CHAPTER 6

CHEMICAL
EQUILIBRIUM
DR NURUL IZZA BINTI TAIB
UiTM CAWANGAN PERAK
KAMPUS TAPAH
OBJECTIVES
• Explain reversible reaction and dynamic
equilibrium graph
• Write expression of Kc, Kp and Qc
• Calculate Kc, Kp and Qc
• Derive and use the equation Kp = Kc (RT)Δn
• State Le Chatelier’s principle and explain factor
affecting equilibrium
REVERSIBLE REACTION
• A reversible reaction is a chemical reaction where
the reactants form products that, in turn, react
together to give the reactants back.
• A reversible reaction is denoted by a double arrow
(reversible arrow) pointing both directions in a
chemical equation.

A+B⇆C+D
CONCEPT OF EQUILIBRIUM
• Equilibrium is a state in which there are no observable
changes as time goes by.
• Reversible reaction.
forward
H2(g) + I2(g) 2HI(g)
reverse

• When there is no further change in the amounts of

reactants and products – equilibrium.
• At equilibrium:

rateforward = ratereverse
• 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
CHARACTERISTIC OF A
SYSTEM IN EQUILIBRIUM

Closed system

The rates of the forward and reverse

reactions are equal

Properties such as concentrations of

reactants & products, colors are constant
EQUILIBRIUM
CONSTANT,
KC AND KP
EQUILIBRIUM CONSTANT, KC
• The equilibrium constant, Kc, is the ratio of the
equilibrium concentrations of products over the
equilibrium concentrations of reactants each
raised to the power of their stoichiometric
coefficients.

Equilibrium constant: Kc =
[Products] [C ]c [ D]d
Kc =
[Reactants] [ A]a [ B ]b
Where:
- small superscript letters are the stoichiometry coefficients
- [A] concentration chemical species A relative to standard state
• The symbol ‘c’ in Kc indicates that concentration
units of the reactants and the products.
• For some equilibrium reactions, the Kc has no units
RANGE OF EQUILIBRIUM
CONSTANT
DETERMINING KC UNIT
Write the equilibrium expression for Kc for the
following reactions:
EXERCISE
Determine Kc for the reaction
2HI(g) ⇌ H2(g) + I2(g)
given that the concentrations of each species
at equilibrium are as follows: [HI] = 0.85 mol/L,
[I2] = 0.60 mol/L, [H2] = 0.27 mol/L.
EXERCISE
On analysis, an equilibrium mixture for the
reaction 2H2S(g) ⇌ 2H2(g) + S2(g) was found
to contain 1.0 mol H2S, 4.0 mol H2, and 0.80
mol S2 in a 4.0 L vessel. Find the equilibrium
constant, Kc, for this reaction.
EXERCISE
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
0.041mol of CH4. What is the [H2O] at equilibrium? Kc
= 0.26 for the equation.
EXERCISE
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
0.041mol of CH4. What is the [H2O] at equilibrium? Kc
= 0.26 for the equation.
EXERCISE
VARIATIONS IN
EQUILIBRIUM CONSTANT

1
• Kreverse of a reaction =
K forward

• If all coefficient of the balanced equation are

multiplied by some factor, that factor becomes the
exponents for the equilibrium constant.
EXAMPLE:
N2 (g) + 3H2 (g) 2NH3(g) Kc = 2.4 x 10-3

Determine the Kc value of :

a. 2 NH3 (g) N2(g) + 3H2(g)
b. 1/3 N2 (g) + H2(g) 2/3 NH3 (g)
c. NH3(g) ½ N2(g) + 3/2 H2 (g)

