m

& mm

m)

Chapter

Maxwell-Boltzmann

11(c).1. PHASE SPACE

Consider a static system in which n particles are distributed in volume V. In static system the
particles are at rest and hence at fixed positions. In a three dimensional space the position of a
particle can be determined by three position co-ordinates {x, y, z), such a space is called Position
Space. If the system consists of n particles then we can get a complete information about this static
system if we know 3n co-ordinates.

In case of a dynamic system, the particles are in motion. They are moving with different
velocities and hence have linear momentum. In a three dimensional space the momentum of a particle
can be determined by three momentum co-ordinates (pv, Py, pz), such a space is called momentum
space. In order to have a complete knowledge about the position and momentum of a particle at any
instant we need its three position coordiinates (x, y, z) and three momentum co-ordinates (pv py p-L)
(i.e. total six co-ordinates) in such a space is called phase space.

Thus a Phase space is a combination of Position space and Momentum space. It is a six
dimensional space. If a dynamic system consists of n particles we need 6n co-ordinates in Phase
space for a complete information about the position and momentum of its particles at any instant.

POINT TO REMEMBER
The concept of Phase space was developed in late 19th century by Ludwig Boltzmann,
Henri Poincare and Joseph Gibbs

11(c).2. DIVISION OF PHASE SPACE INTO ELEMENTARY CELLS

Consider certain volume t of a dynamic system in phase space. The volume of this system in
Position space (V) is determined by minimum and maximum values of position co-ordinates {x, y, z).
 74
Statistical Mechaiiics

Similarly volume of this system in momentum space (F) is determined by the minimum and maxinm
values of momentum co-ordinates (px, py, pz). The volume available in Phase Space (x) is eqUaj ^
the product of volume in position space (V) and volume in momentum space (F)

T = Vr
-(Uc)^
Let this volume x of dynamic system in phase space is divided into large number of compartments
Each compartment has a particular volume. Consider these compartments are further divided into
very large number of elementary cells of equal volume.

Consider an elementary cell. Let the position co-ordinates of the elementary cell varies from
v to x + dx, y to y + dy and z to ^ + dz.
Let the momentum coordinates of the cell varies from px to px + dpx, pv to pv + dpv and dn
to dz + dpz. y y y ri
The volume of elementary cell in position space

dN = dx dy dz ...(l(c).60)
Volume of elementary cell in momentum space

dT = dpx dpy dpz ...(1(c).61)

.••Volume of elementary cell in phase space

dx = dV x dT (using eqn. l(c).60 & l(c).61)

dx - dx dy dz dpx dpy dpz = hQ (say) ...(1(c).62)
In classical mechanics the volume of elementary cell (i.e. h0) can be as small as we like. It
can be even taken as a point in phase space (i.e. hQ can be even taken as zero).
But in the Quantum mehanics the choice of value of h0 is not in our hand. We can not take
h0 as small as we like. Because in Quantum mechanics according to Heisenberg's Uncertainty
Principle both the position and momentum of a particle can not be simultaneously measured with
accuracy.
According to this Principle
dx dpx > h ...(1(c).63)
where h is Planck's constant. The value of h = 6.6256 x KF27 ergs.sec.
Similarly
dy dpy > h ^ (1(c).64)

dz h
^ " ...(l(c).65)
Multiplying eqn. (l(c).45), (l(c).46) and (l(c),47)
Volume of eletermentary cell

dx = dx dy dz dpx dpy dpz > h3

7)
(h- - 2.9 x 10 erg3-sec3, which is very small quantity.)
Total number of cells in phase space

_TotaI volume in phase space \dx\dy\dz\dpx\dpv\dp.

_
Vol. of an elementary cell

\\\dx dy dz\\\dpx dpy dpz

dx
 Maxwell-Boltzmann Distribution Law
75

vr
Total nos. of cells in phase space ...(1(c).66)
(k

In classical mechanics the volume ol dx - which can even approach zero. But in Quantum
y
mechanics dx = h where h is Planck's constant.

11(c).3. THREE KINDS O STATISTICS

Statistical mechanics deals with the study of some average or most probably properties of
a system consisting ol laige numbei of electrons, atoms, molecules, photons etc. Statistical mechanics
can be divided into two types.
1. Classical Statistics or Maxwell Boltzmann Statistics.

2. Quantum Statistics.

1. Classical Statistics

In classical statistics the particles of the system are distinguishable. The volume (or size) of an

elementary phase space cell (/iq) can be made as small as we please. Hence the available number

of cells in phase space can be made as large as we like. There is no restriction on the number of
particles going into cell. Each particle has equal priori probability of going into any cell.

Let /ij are the number of particles and are the number of cells of ith compartment of the
system.

Since g;- can be made as large as we like.

Then gi » ni

k Hi
— « 1 where — is called occupation index.

Since we can choose the size of the elementary cell as small we like hence nos. of cells are
very large as compared to number of particles. Hence probability of a particular cell to contain more
than one particle can be neglected.

Quantum statistics can be further divided into two types

(I) Bose-Einstein statistics (B. E. Statistics)
(II) Fermi-Dirac statistics (F. D. statistics)
101
(') Bose-Einsteln Statistics

Einstein
an ele* statistics particles of the system are indistinguishable. The volume (or size) of
16111517 0611 in phaSe SpaCe Can n0t be leSS than h3 where h is Planck,s
numb" constant. Hence total
61 0f elementary cells in hase s ace can not be made
ityl on the P P large as we like. There is no restriction
riUrnber
0r c of particles going to any cell. In this case the number of elementary cells is less than
oiparable to the number of particles.

tbe number 0
Then 1 n I particles and g;- are the number of elementary cells of ith compartment.
B.E. statistics

gi ^ nt
 76
Statistical Mechanic
Hi

Occupation index is greater than or equal to one

Statistics

I i
Classical Quantum Statistics
-
Statistics J "
Bose-Einstein Fermi Dirac
/nx ^ Statistics Statistics
(il) Fermi-Dirac Statistics

an eleniemarv ''f5''08 PartiCleS 0f lhe SyStem

^ indistin uish
g able. The volume (or size) of
m SPaCe Can n0t be leSS thai1 h3 where h is planck s
nos of ele^ n ' constant. Hence total
3 7 Can n 0t made lar8e 38 We ike TheSe parlicll5s obey Pauli
Principle Hence " T , ^ ' ' delusion
Part K Can 0CCUpy the Same ceIL In this case nllmber of cells
vreater
&reater or CO ^ ? T u
equal to the number of particles. "as to be

If n; are the number of particles and gj are the number of cells in the compartment, then in this
case

Si ^ «/
n
i
or — < 1
Si -
or occupation index is less than or equal to 1.

