5

UNIT

Chemical Equilibrium and

Phase Equilibrium
Unit Outcomes
At the end of this unit, you should be able to:
( understand how equilibrium is established;
( explain characteristics of dynamic equilibrium;
( state the law of mass action, and write an expression for equilibrium
constants, Kc and Kp, from a given chemical reaction;
( apply the law of mass action to calculate Kc,and Kp, the concentration and
pressure of substances in equilibrium;
( understand how the reaction quotient is used to indicate the position of
equilibrium;
( state Le Chateliers’ principle and use it to predict and explain the effects of
changes in temperature, pressure, concentration and presence of catalyst on
a reaction;
( perform an activity to demonstrate the effects of changes in concentration
on the position of equilibrium and to determine Kc and Kp values;
( explain how equilibrium principles are applied to optimize the production of
industrial chemicals (e.g. the production of ammonia and sulphuric acid);
and
( demonstrate scientific enquiry skills, observing, predicting, comparing and
contrasting, communicating, asking questions and making generalizations.
 CHEMISTRY GRADE 11

MAIN CONTENTS
5.1 Chemical Equilibrium
– Reversible and Irreversible Reactions
– Equilibrium
– Dynamic Chemical Equilibrium
– Conditions for Attainment of Chemical Equilibrium
– Characteristics of Chemical Equilibrium
– Law of Mass Action
– Factors affecting position of Chemical Equilibrium
– Equilibrium Constant
– Equilibrium Quotient
– Le Chatelier’s Principle
– Chemical Equilibrium and Industry
5.2 Phase Equilibrium
– Force of Attraction, Kinetic Energy and States of Matter
– Common terms: Phase, Component and Degree of freedom
– Phase Rule
– Temperature, Pressure and Phase Changes of Pure Substance
– Phase Diagram

Start-up Activity
Form a group and perform the following activity:
1. Mix 10 mL of 0.1 mol L–1 HCl solution with 10 mL of 0.1 mol L–1 NaOH
solution. Now, discuss each of the following questions:
a What is the concentration of NaCl formed?
b How much HCl and NaOH remain unreacted?
c Is the reaction complete?

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2. Can you predict how much ammonia will be formed when 0.1 mol of nitrogen
gas and 0.3 mol of hydrogen gas are allowed to react in a closed 2-litre flask?
Share your ideas with the rest of the class.

INTRODUCTION

In the unit on chemical kinetics you have studied about one aspect of a chemical
reaction, which is the rate of the reaction. You have also studied the time taken for
half the reaction to be over. However, some questions such as the following still
remain. Do all reactions reach completion? If not then how much of the reactants
remain unreacted, that is, what is the extent of the reaction? Why does the reaction
not reach completion? Why does it attain equilibrium? These questions can be
answered after studying chemical equilibrium.

In this unit, you will study about equilibrium, how it is attained, different phases in
which a system can exist and stability of these phases under different conditions of
temperature and pressure.

5.1 CHEMICAL EQUILIBRIUM

At the end of this section, you should be able to:

• explain reversible and irreversible reactions;
• define dynamic chemical equilibrium;
• state the necessary conditions for the attainment of equilibrium;
• describe the microscopic events that occur when a chemical system is in
equilibrium;
• describe characteristics of chemical equilibrium;
• state the law of mass action;
• define equilibrium constant;
• write the equilibrium constant expression for chemical reactions that involve
concentration and partial pressure;
• calculate values for equilibrium constants involving concentration and partial
pressure;
• state the relationship of Keq to relative amounts of product and reactants in a
given reaction;

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• show the relationship between Kc and Kp;

• distinguish between homogeneous and heterogeneous reactions;
• define reaction quotient;
• use the equilibrium quotient to predict the direction of a reaction and the
position of equilibrium;
• calculate equilibrium concentrations, given initial concentrations;
• determine whether the reactants or the products are favoured in a chemical
reaction, given the equilibrium constants;
• list factors that affect chemical equilibrium;
• state Le-Chatelier’s principle;
• use Le-Chatelier’s principle to explain the effect of changes in temperature,
pressure/volume, concentration and presence of a catalyst on a reaction;
• describe the effects of changes in concentration, pressure/volume and
temperature on Keq;
• perform an activity to demonstrate the effects of changes in concentration and
temperature on the position of equilibrium;
• perform an activity to determine Kc for esterification of organic acids;
• define optimum condition; and
• explain how Le-Chatelier’s principle is applied to the Haber process for
manufacturing ammonia and to the contact process for manufacturing sulphuric acid.

5.1.1 Reversible and Irreversible Reactions

Activity 5.1
Form a group and perform the following activity:
In a test tube take crushed ice. Dip a thermometer in it and note the temperature. Heat it
slowly for a few seconds.
Now stop heating and place the test tube in a beaker containing large amount of crushed
ice. Discuss the following questions in your group:
1. What is the temperature of crushed ice?
2. What happens when it is heated slightly?
3. What happens when it is cooled again?
4. What is the final temperature?
Share your ideas with the rest of the class.

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A reversible reaction is a chemical reaction that results in an equilibrium mixture of

reactants and products; for example, formation of ammonia is a reversible reaction.
N2(g) + 3H2(g) 2NH3(g)
Another example of reversible reaction is the formation of hydrogen iodide from
hydrogen gas and iodine vapours.
H2(g) + I2(g) 2HI(g)

Activity 5.2

Form a group and perform the following activity:

1. Take 10 mL of 0.1 M HCl solution in a test tube and dip the corner of blue and red
litmus papers respectively in it. What happens?
2. In another test tube take 10 mL of 0.1 M NaOH solution and dip the corner of blue
and red litmus papers respectively in it. What happens?
3. Mix the above two solutions and again test with litmus papers.
4. Dissolve a few crystals of sodium chloride in 10 mL water and test it with blue and
red litmus papers. Will the resulting solution be acidic or basic? Compare the results
of 3 and 4.
Share your findings with rest of the class.

Chemical reactions which proceed in only one direction are known as irreversible
reactions. When the equation for irreversible reaction is written, a single arrow (→) is
used indicating that the reaction can proceed in only one direction.
While writing reversible reaction, double arrow ( ) is used indicating that the
reaction can go from reactant to product side and also from the product to the
reactant side. The reaction from the reactant side to the product side is known as
forward reaction and reaction from product to the reactants is known as reverse or
backward reaction.

Exercise 5.1
Answer the following questions:
1. Define the terms reversible reaction and irreversible reaction.
2. Give examples of reversible and irreversible reactions.
3. Which symbol or sign is used to represent the reversibility and irreversibility of
the reaction?

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5.1.2 Attainment and Characteristics of Chemical

Equilibrium
Equilibrium

Activity 5.3

Form a group and perform the following activity:

Take 10 mL of acetone in a test tube. Close the mouth of the test tube immediately.
Clamp the test tube vertically. Mark the level of acetone with the marker. Allow it to stand
for half an hour and note the level of acetone at regular intervals.

Discuss the findings with the class.

The equilibrium is dynamic in nature which means that although at the macroscopic
level the properties do not change with time, however, at the molecular level the two
processes are still taking place. So the equilibrium is attained when the rate of two
opposing processes become equal.

Ice and water present together in a thermos flask at 0°C is another example of
dynamic equilibrium. The equilibrium is attained when the rates of melting and freezing
become equal.

The saturated solution is also an example of dynamic equilibrium. Saturated solution is

a solution in which undissolved solute is in equilibrium with the solute dissolved in the
solution. The molecules from undissolved solute go into the solution and equal number
of solute molecules get precipitated from the solution. Therefore, the concentration of
the solution remains constant.

Chemical Equilibrium

An equilibrium involving a chemical reaction is known as chemical equilibrium. When a

chemical reaction takes place, the reactants are consumed and the products are
formed. As a result the concentrations of reactants decrease with time and that of
products increase. If the reaction is reversible in nature and it takes place in a closed
vessel then the products decompose to give back reactants. After some time the
concentrations of the reactants and products become constant, that is they do not
change with time. This state is known as chemical equilibrium.

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Chemical equilibrium is the state of the reaction when the macroscopic

properties like temperature, pressure, volume and concentration of the reaction
do not change with time.

Conditions for Attainment of Chemical Equilibrium

In a reversible reaction, reactant molecules react to give products and at the same
time some product molecules give back reactants. The rate of reaction depends upon
the concentration of reactants. The rate of forward reaction depends upon the
concentration of reactants while the rate of reverse reaction depends upon the
concentration of products as shown in Figure 5.1. Initially only the reactants are
present, therefore, the rate of forward reaction is fast. The reaction in the reverse
direction does not take place as no product is present. As the reaction progresses,
due to the decrease in the concentration of reactants, the rate of forward reaction
decreases. At the same time, due to the increase in the concentration of products, the
rate of reverse reaction increases. As the reaction further progresses a stage is
reached when the rate of forward reaction becomes equal to the rate of reverse
reaction. When this stage is attained, the concentrations of reactants and products do
not change. The reaction has attained chemical equilibrium.

Forward reaction
Rate of reaction

Equilibrium

Backward reaction

Time

Fig 5.1 Change in the rate of reaction with time for the forward and reverse reactions.

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For example, as seen earlier, formation of ammonia from nitrogen and hydrogen is a
reversible process. At the start of the reaction only nitrogen and hydrogen are present.
They combine to form ammonia. The rate of formation of ammonia is large. With the
progress of reaction, the concentrations of nitrogen and hydrogen decrease so the rate
of formation of ammonia decreases. As more and more ammonia molecules are
formed, some of the molecules start decomposing to give back nitrogen and
hydrogen. With the progress of reaction, the number of ammonia molecules increases,
so the rate of decomposition of ammonia also increases. As the reaction proceeds, the
rate of formation of ammonia decreases while the rate of decomposition of ammonia
increases. A stage is reached when the two rates become equal and equilibrium is
attained.
N2(g) + 3H2(g) 2NH3(g)
The chemical equilibrium is also dynamic in nature since the reaction does not stop at
equilibrium. The macroscopic properties remain constant because the rate of forward
reaction becomes equal to the rate of reverse reaction and hence no net reaction
takes place.
Another example is the decomposition of dinitrogen tetraoxide to form nitrogen
dioxide.
N2O4(g) 2NO2(g)
colourless reddish brown

When colourless N2O4 is taken in a closed vessel, after some time its colour changes
to brown indicating that NO2 has been formed.
Similarly, if NO2 is taken in a closed vessel, initially the colour is reddish brown but
the colour starts fading and after some time it becomes brown. This colour change
takes place because some NO2 molecules dimerize to form N2O4.
In both the cases, the final colour is same indicating that at equilibrium both N2O4 and
NO2 are present.
From these observations it can be concluded that the chemical equilibrium is attained
whether the reaction is started with reactants or with products. That is, chemical
equilibrium can be obtained from forward direction as well as reverse direction.
It should be noted that the concentrations of products and reactants are not
necessarily equal at equilibrium, only the rate of forward and reverse reactions are
equal.

