CHAPTER 6:

CHEMICAL EQUILIBRIUM

BY:

DR. NAZRIZAWATI AHMAD TAJUDDIN

LEARNING OUTCOME
 Kc and Kp

 Equilibrium expressions

 Factors affecting Kc and Kp

 Conversion of Kc and Kp

 Homogeneous vs heterogeneous equilibrium

 Le Chatelier’s Principle and the effect of temperature,

pressure, concentration and catalyst on equilibirum

WHAT IS EQUILIBRIUM?
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
rate forward = rate reverse
 Physical equilibrium
Equilibrium between 2 phases
of the same substance

Example :
Vaporization of water in a
closed container

H2O (l) H2O (g)

Liquid water in equilibrium
with its vapors in a closed
system at room temperature
• Most chemical reactions go to completion.

• Some changes go only one direction

Example: baking bread

Flour + baking powder + water bread
• But many other changes are reversible or do not
proceed to completion.

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

• The sign indicates that the reaction does not

go to completion

• A reversible reaction is one that goes in both

directions at the same temperature.
• When there is no further change in the amounts of
reactants and products – equilibrium.

• The rates of the forward and reverse reaction are

equal - dynamic equilibrium.

rate fwd = rate rev

Example: A+B C+D
• At the beginning, concentration of A & B at max.

• The rate of the reaction was at its fastest.

• As A and B react, their concentrations fall.

• They are less collide and react, the rate of

forward reaction falls as time goes on.
Example: A+B C+D
 With time, the rate of the reaction between C &
D increases.

 The rates of the two reactions will become

equal.

 A & B will be converting into C & D at exactly

the same rate as C & D convert back into A & B
again.
Example: A+B C+D
• As fast as something is being removed, it is
being replaced again by the reverse reaction.

• Have reached a position of dynamic

equilibrium.

The reaction do not stop when

equilibrium is reached.
 N2O4 (g) 2NO2 (g)
colorless gas dark-brown color
Characteristic of a system in equilibrium

1 Closed system

The rates of the forward and reverse reactions

2 are equal

Properties such as concentrations of reactants

3 & products, colors are constant
 EQUILIBRIUM CONSTANT, Kc

aA + bB cC + Dd

For a reaction in equilibrium, the equilibrium

constant ,Kc is given by the equilibrium law.

Kc = [product] = [C]c[D]d
[reactant] [A]a[B]b

LAW OF MASS ACTION

• The symbol ‘c’ in Kc indicates that units for the
reactants and the products are those in
concentration, moles percubic decimetre.

• For some equilibrium reactions, the Kc has no

units
Example : 2SO2(g) + O2(g) 2SO3(g)

[SO3]2
Kc =
[O2]2[O2]

Unit of Kc :

(mol dm-3)2
(mol dm-3)2(mol dm-3) = dm3 mol-1
• For a reaction, the equilibrium constant for the
forward reaction is Kfwd and the equilibrium
constant for the reverse reaction is Krev.

Kfwd
aA + bB cC + dD
Krev

1
Kfwd = or Kfwd x Krev = 1
Krev
 The range of equilibrium constants

small K intermediate K
Very little large K Significant amount
product of reactant and
Very little product
reactant
 [C]c[D]d
K= aA + bB cC + dD
[A]a[B]b

Equilibrium Will

K >> 1 Lie to the right Favor products

K << 1 Lie to the left Favor reactants
 EXERCISE 1

In a study concerning the conversion of methane to other

fuels, a chemical engineer mixes gaseous CH4 and H2O in a
0.32-L flask at 1200 K. At equilibrium the flask contains 0.26
mol of CO, 0.091 mol of H2, and 0.041 mol of CH4. What is
the [H2O] at equilibrium? Kc = 0.26 for the equation

CH4(g) + H2O(g) CO(g) + 3H2(g)

Solution:

CH4(g) + H2O(g) CO(g) + 3H2(g)

[CO][H2]3
[CH4]eq = 0.041 mol = 0.13 M [H2O] =
0.32 L [CH4] Kc

0.26 mol (0.81)(0.28)3

[CO]eq = = 0.81 M =
0.32 L (0.13)(0.26)

[H2]eq = 0.091 mol = 0.28 M = 0.56 M

0.32 L
 EQUILIBRIUM CONSTANT, Kp

• For reactions involving gases, the equilibrium

constant is often expressed in terms of the partial
pressures of the gases rather than concentrations.

