Chemistry 140 Fall 2002

General Chemistry
Principles and Modern Applications
Petrucci Harwood Herring
9th Edition

Chapter 15: Principles of Chemical Equilibrium

Yrd. Do. Dr. Burak ESAT
Fatih University

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Contents
15-1
15-2
15-3
15-4
15-5

Dynamic Equilibrium
The Equilibrium Constant Expression
Relationships Involving Equilibrium Constants
The Significance of the Magnitude of an
Equilibrium Constant
The Reaction Quotient, Q: Predicting the
Direction of a Net Change

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Chemistry 140 Fall 2002

Contents
15-6
15-7

Altering Equilibrium Conditions:

Le Chtelliers Principle
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)
NaCl(s)

H2O(g)
H2O

I2(H2O)
CO(g) + 2 H2(g)

NaCl(aq)
I2(CCl4)
CH3OH(g)
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Chemistry 140 Fall 2002

15-2 The Equilibrium Constant Expression

k1

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

k-1

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

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

You may refer to Chapter 14

for discussion of rates of reaction

At Equilibrium:
Rfwrd = Rrvrs

CO(g) + 2 H2(g)

k1
k-1

CH3OH(g)

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

[CH3OH]
[CO][H2]2

= Kc
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Three Approaches to Equilibrium

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Chemistry 140 Fall 2002

Three Approaches to the Equilibrium

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Three Approaches to Equilibrium

CO(g) + 2 H2(g)

k1
k-1

CH3OH(g)

[CH3OH]

[CH3OH]

[CH3OH]

[CO][H2]

[CO](2[H2])

[CO][H2]2

Kc(1) =

1.19 M-1

0.596 M-1

14.2 M-2

Kc(2) =

2.17 M-1

1.09 M-1

14.2 M-2

Kc(3) =

2.55 M-1

1.28 M-1

14.2 M-2

Kc =

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Chemistry 140 Fall 2002

General Expressions
a A + b B . g G + h H .
Equilibrium constant = Kc=
Thermodynamic
Equilibrium constant = Keq=

aB =

[B]
= B[B]
cB0

[G]g[H]h .
[A]a[B]b .

(aG)g(aH)h .
(aA)a(aB)b .

cB0 is a standard reference state

= 1 mol L-1 (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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Chemistry 140 Fall 2002

Combining Equilibrium Constant

Expressions
N2O(g) + O2

2 NO(g) Kc= ?

N2(g) + O2
N2(g) + O2

Kc=

Kc(2)= 2.7x10+18 =

N2O(g)

Kc(3)= 4.7x10-31 =

2 NO(g)

[N2O]
[N2][O2]
[NO]2
[N2][O2]

[NO]2
[NO]2 [N2][O2]
1
=
= Kc(3)
= 1.7x10-13

[N2][O2] [N2O]
[N2O][O2]
Kc(2)
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Gases: The Equilibrium Constant, KP

Mixtures of gases are solutions
just as liquids are.
Use KP, based upon partial
pressures of gases.
2 SO2(g) + O2(g)

[SO3]=

nSO3
V

2 SO3(g)

PSO3

[SO3]2
[SO2]2[O2]

[SO2]=

RT
[O2] =

Kc =

nO2
V

nSO2
V

PSO2
RT

PO2
RT
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Chemistry 140 Fall 2002

The Equilibrium Constant, KP

2 SO2(g) + O2(g)
PSO3
Kc =

2 SO3(g)
2
2

[SO3]
PSO3
RT
=
=
RT
2
2
2
[SO2] [O2]
PSO2 PO2
PSO2 PO2
RT

RT
KP = Kc(RT)-1

Kc = KP(RT)

KP = Kc(RT)n
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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)

Kc =

CO(g) + H2(g)

PCOPH2
[CO][H2]
(RT)-1
=
[H2O]
PH2O

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Chemistry 140 Fall 2002

Burnt Lime
CaCO3(s)
Kc = [CO2]

CaO(s) + CO2(g)
KP = Kc (RT)

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15-4 The Significance of the Magnitude of

the Equilibrium Constant.

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Chemistry 140 Fall 2002

15-5 The Reaction Quotient, Q: Predicting

the Direction of Net Change.
CO(g) + 2 H2(g)

k1
k-1

CH3OH(g)

Equilibrium can be approached various ways.

