2 2 1.933M [Cu ]
E E
+
+
= = = + =
88. (M)(a)

2
Anode: Zn(s) Zn (aq) 2e 0.763 V E
+
+ = +

- -
2+ -
cell
Cathode: {AgCl(s) +e(aq) Ag(s) +Cl (1 M)} 2 E=+0.2223 V
Net: Zn(s) +2AgCl(s) Zn (aq) +2Ag(s) +2Cl (1 M) E = +0.985 V

(b) The major reason why this electrode is easier to use than the standard hydrogen
electrode is that it does not involve a gas. Thus there are not the practical difficulties
involved in handling gases. Another reason is that it yields a higher value of
cell
E ,
thus, this is a more spontaneous system.

(c)
o
Oxidation: Ag(s) Ag (aq) e 0.800 V E
+
+ =

o
cell
Reduction: AgCl(s) e Ag(s) Cl (aq) 0.2223 V
Net: AgCl(s) Ag (aq) Cl (aq) 0.578 V
E
E

+
+ + = +
+ =

The net reaction is the solubility reaction, for which the equilibrium constant is K
sp
.

sp
ln K RT nFE G = = A

sp
1 1
22.5 10
sp
-10
96485C 1 J
1mol e ( 0.578 V)
1 V.C 1mol e
ln 22.5
8.3145 J mol K 298.15 K
e 1.7 10
This value is in good agreement with thevalue of 1.8 10 given in Table 18-1.
nFE
K
RT
K

= = =

= =

89. (D) (a) Ag(s) Ag
+
(aq) +e
-
-E

= -0.800 V

AgCl(s) +e
-
Ag(s) +Cl
-
(aq) E = 0.2223 V

AgCl(s) Ag
+
(aq) +Cl
-
(aq) E
cell
=-0.5777 V

E
cell
=E
cell
-
0.0592
1
log
[Ag
+
][Cl
-
]
1
|
\

|
.
|
=-0.5777 V
0.0592
1
log
[1.00][1.0010
-3
]
1
|
\

|
.
|
=-0.400V


(b) 10.00 mL of 0.0100 M CrO
4
2-
+100.0 mL of 1.00 10
-3
M Ag
+
(V
total
=110.0 mL)
Chapter 20: Electrochemistry
1049
Concentration of CrO
4
2-
after dilution: 0.0100 M10.00 mL /110.00 mL =0.000909 M
Concentration of Ag
+
after dilution: 0.00100 M100.0 mL /110.00 mL =0.000909 M
Ag
2
CrO
4
(s)
12
1.1 10
sp
K

=

2Ag
+
(aq) + CrO
4
2-
(aq)

Initial 0.000909 M 0.000909 M
Change(100% rxn) -0.000909 M -0.000455 M
New initial 0 M 0.000455 M
Change +2x +x
Equilibrium 2x 0.000455 M+x ~ 0.000455 M
1.1 10
-12
=(2x)
2
(0.000454)
x =0.0000246 M Note: 5.4% of 0.000455 M (assumption may be considered valid)
(Answer would be x =0.0000253 using method of successive approx.)
[Ag
+
] =2x =0.0000492 M (0.0000506 M using method of successive approx.)
- 4
cell cell
0.0592 0.0592
log[ ][Cl ] 0.5777 log[1.00 ][4.92 10 ]
1 1
0.323V (-0.306 V for method of successive approximations)
E E Ag M M
+
= =
=


(c) 10.00 mL 0.0100 M NH
3
+10.00 mL 0.0100 M CrO
4
2-
+100.0 mL 1.0010
-3
M Ag
+

(V
total
=120.0 mL)
Concentration of NH
3
after dilution: 10.0 M10.00 mL /120.00 mL =0.833 M
Concentration of CrO
4
2-
after dilution: 0.0100 M10.00 mL /110.00 mL =0.000833 M
Concentration of Ag
+
after dilution: 0.00100 M100.0 mL /110.00 mL =0.000833 M

In order to determine the equilibrium concentration of free Ag
+
(aq), we first consider
complexation of Ag
+
(aq) by NH
3
(aq) and then check to see if precipitation occurs.


Ag
+
(aq) + 2NH
3
(aq)
7
1.6 10
f
K =

Ag(NH
3
)
2
+
(aq)

Initial 0.000833 M 0.833 M 0 M
Change(100% rxn) -0.000833 M -0.00167 M +0.000833 M
New initial 0 M 0.831 M 0.000833 M
Change +x +2x -x
Equilibrium x (0.831+2x) M (0.000833 x) M
Equilibrium (x ~0) x 0.831 M 0.000833 M

1.6 10
7
=0.000833 /x(0.831)
2
x =7.5410
-11
M =[Ag
+
]
Note: The assumption is valid
Now we look to see if a precipitate forms: Q
sp
=(7.5410
-11
)
2
(0.000833) =4.7 10
-24

Since Q
sp
<K
sp
(1.1 10
-12
), no precipitate forms and [Ag
+
] =7.54 10
-11
M

+ - -11
cell cell
cell
0.0592 0.0592
E =E - log[Ag ][Cl ]=-0.5777 V - log[1.00M][7.54 10 M]
1 1
E =0.0215V


90. (M) We assume that the Pb
2+
(aq) is ignored by the silver electrode, that is, the silver
electrode detects only silver ion in solution.

Chapter 20: Electrochemistry
1050
V 800 . 0 Ag(s) 2 (aq) H 2 Ag 2 (g) H : Net
V 800 . 0 2 Ag(s)} e (aq) {Ag : Reduction
V 000 . 0 e 2 aq) ( H 2 (g) H : Oxidation
cell 2
2
= + +
= +
= +
+ +
+
+
E
E
E

2 2
cell cell
2 2
0.0592 [H ] 0.0592 1.00
log 0.503 V 0.800 V log
2 2 [Ag ] [Ag ]
E E
+
+ +
= =

10 0 . 10
2
2
2
2
10 0 . 1 10
] Ag [
00 . 1
0 . 10
0592 . 0
) 503 . 0 800 . 0 ( 2
] Ag [
00 . 1
log = = =

=
+
+ +




[Ag
+
]
2
=1.010
-10
M
2
[Ag
+
]=1.010
-5


Ag g 10 4 . 5
Ag mol 1
Ag g 87 . 107
Ag mol 1
Ag mol 1
soln L 1
Ag mol 10 0 . 1
L 0.500 Ag mass
4
5

+
+
=

=
Ag % 051 . 0 % 100
sample g 050 . 1
Ag g 10 5.4
Ag %
4
=

=

(by mass)
91. (M) 250.0 mL of 0.1000 M CuSO
4
=0.02500 moles Cu
2+
initially.

moles of Cu
2+
plated out

=
3.512C
s
1368 s
1 mol e
-
96,485 C

1 mol Cu
2+
2 mole
-
= 0.02490mol Cu
2+


moles of Cu
2+
in solution =0.02500 mol 0.02490 mol =0.00010 mol Cu
2+


[Cu
2+
] =0.00010 mol Cu
2+
/0.250 L =4.0 10
-4
M

Cu
2+
(aq) + 4NH
3
(aq)
13
1.1 10
f
K =

Cu(NH
3
)
4
2+
(aq)

Initial 0.00040 M 0.10 M 0 M
Change(100% rxn) -0.00040M maintained +0.00040 M
New initial 0 M 0.10 M 0.00040 M
Change +x maintained -x
Equilibrium x 0.10 M (0.00040 x) M ~ 0.00040 M

2+
13 2+ 13 3 4
f
2+ 4 2+ 4
3
[Cu(NH ) ] 0.00040
K = = 1.1 10 [Cu ] =3.6 10
[Cu ][NH ] [Cu ](0.10)
M

=
Hence, the assumption is valid. The concentration of Cu(NH
3
)
4
2+
(aq) =0.00040 M which is
40 times greater than the 1 10
-5
detection limit. Thus, the blue color should appear.

92. (M) First we determine the molar solubility of AgBr in 1 M NH
3
.
2 6
3 3 sp f
um AgBr(s) 2NH (aq) Ag(NH ) (aq) Br (aq) K K K 8.0 10
Initial 1.00 M 0 M 0 M
quil. 1.00-2s
S
E
+
+ + = =
2
2
6 3 3
2
3
13
sp 10
3
s s {s AgBr molar solubility}
[Ag(NH ) ][Br ]
K 8.0 10 s 2.81 10 M (also [Br ])
[NH (aq)] (1 2 )
K
5.0 10
So [Ag ] 1.8 10
[Br ] 2.81 10
s
s
M
+

= = = =

= = =

Chapter 20: Electrochemistry

1051
13
sp
7
2
3 3 f
6
2
3 3 sp f
AgBr(s) Ag Br K 5.0 10
Ag 2NH Ag(NH ) K 1.6 10
(sum) AgBr(s) 2NH (aq) Ag(NH ) Br K K K 8.0 10
+
+ +
+
+ =
+ =
+ + = =

Now, let's construct the cell, guessing that the standard hydrogen electrode is the anode.
o
2
Oxidation: (g) 2 H 2 e 0.000 V H E
+
+ =

Reduction: {Ag
+
(aq) + e

Ag(s) } 2 E
o
= +0.800 V
Net: 2 Ag
+
(aq) + H
2
(g) 2 Ag(s) + 2 H
+
(aq) E
cell
o
= +0.800V

2 2
o o
10 10
2 10 2
From the Nernst equation:
0.0592 0.0592 [ ] 0.0592 1
E E - log E - log 0.800 V log
n n 2 [ ] (1.78 10 )
and E 0.223 V. Since the voltage is positive, our guess is correct and the standard
hydrogen
H
Q
Ag
+
+
= = =

=
electrode is the anode (oxidizing ele ). ctrode

93. (M) (a) Anode: 2H
2
O(l) 4 e
-
+4 H
+
(aq) +O
2
(g)
Cathode: 2 H
2
O(l) +2 e
-
2 OH
-
(aq) +H
2
(g)
Overall: 2 H
2
O(l) +4 H
2
O(l) 4 H
+
(aq) +4 OH
-
(aq) +2 H
2
(g) +O
2
(g)
2 H
2
O(l) 2 H
2
(g) +O
2
(g)

(b) 21.5 mA =0.0215 A or 0.0215 C s
-1
for 683 s


mol H
2
SO
4
=
0.0215 C
s
683s
1 mol e
-
96485C

1 mol H
+
1 mol e
-

1 mol H
2
SO
4
2 mol H
+
=7.6110
-5
mol H
2
SO
4
7.6110
-5
mol H
2
SO
4
in 10.00 mL. Hence [H
2
SO
4
] =7.6110
-5
mol / 0.01000 L =7.6110
-3
M


94. (D) First we need to find the total surface area


Volume of metal needed =surface area thickness of plating =43.91 cm
2
0.0050 cm =0.22 cm
3

Charge required =

0.22 cm
3

8.90 g
cm
3

1 mol Ni
58.693 g Ni

2 mol e
-
1 mol Ni

96485 C
1 mol e
-
= 6437.5 C
Time =charge/time =6437.5 C / 1.50 C/s =4291.7 s or 71.5 min

Outer circumference =2tr =2t(2.50 cm) =15.7 cm
Surface area =circumference thickness =15.7 cm 0.50 cm =7.85 cm
2


Inner circumference =2tr =2t(1.00 cm) =6.28 cm
Surface area =circumference thickness =6.28 cm 0.50 cm =3.14 cm
2


Area of small circle =tr
2
=t(1.00 cm)
2
=3.14 cm
2

Area of large circle =tr
2
=t(2.50 cm)
2
=19.6 cm
2

Total area =7.85 cm
2
+3.14 cm
2
+2(19.6 cm
2
) 2(3.14 cm
2
) =43.91 cm
2

Chapter 20: Electrochemistry
1052
95. (M) The overall reaction for the electrolytic cell is:


Cu(s)+Zn
2+
(aq) Cu
2+
(aq)+Zn(s) E
cell
o
= 1.103V
Next, we calculate the number of moles of Zn
2+
(aq) plated out and number of moles of
Cu
2+
(aq) formed:


n(Cu
2+
) = =
0.500C
s
10 h
60min
1h

60s
1min

1 mol e
-
96,485 C

1 mol Cu
2+
2 mol e
-
= 0.0935mol Cu
2+
n(Zn
2+
) = n(Cu
2+
)=0.0935mol

Initially, solution contained

1.00molL
-1
0.100L=0.100 mol Zn
2+
(aq). Therefore, at the end
of electrolysis we are left with:


n(Zn
2+
)
LEFT
=(0.100-0.0935)mol=6.510
-3
mol [Zn
2+
]=
6.510
-3
mol
0.1L
=6.510
-2
M
n(Cu
2+
)
FORMED
=0.0935mol [Cu
2+
]=
0.0935mol
0.1L
=0.936M

The new potential after the cell was switched to a voltaic one can be calculated using Nernst
equation:


E
cell
= E
cell

0.0592
2
log
[Zn
2+
]
[Cu
2+
]
= 1.103
0.0592
2
log
6.510
3
M
0.935M
= 1.103+ 0.064= 1.167V

96. (M) (a) The metal has to have a reduction potential more negative than -0.691 V, so that
its oxidation can reverse the tarnishing reactions -0.691 V reduction potential.
Aluminum is a good candidate, because it is inexpensive, readily available, will not react
with water and has an E
o
of -1.676 V. Zinc is also a possibility with an E
o
of -0.763 V,
but we don't choose it because there may be an overpotential associated with the
tarnishing reaction.

3
- 2
2
Oxidation: {Al(s) Al (aq) 3 e } 2
Reduction: {Ag S(s) 2 e Ag(s) S (aq) } 3
Net:
+

+
+ +
(b)
3 2
2
2 Al(s) 3 Ag S(s) 6Ag(s) 2 Al (aq) 3 S (aq)
+
+ + +


(c) The dissolved NaHCO
3
(s) serves as an electrolyte. It would also enhance the electrical
contact between the two objects.

(d) There are several chemicals involved: Al, H
2
O, and NaHCO
3
. Although the aluminum
plate will be consumed very slowly because silver tarnish is very thin, it will,
nonetheless, eventually erode away. We should be able to detect loss of mass after
many uses.

