STATISTICAL PHYSICS

CHAPTER II
Fundamental Definitions in Statistical Physics

The stationary states of the particles in quantum mechanics that make up the macroscopic
system, which should be known in determining the macroscopic quantities by quantum
mechanical laws.

If the quantum states of a system of particles are known, the macroscopic quantity of that
system, entropy, can be found. In a system whose entropy can be determined, other
quantities such as temperature, pressure, chemical potential and magnetization can be
found.

A stationary quantum state in a system whose energy remains constant means that the
probability of a particle being in a certain volume element is independent of time. That is,
the stationary quantum state of a system is the condition that ensures that all observable
physical quantities of that system are time independent and the system is in equilibrium.
Macrostate and Microstate

Since a physical system consists of a large number of atoms or molecules, it often has a
large number of dynamic degrees of freedom. In such a system, the condition determined
by measuring only physical quantities such as temperature, energy and pressure is called
the macroscopic state of that system.

Determining the position and momentum of each of the particles that make up this system
determines the microscopic state of the system. In determining a thermodynamic quantity
such as energy, it is not necessary to know the microscopic states of the system in detail.
The energy of the system will be the sum of the energies of the particles that make up the
system. Therefore, it will be sufficient to know how many particles have certain energy
values ​without needing to know the microscopic states of the system to find energy.

Regardless of the properties of the particles in a system, determining how many particles
there are in each energy state is to establish the macroscopic state of that system.
The physical quantities that can be measured in a system with a large number of dynamic
degrees of freedom are those that correspond to the most probable macroscopic state.
The most likely macroscopic state consists of a large number of microscopic states.
A microscopic state (microstate) of a system can be described by specifying the particular
quantum state r in which the system is found A microstate refers to a microscopic description
of all subsystems (constituents) of the system.

A macroscopic state (macrostate) can be defined as a complete specification of a system in

terms of macroscopically measurable parameters. Macrostate refers to the state of the
system as a whole. The quantities such as volume, pressure, and temperature are
macroscopic quantities.

Phase Space
Let's say that the generalized space coordinates of a system with degrees of freedom f are
(q1, q2, . . . , qn) and the corresponding momentum coordinates are (P1 , P2, . . . , Pn).A
microscopic state of this system can be defined by determining the values (q1, q2, ... , qf,
P1 P2,. .... , Pf).

The 2f dimensional space formed by 2f variables is called the Phase space. Every point
determined in this space, called the phase point, corresponds to a microscopic state. Thus,
microscopic states in classical statistical physics, constitute a set of points in phase space.

The motion of the phase point produces an orbit in the phase space called phase
trajectory. If the energy of the system is conservative, this orbit remains on a surface with
constant energy.
Quantum States
Since q and p cannot be determined at the same time in quantum mechanics due to the
Heisenberg uncertainty principle, the phase space, which is valid in classical physics, loses
its meaning. Therefore, the definition of microscopic state, which is valid in quantum
statistical physics, is made entirely according to the principles of quantum mechanics.
According to quantum mechanics, the state of a system is one of the quantum states
that can be defined with the equation given below.

where H is the energy hamiltonian of the system, is the wave function

determining the quantum state, and the En is the energy value corresponding to the
quantum state n.

Let's analyze the quantum state for a free particle with mass M, momentum P, and
energy hamiltonian H.
 Wavelength of the standing waves,

where

If the particle moves in a cube of side length L, the components of the momentum
corresponding to this motion in a perpendicular coordinate system parallel to the sides
of the cube are,
If the volume of the container in which the particle is moving is V = L3,

This relation also applies to any other container of any shape. however, the dimensions
of the container must be greater than the Schrödinger wavelength. For a rectangular
container with sides Lx, Ly, Lz,
An energy level may contain more than one energy states. These energy levels called
degenerade energy levels. The number of the states represented by gn and called
multiplicity function (gn = 0, 1, 2, 3, …).

Each of these quantum states corresponds to a

microscopic state.

If the particle under study has a non-zero spin, each

of the energy levels may be overlapped with an
extra (2j + 1) layer. where J is the spin quantum
number of the particle.
States Accessible

If the energy of a system is known in advance, it can be said that the system can be
found in any of the quantum states that are in corresponds with this energy. Such
quantum states are called the accessible quantum states of that system.

β
Basic Postulate
An isolated system in equilibrium is equally likely to be in any of its accessible states.

Phase Space
 Quantum States for a Particle Moving in One Dimension

where nx corresponds to states accessible of the particle

number of states accessible having energies less than Enx is,

corresponding increase in states accesible with an increase in dEx

where D(Enx) is density of states

Density of states is a measure of number of quantum states per unit energy.

According to the expression

number of states accessible is an increasing function of energy.

Example: Number of quantum states corresponding to one

dimensional motion of an nitrogen molecule, along a
straight line with length L=10-2 m (m=5x10-26 kg and
energy of the molecule Enx=10-21 joule at room
temperature) is,
 Quantum States for a Particle Moving in Two Dimensions

Now consider a particle moves in a plane whose dimensions LxL.

number of states accessible will be

The number of states accessible of the particle

will be the sum of the number of cells remaining
inside the circle with radius R.

