KENYATTA UNIVERSITY

SCHOOL OF PURE AND APPLIED SCIENCES

DEPARTMENT OF CHEMISTRY
BSc Ed., BSc. and BSc. Analytical & Industrial Management
SCH 201 CHEMICAL THERMODYNAMICS

LEVEL : II SEMESTER: I ACADEMIC YEAR: 2020/2021

Series -1 (Introduction and First Law of Thermodynamics)

Prof. Charles Onindo

1
 Course Objective & Content
Course objective:
To provide a basic introduction to chemical thermodynamics for science
and education students.
Course Content:
Chemical thermodynamic systems, states, state function and equilibrium
state. First law of thermodynamics, constant volume, constant pressure and
the reversible process. Isothermal and adiabatic expansion of an ideal gas.

Thermochemistry: Heat changes involved in chemical reactions and Hess’s

law. Heat capacities and enthalpy dependence on temperature.
Second law of thermodynamics: entropy and disorder. Temperature
dependence on entropy and the third law of thermodynamics.

Free energy (G), pressure dependence of G on ideal gases, relationship

between G and the equilibrium constant.
2
 Learning 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
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
3
 Learning objectives (Cont-1):
iii. Relate heats of reaction at constant pressure and constant volume
a) Calculate the change in enthalpy accompanying a chemical
reaction
b) Apply the enthalpies of combustion, formation and thermo-
chemical laws in solving problems
iv. Demonstrate the dependence of enthalpies of reaction on
temperature
v. Define entropy and state the second law of thermodynamics
a. Calculate the change of entropy when an ideal gas undergoes an
expansion or compression
b. Calculate the entropy changes of systems and surroundings
during temperature/pressure/volume change
c. Calculate the entropy changes during phase transitions
d. Calculate the entropy changes for irreversible processes
e. Describe the Carnot cycle and calculate efficiency of heat
engines
f. Relate entropy changes to irreversibility and spontaneity of
transformations 4
 Learning objectives (Cont-2):
vi. Define Helmholtz and Gibb’s Free Energies
a) Calculate the Gibb’s Free Energy changes for different
physical and chemical transformations.
b) Relate the Gibb’s Free Energy changes to Spontaneity of
transformations.
c) Relate changes in Gibb’s Free Energy with Temperature,
Enthalpy, Entropy and Equilibrium Constant.
d) Apply the Clausius-Clapeyron Equation

5
Suggested 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 6
 1.0 INTRODUCTION
The term THERMODYMAMICS means flow of heat. The study
of energy and its transformations.
(Greek: therm, ‘heat’ dynamis ‘power’). In general it deals with
the inter conversion of various kinds of energy in physical and
chemical systems.

Thermodynamics
1. Predicts the feasibility of a physical process or chemical
reaction under given condition of temperature and pressure
2. Predicts whether a chemical reaction would occur
spontaneously or not under a given set of conditions
3. Helps to determine the extent to which a reaction would take
place.
.

7
 Introduction ….
Limitations of Thermodynamics
1. It predicts the extent to which a reaction can take place.
However it does not say anything about the rate.
2. It applies only to matter in bulk and not to individual atoms or
molecules

Importance of thermodynamics
Thermodynamics is important not only to chemistry but to other
areas of science and engineering as well. It touches our daily lives
as we use energy for manufacturing, travel and communications.
.

8
Pictorial Application Areas of Thermodynamics

9
1.1 THE NATURE OF ENERGY
Definitions
FORCE
A force is any kind of push or pull exerted on an object. For
example force of gravity ‘pull’ us to the ground. In chemistry,
positively charged nuclei exert a ‘pull’ on negatively charged
electrons.

WORK
When we increase the distance between a proton and an
electron, we perform work to overcome the attractive force
between them. The work, w, that we do in moving objects
against a force equals the product of the force, F, and the
distance,d, that the object is moved. w=F x d

10
1.1 THE NATURE OF ENERGY
Definitions
ENERGY
Energy in the form of work, must be used to move an object
against a force. As we perform work, heat may be generated.

HEAT
Heat is the energy that is transferred from one object to another
because of difference in temperature.

WORK and HEAT are the two ways that we experience energy
changes in our MACROSCOPIC environment. Energy is the
capacity to do work or to transfer heat

11
1.1 THE CONCEPT OF ENERGY

ENERGY may take various forms:-

 kinetic energy (due to motion)
 potential energy (due to position)
 heat energy (as measured by temperature)
 chemical energy, etc

A basic definition given by the great physicist, Albert Einstein is:

E = mc2
where

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

12
 Some SI derived Units
Physical Quantity Unit Symbol Definition of unit

force newton N 1N = 1mkgs-2

pressure pascal Pa 1Pa = 1Nm-2 = 1kgm-1s -2
Celcius temperature degree Celcius ˚C t/˚C = T/K - 273.15
energy joule J 1J = 1 NM = 1m2kgs-2
power watt W 1W =1Js-1 = 1m2kgs-3
frequency hertz Hz 1Hz = 1s -1
electric charge coulomb C 1C = 1As
electric potential volt V 1V = 1JC-1 = 1m2kgs-3A-1
electric resistance ohm Ω 1Ω = 1VA-1 =1m2kgs-3A-2

13
1.2 BASIC DEFINITIONS
System and surroundings:
• Any part of the universe which is selected for
thermodynamic study is called a system and the rest
of the Universe in its neighborhood is known as
surroundings .
• The system is separated from the surroundings by a
real or imaginary boundary through which exchange
of energy or matter may take place.
• Interactions between the system and its surrounding
can be classified as: (i) Open , (ii) Closed or (iii)
Isolated system.