97. (M) (a) Overall: C
3
H
8
(g) +5 O
2
(g) 3 CO
2
(g) +4 H
2
O(l)
Anode: 6 H
2
O(l) +C
3
H
8
(g) 3 CO
2
(g) +20 H
+
(g) +20 e
-

Cathode: 20 e
-
+20 H
+
(g) +5 O
2
(g) 10 H
2
O(l)

AG
rxn
=3(-394.4 kJ /mol) +4(-237.1 kJ /mol) 1(-23.3 kJ /mol) =-2108.3 kJ /mol

Chapter 20: Electrochemistry
1053
AG
rxn
=-2108.3 kJ /mol =-2,108,300 J /mol
AG
rxn
=-nFE
cell
=-20 mol e
-
(96485 C/mol e
-
) E
cell

E
cell
=+1.0926 V

20 e
-
+20 H
+
(g) +5 O
2
(g) 10 H
2
O(l) E
cathode
=+1.229 V

Hence E
cell
=E
cathode
E
anode
+1.0926 V =+1.229 V E
anode


E
anode
=+0.136 V (reduction potential for 3 CO
2
(g) +20 H
+
(g) +20 e
-
6 H
2
O(l) +C
3
H
8
(g))

(b) Use thermodynamic tables for 3 CO
2
(g) +20 H
+
(g) +20 e
-
6 H
2
O(l) +C
3
H
8
(g)

AG
rxn
=6(-237.1 kJ /mol) +1(-23.3 kJ /mol) [(-394.4 kJ /mol) +20( 0kJ /mol)]=-262.7 kJ /mol

AG
red
=-262.7 kJ /mol =-262,700 J /mol =-nFE
red
=-20 mol e
-
(96,485 C/mol e
-
)E
red


E
red
=0.136 V (Same value, as found in (a))

98. (D) (a) Equation 20.15 (AG
o
= zFE
cell
o
) gives the relationship between the standard Gibbs
energy of a reaction and the standard cell potential. Gibbs free energy also varies with
temperature (AG
o
= AH
o
TAS
o
). If we assume that AH
o
and AS
o
do not vary
significantly over a small temperature range, we can derive an equation for the temperature
variation of E
cell
o
:
AG
o
= AH
o
TAS
o
= zFE
cell
o
E
cell
o
=
AH
o
TAS
o
zF

Considering two different temperatures one can write:

E
cell
o
(T
1
) =
AH
o
T
1
AS
o
zF
and E
cell
o
(T
2
) =
AH
o
T
2
AS
o
zF
E
cell
o
(T
1
) E
cell
o
(T
2
) =
AH
o
T
1
AS
o
zF

AH
o
T
2
AS
o
zF
E
cell
o
(T
1
) E
cell
o
(T
2
) =
T
1
AS
o
+ T
2
AS
o
zF
=
AS
o
zF
T
2
T
1
( )

(b) Using this equation, we can now calculate the cell potential of a Daniel cell at 50
o
C:

E
cell
o
(25
o
C) E
cell
o
(50
o
C) =
10.4JK
1
mol
1
2 96485Cmol
1
50 25 ( )K = 0.00135
E
cell
o
(50
o
C) = 1.103V + 0.00135= 1.104V


99. (D) Recall that under non-standard conditions AG = AG
o
+ RT lnK . Substituting
AG
o
= AH
o
TAS
o
and AG = zFE
cell
one obtains:
zFE
cell
= AH
o
TAS
o
+ RT lnQ
For two different temperatures (T
1
and T
2
) we can write:
Chapter 20: Electrochemistry
1054

zFE
cell
(T
1
) = AH
o
T
1
AS
o
+ RT
1
lnQ
zFE
cell
(T
2
) = AH
o
T
2
AS
o
+ RT
2
lnQ
E
cell
(T
1
)+ E
cell
(T
2
) =
AH
o
T
1
AS
o
+ RT
1
lnQ AH
o
+ T
2
AS
o
RT
2
lnQ
zF
E
cell
(T
1
)+ E
cell
(T
2
) =
T
1
AS
o
+ RT
1
lnQ + T
2
AS
o
RT
2
lnQ
zF
E
cell
(T
1
) E
cell
(T
2
) =
T
1
AS
o
RT
1
lnQ
zF

T
2
AS
o
+ RT
2
lnQ
zF
E
cell
(T
1
) E
cell
(T
2
) = T
1
AS
o
RlnQ
zF
|
\

|
.
|
T
2
AS
o
RlnQ
zF
|
\

|
.
|
E
cell
(T
1
) E
cell
(T
2
) = (T
1
T
2
)
AS
o
RlnQ
zF
|
\

|
.
|

The value of Q at 25
o
C can be calculated from E
cell
o
and E
cell
. First calculate E
cell
o
:
Oxidation: Cu(s)Cu
2+
(aq)+2e
-
E
o
= 0.340V
Reduction: 2Fe
3+
(aq)+2e
-
2Fe
2+
(aq) E
o
= +0.771V
_____________________________________________________________________________________________________________
Overall: Cu(s)+2Fe
3+
Cu
2+
(aq)+2Fe
2+
E
cell
o
= 0.431V

0.370= 0.431
0.0592
2
logQ 0.296logQ = 0.431 0.370= 0.061
logQ = 0.206Q = 10
0.206
= 1.61

Now, use the above derived equation and solve for AS
o
:

0.394 0.370= (50 25)
AS
o
8.314 ln1.61
2 96485
|
\

|
.
|
0.024= 25 (
AS
o
3.96
192970
) AS
o
3.96= 185.3 AS
o
= 189.2JK
-1

Since AG
o
= AH
o
TAS
o
= zFE
cell
o
we can calculate AG
o
, K (at 25
o
C) and AH
o
:

AG
o
= zFE
cell
o
= 2 96485 0.431= 83.2kJ
AG
o
= RT lnK 83.21000= 8.314 298.15 lnK
lnK = 33.56 K = e
33.56
= 3.7710
14
-83.2kJ=AH
o
298.15
189.2
1000
kJ AH
o
= 83.2+ 56.4= 26.8kJ

Since we have AH
o
and AS
o
we can calculate the value of the equilibrium constant at 50
o
C:

AG
o
= AH
o
TAS
o
= 26.8kJ (273.15+ 50)K
189.2
1000
kJK
-1
= 87.9kJ
87.91000J = 8.314JK
-1
mol
-1
(273.15+ 50)K lnK
lnK = 32.7 K = e
32.7
= 1.5910
14

Chapter 20: Electrochemistry
1055
Choose the values for the concentrations of Fe
2+
, Cu
2+
and Fe
3+
that will give the value of
the above calculated Q. For example:

Q=
Fe
2+

2
Cu
2+

Fe
3+

2
=1.61
0.1
2
1.61
0.1
2
= 1.61

Determine the equilibrium concentrations at 50
o
C. Notice that since Q<K, a net change
occurs from left to right (the direction of the forward reaction):
Cu(s)+2Fe
3+
Cu
2+
(aq)+2Fe
2+

Initial: 0.1 1.61 0.1
Change: 0.1-x 1.61+x 0.1+x
K=
Fe
2+

eq
2
Cu
2+

eq
Fe
3+

eq
2
=1.5910
14
=
(0.1+ x)
2
(1.61+ x)
(0.1 x)
2

Obviously, the reaction is almost completely shifted towards products. First assume that
the reaction goes to completion, and then let the equilibrium be shifted towards reactants:
Cu(s)+2Fe
3+
Cu
2+
(aq)+2Fe
2+

Initial: 0.1 1.61 0.1
Fina l 0 1.71 0.2
Equilibrium 0+x 1.71-x 0.2-x

K=
Fe
2+

eq
2
Cu
2+

eq
Fe
3+

eq
2
=1.5910
14
=
(0.2 x)
2
(1.71 x)
(x)
2
~
0.2
2
1.71
x
2
x
2
~
0.2
2
1.71
1.5910
14
~ 4.310
16
x ~ 2.110
8
M

Therefore, [Cu
2+
]~1.7M, [Fe
2+
]~0.2M and [Fe
3+
]~2.1x10
-8
M

100. (D) This problem can be solved by utilizing the relationship between AG
o
and E
cell
o
(AG
o
=-
zFE
cell
o
):
Consider a hypothetical set of the following reactions:

A + ne

A
n
E
1
o
and AG
1
o
B + me

B
m
E
2
o
and AG
2
o

Overall: A + B + ne

+ me

A
n
+ B
m
E
rxn
o
= ? and AG
rxn
o
= AG
1
o
+ AG
2
o


AG
rxn
o
= AG
1
o
+ AG
2
o
= nFE
1
o
mFE
2
o
(n + m)FE
rxn
o
= nFE
1
o
mFE
2
o
(n + m)FE
rxn
o
= nFE
1
o
+ mFE
2
o
E
rxn
o
=
nFE
1
o
+ mFE
2
o
n + m

Therefore, for n-sets of half-reactions:
Chapter 20: Electrochemistry
1056
E
o
=
n
i
E
i
o

n
i

The E
o
for the given half-reaction can be determined by combining four half-reactions:
H
6
IO
6
+H
+
+2e
-
IO
3
-
+3H
2
O E
o
= 1.60V
IO
3
-
+6H
+
+5e
-

1
2
I
2
+3H
2
O E
o
= 1.19V
I
2
+2H
2
O2HIO+2H
+
+2e
-
E
o
= 1.45V
2I

I
2
+ 2e

E
o
= 0.535V
Overall :
H
6
IO
6
+H
+
+2e
-
+ IO
3
-
+6H
+
+5e
-
+ I
2
+2H
2
O+2I

IO
3
-
+3H
2
O+
1
2
I
2
+3H
2
O+2HIO+2H
+
+2e
-
+ I
2
+ 2e

H
6
IO
6
+5H
+
+2I
-
+3e
-

1
2
I
2
+4H
2
O+2HIO
E
o
=
1.60 3+1.19 51.45 2 0.535 2
2+ 5 2 2
= 2.26V


FEATURE PROBLEMS


101. (D) (a) Anode: ( ) ( )
+
2
H g,1atm 2H 1M +2e

o
= 0.0000V E
Cathode: ( ) ( )
+
{Ag M +e Ag s } 2 x


o
=0.800V E
_________________________________________
Net: ( ) ( ) ( ) ( )
+ +
2
H g,1atm +2Ag aq 2H 1M +2Ag s
o
cell
=0.800 E

(b) Since the voltage in the anode half-cell remains constant, we use the Nernst equation to
calculate the half-cell voltage in the cathode half-cell, with two moles of electrons.
This is then added to E for the anode half-cell. Because E
o
=0.000 for the anode
half cell, E E
cell cathode
=
o +
2
+
0.0592 1
= log 0.800+0.0592log Ag 0.800 0.0592log
2
Ag
E E x ( = = +

(


(c) (i) Initially
+
Ag =0.0100 (

;
cell
=0.800+0.0592log0.0100=0.682V = E E
Note that 50.0 mL of titrant is required for the titration, since both AgNO
3
and
KI have the same concentrations and they react in equimolar ratios.

(ii) After 20.0 mL of titrant is added, the total volume of solution is 70.0 mL and the
unreacted Ag
+
is that in the untitrated 30.0 mL of 0.0100M AgNO
3
aq ( ).

Chapter 20: Electrochemistry
1057
( )
+
+
cell
30.0mL 0.0100M Ag
Ag = =0.00429M
70.0mL
=0.800+0.0592log 0.00429 =0.660V = E E

(



(iii) After 49.0 mL of titrant is added, the total volume of solution is 99.0 mL and the
unreacted Ag
+
is that in the untitrated 1.0 mL of 0.0100M AgNO
3
aq ( ).

( )
+
+
cell
1.0mL 0.0100M Ag
Ag = =0.00010M
99.0mL
=0.800+0.0592log 0.00010 =0.563V = E E

(



(iv) At the equivalence point, we have a saturated solution of AgI, for which

+ 17 9
sp
Ag = (AgI) 8.5 10 9.2 10 K

( = =



( )
9
cell
=0.800+0.0592log 9.2 10 =0.324V = E E

.

After the equivalence point, the Ag
+
is determined by the I

resulting from
the excess KI(aq).

(v) When 51.0 mL of titrant is added, the total volume of solution is 101.0 mL and
the excess I

is that in 1.0 mL of 0.0100 M KI(aq).

I
-

=
1.0mL 0.0100M I
-
101.0mL
=9.910
-5
M Ag
+

=
K
sp
I
-

=
8.510
-17
0.000099
=8.610
-13
M
( )
13
cell
=0.800+0.0592log 8.6 10 =0.086V = E E

(vi) When 60.0 mL of titrant is added, the total volume of solution is 110.0 mL and
the excess I

is that in 10.0 mL of 0.0100 M KI(aq).

-
-
-17
sp
+ -14
-
10.0mL0.0100M I
I = =0.00091M
110.0mL
K
8.510
Ag = = =9.310 M
0.00091
I
(

(

(

E =0.800+0.0592 log 9.310
14
( )
=0.029V =E
cell


Chapter 20: Electrochemistry
1058
(d) The titration curve is presented below.












102. (D) (a) (1) anode: Na s ( )Na
+
in ethylamine ( )+e

cathode: Na (in ethylamine) Na(amalgam, 0.206%)
+


Net: ( ) ( ) Na s Na amalgam, 0.206%

(2) anode: ( ) ( )
+
2Na amalgam, 0.206% 2Na 1M +2e

cathode: ( )
+
2
2H (aq,1M) +2e H g,1atm

Net:
+ +
2
2Na (amalgam, 0.206%) +2H (aq,1M) 2 Na (1M) +H (g,1atm)

(b) (1)
4
96,485C
= 1mol e 0.8453V = 8.156 10 J
1mol e
G

A or 81.56 kJ
(2)
4
96,485C
= 2mol e 1.8673V = 36.033 10 J
1mol e
G

A or 360.33 kJ

(c) (1)
4
1
2Na(s) 2Na(amalgam, 0.206%) 2 8.156 10 J G A =
(2)
+
2
2Na(amalg, 0.206%) +2H (aq,1M) 2Na (1M) +H (g, 1atm)
+


4
2
36.033 10 J G A =
Overall: 2 2 Na(s) +2H aq) Na (1M) +H g, 1atm)
+
2
( (
+


4 4 4
1 2
= + = 16.312 10 J 36.033 10 J = 52.345 10 J G G G A A A or 523.45 kJ
Since standard conditions are implied in the overall reaction,
o
G G A = A .

