Entropy and Probability (A statistical

view)
Entropy- a measure of the disorder of a
system.
A state of high order = low probability
A state of low order = high probability
In an irreversible process, the universe
moves from a state of low probability to a
state of higher probability.
We will illustrate the concepts by
considering the free expansion of a gas
from volume Vi to volume Vf.
The gas always expands to fill the
available space.
It never spontaneously compresses itself
back into the original volume.
First, two definitions:
Microstate: a description of a system that
specifies the properties (position and/or
momentum, etc.) of each individual
particle.
Macrostate:
a
more
generalized
description of the system; it can be in
terms of macroscopic quantities, such as P
and V, or it can be in terms of the number
of particles whose properties fall within a
given range. In general, each macrostate
contains a large number of microstates.
Entropy and probability
In 1896 Boltzmann discovered a relation
between entropy and probability. Boltzmann stated
from a simple idea that the equilibrium state of the
system is the state of maximum probability, ie., the
probability of the system in equilibrium state is
maximum. But from the thermo dynamical point of view
the equilibrium state of the system is the state of
maximum entropy. If the system is not in equilibrium,
then changes takes place within the system until the
equilibrium state or the state of maximum entropy is
reached. Thus in the equilibrium state both the entropy
and thermo dynamical probability have the maximum
values which led Boltzmann to expect the co-relation
between them.
According to Boltzmann, the relation between
entropy and probability is

S = k ln
Where S is the entropy, k is Boltzmann constant
and is the probability of the state.

The kinetic theory of gases attempts to explain

the microscopic properties of a gas in terms of the
motion of its molecules. The gas is assumed to
consist of a large number of identical, discrete
particles called molecules, a molecule being the
smallest unit having the same chemical properties as
the substance. Elements of kinetic theory were
developed by Maxwell, Boltzmann and Clausius
between 1860-1880s. Kinetic theories are available
for gas, solid as well as liquid. However, we will
discuss here about the kinetic theory of gases only.
Molecular Model of An Ideal Gas
A microscopic model of an ideal gas is developed
based on the following assumptions
1.

The number of molecules is large, and the

average separation between molecules is great
compared with their dimensions. This means that the
volume of the molecules is negligible when compared
with the volume of the container.

2.

The molecules obey Newton's law of motion,

but as a whole they move randomly. By "randomaly"
we means that any molecules can move in any
direction with equal probability. We also assume that
the distribution of speeds does not change in time,
despite the collisions between molecules. That is, at
any

given

moment,

certain

percentage

of

molecules move at high speeds, a certain percentage

move at low speeds, and a certain percentage move
at speeds intermediate between high and low.
3.

The molecules undergo elastic collisions with

each other and with the walls of the container. Thus,
in the collisions, both kinetic energy and momentum
are constant.

4.

The forces between molecules are negligible

except during a collisions. The forces between
molecules are short-range, so the molecules intract
with each other during collsions.

5.

The

gas

under

consideration

is

pure

substance. That is, all of its molecules are identical.

Distribution of Molecular Velocities in Direction
Let us imagine that to each molecule is attached with
a vector representing the magnitude and direction of
its velocity. When all these velocity vectors are
transferred to a common origin, we have a
distribution in velocity space (Fig.4.1). Now construct
a sphere of arbitrary radius r with its center at the
origin (Fig.4.2). The velocity vectors, extended if
necessary, intersect the surface of the sphere at as
many points as there are molecules. The average
number of these velocity points per unit area
is
. An element of area on the surface of
radius r in an arbitrary direction specified with
reference to a polar coordinate system by the angle
and (Fig 4.2) is given by
(4.1
)
Planer and Solid Angle

The number of molecules having velocities in

direction between and + 2 and also and +
d, which is denoted by d N , is
2

When we divide the two sides of the equation by

volume V and substitute n = N/V, we get
The magnitude of the molecular velocity is the speed.
Not all the molecules have the same speed. The
speed of the molecules can vary from zero to the
speed
of
light.
However,
for
mathematical
convenience, we will assume the molecular speed
varying from zero to infinity.