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1.2.1 Types of System
A. Open system: Exchange both energy and matter
with its surroundings.
B. Closed system: Can exchange energy but not matter
with the surroundings.
C. Isolated System: There is no transfer of either
energy or matter with the surroundings.

(A) (B) (C)

15
1.3 SAQ-1
Classify the following systems as open, closed or
isolated.

1) Nitrogen and hydrogen reacting to form ammonia in

a sealed tube.
2) Potassium chlorate and manganese dioxide are
heated in an unsealed test tube to form potassium
chloride and oxygen.
3) A glass vial containing conc. Hydrochloric acid is
broken inside water in a beaker.
4) A glass vial containing hydrochloric acid is broken
inside a solution of sodium hydroxide kept in a
closed polythene bottle insulated with a cork. 16
 1.5 Properties of a System
The properties associated with a macroscopic system are called
thermodynamic properties or variables

Two main categories:

1) EXTENSIVE PROPERTIES:- Depend upon the amount/quantity
of matter present in the system e.g.mass, volume, energy etc.

2) INTENSIVE PROPERTIES: depends on characteristics of matter

but independent of its amount e.g. pressure, temperature, density,
viscosity, surface tension, refractive index, electromotive force,
chemical potential, specific heat, etc.

17
1.4 State functions
Internal energy, a state function, depends only on the present
state and NOT on the path by which it arrived at that state.

Example:
The internal energy of 50g of water at 25ºC is the same whether
the water is cooled from a higher temperature to 25ºC or is
obtained by melting 50 g of ice and then warming to 25ºC

The value of a state function does not depend on the particular

history of the sample, only on its present condition. The properties
that depend only on the state of the system and not on its past
history are called STATE FUNCTIONS.
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STATE FUNCTION
1. Must have a definite value for a given system in a
given state, independent of the history of that system

and
2. Change by a definite amount in a given change of state,
independent of the path along which that change proceeds.

19
Thermodynamic process:
The method by which the state of a system is changed is called
a ‘process’. It can be effected by changing any one of the state
variables viz P, T, C etc.
Isothermal process: It is a process carried out at constant
temperature dT=0

Adiabatic process: It is a process in which no exchange of heat

takes place. The temperature of the system may increase or
decrease during adiabatic process. dQ=0

Isobaric process: Carried out at constant pressure

Isochoric process: Carried out at constant volume

20
Reversible process:
A process which occurs infinitely slowly, can be reversed along
the same path and performs maximum work is referred to as
being thermodynamically reversible.

It is a process which takes place infinitesimally slowly so that

the system is in thermodynamic equilibrium at any instant of
the change.

Since the process is carried out extremely slowly the properties

of the system remain virtually unchanged and the direction may
be reversed by small change in a variable like temperature,
pressure etc.

The driving force is greater than the opposing force only by a

infinitesimal quantity and hence the process would require
21
infinite time for completion.
Irreversible process:
It is a process which takes place rapidly or spontaneously so
that it is in equilibrium with the surroundings. The driving force
differ from the opposing force by a large amount and hence it
cannot be reversed unless some external force is applied. All
the natural processes are irreversible.

22
Reversible process:
.
Reversible Process Irreversible process

1 Driving force and opposing force differ Driving force and opposing force differ by
by small amount a large amount

2 It is a sloprocess It is a rapid process

3 The work obtained is more The work obtained is less

4 It is an imaginary process It is a real process

5 It consists of many steps It has only two steps i.e. initial and final

6 It occurs in both directions It occurs in only one direction

7 It can be reversed by changing It cannot be reversed

thermodynamic variables

23
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

24
1.6 The First law of Thermodynamics:
Define first law of thermodynamics both verbally and by means
of a equation
In general, energy can be converted from one form to another.
But energy can neither be created nor destroyed: Energy is
conserved.
• The total energy lost by a system equals the total energy
gained by its surroundings. This is the law of conservation of
energy also known as the first law of thermodynamics

Alternatively:
The total energy of a system and its surroundings must remain
constant, although it may be changed from one form to
another"

25
Internal Energy
• The total energy of a system is the sum of all the kinetic and
potential energies of its component parts. For the system of
H2 and O2 molecules, the total energy include not only the
motions and interactions of the H2 and O2 molecules
themselves but also of the component nuclei and electrons.
• The total energy is called the internal energy of the system
• Because there are so many types of motions and interactions,
we cannot determine the exact energy of any system of
practical interest. We can, however, measure the change in
internal energy that accompany chemical and physical
processes.
• ΔE = Efinal - Einitial

26
In terms of the work performed (w), the heat (q) transferred and the
change in internal energy (ΔE) that is stored in the system; first law
of Thermodynamics is mathematically expressed as:

ΔE = q – w or q = ΔE + w
For very small changes: dE = q - w
Where dE is the small change in the internal energy, q is the small
amount of heat absorbed and w is the small amount of work done
by the system.

 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".

