THERMODYNAMICS

The scientific study of the interconversion of heat and other kinds of energy is called thermodynamics. The
word 'thermodynamics implies flow of heat. Thermodynamics is based on generalizations called laws of
thermodynamics. Laws of thermodynamics apply only when a system is in equilibrium or moves from one
equilibrium state to another equilibrium state.
Fundamentals of Thermodynamics:
System: The macroscopic part of universe under study is called the system. The remaining part of the
universe that can interact with the system is called Surroundings. The boundary or wall separates a system
from its surroundings. The boundary may be either fixed or moving (real or imaginary). The system and
the surroundings together constitute the universe.

Universe = System + Surroundings

Types of systems
There are three types of systems depending on the kinds of exchanges taking place between a system and
surroundings during a process.

(i) Open system: A system which can exchange matter as well as energy with its surroundings is called
open system.
Example: The presence of reactants in an open beaker.

(ii) Closed system: A system which can exchange only energy but not matter with its surroundings is
called closed system.
Example: Pressure cooker.

(iii) Isolated system: A system which can exchange neither matter nor energy with its surroundings is
called isolated system.
Example: The presence of reactants in a thermoflask.

State of a systems: The state of a thermodynamic system is described by its measurable properties and
characterized by thermodynamic variables such as pressure, temperature, volume and composition.

State functions: State functions are thermodynamic variables whose magnitude depend only on the state
of a system and not on the process or path taken to reach that state.

Thermodynamic process
Process is a path which changes the system from one state to another. Whenever a system changes from
one state to another, it is accompanied by change in energy.

Different types of processes

Isothermal process: A process which is carried out at constant temperature is called isothermal process.
During isothermal process heat exchange takes place. For isothermal process ∆T = 0 and q ≠ 0.
Adiabatic process: A process in which there is no exchange of heat between the system and surrounding
is known as adiabatic process. In an adiabatic process there is a change in temperature of the system but
there is no heat exchange between the system and surroundings. Therefore, ∆T # 0 and q = 0.
Isobaric process: A process is said to be isobaric if the pressure of the system remains constant during
each step of the process.
Isochoric process: A process is said to be isochoric if the volume of the system remains constant during
each step of the process.
Cyclic process: A process in which a system returns to its initial state after passing through different states,
the process is said to be a cyclic process.
Reversible process: A process which is carried out infinitesimally slowly so that it can be reversed at any
instant of time by reversing the driving force by infinitesimal amount is called a reversible process.
Irreversible process: A rapid process which cannot be reversed at any instant of time by reversing the
driving force by a small amount is called irreversible process.

Thermodynamic properties
There are two types of thermodynamic properties.
1. Extensive property
2. Intensive property

Extensive property: A property which depends on the quantity of matter present in the system is called
extensive property.
Examples: Mass, volume, internal energy, heat, free energy, entropy, etc.

Intensive property: A property which is independent on the quantity of matter present in the system is
called intensive property.
Examples: Density, surface tension, viscosity, specific heat, thermal conductivity, refractive index,
pressure, temperature, boiling point, freezing point, vapour pressure of a liquid, etc.

Internal energy (U)

The internal energy is the total amount of kinetic and potential energy possessed by the system. The change
in the internal energy (∆U) of a system depends only on the amount of energy in the system at the beginning
and end. It is denoted by the symbol U.

Internal energy is a state function, i.e., its value depends only upon the state of the substance but does not
depend upon how that state is achieved. The absolute value of internal energy of a substance cannot be
determined. But change in internal energy can be measured experimentally.
∆U = U final – U initial
∆U reaction = U products – U reactants

∆U = U2 ̶ U1, where U1 is initial internal energy and U2 final internal energy. The internal energy is made
up of different kinds of energies like translational energy of molecules (Ut), rotational energy of molecules
(Ur), vibrational energy of molecules (Uv,), electronic energy (Ue), nuclear energy (Un.), and gravitational
energy (Ug).

U = Ut + Ur +Uv + Ue + Un + Ug

Note: Internal energy of any substance depends on temperature and amount of the sample. ‘U’ of the
system, will change, when
 Heat passes into or out of the system.
 Work is done on or by the system.
 Matter enters or leaves the system.

