1

Chemical Equilibrium a dynamic process

Chemical equilibrium is a state of a system
when reaction rates in both directions are
equal.
Changes continue at the molecular level,
but the macroscopic properties stay the
same.
Equilibrium is a dynamic rather than static
process.
3

 There is a spontaneous tendency towards equilibrium.

The driving force towards equilibrium diminishes as
equilibrium is approached.
Heat is energy flowing from a high temperature object to
a low temperature object. Equilibrium is reached when
the temperatures are the same.
Molecules still exchange kinetic energies during collision.

Water flows from a high potential-energy place to a low

potential-energy place. When potential energies are the
same, water stops flowing.
Water-molecule diffusion continues.
4

 Chemical equilibrium is achieved when:

1. The rates of the forward and reverse
reactions
are equal (Forward rate = reverse rate of reaction) and
1. The concentrations of the reactants and products
remain constant.
Examples:

Vapor pressure: rate of vaporization = rate of condensation

Saturated solution: rate of dissociation = rate of crystallization

Expressing concentrations:
Gases: partial pressures, PX
Solutes in liquids: molarity, [X]

Reversible reactions
[A]0 or PA0 / RT

PX or [X]

[A] or PA / RT
[B] or PB / RT

Equilibrium is established

Time
6

Reversible Reactions and Rate

Reaction Rate

Forward rate

Equilibrium is established:
Forward rate = Backward rate

Backward rate
Time
When equilibrium is achieved:
[A] [B] and
kf/kr = Keq
7

 The equilibrium position is the same at a

given temperature, no matter from which
direction it is approached.
It is possible to force an equilibrium one
way or the other temporarily by altering
the reaction conditions, but once this
stress is removed, the system will return
to its original equilibrium. (Le Chteliers
Principle)
8

The equilibrium constant (K): Law of

Mass Action
Law of Mass Action- For a reversible reaction
at equilibrium and constant temperature, a
certain ratio of reactant and product
concentrations has a constant value (K).
The Equilibrium Constant (K)- A number equal
to the ratio of the equilibrium concentrations
of products to the equilibrium concentrations
of reactants each raised to the power of its
stoichiometric coefficient.

 Derived from rate laws by Guldberg and

Waage (1864)
For a balanced chemical reaction
in equilibrium:

aA+bBcC+dD
Equilibrium constant expression (Keq):
c

[C] [D]
Kc =
a
b
[A] [B]

Cato Guldberg
(1836-1902)

or

Peter Waage
(1833-1900)

(PC ) (PD )
Kp =
a
b
(PA ) (PB )

10

Relating Kc and Kp
Convert [A] into PA:

n
P
M= =
V RT

PA = [ A]RT

(PC ) c (PD ) d ([C]RT) c ([D]RT) d [C]c [D]d (RT) c + d

Kp =
= a b
a
b =
a
b
(PA ) (PB ) ([A]RT) ([B]RT) [A] [B] (RT) a + b

K p = K c (RT)

(c + d) - (a + b)

= K c (RT)

where n =
= change in coefficents of products reactants (gases only!)
= (c+d) - (a+b)
11

Equilibrium constant - mass action law

When a chemical reaction in a closed system is at
equilibrium, the reaction quotient is defined as the
equilibrium constant, K, which depends on T. For a
chemical reaction in a closed system,
then

aA+bB cC+dD

[C]c [D]d
Q = = K
(at equilibrium)
[A]a [B]b
Units of K depends on units of [ ]s, M(a+b-c-d) if M is used.
If Q < K, the reaction goes forward
if Q = K, the system is at equilibrium
if Q > K, the reaction goes backward

| to increase [product]
|the law of mass action
| to decrease [product]
12

Reaction Quotient and Reaction

constant

Significance of Kc

Kc= kf/kr, at equilibrium,

if K> 1, then more products at equilibrium.
if k<1, then reactants favored at equilbrium.
K=1 (conc. of reactants and products nearly same at
equilibrium)

The magnitude of Kc gives us an indication of how

far the reaction has proceeded toward the
formation of products, when the equilibrium is
achieved.
The larger the value of K, the further the reaction will
have proceeded towards completion when
equilibrium is reached.
14

