KENYATTA UNIVERSITY

INSTITUTE OF OPEN LEARNING

SCH 201
CHEMICAL THERMODYNAMICS

M. N. GITARI MUGAMBI
Dr. wa-THIONG’O J. KARANJA

DEPARTMENT OF CHEMISTRY
 TABLE OF CONTENTS

UNIT 1: THE FIRST LAW OF THERMODYNAMICS---------3

UNIT 2: THERMOCHEMISTRY----------------------------------25

UNIT 3: THE SECOND LAW OF THERMODYNAMICS----38

UNIT 4: FREE ENERGY AND EQUILIBRIA-------------------59

USEFUL PHYSICAL CONSTANTS------------------------------83

REFERENCES--------------------------------------------------------84

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Unit 1: THE FIRST LAW OF THERMODYNAMICS

1.0 Structure

1.01 Introduction
1.02 Objectives
1.03 The concept of energy
1.04 Basic definitions
1.05 Conservation of Energy
1.06 Internal Energy and work of expansion
1.07 Heat changes at constant pressure and volume
1.08 Maximum work of isothermal expansion of a gas
1.09 Internal Energy of an ideal gas
1.10 Molar heat capacities at constant pressure and constant volume
1.11 Adiabatic changes
1.12 Summary
1.13 Terminal questions
1.14 Answers to SAQS
1.15 Answers to terminal questions

1.01 Introduction

The study of energy transformations that accompany physical and chemical

changes constitutes the subject matter of Thermodynamics. Three concise
statements are made that sum up experiences with energy and natural processes.
These statements constitute the three laws of thermodynamics. From these laws,
logical deductions are made that bear on almost every aspect of chemistry. The
subject is important because it is applied in every day life. We light up a fire to
warm ourselves, cook food and to generate electricity energy through steam. The
latter example is illustrative of what thermodynamics is all about. Heat energy
from charcoal or coal is used to transform water from a liquid into a gas that turns
a turbine the mechanical energy of which is transformed into electricity. The
steam on cooling gets back to a liquid. A careful scrutiny of all transformations
and changes forms the study of thermodynamics. As the name suggests, we are
dealing with thermo or heat and dynamics meaning movements.

1.02 Objectives

By the end of this lesson you should be able to:

i) Define:

a. System, surroundings, universe

b. Open, closed and isolated systems
c. Energy, heat and work

3
 d. Isothermal, adiabatic, reversible and irreversible processes or changes
e. Thermodynamic functions such as internal energy (E) and enthalpy (H)
f. Heat capacity at constant volume (Cv), and Heat capacity at constant pressure
(Cp) and relate the two.
ii) Solve problems relating to thermodynamics, for example:
a) The change, during expansion or compression of an ideal gas, of Enthalpy,
internal energy and the work done.
b) Adiabatic changes in systems

1.03 THE CONCEPT OF ENERGY

The energy of a body is broadly defined as its capacity to perform work. This
energy may take various forms:-
- kinetic energy (due to motion)
- potential energy (due to position)
- heat energy (as measured by temperature)
- chemical energy, etc

By definition, energy is the capacity to do work. The forms of energy show that
the energy may be in active form, when it is doing work or stored, in which case it
is said to be potential. A basic definition given by the great physicist, Albert
Einstein is:

E = mc2 (1.03.1)
Where

E = energy, m = mass and c = velocity of light.

Since energy is capacity to do work, work is an expression of energy and
therefore:

Energy (work) = force x distance

Which can be also expressed as:

Energy = mass x acceleration x distance

= mass x length2 x time-2

Energy, therefore, can be expressed in terms of grams square meters per square
seconds. One can see that for conciseness, there is need to have a unit of energy.
The JOULE is the SI unit of energy. This is taken to be the energy required to
move a force of 1Newton through a distance of 1 meter. A Newton is a force that
produces an acceleration of one meter per second squared when applied to a one-
kilogram mass.

4
 Finally, it should be noted that there is a natural tendency for other forms of
energy to ultimately change to HEAT energy.

1.04 BASIC DEFINITIONS

SYSTEM

The term system is used to refer to some specified portion of matter under
consideration. When some tea is put in a good thermos flask, one can refer to the
inside contents and conditions in terms of the system. Likewise, 2 moles of an
ideal gas in a closed vessel would also comprise a system.

SURROUNDINGS

Outside the flask or the vessel are completely different conditions and contents.
This portion of matter other than the system itself is called the surroundings.

UNIVERSE

The system and its surroundings together are called the universe. One can
therefore appreciate that there are boundaries between the system and its
surroundings, which can be open or closed.

When matter can be transferred between the system and its surroundings we
regard it as ‘an open system’ otherwise, it is a ‘closed system’.
An ‘isolated system’ is a closed system in which there is neither mechanical nor
thermal contact with the surroundings. If heat is allowed to flow from the
surroundings into the system and vice versa during a change such that the
temperature of the system is maintained at a constant value, then the change is
said to be ‘isothermal’. If the pressure is likewise maintained, then the change is
termed ‘isobaric’. If the system is completely isolated from its surroundings the
changes occurring therein are said to be ‘adiabatic’.

SAQ 1

Classify the following systems as open, closed or isolated.

(a) Nitrogen and hydrogen reacting to form ammonia in a

sealed tube:

(b) Potassium chlorate and manganese dioxide are heated in

an unsealed test tube to form potassium chloride and
oxygen.

5
 (c) A glass vial containing sulphuric acid is broken inside
water in a beaker.

(d) A glass vial containing hydrochloric acid is broken inside

a solution of sodium hydroxide kept in a closed
polythene bottle insulated with a cork.

STATE FUNCTIONS

The most frequently used variables in chemistry are Temperature, Pressure, Volume
and Chemical Composition. Consider, for example water. The chemical formula
H2O gives us a definition or the identity of the material. We can start with liquid
water at 25 oC, freeze it at –5oC, warm it to the liquid form and finally boil it off.
The water can be said to have undergone several state changes that are:

liquid solid liquid gas

A system is said to be in a certain state when all its properties have definite values.
The net energy change, in the example above, is taken to be that from liquid to the
vapor. The properties that depend only on the state of the system and not on its past
history are called STATE FUNCTIONS.

6
 EXTENSIVE PROPERTIES

These are properties that depend on the quantity of matter present for example mass
and volume.

INTENSIVE PROPERTIES

These are properties that do not depend on quantity of matter present for example
temperature and pressure.

REVERSIBLE PROCESS

Some changes take place in such a way that one can go back to the original state.
Such changes need to be undertaken very very slowly so that there is no ‘shock’ to
the system. As an example, one can heat water reversibly from 5 to 10 oC by
increasing the temperature by small incremental steps at a very slow rate. In order to
go back one will need to cool in such a slow rate. A reversible process is a change
that takes place infinitesimally slowly while the system is in equilibrium with its
surroundings in terms of temperature and pressure.

SAQ 2.

Which of the following are extensive properties and which are intensive properties?
a. Viscosity
b. Weight
c. Mass
d. Volume of a solid
e. Temperature
f. Pressure

1.05 CONSERVATION OF ENERGY

This is regarded as ‘The first law of thermodynamics’. The law is based

on experience, with no exception having been found. Energy is always being
changed from one form to another. When we eat food, the energy in the food is
converted to a form that is used by the body to work. The body then uses that energy
to cultivate more food for eating and also to do other activities. Looked at from way
beyond the earth, one is just recycling the energy. It can therefore be stated that:
"Although energy can be converted from one form to another, it can not be
created or destroyed".
Alternatively,
"The total energy of a system and its surroundings must remain constant,
although it may be changed from one form to another".

7
A system will have a thermal energy reservoir and a mechanical energy reservoir,
and these can be expressed in the following diagram:

Universe of the system

System Thermal
Reservoir

Mechanical
Reservoir

The three blocks describes the universe of the system and any processes that would
take place within. Nothing else is affected by happenings in the system and hence
the encompassing ‘universe’ of the system.

If a chemical reaction takes place in the system, there will be a change from the
initial state A to the new state B. State A is described by some chemical constituents
at some temperature and pressure, while the new state B will also be described by
some new or (more often) mix of new and old chemical constituents at different,
temperature or pressure, vice versa or both. In such a case, the energy will
universally be expressed as:

E = mc2 (1.03.1)

Where

E = energy, m = mass and c = velocity of light.

The universal energy of the system depends upon its P, V, T, Mass and composition.
For a system of fixed mass and composition, fixing two variables implies that the
third is automatically fixed.

We can determine the energy changes taking place from state A to state B by
making use of the first law. The conservation principle applied to the universe of the
process is expressed by:

∆E universe= 0
or
∆E thermal reservoir + ∆E mechanical reservoir + ∆Estate A to State B = 0 (1.05.1)

From the equation above,

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 ∆E A to B = -∆E thermal reservoir - ∆E mechanical reservoir (1.05.2)

The energy of a given state of a system is a fixed quantity and does not depend on
the previous history of the system. If EA represents the energy of state A and EB that
of state B, then

∆E = EB - EA, (1.05.3)

and it is independent of the path. E is therefore a state function.

For an infinitesimal process the small change dE is an exact differential. E is known

as the internal energy. The actual value of E is generally not known but this is of no
significance since thermodynamics is concerned with changes in energy and these
are measurable quantities.

1.06 INTERNAL ENERGY AND WORK

In changing from one state to another, a system may do external work, denoted by w
(say work of expansion against external pressure).

w is positive? if the system does external work. w is negative if work is done on the
system (e.g. when the system is compressed).

The system may absorb heat q, from the surroundings in which case q is positive
other wise it is negative if the system gives out heat.

When a system changes from state A to B, its internal energy changes by ∆E, while
at the same time the system does work w, and absorbs heat, q.

By the first law

∆E = q - w or q = ∆E + w (1.06.1)

For small changes, dE = δq - δw (1.06.2)

q = ∆E + w (1.06.3)

This implies that "of the total heat, q, absorbed from the surroundings a portion
raises the internal energy of the system by ∆E and the rest is used as the work of
expansion".

9
WORK DONE IN GAS EXPANSION OR COMPRESSION
p

A a

One does work when, for example pumping, air into a bicycle tube. The
compressed air in the pump does work of expansion of the tube, against the
constant atmospheric pressure. The action of the pump is illustrated above.
Pressure is applied to a piston in a cylinder of area (A) so that it compresses the
gas inside to a distance h. We can express the energy changes as follows:

External work done (w) = force (F) x distance (h)

Given that Pressure (P) = Force (F) per Unit area (A)

It then follows that

W = PextAh

= Pext∆V (1.06.4)

The volume change (∆V) above is really the change in volume represented by the
changed piston level, implied by the area x height. This is the work of expansion
expected on the tube.

EXAMPLE 1.5

When one mole of water, at 1000C and 1 atm. pressure, is converted to steam (at
1000C) the amount of heat absorbed is 40670J. Calculate ∆E for the change.

SOLUTION

The work done in expanding against the atmospheric pressure is:

w = Pext (V2 - V1)

V1 = volume of 1 mole of liquid water

10
 = 18cm3
= 18 x 10-6m3
V2 = volume of 1 mole of water vapour at 100 0C

From the gas laws and at constant pressure,

V1/T1=V2/T2

At STP, that is 00C and 1atmosphere pressure, 1mole of an ideal gas occupies
approximately 22.4 litres or 0.0224 m3. The volume at 1000C (V2)will be:

= 0.0224 x 373/273
= 0.0306m3

Then
Pext (V2 - V1) = 101325 (0.0306 - 18 x 10-6)
= 3099 Joule

From first law

∆E = q - w
= 40670 - 3099
= 37571 J

It is seen that most of the energy received by water from the source goes to
raising the internal energy of the water as it goes from liquid to vapour.

SAQ3

Two moles of an ideal gas at 273 K and 101325 NM-2 pressure expand from 0.056
M3 to 0.28 M3 at the same temperature. Determine the work done.

1.07 HEAT CHANGES AT CONSTANT PRESSURE AND

CONSTANT VOLUME

From the first law, we write

∆E = q – w (1.06.1)

meaning
q = ∆E + w (1.06.1)

and if w is only the mechanical work of expansion or compression,

11
then
w = P∆V, (1.06.4)

such that P is the external pressure, and ∆V is the change in volume.

