Chapter 15

Chemical Equilibrium
Chemical Equilibrium: The state reached when the
concentrations of reactants and products remain constant
over time.
N2O4(g) 2NO2(g)
Colorless Brown
The Equilibrium State
N2O4(g) 2NO2(g)

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 The 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 Equilibrium Constant Kc

Why?
 The Equilibrium Constant Kc

Experiment 1 Experiment 5

[NO2]2 (0.0125)2 (0.0141)2

Kc = = 4.64 x 10-3 = 4.63 x 10-3
[N2O4] 0.0337 0.0429
 The Equilibrium Constant Kc
For a general reversible reaction:
aA + bB cC + dD

[C]c[D]d Products
Equilibrium equation: Kc =
[A]a[B]b Reactants
Equilibrium constant
Equilibrium constant expression

For the following reaction: N2O4(g) 2NO2(g)

[NO2]2
Kc = = 4.64 x 10-3 (at 25 °C)
[N2O4]
 Another Equilibrium—
The Haber Process
• Consider the Haber Process, which is the
industrial preparation of ammonia:
N2(g) + 3 H2(g) ⇌ 2 NH3(g)
• The equilibrium constant depends on
stoichiometry:
 The Equilibrium Constant
• Consider the generalized reaction
aA + bB⇌ dD + eE
• The equilibrium expression for this reaction would
be

• Also, since pressure is proportional to concentration

for gases in a closed system, the equilibrium
expression can also be written
 More with Gases and Equilibrium
• We can compare the equilibrium constant
based on concentration to the one based on
pressure.
• For gases, PV = nRT (the Ideal Gas Law).
• Rearranging, P = (n/V)RT; (n/V) is [ ].
• The result is

• where
Magnitude of K
• If K>>1, the reaction
favors products; products
predominate at
equilibrium.
• If K<<1, the reaction
favors reactants;
reactants predominate at
equilibrium.
The Direction of the Chemical Equation and K

The equilibrium constant of a reaction in

the reverse reaction is the reciprocal of the
equilibrium constant of the forward
reaction:
N2O4(g) ⇌ 2 NO2(g) Kc =
[NO2]2
= 0.212 at 100 C
[N2O4]

[N2O4]
⇌
2 NO2(g) N2O4(g) Kc =
[NO2]2
= 4.72 at 100 C
 Stoichiometry and Equilibrium
Constants
To find the new equilibrium constant of a reaction
when the equation has been multiplied by a
number, simply raise the original equilibrium
constant to that power.

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

[NO2]4
2 N2O4(g) ⇌ 4 NO2(g) Kc =
[N2O4]2
= (0.212)2 at 100 C
 Consecutive Equilibria
• When two consecutive equilibria occur, the
equations can be added to give a single
equilibrium.
• The equilibrium constant of the new reaction is the
product of the two constants:
K3 = K1 × K2
• Example
2 NOBr ⇌ 2 NO + Br2 K1 = 0.014
Br2 + Cl2 ⇌ 2 BrCl K2 = 7.2

2 NOBr + Cl2 ⇌ 2 NO + 2 BrCl

K = K × K = 0.014 × 7.2 = 0.10
 The Equilibrium Constant Kc
The equilibrium constant and the equilibrium constant
expression are for the chemical equation as written.
[NH3]2
N2(g) + 3H2(g) 2NH3(g) Kc =
[N2][H2]3

[N2][H2]3 1
2NH3(g) N2(g) + 3H2(g) K´c = =
[NH3]2 Kc

[NH3]4
2N2(g) + 6H2(g) 4NH3(g) K´´c = = Kc 2

[N2]2[H2]6
 Heterogeneous Equilibria
CaCO3(s) CaO(s) + CO2(g)
Limestone Lime

[CaO][CO2] (1)[CO2]
Kc = = = [CO2]
[CaCO3] (1)

Pure solids and pure liquids are not included.

Kc = [CO2] Kp = P CO
2
 Calculating Equilibrium Constants
1) Tabulate all known initial and equilibrium
concentrations.
2) For anything for which initial and equilibrium
concentrations are known, calculate the change.
3) Use the balanced equation to find change for all other
reactants and products.
4) Use initial concentrations and changes to find
equilibrium concentration of all species.
5) Calculate the equilibrium constant using the
equilibrium concentrations.
 An Example
A closed system initially containing
1.000 × 10–3 M H2 and 2.000×10–3 M
I2 at 448 °C is allowed to reach equilibrium.
Analysis of the equilibrium mixture shows that
the concentration of HI is 1.87 × 10–3 M. Calculate
Kc at 448 °C for the reaction taking place, which is
H2(g) + I2(g) ⇌ 2 HI(g)
 H2(g) + I2(g) ⇌ 2 HI(g)

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

Initially

Change

At equilibrium

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 Reaction Quotient
aA + bB cC + dD

[C]tc[D]td
Reaction quotient: Qc =
[A]ta[B]tb

The reaction quotient, Qc, is defined in the same way as the

equilibrium constant, Kc, except that the concentrations in Qc are
not necessarily equilibrium values.
Altering an Equilibrium Mixture:
Concentration
N2(g) + 3H2(g) 2NH3(g)
 Altering an Equilibrium Mixture:
Concentration
N2(g) + 3H2(g) 2NH3(g) at 700 K,
Using the Equilibrium Constant
• If Qc < Kc net reaction goes from left to right
(reactants to products).