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Characteristics of Chemical Equilibrium

The reaction is reversible in nature.
• The reaction takes place in a closed vessel, that is, during the reaction;
reactants and products are neither added nor removed from the reaction vessel.
• The rate of forward reaction is equal to the rate of reverse reaction.
• All the reactants and products are present at equilibrium.
• The macroscopic properties like temperature, pressure, volume and
concentration do not change with time.
• The equilibrium is dynamic in nature.
• The state of equilibrium can be obtained from either side.
• The concentrations of reactants and products are generally not equal.
• The free energy change of the reaction is zero at equilibrium.

Exercise 5.2
Answers the following questions:
1. When a mixture of SO2 and O2 is introduced into a reaction vessel at a
temperature of 700 K, a reaction that produces SO3 occurs as:
2SO2(g) + O2(g) → 2SO3(g)
a When do we say that the system has reached chemical equilibrium? Explain
your answer.
b Why is the equilibrium state referred to as dynamic?
c Write the equation that shows the presence of the three species in
equilibrium.
2. Label a, b and c for the figure below. Explain trends of the rate of the forward
reaction and the rate of the reverse reaction.

(a)
Reaction rate

(c)

(b)

Time

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3. Label a, b and c for the figure shown below. Explain what happens to the
concentration of the reactants and the concentration of the products.

(a)
Concentration

(c)

(b)

Time

4. What are the conditions that remain constant at equilibrium?

5.1.3 Equilibrium Expression and Equilibrium Constant

Law of Mass Action
Two Norwegian scientists C.M. Guldberg and Peter Waage studied reversible
chemical reactions and gave a law characterizing the dynamic chemical equilibrium.
This law is known as law of mass action. According to this law:
• The combining power of two reactants A and B depends upon their nature as
well as their active concentrations.
• The rate at which A and B combine is directly proportional to the product of
their concentration terms each raised to the power of its respective coefficient in
the balanced chemical reaction.
The general equation that represents a reversible reaction is:
aA + bB mM + nN
For the forward reaction A and B are reactants and M and N are products.
It is assumed that the reaction is homogeneous in nature, that is all the reactants and
the products are present in the same state.
The rate of forward reaction (rf ) depends upon the concentrations of A and B and is
given by the expression
rf ∝ [A]a [B]b or rf = kf [A]a [B]b

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where [A] and [B] are the concentrations of A and B respectively. The rate of reverse
reaction is given by the expression
rb ∝ [M]m [N]n or rb = kb [M]m [N]n
where [M] and [N] are the concentrations of M and N respectively. kf and kb are
rate constants for forward and reverse reactions, respectively.

At equilibrium, the rate of forward reaction is equal to the rate of reverse reaction.
Therefore,
rf = rb
or kf [A]a [B]b = kb [M]m [N]n
kf and kb are constant. Therefore, the ratio of kf to kb is also a constant.

kf [M]m [N]n
= = K eq
kb [A]a [B]b
The ratio of kf and kb is represented by Keq. Since this constant represents the
reaction at equilibrium it is known as equilibrium constant. [M], [N], [A] and [B] are
concentrations at equilibrium.

When the concentrations are expressed in molarities, the equilibrium constant is

represented by Kc.

When the reactants and the products are in the gaseous state, their concentrations can
be expressed in terms of partial pressures. In such cases, the equilibrium constant is
denoted by Kp.

Rules for Writing the Equilibrium Constant Expression for

Homogeneous Reactions
Homogeneous reaction is a reaction in which all the reactants and the products are
present in the same physical state.
For a homogeneous reaction, rules followed while writing the expression for
equilibrium constant are:
• The concentrations of all the substances formed as products are written in the
numerator.
• The concentrations of all the reactants are written in the denominator.
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• Each concentration term is raised to the power by its respective coefficient as

written in the balanced chemical reaction.
For a general reaction at equilibrium
aA + bB mM + nN
the expression for Kc is:

[M]m [N]n
Kc =
[A]a [B]b

When all the reactants and the products are in the gaseous state, their concentrations
can be written in terms of partial pressures. In such cases the equilibrium constant is
denoted by Kp. The expression for Kp is

(pM )m ( pN )
n

Kp =
( pA ) a ( pB ) b
For the formation of ammonia,
N2(g) + 3H2(g) 2NH3(g)
the expression of equilibrium constant in terms of molarities is:

[NH3 ]2
Kc =
[N 2 ][H 2 ]3
The expression of Kp is:

( pNH )
2
3
Kp =
( pN 2 ) ( pH 2 )
3

Exercise 5.3
Write the equilibrium constant expression for the following reactions:
1. NH3(g) + CH3COOH(aq) NH+4(aq) + CH3COO–(aq)
2. HF(aq) H+(aq) + F–(aq)
3. 2NO(g) + Br2(g) 2NOBr(g)
4. 2HF(g) H2(g) + F2(g)

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Units of Kc

The unit of Kc of a reaction depends upon the number of moles of the reactants and
products involved in the reaction. Therefore, for a general reaction;
aA + bB mM + nN

the unit of Kc will be:

[M]m [N]n [mol L-1 ]m [mol L-1 ]n

Kc = a b
= -1 a -1 b
= (mol L–1)(m+n)–(a+b)
[A] [B] [mol L ] [mol L ]

Example 5.1
1. For the reaction:

NH3(g) + CH3COOH(aq) NH+4(aq) + CH3COO–(aq)

Kc =
 NH +4   CH 3 COO – 
    =
mol L-1 ( ) ( mol L ) = 1
-1

[ NH 3 ][ CH 3COOH ] mol L-1 ( )( mol L )

-1

2. For the reaction:

2HF(g) H2(g) + F2(g)

 H +   F–  (
mol L-1 mol L-1 )( )
Kc =     = = mol L-1
[ HF] mol L-1
( )
Unit of Kp

The unit of Kp is decided by the unit of pressure. If the partial pressure is expressed
in atm, then the unit of Kp, will be:

Kp =
( p M ) m ( p N )n =
(atm)m (atm) n
= (atm)(m+n)–(a+b)
( p A )a ( p B ) b (atm)a (atm) b

If the partial pressure is measured in kPa, then the unit of Kp will be (kPa)(m+n)–(a+b)

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Example 5.2
Kp units for the following reactions are shown.

( PNH ) = atm2 = 1
2
3
1. N2(g) + 3H2(g) 2NH3(g) K p =
( PN )( PH ) atm . atm atm
3 3 2
2 2

2. H2(g) + I2(g) 2HI(g) Kp =

( PHI )2 =
( atm )
2
=1
( PH )( PI
2 2
) ( atm ) ( atm )
( PNO )
2

3. N2O4(g) 2NO2(g) Kp = 2
=
( atm )
2
= atm
( PN O ) ( atm )
2 4

Equilibrium Constant for Heterogeneous Reactions

Activity 5.4

Form a group and discuss the following questions:

Consider the reaction
Mg(s) + HCl(aq) MgCl2(aq) + H2(g)
1. Identify the phases of the reactants and the products. Are the reactants and the
product in the same or different phases?
2. What is the name of the equilibrium that involves such reactants and the product?
Share your ideas with the rest of the class.

In heterogeneous reactions, the reactants and products are present in more than one
physical state. For example, thermal decomposition of calcium carbonate is an
example of heterogeneous reaction.

CaCO3(s) CaO (s) + CO2(g)

Some other examples of heterogeneous reactions are

NH4Cl(s) NH3(g) + HCl(g)

CO2(g) + H2O(l) H+(aq) + HCO3– (aq)

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Rules for Writing the Expression for Equilibrium Constant for

Heterogeneous Reaction
• The concentration terms of products are written in the numerator and the
concentration terms of reactants are written in the denominator raised to the
power of their respective coefficient in the balanced chemical equation.

• While writing the expression for Kc, the molarities of gaseous reactants and
products and species present in the solution are written.

• Concentration terms of solids and pure liquids do not appear in the

expression, as they are taken to be unity.

• While writing the expression for Kp, partial pressures of only the gaseous
reactants and products are written in the expression for equilibrium constant.

Example 5.3
The equilibrium constant expression for some heterogeneous reactions are
shown below:
a CaCO3(s) CaO(s) + CO2(g) Kp = pCO
2
b NH4Cl(s) NH3(g) + HCl(g) Kp = (pNH )(pHCl )
3

H + –
   HCO3 
c CO2(g) + H2O(l) H+(aq) + HCO3–(aq) Kc =
[ CO2 ]
1
d Fe3+(aq) + 3OH–(aq) Fe(OH)3(s) Kc = 3
 Fe3+   OH – 
  

Exercise 5.4
Answer the following questions:
1. 5.0 mole of ammonia were introduced into a 5.0 L reaction chamber in which
it is partially decomposed at high temperatures.

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

At equilibrium at a particular temperature, 80.0% of the ammonia had reacted.
Calculate Kc for the reaction.
2. 1.25 mol NOCl was placed in a 2.50 L reaction chamber at 427°C. After
equilibrium was reached, 1.10 moles NOCl remained. Calculate the
equilibrium constant for the reaction.
2NOCl(g) 2NO(g) + Cl2(g)
3. A sample of nitrosyl bromide was heated to 100°C in a 10.0 L container in
order to partially decompose it.
2NOBr(g) 2NO(g) + Br2(g)
At equilibrium the container was found to contain 0.0585 mol of NOBr, 0.105
mol of NO, and 0.0524 mol of Br2. Calculate the value of Kc.
4. The brown gas NO2 and the colourless gas N2O4 exist in equilibrium.
N2O4(g) 2NO2(g)
0.625 mol of N2O4 was introduced into a 5.00 L vessel and was allowed to
decompose until it reached equilibrium with NO2. The concentration of N2O4
at equilibrium was 0.0750 M. Calculate Kp for the reaction.

