CHEMICAL

EQUILIBRIUM
Basic Concepts
Reversible reactions do not go to completion.
They can occur in either direction
Symbolically, this is represented as:

dD cC bB + aA +

Basic Concepts
Chemical equilibrium exists when two
opposing reactions occur simultaneously at
the same rate.
A chemical equilibrium is a reversible reaction
that the forward reaction rate is equal to the
reverse reaction rate.
Chemical equilibria are dynamic equilibria.
Molecules are continually reacting, even though
the overall composition of the reaction mixture
does not change.
Basic Concepts
4
One example of a dynamic equilibrium can be
shown using radioactive
131
I as a tracer in a
saturated PbI
2
solution.
{ }
{ }
solution. into go will iodine e radioactiv the of Some
solution. filter the then minutes, few a for Stir 2
I 2 Pb PbI
solution. PbI saturated a in PbI solid Place 1
-
(aq)
2
(aq)
O H
2(s)
2
*
2
2
+

+
Basic Concepts
5
Graphically, this is a representation of the rates
for the forward and reverse reactions for this
general reaction.
aA
(g)
+ bB
(g)
cC
(g)
+ dD
(g)

Basic Concepts
6
One of the fundamental ideas of chemical
equilibrium is that equilibrium can be
established from either the forward or reverse
direction.
2SO
2(g)
+ O
2(g)
2SO
3(g)

7
The Equilibrium Constant
| || |
| || | rate. reverse the represents which D C k Rate
rate. forward the represents which B A k Rate
r r
f f
=
=
For a simple one-step mechanism reversible
reaction such as:
The rates of the forward and reverse
reactions can be represented as:
+

+
(g) (g) (g) (g)
D C B A
The Equilibrium Constant
10
When system is at equilibrium:
Rate
f
= Rate
r

| || | | || |
| || |
| || | B A
D C
k
k
to rearranges which
D C k B A k
: give to ip relationsh rate for the Substitute
r
f
r f
=
=
The Equilibrium Constant
11
Because the ratio of two constants is a
constant we can define a new constant as
follows :
| || |
| || |
k
k
K and
K
C D
A B
f
r
c
c
=
=
The Equilibrium Constant
Similarly, for the general reaction:
we can define a constant

12
| | | |
| | | |
reactions. all for valid is expression This
B A
D C
K
products
reactants
b a
d c
c

=
+

+ D d C c B b A a
(g) (g) (g) (g)
The Equilibrium Constant
13
K
c
- Equilibrium constant

K
c
- product of the equilibrium concentrations (in
M) of the products, each raised to a power equal to
its stoichiometric coefficient in the balanced
equation, divided by the product of the equilibrium
concentrations (in M) of the reactants, each raised
to a power equal to its stoichiometric coefficient in
the balanced equation.

K
c
values

are dimensionless because they
actually involve a thermodynamic quantity called
activity.
Activities are directly related to molarity

The Equilibrium Constant
14
Write equilibrium constant expressions for the
following reactions at 500
o
C. All reactants and
products are gases at 500
o
C.
| || |
| |
5
2 3
c
2 3 5
PCl
Cl PCl
K
Cl PCl PCl
=
+

The Equilibrium Constant

15

HI 2 I + H
2 2
| |
| || |
2 2
2
c
I H
HI
K =
| | | |
| | | |
5
2
4
3
6
2
4
c
2 2 3
O NH
O H NO
= K
O H 6 + NO 4 O 5 + NH 4