The particles which obey Fermi Dirac statistics are called Fermions. For examples electrons,
protons, neutrons etc.

These particles have half integral spin.

ll£<h-4. MAXWELL BOLTZMANN DISTRIBUTION

(Applied to an Ideal Gas in Equilibrium State)

Let n number of molecules are enclosed in an isolated vessel of volume V. These molecule?
are in random motions with different velocities hence they possess different momentum and energies
During their random motions, the molecules are colliding with one another and with walls of the
vessel. Therefore their momentum and energies are continuously changing. Since the gas is thennallv
isolated hence its total energy U remains constant.

In this case the gas remains in equillibrium state or most probable macrostate. We are interestec
in the energy distribution of these n molecules in the most probable macrostate.

Let total energy u of the ideal gas is divided into k intervals. This is similar as n molecules are
to be distributed in k compartments.
w ll aie
Let tq, wg' 3' k ^ie nie ,n
' energies ol intervals (compartments) I, 2, 3, ^
respectively.
 Maxwell-Boltzmann Distribution Law 77

I 1 1 1 1 H 1 1 1 1 1 1
l
ui "2 h "4

Let Hi, 112, 113, are the number of molecules of intervals (compartments) 1, 2, 3, k
respectively.

Let these compartments (intervals) are further divided into large number of elementary cells
each of equal size.
are
Let gj, g2' £3 Sk number of elementary cells of compartments (integrals) 1, 2, 3,
4, k respectively. This problem is like distribution of n molecules into k compartments of unequal
size which are further divided into large number of elementary cells each of equal size.
Let n; are number of molecules and gj are the number of cells of ith interval (compartment).

We know that the thermodynamic probability of most probable macrostate (n^ n2, n3, nk) is
given by

w
(«!' "2^ n3, nk) = n! ^ ^y-

Taking logarthm both sides.

k k
In W = In n! + Ing, - ^In im ! ...(l(c).67)

Assuming that n and n; are very large numbers hence by using Stirling's eq. (1(c).67) reduces to
k k
In W = n In n - n + 2X' ln gi - In ry - ry)
i=l i=l
k k k
= n In n - n + 2"/ In^/- S("( In ry) + Ypi
1=1 /=i 1=1
k k k
- 11 In n — n + Il'V Ing/ - 2/?/ In n, + n ( Tni - n\
v ;
/=i /=i - i=i
k k
In W = n In n + 2^ Ing, - In ty •(1(c).68)
/=1 i=l
Since n and gj are constants.

Differentiating both sides of eq. (l(c).27)

k A' Ic ^
dlnW = 0 + ^dn, In gj - ^diy In ty - %y ~ dry
1=1 (=1 ;=1 ni
k k k
= ^Zdry In gi - Y.d'y In ty -
i=l (=1 f=l
k k k
= ^Zdrylngi - ^diy In ty - 0 . ^dty = 0)
i=i
k k
= Yjdty In gi - ^diy In ty
i=\ i=l
 78
Statistical MechatiiCs

dlnW = X(ln^,—In/?,) dty

i=l •••(l(c).69)
For most probable macrostate, thermodynamrc probability is maximum,
i.e. W = W
max
Hence d In W = 0

Applying conditions that total number of molecule („) and total energy (U) of the system ^
constant,

i.e. n - = constant
i=i
k
or
dn = Yjdrii = Q
i=i
k
i.e. = o
i=l ...(1(c).71]
k
U = = constant
i=l
k
or dU = = o
i=i
k
i.e. *2jUi dni = o
=1
'■ ■•-(1(c).72)
Mutipllying eq. a(c).71) by a and eq. (l(c).72) by fS and subbract them from eq. (l(c).54)

dlnW - ^adni - dr* = 0

1=1 i=i
k k k
.2(in gi ~ In ry) diy — ^adry - diy , .
i=i
'=, i=l
-■ •i=l- (using eq. 3.69)
k
2(ln gi - In - a-fiuMri: = n
-i -.(l(c).73)
As drii are independent variables hence eq (5 73) win hf- i -f i.
q P 111 be Valld 0nl lf the
bracket is zero. ' ^ y quantity ^side the
In gi - In «• - a - (3 m(. = 0

gi
In ry - a - p M(. = o

In OC + p 11 j
yryj

gi
or ~ = ea+P*

Hi gi
or a or
gi e +P"i e<*+P"i

gi
or "i - ...(3.74
Maxwell-Boltzmann Distribution Law 79

This result is known as Maxwell Boltzmaun's law of energy distribution. Here ~ is

called occupation index i.e. number ol molecules per phase space cell.
IV
In Maxwell Boltzmaun's Distribution the value of — « 1.
§i
Here a and (3 aie constants yet to be determined. To find the values of a and p let us assume
a continuous distribution of energy of the molecules rather than discrete energies Mj, U2, u^, ... Uj, etc.
Let the number of molecules in the unit energy interval around u i.e. (in energy interval

u - \ and u + -^) is n (w)

Then eq. (5.33) becomes

n {u) = g {u) e-v- g-P" ...(1(c).75)

Where g (u) are number of phase space cell in the unit energy interval around u.

Let mass of a molecule = m

velocity of molecule = v

Then momentum of the molecule p = mv

Kinetic energy of molecule u = ^ mv2

_ m2v2 _ (mv)2
u =
2m 2m

.2
P u =
2m ...(l(c).76)
Putting this value in eq. (3.75)

-Pp2
n (P) - g if) e""
e 2m ^
Where n (p) are the number of molecules and g (p) the number of cells
m unit momentum
interval fn---L> ancl, , 1
y
i 2* (p+w)J XI71
with f V-* mean momentum
1 p.

