PHY304 - Statistical Mechanics

Spring Semester 2021

Dr. Anosh Joseph, IISER Mohali

LECTURE 02

Wednesday, January 6, 2021

(Note: This is an online lecture due to COVID-19 interruption.)

Contents
1 Heat and Heat Capacity 1

2 Equation of State for a Real Gas 2

3 Reversible and Irreversible Processes 4

3.1 An Example Using Isothermal Expansion . . . . . . . . . . . . . . . . . . . . . . . . 5

4 Exact and Inexact Differentials, Line Integrals 6

1 Heat and Heat Capacity

Heat is a specific form of energy.
How do we define heat?
In 1871, James Clerk Maxwell defined heat in four different ways:

1. It is something which may be transferred from one body to another, according to the second
law of thermodynamics.

2. It is a measurable quantity, and so can be treated mathematically.

3. It cannot be treated as a material substance, because it may be transformed into something

that is not a material substance, e.g., mechanical work.

4. Heat is one of the forms of energy.

Work performed on a system (of mechanical or electrical origin) often increases the temperature.
We can use this property to define heat.
PHY304 - Statistical Mechanics Spring Semester 2021

We have
δQ ≡ C dT (1)

Here δQ is the small amount of heat which causes the increase dT in the temperature of a
system.
C is called the total heat capacity of the system.
The unit of heat is calorie.
1 cal of heat is equivalent to 4.184 Joule of mechanical work.
The SI unit of heat capacity is J/K.
Work and heat are qualitatively different.
We can invoke the microscopic picture of matter to explain the difference.
In this picture heat is energy which is statistically distributed over all particles.
The amount of heat δQ is an extensive quantity.
Since temperature is an intensive quantity, the total heat capacity has to be an extensive quan-
tity.
We can define an intensive quantity, the specific heat c, via

C = mc, (2)

where m is the mass of the substance.

In experiments it matters if a measurement is performed at constant pressure or at constant
volume.
We can distinguish the specific heats as cV (for specific heat at constant volume) or cp (for
specific heat at constant pressure).

2 Equation of State for a Real Gas

The ideal gas law
pV = N kB T (3)

is a general equation of state that connects all relevant variables.

Here kB is the Boltzmann’s constant.
This equation is valid only for dilute gases (low pressure).
In most cases one takes N = NA particles (one mole).
Thus we have
NA kB = R = 8.3145 JK −1 mol−1 . (4)

The constant NA kB = R is called the gas constant.

In thermodynamics we often assume equations of state to be polynomials of a variable.
Let’s introduce an ansatz for a sophisticated equation of state for larger pressures.

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We have
pV = N kB T + B(T )p + C(T )p2 + · · · . (5)

At p ≈ 0 we recover the original equation.

The above expansion is called the virial expansion.
As a first approximation we can terminate the expansion after the linear term.
The coefficient B(T ) can be determined experimentally.
B(T ) is called the virial coefficient.
We can also expand the equation of state of a real gas in terms of low density.
We get an analogues equation (another form of virial expansion)
   2
0 N 0 N
pV = N kB T + B (T ) + C (T ) + ··· (6)
V V

Another well-known equation of state for real gas is the equation of van der Waals (1873).
We can incorporate the effect of the volume of the gas particles.
For the ideal gas we have
V → 0 when T → 0. (7)

We introduce the following correction factor

V → V − N b, (8)

where b is a measure of the proper volume of the particle.

In an ideal gas we neglect the interaction between the particles.
The interaction is mainly attractive.
We can incorporate this by modifying the pressure

p → p + p0 . (9)

Here p0 is called the inner pressure.

The inner pressure depends on the mean distance between the particles and on how many
particles are on the surface.
Both the dependencies are a crude approximation proportional to the particle density N/V .
Thus we have  2
N
p0 = a , (10)
V
with a denoting a constant.
Van de Waals equation therefore reads
 2 !
N
p+ a (V − N b) = N kB T. (11)
V

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For high temperatures and low densities, van der Waals’ equation becomes the equation for the
ideal gas.
We can express van der Waals equation by a virial expansion by setting N/V in the inner
pressure equal to that of an ideal gas
N p
≈ . (12)
V kB T
Then we have
p2
 
p+ a (V − N b) = N kB T. (13)
(kB T )2
Simplifying
N kB T
pV = + pN b. (14)
1 + (kBpaT )2

For low pressures and high temperatures we have

pa
1 (15)
(kB T )2

and we can expand the denominator

 
a
pV = N kB T + N b− p + ··· (16)
kB T

This has the form of a virial expansion with

 
a
B(T ) = N b − . (17)
kB T

3 Reversible and Irreversible Processes

A process in an isolated system proceeds by itself until an equilibrium state is reached.
Since such processes do not reverse themselves they are called irreversible.
Examples: (i.) expansion of a gas from a smaller into a larger volume.
(ii.) All processes which produce friction and heat.
It is a characteristic for irreversible processes that they proceed over nonequilibrium states.
On the other hand, processes which proceed only over equilibrium states are called reversible.
If a system is in an equilibrium state, the variables of state have time-independent value and
nothing happens.
Thus reversible processes, strictly speaking, are non existent.
We can attribute the following importance to reversible changes of the state.
For every small step of the process the system is in an equilibrium state with definite values of
the state quantities, so that the total changes of the state variables can be obtained by integrating
over the infinitesimal reversible steps.
For irreversible processes this is not possible.