(d) ( ) ( ) { } ( ) ( ) { }
4
o o + o +
2
52.345 10 J
= = H 1 M /H 1atm Na 1M /Na s
96,485C 1J
2mol e
1V C 1mol e
cell
E E E

( ) ( ) { }
o +
Na 1M /Na s = 2.713V E . This is precisely the same as the value in
Appendix D.

Plot of Volt age ver sus volume of I
-
(aq)
0
0.2
0.4
0.6
0.8
0 20 40 60 Volume of I
-
(mL)
V
o
l
t
a
g
e

(
V
)
Chapter 20: Electrochemistry
1059
103. (D) The question marks in the original Latimer diagram have been replaced with letters in the
diagram below to make the solution easier to follow:

By referring to Appendix D and by employing the correct procedure for adding together half-
reactions of the same type we obtain:
(c)
2
Br (l) 2e 2Br (aq)

+
o
c
1.065V E = (Appendix D)
(d)
2
BrO (aq) H O(l) 2e Br (aq) 2OH (aq)

+ + +
o
d
0.766V E = (Appendix D)
(b)
2 2
2BrO (aq) 2H O(l) 2e Br (l) 4OH (aq)

+ + +
o
b
0.455V E = (Appendix D)
(a)
3 2
{BrO (aq) 2H O(l) 4e BrO (aq) 4OH (aq)} 2

+ + +
o
a
? E =
(b)
2 2
2BrO (aq) 2H O(l) 2e Br (l) 4OH (aq)

+ + +
o
b
0.455V E =
(c)
2
Br (l) 2e 2Br (aq)

+
o
c
1.065V E =
__________________________________
(e)
3 2
2BrO (aq) 6H O(l) 12e 12OH (aq) 2Br (aq)

+ + +
o
e
0.584V E =

o o o o
(a) (b) (c) Total
G G G G A = A + A + A

( ) ( ) ( ) ( )
o o o o
e a b c
12 8 -2 -2 F E F E F E F E = + +
( ) ( ) ( ) ( )
o
a
12 0.584V 8 -2 0.455V -2 1.065V F F E F F = + +
( ) ( ) ( )
o
a
12 0.584V 2 0.455V 2 1.065V
=0.496 V
8
F F F
E
F
+ +
=

104. (D) (a) The capacitance of the cell membrane is given by the following equation,


0
A
C
l
c c
=
where c
0
c =3 8.854 10
12
C
2
N
1
m
2
;
A =1 10
6
cm
2
; and l =1 10
6
cm.
Together with the factors necessary to convert
from cm to m and from cm
2
to m
2
, these data yield


( )
2
2
12 6 2
1 2
6
C 1 m
3 8.854 10 (1 10 cm)
N m 100 cm

1 m
(1 10 cm)
100 cm
C

| |
| |

| |
\ .
\ .
=
| |

|
\ .
=2.66 10
13

2
C
Nm


2
13 13
2
C 1F
2.66 10 = 2.66 10 F
C Nm
1
Nm
C

| |
|
| |
|
=
|
|
\ .
|
\ .

BrO
4
-
BrO
3
-
BrO
-
Br
2
Br
-
(a) (b) (c)
(d)
1.025 V
0.584 V
(e)
Chapter 20: Electrochemistry
1060

(b) Since the capacitance C is the charge in coulombs per volt, the charge on the membrane,
Q, is given by the product of the capacitance and the potential across the cell membrane.
Q =2.66 10
13

C
V
0.085 V =2.26 10
14
C

(c) The number of K
+
ions required to produce this charge is
14
5 +
19
2.26 10 C
= 1.41 10 K ions
e 1.602 10 C/ion
Q

(d) The number of K
+
ions in a typical cell is
23 3 8 3 11
3
ions mol 1L
6.022 10 155 10 (1 10 cm)= 9.3 10 ions
mol L 1000cm

| |
| || |

| | |
\ .\ .
\ .


(e) The fraction of the ions involved in establishing the charge on the cell membrane is
5
7
11
1.4 10 ions
=1.5 10 (~0.000015 %)
9.3 10 ions

Thus, the concentration of K
+
ions in the cell remains constant at 155 mM.

105. (M) Reactions with a positive cell potential are reactions for which AG
o
< 0, or reactions
for which K>1. AS
o
, AH
o
and AU
o
cannot be used alone to determine whether a
particular electrochemical reaction will have a positive or negative value.

106. (M) The half-reactions for the first cell are:
Anode (oxidation): X(s)X
+
(aq)+e
-
E
X
+
/X
o

Cathode (reduction): 2H
+
(aq)+2e
-
H
2
(g) E
o
= 0V
Since the electrons are flowing from metal X to the standard hydrogen electrode,
E
X
+
/X
o
< 0V .
The half-reactions for the second cell are:
Anode (oxidation): X(s)X
+
(aq)+e
-
E
X
+
/X
o

Cathode (reduction): Y
2+
+2e
-
Y(s) E
Y
2+
/Y
o

Since the electrons are flowing from metal X to metal Y, E
X
+
/X
o
+E
Y
2+
/Y
o
>0.
From the first cell we know that E
X
+
/X
o
< 0V . Therefore, E
X
+
/X
o
>E
Y
2+
/Y
o
.
107. (M) The standard reduction potential of the Fe
2+
(aq)/Fe(s) couple can be determined from:

Fe
2+
(aq)Fe
3+
(aq)+e
-
E
o
= 0.771V
Fe
3+
(aq)+3e
-
Fe(s) E
o
= 0.04V
Overall:
Fe
2+
(aq)+2e
-
Fe(s)

We proceed similarly to the solution for 100:
Chapter 20: Electrochemistry
1061
E
o
=
n
i
E
i
o

n
i
=
0.771 (1) 0.04 3
31
= 0.445V

SELF-ASSESSMENT EXERCISES

108. (E) (a) A standard electrode potential E
o
measures the tendency for a reduction process to
occur at an electrode.
(b) F is the Faraday constant, or the electric charge per mole of electrons (96485 C/mol).
(c) Theanode is the electrode at which oxidation occurs.
(d) The cathode is the electrode at which reduction occurs.

109. (E) (a) A salt bridge is a devise used to connect the oxidation and reduction half-cells of a
galvanic (voltaic) cell.
(b) The standard hydrogen electrode (abbreviated SHE), also called normal hydrogen
electrode (NHE), is a redox electrode which forms the basis of the thermodynamic scale of
oxidation-reduction potentials. By definition electrode potential for SHE is 0.
(c) Cathodic protection is a technique commonly used to control the corrosion of a metal
surface by making it work as a cathode of an electrochemical cell. This is achieved by
placing in contact with the metal to be protected another more easily corroded metal to act as
the anode of the electrochemical cell.
(d) A fuel cell is an electrochemical cell that produces electricity from fuels. The essential
process in a fuel cell is fuel+oxygenoxidation products.

110. (E) (a) An overall cell reaction is a combination of oxidation and reduction half-
reactions.
(b) In a galvanic (voltaic) cell, chemical change is used to produce electricity. In an
electrolytic cell, electricity is used to produce a nonspontaneous rection.
(c) In a primary cell, the cell reaction is not reversible. In a secondary cell, the cell
reaction can be reversed by passing electricity through the cell (charging).
(d) E
cell
o
refers to the standard cell potential (the ionic species are present in aqueous
solution at unit activity (approximately 1M), and gases are at 1 bar pressure (approximately 1
atm).

111. (M) (a) False. The cathode is the positive electrode in a voltaic cell and negative in
electrolytic cell.
(b) False. The function of the salt bridge is to permit the migration of the ions not
electrons.
(c) True. The anode is the negative electrode in a voltaic cell.
(d) True.
(e) True. Reduction always occurs at the cathode of an electrochemical cell. Because of
the removal of electrons by the reduction half-reaction, the cathode of a voltaic cell is
positive. Because of the electrons forced onto it, the cathode of an electrolytic cell is
negative. For both types, the cathode is the electrode at which electrons enter the cell.
Chapter 20: Electrochemistry
1062
(f) False. Reversing the direction of the electron flow changes the voltaic cell into an
electrolytic cell.
(g) True. The cell reaction is an oxidation-reduction reaction.

112. (M) The correct answer is (b), Hg
2+
(aq)is more readily reduced than H
+
(aq).

113. (M) Under non-standard conditions, apply the Nernst equation to calculate E
cell
:

E
cell
= E
cell
o

0.0592
z
logQ
E
cell
= 0.66
0.0592
2
log
0.10
0.01
= 0.63V

The correct answer is (d).

114. (E) (c) The displacement of Ni(s) from the solution will proceed to a considerable extent,
but the reaction will not go to completion.

115. (E) The gas evolved at the anode when K
2
SO
4
(aq) is electrolyzed between Pt electrodes is
most likely oxygen.

116. (M) The electrochemical reaction in the cell is:
Anode (oxidation): {Al(s)Al
3+
(aq)+3e
-
} 2
Cathode (reduction): {H
2
(g)+2e
-
2H
+
(aq)} 3
Overall: 2Al(s)+3H
2
(g)2Al
3+
(aq)+6H
+
(aq)

4.5g Al
1mol Al
26.98g Al

3 mol H
2
2 mol Al
= 0.250mol H
2
0.250 mol H
2

22.4L H
2
1mol H
2
=5.6L H
2


117. (E) The correct answer is (a) AG.

118. (M) Anode (oxidation):{Zn(s)Zn
2+
(aq)+2e
-
} 3 E
o
= 0.763V
Cathode (reduction):{NO
3
-
(aq)+4H
+
(aq)+3e
-
NO(g)+2H
2
O(l)} 2 E
o
= +0.956V
_________________________________________________________________________________________________________
Overall: 3Zn(s)+2NO
3
-
(aq)+8H
+
(aq)3Zn
2+
(aq)+2NO(g)+4H
2
O(l) E
cell
o
= 1.719V
Cell diagram: Zn(s) Zn
2+
(1M) H
+
(1M),NO
3
-
(1M) NO(g,1atm) Pt(s)

119. (M) Apply the Nernst equation:
Chapter 20: Electrochemistry
1063

E
cell
= E
cell
o

0.0592
z
logQ
0.108= 0
0.0592
2
logx
2
logx
2
= 3.65
x
2
= 10
3.65
x = 0.0150M
pH = log(0.0150) = 1.82


120. (M) (a) Since we are given E
cell
o
, we can calculate K for the given reaction:

E
cell
o
=
RT
nF
lnK
0.0050V =
8.314JK
1
mol
1
298K
2 96485Cmol
1
lnK lnK = 0.389
K = e
0.389
= 0.68

Since for the given conditions Q=1, the system is not at equilibrium.
(b) Because Q>K, a net reaction occurs to the left.

121. (M) (a) Fe(s)+Cu
2+
(1M)Fe
2+
(1M)+Cu(s) , E
cell
o
= 0.780V , electron flow from B to A
(b) Sn
2+
(1M)+2Ag
+
(1M)Sn
4+
(aq)+2Ag(s), E
cell
o
= +0.646V , electron flow from A to B.
(c) Zn(s)+Fe
2+
(0.0010M)Zn
2+
(0.10M)+Fe(s) , E
cell
o
= +0.264V ,electron flow from A to
B.

122. (M) (a) Cl
2
(g) at anode and Cu(s) at cathode.
(b) O
2
(g) at anode and H
2
(g) and OH
-
(aq) at cathode.
(c) Cl
2
(g) at anode and Ba(l) at cathode.
(d) O
2
(g) at anode and H
2
(g) and OH
-
(aq) at cathode.

1163
CHAPTER 24

COMPLEX IONS AND COORDINATION COMPOUNDS

PRACTICE EXAMPLES

1A (E) There are two different kinds of ligands in this complex ion, I

and CN

. Both are
monodentate ligands, that is, they each form only one bond to the central atom. Since there
are five ligands in total for the complex ion, the coordination number is 5: C.N.=5. Each
CN

ligand has a charge of 1, as does the I

ligand. Thus, the O.S. must be such that:

O.S.+ 4+1 ( ) 1 ( )

=3= O.S. 5. Therefore, O.S. =+2.

1B (E) The ligands are all

CN

. Fe
3+
is the central metal ion. The complex ion is
Fe CN ( )
6

3
.

2A (E) There are six Cl

ligands (chloride), each with a charge of 1. The platinum metal
center has an oxidation state of +4. Thus, the complex ion is PtCl
6
| |
2
, and we need two
K
+
to balance charge: K
2
PtCl
6
| |
.

2B (E) The SCN

ligand is the thiocyanato group, with a charge of 1, bonding to the
central metal ion through the sulfur atom. The NH
3
ligand is ammonia, a neutral ligand.
There are five (penta) ammine ligands bonded to the metal. The oxidation state of the
cobalt atom is +3. The complex ion is not negatively charged, so its name does not end
with -ate. The name of the compound is pentaamminethiocyanato-S-cobalt(III) chloride.

3A (M) The oxalato ligand must occupy two cis- positions. Either the two NH
3
or the two Cl

ligands can be coplanar with the oxalate ligand, leaving the other two ligands axial. The
other isomer has one NH
3
and one Cl

ligand coplanar with the oxalate ligand. The

structures are sketched below.


3B (M) We start out with the two pyridines, C
5
H
5
N, located cis to each other. With this
assignment imposed, we can have the two Cl

ligands trans and the two CO ligands cis, the

two CO ligands trans and the two Cl

ligands cis, or both the Cl

ligands and the two CO

ligands cis. If we now place the two pyridines trans, we can have either both other pairs
trans, or both other pairs cis. There are five geometric isomers. They follow, in the order
described.

Co NH
3
NH
3
Cl
Cl
ox
Co Cl
Cl
H
3
N
NH
3
ox
Co NH
3
Cl
H
3
N
Cl
ox
Chapter 24: Complex Ions and Coordination Compounds
1164
4A (M) The F

ligand is a weak field ligand. MnF

6

2
is an octahedral complex.

Mn
4+
has
three 3d electrons. The ligand field splitting diagram for MnF
6

2
is sketched below. There
are three unpaired electrons.
e
g



t
2g


4B (M)

Co
2+
has seven 3d electrons. Cl

is a weak field ligand. H

2
O is a moderate field
ligand. There are three unpaired electrons in each case. The number of unpaired electrons
has no dependence on geometry for either metal ion complex.

