Chemical Thermodynamics

Basic concepts
System, surroundings and Boundary: A specified part of
the universe which is under observation is called the system
and the remaining portion of the universe which is not a part
of the system is called the surroundings.
Types of systems
(i) Isolated system: This type of system has no interaction
with its surroundings. The boundary is sealed and insulated.
Neither matter nor energy can be exchanged with
surrounding. A substance contained in an ideal thermos flask
is an example of an isolated system.
(ii) Closed system: This type of system can exchange energy
in the form of heat, work or radiations but not matter with its
surroundings. The boundary between system and
surroundings is sealed but not insulated. For example, liquid
in contact with vapor in a sealed tube and pressure cooker.
(iii) Open system: This type of system can exchange matter as
well as energy with its surroundings. The boundary is neither
sealed nor insulated. Sodium reacting with water in an open
beaker is an example of open system.
The macroscopic properties can be subdivided into two
types,
(i) Intensive properties: The properties which do not depend
upon the quantity of matter present in the system or size of
the system are called intensive properties. Its examples are
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 pressure, temperature, density, specific heat, surface tension,
refractive index, viscosity, melting point, boiling point,
volume per mole, concentration etc.
(ii) Extensive properties: The properties whose magnitude
depends upon the quantity of matter present in the system
are called extensive properties. Its examples are total mass,
volume, internal energy, enthalpy, entropy etc. These
properties are additive in nature.
Any extensive property if expressed as per mole or per gram
becomes an intensive property.

State of a system and State Variables

Macroscopic properties that specify the state of a system are
referred to as state variables or state functions or parameters
of thermodynamics. The change in the state properties is
depends only on the system’s initial and final state. It is
independent on the path by which the change has been
brought out.

Thermodynamic equilibrium: “A system is said to have

attained a state of thermodynamic equilibrium when it does not
show any further tendency to change its property with time”.
The thermodynamic equilibrium criterion specifies that the follo
wing three equilibrium forms occur simultaneously in a system;

(i) Chemical Equilibrium: A

system where system composition stays constant and definit
e.
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(ii) Mechanical Equilibrium: No chemical work is done
between the different parts of the system or between the
system and the surrounding. To achieve it keep the pressure
constant.
(iii) Thermal Equilibrium : It can be achieved when the
temperature remains constant i.e. no flow of heat between
the system and the surrounding.

Thermodynamic process: When the thermodynamic system

changes from one state to another, the operation is called a
process. The various types of the processes are
(i) Isothermal process: In this process operation is done at
constant temperature. dT = 0 thus E  0 .
(ii) Adiabatic process: In this a process there is no exchange
of heat takes place between the system and surroundings.
The system is thermally isolated, i.e., dQ = 0 and its
boundaries are insulated.
(iii) Isobaric process: In this process the pressure remains
constant throughout the change i.e., dP = 0.
(iv) Isochoric process: In this process volume remains
constant throughout the change, i.e., dV = 0.
(v) Cyclic process: When a system undergoes a number of
different processes and finally return to its initial state, it is
termed cyclic process. For a cyclic process dE = 0 and dH =
0.

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 (vi) Reversible process: A process which occurs
infinitesimally slowly, i.e. opposing force is infinitesimally
smaller than driving force and when infinitesimal increase in
the opposing force can reverse the process, it is said to be
reversible process.
(vii) Irreversible process: When the process occurs from
initial to final state in single step in finite time and cannot be
reversed, it is termed an irreversible process. Amount of
entropy increases in irreversible process.
Irreversible processes are spontaneous in nature. All natural

processes are irreversible in nature

Internal energy, heat and Work

Internal energy (E): “Every system having some quantity of

matter is associated with a definite amount of energy so It is
the energy contained within the system. This energy is sum
of all types of energies (chemical, mechanical electrical etc.)
and is a state function.
First law of thermodynamics
This law is also known as law of conservation of energy. It
is proposed by Helmholtz and Robert Mayer. It states that,
“Energy can neither be created nor destroyed although it
can be converted from one form into another.”

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 i.e. Change in internal energy = Heat added to the system
+Work done on the system
E2  E1  E  q  w

If a system does work (w) on the surroundings, its internal

energy decreases. In this case,
Change in internal energy = Heat added to the system – work
done by the system
E  q  (w)  q  w

Enthalpy and Enthalpy change

The heat content of a system at constant pressure is called
enthalpy. It is denoted by 'H'.
From the first law of thermodynamics, q  E  W ;
q  E  PV ............(i )

Heat change in constant pressure can be given,

q  E  PV ........(ii )

At constant pressure heat can be replaced at enthalpy.

