CHEM 301 LECTURE

Unit 4. CHEMICAL EQUILIBRIUM

Chapter 13 in Atoms First by Zumdahl
I. Chemical Equilibrium
the state where the concentrations of all reactions and products remain constant with time
the rate of the forward reaction is equal to the rate of the reverse reaction
reversible reactions do not go into completion
reactants products
II. Equilibrium Constant, K
Law of Mass Action
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 the balanced equation.
aA + bB

Kc

cC + dD

[C]c [D]d
[A]a [B]b

Example 1: The following equilibrium concentrations were obtained for the Haber process for the synthesis of
ammonia at 127 C:
N2 (g) + 3H2 (g) 2NH3 (g)
-1

[N2] = 8.5 x 10 M

-3

[H2] = 3.1 x 10 M

-2

[NH3] = 3.1 x 10 M

Calculate the equilibrium constant K at 127 C:

Example 2: The following equilibrium concentrations were observed for the reaction between sulfur dioxide and
oxygen gases at 600 C:
2SO2 (g) + O2 (g) 2SO3 (g)
[SO2] = 0.590 M

[O2] = 0.0450 M

[SO3] = 0.260 M

Calculate the equilibrium constant K at 600 C:

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Equilibrium Expressions Involving Pressures, Kp

aA + bB
Kp

PC PD

PA PB

cC + dD

Kp= Kc(RT)n

where n = n(products) n(reactants)

Example 3: The following equilibrium pressures were obtained for the formation of nitrosyl chloride at 25 C:
2NO (g) + Cl2 (g) 2NOCl (g)
-2

P NO = 5.0 x 10 atm

-1

P Cl2 = 3.0 x 10 atm

P NOCl = 1.2 atm

Calculate the equilibrium constant Kp at 25C.

Example 4: For the reaction:

N2 (g) + 3H2 (g) 2NH3 (g)

KP = 7.8 x 10 at 250 C.
-6

Calculate the equilibrium constant Kc at this temperature.

Example 5: For the reaction:

2NO2 (g) 2NO (g) + O2 (g)

If P = 0.468 atm for all gases at equilibrium, calculate KC and KP at 301 C

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CHEM 301 LECTURE

Heterogeneous Equilibria

the position of a heterogeneous equilibrium does not depend on the amounts of pure solids or liquids
present
the concentrations of liquids and solids are treated as constant and are not included in the equilibrium
expression
CaCO3 (s) CaO (s) + CO2 (g)

Example 6: Consider the reaction:

K = [CO2]

3Fe (s) + 4H2O (g) Fe2O3 (s) + 4H2 (g)

Calculate Kc if the equilibrium concentrations at 850 C are: [H2O(g)] = 0.15 M and [H2 (g)] = 0.69 M

Multiple Equilibria
H2CO3 + H2O HCO3 + H3O
-2
+
HCO3 + H2O CO3 + H3O
-

H2CO3 + 2H2O CO3 + 2H3O

-2

-7

K1 = 4.2 x 10
-11
K2 = 4.8 x 10
+

K = K1 x K2 = 2.0 x 10

-17

Kinetics (k) and Equilibrium (K)

Consider the reaction:

A + B AB

ratefwd = kf[A][B] and raterev = kr[AB]

then:

III. Applications of the Equilibrium Constant

The Extent of Reaction: Reaction Quotient, Q

Q is obtained by applying the law of mass action, using initial concentrations instead of equilibrium
concentration
aA + bB

cC + dD

[C]c [D]d
[A]a [B]b

Q is compared to K:
If Q = K, the system is at equilibrium, no shift
If Q > K, the ratio of products to reactants is too large, the system will shift to the left
If Q < K, the ratio of products to reactants is too small, the system will shift to the right

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CHEM 301 LECTURE

Predicting the Direction of a Reaction:

Example 7:

Consider the reaction: N2 (g) + 3H2 (g) 2NH3 (g)

If the initial concentrations are:
[N2] = 5.0 M;
[H2] = 2.6 M;
Predict the direction of the reaction.

Example 8:

Consider the reaction: 2BrF5 (g) Br2 (g) + 5F2 (g)

Kc = 2.2 x 10 at 25 C
If the initial concentrations are: [BrF5] = 0,025 M;
[Br2] = 0.43M;
[O2] = 1.8 M
Determine the direction of the reaction.

-5

Kc = 1.7 x 10 at 500 C
[NH3] = 0.18 M

-13

Calculating the Equilibrium Concentrations:

Example 9:

Carbon monoxide reacts with steam to produce carbon dioxide and water:
CO (g) + O2 (g) CO2 (g) + H2O (g)
The equilibrium constant at 700 K is 5.10.
If the initial concentration of all species is 1.000 M, what are the concentrations of each species
at equilibrium?
Initial Concentration, M
[CO] = 1.000
[O2] = 1.000
[CO2} = 1.000
[H2O] = 1.000

Change, M
-x
-x
+x
+x

Equilibrium Concentration, M
1.000 - x
1.000 x
1.000 + x
1.000 + x

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Example 10:
Consider the reaction: H2 (g) + I2 (g) 2HI(g)
Kc = 54.3 at 35 C
If the initial concentrations of H2 and I2 are 0.25 M, what are the equilibrium concentrations of each species?
Since there is no product yet at the start of the reaction, the forward reaction is favored.

initial
change
final

H2
0.25 M
-x
0.25 - x

I2
0.25 M
-x
0.25 - x

HI
0
+ 2x
2x

IV. Factors that Affect Equilibrium

Le Chateliers Principle:
if a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a direction
that tends to reduce that change
if an external stress is applied to a system that is in equilibrium, the system will adjust in such a way as to
relieve the stress and reach a new equilibrium position, maintaining Keq constant.
Concentration
if a component (reactant or product) is added to a reaction system at equilibrium, the equilibrium
position will shift to the direction that lowers the concentration of that component
A + B C + D
Condition
Increasing the amount of A or B
Increasing the amount of C or D
Decreasing the amount of A or B
Decreasing the amount of C or D

Reaction favored
forward
reverse
reverse
forward

Temperature
increase in temperature favor an endothermic reaction
decrease in temperature favor an exothermic reaction
Volume and Pressure
affect only systems involving gases
increase in pressure (or decrease in volume) favor less total number of moles
decrease in pressure (or increase in volume) favor more total number of moles
Catalyst
The presence of a catalyst DOES NOT affect the state of equilibrium.
It only allows the system to reach equilibrium faster.
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