FURTHER TOPICS ON

CHEMICAL
EQUILIBRIUM

KNOCKHARDY PUBLISHING

2015

SPECIFICATIONS

KNOCKHARDY PUBLISHING

CHEMICAL EQUILIBRIUM (2)

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CHEMICAL EQUILIBRIUM (2)

CONTENTS
The Equilibrium Law
The equilibrium constant Kc
Calculations involving Kc
Calculations involving gases
Mole fraction and partial pressure calculations
Calculations involving Kp

THE EQUILIBRIUM LAW

Simply states
If the concentrations of all the substances present at equilibrium are
raised to the power of the number of moles they appear in the equation,
the product of the concentrations of the products divided by the product
of the concentrations of the reactants is a constant, provided the
temperature remains constant
There are several forms of the constant; all vary with temperature.

Kc

the equilibrium values are expressed as concentrations in mol dm-3

Kp

the equilibrium values are expressed as partial pressures

The partial pressure expression can be used for reactions involving gases

THE EQUILIBRIUM CONSTANT Kc

for an equilibrium reaction of the form...

aA

bB

then (at constant temperature)

cC

dD

[C]c . [D]d = a constant, (Kc)

[A]a . [B]b

where

[ ]
Kc

denotes the equilibrium concentration in mol dm-3

is known as the Equilibrium Constant

THE EQUILIBRIUM CONSTANT Kc

for an equilibrium reaction of the form...

aA

bB

then (at constant temperature)

cC

dD

[C]c . [D]d = a constant, (Kc)

[A]a . [B]b

where

[ ]
Kc

denotes the equilibrium concentration in mol dm-3

is known as the Equilibrium Constant

VALUE OF Kc
AFFECTED by

a change of temperature

NOT AFFECTED by

a change in concentration of reactants or products

a change of pressure
adding a catalyst

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units
Example 1
One mole of ethanoic acid reacts with one mole of ethanol at 298K. When equilibrium is
reached it is found that two thirds of the acid has reacted. Calculate the value of Kc.

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units
Example 1
One mole of ethanoic acid reacts with one mole of ethanol at 298K. When equilibrium is
reached it is found that two thirds of the acid has reacted. Calculate the value of Kc.
CH3COOH(l) + C2H5OH(l)

CH3COOC2H5(l) +

H2O(l)

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units
Example 1
One mole of ethanoic acid reacts with one mole of ethanol at 298K. When equilibrium is
reached it is found that two thirds of the acid has reacted. Calculate the value of Kc.
CH3COOH(l) + C2H5OH(l)
moles (initially)
moles (at equilibrium)

1
1 - 2/3

Initial moles of CH3COOH = 1

For every CH3COOH that reacts;

1
1 - 2/3

moles reacted = 2/3

CH3COOC2H5(l) +

H2O(l)

0
2/3

0
2/3

equilibrium moles of CH3COOH = 1/3

a similar number of C2H5OHs react (equil moles = 1 - 2/3)

a similar number of CH3COOC2H5s are produced
a similar number of H2Os are produced

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units
Example 1
One mole of ethanoic acid reacts with one mole of ethanol at 298K. When equilibrium is
reached it is found that two thirds of the acid has reacted. Calculate the value of Kc.
CH3COOH(l) + C2H5OH(l)
moles (initially)
moles (at equilibrium)
equilibrium concs.

1
1 - 2/3
1/3 / V

1
1 - 2/3
1/3 / V

V = volume (dm3) of the equilibrium mixture

CH3COOC2H5(l) +
0
2/3
2/3 / V

H2O(l)
0
2/3
2/3 / V

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units
Example 1
One mole of ethanoic acid reacts with one mole of ethanol at 298K. When equilibrium is
reached it is found that two thirds of the acid has reacted. Calculate the value of Kc.
CH3COOH(l) + C2H5OH(l)
moles (initially)
moles (at equilibrium)
equilibrium concs.

1
1 - 2/3
1/3 / V

1
1 - 2/3
1/3 / V

V = volume (dm3) of the equilibrium mixture

Kc

[CH3COOC2H5] [H2O]
[CH3COOH] [C2H5OH]

CH3COOC2H5(l) +
0
2/3
2/3 / V

H2O(l)
0
2/3
2/3 / V

CALCULATIONS INVOLVING Kc
construct the balanced equation, including state symbols (aq), (g) etc.
determine the number of moles of each species at equilibrium
divide moles by volume (in dm3) to get the equilibrium concentrations in mol dm-3
(If no volume is quoted, use a V; it will probably cancel out)
from the equation constructed in the first step, write out an expression for Kc.
substitute values from third step and calculate the value of Kc with any units
Example 1
One mole of ethanoic acid reacts with one mole of ethanol at 298K. When equilibrium is
reached it is found that two thirds of the acid has reacted. Calculate the value of Kc.
CH3COOH(l) + C2H5OH(l)
moles (initially)
moles (at equilibrium)
equilibrium concs.

