Chemical Equilibrium

U N IVERSIT Y OF IN D ON ESIA
Chemical Equilibrium
Chemical
Equilibrium
The Equilibrium State

The Equilibrium Constant, Kc
The Equilibrium Sonstant, KP
Heterogenous Equilibria
Using the Equilibrium Constant
Factors that Alter the Composition of an
Equilibrium Mixture
The Equilibrium
State
Reversible reaction - reaction in which the

product molecules can recombine to form
reactant molecules.
Reactants - substances on the left side of the
equation.
Products - substances on the right side of the
equation.
Use a double arrow to indicate a reaction that is at
equilibrium.
a. reactants products
The Equilibrium
State
With time, the concentration of reactant

decreases and the concentration of product
increases until both concentrations level off at
constant, equilibrium values.
Rates of the forward and reverse reactions are equal.
State of chemical equilibrium.
Equilibrium mixture - a mixture of reactants and
products in the equilibrium state.
Dynamic state - forward and reverse reactions
continue at equal rates.
no net conversion of reactants to products
The Equilibrium
State
The Equilibrium
State
The Equilibrium
State
The Equilibrium
Constant, Kc
Equilibrium mixture obeys an

equation (or law of mass action).
equilibrium
For the reaction: a A + b B c C + d D.

C ] [D]
[
Kc =
[A]a [B]b
c
Kc = equilibrium constant
units depend on the particular equilibrium expression
units usually omitted when quoting values of equilibrium
constants
equilibrium constant expression - expression on right

side of equilibrium equation
The Equilibrium
Constant, Kc
Equilibrium mixture obeys an equilibrium

equation (or law of mass action).
For the reverse reaction.
equilibrium expression = reciprocal of the original
expression
1
'
K
=
equilibrium constant
c
K
c
The Equilibrium
Constant, Kc
EXAMPLE:
For the reaction
CO (g) + 2 H2 (g) CH3OH (g),
the equilibrium concentrations are:
[CO]e = 2.58 M;
[H2]e = 0.280 M;
[CH3OH]e = 2.93 M
at a temperature of 210o C.
Calculate the equilibrium constant, Kc, for this

reaction.
The Equilibrium
Constant, Kc
CO (g) + 2 H2 (g) CH3OH (g),

[CO]e = 2.58 M;
[H2]e = 0.280 M;
[CH3OH]e = 2.93 M
Kc =
Kc =
[CH3 OH]
[CO][H 2 ]2
(2.93)
2 = 14.5
(2.58)(0.280)
The Equilibrium
Constant, Kp
For gas-phase reactions use partial pressures

rather than molar concentrations in equilibrium
equations.
Kp - equilibrium constant is defined using partial
pressures.
Relationship between Kc and Kp.

K p = K c (RT ) n
n = the sum of the coefficients of the gaseous

products minus the sum of the coefficients of the
gaseous reactants
The Equilibrium
Constant, Kp
EXAMPLE:
Calculate Kp for the reaction in the previous
example.
The Equilibrium
Constant, Kp
CO (g) + 2 H2 (g) CH3OH (g),

[CO]e = 2.58 M;
[H2]e = 0.280 M;
[CH3OH]e = 2.93 M
n = 1 (1+2) = -2
Kc =
(2.93)
2 = 14.5
(2.58)(0.280)
K p = K c (RT ) n
L atm
(483K )
K p = (14.5) 0.0821
mol K
= 9.22 10
The Equilibrium
Constant, Kp
Heterogenous
Equilibria
Homogeneous equilibria - reactants and products

are in a single phase.
Heterogeneous equilibria - reactants and
products are present in more than one phase.
Solids - molar concentrations are constants
can be calculated from the densities and molar masses.
independent of its amount
Concentrations of pure solids or pure liquids are not

included when writing the equilibrium equation for
any heterogeneous equilibrium.
Using the Equilibrium

Constant
Judging the extent of reaction.

Large value of Kc ( > 103)
products predominate over reactants
reaction proceeds almost to completion
position of reaction is to the right

Constant
Judging the extent of reaction.

