Chemical Equilibrium

Chapter 14

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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)

14.1
 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

14.1
constant

14.1
 N2O4 (g) 2NO2 (g)

[NO2]2
K= = 4.63 x 10-3
[N2O4]

aA + bB cC + dD

[C]c[D]d
K= Law of Mass Action
[A]a[B]b

14.1
 [C]c[D]d
K= aA + bB cC + dD
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants

14.1
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.

N2O4 (g) 2NO2 (g)

2
PNO
[NO2]2 2
Kc = Kp =
[N2O4] PN2O4
In most cases
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)Dn

Dn = moles of gaseous products – moles of gaseous reactants

= (c + d) – (a + b)
14.2
 Homogeneous Equilibrium

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-][H3O+]
Kc‘ = [H2O] = constant
[CH3COOH][H2O]

[CH3COO-][H3O+]
Kc = = Kc‘ [H2O]
[CH3COOH]

General practice not to include units for the

equilibrium constant.

14.2
 The equilibrium concentrations for the reaction between
carbon monoxide and molecular chlorine to form COCl2 (g)
at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] =
0.14 M. Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COCl2] 0.14
Kc = = = 220
[CO][Cl2] 0.012 x 0.054

Kp = Kc(RT)Dn

Dn = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

14.2
The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2 if
the PNO2 = 0.400 atm and PNO = 0.270 atm?

2
PNO PO2
Kp = 2
PNO2

2
PNO2
PO2 = Kp
2
PNO

PO2 = 158 x (0.400)2/(0.270)2 = 347 atm

14.2
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constant

Kc‘ = [CaO] = constant
[CaCO3]

[CaCO3]
Kc = [CO2] = Kc‘ x Kp = PCO2
[CaO]

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.

14.2
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

14.2
Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm. Calculate
Kp and Kc for the reaction?

Kp = PNH PH S = 0.265 x 0.265 = 0.0702

3 2

Kp = Kc(RT)Dn

Kc = Kp(RT)-Dn

Dn = 2 – 0 = 2 T = 295 K

Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4

14.2
 [C][D] [E][F]
A+B C+D Kc‘ Kc‘ = Kc‘‘ =
[A][B] [C][D]
C+D E+F Kc‘‘
[E][F]
A+B E+F Kc Kc =
[A][B]

Kc = Kc‘ x Kc‘‘

If a reaction can be expressed as the sum of

two or more reactions, the equilibrium
constant for the overall reaction is given by
the product of the equilibrium constants of
the individual reactions.

14.2
N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
K= = 4.63 x 10-3 K‘ = = = 216
[N2O4] [NO2] 2 K

When the equation for a reversible reaction

is written in the opposite direction, the
equilibrium constant becomes the reciprocal
of the original equilibrium constant.

14.2
 Writing Equilibrium Constant Expressions
1. The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in atm.
2. The concentrations of pure solids, pure liquids and solvents
do not appear in the equilibrium constant expressions.
3. The equilibrium constant is a dimensionless quantity.
4. In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
5. If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall reaction is
given by the product of the equilibrium constants of the
individual reactions.

14.2
Chemical Kinetics and Chemical Equilibrium

kf ratef = kf [A][B]2
A + 2B AB2
kr rater = kr [AB2]

Equilibrium
ratef = rater

kf [A][B]2 = kr [AB2]

kf [AB2]
= Kc =
kr [A][B]2

14.3
 Q - The Reaction Quotient

At any time, t, the system can be sampled to determine the amounts of

reactants and products present. A ratio of products to reactants,
calculated in the same manner as K tells us whether the system has come
to equilibrium (Q = K) or whether the reaction has to proceed further from
reactants to products (Q < K) or in the reverse direction from products to
reactants (Q > K).

The reaction quotient (Qc) is calculated by substituting the

initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
For a general reaction aA + bB cC + dD where a, b, c, and d
are the numerical coefficients in the balanced equation, Q (and K) can be
calculated as
[C]c[D]d
Q=
[A]a[B]b
IF
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium

14.4
Sample Problem Writing the Reaction Quotient and Finding K for an
Overall Reaction
PROBLEM: Understanding reactions involving N2 and O2, the most abundant
gases in air, is essential for solving problems dealing with
atmospheric pollution. Here is a reaction sequence between N2 and
O2 to form nitrogen dioxide, a toxic pollutant that contributes to
photochemical smog.
(1) N2(g) + O2(g) 2NO(g) Kc1 = 4.3x10-25
(2) 2NO(g) + O2(g) 2NO2(g) Kc2 = 6.4x109

(a) Show that the Qc for the overall reaction sequence is the same as the
product of the Qcs of the individual reactions.
(b) Calculate the Kc for the overall reaction.

