Chapter five

Simple Applications of Statistical

 Contents
❖ Partition function and their
properties
❖ Calculations of thermodynamic
quantities
❖ Gibbs paradox
❖ Validity of the classical
approximation
❖ Proof of equipartition
❖ Simple applications
❖ Specific heat of solids
❖ General calculation of magnetism
❖ Maxwell’s velocity distribution
❖ Number of molecule striking a
surface
❖ Effusion
❖ Pressure and momentum
 Partition function and their properties
❖ Consider a system in contact with a heat reservoir.
❖ The systems in the representative ensemble are distributed over their
accessible states in accordance with the Boltzmann distribution.
❖ Thus, the probability of occurrence of some state r with energy Er is
given by

over all states of the system, irrespective of their energy.

❖ The quantity Z, which is defined as the sum of the Boltzmann factor over
all states, irrespective of their energy, is called the partition function.
❖ It is clear that all important macroscopic quantities associated with a
system can be expressed in terms of its partition function Z.
❖ Partition function is the basic parameter in statistical physics.
❖ The partition function Z is a function of both β and x (where x is the
single external parameter)
❖ If the system can be treated in the classical approximation, then its energy
E(q1, . . . , qf, p1, . . . ,pf) depends on some f generalized coordinates and f
momenta.
❖ If phase space is subdivided into cells of volume h0f, the Z can be evaluated
by first summing over the number (dq1, . . . dqfdp1. . . dpf)/h0f of cells of
phase space which lie in the element of volume (dq1, . . . dqfdp1. . . dpf) at the
point {q1, . . . qf , p1. . . pf}and which have nearly the same energy E(q1, . . .
qf , p1. . . pf); and then summing (or integrating) over all elements of volume.
❖ Thus one obtains in the classical approximation
❖ The energy of a system is only defined to within an arbitrary additive
constant.
❖ If one changes by a constant amount ϵ0 the standard state with respect to
which the energy is measured, the energy of each state r becomes Er* = Er +ϵ0

❖ Thus the partition function is also changed, then the new mean energy is
then given by

I.e., it is properly shifted by the amount ϵ0 .

❖ The entropy is properly unchanged;

❖ Similarly, all expressions for generalized forces (i.e., all equations of state)
are unchanged, since they involve only derivatives of lnZ with respect to an
external parameter.
❖ The decomposition of the partition function for a system A when the latter
consists of two parts A' and A' ' which interact only weakly with each other.
❖ If the states of A' and A' ' are labeled respectively by r and s, then a state of
A can be specified by the pair of numbers and its corresponding energy Ers
is simply additive, i.e.,
❖ The partition function Z for the total system A is a sum over all states labeled
by rs, i.e.,

where Z' and Z" are the partition functions of A' and A' ' , respectively.
❖ Thus, we have shown that if a system consists of distinct noninteracting parts,
the partition function factors into a simple product.
❖ This is a useful result and one which clearly is equally valid when one is
dealing with more than two weakly interacting parts.
 Calculations of thermodynamic quantities
❖ Consider a gas consisting of N identical monatomic molecules of mass
m enclosed in a container of volume V.
❖ Let us denote the position and momentum vectors of the i th molecule
by ri and pi, respectively.
❖ The total energy of the gas is given by

❖ Since the gas is ideal, there are no interatomic interaction forces (the gas is
sufficiently dilute), and the total energy is becomes
❖ Let us treat the problem classically and divide the phase-space into cells of
equal volume h0f.
❖ Here, f is the number of degrees of freedom, and h0 is a small constant with
dimensions of angular momentum which parametrizes the precision to which
the positions and momenta of molecules are determined.
❖ Each cell in phase-space corresponds to a different state.
❖ The partition function is the sum of the Boltzmann factor exp(−βEr) over all
possible states, where Er is the energy of state r.

where 3N is the number of degrees of freedom of a monatomic gas containing N

molecules.
❖ Note that the integral over the coordinates of a given molecule simply
yields the volume of the container, V, since the energy E is independent of
the locations of the molecules in an ideal gas.
❖ There are N integrals, so we obtain the factor VN in the above expression.
❖ The partition function Z of the gas is made up of the product of N identical
factors: i.e.
 Gibbs paradox
❖ Suppose that we have a system of volume V containing ν moles of ideal
gas at temperature T.
❖ Doubling the size of the system is like joining two identical systems
together to form a new system of volume 2V containing 2 ν moles of gas
at temperature T.
❖ Let the entropy of the original system becomes

❖ The entropy of the double-sized system becomes

❖ So, the entropy of the double-sized system is more than double the entropy
of the original system.
❖ Where does this extra entropy come from?
❖ The correct partition function Z, which does take into account the essential
indistinguishability of the molecules and does not lead to the Gibbs
paradox difficulties, is then given
 Validity of the classical approximation
❖ An approximate criterion for the validity for the classical description can be
obtained by appealing to the Heisenberg uncertainty principle

❖ This relates the uncertainties Δq and Δp introduced by quantum effects in any

attempt at simultaneous specification of a position q and corresponding
momentum p of a particle.
❖ Suppose that one tries to describe the motion of the gas molecules by classical
mechanics and can find the certainly expect a classical description is given by
the mean separation between molecules respectively and its equivalently can be
expressed in the condition that

❖ the quantum description ought to be equivalent to the motion of wave

packets describing individual particles which move independently in a
quasi-classical manner.