The Equilibrium Constant

Example: One liter of equilibrium mixture from
the following system at a high temperature was
found to contain 0.172 mole of phosphorus
trichloride, 0.086 mole of chlorine, and 0.028
mole of phosphorus pentachloride. Calculate K
c

for the reaction.
Equil [ ]s 0.028 M 0.172 M 0.086 M

16
+

2 3 5
Cl PCl PCl
The Equilibrium Constant
17

K
c
=
PCl
3
| |
Cl
2
| |
PCl
5
| |
K
c
=
0.172 ( ) 0.086 ( )
0.028 ( )
K
c
= 0.53
| |
| || |
( )
( )( )
K
PCl
PCl Cl
K
K
or K
K
c
'
5
3 2
c
c
' c
'
c
= = =
= = = =
0 028
0172 0 086
19
1 1 1
053
19
.
. .
.
.
.
+

2 3 5
Cl PCl PCl
The Equilibrium Constant
18
Example: The decomposition of PCl
5
was
studied at another temperature. One mole of
PCl
5
was introduced into an evacuated 1.00
liter container. The system was allowed to
reach equilibrium at the new temperature. At
equilibrium 0.60 mole of PCl
3
was present in
the container. Calculate the equilibrium
constant at this temperature.
( ) ( ) ( )
0 0 1.00 Initial
Cl PCl PCl
g 2 g 3 g 5
M
+

The Equilibrium Constant

( ) ( ) ( )
( )( )
( )
T another at 90 . 0
40 . 0
60 . 0 60 . 0
K
0.60 0.60 0.40 m Equilibriu
0.60 + 0.60 + 0.60 - Change
0 0 1.00 Initial
Cl PCl PCl
'
c
g 2 g 3 g 5
= =
+

M M M
M M M
M
The Equilibrium Constant
Example : At a given temperature 0.80 mole of
N
2
and 0.90 mole of H
2
were placed in an
evacuated 1.00-liter container. At equilibrium
0.20 mole of NH
3
was present. Calculate K
c

for the reaction.

N
2(g)
+ 3 H
2(g)

2 NH
3(g)

Initial 0.80 M 0.90 M 0

Change - 0.10 M - 0.30 M +0.20 M
Equilibrium 0.70 M 0.60 M 0.20 M
K
c
=
NH
3
| |
2
N
2
| |
H
2
| |
3
=
0.20 ( )
2
0.70 ( ) 0.60 ( )
3
= 0.26
Variation of K
c
with the
Form of the Balanced Equation
Large equilibrium constants indicate that most of
the reactants are converted to products.
Small equilibrium constants indicate that only
small amounts of products are formed.
2 main calculations:

Equilibrium Concentrations K
c

K
c
equilibrium concentrations

ICE table
Predicting the direction of
reactions: The REACTION
COEFFICIENT, Q
c

Tank of water in Equilibrium
The Reaction Quotient

For this general reaction:
aA+bB

cC+dD
Q =
C
| |
c
D
| |
d
A
| |
a
B
| |
b
The mass action expression or reaction
quotient has the symbol Q.
Q has the same form as Kc
The major difference between Q and Kc is
that the concentrations used in Q are not
necessarily equilibrium values.
The Reaction Quotient
Why do we need another equilibrium
constant that does not use equilibrium
concentrations?
Q will help us predict how the equilibrium will
respond to an applied stress - compare Q
with K
c
.
When

Q = K
c
: the system is in equilibrium

Q > K
c
: the system goes to the left (), towards reactants

Q < K
c
: the system goes to the right (), towards products

The Reaction Quotient
The equilibrium constant for the following reaction is
49 at 450
o
C. If 0.22 mole of I
2
, 0.22 mole of H
2
, and
0.66 mole of HI were put into an evacuated 1.00-liter
container, would the system be at equilibrium? If not,
what must occur to establish equilibrium?

