Acid-Base Equilibria

The reaction of weak acids with water,

OR
the reaction of weak bases with water,
always results in an equilibrium!!

●
The equilibrium constant for the reaction of a
weak acid with water is Ka

1
 Acid-Base Equilibria
eg. HF(aq) + H2O(l) H3O+(aq) + F-(aq)

Keq = ?
Ka = [H 3 O+] [F -
]
[HF]

2
Acid-Base Equilibria
●
For any weak acid

Ka = [H3O+] [conjugate base]

[weak acid]

● Why is H2O(l) omitted from the Ka

expression?

3
 Acid-Base Equilibria
●
the equilibrium constant for the reaction of a
weak base with water is Kb

HS-(aq) + H2O(l) H2S(aq) + OH-(aq)

Kb = [OH-] [H2S]
-
[HS ]

4
Acid-Base Equilibria
●
For any weak base

Kb = [OH-] [conjugate acid]

[weak base]

5
eg.
Write the expression for Kb for S2-(aq)

ANSWER:
S2-(aq) + H2O(l) HS-(aq) + OH-(aq)

Kb = [OH-] [HS-]
[S2-]

6
5.a) Use Ka to find [H3O+] for 0.100 mol/L HF(aq)

HF(aq) + H2O(l) H3O+(aq) + F-(aq)

 -
[H 3O ] [F ]
Ka = 6.6 x 10 Ka 
-4

[HF]
1st try - Ignore x
[x] [x]
6.6 x 10  -4

[0.100 - x]

x 2 = (0.100)(6.6 x 10-4)
x 2 = 6.6 x 10-5
x = 8.1 x 10-3 mol/L
x = 0.0081 mol/L
2nd try– Include x
[x] [x]
6.6 x 10  -4

[0.100 - 0.0081]
x 2 = (0.0919)(6.6 x 10-4)
x 2 = 6.0654 x 10-5
x = 7.8 x 10-3 mol/L

Different than 1st try:

CANNOT IGNORE
DISSOCIATION
3rd try– Include new x
[x] [x]
6.6 x 10  -4

[0.100 - 0.0078]

x 2 = (0.0922)(6.6 x 10-4)
Same as x 2 = 6.0852 x 10-5
2nd try:
x = 7.8 x 10-3 mol/L
[H3O+] = 7.8 x 10-3 mol/L
5.b) find [H3O+] for 0.250 mol/L CH3COOH(aq
CH3COOH(aq) + H2O(l)  H3O+(aq) + CH3COO-(aq)

 -
Ka = 1.8 x 10-5 [H3O ] [CH3COO ]
Ka 
[CH3COOH]
1st try - Ignore x
[x] [x]
1.8 x 10  -5

[0.250 - x]

x 2 = (0.250)(1.8 x 10-5)
x 2 = 4.5 x 10-6
x = 2.1 x 10-3 mol/L
2nd try– Include x
[x] [x]
1.8 x 10  -5

[0.250 - 0.0021]

x 2 = (0.2479)(1.8 x 10-5)
Same as x 2 = 4.462 x 10-6
1st try:
x = 2.1 x 10-3 mol/L
[H3O+] = 2.1 x 10-3 mol/L
To ignore OR
not to ignore:
that is the
question

14
 pH of a weak acid
Step #1: Write a balanced equation

Step #2: ICE table OR assign variables

Step #3: Write the Ka expression

Step #4: Check (can we ignore dissociation?)

Step #5: Substitute into Ka expression

15
 pH of a weak acid
eg. Find pH of 0.100 mol/L HF(aq).

Step #1: Write a balanced equation

HF(aq) + H2O(l) H3O+(aq) + F-(aq)

16
Step #2: Equilibrium Concentrations

Let x = [H3O+] at equilibrium

[F-] = x
[HF] = 0.100 - x

17
Step #3: Write the Ka expression

Ka = [H3O+] [F-]
[HF]

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 Step #4: Check (can we ignore dissociation?)

If [weak acid] dissociation (- x)

> 500 may be IGNORED
Ka
(0.100)
= 151
6.6 x 10-4
Acid dissociation CANNOT be
IGNORED in this question.

