Equilibrium

Equilibrium is a state in which there are no observable changes as

time goes by.

Chemical equilibrium is achieved when:

• the rates of the forward and reverse reactions are equal and
• the concentrations of the reactants and products remain constant

Physical equilibrium
H2O l   H2O g 

Chemical equilibrium
N2O4 g   2NO2 g 
© McGraw-Hill Education. 14-1
© McGraw-Hill Education. 14-2
Equilibrium of N2O4 (1 of 3)
N2O4 g   2NO2 g 

Start with NO2 Start with N2O4 Start with NO2 & N2O4

© McGraw-Hill Education. 14-3

Equilibrium of N2O4 (2 of 3)
N2O 4 ( g )  2NO 2 ( g )

[NO2 ]2
K 4.63 10 –3
N2O4 
aA  bB  cC  dD
 C  D
c d

K Law of Mass Action

 A  B
a b

© McGraw-Hill Education. 14-4

Equilibrium of N2O4 (3 of 3)

Table 14.1 The NO2–N2O4 System at 25°C

Initial Equilibrium Ratio of Ratio of
Concentrations Concentrations Concentrations at Concentrations at
M  M  Equilibrium Constant  Equilibrium Constant 

NO2  NO2 
2

NO2  N2O4  NO2  N2O4 

N2O4  N2O4 
0.000 0.670 0.0547 0.643 0.0851 4.65 10 –3
0.0500 0.446 0.0457 0.448 0.102 4.66 10 –3
0.0300 0.500 0.0475 0.491 0.0967 4.60 10 –3
0.0400 0.600 0.0523 0.594 0.0880 4.60 10 –3
0.200 0.000 0.0204 0.0898 0.227 4.63 10 –3

© McGraw-Hill Education. 14-5

Example 14.1 (1 of 4)

Write expressions for Kc , and Kp if applicable, for the

following reversible reactions at equilibrium:

a  HF aq   H2O l   H3O  aq   F – aq 

b  2NO g   O2 g   2NO2 g 

c  CH3COOH aq   C2H5OH aq   CH3COOC2H5 aq   H2O l 

© McGraw-Hill Education. 14-6

Example 14.1 (2 of 4)
Strategy

Keep in mind the following facts: (1) the Kp expression

applies only to gaseous reactions and (2) the concentration
of solvent (usually water) does not appear in the equilibrium
constant expression.

© McGraw-Hill Education. 14-7

Example 14.1 (3 of 4)
Solution

(a) Because there are no gases present, Kp does not apply

and we have only Kc.
 H3O   F – 
K' c 
HF H2O
HF is a weak acid, so that the amount of water consumed in
acid ionizations is negligible compared with the total amount
of water present as solvent. Thus, we can rewrite the
equilibrium constant as

 H3O   F – 
Kc 
HF
© McGraw-Hill Education. 14-8
Example 14.1 (4 of 4)
 NO2 
2 2
PNO
b  Kc  Kp  2

NO  O2 
2 2
PNO PO2

(c) The equilibrium constant is given by

K' c 
 CH3COOC2H5  H2O 
 CH3COOH  C2H5OH

Because the water produced in the reaction is negligible

compared with the water solvent, the concentration of water does
not change. Thus, we can write the new equilibrium constant as

Kc 
CH3COOC2H 5 
CH3COOHC2H5OH
© McGraw-Hill Education. 14-9
Example 14.2 (1 of 3)

The following equilibrium process has been studied

at 230°C:
2NO g   O2 g   2NO2 g 

In one experiment, the concentrations of the

reacting species at equilibrium are found to be
NO = 0.0542 M,  O2  = 0.127 M, and NO 2  = 15.5 M.
Calculate the equilibrium constant (Kc) of the
reaction at this temperature.

© McGraw-Hill Education. 14-10

Example 14.2 (2 of 3)
Strategy
The concentrations given are equilibrium concentrations. They have
units of mol/L, so we can calculate the equilibrium constant (Kc)
using the law of mass action [Equation (14.2)].

Solution
The equilibrium constant is given by

NO2 
2

Kc 
NO  O2 
2

Substituting the concentrations, we find that

15.5 
2

Kc  6.44 105
0.0542  0.127 
2

© McGraw-Hill Education. 14-11

Example 14.2 (3 of 3)

Check

Note that Kc is given without units. Also, the large

magnitude of Kc is consistent with the high product (NO2)
concentration relative to the concentrations of the reactants
(NO and O2).