Calculate Q
c
, compare with K
c



Use ICE table to calculate equilibrium [ ]s

H
2
+ I
2
2HI
Equilibrium calculations and
reaction quotient
The equilibrium constant K
c
, is 3.00 for the
following reaction at a given temperature. If
1.00 mole of SO
2
and 1.00 mole of NO
2
are put
into an evacuated 2.00 L container and allowed
to reach equilibrium, what will be the
concentration of each compound at equilibrium?
+

+
(g) 3(g) 2(g) 2(g)
NO SO NO SO
The equilibrium constant is 49 for the following reaction at
450
o
C. If 1.00 mole of HI is put into an evacuated 1.00-liter
container and allowed to reach equilibrium, what will be the
equilibrium concentration of each substance?
H
2
+ I
2
2HI
An equilibrium mixture from the following reaction was found
to contain 0.20 mol/L of A, 0.30 mol/L of B, and 0.30 mol/L of
C.



(a) What is the value of K
c
for

this reaction?

(b) If the volume of the reaction vessel were suddenly doubled
while the temperature remained constant, what would be the new
equilibrium concentrations?
( ) ( ) ( )
+

g g g
C B A
A 2.00 liter vessel in which the following system is in
equilibrium contains 1.20 moles of COCl
2
, 0.60 moles
of CO and 0.20 mole of Cl
2
.



a) Calculate the equilibrium constant.

b) An additional 0.80 mole of Cl
2
is added to the vessel
at the same temperature. Calculate the molar
concentrations of CO, Cl
2
, and COCl
2
when the new
equilibrium is established
( ) ( ) ( )

+
g 2 g 2 g
COCl Cl CO
Comparing Q and K
c

K
Q
K
Q
K Q
Equilibrium
Formation of
reactants
Formation of
products
Q = K
c
Q > K
c
Q < K
c

Equilibrium is a
STABLE condition
Disturbing a System at
Equilibrium: Le Chateliers Principle
Le Chateliers Principle - If a change of conditions
(stress) is applied to a system in equilibrium, the
system responds in the way that best tends to reduce
the stress in reaching a new state of equilibrium.

Some possible stresses to a system at equilibrium
are:
1. Changes in concentration of reactants or products.
2. Changes in pressure or volume (for gaseous reactions)
3. Changes in temperature.
Le Chateliers Principle
Changes in Concentration of Reactants
and/or Products
Look at the following system at equilibrium at 450
o
C.
H
2
+ I
2
2HI
K
c
= 49
] I ][ [H
HI] [
K
2 2
2
c
=
- Removing HI: forward toward product-side

- Removing I
2
: backward toward reactant-side

- Adding H
2
: forward product-side

- Adding HI and removing I
2
: backward reactant-side

- Adding HI and adding H
2
: ? Calculate Q
Le Chateliers Principle
Changes in Volume
(and pressure for reactions involving gases)
Consider the following system


2NO
2(g)


N
2
O
4(g)

Move the piston downward: volume, pressure
Shift toward products (lower #molecules)
Move the piston upward: volume, pressure
Shift toward reactants (greater #molecules)
Le Chateliers Principle
Effect of Temperature on Equilibrium
Consider the following reaction at equilibrium:
reaction? in this product or reactant a heat Is
kJ/mol 198 H SO 2 O SO 2
o
rxn 3(g) 2(g) 2(g)
= A

+
2SO
2(g)
+ O
2(g)
2SO
3(g)
+ 198 kJ
Add heat to the system: increase O
2
and SO
2

Remove heat from the system: increase SO
3

Place the system in an ice bath: decrease SO
2
and O
2,
increase SO
3

Predictions are only true for EXOTHERMIC reactions
Le Chateliers Principle
Effect of Temperature on Equilibrium


Add heat to the system: clear solution
Remove heat from the system: increase precipitate
Place the system in an ice bath: increase precipitate

NH
4
NO
3 (s)
+ 98.9 kJ NH
4
+
(aq)
+ NO
3
-
(aq)

The effect of temperature on reactions in equilibrium depends on the sign of
H
rxn

