17

Chemical
Equilibrium

Chapter Goals
1. Basic Concepts
2. The Equilibrium Constant
3. Variation of Kc with the Form of the
Balanced Equation
4. The Reaction Quotient
5. Uses of the Equilibrium Constant, Kc
6. Disturbing a System at Equilibrium:
Predictions
2

Chapter Goals
8. Disturbing a System at Equilibrium:
Calculations
9. Partial Pressures and the Equilibrium
Constant
10. Relationship between Kp and Kc
11. Heterogeneous Equilibria
12. Evaluation of Equilibrium Constants at
Different Temperatures
3

Basic Concepts
Reversible reactions do not go to completion.
They can occur in either direction
Symbolically, this is represented as:

a Ag +bBg

cCg +dD g

Basic Concepts
Chemical equilibrium exists when two
opposing reactions occur simultaneously
at the same rate.
A chemical equilibrium is a reversible reaction
that the forward reaction rate is equal to the
reverse reaction rate.

Chemical equilibria are dynamic equilibria.

Molecules are continually reacting, even
though the overall composition of the reaction
mixture does not change.
5

Basic Concepts
One example of a dynamic equilibrium can
be shown using radioactive 131I as a tracer
in a saturated PbI2 solution.
*
2
H 2O

1 Place solid PbI in a saturated PbI 2 solution.

PbI 2(s)

Pb

2
(aq)

2I

(aq)

2 Stir for a few minutes, then filter the solution.

Some of the radioactiv e iodine will go into solution.
6

Basic Concepts
Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.

aAg +bBg

cCg +dD g

Basic Concepts
One of the fundamental ideas of chemical
equilibrium is that equilibrium can be
established from either the forward or
reverse direction.

Basic Concepts

Basic Concepts

10

The Equilibrium Constant

For a simple one-step mechanism reversible
reaction such as:

A(g)

B(g)

C(g)

D(g)

The rates of the forward and reverse reactions

can be represented as:
Rate f

k f A B which represents the forward rate.

Rate r

k r C D which represents the reverse rate.

11

The Equilibrium Constant

When system is at equilibrium:
Ratef = Rater

Substitute for the rate relationsh ip to give :

kf A B kr C D
which rearranges to
kf
C D
kr A B
12

The Equilibrium Constant

Because the ratio of two constants is a
constant we can define a new constant as
follows :

kf
kr

Kc and

Kc

C D
A B
13

The Equilibrium Constant

Similarly, for the general reaction:

a A(g)

b B(g)

c C(g) d D(g)

we can define a constant

c

products
C D
Kc
a
b
reactants
A B
This expression is valid for all reactions.
14

The Equilibrium Constant

Kc is the equilibrium constant .
Kc is defined for a reversible reaction at a
given temperature as the product of the
equilibrium concentrations (in M) of the
products, each raised to a power equal to
its stoichiometric coefficient in the
balanced equation, divided by the product
of the equilibrium concentrations (in M) of
the reactants, each raised to a power
equal to its stoichiometric coefficient in the15
balanced equation.

The Equilibrium Constant

Example 17-1: Write equilibrium constant
expressions for the following reactions at 500oC.
All reactants and products are gases at 500oC.

PCl5

PCl3 Cl2

16

The Equilibrium Constant

H2 + I2

2 HI

You do it!
17

The Equilibrium Constant

4 NH3 + 5 O 2

4 NO + 6 H 2O

You do it!

18

The Equilibrium Constant

Equilibrium constants are dimensionless
because they actually involve a
thermodynamic quantity called activity.
Activities are directly related to molarity

19

The Equilibrium Constant

Example 17-2: One liter of equilibrium mixture from
the following system at a high temperature was
found to contain 0.172 mole of phosphorus
trichloride, 0.086 mole of chlorine, and 0.028 mole
of phosphorus pentachloride. Calculate Kc for the
reaction.

PCl5
Equil []s

0.028 M

PCl3 Cl2
0.172 M
You do it!

