Gas

Equilibrium
OVERVIEW

A) Non reversible & reversible reactions

B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
Non-Reversible Reaction
 Some reactions go to completion. The reaction will
continue until one or more reactants are completely
used up in the reaction.

 When this happens, the reaction stops. All

reactants are converted to products

Example:
MgCO3(s) + H2SO4(aq) → MgSO4(aq) + CO2(g) +
H2O (l)
 Reversible Reaction
 There are also reactions which do not go to
completion.

 As soon as some product molecules are formed,

they react with one another to form reactant
molecules.

 Such reactions are called reversible reactions.

A + B  C + D
 Reversible reactions will reach a state called
EQUILIBRIUM where the concentration of
both reactants and products remain
constant with time, but reaction is not
static!
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
Equilibrium definition:
 The DYNAMIC state of a chemical reaction is
where the rate of forward reaction is equal to the
rate of reverse reaction.

Rate forward = Rate reverse

 Rate refers to the ‘’speed’’ of the formation of

products and reactants
 Dynamic means ‘’changing’’, where reaction
does not stop once equilibrium is reached;

 Reactants keep changing into products

 And products keep changing back into

reactants
Equilibrium and Rates
Forward reaction:
N2O4(g) -> 2NO2(g)
Reverse reaction:
2NO2(g) -> N2O4(g)

Initially
The [reactants] is high, so the
forward reaction rate (kf) is
high while the [products] is
zero, so reverse reaction (kr) is
slow.
 As the reaction proceed to equilibrium, the
rate of forward reaction decreases while the
rate of reverse reaction increases until they
become equal.

 Equilibrium is attained.
 Equilibrium and
Concentrations
Initially, [reactants] is high
while [products] is zero;
as the reaction proceeds,
reactants are used up
while more products are
formed until reaction
reaches equilibrium.

At equilibrium, the concentration of each reactant and

product remains constant (stop changing).
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
The Value of Kc

If Kc >1, at equilibrium a
considerable amt. of pdt. is
formed.
Kc >> 1, alot of pdts formed,
v little reactant

If Kc < 1, considerable amt. of

reactant remains.
Kc << 1, alot of reactants
remain, v little pdts formed.
2 Types of Equi Systems

 For homogenous system:

2SO2 (g) + O2 (g)  2 SO3 (g)
Kc = [SO3(g)]2
[SO2(g)]2 [O2(g)]

 For heterogeneous system:

Zn (s) + 2HCl (aq)  ZnCl2 (aq) + H2 (g)
Kc = [ZnCl2(aq)] [H2(g)]
[HCl(aq)]2
*Note: Always omit species in the liquid or solid state
from an equilibrium expression
 Only a change in temperature of equilibrium
system will change the Kc value,

Changes in concentration and pressure will not

change the Kc value.
Advanced calculation: Determining Equilibrium
Concentrations
Reaction Quotient and Equilibrium
Constant a A + b B  c C + d D
 The reaction quotient, Q is the ratio between
[products] over the [reactants] in terms of molar
concentration and at constant temperature.
* Note: Expression for Q and Equilibrium
constant(Kc) are the same. Q is replaced with Kc
when concentrations used for calculation are at
equilibrium conc. of products
[C]c [D]d
K =
Q
[A]a [B]b
conc. of reactants
equilibrium constant
reaction quotient
Example:
1.In an experiment, a mixture of NO2 and N2O4 gases was
allowed to achieve equilibrium in an enclosed container at
250C. At equilibrium, their concentrations were found to be
[N2O4] = 0.47M and [NO2] = 0.052M. Calculate the equilibrium
constant for the reaction below:
2NO2(g) ↔ N2O4(g)