CoCl
4
| |
2
Co H
2
O ( )
6

2+




5A (M) CN

is a strong field ligand. Co

2+
has seven 3d electrons. In the absence of a crystal
field, all five d orbitals have the same energy. Three of the seven d electrons in this case
will be unpaired. We need an orbital splitting diagram in which there are three orbitals of
the same energy at higher energy. This is the case with a tetrahedral orbital diagram.



|+ |+ | | |
t
2g
| | |
e
g
|
In absence of a
crystal field e
g
|+ |+
t
2g
|+ |+ |+
Tetrahedral geometry Octahedral geometry


Thus, Co CN ( )
4

2
must be tetrahedral (3 unpaired electrons) and not octahedral (1
unpaired electron) because the magnetic behavior of a tetrahedral arrangement would
agree with the experimental observations (3 unpaired electrons).

5B (M) NH
3
is a strong field ligand. Cu
2+
has nine 3d electrons. There is only one way to
arrange nine electrons in five d-orbitals and that is to have four fully occupied orbitals (two
electrons in each orbital), and one half-filled orbital. Thus, the complex ion must be
paramagnetic to the extent of one unpaired electron, regardless of the geometry the ligands
adopt around the central metal ion.

6A (M) We are certain that Co H
2
O
( )
6

2+
is octahedral with a moderate field ligand.
Tetrahedral CoCl
4
| |
2
has a weak field ligand. The relative values of ligand field splitting
for the same ligand are A
t
=0.44A
o
. Thus, Co H
2
O
( )
6

2+
absorbs light of higher energy,
E
E
E
Chapter 24: Complex Ions and Coordination Compounds
1165
blue or green light, leaving a light pink as the complementary color we observe. CoCl
4
| |
2

absorbs lower energy red light, leaving blue light to pass through and be seen.
Cl Mo Cl
NC
5
H
5
CO
OC
NC
5
H
5
OC Mo CO
NC
5
H
5
Cl
Cl
NC
5
H
5
Cl Mo CO
NC
5
H
5
Cl
OC
NC
5
H
5
Cl Mo Cl
NC
5
H
5
NC
5
H
5
OC
CO
Cl Mo CO
NC
5
H
5
NC
5
H
5
Cl
CO


6B (M) In order, the two complex ions are Fe H
2
O ( )
6

2+
and Fe CN ( )
6

4
. We know that
CN

is a strong field ligand; it should give rise to a large value of A

o
and absorb light of
the shorter wavelength. We would expect the cyano complex to absorb blue or violet light
and thus K
4
Fe CN ( )
6

3 H
2
O should appear yellow. The compound
Fe H
2
O ( )
6

NO
3
( )
2
, contains the weak field ligand H
2
O and thus should be green. (The
weak field would result in the absorption of light of long wavelength (namely, red light),
which would leave green as the color we observe.)

INTEGRATIVE EXAMPLE
A (M) (a) There is no reaction with AgNO
3
or en, so the compound must be trans-
chlorobis(ethylenediamine)nitrito-N-cobalt(III) nitrite
Co
H
2
N
H
2
N
H
2
N
N
H
2
Cl
NO
2
+
NO
2
-

(b) If the compound reacts with AgNO
3
, but not with en, it must be trans-
bis(ethylenediamine)dinitrito-N-cobalt(III) chloride.
Co
HN
H
N
H
N
N
H
NO
2
NO
2
+
Cl
-

(c) If it reacts with AgNO
3
and en and is optically active, it must be cis-
bis(ethylenediamine)dinitrito-N-cobalt(III) chloride.
Co
H
2
N
H
2
N
H
2
N
N
H
2
NO
2
NO
2
+
Cl
-

Chapter 24: Complex Ions and Coordination Compounds
1166
B (D) We first need to compute the empirical formula of the complex compound:

46.2 g Pt
1 mol Pt
195.1 g Pt
=0.236 mol Pt
0.236
0.236
=1 mol Pt
33.6 g Cl
1 mol Cl
35.5 g Cl
=0.946 mol Cl
0.946
0.236
=4 mol Pt
16.6 g N
1 mol N
14.01 g N
=1.18 mol N
1.18
0.236
=5 mol N
3.6 g Pt
1 mol H
1 g H
=3.6 mol H
3.6
0.236
=15 mol H

The nitrogen ligand is NH
3
, apparently, so the empirical formula is Pt(NH
3
)
5
Cl
4
.
The effective molality of the solution is m =
AT
K
fp
=
0.74
o
C
1.86
o
C / m
= 0.4m. The effective
molality is 4 times the stated molality, so we have 4 particles produced per mole of Pt
complex, and therefore 3 ionizable chloride ions. We can write this in the following way:
[Pt(NH
3
)
5
Cl][Cl]3. Only one form of the cation (with charge 3+) shown below will exist.
Pt
H
3
N
H
3
N NH
3
NH
3
NH
3
Cl
+3



EXERCISES

Nomenclature

1. (E) (a) CrCl
4
NH
3
( )
2

diamminetetrachlorochromate(III) ion

(b) Fe CN ( )
6

3
hexacyanoferrate(III) ion

(c) ( ) ( )
3 4
3 2
Cr en Ni CN ( (

. tris(ethylenediamine)chromium(III) tetracyanonickelate(II)
ion

2. (E) (a) Co NH
3
( )
6

2+
The coordination number of Co is 6; there are six
monodentate NH
3
ligands attached to Co. Since the NH
3
ligand is neutral, the
oxidation state of cobalt is +2, the same as the charge for the complex ion;
hexaamminecobalt(II) ion.

Chapter 24: Complex Ions and Coordination Compounds
1167
(b) AlF
6
3
The coordination number of Al is 6; F

is monodentate. Each F

has a 1
charge; thus the oxidation state of Al is +3; hexafluoroaluminate(III) ion.

(c) ( )
2
4
Cu CN

(

The coordination number of Cu is 4; CN

is monodentate. CN

has a
1 charge; thus the oxidation state of Cu is +2; tetracyanocuprate(II) ion

(d) ( )
+
2 3
4
CrBr NH (

The coordination number of Cr is 6; NH
3
and Br

are
monodentate. NH
3
has no charge; Br

has a 1 charge. The oxidation state of

chromium is +3; tetraamminedibromochromium(III) ion

(e) Co ox ( )
3

4
The coordination number of Co is 6; oxalate is bidentate. C
2
O
4
2
ox ( )
has a 2 charge; thus the oxidation state of cobalt is +2; trioxalatocobaltate(II) ion.

(f) Ag S
2
O
3
( )
2

3
The coordination number of Ag is 2; S O
2 3
2
is monodentate. S O
2 3
2

has a 2 charge; thus the oxidation state of silver is +1; dithiosulfatoargentate(I)
ion. ( Although +1 is by far the most common oxidation state for silver in its
compounds, stable silver(III) complexes are known. Thus, strictly speaking, silver is
not a non-variable metal, and hence when naming silver compounds, the oxidation
state(s) for the silver atom(s) should be specified).

3. (M) (a) Co OH ( ) H
2
O ( )
4
NH
3
( )

2+
amminetetraaquahydroxocobalt(III) ion

(b) Co ONO ( )
3
NH
3
( )
3

triamminetrinitrito-O-cobalt(III)

(c) Pt H
2
O ( )
4

PtCl
6
| |
tetraaquaplatinum(II) hexachloroplatinate(IV)

(d) Fe ox ( )
2
H
2
O ( )
2

diaquadioxalatoferrate(III) ion

(e) Ag HgI
2 4
silver(I) tetraiodomercurate(II)

4. (M) (a) K
3
Fe CN ( )
6

potassium hexacyanoferrate(III)

(b) Cu en ( )
2

2+
bis(ethylenediamine)copper(II) ion

(c) Al OH ( ) H
2
O ( )
5

Cl
2
pentaaquahydroxoaluminum(III) chloride

(d) CrCl en ( )
2
NH
3

SO
4
amminechlorobis(ethylenediammine)chromium(III) sulfate

(e) Fe en ( )
3

4
Fe CN ( )
6

3
tris(ethylenediamine)iron(III) hexacyanoferrate(II)

Chapter 24: Complex Ions and Coordination Compounds
1168
Bonding and Structure in Complex Ions

5. (E) The Lewis structures are grouped together at the end.

(a) H
2
O has 12 +6 =8 valence electrons, or 4 pairs.

(b) CH NH
3 2
has 4+3 1+5+2 1=14 valence electrons, or 7 pairs.

(c) ONO

has 2 6+5+1=18 valence electrons, or 9 pairs. The structure has a 1

formal charge on the oxygen that is singly bonded to N.

(d) SCN

has 6+4+5+1=16 valence electrons, or 8 pairs. This structure,

appropriately, gives a 1 formal charge to N.

S C N
(c) (d) (a)
N C
H
H
H
H
H
(b)
O N O O
H
H


6. (M) The Lewis structures are grouped together at the end.

(a) OH
-
has 6+1 +1=8 valence electrons, or 4 pairs.

(b) SO
4
2-
has 6+6 4+2=32 valence electrons, or 16 pairs.

(c) C
2
O
4
2-
has 2 4+6 4+2=34 valence electrons, or 17 pairs.

(d) SCN

has 6+4+5+1=16 valence electrons, or 8 pairs. This structure,

appropriately, gives a 1 formal charge to N.

S O
O
O
O
2+
O H
O O
O
O O
O
monodentate
or bidentate
C N S
(a) (b) (c) (d)


7. (M) We assume that PtCl
4
2
is square planar by analogy with PtCl
2
NH
3
( )
2

in Figure
24-5. The other two complex ions are octahedral.

Pt Cl
Cl
Cl
Cl
Cr H
2
O
Cl
OH
2
OH
2
OH
2
H
2
O
Co H
2
O
NH
3
NH
3
OH
2
NH
3
H
2
O
2-
2+ 2+ (a) (b) (c)
Chapter 24: Complex Ions and Coordination Compounds
1169
8. (M) The structures for Pt ox ( )
2

2
and Cr ox ( )
3

3
are drawn below. The structure of
Fe EDTA ( )

2
is the same as the generic structure for ( )
2
M EDTA

(

drawn in Figure 24-23,
with M
n+
=Fe
2+
.
(a) (b)





(c) See Figure 24-23.


9. (M) (a) (b)







pentaamminesulfateochromium(III) trioxalatocobaltate(III)

(c)

Co
NH
3
Cl Cl
NH
3
ONO
NH
3
Co
NH
3
NH
3
Cl
Cl
ONO
NH
3
Co
NH
3
ONO Cl
NH
3
Cl
NH
3
fac-triamminedichloronitro-O-cobalt(III) mer-triammine-cis-dichloronitro-O-cobalt(III)
mer-triammine-trans-dichloronitro-O-cobalt(III)


10. (M) (a) pentaamminenitroto-N-cobalt(III) ion (b) ethylenediaminedithiocyanato-S-
copper(II)






Pt
O
O
O
C
C
C C
C
O
O
O
O
O
O
Cr O
O
O
O
C
C
O
O
C
C
O
O
C
C O
O
O
O
Co O
O
O
O
C
C
O
O
C
C
O
O
C
C O
O
2-
3-
3-
Cr
NH
3
OSO
3
H
3
N
NH
3
H
3
N
NH
3
+
Co
NH
3
NH
3
O
2
N
NH
3
H
3
N
NH
3
2+
Cu NCS
H
2
N
NH
2
SCN
CH
2
CH
2
Chapter 24: Complex Ions and Coordination Compounds
1170
(c) hexaaquanickel(II) ion








Isomerism

11. (E) (a) cis-trans isomerism cannot occur with tetrahedral structures because all of the
ligands are separated by the same angular distance from each other. One ligand
cannot be on the other side of the central atom from another.

(b) Square planar structures can show cis-trans isomerism. Examples are drawn following,
with the cis-isomer drawn on the left, and the trans-isomer drawn on the right.

(c) Linear structures do not display cis-trans isomerism; there is only one way to bond
the two ligands to the central atom.
12. (M) (a) CrOH NH
3
( )
5

2+
has one isomer.






(b) CrCl
2
H
2
O ( ) NH
3
( )
3

+
has three isomers.






(c) CrCl
2
en ( )
2

+
has two geometric isomers, cis- and trans-.





M
B
A
A
B
cis-isomer
M
B
B
A
A
trans-isomer
Ni
H
2
O
OH
2
H
2
O
H
2
O
H
2
O
OH
2
2+
Cr
NH
3
NH
3
HO
NH
3
H
3
N
NH
3
2+
Cr
Cl
Cl H
2
O
NH
3
H
3
N
NH
3
+
Cr
Cl
NH
3
H
2
O
NH
3
H
3
N
Cl
+
Cr
Cl
NH
3
H
2
O
Cl
H
3
N
NH
3
+
Cr
N
N N
N
Cl
Cl
C
C
C
C
Cr
Cl
N N
N
N
Cl
C
C
C
C
+
+
Chapter 24: Complex Ions and Coordination Compounds
1171
(d) CrCl
4
en ( )

has only one isomer since the ethylenediamine (en) ligand cannot
bond trans to the central metal atom.







(e) Cr en ( )
3

3+
has only one geometric isomer; it has two optical isomers.








13. (M) (a) There are three different square planar isomers, with D, C, and B, respectively,
trans to the A ligand. They are drawn below.



(b) Tetrahedral ZnABCD
2+
does display optical isomerism. The two optical isomers
are drawn above.

14. (M) There are a total of four coordination isomers. They are listed below. We assume that
the oxidation state of each central metal ion is +3.

Co en ( )
3

Cr ox ( )
3

tris(ethylenediamine)cobalt(III) trioxalatochromate(III)

Co ox ( ) en ( )
2

Cr ox ( )
2
en ( )

bis(ethylenediamine)oxalatocobalt(III)
(ethylenediamine)dioxalatochromate(III)

Cr ox ( ) en ( )
2

Co ox ( )
2
en ( )

bis(ethylenediamine)oxalatochromium(III)
(ethylenediamine)dioxalatocobaltate(III)

Cr en ( )
3

Co ox ( )
3

tris(ethylenediamine)chromium(III) trioxalatocobaltate(III)

Pt
A
D
B
C
Pt
A
C
B
D
Pt
A
B
C
D
Zn
A
D
B
C
Zn
B
D
A
C
Cr
Cl
N Cl
N
Cl
Cl
C
C
-
Cr
N
N N
N
N
N
C
C
C
C
C
C
3+
Chapter 24: Complex Ions and Coordination Compounds
1172
15. (M) The cis-dichlorobis(ethylenediamine)cobalt(III) ion is optically active. The two optical
isomers are drawn below. The trans-isomer is not optically active: the ion and its mirror
image are superimposable.

