Chapter 15: Principles of Chemical Equilibrium

General Chemistry: Chapter 15

 Contents
15-1 Dynamic Equilibrium
15-2 The Equilibrium Constant Expression
15-3 Relationships Involving Equilibrium Constants
15-4 The Magnitude of an Equilibrium Constant
15-5 The Reaction Quotient, Q: Predicting the Direction of a
Net Change
15-6 Altering Equilibrium Conditions:
Le Chteliers Principle
15-7 Equilibrium Calculations: Some Illustrative Examples

General Chemistry: Chapter 15

 15-1 Dynamic Equilibrium

Equilibrium two opposing

processes taking place at
equal rates.

H2O(l) H2O(g)
H2O
NaCl(s) NaCl(aq)
I2(H2O) I2(CCl4)
CO(g) + 2 H2(g) CH3OH(g)

General Chemistry: Chapter 15

Dynamic Equilibrium

General Chemistry: Chapter 15

 15-2 The Equilibrium Constant Expression

Methanol synthesis is a reversible reaction.

k1
CO(g) + 2 H2(g) CH3OH(g)
k-1
CH3OH(g) CO(g) + 2 H2(g)

k1
CO(g) + 2 H2(g) CH3OH(g)
k-1

General Chemistry: Chapter 15

Three Approaches to the Equilibrium

General Chemistry: Chapter 15

Three Approaches to Equilibrium

General Chemistry: Chapter 15

Three Approaches to Equilibrium
k1
CO(g) + 2 H2(g) CH3OH(g)
k-1

General Chemistry: Chapter 15

 The Equilibrium Constant Expression

k1
Forward: CO(g) + 2 H2(g) CH3OH(g) Rfwrd = k1[CO][H2]2
k-1
Reverse: CH3OH(g) CO(g) + 2 H2(g) Rrvrs = k-1[CH3OH]

At Equilibrium: k1
Rfwrd = Rrvrs CO(g) + 2 H2(g) CH3OH(g)
k-1

k1[CO][H2]2 = k-1[CH3OH]

k1 [CH3OH]
= = Kc
k-1 [CO][H2 ]2
General Chemistry: Chapter 15
 The Equilibrium Constant and Activities
Activity
Thermodynamic concept introduced by Lewis.
Dimensionless ratio referred to a chosen reference state.

[B]
aB = 0 = B[B] cB0 is a standard reference state
cB
= 1 mol L-1 (ideal conditions)

Accounts for non-ideal behaviour in solutions and gases.

An effective concentration.

General Chemistry: Chapter 15

 General Expressions
a A + b B . g G + h H .

[G]g[H]h .
Equilibrium constant = Kc=
[A]m[B]n .

Thermodynamic
Equilibrium constant = Keq= (aG)g(aH)h .
(aA)a(aB)b .

[G]g[H]h . (G)g(H)h .
=
m
[A] [B]n . (A)a(B)b .
1
under ideal conditions

General Chemistry: Chapter 15

 15-3 Relationships Involving the
Equilibrium Constant

Reversing an equation causes inversion of K.

Multiplying by coefficients by a common factor
raises the equilibrium constant to the
corresponding power.
Dividing the coefficients by a common factor
causes the equilibrium constant to be taken to
that root.

General Chemistry: Chapter 15

 Combining Equilibrium Constant
Expressions

N2O(g) + O2 2 NO(g) Kc= ?

[N2O]
N2(g) + O2 N2O(g) Kc(2)= 2.710+18 =
[N2][O2]
[NO]2
N2(g) + O2 2 NO(g) Kc(3)= 4.710-31 =
[N2][O2]

[NO]2 [NO]2 [N2][O2] 1

Kc= = = Kc(3) = 1.710-13
[N2O][O2 ] [N2][O2] [N2O] Kc(2)

General Chemistry: Chapter 15

 Gases: The Equilibrium Constant, KP
Mixtures of gases are solutions just as liquids are.
Use KP, based upon activities of gases.

(aSO3)2
2 SO2(g) + O2(g) 2 SO3(g) KP =
(aSO2)2(aO2)

PSO3 PSO2 PO2

aSO3 = aSO2 = aSO3 =
P P P
(PSO3 )2
KP = P
(PSO2)2(PO2 )

General Chemistry: Chapter 15

 Gases: The Equilibrium Constant, KC

In concentration we can do another substitution

2 SO2(g) + O2(g) 2 SO3(g)

nSO3 PSO3 PSO2 PO2

[SO3]= = [SO2]= [O2] =
V RT RT RT

PX
[X] RT PX = [X] RT
(aX ) = = c
c

General Chemistry: Chapter 15

 Gases: The Equilibrium Constant, KC
2 SO2(g) + O2(g) 2 SO3(g)

(aSO3)2 (PSO3 )2
KP = = P PX = [X] RT
(aSO2)2(aO2) (PSO2)2(PO2 )

([SO3] RT)2
= P
([SO2] RT)2([O2] RT)

([SO3])2
= P
KC
= Where P = 1 bar
RT ([SO2])2([O2]) RT

General Chemistry: Chapter 15

 An Alternative Derivation

2 SO2(g) + O2(g) 2 SO3(g)

2 Where P = 1 bar
PSO3
2
[SO3] RT PSO3
Kc = = = RT
[SO2]2[O2] PSO2 PO2
2 2
PSO2 PO2
RT RT

Kc = KP(RT) KP = Kc(RT)-1

In general terms: KP = Kc(RT)n

General Chemistry: Chapter 15
 Pure Liquids and Solids

Equilibrium constant expressions do not contain

concentration terms for solid or liquid phases of a
single component (that is, pure solids or liquids).