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During an irreversible process it is in general not possible to attribute values to the state quan-
tities.

3.1 An Example Using Isothermal Expansion

F a⃗

p1, V1

T = constant

Figure 1: Isothermal system.

Let us consider expansion of gas at constant temperature (isothermal expansion).

We can achieve a constant temperature for the system by immersing it in a heat bath.
That is, the heat bath is in thermal equilibrium with the system.
One way to achieve isothermal expansion of the gas from V1 to V2 is by removing the external
force, which acts on the piston and let the system maintain equilibrium.
Thus the gas will rapidly expand up to the volume V2 .
During this process the work gets wasted through turbulence etc.
This process happens by itself and would never reverse itself.
Therefore it is irreversible.
Note that during expansion we cannot ascribe values to the macroscopic quantities.
We can do this only after an equilibrium is re-established.
The work performed by the expansion of the system is zero as long as one uses an ideal massless
piston.
Another way to perform isothermal expansion is by invoking reversibility (or quasi-reversibility).
That is, by decreasing the force at each step only by an infinitesimal amount and waiting for
the establishment of equilibrium in the new situation.
In this case, the thermodynamic variables have definite values for each intermediate step and
we can apply the equation of state at each stage.

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We can calculate the total amount of work performed in the expansion of the system
Z 2 Z V2 Z V2
dV V2
dW = − pdV = −N kB T = −N kB T ln . (18)
1 V1 V1 V V1

Thus our system has done work against the external force Fa .
This reversible work of the system is the maximum work that can be extracted from the system.

p irreversible p quasireversible p reversible

p1 p1 p1

p2 p2 p2

V1 V2 V V1 V2 V V1 V2 V

Figure 2: Different ways to perform a process.

In the irreversible process we can determine only the initial and final states.
But in the reversible process all points of the pV -isotherm are attained.
Although the initial and final states are identical for the reversible and irreversible process, the
performed work (energy balance) is completely different.
The work performed in the isothermal expansion depends on the way in which the process is
carried out although the initial and final states are the same in both cases.
This tells us that work and heat are not state quantities.
The work and heat are not suited to describing a macroscopic state in a unique way.
Mathematically this means that work and heat are not exact (total) differentials.

4 Exact and Inexact Differentials, Line Integrals

Let us consider a state function
z = f (x, y) (19)

which is a function of two state variables.

It is a characteristic of state quantities, and hence of state functions, that they depend only
on the values of the state variables, but not on the way (that is, on the procedure) in which these
values are assumed.
If we change the state variables by dx and dy with respect to the initial values x and y, as is

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done in reversible changes of state, for the change of z we have

 
∂f (x, y)  ∂f (x, y) 
dz =  dx +  dy. (20)
∂x  ∂y 
y x

Note that y and x are often not independent from each other but are related by the laws of
thermodynamics.
We can write the above equation for the total differential as a gradient

df (~x) = ∇f (~x) · d~x. (21)

The corresponding original function can be obtained (state function), up to an additive constant,
via line integration along an arbitrary curve.
Z
f (~x) − f0 (~x0 ) = ∇f (~x) · d~x. (22)
C

The curve C leads from ~x0 to ~x.

Let us parametrize the curve as ~x(t) with t ∈ [0, 1].
Then we have Z 1
d~x(t)
f (~x) − f0 (~x0 ) = dt∇f (~x(t)) · . (23)
0 dt
Here the integrand is only a function of the parameter t.
We want to know when a given differential is total.
That is, under what conditions the integration in Eqs. (22) and (23) does not depend on the
integration contour.
We can get help from classical mechanics.
In classical mechanics work is a total differential as long as force can be deduced from a potential
via
F~ = −∇V (~r). (24)

But in thermodynamics work is not a total differential.

The existence of a potential is, in the mathematical sense, necessary and sufficient for Eq. (22)
to be independent of the integration contour.
If an arbitrary differential F~ (~x) · d~x is given, this differential is total (or complete) if F~ (~x) =
∇f (~x) for potential f (~x).
From classical mechanics we know a simple condition for deciding if a force possesses a potential.
It is necessary and sufficient that
∇ × F~ = ~0. (25)

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That is,

∂Fz ∂Fy
− = 0, (26)
∂y ∂z
∂Fx ∂Fz
− = 0, (27)
∂z ∂x
∂Fy ∂Fx
− = 0. (28)
∂x ∂y

If F~ = ∇f is valid the above equations reduce to

∂2f ∂2f
− = 0, (29)
∂y∂z ∂z∂y
∂2f ∂2f
− = 0, (30)
∂z∂x ∂x∂z
∂2f ∂2f
− = 0. (31)
∂x∂y ∂y∂x

This is nothing but the right to interchange the sequence of differentiation.

It holds certainly true for a function f (x, y, z) which is totally differentiable.

References
[1] W. Greiner, L. Neise, H. Stocker, and D. Rischke, Thermodynamics and Statistical Mechanics,
Springer (2001).

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