Chapter 15 Thermodynamics of gases

Introduction
Thermodynamic is the study of the laws that govern the conversion of energy from
one form to another, the direction in which heat will flow and the availability of
internal energy to do work.
15.1 Heat Capacity
> Heat capacity, C of an object is the heat required to raise the temperature of the
object by 1 K (or 1C).

The heat, Q required to raise the temperature of a body by T is given by:

> Specific heat capacity, c of a material is the heat required to raise the
temperature of 1 kilogram of the material by 1 K (or 1C).

The heat, Q required to raise the temperature of m kilogram of a material by T is

given by:
>Molar heat capacity, Cm of a material is the heat required to raise the
temperature of 1 mole of the material by 1 K (or 1C).

The heat, Q required to raise the temperature of n mole of a material by T is given

by,

For gases
Gas has two heat capacities, one at constant volume and another at constant
pressure.
Molar heat capacity at constant volume, Cv,m of a gas is the heat required to
raise the temperature of 1 mole of the gas by 1 K (or 1 C) at constant volume.
The heat, Q required to raise the temperature of n mole of a gas by T at constant
volume is given by

Molar heat capacity at constant pressure, Cp,m of a gas is the heat required to
raise the temperature of 1 mole of the gas by 1 K (or 1 C) at constant pressure.
The heat, Q required to raise the temperature of n mole of a gas by T at constant
pressure is given by
Cv,m and Cp,m depend on the degree of freedom.
CV,m =

and Cp,m =

where f is the degree of freedom.

15.2 Work
> When a gas expands, work is done by the gas.
When a gas is compressed, work is done on the gas.

> When the gas at constant pressure expends by pushing a light frictionless piston
as shown in Figure above the work done by the gas is:
> Hence, the work done by a gas when its volume increase from V1 to V2 is given
by

> The work done by gas for various types of changes will be discussed in the
subsequent section. The changes involved are:
Isobaric change (constant pressure)
Isometric change (constant volume)
Isothermal change (constant temperature)
Adiabatic change (no heat flow in or flow out from the system)
15.3 First Law of Thermodynamics
> The first law of thermodynamics is a law of conservation of energy.
> The first law of thermodynamics states that the heat supplied to a system equals
to the sum of increase in internal energy of the system and the work done by the
system.

> The sign convention for Q, U and W used in the formula above is shown below:
Q is positive when heat is supplied to the system.
Q is negative when heat is released from the system.
U is positive when the internal energy (temperature) increases.
U is negative when the internal energy (temperature) decreases.
W is positive when work is done by the system.
W is negative when work is done on the system.
15.4 Internal Energy
> The internal energy, U of a system is the total potential and kinetic energy of the
molecules.
> For an ideal gas, because the force between the molecules is negligible, the
potential energy equal zero. The internal energy is the total kinetic energy of the
molecules only.
Kinetic energy (internal energy) for one mole of gas =

kinetic energy

(internal energy) for n mole of gas = (n)

> The internal energy of the ideal gas depends on:
(a) Amount of gas (number of moles)
(b) Absolute temperature
(c) Degree of freedom
> When temperature of gas increases, internal energy increases and U is positive.
When temperature of gas decreases, internal energy decreases and U is negative.

15.5 Isometric Change

> An isometric process is a constant-volume process.
> Since volume is constant,

> To raise the temperature of n mole of gas by T at constant volume, the heat
required

15.6 Isobaric Change

> An isobaric process is a constant-pressure process.
> Since there is a change in volume and pressure is constant at p,

>To raise the temperature of n mole of gas by T at constant pressure, the heat
required

15.7 relation between Cv,m and Cp,m

The ratio of
Internal energy for n mole of gas at temperature T =
Change in internal energy for n mole of gas when there is a temperature change of
T =
so
=
and

The ratio of Cp,m to CV,m is denoted by

Note: CV,m can also be obtained from the definition

Values of Cp,m , CV,m and at a glance

Monoatomic

Diatomic

Polyatomic

Degree of freedom at room

temperature
CV,m =

Cp,m = CV,m + R =
=

15.8 Isothermal Change

> An isothermal process is a constant-temperature process.
>Since temperature is constant,
> An isothermal change obeys Boyles law.
> For an isothermal change, the gas must be held in a thin-walled, highly
conducting vessel, surrounded by a constant temperature bath. The change must
take place slowly so that heat can flow into the gas or flow out from the gas to
maintain its temperature at every instant during the change.

Work done in an isothermal change

Work done by gas in an isothermal change is given by W =
Using the ideal gas equation pV = nRT

l5.9 Adiabatic Change

> An adiabatic process is a process where no heat is transferred into or out of the
system.
> During an adiabatic expansion, W is positive and U is negative. i.e. during
adiabatic expansion, internal energy decreases and temperature decreases.
>During an adiabatic compression, W is negative and U is positive. i.e. during
adiabatic compression, internal energy increases and temperature increases.
> An adiabatic change observes the following equations:

> For an adiabatic change, the gas must be held in a thick-walled, badly conducting
vessel. The change must take place rapidly so that there is little time for the heat to
escape.
> The magnitude of gradient of the adiabatic curve is greater than that of the
isothermal.
Adiabatic equation
Ideal gas equation
First law of thermodynamics
Adiabatic change
Change in internal energy
Work done
Relation between
From

Note: Work done for adiabatic change may also be obtained directly from change
in internal energy if the temperatures are known.