THERMODYNAMICS-I

Chapter Outline
 Thermodynamic System
 Work done during volume changes
 Different thermodynamic changes
 Isothermal & Adiabatic change
 Path between thermodynamic states
 Internal Energy
 First Law of Thermodynamics
 First Law of Thermodynamics in Different Thermodynamic
Processes
 Specific & Molar Heat Capacity
 C P & CV
 Relation between Pressure & Volume of a Gas in Adiabatic
Change
 Mathematical Problems
 Different Thermodynamic Changes
• Isothermal Change
• Adiabatic Change
• Isochoric Change
• Isobaric Change

Isothermal Change
• When a gas undergoes a change in pressure and volume at
constant temperature, the gas is said to undergo an isothermal
change, the process in which the change takes place is called
‘isothermal process’.
Or,

• Temperature is kept constant by absorption or rejection of

necessary heat.
 Adiabatic Change
• The process in which a system neither receives heat nor rejects
heat is called ‘Adiabatic Process’.
• Alternatively, when no heat is allowed to enter or leave the gas,
it is called an adiabatic process and the change under this process
is called adiabatic change.

• The container of the gas should be non conducting to achieve

adiabatic change.
• Change of pressure of the gas must be very rapid for adiabatic
process, so that heat exchange with the surrounding does not
take place.
 Isochoric Change

• Isochoric process, also called a constant-

volume process, an isovolumetric process, or
an isometric process, is a thermodynamic
process during which the volume of the closed
system undergoing such a process remains
constant.
•
 Isobaric Change

• An isobaric process is a thermodynamic

process in which the pressure remains
constant. This is usually obtained by allowing
the volume to expand or contract in such a
way to neutralize any pressure changes that
would be caused by heat transfer.
 Internal Energy
• Total energy stored in a thermodynamic system is known as
internal energy.
•For ideal gases, the internal energy depends only on the
temperature of the gas.
•In a real gas, intermolecular forces are not zero. Therefore, a
definite amount of work has to be done in changing the distance
between the molecules.

• Thus the internal energy of a real gas is the sum of internal

kinetic energy and internal potential energy. Hence, it would
depend upon both the temperature and the volume of the gas
 First Law of Thermodynamics
 Let us consider a gas inside a cylinder fitted with a
movable frictionless piston. The walls of the cylinder
are made up of non-conducting material and the
bottom is made up of conducting material.

 Let the bottom of the cylinder be brought in

contact with a hot body like burner. The entire heat
energy given to the gas is not converted into work.

 A part of the heat energy is used up in increasing

the temperature of the gas (i.e) in increasing its
internal energy and the remaining energy is used up
in pushing the piston upwards (i.e.) in doing work.
 First Law of Thermodynamics
 If ΔQ is the heat energy supplied to the gas, U1
and U2 are initial and final internal energies and ΔW
is the work done by the system, then

where ΔU is the change in the internal energy of the

system.
 Hence, the first law of thermodynamics states
that, “The amount of heat energy supplied to a
system is equal to the sum of the change in internal
energy of the system and the work done by the
system”. This law is in accordance with the law of
conservation of energy.
 First Law of Thermodynamics in
Different Thermodynamic Processes
 First Law of Thermodynamics in
Different Thermodynamic Processes
 First Law of Thermodynamics in
Different Thermodynamic Processes
 First Law of Thermodynamics in
Different Thermodynamic Processes
 Specific Heat Capacity

 Specific heat capacity of a substance is defined as the quantity

of heat required to raise the temperature of 1 kg of the substance
through 1K. Its unit is Jkg–1K–1.

 Specific heat capacity of a gas may have any value between

–∞ and +∞ depending upon the way in which heat energy is
given.
 Molar Heat Capacity

 Molar specific heat capacity of a gas is defined as the quantity

of heat required to raise the temperature of 1 mole of the gas
through 1K. Its unit is Jmol–1 K–1.