 Heat transfer may occur by conduction, convection or radiation

27
Summary of sign conventions

Positive (+) Negative (-)

Heat (q) System gains System loses

energy energy

Work (w) Work done by the Work done on the

system system

Change in Internal energy of Internal energy of

internal energy the system the system
(ΔE) increases decreases

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 Expansion or compression work :
• The external pressure Pex is
equivalent to a weight pressing
on the piston, and the force
opposing expansion is:

ork (w) = F x d

But F=PexA, then:

w = PexAdz ⇒ w = PexΔV

When a piston of area A moves out

through a distance dz it sweeps out a
volume dV = Adz.
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30
31
32
33
Question-2:
When one mole of water, at 100 0C and 1 atm. pressure, is
converted to steam (at 100 0C) the amount of heat absorbed is
40670 J. Calculate ΔE for the change.
Solution 2:
Work done in expanding against atmospheric pressure:
w = Pext (V2 – V1)
Given: V1 = Volume of one mole of a liquid water
= 18 cm3 = 18 x 10-6 m3
V2 = volume of 1 mole of water vapour at 100 oC
From Gas laws and at constant pressure: V1/T1 = V2/T2
Also, at STP (273 K and 1 atm pressure) 1 mole of ideal gas
occupies ≈ 0.0224 m3
Therefore: V2 = 0.0224 * (373/273) = 0.0306 m3

Then; Pext = 101325(0.0306 – 18x10-6) = 3099 J

From First Law: ΔE = q – w = (40670-3099) = 37571 J. 34
 Question-3:
A balloon is filled with helium is heated and expands, performing
370 J of work on the surrounding gases in the atmosphere. The
internal energy of helium increases by 1220 J. How much heat did
helium absorb?

Solution 3:

ΔE = q - w
Given: w = 370 J, ΔE = 1220 J
1220 J= q - 370 J
q = 1590 J
SAQ-3
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.
35
Question-4:

36
 INTERNAL ENERGY OF AN IDEAL GAS

• Internal energy for an ideal gas is of special

interest. Why?

37
• 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.

38
 INTERNAL ENERGY OF AN IDEAL GAS

• Thus for isothermal expansion, ΔE=0 and

hence at any constant temperature, the
internal energy of an ideal gas is
independent of its volume. Note this could
be in a vacuum or not.

39
INTERNAL ENERGY OF AN IDEAL GAS

This implies that at constant temperature

ΔE=0 and from q=ΔE+w

40
Question-5:
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 5:
Given: n= 0.1 mole, T= 273, V1 = 3 dm3 and V2 = 5 dm3

Using equation (7)

q = 0.1 * 8.314 * 273 ln (5/3)
= 115.94 J

41
 Derivation of T–P–V relations for adiabatic
and reversible process

• An adiabatic process occurs if there is no

exchange of heat (q) between the system and
surroundings. That is, q = 0 in an adiabatic
process.

• In an adiabatic process if work is done by the

system its temperature decreases, if work is
done on the system its temperature increases.

42
 Derivation of T–P–V relations for adiabatic
and reversible process

• It is important to review the concept of heat

capacities at constant pressure and at constant
volume since the heat capacities will feature in
the calculations..

• Molar heat capacity, C, is defined as the heat

required to raise the temperature of one mole
of the system by one degree.

43
Derivation of T–P–V relations for adiabatic
and reversible process

44
Derivation of T–P–V relations for adiabatic
and reversible process

45
Derivation of T–P–V relations for adiabatic
and reversible process

46
1. T-V RELATION FOR AN ADIABATIC PROCESS

47
1. T-V RELATION FOR AN ADIABATIC PROCESS

48
2. T – P RELATION FOR OR AN ADIABATIC
PROCESS

49
2. T – P RELATION FOR OR AN ADIABATIC
PROCESS

50
2. T – P RELATION FOR OR AN ADIABATIC
PROCESS

51
3. P – V RELATION FOR AN ADIABATIC PROCESS

52
3. P – V RELATION FOR AN ADIABATIC PROCESS

53
Question-6:
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=?
Equation (24)
CVln T2/T1 = -RlnV1/V2
Substitution gives

3/2RlnT2/300 = -RlnV1/4V1
lnT2/300 = 2/3ln4

Hence: T2 = 755.95 K Ans

54
Question-7:
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?

55
 Tutorial Question.
Question 1
a) Explain clearly what is meant by a thermodynamically
reversible process.
Solution:
a) A thermodynamic reversible process occurs in infinitely slowly,
can be reversed along the same path and performs maximum
worm.
b) Explain the thermodynamic meaning of a system,
distinguishing among the open, closed and isolated systems.
Solution:
b) A system is part of the universe, the properties of which are
under investigations and has a definite boundary.
 Open system: Exchange both energy and matter with
surroundings.
 Closed system: Exchange energy with surroundings,
matter NOT exchanged.
 Isolated system: No transfer of either energy or matter
56
with surroundings
 Tutorial Question. 1…
c) One mole of an ideal gas at 25 °C and a pressure of 10 x 105
Nm-2 expands isothermally to a pressure of 1 x 105 Nm-2
i. Calculate the final volume, w and q if the expansion
were carried out reversibly.
ii. Calculate w and q for an irreversible expansion

57
Tutorial Question. 2

58
SAQ-3
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

59
 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.

60
Summary (cont.)
 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

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Enthalpy at Constant Volume/ Pressure
Using the symbol q to represent transferred heat and work w =
PΔV; the total internal energy change of the system can be
represented as:

ΔE = q - w = q – PΔV
Rewrite: q = ΔE + PΔV
Constant volume:
Reactions carried out in a closed container are at a constant
volume. Therefore; ΔV = 0, then qv = ΔE (at constant volume).

