CHAPTER 6 : EQUILIBRIA

CHEMICAL EQUILIBRIA
During a game,
players enter
and leave.
Always the
same number
of players on
field.
H
2
O(l) H
2
O(g)
Reversible reaction
a chemical reaction that can occur in both the
forward and the reverse directions
N
2
(g) + 3H
2
(g) 2NH
3
(g)
Chemical equilibrium
a state in which the forward and reverse
reactions balance each other because
they take place at equal rates
dynamic state; no net change
Law of chemical equilibrium
At a given temperature, a chemical
system might reach a state in which a
particular ratio of reactant and product
concentrations has a constant value.
Equilibrium constant expression
ratio of molar concentrations of
products to reactants; each raised to a
power equal to coefficient in balanced
equation
aA + bB cC + dD
Equilibrium constant (K
eq
)
numerical value of the ratio of product
to reactant concentrations
constant only at a specific
temperature
Value of equilibrium constant (K
eq
)
shows
the extent to which reactants are
converted into products.
K
eq
> 1: Products are favored at
equilibrium
K
eq
< 1: Reactants are favored at
equilibrium
Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.
N
2
O
4
(g) 2NO
2
(g)
K
c
=
[NO
2
]
2

[N
2
O
4
]
K
p
=
NO
2

P
2

N
2
O
4

P
aA (g) + bB (g) cC (g) + dD (g)
K
p
= K
c
(RT)
Dn

Dn = moles of gaseous products moles of gaseous reactants
= (c + d) (a + b)
In most cases
K
c
K
p

Homogeneous Equilibrium
CH
3
COOH (l) + H
2
O (l) CH
3
COO
-
(l) + H
3
O
+
(l)
General practice not to include units for
the equilibrium constant.
K
c
=
[CH
3
COO
-
][H
3
O
+
]
[CH
3
COOH][H
2
O]
Homogeneous equilibrium
all reactants and products in
same phase
Write an equilibrium constant expression
for:
N
2
(g) + 3H
2
(g) 2NH
3
(g)
K
C
=

[NH
3
]
2
___________
[N
2
] [H
2
]
3
The equilibrium concentrations for the reaction between carbon
monoxide and molecular chlorine to form COCl
2
(g) at 74
0
C are
[CO] = 0.012 M, [Cl
2
] = 0.054 M, and [COCl
2
] = 0.14 M. Calculate
the equilibrium constants K
c
and K
p
.
CO (g) + Cl
2
(g) COCl
2
(g)
K
c
=
[COCl
2
]
[CO][Cl
2
]
=
0.14
0.012 x 0.054
= 220
K
p
= K
c
(RT)
Dn

Dn = 1 2 = -1 R = 0.0821 T = 273 + 74 = 347 K
K
p
= 220 x (0.0821 x 347)
-1
= 7.7
The equilibrium constant K
p
for the reaction

is 158 at 1000K. What is the equilibrium pressure of O
2

if the P
NO
= 0.400 atm and P
NO
= 0.270 atm?
2
2NO
2
(g) 2NO (g) + O
2
(g)
K
p
=
2
P
NO
P
O

2
P
NO

2
2
P
O

2
= K
p

P
NO

2
2
P
NO

2
P
O

2
= 158 x (0.400)
2
/(0.270)
2
= 347 atm
Heterogeneous equilibrium
reactants and products present in more
than one physical state
H
2
O(l) H
2
O(g)
Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.
CaCO
3
(s) CaO (s) + CO
2
(g)
K
c
=

[CaO][CO
2
]
[CaCO
3
]
[CaCO
3
] = constant
[CaO] = constant
K
c
= [CO
2
] = K
c
x

[CaCO
3
]
[CaO]
K
p
= P
CO

2
The concentration of solids and pure liquids are not
included in the expression for the equilibrium
constant.
Heterogeneous equilibrium
Since concentrations of pure liquids and
solids remain constant, these substances
are omitted from the equilibrium constant
expression.
Write an equilibrium constant expression
for:
H
2
O(l) H
2
O(g)
K
c
= [H
2
O(g)]
Equilibrium constant expression K
eq
= . . .
Products over reactants raised to power
of coefficient; leave out pure solids and
liquids.
Equilibrium concentrations can vary
from trial to trial.
Equilibrium position
H
2
(g) +I
2
(g) 2HI(g)
K
c
K
c
constant
N
2
O
4
(g) 2NO
2
(g)
N
2
O
4
(g) 2NO
2
(g)
= 4.63 x 10
-3
K =
[NO
2
]
2