Types of energy changes

a) Work (w): Exchange of energy between system and surroundings can occur in the form of work which
may be mechanical or electrical work.
For example, let us take a system containing some quantity of water in a thermoflask or in an insulated
beaker. This would not allow exchange of heat between the system and surroundings through its boundary.
Such systems are called adiabatic systems. Let us bring the change in the internal energy of the system by
doing some work on it. Let us call the initial state of the system as state A and its temperature as T A. Let
the internal energy of the system in state A be UA. We can change the state of the system in two different
ways.
One way: Let us do some mechanical work (say 1kJ) by rotating a set of small paddles and thereby churning
water. Let the new state be called B and its temperature T B. The change in temperature
∆T = TB – TA.
Let the internal energy of the system in state B be UB and the change in internal energy,
∆U = UB ̶ UA
Second way: If we do an equal amount of (i.e., 1kJ) electrical work with the help of an immersion rod and
note down the temperature change, we find that the change in temperature is same as in the earlier case, ∆T
= TB – TA.

Note: W adiabatic is positive when work is done on the system.

W adiabatic will be negative when work is done by the system.

b) Heat: Internal energy of a system can change by transfer of heat from the surroundings to the system or
vice-versa without doing any of work. The exchange of energy as a result of temperature difference is called
heat (q).
q α ∆T

In this case change in internal energy, ∆U = q, when no work is done at constant volume.

c) General case: Let us consider the general case in which a change of state is brought about both by doing
work and by transfer of heat.
∆U = q + w

The first law of thermodynamics:

The first law of thermodynamics states that "the energy of an isolated system is constant".

It is commonly stated as the law of conservation of energy "energy can neither be created nor destroyed,
although, it can be transformed from one form to another".

First law of thermodynamics:

Let us consider a system whose initial internal energy is U1. The internal energy of the system can be
increased by two methods.
When 'q' joules of heat is supplied to the system, its internal energy becomes = q + U1
Let 'w' be amount of work be done on it, so that internal energy increases to U1 + q + w
So, final state of internal energy U2 is given by,
U2 = U1 + q + w
U2 – U1 = q + w
∆U = q + w - - - - - - - - - (1)
i.e. Change in internal energy = Heat absorbed by the system + Work done on the system.

Let the change in volume during an isothermal reversible contraction at constant pressure, p, be '∆V' then
the work is referred to as pressure-volume work i.e. w = – p ∆V.

If there is only pressure-volume work, the expression (1) can be written as,
∆U = q + P∆V - - - - - - - - - (2)
For an isothermal expansion at constant P, the expression for the first law will be
∆U = q ̶ P∆V - - - - - - - - - (3)

Sign convention of ‘q’ and ‘w’ according to IUPAC:

 Heat is absorbed by the system = q is positive
 Heat is lost or liberated by the system= q negative
 work is done on the system = w is positive
 work is done by the system= w is negative

Expression for the mechanical work done in isothermal irreversible compression of an ideal gas:

Let us consider a cylinder of cross-sectional area A fitted with a piston. The apparatus is so arranged that
the piston encloses a gaseous sample at pressure (P int) and the piston is attached to a mechanism which will
maintain an external pressure (Pext) on the gas. Let ‘ Vi ’ be the initial volume of the gas. If an externa
pressure is applied on the piston which is greater than the internal pressure, piston moves inward till the
pressure inside is equal to external pressure. The volume of the gas is decreased and final volume is ‘ Vf ’.
During this compression, the piston moves through a distance ' l ' then,

Volume change = l A = ∆V = Vf – Vi

But, Pressure = Force / area

Therefore, force on the piston = Pressure x Area

= Pext x A

If ‘w’ is the work done on the system by the movement of the

piston, then

w = force x distance

= Pext A x l

= Pext ( ̶ ∆V )

= ̶ Pext ( ∆V )

w= ̶ Pext ( Vf – Vi )

Note: ‘w’ becomes positive when work is done on the system during compression. Here, Vf – Vi becomes
negative because Vf < Vi during compression.