16. (M) Complex ions (a) and (b) are identical; complex ions (a) and (d) are geometric
isomers; complex ions (b) and (d) are geometric isomers; complex ion (c) is distinctly
different from the other three complex ions (it has a different chemical formula).

Crystal Field Theory

17. (E) In crystal field theory, the five d orbitals of a central transition metal ion are split into
two (or more) groups of different energies. The energy spacing between these groups often
corresponds to the energy of a photon of visible light. Thus, the transition-metal complex
will absorb light with energy corresponding to this spacing. If white light is incident on the
complex ion, the light remaining after absorption will be missing some of its components.
Thus, light of certain wavelengths (corresponding to the energies absorbed) will no longer
be present in the formerly white light. The resulting light is colored. For example, if blue
light is absorbed from white light, the remaining light will be yellow in color.

18. (E) The difference in color is due to the difference in the value of A , which is the ligand field
splitting energy. When the value of A is large, short wavelength light, which has a blue color,
is absorbed, and the substance or its solution appears yellow. On the other hand, when the
value of A is small, light of long wavelength, which has a red or yellow color, is absorbed,
and the substance or its solution appears blue. The cyano ligand is a strong field ligand,
producing a large value of A , and thus yellow complexes. On the other hand, the aqua ligands
are weak field ligands, which produce a small value of A , and hence blue complexes.

19. (M) We begin with the 7 electron d-orbital diagram for Co
2+
[Ar]

The strong field and weak field diagrams for octahedral complexes follow, along with the
number of unpaired electrons in each case.

Strong Field Weak Field



(1 unpaired (3 unpaired
electron) electrons)

N
Cl
Co N
N
Cl
N
C
C
C
C
N
N
Co N
N
Cl
Cl
C
C
C
C
N
Cl
Co N
N
Cl
N
C
C
C
C
cis-isomers trans-isomer

e
g
e
g
t
2g
t
2g
Chapter 24: Complex Ions and Coordination Compounds
1173

20. (M) We begin with the 8 electron d-orbital diagram for
| |
2+
Ni Ar
The strong field and weak field diagrams for octahedral complexes follow, along with the
number of unpaired electrons in each case.
Strong Field Weak Field



(2 unpaired
electrons)
(2 unpaired
electrons)

The number of unpaired electrons is the same in both cases.

21. (M) (a) Both of the central atoms have the same oxidation state, +3. We give the electron
configuration of the central atom to the left, then the completed crystal field diagram
in the center, and finally the number of unpaired electrons. The chloro ligand is a
weak field ligand in the spectrochemical series.
Mo
3+
Kr 4
3
d weak field
Kr
4d

3 unpaired electrons; paramagnetic
The ethylenediamine ligand is a strong field ligand in the spectrochemical series.
Co
3+
Ar 3
6
d strong field
Ar


no unpaired electrons; diamagnetic

(b) In CoCl
4
2
the oxidation state of cobalt is 2+. Chloro is a weak field ligand. The
electron configuration of Co
2+
is
| |
7
Ar 3d or
| |
Ar

The tetrahedral ligand field diagram is weak field
shown on the right.

3 unpaired electrons

22. (M) (a) In ( )
2+
4
Cu py (

the oxidation state of copper is +2. Pyridine is a strong field
ligand. The electron configuration of
2+
Cu is
| |
9
Ar 3d or
| | Ar

There is no possible way that an odd number of electrons can be paired up, without
at least one electron being unpaired. ( )
2+
4
Cu py (

is paramagnetic.

e
g
t
2g
e
g
t
2g
e
g
t
2g
e
g
t
2g
t
2g
e
g


Chapter 24: Complex Ions and Coordination Compounds
1174
e
g
(b) In Mn CN ( )
6

3
the oxidation state of manganese is +3. Cyano is a strong field
ligand. The electron configuration of Mn
3+
is
| |
4
Ar 3d or
| | Ar
The ligand field diagram follows, on the left-hand side. In
| |
4
FeCl

the oxidation
state of iron is+3. Chloro is a weak field ligand. The electron configuration of Fe
3+

is
| |
5
Ar 3d or [Ar]
The ligand field diagram follows, below.

strong field weak field



2 unpaired electrons 5 unpaired electrons
There are more unpaired electrons in FeCl
4

than in ( )
3
6
Mn CN .

(


23. (M) The electron configuration of Ni
2+
is
| |
8
Ar 3d or
| |
Ar

Ammonia is a strong field ligand. The ligand field diagrams follow, octahedral at left,
tetrahedral in the center and square planar at right.

Octahedral Tetrahedral Square Planar





Since the octahedral and tetrahedral configurations have the same number of unpaired
electrons (that is, 2 unpaired electrons), we cannot use magnetic behavior to determine
whether the ammine complex of nickel(II) is octahedral or tetrahedral. But we can
determine if the complex is square planar, since the square planar complex is diamagnetic
with zero unpaired electrons.

24. (M) The difference is due to the fact that Fe CN
6
( )

4
is a strong field complex ion, while
Fe H
2
O ( )
6

2+
is a weak field complex ion. The electron configurations for an iron atom
and an iron(II) ion, and the ligand field diagrams for the two complex ions follow.

Fe CN ( )
6

4
( )
2
6
[Fe H O ]
2+

iron atom Ar

iron(II) ion [Ar]
3d 4s



e
g
3d 4s



t
2g
e
g
t
2g
e
g
t
2g
t
2g
e
g
t
2g
e
g
t
2g
d
x
2
-y
2

d
xy
d
z
2

d
xz
, d
yz
Chapter 24: Complex Ions and Coordination Compounds
1175
Complex-Ion Equilibria

25. (E) (a) ( ) ( ) ( ) ( ) ( ) ( )
2+
3 3
2 4
Zn OH s +4 NH aq Zn NH aq +2 OH aq

(b) ( ) ( ) ( ) ( )
2+
2
Cu aq +2 OH aq Cu OH s

The blue color is most likely due to the presence of some unreacted [Cu(H
2
O)
4
]
2+
(pale blue)

( ) ( ) ( ) ( ) ( ) ( )
2+
3 3
2 4
Cu OH s +4 NH aq Cu NH aq, dark blue +2 OH aq

( ) ( ) ( ) ( ) ( ) ( )
2+ 2+
+ +
3 3 2 4
4 4
Cu NH aq +4 H O aq Cu H O aq +4 NH aq ( (

26. (M) (a) ( ) ( ) | | ( )
2
2 4
CuCl s +2 Cl aq CuCl aq, yellow

| | ( )
2
4 2
2 CuCl aq +4H O(l)

| | ( ) ( ) ( ) ( )
( ) ( ) ( )
2+
2
4 2
4
2 2
2
CuCl aq, yellow Cu H O aq, pale blue +4 Cl aq
or
2 Cu H O Cl aq, green +4 Cl aq

( +

(





Either | | ( ) ( ) ( ) ( )
2+
2
4 2 2
4
CuCl aq +4 H O(l) Cu H O aq +4 Cl aq

Or ( ) ( ) ( ) ( ) ( )
2+
2 2 2 2
2 4
Cu H O Cl aq +2H O(l) Cu H O aq +2 Cl aq

( (

(b) The blue solution is that of [Cr(H
2
O)
6
]
2+
. This is quickly oxidized to Cr
3+
by O
2
g ( )
from the atmosphere. The green color is due to CrCl
2
H
2
O ( )
4

3+
.


2 +
2 6 2
2 2 4 2
4[Cr(H O) ] (aq, blue)+4H (aq)+8Cl (aq)+O (g)
4[CrCl (H O) ] (aq, green)+10 H O(l)
+
+
+

Over a period of time, we might expect volatile HCl(g) to escape, leading to the
formation of complex ions with more H O
2
and less Cl

.
( ) ( ) ( )
+
H aq + Cl aq HCl g

( ) ( ) ( ) ( ) ( )
2+ +
2 2 2 2
4 5
CrCl H O aq, green +H O(l) CrCl H O aq, blue-green +Cl aq

( (



Chapter 24: Complex Ions and Coordination Compounds
1176
( ) ( ) ( ) ( ) ( )
2+ 3+
2 2 2
5 6
CrCl H O aq, blue-green +H O(l) Cr H O aq, blue +Cl aq

( (

Actually, to ensure that these final two reactions actually do occur in a timely
fashion, it would be helpful to dilute the solution with water after the chromium
metal has dissolved.

27. (M) Co en ( )
3

3+
should have the largest overall K
f
value. We expect a complex ion with
polydentate ligands to have a larger value for its formation constant than complexes that
contain only monodentate ligands. This phenomenon is known as the chelate effect. Once
one end of a polydentate ligand becomes attached to the central metal, the attachment of
the remaining electron pairs is relatively easy because they already are close to the central
metal (and do not have to migrate in from a distant point in the solution).

28. (M) (a) Zn NH
3
( )
4

2+


|
4 1 2 3 4
2 2 2 8
= =3.9 10 2.1 10 1.0 10 50.=4.1 10 K K K K .


(b) Ni H
2
O ( )
2
NH
3
( )
4

2+


|
4 1 2 3 4
2 2 7
= =6.3 10 1.7 10 54 15=8.7 10 K K K K

29. (M) First: ( ) ( ) ( ) ( ) ( ) ( )
3+ 3+
2 2 2
6 4
Fe H O aq +en aq Fe H O en aq +2H O(l) ( (

K
1
=10
4.34


Second: ( ) ( ) ( ) ( ) ( ) ( ) ( )
3+ 3+
2 2 2
4 2 2
Fe H O en aq + en aq Fe H O en aq +2H O(l) ( (

K
2
=10
3.31

Third: ( ) ( ) ( ) ( ) ( ) ( )
3+ 3+
2 2
2 2 3
Fe H O en aq + en aq Fe en aq +2H O(l) ( (

K
3
2.05
=10
Net: ( ) ( ) ( ) ( ) ( )
3+ 3+
2 2
6 3
Fe H O aq +3 en aq Fe en aq +6H O(l) ( (

K K K K
f
=
1 2 3

log
f
K =4.34+3.31+2.05=9.70 K
f
=10 =5.0 10 =
9.70 9
3
|

30. (E) Since the overall formation constant is the product of the individual stepwise formation
constants, the logarithm of the overall formation constant is the sum of the logarithms of
the stepwise formation constants.

log log log log log
f
K K K K K = + + + =2.80+1.60+0.49+0.73=5.62
1 2 3 4


K
f
=10 =4.2 10
5.62 5


Chapter 24: Complex Ions and Coordination Compounds
1177
31. (M) (a) Aluminum(III) forms a stable (and soluble) hydroxo complex but not a stable
ammine complex.

( ) ( ) ( ) ( ) ( ) ( ) ( )
2 2 2
3 3 2 4
Al H O OH s +OH aq Al H O OH aq +H O(l)

( (

(b) Although zinc(II) forms a soluble stable ammine complex ion, its formation constant
is not sufficiently large to dissolve highly insoluble ZnS. However, it is sufficiently
large to dissolve the moderately insoluble ZnCO
3
. Said another way, ZnS does not
produce sufficient Zn
2+
to permit the complex ion to form.

( ) ( ) ( ) ( ) ( )
2+
2
3 3 3 3
4
ZnCO s +4 NH aq Zn NH aq +CO aq

(c) Chloride ion forms a stable complex ion with silver(I) ion, that dissolves the AgCl(s)
that formed when Cl

is low.

( ) ( ) ( ) ( ) ( ) | | ( )
+ +
2
AgCl s Ag aq +Cl aq and Ag aq +2 Cl aq AgCl aq

Overall: ( ) ( ) | | ( )
2
AgCl s + Cl aq AgCl aq

32. (M) (a) Because of the large value of the formation constant for the complex ion,
Co NH
3
( )
6

3+
aq ( ), the concentration of free Co
3+
aq ( ) is too small to enable it to
oxidize water to O
2
g ( ). Since there is not a complex ion present, except, of course,

Co H
2
O ( )
6

3+
aq ( ), when CoCl
3
is dissolved in water, the Co
3+
is sufficiently
high for the oxidation-reduction reaction to be spontaneous.

( ) ( ) ( ) ( )
3+ 2+ +
2 2
4 Co aq +2 H O(l) 4 Co aq +4 H aq +O g

(b) Although AgI(s) is often described as insoluble, there is actually a small
concentration of Ag
+
aq ( ) present because of the solubility equilibrium:

2 AgI(s) Ag
+
(aq) +I
-
(aq)

These silver ions react with thiosulfate ion to form the stable dithiosulfatoargentate(I)
complex ion:

( ) ( ) ( ) ( )
+ 2
2 3 2 3
2
Ag aq +2S O aq Ag S O aq

Chapter 24: Complex Ions and Coordination Compounds
1178
Acid-Base Properties

33. (E) Al H
2
O ( )
6

3+
aq ( ) is capable of releasing H
+
:

( ) ( ) ( ) ( ) ( )
3+ 2+
+
2 2 2 3
6 5
Al H O aq +H O(l) AlOH H O aq +H O aq ( (

The value of its ionization constant (pK
a
=5.01) approximates that of acetic acid.

34. (M) (a) ( ) ( ) ( ) ( ) ( ) ( )
2+ +
2 2 2
5 2 4
CrOH H O aq +OH aq Cr OH H O aq + H O(l)

( (



(b) ( ) ( ) ( ) ( ) ( )
2+ 3+
+
2 3 2 2
5 6
CrOH H O aq + H O aq Cr H O aq + H O(l) ( (



Applications
35. (M) (a) Solubility: ( ) ( ) ( )
13
sp
=5.0 10
+
AgBr s Ag aq +Br aq
K

Cplx. Ion Formation: ( ) ( ) ( ) ( )
13
f
3
=1.7 10
+ 2
2 3 2 3
2
Ag aq +2S O aq Ag S O aq
K

Net: ( ) ( ) ( ) ( )
3
2 -
2 3 2 3 overall sp f
2
AgBr s +2S O aq Ag S O aq + Br (aq) = K K K

13 13
overall
=5.0 10 1.7 10 =8.5 K



With a reasonably high S O
2 3
2
, this reaction will go essentially to completion.
(b) NH
3
aq ( ) cannot be used in the fixing of photographic film because of the relatively
small value of K
f
for Ag NH
3
( )
2

+
aq ( ), K
f
=1.6 10
7
. This would produce a
value of K =8.0 10
6

in the expression above, which is nowhere large enough to
drive the reaction to completion.

