APPLICATION OF STATISTICS MAXWELL-BOLTZMANN

TO DETERMINE THE AVERAGE ENERGY VIBRATION OF

LATTICES AND HEAT CAPACITY OF CRYSTALS

By :

Elisabeth Kadek Anisyawati 1613021027/VIA

PHYSICS EDUCATION DEPARTMENT

MATHEMATICS AND SCIENCE FACULTY
GANESHA EDUCATION UNIVERSITY
SINGARAJA
2019
 PREFACE

Praised be presented to the writer prayed Almighty God for His mercy author
was able to complete the paper on time. The paper entitled " Application Of Statistic
Maxwell-Boltzmann to Determine the Average Energy Vibration of Lattices and Heat
Capacity of Crystals" is expected to provide readers with information about the
Maxwell Boltzmann Application of Statistics and it is hoped that this paper can be used
as a reference in attending Statistics Physics lectures.
This paper aims to fulfill the tasks of the Statistics Physics course.

The author realizes that this paper requires further development and there are
still many things that need fixing. Therefor, suggestions and constructive critismis the
author expected. On this occasion, the author also apologize if there are things that are
not acceptable in this paper and the process through which the formulation. Finally, the
author hope that this paper is useful for all parties.

Singaraja, 6th June 2019

Writer

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 TABLE OF CONTENTS
Preface............................................................................................................……………i
Table of Contents...........................................................................................…………...ii
CHAPTER I INTRODUCTION
1.1 Background........................................................................................…………...1
1.2 Problem Formulation.........................................................................…………...1
1.3 Purpose ..............................................................................................…………...1
1.4 Benefits..............................................................................................…………...2
CHAPTER II DISCUSSION
2.1The Structure of Crystal……………………………………………………………. 3
2.2 Impact of Crystal Defects on Average Vibrational Energy’s Lattice and Heat
Capacity of Crystal …………………………………………………………….… 4
2.3 Average Vibrational Energy’s Lattices and Heat Capacity of Crystal ……………6
CHAPTER III CLOSING
3.1 Conclusions ……………………………………………………………………...15
3.2 Suggestion ……………………………………………………………………….16
BIBLIOGRAPHY

3
 CHAPTER I

INTRODUCTION

1.1 Background

Crystal is a solid that is composed of regular atoms and the pattern repeats in three
dimensions. Crystals in nature contain a large number of defects or imperfections. Most
crystals have various types of crystallographic defects. The type and structure of these
defects can have a large effect on the material properties, especially the thermal
properties of the material. The crystal response to the heat received from the
environment can be determined through the thermal properties of the material. Common
examples of crystals are mostly metals, diamonds, ceramics, ice and salt crystals. One
of the crystal materials that are widely used in daily life is ceramics. In the ceramic
industry, the thermal properties of materials can determine the quality of the ceramics.
One of the important thermal properties of materials in the ceramics industry is the heat
capacity of the material. This is because the heat capacity of the material expresses the
ability of the material to absorb heat from the environment. The greater the heat
capacity of the ceramic, the easier the ceramic will absorb heat. So the greater the heat
capacity of the ceramic, the better quality of the ceramic. The heat which absorbed will
be stored by the material in the form of vibrations of the atoms that make up the
material. The value of heat capacity of a material, especially crystalline materials such
as ceramics, can be determined through Maxwell-Boltzmann statistics. In addition, the
average energy of the vibrational lattice in the crystal can also be determined through
Maxwell-Boltzmann statistics.

1.2 Problem

Based on the background of the previous problem, the problem can be formulated
as follows.

1.2.1 What is the structure of atoms in crystal material?

1.2.2 What is the effect of lattice vibrational energy and heat capacity of crystal on
ceramic quality?

1.2.3 How do we apply the Maxwell-Boltzmann statistic to determine the average

vibrational energy of the lattice and the heat capacity of crystal?

