Chapter 15

Overview
Equilibrium Reactions
Equilibrium Constants K
c
& K
p
Equilibrium Expression product/reactant
Reaction Quotient Q
Calculations
Le Chateliers Principle
disturbing the equilibrium

Overview, contd
All reactions are reversible
Dynamic Equilibrium
When the rates of the forward and
reverse reactions are equal
Reactions do not go to completion
Cannot use stoichiometric methods to calculate
amount of products formed

A B

k
f
[A] = k
r
[B]
forward rate = reverse rate

[B ] = k
f
= constant
[A] k
r

Equilibrium and Rates

Ratio of Products to Reactant
raised to each coefficient
for example,
N
2
+ 3H
2
2NH
3


K = [NH
3
]
2

[N
2
][H
2
]
3


Equilibrium Constant Expression
N
2
+ 3H
2
2NH
3


Large K, more product
Product Favored

Small K, more reactant
Reactant Favored
contd
aA + bB cC + dD

K
c
= [C]
c
[D]
d

[A]
a
[B]
b

products
reactants
concentration
In General:
Forms of Eq. Constant Expression
CO
(g)
+ H
2
O
(g)
CO
2(g)
+ H
2(g)

K
c
= [CO
2
][H
2
]
[CO][H
2
O]

4HCl
(g)
+ O
2(g)
2H
2
O
(g)
+ 2Cl
2(g)

K
c
= [Cl
2
]
2
[H
2
O]
2

[O
2
][HCl]
4

Contd
2HI H
2
+ I
2


K
f
= [H
2
][I
2
]
[HI]
2

H
2
+ I
2
2HI

K
r
= [HI]
2
= 1
[H
2
][I
2
] K
f

Contd
2{ 2HI H
2
+ I
2
}

K
f
= [H
2
][I
2
]
[HI]
2

4HI 2H
2
+ 2I
2


K = K
f
2
= [H
2
]
2
[I
2
]
2

[HI]
4

Example
N
2
O
4
2NO
2

Initial Initial Equilibrium Equilibrium Kc
N
2
O
4
NO
2
N
2
O
4
NO
2

0.0 0.02 0.0014 0.0172 0.211
0.0 0.03 0.0028 0.0243 0.211
0.0 0.04 0.0045 0.0310 0.213
0.02 0.0 0.0045 0.0310 0.213

Kc = [NO
2
]
2

[N
2
O
4
]
generally unitless
N
2
+ 3H
2
2NH
3

Large K, more product
K > > 1 Product Favored

N
2
+ 3H
2
2NH
3

Small K, more reactant
Reactant Favored K < < 1
Review values of K:
Example:
N
2
+ 3H
2
2NH
3

K
c
= 4.34 x 10
-3
at 300C = [NH
3
]
2

[H
2
]
2
[N
2
]
What is K for reverse reaction?

What is K for 2N
2
+ 6H
2
4NH
3
?

What is K for 4NH
3
6H
2
+ 2N
2
?
K
c reverse
= 230
K
c
= 1.88 x 10
-5

K
c
= 5.31 x 10
4

Heterogeneous Equilibria:
When pure solid or liquid is involved
Pure solids & liquids do not appear in the equilibrium
constant expression
When H
2
O is a reactant or product and is the
solvent
H
2
O does not appear in the equilibrium constant
expression

Examples:
CaCO
3(s)
CaO
(s)
+ CO
2(g)

conc. = mol = g/cm
3
= density
cm
3
g/mol MM

K
c
= [CaO] [CO
2
] = (constant 1) [CO
2
]
[CaCO
3
] (constant 2)

K
c
= K
c
(constant 2) = [CO
2
]
(constant 1)

both are
constant
Multi-Step Equilibria

AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)
K
1
= [Ag
+
][Cl
-
]

Ag
+
(aq)
+ 2NH
3(aq)
Ag(NH
3
)
2
+
(aq)
K
2
= [Ag(NH
3
)
2
+
]
[Ag
+
][NH
3
]
2



AgCl
(s)
+ 2NH
3(aq)
Ag(NH
3
)
2
+
(aq)
+ Cl
-
(aq)