PLAN: Write the sum of the overall reactions; write the Qc. Write the Qcs for
the individual reactions and then multiply the expressions.
We are given the Kcs for the individual reactions, so we multiply those
values.
SOLUTION: Qc1 = [NO]2
(1) N2(g) + O2(g) 2NO(g)
(a)
[N2][O2]
(2) 2NO(g) + O2(g) 2NO2(g)
Qc2 = [NO2]2
N2(g) + 2O2(g) 2NO2(g)
[NO]2[O2]
[NO2]2
Qc =
[N2][O2]2

[NO]2 [NO2]2 [NO2]2

Qc1 x Qc2 = =
[N2][O2] [NO]2[O2] [N2] [O2] 2

(b) Kc = Kc1 x Kc2 = (4.3x10-25) x (6.4x109) = 2.8x10-15

Sample Problem Finding the Equilibrium Constant for an Equation
Multiplied by a Common Factor

PROBLEM: For the ammonia formation reaction N2(g) + 3H2(g) 2NH3(g)

the equilibrium constant, Kc, is 2.4x10-3 at 1000 K. If we change the
coefficients of the equation, which we’ll call the reference (ref) equation, what
are the values of Kc for the following balanced equations?
(a) 1/3N2(g) + H2(g) 2/3NH3(g) (b) NH3(g) 1/2N2(g) + 3/2H2(g)

PLAN: Compare each equation to the reference. Keep in mind that

changing the coefficients will be reflected in a power change in Kc
and a reversal of the equation will show up as an inversion of Kc.
SOLUTION:

(a) The reference equation is multiplied by 1/3, so Kc(ref) will be to the 1/3 power.
Kc = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13

(b) The reference equation is reversed and halved, so Kc(ref) is to the -1/2 power.

Kc = [Kc(ref)]-1/2 = (2.4x10-3)-1/2 = 20.

Sample Problem Comparing Q and K to Determine Reaction Direction

PROBLEM: For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 100oC. At

a point during the reaction, [N2O4] = 0.12 M and [NO2] = 0.55 M.
Is the reaction at equilibrium? If not, in which direction is it
progressing?

PLAN: Write an expression for Qc, substitute with the values given, and
compare the Qc with the given Kc.

SOLUTION: [NO2]2 (0.55)2

Qc = = = 2.5
[N2O4] (0.12)

Qc is > Kc, therefore the reaction is not at equilibrium and will

proceed from right to left, from products to reactants, until Qc = Kc.
 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.

14.4
 At 12800C the equilibrium constant (Kc) for the reaction
Br2 (g) 2Br (g)
Is 1.1 x 10-3. If the initial concentrations are [Br2] = 0.063
M and [Br] = 0.012 M, calculate the concentrations of these
species at equilibrium.

Let x be the change in concentration of Br2

Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

[Br]2 (0.012 + 2x)2

Kc = Kc = = 1.1 x 10-3 Solve for x
[Br2] 0.063 - x
14.4
 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
2 -b ± b2 – 4ac
ax + bx + c =0 x=
2a
x = -0.0105 x = -0.00178
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M

At equilibrium, [Br2] = 0.062 – x = 0.0648 M
14.4
Sample Problem Calculating Kc from Concentration Data

PROBLEM: In order to study hydrogen halide decomposition, a researcher fills

an evacuated 2.00-L flask with 0.200 mol of HI gas and allows the
reaction to proceed at 453oC.
2HI(g) H2(g) + I2(g)

At equilibrium, [HI] = 0.078 M. Calculate Kc?

PLAN: First find the molar concentration of the starting material and then find
the amount of each component, reactants and products, at equilibrium.
SOLUTION: [HI] = 0.200 mol
= 0.100 M
2.00 L

Let x be the amount of [H2] at equilibrium. Then x will also be the

concentration of [I2] and the change in of [HI] will be the original
concentration minus the stoichiometric amount that reacted, 2x, or
0.078 M.
concentration (M) 2HI(g) H2(g) + I2(g)

initial 0.100 0 0
change -2x +x +x
equilibrium 0.100 - 2x x x

[HI] = 0.078 = 0.100 - 2x ; x = 0.011 M

[H2] [I2] [0.011][0.011]

Qc = = = 0.020 = Kc
[HI]2 (0.078)2
Sample Problem Determining Equilibrium Concentrations from Kc