1.3 Purpose
Based on the formulation of the problem, the purpose of writing this paper is as follows.
1.3.1 To find out the structure of atoms in a crystal.
1.3.2 To determine the effect of lattice vibrational energy’s lattices and heat capacityof
crystal on ceramic quality

1
1.3.3 To find out the application of the Maxwell-Boltzmann statistic in determining the
average vibrational energy’s lattice and the heat capacity of crystal.
1.4 Benefits
The benefits that expected from writing this paper are that readers and students as
prospective teachers are able to understand the Maxwell-Boltzmann statistical
application in determining the energy of the average lattice vibrations and heat capacity
in crystalline materials.

2
 BAB II
DISCUSSION

2.1 The Structure of Crystals

Solid substances whose particles are arranged in neatly arranged rows

called crystals. The crystal is composed of regular atoms and the pattern repeats
in three dimensions. Crystals have a long-term regularity of atoms. Conversely,
solids that do not have such an order are called amorphous materials or not
o
crystals. Inside crystals, atoms or molecules and cells separate as far as 1A or
o
2 A . Crystals can be formed from solvent, melt, steam or a combination of the
three. If the formation process is slow, then the crystalline atoms can arrange
themselves during the process to occupy such a position so that the potential
energy is minimum. This will result in regular and repetitive arrangement of
atoms in the three-dimensional direction, so that the order of atomic order is
formed in a long range as in Figure 1 (a). Whereas, in amorphous or not
crystalline materials formed in a fast process will have atoms which have a
higher energy level and have a limited range of order as seen in Figure 1 (b).

Figure 1. (a) Crystal atom arrangement, (b) amorphous atomic

arrangement

The crystal structure consists of lattices and bases as seen in Figure 2.

Lattice is a regular and periodic arrangement of points in space. While the base
is a group of atoms, with the number of atoms in a base can contain one atom or
more. Crystal structure will be formed when a base is placed at each lattice point
so that the crystal structure is a combination of lattice and base. If the atom or
group of atoms occupies the lattice points it will form a crystal structure.

3
 Figure 2. The Structure of crystals

Common examples of crystals are mostly metals, diamonds, ceramics, ice

and salt crystal. There are several phases which generally occur in crystal
formation, as follows.:

a. Liquid to solid phase: crystallization of a melt or liquid often occurs on a wide scale
under natural and industrial conditions. In this phase liquid or basic melt forming
crystals will freeze or solidify and then form crystals. This phase usually affected by
changes in ambient temperature.

b. Gas to solid phase (sublimation): crystals are formed directly from steam without
going through the liquid phase. The shape of the crystal is usually small and
sometimes skeletal form. In this phase, the crystals formed are the result of
sublimation of solidified gases due to environmental changes. Generally these gases
are the result of volcanic activity or from volcanoes and then freeze due to changes in
temperature.

c. Solid to solid phase: this process occurs in the crystal agerate under the influence of
pressure and temperature (deformation). Only the crystal structure undergoes
changes in this phase, while the chemical composition remains (recrystallization).
This phase only changes crystals that formed previously because the pressure and
temperature change significantly. So that the crystal will experience changes in shape
and physical elements. However, the composition and chemical elements do not
change due to the absence of other factors involved except pressure and temperature.

2.2 Impact of Crystal Defects on Average Vibrational Energy’s Lattice and Heat
Capacity of Crystal

Crystals in nature contain a large number of defects or imperfections. Some

crystalline materials may exhibit typical electrical properties, such as
ferroelectric effects or piezoelectric effects. Most crystals have various types of
crystallographic defects. The type and structure of these defects can have a large

4
 effect on these material properties. Crystal defects can occur due to solidification
(cooling) or other environmental influences. The simplest defect is the loss of an
atom in a certain position in a crystal called a Schottky defect. Crystal defects
that occur in a material can affect certain physical properties such as mechanical
properties or electrical properties. Crystal defects can be modeled by the
displacement of an atom (or molecule) from a point in a crystal to the surface.
This change is endothermic but is offset by an increase in entropy due to an
increase in crystal irregularities. Crystal defects usually occur because of:

a. Vibration effects that occur in atoms, so that atoms move easily

b. Inclusion or the presence of foreign atoms

c. External forces which allow atoms to move, for example: thermal loads and
mechanical loads. Due to the imperfections of the atomic arrangement, the strength
drops.