Relation between Kc and Kp

For the general reaction

a A(g) + bB(g) mM(g) + nN(g)
m
[M]m [N]n CM CnN
Kc = = a b
[A]a [B]b CA C B

(pM ) m (pN ) n
Kp =
(pA )a (pB )b
It is assumed that all the gaseous species behave like an ideal gas. According to
the ideal gas equation, the partial pressure (p) is given by
p = nRT / V and n/V = C
where n = amount of the gaseous species in moles
R = Gas constant

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T = Temperature in kelvin
V = Volume of the reaction mixture
C = Molarity
Thus, pA = nA RT / V = CART
pB = nB RT / V = CBRT
pM = nM RT / V = CMRT
pN = nN RT / V = CNRT

(CM RT ) m (CN RT ) n CM m n
CN
Kp = a b
= a b
( RT )∆n
(C A RT ) (CB RT ) C ACB

here ∆n = (m + n) – (a + b) for gaseous species

K p = Kc(RT )∆n
When the number of gaseous reactants and products are equal then,
a + b=m+n
Therefore, ∆n = 0 and hence Kp = Kc

Example 5.4
1. The equilibrium constant for the reaction:
2SO3(g) 2SO2 (g) + O2(g)
is 1.8 × 10–3 kPa at 427°C. Calculate Kc for the reaction at the same
temperature.
Solution:
Given: K p = 1.8 × 10–3 kPa = 1.8 Nm–2 T = 427°C = 700 K.
R = 8.314 N m K–1 mol–1
We know that
K p = Kc(RT)∆n
For the given reaction, ∆n = (2+1) – 2 = 1
Therefore, Kc = Kp /(RT)

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1.8 Nm −2
= −1 −1
= 3.09 mol m −3
700 K × 8.314 N m K mol

2. What are the values of Kp and Kc at 1000°C for the reaction

CaCO3(s) CaO(s) + CO2(g)
if the pressure of CO2 in equilibrium with CaCO3 and CaO is 3.87 atm?

Enough information is given to find Kp first. Writing the Kp expression for

this heterogeneous reaction:
K p = pCO = 3.87
2
Then to get Kc, rearrange the equation,
K p = Kc(RT ) ∆n
where n, the change in the number of moles of gas in the reaction is +1.
Calculation:

Kp
Kc =
(RT )∆n

3.87
Kc = = 0.0370
(0.0821)(1273)
3. At 400 °C, Kc = 64 for the reaction
H2(g) + I2(g) 2HI(g)
a What is the value of Kp for this reaction?

b If at equilibrium, the partial pressures of H2 and I2 in a container are

0.20 atm and 0.50 atm, respectively, what is the partial pressure of HI
in the mixture?
Solution:
a The equation relating Kp to Kc is
K p = Kc (RT)∆n
Here the change in the number of moles of gas ∆n is:

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∆n = 2 mol HI – 1 mol H2 – 1 mol I2 = 0

Since, ∆n = 0, Kp and Kc are the same.
K p = Kc(RT)0 = Kc
K p = Kc = 64
b Writing the equilibrium constant expression

2
p HI
Kp = = 64
pH pI
2 2

and substituting the given pressures

2
p HI
= 64
(0.20)(0.50)

the partial pressure of HI is

pHI = (0.20)(0.50)(64)

pHI = 2.53 atm

Exercise 5.5
Answers the following questions:
1. The following equilibrium constants were determined at 1123 K:
C(s) + CO2(g) 2CO(g) Kc = 1.4 × 1012
CO(g) + Cl2(g) COCl2(g) Kc = 5.5 × 10–1
Write the equilibrium constant expression Kc and calculate the equilibrium
constant at 1123 K for the following reaction:
C(s) + CO2(g) + 2Cl2(g) 2COCl2(g)
2. For the decomposition of ammonium chloride,
NH4Cl(s) NH3(g) + HCl(g) at 427°C, Kp = 4.8.
Calculate Kc for this reaction.

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3. Write the equilibrium constant expression for the following equations:

a 2HgO(s) 2Hg(l) + O2(g)
b Ni(s) + 4CO(g) Ni(CO)4(g)
c 2NO(g) + Br2(g) 2NOBr(g)
4. For the reaction:
H2(g) + Br2(g) 2HBr(g)
Kp = 7.1 × 104 at 700 K. What is the value of Kp for the following reactions
at the same temperature?
a 2HBr(g) H2(g) + Br2(g)
b ½ H2(g) + ½ Br2(g) HBr(g)
5. The reversible reaction:
N2O4(g) 2NO2(g)
has a value of Kp = 0.113 at 25°C. Determine the numerical value of Kc at
25°C for the reaction,
½N2O4(g) NO2(g)
Is it greater than, equal to, or less than 0.113? Explain.

Applications of Equilibrium Constant

Activity 5.5

Form a group and discuss the following:

The equilibrium constant, Kc for the formation of hydrogen iodide from molecular
hydrogen and molecular iodine in the gas phase
H2(g) + I2(g) 2HI(g)
is 54.3 at 430°C. Suppose that in a certain experiment we place 0.243 mole of H2, 0.146
mole of I2, and 1.98 moles of HI all in a 1.00 L container at 430°C. Will there be a net
reaction to form more H2 and I2 or more HI ?
Share your ideas with the rest of the class.

The value of equilibrium constant predicts the extent of reaction at equilibrium. It also
tells about the relative concentrations of products and reactants present at equilibrium,

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that is, the position of equilibrium.

Position of equilibrium: Kc can have three types of values.

Case 1: When Kc >1

This indicates that the value of numerator is greater than the denominator. So the
formation of products is favoured at equilibrium.

Case 2: When Kc <1

This indicates that the value of numerator is less than the denominator. So the
formation of products is not favoured at equilibrium.

Case 3: When Kc =1

This indicates that the rate of forward reaction is equal to the rate of backward
reaction.

Extent of reaction: Kc value also predicts the extent of the reaction at equilibrium.
Very large values of Kc indicates that the extent of the reaction is very large at
equilibrium. So most of the reactants have been consumed at equilibrium. A very small
value of Kc indicates that the extent of reaction is very small at equilibrium. Most of
the reactants will be in the unreacted state.

Activity 5.6

Form a group and discuss the following questions:

1. Predict whether the formation of product is favoured for the following reactions:
a N2(g) + 3H2(g) 2NH3(g) Kc = 3.6 × 108
b N2O4(g) 2NO2(g) Kc = 5 × 10–3
c CO2(g) 2CO(g) + O2(g) Kc = 4.45 × 10–24
2. Arrange the following reactions in order of their increasing tendency to proceed
towards completion (least extent to greatest extent).
a CO + Cl2 COCl2 Kc = 13.8
b N2O4 2NO2 Kc = 2.1×10–4
c 2NOCl 2NO + Cl2 Kc = 4.7×10–4
Share your ideas with the rest of the class.

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Reaction Quotient (Q)

Reaction quotient is the ratio of concentrations of products to the concentrations of
reactants raised to the power of their respective coefficients at any stage after the start
of the reaction. For the general reaction,
aA + bB mM + nN
the expression for the reaction quotient is

[M]m [N]n
Q=
[A]a [B]b
[A], [B], [M] and [N] are concentrations at any stage during the reaction. At the
initial stages of the reaction, the amount of product formed is low, therefore, the value
of Q is small. With the progress of the reaction, since the concentration of products
increases, the value of Q also increases. When the reaction attains equilibrium, Q
becomes equal to the equilibrium constant.
Reaction Quotient in Terms of Molarities
When the concentrations are expressed in molarities, the reaction quotient is Qc.

[M]m [N]n
Qc =
[A]a [B]b
At equilibrium,

[M]m [N]n 
Qc =  a b 
= Kc
 [A] [B] eq
Reaction Quotient in Terms of Partial Pressure

When the concentrations are taken in partial pressures, the reaction quotient is Qp
and is given by the expression

( pM )m ( pN )n
Qp =
( pA )a ( pB )b
At equilibrium,

 (pM ) (pN ) 
m n
Qp =  a b 
= Kp
 (pA ) (pB ) eq

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Application of Reaction Quotient

Reaction quotient predicts the direction of the reaction at any stage, that is for the
given concentration of reactants and products. It also decides whether the reaction
has attained equilibrium or not.
When Q is less than K, then the reaction will proceed in the forward direction and
more products will be formed till the equilibrium is reached.
When Q is greater than K, then the reaction will proceed in the reverse direction and
more reactants will be formed till the equilibrium is reached.
When Q is equal to K, then the reaction has attained equilibrium.

Example 5.5
At a certain temperature the reaction:
CO(g) + Cl2(g) COCl2(g)
has an equilibrium constant Kc = 13.8. Is the following mixture an equilibrium
mixture? If not, in which direction (forward or backward) will the reaction
proceed to reach equilibrium? [CO]0 = 2.5 mol L–1; [Cl2]0 = 1.2 mol L–1; and
[COCl2]0 = 5.0 mol L–1.
Solution:

Recall that for the system to be at equilibrium Qc = Kc. Substitute the given
concentrations into the reaction quotient for the reaction, and determine Qc.
5 mol L–1
Qc = = 1.6 ( mol L )
–1 –1

( 2.5 mol L–1 )(1.2 mol L–1 )

Since Qc < Kc the reaction mixture is not an equilibrium mixture, and a net
forward reaction will bring the system to equilibrium.

Calculating the Equilibrium Concentrations

Not only can we estimate the extent of reaction from the Kc value, but also the
expected concentrations at equilibrium can be calculated from knowledge of the initial
concentrations and the Kc value. In these types of problem it will be very helpful to
use the following approach.
1. Express the equilibrium concentrations of all the species in terms of the initial
concentrations and an unknown x, which represents the change in concentration.

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2. Substitute the equilibrium concentrations derived in part 1 into the equilibrium

constant expression, and solve for x. The equilibrium concentration is given by:
equilibrium concentration = initial concentration ± the change due to the reaction
where the + sign is used for a product, and the – sign for a reactant.

3. Use x to calculate the equilibrium concentration of all the species.

Example 5.6
Let us consider the reactioin between hydrogen and iodine in which 1 mole of H2
and 2 moles of I2 were added in 500 mL flask. First we need expressions for the
equilibrium concentrations of H2, I2, and HI. Tabulating the initial concentrations
as:

Concentration H2 + I2 2HI

Initial 1.00 mol/0.50 L 2.00 mol/0.50 L 0

Change – – –

Equilibrium – – –

Since the answer involves three unknowns, we will relate the concentrations to
each other by introducing the variable x. Recall, that the equilibrium concentration
= initial concentration ± change in concentration. Let x = the change in
concentration of H2. That is, let x = the number of moles of H2 reacting per liter.
From the coefficients of the balanced equation we can tell that if the change in H2
is –x, then the change in I2 must also be –x, and the change in HI must be +2x.