❖ a state of the whole gas to be described by a single wave function which

cannot be decomposed in any simple way; it thus results in correlations
between the motions of the particles even if no forces exist between them.
❖ Suppose the mean intermolecular separation R can be estimated by imaging
each molecule at center of a little cube of side R, these cubes filling the
available volume V.

❖ The mean momentum p can be estimated from the known mean energy ε of a
molecule in the gas at temperature T.

❖ This shows that the classical approximation ought to be applicable if the

concentration N/V of molecules in the gas is sufficiently small, if the T is
sufficiently high, and if the mass of the molecules is not too small.
 Proof of eqipartition theorem
❖ The canonical distribution (in its classical system) is a function of coordinates
and momenta which are continuous variables.
❖ Any calculation of mean values can thus be reduced to a calculation of
integrals rather than of discrete sums.
❖ The energy of a system is a function of some f generalized coordinates qk and
corresponding f generalized momenta pk; i.e

❖ The following is a situation of frequent occurrence:.

➢ The total energy splits additively into the form
 where εi volves only the one variable pi and the remaining part E' does
not depend on pi.

➢ The function εi quadratic in pi; i.e., it is of the form, where b is constant,

❖ Suppose that the system under consideration is in thermal equilibrium with a

heat reservoir at an absolute temperature T.
❖ What is the mean value of the energy contribution εi in the above equation?
❖ The probability of finding the system with its coordinates and momenta in a
range near {q1, . . . , pf } is given by the canonical distribution with the
constant C determined by conditions.
❖ By its definition, the mean value of εi is found by performing the appropriate
sum (or integral) over all possible states of the system, i.e.,

where the integrals extend over all possible values of all the coordinates q1, . . . , qf
and all the momenta p1, . . . , pf.

❖ Using the above situation of frequent occurrence, the mean value of εi is

● This expression is called equipartition theorem and it states that the mean
value of each independent quadratic term in the energy is equal to 1/2kT.
 Simple applications
❖ Some of the simple application of equiparttion function can be described as
follows:
➢ Mean kinetic energy of a molecule in a gas
➢ Brownian motion
➢ Harmonic oscillator
❖
 Specific heat of solid
❖ Consider any simple solid with Avogadro's number Na of atoms per mole; e.g.,
the solid might be copper, gold, aluminum, or diamond.
❖ These atoms are free to vibrate about their equilibrium positions, such
vibrations are called lattice vibrations.
❖ Each atom is specified by three position coordinates and three momentum
coordinates, and free to move by small amounts about its equilibrium position.
❖ Since the vibrations are supposed to be small, the potential energy of
interaction between atoms can be expanded about their equilibrium positions
and is therefore quadratic in the atomic displacements from their equilibrium
positions.
❖ The net result is that the total energy of lattice vibrations can be written (when
expressed in terms of appropriate normal mode coordinate) in the simple form

❖ Here the first term is the total kinetic energy involving the 3Na (normal-mode)
momenta of the atoms, while the second term is the total potential energy
involving their 3Na (normal-mode) coordinates.
❖ The coefficients ki are positive constants.
❖ Thus the total energy is the same as that of 3Na independent one-dimensional
harmonic oscillators.
❖ If the temperature T is high enough so that classical mechanics is applicable
(and room temperature is usually sufficiently high for that), application of the
equipartition theorem allows one to conclude immediately that the total mean
energy per mole is

❖ This result asserts that at sufficiently high temperatures all simple solids have
the same molar specific heat equal to 3R (25 joules mole-1 deg-1).
❖ The validity of this result was first discovered empirically and is known as the
law of Dulong and Petit.
❖ The above result is not valid for solids at appreciably lower temperatures.
❖ One can obtain an approximate idea of the behavior of Cv at all temperatures
by making the crude assumption (first introduce by Einstein ) that all atom in
the solid vibrate with the same angular frequency ω.
❖ These can be treated by quantum mechanics so that their total mean energy is
just 3Na times that of the single oscillator; i.e.,