• The equilibrium constant is then given the

symbol, Kp.
• The partial pressure of a gas is related to the
number of moles of the gas by the ideal equation
pV = nRT
Example: N2(g) + 3H2(g) 2NH3(g)

p = nRT , n =c, c = concentration of the gas

V V
p = cRT
Partial pressure of a gas is directly
proportional to its concentration
• We can express the equilibrium law in terms of
concentrations
Kc = [NH3]2
[N2][H2]3

• Terms of the partial pressures of the gases involved

Kp = (NH3)2
N2 x (H2)3

 = partial pressure of the gas

 EXERCISE 2
The equilibrium constant Kp for the reaction below is 158 atm
at 1000K. What is the equilibrium pressure of O2 if the PNO2 =
0.400 atm and PNO = 0.270 atm?

2NO2 (g) 2NO (g) + O2 (g)

(PNO)2 (PO2) (PNO2) 2

Kp = PO2 = Kp
(PNO)2
(PNO2 )2
PO2 = 158 x (0.400)2/(0.270)2 = 347 atm
 HOMOGENEOUS EQUILIBRIA

• Homogeneous equilibria are chemical equilibria in

which all the reactants and the products are in the
same phase.

Example : N2O4 (g) 2NO2 (g)

Expression of Kc for homogeneous system

CH3COOH (aq) + H2O (l) CH3COO- (aq) + H3O+ (aq)

[CH3COO-][H3O+]
Kc = [H2O] = constant
[CH3COOH][H2O]

[CH3COO-][H3O+]
Kc = = Kc′ [H2O]
[CH3COOH]

General practice NOT to include units for the equilibrium

constant.
 HETEROGENEOUS EQUILIBRIA
• Heterogeneous equilibria are those in which
reactants and products are present in more than
one phase.

Example:
CaCO3 (s) CaO (s) + CO2 (g)
 Expression of Kc for heterogeneous system

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

[CaO][CO2]
Kc = Any solid will be constant
[CaCO3] So [CaCO3] = constant
[CaO] = constant
[CaCO3]
Kc = [CO2] = Kc′ x Kp = PCO
[CaO] 2

The concentration of solids and pure liquids are not

included in the expression for the equilibrium
constant.
 CONVERSION OF Kc & Kp
n P n
PV = nRT P= RT = = M
V RT V

P  M so for 2NO(g) + O2(g) 2NO2(g)

Kp = Kc (RT)n(gas)

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

Example:
Find Kc for the following reaction, if Kp = 2.1x10-4 (at
1000. K)
CaCO3(s) CaO(s) + CO2(g)
Solution:
∆ngas = 1 - 0 since there is only a gaseous product
and no gaseous reactants.
Kp = Kc(RT)∆n

Kc = Kp/(RT)∆n = (2.1x10-4) = 2.6x10-6

(0.0821x1000)1
 EXERCISE 3
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)

Solution:
CO (g) + Cl2 (g) COCl2 (g)

Kc = [COCl2] 0.14
= = 216 #
[CO][Cl2] 0.012 x 0.054

Kp = Kc(RT)∆n ∆n = 1 – 2 = -1

Kp = 216 x (0.0821 x 347)-1 R = 0.0821

= 7.58 # T = 273 + 74 = 347 K

 EXERCISE 4
Consider the following equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)

The partial pressure of each gas is 0.265 atm. Calculate Kp and

Kc for the reaction?

Solution:
Kp = PNH PH S = 0.265 x 0.265 = 0.0702
3 2

Kp = Kc(RT)∆n ∆n = 2 – 0 = 2 T = 295 K

Kc = Kp(RT)-∆n = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4 #

 REACTION QUOTIENT, Qc
The reaction quotient (Qc) is calculated by
substituting the initial concentrations of the
reactants and products into the equilibrium constant
(Kc) expression.
For reaction:
aA + bB cC + dD

Q= [C]c[D]d Qfwd = 1
[A]a[B]b Qrev
The change in Q during the N2O4-NO2 reaction

At equilibrium
 EXERCISE 5
Write the reaction quotient, Qc for the decomposition of
dinitrogen pentoxide

N2O5(g) NO2(g) + O2(g)

Solution:

(a) 2 N2O5(g) 4 NO2(g) + O2(g)

[NO2]4[O2]
Therefore Qc =
[N2O5]2
 Variation in the form of the Reaction
Quotient

If an overall reaction is the sum of two or more

reactions, the overall reaction quotient (or
equilibrium constant) is the product of the
reaction quotients (equilibrium constant) for the
steps:

Qoverall = Q1 x Q2 x Q3 x …..