The next step is to complete the table in units of molarity:

Concentration H2 + I2 2HI

Initial (M) 2.0 4.0 0

Change (M) –x –x
Equilibrium (M) (2.0 – x) (4.0 – x) +2x

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Now substitute the equilibrium concentrations from the table into the Kc
expression,

( 2x)
2

Kc =
( 2.0 – x )( 4.0 – x )

and solve for x.

( 2x)
2

Kc = = 64
x 2 – 6.0 x + 8.0

Rearranging, we get:
4x2 = 64x2 – 384x + 512

and grouping yields

60x2 – 384x + 512 = 0

We will use the general method of solving a quadratic equation of the form

ax2 + bx + c = 0

The root x is given by

–b ± b 2 – 4ac
x =
2a

In this case, a = 60, b = –384, and c = 512. Therefore,

– ( –384 ) ± (–384) 2 – 4 ( 60 )( 512 )

x=
2 ( 60 )

384 ± 2.5 ×104

x=
120

384 ± 158
x= = 1.9 and 4.5 mol/L
120

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 CHEMISTRY GRADE 11

Recall that x = the number of moles of H2 (or I2) reacting per liter. Of the two
answers (roots), only 1.9 is reasonable, because the value 4.5 M would mean that
more H2 (or I2) reacted than was present at the start. This would result in a
negative equilibrium concentration, which is physically meaningless. We therefore
use the root x = 1.9 M to calculate the equilibrium concentrations:

[H2] = 2.0 – x = 2.0 M – 1.9 M = 0.1 M

[I2] = 4.0 – x = 4.0 M – 1.9 M = 2.1 M

[HI] = 2x = 2(1.9 M) = 3.8 M. The results can be checked

by inserting these concentrations back into the Kc expression
to see if Kc = 64.

[ HI] ( 3.8 )
2 2

Kc = = = 68
[ H 2 ][ I2 ] ( 0.1)( 2.1)

Thus the concentrations we have calculated are correct. The difference between
64 and 68 results from rounding off which is to maintain the correct number of
significant figures. Therefore, our result is correct only to the number of significant
figures given in the problem.

Experiment 5.1

Determination of Equilibrium Constant for an Organic Acid

Objective: To determine equilibrium constant for the esterification of an acetic
acid.
Apparatus: Round bottom flask, pipette, conical flask, burette, burette stand,
water condenser with inlet and outlet pipes, boiling chips, clamp stand,
burner, water bath.

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Chemicals: 0.5 M acetic acid, 0.5 M propan-1-ol, phenolphthalein, 0.01 M

NaOH solution, ice.
Procedure:

1. In a 100 mL round bottom flask, take 10.0 mL of 0.5 M acetic acid and
10.0 mL of 0.5 M propan-1-ol.

2. Add 5 drops of conc. H2SO4 to the solution in the round bottom flask.

3. Add a few pieces of boiling chips to the solution in the round bottom flask.

4. Attach a water condenser and reflux for 1 hour on a water bath as shown
in (Figure 5.2(a)).

5. Cool the flask and its contents in an ice bath.

6. Pipette out 1.0 mL of the reaction mixture in a conical flask containing 25.0
mL of ice cold water. (Ice cold water is prepared by taking 25.0 mL of
water in a conical flask and keeping on ice bath for some time).

7. Add 2 drops of phenolphthalein indicator to the solution in a conical flask.

8. Titrate the contents against 0.1 M NaOH solution as shown in (Figure

5.2(b)).

9. Repeat steps 6, 7 and 8 three times and take the average volume of NaOH
consumed in titration.

Observations and analysis:

1. What is the purpose of adding small amount of H2SO4 to the reaction
mixture at one beginning of the experiment?

2. Why do we add boiling chips to the reaction mixture before refluxing?

3. Calculate:

a the concentrations of reactions and products at equilibrium.

b the equilibrium constant for the esterification of acetic acid.

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 CHEMISTRY GRADE 11

Hint: The esterification reaction is acid catalysed.

CH3COOH(aq) + CH3CH2CH2OH(aq) CH3COOC3H7(aq) + H2O(aq)

Burette
Condenser
with inlet and
outlet pipes

Round
bottom
flask

Bunsen
burner Conical
flask

a b
Figure 5.2 Laboratory set-up for the esterification of acetic acid.

Exercise 5.6
1. For the equilibrium:
N2O4(g) 2NO2(g) Kc = 0.36 at 100°C
a sample of 0.25 mol N2O4 is allowed to dissociate and come to equilibrium
in a 1.5 L flask at 100°C. What are the equilibrium concentrations of NO2
and N2O4?

2. The decomposition of NOBr is represented by the equation:

2NOBr(g) 2NO(g) + Br2(g) Kc = 0.0169
At equilibrium the concentrations of NO and Br2 are 1.05×10–2 M and
5.24×10–3 M, respectively. What is the concentration of NOBr?

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 CHEMICAL EQUILIBRIUM AND PHASE EQUILIBRIUM

3. The reaction:
PCl5(g) PCl3(g) + Cl2(g)
has the equilibrium constant value Kc = 0.24 at 300 °C.
a Is the following reaction mixture at equilibrium?
[PCl5] = 5.0 mol/L, [PCl3] = 2.5 mol/L, [Cl2] = 1.9 mol/L
b Predict the direction in which the system will react to reach equilibrium

4. At 400°C, the equilibrium constant for the reaction:

H2(g) + I2(g) 2HI(g)
is 64. A mixture of 0.250 mol H2 and 0.250 mol I2 was introduced into an
empty 0.75 L reaction vessel at 400°C, find the equilibrium concentrations of
all components

5. At 700 K, the reaction:

2SO2(g) + O2(g) 2SO3(g)
has an equilibrium constant Kc = 4.3 × 106.
a Is a mixture with the following concentrations at equilibrium?
[SO2] = 0.10 M; [SO3] = 10 M; [O2] = 0.10 M.

b If not at equilibrium, predict the direction in which a net reaction will occur
to reach a new equilibrium.

5.1.4 Changing Equilibrium Conditions–Le Chatelier’s

Principle

Activity 5.7

Form a group and discuss the following questions:

1. Consider the following reaction at 400°C:
H2O(g) + CO(g) H2(g) + CO2(g)
Some amounts of H2O, CO(g), H2(g), and CO2(g) were put into a flask so that the
composition corresponded to an equilibrium mixture. A laboratory technician added

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 CHEMISTRY GRADE 11

an iron catalyst to the mixture, but was surprised when no additional H2(g) and CO2(g)
were formed even after waiting for many days. Explain why the technician should not
have been surprised.
2. Equilibrium is established in the reversible reaction
4HCl(g) + O2(g) 2H2O(g) + 2Cl2(g) ∆H = 114.4 kJ
Describe four changes that could be made to this mixture to increase the amount of
Cl2(g) at equilibrium.
3. Describe how you might be able to drive a reaction having a small value of Kc to
completion.
Share your ideas with the rest of the class.

Factors Affecting the Equilibrium Constant

The equilibrium constant depends upon the following factors:

1. Temperature at which the experiment is performed.

2. The form of equations which describe the equilibrium.

For example, for the reaction

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

If the reaction is multiplied by 2,

2N2(g) + 6H2(g) 4NH3(g)

the expression for Kc becomes

[NH3 ]4
Kc′ =
[N 2 ]2 [H 2 ]6
Kc′ = (Kc)2

If the reaction is reversed, 2NH3(g) N2(g) + 3H2(g)

the Kc becomes
[N 2 ][H 2 ]3
Kc″ =
[NH3 ]2

Kc″ = 1/Kc

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 CHEMICAL EQUILIBRIUM AND PHASE EQUILIBRIUM

The equilibrium constant does not depend upon the initial concentrations of the
reactants. Kc and Kp are independent of pressure.

Le Chatelier’s Principle
When the reaction has attained equilibrium then the temperature, pressure, volume and
concentrations remain constant. These four properties are known as reaction
parameters. Le Chatelier’s principle describe the changes that will take place when
any one of the reaction parameters are changed at equilibrium.
Statement: If any one or more of the reaction parameters is changed at equilibrium
then the reaction will proceed in that direction so as to undo the change in the
parameter and the equilibrium is again attained.
Le Chatelier’s principle describes the effect of the change in parameters on the
position of equilibrium. That is, it predicts whether the changes in reaction parameters
will favour the formation of reactants or products.

Historical Note
Henry Louis Le Chatelier (1850-1936) was a French-
Italian chemist. He is most famous for the law of
chemical equilibrium which is known by his name as
Le Chatelier's principle. This law is used by chemists
to predict the effect of a change in conditions on a
chemical equilibrium

Henry Louis Le Chatelier

Effect of Change in Temperature on the Position of Equilibrium

Activity 5.8

Form a group and perform the following activity to study the effect of temperature on the
position of equilibrium:
Take 0.5 g of cobalt chloride (CoCl2.6H2O) in a test tube and add 10 mL of distilled water
to prepare the solution. Then add 5 mL of concentrated HCl slowly to the solution. What is
the colour of the solution? Now put the test tube in a beaker containing crushed ice. Note

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 CHEMISTRY GRADE 11

the colour of the solution. Take out the test tube from ice bath and keep it at room
temperature for 5 minutes. Note the colour of the solution.
Share your findings with the rest of the class.

According to Le Chatelier’s principle, if the temperature of the reaction at equilibrium

is increased then the reaction will proceed in that direction where heat is absorbed so
as to undo the effect of heating. Similarly if the temperature of the reaction at
equilibrium is lowered then the reaction will proceed in that direction where the heat is
produced so that the equilibrium is again attained.

For an exothermic reaction, when the temperature is lowered, the reaction will
proceed in the forward direction, since the heat produced during forward reaction will
undo the effect of lowering of temperature. When the temperature is increased, then
the reaction will proceed in the reverse direction where the heat is absorbed.

For an endothermic reaction, when the temperature is lowered, the reaction will
proceed in the reverse direction where heat is produced so as to undo the effect of
lowering of temperature. When the temperature is increased, the reaction proceeds in
the forward direction.

