94 An Introduction To Electrical Engineering Materials

3.10.4 Thermal Behaviour in the Solid State

When a crystalline solid is formed, the atomic forces holding the molecules, being fairly strong,
prevent movement of atoms from place to place. Hence the atoms in a solid can be considered as
being more or less permanently positioned at one point. With all temperatures above O °K, the thermal
energy in atoms will however cause vibration about its centre position. The situation is again similar
to that of a large number of balls arranged in a regular manner all coupled to each other by springs.
Again in this case, exchange of energy via. the springs will result in some atoms vibrating at higher
amplitudes (and hence energy) than others. Although each atom has at any instant some kinetic
energy due to its velocity ofvibration, it also possesses some potential energy which may be imagined
to be stored in the springs. However since the vibration of neighbouring atoms exert random forces
on any atom, both the kinetic and potential energies are continuously changing. Due to the random
nature of these forces, the distribution of energies will be of a similar form to that of the Maxwell•
Boltzmann equation for the distribution of energies in a gas (Equation 8).

Atomic movement in a solid will occur when any atom has

enough energy to overcome the forces binding it to the lattice.
We have seen that the atom's position in the lattice will always
be one in which its total energy is minimized. In general,
molecular (or atomic) movement in a solid will take place due to
defects. However, defects, on the other hand, may also be created
by this same process. Consider the case shown in Fig 3. 9 in which
I .
an atom moves from its place into an adjacent vacancy. The atom
is quite stable at positions A and B but not at position C. Some I I

small excess energy will be required if the atom is to move from

A to C and then from C to B. The total energy of the molecule
will have to change as shown as it moves from A to B vi a. C. The
molecule will need a certain excess of energy before it moves.
Note that after movement a vacancy will exist at A into which
other molecules may move. It may be seen that the larger the �
number of vacancies, the greater is the movement of atoms via I I I

this mechanism.
- Diffusion -I
I path

Fig. 3.9 The movement of an atom

in a solid into an adjacent vacancy

Atoms may move even when there are no vacancies or other such defects. Consider the case of
an atom which is surrounded by other atoms on all sides. If this atom acquires enough energy it may
move to a higher energy stable position in an interstitial site. Further motion of this atom may occur
by movement to other interstitial positions until a vacancy is found. Movement of atoms by this
mechanism results in the creation of vacancies and interstitial defects. In this case, thermal vibration
may give certain atoms enough energy to move into interstitial positions and hence cause atomic
movement. These atoms which are capable of motion through the lattice are often referred to as free
atoms.

The number of free atoms in interstitial positions will obviously be equal to the number of
vacancies. This number strongly depends on the temperature. If the temperature is large, the number
of atoms having enough energy to move into interstitial positions will be large. If it is small, this
number too will be small. Due to the random nature of the exchange of energy between vibrating

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 atoms, the number of vacancies is given by an equation containing the Boltzmann factor, e -( !, J ,

thus,

nv =No.of vacancies per unit volume= Kne-kT ... (15)

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 Conductivity ofMetals (Part II) 95

where n = number of atoms per unit volume.

W = energy required to move an atom into an interstitial position.

K =constant

The exponential increase in vacancies (and hence atomic movement) is the main reason why
materials become softer and more ductile as their temperature is raised. Thus the mechanical properties
of materials are very sensitive to the number of defects.

When an atom vibrates, it has an amplitude of vibration. This amplitude being related to the
thermal energy of the atom will also be dependent on the temperature. Now we have seen that there
is a wide distribution of energies between atoms in a solid. Although atoms in a solid have different
amplitudes of vibration, we may associate an average value a to this oscillation. Since each atom is
connected (coupled) to other atoms (by a spring) the vibration of an atom may be described by the
equation for simple harmonic motion. Its distance x from its centre position at any time tis given by

x = a sin (2nft) ... (16)

where a = Average amplitude of vibration

f = frequency of vibration

Each atom has an average thermal energy dependent on the degrees of freedom it has. In this
case, the atom possesses no translational or rotational energy. All its energy is associated with the
vibration of the atom about its centre position. An atom, because of its spring coupling, can change
both its kinetic and potential energies in any of the three dimensions. Each atom therefore can
change 6 independent types of energies, three kinetic and three potential. The average energy of the
atom, from Boltzmann's rule, may hence be evaluated.