Koverall = K1 x K2 x K3 x …..
Example:

(1) N2(g) + O2(g) 2NO(g) Kc1 = 4.3x10-25

(2) 2NO(g) + O2(g) 2NO2(g) Kc2 = 6.4x109

N2(g) + 2O2(g) 2NO2(g)

Qc1 = [NO]2 Qc2 = [NO2]2

[N2][O2] [NO]2[O2]

[NO]2 x [NO2]2 = [NO2]2

Qc= Qc1 x Qc2 =
[N2][O2] [NO]2[O2] [N2][O2]2
 Reaction direction and the relative sizes of Qc
and Kc
• Qc < Kc system proceeds from left to right to reach
equilibrium

• Qc = Kc the system is at equilibrium

• Qc > Kc system proceeds from right to left to reach

equilibrium
 EXERCISE 6
For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 100oC.
At a point during the reaction, [N2O4] = 0.12 M and [NO2] =
0.55 M. Is the reaction at equilibrium? If not, in which
direction is it progressing?

Solution:
[NO2]2 (0.55)2
Qc = = = 2.5
[N2O4] (0.12)

Qc is > Kc, therefore the reaction is not at equilibrium and

will proceed from right to left, from products to reactants,
until Qc = Kc.
Calculating Equilibrium Concentrations

1. Express the equilibrium concentrations of all

species in terms of the initial concentrations and a
single unknown x, which represents the change in
concentration.
2. Write the equilibrium constant expression in terms
of the equilibrium concentrations. Knowing the
value of the equilibrium constant, solve for x.
3. Having solved for x, calculate the equilibrium
concentrations of all species.
 EXERCISE 7
Calculating Kc from Concentration Data
In order to study hydrogen halide decomposition, a
researcher fills an evacuated 2.00-L flask with 0.200 mol of
HI gas and allows the reaction to proceed at 453oC.

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

At equilibrium, [HI] = 0.078 M. Calculate Kc?

Solution:
0.200 mol = 0.100 M
[HI] =
2.00 L
Let x be the amount of [H2] at equilibrium. Then x will
also be the concentration of [I2] and the change in of [HI]
will be the original concentration minus the
stoichiometric amount that reacted, 2x, or 0.078 M.

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

initial 0.100 0 0
change -2x +x +x
equilibrium 0.100 - 2x x x

[HI] = 0.078 = 0.100 - 2x ; x = 0.011 M

[H2] [I2] [0.011][0.011]

Qc = = = 0.020 = Kc
[HI]2 (0.078)2
 EXERCISE 8

Calculating Equilibrium Concentrations with a

Simplifying Assumption

COCl2(g CO(g) + Cl2(g) Kc = 8.3x10-4 (at 360oC)

Calculate [CO], [Cl2], and [COCl2] when the following

amounts of phosgene decompose and reach equilibrium in a
10.0-L flask.

(a) 5.00 mol COCl2 (b) 0.100 mol COCl2

 Solution:
(a) 5.00 mol/10.0 L = 0.500 M (b) 0.100 mol/10.0 L = 0.0100 M
Let x = [CO]eq = [Cl2]eq and 0.500 - x and 0.0100 - x =
[COCl2]eq, respectively, for (a) and (b).
[CO][Cl2]
Kc =
[COCl2]
(x)(x)
(a) Kc = 8.3x10-4 = assume x is << 0.500 so
(0.500 - x) that we can drop x in
(x)(x) the denominator
8.3x10-4 =
(0.500)
4.15x10-4 = x2 x ≈ 2 x 10-2