If the pressure is not constant at every stage of compression, the work is equal to sum of all the steps:

Therefore, w = ̶ Pext ( ∆V)

Expression for work done in an isothermal reversible expansion of an ideal gas

During reversible isothermal expansion of an ideal gas, the gas expands in a large number of steps through
small volumes against the external pressure [P ext].
Suppose the gas expands through a small volume ‘dV’ against external pressure, P ext, the small work done
by
dw = ̶ Pint dV
nRT
For ideal gas equation, Pint = V

nRT
dw = ̶ V
dV

dV
Apply integration, ∫ dw = ̶ n RT ∫ V

Vf
w = −2.303 nRT log10
Vi
In terms of pressure,
Pi
w = −2.303 nRT log10
Pf
Note: Work done during an adiabatic expansion of an ideal gas is w = ̶ n Cv ( T2 – T1 )

Expression for reversible adiabatic expansion:

For an adiabatic process, q = 0
∆U = ± w
For reversible adiabatic contraction, ∆U = + w = C v ( T2 – T1 ) = Cv ∆T
For reversible adiabatic expansion, ∆U = ̶ w = ̶ Cv ( T2 – T1 ) = ̶ Cv ∆T

Problems: (Discussed)

Thermochemical reactions: There are two types,

1. Exothermic reactions:
A reaction during which heat is liberated is called an exothermic reaction.
Example: C (s) + O2 (g) → CO2 (g) ∆H = ̶ 393.5kJ

2. Endothermic reactions:
A reaction during which heat is absorbed is called an endothermic reaction.
Example: N2 (g) + O2 (g) → 2NO (g) ∆H = + 180.7kJ

Enthalpy (H):
The enthalpy of a system may be defined as the sum of the internal energy and the product of its pressure
and volume. The product of pressure and volume is called external energy.
Enthalpy is denoted by the symbol ‘H’ and is given by,
H = U + pV - - - - - - - - (1)
where, U = internal energy, p = pressure and V = the volume of the system. Enthalpy is also called heat
content. The enthalpy change ∆H, of a reaction is the heat evolved in a reaction at constant pressure.
∆H = q reaction at constant pressure = qp
Although g is a path dependent function, H is a state function because it depends on U, p and V, all of which
are state functions. Therefore, ∆H is independent of path. Hence, qp is also independent of path.

For finite changes at constant pressure, we can write equation (1) as

∆H = ∆U + p∆V - - - - - - - - (2)
It is important to note that when heat is absorbed by the system at constant pressure, we are actually
measuring changes in the enthalpy. Remember ∆H = qp , heat absorbed by the system at constant pressure.
∆H is negative for exothermic reactions which evolve heat during the reaction and ∆H is positive for
endothermic reactions which absorb heat from the surroundings.
At constant volume (∆V = 0), ∆U = qv, therefore equation (2) becomes ∆H = ∆U = qv.

The difference between ∆H and ∆U is not significant for systems consisting of only solids and / or liquids.
But, the difference becomes significant when gases are involved. Let us consider a reaction involving gases.
If VA is the total volume of the gaseous reactants, VB is the total volume of the gaseous products, nA is the
number of moles of gaseous reactants and nB is the number of moles of gaseous products, all at constant
pressure and temperature, then using the ideal gas law,
According to ideal gas equation PV = n RT
For state 1, P VA =nA RT
For state 2, PVB = nB RT
Thus, PVB – PVA = nB RT – nA RT
P ( VB – VA ) = (nB – nA ) RT
P∆V = ∆ng RT
Here, ∆ng = number of moles of gaseous products ̶ number of moles of gaseous reactants.
∆H = ∆U + ∆ng RT
This equation is useful for calculating ∆H from ∆U and vice versa.
Free expansion: Expansion of a gas in vacuum (pex = 0) is called free expansion.

 Example for a reaction where ∆H = ∆U.

Ans: H2 (g) + I2 (g) → 2HI (g)
 Relationship between ∆H and ∆U for the following reactions:
(i) N2 (g) + 3H2 (g) → 2NH3 (g) Ans: ∆H =∆U ̶ 2RT
(ii) CO2 (g) + C (s) → 2 CO (g) Ans: ∆H =∆U + RT
(iii) PCl5 (g) → PCl3 (g) + Cl2 (g) Ans: ∆H =∆U + RT

Problems: (Discussed)