Statistical Basis And Classical statistics

Introduction
Statistical Basis:
 A study of thermodynamics gives us various macroscopic properties that are
related through an equation of state having only two independent parameters.
 However the equation of state can be deduced from the laws of thermodynamics.
 The ordinary laws of mechanics was only tool to explain physical phenomena,up to
end of 17 th century.
 In certain cases particularly where the system contains a large number of particles,
ordinary laws of mechanics could not be used as it is impossible to follow the motion
of each particles. for eg. A pinch of matter contains a very large no. of atoms or
26
molecules. (Avogadro's number N =6x10 per kg mole). Therefore, it is impossible to
apply ordinary laws of mechanics to a physical system containing large number of
particles, Particularly that of electrons. Such problems are however, successfully
solved by statistical mechanics. the larger is the number of particles in the physical
system considered, the more nearly correct are statistical prediction.
 Smaller the number of particles in a mechanical system, the statistical mechanics goes
on become meaningless. Before the advent of quantum theory, Maxwell, Boltzmann,
gibbs etc. Applied the statistical methods making the use of classical physics. These
methods are known as classical statistics or, Maxwell-Boltzmann statistics.
The classical statistics successfully explained the phenomenon like temperature, pressure,
energy etc., but failed to explain other observed phenomenon like black body radiation
specific heat at low temperature etc.
For this, new approach was introduced by Bose-Einstein, Fermi and Dirac. The Planck’s
quantum concept of discrete exchange of energy between systems was used.
The new statistics was subdivided into two categories (i) Bose-Einstein Statistics and (ii) Fermi-
Dirac statistics.
 Thus, there are three statistics depending upon three different kinds of particles:
1. Maxwell-Boltzmann statistics: This is applicable to the identical, distinguishable particles
of any spin. The molecules of a gas are the particles of this kind.
2. Bose-Einstein statistics: This is applicable to the identical, indistinguishable particles of zero
or integral spin. These particles are called bosons. The examples of bosons are helium atoms
at low temperature and the photons.
3. Fermi-Dirac statistics: This is applicable to the identical, indistinguishable particles of half
integral spin. These particles obey Pauli exclusion principle and are called fermions. The
examples of fermions are electrons, protons etc

Probability
The probability of an event may be defined as the ratio of the number of cases in which the
event occurs to the total number of cases.

Number of cases in which the event occurs

The probability = ------------------------------------------------
of an event Total number of cases

 Suppose an event can happen in a ways and fails to happen in b ways, then the
probability of happening the event = a/a+b and the probability of failing the event =

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 b/a+b . Here (a + b) represents the total number of equally likely possible ways. It
should be noted that the sum of these two probabilities is always 1; since the event
must either occur or fail.
 To evaluate the probability of random event, we consider a unit of measurement. An
event is called a ‘sure’ event if it Occurs in an experiment. Thus, the probability of a
‘sure’ event is assumed to be equal to 1 and that of impossible event to be equal to
zero. Thus, the probability P of a random event lies between 0 and 1,
O<P<1
This is further explained by the following experiments:
1, Throwing a coin: Suppose we toss a coin Either the ‘head’ can come upward or ‘tail i.e.an
event can occur in a total number of two equally likely ways. The number of ways in which the
‘head can come up is only one. Therefore, the probability that the ‘head’ may come up is 1/2.
Similarly, the probability that the ‘tail’ may come up is also 1/2
2.Throwing a die: A die is a homogeneous, regular and balanced cube with Six faces marked
numbers of dots from 1 to 6.
It is supposed that the die is symmetrical and cannot fall of its edges. When the die is thrown
it falls one of its faces upward i.e., yields one of the six results and no other. All outcomes are
equally likely in a single throw of dice. Out of six possible results only
one is favourable for the appearance of six spots. In other words, the probability of any one
face to come up is 1/6. The set of all possible outcomes can be written as S (1, 2, 3, 4, 5; 6).
The probability of the die coming up with an even number is 3/6 as there are only three even
number on the die 2,4 and 6.
P (even) = 3/6=1/2
the probability of the die coming up with odd number is 3/6=1/2
The probability of the die coming up with any number less than 6 is given by
P (a number <6) = 5/6
as there are five numbers 1, 2, 3, 4, 5 which are less than 6.