Thee number of molecules in the momentum interval dp ie between p and (p + dp) is given by

-ftp2
n d 2m
u/u P = 8 (p) e-v e dp noo™
Where p r \
W dp are the number of
(P + dp) Phase space cells in the momentum interval p to

et
volume of a phase space cell = h]

Then

Sip) dp -Iglume in phase space in momentum interval p to p+dp

Volume of a phase space cell
I 80 Statistical Mechanic

\\\\l\dx dy dz dpx dpy dpi JJ^/x dy dz \i\dpx dpy dpz

g (P) dp = ^ = hi

VJJ\dpx dpy dpz ,1/N_

g (p) dp = —j -(l(c).79)

(Where V = \\\dx dy dz = vol. of gas in position space)

Let us determine the value of

Widpx dpy dpz

Assume three mutually perpendicular axes px, py and pz intersecting at origin O. Draw a
sphere or radius p with origin O as the centre. Then all the points on the sphere will correspond to
momentum p.
Now draw another concentric sphere with radius p + dp.
Then volume unclosed between momentum interval p ivo p + dp is equal to volume of shell
enclosed between two spheres.
Volume of molecules Vol. of sphere with Vol. of sphere with
with momentum = raduis p + dp — radius p
between p and p + dp

\\\dpx dpy dpz = ^ (p + dp)3 - ~p3

= "y [(P + d
P? - P3]
A-jt
= "3- [(P3 + dp3 + 3pdp (p + dp) - p3]

Ajt
= -3- [(p3 + dp3 + 3p2dp + 3pdp2 - p3]

Aoz
jjjdpx dpy dpz = — [3p2dp + 3pdp2 + dp3] ...(1(c).80)

Because dp is small therefore dp2 and dp3 are very small. Hence tenns containing dp2 and
dp3 can be neglected.
eq. (1(c).80) becomes

jjjdpx dpy dpz = -j- x 3p2dp

IWdpx dpy dpz = 4jtp2dp

Putting this value in eq. (l(c).79) we get
Ajt
S(p) dp = p* V dp ...(l(c).81)

Putting this value of g(p) dp in eq. (l(c).78)

4jr/r
n (p) dp = -jJ-Vr" e ^ dp (3,S2)
Maxweli-Boltzmann Distribution Law 81

Evaluation of a and /]

Let these molecules under consideration have momentum ranging from 0 to pmax (say).
Hence total number of molecules of the gas are given by

n = j/i (/?) dp
o

= j4^iVe-a zM
2m dp (using eq. 1(c).82)
J
0 /to

-Pp1
4jrV 2 i
n = " ...(l(c).83)
l? 3 e
o
Using standard integral
CO

_ i IK
1 4 Va3

^£1
2//)
Hence Jp2e' ^ =i , r/5
2/7?

Putting this value in eq. (1(c).83)

4;t 1 JZ
n = —r V e_a x —
W
llQ 4 S o\3
£
2m
i
-a
Ve
n =
ho

nho' p y*2
a
Therefore p~
e
= yTjinij ...(1(c).84)
V
Putting this value in eq. (1(c).82)

471 p nh
B -PP1
n (p) dp = —3- y o o 2m dp
'X> V

f R ^V2
P 2 —
n (p) dp = fan p1 e 2," dp ...(1(c).85)

We know that

u = IL
2m
p- = 2mu .(l(c).86)
Differentiating this equation.
 82 Statistical MechaniCs

2p dp = 2m du

in
dp = — du

m
dp = du (using eq. l(c).86)
J2mu

m
dp = du "•(Uc).46)

Putting the values from eqs. (l(c).86) and (l(c).87) in eq. (l(c).85)

3/2 -8(2™]
p
we get n (u) du = 4jtn 0 I 2/« ) m ,
2jim 2mu e x ,/— du
V 2u

2n
n (u) du = p3/2 mV2 e-P" du ...(1(c).88)

This equation gives the number of molecules having energy between u to u + du.

Therefore total energy {u) of the system consisting of n molecules

U = n(u) du
d
00
2n
J
djl

2n
U = u^t-e-du
4n ...(l(c).89)

Using standard integral

00
Ja:3/2
0 Aa2 Ma
CO
3 ht
ju^^du
2
4/3 V/3

Putting this value is eq. (3.89)

2ii JT
U
= X ^ X 4ft 2
ift
3n
U =
2ft ...(1(c).90)
According to law of equipartition of energy (he average kinetic energy per molecule of gas at

absolute temperature T = ^kT where k is boltzmann's constant.

 83
Maxwell-Boltzmann Distribution Law

Hence total energy of system of n molecules

U nkT
2
2" 3
= 11
(using eq. l(c).91)
Tfi 2

= kT
P

■ .••(1(c).91)
or ^ =T
kT
Putting this value in eq. (5.44)

' i V/2 ~p2

n (p) dp = fan ...(l(c).92)
J p2 ^ d
P

p2
•\/2^:n
n {p) dp = 2 ...(1(c).93)
3/2 P dp
(jimkT)

This equation gives the number of molecules of gas having momentum between p and p + dp
known as.

Maxwell-Boltzmann distribution law of momenta

1
Now puttin /5 = yrp in eq. (l(c).47)
kT

r \3/2
2n
n (u) du = 1
UV e-
l,lkt
du

Inn
or n (u) du — (^-p)^2 e du ...(l(c).94)

This equation gives the number of molecules having energy between u and u + du of an ideal
gas at absolute temp. T and is called the Maxwell-Boltzmann distribution law of energies.

We know that

p = tnw (Where v = velocity)

Differentiating

dp - mdv
Putting these values in eq. (1(c).92) we get

\V2 9 9
1 nrv~
n (v) dv = ^nn m v 2 2
pimki x mdv
TjtmkT

m P2 "iv2
n (v) dv = 4^ v2
2kT dv ...(l(c).95)
e
IxckT J
 84 Statistical Mechanjt

This equation represents the number of molecules having velocities between v

v + of an ideal gas at absolute temp T and is known as Maxwell Boltzmann law of distrib
'Utio,
of moleculer speeds.

1(c).5. GRAPHICAL REPRESENTATION OF MAXWELL

BOLTZMANN'S SPEED DISTRIBUTION
I
According to Maxwell's Boltzmann's law of speed distribution
2
z \^
m
* -my
n (v) dv = ^ 2 2kT
-T v e d\
MT)

\d2 -mw
m
n (v) = fan V2 p 2kJ •••(l(c).96)
InkT
/
\3/2
n(v) m *
or v2 e 2kT
n ~ 4jr
2jtkT ...(l(c).97)
Let us denote

«(v)
n - f which is fraction of number of molecules having velocity v.

• • Eq. (1(c).97) becomes

\2J2 2
m Y -mv
2
f - An TjikT j Y e ...(l(c).98)
If we plot a graph between f and v at different absolute temperatures, it will be shown below
m Fig. l(c).l.

T<T
h 1 •N
r

V,

^ ^ vmp'
Vm
P Vav vrrns

Fig. 1(c).1.

Following informations arc drawn from (his graph.

1. Area under the curve is proportional to (he nos. of molecules.

Maxwell-Boltzmann Distribution Law

2. Peak ol the curves represents most probable speed vnip. This most probable speed increases
with increase of absolute temp. T

i.e. vmp' < vmp

3. Speed of molecules varies from 0 to oo.

-mv2
2kJ
4. At N'ery high speed the term e dominates the distribution of speeds which falls to zero.

