Equilibrium Law

• Deduce expressions for equilibrium constants in terms of

concentrations, Kc.
• Deduce expressions for equilibrium constants in terms of partial
pressures, Kp.
• Use the Kc and Kp expressions to carry out calculations.
• Use the terms mole fraction and partial pressure.
• Calculate the quantities present at equilibrium, given appropriate
data.
• State whether changes in temperature, concentration or pressure or
the presence of a catalyst affect the value of the equilibrium constant
for a reaction
Contents
INTRODUCTION

THE EQUILIBRIUM CONSTANT in terms of concentrations, Kc

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

THE EQUILIBRIUM CONSTANT in terms of pressure, Kp

Contents
INTRODUCTION

THE EQUILIBRIUM CONSTANT in terms of concentrations, Kc

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

THE EQUILIBRIUM CONSTANT in terms of pressure, Kp

 CHECK FOR UNDERSTANDING
1. What is Keq stands for?
2. How are we going to use the coefficients in the equilibrium equation
in the Keq expression?
3. Which physical state(s) that have a constant concentration in the
equilibrium equation?
Contents
INTRODUCTION

THE EQUILIBRIUM CONSTANT in terms of concentrations, Kc

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

THE EQUILIBRIUM CONSTANT in terms of pressure, 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 of 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 cC + dD

then (at constant temperature) [C] . [D]

= a constant, (Kc)
[A] . [B]

where [ ] denotes the equilibrium concentration in mol dm-3

Kc is known as the Equilibrium Constant

Example Fe3+(aq) + NCS¯(aq) FeNCS2+(aq)

[ FeNCS2+ ]
Kc =
with units of dm3 mol-1
[ Fe3+ ] [ NCS¯ ]
 THE EQUILIBRIUM CONSTANT Kc

for an equilibrium reaction of the form...

aA + bB cC + dD

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

[A]a . [B]b

where [ ] denotes the equilibrium concentration in mol dm-3

Kc 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
Contents
INTRODUCTION

THE EQUILIBRIUM CONSTANT in terms of concentrations, Kc

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

THE EQUILIBRIUM CONSTANT in terms of pressure, Kp

 LE CHATELIER’S PRINCIPLE

”When a change is applied to a system in dynamic equilibrium, the

system reacts in such a way as to oppose the effect of the change.”

Everyday example
A rose bush grows with increased vigour after it has been pruned.

Chemistry example
If you do something to a reaction that is in a state of equilibrium, the
equilibrium position will change to oppose what you have just done
 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

CONCENTRATION

The equilibrium constant is not affected by a change in concentration

at constant temperature.

To maintain the constant, the composition of the equilibrium mixture changes.

If you increase the concentration of a substance, the value of Kc will theoretically

be affected.

As it must remain constant at a particular temperature, the concentrations of

the other species change to keep the constant the same.
 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM
CONCENTRATION

example CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)

[CH3CH2OH] [CH3COOH]

increasing • will make the bottom line larger so Kc will be smaller

[CH3CH2OH]
• to keep it constant, some CH3CH2OH reacts with CH3COOH

• this reduces the value of the bottom line and increases the top

• eventually the value of the constant will be restored

 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM
CONCENTRATION

example CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)

[CH3CH2OH] [CH3COOH]

decreasing • will make the top line smaller, so Kc will be smaller

[H2O]
• some CH3CH2OH reacts with CH3COOH to replace the H2O

• more CH3COOC2H5 is also produced

• this reduces the value of the bottom line and increases the top
 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM
SUMMARY

REACTANTS PRODUCTS
THE EFFECT OF CHANGING THE CONCENTRATION ON THE POSITION OF EQUILIBRIUM
INCREASE CONCENTRATION OF A REACTANT EQUILIBRIUM MOVES TO THE RIGHT
DECREASE CONCENTRATION OF A REACTANT EQUILIBRIUM MOVES TO THE LEFT
INCREASE CONCENTRATION OF A PRODUCT EQUILIBRIUM MOVES TO THE LEFT

DECREASE CONCENTRATION OF A PRODUCT EQUILIBRIUM MOVES TO THE RIGHT

Predict the effect of increasing the concentration of O2 on the equilibrium position

2SO2(g) + O2(g) 2SO3(g) EQUILIBRIUM MOVES TO RHS

Predict the effect of decreasing the EQUILIBRIUM MOVES TO RHS

concentration of SO3 on the equilibrium position
 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

PRESSURE
When studying the effect of a change in pressure, we consider the number of gaseous molecules only.