1
1 - 2/3
1/3 / V

CH3COOC2H5(l) +

1
1 - 2/3
1/3 / V

0
2/3
2/3 / V

0
2/3
2/3 / V

V = volume (dm3) of the equilibrium mixture

Kc

[CH3COOC2H5] [H2O]
[CH3COOH] [C2H5OH]

2/3 / V . 2/3 / V
1/3 / V . 1/3 / V

H2O(l)

CALCULATIONS INVOLVING Kc
Example 2
Consider the equilibrium
P + 2Q
R + S
(all species are aqueous)
One mole of P and one mole of Q are mixed. Once equilibrium has been achieved 0.6
moles of P are present. How many moles of Q, R and S are present at equilibrium ?

P
1
06

Initial moles
At equilibrium

2Q
1
02

(04 reacted) (2 x 04 reacted)

1- 06 remain
1- 08 remain

Explanation

R
0
04

S
0
04

(get 1 R and 1 S for every P that reacts)

if 0.6 mol of P remain of the original 1 mol, 0.4 mol have reacted
the equation states that 2 moles of Q react with every 1 mol of P
this means that 0.8 (2 x 0.4) mol of Q have reacted, leaving 0.2 mol
one mol of R and S are produced from every mol of P that reacts
this means 0.4 mol of R and 0.4 mol of S are present at equilibrium

CALCULATIONS INVOLVING GASES

Method
carried out in a similar way to those involving concentrations
one has the choice of using Kc or Kp for the equilibrium constant
when using Kp only take into account gaseous species for the expression
use the value of the partial pressure of any gas in the equilibrium mixture
pressure is usually quoted in Nm-2 or Pa - atmospheres are sometimes used
as with Kc, the units of the constant Kp depend on the stoichiometry of the reaction

CALCULATIONS INVOLVING GASES

Method
carried out in a similar way to those involving concentrations
one has the choice of using Kc or Kp for the equilibrium constant
when using Kp only take into account gaseous species for the expression
use the value of the partial pressure of any gas in the equilibrium mixture
pressure is usually quoted in Nm-2 or Pa - atmospheres are sometimes used
as with Kc, the units of the constant Kp depend on the stoichiometry of the reaction

USEFUL RELATIONSHIPS
total pressure

sum of the partial pressures

partial pressure

total pressure x mole fraction

mole fraction

number of moles of a substance

number of moles of all substances present

MOLE FRACTION AND PARTIAL PRESSURE

Example

A mixture of 16g of O2 and 42g of N2 , exerts a total pressure of

20000 Nm-2. What is the partial pressure of each gas ?

MOLE FRACTION AND PARTIAL PRESSURE

Example

A mixture of 16g of O2 and 42g of N2 , exerts a total pressure of

20000 Nm-2. What is the partial pressure of each gas ?

moles of O2
moles of N2
total moles

= mass / molar mass

= mass / molar mass
= 0.5 + 1.5

= 16g / 32g
= 42g / 28g

= 0.5 mol
= 1.5 mol
= 2.0 mol

MOLE FRACTION AND PARTIAL PRESSURE

Example

A mixture of 16g of O2 and 42g of N2 , exerts a total pressure of

20000 Nm-2. What is the partial pressure of each gas ?

moles of O2
moles of N2
total moles

= mass / molar mass

= mass / molar mass
= 0.5 + 1.5

mole fraction of O2
mole fraction of N2
sum of mole fractions

= 16g / 32g
= 42g / 28g

= 0.5 / 2
= 1.5 / 2
= 0.75 + 0.25

= 0.5 mol
= 1.5 mol
= 2.0 mol

= 0.25
= 0.75
= 1 (sum should always be 1)

MOLE FRACTION AND PARTIAL PRESSURE

Example

A mixture of 16g of O2 and 42g of N2 , exerts a total pressure of

20000 Nm-2. What is the partial pressure of each gas ?

moles of O2
moles of N2
total moles

= mass / molar mass

= mass / molar mass
= 0.5 + 1.5

= 16g / 32g
= 42g / 28g

mole fraction of O2
mole fraction of N2
sum of mole fractions

= 0.5 / 2
= 1.5 / 2
= 0.75 + 0.25

partial pressure of O2

= mole fraction x total pressure

= 0.25
= 0.75
= 1

= 0.25 x 20000 Nm-2

partial pressure of N2

= 0.5 mol
= 1.5 mol
= 2.0 mol

= 5000 Nm-2

= mole fraction x total pressure

= 0.75 x 20000 Nm-2

= 15000 Nm-2

MOLE FRACTION AND PARTIAL PRESSURE

Example

A mixture of 16g of O2 and 42g of N2 , exerts a total pressure of

20000 Nm-2. What is the partial pressure of each gas ?

moles of O2
moles of N2
total moles

= mass / molar mass

= mass / molar mass
= 0.5 + 1.5

= 16g / 32g
= 42g / 28g

mole fraction of O2
mole fraction of N2
sum of mole fractions

= 0.5 / 2
= 1.5 / 2
= 0.75 + 0.25

partial pressure of O2

= mole fraction x total pressure

= 0.25
= 0.75
= 1

= 0.25 x 20000 Nm-2

partial pressure of N2

= 0.5 mol
= 1.5 mol
= 2.0 mol

= 5000 Nm-2

= mole fraction x total pressure

= 0.75 x 20000 Nm-2

= 15000 Nm-2

CALCULATIONS INVOLVING Kp
Example

When nitrogen (1 mole) and hydrogen (3 moles) react at constant

temperature at a pressure of 8 x 106 Pa, the equilibrium mixture
was found to contain 0.7 moles of ammonia. Calculate Kp .