5. At small values of speed mv /2fcT->0 i.e. e0 = 1

f oc v2 hence curve rises parabolically.

6. Since the area of curve on right hand side of most probable speed v^ is greater. Hence
average speed of molecules vav is larger than vmp.

1(c).6. EXPRESSIONS FOR (I) MOST PROBABLE SPEED

(11) AVERAGE SPEED AND (III) R.M.S SPEED
I

(i) Most Probable Speed

We know that number of molecules of an ideal gas having speed between v and v + dv
3/2
—//IV
m
n (v) dv = 4^ v2 e 2KT
dv (using eq. (l(c).95)
InkT
Hence probability that molecules possess speed between v and v + dv
n (v) dv
P (v) dv =
n
3/2
m —mv
P (v) dv = 4^ v2 e 2kl:
dv
y27tkT j
3/2
m -mv
P (v) = 4jr v2 e 2kJ ...(l(c).99)
InkT^]
This equation gives the probability that molecules will passess speed v.

—mv
P (v) =c v2 e 2 T
^ .(1(c).100)
m
Where c = to = constant at a given temp. T.
2jikT

Differentiating w.r.l. v

aP(v)
= c 2ve + v2e x -2mv
dv Ik! 2kT Ik!

3P(v) —mv —mv

= ce 2kr + 2v ...(l(c).101)
dv kT
At most probable speed i.e. v = v
mp
 86
Statistical Mechanic

ap(v)
= 0
d\
.".Eq. (1(c). 101) becomes
2
-mvnip
mv
ce 2kT 2vmp - '"P
= 0
kT

or my
2v _ '"P = 0
mp

2"
mV n
or mp 2 _ ' P
kT = 0

mv m
or 2 — P = 0
kT
mv mp
= 2
kT

2 _ 2kT
mp
m

2kT
v mp= ...(l(c).102)
m

This is the expression of most probable speed,

(ii) Average Speed (vav)

Average speed of gas molecules is defined as

00
Jvn (v) dv

V —
av oo .(1(c).103)
\n (v) dv

We know that nos. of molecules having of speed between v and v + dv is given by

^3/2
m
n (v) dv = 4xn ( '2 ^-mVllk'V dv (using l(c).95)

CO

Also jn (v) dv = n
o
Putting these values in eq, (1(c). 103)
t vV2 „
tn
1 v e ' dv
K2jtkr)

Vav = n

1
Maxwell-Boltzmann Distribution Law

in co
4mi HIV
IjzkT) f 3 2kT
v e dv

in vV2 T _"iX_
v 2
= 4ji
Mf I J ' e ^ dv

r in f2 -3 '"V
v 2kT
= J2 JT e dv ...(1(c),104)
JikT J J

Using standard integral

X3 J-ax2
1 dx =
la1

3
u
Hence IV
| „-mv2/2KTdv = 4k2T
e —
2

2m/

3 2
g-m\ /2kTdv _ 2k2T2
or I"
III'

Putting this value in eq. (l(c).63)

T 2k2T2
V
av \l2 ft
m

8«:T
v„„
av = .(1(c).105)
nut

This is the expression of average speed of gas molecules,

(iii) Root Mean Square Speed Cvrms)

Root mean square speed of gas molecules is defined as

oo
jv2n (v) d\
rms 2 =
_ —
o ...(l(c).106)

|n (v) dv

We know that nos. of gas molecules having speed between v and v + dv is given by
^2
m
n (v) dv = 47tn v2 e-nn~/2kT dv
K2jikTJ

Also jn (v) dv — n

these values in eq. (1(c). 106)

 1

88 Statistical MechaniCs

00
3/2
m ^—mw HkT
j4jin ^
IjckT
V nns 2 _ d\
n
3
'r m 4\w /2
4jzn
InkT 4 —mv^llkl
v e dv
n M

/ m VV2N
2 ,4 -my2/2kT
vv = 471 v e dv ••(1(c).107)
rms TjzkT I

Using standard integral

.4 -ax
x e dx =
J 8a'

Putting this value in eq. (5.66)

3/2
m TT
v nns = dyr X
InkT J If-^L
m
2kT [ 2kT

m >3/2 f 2kT^\2 f2£T

2kT J [ m J m
3 1 3kT
= ^ x — x 2^T =
2 m m

3kT
V™„
nns = ...(1(c).108)
m
This is the expression of root mean square speed of gas molecules.

1(c).7. RELATIONSHIP BETWEEN MOST PROBABLE SPEED,

AVERAGE SPEED AND ROOT MEAN SQUARE SPEED

We know that, Root mean square speed of molecules

3£T
' mis = V3 1.73 JE
m m V m
Average speed of gas molecules

8A:T /AT 8X7 ur

8 I8
Vav = nm \7t \1 m v :22 HI
28 |AT /at
1.59 Aj
I I m V
Most probable speed of gas molecules

2AT kT AT
v
mp -= J2 = 1.44
m m ///
Maxwell-Boltzmann Distribution Law 89
'MM ■

: Vav : vmp = 1.73 ^ : 1.59 JEi 44

= 1.73 : 1.59 : 1.44

1.73 . 159 1.44

1 :
" 1.73 1.73 1.73
= 1: 0.92 : 0.81 ...(l(c).109)

i 1(c).8. EXPERIMENTAL VERIFICATION OF THE MAXWELL

BOLTZMANN DISTRIBUTION OF MOLECULAR SPEEDS

A successful experimental verification of the p

Maxwell Boltzmann law for distribution of
Drum
molecular speeds was carried by Zartman and Ko
in 1930. —1
o
Axis <
su
Principle ass o
cz
plate
If a beam of metallic vapours are incident on
"O
the wall of a rotating drum they get deposited on c
S3
it. The density of depostit will be directly
proportional to the molecular speeds.

Experimental Arrangement
Apparatus used by Zartman and Ko consists \ 1 1 1
of an oven with a fme slit 82. Bismuth is heated \ \ 1 '
OCEEN
in the oven to a temp.of 800oC. Bismuth vapours / Bismuth
\ 1'.i '//
o St
are formed at this high temperature and these Wtl
vapaours come out of slit Sj.

These bismuth molecules are further narrow

down and made unidirectional by passing through
slit Sj. The bismuth molecules after passing through
slit 82 form a fine beam. Above slit 82 a hollow
drum is rotated at about 6000 rpm with the help of
a motor in a plane perpendicular to the plane of
paper. The drum is having a slit S3 and a glass Fig. 1(c).2.
plate mounted on the inner surface of drum opposite
to slit-Sj as shown in fig. l(c).2.