The more particles you have in a given volume, the greater the pressure they exert.
If you apply a greater pressure they will become more crowded (i.e. they are under a greater stress).
However, if the system can change it will move to the side with fewer gaseous molecules - it is less
crowded.

No change occurs when equal numbers of gaseous molecules appear on both sides.
 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

PRESSURE

THE EFFECT OF PRESSURE ON THE POSITION OF EQUILIBRIUM

INCREASE PRESSURE MOVES TO THE SIDE WITH FEWER GASEOUS MOLECULES
DECREASE PRESSURE MOVES TO THE SIDE WITH MORE GASEOUS MOLECULES

Predict the effect of an increase of pressure on the equilibrium position of..

1. 2SO2(g) + O2(g) 2SO3(g) MOVES TO RHS (fewer gaseous molecules)

2. H2(g) + CO2(g) CO(g) + H2O(g) NO CHANGE (equal numbers on both sides)

 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

TEMPERATURE
• temperature is the only thing that can change the value of the equilibrium constant.
• altering the temperature affects the rate of both backward and forward reactions
• it alters the rates to different extents
• the equilibrium thus moves producing a new equilibrium constant.
• the direction of movement depends on the sign of the enthalpy change.
REACTION TYPE ΔH RELEASE OR ΔT INCREASE DECREASE
ABSORB ENERGY TEMPERATURE TEMPERATURE

EXOTHERMIC - RELEASE ENERGY TO THE SURROUNDING + TO THE LEFT TO THE RIGHT

ENDOTHERMIC + ABSORB ENERGY FROM THE SURROUNDING - TO THE RIGHT TO THE LEFT

Predict the effect of a temperature increase on the equilibrium position of...

1. H2(g) + CO2(g) CO(g) + H2O(g) DH = + 40 kJ moves to the RHS

2. 2SO2(g) + O2(g) 2SO3(g) DH = - 197.7 kJ moves to the LHS

 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)
i: 1 1 - -
r: 2/3 2/3 2/3 2/3
e: 1-2/3 1-2/3 2/3 2/3
Initial moles of CH3COOH = 1 moles reacted = 2/3 equilibrium moles of CH3COOH = 1/3
For every CH3COOH that reacts; a similar number of C2H5OH’s react (equilibrium moles = 1 - 2/3)
a similar number of CH3COOC2H5’s are produced
a similar number of H2O’s 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) CH3COOC2H5(l) + H2O(l) Kc = [CH3COOC2H5] [H2O]
i: 1 mol 1 mol - - [CH3COOH] [C2H5OH]
r: 2/3 mols 2/3 mols 2/3 mols 2/3 mols
= 2/3 / V . 2/3 / V
e: 1-2/3 mols 1-2/3 mols 2/3 mols 2/3 mols
Equilibrium : 1/3 / V . 1/3 / V
1/3 1/3 2/3 2/3
concs.
V V V V = 4
V = volume (dm3) of the equilibrium mixture
 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 + 2Q R + S
i: 1 mol 1 mol - -
r: (1 - 0.6 mols = 0.4 mols)
(2 x 0.4 mols = 0.8 mols) 0.4 mols 0.4 mols
e: 0.6 mols 0.2 mols 0.4 mols 0.4 mols

Explanation • 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
 TEST YOURSELF
1. 0,56 moles of NO2 are left to decompose in a vessel with a volume of 0,5 dm3. At equilibrium 0,48
moles of NO are formed.