Evaluating K
The equilibrium mixture is found to contain 0.07,
0.11, 0.03 and 0.03 moles of CO, H2, CH4 and H2O
respectively for the reaction:
CO (g) + 3 H2 (g) CH4 (g) + H2O (g)
What is the equilibrium constant, K?
Solution
CO (g) + 3 H2 (g) CH4 (g) + H2O (g)
start 0.07
0.11
0.03 0.03
(0.03) (0.03)
K = = 9.7
(0.07) (0.11)3

15

Writing Equilibrium Constant Expressions

The concentrations of the reacting species in the
condensed phase are expressed in M. In the gaseous
phase, the concentrations can be expressed in M or in
atm.
The concentrations of pure solids, pure liquids and
solvents do not appear in the equilibrium constant
expressions.
In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
If a reaction can be expressed as a sum of two or more
reactions, the equilibrium constant for the overall
reaction is given by the product of the equilibrium
constants of the individual reactions.

What does the Equilibrium Constant

tell us?
We can:
Predict the direction in which a reaction mixture
will proceed to reach equilibrium
Calculate the concentration of reactants and
products once equilibrium has been reached

Types of Equilibria
1.Homogeneous: all components in same phase
(usually g or aq)
1 N (g) +3 H (g) 2NH (g)
2
2
3
c

(PC ) (PD )
KP =
a
b
(PA ) (PB )

KP =

(PNH3 )
1

Fritz Haber
(1868 1934)

(PN 2 ) (PH 2 )

18

2. Heterogeneous Equilibrium
Heterogeneous Equilibrium- results from a
reversible reaction involving reactants and
products that are in different phases.
Can include liquids, gases and solids as either
reactants or products.
Equilibrium expression is the same as that for
a homogeneous equilibrium.
Omit pure liquids and solids from the
equilibrium constant expressions.

Heterogeneous Equilibrium Constant

CaCO3 (s)
[CaCO3] = constant
[CaO] = constant

CaO (s) + CO2 (g)

Kp = PCO 2

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.

Multiple Equilibria
Multiple Equilibria- Product molecules of one equilibrium constant are
involved in a second equilibrium process.

A+B
C+D
A+B

C+D
E+F
E+F

Kc = Kc x Kc

Kc
Kc
Kc

[C][D]
Kc=
[A][B]
[E][F]
Kc=
[C][D]
[E][F]
Kc =
[A][B]

Le Chteliers Principle
If a system at equilibrium is disturbed by
a change in:
Concentration of one of the components,
Pressure, or
Temperature
Henri Le Chtelier
(1850 1936)

the system will shift its equilibrium

position to counteract the effect of the
disturbance.

22

1. Concentration
Upon addition of a reactant or product, equilibrium
shifts to re-establish equilibrium by consuming part
of the added substance.
Upon removal of reactant or product, equilibrium
shifts to re-establish equilibrium by producing more
of the removed substance.
Ex: Co(H2O)62+ (aq) + 4 Cl1- CoCl42- (aq) + 6 H2O (l)
Add HCl, temporarily increase forward rate
Add H2O, temporarily increase reverse rate
23

2. Volume, with a gas present (T is constant)

Upon a decrease in V (thereby increasing P),

equilibrium shifts to reduce the number of moles
of gas.
(The reaction shifts in the direction of fewer moles of gas.)

Upon an increase in V (thereby decreasing P),

equilibrium shifts to produce more moles of gas.
(The reaction shifts in the direction of more moles of gas.)
Ex: N2 (g) + 3 H2 (g) 2 NH3 (g)
If V of container is decreased, equilibrium shifts right.
XN2 and XH2 decreases
XNH3 increases

24

3. Catalysts
Lower the activation energy of both forward and
reverse rxns, therefore increases both forward and
reverse rxn rates.
Increase the rate at which equilibrium is achieved,
but does not change the ratio of components of the
equilibrium mixture (does not change the Keq)
Ea, uncatalyzed
Ea, catalyzed

Energy

Rxn coordinate

25

4. Temperature:

consider heat as a part of the reaction.