The equation therefore becomes,

q = ∆E + P∆V (1.07.1)

At constant volume,

∆V = O and qv = ∆E (1.07.2)
(subscript v signifies constant volume)

Similarly, at constant pressure (external) one has

qp = ∆E + P∆V (1.07.1)

Writing

∆E = E2 - E1 and ∆V = V2 - V1, one has

qp =E2 - E1 + P (V2 - V1)

= E2 - E1 + PV2 - PV1
= (E2 + PV2) - (E1 + PV1) (1.07.3)

Since P and V are thermodynamic properties of the system, then E + PV is

dependent only on the state of the system. This extensive thermodynamic
property is called ENTHALPY, represented by H. Thus,

H = E + PV (1.07.4)

so that

H2 - H1 = ∆E + ∆(PV) <=> (E2-E1) + P(V2-V1) (1.07.5)

Since P is a constant, leading to,

∆H = ∆E + P∆V = qp (1.07.6)

In physical terms, enthalpy is viewed as the heat content of a system.

12
 SAQ 4

You need to raise the temperature of 1.0 mole of water from 25.0 to 30.0 oC at 1
atm. pressure without heating. Explain how this can be done using the first law?

1.08 MAXIMUM WORK IN ISOTHERMAL EXPANSION OF A GAS

When a gas expands at constant temperature, the external pressure must decrease
during the course of expansion. To carry out such a change in a reversible
manner, the external pressure continuously adjusts itself so as to be always less
than the internal pressure of the gas by an infinitesimal amount.

If P is the internal pressure of the gas at any time during the expansion, the
external pressure is (P - dP) where dP is an infinitesimal change in pressure.

The work , δw , done when the gas changes its volume by dV is

δw = (P - dP) dV = PdV – dPdV

≈ pdv (1.08.1)

The total work done will be

V2
w= ∫ PdV
V1
(1.08 .2)

where V1 and V2 are the initial and final volumes, respectively.

For n mole of gas

nRT
PV = nRT => P = (1.08.3)
V

and thus:

v2 nRT v 2 dv
w= ∫
v1 V
dv = nRT ∫
v1 V

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 V 
= nRT ln 2  (1.08.4)
 V1 

Since the gas is ideal and T is constant P1V1=P2V2

v 2 p1
⇒ = (1.08.5)
v1 p 2

and thus:

p 
w = nRT ln 1  (1.08.6)
 p2 
EXAMPLE

3dm3 of hydrogen initially at STP are expanded isothermally and reversibly to a

volume of 4dm3. Calculate the work done.

SOLUTION

22.415 dm3 is the volume occupied by 1mole at STP and thus 3dm3 is occupied
by = 1x3/ 22.415mole at STP. The work done (w) is the isothermal reversible
work of expansion of the 1x3/ 22.415 mole of gas from 3dm3 to 4dm3 is:

w = 1x 3/22.415RT x ln (V2/V1)

=(3/22.415) x 8.314 x 273ln(4/3)

= 87.39 J

SAQ 5

2 moles of an ideal gas at 10 atm. and 23 oC are expanded isothermally to a

pressure of 1 atm. Determine the work done:

a) If the expansion is reversible and

b) If it is irreversible against an external pressure of 1 atm.

1.09 INTERNAL ENERGY OF AN IDEAL GAS

Molecules of an ideal gas are not supposed to attract each other. This implies that
q = 0, when the gas is allowed to expand into a vacuum and no work is done
since the external pressure is zero, i.e. w = 0.
Thus

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 ∆E = q - w (1.06.1)

= 0.

One can therefore conclude that, the expansion of an ideal gas, at constant
temperature is accompanied by no change in internal energy. Alternatively, one
can state that, "At any constant temperature, the internal energy of an ideal gas is
independent of its volume".

Thus, for isothermal expansion

∆E = 0,

whether expansion is in a vacuum or not.

This implies that at constant temperature,

v  p 
q = w = ∫ pdv = nRT ln 2  = nRT ln 1  (1.09.1)
 v1   p2 
Example:
0.1 mole of an ideal gas is expanded isothermally at 273 K from 3 dm3 to 5 dm3.
Determine the energy (q) absorbed from the surroundings.

Solution:

q = nRTln (v2/v1)
= 0.1x8.314x273ln(5/3)
= 115.94J

SAQ 6

A cylinder fitted with a piston contains 3 moles of helium at 400K and 1.00 atm.
Pressure. The pressure is increased reversibly to 5atm. Determine w, q and ∆E for
this process. (R= 8.314 J/mol/K)

1.10 MOLAR HEAT CAPACITIES AT CONSTANT PRESSURE

AND CONSTANT VOLUME

Molar heat capacity, C, is defined as the heat required to raise the temperature of
one mole of the system by one degree. In differential form this is expressed as

δq (1.10.1)
C=
dT

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The molar heat capacity at constant volume is therefore

δq v (1.10.2)
Cv =
dT

while for constant pressure is

δq p
Cp = (1.10.3)
dT
From equation (1.07.2), we note that
δqv = ∆E (1.10.4)
in which case then we have

dE
Cv =
dT (1.10.5)

or
dE = CvdT (1.10.6)

Integration yields

E2 T2

∫ dE = ∫ CvdT
E1 T1
(1.10.7)

leading to
T2
∆E = E2 -E1 = ∫
T1
CvdT
=Cv(T2-T1) (1.10.8)
if Cv is independent of temperature

Similarly from equation (1.07.6),

δqp = ∆H (1.10.9)
implying

dH
Cp = (1.10.10)
dT

meaning
dH = CpdT (1.10.11)

Integration yields

16
 T2
∆H = H 2 − H 1 = ∫ CpdT
T1

= Cp(T2-T1) (1.10.12)
when Cp is independent of temperature.

Now one wants to find a relationship between Cv and Cp.

From the First Law,

δq = δw + dE (1.06.2)

At constant pressure, one has

δqp = dE + PdV (1.07.1)

Noting that for one mole

PV = RT (1.08.3)
then

PdV = RdT (1.10.13)

And this implies that

δqp = dE + RdT (1.10.14)

Dividing throughout by dT yields

δq p dE
= +R (1.10.15)
dT dT
and thus

Cp = Cv + R (1.10.16)

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1.11 ADIABATIC CHANGES

An adiabatic change is a change that can be carried out reversibly such that no
heat enters or leaves the system. In an adiabatic expansion of a gas the system
does external work (of expansion), and since no heat can be taken up, the
necessary energy comes from the kinetic energy of the molecules. The decrease
in the value of the latter results in a fall in the temperature of the system. On the
other hand, in an adiabatic compression the temperature of the gas will rise.

In mathematical terms: (from First Law)

dE = -dw (1.11.1)

CvdT = - PdV (1.11.2)

For one mole P = RT/V and thus

C v dT − Rdv
= (1.11.3)
T V

T2 V
Cv ln = − R ln 2 (1.11.4)
T1 V1

Since for expansion, V2 > V1 and R is a positive constant, the RHS of the above
equation is negative. Since Cv is a positive quantity, one can see that in an
adiabatic expansion T2<T1, and so the temperature will fall. Conversely, in an
adiabatic compression the temperature will rise.

EXAMPLE

Two moles of an ideal monatomic gas at 300 K are compressed adiabatically to

one quarter of the original volume. What is the temperature of the gas after
compression?

SOLUTION

For a monatomic gas;

Cv=3/2R
Then we are given;
T1=300 K, V2=V1/4, T2=?

18
We know that
CVln T2/T1 = -RlnV1/V2
Substitution gives
3/2RlnT2/300 = -RlnV1/4V1
lnT2/300 = 2/3ln4
Thus giving T2 = 755.95 K Ans

Further from the equation (1.11.4), we can deduce the following.

T2 V
Cv ln = − R ln 2 (1.11.5)
T1 V1

R / Cv
T  V 
=> ln 2  = ln 1  (1.11.6)
 T1   V2 

⇒ T2V2β = T1V1β, where β = R/CV (1.11.7)

Also from equation (1.11.5)

T  V 
Cv ln 2  = − R ln 2  (1.11.5)
 T1   V1 

Cv / R
T  V 
=> ln 2  = ln 1 
 T1   V2 

Cv/ R Cv/ R
=>V1T1 = V2T2 (1.11.8)

From equation (1.11.4) and the ideal gas equation, other equations that interrelate
P, V, T, Cv and Cp can be derived as follows.

For an ideal gas:

P1V1 P2V 2 (1.11.9)

=
T1 T2

T PV (1.11.10)
⇒ 2 = 2 2
T1 P1V1
19
and substitution into the equation 1.11.4 above, leads to:

 PV  V 
Cv ln 2 2  = − R ln 2 
 P1V1   V1 
i.e.
P  V  V 
Cv ln 2  = −(Cv + R) ln 2  = Cp ln 1 
 P1   V1   V2 
(1.11.11)
so that

C P

 P  V  CV
ln  2  = ln  1 
 P1   V2 
and
P2 V γ γ
(1.11.12)
= 1 γ ⇒ P1V 1 γ = P 2 V 2
P1 V2
where
C p
γ =
CV
Also
P1V1 P2V2
=
T1 T2

V2 P1T2
=> =
V1 P2T1
(1.11.9)

Substitution gives

20
 T  V 
Cv ln 2  = − R ln 2 
 T1   V1 

P  P 
= − R ln 1  − R ln 2 
 P2   P1 

T  P 
=> (Cv + R) ln 2  = R ln 2 
 T1   P1 

Cp  T2  P 
ln  = ln 2 
R  T1   P1 

Cp / R
T  P 
ln 2  = ln 2 
 T1   P1 

Cp / R Cp / R (1.11.13)
P1T2 = T1 P2

Examples

1. To what pressure must a given volume of

Helium originally at 100oC and 1 atm. Pressure be adiabatically compressed
in order to raise its temperature to 400oC?

2. At 0oC and 1 atm. Pressure the volume of 1 mole of an ideal monatomic gas is
22.415 litres. The gas is expanded until its pressure is 0.4 atm. by a reversible
adiabatic process. Determine the final volume.

3. The volume of a sample of an ideal monatomic gas at 0oC is 44.83 litres. To

what volume must the gas be compressed adiabatically so as to attain a
temperature of 30oC.

Answers

1.P1 = 1 atm = 101 325 NM-2

T2= 400oC = 673 K
T1 = 100oC = 373 K
P2 = ?

Cp = Cv + R and Cv = 3/2 R for a monatomic gas.

21
∴ Cp = 5/2 R

Then
P1T2 Cp/R =P2T1 Cp/R
And substitution gives
101325x 673 5/2 = 3735/2 P2
∴ P2 = 443080.05NM-2
= 4.37 atm. Ans

2. P1 = 101325NM-2
V1 = 22.415 litres
P2 = 0.4 atm
V2 = ?

Cp/Cv = 5/3

P1V1γ = P2V2γ

V2γ = 101325x22.415 5/3 / 0.4x101325

V2 = 38.842 litres Ans

3. V1 = 44.83 litres

T1 = 0oC
T2 = 30oC
V2 = ?

Cv/R = 1.5
V1T1Cv/R = V2 T2Cv/R
V2 = V1(T1/T2) 1.5
= 44.83(273/303)1.5
= 38.84 litres Ans

SAQ7

To what pressure must a given volume of nitrogen originally at 100oC and 1 atm.
Pressure, be adiabatically compressed in order to raise its temperature to 400oC.

22
1.12 SUMMARY

Energy cannot be created or destroyed but can be transformed from one form to
another.
The heat absorbed by the system is partly stored within it as internal energy and
partly spent on doing work on the surroundings.
Heat absorbed by the system is taken to be positive.
Internal energy is a state function.
Transformations of systems can take place reversibly or irreversibly.
Transformations taking place in an infinite number of steps permitting
equilibrium, to prevail at every stage are called reversible transformations. When
the transformation is rapid and sudden, it is said top be spontaneous or
irreversible.
Work is calculated as a product of the pressure against which work is done and
the change in volume. For an irreversible process the pressure (external) is often
constant. For a reversible process, the pressure changes during the course of the
process.
The heat absorbed by a system at constant volume is equal to the internal energy
change while that absorbed by the system at constant pressure is the enthalpy
change.
The temperature coefficient of the internal energy change at constant volume is
the heat capacity at constant volume and the temperature coefficient of the
enthalpy change at constant pressure is the heat capacity at constant pressure.
An adiabatic change is that which can be carried out reversibly such that no heat
enters or leaves the system.