Qualitative determination of change of initial
conditions as equilibrium is approached is
needed.
mA + nB
Qc =

[G]tg[H]th
[A]tm[B]tn

gG + hH
At equilibrium Qc = Kc
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Reaction Quotient

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Chemistry 140 Fall 2002

15-6 Altering Equilibrium Conditions:

Le Chtelliers 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.

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Le Chtelliers Principle
2 SO2(g) + O2(g)

k1
k-1

2 SO3(g)

Kc = 2.8x102 at 1000K

Q=

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

Q > Kc
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Chemistry 140 Fall 2002

Effect of Condition Changes

Adding or removing a gaseous reactant or product changes
Pgas.(Produces an effect similar to a change in concentration
as explained previously).
Adding an inert gas changes the total pressure.
Relative partial pressures are unchanged. (No change on
equilibrium condition)

Changing the volume of the system causes a change in the

equilibrium position.
2

nSO3
Kc =

[SO3]2
[SO2]2[O2]

nSO2

nSO3

nO2

nSO2 nO2

V
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Effect of change in volume

Kc =

[G]g[H]h
[C]c[D]d

gG + hH

nG nH
nAa

nBb

nG nH
nAa

cC + dD

nBb

V(a+b)-(g+h)

Sum of number of
moles of reactants

n= (g+h)-(a+b)
V -n

Sum of number of
moles of products

Remember that P.V=Constant

When the volume of an equilibrium mixture of gases is
reduced(pressure is increased), a net change occurs in the
direction that produces fewer moles of gas.
When the volume is increased (pressure is decreased), a
net change occurs in the direction that produces more
moles of gas.
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Chemistry 140 Fall 2002

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 catalyist 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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Chemistry 140 Fall 2002

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.

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Predicting the Effect of a Change in Concentration

on the Position of the Equilibrium
Problem: Carbon will react with water to yield carbon monoxide and
and hydrogen, in a reaction called the water gas reaction that was used
to convert coal into a fuel that can be used by industry.
C(s) + H2O (g)
CO(g) + H2 (g)
What happens to:
(a) [CO] if C is added?
(c) [H2O] if H2 is added?
(b) [CO] if H2O is added?
(d) [H2O] if CO is removed?
Plan: We either write the reaction quotient to see how equilibrium will
be effected, or look at the equation, and predict the change in direction
of the reaction, and the effect of the material desired.
Solution: (a) No change, as carbon is a solid, and not involved in the
equilibrium, as long as some carbon is present to allow the reaction.
(b) The reaction moves to the product side, and [CO] increases.
(c) The reaction moves to the reactant side, and [H2O] increases.
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(d) The reaction moves to the product side, and [H2O] decreases.

Chemistry 140 Fall 2002

Predicting the Effect of Temperature and Pressure

Problem: How would you change the volume (pressure) or temperature
in the following reactions to increase the chemical yield of the products?
(a) 2 SO2 (g) + O2 (g)
2 SO3 (g); H0 = 197 kJ
(b) CO(g) + 2 H2 (g)
CH3OH(g); H0 = -90.7 kJ
(c) C(s) + CO2 (g)
2 CO(g); H0 = 172.5 kJ
(d) N2(g) + 3 H2(g)
2 NH3(g); H0 = -91.8 kJ
Plan: For the impact of volume (pressure), we examine the reaction for
the side with the most gaseous molecules formed. For temperature, we
see if the reaction is exothermic, or endothermic. An increase in volume
(pressure) will force a reaction toward fewer gas molecules.
Solution: To get a higher yield of the products you should:
(a) Decrease the pressure, and increase the temperature.
(b) Increase the pressure, and decrease the temperature.
(c) A pressure change will not change the yield, an increase in the
temperature will increase the product yield.
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(d) Increase the pressure, and decrease the temperature.

Focus on the Nitrogen Cycle and the

Synthesis of Nitrogen Compounds.
N2(g) + O2(g)

k1
k-1

NO(g)

KP = 4.7x10-31 at 298K and

1.3 x 10-4 at 1800K

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Chemistry 140 Fall 2002

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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Chapter 15 Questions
Develop problem solving skills and base your strategy not
on solutions to specific problems but on understanding.

Choose a variety of problems from the text as examples.

Practice good techniques and get coaching from people who

have been here before.

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