a) 1/ 2.4 x 10-3 = 416.67

b) (2.4 x 10-3 )1/3 = 0.13
c) ??
EXAMPLE

Carbon tetrachloride reacts at 1000 K with oxygen to

produce two toxic gases, phosgene and chlorine.
CCl4(g) + 1/2O2(g) ⇌ COCl2(g) + Cl2(g), Kc = 4.4x109
Find Kc for the reaction
• 2CCl4(g) + O2(g) ⇌ 2COCl2(g) + 2Cl2(g)
• COCl2(g) + Cl2(g) ⇌ CCl4(g) + 1/2O2(g)
EQUILIBRIUM CONSTANT IN
TERM OF PRESSURE, 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.
aA (g) + bB (g) cC (g) + dD (g)
• For the above gas reaction, at equilibrium,
(PC)c.(PD)d = Kp
(PA)a.(PB)b
EXERCISE
Referring to the reaction below.
2N2​O5​(g)⇋O2​(g)+4NO2​(g)
Given the PN2​O5= 2 atm, PO2 = 0.296 atm PNO2​=
1.70atm​. Find Kp for the reaction.
 HOMOGENOUS AND
HETEROGENOUS EQUILIBRIA
HOMOGENEOUS
EQUILIBRIA
All of the reactants and products are
present in a single solution (by
definition, a homogeneous mixture ).
HETEROGENEOUS
EQUILIBRIA
A system in which reactants and
products are found in two or more
phases. The phases may be any
combination of solid, liquid, or gas
phases, and solutions.

C2H2(aq) + 2Br2(aq) ⇋ C2H2Br4(aq) CO2(g) + C(s) ⇋ 2CO(g)

[C2H2Br4] [CO]2
Kc = Kc = ; C(s) is not included in
C2H2 Br2 2 CO2 the Kc or Kp

REMEMBER : solids and pure

liquids do not appear in equilibrium
constant expressions.
CONVERSION OF KC & KP

Δn = (Total moles of gas on the products side) - (Total moles of gas on

the reactants side).
R = 0.0821 L.atm/mol.K
EXAMPLE
Phosgene, COCl2, a poisonous gas, decomposes
according to the equation
COCl2(g) ⇋ CO(g) + Cl2(g)
Find Kp for this reaction if Kc = 0.083 at 900ºC.

8.0
EXERCISE
Kp for the reaction of SO2(g) with O2 to produce SO3(g)
is 3 x 1024. The chemical equation is given below.
2SO2(g) + O2(g) ⇋ 2SO3(g)
Calculate Kc for this equilibrium at 25ºC.

7x1025
 REACTION
QUOTIENT, QC
THE REACTION QUOTIENT,(QC)

The Reaction Quotient, (Qc) is a mass action

expression just like the equilibrium constant (K) except
it is for a reaction at conditions NOT at equilibrium.
The reaction quotient is used to determine which
direction a system will shift to reach equilibrium.

aA(g) + bB(g) ⇋ cC(g) + dD(g)

Q = [C]c[D]d Where [A], [B], [C], and [D] are molarities

at any time.
[A]a[B]b
COMPARISON OF KC AND QC

• The system is already at equilibrium

Q=K • It will not shift in either direction

• The system will shift to the left

Q>K • Some products will be converted to
reactants

• The system will shift to the right

Q<K • some reactants will be converted to
products
COMPARISON OF KC AND QC
EXAMPLE
2SO2 (g) + O2(g) 2SO3 (g)
At a particular temperature, Kc = 100. If 1 mol of SO2, 2 mol
of O2 and 8 mol of SO3 are placed in a 10 L flask, in which
direction will the reaction proceed?

Solution:
Q= [SO3]2 = (0.8)2__ = 320
[SO2]2[O2] (0.1)2 (0.2)

Since Q>K, The reaction goes backward, from right to left until
Q =K at equilibrium.
EXERCISE

At 700 K, the reaction

2SO2(g) + O2(g) ⇋ 2SO3(g) Kc = 4.3 x 106
and the following concentrations are present:
[SO2] = 0.10 M; [SO3] = 10. M; [O2] = 0.10 M.
Predict the direction of the reaction.
 LE
CHATELIER’S
PRINCIPLE
(RESTORING
BALANCE)
LE CHATELIER’S PRINCIPLE

If a system at equilibrium experiences a change,

the system will shift its equilibrium to try to
compensate for the change

Le Chatelier’s Principle allows us to predict the

effects of changes:

Concentration Pressure

Temperature Catalyst
A) CHANGING IN CONCENTRATIONS
(ONLY GAS & AQUEOUS)