Constant pressure:
Reactions carried out in open flask keeping the pressure
constant and allowing the volume of the system to change;
energy change in the system is due to both heat transfer and PV
work.
qp = ΔE + PΔV (at constant pressure). 1
Enthalpy at Constant Volume/ Pressure con’t
•Most physical and chemical changes, including those in living
systems, take place under the essentially constant pressure of
earth’s atmosphere.
•Chemists use the symbol H, and a special name, enthalpy
(enthalpein to ‘warm’) in dealing with heat absorbed or
released under constant pressure
Therefore qp can be substituted by ΔH;
ΔH = ΔE + PΔV

*enthalpy a state function whose value only depends on the

current state of the system, not on the path taken to arrive.

i. e. ΔH = Hfinal – Hinitial

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

a system.
2
 Enthalpy is an extensive property
The magnitude of ΔH is directly proportional to the
amount of reactants consumed in the process

The enthalpy change for a reaction is equal in magnitude

but opposite in sign to ΔH for the reverse reaction

 The enthalpy change for a reaction depends on the state

of the reactants and products

3
The physical states of the reactants and products need to
be considered when calculating ∆H

HESS’S LAW
•Many enthalpies of reactions have been measured and
tabulated. It is often possible to calculate ∆H values of other
reactions.

•Because enthalpy is a state function, the enthalpy change,∆H,

associated with any chemical process depends only on the
amount of matter that undergoes change and on the nature of
the initial state of reactants and the final state of reactants

4
HESS’S LAW
STATES THAT “If a reaction is carried out in a series of
steps, ΔH for the reaction will be equal to the sum of the
enthalpy changes of the individual steps”

The overall enthalpy change for the process is independent of

the number of steps or the particular nature of the path by
which the reaction is carried out.

5
Example

Calculate ∆H for the reaction

2C(s) + H2(g) →C2H2(g)

Given the following reactions and their respective

enthalpy changes:

C2H2(g) + 5/2O2(g)→2CO2(g)+H2O(l) ∆H=-1299.6 kJ

C(s)+O2(g)→CO2(g) ∆H=-393.5 kJ

H2(g)+1/2O2(g)→H2O(l) ∆H=-285.9 kJ

6
Solution
1) Because the target equation has C2H2 as a product, we turn
the first equation around; the sign of ∆H is therefore
changed

2) Because the target equation has 2C(s) as a reactant, we

multiply the second equation and its ∆H by 2

3) Because the target equation has H2 as a reactant, we keep the

third equation as it is. We then add the three equations and
their enthalpy in accordance with Hess’s law.

4) When the equations are added, there are 2 CO2, 5/2 O2 and
H2O on both sides of the arrow. These are cancelled in
writing the net equation.

7
Enthalpies of Formation
• We can calculate the enthalpy changes from a great many
reactions from a few tabulated ∆H values.

Extensive tables exists for

• Enthalpies of vaporization - ∆Hvap for converting liquid to
gas
• Enthalpies of fusion - ∆Hf for melting solids
• Enthalpies of combustion -∆Hc for combusting a substance
in oxygen and so on

A particularly important process for tabulating thermochemical

data is the formation of a compound from its constituent
elements.

8
 The enthalpy change associated with this process is called
the
ENTHALPY OF FORMATION (or HEAT OF
FORMATION) labeled ∆Hf

 The MAGNITUDE OF ANY ENTHALPY CHANGE

depends on the conditions of TEMPERATURE,
PRESSURE and STATE
(gas,liquid or solid, crystalline form) of the reactants and
products.

 The STANDARD STATE for a substance is the form most

stable at a particular temperature of interest and at standard
atmospheric pressure.

9
• When a reaction occurs with all reactants and products in
their standard states, we refer to its enthalpy change as the
STANDARD ENTHALPY OF REACTON, ∆Hº. The
temperature usually chosen for tabulating data is 298 K (25ºC)

• The STANDARD ENTHALPY OF FORMATION of a

compound, ∆Hºf, is the change in enthalpy that
accompanies the formation of 1 mol of that substance
from its elements in their standard states.

• 2C(graphite)+3H2(g)+½O2(g)→C2H5OH(l) ∆Hºf = -277.7

kJ (O2 most stable NOT O or O3 at 25ºC, Elemental source
of carbon is graphite NOT diamond

10
• We can determine the standard enthalpy change for any
reaction, ∆Hºrxn, by using standard enthalpies of formation
and Hess’s law

∆Hºrxn, = Ʃn∆Hºf(products) – Ʃm∆Hºf(reactants)

• For example, we can calculate ∆Hº for the combustion of

propane from the ∆Hºf(reactants values of the products and
reactants:
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O (l)
∆Hºrxn = [3∆Hºf(CO2)+4 ∆Hºf(H2O)]-[∆Hºf(C3H8)+5∆Hºf, (O2)]
Because O2(g) is the most stable form of the element, ∆Hºf(O2)
= 0. The other enthalpies of formation are obtained from
data tables.

11
We can determine the standard enthalpy change for any
reaction, ∆Hºrxn, by using standard enthalpies of formation
and Hess’s law

∆Hºrxn, = Ʃn∆Hºf(products) – Ʃm∆Hºf(reactants)

For example, we can calculate ∆Hº for the combustion of

propane from the ∆Hºf(reactants values of the products and
reactants:
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O (l)
∆Hºrxn = [3∆Hºf(CO2)+4 ∆Hºf(H2O)]-[∆Hºf(C3H8)+5∆Hºf, (O2)]
Because O2(g) is the most stable form of the element, ∆Hºf(O2)
= 0. The other enthalpies of formation are obtained from
data tables.

