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Work done during an isothermal process

When a gas is allowed to expand isothermally, work is done by it.
Let the initial and final volumes be V1 and V2, respectively. Fig 4.8 represents the indicator
diagram. The area of the shaded strip represents the work done for a small change in volume dV.
When the volume changes from V1 to V2

Here, the change in the internal energy of the system is zero (because the temperature remains
constant). So the heat absorbed by the system is Equal to the work done by it.

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Work done During an Adiabatic Process

During an adiabatic process, the system is thermally insulated from the surroundings. The
gas expands from volume V1 to V2 as shown by indicator diagram [Fig. 4.9]. The work done
by the gas for an increase in volume dV is P dV.
Work done when the gas expands from VI to V2 is given
by

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Substituting these values in equation (4.10)

Hence the work done In adiabatic process depends only upon the initial and final temperature
T1 and T2.

Slopes of adiabatics and isothermals

Therefore, the slope (dp/dV) of an adiabatic is Ƴ times grater than the slope of the isothermal.
Hence, the adiabatic curve is steeper than the isothermal curve (figure) at a point A where the
two curves intersect each other.

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Derivation of Kinetic Gas Equation

Starting from the postulates of the kinetic molecular theory of gases we can develop an
important equation. This equation expresses PV of a gas in terms of the number of molecules,
molecular mass and molecular velocity. This equation which we shall name as the Kinetic
Gas Equation may be derived by the following clauses.
Let us consider a certain mass of gas enclosed in a cubic box (Fig. 2.17) at a fixed
temperature. Suppose that:
The length of each side of the box = l cm
The total number of gas molecules = n
The mass of one molecule = m
The velocity of a molecule = v
The kinetic gas equation may be derived by the following steps:

1. Resolution of Velocity v of a Single Molecule Along X, Y and Z Axes

According to the kinetic theory, a molecule of a gas can move with velocity v in any
direction. Velocity is a vector quantity and can be resolved into the components vx , vy , vz
along the X, Y and Z axes. These components are related to the velocity v by the following
expression.

Now we can consider the motion of a single molecule moving with the component velocities
independently in each direction.

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(2) The Number of Collisions Per Second on Face A Due to One Molecule
Consider a molecule moving in opposite faces direction between A and B. It will strike the
face A with velocity vx and rebound with velocity – vx To hit the same face again, the
molecule must travel l cm to collide with the opposite face B and then again l cm to return to
face A. Therefore,

Figure 2.17: Resolution of velocity v into Figure 2.18: Cubic box showing
components, Vx,Vy and Vz molecular collisions along axis. X

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(3) The Total Change of Momentum on All Faces of the Box Due to One Molecule Only
Each impact of the molecule on the face A causes a change of momentum (mass × velocity):
The momentum before the impact = mvx
The momentum after the impact = m (– vx)
∴ The change of momentum = mvx– (– mvx)
=2 mvx

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(4) Total Change of Momentum Due to Impacts of All the Molecules on All Faces of the Box
Suppose there are N molecules in the box each of which is moving with a different velocity
v1, v2, v3, etc. The total change of momentum due to impacts of all the molecules on all faces
of the box

(5) Calculation of Pressure from Change of Momentum; Derivation of Kinetic Gas Equation
Since force may be defined as the change in momentum per second, we can write

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This is the fundamental equation of the kinetic molecular theory of gases. It is called the
Kinetic Gas equation. This equation although derived for a cubical vessel, is equally valid for a
vessel of any shape. The available volume in the vessel could well be considered as made up of
a large number of infinitesimally small cubes for each of which the equation holds.
Significance of the term u. As stated in clause (4) u2 is the mean of the squares of the
individual velocities of all the N molecules of the gas. But

(or RMS) Velocity.

Kinetic Gas Equation In Terms of Kinetic Energy

If N be the number of molecules in a given mass of gas,

Where e is the average kinetic energy of a single molecule.

