CHEMICAL EQUILIBRIA

Equilibrium: the extent of a reaction

In stoichiometry we talk about theoretical yields, and the many reasons
actual yields may be lower.

Another critical reason actual yields may be lower is the reversibility of

chemical reactions:.

Equilibrium looks at the extent of a chemical reaction.

Equilibrium is a state in which there are no observable changes as time goes by.
Chemical equilibrium is achieved when:
• the rates of the forward and reverse reactions are equal and
• the concentrations of the reactants and products remain
constant Physical equilibrium

H2O (l) H2O (g)

Chemical equilibrium
N2O4 (g) 2NO2 (g)
 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium

Start with NO2 Start with N2O4

constant
The Equilibrium Constant

 No matter the starting composition of reactants and

products, the same ratio of concentrations is achieved
at equilibrium.
 For a general reaction aA + bB(g) pP + qQ

the equilibrium constant expression is

Kc 
 P   Q
p q

 A  B
a b
where Kc is the equilibrium constant.
 N2O4 (g) 2NO2 (g)
[NO2]2 = 4.63 x 10-3
K=
[N2O4]
aA + bB cC + dD

[C]c[D]d
K= Law of Mass Action
[A]a[B]b

Equilibrium Will
K >> 1 Lie to the right Favor products
K << 1 Lie to the left Favor reactants
 Homogenous equilibrium applies to reactions in which all
reacting species are in the same phase.
N2O4 (g) 2NO2 (g)
[NO2]2 PNO
2
Kc = In most cases Kp =
2

[N2O4] PN O
2 4
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)n

n = moles of gaseous products – moles of gaseous reactants

= (c + d) – (a + b)
Homogeneous Equilibrium
CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)
[CH3COO-][H3O+]
K‘c = [H2O] = constant
[CH3COOH][H2O]
[CH3COO-][H3O+]
Kc = = K‘c [H2O]
[CH3COOH]

General practice not to include units for the

equilibrium constant.
The Equilibrium Expression
 Write the equilibrium expression for the
following reaction:
N2(g) + 3H2(g) 2NH3(g)
The equilibrium concentrations for the reaction between carbon monoxide and molecular chlorine
to form COCl2 (g) at 740C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M.
Calculate the equilibrium constants Kc and Kp.

CO (g) + Cl2 (g) COCl2 (g)

[COCl2] 0.14
Kc = = = 220
[CO][Cl2] 0.012 x 0.054
Kp = Kc(RT)n
n = 1 – 2 = -1 R = 0.0821 T = 273 + 74 = 347 K

Kp = 220 x (0.0821 x 347)-1 = 7.7

 2

The equilibrium constant Kp for the reaction

2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of O2
if the PNO2 = 0.400 atm and PNO = 0.270 atm?

2
PNO PO 2
Kp = 2
PNO 2
2
PNO
PO 2 = Kp 2
2
PNO

PO 2 = 158 x (0.400)2/(0.270)2
= 347 atm
 Sample Problem
• Calculate the Kc at 25oC for the reaction

• 2NO(g) + Cl2(g) === 2NOCl(g)

• Kp = 1.9 x103

• Answer: Kc = 4.6 x104

Heterogenous equilibrium applies to reactions in which
reactants and products are in different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2]
K‘c = [CaCO3] = constant
[CaCO3]
[CaO] = constant
[CaCO3]
Kc = [CO2] = K‘c x
[CaO] Kp = PCO 2

The concentration of solids and pure liquids are not

included in the expression for the equilibrium constant.
 CaCO3 (s) CaO (s) + CO2 (g)

PCO 2 = Kp

PCO 2 does not depend on the amount of CaCO3 or CaO

 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.
• The equilibrium constant is a dimensionless quantity.
• In quoting a value for the equilibrium constant, you must
specify the balanced equation and the temperature.
 K‘c [C][D]
A+B C+D K‘c =
[A][B]
C+D E+F K‘c‘ [E][F] [E][F]
Kc = K‘‘c =
[A][B] [C][D]
A+B E+F Kc
Kc = K‘c x K‘c‘

If a reaction can be expressed as the 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.
N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
K= = 4.63 x 10 -3
K‘ = = = 216
[N2O4] [NO2]2 K

