7. Equilibria All reversible reactions reach an dynamic equilibrium state.

Many reactions are reversible

The term dynamic means both forward and backward
N2 + 3H2 2NH3 reactions are occurring simultaneously

Two features of Dynamic Equilibrium We use the expression ‘position of equilibrium’ to

1. Forward and backward reactions are describe the composition of the equilibrium mixture.
occurring at equal rates.
If the position of equilibrium favours the reactants
2. The concentrations of reactants and (also described as “towards the left”) then the
products stays constant equilibrium mixture will contain mostly reactants.

Le Chatelier’s Principle

We use Le Chatelier’s principle to work out how Le Chatelier’s principle states that if an external
changing external conditions such as temperature condition is changed the equilibrium will shift to
and pressure affect the position of equilibrium oppose the change (and try to reverse it).

Effect of Temperature on equilibrium

Typical Exam question: What effect would increasing
If temperature is increased the equilibrium will
temperature have on the yield of ammonia?
shift to oppose this and move in the
endothermic direction to try and reduce the N2 + 3H2 2NH3 H = -ve exo
temperature by absorbing heat.
Exam level answer : must include bold points
And its reverse
If temperature is increased the equilibrium will
shift to oppose this and move in the endothermic,
If temperature is decreased the equilibrium
backwards direction to try to decrease
will shift to oppose this and move in the
temperature. The position of equilibrium will shift
exothermic direction to try and increase the
towards the left, giving a lower yield of ammonia.
temperature by giving out heat.

Low temperatures may give a higher yield of product but will also result in slow
rates of reaction. Often a compromise temperature is used that gives a
reasonable yield and rate
Effect of Pressure on equilibrium
Typical Exam question: What effect would increasing
Increasing pressure will cause the equilibrium to shift
pressure have on the yield of methanol?
towards the side with fewer moles of gas to oppose
the change and thereby reduce the pressure. CO (g) + 2H2(g) CH3OH (g)

And its reverse

Exam level answer : must include bold points
If pressure is increased the equilibrium will shift
Decreasing pressure will cause the equilibrium to shift to oppose this and move towards the side with
towards the side with more moles of gas to oppose fewer moles of gas to try to reduce the
the change and thereby increase the pressure. pressure . The position of equilibrium will shift
towards the right because there are 3 moles of
If the number of moles of gas is the same on both gas on the left but only 1 mole of gas on the right,
sides of the equation then changing pressure will have giving a higher yield of methanol.
no effect on the position of equilibrium
H2 + Cl2 2HCl

Increasing pressure may give a higher yield of product and will produce a faster
rate. Industrially high pressures are expensive to produce ( high electrical
energy costs for pumping the gases to make a high pressure) and the
equipment is expensive (to contain the high pressures)

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Effect of Concentration on equilibrium

I2 + 2OH- I- + IO- + H2O Increasing the concentration OH- ions causes the equilibrium to shift to oppose this
and move in the forward direction to remove and decrease the concentration of OH-
browncolourless ions. The position of equilibrium will shift towards the right, giving a higher yield of I-
and IO-. ( The colour would change from brown to colourless)
Adding H+ ions reacts with the OH- ions and reduces their concentration so the
equilibrium shifts back to the left giving brown colour.

Effect of catalysts on equilibrium

A catalyst has no effect on the position of equilibrium, but it will speed up the rate at which the
equilibrium is achieved.

It does not effect the position of equilibrium because it speeds up the rates of the forward and
backward reactions by the same amount.

Importance of equilibrium to industrial processes

You should be able to apply the above ideas to given reactions
Common examples
Contact process
Haber process
Stage 1 S (s) + O2 (g)  SO2 (g)
N2 + 3H2 2NH3 H = -ve exo
Stage 2 SO2 (g) + ½ O2 (g) SO3 (g) H = -98 kJ mol-1
T= 450oC, P= 200 – 1000 atm, catalyst = iron
T= 450oC, P= 1 or 2 atm, catalyst = V2O5
Low temp gives good yield but slow rate:
Low temp gives good yield but slow rate: compromise moderate
compromise temp used
temp used
High pressure gives good yield and high rate: too
High pressure only gives slightly better yield and high rate: too
high a pressure would lead to too high energy costs
high a pressure would lead to too high energy costs for pumps
for pumps to produce the pressure
to produce the pressure

In all cases catalysts speeds up the rate allowing lower temp to be used (and hence lower energy costs) but have
no effect on equilibrium

In all cases high pressure leads to too high energy costs for pumps to produce the pressure and too high
equipment costs to have equipment that can withstand high pressures.