H  E  PV ........(iii )

H Is the heat of reaction (in chemical process) or the heat

change at constant pressure.

Specific and Molar heat capacity

Specific heat capacity of a substance is the quantity of heat
that is required to raise the temperature of 1g of substance
through

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The specific heat capacity of a substance is the amount of heat
required to raise the temperature of 1g of the substance1o C .

It can be calculated at constant pressure (c p ) and constant

volume (cv ) .
q  mcT
The molar heat capacity of a substance is the amount of
heat required to raise the temperature of 1 mole of the
substance1o C .
 Molar heat capacity = Specific heat capacity  Molecular
weight, i.e., Cm  c M

Since,

Gases on heat show an inclination toward expansion when

heated under constant pressure conditions, with an
additional energy supplied to raise its temperature 1o C
when required under constant volume conditions.
Thus,
C p  Cv
Cp  Cv  Work done in expansion,
Work done in expansion is PV( R).
Here, Cvand Cp are molar heat capacities at constant volume
and constant pressure respectively.

Some useful relations of Cp and Cv

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 (i) C  C  R  2 calories 8.314 J
p v

(ii) C  32 R (for monoatomic gas) and

v Cv 
3
2
x (for di and
polyatomic gas), where x varies from gas to gas.
Cp
(iii) Cv
 (Ratio of molar capacities)
(iv) For monoatomic gas, Cv  3 calories whereas, C p  Cv  R  5 calories
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Cp R
(v) For monoatomic gas, ( ) 
Cv
 2  1 . 66
3
R
2
7
Cp R
(vi) For diatomic gas ( ) 
Cv
 2  1 . 40
5
R
2
Cp
(vii) For triatomic gas ( ) 
Cv

8R
6R
 1 . 33

Second law of thermodynamics

The second law of thermodynamics removes all
limitations of the first law of thermodynamics. This law
states that for spontaneous processes the total energy
change is positive.
The Carnot cycle

The basic condition for a cyclic process is that the net work
done is equal to the heat absorbed. This condition is
satisfied in a Carnot cycle.
w  T2  T1  Thermodynamic efficiency
q T
2 2

Thus,

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 The greater the difference in temperature between high and lo
w temperature reservoirs, the more heat, and
the heat engine converts into work.

Entropy and Entropy change

Definition : Entropy is a measure of randomness or disorder
of the system’s molecules. It is a thermodynamic state
quantity
q rev
Sfinal  Sinitial  S 
T

If heat is absorbed, then S  ve and if heat is evolved, then

S  ve .

Free energy and Free energy change

Gibb's free energy (G) is a measure of maximum work done
which is also known as useful work done from a reversible
reaction at constant pressure and temperature.

We can find it by subtracting the product of absolute

temperature and entropy from the enthalpy of the system.
i.e., G  H  TS

Third law of thermodynamics

This law was first formulated in 1906 by German chemist
Walther Nernst.

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This law states that, “The entropy of all perfectly crystalline
solids approaches zero at the temperature approaches to
absolute zero.
Sinceentropy is a measure of disorder it can be interpreted that a
perfectly crystalline solid has a perfect order of its constitue
nt particles at absolute zero.

Exothermic and Endothermic reactions

Exothermic reactions: Exothermic reactions are those
reactions that proceed with the evolution of heat energy.

H  H p  H r ; H p  Hr ; H   ve

Examples : (i) Fermentation is an example of exothermic

reaction.

(ii) Formation of CO2 gas is also an example of exothermic

reaction.
C(s)  O2 (g)  CO2 (g)  393 .5kJ

It can also be written as;

C(s)  O2 (g)  CO2 (g); H  393 . 5 kJ (at constant temperature
and pressure)

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Endothermic reactions : Endothermic reactions are those
reactions that proceed with the absorption of heat energy.
; H  ve
H  H p  H r ; H p  Hr

Example : formation of NO is an example of endothermic

reaction.
N 2 (g)  O2 (g)  2 NO(g); H  180 .5 kJ

Heat of reaction or Enthalpy of reaction

The heat of reaction or the reaction enthalpy is the
difference between the products and the reactants enthalpies,
that we get when the reactants reacted completelly in the che
mical reaction.
Enthalpy of reaction (heat of reaction)  H  H  H P R

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