© McGraw-Hill Education. 14-12

Example 14.3 (1 of 4)

The equilibrium constant Kp for the decomposition of

phosphorus pentachloride to phosphorus trichloride and
molecular chlorine

PCl5 g   PCl3 g   Cl2 g 

is found to be 1.05 at 250°C. If the equilibrium partial

pressures of PCl5 and PCl3 are 0.875 atm and 0.463 atm,
respectively, what is the equilibrium partial pressure of Cl2
at 250°C?

© McGraw-Hill Education. 14-13

Example 14.3 (2 of 4)

Strategy

The concentrations of the reacting gases are given in atm,

so we can express the equilibrium constant in KP. From the
known KP value and the equilibrium pressures of
PCl3 and PCl5 , we can solve for Pcl2 .

© McGraw-Hill Education. 14-14

Example 14.3 (3 of 4)
Solution
First, we write Kp in terms of the partial pressures of the
reacting species
PPCl3 PCl2
Kp 
PPCl5

Knowing the partial pressures, we write

0.463  PCl2 
1.05 
0.875 
or

PCl2 
1.05 0.875 
1.98 atm
0.463 
© McGraw-Hill Education. 14-15
Example 14.3 (4 of 4)

Check

Note that we have added atm as the unit for Pcl .

2

© McGraw-Hill Education. 14-16

Example 14.7 (1 of 3)
The reaction for the production of ammonia can be written in a number
of ways:

a  N2 g   3H2 g   2NH3 g 

1 3
b  N2 g   H2 g   NH3 g 
2 2
1 2
c  N2 g   H2 g   NH3 g 
3 3

Write the equilibrium constant expression for each formulation.

(Express the concentrations of the reacting species in mol/L.)

© McGraw-Hill Education. 14-17

Example 14.7 (2 of 3)

Strategy

We are given three different expressions for the same

reacting system. Remember that the equilibrium constant
expression depends on how the equation is balanced, that
is, on the stoichiometric coefficients used in the equation.

© McGraw-Hill Education. 14-20

Example 14.7 (3 of 3)

Solution

NH 3 
2

a  Ka 
N2  H2 
3

 NH3 
b  Kb  1 3
N2  2 H2  2
2
 NH3  3
c  Kc  1
N2  3 H2 
© McGraw-Hill Education. 14-21
Relationship of Equilibrium and K

 C D
c d
aA  bB  cC  dD
K
 A  B 
a b

Equilibrium Will

K >1 Lie to the right Favor products

>
K 1 Lie to the left Favor reactants

Products Reactants
K 1
K 1
Reactants   Products

a  b 
© McGraw-Hill Education. 14-22
© McGraw-Hill Education. 14-23
 Interpret Graphs

This graph shows the This graph shows the

progress of a reaction progress of the reaction that
that starts with begins with an initial
concentrations of SO2 concentration of SO3, and
and O2, but with zero zero concentrations for SO2
SO3. and O2.

•Notice that after a certain time, the concentrations remain

constant.
Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved.
 1
 Reactants? 2 and 3 4
 Products?  Reactants?  Reactants?
 Rate of forward and  Products?  Products?
reverse reactions?  Rate of forward and reverse  Rate of forward and reverse
 Equilibrium reactions? reactions?
Reached?  Equilibrium Reached?  Equilibrium Reached?
7.7 Calculating equilibrium concentrations

Learning objectives:

Identify the concentrations or partial pressures of chemical species at

equilibrium based on the initial conditions and the equilibrium

constant.
When we have the initial concentrations/pressure, and you
want to find the equilibrium concentrations:
We use the ICE table
Calculating Equilibrium Concentrations

1.Express the equilibrium concentrations of all species in

terms of the initial concentrations and a single unknown x,
which represents the change in concentration.
2.Write the equilibrium constant expression in terms of the
equilibrium concentrations. Knowing the value of the
equilibrium constant, solve for x.
3.Having solved for x, calculate the equilibrium
concentrations of all species.

© McGraw-Hill Education. 14-30

Example 14.9 (1 of 5)

A mixture of 0.500 mol H2 and 0.500 mol I2 was placed in a 1.00 −

L stainless-steel flask at 430°C. The equilibrium constant Kc for
the reaction H2 g   I2 g   2HI g  is 54.3 at this
temperature. Calculate the concentrations of H 2, I2, and HI at
equilibrium

© McGraw-Hill Education. 14-31

© McGraw-Hill Education. 14-32
Example 14.9 (3 of 5)
Solution

We follow the preceding procedure to calculate the equilibrium

concentrations.