1.13 TERMINAL QUESTIONS

1. Calculate the work that can be done by a mass of 400 g, falling a distance
of 2.75 meters. How much heat could be produced if this mass was
allowed to fall freely this distance? What would be the value of ∆E
mechanical reservoir in the first case and ∆E thermal reservoir in the second?
2. A sample of an ideal monatomic gas at 1 atm pressure and 25oCexpands
reversibly and isothermally from 1 liter to 4 liters. Determine the work
done during the expansion.
3. A cylinder containing 1 mole of liquid water at 100oC is heated until the
liquid is converted to vapour. The cylinder is fitted with a piston which
just resists a pressure of 1 atm. How much work is done by the expanding
gas? If the heat of vaporization of water is 40670 joules, what is the
change in internal energy?
4. At 0oC the volume of 2 moles of an ideal monatomic gas is 22.415liters.
The gas is expanded until its pressure is 1atm. By a reversible adiabatic
process. Determine the final volume, temperature and work done.

23
1.14 ANSWERS TO SAQS

1 (a) Closed (b) Open © Open (d) isolated

2 (a) intensive (b) Extensive (c) Extensive (d) Extensive (e) Intensive
(f) Intensive

3 4539.4 J

4 Use mechanical form of energy, for example, stirring.

5 (a) 11.33kJ (b) 4.43 kJ

6 w = q = -1.61 x 10 4 J ∆E = 0

7 7.891Atm.

1.15 ANSWERS TO TERMINAL QUESTIONS

[1] [2] 140.47J [3] [4] v2 = 34.12 l T2 = 206.31 K

W = 1663.38J

24
UNIT 2 THERMOCHEMISTRY

Structure

2.01 Introduction
Objectives
2.02 Heats of reaction at constant pressure and constant volume
2.03 Enthalpy of formation
2.04 Enthalpy of combustion
2.05 Calorimetry
2.06 Thermochemical laws
2.07 Effect of temperature on enthalpy of reaction
2.08 Summary
2.09 Terminal Questions
2.10 Answers to SAQs
2.11 Answers to Terminal Questions.

2.01 Introduction

Thermochemistry deals with the heat changes accompanying chemical reactions. The
laws of thermochemistry are based on the principle of Conservation of Energy: i.e. The
First Law of thermodynamics.

If heat is liberated in the reaction the process is said to be EXOTHERMIC, but if it is

absorbed it is said to be ENDOTHERMIC. Many reactions normally occur at constant
atmospheric pressure and it is usual to record heat changes by quoting the value of the
heat of reaction at constant pressure, qp. This quantity is referred to as the enthalpy of
reaction. It represents the difference in enthalpies of the reaction products and the
reactants, at constant pressure and at definite temperature with every substance in a
definite physical state.

Objectives

At the end of the unit, the learner should be able to:

• Relate heats of reaction at constant pressure and constant volume
• Calculate the change in enthalpy accompanying a chemical reaction
• Apply the enthalpies of combustion, formation and thermo-chemical laws
in solving problems
• Demonstrate the dependence of enthalpies of reaction on temperature

25
2.02 HEATS OF REACTION AT CONSTANT PRESSURE AND
CONSTANT VOLUME

The relationship between the enthalpy of reaction at constant pressure, ∆H, and enthalpy
change at constant volume. ∆E, is given by the equation:

∆H = ∆E + P∆V (1.07.6)

For a process involving solids or liquids only, the volume change, ∆V, is small and can
be neglected. ∆H and ∆E are, therefore, approximately equal.

GASEOS REACTIONS

In this case, thermal processes lead to dramatic change in volumes. If nA is the number of
moles of the reactants and nB the number of moles of products, the reaction process
maybe accompanied by a change in the number of moles as follows.

∆n = (nB - nA)

If V is the volume of 1 mole of gas, at the given temperature and pressure, then the total
change in volume, ∆V, in the reaction will be V∆n.
Thus
∆H = ∆E + PV(∆n) (2.02.1)

But
PV = RT (1.08.3)

and hence

∆H = ∆E + RT (∆n) (2.02.2)

Further
PV2 = n2RT
PV1 = n1RT
Giving
P∆V = (∆n)RT

EXAMPLE

26
When one mole of liquid benzene is completely burnt in oxygen to form liquid water and
CO2 gas, ∆H = -3264.58 kJ at 298K. Calculate the enthalpy of reaction at constant
volume at the same temperature.

SOLUTION

C6H6(l) + 7.5 O2(g) → 3H2O(l) + 6CO2(g) ∆H298 = -3264.58kJ

∆n = - 1.5 (for gases)

Then

- 3264.58kJ = ∆E - R x 298 x 1.5

⇒ ∆E = - 3264.58 + 3.716358 = - 3260.86 kJ

For reactions in which the same number of gaseous molecules are on both sides of the
equation, the enthalpies of reaction at constant pressure and constant volume are
therefore identical.

SAQ 1

For the reaction

CO(g) + ½ O2 => CO2 ∆Ho298K = -283.3 kJ

Determine ∆E for the reaction at 298 K.

2.03 ENTHALPY OF FORMATION

The enthalpy of formation is the increase in heat content when 1 mole of the substance
is formed from its elements. It is taken that the elements are in their standard states i.e.
their stable forms at ordinary temperatures and 1 atmosphere pressure. Thermodynamic
quantities relating to processes occurring under standard conditions are always identified
by the superscript o, for example a change in enthalpy at standard conditions is written as
∆H*0. The * defines the identity of the change in question.

Examples:

SUBSTANCE ∆Hf0298, kJ

27
H2O(l) - 285.56
CO2(g) - 393.14
H2S(g) - 17.49
CH4(g) - 74.78
CH3OH(l) - 238.34

The enthalpies of all elements in their standard states are arbitrarily taken to be zero at all
temperatures. The enthalpy of a compound is then equal to the enthalpy of formation,
∆Hf0. The standard conditions are taken to be 298K and 1 atmosphere pressure. The
assignment of the arbitrary value of zero for the standard enthalpy (at 25oC and 1atm.) to
all elements is allowed because no chemical reaction converts one element into another.
Enthalpy is a state function and so the change from an initial condition to a final form
will give a definite value regardless of the route taken. Because of this, the enthalpy
change accompanying a reaction is obtained by summing the enthalpies of the products
and subtracting the sum of the enthalpies of the reactants. For the reaction:

A + B => C + D,

∆H0reaction = [∆Hf0 (C) + ∆Hf0(D)] – [∆Hf0(A) + ∆Hf0(B)] (2.03.1)

Example

Species CH4(g) + 2O2(g) => CO2(g) + 2H2O(l)

∆Hf0 -74.78 O -393.14 2(-285.56)

∆H0reaction 298 = [∆Hf0(CO2) + 2x(∆Hf0(H2O)] – [∆Hf0(CH4) + 2∆Hf0(O2)

=[-393.14 + 2(-285.56)] –[-74.78+0] = - 889.48 kJ Ans

SAQ 2

The molar enthalpy of combustion of methanol at 298 K is –725.857 J. Determine the

enthalpy of formation of methanol from its elements at 298K.

2.04 ENTHALPY OF COMBUSTION

The enthalpy change accompanying the complete combustion of 1 mole of a compound is

called the Enthalpy of combustion. It is represented by ∆Hc0 if the substances concerned
are in their standard states. Some examples of standard heats of combustion are:

SUBSTANCE ∆Hc0298,kJ

28
CH4(g) - 889.50
CH3OH(l) - 72585.7
Benzene(l) - 3264.58

Example

The standard enthalpy of combustion of liquid ethanol is - 1365.61 kJ at 250C. Calculate

its enthalpy of formation from the elements in their standard states at this temperature.

C2H5OH(l) + 3O2(g) = 2CO2(g) + 3H2O(l)

x O 2(-393.14) 3(-285.56)

x = -277.35 kJ

Thus

2C(c) + 3H2(g) + ½O2(g) = C2 H5OH, ∆Hf0298 = - 277.35 kJ

2.05 CALORIMETRY

The direct, accurate measurement of heat requires a suitable instrument. This is the
calorimeter, and the associated technique is called calorimetry. The calorimeter consists
of a container in which the reaction releasing (or absorbing) heat is caused to occur. The
evolved heat flows into a known amount of water or other material which surrounds the
reaction vessel. Knowing the heat capacity of this absorbing jacket, and measuring the
rise in its temperature, we may use;

Q = mAc A∆T (2.05.1)

where Q is the heat, mA is the mass, cA is the heat capacity and ∆T is the change in
temperature, to calculate the quantity of heat released.

Depending on the reaction being investigated, the calorimeter used may be of constant
volume or constant pressure type. In the former case, we would be measuring the energy
change while in the latter we would be measuring the enthalpy change.

Thermometer

29
 Insulating shield

Air space

Calorimeter Vessel

Reaction Chamber

Sample

Water

SAQ 3

Draw and explain the working of an adiabatic calorimeter.

2.06 THERMOCHEMICAL LAWS

These are based on the principle of conservation of energy.

LAW ONE

The quantity of heat which must be supplied to decompose a compound into its elements
is equal to the heat evolved when that compound is formed from its elements. This is the
law of Lavoisier and Laplace.

LAW TWO

THE HESS'S LAW OF CONSTANT HEAT SUMMATION

"The resultant heat change in a chemical reaction, carried out either at constant pressure
or constant volume, is the same whether the reaction takes place in one or several steps".

30
This means that the net heat of reaction, at constant pressure or constant volume, depends
only on the initial and final states. As a consequence, thermo-chemical equations can be
added and subtracted like algebraic equations.

Hess law is a direct consequence of the first law of thermodynamics. Let us suppose that
a substance A can be changed to Z directly according to the following equation

A Z + Q1
Where Q1 is the heat evolved in the direct change. When the same change is brought
about through intermediate stages:

A B + q1

B C+ q2

C Z+ q3

the total evolution of heat = q1 + q2 + q3 = Q2

According to Hess law,

Q1= Q2
Illustration:
q1
A

Q1
q2

Z
q3

EXAMPLES

1. C2H4(g) + H2(g) = C2H6(g)

31
From heats of combustion:

(i) C2H4(g) + 3O2(g) = 2CO2(g) + 2H2O(l) ∆H0 = - 1411.59 kJ

(ii) H2(g) + ½O2(g) = H2O(l) - 285.56
(iii) C2H6(g) + (7/2)O2(g) = 2CO2(g) + 3H2O(l) - 1558.30

add (i) and (ii) then subtract (iii) to obtain

C2H4(g) + H2(g) = C2H6(g) ∆H0298 = - 138.85 kJ

2. Carbon can be burnt to carbon dioxide directly or it may first be changed to carbon
monoxide and then oxidized to carbon dioxide.
Either, C + O2 CO2 ∆H = -393.47 J

Or, C + ½ O2 CO ∆H = -110.44 J

CO + ½ O2 CO2 ∆H = -283.03 J
C + O2 CO2 ∆H = -393.47 J…..Total change

Illustration:

C + O2
∆H = -110 44 J

CO + ½ O2
∆H = -393 47 J

∆H = -283 03 J
C O2

SAQ 4

The molar enthalpies of combustion of liquid ethanol, crystalline carbon and hydrogen
gas are: -1365.61, -393.13 and –285.58 kJ respectively, at 298K. Determine the enthalpy
of formation of liquid ethanol at 298K from its elements.

32
2.07 THE EFFECT OF TEMPERATURE ON ENTHALPY OF
REACTION
(THE KIRCHHOFF'S EQUATION)

Consider any process represented thus:

A →B

The enthalpy of reaction at constant pressure, ∆H, is equal to the difference between the
enthalpies HB and HA. Thus

∆H = HB - HA (2.07.1)

In order to determine the variation of ∆H with temperature this expression is

differentiated with respect to temperature at constant pressure. The result is

 ∂∆H   ∂H B   ∂H A 
  =  −  (2.07.2)
 ∂T  p  ∂T  p  ∂T  P
The quantity
 ∂H  (2.07.3)
Hence one has   = Cp
 ∂T  p

 ∂ (∆H )  (2.07.4)
  = C P ( B ) − C P ( A) = ∆C P
 ∂T  p

This expression is known as the KIRCHHOFF’S EQUATION.