12
Standard Enthalpy of Formation (ΔHf˚)
SUBSTANCE Hf0298, kJ
H2O(l) - 285.56
CO2(g) - 393.14
H2S(g) - 17.49
CH4(g) - 74.78
CH3OH(l) - 238.34
C3H8(g)

13
Tutorial Question
Calculate the heat of reaction for CO(g) + H2O(l) → CO2(g) + H2(g)
at 293 K from the given table of heats of formation.
SUBSTANCE Hf0293, kJ
H2O(l) - 286.86
CO(g) - 110.88
CO2(g) - 394.8

Solution
H0r298 = [Hf0(CO2) + (Hf0(H2)] – [Hf0(CO) + Hf0(H2O)]
= [(-394.8)+ (0)]– [(-110.88) + (-286.86)]
= -394.8 + 397.74
= 2.94 kJ

14
 CALORIMETRY
•The value of ∆H is determined experimentally by measuring the
heat flow accompanying a reaction at constant pressure. When heat
flows into or out of a substance, the temperature of the substance
changes.

•Experimentally we can determine the heat flow associated with a

chemical reaction by measuring the temperature change it
produces. The measurement of heat flow is called
CALORIMETRY; an apparatus that measures heat flow is called
CALORIMETER.

15
•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 = mAcAΔT

where Q is the heat, mA is the mass, cA is the heat capacity and ΔT is

the change in temperature.

The calorimeter used may be of constant volume or constant

pressure type.

16
CALORIMETRY Calibration

17
Constant Pressure Calorimetry

Recall: ∆H=qp
Reaction occurs under constant pressure of the atmosphere
Because the calorimeter prevents the gain or loss of heat from its
surroundings, the heat released by the reaction –qrxn = heat gained by
solution qsoln
qrxn = -qsoln = -(specific heat of solution)x(gram of solution)x∆T

= 2.94 kJ

18
Example
When a student mixes 50 mL of 1.0 M HCl and 50 mL of
1.0 M NaOH in a polystyrene cup calorimeter, the
temperature of the resultant solution increases from
21.0°C to 27.5°C. Calculate the enthalpy change for the
reaction, assuming that the calorimeter loses only a
negligible quantity of heat, that the total volume of the
solution is 100 mL, that its density is 1.0 g/mL; and that
its specific heat is 4.18 J/g-K.

19
Answer
Mass of solution = (100 mL)(1.0g/mL) = 100 g
Temperature change (ΔT) = 27 . 5 ºC – 21.0 ºC = 6.5 K (reaction
exothermic)
qrxn = −(100 g) (4.18 J/gK)(6.5 K) = −2700 J = −2.7 J

Process occurs a t constant pressure: ΔH = qp = −2.7 kJ

moles of HCl or NaOH = [(50mL) x 1.0 mol]/1000mL = 0.050 mol
Enthalpy change per mole of HCl or NaOH
ΔH = −2 .7 kJ /0 .0 5 0 mol = −5 4 kJ /mol.

20
Tutorial question
A 3.5 g sample of quinine C6H4O2 was burned in a calorimeter
with a heat capacity of 3.43 kJ/ºC and contained 1.2 kg of water.
The temperature of the calorimeter and water increased from
19.0ºC to 28.0ºC. What is the molar enthalpy of combustion of
quinine? (mm quinine = 108.09 g /mol; Csoln = 4.18 J/gºC)

21
Bomb Calorimetry ( Constant – Volume Calorimetry):
A compound, usually an
organic compound, is allowed
to react completely with
excess oxygen.
After the sample has been
placed in the bomb, the bomb
is sealed and pressurized with
oxygen and placed in an
accurately measured quantity
of water. The heat evolved in
the combustion of the sample
is absorbed by its
surroundings, namely, the
calorimeter contents

22
•To know the heat capacity of the calorimeter, Ccal, we burn a
sample that gives off a known quantity of heat. Combustion of 1 g
of benzoic acid, C7H6O2 , produces 26.38 kJ of heat and if the
temperature increase is 5.022°C, then:

Ccal = 26.38 kJ/5.022ºC = 5.253 kJ/ºC

For other reactions:

qevolved = -Ccalorimeter x ∆T

23
Hydrazine, N2H4 and its derivatives are widely used as
rocket fuels. The combustion of hydrazine with oxygen
produces N2(g) and H2O(g):
N2H4(l) + O2(g) →N2(g) +2 H2O(g)
When 1.00 g of hydrazine is burned in a bomb calorimeter,
the temperature increases by 3.51ºC (heat capacity 5.510
kJ/ºC)

i) What is the quantity of heat evolved

ii) What amount of heat is evolved upon combustion of a mole

of N2H4?

It may be noted in this case, the volume remains constant.

Hence, the enthalpy of reaction gives a measure of qv
qp=qv + ∆nRT 24
Tutorial Question:
0.50 g of benzoic acid was subjected to combustion in a bomb
calorimeter when the temperature of the calorimeter system
(including water) was found to rise by 0.55ºC.
Calculate the enthalpy of combustion of benzoic acid
(i) at constant volume
(ii) At constant pressure.

The thermal capacity of the calorimeter system including water was

found to be 23.85 kJK-1.