The crystal response to the heat received from the environment can be
determined through the thermal properties of the material. In the crystal industry,
especially in ceramic materials, the important thermal properties in ceramic
materials are heat capacity, coefficient of thermal expansion and thermal
conductivity. The heat capacity of materials is the ability of materials to absorb
heat from the environment. The heat absorbed will be stored by the material in
the form of vibrations of the atoms that make up the material.

Ceramics usually have strong bonds and light atoms so that the vibrations
of the atoms will have a high frequency. In addition, because the bond is strong,
a large vibration will not cause too much interference to the crystal lattice.

Heat transfer in materials involves the transfer of energy between vibrating

atoms. Atomic vibration will affect the motion of other atoms next to it and the
result is a wave that moves at the speed of light which called phonon. The
phonon moves in the material until it is scattered by the interaction of phonons
and crystal defects.

The thermal capacity of a material states the amount of heat needed to

increase the solid temperature by one K. While thermal conductivity states an
intensive quantity of material that shows its ability to deliver heat. Materials that
have large thermal conductivity are good heat conductors. While materials that
have small thermal conductivity are poor conductors of heat. Ceramic as one of
the crystalline materials has a good value of heat capacity and low heat
conductivity so that its heat conductivity is low. The lower the heat conductivity

5
 of the ceramic, the better the quality of the ceramic. Because in general ceramics
are used as heat isolators.

The value of heat capacity of a material, especially crystalline material,

can be determined through Maxwell-Boltzmann statistics. In addition, the
average energy of the vibrational lattice in the crystal can also be determined
through Maxwell-Boltzmann statistics.

2.3 The Average Vibrational Energy’s Lattices and Heat Capacity of Crystal

Crystals are composed of atoms that vibrate at the equilibrium position.

The vibrations of atoms at room temperature are a result of thermal energy,
which is the heat energy that atoms have at a certain temperature. Crystals are
composed of atoms that are always vibrating, so that atoms are seen as a
collection of similar harmonic oscillators. To be able to know the average energy
of vibrations of atoms in a crystal, each atom is seen as a free harmonic
oscillator. There is no interaction between one atom and another. Albert Einstein
proposed a simple model by assuming the movements of each atom making up a
free material with each other and in the form of a three-dimensional harmonic
swing. Using this model and using statistical mechanics, the energy of one
molecule can be determined using the Hamilton function, namely:

ε=Ek + E p

1 p
Ek = mv 2 v=
2 , which p=mv and m

1
Ek = mvv
2

1 p2
Ek =
2 m

p2 1
Ek = E p = kx 2
2m (kinetic energy) dan 2 (potential energy)

p 2+ p 2 + p
x y x2 1
ε= + k ( x 2+ y 2+ z2 )
2m 2
(1)

6
 If the principle of equipartition energy is applied in this case, then at a
sufficiently high temperature, the average energy due to this atomic movement
is:

kT
ε̄=6× =3 kT
2
(2)

Because molecules experience polyatomic movements (3 translations, 2 rotations and 1

vibration). So, the value of crystalline heat capacity is 3 Nk or 3R and this result
corresponds to most solids, known as Dulong and Petit Law.

The experimental results show that for low temperatures, it turns out the
heat capacity of the type of solid, no longer equals 3Nk or 3R, but the value is
smaller, even the value is close to zero, when the temperature is close to zero
Kelvin (Sears-Salinger, 1982).

This can be understood using quantum mechanics in discussing the energy

status of harmonic swings. Based on quantum mechanics, vibrating atoms
cannot have arbitrary energy. The energy that the oscillator has is discrete which
satisfies the following equation:

ε n =( n+ 1/ 2 ) ℏ ω (3)

h
ℏ=
with 2π and ω expresses the oscillation characteristic frequency and n
denotes an oscillating quantum number with a value of 0,1,2,… ∞ .