0.086 M

20

The Equilibrium Constant

Example 17-3: The decomposition of PCl5 was
studied at another temperature. One mole of PCl5
was introduced into an evacuated 1.00 liter
container. The system was allowed to reach
equilibrium at the new temperature. At equilibrium
0.60 mole of PCl3 was present in the container.
Calculate the equilibrium constant at this
temperature.

21

The Equilibrium Constant

Example 17-4: At a given temperature 0.80 mole
of N2 and 0.90 mole of H2 were placed in an
evacuated 1.00-liter container. At equilibrium 0.20
mole of NH3 was present. Calculate Kc for the
reaction.
You do it!

22

Variation of Kc with the

Form of the Balanced Equation
The value of Kc depends upon how the balanced
equation is written.
From example 17-2 we have this reaction:

PCl5

PCl3 Cl2

This reaction has a Kc=[PCl3][Cl2]/[PCl5]=0.53

23

Variation of Kc with the

Form of the Balanced Equation
Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.

PCl3 Cl2

PCl5

Equil. []s 0.172 M 0.086 M

0.028 M
The concentrations are from Example 17-2.
K'c

PCl5
PCl 3 Cl 2

0.028
0.172 0.086

Kc

K'c

or K'c

Kc

0.53

1.9
1.9
24

The Reaction Quotient

25

The Reaction Quotient

26

The Reaction Quotient

The mass action expression or reaction quotient
has the symbol Q.
Q has the same form as Kc

The major difference between Q and Kc is that

the concentrations used in Q are not
necessarily equilibrium values.

For this general reaction :

aA + bB cC + dD
c

C D
a
b
A B

27

The Reaction Quotient

Why do we need another equilibrium
constant that does not use equilibrium
concentrations?
Q will help us predict how the equilibrium
will respond to an applied stress.
To make this prediction we compare Q
with Kc.

28

The Reaction Quotient

When:
Q=K c The system is at equilibrium.
Q

K c The reaction occurs to the left to a greater extent.

Q K c The reaction occurs to the right to a greater extent.

To help understand this think of Q and K c as fractions.

29

The Reaction Quotient

Example 17-6: The equilibrium constant for the
following reaction is 49 at 450oC. If 0.22 mole of
I2, 0.22 mole of H2, and 0.66 mole of HI were put
into an evacuated 1.00-liter container, would the
system be at equilibrium? If not, what must occur
to establish equilibrium?

30

Uses of the Equilibrium

Constant, Kc
Example 17-7: The equilibrium constant, Kc, is
3.00 for the following reaction at a given
temperature. If 1.00 mole of SO2 and 1.00 mole of
NO2 are put into an evacuated 2.00 L container
and allowed to reach equilibrium, what will be the
concentration of each compound at equilibrium?

SO2(g)

NO2(g)

SO3(g)

NO(g)

31

Uses of the Equilibrium

Constant, Kc
Example 17-8: The equilibrium constant is 49 for
the following reaction at 450oC. If 1.00 mole of HI
is put into an evacuated 1.00-liter container and
allowed to reach equilibrium, what will be the
equilibrium concentration of each substance?

H 2(g) + I 2(g)

2 HI (g)

You do it!

32

Disturbing a System at
Equilibrium : Predictions

LeChateliers Principle - If a change of conditions

(stress) is applied to a system in equilibrium, the
system responds in the way that best tends to
reduce the stress in reaching a new state of
equilibrium.

We first encountered LeChateliers Principle in Chapter

14.

Some possible stresses to a system at

equilibrium are:
1. Changes in concentration of reactants or products.
2. Changes in pressure or volume (for gaseous reactions)
33
3. Changes in temperature.

Disturbing a System at
Equilibrium : Predictions
1

Changes in Concentration of Reactants and/or Products

Also true for changes in pressure for reactions involving gases.

Look at the following system at equilibrium at 450 oC.

H 2 (g) I 2 (g)
Kc

HI

2 HI g
2

H 2 I2

49
34

Disturbing a System at
Equilibrium : Predictions
1

Changes in Concentration of Reactants and/or Products

Also true for changes in pressure for reactions involving gases.

Look at the following system at equilibrium at 450 oC.

H 2 (g) I 2 (g)
Kc

HI

2 HI g
2

H 2 I2

49

If some H 2 is added, Q<K c .