36. (M) Oxidation:

Co NH
3
( )
6

2+
aq
( )
Co NH
3
( )
6

3+
aq
( )
+e

{ }
2 0.10V. E =
Reduction:

H
2
O
2
aq
( )
+2e

2OH

aq
( ) { }
0.88V E =
Net: ( ) ( ) ( ) ( ) ( )
2+ 3+
2 2 3 3
6 6
H O aq +2 Co NH aq 2 Co NH aq +2OH (aq)

( (


cell =+0.88 V+ 0.10 V =+0.78 V. E

The positive value of the standard cell potential indicates that this is a spontaneous reaction.

37. (M) To make the cis isomer, we must use ligands that show a strong tendency for
directing incoming ligands to positions that are trans to themselves. I

has a stronger
tendency than does Cl

or NH
3
for directing incoming ligands to the trans positions, and
so it is beneficial to convert K
2
[PtCl
4
] to K
2
[PtI
4
] before replacing ligands around Pt with
NH
3
molecules.

Chapter 24: Complex Ions and Coordination Compounds
1179
38. (M) Transplatin is more reactive and is involved in more side reactions before it reaches
its target inside of cancer cells. Thus, although it is more reactive, it is less effective at
killing cancer cells.
Pt
H
3
N
Cl NH
3
Cl
trans-Pt(NH
3
)
2
Cl
2
Pt
Cl
Cl NH
3
NH
3
cis-Pt(NH
3
)
2
Cl
2



INTEGRATIVE AND ADVANCED EXERCISES

39. (M)
(a) cupric tetraammine ion tetraamminecopper(II) ion [Cu(NH
3
)
4
]
2+

(b) dichlorotetraamminecobaltic chloride tetraamminedichlorocobalt(III) chloride [CoCl
2
(NH
3
)
4
]Cl
(c) platinic(IV) hexachloride ion hexachloroplatinate(IV) ion [PtCl
6
]
2

(d) disodium copper tetrachloride sodium tetrachlorocuprate(II) Na
2
[CuCl
4
]
(e) dipotassium antimony(III) pentachloride potassium pentachloroantimonate(III) K
2
[SbCl
5
]

40. (E)[Pt(NH
3
)
4
][PtCl
4
] tetraammineplatinum(II) tetrachloroplatinate(II)

41. (M) The four possible isomers for [CoCl
2
(en)(NH
3
)
2
]
+
are sketched below:
Co
Cl
Cl NH
2
H
2
N
NH
3
NH
3
Co
H
3
N
H
3
N NH
2
H
2
N
Cl
Cl
Co
H
3
N
Cl NH
2
H
2
N
Cl
NH
3
Co
Cl
H
3
N NH
2
H
2
N
Cl
NH
3

42. (M)The color of the green solid, as well as that of the green solution, is produced by the complex
ion [CrCl
2
(H
2
O)
4
]
+
. Over time in solution, the chloro ligands are replaced by aqua ligands,
producing violet [Cr(H
2
O)
6
]
3+
(aq). When the water is evaporated, the original complex is re-
formed as the concentration of chloro ligand, [Cl

], gets higher and the chloro ligands replace the

aqua ligands.

Cr
H
2
O
H
2
O OH
2
OH
2
Cl
Cl
+2H
2
0
Cr
H
2
O
H
2
O OH
2
OH
2
OH
2
OH
2
2Cl
3
+2H
2
0
Cr
H
2
O
H
2
O OH
2
OH
2
Cl
Cl


43. (M)The chloro ligand, being lower in the spectrochemical series than the ethylenediamine ligand,
is less strongly bonded to the central atom than is the ethylenediamine ligand. Therefore, of the
two types of ligands, we expect the chloro ligand to be replaced more readily. In the cis isomer,
the two chloro ligands are 90 from each other. This is the angular spacing that can be readily
spanned by the oxalato ligand, thus we expect reaction with the cis isomer to occur rapidly. On
the other hand, in the trans isomer, the two chloro ligands are located 180 from each other. After
Chapter 24: Complex Ions and Coordination Compounds
1180
the chloro ligands are removed, at least one end of one ethylenediamine ligand would have to be
relocated to allow the oxalato ligand to bond as a bidentate ligand. Consequently, replacement of
the two chloro ligands by the oxalato ligand should be much slower for the trans isomer than for
the cis isomer.

44. (M) Cl
2
+2 e
-
2 Cl
-

[Pt(NH
3
)
4
]
2+
[Pt(NH
3
)
4
]
4+
+2 e
-

Cl
2
+[Pt(NH
3
)
4
]
2+
[Pt(Cl
2
NH
3
)
4
]
2+

45. (M) The successive acid ionizations of a complex ion such as [Fe(OH)
6
]
3+
are more nearly
equal in magnitude than those of an uncharged polyprotic acid such as H
3
PO
4
principally
because the complex ion has a positive charge. The second proton is leaving a species which
has one fewer positive charge but which is nonetheless positively charged. Since positive
charges repel each other, successive ionizations should not show a great decrease in the
magnitude of their ionization constants. In the case of polyprotic acids, on the other hand,
successive protons are leaving a species whose negative charge is increasingly greater with
each step. Since unlike charges attract each other, it becomes increasingly difficult to
remove successive protons.
46. (M)
QuickTime and a
TIFF (LZW) decompressor
are needed to see this picture.
Pt
NH
3
Cl
Cl Cl
K
+
-1
(a)
Pt
NH
3
Cl
Cl NH
3
(b)
Pt
NH
3
Cl
H
3
N NH
3
Cl
-
+1
Pt
NH
3
H
3
N
H
3
N NH
3
2Cl
-
+2
(c)
(d)
Pt
Cl Cl
Cl Cl
2K
+
-2
Conductivity
Number of
Cl ligands
(e)

47. (M) (a)

2+ + 2
-4 2 5 3
3+
2 6
3 +
3
3
[[Fe(H O) OH] ] [H O ]
K = 9.0 10
0.100- [[Fe(H O) ] ]
Solving, we find 9.5 10 M, which is the [H O ] so:
pH log(9.5 10 ) 2.02
x
x
x

= =
=
= =

-4
K 9.0 10
3+ 2
2 6 2 2 5 3
Fe(H O) (aq) H O(l) Fe(H O) OH (aq) H O
Initial 0.100 M 0 M 0 M
Equil. (0.100 ) M x x x
=
+ +
+ +
~

3+
2 6
{where is the molar quantity of Fe(H O) (aq) hydrolyzed} x
Pt
H
3
N
H
3
N NH
3
NH
3
+ Cl-Cl Pt
H
3
N
H
3
N NH
3
NH
3
Cl
Cl
Chapter 24: Complex Ions and Coordination Compounds
1181

(b)
-4
K 9.0 10
3+ 2
2 6 2 2 5 3
[Fe(H O) ] (aq) H O(l) [Fe(H O) OH] (aq) H O
initial 0.100 M 0 M 0.100 M
equil. (0.100 ) x
=
+ +
+ +

3+
2 6
2 +
-4 2 5 3
3+
2 6
-4
2 5
M M (0.100 ) M
{where is [[Fe(H O) ] ] reacting}
[[Fe(H O) OH] ] [H O ] (0.100 )
K 9.0 10
[[Fe(H O) ] ] (0.100- )
Solving, we find 9.0 10 M, which is the [[Fe(H O) OH]
x x
x
x x
x
x
+
+
+
= = =
=
2
]
+


(c)
2 -6
2 5 a
3+ +
2 6 3
3+ -4
+ a 2 6
3
2
2 5
We simply substitute [[Fe(H O) OH] ] =1.0 10 M into the K expression
with [Fe(H O) ] 0.100 M and determine the concentration of H O
K [[Fe(H O) ] ] 9.0 10 (0.100 M)
[H O ]
[[Fe(H O) OH] ]
+
+

= =
-6
+
3
90. M
[1.0 10 M]
To maintain the concentration at this level requires an impossibly high concentration of H O
=

48. (D) Let us first determine the concentration of the uncomplexed (free) Pb
2+
(aq). Because of
the large value of the formation constant, we assume that most of the lead(II) ion is present as
the EDTA complex ion ([Pb(EDTA)]
2-
). Once equilibrium is established, we can see if there
is sufficient lead(II) ion present in solution to precipitate with the sulfide ion. Note: the
concentration of EDTA remains constant at 0.20 M)
Reaction: Pb
2+
(aq) + EDTA
4-
(aq)
18
2 10

[Pb(EDTA)]
2-
(aq)
Initial: 0 M 0.20 M 0.010 M
Change: +x M constant -x M
Equilibrium: x M 0.20 M (0.010-x) M ~ 0.010 M

K
f
=
[Pb(EDTA)
2-
]
[Pb
2+
][EDTA
4-
]
=210
18
=
0.010
0.20(x)
x =2.510
-20
M =[Pb
2+
]
Now determine the [S
2-
] required to precipitate PbS from this solution. K
sp
=[Pb
2+
][S
2
] =810
28
[S
2-
]=
810
-28
(510
-20
)
=2.510
-8
M Recall (i) that a saturated H
2
S solution is ~0.10 M H
2
S
and (ii) That the [S
2-
] =K
a2
=110
-14
Q
sp
=[Pb
2+
][S
2
] = 2.510
-20
110
-14
= 2.510
-34
K
sp
=810
28
Q
sp
<<K
sp
Hence, PbS(s) will not precipitate from this solution.


49. (M) The formation of [Cu(NH
3
)
4
]
2+
(aq) from [Cu(H
2
O)
4
]
2+
(aq) has K
1
=1.9 10
4
, K
2
=3.9
10
3
, K
3
=1.0 10
3
, and K
4
=1.5 10
2
. Since these equilibrium constants are all considerably
larger than 1.00, one expects that the reactions they represent, yielding ultimately the ion
[Cu(NH
3
)
4
]
2+
(aq), will go essentially to completion. However, if the concentration of NH
3

were limited to less than the stoichiometric amount, that is, to less than 4 mol NH
3
per mol of
Chapter 24: Complex Ions and Coordination Compounds
1182
Cu
2+
(aq), one would expect that the ammine-aqua complex ions would be present in
significantly higher concentrations than the [Cu(NH
3
)
4
]
2+
(aq) ions.
50. (D) For [Ca(EDTA)]
2
, K
f
=4 10
10
and for [Mg(EDTA)]
2
, K
f
=4 10
8
. In Table 18-1, the
least soluble calcium compound is CaCO
3
, K
sp
=2.8 10
9
, and the least soluble magnesium
compound is Mg
3
(PO
4
)
2
, K
sp
=1 10
25
. We can determine the equilibrium constants for
adding carbonate ion to [Ca(EDTA)]
2
(aq) and for adding phosphate ion to [Mg(EDTA)]
2
(aq)
as follows:
2 2 4 10
2 2 -9
3 3 ppt
Instability: [Ca(EDTA)] (aq) Ca (aq) EDTA (aq) 1/4 10
Precipitation: Ca (aq) CO (aq) CaCO (s) 1/2.8 10
Net: [Ca(EDTA)
i
K
K
+
+
+ =
+ + =

2 2 4
3 3 ppt
-3
10 -9
] +CO (aq) CaCO (s) +EDTA (aq)
1
9 10
(4 10 )( 2.8 10 )
i
K K K
K

=
= =

The small value of the equilibrium constant indicates that this reaction does not proceed
very far toward products.
2 2 4 3 8 3
2 3 25
4 3 4 2 ppt
2- 3-
4
Instability: {[Mg(EDTA)] (aq) Mg (aq) EDTA (aq)} 3 1/(4 10)
Precipitation: 3 Mg (aq) 2 PO (aq) Mg (PO ) (s) 1/1 10
Net : 3 [Mg(EDTA)] +2 PO (aq)
i
K
K
+
+
+ =
+ =

4- 3
3 4 2 ppt
6 8 3 25
Mg (PO ) (s) +3 EDTA (aq)
1
0.1
(4 10) (1 10 )
i
K K K
K

=
= =

This is not such a small value, but again we do not expect the formation of much product,
particularly if the [EDTA
4
] is kept high. We can approximate what the concentration of
precipitating anion must be in each case, assuming that the concentration of complex ion is
0.10 M and that of [EDTA
4
] also is 0.10 M.
2 2 4
3 3
4
-3 2 2
3 2 2 2
3 3
Reaction: [Ca(EDTA)] CO (aq) CaCO (s) EDTA (aq)
[EDTA ] 0.10 M
9 10 [CO ] 1 10 M
[[Ca(EDTA)] ][CO ] 0.10 M [CO ]
K

+ +
= = = =

This is an impossibly high [CO
3
2
].
2 3 4
4 3 4 2
4 3 3
3
6 4 5 2 3 3 2 3 3 2
4 4
Reaction: 3[Mg(EDTA)] 2 PO (aq) Mg (PO ) (s) 3 EDTA (aq)
[EDTA ] (0.10 M)
0.1 [PO ] 2. M
[[Mg(EDTA)] ] [PO ] (0.10 M) [PO ]
K

+ +
= = = =

Although this [PO
4
3
] is not impossibly high, it is unlikely that it will occur without
the deliberate addition of phosphate ion to the water. Alternatively, we can substitute
[[M(EDTA)]
2
] =0.10 M and [EDTA
4
] =0.10 M into the formation constant
expression:
] EDTA ][ M [
] [[M(EDTA)]

4 2
2
f
+

= K
Chapter 24: Complex Ions and Coordination Compounds
1183
This substitution gives
2
f
1
[M ]
K
+
= , hence, [Ca
2+
] =2.5 10
11
M and [Mg
2+
] =2.5 10
9
M,
which are concentrations that do not normally lead to the formation of precipitates unless the
concentrations of anions are substantial. Specifically, the required anion concentrations are [CO
3
2
] =
1.1 10
2
M for CaCO
3
, and [PO
4
3
] =2.5 M, just as computed above.