Since nx and ny are positive quantities, the cells

tales place in the first quadrant of the circle.
number of states accessible having energies less than En is,

According to the expression

number of states accessible is an increasing function of energy.

Example: Number of quantum states corresponding the motion of

an nitrogen molecule in two dimensions, (m=5x10-26 kg
and energy of the molecule Enx=10-21 joule at room
temperature) is,
 Quantum States for a Particle Moving in Three Dimensions

Now consider a particle moves in a box whose dimensions LxLxL.

The number of states accessible of the particle will be the sum of the number of cells
remaining inside the sphere with radius R.

Since nx , ny , and nz are positive quantities, the cells tales place in the first quadrant of
the upper hemisphere.
 Example: Number of quantum states corresponding the motion of
an nitrogen molecule in two dimensions, (m=5x10-26 kg
and energy of the molecule Enx=10-21 joule at room
temperature) is,

Up to now nucleus spin quantum number of the particle under investigation has been
ignored. We assumed the quantum number as zero. If the quantum number is different
from zero, such as I, number of states accessible given above will be increases by amount
of gn=2I+1.
 Number of Microscopic States (Statistical Weight)
Statistical Weight: Number of microscopic states with equal probability correspond to macroscopic
states known as statistical weight of this macroscopic states.
A microscopic state (microstate) of a system can be described by specifying the particular quantum state
r in which the system is found A microstate refers to a microscopic description of all subsystems
(constituents) of the system.
A macroscopic state (macrostate) can be defined as a complete specification of a system in terms of
macroscopically measurable parameters. Macrostate refers to the state of the system as a whole. The
quantities such as volume, pressure, and temperature are macroscopic quantities.
Using this representation, let's examine some properties that
arise in determining the microscopic states of distinguishable
particles.
The displacement of particles of the same energy level
between their energy states occurs a new microscopic state.
A new microscopic state occurs when particles at two
different energy levels displace.
If the order of particles placed in an energy state
changes, a new microscopic state does not occur.
In a system consisting of a large number of particles,
the total energy and the total number of particles do not change
while forming microscopic states.

If the energy of a system is E and number of particles is N, then we write and

*
We can study the particles those forms a microscopic state in three separate groups.

1) Maxwell-Boltzmann Particles: These particles are distinguishable particles. There is no restriction

on the number of particles placed in any energy level or state, as long as the condition given by * is
complied with.

2) Bose-Einstein Particles: These particles are indistinguishable particles. There is no restriction on the
number of particles placed in any energy level or state, as long as the condition given by equations *
is complied with. The wave functions of these particles are symmetric and spin quantum numbers
are in the form of integers such as 1, 2, 3, ... Such particles are known as Bosons. ( particle (spin 0),
photon (spin 1))

3) Fermi-Dirac Particles: These particles are indistinguishable particles. More than one fermion cannot
be placed in an energy state. That is well known as Pauli exclusion principle. The wave functions of
these particles are asymmetric and spin quantum numbers are in the form of half of integers such as
1/2, 3/2, 5/2, ... Such particles are known as Fermions. (electron (spin 1/2), )
Statistical Weight in Maxwell-Boltzmann Particles
Let we consider a system with energy levels ε1, ε2, ε3, …, εi containing N identical and distinguishable
particles .
The total number of states accessible (ΩN) we want to find is a relation that gives you the most probable
distribution of N particles to the above energy levels.
Consider N identical and distinguishable particles which are placed to the energy levels ε 1, ε2,
ε3, …, εi . Statistical weight (or number of microscopic states) of the such a macroscopic state of k is
given by
g iNi
 k  N !
i N !
i

Total statistical weight of over all k’s is     k

k

Statistical Weight in Bose-Einstein Particles

Let we consider a system with energy levels ε1, ε2, ε3, …, εi containing N identical and indistinguishable
particles .
Consider N identical and indistinguishable particles which are placed to the energy levels ε 1,
ε2, ε3, …, εi, having energy states gi. Statistical weight (or number of microscopic states) of the such a
macroscopic state of k is given by
( g  N i  1)!
 k   i   i
i i N i !( g i  1)!

Total statistical weight of over all k’s is     k

k
Statistical Weight in Fermi-Dirac Particles
Let we consider a system with energy levels ε1, ε2, ε3, …, εi containing N identical and indistinguishable
particles .
gi !
 k   i  
i i N i !( gi  N i )!