What is the value of Kc?

Solution:

i: 0,56 mols - -
1
r:22 x 0,48 mols = 0,48 mols 0,48 mols x
2 0,48 mols = 0,24 mols
e: 0,08 mols 0,48 mols 0,24 mols
2 2
Kc = [NO] [O2] = (0,48 / 0,5) (0,24 / 0,5)- = 17,28 mol dm-3
[NO2] (0,08 / 0,5) 2
 TEST YOURSELF

Solutions:

i: 1.58 mols 4.76 mols -

r: 1 x 2 mols = 1 mol 3 x 2 mols = 3 mols
2.00 mols
2 2
e: 0.58 mols 1.74 mols 2.00 mols
Kc = [NH3] 2 = (2.00 / 0.75)
2
=
6
0,699 dm mol - 2
[N2] [H2] 3 (0.58 / 0.75) (1.74 / 0.75) 3
Contents
INTRODUCTION

THE EQUILIBRIUM CONSTANT in terms of concentrations, Kc

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

THE EQUILIBRIUM CONSTANT in terms of pressure, Kp

 Gas equilibria
For reactions involving gases, it is difficult to measure the
concentration of a particular gas. Instead the quantity of
each gas in an equilibrium mixture is described in terms of
the pressure that it exerts – the partial pressure.

partial pressure = mole fraction × total pressure

(pA) (xA) × (ptot)

The mole fraction is given by:

no. moles of species A

mole fraction of A =
total no. moles of all species
 The equilibrium constant, Kp
The equilibrium constant for gas phase reactions is called Kp.

aA(g) + bB(g) cC(g) + dD(g)

For this general equilibrium, Kp is given by:

p(C)c x p(D)d
Kp =
p(A)a x p(B)b

where p(A) means the partial pressure of species A

 Units of Kp
Like Kc, the units for Kp must be worked out for each reaction.
For the gas phase equilibrium:

A(g) + 2B(g) C(g) + D(g)

The equilibrium constant, Kp, is given by:

p(C) x p(D)
Kp =
p(A) x p(B)2

So units are calculated as follows:

(kPa) (kPa) 1
Kp = = = kPa–1
(kPa) (kPa) 2 kPa
 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 1 : A mixture of 16 g of O2 and 42 g of N2 , exerts a total pressure of 20.000 Nm-2.
What is the partial pressure of each gas ?
moles of O2 = mass / molar mass = 16 g / 32 g = 0.5 mol
moles of N2 = mass / molar mass = 42 g / 28 g = 1.5 mol
total moles = 0.5 + 1.5 = 2.0 mol

mole fraction of O2 = moles of O2 = 0.5 = 0.25

total moles 2.0
mole fraction of N2 = moles of N2 = 1.5 = 0.75
total moles 2.0
sum of mole fractions = 0.75 + 0.25 = 1 (sum should always be 1)
partial pressure of O2 = mole fraction O2 x total pressure
= 0.25 x 20.000 Nm-2 = 5.000 Nm-2
partial pressure of N2 = mole fraction N2 x total pressure
= 0.75 x 20000 Nm-2 = 15.000 Nm-2
 CALCULATIONS INVOLVING Kp
Example 2: 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 0.70 moles of ammonia. Calculate Kp .

N2(g) + 3H2(g) 2NH3(g)

i: 1 mol 3 mols -
1 x 3
0.70 mols= 0.35 mols x 0.70 mol = 1.05 mols 0.70 mols
r: 2 2

e: 1 - 0.35 = 0.65 mols 3 – 1.05 = 1.95 mols 0.70 mols

moles of N2 = 0.65 mols

moles of H2 = 1.95 mols
moles of NH3 = 0.70 mols
Total moles = 3.30 mols
mole fraction of N2 = moles of N2 = 0.65 = 0.196 N2(g) + 3H2(g) 2NH3(g)
total moles 3.30