K
tot
= K
1
K
2
= [Ag(NH
3
)
2
+
][Cl
-
]
[NH
3
]
2

Problem:
1.00 mole of H
2
& 1.00 mole of I
2
are placed in a 1.0 L container at
520 K and allowed to come to equilibrium. Analysis reveals 0.12
mol of HI present at equilibrium. Calculate K
c
.
H
2(g)
+ I
2(g)
2HI
(g)

initial 1.00 1.00 0
change -0.06 -0.06 +0.12
equil. 0.94 mol 0.94 mol +0.12

Kc = (0.12)
2
= 1.6 x 10
-2

(0.94)(0.94)

Conversion between K
p
and K
c

Kc
Equilibrium constant using concentrations
Kp
Equilibrium constant using partial pressures
Kp = Kc (RT)
Dn

P = n RT
V
R = 0.0821 L atm/mol K
T = Temperature in K
Dn = tot. mol product - tot. mol reactant
Problem:
For 2SO
3(g)
2SO
2(g)
+ O
2(g)


K
c
= 4.08 x 10
-3
at 1000 K. Calculate K
p
.

K
p
= K
c
(RT)
Dn
= 4.08 x 10
-3
(0.0821 x 1000)
1


K
p
= 0.0335
Problem:
For 3H
2(g)
+ N
2(g)
2NH
3(g)

K
c
= 0.105 at 472C. Calculate K
p
.

K
p
= K
c
(RT)
Dn
= 0.105 (0.0821 x 745)
-2


K
p
= 2.81 x 10
-5

Applications of Eq. Constants
Reaction Quotient
Non-equilibrium concentrations used in the
equilibrium constant expression

Q = K Reaction is at equilibrium
Q > K Reaction will shift left to equilibrium
Q < K Reaction will shift right to equilibrium
Problem:
K
c
= 5.6 x 10
-12
at 500 K for I
2(g)
2I
(g)

[I
2
] = 0.020 M & [I] = 2.0 x 10
-8
M. Is the reaction at
equilibrium? Which direction will it shift to reach
equilibrium?

Q = [I ]
2
= (2.0 x 10
-8
)
2
= 2.0 x 10
-14

[I
2
] (0.020)

Q < K
(2.0 x 10
-14
) < (5.6 x 10
-12
)
Reaction Shifts Right to get to equilibrium
not at equilibrium
because Q K
Calculation of Eq. Concentrations
use the stoichiometry of reaction
initial concentration of all species
change that occurs to all species
equilibrium concentration of all species
reaction will occur to reach the equilibrium point
no matter the direction of reaction
Problem:
Cyclohexane, C
6
H
12(g)
, can isomerize to form
methylcyclopentane, C
5
H
9
CH
3(g)
. The equilibrium constant at
25C is 0.12. If the original amount was 0.045 mol cyclohexane
in a 2.8 L flask, what are the concentrations at equilibrium?
C
6
H
12
C
5
H
9
CH
3

initial 0.045 mol 0
change -x +x
equil. 0.045 - x x
Contd
0.12 = (x)
(0.045 - x)
Solve for x which is the equilibrium concentration
of methylcyclopentane or the product

x = 4.8 x 10
-3
mol C
5
H
9
CH
3
in 2.8 L flask
[C
5
H
9
CH
3
] = 1.7 x 10
-3
M
[C
6
H
12
] = 1.4 x 10
-2
M
Problem:
For the reaction H
2
+ I
2
2HI the K
c
= 55.64. You start
with 1.00 mol H
2
and 1.00 mol I
2
in a 0.500 L flask. Calculate
the equilibrium concentrations of all species?
H
2
+ I
2
2HI
initial 2.00 M 2.00 M 0
change -x -x +2x
equil. 2.00 - x 2.00 - x 2x
Contd
55.64 = (2x)
2

(2.00 -x)
2

(55.64)