Average Energy= Degree of freedom x (1 I 2)kT

= 6x (l/2)kT = 3kT ... (17)

Differentiating equation (16) we get

v = dxl dt = 2nfacos (2nft) ... (18)

The kinetic energy of the atom at any time tis

Ek.e = (1/ 2)mv

2 2 2
= (1/ 2) m (2n/) a cos2(2nft)
... (19)

At any instant, an atom possesses both kinetic and potential energies that are continuously
changing. However when the atom is in the centre position it has no potential energy, all its energy
being kinetic. The atom is at the centre when t = 0. Equation (19) reduces

to E k.e = 2mn2f2a2 att = 0 ... (20)

Now this energy must be equation to the thermal energy since the atom at this position has no
potential energy.

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 Therefore, Kinetic Energy at t = 0 = Thermal energy

2mn2 f2a2 = 3kT ... (21)

... (22)

The amplitude of vibration is proportional to the square root of temperature.

The frequencies of vibration found in almost all materials are in the infra-red frequency band

(3 x 1011 Hz to 3 x 1014 Hz).

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 96 An Introduction To Electrical Engineering Materials

The amplitude of vibration of copper atom is approximately 2.556 A at its melting point, 1083°C.
Since atoms in a solid such as copper can be considered as tightly packed spheres, the material
structure will break down when the oscillation due to the thermal energy exceeds the atomic separation
between two ions. Since this separation in copper is equal to twice its radius, the material will lose
its regular structure when the amplitude of oscillation exceeds the diameter of the atom. At 1083 °C
the amplitude of oscillation is in fact equal to the atomic separation 2 x r as predicted. Copper loses
its/ c. c. structure and becomes a liquid at this temperature.

The above case for copper atom illustrates the basic reason why solids melt at high temperatures.
At the melting point, the amplitude of vibrations is so large the regularity of the lattice is broken
resulting in a major change in structure.

Certain materials do not pass through the liquid phase with decreasing temperature. For example,
Carbon dioxide gas never forms a liquid but changes directly into a solid. This gas to solid transition,
called sublimation, is found in almost all materials under certain conditions.

This property of sublimation is often used in the electronics industry in producing the extremely
pure pieces of semiconductors needed for the manufacturing of diodes and transistors. Silicon
sublimates at atmospheric pressure upto temperatures near 1200°C. A mixture of hot Silicon
tetrachloride SiC14 and Hydrogen is passed over a small piece of Silicon called the substrate at

temperatures around 1200°C. Silicon tetrachloride and Hydrogen react to form pure Silicon vapour
and Hydrogen chloride.
SiC14 + 2H2 = Si+ 4HC1 ... (23)
The Silicon vapour sublimates onto the substrate since the temperature is lower than its
sublimation point. As deposition continues, a very pure layer of Silicon with very few defects is
grown onto the substrate. This very thin pure layer is used to make the transistors and integrated

circuits needed in the electronics industry.

3.11 THERMAL CONDUCTIVITY OF METALS

It is observed that materials which are good conductors of electricity are also good conductors
of heat (cf Table 3.4) suggesting that conduction of heat must be associated with the movement of
electrons.

When a homogenous isotropic materials is subjected to a temperature gradient, a flow of heat

results in a direction opposite to the gradient. Thus if dT/dx represents the temperature gradient, the
quantity of heat flowing per second is found from the expression.

Q=K.AdT/dx ... (24)

If Q is expressed in watts, dT!dx in °K per metre and the area of cross-section A in sq. metres,
then the coefficient of thermal conductivity, K is given in watts/ metre x OK.

In insulating solids, the heat is carried by the lattice vibrations. This in part, is also the case in
metals, but the thermal conductivity due to the conduction electrons predominates in both insulators
and conductors.

Table 3.4: Thermal Conductivities

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 Substance Thermal conductivity Substance Thermal conductivity

Kea/Im Hr. degree Kea/Im. Hr. degree

Aluminium 180 Cardboard 0.12 - 0.30
Brass 73.5 R.C.C. 1.33
Cast iron 54 Glass 0.64
Copper 335 Paper 0.12

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 Conductivity ofMetals (Part II) 97

Gold 269 Water 0.5

Mercury 25 Cork 0.03 - 0.12
Silver 360 Fire brick 0.3 - 0.9
Steel
} 39 Plastics 0.1- 1.6
Bakelite 0.25 Porcelain 0.7 - 1.6
Varnish Rubber 0.11-0.2

The electrons at the hot end have a higher kinetic energy. They move to the cold end where the
excess energy is released to the atoms whereby the thermal agitation of the atoms and the temperature
increase. The electrons of the cold end have less kinetic energy; so in passing to the hot end they
decrease the thermal agitation and the temperature. Since the same electrons also conduct electric
current, the transfer of heat and the conduction of current must be closely related processes.