 Let m be the mass of a gas and C its specific heat capacity.

Then ΔQ = m × C × ΔT where ΔQ is the amount of heat absorbed
and ΔT is the corresponding rise in temperature.
 Molar Heat Capacity

 Case 1: If the gas is insulated from its surroundings and is

suddenly compressed, it will be heated up and there is rise in
temperature, even though no heat is supplied from outside,

 Case 2: If the gas is allowed to expand slowly, in order to keep

the temperature constant, an amount of heat ΔQ is supplied from
outside, then

As, ΔQ is +ve as heat is supplied from outside

 Molar Heat Capacity

 Case 3: If the gas is compressed gradually and the heat

generated ΔQ is conducted away so that temperature remains
constant, then

As, ΔQ is -ve as heat is supplied by the system

 Thus we find that if the external conditions are not controlled,

the value of the specific heat capacity of a gas may vary from +∞
to -∞.
 Molar Heat Capacity
 Hence, in order to find the value of specific heat capacity of a
gas, either the pressure or the volume of the gas should be kept
constant. Consequently a gas has two specific heat capacities.

(i) Specific heat capacity at constant volume (Cv): Molar specific

heat capacity of a gas at constant volume Cv is defined as the
quantity of heat required to raise the temperature of one mole of
a gas through 1 K, keeping its volume constant.

(ii) Specific heat capacity at constant pressure (Cp): Molar

specific heat capacity of a gas at constant pressure Cp is defined
as the quantity of heat to raise the temperature of one mole of a
gas through 1 K keeping its pressure constant.
 For Ideal Gas, CP > CV
 By keeping the volume fixed, if a
gas of particular mass is heated, its
temperature and pressure increases.
But since the volume is fixed, the gas
does no work. So, all the heat is used
to increase the temperature and
pressure.
 On the other hand, by keeping the pressure constant, if a gas is
heated its temperature and volume increases. As a result, the applied
heat increases the temperature of the gas and at the same time does
work against the external pressure by increasing the volume. So at
constant pressure the amount of heat required to increase the
temperature of 1 mole of a gas by 1K is more than the heat required
to raise the gas by 1K at constant volume. Therefore, Cp = Cv + heat
necessary for doing external work. So, Cp > Cv
 Relation between CP & CV
 Let us consider one mole of an ideal gas enclosed in a cylinder
provided with a frictionless piston of area A. Let P, V and T be the
pressure, volume and absolute temperature of gas respectively .

 A quantity of heat dQ is supplied to the gas. To keep the volume

of the gas constant, a small weight is placed over the piston. The
pressure and the temperature of the gas increase to P + dP
and T + dT respectively. This heat energy dQ is used to increase the
internal energy dU of the gas. But the gas does not do any work
(dW = 0).
 Relation between CP & CV
 The additional weight is now removed from the piston. The piston
now moves upwards through a distance dx, such that the pressure
of the enclosed gas is equal to the atmospheric pressure P. The
temperature of the gas decreases due to the expansion of the gas.

 Now a quantity of heat dQ’ is supplied to the gas till its

temperature becomes T + dT. This heat energy is not only used to
increase the internal energy dU of the gas but also to do external
work dW in moving the piston upwards.
Relation between CP & CV
Relation between CP & CV
 Ratio of CP & CV
 The ratio of the two specific hats of a gas is denoted by ‘γ’

 Since, CP > CV , ‘γ’ is always greater than 1.

Importance of ‘γ’ :
• By knowing the value of γ we can have an idea of the molecular
structure of a gas. For example, the value of γ for monatomic gas
(He, Ar) is 1.66. For diatomic gas (H2, O2, N2) γ=1.40. For tri-
atomic gas γ=1.33.
• It is necessary to find the value of sound in a gaseous medium.
• To study the adiabatic process, the value of γ is essential.
Relation between Pressure & Volume of
a Gas in Adiabatic Change