Rearrangement of the Kirchhoff’s equation and integrating yields:

and hence T2 T2
(2.07.5)
∫
T1
d ( ∆Η ) = ∫ ∆C p dT
T1
T2
∆Η T2 = ∆Η T1 + ∫ ∆C p dT (2.07.6)
T1

If ∆Cp is not a function of temperature then

∆Η T2 = ∆Η T1 + ∆C P (T2 − T1 ) (2.07.7)

33
For the purpose of more accurate calculations, it is necessary to express the heat
capacities of products and reactants as functions of temperature and an expression for
∆Cp can be obtained.

EXAMPLE

For the reaction

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

the value of ∆H0298 is - 92.29 kJ at 250C. The molar heat capacities at constant pressure
of nitrogen, hydrogen and ammonia are given as:

C H 2 = (29.038 − 0.836 x10 −3 T + 20.097 x10 −7 T 2 )JK −1

C N 2 = (26.957 + 5.906 x10 −3 T − 3.373x10 −7 T 2 )JK −1

C NH 3 = (25.870 + 32.968 x10 −3 T − 30.430 x10 −7 T 2 )JK −1

Calculate the standard enthalpy of reaction at 1250C.

SOLUTION

The value of

(
∆C p = 2C NH 3 − C N 2 + 3C H 2 )
= - 62.332 + 62.537 x 10-3T - 117.79 x 10-7T2JK-1

To get the integral part,

T2

]
T2

∫ ∆CpdT = −62.332T ] + 31.271x10 T

−3 T2 −7 T2
2
− 39.25 x10 T 3 T 1
T1
T1 T1

Giving,

∫T1
T2
( 2 2
)
∆C p dT = 62.332(T2 − T1 ) + 31.271x10− 3 T2 − T1 − 39.25 x10− 7 T2 − T1 ( 3 3
)
With T1 = 298K, T2 = 398K, then

∆Η o2 (298K ) = ∆Η 10 (298K ) + (− 4.02kJ )

34
 = - 92.294 - 4.02 kJ

= - 96.314 kJ

SAQ5

Given the following information

CO(g) + ½ O2 => CO2 ∆Ho298K = -283.3 kJ

And

Substance Cp(JK-1mol-1)
CO(g) 26.6 + 0.76 x 10 -2T
CO2(g) 26.4 + 4.26 x 10-2 T
O2(g) 25.6 + 1.32 x 10-2T

Determine ∆H for the formation of CO2(g) at 398K.

2.08 SUMMARY

• The relationship between enthalpy of reaction at constant pressure and

at constant volume is governed by the number of moles of the
reactants and the number of moles of products.
• The definitions of various forms of enthalpy are dependent on the type
of change involved.
• Hess’s law of constant heat summation provides a tool for calculating
the enthalpy changes by consideration of alternative sequences of
reactions.
• The effect of temperature on the enthalpy change of reactions is
related to the molar heat capacities of the reactants and products in a
relationship defined by the Kirchhoff’s equation.

35
2.09 TERMINAL QUESTIONS

1. From the following data, calculate the enthalpy of formation of

anhydrous aluminium chloride.

(i) 2Al(s) + 6HCl(aq) = Al2Cl6(aq) + 3H2(g) ∆H = -1007 kJ

(ii) H2(g) + Cl2 (g) = 2HCl(g) ∆H = -184.8 kJ
(iii) HCl(g) + aq. = HCl(aq.) ∆H = -72.73 kJ
(iv) Al2Cl6(s) + aq. = Al2Cl6(aq) ∆H = -645.5 kJ

2. The enthalpy of formation of 1 mole of Hydrogen Iodide gas from

hydrogen and iodine vapour at 25 oC is –33.6 kJ. Find the enthalpy
of formation at 10 oC given that the heat capacities of hydrogen,
iodine vapour and hydrogen iodide vapour are given as:

Hydrogen; Cp = 27.3 + 0.0071T JK-1Mole-1

Iodine Vapour; Cp = 27.3 + 0.0160T JK-1Mole-1
Hydrogen Iodide gas; Cp = 27.3 + 0.0067T JK-1Mole-1

3. The molar enthalpies of formation of carbon monoxide and steam

are 111 and 244 kJ respectively. Calculate the enthalpy of the
reaction;

H2O(g) + C(s) = CO(g) + H2(g)

4. Calculate the enthalpy of the reaction;

C2H4(g) + H2(g) = C2H6(g)

at 298 K from the following data:

(i) C2H4(g) + 3O2(g) = 2CO2(g) + 2H2O(g) ∆H = --1395kJ

(ii) C2H6(g) + 7/2O2(g) = 2CO2(g) + 3H2O(g) ∆H = --1550kJ
(iii) H2(g) + 1/2O2(g) = H2O(g) ∆H = --243kJ

5. Derive the Kirchhoff equation.

6. State the thermochemical laws associated with Hess and Kirchhoff,

and show their thermodynamic basis.

36
2.10 ANSWERS TO SAQS

[1] -282.06 kJ [2] -238.403 kJ [3] to do. [4] –277.39kJ

[5] –283.62 kJ

2.11 ANSWERS TO TERMINAL QUESTIONS

[1] –1352.28kJ [2] –33579J [3] 133kJ [4] –88kJ [5 & 6] Do.

37
UNIT 3 THE SECOND LAW OF THERMODYNAMICS

STRUCTURE

3.01 Introduction
Objectives
3.02 Entropy
3.03 Entropy Changes for an ideal gas
3.04 Entropy changes at constant pressure or constant volume
3.05 Graphical interpretation of change in entropy
3.06 Entropy change accompanying phase change
3.07 Entropy change in a spontaneous (irreversible) process
3.08 Physical significance of entropy
3.09 Efficiency of a reversible cycle
3.10 Alternate derivation for the Carnot cycle
3.11 Entropy and third law of thermodynamics
3.12 Summary
3.13 Terminal Questions
3.14 Answers to SAQs
3.15 Answers to Terminal Questions

3.01 Introduction

Consider a bar of metal that is hot at one end and cold at the other. Heat will be
conducted spontaneously along the bar from the hot end to the cold end until the
temperature is uniform.

The reversal could be attained if heat is allowed to pass from one end of the bar to a
machine where it is converted into an equivalent amount of work. By means of friction
the work is reconverted into an equivalent amount of heat that is now transferred to the
other end of the bar.

But it is a matter of experience that a complete reversal is impossible due to the fact that,
"heat can not be completely converted into an equivalent amount of work without
causing other changes in some part of the system or its surroundings". This is the 2nd
Law of Thermodynamics. The law can also be stated as, “All natural or spontaneous
processes (i.e. those occurring without external aid) are thermodynamically
IRREVERSIBLE in character”. The fact that a process is spontaneous means that it is
taking place at a finite rate.

38
Objectives
By the end of the unit, the learner should be able to:
• Define entropy and state the second law of thermodynamics
• Calculate the change of entropy when an ideal gas undergoes an expansion or
compression
• Calculate the entropy changes of systems and surroundings during
temperature/pressure/volume change
• Calculate the entropy changes during phase transitions
• Calculate the entropy changes for irreversible processes
• Describe the Carnot cycle and calculate efficiency of heat engines
• Relate entropy changes to irreversibility and spontaneity of transformations

3.02 ENTROPY(S)

Entropy is a measure of disorder. The physical change experienced from solid to liquid
and to gas is accompanied by an increase in disorder of the molecules. One can say that
the entropy of the system increases from solid to liquid to gas. Systems change in such a
way as to attain maximum entropy. Entropy is a state function and serves as a criterion
for spontaneity. Entropy is represented by the symbol S.

The change in entropy, dS, in the course of an infinitesimal change is equal to δqrev, the
heat absorbed when change is carried out in a reversible manner, divided by the absolute
temperature, T as given in the following equation.

δq rev
dS = (3.02.1)
T

Integration of the above equation yields

T2 δq rev
∆S = S 2 − S 1 = ∫ (3.02.2)
T1 T

3.03 ENTROPY CHANGES FOR AN IDEAL GAS

For an ideal gas

δqrev = CvdT + PdV (3.03.1)

where only pressure - volume work is involved.

39
For one mole of gas

RT (1.08.3)
PV = RT ⇒ P =
and thus V

dV (3.03.2)
δq rev = CV dT + RT
V
such that
δq rev
dS = yields :
T

T2 dT V2 dV (3.03.4)
∆S = S 2 − S 1 = C v ∫ + R∫
T1 T V1 V

T  V 
= CV Ln 2  + RLn 2  (3.03.5)
 T1   V1 

The entropy change for a process involving an ideal gas thus depends on the initial and
final temperature and volume.

Since

P1 V1 = RT1 and P2V2 = RT2

then
V2 T2 P1
=
V1 T1 P2

and substitution yields

T   PT 
∆S = CV Ln 2  + RLn 1 2  (3.03.6)
 T1   P2 T1 

T  T  P 
= Cv Ln 2  + RLn 2  − RLn 2 
 T1   T1   P1  (3.03.7)
But

40
 Cv + R = CP (1.10.16)
and thus

T  P 
∆S = C P Ln 2  − RLn 2  (3.03.8)
 T1   P1 
for one mole of gas.

Consider a case where there is no change in temperature:

There is no change in temperature and therefore:

T2 = T1 (i.e. ISOTHERMAL CHANGE)

This implies

V  P 
∆ST = RLn 2  = − RLn 2  (3.03.9)
 V1   P1 

For isothermal expansion,

V2 > V1

and thus isothermal expansion is accompanied by an increase in entropy. Likewise,

isothermal compression is accompanied by a decrease in entropy.

Consider a case where there is no change in pressure:

This is an isobaric process (Constant Pressure)

P1 = P2
and

T 
∆S P = C P Ln 2  (3.03.10)
 T1 
Thus, increase in temperature at constant pressure is accompanied by an increase in
entropy.
Consider a case where there is no change in volume:
This is an isochoric change (Constant Volume)

V1 = V2

and one has,

T 
∆SV = CV Ln 2 
 T1  41
 (3.03.11)

Examples:

1. One mole of an ideal monatomic gas at STP is heated at constant volume to a

temperature of 323 K. Determine the change in entropy for the process.

2. Two mole of an ideal gas at STP are heated at constant volume to a temperature
of 350 K .Determine the increase in entropy for the system. Cv = 12.47 J/Mol/K)

Solutions:

1. P1/T1 = P2/T2 => P2 = P1T2/T1

= 101325 x 323/273
=119882.69 N/M2

Cp = Cv + R = 3/2 R + R = 5/2 R

From equation 2.03.05

∆S = 5/2 Rln 323/273 – Rln 119882.69/101325

=2.1J/K/Mol

2. From equation 3.03.08 and for two moles of gas

∆S = 2 x 12.47 ln 350/273
= 6.20 J/K

SAQ 1

Calculate the entropy change when 3 moles of a perfect gas is allowed to expand at 300K
from a volume of 2 dm3 to 13 dm3.

3.04 ENTROPY CHANGES AT CONSTANT PRESSURE OR

CONSTANT VOLUME

From earlier work

δqP = CPdT (1.10.3)

and
δqV = CvdT (1.10.2)

42
Then

δq P dT
dS P = = CP (3.04.1)
T T

and

dT
dSV = CV
T (3.04.2)
For a change from T1 to T2

dT T2
∆S P = ∫ C P
T1 T (3.04.3)
If CP is independent of temperature then

T2 dT T 
∆S P = C P ∫ = C P ln 2  (3.04.4)
T1 T  T1 

for one mole.

Similarly,
T2 dT T2
∆ S V = ∫ CV = ∫ CV dLnT (3.04.5)
T1 T T1

when Cv is dependent on temperature and

T2 dT T 
∆S V = CV ∫ = CV Ln 2  (3.04.6)
T1 T  T1 

for one mole and when Cv is independent of temperature.