Effect of temperature in terms of amount of reactants and products formed can be

summarized as:

When the equilibrium shifts in the forward direction, then the concentration of
products increases and that of reactants decreases.

So for exothermic reactions when the temperature is lowered, more products are
formed. That is, the decrease in temperature favours exothermic reactions.

For endothermic reactions, when the temperature is increased, more products are
formed, That is, increase in temperature favours endothermic reactions.

For example, formation of ammonia is an exothermic process.

N2(g) + 3H2(g) 2NH3(g) ∆H = – 92 kJ mol–1

If the temperature is lowered at equilibrium, the reaction will proceed in the forward
direction till the new equilibrium is established. So the concentration of ammonia will

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 CHEMICAL EQUILIBRIUM AND PHASE EQUILIBRIUM

increase. If the temperature is increased at equilibrium, then the reaction will proceed
in reverse direction which is endothermic in nature. So the concentration of ammonia
will decrease.

Dissociation of dinitrogen tetroxide is endothermic in nature.

N2O4(g) 2NO2(g)

Therefore, according to Le Chatelier’s principle, the formation of NO2 is favoured by

increase in the temperature at equilibrium.

Experiment 5.2

Effect of Change in Temperature on the Equilibrium Position

Objective: Determination of the effect of changes in temperature on the position
of equilibrium of iodine and starch.
Apparatus: Test tubes, water bath, stands, Bunsen burner, thermometer.
Chemicals: Iodine, starch.
Procedure:

1. Add a few drops of tincture of iodine to some starch solution in a test tube.
Record your observations.
2. Heat the solution to about 80°C using a water bath. Record your
observation. What can we deduce from this?
3. Cool the container by placing it in an ice box. Record your observation.
Observations and analysis:
1. Explain the concept of a starch-iodine complex. Is this an example of an
equilibrium reaction?

2. Which direction is exothermic and which is endothermic? How do you

explain your results?

3. What can you conclude based on your observations?

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 CHEMISTRY GRADE 11

Stand

Figure 5.3 Laboratory set-up for the effect of changes in temperature

on equilibrium of iodine and starch.

Effect of Change in Pressure on the Position of Equilibrium

According to Le Chatelier’s principle, if the pressure at equilibrium is increased then
the reaction will proceed in that direction where the pressure is reduced. Since the
pressure depends upon the number of moles, on increasing the pressure the reaction
will proceed in that direction where the number of moles are reduced.
If the pressure at equilibrium is decreased then the reaction will proceed in that
direction where the number of moles is more.
For a general reaction,
aA + bB mM + nN

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 CHEMICAL EQUILIBRIUM AND PHASE EQUILIBRIUM

the effect of pressure is decided by ∆n.

∆n = (m + n) – (a + b)
If ∆n > 0, that means the total moles of products is greater than the total moles of
reactants. Lowering of pressure will favour the reaction in forward direction. That is,
more products will be formed at equilibrium if the pressure is lowered.
If ∆n < 0, that means the total moles of products is less than the total moles of
reactants. Increasing the pressure will favour the reaction in forward direction. That is,
more products will be formed at equilibrium if the pressure is increased.
If ∆n = 0, then the change in pressure has no effect on the position of equilibrium.
For example, in the formation of ammonia,
N2(g) + 3H2(g) 2NH3(g)
∆n = 2–(1+3) = –2
Therefore, an increase in pressure at equilibrium will favour the forward reaction.
For the dissociation of dinitrogen tetroxide, N2O4(g) 2NO2(g)
∆n = 2 – 1= 1
The decrease in pressure at equilibrium, favours the forward reaction.
Hydrolysis of ester is not affected by the change in pressure. Why is it so?

Effect of Change in the Concentration on the Position of Equilibrium

Activity 5.9

Form a group and consider the following reaction at 400°C:

H2(g) + I2(g) 2HI(g)

H2 and I2 were placed into a flask and allowed to react until equilibrium was reached. Then
a small amount of H131 I was added. 131 I is an isotope of iodine that is radioactive. Discuss
131
whether radioactive I will remain in the HI molecule or some, or all, of it will find its
127 131
way into the I2 molecule forming I I.

Share your ideas with the rest of the class.

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 CHEMISTRY GRADE 11

At equilibrium, on increasing the amount of a substance, the reaction proceeds in that

direction where the substance is consumed. When the amount of the reactants is
increased the reaction proceeds in the forward direction and when the amount of
products is increased, the reaction proceeds in the backward direction.

The forward reaction is favoured if the products formed are removed from the vessel.

Experiment 5.3

Effect of Change in Concentration on Equilibrium Position

Objective: To study the effect of concentration on the position of equilibrium.
Apparatus: Test tubes (5), test tube stand, 100 mL beakers (2),
Chemicals: 0.05 M Fe(NO3)3 solution, 0.01M KSCN solution, 0.1M HNO3
acid.
Procedure:
1. Take 5 test tubes and label them as 1, 2, 3, 4 and 5. Keep them on a test
tube rack.
2. Take 50 mL of 0.05 M solution of Fe(NO3)3 in a beaker.
3. In separate beakers take 10 mL of 0.01 M KSCN solution and 20 mL of
0.1 M HNO3 acid solution.
4. Mix the solutions according to the given table to prepare 5 different
solutions.

Test tube No. Volume in mL of

0.05 M Fe(NO3)3 0.1 M HNO3 0.01 M KSCN

1 1.0 4.0 1.0

2 2.0 3.0 1.0

3 3.0 2.0 1.0

4 4.0 1.0 1.0

5 5.0 0.0 1.0

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 CHEMICAL EQUILIBRIUM AND PHASE EQUILIBRIUM

5. Note the colour of the solution in each test tube.

6. Arrange the test tubes in the increasing order of colour intensity.

Observations and analysis:

1. Which direction is exothermic and which is endothermic? How do you
explain your results?

2. Correlate the colour intensity with the concentration of Fe3+ in the test tube.

Hint: Fe3+ forms deep red colour complex with SCN– ions.

Fe3+(aq) + SCN–(aq) Fe(SCN)2+(aq)

deep red
3. By taking different volumes of Fe(NO3)3 in the test tubes the concentration
of Fe3+ is varied in the solution. Calculate the concentration of Fe3+ ions in
each test tube and correlate with the colour intensity.

4. In the test tube take 1.0 mL of Fe(NO3)3 solution and add 4.0 mL of
HNO3 solution followed by 1.0 mL of KSCN solution. Mix well and note
the colour. Add 1.0 mL of Fe(NO3)3 solution and again note the colour of
the solution.

Test tubes

Test tube
rack
Fe(NO3)3 0.01 M KSCN 0.1 M HNO3

Figure 5.4 Laboratory set-up for the effect of changes in concentration on

equilibrium of Fe3+(aq) and SCN–(aq).

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 CHEMISTRY GRADE 11

Effect of Catalyst on the Position of Equilibrium

Catalyst is a substance that alters the rate of a reaction without being consumed
during the reaction. The catalyst does not effect the position of equilibrium. It alters
the time in which the equilibrium is attained. This is due to the fact that the catalyst
changes the rate of the forward reaction and the reverse reaction by the same extent
so the equilibrium is not effected.

Effect of Addition of Inert Gases on the Position of Equilibrium

When a non reactive gas is added to a reaction at equilibrium, the effect depends on
various factors.
Case 1. When the non-reactive gas is added at constant volume there is no change
on the position of equilibrium.
Case 2. When the non-reactive gas is added and the volume of the system changes
then the effect of position is decided by the stoichiometry of the reaction.
For a general reaction,
aA + bB mM + nN
∆n = (m + n) – (a + b)

If ∆n < 0, then the addition of inert gas favours the formation of the reactants.
If ∆n > 0, then the addition of inert gas favours the formation of products.
If ∆n = 0, then the addition of inert gas has no effect on the position of equilibrium.

Example 5.7
For the reaction at equilibrium:

2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g) ∆H°rxn = 128 kJ

state the effects (increase, decrease, no change) of the following stresses on

the number of moles of sodium carbonate, Na2CO3, at equilibrium in a closed
container. Note that Na2CO3 is a solid (this is a heterogeneous equation); its
concentration will remain constant, but its amount can change.

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 CHEMICAL EQUILIBRIUM AND PHASE EQUILIBRIUM

a Removing CO2(g) c Raising the temperature

b Adding H2O(g) d Adding NaHCO3(s).

Solution:

a If the CO2 concentration is lowered, the system will react in such a way as
to offset the change. That is, a shift to the right will replace some of the
missing CO2. The number of moles of Na2CO3 increases.

b Addition of H2O(g) exerts a stress on the equilibrium that is partially offset

by a shift in the equilibrium to the left (net reverse reaction). This consumes
Na2CO3 as well as some of the extra H2O. The number of moles of
Na2CO3 decreases.

c An increase in temperature will increase the Kc value of an endothermic

reaction. There is a shift to the right, and more Na2CO3 is formed.

d The position of a heterogeneous equilibrium does not depend on the

amount of pure solids or liquids present. The same equilibrium is reached
whether the system contains 1 g of NaHCO3(s) or 10 g of NaHCO3. No
shift in the equilibrium occurs. No change in the amount of Na2CO3 occurs.

Optimum Conditions
The conditions that give maximum yield of the products are known as optimum
conditions. These conditions are decided by the enthalpy of reaction and its
stoichiometry applying Le Chatelier’s principle.

1. For exothermic reactions the yield of products is increased by performing the

reaction at lower temperatures.

2. For endothermic reactions the yield of products is increased by performing the

reaction at higher temperatures.

3. When ∆n > 0, the decrease in pressure favours the formation of products.

4. When ∆n < 0, the increase in pressure favours the formation of products.

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 CHEMISTRY GRADE 11

5. Removing the products from the reaction vessel shifts the equilibrium reaction in
the forward direction.

5.1.5 Chemical Equilibrium and Industry

Industrial processes are designed to give maximum possible yield of the products. The
conditions for carrying out the reactions are based on Le Chatelier’s principle. The
following processes illustrate the application of Le Chatelier’s principle in the industry.