Recycling unreacted reactants back into the reactor can improve the overall yields of all these processes
Both methanol and ethanol can be used as fuels
Equilibrium Equations
Equilibrium constant Kc Kc = equilibrium constant
Example 1
For a generalised reaction
mA + nB pC + qD [ C]p [D]q N2 (g) + 3H2 (g) 2 NH3 (g)
Kc=
m,n,p,q are the stoichiometric balancing [ A]m [B]n
numbers [NH3 (g)]2
Kc=
A,B,C,D stand for the chemical formula [N2 (g)] [H2 (g)]3
[ ] means the equilibrium concentration

The unit of Kc changes and depends on the equation.

Working out the unit of Kc

Put the unit of concentration (mol dm -3) into the Kc equation
Cancel out
[NH3 (g)]2 [mol dm-3]2 units 1
Unit = [mol dm-3]-2
Kc= Unit = Unit =
[N2 (g) ] [H2 (g)]3 [mol dm-3]2
[mol dm-3] [mol dm-3]3
Unit = mol-2 dm+6

Example 2: writing Kc expression

Working out the unit
H2 (g) +Cl2 (g) 2HCl (g) [HCl (g)]2
Kc= [mol dm-3]2
Unit Kc= = no unit
[H2 (g) ] [Cl2 (g)]
[mol dm-3] [mol dm-3]

Calculating Kc Calculating the moles at equilibrium

Most questions first involve having to work out the equilibrium moles and moles of reactant at equilibrium
then concentrations of the reactants and products. = initial moles – moles reacted
Usually the question will give the initial amounts (moles) of the reactants,
and some data that will help you work out the equilibrium amounts. moles of product at equilibrium
= initial moles + moles formed

Example 3
H2 (g) +Cl2 (g) 2HCl (g)
For the following equilibrium
In a container of volume 600cm 3 there were initially 0.5mol of H2 and 0.6 mol of Cl2.
At equilibrium there were 0.2 moles of HCl. Calculate Kc

H2 Cl2 HCl
It is often useful Using the balanced equation if 0.2 moles of
Initial moles 0.5 0.6 0
to put the mole HCl has been formed it must have used up
data in a table. 0.1 of Cl2 and 0.1 moles of H2 (as 1:2 ratio)
Equilibrium moles 0.2

Work out the moles at equilibrium for the reactants moles of reactant at equilibrium = initial moles – moles reacted

moles of hydrogen at equilibrium = 0.5 – 0.1 = 0.4 moles of chlorine at equilibrium = 0.6 – 0.1 = 0.5

H2 Cl2 HCl If the Kc has no unit then there are equal numbers of
reactants and products. In this case you do not have to
Initial moles 0.5 0.6 0 divide by volume to work out concentration and equilibrium
moles could be put straight into the kc expression
Equilibrium moles 0.4 0.5 0.2

Equilibrium 0.4/0.6 0.5/0.6 0.2/0.6

[HCl (g)]2
concentration (M) =0.67 =0.83 =0.33 Kc=
[H2 (g) ] [Cl2 (g)]

Work out the

Finally put
Kc
= 0.332 = 0.196 no unit
concentrations into 0.67x0.83
equilibrium
conc = moles/ vol (in dm3) Kc expression
concentrations

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Example 4
N2 (g) + 3H2 (g ) 2 NH3 (g)
For the following equilibrium
Initially there were 1.5 moles of N2 and 4 mole of H2, in a 1.5 dm3 container. At
equilibrium 30% of the Nitrogen had reacted. Calculate Kc

N2 H2 NH3
30% of the nitrogen had reacted = 0.3 x1.5 = 0.45 moles reacted.
Initial moles 1.5 4.0 0 Using the balanced equation 3 x 0.45 moles of H 2 must have
reacted and 2x 0.45 moles of NH3 must have formed
Equilibrium moles

Work out the moles at equilibrium for the reactants and products
moles of reactant at equilibrium = initial moles – moles reacted

moles of nitrogen at equilibrium = 1.5 – 0.45 = 1.05 moles of hydrogen at equilibrium =4.0 – 0.45 x3 = 2.65

moles of product at equilibrium = initial moles + moles formed

moles of ammonia at equilibrium = 0 + (0.45 x 2) = 0.9

N2 H2 NH3
Finally put concentrations into Kc expression
Initial moles 1.5 4.0 0

Equilibrium moles 1.05 2.65 0.9 [NH3 (g)]2

Kc=
Equilibrium 1.05/1.5 2.65/1.5 0.9/1.5 [N2 (g) ] [H2 (g)]3
concentration (M) =0.7 =1.77 =0.6