SAQ2

The molar heat capacity at constant pressure of ammonia gas is expressed by;

Cp = 25.87 + 3.3x 10 –2T – 3.04 x 10 –6T2 JK-1Mole-1

43
Calculate the increase in entropy when 1 mole of ammonia is heated from
298K to 398 K.

3.05 GRAPHICAL INTERPRETATION OF CHANGE IN ENTROPY

The change of entropy with temperature at constant pressure is determinable by graphical

integration. This method is useful for solids and liquids because the variation of the heat
capacity cannot be expressed as a simple function of temperature.

From
T2 CP T2
(3.05.1)
∆S = ∫ dT = ∫ C P dLnT
T1 T T1

one notes that if the experimental values of the heat capacities at constant pressure
divided by the temperatures (CP/T are plotted against the temperatures, then the area
under the curve between the initial and the final temperature will give the entropy
change.

Alternatively, if the experimental values of the heat capacities at constant pressure

(CP) are plotted against the natural logarithm of the temperatures, then the area under the
curve between the logarithms of the initial and final temperature gives the entropy
change.

3.06 ENTROPY CHANGE ACCOMPANYING PHASE CHANGE

When a substance changes phase, for example,

solid → liquid or liquid → vapour,

there is an absorption of heat energy and hence a change in entropy. Both fusion and
vaporization may be carried out reversibly and the heat energy taken up, at constant
pressure, is equal to the enthalpy of fusion or vaporization at the given temperature.

For fusion,

∆Η f
∆S f = (3.06.1)
Tf

44
Where ∆Hf = enthalpy of fusion
Tf = freezing temperature

For vaporization

∆Η V
∆S V = (3.06.2)
Tb

where Tb is the boiling point.

Heat is absorbed in both fusion and vaporization and hence both are accompanied by an
increase in entropy. The reverse is also true.

Transition from one crystalline form to another is also associated with reversible heat
change, hence a change in entropy.

The entropy of transition is the enthalpy of transition divided by the transition

temperature.

Thus

∆Η t
∆S t = (3.06.3)
Tt
Examples:
1. Determine the entropy change when one mole of water at boiling point is
converted to steam given that the enthalpy of vaporization of water is
40.85kJ/mol.
2. The enthalpy of transition from rhombic to monoclinic sulphur at the transition
temperature of 95.6 oC is 0.361 kJ/mole. Determine the entropy of transition.
3. The enthalpy of fusion of monoclinic sulphur is 1.26 kJ/mole. Determine the
entropy change when two moles of monoclinic sulphur melts at 392 K.

Answers:
1. ∆Sv = ∆Hv/Tb = 40850/373

= 109.5 J/mol/K

2. ∆St = ∆Ht/Tt = 361/368.6

= 0.98 J/mol/K
3. ∆Sf = ∆Hf / Tf = 2 x 1260/392

=6.43 J/K

45
SAQ 3

This question deals with changes involving water.

(a) Calculate the change in entropy when 2 moles of water are converted into
vapour at 100oC, given that the heat of vaporization is 40.85 kJ per mole.
(b) Calculate the entropy of fusion of 2 moles of ice if its heat of fusion is 6.0 kJ
per mole at 0oC.
(c) Comment on your answers and state an approximate value of entropy that
would be expected if two moles of ice were sublimated.

3.07 ENTROPY CHANGE IN A SPONTANEOUS (IRREVERSIBLE)

PROCESS

Spontaneous processes are thermodynamically irreversible. This is a direct consequence

of the second law. Consider an ideal gas allowed to spontaneously expand into a vacuum
at constant temperature. (The gas is ideal and there exists no attractions between the
molecules). No heat is absorbed or evolved in this process. Consequently, no heat is
supplied or removed from the surroundings and hence the entropy of the surroundings
remains unchanged. However, the entropy of the system, that is, the gas increases since
its volume has increased in the expansion.

The entropy depends only on the temperature and pressure (volume) of the system (and
not on previous history). Increase in the volume from V1 to V2 at T, implies increase in
entropy. This is given by,

V2
∆S = RLn (3.07.1)
V1

The entropy change of the surrounding being zero implies that the total change in entropy
is

V2
∆S + O = RLn
V1 (3.07.2)

a positive quantity since V2 > V1.

One can therefore state, "The spontaneous (thermodynamically irreversible) isothermal

expansion of an ideal gas is accompanied by an increase of entropy of the system and its
surroundings".

46
On the other hand, if the gas is expanded reversibly from an initial volume V1 to a final
volume V2 at a given temperature T, work is done and the entropy increase would be
equivalent to the heat absorbed from the surroundings divided by the temperature (q/T).
The surroundings will have lost the heat, q, implying a decrease in entropy equivalent to
q/T. The total entropy change of the system and surroundings in the reversible process is
thus zero.
We can therefore state: "A spontaneous (thermodynamically irreversible) process is
always accompanied by an increase in entropy of the system and its surroundings, but for
a thermodynamically reversible change the entropy of the system plus the surroundings
remains unchanged.

Thus
∆S ≥ O.

A system subjected to an irreversible process at constant temperature T absorbs qIRR heat

from its surroundings. The change in entropy will be equal to the heat divided by the
temperature. If the process is carried out reversibly, it will have the same change in
entropy. The increase in entropy, ∆S, therefore, is the same whether the process is carried
out reversibly or not. The change in entropy depends on the state of the system and not
on how the state is attained.

Consider the entropy of the surroundings:

Suppose the surroundings are restored reversibly to their original state. This can be done
by supplying qIRR from the system to the surroundings, in a reversible manner at
temperature, T. This implies an increase of entropy equivalent to qIRR/T in the
surroundings. The entropy change of the system under consideration is therefore -
qIRR/T. For an irreversible process, there must be an increase in the entropy of the
system plus its surroundings.

Thus

q IRR
∆S − >O (3.07.3)
T

T∆S > qIRR (3.07.4)

Then,

47
"For a thermodynamically irreversible process at constant temperature, the heat absorbed
by the system is less than the product of temperature and the entropy increase. For a
reversible process"
T∆S = qrev (3.07.5)

When considering an infinitesimal stage of a process, the results for the system alone are:

TdS ≥ δq (3.07.6)

The 'greater than' sign refers to an irreversible process and the equal sign refers to a
thermodynamically reversible (equilibrium) process.

3.08 THE PHYSICAL SIGNIFICANCE OF ENTROPY

A characteristic of spontaneous processes is that they are accompanied by an increase in

the 'disorder' or 'chaos' of the system. An expansion of a gas into a vacuum is
accompanied by an increase of entropy of the system. Since expansion of a gas is
accompanied by an increase in disorder, so is the increase in entropy.

Further, fusion and vaporization are accompanied by increase in entropy. This increase
in entropy causes an increase in disorder since the molecules of a liquid are less orderly
than those in a solid. Likewise the molecules of vapour are less orderly than those of a
liquid. Systems tend to a state of maximum entropy. A gas will therefore tend to occupy
all the space or volume available to it. Is it the same with animals and/or human beings?

3.09 EFFICIENCY OF A REVERSIBLE CYCLE

The concept of entropy is used to derive an expression for the maximum efficiency of an
engine for the conversion of heat into work. Such an engine must function in cycles; a
cycle being a succession of changes as a result of which the system returns to the original
state (all properties of the system thus assuming their original values).

The internal energy change, ∆E = 0 and hence the resultant work done is equal to the net
heat absorbed. Maximum work is obtainable from a process when that process is carried
out reversibly. Thus maximum efficiency for conversion of heat into work is obtained
from a reversible cycle.

THE CARNOT CYCLE

The system is an ideal gas and is subjected to a series of reversible changes in the
following manner:-

48
 Adiabatic Expansion
q=0

II

ENTROPY

Isothermal Isothermal
Compression III I Expansion
-q1 q2

IV
Adiabatic Compression
q=0

T1 T2
TEMPERATURE

I. ISOTHERMAL EXPANSION

The gas is expanded isothermally and reversibly at the higher temperature T2. This is
accompanied by absorption of heat q2 from the source, and the entropy change for the gas
is q2/T2.

II. ADIABATIC EXPANSION

This results in a fall of temperature from T2 to that of the 'sink', T1. Since the change is
adiabatic the entropy of the gas remains constant, ∆S = O.

III. ISOTHERMAL COMPRESSION

At T1. there is liberation of heat q1 to the 'sink'. The entropy change of gas at this stage
is - q1/T1.

IV. ADIABATIC COMPRESSION

This results in a return of the gas to its original temperature T2. The entropy change for
this stage is zero.

49
The net heat absorbed, (q2 - q1), represents the work, w, done in the reversible cycle.

The efficiency of the engine is the fraction of the heat taken in at the higher temperature
that is converted into work.

Thus

w q 2 − q1
Efficiency = = (3.09.1)
q2 q2

Since the total entropy change for the complete cycle is zero, one has:

q 2 q1
− =0 (3.09.2)
T2 T1

q1
⇒ q2 = T2 (3.09.3)
T1
Since

q 2 − q1
Efficiency = (3.09.1)
q2

one has

 q1T2 
  − q1
 T1 
Efficiency =
q1T2
T1
T2 − T1
= (3.09.4)
T2

3.10 ALTERNATE DERIVATION FOR THE EFFICIENCY FROM

THE CARNOT CYCLE

P1,V1,T2
I

P2,V2,T2

50
Pressure

IV
II

P4,V4,T1
P3,V3,T1

III

Volume

STEP 1

ISOTHERMAL EXPANSION AT T2

The gas is expanded isothermally at a temperature T2 from an initial value V1 to V2.

∆E = O and the first law requires that:

V2
q1 = w1 = ∫ pdV = RT2 Ln (3.10.1)
V1
STEP 2

ADIABATIC EXPANSION

The gas is expanded adiabatically from V1 to V3 and the temperature drops to value T1.

Since q = 0, then

w2 = -∆E = -Cv (T1 - T2)

= Cv (T2 - T1) (3.10.2)

STEP 3

ISOTHERMAL COMPRESSION AT T1

The gas is compressed isothermally at T1. ∆E = 0. The volume changes from V3 to V4.

Then
V4
w3 = RT1 Ln ,
V3
51
 (3.10.3)

V4 < V3

STEP 4

ADIABATIC COMPRESSION

The gas is compressed adiabatically from V4 to the original volume V1.

The temperature rises from T1 to T2

w4 = -∆E = -Cv (T2 - T1) (3.10.4)

w = w1 + w2 + w3 + w4 (3.10.5)

w3 and w4 are negative

w1 and w2 are positive
w2 and w4 are numerically equal and cancel one another.

Thus
w = w1 + w3 (3.10.6)

V  V 
= RT2 Ln 2  − RT1 Ln 3  (3.10.7)
 V1   V4 

q = q2 + q1 (3.10.8)

V  V 
= RT2 Ln 2  − RT1 Ln 3  (3.10.7)
 V1   V4 
w
Efficiency =
q2 (3.10.8)

Further, for the adiabatic steps 2 and 4:

Cv CV (3.10.9)
V 2 T2 R
= V3T1 R
and
CV CV
V1T2 R
= V4T1 R
(3.10.10)

52
Division of the first equation by the second gives:

V2 V3
= (3.10.11)
V1 V 4

and thus
V2 V V
w = RT2 ln − RT1 ln 2 = R(T2 − T1 ) ln 2
V1 V1 V1 (3.10.12)

From earlier work:

V2
q2 = RT2 ln
V1 (3.10.1)
and one obtains

V2
R(T2 − T1 ) ln
V1 T2 − T1
Efficiency = = (3.10.13)
V2 T2
RT2 ln
V1

Note that the smaller T1 is and the larger T2 is, the closer the reversible efficiency
approaches the limit of 1, which represents complete conversion of the heat input into
work output. One has to realize that a reversible heat engine is an idealization of real heat
engines which involve quite some degree of irreversibility in their operation. The
efficiency, given by the equation above, is an upper limit to efficiency of real heat
engines. Typical efficiencies of currently available heat engines are between10 and 40
per cent. A motor vehicle engine has an efficiency of approximately 20 per cent.

The Carnot cycle in the reverse order that is, in the order of steps 4 3 2 and 1can be used
as a heat pump or refrigerator. In the refrigerator, heat is transferred from a lower
temperature Tc to the higher temperature Th by performing work on the material used in
the heat pump. The performance of the refrigerator is measured in terms of the
coefficie3nt of performance c which is the ratio of the heat removed from the cold
reservoir to the net work done on the working material. The coefficient of performance
is given by:

qc qc Tc
c= = = (3.10.14)
w qh − qc Th − Tc

One can therefore see that the smaller the difference between Th and Tc the greater the
coefficient of performance meaning that less work has to be done to transfer the heat qc at
Tc to the higher temperature Th.