Total statistical weight of over all k’s is    k

k

Simple Interactions in a Macroscopic System

Consider a system of A which is divided in two parts such as A1 and A2. The energy, number of particles
and volume of the first part is represented by E1, N1, and V1, respectively, where as E2, N2, and V2 for the
second part, respectively. Energy, number of particles, and volume of the system A is E, N, and V,
respectively.
E1 A1 A2 E2 Since the system A is closed and isolated, there will be no change
N1 N2 in energy and number of particles
E  E1  E2
V1 V2
N  N1  N 2
V  V1  V2
Since the system A is closed and isolated, there will be no change
in energy and number of particles
E=E1+E2
N=N1+N2
V=V1+V2
Let the number of states accessible for the system A1 be Ω1(E1, N1, V1) and for A2 be Ω2(E2, N2, V2 ).
The number of states accessible of the system (having energy, E, number of particles, N, and volume, V) is

Ω(E, N, V) = Ω1(E1, N1, V1). Ω2(E2, N2, V2 )

Total number of states accessible of the system A is

The change in, energy, number of particles and volume for the A1 is dE1, dN1 and dV1, respectively. The
changes are dE2, dN2 and dV2 for A2. Since the system is closed and isolated, the changes arises from
interaction of the two system. Thus, the change in states accessible for the system A is,

Since the system is closed and isolated, dE=0, dN=0, and dV=0 for the system A.
The changes in A1 and A2 occur due to interaction of the systems A1 and A2,


dE1= - dE2 In equilibrium of
the system dΩ =0,
dN1= - dN2 and by
dV1= - dV2 substituting the
values in to the
equation given
above
In order to satisfy the equation given above,

By dividing both sides of the equations by Ω1.Ω2

In calculus notation the expressions can be written as

The equations are the conditions for equilibrium of the system

If an interaction occurs between the A1 and A2 system, the particle number and volume remain
constant, this interaction is in the form of energy sharing between the A1 and A2 system.

By considering the number of particles and volume remain constant, if an interaction occurs
between the A1 and A2 system this interaction is in the form of energy sharing between the A1 and A2
system. This type of interaction called thermal interaction.

When the condition is satisfied in the red box given above, the system is said to be in thermal
equilibrium.
We can write a relation between average change in energy of the system A1 and system A2.
 E1   E2  0
Energy transferred from one of the two systems in thermal interaction to another is called heat.

Average change in energy ( E1 ) of system A1 which is in thermal interaction with system A2 is the
heat that this system cools down. If the average change in energy of the system A2 is represented by
 E2  Q2 , we write Q1  Q2

In thermal interaction, the heat given by a system is cooled by the other.

If there is an interaction between systems A1 and A2 that only their volumes can be adjusted, this is
called mechanical interaction. When the condition is satisfied in the orange box given above, the system
is said to be in mechanical equilibrium.

Since there is no energy and particle sharing between the systems in mechanical interaction, their
adjustment of their volumes with respect to each other is provided by doing a work the first one on the
other.

If there is a corresponding change in energy ( E1 ) of the system A1 with respect to increment in

dV1 in volume V1, the macroscopic work done on the system A1 is W1   E1 . Similarly we can write
for the system A2, as W2   E2
Since the compound system formed by A1 and A2 is closed and isolated, we write
 E1   E2  0 and W1 W2  0 .
In mechanical interaction, work done by the system A1 is equal to work done by the system A2.

In a macroscopic system, thermal and mechanical interactions may occur at the same time. In this case
equilibrium state of the total system (A1 and A2) can be defined by satisfying the conditions given by the
equations in the red and orange colored box.
This type of interaction process known as general interaction, and we write,

d E1  dQ1  dW1
The quantities dQ1 and dW1 determine a small amount of work done with a small amount of heat
absorbed.
Finally, If there is only particle interaction between A1 and A2 systems, these two systems are called in
chemical interaction. When the condition given by the equations in blue colored box is satisfied, the
system A formed by the A1 and A2 systems is said to have reached the state of chemical equilibrium.

Reversible and Irreversible Process

If the direction of the process changes when any external parameter of a macroscopic system such as
volume is changed slightly, this process is reversible. Otherwise, the process is irreversible.
If both the system and its local environment maintain their initial equilibrium when the direction of a
process changes, this process is reversible.
Quasi-static processes are reversible.
Suppose that when a heat of dQ is transferred to molecules in a container having moving piston, work is
done (dW) on the piston by the molecules. In this case, the change in the energy of the gas molecules
will be dE = dQ-dW. If dQ=dW, the change in average energy of the gas molecules is zero. That is, the gas
molecules in the container have maintained their initial equilibrium state, so this is a reversible process.
Consider a container that is divided in two parts, part A and B. The part A is filled with gas molecules,
and some later time the gas molecules reach to equilibrium. When a hole is placed between the two
parts of the container the gas molecules in part A flows towards to part B. Because no matter how long
it is waited, it cannot be observed that the molecules that spread to part B settle back into part A. This
process is not reversible.
Irreversible processes are generally processes occurring under the influence of resistive forces.
Therefore, there is a relation between the work done during a reversible process and the work done
during a non-reversible process as dWreversible < dWirreversible .

References: "Fundamentals of Statistical and Thermal Physics ", by F. Reif , McGraw-Hill, 1965.
"Thermal Physics", by C. Kittel, H. Kroemer, W.H. Freeman and Company, 1980.
"İstatistik Fizik", Prof. Dr. Fevzi Apaydın, Hacettepe Üni., Müh. Fak. Yayınları
"Statistical Mechanics", by R.K. Pathria , Pergamon, 19