The apparaturs is highly evaccuated so that the bismuth molecules do not suffer any collision
of bismuth molecules. Hence the speed and direction of bismuth molecules are not changed.

Working

When the drum is stationary the slits Sj, 82 and S3 will be in the same straight line. All the
ismuth molecules will get deposited at point 0 on the glass plate just opposite to slit S3. Now if the
rum is rotated at constant angular velocity short burst of molecules of bismuth will enter the drum
uring each rotation. Since the molecules of bismuth have different speeds hence the fast moving
 90 Statisticai Mechanics

molecules will reach the glass plate earlier than slow molecules. As the drum is rotating in anticlockwise
direction hence faster molecules will get deposited on the left part and slow molecules on right
of glass plate. After sometimes a sufficient amount of molecules of bismuth will be deposited on the
glass plate. The rotation of drum is stopped and glass plate is taken out. The relative intensity of
bismuth molecules at different points is measured with the help of a microphotometer. It is found that
there is a very close agreement between experimental and theoretical results of Maxwell Boltzmann
velocity distribution.

SOLVED PROBLEMS

PROBLEM 1. For hydrogen gas at N.TP. Calculate : (i) vmp (ii) vav and (Hi) vrms. Given
k = 1.38 X 10~16 ergs/K N = 6 x 1023 molecules/mole

SOLUTION. T = 273 K

Molecular weight of hydrogen M = 2

Avogadro's Number N = 6 x 1023 molecules/mole

Mass of hydrogen molecule is

Mol. wt. M 2
m — = 3.3 x 10 24
gm
N N 6xl023
k = 1.38 x 10-16 erg/K

2.kT 2X1.38X10-16
+8
(0 V mp = Vm,32x10
rn 3.3 X 10"" 24

vmp =1.51 x 105 cm/sec.

8 kT _ 8 x 1.38 x 10""16 x 273x7

(ii) V av
V nvrc 3.3x10 24
x 22

== V2.9X1010

= 1.73 x 105 cm/sec,

3 kT = 13 x 1.38 x 10""16 x 273

(in) v rms
V m "y 3.3 X 10~24

= V3.41X 1010
= 1.84 x I05 cm/sec.

PROBLEM 2. Calculate the r.m.s. speed of nitrogen at 270C. Given N = 6 x 10\23

molecules/mole, k = 1.38 x KC16 ergs/K.

SOLUTION. T = 27 + 273 = 300 K

Mass of Nitrogen molecule

Maxwell-Boltzmann Distribution Law 91

Mol. Wl. 28
in 4.66 X 101 mn
N .23
(>x 10

jJFr 3x 1.38 x lO-10 x 300

''mis — ,65 x 10'
= ^^2A6t
m -23
4.66 x 10

nns = 5.16 x K)4 cm/sec. Ans.

PROBLEM 3. ( alculate the unns and um[) for a gas whose density is 1.4 gm/litre at
pressure 10 dynes/cm2.

SOLUTION. Pressure P = I06 dynes/cm2

Density p -1.4 gm/litre = 1.4 X 10-3 gm/cm3

^spV72 .6 V/2
3X10
We know, V nns —
-v-3
. p . 1.4 x 10"

= (2.14 X 109)i/2 =V21.4X 10s

= 4.62 x 104 cm/sec.

3 kT
Also V rms
m

2 IcT
Since V nip
m

2kT
v nip
m
= = j- = A/0.666
V nns 3/cT
i in
v nip
0.816
V
nns

^nip ~ 8-16 X Vriils

= 8.16 x 4.62 X 104

vnip = 3.75 x 104 cm/see. Ans.

PROE^gf, 4_ Calclllal(, tlle s j 0j> nilro moiecujes 280 K lies
between 149.5 mis ami 1511.5 mis.

■
dv lb ^UTION. We know thai probability ol a molecule possesses speed between v and v +
given by

\3/2
in
P (v) dv =4-ji v~ e -imrilkT dv
27c kT
Molecular weight of nitrogen = 28
 92
Statistical Mech^.
na
*ics
Avogadro's Number,

N = 6 X 1023 molecules/mole
Mass of nitrogen molecule

_ Mol. wt. _ 28
m
N 6X1023
23
= 4.66 x 10 gm

= 4.66 x 10-26 Kgm

k = 1.38 X 10_23 Joules/K

T = 280 K

v = 149.5 m/s

dv = 150.5 - 149.5 = 1 m/s

\3/2
4x22 f 4.66 x 10"26 x 7
P (v) dv =
x (149.5):
7 2 x 22 x 1.38 x 10-23 x 280

v -4.66x10 26 X (1495)2
x e — —x1
2 x 1.38 x 10~23 x 280
= 7.4 X lO"3

rK?7BLthe
double fMaverage
5
' At speed
What tem erature wil1
of P
oxygen at 300average
K. speed of molecules of hydrogen gas be
/
SOLUTION. Let mass of hydrogen molecule = m

Mass of oxygen molecule = M

Average speed of hydrogen molecules

18 kT
(^au)hydrogen —
mrc
where k = Boltzmann's constant

T = Absolute temperature

Average speed of oxygen molecules

8kV 8k x 300
(^ai))oxygen
Mji V MJT
where r = 300 K

Given (v«u)hydrogen ^ ^ (^'ay)oxygen

18 kT 8kx300
=2
nm V Mjt
Squaring both sides
 lXwell-Boltzmann Distribution Law 93
Ma

8 AT , 8/c x 300
=4X —
nm Mar
T 4 x 300
in M
4 X 300 x in 4 X 300 x 2
T
M 32
= 75 K Ans.

PROBLEM 6. Calculate the kinetic energy of each molecule of an ideal monoatomic gas
at N.TR Boltznmnn's constant - 1.38 X lO'23 joules per degree kelvin.

SOLUTION. Since molecule of an ideal monoatomic gas has only translatory motion and
hence has three degrees of freedom.
_ 1
Using law of equipartition of energy, energy associated with each degree of freedom — AT

Kinetic energy of each molecule of an ideal monoatomic gas

E = — kT
2
Given k = 1.38 X 10"23 joules/degree K
T = 273 K
3
E =-AT
2

= — x 1.38 X 10-23 X 273

2
= 5.65 x lO-21 joule

PROBLEM 7. A certain gas possesses 3 degrees of freedom corresponding to the translational

motion and 2 degrees of freedom corresponding to rotational motion.
(i) What is the kinetic energy of translational motion of one such molecule of the gas at
300 K ?
(ii) If the temperature is raised by 10C, what energy must be supplied to one mole of the
gas. Given that Avogadro's number, N = 6.023 x 1023 mole'1 and Boltzmann's
constant k = 1.38 X 10~23 J molecule'1 IC

SOLUTION. Here N = 6.023 X 1023 mole"1

A = 1.38 X !0-23 J molecule-1 K_1.