Example:

53
 The boiling point of water at a pressure of 50 atm. is 265 oC and at 1 atm. it is
100 C. Assuming the temperature of the sink is 40 oC, compare the theoretical
o

efficiencies of a steam engine operating between the boiling point of water and that of the
sink at:
a. 1atm.
b. 50 atm.

Answer:
a. At 1 atm. pressure,

Efficiency = (T2-T1)/ T2

= (373-313)/373
= 0.161
b. At 50 atm. pressure,
Efficiency = (T2-T1)/T2
= (538 – 313)/538
= 0.418
This shows that the engine is more efficient when operating at 50
atm. pressure.
SAQ4

Compare the maximum efficiencies of reversible engines in which the working

substances are;
(a) water and
(b) mercury
The temperatures of the sources being the respective boiling points at 1 atmosphere
pressure namely 373K and 630K. The temperature of the heat sink is 298K in each
case.

3.11 ENTROPY AND THE THIRD LAW OF THERMODYNAMICS

Spontaneous processes are accompanied by an increase in the 'disorder' or 'chaos' of the

system, or random arrangement of the molecules.
Increase in temperature gives rise to an increase in disorder. Decrease in temperature
decreases disorder. Otherwise decrease in temperature results in an increase in order.
This leads to the third law of thermodynamics. This law states "The entropy of a perfect
crystalline solid of a pure substance is zero at the absolute zero of temperature".

The entropy changes of a substance between temperatures T1 and T2 are determined

from calorimetric measurements then from the definition of entropy increase

54
 T2 T2
CpdT
ST2 − ST1 = ∫ = ∫ Cpd ln T (3.11.1)
T1 T T1

This means that the increase in entropy for a substance between 0 K and T is deduced
thus:

T
CpdT
ST = S 0 + ∫ (3.11.2)
0 T
The third law enables one to write

T T
CpdT
ST = ∫0 T = ∫0 Cpd ln T (3.11.3)

The third law then makes it possible to obtain absolute entropies of chemical substances
from calorimetric measurements. The standard reaction entropies can then be calculated.
The entropy of a reaction is the difference between the entropies of the pure separated
products and the pure separated reactants, all substances being in their states at the
specified temperature. The entropies of substances are usually reported at 1 atm. pressure
and 25oC. These are standard entropies and are indicated by a superscript o.

ENTROPIES OF SOME SUBSTANCES AT 1 ATMOSPHERE AND 25OC

SUBSTANCE SO(Jmol-1 K-1)

H2(g) 130.59
C(c, diamond) 2.44
C(c, graphite) 5.69
C(g) 157.99
CO(g) 197.91
CO2(g) 213.64
CH4(g) 186.19
C2H2 (g) 200.82
C2H4 (g) 219.45
C2H6 (g) 229.49
O2(g) 205.03
H2O(g) 188.72
H2O(l) 69.94
Examples

Determine the changes in entropy for the following reactions.

a) C2H2 (g) + H2(g) C2H4 (g)

b) 2 C(c, graphite) + 3 H2(g) C2H6 (g)

55
Solutions
a) ∆S o = S o C 2 H 4 − ( S 0C 2 H 2 + S o H 2 )

= 219-(200.82 + 130.59)

= -112.41J/K Ans

b) ∆S o = SCo 2 H − (2 SCo ( g ) + 3S Ho 2 )
6

= 229.3 – (2x5.68 + 3 x 130.5)

= -173.56 J/K Ans

3.12 SUMMARY

• The thermodynamic function, Entropy, is defined as a measure of chaos.

• An increase in temperature at constant pressure is accompanied by an increase in
entropy.
• The second law of thermodynamics can be stated as, “heat can not be completely
converted into an equivalent amount of work without causing other changes in
some part of the system or its surroundings". The law makes it impossible to
‘freely’ harvest energy from the warm tropical ocean water, for example. The law
is also stated as, “All natural or spontaneous processes are thermodynamically
irreversible in character”.
• If the experimental values of the heat capacities at constant pressure divided by
the temperatures (CP/T) are plotted against the temperatures, then the area under
the curve between the initial and the final temperature will give the entropy
change. Alternatively, if the experimental values of the heat capacities at
constant pressure (CP) are plotted against the natural logarithm of the
temperatures, then the area under the curve between the logarithms of the initial
and final temperature gives the entropy change.
• The entropy change for a process involving an ideal gas depends on the initial and
final temperature and volume.
• The efficiency of the engine is the fraction of the heat taken in at the higher
temperature that is converted into work.

56
3.13 TERMINAL QUESTIONS

1. 10 g of ice at 273K is added to 20g of water at 363K in an insulated flask. The

heat of fusion of ice is 6000 Joule per mole and the specific heat capacity of
water is 4.2 joule per Kelvin per gram. Ignoring the heat capacity of the flask:
a. Determine the final temperature of the system
b. Determine ∆S for the system

2. Calculate the entropy change when 4.8 g of liquid water at 25 oC is

completely converted into vapour at 100oC. The molar enthalpy of
vaporization is 40.85 kJ per mole and the heat capacity for water is 4.18 joules
per gram.

3. What is the change in entropy on heating 2 grams of water from 0oC to 100
o
C. The mean specific heat capacity of water between 0 oC and 100 oC is 4.18
joule per gram.

4. A heat engine operated with mercury vapour between 350 oC and 50 oC. What
is the amount of heat that must be withdrawn from the reservoir to produce
500 joules of work?

5. Calculate the entropy change per mole when helium at 1 atmosphere pressure
and 27 oC is heated to 250 oC.

6. Calculate the entropy change for the reaction:

2C(graphite) + 2H2(g) = 2C2H4(g)

given the following standard entropies at 25 oC in units JK-1mole-1;

C(graphite) 5.7
H2(g) 131.2
C2H4(g) 221.0

7. Using the second law, Carnot cycle, and knowledge of how the current
vehicle engine works, suggest and explain how the efficiency of a car engine
could be enhanced from the current 20 per cent.

57
3.14 ANSWERS TO SAQS

[1] 46.69JK-1 [2] 10.89JK-1Mole-1 [3] (a) 219.03JK-1 (b) 43.96JK-1

[4] (a) 0.201 (b) 0.527

3.15 ANSWERS TO TERMINAL QUESTIONS

[1] (a) 306.5 K. (b) 2.72 JK-1. [2] 33.7 JK-1. [3] 2.61 JK-1.
[4] 1038 J. [5] 6.93 JK-1mol-1. [6] –52.8 JK-1.

58
UNIT 4: FREE ENERGY AND EQUILIBRIA

STRUCTURE

4.01 Introduction
Objectives
4.02 Free Energy and Maximum Work Functions
4.03 Physical Interpretation of ∆A and ∆G
4.04 Variation of Free Energy with Temperature or Pressure
4.05 Conditions for Spontaneous Change and Equilibrium
4.06 Phases in equilibrium: The Clausius-Clapeyron Equation
4.07 The Gibb’s Helmholtz Equation
4.08 Thermodynamic Derivation of Equilibrium Constant
4.09 Forms of Equilibrium Constant: Gaseous Reactions
4.10 Temperature and Equilibrium: Vant Hoff Equation
4.11 Standard Free Energies
4.12 Standard Free Energy of Reaction
4.13 Standard Free Energies of Compounds
4.14 Summary
4.15 Terminal Questions
4.16 Answers to SAQ’s
4.17 Answers to Terminal Questions

4.01 Introduction

So far, we have seen how enthalpy and entropy changes are used as criteria for
checking spontaneity of reactions. A negative enthalpy change suggests spontaneity
while a positive value suggests spontaneity in the reverse direction. Conversely, a
positive entropy change of the universe implies a spontaneous change. Previously
equilibrium constant and Le Chatelier’s principle was used to show the effect of
certain changes on the position of the equilibrium. One is always interested to know
the thermodynamic nature of any chemical reaction so as to determine whether and
how a useful product can be manufactured with ease.

The Gibb’s Free Energy Function (G) is another criterion used to check on
equilibrium and spontaneity. Free energy changes (∆Gs) will be developed with
reference to changes in the system only.

59
 Objectives

By the end of the lesson, the learner should be able to:

• Define Helmholtz and Gibb’s Free Energies
• Calculate the Gibb’s Free Energy changes for different physical and chemical
transformations.
• Relate the Gibb’s Free Energy changes to Spontaneity of transformations.
• Relate changes in Gibb’s Free Energy with Temperature, Enthalpy, Entropy
and Equilibrium Constant.
• Apply the Clausius-Clapeyron Equation.

4.02 FREE ENERGY AND MAXIMUM WORK FUNCTIONS

Helmholtz Free Energy function, represented by A and Gibb’s Free Energy function,
represented by G are functions used to determine spontaneity and equilibria of
transformations. The functions are defined as:

A = E - TS (4.02.1)
and

G = H - TS (4.02.2)
where
E = internal energy,
and
H = E + PV (4.02.3)

The other symbols are as defined earlier.

Since E, H, T and S are thermodynamic variables, A and G also belong to this category.
The variables have been classed as ‘State Functions’ meaning that changes associated
with them, ∆A and ∆G, are independent of the path of the process.

Let E1, A1 and S1 be at T1.

Then
A1 = E1 - T1 S1. (4.02.4)

After an appreciable change to T2 one has A2, E2 and S2 so that:

A2 = E2 - T2 S2 (4.02.5)

The subsequent change in A is therefore:

A2 - A1 = (E2 - E1) - (T2 S2 - T1 S1) (4.02.6)

60
or
∆A = ∆E - ∆(TS) (4.02.7)

For an isothermal change, the temperature T is constant and one has:

∆A = ∆E - T∆S (4.02.8)

In a similar manner:

G1 = H1 - T1 S1 (4.02.9)
G2 = H2 - T2 S2
G2 - G1 = (H2 - H1) - (T2 S2 - T1 S1) (4.02.10)

∆G = ∆H - ∆ (TS)

so that at constant temperature:

∆G = ∆H - T∆S (4.02.11)

For an isobaric change, the pressure is constant and we have:

∆H = ∆E + P∆V (1.07.6)

and hence

∆G = ∆A + P∆V - T∆S
= ∆E - T∆S + P∆V (4.02.12)
Implying that

∆G = ∆A + P∆V (4.02.13)

for a process at constant temperature and pressure.

4.03 PHYSICAL INTERPRETATION OF ∆A AND ∆G

For a thermodynamically reversible process, taking place at constant temperature T, the

increase in entropy is given by

q rev
∆S = (4.03.1 refer to 3.02.1)
T

Where qrev is the heat absorbed.

61
Substitution in the equation

∆A = ∆E - T∆S (4.02.8)

yields

q rev
∆A = ∆E − T (4.03.2)
T

= ∆E - qrev (4.03.3)

From the By 1st Law of thermodynamics,

qrev - wrev = ∆E (1.06.1)

Implying
∆E - qrev = - wrev (4.03.4)

This shows that

∆A = - wrev (4.03.5)

Since a reversible, isothermal process has been postulated, wrev is the maximum work
that can be obtained from the system. For this reason A is called the maximum work
function or simply the work function.

From
∆G = ∆A + P∆V (4.02.13)

We can replace, ∆A with - wrev,

So that:

∆G = - wrev + P∆V (4.03.6)

or
- ∆G = wrev - P∆V (4.03.7)

P∆V is the work of expansion done against external pressure. ∆G therefore represents the
maximum work at constant temperature and pressure other than that due to volume
change. Thus the decrease, - ∆G, is equal to the net work obtainable (at constant T and
P) for the system. The function, G, is known as the Free Energy.