Finally, the total energy transferred across a cross-section is dependent upon

(i) N, the number of electrons/m3

(ii) V, the average velocity of the electrons

(iii) dW the energy gradient

dx '

(iv) '"A, the mean free path, and

(v) A, the area of cross-section or QaNV. dW!dx x A x '"A. The above formula checks
dimensionally, hence we conclude that

Q = constantxNV.xdW /dx.M ... (i)

the constant is a numeric (having no dimensions) and will, accordingly, have the same value for
all materials. Further, since energy is a function of temperature which in tum is a function of position,
we may write.

Q = constant x NV.'"A::;: · 1 ·A ... (ii)

Comparing expression (i) and (ii), we observe that the coefficient of thermal conductivity is
given by

K = constant x NV'"A ::;: .

dW/dT is the rate at which the average energy of an electron increases with temperature. It is
called the specific heat of an electron in the metal.

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 3.12 SPECIFIC HEAT OF METALS

Electron gas theory is the starting point in making the study of specific heat. From the kinetic

theory of gases we know that the total internal energy of simple gases is I RT , where R is the
2
universal gas constant. R equals KA where K is the Boltzmann constant and A is the Avogadro's
number. The specific heat of gases at constant volume, which is denoted by Cv, is the rate of change
of internal energy with temperature.

C, = :/r ( f RT J per gm. mole

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 98 An Introduction To Electrical Engineering Materials

3
= r per gm. mole
2

== 3 cals. I mole I °C ... (25)

For solid materials, the total energy is 3RT and therefore the specific heat is 6 cals/mole/°C. For
solids, the specific heat depends upon the vibration of atoms about their mean position. This lattice
contribution to the specific heat can be shown to be approximately 3 cals/mole/°C for temperatures
near room temperature. This value is found experimentally to be reasonably accurate for both metals
and insulators.

The simple electron "cloud" picture of a metal breaks down badly for specific heats of metals.
The simple electron gas theory leads to an electronic contribution of 3 cals/°C/0mole. This discrepancy
was the earliest one to be noted and led to the abandonment of the simple gas theory. The difficulty
was not overcome until it was realised that electrons obey Fermi quantum statistics rather than the
Maxwell-Boltzmann statistics assumed in the classical model of a "free electron gas".

3.13 CONTRIBUTION OF ELECTRONS TO THE HEAT CAPACITY OF METALS

The electronic contribution to the heat capacity of metals is small in relation to the total value.
From Fermi-Dirac statistics, it can be shown that the specific heat of the electron gas is equal to

n2 K
- -2T n2 K
- or - -2T, - per e 1 ectron w here VF i.s theve 1 oci. ty o f th e e 1 ectrons wi.t h t he Fermi. energy and

2EF mT,,�-

K is the Boltzmann constant. This expression leads to a relatively small contribution to the total heat
capacity of a metal and is in reasonable agreement with experiment. Comparison with the classical
value of specific heat, i.e., 3/2 R or 3/2 K per electron shows that the quantum statistical value is
2

smaller by a factor of the order n KT. The reason for this is that only a small fraction of the

3EF
electrons at the top of the energy distribution curve are able to increase their kinetic energy. Electrons
in the middle of the band cannot be raised to higher energies unless they reach energy levels above

EF' since all the energy levels in the middle are already occupied by electrons.

2 2

Using n K � as the value of specific heat, the expression for coefficient of thermal conductivity
mT,,�-

becomes

. '\ dW
K = a Numenc x NVF/\, dT

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 T
= a constant x NVF"A V
F2

N'lT
= a constant x ----V:-
F

= a constant x N.T't

where -r is the collision time.

Comparing this expression for thermal conductivity with that for electrical conductivity
21

(a= Ne.u. = Ne = constant x N x t) it is seen that the ratio a/KT is a universal constant and is
m

called the Lorentz number. The constancy of the ratio o/KT was observed experimentally by
Wiedemann and Franz (1853) and emphasises that good electrical conductors are also good thermal
conductors.