(0 At temperature T, an energy equal to ~ AT is associated with each degree of free

dom of a molecule.
Therefore kinetic energy of one gas molecule at 300 K

1 ^
= 3 x — AT
2
 94
Statistical Mech

23
-3x^x 1.38x 10 x 300

= 6.21 x 10-21 J
00 The eneigy required to raise the temperature of one mole of gas by 10C (or 10K)

£
=:5x^/c(l)xN

- 5 , _ 5 -9.
X 38X 10 x
~ 2 " J 6.023 X I023
= 20.78 J

PROBLEM 8 A "
0farSOn
r- Neglecting 'all ZZtZ ZZZndlhe ftT^" t 'Mature
at modes, find the total energy of the system.

665 0f fieedom ol an ox
(monoatomic) is 3. ^ ygen molecule (diatomic) is 5 and that of argon
If Avogadro's number is N, then

degices of reedom of 2 moles of oxygen = 2N X 5 = 10N

an degrees of freedom of 4 moles of argon = 4N x 3 = 12 N

erefore. total degrees of freedom of mixture of two gases

- 72i + «2 = 10N + 12N = 22N

ccor mg to the principle of equipartition of energy, energy associated with each degree

freedom is ~kT ^

Therefore, total energy of the system

1
- 2 /:TX22N = n ^N) T

= 11RT Ans.
(•.• m = r)
PkOBLcM 9. In low density oxygen gas at low temperature nnlv th* t 1*1
rotatwnal modes of molecules are excited. What is the specifii heat per mile T'he gZ?

^OI 1 ON. 9tal degrees of freedom

= 3 translational modes + 2 rotational modes

Since oxygen is diatomic,

so degrees of freedom / = 2

I 5 /- T
Internal energy (J = / - x kfV = ' T-

Now, we know that specific heat is

dU d
Cv — ~ — —- Ah X /CB
df df V2 '] " 2 -
Maxwell-Boltzmann Distribution Law 9S

1. Explain what is phase space ?

Ans. We can completely specify the position of a particle by knowing three position
co-ordinates (v, i/, z) in a three dimensional space called position space. Similarly we can
completely specif}^ the momentum of a particle by knowing three momentum
co-ordinates (px, py, pz) in another three dimensional space called momentum space.

A combination of position space and momentum space is called phase space.

2. What is minimum size of a phase space cell in classical and quantum mechanical
system ? Classically.

Ans. The minimum size of a phase space cell in classical mechanics is li(f which may
even approach to zero.
In quantum mechanics the minimum size of a phase space cell is h3 where h is Planck's
constant.

3. In classical statistics, how can we treat the identical gas molecules as distinguishable
from each other ?
Ans. In classical mechanics there is no restriction on the size of phase space cell. We
can choose the size as small as we like hence phase space may be divided into so large
number of cells such each cell contains either one molecule or none. Hence we
distinguish the molecules from the cells they occupy. Even though they may be
identical to each other.
4. When the temperature of the gas sample rises, how does the area under v and n(v)
curve vary ?
Ans. It remains constant because area under the v and n(v) curve is equal to the
number of molecules in the sample, which does not vary with temperature.

n(v)dv ^ , ,
5. How does the fraction — for a given volume V vary when the temperature rises ?
n

Ans. As the temperature rises more and more molecules acquire higher speeds. So the

fraction -^^-for a given volume V goes on decreasing.

n
6. Discuss the dependence of average speed and average velocity of the molecules of
a gas sample on temperature.

B/cT 80
„ (
Ans. The average speed is given by v,,v = h increases with temperature, but
the average velocity of the molecules remains zero at all the temperatures.
Explain the escape of gases from the earth's atmosphere with Maxwell Joltzmann
law of distribution of speeds.
Ans. We know that a body must possess velocity equal or greater than escape velocity
to escape from gravitational pull of earth. According to MaxweJI Boltzmann law of
96 Statistical Mechanics

distribution of speed some molecules possess very high velocities and escape frorn
earth's atmosphere.
8. Why hydrogen escape faster from earth's atmosphere than oxygen?

Ans. Hydrogen escapes faster from earth's atmosphere because hydrogen has higher
most probable velocity than oxygen.
9. State the condition which a system should satisfy so that its energy remains constant.

Ans. The system should be isolated from the surroundings.

10. What determines the distribution of molecular speeds in an ideal gas ?

Ans. The temperature determines the distribution of molecular speeds in an ideal gas.
11. A gas has two specific heats whereas a liquid and solid have only one. Why?
Ans. A solid or a liquid when heated undergoes no (or negligible) change in volume
or pressure. But in case of a gas, both the pressure and volume change on heating.
Therefore, specific heat of a gas is defined at constant volume or at constant pressure
and hence gas has two specific heats.
12. Write down the number of degrees of freedom (i) earth (ii) bob of a simple pendulum
hung by means of an elastic thread (iii) mosquito.
Ans.
(z) Tire earth moves m a plane round the sun in an elliptical orbit and, therefore
possesses two degrees of freedom.
(ii) The bob of a simple pendulum moves along a straight line (for small amplitude)
and hence possesses only one degree of freedom
(iii) A mosquito can fly in air and hence possesses three degrees of freedom
13. Should the specific heat of a monoatomic gas be less or equal to or greater than that
of a diatomic gas at room temperature ? Explain.

Ans, The specific heat of a gas at constant volume is -R For a ■

2 • a monoatomic gas
degrees of freedom n = 3 and for a diatomic eas n = S ai r™™ ^
heat for a monoatomic gas is less than that for a diatomic j^s6 nce s ecific
P

14' r Tr the rati0 0f tWO SPeCifiC hea,S 0f a

8- Of freedomr
Ans. The two specific heats of a gas are given by

C„ = - R / where n = degrees of freedom

and Cp = I H— R
V 2
Maxwell-Boltzmann Distribution Law |:r| W'
97

15. What are the values of Cv, Cp and y for a monoalomic gas ?
Ans. For a monoatomic gas, degrees of freedom ,t = 3
" 3

fn 3 f3 3
c, = R = - + ] R = —R
I
U J 2

y _Cr fR 5
= =
"^ i^ r1-66
2
16. What are the values of Cv, Cp and y for a diatomic gas ?
Ans. For a diatomic gas, degrees of freedom n = 5

^ n 5
c
„ =-R = -R

n (5 }
and Cp = ( - + 1 R = - + 1 R = —R
-
v.2 > U j 2

-R n
Hence — p _
y = 2- = ^ = I.4
5
1R
2
17. Is negative temperature possible ?