[N
2
O
4
]
2NO
2
(g) N
2
O
4
(g)
K =
[N
2
O
4
]
[NO
2
]
2


=
1
K
= 216
When the equation for a reversible
reaction is written in the opposite
direction, the equilibrium constant
becomes the reciprocal of the
original equilibrium constant.
Each set of equilibrium concentrations
represent an equilibrium position.
A system has only one value for K
c
at a
specific temperature, however there are
unlimited number of equilibrium positions.
A system at equilibrium must:
take place in closed
system
temperature remain
constant
all reactants and products are present
(both reactions can occur)
Write the equilibrium constant expression
for

N
2
(g) + O
2
(g) 2NO(g)
Calculate the value of K
eq
if
[N
2
] = 0.20 mol/L,
[O
2
] = 0.15 mol/L, and
[NO] = 0.0035 mol/L.
K
eq
= 4.1 x 10
-4
What does the value of K
eq
tell you about
the equilibrium?
The reaction quotient (Q
c
) is calculated by substituting the initial
concentrations of the reactants and products into the equilibrium
constant (K
c
) expression. Vice versa for K
p
IF
Q
c
> K
c
system proceeds from right to left to reach equilibrium
Q
c
= K
c
the system is at equilibrium
Q
c
< K
c
system proceeds from left to right to reach equilibrium
At 1280
0
C the equilibrium constant (K
c
) for the reaction

Is 1.1 x 10
-3
. If the initial concentrations are [Br
2
] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
Br
2
(g) 2Br (g)
Br
2
(g) 2Br (g)
Let x be the change in concentration of Br
2

Initial (M)
Change (M)
Equilibrium (M)
0.063 0.012
+x -2x
0.063 + x 0.012 - 2x
[Br]
2

[Br
2
]
K
c
= K
c
=
(0.012 - 2x)
2

0.063 + x
= 1.1 x 10
-3

Solve for x
[Br]
i
2

[Br
2
]
i
Q
c
=
Q
c
=
(0.012)
2

0.063
= 2.29 x 10
-3
> K
c
Rx proceeds to the left to achieve eqm; prodt
decompose to yield rxt
K
c
=
(0.012 - 2x)
2

0.063 + x
= 1.1 x 10
-3

ax
2
+ bx + c =0
-b b
2
4ac
2a
x =
Br
2
(g) 2Br (g)
Initial (M)
Change (M)
Equilibrium (M)
0.063 0.012
+x -2x
0.063 + x 0.012 - 2x
x = 0.00178 x = 0.0105
At equilibrium, [Br] = 0.012 - 2x = -0.009 M or 0.00844 M
At equilibrium, [Br
2
] = 0.063 + x = 0.06478 M
What happens when a
system is at equilibrium
and you upset the
balance?
When a system in dynamic equilibrium is to change, the
system reacts to remove the change so equilibrium
reestablish.
Le Chteliers Principle
Changes in Concentration
N
2
(g) + 3H
2
(g) 2NH
3
(g)
Add
NH
3

Equilibrium
shifts left to
remove
change
Le Chteliers Principle
Changes in Concentration continued
Change Shifts the Equilibrium
Increase concentration of product(s) left
Decrease concentration of product(s) right
Decrease concentration of reactant(s)
Increase concentration of reactant(s) right
left
aA + bB cC + dD
Add Add Remove
Remove
Le Chteliers Principle
Changes in Volume and Pressure
PCl
3
(g) + Cl
2
(g) PCl
5
(g)
Change Shifts the Equilibrium
Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Decrease volume
Increase volume Side with most moles of gas
Side with fewest moles of gas
Le Chteliers Principle
Changes in Volume and Pressure
H
2
(g) + I
2
(g) 2Hl(g)
Change Shifts the Equilibrium
Increase pressure
No effect on eqm system
since both sides contain
same no of molecules
Decrease pressure
Decrease volume
Increase volume
Le Chteliers Principle
Changes in Temperature
Change
Exothermic Rx
Eqm position & eqm constant
Endothermic Rx
colder hotter
The Effect Temperature on Equilibrium
Consider the following exothermic reaction:
N
2
(g) + 3H
2
(g) 2NH
3
(g); DH
o
= -92 kJ,
The forward reaction produces heat => heat is
a product.
When heat is added to increase temperature,
reverse reaction will take place to absorb the
heat;
If heat is removed to reduce temperature, a net
forward reaction will occur to produce heat.
The Effect Temperature on Equilibrium
Consider the following endothermic reaction:
N
2
O
4
(g) 2 NO
2
(g); DH
o
= +57 kJ
1. Endothermic reaction absorbs heat heat is
a reactant;
2. If heat is added to increasing the
temperature, it will cause a net forward
reaction.
3. If heat is removed to reduce the temperature,
it will cause a net reverse reaction.
uncatalyzed catalyzed
Catalyst lowers E
a
for both forward and reverse reactions.
Catalyst does not change equilibrium constant or shift equilibrium.
Adding a Catalyst
does not change K
does not shift the position of an equilibrium system
system will reach equilibrium sooner
Le Chteliers Principle
Relationship between K
eq
& T
Given by Vant Hoff equation; ln K = - H + C
RT
K = eqm constant
H = enthalpy change of rx
R = gas constant
T = temperature (K)
C = constant
i) Exothermic rx : ii) Endothermic rx
ln K
1/T (K
-1
)
Grad = -H
R
ln K
1/T (K
-1
)
o
o
o
o
Grad = -H
R
* +ve slope * -ve slope
Chemical Equilibria in Industrial Processes
Production of Sulfuric Acid, H
2
SO
4
in Contact process;
1. S
8
(s) + 8 O
2
(g) 8SO
2
(g)
2. 2SO
2
(g) + O
2
(g) 2SO
3
(g); DH = -198 kJ
3. SO
3
(g) + H
2
SO
4
(l) H
2
S
2
O
7
(l)
4. H
2
S
2
O
7
(l) + H
2
O(l) 2H
2
SO
4
(l)

