Chapter 15

Chemical Equilibrium
Learning goals and key skills:
 Explain what is meant by chemical equilibrium and how it relates to reaction rates
 Write the equilibrium-constant expression for any reaction
 Convert Kc to Kp and vice versa
 Relate the magnitude of an equilibrium constant to the relative amounts of reactants and
products present in an equilibrium mixture.
 Manipulate the equilibrium constant to reflect changes in the chemical equation
 Write the equilibrium-constant expression for a heterogeneous reaction
 Calculate an equilibrium constant from concentration measurements
 Predict the direction of a reaction given the equilibrium constant and the concentrations of
reactants and products
 Calculate equilibrium concentrations given the equilibrium constant and all but one
equilibrium concentration
 Calculate equilibrium concentrations given the equilibrium constant and the starting
concentrations
 Use Le Chatelier’s principle to predict how changing the concentrations, volume, or
temperature of a system at equilibrium affects the equilibrium position.

The Concept of Equilibrium

Chemical equilibrium occurs when a reaction and

its reverse reaction proceed at the same rate.

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 Concept of Equilibrium
• As a system approaches
equilibrium, both the
forward and reverse
reactions are occurring.
• At equilibrium, the
forward and reverse
reactions are proceeding
at the same rate.
• Once equilibrium is
achieved, the amount of
each reactant and
product remains
constant.

The same equilibrium is reached whether we

start with only reactants (N2 and H2) or with
only product (NH3).

Equilibrium is reached from either direction.

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 The Equilibrium Constant
• Consider the generalized reaction
aA + bB cC + dD
The equilibrium expression for this
reaction would be [C]c[D]d
Kc =
[A]a[B]b
Since pressure is proportional to
concentration for gases in a closed
system, the equilibrium expression can
also be written
(PC) (PD)
c d
Kp =
(PA)a (PB)b

Chemical equilibrium occurs when

opposing reactions are proceeding at equal rates.

N2O4 (g) 2 NO2 (g)

Since, in a system at equilibrium, both the forward
and reverse reactions are being carried out, we
write its equation with a double arrow.

Forward reaction: Reverse reaction:

N2O4 (g)  2 NO2 (g) 2 NO2 (g)  N2O4 (g)

Rate Law: Rate Law:

Rate = kf [N2O4] Rate = kr [NO2]2

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 Equilibrium Constant

• Therefore, at equilibrium
Ratef = Rater
kf [N2O4] = kr [NO2]2
• Rewriting this, it becomes

kf [NO2]2
=
kr [N2O4]

k [NO2]2
Keq = f = = a constant
kr [N2O4]

Example
Write the equilibrium constant expression of the
following reaction:
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

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 Relationship Between Kc and Kp
From the Ideal Gas Law we know that:
PV = nRT and P = (n/V)RT = [A]RT

Plugging this into the expression for Kp

for each substance, the relationship
between Kc and Kp becomes

Kp = Kc (RT)n
where
n = (moles of gaseous product) - (moles of gaseous reactant)

What Does the Value of K Mean?

• If K>>1, the reaction is
product-favored;
product predominates
at equilibrium.

• If K<<1, the reaction is

reactant-favored;
reactant predominates
at equilibrium.

*When 10-3 < K < 103, the reaction is considered to contain a

significant amount of both reactants and products at equilibrium.

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Direction of Chemical Equation and K

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N2O4 (g) ⇌ 2 NO2 (g) Kc = [NO2] = 0.212 at 100 C
[N2O4]
[N2O4]
2 NO2 (g) ⇌ N2O4 (g) Kc = = 4.72 at 100 C
[NO2]2

The equilibrium constant of a reaction in the

reverse direction is the reciprocal of the
equilibrium constant of the forward reaction.

Stoichiometry and K
[NO2]2
N2O4(g) ⇌ 2 NO2(g) Kc = = 0.212 at 100 C
[N2O4]
[NO2]4
2 N2O4(g) ⇌ 4 NO2(g) Kc = = (0.212)2 at 100 C
[N2O4]2

The equilibrium constant of a reaction that has

been multiplied by a number, is the equilibrium
constant raised to a power that is equal to that
number.