51. (M) If a 99% conversion to the chloro complex is achieved, which is the percent conversion
necessary to produce a yellow color, [[CuCl
4
]
2
] = 0.99 0.10 M = 0.099 M, and
[[Cu(H
2
O)
4
]
2+
] =0.01 0.10 M =0.0010 M. We substitute these values into the formation
constant expression and solve for [Cl

].

M 0.12
10 4.2 0.0010
0.099
] Cl [
] [Cl M 0.0010
M 0.099
10 4.2
] [Cl ] ] O) Cu(H [[
] ] [[CuCl

5
4
4
5
4 2
4 2
2
4
f
=

=
= = =

K


This is the final concentration of free chloride ion in the solution. If we wish to account for all
chloride ion that has been added, we must include the chloride ion present in the complex ion.
total [Cl

] =0.12 M free Cl

+(4 0.099 M) bound Cl

=0.52 M


52. (M)(a)
-
2 2
Oxidation: 2H O(l) O (g) 4 H (aq) 4 e -1.229 V E
+
+ + =

3 - 2
3 2
2 2 cell
Reduction: {Co ((aq) e Co (aq)} 1.82 V
Net: 4 Co (aq) 2 H O(l) 4 Co (aq) 4 H (aq) O (g) 0.59 V
E
E
+ +
+ + +
+ = +
+ + + = +


(b)
3 3
3 3 6
Reaction: Co (aq) 6 NH (aq) [Co(NH ) ] (aq)
+ +
+

3
3 6
f
3 6
3
Initial: 1.0 M 0.10 M 0 M
Changes: M constant M
Equil: (1.0 )M 0.10 M M
[[Co(NH ) ] ]
4.5 1
[Co ][NH ]
x x
x x
K
+
+
+

= =
33 27
6
0 4.5 10
1.0 (1.0 )(0.10)
x x
x x
= =


Thus [[Co(NH
3
)
6
]
3+
] =1.0 M because K is so large, and
M 10 2 . 2
10 4.5
1
] Co [
28 -
27
3
=

=
+


Chapter 24: Complex Ions and Coordination Compounds
1184
(c) The equilibrium and equilibrium constant for the reaction of NH
3
with water follows.
3 2 4
- 2
5 5 4
3
NH (aq) H O(l) NH (aq) OH (aq)
[NH ][OH ] [OH ]
1.8 10 [OH ] 0.10(1.8 10 ) 0.0013 M
[NH ] 0.10
b
K
+
+

+ +
= = = = =

In determining the [OH

], we have noted that [NH
4
+
] =[OH

] by stoichiometry, and also that
[NH
3
] =0.10 M, as we assumed above. M 10 7.7
0013 . 0
10 1.0

] OH [
] O H [
12
14
3

+
=

= =
w
K

We use the Nernst equation to determine the potential of reaction (24.12) at the conditions
described.
2 4 4
2
cell
3 4
4 4 12 4
28 4
[Co ] [H ] [O ] 0.0592
log
4 [Co ]
0.0592 (1 10 ) (7.7 10 ) 0.2
0.59 log 0.59 V 0.732 V 0.142 V
4 (2.2 10 )
P
E E
E
+ +
+

=

= + = + =

The negative cell potential indicates that the reaction indeed does not occur.


53. (M) We use the Nernst equation to determine the value of [Cu
2+
]. The cell reaction follows.

M 10 8 ] Cu [ 1 . 14
0592 . 0
) 08 . 0 337 . 0 ( 2
] [Cu log
) 00 . 1 (
] [Cu
log
2
0592 . 0
337 . 0 V 0.08
] H [
] [Cu
log
2
0.0592

V 337 . 0 g) ( H aq) ( Cu aq) ( H 2 Cu(s)
15 2 2
2
2
2
2
cell 2
2
+ +
+
+
+
+ +
= =

=
= = =
= + +
E E
E

Now we determine the value of K
f
.

14
4 15 4
3
2
2
4 3
f
10 1
) 00 . 1 ( 10 8
1.00

] [NH ] Cu [
] ] ) [[Cu(NH
=

= =
+
+
K

This compares favorably with the value of K
f
=1.1 10
13
given in Table 18-2, especially
considering the imprecision with which the data are known. (E
cell
=0.08 V is known to but
one significant figure.)

Chapter 24: Complex Ions and Coordination Compounds
1185
54. (M) We first determine [Ag
+
] in the cyanide solution.
18
2 18
2
18
2
2
f
10 1.8
(0.10) 10 5.6
0.10
] Ag [
(0.10.) ] [Ag
0.10
10 5.6
] CN ][ Ag [
] ] [[Ag(CN)

+
+ +

=
= = = K
The cell reaction is as follows. It has
V 0.000
cell
= E ; the same reaction occurs at both anode and cathode and thus the Nernstian
voltage is influenced only by the Ag
+
concentration.
KCN) M 0.10 , ] [Ag(CN) M (0.10 Ag M) 10 . 0 ( Ag
2
+ +

V 0.99
10 . 0
10 1.8
log 0.0592 0.000
] Ag [
] [Ag
log
1
0592 . 0

18
CN
+ =

= =

+
+
E E
55. (M)
Co
H
3
N
H
3
N NH
3
NH
3
OH
2
Cl
+
Cl
-
Co
H
3
N
H
3
N NH
3
NH
3
OH
2
OH
2
+2
2Cl
-

A 0.10 mol/L solution of these compounds would result in ion concentration of
0.20 mol/L for [Co Cl (H
2
O(NH
3
)
4
)]ClH
2
O or 0.30 mol/L for [Co(H
2
O)
2
(NH
3
)
4
]Cl
2
.
Observed freezing point depression =-0.56 C.
AT =-K
f
mi =-0.56 deg =-1.86 mol kg
-1
deg(0.10 mol/L)i
Hence, i =3.0 mol/kg or 3.0 mol/L. This suggests that the compound is [Co(H
2
O)
2
(NH
3
)
4
]Cl
2
.

56. (M) Sc(H
2
O)
6
3+
and Zn(H
2
O)
4
2+
have outer energy shells with 18 electrons, and thus they do not
have any electronic transitions in the energy range corresponding to visible light. Fe(H
2
O)
6
3+
has 17
electrons (not 18) in its outer shell; thus, it does have electronic transitions in the energy range
corresponding to visible light.

57. (M) The Cr
3+
ion would have 3 unpaired electrons, each residing in a 3d orbital and would be sp
3
d
2

hybridized. The hybrid orbitals would be hybrids of 4s, 4p, and 3d (or 4d) orbitals. Each CrNH
3

coordinate covalent bond is a bond formed when a lone pair in an sp
3
orbital on N is directed
toward an empty sp
3
d
2
orbital on Cr
3+
. The number of unpaired electrons predicted by valence bond
theory would be the same as the number of unpaired electrons predicted by crystal field theory.

58. (M) Since these reactions involve Ni
2+
binding to six identical nitrogen donor atoms, we can
assume the AH for each reaction is approximately the same. A large formation constant indicates
a more negative free energy. This indicates that the entropy term for these reactions is different.
The large increase in entropy for each step, can be explained by the chelate effect. The same
number of water molecules are displaced by fewer ligands, which is directly related to entropy
change.

Chapter 24: Complex Ions and Coordination Compounds
1186
59. (M)
Co(acac)
3
Co
O
O O
O
O
O
H
3
C
CH
3
H
3
C
CH
3
CH
3
CH
3
Co
O
O O
O
O
O
CH
3
H
3
C
CH
3
H
3
C
H
3
C
H
3
C

This compound has a non-
superimposable mirror image
(therefore it is optically active). These
are enantiomers. One enantiomer
rotates plane polarized light clockwise,
while the other rotates plane polarized
light counter-clockwise. Polarimetry
can be used to determine which isomer
rotates plane polarized light in a
particular direction.
trans-[Co(acac)
2
(H
2
O)
2
]Cl
2
Co
O
O O
O
OH
2
OH
2
CH
3
CH
3
H
3
C
H
3
C
Co
O
O O
O
OH
2
OH
2
H
3
C
H
3
C
CH
3
CH
3

This compound has a
superimposable mirror image
(therefore it is optically inactive).
These are the same compound.
This compound will not rotate
plane polarized light (net rotation
=0).
cis-[Co(acac)
2
(H
2
O)
2
]Cl
2
Co
OH
OH
2
O
O
O
O
H
3
C
CH
3
H
3
C
OH
2
Co
HO
H
2
O O
O
O
O
CH
3
H
3
C
CH
3
H
2
O

This compound has a non-
superimposable mirror image
(therefore it is optically active).
These are enantiomers. One
enantiomer rotates plane
polarized light clockwise, while
the other rotates plane polarized
light counter-clockwise. By
using a polarimeter, we can
determine which isomer rotates
plane polarized light in a
particular direction.

60. (D)
[Co(H
2
O)
6
]
3+
(aq) +e
-
[Co(H
2
O)
6
]
2+
(aq)
log K =nE/0.0592 =(1)(1.82)/0.0592 =30.74
K =10
30.74


[Co(en)
3
]
3+
(aq) +6 H
2
O(l) [Co(H
2
O)
6
]
3+
(aq) +3 en K =1/10
47.30
[Co(H
2
O)
6
]
2+
(aq) +3 en [Co(en)
3
]
2+
(aq) +6 H
2
O(l) K =10
12.18
[Co(H
2
O)
6
]
3+
(aq) +e
-
[Co(H
2
O)
6
]
2+
(aq)
K =10
30.74

[Co(en)
3
]
3+
(aq)
+e
-

[Co(en)
3
]
2+
(aq) K
overall
=?

Chapter 24: Complex Ions and Coordination Compounds
1187
K
overall =
1/10
47.30
10
12.18
10
30.74
=10
-4.38
=0.0000417
E =(0.0592/n)log K =(0.0592/1)log(0.0000417) =-0.26 V

4 Co
3+
(aq) +4 e
-
4 Co
2+
(aq) E
cathode
=1.82 V

2 H
2
O(l) 4 H
+
(aq) +O
2
(g) +4 e
-
E
anode
=1.23 V
4 Co
3+
(aq) +2 H
2
O(l) 4 H
+
(aq) +O
2
(g) +4 Co
2+
(aq)
E
cell
=E
cathode
E
anode
=1.82V 1.23 V =+0.59 V (Spontaneous)

4 [Co(en)
3
]
3+
(aq) +4 e
-
4 [Co(en)
3
]
2+
(aq) E
cathode
=-0.26 V

2 H
2
O(l) 4 H
+
(aq) +O
2
(g) +4 e
-
E
anode
=1.23 V
4 [Co(en)
3
]
3+
(aq) +2 H
2
O(l) 4 H
+
(aq) +O
2
(g) +4 [Co(en)
3
]
2+
(aq)
E
cell
=

E
cathode
E

= -0.26 V 1.23 V = -1.49 V (non-spontaneous)

61. (M) There are two sets of isomers for Co(gly)
3.
Each set comprises two enantiomers (non-
superimposable mirror images). One rotates plane polarized light clockwise (+), the other counter-
clockwise (). Experiments are needed to determine which enantiomer is (+) and which is ().
Co
H
2
N
O O
NH
2
H
2
N
O
O
O
O
Co
NH
2
O O
H
2
N
NH
2
O
O
O
O
Co
H
2
N
O NH
2
NH
2
O
O
O
O
O
Co
NH
2
O H
2
N
H
2
N
O
O
O
O
O

(+)-fac-tris(glycinato)cobalt(III) (+)-mer-tris(glycinato)cobalt(III)
()-fac-tris(glycinato)cobalt(III) ()-mer-tris(glycinato)cobalt(III)
[Co(gly)
2
Cl(NH
3
)] has 10 possible isomer, four pairs of enantiomers and two achiral isomers.

Co
H
2
N
O
H
2
N
O
Cl
O
NH
3
O
Co
H
2
N
O O
NH
2
Cl
O
NH
3
O

Co
H
3
N
Cl NH
2
NH
2
O
O
O
O
Co
NH
3
Cl H
2
N
H
2
N
O
O
O
O

Chapter 24: Complex Ions and Coordination Compounds
1188
Co
H
3
N
Cl O
O
H
2
N
H
2
N
O
O
Co
NH
3
Cl O
O
NH
2
NH
2
O
O

Co
H
3
N
Cl O
NH
2
H
2
N
O
O
O
Co
NH
3
Cl O
H
2
N
NH
2
O
O
O

Co
Cl
H
3
N O
NH
2
H
2
N
O
O
O
Co
Cl
NH
3
O
H
2
N
NH
2
O
O
O


62. (M) The coordination compound is face-centered cubic, K
+
occupies tetrahedral holes, while
PtCl
6
2-
occupies octahedral holes.

63. (M)
#NH
3
0 1 2 3
Formula: K
2
[PtCl
6
] K[PtCl
5
(NH
3
)] PtCl
4
(NH
3
)
2
[PtCl
3
(NH
3
)
3
]Cl

Total #ions 3 2 0 2
(per formula
unit)

#NH
3
4 5 6
Formula: [PtCl
2
(NH
3
)
4
]Cl
2
[PtCl(NH
3
)
5
]Cl
3
[Pt(NH
3
)
6
]Cl
4
Total #ions 3 4 5
(per formula
unit)

Chapter 24: Complex Ions and Coordination Compounds
1189

FEATURE PROBLEMS


64. (M)(a) A trigonal prismatic structure predicts three geometric isomers for [CoCl
2
(NH
3
)
4
]
+
,
which is one more than the actual number of geometric isomers found for this complex ion.
All three geometric isomers arising from a trigonal prism are shown below.
Cl
Cl
Cl
Cl Cl
Cl
(i) (ii) (iii)


The fact that the trigonal prismatic structure does not afford the correct number of isomers is a
clear indication that the ion actually adopts some other structural form (i.e., the theoretical model
is contradicted by the experimental result). We know now of course, that this ion has an
octahedral structure and as a result, it can exist only in cis and trans configurations.

(b) All attempts to produce optical isomers of [Co(en)
3
]
3+
based upon a trigonal prismatic structure are
shown below. The ethylenediamine ligand appears as an arc in diagrams below:

(i) (ii) (iii)

Only structure (iii), which has an ethylenediamine ligand connecting the diagonal corners of a
face can give rise to optical isomers. Structure (iii) is highly unlikely, however, because the
ethylenediamine ligand is simply too short to effectively span the diagonal distance across the
face of the prism. Thus, barring any unusual stretching of the ethylenediamine ligand, a trigonal
prismatic structure cannot account for the optical isomerism that was observed for [Co(en)
3
]
3+
.