Upon an increase in T, endothermic reaction is favored (equilibrium shifts
to consume the extra heat)
Upon a decrease in T, equilibrium shifts to produce more heat.

Effect on Keq
1. Exothermic equilibria: Reactants Products + heat

Increase in T increases reverse reaction rate which decreases Keq.

2. Endothermic equilibria: Reactants + heat Products

Increase in T increases forward reaction rate increases Keq.

Example: Co(H2O)62+ (aq) + 4 Cl1- CoCl42- (aq) + 6 H2O (l); H=+?

Increase T temporarily increases forward rate
Decrease T temporarily increases reverse rate
26

Effect of Various Changes on Equilibrium

Disturbance

Net Direction of
Rxn

Effect of Value
of K

Towards formation of
product

None

Decrease(reactant)

Towards formation of
reactant

None

Increase (product)

Towards formation of
reactant

None

Decrease (product)

Towards formation of
product

None

Concentration
Increase (reactant)

27

Effect of Pressure on Equilb.

Pressure
Increase P
(decrease V)
Decrease P
(Increase V)
Increase P
( Add inert gas,
no change in V)

Towards formation
of fewer moles of
gas

None

Towards formation
of more moles of
gas
None,
concentrations
unchanged

None

None

28

Effect of Temperature on Equilb

Temperature
Increase T

Decrease T

Catalyst Added

Towards absorption of
heat

Increases if
endothermic
Decreases if
exothermic

Towards release of heat Increases if exothermic

Decreases if
endothermic
None, forward and
reverse equilibrium
attained sooner

None

29

Calculating Equilibrium Quantities

Steps to use ICE table:
1. I = Tabulate known initial and equilibrium
concentrations of all species in equilibrium
expression
2. C = Determine the concentration change for the
species where initial and equilibrium are known
Use stoichiometry to calculate concentration
changes for all other species involved in
equilibrium
3. E = Calculate the equilibrium concentrations

30

Examples
Example1: When 0.10 moles CO and 0.20 moles of H2 are
placed in a 1-L vessel at temperature T and allowed to
come to equilibrium. The mixture is found to contain
0.03 moles H2O for the reaction:
CO (g) + 3 H2 (g) CH4 (g) + H2O (g)
What is the equilibrium constant, K?
Solution (note the strategy please)
CO (g) + 3 H2 (g) CH4 (g) + H2O (g)
start 0.10
0.20
0
0
change - x
- 3x
+x
+x (x=0.03)
eqlbm 0.1-x 0.2-3x
0.03 0.03
[]
0.07 0.11
0.03 0.03
K = (0.03) (0.03) / (0.07) (0.11)3 = 9.7
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 Example: Enough ammonia is dissolved in

5.00 L of water at 25C to produce a solution
that is 0.0124 M ammonia. The solution is
then allowed to come to equilibrium. Analysis
of the equilibrium mixture shows that [OH1-] is
4.64 x 10-4 M. Calculate Keq at 25C for the
reaction:

NH3 (aq) + H2O (l) NH41+ (aq) + OH1- (aq)

32

NH3 (aq) + H2O (l) NH41+ (aq) + OH1- (aq)

NH3 (aq)
Initial

0.0124 M

Change

-x

Equilibrium

0.0119 M

H 2O
(l)

X
X
X

NH41+ (aq)

OH1- (aq)

0M

0M

+x
4.64 x 10-4 M

+x
4.64 x 10-4 M

x = 4.64 x 10-4 M
1+
4

[NH ][OH1- ] (4.64 10-4 ) 2

Kc =
=
= 1.81x 10-5
[NH 3 ]
0.0119
33

 Example 2: A 5.000-L flask is filled with 5.000

x 10-3 mol of H2 and 1.000 x 10-2 mol of I2 at
448C. The value of Keq is 1.33. What are the
concentrations of each substance at
equilibrium?