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 Multiple equilibria and K
2 NOBr ⇌ 2 NO + Br2 K1 = 0.014
Br2 + Cl2 ⇌ 2 BrCl K2 = 7.2
2 NOBr + Cl2 ⇌ 2 NO + 2 BrCl
K3 = K1 × K2 = 0.014 × 7.2 = 0.10

The equilibrium constant for a net reaction

made up of two or more steps is the
product of the equilibrium constants for the
individual steps.

Example
Consider the following reactions at 1200 K.

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g) K1 = 3.92

CH4(g) + 2H2S(g) ⇌ CS2(g) + 4H2(g) K2 = 3.3x104

Use the above reactions to determine the equilibrium

constant for the following reaction at 1200 K.
CO(g) + 2H2S(g) ⇌ H2O(g) + CS2(g) + H2(g)

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 Homogeneous vs Heterogeneous
Homogeneous equilibria occur when all reactants and
products are in the same phase.
Heterogeneous equilibria occur when reactant or
product in the equilibrium is in a different phase.
• The value used for the concentration of a pure
substance is always 1.
Therefore, the concentrations of solids and liquids do not
appear in the equilibrium expression.

PbCl2 (s) ⇌ Pb2+(aq) + 2 Cl-(aq)

Kc = [Pb2+][Cl-]2

As long as some CaCO3 or CaO remain in the system, the

amount of CO2 above the solid will remain the same.

Kc = [CO2] and Kp = PCO2

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 Equilibrium constant, Kc (Keq or K)
• Always products divided by reactants. (Although
sometimes products are equal to 1 and reactants
are equal to 1.)
• All concentrations are equilibrium values.
• Each concentration is raised to its stoichiometric
coefficient.
• Kc depends on the rate constants which in turn
depend on the reaction (Ea) and temperature.
• No units on Kc.
• Pure solids and pure liquids are excluded from Kc.
• A catalyst does not change the equilibrium
concentrations, so it does not change Kc.

Calculating Equilibrium Constants

A closed system initially containing 1.000 x
10-3 M H2 and 2.000 x 10-3 M I2 at 448 C
is allowed to reach equilibrium. Analysis of
the equilibrium mixture shows that the
concentration of HI is 1.87 x 10-3 M.
Calculate Kc at 448 C for the reaction
taking place, which is
H2 (g) + I2 (g) ⇌ 2 HI (g)

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 What Do We Know?

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

Equilibrium 1.87 x 10-3

[HI] Increases by 1.87 x 10-3 M

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change +1.87 x 10-3

Equilibrium 1.87 x 10-3

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 Stoichiometry tells us [H2] and [I2]
decrease by half as much.

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

Equilibrium 1.87 x 10-3

Calculate the equilibrium concentrations

of all three compounds…
[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

Equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

[HI]2 (1.87 x 10-3)2

Kc = = = 51
[H2] [I2] (6.5 x 10-5)(1.065 x 10-3)

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 Example
Phosphorus pentachloride gas partially decomposes
to phosphorus trichloride gas and chlorine gas.
1.20 mol PCl5 is placed in a 1.00 L container at 200
°C. At equilibrium 1.00 mol PCl5 remains. Calculate
Kc and Kp at 200 °C.

The Reaction Quotient (Q)

• Q gives the same ratio the
equilibrium expression
gives, but for a system
that is not at equilibrium.
• To calculate Q, substitute
the (initial) concentrations
of reactants and products
into the equilibrium
expression.

aA + bB ⇌ cC + dD

[ C ] c [ D]d
Q 
[ A]a [ B]b

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 Comparing K and Q

If Q < K
• There’s too much reactant
• Need to increase the amount of products and
decrease the amount of reactants

If Q > K
• There’s too much product
• Need to decrease the amount of products and
increase the amount of reactants

Example

A 50.0 L reaction vessel contains 1.00 mol N2, 3.00

mol H2, and 0.500 mol NH3. Will more ammonia
(NH3) be formed or will NH3 dissociate when the
reaction mixture approaches equilibrium at 400 °C?