(0.500 - x) = 4.8x10-2
CHECK: 0.020/0.500 = 0.04 or 4% percent error
 (x)(x) assume x is << 0.010 so
(b) Kc = 8.3x10-4 =
(0.010 - x) that we can drop x in
the denominator
(x)(x)
8.3 x 10-4 = x ≈ 2.9x10-3 M
(0.010)
8.3 x10-6 = x2
(0.010 - x) = 0.0071 M

CHECK: 0.0029/0.010 = 0.29 or 29% percent error

Using the quadratic formula produces x = 2.5x10-3 and

0.0100 - x = 7.5x10-3 M
 EXERCISE 9
Predicting Reaction Direction and Calculating Equilibrium
Concentrations

CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol
of H2S, and 2.00 mol of H2 are mixed in a 250-mL vessel at
960oC. At this temperature, Kc = 0.036.

a) In which direction will the reaction proceed to reach

equilibrium?
b) If [CH4] = 5.56 M at equilibrium, what are the
equilibrium concentrations of the other substances?
Solution:

a) In which direction will the reaction proceed to reach

equilibrium?
[CH4]initial = 1.00 mol/0.25 L = 4.0 M
[H2S]initial = 2.00 mol/0.25 L = 8.0 M
[CS2]initial = 1.00 mol/0.25 L = 4.0 M
[H2]initial = 2.00 mol/0.25 L = 8.0 M

[CS2][H2]4 [4.0][8.0]4
Qc = = = 64
[CH4][H2S]2 [4.0][8.0]2

A Qc of 64 is >> than Kc = 0.036

The reaction will progress to the left.
b) If [CH4] = 5.56 M at equilibrium, what are the
equilibrium concentrations of the other substances?

Concentration (M) CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

initial 4.0 8.0 4.0 8.0

change +x +2x -x -4x
equilibrium 4.0 + x 8.0 + 2x 4.0 - x 8.0 - 4x

At equilibrium [CH4] = 5.56 M, so 5.56 = 4.0 + x and x = 1.56 M

Therefore - [H2S] = 8.0 + 2x = 11.12 M

[CS2] = 4.0 - x = 2.44 M
[H2] = 8.0 - 4x = 1.76 M
 Steps in solving equilibrium problems
PRELIMINARY SETTING UP WORKING ON A REACTION TABLE

1. Write the balanced equation. 4. When reaction direction is not

2. Write the reaction quotient, Q. known compare Q with K.
3. Convert all of the amounts 5. Construct a reaction table.
into the correct units (M or  Check the sign of x, the
atm). change in the quantity.

SOLVING FOR X AND EQUILIBRIUM QUANTITIES

Check that assumption is
6. Substitute the quantities into Q.
justified (<5% error).
7. To simplify the math, assume that x
is negligible. Check to see that calculated
8. [A]ini - x = [A]eq = [A]init values give the known K.
9. Solve for x.
10. Find the equilibrium quantities.
 LE CHATELIER’S PRINCIPLE

When a chemical system at equilibrium

is subjected to a stress, the system will return
to equilibrium by shifting to reduce the stress.

If the concentration increases, the system reacts

to consume some of it.

If the concentration decreases, the system reacts

to produce some of it.
Le Chatelier's Principle

Le Chatelier's principle states that when a

system in chemical equilibrium is disturbed
by a change of temperature, pressure, or a
concentration, the system shifts in
equilibrium composition in a way that tends
to counteract this change of variable.
• Is qualitative guide to the effect changes in
concentration, pressure or temperature on a system
at equilibrium

• An idea that can be used to predict the way in

which a system at equilibrium alters as the physical
and chemical conditions are changed
EFFECT ON CONCENTRATION

• A change in the concentration of a reactant will

alter the rate of the forward reaction.

• A change in the concentration of a product will alter

the rate of the reverse reaction.
 Changes in concentration

Remove Remove
Add 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
Complete the table below

A+B C+D
How does the
Disturbance equilibrium mixture The result
respond?
Concentration of
A increases
Concentration of
D increases
Concentration of
D decreases
 A+B C+D
How does the equilibrium
Disturbance The result
mixture respond?

