Chemistry 140 Fall 2002

Petrucci • Harwood • Herring • Madura

GENERAL
Ninth
Edition

CHEMISTRY
Principles and Modern Applications

Principles of Chemical Equilibrium

Dynamic Equilibrium

 Equilibrium – two opposing

processes taking place at
equal rates.

H2O(l) H2O(g)
H2O
NaCl(s) NaCl(aq)

CO(g) + 2 H2(g) CH3OH(g)

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Chemistry 140 Fall 2002

Dynamic Equilibrium

131I
AgI(s)  Ag+(aq) + I-(aq)

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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Chemistry 140 Fall 2002

Three Approaches to the Equilibrium

Three Approaches to Equilibrium

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Chemistry 140 Fall 2002

Three Approaches to Equilibrium

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

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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Chemistry 140 Fall 2002

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 ….
= 
[A]m[B]n …. (A)a(B)b ….
1
under ideal conditions

Relationships Involving the Equilibrium

Constant
 When we reverse an equation, we invert the value
of K (K’=1/K).
 When we multiply the coefficients in a balanced
equation by a common factor (2, 3, …), we raise
the equilibrium constant to the corresponding
power (2, 3, …).
 When we divide the coefficients in a balanced
equation by a common factor (2, 3, …), we take
the corresponding root of the equilibrium
constant (square root, cube root, …).

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Chemistry 140 Fall 2002

Tabela 9.3

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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Chemistry 140 Fall 2002

Combining Equilibrium Constant

Expressions

K1

K2

K3

Gases: The Equilibrium Constant

 Mixtures of gases are solutions just as liquids are.
 Use KP, based upon activities of gases.

[SO3]2
2 SO2(g) + O2(g) 2 SO3(g) Kc =
[SO2]2[O2]

(PSO3 )2
Kp =
(PSO2)2(PO2)

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Chemistry 140 Fall 2002

Gases: The Equilibrium Constant

 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

K P = K C (RT )
PX = [X] RT n gás

Gases: The Equilibrium Constant

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Chemistry 140 Fall 2002

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][C] PH2O

The Significance of the Magnitude of the

Equilibrium Constant.

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Chemistry 140 Fall 2002

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

Reaction Quotient

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Chemistry 140 Fall 2002

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?

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

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

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Chemistry 140 Fall 2002

Effect of the Change of Volume

k1
2 SO2(g) + O2(g) 2 SO3(g)
k-1

ntot = 1.16 mol gas 1.085 mol gas

KP = 415 338

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.

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

Hfo (SO3, g) = -395,7 kJ

Hfo (SO2, g) = -296,8 kJ

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Chemistry 140 Fall 2002

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.

Cálculos de Equilíbrio

Consulte os livros recomendados para este

conteúdo e/ou anotações de aula

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Chemistry 140 Fall 2002

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Chemistry 140 Fall 2002

For the reaction

C(s) + 1/2N2(g) + 5/2H2(g) ⇌ CH3NH2(g)

with K = 1.8×10−6. If you begin the reaction with 1.0 mol

of N2, 2.0 mol of H2, and sufficient C(s) in a 2.00 L
container, what are the concentrations of N2 and CH3NH2 at
equilibrium? What happens to K if the concentration of H2 is
doubled?

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