Maxwell-Boltzmann distribution Of Energy

T
1 dnE 2π
he most probable distribution for an ideal gas is a well-known function called the Boltzmann
distribution (or the Maxwell-Boltzmann distribution). It can be derived by statistical
mechanics and is given by:
2
1
. = 3
. e− Mc /2 RT E 2
n dE
(πRT ) 2
The general shape of this function is shown in Fig. 1.0. Notice now we have not written the
distribution in the form of a set of numbers n corresponding to specific energies E but rather in the
form of a continuous function that can tell us the number of molecules having energies within a range
of energies. The model for an ideal gas is a system of small round particles whose only energy is their
kinetic energy. That means that their distribution function could be in terms of speed instead of energy
simply by substituting E = mv2/2 and dE = mv dv. Thus, the speed distribution of an ideal gas is:

1 dnc 3
M
( )
2

. =4 π 2
. e− Mc /2 RT c2
n dc 2 πRT

The functions dn=dE and dn=dv plotted as functions of E and v, respectively, obviously do not have
the same shape.2 Nevertheless, they do have several characteristics in common: they are equal to zero
at E = 0 or v = 0; both go to zero exponentially at high values of E or v; and both have a maximum at
some most probable value of E or v, the position and shape of the peak depending on the temperature
T . At low temperatures both dn=dE and dn=dv have high, narrow peaks near E = 0 or v = 0,
corresponding to a system with most of its particles moving relatively slowly. At high temperatures,
on the other hand, both functions have low, broad peaks at high values of E or v, corresponding to a
system of particles moving both rapidly and with a relatively wide range of speeds.

Figure 1.0

Derivation of Maxwell Boltzmann distribution of energy:

According to Maxwell’s law of distribution of molecular velocities

1 dnc 3
M
( )
2

. =4 π 2
. e− Mc /2 RT c2
n dc 2 πRT

If E represents the kinetic energy of one mole of molecule having the velocity c, i.e.,
E=1/2Mc2 which give
2E
c 2=
M
 2E 2
Or c=
√ √
M
=
M
√ E … … … … …(1.0)

Differentiating the Equation (1.0) we have

dc 2 1 −1
dE
=
√
M 2
E2

−1
dc 2 1
dE
=
√ ×
M √2 × √ 2
.E 2

−1
dc 1 2
= .E
dE √ 2 M
−1
2
dc × √ 2 M =dE . E … … … … … … … … .(1.1)
Multiplying by ½ Mc2 on left hand side and E on right hand side of Equation (1.1) we have
−1
1
√ 2 M × M c2 . dc=E . E 2
dE
2
1 1
1
Or √ 2 .. M × M c 2 . dc=. E 2 dE
2
2
3 1
1
Or M 2 c 2 dc=E 2 dE
√2
3 1
Or M 2 c2 dc=√ 2 E 2 dE … … …. (1,2)
3
M 2 c2 dc=√ 2 E dE

Subtracting this value in Maxwell’s law equation, we can get

2
3 −M c
dnc 1 3

n
=4 π (
2 πRT ) . M . c dc e
2 2 2 2 RT

2
−M c
dn E 1 3

n
=4 π
2 πRT( ) .√ 2 E dE e
2 2 RT

2
−M c
1 dn E 1 2 RT
Or =4 π 3
.√ 2 E e
n dE 2
2 √2(π RT )
2
−M c
1 dnE 2π 2 RT
. = . Ee
3 √
n dE 2
( πRT )
2
−Mc 1
1 dnE 2π 2 RT 2
. = 3
.e E … … … … …(1.3)
n dE 2
( πRT )
 1 dnE
Equarion 1.3 represents Maxwell’s law for energy distribution. Fig 1. Show the plot of . versus
n dE
E. Shape of this curve is different from that of speed distribution curve. The energy distribution has a
vertical tangent at the region and thus it rises much more repidly than the speed distribution curves
which starts with a horizontal tangent. After passing the maximum the energy distribution falls of
more gently than does the speed distribution. As usual, the distribution is broadened at higher
temperatures. Thus, a greater proportion of molecules posses higher energies.

Determination of avaogadro contant via X-Ray Crystal

Density Method (XRCD)

I t has been almost two centuries since Avogadro presented his hypothesis, then, more than fifty
years later Austrian Loschmidt developed a method for measuring the diameter of air molecules
which was a big step for calculating a first approximation of the number of molecules or atoms per
unit volume. Computing Avogadro’s with Loschmidt’s diameter results give ten times the real value.
It was until the beginning of the 19th century when Jean Perrin measured an accurate value of
Avogadro’s constant, which is the amount of elementary entities in one mole of substance. After him,
many scientists have measured this constant using more accurate methods, one of them is the X ray
diffraction method, which can reach accuracy of 99.99% using 28Si.
A modern way to get the Avogadro´s number is the X-ray diffraction experiments using the silicon
28Si, which determines the size of an edge for a cubic crystal system. The unit cell volume is then
deduced, and used to calculate a value for Avogadro's constant. First, one must get an adequate crystal,
pure in composition and regular in structure, with no significant internal imperfections. In principle, an
atomic structure could be determined from applying X-ray scattering to non-crystalline samples.
The parameter of the crystals is determined Via X-Ray scattering on the crystal surface. It gives the
value of different parameter like
 Volume - V  Molar mass-m
 Density - ρ  Unit cell Volume-a
 Molar Mass- M  Atoms in unit cell-n

Formula of NA:
nM
N A=
ρ0 a30

Protocol:
 (1) Isotope enrichment, crystal growth and crystal purity:
Si crystal must be pure. The isotope enrichment was carried out by centrifugation of SiF4 gas.
After conversion of the enriched gas into SiH4, a polycrystal was grown by chemical vapor
deposition. The 5 kg crystal was grown and purified by multiple float-zone. The concentrations of
the residual impurities (carbon, oxygen and boron) were determined by optical spectroscopy.

(2) Lattice Parameter

To measure the lattice parameter upgraded a combined X-ray and optical interferometer to expand
the measurement capabilities to many centimeters and to achieve a relative uncertainty
approaching 10-9. To exploit this capability, An X-ray interferometer crystal (XINT) manufactured
with an unusually long 5 cm analyzer crystal.

(3)
Shape: Diamond Cubic
Unit cell atom: 8
Volume: 543.0996240 Pm

Silicon Unit Cell

Surface:
Due to highly reactivity silicon is covered with oxides layer and form SiO 2 which reduce the
reactivity of the silicon and layer parameters are surface layer mass 222.1 mg & surface layer
thickness 2.88 nm

(4) Volume
The spheres were shaped and optically polished and their volumes were determined via diameter
measurements. The measured sets of diameters by means of a Saunders-type interferometer. (Si
Crystal= 431.059 061 cm3)

(5) Mass
Mass comparisons of spheres with Pt–Ir kilogram standards were carried out in vacuum by the
Bureau International des Poids et Mesures (BIPM), (SI Crystal= 1000.087 558)

(6) Molar mass

The amount-of-substance fractions of the Si isotopes were measured via gas mass spectrometry of
the SiF4 gas, and other via isotope dilution combined with multi-collector inductively coupled
plasma mass spectrometry. The spectrometer was calibrated by using synthetic mixtures of
enriched Si isotopes (Si= 27.976 970 26 gmol-1)

Calculation and Result:

 Experimental Crystal Parameters

nM
N A=
ρ0 a30
8 × 27.9769026
N A= −8 3
2.320070841×(5.43099× 10 )

N A =6.02214095 ×1023