25
 The Effect of Temperature on Enthalpy of
Reaction (The Kirchhoff's Equation):

• Reactions are carried out at various

temperatures and it is necessary to determine
heats of reaction at temperatures other than
those calculated from heats of formation or
obtained calorimetrically.

• Consider any process represented thus:

A B
• The enthalpy of reaction at constant pressure
H = HB - HA
26
• 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 𝜕𝐻𝐵 𝜕𝐻𝐴
• 𝑝= 𝑝− ( )𝑝
𝜕𝑇 𝜕𝑇 𝜕𝑇

𝜕𝐻
• By definition 𝐶𝑝 = ( )𝑝
𝜕𝑇
𝜕∆𝐻
• Therefore ( )𝑝 = 𝐶𝑝(𝐵) − 𝐶𝑝 𝐴 = ∆𝐶𝑝
𝜕𝑇
27
• Hence its necessary to know the difference in
heat capacities of the products and reactants
in order to determine the variation of heat of
reaction with temperature. This is known as
KIRCHOFF’S EQUATION.

28
• For a small range of temperature ΔCp can be
taken as constant and
• ‫𝑇𝑑 𝑝𝐶∆ ׬ = 𝐻∆ 𝑑 ׬‬
∆𝐻2 𝑇2
• ‫𝐻∆ 𝐻∆׬‬ = ‫𝑇𝑑 𝑝𝐶∆ 𝑇׬‬
1 1
• If ΔCp is constant, then
• ∆𝐻2 − ∆𝐻1 = ∆𝐶𝑝 (𝑇2 − 𝑇1 )
• Re-arranging:
• ∆𝐻2 = ∆𝐻1 + ∆𝐶𝑝 (𝑇2 − 𝑇1 )
• Where ΔH2 and ΔH1 are the heat of reaction at
T2 and T1 respectively 29
 The Kirchhoff's Equation (cont.…):
Question: Consider the reaction below,
N2(g) + 3H2(g) ⇆ 2NH3(g)
the value of H0298 is - 92.29 kJ at 25 0C. 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 125 0C

Solution: The value of ΔCp is : C p  2C NH  C N  3C H 3 2 2

= - 62.332 + 62.537 x 10-3T - 117.79 x 10-7T2JK-1
T2

Integral part:  CpdT  62.332T   31.271x10 T  39.25 x10 T 

T2
3 2 T2 7 3 T2
T1 T1

   
T1 T1

 
T
T
3 7
      
2 2 2 3 3
Giving: C p dT 62.332 T2 T1 31.271x10 T2 T1 39.25 x10 T2 T1

 298K    10 298K    4.02kJ 

1
o
2

= - 92.294 - 4.02 kJ = - 96.314 kJ 30

The Kirchhoff's Equation (cont.):

31
The Kirchhoff's Equation (cont.):

32
Tutorial Question – Kirchoff’s Equation:
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.

Answer: H = –283.62 kJ

33
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.

34
THE SECOND LAW OF THERMODYNAMICS
Introduction
•For a particular process or change, the first law helps us
balance the books, so to speak, on the heat released,
work done and so forth. [q=ΔE + w]

•However, it says nothing about whether the process

or change we specify can in fact occur.

•That question is encompassed in the second law of

thermodynamics.

1
Introduction Con’t:
Examples of Spontaneous Processes
•If you drop a brick, it falls to the floor

•A shiny nail left outdoors eventually rusts

•Expansion of an ideal gas into an evacuated space.

Reverse not spontaneous

•If we add solid KCl to a glass of water at room

temperature, we feel the solution growing colder as the
salt dissolves. Endothermic and yet spontaneous.

•At a temperature of 0 ˚C ice spontaneously absorbs heat

from the surrounding to turn into a liquid. 2
Introduction Con’t:
Which of the following processes are spontaneous? Which ones
are non-spontaneous?
a)Diffusion of perfume molecules from one side of a room to the
other side.

b) Heat flow from a cold object to a hot object.

c) Decomposition of rust (Fe2O3.H2O) to iron, oxygen and water

d) Decomposition of solid CaCO3 to solid CaO and gaseous CO2 at

25 ˚C and 1 atm pressure.

(a) Spontaneous while (b), (c) and (d) are nonspontaneous

3
Introduction Con’t):
Conclusion:

In each instance, the product of the process are

in a more random or disordered state than the
reactants

In addition to enthalpy, the change in

randomness or disorder of a chemical system is
extremely important in determining whether
equilibrium favours reactants or products.

4
Introduction Cont.:
The second law of thermodynamics expresses the notion that there
is an inherent direction in which any system moves if it is not at
equilibrium.

For example

•If you drop a brick, it falls to the floor

•Water placed in a freezer compartment turns into ice

•A shiny nail left outdoors eventually rusts

•Processes that are spontaneous in one direction are not

spontaneous in the reverse direction.
5
Introduction (cont.):
• SPONTANEITY is associated with an increase in randomness or
disorder of a system.

•This randomness is expressed by a thermodynamic quantity called

ENTROPY, given a symbol S expressed in units of J/K (not
kJ/K). The more disordered a system, the larger its entropy.

•ENTOPY is an absolute quantity, not a relative quantity. Therefore

the entropy of a substance is S , not ∆S

•Entropy is a state function. ∆S > 0 indicates an increase in

randomness or disorder. ∆S < 0 indicates a decrease in randomness
or disorder.