Step 1: The stoichiometry of the reaction is 1 mol H2 reacting with 1 mol

I2 to yield 2 mol HI. Let x be the depletion in concentration
(mol/L) of H2 and I2 at equilibrium. It follows that the equilibrium
concentration of HI must be 2x. We summarize the changes in
concentrations as follows:
H2  I2  2HI
Initial M  : 0.500 0.500 0.000
Change M  : –x –x 2 x
Equilibrium M   0.500 – x   0.500 – x  2x
© McGraw-Hill Education. 14-33
Example 14.9 (4 of 5)

Step 2: The equilibrium constant is given by

HI
2

Kc 
H2  I2 
Substituting, we get

2x 
2

54.3 
 0.500 – x   0.500 – x 
Taking the square root of both sides, we get

2x
7.37 
0.500 – x
x 0.393 M
© McGraw-Hill Education. 14-34
Example 14.9 (5 of 5)

Step 3: At equilibrium, the concentrations are

H2  0.500 – 0.393 M 0.107M

I2  0.500 – 0.393 M 0.107M
HI 2 0.393M 0.786M
Check You can check your answers by calculating Kc using the
equilibrium concentrations. Remember that Kc is a constant for
a particular reaction at a given temperature.

© McGraw-Hill Education. 14-35

Example 14.10 (1 of 8)

For the same reaction and temperature as in Example 14.9,

H2 g   I2 g   2HI g ,
suppose that the initial concentrations of H 2, I2, and HI are
0.00623 M, 0.00414 M, and 0.0224 M respectively. Calculate
the concentrations of these species at equilibrium. Given that
Kc =(54.3),

© McGraw-Hill Education. 14-39

Example 14.10 (2 of 8)

Strategy

From the initial concentrations we can calculate the reaction

quotient (Qc) to see if the system is at equilibrium or, if not, in
which direction the net reaction will proceed to reach equilibrium.
A comparison of Qc with Kc also enables us to determine if there
will be a depletion in H2 and I2 or HI as equilibrium is established.

© McGraw-Hill Education. 14-40

Example 14.10 (4 of 8)

Step 1: Let x be the depletion in concentration (mol/L) of H2

and I2 at equilibrium. From the stoichiometry of the
reaction it follows that the increase in concentration
for HI must be 2x. Next we write

H2  I2  2HI
Initial M  : 0.00623 0.00414 0.0224
Change M  : –x –x  2x
Equilibrium M  0.00623 – x  0.00414 – x  0.0224  2x 

© McGraw-Hill Education. 14-41

Example 14.10 (5 of 8)
Step 2: The equilibrium constant is

Kc 
HI
2

H2 I2 
Substituting, we get

0.0224  2x 
2

54.3 
0.00623 – x 0.00414 – x 
It is not possible to solve this equation by the square root shortcut,
as the starting concentrations [H2] and [I2] are unequal. Instead, we
must first carry out the multiplications

54.3 2.58 10 –5 – 0.0104 x  x 2  5.02 10 –4  0.0896 x  4 x 2

© McGraw-Hill Education. 14-42
Example 14.10 (6 of 8)
Collecting terms, we get

50.3 x 2 – 0.654 x  8.98 10 –4 0

This is a quadratic equation of the form a x2 + b x + c = 0. The solution for a

quadratic equation (see Appendix 4) is

– b  b 2 – 4ac
x
2a

Here we have a = 50.3, b = − 0.654, and c 8.98 10 –4 , so that

– 0.654  – 4 50.3  8.98 10 –4 

2
0.654 
x
2 50.3
x 0.0114 M or x 0.00156 M

© McGraw-Hill Education. 14-43

Example 14.10 (7 of 8)
The first solution is physically impossible because the amounts of
H2 and I2 reacted would be more than those originally present.
The second solution gives the correct answer. Note that in solving
quadratic equations of this type, one answer is always physically
impossible, so choosing a value for x is easy.

Step 3: At equilibrium, the concentrations are

H2   0.00623 – 0.00156 M  0.00467 M

I2   0.00414 – 0.00156 M – 0.00258 M
HI  0.0224  2  0.00156 M  0.0255 M

© McGraw-Hill Education. 14-44

Example 14.10 (8 of 8)

Check

You can check the answers by calculating Kc using the

equilibrium concentrations. Remember that Kc is a constant for
a particular reaction at a given temperature.

© McGraw-Hill Education. 14-45

Reaction Quotient
The reaction quotient (Qc)is calculated by substituting the initial
concentrations of the reactants and products into the equilibrium
constant (Kc) expression.
IF
Qc < Kc system proceeds from left to right to reach equilibrium
Qc = Kc the system is at equilibrium
Qc > Kc system proceeds from right to left to reach equilibrium

Jump to long description

© McGraw-Hill Education. 14-46