PROBLEM: In a study concerning the conversion of methane to other fuels, a

chemical engineer mixes gaseous CH4 and H2O in a 0.32-L flask at
1200 K. At equilibrium the flask contains 0.26 mol of CO, 0.091 mol
of H2, and 0.041 mol of CH4. What is the [H2O] at equilibrium?
Kc = 0.26 for the equation
CH4(g) + H2O(g) CO(g) + 3H2(g)
PLAN: Use the balanced equation to write the reaction quotient and then
substitute values for each component.
[CO][H2]3
SOLUTION: CH4(g) + H2O(g) CO(g) + 3H2(g) Qc =
[CH4][H2O]
0.041 mol
[CH4]eq = = 0.13 M [CO][H2]3
0.32 L [H2O] =
[CH4] Kc
0.26 mol
[CO]eq = = 0.81 M (0.81)(0.28)3
0.32 L
= = 0.53 M
0.091 mol (0.13)(0.26)
[H2]eq = = 0.28 M
0.32 L
Sample Problem Determining Equilibrium Concentrations from Initial
Concentrations and Kc

PROBLEM: Fuel engineers use the extent of the change from CO and H2O to
CO2 and H2 to regulate the proportions of synthetic fuel mixtures. If
0.250 mol of CO and 0.250 mol of H2O are placed in a 125-mL flask
at 900 K, what is the composition of the equilibrium mixture? At this
temperature, Kc is 1.56 for the equation
CO(g) + H2O(g) CO2(g) + H2(g)

PLAN: We have to find the concentrations of all species at equilibrium and

then substitute into a Kc expression.
SOLUTION: All concentrations must be recalculated as M, so [CO] = 0.250/0.125 L

concentration CO(g) + H2O(g) CO2(g) + H2(g)

initial 2.00 2.00 0 0

change -x -x +x +x
equilibrium 2.00 - x 2.00 - x x x
 [CO2][H2] (x) (x) (x)2
Qc = Kc = = =
[CO][H2O] (2.00 - x) (2.00 - x) (2.00 - x)2

x
1.56 = = +/-1.25
2.00-x

x = 1.11 M [CO] = [H2O] = 0.89 M

[CO2] = [H2] = 1.11 M

2.00 - x = 0.89 M
 Sample Problem Calculating Equilibrium Concentrations with a
Simplifying Assumption

PROBLEM: Phosgene is a potent chemical warfare agent that is now outlawed

by international agreement. It decomposes by the reaction
COCl2(g) CO(g) + Cl2(g) Kc = 8.3x10-4 (at 360oC)
Calculate [CO], [Cl2], and [COCl2] when the following amounts of phosgene
decompose and reach equilibrium in a 10.0-L flask.
(a) 5.00 mol COCl2 (b) 0.100 mol COCl2

PLAN: After finding the concentration of starting material, write the expressions
for the equilibrium concentrations. When solving for the remaining
amount of reactant, see if you can make an assumption about the initial
and final concentrations which could simplify the calculating by ignoring
the solution to a quadratic equation.

SOLUTION: (a) 5.00 mol/10.0 L = 0.500 M (b) 0.100 mol/10.0 L = 0.0100 M

Let x = [CO]eq = [Cl2]eq and 0.500 - x and 0.0100 - x = [COCl2]eq,
respectively, for (a) and (b).
 (x)(x)
[CO][Cl2] (a) Kc = 8.3x10-4 =
Kc = (0.500 - x)
[COCl2]
assume x is << 0.500 so that we can drop x in the denominator
(x)(x) 4.15x10-4 = x2 x ≈ 2 x 10-2
8.3x10-4 =
(0.500) (0.500 - x) = 4.8x10-2
CHECK: 0.020/0.500 = 0.04 or 4% percent error

(x)(x)
(b) Kc = 8.3x10-4 =
(0.010 - x)
Dropping the -x will give a value for x = 2.9x10-3 M. (0.010 - x) ≈ 0.0071 M

CHECK: 0.0029/0.010 = 0.29 or 29% percent error

Using the quadratic formula produces x = 2.5x10-3 and
0.0100 - x = 7.5x10-3 M
 Sample Problem Predicting Reaction Direction and Calculating
Equilibrium Concentrations

PROBLEM: The research and development unit of a chemical company is studying

the reaction of CH4 and H2S, two components of natural gas.
CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of H2S, and 2.00 mol
of H2 are mixed in a 250-mL vessel at 960oC. At this temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to reach equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the equilibrium concentrations of the
other substances?
PLAN: Find the initial molar concentrations of all components and use these to
calculate a Qc. Compare Qc to Kc, determine in which direction the
reaction will progress, and draw up expressions for equilibrium
concentrations.
SOLUTION: [CH4]initial = 1.00 mol/0.25 L = 4.0 M [CS2]initial = 1.00 mol/0.25 L = 4.0 M

[H2S]initial = 2.00 mol/0.25 L = 8.0 M [H2]initial = 2.00 mol/0.25 L = 8.0 M

 [CS2][H2]4 [4.0][8.0]4 A Qc of 64 is >> than Kc = 0.036
Qc = = = 64
[CH4][H2 S]2 [4.0][8.0]2 The reaction will progress to the
left.