We have to use the (– x) part

19
Step #5: Substitute into Ka expression
[x] [x]
6.6 x 10 
-4

[0.100 - x]

x2 = 6.6 x 10-5 - 6.6 x 10-4 x

x2 + 6.6 x 10-4 x - 6.6 x 10-5 = 0

●
Need the Quadratic Equation!!
a=1 b = 6.6 x 10-4 c = -6.6 x 10-5
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  b  b  4ac
2
x
2a

 6.6 x 10  (6.6 x 10 )  4(1)(-6.6 x 10 )

-4 -4 2 -5
x
2(1)

 6.6 x 10  0.000264
-4
x
2
Ignore
negative x  0.0078 mol/L
roots
21
 Try these:
a) Find the [H3O+] in 0.250 mol/L HCN(aq)
Check: 4.0 x 108
x = 1.24 x 10-5
[H3O+] = 1.24 x 10-5

b) Calculate the pH of 0.0300 mol/L HCOOH(aq)

Check: 167
x = 2.24 x 10-3
pH = 2.651
 HCN + H2O ⇋ H3O+ + CN-
Let x = [H3O+]
x = [CN-]
0.250 – x = [HCN]

Ka = [H3O+] [CN-]
[HCN]
Check:
0.250
= 4.0 x 108
6.2 x 10-10
Quadratic NOT
needed
23
 [x] [x]
6.2 x 10 -10

[0.250 - x]
x2 = 1.55 x 10-10

x = 1.25 x 10-5

pH = 4.904

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 HCOOH + H2O ⇋ H3O+ + HCOO-
0.0300 0 0
-x +x +x
0.0300 – x x x
Ka = [H3O+] [HCOO-]
[HCOOH]
Check: Quadratic needed
0.0300
= 167
1.8 x 10-4

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 [x] [x]
1.8 x 10 
-4

[0.0300 - x]
x2 = 5.4 x 10-6 - 1.8 x 10-4x
x2 + 1.8 x 10-4x - 5.4 x 10-6 = 0

A=1 B = 1.8 x 10-4 C = -5.4 x 10-6

x = 2.24 x 10-3
pH = 2.651

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 Practice
1. Formic acid, HCOOH, is present in the sting of
certain ants. What is the [H3O+] of a 0.025 mol/L
solution of formic acid? (0.00203 mol/L)
2. Calculate the pH of a sample of vinegar that
contains 0.83 mol/L acetic acid.
( [H3O+] = 3.87 x 10-3 pH = 2.413 )
3. What is the percent dissociation of the vinegar in
2.?
% diss = 0.466 %
 Practice
4. A solution of hydrofluoric acid has a molar
concentration of 0.0100 mol/L. What is the pH of this
solution?
( [H3O+] = 0.00226 pH = 2.646 )
5. The word “butter” comes from the Greek butyros.
Butanoic acid, C3H7COOH, gives rancid butter its
distinctive odour. Calculate the [H3O+] of a 1.0 × 10−2
mol/L solution of butanoic acid.
(Ka = 1.51 × 10−5 ) (Ans: 3.89 x 10-4 mol/L)
 pH of a weak base
 same method as acids
 ignore dissociation if [weak base]
> 500
Kb

 to calculate Kb (usually given on the exam)

Kw
K a x Kb  K w Kb 
Ka

29
 pH of a weak base
Calculate the pH of 0.0100mol/L Na2CO3(aq)

30
 CO32- + H2O ⇋ HCO3- + OH-
0.0100 0 0
-x +x +x
0.0100 – x x x

Kb = [OH ] [HCO ]
-
3
- Kb = 1.00 x 10-14
[CO32-] 4.7 x 10-11
Check:
= 2.13 x 10-4
0.0100
= 47 → Quadratic
2.13 x 10-4 needed

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 [x] [x]
2.13 x 10 -4

[0.0100 - x]
x2 = 2.13 x 10-6 - 2.13 x 10-4x
x2 + 2.13 x 10-4x - 2.13 x 10-6 = 0

A=1 B = 2.13 x 10-4 C = -2.13 x 10-6

x = 1.36 x 10-3
[OH-] = 1.36 x 10-3 mol/L
pOH = ?? pH = 11.13
32
 pH of a weak base
Calculate the pH of 0.500 mol/L NaNO2(aq)

33
 NO2- + H2O ⇋ HNO2 + OH-
0.500 0 0
-x +x +x
0.500 – x x x

Kb = [OH ] [HCO ]
-
3
- Kb = 1.00 x 10-14
[CO32-] 7.2 x 10-4
Check:
= 1.39 x 10-11
0.500
= 3.6 x 1010
1.39 x 10-11
OK to ignore –x here
ie. NO Quadratic
34
 [x] [x]
1.39 x 10 -11

[0.500 - x]
x2 = 6.95 x 10-12
x = 2.6 x 10-6

[OH-] = 2.6 x 10-6 mol/L

pOH = ??
pH = 8.42

35
 Calculating Ka from [weak acid] and pH
eg. The pH of a 0.072 mol/L solution of benzoic
acid, C6H5COOH, is 2.68. Calculate the numerical
value of the Ka for this acid.
- Equation