• If Qc > Kc net reaction goes from right to left

(products to reactants).

• If Qc = Kc no net reaction occurs.

 Using the Equilibrium Constant
At 700 K, 0.500 mol of HI is added to a 2.00 L container and
allowed to come to equilibrium. Calculate the equilibrium
concentrations of H2, I2, and HI . Kc is 57.0 at 700 K.

H2(g) + I2(g) 2HI(g)

 Le Châtelier’s Principle
Le Châtelier’s Principle: If a stress is applied to a reaction
mixture at equilibrium, net reaction occurs in the direction
that relieves the stress.
• The concentration of reactants or products can be
changed.

• The pressure and volume can be changed.

• The temperature can be changed.

 Altering an Equilibrium Mixture:
Concentration
In general, when an equilibrium is disturbed by the addition or
removal of any reactant or product, Le Châtelier’s principle
predicts that

• the concentration stress of an added reactant or product is

relieved by net reaction in the direction that consumes the
added substance.

• the concentration stress of a removed reactant or product is

relieved by net reaction in the direction that replenishes the
removed substance.
Altering an Equilibrium Mixture: Pressure
and Volume
N2(g) + 3H2(g) 2NH3(g)
 Altering an Equilibrium Mixture: Pressure
and Volume
In general, when an equilibrium is disturbed by a change in
volume which results in a corresponding change in pressure, Le
Châtelier’s principle predicts that

• an increase in pressure by reducing the volume will bring

about net reaction in the direction that decreases the
number of moles of gas.

• a decrease in pressure by enlarging the volume will bring

about net reaction in the direction that increases the
number of moles of gas.
Altering an Equilibrium Mixture: Pressure
and Volume
N2(g) + 3H2(g) 2NH3(g) at 700 K, Kc = 0.291

An equilibrium mixture of 0.50 M N2, 3.00 M H2, and

1.98 M NH3 is disturbed by reducing the volume by a
factor of 2.

[NH3]2 (3.96)2
Qc = = = 0.0726 < Kc
[N2][H2]3 (1.00)(6.00)3

Since Qc < Kc, more reactants will be consumed and the

net reaction will be from left to right.
 Altering an Equilibrium Mixture:
Temperature
N2(g) + 3H2(g) 2NH3(g) DH° = -2043 kJ

As the temperature increases, the equilibrium shifts from

products to reactants.
 Altering an Equilibrium Mixture:
Temperature
In general, when an equilibrium is disturbed by a change in
temperature, Le Châtelier’s principle predicts that
• the equilibrium constant for an exothermic reaction
(negative DH°) decreases as the temperature increases.

• the equilibrium constant for an endothermic reaction

(positive DH°) increases as the temperature increases.
The Effect of a Catalyst on Equilibrium
 Solubility Equilibria
A saturated solution of calcium fluoride in contact with
solid CaF2 contains constant equilibrium concentrations
of Ca2+(aq) and F1-(aq) because at equilibrium the ions
crystallize at the same rate as the solid dissolves.

CaF2(s) Ca2+(aq) + 2F1-(aq)

Ksp = [Ca2+][F1-]2
Solubility Equilibria

MmXx(s) mMn+(aq) + xXy-(aq)

Ksp = [Mn+]m [Xy-]x

Measuring Ksp and Calculating Solubility from Ksp

If the concentrations of Ca2+(aq) and F1-(aq) in a

saturated solution of calcium fluoride are known, Ksp
may be calculated.

CaF2(s) Ca2+(aq) + 2F1-(aq)

[Ca2+] = 3.3 x 10-4 M

Measuring Ksp and Calculating Solubility from Ksp
Measuring Ksp and Calculating Solubility from Ksp

Solubility and the Common-Ion Effect

Calculate the molar solubility of MgF2 in water at 25 °C.

Ksp = 7.4 x 10 -11
 Factors That Affect Solubility
Solubility and the Common-Ion Effect

Calculate the molar solubility of MgF2 in 0.10 M NaF at 25 °C.

MgF2(s) Mg2+(aq) + 2F1-(aq)

 Factors That Affect Solubility
Solubility and the Common-Ion Effect

MgF2(s) Mg2+(aq) + 2F1-(aq)

Molar solubility: 2.6 x 10-4 M

Molar solubility in 0.10 M NaF: 7.4 x 10-9 M

Why does the solubility decrease in the presence

of a common ion?

Le Châtelier’s Principle
 Factors That Affect Solubility
Solubility and the pH of the Solution

CaCO3(s) + H3O1+(aq) Ca2+(aq) + HCO31-(aq) + H2O(l)

Precipitation of Ionic Compounds
CaF2(s) Ca2+(aq) + 2F1-(aq)

Ksp = [Ca2+][F1-]2

Qc = [Ca2+]t [F1-]t2

Qc is called the ion-product (IP).

 Precipitation of Ionic Compounds
Compare the IP to Ksp

• If IP > Ksp: The solution is supersaturated and precipitation will

occur.

• If IP = Ksp: The solution is saturated and equilibrium exists

already.

• If IP < Ksp: The solution is unsaturated and precipitation will not

occur.