When the equation for a reversible reaction is

written in the opposite direction, the
equilibrium constant becomes the reciprocal
of the original equilibrium constant.
 Sample Problem
1. For the equilibrium Reaction
N2O(g) + ½ O2(g) == 2 NO (g) Kc =?
Individual chemical reactions:

N2(g) + 1/2O2(g) == N2O (g) Kc = 2.4 x 10-18

N2(g) + O2 (g) == 2 NO (g) Kc = 4.1 x 10-31
Relationships involving Equilibrium Constants Kc to the balanced

Chemical Equations
When we multiply the coefficients in a balanced
equation by a common factor (2,3), we raise the
equilibrium constant to the corresponding power (2,3)
When we divide the coefficients in a balanced
equation by a common factor (2,3), we take the
corresponding roots of the equilibrium constant
( square root, cube root)
 Sample Problem
The following Kc value is given at 298K for the synthesis of NH3
from its elements.

N2(g) + 3H2(g) === 2NH3(g)

Kc =3.6 x 108

What is the value of Kc at 298 K for the reaction

NH3 == 1/2 N2(g) + 3/2 H2(g)

Answer: 5.3 x 10-5

 Calculating Kc
A mixture of 5.00 x 10-3mol of H2 and 1.00 x 10-2 mol of I2 is
placed in a 5.00 L container at 448oC and allowed to come to
equilibrium. Analysis of the equilibrium mixture shows that
the concentration of HI is 1.87 x 10-3M. Calculate Kc at 448oC
for the reaction

H2(g) + I2(g) === 2HI (g)

Answer : Kc =50
 Calculating Kp
The gas arsine, AsH3 decomposes as follows:
2 AsH3(g) === 2 As (s) + 3H2(g)
In an experiment at a certain temperature, pure AsH3 (g) was placed in an
empty rigid sealed flask at a pressure of 392.0 torr. After 48 hours the
pressure in the flask was observed to be 488.0 torr.
Calculate the equilibrium pressure of H2 and Kp of the reaction.

Answer: 0.786 atm

 Calculating Kc
At a particular temperature, 12.0 moles of SO3 is placed into a 3.0
L rigid container, and the SO3 dissociates by the reaction
2SO3(g) === 2 SO2 (g) + O2(g)
At equilibrium, 3.0 moles of SO2 is present. Calculate K for this
reaction.

Answer: Kc = 0.056
Calculating Equilibrium Concentrations

Note the moles into a 10.32 L vessel stuff ... calculate molarity.
Starting concentration of HI: 2.5 mol/10.32 L = 0.242 M
2 HI H2 + I2

0.242 M 0 0 [ H 2 ][ I 2 ]
Initial: Keq 
Change: -2x +x +x [ HI ]2
Equil: 0.242-2x x x
[ x][ x] x2 3
Keq    1. 26 x10
[0.242  2 x]2 [0.242  2 x]2
What we are asked for here is the equilibrium concentration of H2 ...
... otherwise known as x. So, we need to solve the x.
And yes, it’s a quadratic equation. Doing a bit of rearranging:

x2 3
 1 . 26 x10
[0.242  2 x]2
3
x  1.26 x10 [0.242  2 x]
2 2

3
 1.26 x10 [0.0586  0.968 x  4 x ] 2

5 3 3 2
 7.38 x10  1.22 x10 x  5.04 x10 x
3 5
0.995 x  1.22 x10 x  7.38 x10  0
2

x = 0.00802 or –0.00925
 b  b  4ac 2 Since we are using this to
x model a real, physical system,
2a we reject the negative root.
The [H2] at equil. is 0.00802 M.
 Initial Concentration of I2: 0.50 mol/2.5L = 0.20 M More than 3
orders of mag.
I2 2I
[ I ]2 between these
Initial 0.20 0 Keq   2.94 x10 10 numbers. The
[I2 ]
change -x +2x simplification will
work here.
2
0.20-x 2x [ 2 x ]
equil:   2.94 x10 10
[0.20  x]
With an equilibrium constant that is very small, whatever x is,
0.20 – x is the same as 0.20

2
[2 x] 10
 2.94 x10 x = 3.83 x 10-6 M
0.20
 Initial Concentration of I2: 0.50 mol/2.5L = 0.20 M
I2 2I [ I ]2 These are too close to
Initial 0.20 0 Keq   0. 209 each other ...
[I2 ]
change -x +2x 0.20-x will not be
2 trivially close to 0.20
equil: 0.20-x 2x  [ 2 x ]
 0.209 here.
[0.20  x]

Looks like this one has to proceed through the quadratic ...
 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium,
the system adjusts in such a way that the stress is partially offset
as the system reaches a new equilibrium position.