Ans. Yes, negative temperature is possible. In some systems, by increasing the energy
past a certain point causes less number of states to be available instead of more. At this
situation temperature becomes negative, below zero kelvin.
18. How is negative temperature attained ?

Ans. We know that the entropy is directly proportional to the log of the number of
states. The slope of energy versus entropy is equal to the reciprocal of the temperature.
Hence the sign of the number of states versus energy slope determines the sign of
temperature. Below the peak in the graph between entropy and energy, temperature is
positive and above the peak, the systems attain negative temperature.
19 Give the physical significance of the negative temperature.
Ans. A substance with a negative temperature is not colder than zero kelvin, but rather
it is hotter than infinite temperature. Normally, when energy is added to a system with
negative temperature, its entropy decreases. Whereas, if the same energy is added to a
system with positive temperature, then its entropy increases.
20 Is it possible to cool a potassium gas to one billionth of a degree below absolute zero?
If yes, will it be hotter or colder ?
Ans. Yes, it is possible to cool a potassium gas to one billionth of a degree below
absolute zero. In terms of quantum statistical mechanics, actually the gas will be hotter
than the sun. It will be hotter even than infinite degrees kelvin.
98
Statistica! Mechanics

21. What docs the Gibb's paradox allow ?

Ans. The Gibb's paradox allows for Ihe enlropy of closed systems to decrease which
violates lire second law of Ihermodynamies.

22. Why is Gibb's paradox considered a paradox ?

Ans. Gibbs paradox is considered to be a paradox as the statistical appraoch to calcu-

la on ot entropy being pursued by classical mechanics is inconsistent with the second
law ot thermodynamics.

23. \Vhat is an ensemble in statistical physics ?

ms. nsemble is defined as the collection of large number of systems which are
microscopically different but macroscopically identical.

wiMMm
i A '-Mm
1 a d namic
' y system consisting of n particles, the number of coordinates required to
specif}' their position and momentum at any instant are
(r) 77
(b) 2n (c) 3n (d) 6n.
2. The minimum size of a phase space cell in classical statistics is
(a) point size (b) h3 (c) infinite size (d) None of these.
3. The expression of root mean square speed of gas molecules is

/m /M fdmT
wn- ("Wif
4. The ratio of vwp to vrws to a gas molecule is

(tf) 0-81 (b) 0.5 (c) 0.3 (^) i

5. For hydrogen gas at N.T.P. which is maximum

(a) v
u,p (b) vrws (c) vai,.
6. In Maxwell Boltzmann Statistics, the particles are
(a) distinguishable {b) Indistinguishable (c) partly indistinguishable.
7. The average energy of the molecule of a mono-atomic gas at temperature T is ?

1
(") j ' C') 'tT (0 -IT (,() -i/;T

8
- peTLkcl ?elillnn 8 SeS are
" 'he SanlC CO
"tainCr- Which
has greater kinetic energy

(a) Oxygen (/,) Helium

(c) Both have equal K.E.
(d) Sometimes oxygen and sometimes helium may have greater K E

9. The root mean square velocity of a gas molecules of mass m at . w .

at a
proportional to S've11 temperature is

(a) m C') (c) (d) in-Vi

 B0 tzmann Distribution Law
axwell- ' 99

^0 Which of the following gases possess maximum root mean square velocity at a given
temPerature
temp eratlire

{b) Nitrogen (c) Oxygen {d) Helium

(a) Hydrogen

Answers

1. {d) 2. (a) 3. (h) 4. (a) 5. {b) 6. (a) 7. (c) 8. (a) 9. id) 10. (a)

1. Phase space is a six dimensional space. It is the combination of position space and
momentum space.

2. In position space three co-ordinates {x, y, z) determine the position of a particle and in
momentum space three co-ordinates (px/ yy, pz) determine the momentum of the particle.
3. If a dynamic system consists of n particles then total number of co-ordinates required
to specify their positions and momentums at any instant are 6n.
4. The volume of an elementary cell can be taken as small as we please in classical statistics.
5. The accessible volume in phase space (t) is equal to the product of accessible volume
(V) in position space and accessible volume F in momentum space
t = vr
6. The minimum volume of an elementary cell is h3 in quantum statistics where h is the
Planck's constant.
7. Equation for basic approach to three statistics is
rf(ln W) - 2(a + ySw,) dn, = 0
8. Maxwell's Boltzmann's distribution law is

ni = gi e-P"1
9. Maxwell Boltzmann law of molecular speed is

\3/2 mv,2
m
n
(v)dv = 4jrn ^Ff v2 e 2kT
dv

HE The most probable velocity at temp. T0K is given by

2kT
v mp
m
The average velocity at temperature T0K is given by

jSkT
vflv or v =
nut
12
- The root mean square velocity at temperature T0K is given by

3kT
v rms
m
Specific heats of ideal gas
nR
Cv —
~Z~ / Cp = R and y = H—
^2 y V
loo

'^L
\ y

Short Answer Questions.

ttini phase space and momentum space.

7
^ \\ 1 '
he purpose of dividing phase space into cells ?

1S th0 m,nimum
j' size of a phase space cell in classical and quanh
^ Kplam (he phase space and its division into cells. * st^
a V hat is mea
' nt by available volume ?

I' "0U VVC Can treat the identical molecules as distinguishable in classical f
• Discuss the dependence of average speed of molecules of a gas on temp^

be differe
' than "t if We haTC a
gase

9. Hjdiogen escapes faster from the earth atmosphere than oxygen. Why?
10. In arder to describe a dynamic system which physical quantities we must k»

Long Answer Questions

StatiSl CS
^ the distribution
t
an ideal SaS in
ofi molecular
. speeds ?
e
<luilib™. Experimentally
7 how do7
J your
2. Calculate the average and root mean square speed of the molecules obeying:
0
statistics. '

3. Assuming M-B distribution of molecular speeds calculate average and rms spe«i
0
molecules.

4. Derive an expression for the number of phase space cells lying in the kinetic»
0
interval u and it + du.

5. Treating ideal gas as a system governed by classical statistics, derive

Boltzmann law of distribution of speeds.

6. Explain the terms : position space, momentum space and phase space. What ^
purpose of dividing phase space into cells ?

7. For any classical, system occupying volume V, derive an expression for the nu^'
phase space cells in the momentum interval p to (/; + dp).

8. (n) Using expression for M-B law of distribution of molecular speeds derive thU'
of average speed.

