Equilibrium

Chemistry

Gordon Watson
Chemistry Department, Kelso High School

Adv Higher Unit 2 Topic 2 part 1

KHS Chemistry Unit 2.2 Equilibrium Chemistry 1
Introduction

This topic explores various aspects of Reversible Reactions, leading

to an appreciation of the importance of Equilibria in Chemistry.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 2

Attaining Equilibrium 1
Starting with a frozen sample
containing the dimer, N2O4(g)

As the sample warms up the only

reaction will be:

N2O4(g)  2NO2(g)

KHS Chemistry Unit 2.2 Equilibrium Chemistry 3

Attaining Equilibrium 2

When enough NO2 has formed, it

can react to form N2O4.

2NO2(g)  N2O4(g)

At this stage the forward reaction will

still be faster:

N2O4 2NO2

KHS Chemistry Unit 2.2 Equilibrium Chemistry 4

Attaining Equilibrium 3
The concentration of NO2 will
continue to increase while the
concentration of N2O4 will
decrease.

At normal temperatures, the

reverse reaction is more favoured,
but the high concentration of N2O4
means:

N2O4 2NO2

KHS Chemistry Unit 2.2 Equilibrium Chemistry 5

Attaining Equilibrium 4
Eventually, however, the rising
concentration of NO2 means that
the reverse reaction will become as
fast as the forward reaction:

N2O4 2NO2

From now on the concentrations of

N2O4 and NO2 will not change - the
reaction will have reached
equilibrium.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 6

Attaining Equilibrium 5

KHS Chemistry Unit 2.2 Equilibrium Chemistry 7

Equilibrium Constant 1
Initial and Equilibrium Concentrations
for the N2O4 - NO2 System at 100°C

Initial Equilibrium Ratio

[N2O4] [NO2] [N2O4] [NO2] [NO2]2 [N2O4]

0.1000 0.0000 0.0491 0.1018 0.211

0.0000 0.1000 0.0185 0.0627 0.212

0.0500 0.0500 0.0332 0.0837 0.211

0.0750 0.0250 0.0411 0.0930 0.210

KHS Chemistry Unit 2.2 Equilibrium Chemistry 8
Equilibrium Constant 2
No matter the starting composition of reactants and
products, the same ratio of concentrations is achieved at
equilibrium.

For a general reaction

the equilibrium constant expression is

where Kc is the equilibrium constant.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 9
Equilibrium Constant 3
The equilibrium constant provides information about
which of the reactions is most favoured at that particular
temperature

K small N2(g) + O2(g) 2 NO(g) K = 1 x 10-30

You would predict that under

most conditions there would
be very little NO produced.

Equilibrium position likely to lie

well over to left

KHS Chemistry Unit 2.2 Equilibrium Chemistry 10

Equilibrium Constant 4

K large 2CO(g) + O2(g) 2 CO2(g) K = 2 x 1022

You would predict that under

most conditions there would
be very little CO left.

Equilibrium position likely to lie

well over to right

KHS Chemistry Unit 2.2 Equilibrium Chemistry 11

Equilibrium Constant 5

Intermediate K 2BrCl(g) Br2(g) + Cl 2(g) K=5

You would predict that under

most conditions there would
be reasonable amounts of
BrCl, Br2 and Cl2.

Equilibrium position likely to lie

somewhere in the middle

KHS Chemistry Unit 2.2 Equilibrium Chemistry 12

Equilibrium Position and K
Consider the chromate/dichromate equilibrium

2CrO42- (aq) + 2H+ Cr2 O7 2-(aq) + H2O(l)

H+ H+

KHS Chemistry Unit 2.2 Equilibrium Chemistry 13

Equilibrium Position and K
2CrO42- (aq) + 2H+ Cr2 O7 2-(aq) + H2O(l)

Visually, we would see the mixture change from yellow to

orange.

We would say that the equilibrium has shifted to the right.

We might talk in terms of [Products] increasing

[Reactants] decreasing

Does this mean that K has increased, since

KHS Chemistry Unit 2.2 Equilibrium Chemistry 14

Equilibrium Position and K
2CrO42- (aq) + 2H+ Cr2 O7 2-(aq) + H2O(l)

In fact, K is not just about CrO42- and Cr2O72- :

[H2O] will be so large that any

change will be negligible
[H+] will have increased

Overall the ratio of products to reactants will remain the same.

