Chapter 15: Principles of Chemical Equilibrium

Philip Dutton
University of Windsor, Canada
Prentice-Hall © 2007

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 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 Châtelier’s Principle
15-7 Equilibrium Calculations: Some Illustrative Examples

➢ Focus On The Nitrogen Cycle and the

Synthesis of Nitrogen Compounds
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 15-1 Dynamic Equilibrium

 Equilibrium – two opposing

processes taking place at
equal rates.

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

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 Dynamic Equilibrium

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 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

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 Three Approaches to the Equilibrium

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 Three Approaches to Equilibrium

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

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 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
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 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.

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 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

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 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.

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 Combining Equilibrium Constant
Expressions

N2O(g) + ½O2 2 NO(g) Kc= ?

[N2O]
N2(g) + ½O2 N2O(g) Kc(2)= 2.710+18 =
[N2][O2]½
[NO]2
N2(g) + O2 2 NO(g) Kc(3)= 4.710-31 =
[N2][O2]

[NO]2 [NO]2 [N2][O2]½ 1

Kc= ½
= = Kc(3) = 1.710-13
[N2O][O2] [N2][O2] [N2O] Kc(2)

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 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)

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 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◦

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 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

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 An Alternative Derivation

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

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

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

In general terms: KP = Kc(RT)Δn

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 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

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

Kc = [CO2] KP = PCO2(RT)

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

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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

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 Reaction Quotient

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 15-6 Altering Equilibrium Conditions:
Le Châtelier’s 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?

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 Le Châtelier’s Principle
k1
2 SO2(g) + O2(g) 2 SO3(g) Kc = 2.8102 at 1000K
k-1

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

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 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
[SO2]2[O2] nSO2 nO2
2 2
nSO2 nO2
V V

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 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-Δn
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.
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 Effect of the Change of Volume

ntot = 1.16 mol gas 1.085 mol gas

KP = 415 338

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 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.

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 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.

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 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.

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 Focus on the Nitrogen Cycle and the
Synthesis of Nitrogen Compounds.
k1
N2(g) + O2(g) NO(g) KP = 4.7 10-31 at 298K and
k-1
1.3 x 10-4 at 1800K

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 Synthesis of Ammonia

The optimum conditions are

only for the equilibrium
position and do not take into
account the rate at which
equilibrium is attained.

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 End of Chapter Questions
 Problems can be solved by eliminating errors
from your approach.
• There may be nothing wrong with your strategy,
but for some reason the problem is not solving.
 Be willing to make errors.
 Be able to recognize them.

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