1.Zero Probability;-. If we want to know the probability of the die coming up with a face
marked with a number 7. The die has only six faces marked serially from 1 to 6. There is no
face marked as 7. Therefore, probability of appearing a number 7 is zero,
P (number 7)=0/6=0
- In other words, impossible event is always zero.
2.Probability one;-. The probability of appearing any number less than 7 is one. This is
because all the, six faces of the die are marked from 1 to 6, i.e., the numbers less than 7.
P (number <7) =6/6=1
3.Total probability:- If a is the number of cases in which an event occurs and b the number of
cases in which an event fails, then
a
. Probability of occurrence the event = -------
. a+b
And
b
. Probability of failing the event = -------
. a+b
The sum i.e., the total probability is always one, since the event may either occur or fail.
Principle of Equal A Priori Probability;

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  Suppose we toss a coin it is clear in mind that the coin will fall
either with its ‘Head’ up or ‘Tail’ up.
 Similarly if a six faced cubical dice is thrown, it is sure that the dice will fall with one
of its six faces upward.
 In the same way If we have an open box divided into two equal sized Compartments
X and Y (Fig.), and a small particle is thrown from a large distance in such a way that it
must fall in either of the two compartments,
 then the probability of the particle to fall in the compartment marked X is equal to
the probability that it may fall into the compartment marked Y, Again there is an equal
Probability,
 This principle of assuming equal probability
events which are equally likely to occur i s
known as the principle of equal a priori X Y
probability. fig
Probability and Frequency
 Suppose, the die is asymmetric by adding a little load (by wax) to one of its faces. Now
all the outcomes are not equally likely and we cannot say that the probability at
appearance of six spots is 1/6. For all such cases, we adopt a technique as under
 Suppose we toss a coin; say N times and we find that ‘Head’ appears M times. Here
we introduce a term frequency of an event F as
F No-of- trials in which Head occurs. _ M_
˭ Total number of trials ˭ N
 Thus, if a coin is tossed 50 time and in 10 of them the coin shows Heads, the frequency
of this event is 10/50 = 0.2. From the classical definitions of probability, the probability
of occurrence of ‘Head’ is 0.5 or 50%. Hence, we conclude that frequency is not the
same as probability. There must be a relationship between frequency and probability,
As the number of trials is increased, the frequency of the event progressively tends to
stabilize and gradually approaches a constant value, known as the probability of the
event. We define probability in terms of frequency as
𝑀
. P= lim ( 𝑁 )
𝑁→∞

 Thus in order to obtain sufficiently accurate result, trials must be conducted until the
ratios M/N differ from one another by very small value.
Some Basic Rules of Probability Theory
Additive Law of Probability
 This is applicable to mutually exclusive events. Two or more events are said to be
mutually exclusive if the occurrence of any one of them prevents the occurrence of
others. Such events never occurs simultaneously.
 For example, consider two small non-overlapping region ΔV₁ and ΔV₂ in a box of
volume V as shown in (Fig.). A particle in ΔV₁ rules out the possibility of its being
present, at the same instant in ΔV₂ and vice versa. The two events, thus, are mutually
exclusive.

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  Suppose in N trials the particle is found m₁ times in ΔV₁ and m₂ times in ΔV₂. The
probabilities of finding particles in the two regions are ,
p₁= m₁ /N and p₂= m₂ /N
respectively
The number of times that the particle will be found at least one of the two regions in N trials
is(m₁ + m₂ ). Hence, the probability will be
P (ΔV₁ or ΔV₂) = m₁ + m₂ / N = m₁ /N + m₂ /N = p₁ + p₂
 This law can be generalized to any number of mutually exclusive events, giving
probabilities say p₁, p₂, p₃..... pn then the probability that any one of them occurs is
the sum of the probability of these event
P = p₁+ p₂+ p₃+....+ pn = ∑𝑛𝑖=1 𝑝i
This is known as additive law of probability
EXAMPLE
A card is drawn from a well shuffled pack of 52 cards. Calculate. the probability for this card
to be either a king or a queen.
SOLUTION.
We are taking out one card out of 52 cards of pack. So the total number ways in Which
the event can occur is, N= 52.
But we want to draw a specific card i.e. king. There are 4 kings in a pack of cards. Therefore,
the number of ways favourable to the first event, m₁ = 4
.᾽. Probability of drawing a king, p₁= m₁ /N =4/52 =1/13
The number of ways in which second event i.e. drawing a queen may happen, m₂ = 4, as there
are four queens too.
.᾽. Probability of drawing a queen, p₂ = m₂ /N = 4/52 = 1/13
Both the events are mutually exclusive. Therefore the probability that the card drawn is
either a king or a queen is P = p₁+ p₂ = 1/13 + 1/13 = 2/13

