STATISTICAL THERMODYNAMICS

 Statistical thermodynamics (also called statistical mechanics), unlike kinetic theory, does not concern itself
with detailed considerations of such things as collisions of molecules with one another or with a surface.
Instead, it takes advantage of the fact that molecules are very numerous and average properties of a large
number of molecules can be calculated even in the absence of any information about specific molecules

ENERGY STATES AND ENERGY LEVELS

 as far as the methods of statistics are concerned, it is enough to know that quantized energy states exist
 exactly analogous to the wave equation describing the propagation of transverse waves in a stretched string,
fixed at both ends.

 The important result is that there is always an integral number of antinodes in the steady-state modes of
vibration; one antinode in the upper diagram, two in the next, and so on.
 The distance between nodes (or antinodes) is one-half a wavelength, so if L is the length of the string, the
wavelengths λ of the possible stationary waves are

 According to quantum mechanics, a stationary Schrodinger wave is in fact completely equivalent to such a
particle, and the wavelength λ .

The values of nx, ny and nz, are said to define the state of a particle, and the energies corresponding to the different
possible values of n: are the possible energy levels.
 The energy levels depend only on the values of n2 and not on the individual values of nx, ny and nz.
 In other words, the energy depends only on the magnitude of the momentum p 2 and not on its direction, just
as in classical mechanics.
 The energy level is then said to be degenerate, and we shall use the symbol gito designate the degeneracy of
level j, that is, the number of states having the same energy ϵ j
 The volume V of a cubical box of side length L equals V=L3, L2 =V2/3

 The energy of the j th level therefore depends on the quantum number nj and on the volume V. If the volume
is decreased, the value of given ϵ j increases


 There is only one state (one set of quantum numbers nx, ny and nj) having this energy. The lowest level is
therefore nondegenerate and g1 = I. The x, y, and z components of the corresponding momentum p1 are all
equal, and each equals h/2L



 The energy levels can be thought of as a
set of shelves at different elevations
 energy states correspond to a· set of
boxes on each shelf.
 The degeneracy gj of level j is the
number of boxes on the corresponding
shelf.
 The total number of marbles in the
boxes at any level j is called the
occupation number Nj of that level.
  the sum of the occupation numbers Nj over all levels equals the total n umber of particles N

MACROSTATES AND MICROSTATES

 A number N of identical entities is called an assembly

 the particles are distinguishable or not, a specification of the number of particles Nj in each energy level is
said to define a macrostate of the assembly
 If the particles are indistinguishable, a specification of the total number of particles in each energy state is
said to define a microstate of the assembly
 If the particles are distinguishable, a specification of the energy state of the particle is said to define a
microstate of the assembly.

THERMODYNAMIC PROBABILITY

 The fundamental postulate of statistical thermodynamics is that all possible microstates of an isolated
assembly are equally probable.
 The number of equally probable Microstates that correspond to a given macrostate k is called the
thermodynamic probability Wk. of the macrostate.
 For most macrostates of an assembly of a large number of particles, the thermodynamic probability is a very
large number
 The total number Ω of possible microstates of an assembly, or the thermodynamic probability of the
assembly
The time average is therefore

Since Δt is the same for all microstates, we can cancel it from numerator and denominator

THE BOSE-EINSTEIN STATISTICS

 the particles are considered indistinguishable, and there is no restriction on the number of particles that can
occupy any energy state.
 The energy states, however, are distinguishable.
 the number of different distributions for the j th level is

 If a level is nondegenerate gi = 1

 total number of possible distributions, or the thermodynamic probability w BE of a macrostate