6
Question
By considering the relative extents of randomness or disorder in
the reactants and products, predict whether ∆S is positive or
negative for each of the following processes.

(a) H2O(l) →H2O(g)

(b) Ag+(aq) + Cl-(aq) →AgCl(s)

(c) 4Fe(s) + 3O2(g) →2Fe2O3(s)

7
Prediction for ΔS sign:
•It is possible for a system to be disfavoured by enthalpy
(endothermic, +ve ΔH), yet be spontaneous because its strongly
favoured by entropy (+ve ΔS). For example melting of ice [ΔH =
+6.01 kJ/mol and ΔS =+22 J/(K.mol)].

•Ethane, C2H6 can be prepared by the reaction of acetylene

(C2H2) with hydrogen.
C2H2(g) + H2(g) → C2H6(g)
Is ΔS˚ for the reaction positive or negative? Explain.

8
Prediction for ΔS sign (cont.):

Predict whether ΔS˚ is likely to be positive or negative for each

of the following reactions.
a) C6H6(l) + 7.5 O2(g)  3H2O(l) + 6CO2(g)
b) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

c) C(s) + O2(g) → CO2(g)

d) HC≡CH(g) + H2(g) → H2C=CH2(g)

9
The Second Law of Thermodynamics:
To develop a statement, we must think of an ISOLATED system,
one that does not exchange energy or matter with the surroundings.

•When a process occurs spontaneously in an isolated system,

the system always end up in a more random state

•In the real word, we really deal with isolated systems. We are
usually concerned with systems that exchange energy with their
surroundings in the form of heat and work. If we consider the entire
universe as a giant isolated system, however, we can state the
second law as follows:

•In any spontaneous process, there is always an increase in the

entropy of the universe.

10
The Second Law of Thermodynamics:
• The second law tells us that the increase in the entropy of the
surroundings must be greater than the decrease in the entropy of
the system, so that the total entropy increases:

ΔSuniverse = ΔSsystem + ΔSsurroundings >0

• No process that produce order (a decrease in entropy) in a

system can proceed without producing an even larger disorder
(an increase in entropy) in its surroundings.

• Thus, while the energy of the Universe is conserved (the first

law), the entropy of the Universe continues to increase (the
second law)

11
The Second Law of Thermodynamics:
Other Statements of the Second Law
Clausius statement: It states that heat cannot flow itself from a
cold body to a hot body spontaneously without the intervention of
an external energy.

Kelvin statement: It is impossible to take heat from a hot body and

convert it completely into work by a cyclic process without
transferring a part of heat to a cold body.

Thus, the Second Law predicts the direction of heat flow. It

explains the reason for why complete conversion of energy into
work is not possible.
• It predicts the feasibility of a process
• It introduces two new thermodynamic functions entropy and free
energy to explain spontaneity.
12
The Second Law of Thermodynamics:
•Thus, even if the entropy of a particular system decreases in a
spontaneous process, the total change in the entropy (System +
Surroundings) must be positive.

•No process that produces order (a decrease in entropy ) in a system

can proceed without producing an even larger disorder (an increase
in entropy) in its surroundings.

•Thus, while the energy of the Universe is conserved (the first law),
the entropy of the Universe continues to increase (the second law)

•Molecular systems therefore tend to move spontaneously toward a

state of minimum enthalpy and maximum entropy.

13
To quantify entropy:
•To calculate disorder or chaotic distribution of energy among
molecules requires statistical method – DIFFICULT !!

•However, we can relate the process to the heat involved in a

process

•Whenever heat is added to the system, it increases molecular

motions causing increased randomness in the system. Thus heat (q)
has a randomising influence on the system.

•Can we then equate ΔS with q? WAIT!

•From experience, distribution of heat also depends on the
temperature at which heat is added to the system.

14
To quantify entropy:
•A system at higher temperature has greater randomness in it than at
lower temperature. Thus temperature is the measure of average
chaotic motion of particles in the system.

•Heat added to a system at a lower temperature causes greater

randomness than when the same quantity is added to it at a higher
temperature.
𝑞
•Thus ∆𝑆 = 𝑟𝑒𝑣𝑇
•The change in entropy ΔS of a system is equal to the ratio of heat
change q to the temperature (T) of the reversible process.

15
The Second Law of Thermodynamics:

16
ENTROPY CHANGES FOR AN IDEAL GAS

17
18
19
20
21
22
Entropy Changes for an Ideal Gas (Examples.) –cont.:

24
Entropy Changes (Calculations):
Example:
Calculate the entropy change when 1 mole of a perfect gas expands
isothermally thus doubling its volume;

25
Entropy Change accompanying Phase Change:

26
Entropy Change accompanying Phase Change (examples):
Example:
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.
Solution:
Sv = Hv/Tb = 40850/373
= 109.5 J/K
Example:
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.
Solution:
St = Ht/Tt = 361/368.6
= 0.98 J/K

27
Entropy Change accompanying Phase Change (examples):
Example:
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.
Solution:
Sf = Hf / Tf = 2 x 1260/392
=6.43 J/K

28
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.