Multiplication Rule: Joint Probability

 In the calculations of probabilities, we sometimes come across random events; such
that the probability of occurrence of one does not affect the probability of occurrence
of the other.
 For example in fig. the probability that a molecule A gets into ΔV₁ ,at a particular instant
is p₁ = ΔV₁/V the probability that another molecule gets into volume ΔV₂ at the same
instant is p₂ = ΔV₂/V regardless of whether or not the molecule A gets into ΔV₁ , We
want to calculate the probability of joint occurrence of these events, i e., the
probability of A getting into ΔV₁ and B getting into ΔV₂ at the same instant.
 Suppose in N trials, the molecule A is found m times in ΔV₁ . If p₂ is the probability that
B gets into ΔV₂, irrespective of the presence of A in ΔV₁ ,the number of times the two
events will occur simultaneously is m p₂ .Thus, the joint probability of occurrence of
these two events, is
P = m p₂ /N
= m /N x p₂
P = p₁ x p₂ (p₁ = m /N)
 Thus, probability of joint occurence of two independent events is equal to the product
of the probabilities of each of these independent events.

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Conditional Probability
 The probability for an event A to occur the condition that event B has occurred is called
the conditional probability and is denoted by P (A/B).
This can be better understood by the following numerical.
Example
We throw a die twice and obtain two numbers. What is the probability that these.
numbers are 6 and 4 precisely in that order?
SOLUTION.
The probability that the first throw gives a 6 is 1/6.
Similarly, the probability that second throw gives a 4 is also 1/6
these two events are independent.
Required probability = 1/6 x1/6 =1/36
Example; -
An urn contains 4 black and 3 white balls, What is the probability that on two
successive draws, the balls drawn are both black ?
SOLUTION.
Suppose the first ball drawn is black. Let the event be called as A. Its probability is
P( A) = 4/4+3 = 4/7 This event is followed by second event B in which the second ball drawn is
also black (conditional). Since an event A is already realized, the balls remained are 3 black
and 3 white out of which the event B is taking place, i.e. second ball out of 6 balls. Hence, the
probability of the event B to occur under the condition that A has already realized is P(B/A) =
3/3+3 = 3/6 =1/2
The first event thus has an effect on the probability of the second event:
The probability of the composite event (A + B) is
P(A+B) = P(A). P(B/A) = 4/7 x 1/2 =2/7
Permutations and Combinations
 permutations: The word permutation means arrangement and combination means
formation of groups. To understand the meaning of permutation i.e. arrangement,
let us consider an example of four distinguishable objects marked a, b, c and d. Taking any two
objects at a time, the possible arrangements are
ab, ba, ac, ca, ad, da, bc, cb, bd, db, cd, dc.
 There are total 12 arrangements possible. In arranging these objects the order of their
placing is also taken into consideration. Thus, ab and ba are two different
permutations. Thus, 4 objects can be arranged in 12 ways by taking 2 objects at a time,
i.e. the number of permutations is 12.
4
Symbolically, p2= 12
 Instead, if 3 objects are taken at a time out of 4 objects a, b, c and d the various
arrangements are
abc abd acd bcd
acb adb ade bdc
bca bad cda cbd
bac bda cad cdb
cab dab dac dbc .
cba dba dca dcb
 Thus, 4 objects can be arranged in 24 different ways by taking 3 at a time out of 4
4
objects. Symbolically, p2= 24

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In general, the number of arrangements of n distinguishable objects by taking r at a time is
given by
n
pr = n ᴉ/(n-r) ᴉ .......(1)
4
p2 = 4ᴉ/(4-2) ᴉ = 4ᴉ/2ᴉ = 4x3x2x1 / 2x1 = 12
4
p3 = 4ᴉ/(4-3) ᴉ = 4ᴉ/1ᴉ = 4x3x2x1 / 1 = 24
This includes all types of arrangements, meaningful as well as meaningless.
Combinations: Here we consider only combinations i.e. groups without considering the
order of their placement i.e. only meaningful combinations. Thus, the combinations of 4
objects a, b, c and d taking two at a time are
ab, ac, ad, bc, bd, cd
4
i.e. only 6 combinations. Symbolically, C2 = 6 .
 Similarly, combinations of 4 objects a, b, c and d taking three at a time are
abc, abd, acd, bcd
4
i.e. only 4 combinations. Symbolically, C3 = 4
In general, the number of groups i.e. meaningful combinations of n distinguishable by
taking r at a time is given by
n
Cr = n!/r!(n-r)! .........(2)
n
pr = n ᴉ/(n-r) ᴉ
n n
Cr = Pr/r!
n n
Pr = r! Cr
n
from equation 1 pn = n ᴉ/(n-n) ᴉ = n ᴉ/ 0 ᴉ = n ᴉ (0 ᴉ =1)
n
from equation 2 Cn = n!/n!(n-n)! = n!/n!(0)! = 1
Macrostate and Microstate
 Macrostate: Consider 4 distinguishable particles and we wish to distribute them into
two exactly similar compartments in an open box. Let the particles be a, b, c and d.
When any particle thrown into the box, it must fall into one of the two compartments.
Since the compartments are alike, the particles have the same a priori probability of
going into either of them and will be ½. The possible ways in which 4 particles can be
distributed in two compartments as shown in table
Compartment NO. of particles