= (2x)
2

(2.00 -x)
2

x = 1.58 M

[HI] = 3.16 M [H
2
] = 0.42 M [I
2
] = 0.42 M
= 2x = 2.00 - x = 2.00 - x

perfect
square
Problem:
For the reaction H
2
+ I
2
2HI the K
c
= 55.64. You start with
1.00 mol H
2
and 0.50 mol I
2
in a 0.500 L flask. Calculate the
equilibrium concentrations of all species?
H
2
+ I
2
2HI
initial 2.00 M 1.00 M 0
change -x -x +2x
equil. 2.00 - x 1.00 - x 2x
Contd
K
c
= [HI]
2

[H
2
][I
2
]

55.64 = (2x)
2

(2.00 -x)(1.00 -x)

reduces to a quadratic equation:

x
2
- 3.232 x + 2.155 = 0
not a perfect square
Quadratic Equation
x = - b b
2
- 4ac
2a

for

ax
2
+ bx + c = 0


Contd
x = +3.232 10.446 - 8.62
2
x = 1.616 0.6755


[HI] = 1.88 M [H
2
] = 1.06 M [I
2
] = 0.060 M
= 2x = 2.00 - x = 1.00 - x

Le Chateliers Principle
When a stress is applied to an equilibrium
reaction, the equilibrium shifts to reduce the
stress
Types of Stress
Addition or removal of reactant
Addition or removal or product
Increase or decrease of temperature
Change in pressure or volume
2NOCl
(g)
Cl
2(g)
+ 2NO
(g)
DH = +77 kJ
temp.
NOCl
reaction
shifts
temp.
NOCl
reaction
shifts
pressure
volume
reaction
shifts
Cl
2

NO
Cl
2

NO
[C
6
H
12
] [C
5
H
9
CH
3
]
initial 1.4 x 10
-2
+ 1.0 x 10
-2
M 1.7 x 10
-3
M
change -x +x
equil. 2.4 x 10
-2
- x 1.7 x 10
-3
+ x

0.12 = (1.7 x 10
-3
+ x) x = 1.05 x 10
-3
M
(2.4 x 10
-2
- x)

[C
6
H
12
] = 0.023 M [C
5
H
9
CH
3
] = 0.0028 M
Addition of Reactant or Product
Changes in Temperature
will change K
for an endothermic reaction
increasing T increases K
for an exothermic reaction
increasing T decreases K
A
B
E
n
e
r
g
y

Reactions Path
without
catalyst
with
catalyst
r
f
r
r

E
a (f)

E
a (r)

Effect of a Catalyst
2O
3(g)
3O
2(g)
overall rxn
O
3(g)
O
2(g)
+ O
(g)
fast
equil. rate1 = k
1
[O
3
]
rate2 = k
2
[O
2
][O]
O
(g)
+ O
3(g)
2O
2(g)
slow
rate3 = k
3
[O][O
3
]
rate 3 includes the conc. of an intermediate and the
exptl. rate law will include only species that are
present in measurable quantities
Reaction Mechanisms & Equilibria
k
1
k
3
k
2
Substitution Method
at equilibrium k
1
[O
3
] = k
2
[O
2
][O]

rate3 =k
3
[O][O
3
] [O] = k
1
[O
3
]
k
2
[O
2
]

rate3 = k
3
k
1
[O
3
]
2
or
k
2
[O
2
]

overall rate = k [O
3
]
2

[O
2
]
substitute
Problem:
Derive the rate law for the following reaction given
the mechanism step below:
OCl
-

(aq)
+ I
-
(aq)
OI
-
(aq)
+ Cl
-
(aq)


OCl
-
+ H
2
O HOCl + OH
-
fast
I
-
+ HOCl HOI + Cl
-
slow
HOI + OH
-
H
2
O + OI
-
fast

k
1

k
2

k
3

k
4

Contd
rate1 = k
1
[OCl
-
][H
2
O] = rate 2 = k
2
[HOCl][OH
-
]
[HOCl] = k
1
[OCl
-
][H
2
O]
k
2
[OH
-
]
rate 3 = k
3
[HOCl][I
-
]
rate 3 = k
3
k
1
[OCl
-
][H
2
O][I
-
]
k
2
[OH
-
]

overall rate = k [OCl
-
][I
-
]
[OH
-
]
solvent