This favors the forward reaction.
35
Equilbrium will shift to the right or product side.

Disturbing a System at
Equilibrium : Predictions
1

Changes in Concentration of Reactants and/or Products

Also true for changes in pressure for reactions involving gases.

Look at the following system at equilibrium at 450 oC.

H 2 (g) I 2 (g)
Kc

HI

2 HI g
2

H 2 I2

49

If we remove some H 2 ,Q>K c

This favors the reverse reaction.
Equilbrium will shift to the left, or reactant side.

36

Disturbing a System at
Equilibrium : Predictions
2 Changes in Volume
(and pressure for reactions involving gases)
Predict what will happen if the volume of this system at
equilibrium is changed by changing the pressure at
constant temperature:

2 NO2 g

N 2O 4 g

N 2O 4
Kc =
2
NO2

37

Disturbing a System at
Equilibrium : Predictions
2 NO2 g

N 2O 4 g

N 2O 4
Kc =
2
NO2
If the volume is decreased, which increases the pressure, Q < K c .
This favors product formation or the forward reaction.
The forward reaction produces fewer moles of gas.

38

Disturbing a System at
Equilibrium : Predictions
2 NO2 g

N 2O 4 g

N 2O 4
Kc =
2
NO2
If the volume is increased, which decreases the pressure, Q > K c .
This favors the reactants or the reverse reaction.
More moles of gas are produced.

39

Disturbing a System at
Equilibrium : Predictions

40

Disturbing a System at
Equilibrium : Predictions
3 Changing the Temperature

41

Disturbing a System at
Equilibrium : Predictions
3 Changing the Reaction Temperature
Consider the following reaction at equilibrium:
o
2
SO
+
O
2
SO
198198
kJ kJ/mol
2 SO
O
2
SO
H
2 SO
O 2 2g g 23(g)
SO3 3g grxn
++198
kJ
2(g) 2 g2 g+
2(g)

Heat
isaaproduct
product
this reaction
reaction.
Heat
ofofthis
Is heat
aisreactant
or product
in
this reaction?
Increasing
Decreasingthethereaction
reactiont emperature
t emperaturestresses
stressesthe
theproducts.
reactants.
This
reactant
This favors
favors the
the reverse
reactantsoror
forwardreaction.
reaction.

42

Disturbing a System at
Equilibrium : Predictions
Introduction of a Catalyst
Catalysts decrease the activation energy of both the forward and
reverse reaction equally.

Catalysts do not affect the position of equilibrium.

The concentrations of the products and reactants will be the
same whether a catalyst is introduced or not.
Equilibrium will be established faster with a catalyst.

43

Disturbing a System at
Equilibrium : Predictions
Example 17-9: Given the reaction below at
equilibrium in a closed container at 500oC. How
would the equilibrium be influenced by the
following?
N 2(g)

3 H 2(g)

2 NH 3(g) H orxn

Factor

92 kJ/mol
Effect on reaction procedure

a. Increasing the reaction temperature

b. Decreasing the reaction temperature
c. Increasing the pressure by decreasing the volume
d. Increase the concentration of H 2
e. Decrease the concentration of NH 3
f. Introducing a platinum catalyst

44

Disturbing a System at
Equilibrium : Predictions
Example 17-10: How will an increase in pressure (caused by
decreasing the volume) affect the equilibrium in each of the
following reactions?

Reaction
a. H 2 g + I 2 g

Effect on Equilibrium
2 HI g

b. 4 NH3 g +5 O 2(g)
c. PCl3 g +Cl2 g
d. 2 H 2 g

O2 g

4 NO g +6 H 2O g
PCl5 g
2 H 2O g

45

Disturbing a System at
Equilibrium : Predictions
Example 17-11: How will an increase in
temperature affect each of the following reactions?

Reaction
a. 2 NO 2(g)
b. H 2 g

Cl2 g

c. H 2 g + I 2 g

Effect on Equilibrium
N 2O 4(g) H

o
rxn

2 HCl g + 92 kJ
2 HI g

25 kJ

46

Partial Pressures and the

Equilibrium Constant
For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
For gases, the pressure is proportional to the
concentration.
We can see this by looking at the ideal gas law.