C(s) + H2O(g) CO(g) + H2(g)

[CO][H2] PCOPH2
Kc = = (RT)1
[H2O]2 PH2O2

General Chemistry: Chapter 15

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

Kc = [CO2] KP = PCO2(RT)

General Chemistry: Chapter 15

15-4 The Significance of the Magnitude of
the Equilibrium Constant.

General Chemistry: Chapter 15

15-5 The Reaction Quotient, Q: Predicting
the Direction of Net Change.
k1
CO(g) + 2 H2(g) CH3OH(g)
k-1

Equilibrium can be approached various ways.

Qualitative determination of change of initial
conditions as equilibrium is approached is needed.

[G]tg[H]th
Qc = At equilibrium Qc = Kc
[A]tm[B]tn

General Chemistry: Chapter 15

Reaction Quotient

General Chemistry: Chapter 15

15-6 Altering Equilibrium Conditions:
Le Chteliers Principle
When an equilibrium system is subjected to a
change in temperature, pressure, or concentration
of a reacting species, the system responds by
attaining a new equilibrium that partially offsets
the impact of the change.

What happens if we add SO3 to this equilibrium?

General Chemistry: Chapter 15
 Le Chteliers Principle
k1
2 SO2(g) + O2(g) 2 SO3(g) Kc = 2.8102 at 1000K
k-1

[SO3]2
Q= 2
= Kc Q > Kc
[SO2] [O2]

General Chemistry: Chapter 15

 Effect of Condition Changes
Adding a gaseous reactant or product changes Pgas.
Adding an inert gas changes the total pressure.
Relative partial pressures are unchanged.
Changing the volume of the system causes a change
in the equilibrium position.
2
nSO3
2
[SO3] V nSO3
Kc = = = V
2
[SO2] [O2] 2 2
nSO2 nO2 nSO2 nO2
V V

General Chemistry: Chapter 15

 Effect of Change in Volume
g h
[G]g[H]h nG nH
Kc = = V(a+b)-(g+h)
[C]c[D]d nAa nBa
g h
nG nH
= V-n
nAa nBa

When the volume of an equilibrium mixture of

gases is reduced, a net change occurs in the
direction that produces fewer moles of gas. When
the volume is increased, a net change occurs in the
direction that produces more moles of gas.
General Chemistry: Chapter 15
 Effect of the Change of Volume

ntot = 1.16 mol gas 1.085 mol gas

KP = 415 338

General Chemistry: Chapter 15

 Effect of Temperature on Equilibrium

Raising the temperature of an equilibrium

mixture shifts the equilibrium condition in the
direction of the endothermic reaction.

Lowering the temperature causes a shift in the

direction of the exothermic reaction.

General Chemistry: Chapter 15

 Effect of a Catalyst on Equilibrium

A catalyst changes the mechanism of a

reaction to one with a lower activation energy.
A catalyst has no effect on the condition of
equilibrium.
But does affect the rate at which equilibrium is
attained.

General Chemistry: Chapter 15

 15-7 Equilibrium Calculations:
Some Illustrative Examples.
Five numerical examples are given in the text
that illustrate ideas that have been presented in
this chapter.
Refer to the comments which describe the
methodology. These will help in subsequent
chapters.
Exercise your understanding by working
through the examples with a pencil and paper.

General Chemistry: Chapter 15

 Question

0.75 mol of N2 and 1.20 mol of H2 are placed in a 3.0 liter container.
When the reaction N2(g) + 3H2(g) 2 NH3(g) reaches equilibrium,
[H2] = 0.100 M. Which of the following is true?

A) [NH3] = 0.150 M

B) [NH3] = 0.200

C) [N2] = 0.650 M

D) [N2] = 0.250

E) none of these

Slide 42 of 33 General Chemistry: Chapter 15 Prentice-Hall 2007

 Question
Consider the following reaction occurring at 960 K:
CO2(g) + H2(g) CO(g) + H2O(g)
At equilibrium, the concentrations of reactants and products are: [CO2] = 0.0400 M, [H2]
= 0.0220 M, [CO] = 0.0240 M, and [H2O] = 0.0190 M. This equilibrium is perturbed by
adding CO2(g) to the system such that when a new equilibrium is reached, the
concentration of CO2 is 0.050 M. What is the concentration of H2(g) at this equilibrium?

A) 0.050 M

B) 0.482 M

C) 0.462 M

D) 0.300 M

E) 0.0204 M

Slide 43 of 33 General Chemistry: Chapter 15 Prentice-Hall 2007