CALCULATIONS INVOLVING Kp
Example

When nitrogen (1 mole) and hydrogen (3 moles) react at constant

temperature at a pressure of 8 x 106 Pa, the equilibrium mixture
was found to contain 0.7 moles of ammonia. Calculate Kp .

moles (initially)
moles (equilibrium)

N2(g)
1
1-x

3H2(g)
3
3 - 3x

2NH3(g)
0
2x
(x moles of N2 reacted)

CALCULATIONS INVOLVING Kp
Example

When nitrogen (1 mole) and hydrogen (3 moles) react at constant

temperature at a pressure of 8 x 106 Pa, the equilibrium mixture
was found to contain 0.7 moles of ammonia. Calculate Kp .

moles (initially)
moles (equilibrium)
mole fractions
partial pressures

N2(g)
1
1-x

3H2(g)
3
3 - 3x

2NH3(g)
0
2x
(x moles of N2 reacted)

(1-x)/(4-2x)

(3-3x)/(4-2x)

2x/(4-2x)

P.(1-x)/(4-2x)

P.(3-3x)/(4-2x)

P.2x/(4-2x)

(total moles = 4 - 2x)

(total pressure = P )

CALCULATIONS INVOLVING Kp
Example

When nitrogen (1 mole) and hydrogen (3 moles) react at constant

temperature at a pressure of 8 x 106 Pa, the equilibrium mixture
was found to contain 0.7 moles of ammonia. Calculate Kp .

moles (initially)
moles (equilibrium)
mole fractions
partial pressures

N2(g)
1
1-x

3H2(g)
3
3 - 3x

2NH3(g)
0
2x
(x moles of N2 reacted)

(1-x)/(4-2x)

(3-3x)/(4-2x)

2x/(4-2x)

P.(1-x)/(4-2x)

P.(3-3x)/(4-2x)

P.2x/(4-2x)

at equilibrium there are 0.7 moles of ammonia, so 2x = 0.7

the total pressure (P) = 8 x 106 Pa.

and

(total moles = 4 - 2x)

(total pressure = P )

x = 0.35

CALCULATIONS INVOLVING Kp
Example

When nitrogen (1 mole) and hydrogen (3 moles) react at constant

temperature at a pressure of 8 x 106 Pa, the equilibrium mixture
was found to contain 0.7 moles of ammonia. Calculate Kp .
N2(g)
1
1-x

moles (initially)
moles (equilibrium)
mole fractions
partial pressures

3H2(g)
3
3 - 3x

2NH3(g)
0
2x
(x moles of N2 reacted)

(1-x)/(4-2x)

(3-3x)/(4-2x)

2x/(4-2x)

P.(1-x)/(4-2x)

P.(3-3x)/(4-2x)

P.2x/(4-2x)

at equilibrium there are 0.7 moles of ammonia, so 2x = 0.7

the total pressure (P) = 8 x 106 Pa.
applying the equilibrium law

Kp =

and

(PNH3)2
(PN2) . (PH2)3

(total moles = 4 - 2x)

(total pressure = P )

x = 0.35

with units of Pa-2

CALCULATIONS INVOLVING Kp
Example

When nitrogen (1 mole) and hydrogen (3 moles) react at constant

temperature at a pressure of 8 x 106 Pa, the equilibrium mixture
was found to contain 0.7 moles of ammonia. Calculate Kp .
N2(g)
1
1-x

moles (initially)
moles (equilibrium)
mole fractions
partial pressures

3H2(g)
3
3 - 3x

2NH3(g)
0
2x
(x moles of N2 reacted)

(1-x)/(4-2x)

(3-3x)/(4-2x)

2x/(4-2x)

P.(1-x)/(4-2x)

P.(3-3x)/(4-2x)

P.2x/(4-2x)

at equilibrium there are 0.7 moles of ammonia, so 2x = 0.7

the total pressure (P) = 8 x 106 Pa.
applying the equilibrium law

Kp =

and

(PNH3)2
(PN2) . (PH2)3

Substituting in the expression gives

Kp = 1.73 x 10-14 Pa-2

(total moles = 4 - 2x)

(total pressure = P )

x = 0.35

with units of Pa-2

FURTHER TOPICS ON

CHEMICAL
EQUILIBRIUM
THE
END

2015 JONATHAN HOPTON & KNOCKHARDY PUBLISHING