Concentration System moves to right - More C and D

of A increases some A is removed by form
reaction with B

Concentration System moves to left – More A and B

of D increases some of the added D is form
removed by reaction
with C
Concentration System moves to the There is more C
of D decreases right to make up for the and less A and B
loss of D in the new
equilibrium
The Effect of Added Cl2 on the PCl3-Cl2-PCl5 System

Concentration (I) PCl3(g) + Cl2(g) PCl5(g)

Original equilibrium 0.200 0.125 0.600

Disturbance +0.075

New initial 0.200 0.200 0.600

Change -x -x +x

New equilibrium 0.200 - x 0.200 - x 0.200 + x

(0.637)*

*Experimentally determined value.

PCl3(g) + Cl2(g) PCl5(g)
 EXERCISE 10
Predicting the Effect of a Change in Concentration on the
Equilibrium Position
To improve air quality and obtain a useful product, chemists
often remove sulfur from coal and natural gas by treating the
fuel contaminant hydrogen sulfide with O2:

2H2S(g) + O2(g) 2S(s) + 2H2O(g)

What happens to

(a) [H2O] if O2 is added? (b) [H2S] if O2 is added?

(c) [O2] if H2S is removed? (d) [H2S] if sulfur is added?
Solution:
[H2O]2
Q=
[H2S]2[O2]

a) When O2 is added, Q decreases and the reaction progresses

to the right to come back to K. So [H2O] increases.
b) When O2 is added, Q decreases and the reaction progresses
to the right to come back to K. So [H2S] decreases.

c) When H2S is removed, Q increases and the reaction

progresses to the left to come back to K. So [O2] increases.
d) Sulfur is not part of the Q (K) expression because it is a
solid. Therefore, as long as some sulfur is present the
reaction is unaffected. [H2S] is unchanged.
EFFECT OF PRESSURE & VOLUME

• A change in total pressure may alter the

equilibrium position of a system but only if it
involves gases.

• The direction of change depends upon total

number of gas molecules on each side of the
equilibrium.
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
 EXERCISE 11
Predicting the Effect of a Change in Volume (Pressure) on
the Equilibrium Position
How would you change the volume of each of the
following reactions to increase the yield of the products.
(a) CaCO3(s) CaO(s) + CO2(g)
(b) S(s) + 3F2(g) SF6(g)

Solution:
a) CO2 is the only gas present. To increase its yield, we
should increase the volume (decrease the pressure).
b) There are more moles of gaseous reactants than
products, so we should decrease the volume (increase
the pressure) to shift the reaction to the right.
EFFECT OF TEMPERATURE

• Only temperature changes can alter K.

• Consider heat as a product or a reactant

• In an exothermic reaction, heat is a product.
• In an endothermic reaction, heat is a
reactant.
Changes in Temperature

 A temperature rise will increase K for a system

with a positive Horxn

 A temperature rise will decrease K for a system

with a negative Horxn

Temp.Change Exothermic Rx Endothermic Rx

Increase K decreases K increases
Decrease K increases K decreases
 Example

N2O4 (g) 2NO2 (g)

• The reaction is endothermic left to right

• An increase in temperature will move the
position in the endothermic direction (to the
right)
• More of the dinitrogen tetroxide to decompose.
• N2O4 is a colorless gas, 2NO2 is a brown gas

• When N2O4 is heated, the gas darkens as

increasing amounts of brown NO2 are formed
from N2O4.
 EXERCISE 12
Predicting the Effect of a Change in Temperature on the Equilibrium
Position
How does an increase in temperature affect the concentration of
the bold substance and K for the following reactions?
(a) CaO(s) + H2O(l) Ca(OH)2(aq) ∆Ho = -82 kJ
(b) CaCO3(s) CaO(s) + CO2(g) ∆Ho = 178 kJ

Solution:
(a) CaO(s) + H2O(l) Ca(OH)2(aq) + heat
An increase in temperature will shift the reaction to the left, decrease
[Ca(OH)2], and decrease K.
(b) CaCO3(s) + heat CaO(s) + CO2(g)
The reaction will shift right resulting in an increase in [CO2]
and increase in K.
EFFECT OF CATALYST
A catalyst works by providing an alternative
route that has a lower Ea forward and backward
reaction. The rate of reaction with a catalyst is
much faster and system will reach equilibrium
more quickly

TAKE NOTE!!!!!!
• does not change K
• does not change equilibrium constant
• does not shift the position of an equilibrium
system
SUMMARY OF LE CHATELIER’S PRINCIPLE