Distribution Distribution Distribution Distribution4 Distribution

1 2 3 5
1 0 1 2 3 4

2 4 3 2 1 0

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Thus, there are 5 different distribution (0, 4), (1, 3), (2, 2), (3, 1) and (4, 0). Each
compartmentwise distribution of system of particles is known as macrostate
In general, for a system of n particles to be distributed in two similar compartment, the
various macrostates are (0, n), (1, n -1),(2, n- 2),...... (n-1,1) and (n, 0)
Therefore, the total no. of macrostates n particles is (n+1).

Microstates: Since the particles are distinguishable, the number of different possible
arrangements in each compartment is shown below
Macrostate Possible arrangemtents No. Of microstates W
(Thermodynamics
Compartment 1 Compartment 2
probability)
0,4 0 Abcd 1
1,3 A bcd 4
b cda
c dab
d abc
2,2 Ab cd 6
ac bd
ad bc
bc ad
bd ac
cd ab
3,1 Bcd a 4
cda b
dab c
abc d
4,0 Abcd 0 1
Each distinct arrangement is known as the microstate of the system. The distribution (0, 4)
can have only one arrangement, distribution (1, 3) can have 4 distinct arrangements,
distribution (2, 2) can have 6, distribution (3, 1) have 4 and distribution (4, 0) have only one.
Thus, a given macrostate may consists of a number of microstates. In the above example of 4
particles, the total number of microstates are 16 = 2⁴. In general, for a system of n particles,
the total number of microstates are 2ⁿ.
 Suppose we consider a thermodynamic system of N identical, non-interacting particles
occupying a volume V. Let E₁, E₂, E₃, ....... Eᵢ be the energy of particles n₁, n₂, n₃...... nᵢ
respectively then, total energy of the system, E = n ₁ E₁+n ₂ E ₂ + .......+nᵢEᵢ
=∑ nᵢEᵢ and N= ∑ nᵢ
 According to quantum theory, the possible values of energy of each particle are
discrete and hence the total energy E also has a discrete value. But when the volume
V is very large, the spacings of different energy levels are so small in comparison with
total energy of the system that E may be regarded as almost continuous.

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  The actual values of parameters N, V and E defines a particular macrostate (N, V, E)
of the given system. There are a large number of different ways in which the individual
Ei’s can be chosen, so as to Make total energy equal to E. _
 Each of the different ways in which the total energy E of the system can be distributed
among N Particles constituting it specifies a microstate. Thus, a given macrostate
corresponds to many “microstates and it is very natural to assume that at any time the
system is equally likely to be in any of these microstate.

Phase Space
The three dimensional space in which the location of the particle is completely specified by
the three position coordinates(dx,dy,dz) is known as the position space. A small volume
element in the position space is given by: dV = dx dy dz
Similarly, The three dimensional space in which the momentum of the particle is completely
specified by the three momentum coordinates(dpx, dpy , dpz,) is known as the momentum
space.
A small volume element Γ in the momentum space is given by:
d Γ = dp dp dp
x y z
A combination of position space and momentum space is known as phase space. A small
volume in phase space is given by:
dτ= dx dy dz dp dp dp
x y z
i.e. dτ= dV d Γ
Thus a volume element dτ in phase space is the product of a volume element dV in position
space and volume element d Γ in momentum space.

Cells in Phase Space:

The small volume dτ in phase space is called a cell.
The total no. of cells in phase space is given by:

.
Thermodynamic Probability
 The number of microstates corresponding to any given macrostate is called its
thermodynamic probability.
 In other words, the thermodynamic propability of a particular macrostate ls defined
as
 the number of microstates corresponding to that macrostate. In general, this is a very
large number and is represented by W (or Ώ)
 The number of microstates corresponding to a given macrostate 1s equal to the
number of meaningful arrangements or permutations of various particles in the
macrostate excluding those permutations which are meaningless i.e. merely
interchange the order of particles in a particular compartment (or cell). For the case
of n particles and two compartments (or cells), if r 5 the number of particles in the
compartment No. 1 and the remaining (n-r) are in compartment No. 2, then
No. of meaningful arrangements = n! /r! (n-r)!
n
= Cr