65. (D) Assuming that each hydroxide ligand bears its normal 1 charge, and that each ammonia
ligand is neutral, the total contribution of negative charge from the ligands is 6 . Since the
net charge on the complex ions is 6+, the average oxidation state for each Co atom must be
+3 (i.e., each Co in the complex can be viewed as a Co
3+
3d
6
ion surrounded by six
ligands.) The five 3d orbitals on each Co are split by the octahedrally arranged ligands into
three lower energy orbitals, called t
2g
orbitals, and two higher energy orbitals, called e
g

orbitals. We are told in the question that the complex is low spin. This is simply another
way of saying that all six 3d electrons on each Co are paired up in the t
2g
set as a result of the
e
g
and t
2g
orbitals being separated by a relatively large energy gap (see below). Hence, there
should be no unpaired electrons in the hexacation (i.e., the cation is expected to be
diamagnetic).

Chapter 24: Complex Ions and Coordination Compounds
1190
Low Spin Co
3+

(Octahedral Environment):
Relatively Large Crystal Field Splitting


The Lewis structures for the two optical isomers (enantiomers) are depicted below:












66. (D) The data used to construct a plot of hydration energy as a function of metal ion atomic
number is collected in the table below. The graph of hydration energy (kJ /mol) versus
metal ion atomic number is located beneath the table.

Metal ion Atomic number Hydration energy
Ca
2+
20 2468 kJ /mol
Sc
2+
21 2673 kJ /mol
Ti
2+
22 2750 kJ /mol
V
2+
23 2814 kJ /mol
Cr
2+
24 2799 kJ /mol
Mn
2+
25 2743 kJ /mol
Fe
2+
26 2843 kJ /mol
Co
2+
27 2904 kJ /mol
Ni
2+
28 2986 kJ /mol
Cu
2+
29 2989 kJ /mol
Zn
2+
30 2936 kJ /mol












Hydration Enthalpy of M
2+
ions (Z = 20-30)
-3000
-2800
-2600
20 22 24 26 28 30
Atomi c Number (Z)
H
y
d
r
a
t
i
o
n

E
n
e
r
g
y

(
k
J
/
m
o
l
)
Co
NH
3
NH
3
NH
3
NH
3
Co
O
O
O O
O O
Co
NH
3
H
3
N
H
3
N
H
3
N
Co
NH
3
H
3
N
H
3
N
NH
3
H
H
H
H
H
H
Co
H
3
N
H
3
N
H
3
N
H
3
N
Co
O
O
O O
O O
Co
H
3
N
NH
3
NH
3
NH
3
Co
H
3
N
NH
3
NH
3
NH
3
H
H
H
H
H
H
Non-superimposable mirror images of one another

e
g
t
2g
(a)
Chapter 24: Complex Ions and Coordination Compounds
1191
(b) When a metal ion is placed in an octahedral field of ligands, the five d-
orbitals are split into e
g
and t
2g
subsets, as shown in the diagram below:
3
/
5
A
o
2
/
5
A
o
d-orbitals
(symmerical field)
(octahedral field)
d
xy
d
yz
d
xz
d
z
2 d
x - y
2 2
t
2g
e
g

Since water is a weak field ligand, the magnitude of the splitting is relatively small. As a
consequence, high-spin configurations result for all of the hexaaqua complexes. The
electron configurations for the metal ions in the high-spin hexaaqua complexes and their
associated crystal field stabilization energies (CFSE) are provided in the table below

Metal Ion Configuration t
2g
e
g number of unpaired e

CFSE(A
o
)
Ca
2+
3d
0
0 0 0 0
Sc
2+
3d
1

1 0 1
2
/
5

Ti
2+
3d
2

2 0 2
4
/
5

V
2+
3d
3

3 0 3
6
/
5

Cr
2+
3d
4

3 1 4
3
/
5

Mn
2+
3d
5

3 2 5 0
Fe
2+
3d
6

4 2 4
2
/
5

Co
2+
3d
7
5 2 3
4
/
5

Ni
2+
3d
8
6 2 2
6
/
5

Cu
2+
3d
9
6 3 1
3
/
5

Zn
2+
3d
10
6 4 0 0
Thus, the crystal field stabilization energy is zero for Ca
2+
. Mn
2+
and Zn
2+
.

(c) The lines drawn between those ions that have a CFSE =0 show the trend for the enthalpy of
hydration after the contribution from the crystal field stabilization energy has been subtracted
from the experimental values. The Ca to Mn and Mn to Zn lines are quite similar. Both line
have slopes that are negative and are of comparable magnitude. This trend shows that as one
proceeds from left to right across the periodic table, the energy of hydration for dications
becomes increasingly more negative. The hexaaqua complexes become progressively more
stable because the Z
eff
experienced by the bonding electrons in the valence shell of the metal
ion steadily increases as we move further and further to the right. Put another way, the Z
eff

climbs steadily as we move from left to right and this leads to the positive charge density on
the metal becoming larger and larger, which results in the water ligands steadily being pulled
closer and closer to the nucleus. Of course, the closer the approach of the water ligands to the
metal, the greater is the energy released upon successful coordination of the ligand.
Chapter 24: Complex Ions and Coordination Compounds
1192
(d) Those ions that exhibit crystal field stabilization energies greater than zero have heats of
hydration that are more negative (i.e. more energy released) than the hypothetical heat of
hydration for the ion with CFSE subtracted out. The heat of hydration without CFSE for
a given ion falls on the line drawn between the two flanking ions with CFSE =0 at a
position directly above the point for the experimental hydration energy. The energy
difference between the observed heat of hydration for the ion and the heat of hydration
without CFSE is, of course, approximately equal to the CFSE for the ion.
(e) As was mentioned in the answer to part (c), the straight line drawn between manganese
and zinc (both ions with CFSE =0) on the previous plot, describes the enthalpy trend
after the ligand field stabilization energy has been subtracted from the experimental
values for the hydration enthalpy. Thus, A
o
for Fe
2+
in [Fe(H
2
O)
6
]
2+
is approximately
equal to
5
/
2
of the energy difference (in kJ /mol) between the observed hydration energy
for Fe
2+
(g) and the point for Fe
2+
on the line connecting Mn
2+
and Zn
2+
, which is the
expected enthalpy of hydration after the CFSE has been subtracted out. Remember that
the crystal field stabilization energy for Fe
2+
that is obtained from the graph is not A
o
, but
rather
2
/
5
A
o
, since the CFSE for a 3d
6
ion in an octahedral field is just
2
/
5
of A
o
.
Consequently, to obtain A
o
, we must multiply the enthalpy difference by
5
/
2
. According
to the graph, the high-spin CFSE for Fe
2+
is 2843 kJ /mol (2782 kJ /mol) or 61
kJ /mol. Consequently, A
o
=
5
/
2
(61 kJ /mol) =153 kJ /mol, or 1.5 10
2
kJ /mol is the
energy difference between the e
g
and t
2g
orbital sets.
(f) The color of an octahedral complex is the result of the promotion of an electron on the
metal from a t
2g
orbital e
g
orbital. The energy difference between thee
g
and t
2g
orbital
sets is A
o
. As the metal-ligand bonding becomes stronger, the separation between the t
2g

and e
g
orbitals becomes larger. If the e
g
set is not full, then the metal complex will exhibit
an absorption band corresponding to a t
2g
e
g
transition. Thus, the [Fe(H
2
O)
6
]
2+
complex
ion should absorb electromagnetic radiation that has E
photon
=A
o
. Since A
o
~ 150 kJ /mol
(calculated in part (e) of this question) for a mole of [Fe(H
2
O)
6
]
2+
(aq),
E
photon
=
2+ 2
2 6
2+ 23 2+
2 6 2 6
1mol [Fe(H O) ] 1.5 10 kJ 1000J
1mol[Fe(H O) ] 6.022 10 [Fe(H O) ] 1kJ

=2.5 10
19
J per ion
v =
19
34
2.5 10 J
=
6.626 10 J s
E
h

=3.8 10
14
s
1

=
8 -1
14 -1
2.998 10 ms
=
3.8 10 s
c
h

=7.8 10
7
m (780 nm)

So, the [Fe(H
2
O)
6
]
2+
ion will absorb radiation with a wavelength of 780 nm, which is
red light in the visible part of the electromagnetic spectrum.

Chapter 24: Complex Ions and Coordination Compounds
1193
SELF-ASSESSMENT EXERCISES


67. (E) (a) Coordination number is the number of ligands coordinated to a transition metal
complex.
(b) A
0
is the crystal field splitting parameter which depends on the coordination geometry
of a transition metal complex.
(c) Ammine complex is the complex that contains NH
3
ligands.
(d) An enantiomer is one of two stereoisomers that are mirror images of each other that
are "non-superposable" (not identical).

68. (E) (a) A spectrochemical series is a list of ligands ordered on ligand strength and a list
of metal ions based on oxidation number, group and identity.
(b) Crystal field theory (CFT) is a model that describes the electronic structure of
transition metal compounds, all of which can be considered coordination complexes.
(c) Optical isomers are two compounds which contain the same number and kinds of
atoms, and bonds (i.e., the connectivity between atoms is the same), and different spatial
arrangements of the atoms, but which have non-superimposable mirror images.
(d) Structural isomerism in accordance with IUPAC, is a form of isomerism in which
molecules with the same molecular formula have atoms bonded together in different
orders.

69. (E) (a) Coordination number is the number of ligands coordinated to a transition metal
complex. Oxidation number of a central atom in a coordination compound is the charge
that it would have if all the ligands were removed along with the electron pairs that were
shared with the central atom.
(b) A monodentate ligand has one point at which it can attach to the central atom.
Polydentate ligand has many points at which it can coordinate to a transition metal.
(c) Cis isomer has identical groups on the same side. In trans isomer, on the other hand,
identical groups are on the opposite side.
(d) Dextrorotation and levorotation refer, respectively, to the properties of rotating plane
polarized light clockwise (for dextrorotation) or counterclockwise (for levorotation). A
compound with dextrorotation is called dextrorotary, while a compound with levorotation
is called levorotary.
(e) When metal is coordinated to ligands to form a complex, its "d" orbital splits into high
and low energy groups of suborbitals. Depending on the nature of the ligands, the energy
difference separating these groups can be large or small. In the first case, electrons of the
d orbital tend to pair in the low energy suborbitals, a configuration known as "low spin".
If the energy difference is low, electrons tend to distribute unpaired, giving rise to a "high
spin" configuration. High spin is associated with paramagnetism (the property of being
attracted to magnetic fields), while low spin is associated to diamagnetism (inert or
repelled by magnets).

70. (E) (d)

71. (E) (e)
Chapter 24: Complex Ions and Coordination Compounds
1194

72. (E) (b)

73. (E) (a)

74. (E) (d)

75. (E) (c)

76. (E) (b)

77. (M) (a) pentaamminebromocobalt(III)sulfate, no isomerism.
(b) hexaamminechromium(III)hexacyanocobaltate(III), no isomerism.
(c) sodiumhexanitrito-N-cobaltate(III), no isomerism
(d) tris(ethylenediamine)cobalt(III)chloride, two optical isomers.

78. (M) (a) [Ag(CN)
2
]
-
; (b) [Pt(NO
2
)(NH
3
)
3
]
+
; (c) [CoCl(en)
2
(H
2
O)]
2+
; (d) K
4
[Cr(CN)
6
]

79. (M)
Pt
Cl
Cl Cl
Cl
2-
Fe
H
2
N
H
2
N Cl
Cl
Cl
Cl
Fe
O
O Cl
NH
2
Cl
H
2
N
O
O
Cr
H
3
N
H
3
N NH
3
NH
3
Cl
OH
-
-
+
(a) (b) (c) (d)


80. (M) (a) one structure only (all positions are equivalent for the H
2
O ligand; NH
3
ligands
attach at the remaining five sites).
Co
H
3
N
H
2
O NH
3
NH
3
NH
3
NH
3
+3


(b) two structures, cis and trans, based on the placement of H
2
O.
Co
H
3
N
H
2
O NH
3
OH
2
NH
3
NH
3
+3
trans
Co
H
2
O
H
2
O NH
3
NH
3
NH
3
NH
3
+3
cis

Chapter 24: Complex Ions and Coordination Compounds
1195
(c) two structures, fac and mer.
Co
H
2
O
H
3
N NH
3
OH
2
NH
3
OH
2
+3
fac
Co
H
2
O
H
2
O OH
2
NH
3
NH
3
NH
3
+3
mer

(d) two structures, cis and trans, based on the placement of NH
3
.
Co
H
2
O
H
2
O OH
2
OH
2
NH
3
NH
3
+3
trans
Co
H
3
N
H
3
N OH
2
OH
2
OH
2
OH
2
+3
cis


81. (M) (a) coordination isomerism, based on the interchange of ligands between the
complex cation and complex anion.
(b) linkage isomerism, based on the mode of attachment of the SCN
-
ligand (either
SCN
-
or NCS
-
).
(c) no isomerism
(d) geometric isomerism, based on whether Cl
-
ligands are cis or trans.
(e) geometric isomerism, based on whether the NH
3
or OH
-
ligands are fac or mer.

82. (M) (a) geometric isomerism (cis and trans) and optical isomerism in the cis isomer.
(b) geometric isomerism (cis and trans), optical isomerism in the cis isomer, and linkage
isomerism in the thiocyanate ligand.
(c) no isomers.
(d) no isomers for this square-planar complex.
(e) two geometric isomers, one with the tridentate ligand occupying meridional positions
and the other with the tridentate ligand occupying facial positions.

83. (M) Because ethylenediamine (en) is a stronger field ligand than H
2
O, more energy must
be absorbed by [Co(en)
3
]
3+
than by [Co(H
2
O)
6
]
3+
to simulate an electronic transition.
This means that [Co(en)
3
]
3+
(aq) absorbs shorter wavelength light and transmits longer
wavelength light than does [Co(H
2
O)
6
]
3+
(aq). Thus [Co(en)
3
]
3+
(aq) is yellow and
[Co(H
2
O)
6
]
3+
(aq) is blue.