29
Entropy and the Third Law of Thermodynamics:

30
Entropy and the Third Law of Thermodynamics:

31
 Entropy and the Third Law of Thermodynamics (cont.):
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 25 OC
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 32
Entropy and the Third Law of Thermodynamics (cont.):
Examples

Determine the changes in entropy for the following reactions.

a) C2H2 (g) + H2(g) → C2H4 (g)

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

Solutions
a)
= 219-(200.82 + 130.59)

= -112.41J/K

b)
= 229.3 – (2x5.68 + 3 x 130.5)

= -173.56 J/K
33
Summary:
The thermodynamic function, Entropy, is defined as a measure of chaos/disorder.
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. 34
SAQs
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 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

Answers:
[1] (a) 306.5 K. (b) 2.72 JK-1.
[2] –52.8 JK-1.
35
Entropy : Examples:

36
Entropy : Examples:

37
 CONSIDER A SYSTEM HELD AT CONSTANT
T AND CONSTANT P CAPABLE OF PV WORK
𝑞𝑝
∆S ≥
𝑇
0 ≥ 𝑞𝑝 − 𝑇∆𝑆
0 ≥ ∆𝐸 − 𝑇∆𝑆
or 𝑞𝑝 − 𝑇∆𝑆 ≤ 0
∆𝐻 − 𝑇∆𝑆 ≤ 0
𝐺 ≡ 𝐻 − 𝑇. 𝑆
and H = E + PV
In a similar manner:
G1 = H 1 - T S 1
G2 = H 2 - T S 2
1
G = H - TS
For an isobaric change, the pressure is constant and we
have: H = E + PV
and hence G = A + PV - TS
= E - TS + PV
Implying that
G = A + PV
−∆𝐺 = 𝑤𝑟𝑒𝑣 − 𝑃∆𝑉
−∆𝐺 = 𝑤𝑛𝑒𝑡

2
•Thermodynamics tells us that the change in free
energy for a process, ΔG, equal the maximum useful
work that can be done by the system on its
surroundings in a spontaneous process occurring at
constant temperature and pressure.

•−∆𝐺 = 𝑤𝑛𝑒𝑡 ( net work obtainable (at constant T and

P) for the system.

•The function, G, is known as the Free Energy.

3
 VARIATION OF FREE ENERGY
WITH TEMPERATURE OR PRESSURE
We have already seen that
H = E + PV
G = H – TS
Therefore one has
G = E + PV - TS
For small changes,
dG = dE + PdV + VdP - TdS - SdT

4
From the 1st Law, q = dE + w
If w is due to volume change, then
q = dE + PdV
If it is assumed that the process is reversible, P is the
pressure of the system and further
q/T = dS
meaning
TdS = q
Such that
TdS = dE + PdV
5
Then
dG = dE + PdV + VdP - TdS - SdT
dG = TdS + VdP - TdS - SdT
dG = VdP - SdT

at constant temperature, dT, =0

For an appreciable process taking place at constant temperature,

between two pressures P1 and P2, we can obtain the free energy
change by integrating:

6
Since temperature is constant and
PV = RT
V = RT/P
then

For n moles ,

7
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.

8
Solution
T = 273 K, R = 8.314 J/mol/K, P1 = 760 mm Hg, P2 = 190 mm Hg

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

n = 0.5 mol
Then
G = nRT ln (P1/P2)

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

= -1573.3 J Ans.

9
 PHASES IN EQUILIBRIUM:
THE CLAUSIUS - CLAPEYRON EQUATION
Consider two phases of the same substance in equilibrium with
one another at temperature T and Pressure P

10
Consider a liquid in equilibrium with its vapors at a temperature T
and pressure P.
At equilibrium GA = GB where A and B signify the two phases.
For a small change in P and T
Thus:
T  T + dT  P  P + dP.
For an infinitesimal change where the only work done is that due
to expansion, one has:
dGA = VAdP - SAdT

dGB = VBdP - SBdT

•One can see that, at equilibrium
VAdP - SAdT = VBdP - SBdT
11
and hence
(VB - VA)dP = (SB - SA)dT

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,

12
where H is the enthalpy absorbed per mole in the phase change.
This implies that:

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

For conversion of liquid to vapour

H = HV and VB >> VA

 VB - VA  VB = V
13
For a mole of water for example,
Vvapour = 22400 ml while Vliquid = 18 ml

Such that Vvapour – Vliquid = 22382 ml  Vvapour

Hence

14
•For a mole of gas
PV = RT

15
16
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.

17
 STANDARD FREE- ENERGY CHANGES (ΔG°)
Free energy is a state function. It is possible to tabulate standard
free energies of formation for substances.

Temperature chosen for tabulating data is 25°C but ΔG° at other

temperatures may be calculated

The standard free energies of formation for substances are useful

in calculating the standard free-energy in a chemical process.

Thus ΔG° = ∑nG°f(products) - ∑mG°f(reactants)

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 STANDARD FREE ENERGIES
STATE OF MATTER STANDARD STATE
.
Solid Pure solid
Liquid Pure liquid
Gas 1 atm pressure
Solution 1 M concentration
Elements Standard free energy of
formation of an element
in its normal state is
defined as zero
19
 STANDARD FREE ENERGIES
EXAMPLE
Determine the standard free-energy change for the following
reaction at 298 K:
N2(g) + 3H2(g) → 2NH3(g)

SOLUTION:
From tables, for N2(g), ΔG°f=0.0; H2(g), ΔG°f=0.0; NH3(g), ΔG°f=
−16.66 kJ/mol
ΔG° = 2ΔG°f(NH3) - [3ΔG°f(H2) + ΔG°f(N2)]

Inserting numerical quantities, we obtain ΔG° = −33.32 kJ

20
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 21
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
.

22
23
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.

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•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.

. 25