Small value of Kc ( < 10-3)
reactants predominate over products
reaction hardly proceeds
position of the reaction is to the left
10-3 < Kc < 103

appreciable amounts of both reactants and products
present.

Constant

Constant
Predicting the direction of reaction.

Reaction quotient, Qc, same as the equilibrium
constant
expression
except
that
the
concentrations are not necessarily equilibrium
values.
Predict direction of reaction by comparing the
value of Qc to Kc.
Qc < Kc; reaction goes form left to right
Qc > Kc; reaction goes from right to left
Qc = Kc; reaction is at equilibrium

Constant

Constant
EXAMPLE:
Kc = 4.18 10-9 at 425o C for the following reaction:
2 HBr (g) H2 (g) + Br2 (g)
What is the position of equilibrium? If the
concentrations of all species present are:
[HBr] = 0.75 M;
[H2] = [Br2] = 2.5 10-4 M
is the reaction mixture at equilibrium? In which

direction will the reaction proceed?

Constant
EXAMPLE:
Kc = 4.18 10-9 at 425o C
2 HBr (g) H2 (g) + Br2 (g)
[HBr] = 0.75 M;
[H2] = [Br2] = 2.5 10-4 M
)(
2.5 10
2.5 10
[H2 ][Br2 ]
Qc =
=
[HBr] 2
(0.75)2
) = 1.1 107
Since Qc > Kc, the reaction is not at equilibrium and

will proceed from right to left.

Constant
EXAMPLE:
The reaction
PCl5 (g) PCl3 (g) + Cl2 (g)
has Kc = 85.0 at a temperature of 760oC.
Calculate the equilibrium concentrations of
PCl5, PCl3, and Cl2 if the initial concentration of
PCl5 is 5.00 M.
Assume a volume of 1.00 L

Constant
PCl5 (g) PCl3 (g) + Cl2 (g)

Kc = 85.0 at a temperature of 760oC.
PCl3 ][Cl 2 ]
[
Kc =
[PCl5 ]
85.0 =
x=
85.0
(x )(x )
(5.00 x )
(7.23 10 3)+ (1.7 10 3)

2
x = -89.7 or 4.74.
The mathematical solution that makes
chemical sense is 4.74.

Constant
PCl3 ][Cl 2 ]
[
Kc =
[PCl5 ]
85.0 =
x=
85.0
(x )(x )
(5.00 x )
(7.23 10 3)+ (1.7 10 3)

2
x = 4.74.
[PCl]5 = 5 4.74 = 0.26

Constant
Factors that Alter the

Composition of an
Equilibrium Mixture
Factors that alter the composition of an

equilibrium mixture:
Concentration of reactants or products.
Pressure and volume.
Temperature.
B. Le Chtelier's Principle: If a stress is applied to

a reaction mixture at equilibrium, reaction occurs
in the direction that relieves the stress.
Predicts changes in the composition of an equilibrium
mixture if above changes occur.
Altering an Equilibrium
Mixture:
Changes in Concentration
Disturb an equilibrium by adding or removing

a reactant or product.
Stress of an added reactant or product is relieved
by reaction in the direction that consumes the
added substance.
add reactant - reaction shifts right (toward product)
add product - reaction shifts left (toward reactant)
Mixture:
Disturb an equilibrium by adding or removing

a reactant or product.
Stress of removing reactant or product is relieved
by reaction in the direction that replenishes the
removed substance.
remove reactant - reaction shifts left
remove product - reaction shifts right
Mixture:
Changes occur due to change in value of Qc.