Kc
= 0.62 = 0.0927 mol-2 dm+6
Work out the 0.7x1.773
equilibrium
conc = moles/ vol (in dm3)
concentrations

Effect of changing conditions on value of Kc

Kc only changes with temperature.
The larger the Kc the greater the amount of products. It does not change if pressure or
If Kc is small we say the equilibrium favours the reactants concentration is altered.
A catalyst also has no effect on Kc
Effect of Temperature on position of equilibrium and Kc

In this equilibrium which is exothermic in the forward direction

Both the position of equilibrium
and the value of Kc will change it N2 (g) + 3H2 (g ) 2 NH3 (g)
temperature is altered
If temperature is increased the reaction will shift to oppose the change and
move in the backwards endothermic direction. The position of equilibrium
shifts left. The value of Kc gets smaller as there are fewer products.

Effect of Pressure on position of equilibrium and Kc

The position of equilibrium will In this equilibrium which has fewer moles of gas on the product side
change it pressure is altered but N2 (g) + 3H2 (g ) 2 NH3 (g)
the value of Kc stays constant as
Kc only varies with temperature If pressure is increased the reaction will shift to oppose the change and
move in the forward direction to the side with fewer moles of gas. The
position of equilibrium shifts right. The value of Kc stays the same though as
only temperature changes the value of Kc.

Catalysts have no effect on the value of Kc or the position of equilibrium

as they speed up both forward and backward rates by the same amount.

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Calculating the amounts of the equilibrium mixture from Kc

Using algebra it is possible to work out the amounts of each

component in an equilibrium mixture using the value of Kc

Example 5

For the following equilibrium H2 (g) + Br2 (l) 2HBr (g)

If 0.200 mol of H2 and 0.200 mol of Br2 are mixed and allowed to reach equilibrium. If Kc = 0.210
what are the equilibrium amounts of each substance.

[HBr (g)]2 Make x = moles of H2 that have reacted

Kc=
[H2 (g) ] [Br2 (g)] at equilibrium
V = volume of container

(2x/V)2 This reaction is equimolar (same number

0.21 = (0.2-x)/V . (0.2-x)/V of moles of reactant as products) so it is
possible to cancel out the volume V
(2x)2
0.21 =
(0.2-x) . (0.2-x)

(2x)2
0.21 = Square root both sides
(0.2-x)2

2x
√0.21 = Rearrange to give x
0.2-x

0.458(0.2-x) = 2x
This example has been carefully set up to
0.0917 - 0.458x = 2x avoid the formation of a quadratic equation.
0.0917 = 2x + 0.458x It is not on the A-level syllabus to solve
quadratic equations.
x = 0.0917/2.458
x = 0.0373

So at equilibrium
Moles of H2 = 0.2000- 0.0373 Moles of Br2 = 0.2000- 0.0373 Moles of HBr = 2x 0.0373
= 0.163 mol = 0.163mol = 0.0746mol
 Partial Pressures and Kp
If a reaction contains gases an alternative equilibrium expression can be
set up using the partial pressures of the gases instead of concentrations

Partial Pressure

The partial pressure of a gas in a mixture is the pressure

that the gas would have if it alone occupied the volume partial pressure = mole fraction x total pressure
occupied by the whole mixture. of gas 1 of gas 1

If a mixture of gases contains 3 different gases then the p1 = x1 P

total pressure will equal the 3 partial pressure added
together
P =p1 + p2 + p3

mole fraction
mole fraction = number of moles of a gas
total number of moles of all gases

For a 3 part mixture

x1 = y1
y1+y2 +y3

Example 6 : A mixture contains 0.2 moles N2, 0.5 moles O2 and 1.2 moles of CO2. If the total pressure is
3kPa. What are the partial pressures of the 3 gases?

Total moles of gas = 0.5 + 1.2+ 0.2

= 1.9

mole fraction = 0.2/1.9 mole fraction = 0.5/1.9 mole fraction = 1.2/1.9

of N2 =0.105 of O2 =0.263 of CO2 =0.632

Partial pressure =0.105x 3 Partial pressure = 0.263 x 3 Partial pressure = 0.632 x 3

of N2 =0.315 of O2 =0.789 of CO2 =1.896

Writing an expression for Kp

N2 (g) + 3H2 (g) 2 NH3 (g) p means the partial pressure of that gas

p 2 NH3 Kp = equilibrium constant

Kp=
p N2 p 3 H2 Only include gases in the Kp expression. Ignore
solids, liquids, and aqueous substances.