Or
..(1)

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Where E is the total kinetic energy of all the N molecules. The expression (1) may be called the kinetic
gas equation in terms of kinetic energy.
We know that the General ideal gas equation is

Substituting the values of R, T, N0, in the equation (5), the average kinetic energy of a gas molecule
can be calculated.

SOLVED PROBLEM 1. Calculate the average kinetic energy of a hydrogen molecule at

0°C.
SOLUTION

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SOLVED PROBLEM 2. Calculate the kinetic energy of two moles of N2 at 27°C. (R =

8.314 JK–1 mol–1)
SOLUTION

Two Specific Heats of A Gas

Consider a gas of mass mat a pressure P and volume F. If the gas is compressed, there is rise in
temperature. In this case, no heat has been supplied to the gas to raise its temperature.

Specific heat, C = H/m.T But If H= 0 Thus C= 0

on the other hand, if heat is supplied to the gas and the gas is allowed to expand such that
there is no rise of temperature, then C = H/mT Here T=0 Thus C= H/m*0= ∞
Thus, the specific heat of a gas varies from zero to infinity. In order to fix the value of the
specific heat of a gas, the pressure or volume has to be kept constant. Consequently. a gas
has two specific heats.

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1. Specific heat at constant volume Cv: It is defined as the quantity of heat required to raise
the temperature of one gram of a gas through I °C at constant volume.
2. Specific heat at constant pressure Cp: It is defined as the quantity of heat required to
raise the temperature of one gram of a gas through 1°C at constant pressure.

Cp is greater than Cv. When a gas is heated at constant volume, the heat supplied to the gas
is wholly used up to raise its temperature. On the other hand when a gas is heated at
constant pressure, a part of the heat is used to raise its temperature and a part is used to do
external work to keep the pressure constant.

Specific Heat at Constant Volume

It is the amount of heat required to raise the temperature of one gas through 1°C while the
volume is kept constant and the pressure allowed to increase. It is denoted by the symbol Cv.
In Physics it is more common, however, to deal with one gram mole of the gas and the heat
required in such case is called Molecular Heat and is represented at constant volume by Cv.
It is possible to calculate its value by making use of the Kinetic theory.
1
Consider one mole of a gas at the temperature T. Its kinetic energy is 2 mnu2. From the kinetic
gas equation

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3
If the temperature is raised by 1°C to (T + 1) K kinetic energy becomes 2 R (T+1)

If, therefore, it be assumed that the heat supplied to a gas at constant volume is used up entirely
in increasing the kinetic energy of the moving molecules, and consequently increasing the
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temperature, the value of Cv should be equal 2 R.

It is actually so for monoatomic gases and vapors because such molecules can execute only
translatory motion along the three co-ordinate axes. Motion of monoatomic gas molecules is
the simplest and can be resolved into three perpendicular components along the co-ordinate
axes. Thus the energy of such a molecule can be considered to be composed of three parts as

The number of square terms involved in determining the total kinetic energy of a molecule is
often referred to as the Degrees of freedom of motion. Such molecules have three degrees of
freedom of motion. According to the principle of equipartition of energy, total energy of the
molecule is equally distributed among all its degrees of freedom.

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But in the case of diatomic and polyatomic molecules, the heat supplied may not only increase
this kinetic energy of translation of the molecules as a whole but also cause an increase in
the energy in the inside of the molecules which we may call as intramolecular energy. This
intramolecular energy may be the vibration energy i.e., energy of the atoms executing
vibrations with respect to each other along their line of centres or rotational energy which
manifests itself in the rotation of the molecules about axes perpendicular to the line of centres.
There will be other degrees of freedom for rotational and vibrational modes of motion also.

For such cases the heat needs will be complex and are denoted by ‘x’ – a factor which
depends upon vibrational and rotational degrees of freedom. Vibrational degrees of freedom
rapidly increase with the increase in the total number of atoms in a molecule but the degrees
of freedom are two for linear diatomic and three for non-linear diatomic molecules in case of
rotational motion.
Consequently in such cases the molecular heat will be greater than 32 R by the factor x.

The value of x varies from gas to gas and is zero for monoatomic molecules.