(b) Briefly discuss the Zartmann and K0 experiment for verification of M-B
law of molecular speeds.
statI
9. (a) Discuss the common approach in dealing with M-B, B-E and F-D ^/'
(h) Give a brief account of Zartmann and K0 experiment for the verification ^
Boltzmann law of distribution of molecular speeds.
Maxwell-Boltzmann Distribution Law 101

10 (fl) Derive Maxwell Boltzmann law ol distribution of speeds. Show that the number of
molecules in speed range from v to v + r/v is given by

- ,,, \m 'iiyl
n{v)dv = 4jin
2Ba)

(b) Calculate the root mean square velocity from the above relation.
11 Derive Maxwell-Boltzmann law of distribution of molecular speeds. Use this law to
obtain an expression for the most probable speed of the molecules.

12. Define root mean square veloity using M-B distribution of molecular speeds, show that
the rms velocity of the molecules is given by
ISkT
v.rms
m
13. Derive Maxwell law of distribution of molecular speeds. Show that average molecular
speed is given by
I BUT
Vflv =
Jtm
14. Distinguish between the most probable speeds vmv and rms speed. Show that the ratio
(3
of Vj^s and vmp is ^ 2 *

15. Show that mean speed (v), most probable vmp and root mean square speed (v)2 of
molecules are given by
1/2 1/2
UT 2kT 3kT
v
(0 v = (n)Vmp — and {Hi) mis
Jim m m

totgsdl'vKPiytiJMERICALvPROBLEMS

1. Discuss the possible arrangements of three particles in two cells, assuming that the
particles obey (a) M.B. statistics {b) B.E. statistics (c) RD. statistics
[Ans. (a) 8 (b) 4 (c) Not possible {i.e. 0)]

2. Discuss the possible arrangements of two particles in three cells assuming that particles
obey {a) M.B. statistics {b) B.E. statistics (c) F.D. statistics. [Ans. {a) 9 {b) 6 (c) 3]
3- Discuss the distribution of 3 particles in 3 cells, assuming that they obey («) M.B.
statistics {b) B.E. statistics and (c) RD. statistics.(H.P.U. 1992) [Ans. {a) 27 {b) 9 (c) 1]
Calculate the root mean square and most probable speed for a gas whose density is 1.4
gm/litre at a pressure 106 dynes/cm2.

3kT 2^T '3P)1/2

[Hints. 'rms Vmp . Also v rms
m m P )
vi
1.49 3
P = 106 dynes/cm2 p = = 1.4 X 10 3
g/cnr1 Vrms ]

[Ans. vrms = 4.6 104 cm/s, = 3.79 104 cm Is]

102
Statistical Mech^

5. Calculate the most probable speed of nitrogen at 27 t Civen N 5 ^

molecules/mole, K = 1.38 x lO"16 ergs/K.

Mol. wt. 28 [Ans. 4.2 X 104 CIn/s(

[Hints, w - v
m\) ]
N
r III ^c.]
b x 10
For O2 gas at N.T.P. calculate (he most probable speed.
Ul
Given K = 1.38 X 10 ergs/K. Avogadro's number = 6.02 X 1023 molecules/mole.
[Ans. 3.76 X 102
nils]
16
7. For O; gas at N.T.P. calculate the average speed. Given K - 1.38 X 10 ergs/}(
An ogadro s number = 6.02 X 1023 molecules/mole. [Ans. 4.25 X 102 mysj

8. For CP gas at N.T.P. calculate the root mean square speed (vrms) when K = l.sg x
0 23 2
10- ergs/K. Avogadro's number = 6.02 X 10 molecules/mole. [Ans. 4.6 X lO m/sj

9. Calculate the probability that speed of nitrogen molecules lie between 149.5 m/s and
150 m/s at 7 C. [Ans. 7.4 X Kty]
10. In a Zattman and Ko experiment Bismuth atoms heated to 800oC pass through the
slits and hit the plate directly when the drum is stationary. If the drum radius is 14
cm and rotates at the rate of 80 rps, at what distance from the right end will the
density of condensed atoms be maximum. Given mass of Bi atoms is 3.4 X lO-21 em
and K = 1.38 X lO"16 ergs/K.]

-11/2
2kT 2r
[Hints. vmp =
m - 9.33 x 1033 cm/s, t =
< mp

vel. of v - 2jir = nos. of rev. of drum ....]

Distance covered on plate = v X t jAnSi 2L1 cm|

11. Ca^uiaue the rms speed of a molecule of hydrogen at N.T.P. Given K = 1 38 X 10"16
ergs/K, N = 6 xlO23 molecules/mole]
[Ans. 1.84 x 105 cm/s]

EI^inthe

1. The probability of an impossible event is

2. Each compartmentwise distribuHon of a system of particles is known as a
3. Each distinct arrangement is known as the of a SyS|;em

4. The number of microstates corresponding to any given mlcroZle is called

5 T
' ^,,m.aCmacrosmheiCh ^ ^ maXimUm 0f 0
««^nce is known as «

6 Pr0dUCt BOltZmann S COnstant

' probability.^ ^ ^ ' of thermodynam

7, The entropy is a measure of

8. A phase space is a dimensional space for a single particle.

9. A« canonical ensemble is a collection of a large number of independent systems hav*

me
same
Maxwell-Boltzmann Distribution Law

JO, Electrons, protons, neutrons are examp.es of Darticl(„

11 is defined as the collection of 1 ■

31 number
independent systems. ^ of macroscopically identical but

12. A collection of lame number of j

SyStemS havm same
number of identical particles is known as § ^ergy volume and

13. For irreversible processes entropy increases and tZ u

Fy aeases and
greater than hence change of entropy is always

14. Tire value of entropy of one mole of a perfect gas at 0 K is

15. Tire most probable state in the dynamic system is known as the state.

16. A gas of non-relatmstic classical particles in one dimension is subjected to a potential

V(x) a <x) where a is constant, then the partition function is i P ~ —

given as
V kTJ
17, A system of N non interacting classical point particles is constrained to move on the
two dimensional surface of a sphere. The internal energy of the system is

18. Entropy was discovered by in 1854 during application of second law of

thermodynamics.

Answers

1. Zero, 2. macrostate, 3. microstate, 4. thermodynamic probability, 5. most probable.

6. natural log, 7. disorder, 8. six, 9. T, V and N, 10. Fertnions, 11. Ensemble,

Bmjr
12. Macro canonical ensemble, 13. zero, 14. zero, 15. equilibrium, 16. -J j3 a2h2 '
3

17, n/cbT 18. Clausius