Haber Process for the Manufacture of Ammonia

In 1909 Fritz Haber established the conditions under which nitrogen, N2(g) and
hydrogen, H2(g), would combine to give ammonia. This process produces ammonia
with yield of approximately 10-20%. The Haber synthesis was developed into an
industrial process by Carl Bosch.
The reaction between nitrogen gas and hydrogen gas to produce ammonia gas is an
exothermic equilibrium reaction, releasing 92.4 kJ/mol of energy at 298K (25°C).

heat, pressure
ZZZZZZZ
N2(g) + 3H2(g) YZZZZZZ
catalyst
Z 2NH3(g) ∆H = –92 kJ mol–1
X ...(1)

According to Le Chetalier’s Principle:

• Increasing the pressure causes the equilibrium to move in the forward
direction resulting in a higher yield of ammonia since there are more gas
molecules on the left hand side of the equation (4 in total) than there are on
the right hand side of the equation (1). Increasing the pressure means the
system adjusts to reduce the effect of the change, that is, to reduce the
pressure by having fewer gas molecules.
• Decreasing the temperature causes the equilibrium to move in the forward
direction resulting in a higher yield of ammonia since the reaction is
exothermic (releases heat). Reducing the temperature means the system will
adjust to minimize the effect of the change, that is, it will produce more heat
since energy is a product of the reaction, and will therefore produce more
ammonia gas as well. However, the rate of the reaction at lower temperature
is extremely slow, so a higher temperature must be used to speed up the
reaction which results in a lower yield of ammonia.

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The equilibrium expression for this reaction is:

[NH3 ]2
Kc =
[N 2 ][H 2 ]3

As the temperature increases, the equilibrium constant decreases and the yield of
ammonia decreases.

Temperature (°C) Keq

25 6.4 × 102

200 4.4 × 10–1

300 4.3 × 10–3

400 1.6 × 10–4

500 1.5 × 10–5

Rate Considerations:
• The use of catalyst such as an iron, speeds up the reaction by lowering the
activation energy so that the N2 bonds and H2 bonds can be more readily
broken.
• Increased temperature means more reactant molecules have sufficient energy
to overcome the energy barrier to reacting (activation energy) so the reaction
is faster at higher temperatures (but the yield of ammonia is lower as
discussed above). A temperature range of 400 – 500 °C is a compromise
designed to achieve an acceptable yield of ammonia (10-20 %) within an
acceptable time period.
At 200 °C and pressure above 750 atm there is an almost 100 % conversion of
reactants to the ammonia product. Since there are difficulties associated with
containing larger amounts of materials at such high pressure, lower pressure of around
200 atm are used industrially. By using a pressure of around 200 atm and a
temperature of about 500 °C, the yield of ammonia is 10-20 %, while costs and
safety concerns during operation of the plant are minimized.

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100 200°C

80 300°C
% ammonia

400°C
60

40 500°C

600°C
20
700°C

0
200 400 600 800 1000
Pressure (atm)

Figure 5.5 Effect of pressure on percentage yield of ammonia.

During industrial production of ammonia, the reaction never reaches equilibrium as the
gas mixture leaving the reactor is cooled to liquefy and remove the ammonia. The
remaining mixture of reactant gases is recycled through the reactor. The heat released
by reaction is removed and used to heat the incoming gas mixture.
A flow diagram for the Haber process of manufacturing ammonia is shown below:

Haber Process-manufacture of ammonia

Hydrogen 3H2 + N2 2NH3

Ammonia
Pressure
(200 atmospheres)
Reaction vessel Separation by
and containing iron cooling and
catalyst condensing the
heat ammonia
Nitrogen
(400°C)

Unreacted nitrogen and hydrogen recycled

Figure 5.6 A flow scheme for Haber Process.

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Contact Process for the Manufacture of Sulphuric acid

The manufacture of sulphuric acid by contact process involves the catalytic oxidation
of sulphur dioxide SO2 to sulphur trioxide SO3, which is a reversible reaction.
2SO2(g) + O2(g) 2SO3(g) ∆H = – 196 kJ mol–1

Contact Process for Production of Sulphric Acid

Contact process involves the following steps:
(i) Solid sulphur, S(s), is burned in air to form sulphric dioxide gas, SO2;
S(s) + O2(g) —→ SO2(g)
(ii) The gases are mixed with more air then cleaned by electrostatic precipitation
to remove any particulate matter.
(iii) The mixture of sulphur dioxide and air is heated to 450 °C and subjected to
a pressure of 101.3 - 202.6 kPa (1-2 atmospheres) in the presence of a
vanadium catalyst (vanadium (V) oxide) to produce sulphur trioxide, SO3(g),
with a yield of 98 %.
2SO2(g) + O2(g) —→ 2SO3(g)
(iv) Any unreacted gases from the above reaction are recylced back into the
above reaction.
(v) Sulphur trioxide, SO3(g) is dissolved in 98 % (18 M) sulphuric acid, H2SO4,
to produce disulphuric acid or pyrosulpuric acid, also known as fuming
sulphuric acid or oleum, H2S2O7.
SO3(g) + H2SO4 —→ H2S2O7
This is done because when water is added directly to sulphur trioxide to
produce sulphuric acid,
SO3(g) + H2O(l) —→ H2SO4(l)
the reaction is slow and tends to form a mist in which the reaction becomes
very slow.
(vi) Water is added to the disulphuric acid, H2S2O7, to produce sulphuric acid,
H2SO4.
H2S2O7(l) + H2O(l) —→ 2H2SO4(l)
The oxidation of sulphur dioxide to sulphur trioxide in step (iii) above is an
exothermic reaction (energy is released), so according to Le Chatelier’s Principle,

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higher temperatures will force the equilibrium position to shift to the left hand side of
the equation favouring the production of sulphur dioxide. Lower temperatures would
favour the production of the product sulphur trioxide and result in a higher yield.
However, the rate of reaching equilibrium at the lower temperatures is extremely low.
A higher temperature means equilibrium is established more rapidly but the yield of
sulphur trioxide is lower. The temperature about 450°C is a compromising situation
whereby a faster reaction rate results in a slightly lower yield.
Similarly, at higher pressures, the equilibrium position shifts to the equation in which
there are the least numbers of gaseous molecules.
2SO2(g) + O2(g) —→ 2SO3
On the left hand side of the reaction there are 3 moles of gaseous reactants, and the
right hand side are 2 moles of gaseous products, so higher pressure favours the right
hand side, by Le Chatelier’s Principle. Higher pressure results in a higher yield of
sulphur trioxide. A vanadium catalyst (vanadium (V) oxide) is also used in this reaction
to speed up the rate of the reaction.

Combustion Absorption Tower Hydration of

Converter
Chamber Oleum

(combustion of sulphur (formation of sulphur (sulphur trioxide absorbed (to produce sulphuric acid)
to form SO 2 ) trioxide) into the sulphuric acid mist)

Figure 5.7 A flow scheme for Contact process.

Exercise 5.7
Answers the following questions:
1. Which compound is manufactured by Haber process?
2. What are the raw materials used in Haber process?
3. What is the role of iron in Haber process?
4. How are the reactions made to run faster in the Haber process?
5. Draw a flow chart to show what happens in the three stages of Haber process.
6. What is a mixture of H2SO4 and free SO3?
7. What are the raw materials for making SO2 in the contact process?
8. Why is SO3 not directly added to make sulphuric acid?

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5.2 PHASE EQUILIBRIUM

At the end of this section, you should be able to:
• explain the interplay between kinetic and potential energy that underlies the
properties of the three states of matter and their phase changes;
• explain the process involved, both within a phase and through a phase change,
when heat is added or removed from a pure substance;
• explain the meaning of vapour pressure and explain how phase changes are
dynamic equilibrium processes;
• explain the relationship between vapour pressure and boiling point;
• describe how a phase diagram shows a phase of a substance at different
conditions of pressure and temperature; and
• use a phase diagram to determine melting point, boiling point, critical
temperature, critical pressure and triple point of a substance.
There are many physical processes that attain equilibrium under certain conditions.
You have already performed an activity where equilibrium exists between ice and
water. You also know that there are three states of matter, namely, solid, liquid and
gas. Each substance can exist in any one state depending upon the temperature and
pressure. A substance will exist in the gaseous state at high temperatures and low
pressures. It will exist in solid state at low temperature and high pressure. In between
the two conditions the substance will exist in the liquid state. These conditions are
decided by the nature of the substance. At molecular level this can be interpreted in
terms of forces of attraction and repulsion between the molecules.

5.2.1 Force of Attractions, Kinetic Energy and States of Matter

Activity 5.10

Form a group and perform the following activity:

In a test tube mix 1 mL of water with 1 mL of ethanol. Label it as A.
In another test tube take 1 mL of water and 1 mL of chloroform. Label it as B.
Discuss the following questions:
1. Find out in how many states the matter is present in test tubes A and B?
2. What is the difference between the liquids in the test tubes?
Share your ideas with the rest of the class.

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In a substance the molecules are held together by the forces of attraction. At the same
time each molecule possesses kinetic energy due to its motion. These two are
opposing forces; forces of attraction bind the molecules together while kinetic energy
tends to move the molecules apart.
• At very high temperatures, the molecules possess large kinetic energy, so
kinetic energy >> forces of attraction
As a result, molecules are far apart, the substance does not have definite shape or
volume. This state is known as gaseous state.
• At very low temperatures, the molecules possess small kinetic energy, so
kinetic energy << forces of attraction
As a result, the molecules are held together strongly and the substance has definite
shape and volume. This state is known as solid state.
• At intermediate temperatures the kinetic energy and forces of attraction match
each other, that is,
kinetic energy ≈ forces of attraction
As a result, the molecules are held together, but not strongly, so that the substance has
a definite volume but no definite shape. This state is known as liquid state.

5.2.2 Common terms: Phase, Component and Degree of

Freedom
Phase: It is that part of the system which is physically and chemically homogeneous
and separated from rest of the system by a discrete boundary. In this part the physical
and chemical properties are uniform.

For some simple systems it is physically distinct part of the system that may be
mechanically separated from other distinct parts.

The number of phases is represented by P. For example, a mixture of water and

chloroform has two distinct layers, one of water and the other of chloroform
(Activity 5.5). Therefore, there are two different phases although both are in the
liquid state. Similarly, a mixture of two solids constitutes two different phases
(Activity 5.6).

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The simple rules for determining the number of phases are.

• Pure substance present in one state of matter constitutes one phase.
• Same substance present in different states of matter constitutes different
phases. For example, ice and water are two different phases of H2O.
• A mixture of gases constitutes one phase system.
• A homogeneous solution is a one phase system.
• For immiscible liquids, the number of layers formed is equal to the number of
phases.
• For solids, each chemical species is a different phase. Different allotropic
forms of the same substance constitute different phases. For example,
diamond and graphite are different forms of carbon so they are different
phases.