62
4.04 VARIATION OF FREE ENERGY WITH TEMPERATURE OR
PRESSURE

We have already seen that

H = E + PV (1.07.4)

Also

G = H – TS (4.02.2)

Therefore one has

G = E + PV - TS (4.04.1)

For small changes,

dG = dE + PdV + VdP - TdS - SdT (4.04.2)

From the 1st Law,

δq = dE + δw (1.06.2)

If δw is due to volume change, then

δq = dE + PdV (1.07.1)

If it is assumed that the process is reversible, P is the pressure of the system and further

δq/T = dS (3.02.1)

meaning
TdS = δq (4.04.3)

Such that

TdS = dE + PdV (4.04.4)

Then
dG = dE + PdV + VdP - TdS - SdT (4.04.5)

= TdS + VdP - TdS - SdT (4.04.6)

= VdP - SdT (4.04.7)

63
At constant pressure, dP = O, and so

dG = - SdT (4.04.8 )

On the other hand, at constant temperature,

 ∂G 
V =  (4.04.9)
 ∂P T
For an appreciable process taking place at constant temperature, between two pressures
P1 and P2, we can obtain the free energy change by integrating:

G2 P2
∫
G1
dG = ∫ VdP
P1 (4.04.10)

P2
⇒ ∆G = G 2 − G1 = ∫ VdP
P1 (4.04.11)

G is a state function and is same whether the process is reversible or not.

Since temperature is constant and

PV = RT

V = RT/P (1.08.3)

then

P2 dP
∆G = RT ∫
P1 P (4.04.12)
P2
= RT ln
P1 (4.04.13)

for one mole.

For n mole

P 
∆G = nRT ln 2  (4.04.14)
 P1 

64
Example
Calculate the change in free energy when 11.21 dm3 of a perfect gas at 0oC
and 760 mmHg pressure expands isothermally until its pressure is 190
mmHg.

Solution

T = 273 K, R = 8.314 J/mol/K, P1 = 760 mmHg, P2 = 190 mmHg

n = PV/RT = (101325 x 11.21 x 10-3)/(8.314x273)

= 0.5 mol

Then

∆G = nRT ln (P1/P2)

= 0.5 x 8.314 x 273ln(190/760)

= -1573.3 J Ans.

SAQ 1

2 dm3 of hydrogen, initially at STP, are expanded isothermally and reversibly to a

volume of 4 dm3. Calculate ∆G for the process.

4.05 CONDITIONS OF SPONTANEOUS CHANGE AND

EQUILIBRIUM

For an infinitesimal change of a process in a system,

TdS ≥ δq (3.07.6)
(NB: > for Irreversible; = for reversible process)

From the 1st Law,

δq = dE + PdV (1.07.1)

65
when δw is external work, then, for the system:

TdS ≥ dE + PdV (4.05.1)

When this is introduced into:

dG = dE + PdV + VdP - TdS - SdT (4.04.2)

we have:
dG ≤ VdP - SdT (4.05.2)

Hence, at constant pressure and constant temperature ( dP=dT=0), we have,

(dG )T ,P ≤ O (4.05.3)

The ‘equals’ sign implies a state of equilibrium and the ‘less than’ sign implies
spontaneity.

For an appreciable process, we have ∆G which is given by:

(∆G)T,P ≤ O (4.05.4)

Thus, a spontaneous process at constant temperature and pressure is accompanied by a

decrease in free energy of the system. Recalling that:

∆G = ∆H - T∆S (4.02.11)

One can see that a measure of the change in free energy encompasses both entropy and
enthalpy changes. Because of this, the change in free energy is a better determinant of
spontaneity than either of the other two functions.

Example

You are given the following entropies and enthalpies of combustion at 25oC;

Substance S (JK-1) ∆H (kJ)

C(graphite) 5.9 -396
H2(g) 131.0 -287
C2H6(g) 231.0 -1567

State whether the following reaction is thermodynamically possible.

66
 2 C(graphite) + 3 H2(g) C2H6(g)

Solution (Students to work this out!)

Step I: Determine the entropy change for the reaction.

Step II: Determine the enthalpy change for the reaction
Step III. Determine the Gibb’s free energy change for the reaction.
Final Step: From the value of Gibb’s free energy change comment on the spontaneity of
the reaction, and hence give the answer to the question.

4.06 PHASES IN EQUILIBRIUM: THE CLAUSIUS - CLAPEYRON

EQUATION

Consider two phases of the same substance in equilibrium with one another at a
temperature T and pressure P. By supplying or withdrawing heat very slowly from the
system, it is possible to change reversibly from one phase to another, the system
remaining at equilibrium all the time. This means that ∆G will be zero for the system.
Equal amounts of a given substance must therefore have exactly the same free energy in
the two phases at equilibrium.

One can therefore write,

GA = GB , (4.06.1)
where A and B signify the two phases.

A change in temperature requires a corresponding change in pressure so that equilibrium

is maintained. Thus:

T → T + dT ⇒ P → P + dP. (4.06.2)

The free energy also changes as follows:

GA → GA + dGA, GB → GB + dGA (4.06.3)

Since the system is in equilibrium the new free energies must be equal.

GA + dGA = GB + dGB (4.06.4)

Since

GA = GB (4.06.1)

one has:

67
 dGA = dGB (4.06.5)

For an infinitesimal change where the only work done is that due to expansion, one has:

dGA = VAdP - SAdT (4.06.6)

and

dGB = VBdP - SBdT (4.06.7)

One can see that:

VAdP - SAdT = VBdP - SBdT (4.06.8)

and hence

(VB - VA)dP = (SB - SA)dT (4.06.9)

dP S B − S A ∆S
⇒ = =
dT VB − VA ∆V (4.06.10)

SB - SA is the entropy change accompanying phase change. If B is the phase which

tends to be formed as T is raised, then as stated earlier,

∆H dq
∆S = = (3.06.1)
T T

∆H
∴SB − S A = (4.06.11)
T

where ∆H is the enthalpy absorbed per mole in the phase change. This implies that:

dP ∆H
=
dT T (V B − V A ) (4.06.12)

This is the general form of the Clapeyron - Clausius Equation.

For conversion of liquid to vapour

∆H = ∆HV and VB >> VA

68
 ⇒ VB - VA ≈ VB = V (4.06.13)

For a mole of water for example,

Vvapour = 22400 ml

While
Vliquid = 18 ml

Such that Vvapour – Vliquid = 22382 ml ≈ Vvapour

Hence

dP ∆H V
= (4.06.14)
dT TV

∆HV ≡ molar enthalpy change of vaporization.

For a mole of gas

PV = RT (1.08.3)

RT
⇒V =
P
Rearrangement and integration gives:

dP ∆ H V .P
= (4.06.15)
dT T 2R

P dP ∆Η V T2
∫P1 P
=
R ∫
T1
T − 2 dT (4.06.16)

 P  ∆ΗV  1 1  ∆ΗV  T2 − T1  (4.06.17)

ln 2  =  −  =  
P
 1 R T
 1 T2  R T T
 2 1 

Further dP ∆Η V P
= (10.06.15)
dT RT 2

dP ∆H V
⇒∫ = ∫T
−2
dT (4.06.18)
P R
− ∆ΗV
⇒ ln P = +C
RT (4.06.19)

69
Thus a plot of the natural logarithm of the vapour pressure against the reciprocal of
temperature should give a straight line graph with slope equal to (-∆HV/R) from which
the molar enthalpy of vaporization (∆HV ) may be determined.

Example:

Determine the enthalpy of vaporization of water from the following data, expressing the
results in J/mol.

Information:
Boiling Temperature = 373K
The rate of change of pressure with temperature = 2.717 cmHg/K
Density of water = 0.962 g/ml
Density of water vapour = 5.973 x 10-4 g/ml
Density of mercury = 13.59 g /ml
Acceleration due to gravity = 981 cm/square second

Solution

The enthalpy of vaporization in J/g (∆Hv) of water is determined using the equation,

dP ∆H v
=
dT T (VB − VA )

where T = B.Pt. (K)

VA = Vol. (M3/g of water)
VB = Vol. (m3/g of water vapour)
dP/dT = rate of change of pressure with temperature (N/m2/K)

∆HV = (dP/dT) x T(VB - VA )

= 2.717 x 13.59 x 981 x 10-1 x 373 x (1.67 x 10-3 – 1.04 x 10-6)

= 2260.6 J/g

For one mole

∆HV = 2260.6 x 18

= 40690.8 J/mol Ans.

70
SAQ 2

From the data given, determine the molar enthalpy change of vaporization of chloroform.

Temperature (oC) 30 50
Saturated Vapour Pressure (mmHg) 248 538

4.07 THE GIBBS-HELMHOLTZ EQUATION

Apart from dealing with equilibrium and spontaneity other results may be obtained from
2nd law of thermodynamics. The Gibb's-Helmholtz equation gives a relationship that is
applicable to any physical or chemical change. It is valuable because it can be used to
calculate the enthalpy change in a reaction from a knowledge of the free energy change
and its variation with temperature at constant pressure.

Let G1 be the free energy of a system in its initial state at T and G1 + dG1 is the value at
T + dT.

Similarly, G2 is the free energy after the change has occurred at T, and G2 + dG2 be at
T + dT

We have seen that,

dG = VdP – SdT (4.04.7)

Therefore, for a change taking place at constant pressure,

dG1 = S1dT
and
dG2 = S2dT (4.07.1)
Thus
d(G2 - G1) = -(S2 - S1)dT (4.07.2)

⇒ d(∆G) = -(∆S)dT (4.07.3)

Constant pressure has been assumed and thus

Substitution for ∆S in

 ∂ (∆G )  (4.07.4)
  = − ∆S
 ∂T  P

∆G = ∆H - T∆S (4.02.11)

71
yields

 ∂ (∆G ) 
∆G = ∆Η + T   (4.07.5)
 ∂T  P

This is a form of the Gibb's - Helmholtz equation.

4.08 THERMODYNAMIC DERIVATION OF EQUILIBRIUM

CONSTANT

Consider a general reaction

aA + bB + … = lL + mM + … (4.08.1)

Free energy of products = lGL + mGM + …

Free energy of reactants = aGA + bGB + … (4.08.2)

At constant temperature and pressure

∆G = (lGL + mGM + …) - (aGA + bGB + ...) (4.08.3)

For each of the species, the free energy is expressed as:

G = G0 + RTln a (4.08.4)

where G0 refers to the free energy at standard state (unit activity at 298K).

Then
∆G = (l (GL0 + RT ln aL ) + m(GM0 + RT ln aM ) + ...)

− (a (G A0 + RT ln a A ) + b(GB0 + RT ln aB ) + ...) (4.08.5)

Rearrangement yields:
 a l a m ... 
∆G = ∆G 0 + RT ln La Mb  (4.08.6)
 a A a B ... 
For a system at equilibrium ∆G = 0 and thus

 a l a m ...  (4.08.7)
∆G 0 = − RT ln La Mb 
 a A a B ... 

72
At constant temperature T, ∆G0 is a constant and consequently the RHS of the above
equation is constant. This implies that

 aLl aMm ... 

 a b  = cons tan t = K
 a A a B ...  (4.08.8)

where K is the thermodynamic equilibrium constant for the reaction.

4.09 FORMS OF EQUILIBRIUM CONSTANT: GASEOUS

REACTIONS

If the reactants A, B, etc, and the products L, M, etc of the reaction are ideal gases or
approximate closely to ideal behavior, the activity of each substance is proportional to its
partial pressure and also to its molar concentration.

Then, one writes

ρ Ll ρ Mm ... (4.09.1)
KP =
and ρ Aa ρ Bb ...

C Ll C Mm ...
KC = (4.09.2)
C Aa C Bb ...
where the ρ and C terms are the partial pressures and molar concentrations.

For gases
PI V = ni RT (1.08.3)

ni
⇒ Pi = RT = c i RT (4.09.3)
V
Then

C Ll CMm ... (RT )

l + m +...
= K C (RT ) (4.09.4)
∆n
KP =
C AC B ... (RT )
a b a + b +...

where
∆n = (l + m + …) - (a + b + …)

and is equal to the increase in the number of molecules in the chemical reaction as
written.

73
Example

For the reversible reaction

N2 + 3H2 = 2NH3

at 773K, the value of KP, with partial pressures in atmospheres, is 1.44 x 10-5 at low
pressures where the gases behave ideally.

Determine the corresponding value of KC with concentrations in mole litre-1.