The average energy of atomic vibrations in the crystal can be determined by

assuming that the distribution of the oscillator at a given energy follows the Maxwell-
Boltzmann distribution. Thus, the chance of an oscillator having an energy equal to
ε n =( n+ 1/ 2 ) ℏ ω satisfies the following equation .

−ε n /kT
Pn ∝e

or

Pn =C exp (−ε n / kT )
(4)

7
with C declaring the normalization constant. The opportunity to get an oscillator at all
∞
∑ Pn=1
energy levels is one or n=0 . The sum of these equations produces normalization
factor values in the following forms:

1
C= ∞
−εn /kT
∑e
n =0 (5)

Then, the probability of finding an oscillator in a state with a quantum number n is as

follows.

exp (−ε n / kT )
Pn = N
∑ exp (−ε n / kT )
n=0 (6)

Based on equation (4), it can be seen that the average energy of the oscillator is as
follows:
∞
ε̄= ∑ ε n Pn
n−0
∞
∑ ε n exp (−ε n/kT )
ε̄= n=0∞
∑ exp (−εn /kT )
n=0 (7)

To facilitate the sum of equations (7), β can be used to states −1 /kT , so equation
(7) can be stated as follows.
∞
∑ εn exp ( βεn )
ε̄= n=0∞
∑ exp ( βε n )
n=0
(8)

By using the following example.

∞
βε n
Z =∑ e
n=0
(9)

8
If equation (9) is differentiated against β , it will be obtained :

dZ ∞ d βεn ∞ −ε
=∑ e = ∑ ε n e n
dβ n=0 dβ n=0
(10)

Thus, the average energy of the oscillator is as follows.

1 dZ
ε̄=
Z dβ
d
ε̄= ln Z
dβ
(11)

The value of Z in equation (11) can be determined in the following way.

∞ ∞
βε n
Z =∑ e =∑ e
β ( n+1 /2 ) ℏ ω

n=0 n=0

∞
β ℏ ω /2
Z =e ∑ e nβ ℏ ω
n=0 (12)

Using the Maclaurin series, if |x|<1 then applies :

∞
1
1+x+x 2 + x3 +.. .= ∑ x n=
n=0 1−x (13)

By comparing equations (12) and (13), it can be seen that x in equation (11) is
β ℏω
equivalent to e . So that it can be written as follows.

1
Z =e
β ℏ ω /2
( 1−e
βℏω )
(14)

Based on equation (14) then :

β ℏω
ln Z = −ln ( 1−e β ℏ ω )
2

d ℏω 1
ln Z= − ×(−ℏ ωe β ℏ ω )
dβ 2 ( 1−e β ℏ ω )

9
 d ℏ ω ℏ ωe β ℏ ω
ln Z= +
dβ 2 ( 1−e β ℏ ω )

Thus, the average energy of the oscillator becomes:

βℏω
d ℏ ω ℏ ωe
ε̄= ln Z= +
dβ 2 ( 1−e β ℏ ω )

ℏω ℏω
ε̄= +
2 ( e−β ℏ ω −1 )

ℏω ℏω
ε̄= +
2 ( e ℏω /kT −1 )
(15)
ℏ ω/ kT
Based on equation (15), if T →0 then e →∞ . Based on these properties,
ℏω ℏω
ε̄ → ε̄ →
2 . Energy 2 is called energy at zero point.

The form of the Hamilton equation as in equation (1) shows that

oscillations in three dimensions can be considered as three ordinary harmonic
swings, each in the direction of the x axis, y axis and z axis. Thus the status and

energy state are determined by three quantum numbers x y and n z , each

n ,n ,
of which can be worth 0, 1, 2,3 and so on. The amount of energy for this status is
:

ε n =ℏ ω ( n+1/ 2 )

ε ( n x , n y , nz ) =ℏ ω [ ( n x +1/ 2 ) + ( n y +1/ 2 ) + ( n z +1/ 2 ) ]

(16)

Using the same method, according to equation (15), obtained:

1 1
ε̄=3 ℏ ω
( + ℏω /kT
2 (e −1 ) )
(17)

