Average Energy of the Particle

Consider a system of “n” number of particles. The total energy of

an isolated system is given by
E   ni Ei  n1 E1  n2 E 2  n3 E3  .....
i

 E  g1e   E1 E1  g 2 e   E2 E 2  g 3 e   E3 E3  ......

m
N N
N

ye
Ee 
 gi e  Ei
Ei   i Ei
g e  Ei
(1)

Sa
i Z i
N
Z   gie   Ei r.

dZ

d N

 gie   Ei
N
   g i e   Ei E i
D
We know,
i d d i i

From (1) E

N dZ
 N
d
log Z 
Z d d
The average energy of a particle is given by,

E
 E av   
d
log Z  (2)
N d 1
This shows that for a given system, the total energy E, the
partition function Z, and the average energy of the particle Eav
depends on the parameter . Therefore,  may be taken to
characterize the internal energy of the system. So, it is
customary to represent parameter  as follows:
1
 k: Boltzmann constant

m
kT T: Temperature

ye
 
Sa
N
M-B distribution law in terms of temperature n i  g i e  Ei / kT
r. Z
D

1 dT
 d   2 Energy of the particle: E  ( NkT )
2 d
log Z  (3)
kT kT dT

Average energy of the particle: E av  (kT 2 )

d
log Z  (4)
dT
Thus the temperature of a system can be regarded as the
average energy of the particle of the system.
2
 Partition function
The probability of finding the system in one g i e  Ei / kT
pi 
particular state of energy Ei is given by: N

N
 i
g e  Ei / kT

Z   gi e
i
 Ei / kT
The sum in the denominator:
i

m
is called the partition function or “sum-over states”. The partition

ye
function depends on the temperature T and on the parameters that

Sa
determine the energy levels.
r.
D
Importance: Although the partition function itself is not a measurable
quantity, it however does form an important bridge between the
statistical expressions for the state of a system and the corresponding
thermodynamic functions. For example: physical quantities like mean
energy, entropy etc or even dispersion can be immediately obtained by
taking suitable derivatives of logZ. Thus by the partition function it can
be evaluated the macroscopic properties easily in statistical mechanics.
3
Derive the Maxwell-Boltzmann Distribution in the form:
2N
n( E )dE  E e  E / kT dE
kT 3 / 2
Consider an ideal gas of N identical non-interacting point
particles, each of mass m, confined in a volume V at absolute
temperature T. The M-B distribution law is given by,

m
n i  g i e  Ei

ye
(1)

Sa
If the gas has a continuous distribution of molecular energies
r.
instead of the discrete sets E1, E2, E3,…., the eq(1) becomes
D

n(E)dE  g(E)e  E dE (2)

Here, n(E)dE represents the number of molecules having

energies between E and E+dE and g(E)dE represents the
number of states having energies between E and E+dE.
4
Let us first find g(E)dE. A molecule of energy E has a momentum
whose magnitude is given by,
p  2mE  p x2  p y2  p z2
Each set of momentum components px, py, pz specifies a different
state of motion. Let us imagine a momentum space whose
coordinate axes are px, py, pz. The available number of

m
momentum states of particles between p and p+dp is

ye
proportional to the volume of a spherical shell in momentum

Sa
space of radius p and thickness dp. Volume of this spherical shell
is 4p2dp. Hence, r.
D
g(p)dp  Bp 2 dp (3)

where B is constant.
dE mdE
Again p 2  2mE  2p  2m  dp 
dp 2mE
From Eq. (3) g(E)dE  2m 2/3 B EdE (4)
5
Substituting eq(4) into eq (2)

n(E)dE  C E e  E dE (5)

Where C is constant. C  2m 2/3 B E e -

To find the value of C, normalization condition is used where the total

number of molecules is N.

m
 
 

ye
N   n(E)dE  C  E e  E
dE  C
1
C kT 3 / 2 (6)

Sa
0 0
2  2
r. 
1 
D
Where used the integration rule: 
0
xe  ax dx 
2a a
2N
C
Use eq (6)
kT 3 / 2
2N
Use eq (5) n(E)dE  E e  E / kT dE (7)
kT 3 / 2 6
The total internal energy of the system is:
 
2N
E   E n(E)dE  3/ 2 
E 2 / 3  E / kT
e dE
0 kT  0
2N 3
 kT 2
2 T 
3
NkT (8)
kT  4
3/ 2
2
The average energy of an ideal gas molecule

m
ye
E 3
E av   kT

Sa
N 2
r.
D
M-B Velocity Distribution Law: The number of molecules with
speeds between v and v+dv in an assembly of ideal gas
containing N molecules at absolute temperature T can be
found by substituting E=1/2 mv2 and dE=mvdv in eq(7). We get

2 Nm 3 / 2 2 mv 2 / 2 kT
n(v)dv  v e dv (9)
kT 3/ 2