mole fraction of H2 = moles of H2 = 1.95 = 0.590 Kp = p(NH3)2

total moles 3.30 p(N2) x p(H2)3
mole fraction of NH3 = moles of NH3 = 0.70 = 0.210
total moles 3.30 (1680000 Pa) 2
=
sum of mole fractions = 0.196 + 0.590 + 0.210 = 0.998 = 1 (1568000 Pa) (4720000 Pa) 3

partial pressure of N2 = mole fraction N2 x total pressure = 1.71 x 10-14 Pa-2

= 0.196 x 8 x 106 = 1568000 Pa
partial pressure of H2 = mole fraction H2 x total pressure
= 0.590 x 8 x 106 = 4720000 Pa
partial pressure of NH3 = mole fraction NH3 x total pressure
= 0.210 x 8 x 106 = 1680000 Pa
 B.)
Example 3: Hydrogen, Iodine and hydrogen iodide are in equilibrium in a
sealed tube at constant temperature. The equation for the reaction
is:

H2 + I2⇌ 2HI

The partial pressures of each gas are shown in the table below:

Gas Partial Pressure/Pa

H2 2.330 x 106
I2 0.925 x 106
HI 10.200 x 106

Calculate a value for Kp for this reaction, including units.

Solution:

p (HI)2
Kp =
p (H2) x p (I2)

= (10.200 x 106 Pa) 2

(2.330 x 106 Pa) (0.925 x 106 Pa)

= 48272.8 (no units)

 TEST YOURSELF

Solution:
moles of HI = 0.788 mols
i: 1.00 mols - - moles of H2 = 0.222 mols
r: 0.222 mols 0.222 mols 0.222 mols moles of I2 = 0.222 mols
e: 0.788 mols 0.222 mols 0.222 mols Total moles = 1.22 mols
mole fraction of H2 = moles of H2 = 0.222 = 0.182
total moles 1.22 sum of mole fractions :
mole fraction of I2 = moles of I2 = 0.222 = 0.182 0.182 + 0.182 + 0.637 = 1.00
total moles 1.22
mole fraction of HI = moles of HI = 0.788 = 0.637
total moles 1.22
 p (H2) x p (I2)
partial pressure of H2 = mole fraction H2 x total pressure Kp =
= 0.182 x 100 kPa p (HI)2
= 18.2 kPa (18.2 kPa) x (18.2 kPa)
=
(63.7 kPa)
partial pressure of I2 = mole fraction I2 x total pressure
= 0.182 x 100 kPa
= 0.0816
= 18.2 kPa
partial pressure of HI = mole fraction HI x total pressure
= 0.637 x 100 kPa
= 63.7 kPa
 TEST YOURSELF

Solution:

PCl3 + Cl2  PCl5 moles of PCl3 = 0.368 mols

i: 0.546 mols 0.373 mols - moles of Cl2 = 0.195 mols
r: 0.178 mols 0.178 mols 0.178 mols moles of PCl5 = 0.178 mols
e: 0.368 mols 0.195 mols 0.178 mols Total moles = 0.741 mols
mole fraction of PCl3 = moles of PCl3 = 0.368 = 0.497
total moles 0.741
mole fraction of Cl2 = moles of Cl2
= 0.195 = 0.263
total moles 0.741
mole fraction of PCl5 = moles of PCl5 = 0.178 = 0.240
total moles 0.741
 PCl3 + Cl2  PCl5
p (PCl5)
partial pressure of PCl3 = mole fraction PCl3 x total pressure Kp =
= 0.497 x 225 kPa p (PCl3) x p (Cl2)
= 111.825 kPa (54 kPa)
=
partial pressure of PCl5 = mole fraction PCl5 x total pressure (111.825 kPa) x (59.175 kPa)
= 0.240 x 225 kPa
= 8.16 x 10-3 kPa-1
= 54 kPa
partial pressure of Cl2 = mole fraction Cl2 x total pressure
= 0.263 x 225 kPa
= 59.175 kPa