2. In another similar experiment, another mixture of NO2 and

N2O4 was allowed to achieve equilibrium. After some time
has elapsed, the concentration of the gases were found to be:
[N2O4] = 0.38M & [NO2] = 0.092M
Using the Kc calculated above, determine whether the
reaction has achieved equilibrium. If not, how would the
reaction proceed before equilibrium is achieved?
Determining whether
equilibrium has been achieved?
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
 Le Châtelier’s Principle
“If a system at equilibrium is
disturbed by a change in
temperature, pressure, or the
concentration of one of the
components, the system will
shift its equilibrium position so as
to counteract the effect of the
changes.”
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
i) Effect of Concentration on the
Position of Equilibrium
 According to Le Chatelier’s Principle, when the
[reactants] in an equilibrium system is
increased, the equilibrium will shift to the right
hand side

This is so that part of the added reactant is

converted into products, in order to counteract
the changes / disturbance.
 Consider:
N2(g) + 3H2(g)  2NH3(g)

Equilibrium position shifted

• If H2 is added at ta, [H2]
increases
• According to LCP,
equilibrium position will
shift to the right to
counteract the changes
(ta to tb)
• Forward reaction is
favored.
ta tb
• At tb attained new
equilibrium
At New
equilibrium equilibrium • N2 will be consumed and
will form more NH3.
 Example
With regards to the equation:
PCl3 (g) + Cl2 (g)  PCl5 (g)
complete the calculation for the equilibrium
constant expression in each case and then answer
the questions that follow.
[ PCl 5 ]
  [PCl3 (g)] [C12 (g)] [PCl5 (g)] [ PCl 3 ][Cl 2 ]

Equilibrium 0.80 1.2 2.4 2.5 

Cl2 (g) added 0.80 2.0 2.4 1.5 
Equilibrium
0.59 1.8 2.7  2.5
re-established
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
 ii) Effect of Pressure on the
Position of Equilibrium
 According to Le Chatelier’s Principle, an increase in
the pressure to the system, will cause the equilibrium
to shift to the side with lesser number of moles of
gas, in order to counteract the disturbance.
 Pressure only affects gaseous systems, because the V
occupied by a gas can be altered by pressure.
 Total no. of moles of R ≠ total no. of moles of P
 Consider: N2(g) + 3H2(g)  2NH3(g)

4 moles of gas ≠ 2 moles of gas

 When the pressure of the above equilibrium is

increased, the volume occupied by the gas will
decreased.

 The molecules are crowded closer to one another. The

additional pressure can be relieved if the molecules are
able to react so as to reduce the total number of
molecules present.

 Hence the equilibrium will shift to the right hand side,

according to LCP.
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
iii) Effect of Temperature on
the Position of Equilibrium
• According to Le Chatelier’s Principle, an
increase in the temperature of the system, will
cause the equilibrium to favor the side which
is an endothermic reaction, in order to
counteract the disturbance.

–For reaction that goes to completion [→],

if ΔH = -ve, this means that the reaction is
exothermic.
 For reversible reaction []; if
ΔH = -ve means that the forward reaction is
exothermic, while the reverse reaction is
endothermic.

The effects of temperature on an endo. and an exo.

reaction system are summarized in the table
below.

Temperature
Type of reaction Direction favored
change
Endothermic Increase Forward
Endothermic Decrease Reverse
Exothermic Increase Reverse
Exothermic Decrease Forward
PEQ
2CH3OH (g) CH3OCH3 (g) + H2O (g)
H = –24 kJ mol–1

State whether the value of Kc will increase or

decrease when the temperature of the reaction
mixture is lowered. Explain.
 When temperature is lowered, according to LCP,
system will favour exothermic reaction.
 As forward reaction is exothermic, equilibrium
shifts to the right and amount of product will
increase.
 Hence value of Kc will increase
Overview
A) Non reversible & reversible reactions
B) Intro to Equilibrium
C) Equilibrium Constant, Kc and calculations
D) Le Chatelier’s Principle
i) Effect of Concentration on Equilibrium
ii) Effect of Pressure on Equilibrium
iii) Effect of Temperature on Equilibrium
iv) Effect of Catalyst on Equilibrium
Catalysts increase the rate of both the
forward and reverse reactions.

Equilibrium is achieved faster, but the

equilibrium composition remains
unaltered (equilibrium position will not
change).

Catalysts do not increase the TOTAL

yield of a reversible reaction but
increases yield per unit time.