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Specific Heat at Constant Pressure

It may be defined as the amount of heat required to raise the temperature of one gram of gas
through 1°C, the pressure remaining constant while the volume is allowed to increase. It is
written as cp and the Molecular heat in this gas is represented as Cp.
Now, whenever a gas expands it has to do work against external pressure. It means that
when a gas is heated under constant pressure, the heat supplied is utilised in two ways:

(1)In increasing the kinetic energy of the moving molecules and this has already been shown
to be equal to 3/2 R + x cal.
(2) In performing external work done by the expanding gas. The work done by the gas is
equivalent to the product of the pressure and the change in volume. Let this change in
volume be ΔV when the constant pressure is P and the initial volume is V.
For 1 g mole of the gas at temperature T,

Hence R cal must be added to the value of 3/2 R cal in order to get the thermal equivalent of
the energy supplied to one gram mole of the gas in the form of heat when its temperature is
raised by 1°C.

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Specific Heat Ratio

The ratio of the molecular heats will be the same as the ratio of the specific heats. It is
represented by the symbol γ .

These results are found to be in accord with experimental observations at 15°C given in the
Table that follows and thus specific heat ratio helps us to determine the atomicity of gas
molecules. The theoretical difference between Cp and Cv as calculated above is R and its
observed value also shown in the table below comes out to about 2 calories.

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Concept of Heat
Heat is defined as energy in transit. If a body is at a constant temperature, it has both
mechanical and thermal energies due to the molecular agitations and it is not possible to
separate them. So, in this ease, we cannot talk of heat energy. It means, if the flow of heat
stops, the word heat cannot be used. It is only used when there is transfer of energy between
two or more systems. Consider two systems A and B in thermal contact with one another and
surrounded by adiabatic walls.
For the system A.
Q = U2 – U1 + W ...(I )
where Q is the heat energy transferred, Ul is the initial internal energy, U2 IS the final internal
energy and W is the work done.

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Similarly for the system B,

- - - -
Q = U 2 – U 1 + W ...(2)
Adding (1) and (2)

- - - -
Q+ Q = (U2 – U1)+ W + (U 2 – U 1 )+ W
- - - -
Q+ Q = [(U2 + U 2) - (U1 + U 1 )]+ (W+W ) …. (3)
The total change in the internal energy of the composite system
- -
= [(U2 + U 2) - (U1 + U 1 )]
-
The work done by the composite system= W+W

-
It means that the heat transferred by the composite system = Q+ Q . But the composite
system is surrounded by adiabatic walls and the net heat transferred is zero.
-
Q+ Q = 0
-
Or Q = -Q ….(iv)
Thus, for two systems A and B in thermal contact with each other, and the composite system
surrounded by adiabatic walls, the heat gained by one system is equal to the heat lost by the
other system.

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Thermodynamic Equilibrium
Any state of homogeneous system in which any two of the three variables P, V and T remain
constant, as long as the external conditions remain unchanged is said to be in thermodynamic
equilibrium.
A system in thermodynamic equilibrium must satisfy the following requirements strictly:
(i) Mechanical Equilibrium. For a system to be in mechanical equilibrium, there should be
no macroscopic movement within the system (i.e. no unbalanced forces acting) or of the
system with respect to its surroundings.
(ii) Thermal Equilibrium. For a system to be in thermal equilibrium, there should be no
tem-perature difference between the parts of the system or between the system and the
surroundings.

(iii) Chemical Equilibrium. For a system to be in chemical equilibrium, there should be no

chemical reaction within the system and also no movement of any chemical constituent from
one part of the system to the other.
Quasistatic Process
A finite unbalanced force may cause the system to pass through non-equilibrium states. A
quasistatic process is defined as the process in which the deviation from thermodynamic
equilibrium is infinitesimal and all the states through which the system passes during a
quasistatic process can be considered as equilibrium states.
A quasistatic process is an ideal concept which can never be satisfied rigorously in practice.
However, in actual practice, many processes closely approach a quasistatic process with no
significant error.

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