❖ The molar specific heat of the solid on the basis of this simple Einstein model
is given by
❖ Thus the specific heat should approach zero exponentially as T approaches zero.
❖ Experimentally the specific heat approaches zero more slowly than this, indeed
Cv ∝ T3. The reason for this discrepancy is the crude assumption that all atoms
vibrate with the same characteristic frequency.
 General calculation of magnetism
❖ Consider a system consisting of N non-interacting atoms in a substance at
absolute temperature T and placed in an external magnetic field H pointing
along the z direction.
❖ Magnetic energy of an atom can be written as
❖ Here µ is the magnetic moment of the atom and it is proportional to the total
angular momentum ћJ of the atom and is conventionally written in the form:

❖ Since H points in the z direction, then

❖ In a quantum mechanical description the values which Jz can assume are
discrete and are given by

❖ Thus there are 2J + 1 possible values of m corresponding to that many possible

projections of the angular momentum vector along the z axis.
❖ The possible magnetic energies of the atom are given by

For example, if J = 1/2 as would be the case for an atom with a single net electron
spin, there are only two possible energies corresponding to m = +1/2 or -1/2.
❖ The probability Pm that an atom is in a state labeled m is given by

❖ The z component of its magnetic moment in this state is equals to ,

❖ The mean z component of the magnetic moment of an atom is therefore

 Maxwell’s velocity distribution
❖ Consider a molecule of mass m in a dilute gas and it may possibly consist of
several different kinds of molecules.
❖ Let us denote the position of the center of mass of this molecule by r and the
momentum of its center of mass by p.
❖ If external force fields (e.g., gravity) are neglected, the energy ϵ of this
molecule is equal to

❖ Since the gas is dilute, any potential energy of interaction with other molecules
is supposed to be negligible; thus ϵ does not depend on r.
❖ The state of the molecule can be described by specifying that the position of
❖ the center of mass of the molecule lies in the range (r; dr), i.e., in a volume
element of magnitude d3r = dxdydz near the position r; that the momentum of
its center of mass lies in the range (p; dp), i.e., within the momentum space
volume d3p = dpxdpydpz near the momentum p; and that the state of internal
motion of the molecule is labeled by some quantum numbers s with
corresponding internal energy ϵs(int).
❖ This particular molecule is in weak interaction with all the other molecules
which act as a heat reservoir at the temperature T of the gas.
❖ If the gas is sufficiently dilute, it is also permissible to think in classical terms
and to focus attention on the particular molecule as a distinguishable entity.
❖ Then the molecule satisfies all the conditions of a distinct small system in
contact with a heat reservoir and obeys the canonical distribution.
❖ The probability Ps(r, p) d3r d3p of finding the molecule with center-of-mass
variables in the ranges (r; dr) and (p; dp) and with internal state specified by s
the result

❖ The P(r, p) d3r d3p ; irrespective of its internal state, is obtained by summing
above equation over all possible internal states s.
❖ The mean number of molecules in this position and momentum range can be
obtain multiplies the probability by the total number N of molecules of the
type under consideration,.
❖ If Maxwell velocity distribution is divided by the element of volume d3r., one
obtains
 Number of molecule striking a surface
❖ Let us focus attention on a dilute gas enclosed in a container and ask the
following question;
➢ How many molecules per unit time strike a unit area of the wall of this
container'?
➢ If there is a very small hole in the wall of the container, how many
molecules will stream out of this hole per unit time?

Crude calculation

❖ Imagine that the container is a box in the form of a parallelepiped, the area of
one end-wall being A. How many molecules per unit time strike this end-wall?
❖ Suppose that there are in this gas n molecules per unit volume.
❖ Since they all move in random directions, we can say roughly that one-third
of them, or n/3 molecules per unit volume, have their velocities in a direction
predominantly along the z axis .
Area A

Fig: Molecules colliding with a wall

❖ Half of these molecules, i.e., n/6 molecules per unit volume, have their
velocity in the +z direction so that they will strike the end-wall under
consideration.
❖ Hence all those molecules with velocity v in the z direction which lie within a
distance v dt from the end- wall will within a time dt strike the end-wall.
❖ Thus we arrive at the result that [the number of molecules which strike the
end-wall of area A in time dt] is equal to [the number of molecules having
velocity v in the z direction and contained in the cylinder of volume Avdt; i.e.,
it is given by
❖ The total number of molecules which strike unit area of the wall per unit time
is then given by