 Lower the concentration or remove some of a

species
 The system will shift to produce more of that
species

 Increase the concentration or add some of a

species
 The system will shift to produce less of that
species
EXAMPLE
A(g) + 2B(g) ⇋ C(g)
EQUILIBRIUM
CONCENTRATION DIRECTION THE RESULT
(SHIFTING)
Increase A Right Producing more product

Decrease A Left Producing more reactant

Increase B Right Producing more product

Decrease B Left Producing more reactant

Increase C Left Producing more reactant

Decrease C Right Producing more product

EXERCISE
2NOBr(g) ⇋ 2NO(g) + Br2(g) ΔHºrxn = 30 kJ/mol
Predict the direction of the above reaction if:
a) Br2(g) is removed
b) NO(g) is added
c) NOBr(g) is added
d) NOBr(g) is removed
e) Br2(g) is added
B) CHANGING THE VOLUME /
PRESSURE (ONLY GASES)

 Increase the pressure (decrease volume)

 The system will shift to the least number
of gas molecules
 Decrease the pressure (increase volume)
 The system will shift to the highest
number of gas molecules
 EXAMPLE
A(g) + 2B(g) ⇋ C(g)
3 moles 1 moles
MOLES
Higher moles Lower moles

EQUILIBRIUM
STRESS DIRECTION THE RESULT
(SHIFTING)
Increase Pressure Right Producing more products

Decrease Pressure Left Producing more reactants

Increase Volume Left Producing more reactants

Decrease Volume Right Producing more products

EXERCISE
For the equilibrium reaction
2SO2(g) + O2(g) ⇋ 2SO3(g), ΔHºrxn= -198 kJ/mol.
Predict the direction of the above reaction if:
a) Pressure is increased
b) Pressure is decreased
c) Volume is increased
d) Volume is decreased
C) CHANGING TEMPERATURE
 For every reversible reaction, if one direction is
endothermic and the other is exothermic.

 For endothermic reaction (absorb heat from

surrounding) :
 Increase temperature : Reaction goes forward
 Decrease temperature : Reaction goes backward

 For exothermic reaction (release heat to

surrounding) :
 Increase temperature : Reaction goes backward
 Decrease temperature : Reaction goes forward
EXERCISE

2NOBr(g) ⇋ 2NO(g) + Br2(g) ΔHºrxn = 30 kJ/mol

Predict the direction of the above reaction if:
a) Temperature is increased
b) Temperature is decreased
EXERCISE
For the equilibrium reaction
2SO2(g) + O2(g) ⇋ 2SO3(g) ΔHºrxn= -198 kJ/mol.
Predict the direction of the above reaction if:
a) Temperature is increased
b) Temperature is decreased
D) USING CATALYST
 A catalyst works by providing an alternative route
with lower activation energy (Ea) for forward and
reverse reaction.

 Catalyst
 Does not shift the position of an equilibrium
system.
 Does not change equilibrium constant
 Only increase the rate of reaction, thus shorten
the time taken for the reaction to reach
equilibrium.
EXERCISE
Consider the equilibrium
N2O4(g) ⇋ 2NO2(g) ΔH°= 58.0 kJ
In which direction will the equilibrium shift when
(a) N2O4 is added,
(b) NO2 is removed,
(c) The pressure is increased by addition of N2(g)
(d) The volume is increased
(e) The temperature is decreased?
EXERCISE
Consider the equilibrium
PCl5(g) ⇋ PCl3(g) + Cl2(g) ΔH°= 58.0 kJ
in which direction will the equilibrium shift when
(a) Cl2(g) is removed,
(b) the temperature is decreased,
(c) the volume of the reaction system is increased,
(d) PCl3(g) is added?
EXERCISE
Consider the equilibrium
PCl5(g) ⇋ PCl3(g) + Cl2(g) ΔH°= 58.0 kJ
in which direction will the equilibrium shift when
(a) Cl2(g) is removed,
(b) the temperature is decreased,
(c) the volume of the reaction system is increased,
(d) PCl3(g) is added?