Introduction of a Catalyst
Catalysts decrease the activation energy of both the forward and reverse
reaction equally.
Catalysts do not affect the position of equilibrium.
The concentrations of the products and reactants will be the same whether a
catalyst is introduced or not.
Equilibrium will be established faster with a catalyst.
Le Chateliers Principle
Given the reaction below at equilibrium in a closed
container at 500
o
C. How would the equilibrium be
influenced by the following?
a) Increasing the temperature
b) Decreasing the external temperature
c) Increasing the volume
d) Increasing the pressure
e) Adding He
(g)
in the system
f) Adding N
2(g)
in the system
g) Placing solid Pt in the system as catalyst
Backward, decrease products
Forward, increase products
Forward, increase products
Backward, decrease products
Forward, increase products
No effect
No effect
A certain indicator was extracted from mayana leaves, and its
dissociation in water can be shown in the following thermochemical
equation:



At 25
o
C the predominant color of the neutral extract is light green.
Determine the expected color when a solution of the extract is applied
with the following stress:



a) Placed in an ice bath
c) Placing sodium carbonate in the solution
b) Placing sodium sulfate in the system
d) Compressing the solution
e) Adding 3 drops of nitric acid
f) Adding hot water to the system
g) Adding small amounts of red dye in c)
Yellow
Yellow
Light Green
Light Green
Dark Green
Dark Green
Orange
Equilibrium Constant Expression in
Gas-Phase Reactions
For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
For gases, the pressure is proportional to the
concentration.
PV = nRT
P = nRT/V
n/V = M
P= MRT and M = P/RT
For systems involving gases, we can use K
p
instead of K
c

Equilibrium Constant Expression in
Gas-Phase Reactions
Consider this system at equilibrium at
500
0
C.
Equilibrium Constant Expression in
Gas-Phase Reactions
Using the expression [ ] = P/RT
From the previous slide we can see that the relationship
between K
p
and K
c
is:
( ) ( )
reactants) gaseous of moles of (# - products) gaseous of moles of (# = n
RT K K or RT K K
n
p c
n
c p
A
= =
A A
Relationship Between K
p
and K
c

Relationship Between K
p
and K
c

Nitrosyl bromide, NOBr, is 34% dissociated by
the following reaction at 25
o
C, in a vessel in
which the total pressure is 0.25 atmosphere.
What is the value of K
p
?
( ) ( ) ( )

g 2 g g
Br + NO 2 NOBr 2
K
c
is 49 for the following reaction at 450
o
C. If
1.0 mole of H
2
and 1.0 mole of I
2
are allowed
to reach equilibrium in a 3.0-liter vessel,



What is the total pressure inside the reaction
vessel after equilibrium is reached?
( ) ( ) ( )

+
g g 2 g 2
HI 2 I H
Heterogeneous Equilibria
Heterogeneous equilibria have more than
one phase present.
For example, a gas and a solid or a liquid and a gas.



How does the equilibrium constant differ
for heterogeneous equilibria?
Pure solids and liquids have activities of unity.
Solvents in very dilute solutions have activities that are
essentially unity.
The Kc and Kp for the reaction shown above are:


( ) 2(g) (s) s 3
O 3 2KCl 2KClO +

3
O p
3
2 c
2
P = K ] [O = K
2(g) (l) 2
(aq)
3 2
CO O H CO H +

( ) ( ) ( )
C) 25 at ( F 2 Ca CaF
o -
aq
2
aq s 2
+
+
Gibbs Free Energy and
Equilibrium
AG
0
is the standard free energy change.
AG
0
is defined for the complete conversion of all reactants to all
products.
With superscript 0

AG is the free energy change at nonstandard
conditions
For example, concentrations other than 1 M or pressures other
than 1 atm.
Temperature, however, is same as in AG
0
rxn