- Find [H3O+] from pH

- Subtract from [weak acid]

- Substitute to find Ka

36
C6H5COOH(aq) + H2O(l) ⇋ H3O+(aq) + C6H5COO-(aq)

[H3O+] = 10-2.68 = 0.00209 mol/L

[C6H5COO-] = 0.00209 mol/L

[C6H5COOH] = 0.072 – 0.00209
Find Ka = 0.06991 mol/L

Ka = (0.00209)(0.00209)
= 6.2 x 10-5
(0.06991)

37
 Calculating Ka from [weak acid] and pH
eg. The pH of a 0.072 mol/L solution of benzoic
acid, C6H5COOH, is 2.68. Calculate the %
dissociation for this acid.
[H3O+] = 10-2.68
= 0.00209 mol/L

[H3O ]
% diss  x 100%
[weak acid]
0.00209
 x 100% = 2.9 %
0.072
38
 Apr. 4

Calculate the acid dissociation constant, Ka ,

and the percent dissociation for each acid:

a) 0.250 mol/L chlorous acid, HClO2(aq); pH = 1.31

0.012 19.5%
b) 0.150 mol/L cyanic acid, HCNO(aq); pH = 2.15
0.00035 4.7%
c) 0.100 mol/L arsenic acid, H3AsO4(aq); pH = 1.70
0.0050 20%
0.500 mol/L iodic acid, HIO3(aq); pH = 0.670
0.160 42.8%

39
More Practice:
●
Weak Acids:
pp. 592 # 8
●
Weak Bases:
p. 595 #’s 13, 15, 16 (Kb’s on p. 592)

40
 Acid-Base Stoichiometry
Solution Stoichiometry (Review)
1. Write a balanced equation
2. Calculate moles given ( n 
m OR n = CV)
3. Mole ratios M
4. Calculate required quantity
n OR n OR m = nM
V C
C V

41
eg. 25.0 mL of 0.100 mol/L H2SO4(aq) was used to
neutralize 36.5 mL of NaOH(aq). Calculate the
molar concentration of the NaOH solution.

H2SO4(aq) + 2NaOH(aq) → 2 H2O(l) + Na2SO4(aq)

nH SO = C x V = 0.100 mol/L x 0.0250L = 0.00250 mol

2 4

NNaOH = 2 x nH SO = 0.00500 mol/L

2 4

CNaOH = n = 0.00500 mol/L = 0.137 mol/L

V 0.0365 L
42
Dilution
●
Given 3 of the four variables
●
Only one solution
● CV = CV
i i f f

Stoichiometry
●
Given 3 of the four variables
●
Two different solutions
●
4 step method

44
 Excess Acid or Base
To calculate the pH of a solution produced by
mixing an acid with a base:
 write the B-L equation (NIE)

 calculate the moles of H3O+ and OH-

 subtract
to determine the moles of excess
H3O+ or OH-
 divide by total volume to get concentration
 calculate pH

45
eg. 20.0 mL of 0.0100 M Ca(OH)2(aq) is mixed
with 10.0 mL of 0.00500 M HCl(aq).
Determine the pH of the resulting solution.
ANSWER:
Species present:
Ca2+ OH- H3O+ Cl- H2O

SB SA

46
 B-L Equation: OH- + H3O+ → 2 H2O

C = 0.0200 mol/L C = 0.00500 mol/L

V = 0.0200 L V = 0.0100 L

n = CV n = CV

4.00 x 10-4 mol OH- 5.0 x 10-5 mol H3O+

3.5 x 10-4 mol excess OH-

47
 n
C
Vtotal
3.5 x 10  4 mol

0.0300 L
= 0.01167 mol/L

[OH-] = 0.01167 mol/L

pOH = 1.933

pH = 12.067

48
Indicators
●
An indicator is a weak acid that changes
color with changes in pH
●
HIn is the general formula for an indicator
●
To choose an indicator for a titration, the pH
of the endpoint must be within the pH range
over which the indicator changes color

49
HIn(aq) + H2O(l) ⇋ H3O+(aq) + In-(aq)
Colour #1 Colour #2

●
HIn is the acid form of the indicator.
● Adding H3O+ causes colour 1 (LCP)
● Adding OH- removes the H3O+ & causes
colour #2

50
methyl orange
HMo(aq) + H2O(l) ⇋ H3O+(aq) + Mo-(aq)
red yellow

bromothymol blue
HBb(aq) + H2O(l) ⇋ H3O+(aq) + Bb-(aq)
yellow blue

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