Add reactant - denominator in Qc expression
becomes larger.
Qc < Kc
to return to equilibrium, Qc must increase
numerator of Qc expression must increase and the
denominator must decrease
implies net conversion of reactants to products
reaction shifts right
Mixture:

Remove reactant - denominator in Qc expression
becomes smaller.
Qc > Kc
to return to equilibrium, Qc must decrease
numerator of Qc expression must decrease and the
denominator must increase
implies net conversion of products to reactants
reaction shifts left
Mixture:
Changes in Pand V
Number of moles of gaseous reactants in the

balanced equation is different from the number
of moles of gaseous products.
Change in pressure (due to changing volume) changes
composition of equilibrium mixture.
Increase in pressure (due to decrease in volume)

results in reaction in the direction of fewer
number of moles of gas.
Decrease in pressure (due to increase in volume)
results in reaction in the direction of greater
number of moles of gas.
Mixture:
Changes in Pand V

Decrease volume - molarity (= n/V) increases.
If reactant side has more moles of gas.
increase in denominator is greater than increase in
numerator
Qc < Kc
to return to equilibrium, Qc must increase
numerator of Qc expression must increase and the
denominator must decrease
implies net conversion of reactants to products (shifts towards
fewer moles of gas)
Mixture:
Changes in Pand V

If product side has more moles of gas.
increase in numerator is greater than increase in
denominator
Qc > Kc
denominator of Qc expression must decrease and the
numerator must increase
implies net conversion of products to reactants (shifts towards
fewer moles of gas)
Mixture:
Changes in Pand V

If product side has more moles of gas.
increase in numerator is greater than increase in
denominator
Qc > Kc
denominator of Qc expression must decrease and the
numerator must increase
implies net conversion of products to reactants (shifts towards
fewer moles of gas)
Mixture:
Changes in Pand V
Reaction involves no change in the number of moles of

gas.
No effect on composition of equilibrium mixture.
For heterogeneous equilibrium.

Effect of pressure changes on solids and liquids can be
ignored.
a. volume is nearly independent of pressure
Change in pressure due to addition of an inert gas.

No change in the molar concentrations of reactants or
products.
No effect on composition of equilibrium mixture.

Constant

Constant

Constant
Le Chatelier's principle

Constant

Constant
Nitrogen dioxide and dinitrogen tetroxide
Mixture:
Changes in T
Disturb an equilibrium by a
concentration, pressure, or volume.
change
in
Qc Kc.
Kc remains constant with constant T.
Change in temperature
equilibrium constant.
always
changes
Depends on sign of Ho for the reaction.

Exothermic reaction (-Ho) - equilibrium constant
decreases as the temperature increases.
Endothermic reaction (+Ho) - equilibrium constant
increases as the temperature increases.
Mixture:
Changes in T
Le Chtelier's principle - add heat to an

equilibrium mixture, net reaction occurs in the
direction that relieves the stress of the added
heat.
Endothermic reaction - heat is absorbed by
reaction in the forward direction. (H is written
on the reactant side of the reaction.)
equilibrium mixture contains more product than
reactant
Kc increases with increasing temperature
Mixture:
Changes in T
Le Chtelier's principle - add heat to an

equilibrium mixture, net reaction occurs in the
direction that relieves the stress of the added
heat.
Exothermic reaction - heat is absorbed by reaction
in the reverse direction. (H is written on the
product side of the reaction.)
equilibrium mixture contains more reactant than
product
Kc decreases with decreasing temperature
Mixture:
Changes in T
EXAMPLE:
How will the following changes alter the equilibrium
for the reaction:
3 Fe (s) + 4 H2O (g) Fe3O4 (s) + 4 H2 (g)

Ho = -150 kJ
a. H2O is removed from the system.
b. H2 is removed from the system.
c. The volume of the container is increased.
d. Fe3O4 is added to the system.
e. The temperature is raised.
Mixture:
Changes in T
SOLUTION:
a. When H2O is removed from the system, the
equilibrium shifts left.
b. When H2 is removed from the system, the
equilibrium shifts right.
c. Increasing the volume of the container
decreases the pressure in the container.
However, the number of moles of gas is equal on
both sides of the reaction. Therefore, a change in
volume and pressure does not affect the
equilibrium.
Mixture:
Changes in T
SOLUTION:
d. Adding a solid to the system does not
affect the equilibrium since solids are not
included in the equilibrium expression.
e.
Raising the temperature causes the
equilibrium to shift left.
Mixture:
Changes in T
Temperature dependence of equilibrium
Mixture:
Changes in T
The Effect of Catalyst

Catalyst increases the rate of a chemical reaction.
Provides a new, lower energy pathway.
Forward and reverse reactions pass through the same
transition state.
rate for forward and reverse reactions increases by the same
factor
Does not affect the composition of the equilibrium

mixture.
does not alter the equilibrium constant or equilibrium
concentrations
does not appear in the balanced chemical equation
Can influence choice of optimum conditions for a reaction.
The Effect of Catalyst
The Link Between

Chemical Equilibrium and
Chemical Kinetics
For the reaction: A + B C + D.