Heat capacity at T temperature, obtained through:

10
 d ε̄
c v =N
dT
(18)

And obtained :

ℏω
ℏω ( kT )
exp
c =3 Nk
v ( kT ) exp ℏ ω −12 2

[ ( kT ) ]
(19)

or

hv
hv ( kT ) exp
c =3 Nk
v ( kT ) exp hv −1 2 2

[ ( kT ) ]
The above equation is obtained from the heat capacity that defined as follows:

dU
C v=
dT (U = Internal Energy and T = Temperature)
∞
d hv
C v=
dT ∑ ∫ gp( v) hv
dv
p=0
exp ( )
kT
−1

{()}
d 1
C v= ∑ ∫ g p ( v ) hv dv
p=0 dT hv
exp −1
kT
(20)

To simplify equation (20), it can be done by considering the differential

hv
y=
terms in the equation. To simplify the solution, you can specify kT , then:

d d dy
=
dT dy dT

11
 d hv d
=− 2
dT kT dy

{ ( )}
{ }
d 1 dy 1
=
dT hv dT e y−1
exp −1
kT

{ ( )}
{ }
d 1 hv d 1
=− 2
dT hv kT dy e y −1
exp −1
kT

d
dT
{ ( )}
1
hv
exp −1
kT
hv d
=− 2
ey
kT dy ( e y−1 ) 2 { }
d
dT
{ ( )}
1
hv
exp −1
kT
hv
= 2
ey
kT ( e y −1 )2 { }

{ [ ]
}
hv
exp

{ }
d 1 hv kT
= 2 2
dT hv
exp
kT (
−1
kT
) ( [ ] )
exp
hv
kT
−1

Thus, heat capacity can be written as follows:

{ [ ]
}
hv
∞ exp
hv kT
C v= ∑ ∫ g p ( v ) hv dv
kT 2 2
p=0
( [ ] )
exp
hv
kT
−1

12
 { }
[ ] hv
2 ∞ exp
h kT 2
C v= ∑ ∫ gp v
kT 2 p=0
( ) 2
v dv

( [ ] )
exp
hv
kT
−1

To determine the crystal heat capacity, Einstein proposed a model that all
phonons oscillate with the same characteristic frequency, v 0 . With this
assumption, it can be written as follows :

g p ( v )=Nδ ( v−v 0 )

δ ( v−v 0 )
Where is the Dirac delta function. With this model, the crystal heat capacity
is obtained for just one type of polarization :

{ }[ ] hv
2 ∞ exp
h kT 2
C v= ∑ ∫ gp v
kT 2 p=0
( ) 2
v dv

( [ ] )
exp
hv
kT
−1

{( [ ] ) }
[ ] hv
2 ∞ exp
h kT 2
C v= ∑ ∫ Nδ ( v−v 0 )
kT 2 p=0 2
v dv
hv
exp −1
kT

C v=
Nh 2 [ ]
exp
hv 0
kT
v
kT 2 2 02

( [ ] )
exp
hv 0
kT
−1

For 3-dimensional crystals, there are three possible phonon directions (direction of x, y
and z). Assuming that the three polarizations contribute the same amount of energy, the
total heat capacity becomes three times that seen in the equation above, which is to be:

C v=
3 Nh 2 [ ]
exp
hv 0
kT
v
kT 2 2 02

( [ ] )
exp
hv 0
kT
−1

13
In special cases, namely when T →0 and T →∞ . In condition T →0 , then

exp [ ]
hv 0
kT
>> 1
, so
exp [ ]
hv 0
kT
−1→exp [ ]
hv 0
kT . And then as a result

C v≈
3 Nh 2 [ ]
exp
hv 0
kT
v
kT 2 2 02

( [ ] )
exp
hv 0
kT
−1

2
3 Nh v
C v=
kT 2
0
2
exp [ ]
hv 0
kT (21)

In equation (21), if T →0 is the denominator T 2 →0 and the numerator is

exp − [ ]
hv 0
kT
→0
, but the numerator goes to zero much faster than the denominator.

