Chemical Equilibrium

Chapter 14
1
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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)

NO2
Chemical equilibrium
N2O4 (g) 2NO2 (g)
2
 N2O4 (g) 2NO2 (g)

equilibrium equilibrium

equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

3
constant

4
 The Equilibrium Constant

Consider the reaction N2O4(g) 2NO2(g)

At equilibrium ratefwd = raterev

2
so k[N2O4]eq = k[NO2] eq
kfwd [NO2] 2eq
then =
krev [N2O4]eq

The ratio of constants gives a new constant, the equilibrium

constant:
2
kfwd
K= = [NO2] eq
krev [N2O4]eq
 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

6
 K and the extent of reaction
K reflects a particular ratio of product concentrations to
reactant concentrations for a reaction.

K therefore indicates the extent of a reaction, i.e., how

far a reaction proceeds towards the products at a
given temperature.
A small value for K indicates that the reaction yields little
product before reaching equilibrium. The reaction favors
the reactants.

A large value for K indicates that the reaction reaches

equilibrium with very little reactant remaining. The
reaction favors the products.
 [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

8
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.

N2O4 (g) 2NO2 (g)

2
PNO
[NO2]2
Kc = Kp =
2

[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)
9
 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.

10
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

11
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
PNO = 0.400 atm and PNO = 0.270 atm?
2

2
PNO PO2
Kp = 2
PNO2

2
PNO2
PO2 = Kp
2
PNO

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

12
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

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

[CaO][CO2]
Kc = [CaCO3] = constant
[CaCO3] [CaO] = constant

[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.

13
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

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

14
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

15
 [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.

16
Sample Problem 2.1 Writing the Reaction Quotient and Finding
K for an Overall Reaction
PROBLEM: Nitrogen dioxide is a toxic pollutant that contributes to
photochemical smog. One way it forms is through the
following sequence:

(a) Show that the overall Qc for this reaction sequence is the same as
the product of the Qc's of the individual reactions.
(b) Given that both reactions occur at the same temperature, find Kc
for the overall reaction.

PLAN: We first write the overall reaction by adding the individual

reactions and then write the overall Qc. Then we write the Qc
for each step. We add the steps and multiply their Qc's,
canceling common terms. We can then calculate the overall Kc.
Sample Problem 2.2

SOLUTION:
(a)

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

Qc(overall) = Qc1 = Qc2 =
[N2][O2]2 [N2][O2] [NO]2[O2]

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

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

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

Sample Problem 2.3 Finding the Equilibrium Constant for an
Equation Multiplied by a Common Factor

PROBLEM: For the ammonia formation reaction, the reference

equation is

Kc is 2.4x10-3 at 1000 K. What are the values of Kc for

the following balanced equations:
(a) (b)

PLAN: We compare each equation with the reference equation to

see how the direction and/or coefficients have changed.
SOLUTION:
(a) The reference equation is multiplied by , so Kc(ref) will be to the
power.
Kc = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13
Sample Problem 17.3

(b) This equation is one-half the reverse of the reference equation, so Kc

is the reciprocal of Kc(ref) raised to the power.

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

21
 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.
22
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

23
 The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
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

24
Table 17.2 Ways of Expressing Q and Calculating K
 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.

26
At 1280oC 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
27
 (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
28
Example:

1. For the nitrogen fixation reaction 3H2(g) + N2(g) 2NH3(g), Kc =

6.0 10-2 at 500 C. If 0.250 M H2 and 0.050 M NH3 are
present at equilibrium, what is the equilibrium concentration
of N2? (Soln = 2.7 M)

2. 1.25 moles of NOCl were placed in a 2.50 L reaction chamber

at 427 C. After equilibrium was reached, 1.10 moles of NOCl
remained. Calculate the equilibrium constant, Kc, for the
reaction (Soln: 5.6 10-4)

2NOCl(g) 2NO(g) + Cl2(g)

29
3. Compounds A, B, and C react according to the following
equation.

3A(g) + 2B(g) 2C(g)

At 100 C a mixture of these gases at equilibrium showed

that [A] = 0.855 M, [B] = 1.23 M, and [C] = 1.75 M. What is
the value of Kc for this reaction? (Soln = 3.24)

30
 Le Chteliers 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

31
 Le Chteliers Principle

Changes in Concentration continued

Remove Add Add Remove

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
32
 Le Chteliers 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

33
 Le Chteliers Principle
Changes in Temperature
Change Exothermic Rx Endothermic Rx
Increase temperature K decreases K increases
Decrease temperature K increases K decreases

N2O4 (g) 2NO2 (g)

colder hotter 34
 Le Chteliers Principle
Adding a Catalyst
does not change K
does not shift the position of an equilibrium system
system will reach equilibrium sooner

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift 35
equilibrium.
Example

1. Carbon monoxide and chlorine combine in an

equilibrium reaction to produce the highly toxic product,
phosgene (COCl2).

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

If the equilibrium constant for this reaction is Kc = 248,

predict, if possible, what will happen when the reactants and
product are combined with the concentrations shown. [CO]
= [Cl2] = 0.010 M; [COCl2] = 0.070 M (soln: proceed to the
left)

36
 Chemistry In Action
Life at High Altitudes and Hemoglobin Production

Hb (aq) + O2 (aq) HbO2 (aq)

[HbO2]
Kc =
[Hb][O2]

37
Chemistry In Action: The Haber Process

N2 (g) + 3H2 (g) 2NH3 (g) DH0 = -92.6 kJ/mol

38
 Le Chteliers Principle - Summary

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

*Dependent on relative moles of gaseous reactants and products

39