H2 (g) + I2 (g) 2 HI (g)

34

H2 (g) + I2 (g) 2 HI (g)

H2 (g)
Initial
Change
Equilibrium

1.000x10-3 M

I2 (g)

HI (g)

2.000x10-3 M

0M

-xM

+ 2x M

-xM

(1.000x10-3 x) M (2.000x10-3 x) M

2x M

2
[HI]2
(2x)
Kc =
=
= 1.33
-3
-3
[H 2 ][I 2 ] (1.000 10 - x)(2.000 10 - x)

4x2 = 1.33[x2 + (-3.000x10-3)x + 2.000x10-6]

0 = -2.67x2 3.99x10-3x + 2.66x10-6
Using quadratic eqn: x = 5.00x10-4 or 1.99x10-3; x = 5.00x10-4
Then [H2]=5.00x10-4 M; [I2]=1.50x10-3 M; [HI]=1.00x10-3 M

35

Acid-Ionization Equilibria
An acid reacts with water to produce hydronium ion
(hydrogen ion) and the conjugate base ion. The
process is called acid ionization or acid dissociation.
Consider an aqueous solution of the weak acid acetic
acid, HC2H3O2, the sour constituent of vinegar.
When the acid is added to water, it reacts according
to the equation
HC2H3O2(aq) H2O(l) BA H3O(aq) C2H3O2(aq)
Because acetic acid is a weak electrolyte, the acid
ionizes to a small extent in water. (about 1% or less,
depending on the concentration of acid).
36

37

 Acids and bases are classified as strong or

weak.
Strong - essentially complete (100%) ionization
of an acid or base in water (leveling effect)
Weak- less than complete ionization in water
(typically < 10%)

38

6 strong acids (ionize 100%)

HCl, HNO3, HBr, HI, HClO4, H2SO4

6 strong bases (dissociate 100%)

NaOH, KOH, LiOH, Ca(OH)2, Ba(OH)2, Sr(OH)2

HCl +
HCl

100%
H2O
+ +
O
H
3 H

+ Cl+ Cl-

<5%
HCN + H2O
HCN

H3O+ + CN+ CNH+

Bulk

small amount

39

 For a strong acid, which ionizes completely in

solution, the concentrations of ions are
determined by the stoichiometry of the reaction
from the initial concentration of acid.
However, for a weak acid such as acetic acid,
the concentrations of ions in solution are
determined from the acid-ionization constant
(also called the acid-dissociation constant),
which is the equilibrium constant for the
ionization of a weak acid.
To find the acid-ionization constant, write HA for
the general formula of a weak, monoprotic acid.

40

The acid-ionization equilibrium in aqueous solution is

41

Experimental Determination of Ka
The ionization constant for a weak acid is usually
determined experimentally by one of two methods.
1. The electrical conductivity or some colligative
property of a solution of the acid is measured to
obtain its degree of ionization. The degree of
ionization of a weak electrolyte is the fraction of
molecules that react with water to give ions. This
may also be expressed as a percentage, giving the
percent ionization.
2. The pH of a solution of the weak acid is
determined. From the pH one finds the
concentration of H3O ion and then the
concentrations of other ions.
42

 The following example shows how to calculate Ka from

the pH of a solution of nicotinic acid. It also shows
how to calculate the degree of ionization and the
percent ionization.

Example: Nicotinic acid (niacin) is a monoprotic acid

with the formula HC6H4NO2. A solution that is 0.012 M
in nicotinic acid has a pH of 3.39 at 25C. What is the
acid-ionization constant, Ka, for this acid at 25oC?
What is the degree of ionization of nicotinic acid in
this solution?

43

Solution
Step 1: Abbreviate the formula for nicotinic acid as
HNic. Then 1 L of solution contains 0.012 mol HNic and 0
mol Nic, the acid anion, before ionization. The H3O ion
concentration at the start is that from the selfionization of water. It is usually much smaller than that
obtained from the acid (unless the solution is extremely
dilute or Ka is quite small), so you can write [H3O] 0
(meaning approximately zero). If x mol HNic ionizes, x
mol each of H3O and Nic is formed, leaving (0.012 x)
mol HNic in solution. You can summarize the situation
as follows:

44

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Darrell_Ebbing,_Steven_D._Gammon
General_Chemistry,_Enhanced_9th_Edition__Brooks_Cole(2009) Page 657

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