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Therefore, the number of microstates in a macrostate (r, n -r) or thermodynamic probability
n
W(r,n-r) = n! /r! (n - r)! = C r ………….(1)
Applying this to a system of 4 distinguishable particles, for a macrostate (1, 3), r= 1, (n-r) =3
and n = 4 the number of microstates.
ῼ(1, 3) or W(1,3) = 4! /1!3! =4
Similarly, for a macrostate (2, 2), r= 2,(n- r) = 2 and n = 4 the thermodynamic probability ie.
no. of microstates will be
W(2,2) = 4! /2!2! =6
and for macrostate (0, 4) or (4, 0) will be
W(0,4) = W(0,4) = 4! /0!4!= 4! /4!=1 (0!=1)
This agrees with the above table
Probability (P).
The probability (or occurrence) of a macrostate is defined as the ratio of the number of
microstates (i.e. thermodynamic probability W) in it to the total number of possible
microstates of the system.
Thus, Pmacro = No. of microstates in the macrostate
Total no. of microstates of the system ………..(2)
The total number of ways of arranging n distinguishable particles in c numbered
n
compartments = c
If there are only 2 compartments or cells, then the total no. of microstates.of the system
n 4
= 2 .For 4 particles system, total no. of microstates will be 2 = 16. From equation (2) we get.
n n
Pmacro =W/ c =W/ 2
Substituting for W from equation (1),
n n n
P(r,n-r) = n! /r! (n-r)! x 1/ 2 =1/ 2 Cr
This gives the probability (of occurrence) of macrostate (r, n-r).
combination Possessing Maximum Probability
n
We know from elementary algebra that if n is even the value of C r is maximum (greatest)
when r=n/2refer table 9.2. Hence the maximum value of probability is given by
n n n
Pmax =1/ 2 C n/2 = n! /(n/2) ! (n/2) ! x 1/ 2

2 n
= n! /[(n/2) !] x 1/ 2
combination Possessing Minimum Probability
n
We know from elementary algebra that C n is minimum, if r is equal to either zero or n.
If r =0, the probability is
n
Pmin = n! /r! (n-r)! x 1/ 2
n
= n! / 0!(n- 0)! x 1/ 2 (0!=1)
n
= 1/ 2 …….(i)
If r=n, the probability is
n
Pmin = n! /r! (n-r)! x 1/ 2

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 n
= n! /n! (n-n)! x 1/ 2
n
= n! /n! 0! x 1/ 2 (0!=1)
n
= 1/ 2 …….(ii)
Thus, from (i) and (ii), we conclude that the minimum probability is given by
n
Pmin = 1/ 2
Relation between P and W
The probability of occurrence of a particular microstate is given by
n
P = 1/ 2
n
because 2 gives the total no. of microstates of a system of n particles to be arranged in two
compartments (or cells) and all the microstates of a system have a priori probability.
P=Wxp
= No. of microstates in the macrostate x probability of
ccurrence o of a microstate
or PὰW
Therefore the probability (of occurrence ) of macrostate (P) is directly proportional to the
thermodynamics probability (W)
Division of compartments in to cells:
 In practice, if we wish to distribute n distinguishable particles in k compartments which
are of unequal size, we find that the a priori probability of a particle going into a
particular compartment is not the same. Large probability in a bigger compartment.
This is because of unequal size of the compartment. This difficulty is over come by
introducing the concept of a cell.
 Each compartment is divided into a very large number of sub-compartments, called
as cells, in such a way that each cell is of the same size. Therefore, all the cells have
the same a priori probability. The size of the cell is very very small and hence the
number of cells in each compartment is exceedingly large. For a given size of the cell,
the number of cells in each compartment is fixed.
Distribution of particles
(in compartments of unequal size)
The concept of a cell is well understood by considering the distribution of particles in different
compartments marked as 1, 2, 3, -- i... K-1, k of unequal size (Fig. ) We wish to distribute n
distinguishable particles in these k compartments. As the compartments are of unequal size,
a priori probability of a particle going into particular compartment is not the same. To
overcome this difficulty we introduce a concept of a cell. For this purpose we divide each
compartment, from compartment 1 to k, into cells of equal sizes, so that compartment 1
contains g1 cells, compartment 2 contain, g2 cell compartment 3 contains g3 cells and so
th th
on, the i compartment containing gi Cells and lastly k compartment has gk cells.
as the compartments are of unequal size, the number of cells in each compartment will be
different. The total number of cells, each of same size = g1 + g2+.......+ gi +..... gk = G
Hence.
(i) Since all the cells are of same size, there is an equal a priori probability i.e. a particle in a
given compartment can go into any cell within the compartment with equal probability.

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