Concentration (M) CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

initial 4.0 8.0 4.0 8.0

change +x +2x -x -4x

equilibrium 4.0 + x 8.0 + 2x 4.0 - x 8.0 - 4x

At equilibrium [CH4] = 5.56 M, so 5.56 = 4.0 + x and x = 1.56 M

Therefore - [H2S] = 8.0 + 2x = 11.12 M

[CS2] = 4.0 - x = 2.44 M
[H2] = 8.0 - 4x = 1.76 M
 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the
system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.

• Changes in Concentration

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

Equilibrium
Add
shifts left to
NH3
offset stress

14.5
 Le Châtelier’s Principle

• Changes in Concentration

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left

14.5
Sample Problem Predicting the Effect of a Change in Concentration
on the Equilibrium Position

PROBLEM: To improve air quality and obtain a useful product, chemists often
remove sulfur from coal and natural gas by treating the fuel
contaminant hydrogen sulfide with O2:
2H2S(g) + O2(g) 2S(s) + 2H2O(g)

What happens to
(a) [H2O] if O2 is added? (b) [H2S] if O2 is added?

(c) [O2] if H2S is removed? (d) [H2S] if sulfur is added?

PLAN: Write an expression for Q and compare it to K when the system is

disturbed to see in which direction the reaction will progress.

SOLUTION: Q = [H2O]2
[H2S]2[O2]
(a) When O2 is added, Q decreases and the reaction progresses
to the right to come back to K. So [H2O] increases.
 Q= [H2O]2
[H2S]2[O2]

(b) When O2 is added, Q decreases and the reaction progresses

to the right to come back to K. So [H2S] decreases.

(c) When H2S is removed, Q increases and the reaction

progresses to the left to come back to K. So [O2] increases.

(d) Sulfur is not part of the Q (K) expression because it is a solid.

Therefore, as long as some sulfur is present the reaction is
unaffected. [H2S] is unchanged.
 Le Châtelier’s Principle

• Changes in Volume and Pressure

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas

14.5
Sample Problem Predicting the Effect of a Change in Volume
(Pressure) on the Equilibrium Position

PROBLEM: How would you change the volume of each of the following
reactions to increase the yield of the products.
(a) CaCO3(s) CaO(s) + CO2(g)

(b) S(s) + 3F2(g) SF6(g)

(c) Cl2(g) + I2(g) 2ICl(g)

PLAN: When gases are present a change in volume will affect the
concentration of the gas. If the volume decreases (pressure
increases), the reaction will shift to fewer moles of gas and vice versa.

SOLUTION: (a) CO2 is the only gas present. To increase its yield, we
should increase the volume (decrease the pressure).
(b) There are more moles of gaseous reactants than products, so we should
decrease the volume (increase the pressure) to shift the reaction to the right.
(c) There are an equal number of moles of gases on both sides of the
reaction, therefore a change in volume will have no effect.
 Le Châtelier’s Principle
• Changes in Temperature
In an exothermic reaction, heat is a product.
In an endothermic reaction, heat is a reactant.

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases

colder hotter 14.5

Sample Problem Predicting the Effect of a Change in Temperature
on the Equilibrium Position
PROBLEM: How does an increase in temperature affect the concentration of
the underlined substance and K for the following reactions?
(a) CaO(s) + H2O(l) Ca(OH)2(aq) DHo = -82 kJ

(b) CaCO3(s) CaO(s) + CO2(g) DHo = 178 kJ

(c) SO2(g) S(s) + O2(g) DHo = 297 kJ

PLAN: Express the heat of reaction as a reactant or a product. Then consider
the increase in temperature and its effect on K.

SOLUTION: (a) CaO(s) + H2O(l) Ca(OH)2(aq) heat

An increase in temperature will shift the reaction to the left, decrease
[Ca(OH)2], and decrease K.
(b) CaCO3(s) + heat CaO(s) + CO2(g)
The reaction will shift right resulting in an increase in [CO2] and increase in K.
(c) SO2(g) + heat S(s) + O2(g)
The reaction will shift right resulting in an decrease in [SO2] and increase in K.
 Le Châtelier’s Principle
• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner

uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.

14.5
 Le Châtelier’s Principle

Change Equilibrium
Change Shift Equilibrium Constant
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no

14.5