The second reaction is exothermic and has high activation
energy;
reaction is very slow at low temperature,.
At high temperature reaction goes faster, but the yield would
be very low.
An optimum condition is achieved at moderate temperatures
and using catalysts to speed up the reaction. Reaction also
favors high pressure.
Chemical Equilibria in Industrial Processes
The production of ammonia by the Haber process:
N
2
(g) + 3H
2
(g) 2NH
3
(g); DH = -92 kJ
This reaction is exothermic and very slow at low
temperature.
Increasing the temperature will increase reaction rate,
but will lower the yield.
An optimum condition is achieved at moderate
temperature of 250 to 300
o
C with catalyst added to
increase the reaction rate.
Increasing the pressure will favor product formation.
Reaction favors low temperature and high pressure
conditions.

The production of nitric acid by the Ostwald process:
Step 1:
4NH
3
(gas) + 5O
2
(gas) 4NO (gas) + 6H
2
O (gas)
Step 2:
2NO (gas) + O
2
(gas) 2NO
2
(gas)
Step 3:
3NO
2
(gas) + H
2
O (liquid) 2HNO
3
(aqueous solution) + NO (gas)
Step 4:
4NO
2
(gas) + O
2
(gas) + 2H
2
O (liquid) 4HNO
3
(aqueous)

reaction is exothermic decreasing the temperature,
increase the concentration , and increasing the pressure
and volume = optimum yield
The catalyst that is used for this reaction is a
platinum gauze or a copper wire/rod
Concentration of Stratospheric Ozone
Formation of Ozone in
Stratosphere
Depletion of Ozone in
Stratosphere
Formation of ozone in the stratosphere
Ozone, O3 is formed from chemical
reaction between nitrogen dioxide and
oxygen in 2 steps.
Step 1
Photo
dissociation of
nitrogen dioxide
Step 2
Formation of
Ozone
Step 1: Photo dissociation of nitrogen dioxide
In the presence of UV light, nitrogen dioxide dissociates to
form nitrogen monoxide and oxygen free radicals
NO
2
(g) NO(g) + O (g)
Step 2: Formation of ozone
The oxygen free radicals rapidly react with oxygen in the air
to form ozone molecules.
O (g) + O
2
(g) O
3
(g)
Depletion of ozone in stratosphere
Ozone reacts with nitrogen monoxide (formed
in Step 1 of formation of O3)
to produce nitrogen dioxide and oxygen.

O3(g) + NO(g) O2(g) + NO2(g)

Its actually the reverse of the
formation of stratospheric ozone!
Rate of
formation of
ozone
The system is in dynamic equilibrium.
Rate of
depletion of
ozone
=
NO2(g) + O2(g) NO(g) + O3(g)
Concentration of ozone remains constant
UV light
Everyday, 3x10
8
tons of stratospheric ozone
formed & destroyed by natural processes.
Stratospheric O
3
IMPORTANT ; photodissociation
rx, prevent harmful uv radiation frm reaching
earths surface.
(200 310 nm) are absorbed frm the uv rays
Photons in this range ; enough energy to cause
skin cancer & damage to living plants
For every 1% in stratospheric ozone, additional
2% damaging uv rays reach earths surface.
Le Chteliers Principle
Change Shift Equilibrium
Change Equilibrium
Constant
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no