❖ We emphasize that this result was obtained by a very crude argument in which
we did not consider in any detail the velocity distribution of the molecules,
either in magnitude or in direction.
❖ The relation assertion that the total molecular flux is proportionately increased
if the concentration of molecules is increased or if their speed is increased.
❖ The dependence of total molecular flux on the temperature T and mean
pressure p can be described as
 Effusion
❖ Consider a gas in equilibrium inside some container and suppose that a small
hole of diameter D (or a narrow slit of width D) is now made in one of the
walls of this container.
❖ If the hole is sufficiently small, the equilibrium of the gas inside the container
should be disturbed to a negligible extent.
❖ The few molecules escaping through the hole into a vacuum surrounding the
container should then constitute a representative sample of the molecules of
the gas in its equilibrium state.
❖ Indeed, the molecules that have thus escaped can be collimated by slits to form
a well-defined beam and, since they are few in number, their mutual
interaction in this beam is insignificant.
❖ The molecules in such a beam can then be studied very effectively with two
possible aims:
➢ (i) It may be of interest to study the properties of the molecules in the gas
in equilibrium inside the container.
➢ (ii) It may be of interest to study the properties of essentially isolated
molecules or atoms in order to investigate fundamental atomic or nuclear
properties.
❖ Indeed, the molecules that have thus escaped can be collimated by slits to form
a well-defined beam and, since they are few in number, their mutual
interaction in this beam is insignificant.
❖ The molecules in such a beam can then be studied very effectively with two
possible aims:
➢ (i) It may be of interest to study the properties of the molecules in the gas
in equilibrium inside the container.
➢ (ii) It may be of interest to study the properties of essentially isolated
molecules or atoms in order to investigate fundamental atomic or nuclear
properties.
❖ How small must be the size D of the hole so that the equilibrium of the gas
inside the container is disturbed to a negligible extent?
❖ The hole must be sufficiently small so that the few molecules which are in the
vicinity of the hole do not affect appreciably the large number of molecules in
the remainder of the gas.
❖ This condition is satisfied if, during the time that a molecule spends in the
vicinity of the hole, it suffers practically no collisions with other molecules.
❖ How small must be the size D of the hole so that the equilibrium of the gas
inside the container is disturbed to a negligible extent?
❖ The hole must be sufficiently small so that the few molecules which are in the
vicinity of the hole do not affect appreciably the large number of molecules in
the remainder of the gas.
❖ This condition is satisfied if, during the time that a molecule spends in the
vicinity of the hole, it suffers practically no collisions with other molecules.
Fig:Formation of a molecular beam by
molecules escaping through a small
hole in a container.

the molecules inside the container remain essentially in equilibrium (although

their total number decreases slowly) and the escape of the molecules through the
hole is said to constitute effusion.
❖ The situation is appreciably different if D >> l so that molecules suffer
frequent collisions with each other near the hole.
 Pressure and momentum
❖ How a gas exerts a pressure?
❖ The mean force exerted on the wall of the container is due to collision of
molecules with the wall. If there are a collision between the molecules, there
will be a change of momentum.
❖ How to calculate the mean force exerted by the gas on a small element of area
dA of the container wall?

Fig shows an element of

chosen the z axis
area dA of the container
to be normal to
wall and a surface of area
the clement of
dA lying inside the gas
area.
just in front of the wall.
❖ If we focus attention on an element of area dA lying inside the gas an
infinitesimal distance in front of the wall, then to find the mean net molecular
momentum which is transported per unit time across this surface from left to
right as the molecules cross this surface from both directions.
❖ Let us denote by G(+) the mean molecular momentum crossing this surface dA
per unit time from left to right, and by G(-) the mean molecular momentum
crossing this surface dA per unit time from right to left.

❖ To calculate G(+), consider the clement of surface dA in the gas and focus first
attention on those molecules with velocity between v and v + dv.
❖ Figure: Molecules crossing a surface dA in a gas from left to right (+) and
from right to left zero as dt (-)
❖ The mean number of such molecules which cross this area in an infinitesimal
time dt is again the mean number of such molecules contained in the cylinder
of volume |dA v dt cos θ|; i.e., it is equal to f(v)d3v |dA vdt cosθ|.
❖ By multiplying; this number by the momentum of each molecule and dividing
by the time dt, one can obtains the mean momentum transported across the area
dA per unit time by molecules with velocity between v and v + dv.
❖ By summing over all molecules which cross this area from left to right, i.e.,
over all molecular velocities with vz > 0, one then gets for the total mean
molecular momentum G(+) transported across this area from left to right the

❖ A similar expression gives the total mean molecular momentum G (-) transported
across this area from right to left, except that the integration must now be over
all molecules for which vz < 0.
❖ Then, the net mean momentum transported across the surface is given as

❖ The last expression of the above equation is a very general expression and
would be valid even if the gas is not in equilibrium, i.e., even if f is completely
arbitrary.
❖ If the gas is in equilibrium, then f(v) is only a function of v ≡ |v|.

since the integrand is odd, having opposite signs for +vz and -vz.

❖ Equation expresses the obvious fact that there can be no mean tangential force
on the wall in an equilibrium situation.
❖ The mean normal force does not vanish. Measured per unit area it gives the
mean pressure, which is equal to
❖ Hence, the mean pressure can be written equivalently