Working out the unit of Kp

Put the unit of pressure(kPa) into the Kp equation

kPa2 However, if the equation is

2 NH Unit = written the other way round, the
p 3 (g) kPa kPa3
Kp= value of Kp will be the inverse of
pN2 (g) p 3H 2 (g) above and the units will be
1
Cancel out units Unit = kPa2.
kPa2 It is important therefore to write
an equation when quoting
Unit = kPa-2 values of Kp.
Example 7
N2 (g) + 3H2 (g ) 2 NH3 (g)
For the following equilibrium

1 mole of N2 and 3 moles of H2 are added together and the mixture is allowed to reach equilibrium. At
equilibrium 20% of the N2 has reacted. If the total pressure is 2kPa what is the value of Kp?

N2 H2 NH3
20% of the nitrogen had reacted = 0.2 x1.0 = 0.2 moles reacted.
Initial moles 1.0 3.0 0 Using the balanced equation 3 x 0.2 moles of H2 must have
reacted and 2x 0.2 moles of NH3 must have formed
Equilibrium moles

Work out the moles at equilibrium for the reactants and products
moles of reactant at equilibrium = initial moles – moles reacted

moles of nitrogen at equilibrium = 1.0 – 0.2 = 0.8 moles of hydrogen at equilibrium =3.0 – 0.20 x3 = 2.40

moles of product at equilibrium = initial moles + moles formed

moles of ammonia at equilibrium = 0 + (0.2 x 2) = 0.4

N2 H2 NH3
Finally put concentrations into Kp expression
Initial moles 1.0 3.0 0

Equilibrium moles 0.80 2.40 0.40 p 2 NH3 (g)

Kp=
Mole fractions 0.8/3.6 2.40/3.6 0.40/3.6 pN2 (g) p 3H2 (g)
=0.222 =0.667 =0.111

Partial pressure 0.222 0.667 x2 0.111 x2 Kp = 0.2222 = 0.0469 kPa-2

x2 = =1.33 = 0.222 0.444x1.333
0.444

Heterogeneous equilibria for Kp

Kp expressions only contain gaseous substances. Any substance with another state is left out
CaCO3 (s) CaO (s) + CO2 (g)

Kp =p CO2
Unit kPa
Effect of changing conditions on value of Kc or Kp
Kc and Kp only change with temperature.
The larger the Kc the greater the amount of products. It does not change if pressure or
If Kc is small we say the equilibrium favours the reactants concentration is altered.
A catalyst also has no effect on Kc or Kp
Effect of Temperature on position of equilibrium and Kc
In this equilibrium which is exothermic in the forward direction
Both the position of equilibrium
and the value of Kc or Kp will N2 (g) + 3H2 (g ) 2 NH3 (g)
change it temperature is altered If temperature is increased the reaction will shift to oppose the change and
move in the backwards endothermic direction. The position of equilibrium
shifts left. The value of Kc gets smaller as there are fewer products.

Effect of Pressure on position of equilibrium and Kp

In this equilibrium which has fewer moles of gas on the product side
The position of equilibrium will
change it pressure is altered but N2 (g) + 3H2 (g ) 2 NH3 (g)
the value of Kp stays constant as If pressure is increased the reaction will shift to oppose the change and
Kp only varies with temperature move in the forward direction to the side with fewer moles of gas. The
position of equilibrium shifts right. The value of Kp stays the same though
as only temperature changes the value of Kp.

Increasing pressure does not change Kp. p 2 NH3

The increased pressure increases the pressure terms on Kp=
p N2 p 3 H2
bottom of Kp expression more than the top. The system is
now no longer in equilibrium so the equilibrium shifts to the x 2 NH3 . P2
right increasing mole fractions of products and decreases Kp= Where P is total
the mole fractions of reactants. The top of Kp expression x N2.P x3 H 3 pressure and x
2.P
therefore increases and the bottom decreases until the mole fraction
original value of Kp is restored x 2 NH3 . P2
Kp=
x N2 x3 H2. P4

N Goalby chemrevise.org
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Ionic Equilibria
Bronsted-Lowry Definition of acid Base behaviour

A Bronsted-Lowry acid is defined as a substance that can donate a proton.

A Bronsted-Lowry base is defined as a substance that can accept a proton.

HCl (g) + H2O (l)  H3O+ (aq) + Cl- (aq)

Each acid is linked to a conjugate base on
acid base acid base the other side of the equation.

Calculating pH
pH = - log [H+] Where [H+] is the concentration of hydrogen ions in the solution.

The concentration of hydrogen ions in a monoprotic strong acid

Strong acids completely dissociate
will be the same as the concentration of the acid.

For HCl and HNO3 the [H+(aq)] will be the same as the
original concentration of the acid. Always give pH values to 2d.p. In the exam
For 0.1M HCl the pH will be –log[0.1] =1.00