PV = nRT
P = nRT/V
n/V = M
P= MRT and M = P/RT
47

Partial Pressures and the

Equilibrium Constant
For convenience we
express the amount of
PVmaynRT
a gas in terms of its partial pressure rather than
n
its concentration. P
RT
V we must solve the
To derive this relationship,
ideal gas equation.
n

Because

has the units mol/L,

P = []RT
Thus at constant T, the partial pressure of a gas
is directly proportion al to its concentrat ion.
48

Partial Pressures and the

Equilibrium Constant
Consider this system at equilibrium at
5000C.

2 Cl2 g + 2 H 2O g
4

Kc

4 HCl g + O 2 g

HCl O 2
and K p
2
2
Cl2 H 2O

PHCl
PCl 2

PO 2

PH 2O

49

Partial Pressures and the

Equilibrium Constant
Kc

PHCl 4 PO2
RT
RT
2 P
2
P
Cl2

RT

Kc

PHCl
PCl 2

H 2O

RT

Kp

1
RT

PO 2

PH 2O

1 5
RT
1 4
RT

so for this reaction

-1

K c = K p (RT) or K p = K c (RT)
L atm
Must use R 0.0821
mol K

50

Relationship Between Kp and Kc

From the previous slide we can see that
the relationship between Kp and Kc is:
Kp

K c RT

or K c

K p RT

n = (# of moles of gaseous products) - (# of moles of gaseous reactants)

51

Relationship Between Kp and Kc

Example 17-15: Nitrosyl bromide, NOBr, is 34%
dissociated by the following reaction at 25oC, in a
vessel in which the total pressure is 0.25
atmosphere. What is the value of Kp?

2 NOBr g

2 NO g + Br2 g

52

Relationship Between Kp and Kc

The numerical value of Kc for this reaction
can be determined from the relationship of
Kp and Kc.

K p = Kc RT
Kc

9.3 10

n
3

or Kc = K p RT
0.0821 298

n =1

38
. 10

53

Relationship Between Kp and Kc

Example 17-16: Kc is 49 for the following reaction
at 450oC. If 1.0 mole of H2 and 1.0 mole of I2 are
allowed to reach equilibrium in a 3.0-liter vessel,

H2 g

I2 g

2 HI g

(a) How many moles of I2 remain unreacted at

equilibrium?
You do it!

54

Relationship Between Kp and Kc

(b) What are the equilibrium partial
pressures of H2, I2 and HI?
You do it!

55

Relationship Between Kp and Kc

(c) What is the total pressure in the reaction
vessel?
You do it!

56

Heterogeneous Equlibria
Heterogeneous equilibria have more than one
phase present.
For example, a gas and a solid or a liquid and a gas.

CaCO3 s

CaO s

CO2 g

at 500 C

How does the equilibrium constant differ for heterogeneous

equilibria?
Pure solids and liquids have activities of unity.
Solvents in very dilute solutions have activities that are essentially
unity.
The Kc and Kp for the reaction shown above are:

K c = [CO 2 ]

K p = PCO 2

57

Heterogeneous Equlibria
SO

For this reaction :

HO
H SO
(at 25 C)
o

2 g

3 aq

H O is the solvent.

What are the forms of K and K ?

c

You do it!

H SO
K =
SO
2

1
P

SO 2

58

Heterogeneous Equlibria
What are Kc and Kp for this reaction?

CaF2 s

Ca

2
aq

1aq

2F

(at 25 C)

You do it!

Kc = Ca

K p is undefined
59

Heterogeneous Equlibria
What are Kc and Kp for this reaction?

3 Fe s

4 H 2O g

Fe3O4 s

4 H2 g

H2
Kc =
4
H 2O

Kp

(at 500 C)

PH 2
PH 2O

4
4

60

Evaluation of Equilibrium Constants at

Different Temperatures
Example 17-19: For the reaction in example 17-18,
Ho = 114 kJ/mol and Kp = 4.3 x 10-13 at 25oC.
Estimate Kp at 250oC.

2 NO

2(g)

2NO

(g)

2(g)

61