Rate of forward reaction = kf[A][B].
Rate of reverse reaction = kr[C][D].
kf
At equilibrium: kf[A][B] = kr[C][D] or . k
C ][
D]
[
]
[
=
= Kc
A
B
[ ]][[ ]
The Link Between

Chemical Kinetics
Relative values of kf and kr determine the

composition of the equilibrium mixture.
kf >> kr; Kc is very large; reaction goes to
completion.
irreversible reaction
reverse reaction is too slow to be detected
kf kr; Kc 1; reactants and products are present

at equilibrium.
reversible reaction
The Link Between

Chemical Kinetics
EXAMPLE:
Calculate the equilibrium constant Kc for the
reaction:
H2O (l) H+ (aq) + OH- (aq)
given that kf = 2.4 10-5 s-1 and kr = 1.3 1011 M1s-1 and that K is for the expression
SOLUTION: To calculate Kc, we use the equation
k f [C ][D]
=
= Kc
k r [A ][B ]
2.4 10 5 s -1
16
Kc =
=
1.8
10
1.3 1011 M-1 s-1

Chemical Equilibrium

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Chemical Equilibrium

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U N IVERSIT Y OF IN D ON ESIA

The Equilibrium State

Reversible reaction - reaction in which the

With time, the concentration of reactant

Equilibrium mixture obeys an

For the reaction: a A + b B c C + d D.

equilibrium constant expression - expression on right

Equilibrium mixture obeys an equilibrium

Calculate the equilibrium constant, Kc, for this

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

For gas-phase reactions use partial pressures

Relationship between Kc and Kp.

n = the sum of the coefficients of the gaseous

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

Homogeneous equilibria - reactants and products

Concentrations of pure solids or pure liquids are not

Using the Equilibrium

Judging the extent of reaction.

Using the Equilibrium

Judging the extent of reaction.

10-3 < Kc < 103

Using the Equilibrium

Using the Equilibrium

Predicting the direction of reaction.

Using the Equilibrium

Using the Equilibrium

is the reaction mixture at equilibrium? In which

Using the Equilibrium

Since Qc > Kc, the reaction is not at equilibrium and

Using the Equilibrium

Using the Equilibrium

PCl5 (g) PCl3 (g) + Cl2 (g)

(7.23 10 3)+ (1.7 10 3)

Using the Equilibrium

(7.23 10 3)+ (1.7 10 3)

Using the Equilibrium

Factors that Alter the

Factors that alter the composition of an

B. Le Chtelier's Principle: If a stress is applied to

Disturb an equilibrium by adding or removing

Disturb an equilibrium by adding or removing

Changes occur due to change in value of Qc.

Changes occur due to change in value of Qc.

Number of moles of gaseous reactants in the

Increase in pressure (due to decrease in volume)

Changes occur due to change in value of Qc.

Changes occur due to change in value of Qc.

Changes occur due to change in value of Qc.

Reaction involves no change in the number of moles of

For heterogeneous equilibrium.

Change in pressure due to addition of an inert gas.

Using the Equilibrium

Using the Equilibrium

Using the Equilibrium

Using the Equilibrium

Using the Equilibrium

Nitrogen dioxide and dinitrogen tetroxide

Depends on sign of Ho for the reaction.

Le Chtelier's principle - add heat to an

Le Chtelier's principle - add heat to an

3 Fe (s) + 4 H2O (g) Fe3O4 (s) + 4 H2 (g)

Temperature dependence of equilibrium

The Effect of Catalyst

Does not affect the composition of the equilibrium