Kc is a constant that is unaffected by changes in concentration.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 15

Effect of Temperature 1
N2O4 2NO2

KHS Chemistry Unit 2.2 Equilibrium Chemistry 16

Effect of Temperature 2
N2O4 2NO2
Low temperature favours the exothermic reaction:

N2O4 2NO2

The equilibrium position will shift to the left.

N2O4 2NO2
[Reactants] [Products]
increases decreases

As temperature drops the value of K will decrease. K is

temperature dependent.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 17

Effect of Temperature 3
N2O4 2NO2
High temperature favours the endothermic reaction:

N2O4 2NO2

The equilibrium position will shift to the right.

N2O4 2NO2
[Reactants] [Products]
decreases increases

As temperature drops the value of K will increase. K is

temperature dependent.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 18

Effect Of a Catalyst
A catalyst lowers the activation energy barrier for a reaction.

A catalyst speeds up a reaction.

A catalyst lowers the activation energy for the forward and the
backward reaction equally.

Therefore, a catalyst will decrease the time taken to reach equilibrium.

A catalyst does not effect the composition of the equilibrium mixture.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 19

Effective Concentrations
In some circumstances chemicals don’t ‘punch their weight’

e.g. 0.1 M Na Cl has a conductivity of 80.

0.2 M NaCl has twice as many ions but its
conductivity is 120 not 160

At the higher concentration, there are more and stronger interactions

between ions and their conductivity is reduced as a result.

The 0.2 M Na Cl is behaving as if it has an effective concentration of

0.15 M.
Though beyond the scope of the Advanced Higher Course, we need
The concept of effective concentration to explain units of K.
KHS Chemistry Unit 2.2 Equilibrium Chemistry 20
Units for Equilibrium Constants
Strictly speaking K is based on effective concentrations
present in the equilibrium mixture rather than actual
concentrations.

A value known as the activity, a, is used, which is a measure of the

effective concentration relative to a standard concentration.

effective [P] a(P)q

a(P) = standard [P] Kc = s
a(R)

KHS Chemistry Unit 2.2 Equilibrium Chemistry 21

Units for Equilibrium Constants
effective [P]
a(P) = standard [P] a(P)q
Kc = s
a(R)
The significant point is that activities involve dividing a
concentration in mol l-1 by another concentration in mol l-1.

Activities, a, are without units and so, therefore, is K.

Standard concentration is 1 mol l-1 and at low concentrations,

effective concentration is very close to actual concentration.

This allows us to use actual concentrations to calculate K - but

assigning units to K is pointless ( and wrong!).

KHS Chemistry Unit 2.2 Equilibrium Chemistry 22

Gas Equilibria
Though we could use moles l-1 to describe the
‘concentration’ of a gas, it’s not really satisfactory.

Physicists will know that (for an ideal gas):

PV = n R T
where, P = pressure
V = volume
n = moles of gas
R = a constant
T = temperature

KHS Chemistry Unit 2.2 Equilibrium Chemistry 23

Gas Equilibria
PV = n R T
From this equation we can see that:

P is proportional to n / V

Therefore, we can use pressures instead of concentrations in

our equilibrium expression.

But there is only one value for pressure, even if there is a

mixture of gases.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 24

Partial Pressures
However, pressure depends on a number of gas particles
pushing against a surface.
The pressure of a mixture of gases is due to the total number
of particles present.
The pressure exerted by a particular group of
particles is called their partial pressure and is:

Partial pressure = (particles in group/

particles in total) x P

Partial pressures, or even moles, of gases can

be used in to derive equilibrium constants.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 25

Special - Solubility Products
The dissolving of a substance can be considered a
reversible reaction:

Ba2+SO4 2-(s) + aq Ba2+(aq) + SO4 2-(aq)

[ Ba2+ ][ SO42- ] [Ba2+SO42-] has activity of 0

K = 2+ 2- [aq] remains constant
[ Ba SO4 ][ aq ]
2+ 2-
Ksp = [ Ba ][ SO4 ]

This gives a much better measure of solubility.

KHS Chemistry Unit 2.2 Equilibrium Chemistry 26

Special - Partition Coefficient
When a solute is soluble in two different
immiscible solvents, the following
equilibrium is set up:

[ solute ] in solvent A
K =
[ solute ] in solvent B

Applications of partition coefficients

include:
solvent extraction
paper chromatography
gas chromatography

KHS Chemistry Unit 2.2 Equilibrium Chemistry 27

Equilibrium
Chemistry

End of Topic 2 - part 1

KHS Chemistry Unit 2.2 Equilibrium Chemistry 28