Gibbs Free Energy and
Equilibrium
AG is related to AG
o
by the following
relationship -
quotient reaction = Q
re temperatu absolute = T
constant gas universal = R
Q log RT 303 . 2 G = G
or lnQ RT G = G
o
o
+ A A
+ A A
Gibbs Free Energy and
Equilibrium
At equilibrium, AG=0 and Q=K
c
.
Then we can derive this relationship:
K log RT 2.303 - = G
or K ln RT - = G
: to rearranges which
K log RT 303 . 2 G 0
or K ln RT G 0
0
0
0
0
A
A
+ A =
+ A =
Gibbs Free Energy and
Equilibrium
( ) ( )
( ) ( )
D of activity the is C of activity the is
B of activity the is A of activity the is
where = K
dD + cC bB + aA
D C
B A
b
B
a
A
d
D
c
C
a a
a a
a a
a a

For the following generalized reaction, the thermodynamic

equilibrium constant is defined as follows:
Gibbs Free Energy and
Equilibrium
General equation; THERMODYNAMIC
FORM
All gaseous reactants and products
All solutions of reactants and products
Used when both gaseous and solution
forms appear in the chemical equation
Gibbs Free Energy and
Equilibrium
Calculate the equilibrium constant, K
p
, for
the following reaction at 25
o
C.
( ) ( )

g 2 g 4 2
NO 2 O N
( ) ( )

g 2 g 4 2
NO 2 O N
NON SPONTANEOUS
FORWARD
[N
2
O
4
] > [NO
2
]
K
p
for the reverse reaction at 25
o
C can be
calculated easily - it is the reciprocal of the
above reaction.

2 NO
2(g)

N
2
O
4(g)

AG
rxn
o
= 4.78 kJ/mol

K
p
'
=
1
K
p
=
1
0.145
= 6.90 =
P
N
2
O
4
( )
P
NO
2
( )
2
Gibbs Free Energy and
Equilibrium
It is difficult to analyze the relationship
between free energy and equilibrium
constant at non-standard conditions



The basic relationship between G
0
rxn
and
K
c
appears only for the standard conditions
form
AG
o
rxn
K Spontaneity at unit concentration
< 0 > 1
Forward reaction spontaneous,
More products than reactants at equilibrium
= 0 = 1 IDEAL system, very RARE
> 0 < 1
Reverse reaction spontaneous,
More reactants than products at equilibrium
Gibbs Free Energy and
Equilibrium
Gibbs Free Energy and
Equilibrium
Gibbs Free Energy and
Equilibrium
Nitrosyl bromide, NOBr, is 34% dissociated by the
following reaction at 25
o
C, in a vessel in which the total
equilibrium pressure is 0.25 atmosphere.
Calculate the G
0
rxn
.
What is the G when 5.00% of 2.00 atm NOBr has
dissociated?

EVALUATION OF EQUILIBRIUM CONSTANTS
AT DIFFERENT TEMPERATURES
From the value of AH
o
and K at one
temperature, T
1
, we can use the vant Hoff
equation to estimate the value of K at
another temperature, T
2
.
OR
The equilibrium constant K
c
of the reaction
H
2(g)
+ Br
2(g)
2HBr
(g)

is 1.6 x 10
5
at 1297 K and 3.5 x 10
4
at 1495 K.

(a) Is the reaction exothermic or endothermic?
(b) Find K
c
for the reaction: H
2(g)
+ Br
2(g)

HBr
(g)

(c) Pure HBr is placed in a container of constant
volume and heated to 1297 K. What
percentage of the HBr is decomposed to Br
2

and H
2
at equilbrium?
At its normal boiling point of 100
o
C, the heat of vaporization is
40.66 kJ/mole. What is the equilibrium vapor pressure of water at
25
o
C?
In the distant future, when hydrogen may be cheaper than coal,
steel mills make iron by the reaction


Fe
2
O
3(s)
+ 3H
2(g)
2Fe
(s)
+ 3H
2
O
(g)



For this reaction, H
0
= 96 kJ/mole and K
c
= 8.11 at 1000 K.
(a)What percentage of the H
2
remains unreacted after the reaction
has come to equilibrium at 1000 K?
(b) Is this percentage greater or less if the temperature is decreased
below 1000 K?