Thus,
C v →0 if T →0 .

hv 0
→0
For case T →∞ , then kT , it can be approximated to be the following
equation:.

exp [ ]
hv 0
kT
≈1+
hv 0
kT

hv 0
1+
3 Nh 2 kT
C v≈ v
2 02
kT 2 hv 0
( 1+
kT
−1 )
2 2
3 Nh kT
C v≈ 2 v2
kT hv0 0 ( )
C v=3 Nk

C v=3 ( nN A ) k

C v=3 n ( N A k )

14
 C v=3 nR

To determine the heat capacity of a crystal, you can use the example
x= ( kThv ) . At a
high enough temperature x << 1 , it can be stated:
2
x
exp ( x )−1=1+x + +. ..−1=x
2! (22)

So :
2
x
C v=3 Nk
exp ( x ) (23)

hv 2
C v=3 Nk
kT( )
hv
exp ( )
kT

If x is greater, then the square of x gets bigger, much faster than any rank, consequently:
C v →0 for x →∞ .

Although the model proposed by Einstein is very simple, it qualitatively matches the
type of heat capacity based on experiments, which can be used to develop other models,
to understand the motion of the atoms in the crystal lattice.

CHAPTER III

CLOSING

3.1 Conclusion

15
Based on the discussion described in the previous chapter, it can be concluded that:

1. The crystal is composed of regular atoms and the pattern repeats in three dimensions.
Crystals have a long-term regularity of atoms. Crystal structure will be formed when
a base is placed at each lattice point so that the crystal structure is a combination of
lattice and base.
2. The type and structure of crystal defects can have a large effect on the properties of
the crystalline material in particular the thermal properties of crystals. Due to the
imperfections of the atomic arrangement, the strength drops. In the crystal industry,
especially in ceramic materials, the important thermal properties in ceramic materials
are heat capacity, coefficient of thermal expansion and thermal conductivity. The heat
capacity of materials is the ability of materials to absorb heat from the environment.
The heat absorbed will be stored by the material in the form of vibrations of the
atoms that make up the material.
3. Based on Maxwell-Boltzmann statistics it can be seen that :
a. The average energy of crystalline atoms assumed to be an oscillator can be stated
as follows:
ℏω ℏω
ε̄= +
2 ( e ℏω / kT −1 )
b. The heat capacity of crystals using the Maxwell-Boltzmann statistical obtained as
follows:
hv 0
→0
 For case T →∞ , then kT , it can be approximated to the following
equatio:
C v=3 Nk
 At a high enough temperature, x << 1 , the heat capacity of the crystal is stated
as follows:
2
x
C v=3 Nk
exp ( x )
or
2
hv
C v=3 Nk
( )
kT
hv
exp ( )
kT

3.2 Suggestion

The suggestion that the writer can give to the reader is that the reader should
better understand the other Maxwell-Boltzmann statistical applications. For

16
writing an application paper with the same title the author should use Debye's
theory in explaining the heat capacity of crystal types in order to obtain results
that are in accordance with the experiment.

17
 DAFTAR PUSTAKA

Abdullah, Mikrajuddin. 2007. Pengantar Fisika Statistik untuk Mahasiswa. Bandung : Institut
Teknologi Bandung.

Efendi, Mutiara. 2014. Pengantar Fisika Zat Padat (Struktur Kristal). Diakses pada
https://www.academia.edu/6402506/PENGANTAR_FISIKA_ZAT_PADAT_struktur
_Kristal_ pada tanggal 4 Juni 2019.

nn. Statistik Maxwell-Boltzmann. Diakses pada

https://ranahfisika.files.wordpress.com/2014/06/fisika-statistik-maxwell-
boltzman1.pdf pada tanggal 4 Juni 2019

Sears, Salinger. 1982. Thermodynamics, Kinetic Theory, and Statistical Thermodynamics Third
Edition. America : Addison-Wesley Publishing Company.

Sudiarta, Wayan. 2012. Fisika Statistik. Mataram : Universitas Mataram.