Component: It is the chemically distinct quantity present in the system. The number of
components in a system is represented by C. When no chemical reaction takes place
in the system, the number of components is equal to the total number of chemical
species present in all the phases of the system. For example, an aqueous solution of
sodium chloride has two components, NaCl and water.

Degree of Freedom: It is the minimum number of variables required to describe each

component in each phase of the system. It is represented by F. In the case of a pure
substance present in one phase, the substance can be described completely if its
temperature and pressure are known. For example, if you have H2O and you also
know its temperature and pressure, then you can predict all the properties, such as,
whether it is in the solid, liquid or vapour state, as well as its density, refractive index,
viscosity and other properties. Since only temperature and pressure are required to
describe a pure substance, the degree of freedom of pure substance is 2.

Similarly, H2O can coexist as ice and liquid water under specific conditions of
temperature and pressures only. If the temperature is known then the pressure is fixed,
similarly if the pressure is known the temperature is fixed. Since only one variable is
required to completely describe a pure substance simultaneously present in two
phases, its degree of freedom is two.

All the three states of matter of a substance coexist (present together) at a point
known as triple point. The triple point has a fixed value of temperature and pressure
and no variable is required to describe the system, so the degree of freedom is zero.

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Example 5.8
1. Describe the number of phases present in the following systems:
a Solution of sodium chloride in water.
b A mixture of oil and water.
c A mixture of hydrogen, oxygen and methane gases.
d A mixture of powdered sodium chloride and potassium chloride.
e Ice floating on water.
Solution:
a P = 1 since the solution is homogeneous.
b P = 2 since oil and water are immiscible and they form two layers.
c P = 1 since a mixture of gases is a homogeneous mixture.
d P = 2 since NaCl and KCl are two different chemical species present in
the solid state.
e P = 2 since pure substance is present in two different states of matter.
2. Describe the number of components present in the following systems:
a Solution of sodium chloride in water.
b A mixture of hydrogen, oxygen and methane gases.
c Ice floating on water.
Solution:
a C = 2 since two chemical species are present.
b C = 3 since three chemical species, namely, hydrogen, oxygen and methane
gas are present.
c C = 1 since only one chemical substance, H2O is present.

Exercise 5.8
Determine the number of phases and components that exist in each of the
following systems:

a NH4Cl solid is placed in an evacuated chamber. After a while, some ammonia

and HCl appear in the gas phase above it.

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b COCl2, CO and Cl2 at equilibrium with no excess of CO or Cl2.

c COCl2, CO and Cl2 at equilibrium with excess of CO added (i.e., the

concentrations of CO and Cl2 are unequal).

5.2.3 Phase Rule

It is an important equation in the study of equilibrium between different phases in a

system. It relates the number of phases and components to the degree of freedom by
the following equation:

F=C–P+2

This equation was given by Josiah William Gibbs, hence it is known as Gibbs Phase
rule equation. This shows that the number of degrees of freedom (F) is equal to the
number of components (C ) minus the number of phases (P) plus the constant 2. The
factor 2 stands for two parameters, namely, temperature and pressure.

Let us calculate the degree of freedom for one component system (C = 1). A simple
example of one component is a pure substance. At a given time the pure substance
can exist in one phase or more than one phases present together in equilibrium. The
degree of freedom for various values of phases (1 – 4) can be calculated using the
Phase rule equation.
For P = 1,
F = 1 – 1 + 2 = 2; such a system is known as bivariant system.
For P = 2,
F = 1 – 2 + 2 = 1; such a system is known as monovariant system.
For P = 3,
F = 1 – 3 + 2 = 0; such a system is known as invariant system.
For P = 4,
F = 1 – 4 + 2 = – 1. This system is not possible as the degree of freedom
can not be negative.
From this we can conclude that for one component system, at a given time, maximum
of three phases can coexist in equilibrium.

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Historical Note

Josiah Willard Gibbs (1839 – 1903) was an American theoretical

physicist, chemist and mathematician. He devised much of the
theoretical foundation for both chemical thermodynamics and
physical chemistry. He proposed Gibbs' phase rule, in the 1870s.

Josiah Willard Gibbs

5.2.4 Temperature, Pressure and Phase Changes of Pure

Substance

In this section, we will study how the phase of a pure substance changes when it is
heated or cooled. The change in temperature may also be accompanied by the change
in the pressure of system.

Changes Involved During Heating of the Pure Substance (one

Component System)

When a pure substance is heated it undergoes various physical changes. These

changes depend upon initial pressure at which the heating starts.

Activity 5.11

Form a group and perform the following activity:

Take 10 ice cubes in a beaker, dip a thermometer in it and start heating. Note the
temperature and the physical changes taking place in the system.
Discuss the following questions in the group and afterwards share your ideas with rest of
the class.
1. What happens when ice is heated?
2. Does the temperature change when the ice is melting?
3. How does the temperature vary when the ice has melted completely?
4. What will happen if water formed is further heated?

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Reason for the Change in Phase on Heating

When a substance in the solid state is heated, the kinetic energy of its molecules
increases and they start moving. At a higher temperature, the kinetic energy of the
molecules becomes equal to the intermolecular forces of attraction, so these
intermolecular forces start breaking and the liquid is formed. This temperature is
known as melting point. On further heating the kinetic energy of the molecules goes on
increasing and ultimately becomes much greater than the forces of attraction between
the molecules. The molecules are able to overcome the forces of attraction and they
start moving randomly. This is the stage when the substance gets converted into
vapours.

Vapour Pressure and Boiling Point

When a liquid is taken in an evacuated closed vessel, some molecules at the surface
of the liquid escape to the vapour phase. This happens when the kinetic energy of the
surface molecules becomes greater than the intermolecular forces of attraction. This
process is known as vapourization. As a result, the pressure inside the vessel starts
increasing. When more and more molecules go from the liquid state to the vapour
state, some molecules present in the vapour phase near the surface of the liquid go
back to the liquid state. This process is known as condensation. The rate of
condensation increases as more and more molecules go into the vapour phase. A
stage comes when the rate of vapourzation becomes equal to the rate of condensation
and dynamic equilibrium is attained. (Refer to Activity 5.3). The pressure exerted by
the vapours at this stage is known as the vapour pressure of the liquid.

Vapour pressure is defined as the pressure exerted by the vapours in equilibrium with
the liquid at a specific temperature.

As the temperature is increased, the kinetic energy of the molecules increases, so

more molecules go from liquid phase to the vapour phase. As a result the total vapour
pressure increases with the increase in temperature. When the vapour pressure
becomes equal to the external pressure the liquid starts boiling. The temperature at
which the vapour pressure of the liquid becomes equal to its external pressure is
known as boiling point of the liquid. When the external pressure is equal to 1 atm, the
boiling point is known as normal boiling point.

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Exercise 5.9
Calculate the degree of freedom, F for each of the following:
1. An equilibrium gas phase containing N2O4 and NO2.
2. Phosgene, CO and Cl2 (with CO and Cl2 derived from decomposition
exclusively).
3. Phosgene, CO and Cl2, with excess CO added.
4. NH4Cl, initially in an evacuated chamber, with NH3 and HCl present from
decomposition.
5. Water, water vapor and ice in equilibrium.

5.2.5 Phase diagram

A Phase diagram is defined as a graphical representation the conditions when two or
more phases (such as vapor-liquid, liquid-solid) of a system can exist in equilibrium.

Phase Diagram for one Component System

As we know one component system has only one chemical species (pure substance)
and it can be described if the temperature and pressure of the system are known.
Under specific conditions of temperature and pressure, the system can exist in one
phase or two or three phases may be present in equilibrium. Phase diagram for a one
component system is a graph which shows the variation of pressure of the system with
temperature. It gives complete information about the conditions under which the
different phases of the system are stable. It also gives the information about the
temperature and pressure when the system changes from one phase to another phase.

Liquid
Pressure

Solid

Vapours

Temperature

Fig. 5.8 Sketch of phase diagram of one component system.

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Characteristics of a Phase Diagram for Pure Substance

• Temperature is plotted on x-axis and pressure on y-axis.

• The different regions of the graph represent different phases in which the
substance can exist.

• A substance exists in solid state at low temperatures and high pressures. So the
high pressure and low temperature region in the graph represents solid.

• A substance exists in vapour phase at high temperatures and low pressures, so

this area in the graph represents vapour.

• The remaining area between the two regions represents liquid phase.

• The boundary between the phases is represented by a line. This line is obtained
by joining the transition temperature between the two phases at different
pressures. For example, the boundary between the solid and liquid phase
represents points when solid changes to liquid or vice-versa. That is, it is the
melting point temperatures at different pressures, so it is known as melting point
curve. A boundary between liquid and vapour phase is known as vapourization
curve. The solid and vapour phases are separated by sublimation curve.

• On transition line two phases are at equilibrium. For example, on melting line
(OB) solid and liquid are in dynamic equilibrium. On boiling line (OC) liquid
and its vapours are at equilibrium and at sublimation temperature, solid is in
equilibrium with its vapours.

• The boundary line between two phases represents the two phase equilibria.

• The slope of the transition curves depends upon the nature of variation of
transition temperature with pressure.

• A triple point represents three phases at equilibrium, i.e., at triple point all three
phases coexist.

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Phase Diagram of Pure Water

Critical
point
Critical
B
pressure

218 atm C
Pressure (atm)

Solid water Liquid water

(ice)

1 atm
O
0.006 atm

Water Vapour
Triple point
Critical
temperatue
A

0°C 0.01°C 100°C 374°C

Temperature (°C)

Fig. 5.9 Phase diagram of pure water.

The phase diagram for water shows three regions, namely, ice, liquid water and water
vapour (Figure 5.6). Water is present in the form of ice at low temperatures and high
pressures. So ice is represented by the region on the left of AOB. Water vapour is
present at high temperatures and low pressures. So the region below AOC represents
water vapour. Liquid water is present in the intermediate conditions. Therefore, it is
represented by the region between BOC.

Curve AO is the boundary between ice and water vapour. On one side of the curve
is the region representing ice; on the other side is the region representing water
vapours. Along this curve, ice and vapours are present together at equilibrium, so it is
known as sublimation curve. It gives the sublimation temperature of ice at different
pressures. The slope of the curve is positive indicating that as the pressure increases,
the sublimation temperature of ice also increases.