N2(g) + 3H2(g) ⇌ 2NH3(g) Kc = 0.500 at 400 °C.

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 Example

In the steam-reforming reaction, methane reacts with

water vapor to form carbon monoxide and hydrogen
gas. At 900 K, Kc = 2.4 × 10-4.

If 0.012 mol of methane, 0.0080 mol of water vapor,

0.016 mol of carbon monoxide and 0.0060 mol of
hydrogen gas are placed in a 2.0-L steel reactor and
heated to 900 K, which way will the reaction proceed:
to the right (products) or left (reactants)?

Example
Problem: Finding equilibrium concentrations from
initial concentrations and the equilibrium constant.

N2(g) + O2(g) ⇌ 2NO(g) Kc = 0.10 at 2000 °C

A reaction mixture at 2000 °C initially contains [N2]

= 0.200 M and [O2] = 0.200 M.
Find the equilibrium concentrations of the reactants
and products at this temperature.
• Represent the change in concentration of one of the
reactants (or products) with the variable ‘x’.
• Define the changes in concentration of the other reactants
and/or products in terms of x.
• Tip: Usually convenient to let x represent the change in
concentration of the reactant (or product) with the smallest
stoichiometric coefficient.

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 Example
Problem: Finding equilibrium concentrations from
initial concentrations and the equilibrium constant.

N2O4(g) ⇌ 2NO2(g) Kc = 0.36 at 100 °C

A reaction mixture at 100 °C initially contains

[NO2] = 0.100 M. Find the equilibrium
concentrations of the reactants and products at
this temperature.

Le Châtelier’s Principle

If a system at equilibrium is disturbed by a

change in temperature, pressure or the
concentration of one of the components, the
system will shift its equilibrium position so as
to counteract the effect of the disturbance.

Changing concentration
Temperature
Changing volume/pressure

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 Example: Le Châtelier’s Principle

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) Kp = 0.0214 at 540 K

At equilibrium
PH2 = 2.319 atm
PNH3 = 0.454 atm
PN2 = 0.773 atm

What happens
upon addition of 1
atm of H2?

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 The Haber Process
This apparatus helps push the equilibrium
to the right by removing the ammonia
(NH3) from the system as a liquid.

Change in Volume or Pressure

If gases are involved in an equilibrium, a
change in pressure or volume will affect K:
• Higher volume or lower pressure favors the
side of the equation with more moles of gas (and
vice-versa).

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 Le Châtelier’s Principle: pressure

CO(g) + 3H2(g) ⇌ CH4(g) + H2O(g)

Boyle’s law: at a fixed temperature, PV = k
[CH 4 ][H 2 O]
Kc 
[CO][H 2 ]3
Double the pressure (concentration)

(2[CH 4 ])(2[H 2 O]) K c Qc < Kc, reaction

Qc  
(2[CO])(2[H 2 ])3 4 forms products

In summary, if the pressure is increased by

decreasing the volume of a reaction mixture, the
reaction shifts in the direction of fewer moles of gas.

Le Châtelier’s Principle: temperature

endothermic H > 0
heat can be thought of as a reactant
increasing T results in an increase in K

exothermic H < 0
heat can be thought of as a product
increasing T results in an decrease in K

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The Effect of Changes in Temperature
Co(H2O)62+ (aq) + 4 Cl- (aq) ⇌ CoCl42- (aq) + 6 H2O (l)

Example: Le Châtelier’s Principle

N2O4 (g) ⇌ 2 NO2 (g) is endothermic.
What occurs with increasing temperature?

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 Catalysts

Catalysts increase the rate of both the forward and

reverse reactions.
When one uses a catalyst, equilibrium is achieved faster,
but the equilibrium composition remains unaltered.

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