Solution:

From

Pi = (ni/V) RT = ci RT, R = 0.0820 litre-atm mol-1K-1, ∆n = -2,

the equation KP = KC (RT)∆n yields KC = 1.44 x 10-5 (0.0820 x 773)2 = 5.79 x 10-2

SAQ 3

When the reaction

C(cr.) + CO2(g) = 2CO(g)

takes place at 850 oC and 1 atm. Pressure, the equilibrium mixture contains 93.77% of the
CO and 6.23% CO2 by volume. Calculate the value of Kp.

4.10 TEMPERATURE AND EQUILIBRIUM

(THE VAN'T HOFF EQUATION)

From equilibrium one has

∆G0 = - RTlnK (4.10.1)

such that K is the thermodynamic equilibrium constant.

For an ideal gas (or one nearing ideality) one has

∆G0 = - RT ln KP (4.10.2)

The RHS has T and KP as variables (∆G0 changes with temperature and pressure).

74
At constant pressure,

 ∂
 ( )

∆G 0  = − R ln K P − RT
d
ln K P (4.10.3)
 ∂T P dT

Multiplication by T and substitution of ∆G0 for -RTlnKP yields

 ∂
T (∆G 0 ) = ∆G 0 − RT 2
 d
LnK P (4.10.4)
 ∂T P dT

For standard state, the Gibb's-Helmholtz equation yields

 ∂
∆G o = ∆Η o + T  (∆G 0 )

(4.10.5)
 ∂T P
Comparison of the above two equations yields

d
RT 2 ln K P = ∆Η 0 (4.10.6)
dT
d ∆Η 0
⇒ ln K P = (4.10.7)
dT RT 2

This is the Van't Hoff equation in which ∆H0 is the enthalpy change of reaction at
constant pressure with the reactants and products in their standard states.

Enthalpy change does not vary much with pressure of the substance concerned and so
∆H0 may be replaced by ∆H to make the equation more general.

Thus

d ∆Η (4.10.8)
ln K P =
dT RT 2

Rearrangement and integration of the above equation yields

− ∆Η
ln K P = + cons tan t
RT (4.10.9)

Thus a plot of lnKP against T-1 yields a straight line with slope equal to (-∆H/R)

Further, integration between T1 and T2 yields

75
  (K )  ∆Η  1 1  ∆Η  T2 − T1 
ln P 2  = −  − =  
 (K P )1  R  T2 T1  R  T2T1  (4.10.10)

Example:

The equilibrium constant KP for the reaction:

N2 + 3H2 = 2NH3

is 1.64 x 10-4 at 673K and 1.44 x 10-5 at 773K. Determine the mean enthalpy of
formation, ∆HV, for one mole of ammonia from its elements in this temperature range.

Solution:

T1 = 673K T2 = 773K

KP1 = 1.64 x 10-4 KP2 = 1.44 x 10-5

 K  ∆ΗV  T2 − T1 
ln P 2  =   yields
 K P1  R  T2T1 

 1.44 x10 −5  ∆ΗV  773 − 673 

ln =
−4   
 1.64 x10  8.314  673 x773 

8.314 x773 x673  1.44 x10 −5 

⇒ ∆ΗV = ln 
−4 
773 − 673  1 . 64 x10 

= - 105.216 kJ

This is the enthalpy of reaction for the formation of two moles of ammonia.

For I mol. ∆HV = ½ x –105.216

= -52.608 kJ Ans.

76
4.11 STANDARD FREE ENERGIES

Changes in free energies correlate with the tendency of the system to proceed to a state of
equilibrium (∆G ≤O for the system). It is therefore useful to have a tabulation of free
energies of chemical compounds so that the free-energy change of a possible reaction can
be easily calculated.

Free energies must have some reference point. A zero value is assigned to the free
energies of stable forms of the elements at 250C and 1 atmosphere pressure. These, and
the free energies of compound based on these references, are known as standard free
energies of formation. The data can be determined from the free energies of reactions in
exactly the same way as were standard enthalpies of formation. Standard free energies
are normally tabulated.

Example:
C2H2(g) + H2(g) → CH3CH3(g)

G 0f ( 250 C ) 68058.76J (O) - 32854.8J

∆G298
0
= −32854.8 − 68058.76 = −100913.56 J

Tabulated standard free energies allow predictions to be made on the possibility of a

reaction taking place for the (single) conditions of 250C and 1 atmosphere pressure. A
means must be available for calculating free energies at other pressures and temperatures.

G is a state function and its dependence on P and T is given by:-

G2 - G1 = nRTln (P2/P1) (4.11.1)

If state 1 is the standard then:

P1 = 1 atm and
G1 = G0

State 2 corresponds to some general pressure other than 1 atm. and the subscripts on state
2 may be dropped.

Then, for one mole

G = G0 + RTlnP (4.11.2)

where P must be expressed in atmosphere units in order to cancel the standard 1 atm.

77
The equation above shows that the free energy of a gas at pressure P is made up of the
free energy that it has at 1 atmosphere pressure plus an addition term that is positive for P
greater than 1 atmosphere and negative for P less than 1 atmosphere.

4.12 STANDARD FREE ENERGY OF REACTION

A reaction can take place spontaneously only if it is accompanied by a decrease of free

energy. The sign of the standard free energy change gives an indication of whether the
process is possible or not under the standard conditions. If it is negative it means that the
reaction, with reactants and products in their standard states, can take place at the
particular temperature. The quantity ∆G0 has a definite value at every temperature for a
given reaction and is related to the equilibrium constant at the same temperature by the
equation.

∆G0 = - RTlnK (4.10.1)

The free energy is a property that depends only on the state of a system. It is thus
possible to add and subtract free energy changes for different reactions. Further, reversal
of a particular reaction only leads to a change in sign of the standard free energy change.

Example:

Given

(i) 2H2O(g) → 2H2(g), + O2(g) , ∆G0298 = 456.79 kJ

(ii) CO2(g) + H2(g), → H2O(g) + CO(g) , ∆G0298 = 28.51 kJ

then

2x(ii) + (i) yields

2CO2(g) = 2CO(g) + O2(g)

and ∆G0298 = (2 x 28.51) + 456.79 kJ

= 513.81 kJ

78
SAQ 4

Calculate the Gibb’s Free Energy change (∆G), at 25oC for the reaction:

C2H5OH(l) + O2(g) CH3COOH(l) + H2O(l)

from the following data, at 25oC.

(i) H2(g) + ½ O2(g) H2O(l) ∆G= -238kJ

(ii) 2C(graphite) + 3H2O(g) + 1/2 O2(g) C2H5OH(l) ∆G= -176kJ

(iii) 2C(graphite) + 2H2O(g) + O2(g) CH3COOH(l) ∆G = -394kJ

4.13 STANDARD FREE ENERGIES OF COMPOUNDS

For purposes of calculation, it is convenient to tabulate the molar free energies of

substances in their standard states, that is, 1 atmosphere pressure for ideal gases and the
pure state for solids and liquids. These are employed to calculate the standard free
energy changes in reactions and hence it is not necessary to know the absolute free
energies of the various substances concerned. The convention is adopted whereby, "The
free energies of all elements in their standard states is arbitrarily taken as zero at all
temperatures".

The standard free energy changes accompanying the formation of various compounds
from their elements have been determined and these represent the standard (molar) free
energies of the substances.

79
TABLE OF THE STANDARD MOLAR FREE ENERGIES OF
FORMATION OF SOME COMPOUNDS AT 298K

SUBSTANCE ∆G0f(298) , kJ

H2O(l) - 236.9650
CH3OH(l) - 166.0714
C2H5OH(l) - 174.5986
C6H6(l) + 124.3801
NaCl(s) - 383.6613
H2O(g) - 228.3772
C2H2(g) + 209.0
C2H6(g) - 32.8548
CO2(g) - 394.0040
CO(g) - 137.1370

The above data may be made clearer if the equations are written in full.

For example

C(c) + O2 (g, 1 atm) = CO2 (g, 1 atm), ∆G0f(298) = - 394.004 kJ

C(c) + 2H2 (g, 1 atm) + ½ O2 (g, 1 atm) = CH3OH(l) , ∆G0f(298) = - 166.0714 kJ

The tabulated standard free energies may be used to determine the standard free energy
changes for reactions at 250C.

Example:

CH4(g) + 2O2(g) = CO2(g) + 2H2O(l)

- 50.75 O - 394.00 2(-236.97)

∆G0f(298) = [(-394.00) + 2(-236.97)] - [(-50.75) + 0]

= - 817.19 kJ

SAQ5:

Reference tables give:

3C2H2(g) = C6H6(g) , ∆H0298 = - 550 kJ

and the molar entropy values, also at 298K,

S (0C2 H 2 , g ) = 202 JK −1 and

S (0C6 H 6 , g ) = 271JK −1
80
From these data, determine the equilibrium constant at 298 K for this benzene synthesis.

4.14 SUMMARY

• Gibb’s free energy change (∆G) is a better determinant of spontaneity than

entropy and enthalpy change.
• The condition for spontaneity is that ∆G must be negative.
• At equilibrium, ∆G equals zero.
• Standard Gibb’s Free Energy, G, is taken as zero for all elements in their most
stable form at a temperature of 298K and a pressure of one atmosphere.
• The Clausius-Clapeyron equation can be used to predict the equilibrium vapour
pressure P2 of a pure liquid at a desired temperature T2 from its known enthalpy
of vaporization and its known vapour pressure P1 at some other temperature T1.

4.15 TERMINAL QUESTIONS

1. Given that the values of the standard free energies of formation of NO2 and N2O4
at 25oC are 51.5 and 98.5 kJ per mole, respectively, calculate Kp and Kc at one
atmosphere and 25oC for the reaction;

N2O4(g) = 2NO2(g)

2. For the reaction;

1/2N2(g) + 3/2 H2(g) NH3(g),

the value of Kp is 6.59 x 10 –3 at 450oC. Determine the change in free energy.

3. Calculate the enthalpy of vaporization in units of kJ per mole for ethanol using
the following data for 77 oC and 1 atmosphere pressure.

DP/dT(mmHgK-1) 28.6
Volume per gram vapour (cm3) 606.3
Volume per gram liquid (cm3) 0.737
Acceleration due to gravity (cmsec-2) 981
Density of mercury(gcm-3) 134.59

4. Calculate the equilibrium constant at 25oC for the reaction;

Fe2O3(s) + H2(g) = 2FeO(s) + H2O(g) ;

81
 The appropriate standard free energies of formation at 25oC, in kJmol-1, are given
as:
Fe2O3(s) -744, FeO(s) -245, H2O(g) -229.

4.16 ANSWERS TO SAQs

[1] –140.47J [2] 31.28kJmol-1 [3] 14.11 [4] –456kJ [5] -450.17kJ

4.17 ANSWERS TO TERMINAL QUESTIONS

[1] Kp = 0.1625atm. Kc = 6.65 x10-3 moldm-3 [2] 18789.564J

[3] 37.23kJmol-1 [4] 4.17 x10-5

82
Useful Physical Constants

1 litre = 1000 cm3 = 1 dm3=1000 ml = 10-3 m3

1 calorie = 4.184J
1 atmosphere = 76.0 cm Hg = 101325 Nm-2
0oC = 273.15K
Molar Gas Volume at STP = 22.415 l
Gas Constant R = 0.08205 litre-atm.K-1mole-1 = 8.314 J K-1mole-1
Avogadro’s Number (NA) = 6.023 x 10 23 mol-1
Acceleration due to gravity (g) = 9.8066 ms-2

83
References

1 Glasstone S., Lewis D. Elements of Physical Chemistry , Macmillan, 2nd. Edition,

1974.
2 Barrow G. M., Physical Chemistry, McGraw-Hill, 3rd Edition, 1973
3 Sharma K. K., Sharma L.K. A Textbook of Physical Chemistry, Vika’s
4 Bahl B.S., Tuli G.D., Essentials of Physical Chemistry, Chand and Co., 1985
5 Mahan B.H. College Chemistry, Addison Wesley
6 Griffith’s P.J.F., Thomas J.D.R., Calculations in Advanced Physical Chemistry,
Edward Arnold.
7 Ritchie I.M. Graig R.A., Thistlethwaite P.J. Problems in Physical Chemistry
J.Wailey
8 Atkins P.W., Physical Chemistry, ELBS
9 Dickerson R.E., Molecular Thermodynamics, W.A. Benjamin
10 Levine I.N. Physical Chemistry

84