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Curve OB represents the boundary between ice and liquid water. Along this curve
water and ice exist in equilibrium, therefore it is known as fusion or melting curve. It
represents the variation of melting point of ice at different temperatures. The slope of
the curve is negative indicating that as the pressure is increasing the melting point of
ice is decreasing.

Curve OC represents the boundary between water vapour and liquid water, therefore
it is known as vapourization curve. It represents the variation of boiling point of water
at different temperatures. The slope of the curve is positive indicating that as the
pressure is increasing the boiling point of water is also increasing. This behaviour of
decrease in melting point with increasing pressure is not common in the case of other
substances. This special property is known as the anomalous behaviour of water.

At point O, ice, water and water vapour regions meet, so this point represents the
triple point of water where all the three phases of water are at equilibrium. The
temperature and pressure at triple point are 0.01°C and 0.006 atm respectively.

Point C represents critical point. At this temperature and pressure the meniscus
between the liquid and the vapours disappears. Critical temperature is the maximum
temperature at which the substance can exist in liquid state. The minimum pressure
required to liquefy the vapours at critical temperature is known as critical pressure.
For water the critical point lies at 374°C and 218 atm.

Exercise 5.10
Consider the phase diagram of pure water (Figure 5.9) and answer the following
questions:
1. Under a pressure of 1 atmosphere, what is the maximum temperature at which
the water can exist in liquid phase?
2. What will happen to ice if it is compressed at 0°C?
3. What is the point at which ice, liquid water and water vapour can coexist at
equilibrium? Calculate the degree of freedom at this point.
4. The triple point of CO2 is 518 kPa at – 56.6°C. Its critical point lies at 7.38
MPa at 31.1°C. The sublimation curve, fusion curve and vapourization curve
have positive slope. Sketch the phase diagram of CO2 and label it.

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Applications of Phase Diagram

1. The phase diagram can be used to determine the phase of the system under the
given conditions of temperature and pressure.
2. It can be used to determine the melting point, boiling point and sublimation
temperature at different pressures.
3. Triple point and critical point can be determined from the phase diagram.
4. The changes taking place in a substance when it is heated at constant pressure
can be predicted with the help of phase diagram.
5. The changes taking place in a substance when it is compressed at constant
temperature can be predicted by phase diagram.

Unit Summary
• A system is said to be at equilibrium when its macroscopic properties like
temperature, pressure, concentration and energy do not change with time
without any outside help.
• The equilibrium is dynamic in nature which means that although the
macroscopic properties do not change, the processes do not stop at
molecular level.
• Chemical equilibrium is the state of the reaction when the macroscopic
properties like temperature, pressure, volume and concentration of the
reaction do not change with time.
• According to the law of mass action the rate at which A and B combine
is directly proportional to the product of their concentration terms each
raised to the power of its respected coefficient in the balanced chemical
reaction.
• For a general reaction at equilibrium a A + bB mM + nN the
expression for Kc is
[M]m [N]n
Kc =
[A]a [B]b
• The expression for Kp is
[ pM ]m [ pN ]n
Kp =
[ pA ]a [pB ]b

provided that all A, B, M and N are in gaseous state.

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• The unit of Kc is (mol L–1)(m+n)–(a+b) and the unit of Kp is (atm)(m+n)–(a+b)

• Kp = Kc(RT)∆n

• When Kc > 1 the formation of products is favoured at equilibrium.

• When K c < 1, So the formation of products is not favoured at

equilibrium.

• When Kc = 1, it indicates that the reactants and the products are present
in equal amounts.

• Reaction quotient is the ratio of concentrations of products to the

concentrations of reactants raised to the power of their respective
coefficients at any stage after the start of the reaction.

• For the reaction, a A + bB mM + nN the expression for the reaction

quotient is

[M]m [N]n
• Q=
[A]a [B]b
• When Q < K, then the reaction will proceed in the forward direction and
more products will be formed till the equilibrium is reached.

• When Q > K, then the reaction will proceed in the reverse direction and
more reactants will be formed till the equilibrium is reached.

• When Q = K, then the reaction has attained equilibrium.

• Le Chatelier’s principle gives the effect of any one or more of the

reaction parameters namely, temperature, pressure or concentration on
equilibrium.

• For exothermic reactions the yield of products is increased by performing

the reaction at lower temperatures.

• For endothermic reactions the yield of products is increased by

performing the reaction at higher temperatures.

• When ∆n > 0 the decrease in pressure favours the formation of products.

• When ∆n < 0 the increase in pressure favours the formation of products.

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• Removing the products from the reaction vessel shifts the reaction in the
forward direction.

• Phase (P) is that part of the system which is physically and chemically
homogeneous and separated from rest of the system by a discrete
boundary.

• Component (C) is the chemically distinct quantity present in the system.

• Degree of freedom (F) is the minimum number of variables required to

describe each component in each phase of the system.

• Gibbs Phase rule equation: F = C – P + 2.

• Vapour pressure is defined as the pressure exerted by vapours in

equilibrium with the liquid at a given temperature.

• The temperature at which the vapour pressure of the liquid becomes

equal to its external pressure is known as boiling point of the liquid.

• Phase diagram for a one component system is a graph which shows the
variation of pressure with temperature. It gives the transition temperature
between various phases.

Check List
Key terms of the unit

• Chemical equilibrium • Le Chateliers' principle

• Components • Phase
• Critical point • Phase diagram
• Critical temperature • Phase equilibrium
• Degree of freedom • Reaction quotient
• Equilibrium constant • Sublination curve
• Gibbs' phase rule • Triple point
• Law of mass action • Vaporization curve

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REVIEW EXERCISE

Part I: Multiple Choice Questions

1. Which of the following is correct about a reaction at equilibrium?

a The concentrations of reactants and products are equal.

b The system is static in nature.

c The forward and backward rates are equal.

d None.

2. For a reaction to shift towards the product direction, which of the following
condition holds true?

a Qc = Kc = 0 c Qc > Kc

b Qc < Kc d Qc = Kc

3. Given the equation 2C(s) + O2(g) 2CO(g), the expression for Kc is:

a 2[CO] / 2[C][O2] c [CO]2 / [O2]

b [CO]2 / [C]2[O2] d 2[CO] / [O2]

4. In which of the following cases does the reaction go farthest towards
completion:
a K = 103 c K = 10
b K = 10–2 d K=1
5. For the reaction C(s) + CO2(g) 2CO(g), the partial pressures of CO2 and
CO are 2.0 atm and 4.0 atm, respectively, at equilibrium. What is the value of
Kp for this reaction?
a 0.5 atm c 8.0 atm
b 4.0 atm d 32.0 atm
6. The equilibrium partial pressures of SO2, O2 and SO3 are 0.1 atm, 0.25 atm
and 0.5 atm respectively. The equilibrium constant for the reaction SO3(g)
SO2(g) + ½O2(g) is:

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a 0.1 c 0.05
b 10 d 20
7. Which of the following is likely to happen when pressure is applied to the
following system at equilibrium:
H2O(s) H2O(l)
a More water will be formed
b More ice will be formed
c Water will evaporate
d No change occurs
8. The equilibrium constant for the reaction N2(g) + 3H2(g) 2NH3(g) is K1
and for the reaction 2NH3(g) N2(g) + 3H2(g) is K2. The relation between
K1 and K2 is:
a K1 = K2 c K1 = – K2
b K1 = 1/ K2 d K1 = (K2)0.5
9. What will happen when CaO is added to the following reaction at equilibrium?
CaCO3(s) CaO(s) + CO2(g)
a No change occurs.
b Reaction shifts in the forward direction.
c More CaCO3 is formed.
d Total pressure increases.
10. Under what conditions are Kp and Kc equal?
a ∆n = 1 c ∆n = –1
b ∆n = 0 d They are never equal

Part II: Answer the following questions

11. For the reaction at equilibrium,
2SO2(g) + O2(g) 2SO3(g); ∆H = – 196 kJ mol–1
Predict the direction of the change on:

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a Removal of SO2.
b Addition of noble gas (argon) at constant pressure.
c Decreasing volume of the system.
d Increasing temperature of the system.
e Addition of a catalyst.
12. Balance the following equations and write the equilibrium constant expressions,
in terms of Kc and Kp.
a NH3(g) + O2(g) N2(g) + H2O(g)
b N2(g) + H2(g) NH3(g)
c CaCO3(s) CaO(s) + CO2(g)
13. For the reaction at 200°C
2A(g) + B(g) 3C(g)
the equilibrium constant is 3.0. Given the following information,

Species Concentration

[A] 2.0 M

[B] 3.0 M

[C] 2.0 M

Predict the direction in which the reaction should proceed to reach equilibrium.
14. Given the reaction
2CO2(g) 2CO(g) + O2(g)
what is the concentration of CO in equilibrium at 25°C in a sample of gas
originally containing 1.00 mol L–1 of CO2? For the dissociation of CO2 at
25°C, Kc = 2.96 × 10–92.
15. A saturated solution of Na2SO4 with an excess of solid is present in equilibrium
with its vapor in a closed vessel. Calculate the system's number of degrees of
freedom. Also, identify the independent variables.
16. What happens to water when the pressure remains constant at 1 atm but the
temperature changes from –10°C to 75°C? (refer to phase diagram for water)?

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17. 5.0 moles of ammonia were introduced into a 5.0 L reaction chamber in which
it partially decomposed at high temperatures;
2NH3(g) 3H2(g) + N2(g)
At equilibrium at a particular temperature, 80.0% of the ammonia had reacted.
Calculate Kc for the reaction.
18. 1.25 mol NOCl was placed in a 2.50 L reaction chamber at 427°C. After
equilibrium was reached, 1.10 moles of NOCl remained. Calculate the
equilibrium constant Kc for the reaction.
2NOCl(g) 2NO(g) + Cl2(g)
19. A sample of nitrosyl bromide was heated to 100°C in a 10.0 L container in
order to partially decompose it.
2NOBr(g) 2NO(g) + Br2(g)
At equilibrium the container was found to contain 0.0585 mole of NOBr, 0.105
mole of NO, and 0.0524 mole of Br2. Calculate the value of Kc.
20. The brown gas NO2 and the colorless gas N2O4 exist in equilibrium.
N2O4(g) 2NO2(g)
0.625 mole of N2O4 was introduced into a 5.00 L vessel and was allowed to
decompose until it reached equilibrium with NO2. The concentration of N2O4
at equilibrium was 0.0750 M. Calculate Kc for the reaction.

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