• Changes in Concentration
N2 (g) + 3H2 (g) 2NH3 (g)

Equilibrium
shifts left to Add
offset stress NH3
 Le Châtelier’s Principle

• Changes in Concentration continued

Remove
Add Remove
Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s) left
Decrease concentration of product(s) right
Increase concentration of reactant(s) right
Decrease concentration of reactant(s) left
 Le Châtelier’s Principle

• Changes in Volume and Pressure

A (g) + B (g) C (g)

Change Shifts the Equilibrium

Increase pressure Side with fewest moles of gas
Decrease pressure Side with most moles of gas
Increase volume Side with most moles of gas
Decrease volume Side with fewest moles of gas
 Le Châtelier’s Principle

• Changes in Temperature

Change Exothermic Rx Endothermic Rx

Increase temperature K decreases K increases
Decrease temperature K increases K decreases
 Le Châtelier’s Principle

• Adding a Catalyst
• does not change K
• does not shift the position of an equilibrium system
• system will reach equilibrium sooner

uncatalyzed catalyzed

Catalyst lowers Ea for both forward and reverse reactions.

Catalyst does not change equilibrium constant or shift equilibrium.
 Le Châtelier’s Principle
Change Equilibrium
Constant
Change Shift Equilibrium
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no

14.5
 Using Le Chatelier’s Principle to Predict
Shifts in Equilibrium
Consider the equilibrium; N2O4 (g) ==== 2 NO2(g) ΔHo =58.0 kJ
To which direction will the equilibrium shift when
a.) N2O4 is added
b.) NO2 is removed
c.) the pressure is increased
d.) the volume is decreased
e.) the temperature is decreased
 Sample Problem
• Predict the shift in equilibrium position that will occur for each of
the following processes when the volume is reduced
a.) preparation of liquid phosphorus trichloride by the reaction
P4(s) + 6 Cl2(g) == 4 PCl3(l)
b.) preparation of gaseous phosphorus pentachloride according to
the equation
PCl3(g) + Cl2(g) == PCl5(g)
 Sample Problem
• For each of the following reactions, predict how the
value of K changes as the temperature is increased

N2(g) + O2 (g) == 2 NO (g) ΔH = 181kJ

2SO2(g) + O2(g) === 2 SO3(g) ΔH = -198kJ
 Gibbs Free Energy and
Chemical Equilibrium
G = H -T

G = G0 + RT lnQ
T is the absolute temperature (K)
Q is the reaction quotient
R is the gas constant (8.314 J/K•mol)

At Equilibrium
G = 0 Q=K
0 = G0 + RT lnK

G0 =  RT lnK
G0 =  RT lnK
 Sample Problem
• Consider the ammonia synthesis reaction
N2(g) + 3H2 (g) === 2 NH3(g)
where ΔGo = -33.3 Kj per mole of N2 consumed at
25oC. For each of the following mixtures of reactants
and products at 25oC, predict the direction in which
the system will shift to reach equilibrium
PNH3 = 1.00 atm, PN2 = 1.00 atm ,PH2 = 1.00 atm
 Sample Problem
• The overall reaction for the corrosion of iron by oxygen is

4 Fe(s) + 3 O2 (g) == 2 Fe2O3 (s)

Using the following data, calculate the equilibrium constant for this reaction at 25 oC.

Substance ΔHof (kj/mol) Sof (J/Kmol)

Fe2O3 -826 90
Fe 0 27
O2 (g) 0 205

Ans. K e601 (the rusting of iron is clearly very favorable from a thermodynamic point of view)