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 Conductivity ofMetals (Part II) 99

Inserting numerical values we find that the Lorentz number is equal to 2.45 x 10- 8 W -n I

degree'.

In the above treatment, we have made use of only the electronic contribution to the thermal
conductivity, and have neglected the contribution due to lattice vibrations.

3.14 THERMO - ELECTRIC EFFECT

There are great many intimate relations between heat and electricity. The basis of the study of
thermo-electric effects arises from the fact that electron motion is altered by the flow of current or
by the application of temperature gradient.

(1) Thomson effect: If a piece of metal is made to have a temperature gradient between its two
ends, an e.m.f is observed to exist between those ends. This effect known as the Thomson effect,
arises since electrons at the hot end tend to move to the cold end. A space charge is established in the
metal producing an electric field the direction of which is from the hot end to the cold end. This
electric field tends to drive the electrons from the cold end to the hot end. When equilibrium is
reached the two effects cancel. Under these conditions the electric field should be proportional to
the temperature gradient. The temperature gradient is negative, because as the distance from the hot
end increase, the temperature decreases. Thus the electric field is in opposite direction to the
temperature gradient, or E = - o dT!dx where dT!dx where dTIdx is the temperature gradient, and o is
the Thomson coefficient which is expressed in units of volts/rC, o varies from metal to metal. For
common metals, it is of the order of a few microvolts per degree. Although the direction detection of
Thomson heat by calorimetric methods is very difficult because it is masked by Joule heat o has
been measured for various metals to a high degree of accuracy.

(ii) Seebeck effect: The thermocouple was discovered by seebeck in 1822 when he demonstrated
that a loop composed of two dissimilar metals could be made to carry a continuous current simply
by maintaining the two junctions at different temperatures. The magnitude of the current depends on
the resistance the metals happen to have; what is characteristic of the thermocouple is its electromotive
force. When the two metals are placed in contact, then a contact potential equal to the difference in
the work function of the two metals is established at the junction (cfArt./3. 6). The work function is
defined as the difference between the escape level and the Fermi level. The Fermi level is subjected

to a small temperature change and this is of the order of 1 o- 5 - 1 o- 4 e V/°K. This causes a difference

in the contact potentials at the two junctions due to the different temperatures at the two ends and the
result is an e.m.f which is free to drive the current. The magnitude of e.m.f is of the order of a few
microvolts per degree temperature difference between the two junctions.

(iii) Peltier effect: In 1834, Peltier discovered the converse effect and the showed that when a
current is passed through the junction of two different metals, heat is absorbed or liberated depending
on the direction of the current. Thus if the Seebeck e.m.f is from metal A to metal B at the hot
junction, an external e.m.f applied in this direction will produce a cooling effect at this junction.
The heat is often referred to as "Peltier heat" and it is equal to the work done in transferring a charge
q from metal A to metal B or nA �B joules, where n is the Peltier coefficient. If heat is absorbed
when current flows across a junction from A to B nA�B is taken as positive nA�B thus equals

= n A� 8 x q . holds both for currents sent through the junction by an external source and for currents

generated by the action of the couple it self.

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 Peltier heat is reversible in the sense that absorption can be changed to liberation simply by
reversing the current. Joule heat is, of course, always liberated and is proportional to the current.
The practical use of Peltier effect is in refrigeration.

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 100 An Introduction To Electrical Engineering Materials

3.15 OPERATION OF THERMOCOUPLE

Consider a thermocouple withjunctions.Z, and.Z, at temperatures T1 and T1 respectively such that

T1 > T1• In order to study the operation of the couple, usually the reversible Peltier and Thomson heats
only are taken into account, and the Joule heat and the heat conducted from the hot end to the
cold end both irreversible effects are ignored.

The net e. m.f acting around the circuit thus is the summation of (i) Thomson effect in metal A,

(ii) Thomson effect in metal B, (iii) Peltier effect at junction JI' and (iv) Peltier effect atjunction.Z;

The Thomson e.m.f in metal A = p.d. between.Z, and J1 in metal A

(-.- E=-<�J
(J A (T4 -T,)

Similarly, the Thomson e.m.f in metal B

-crB(T1 -7;)

Peltier e. m.f at J1 at temperature T1

-7tA�B

Peltier e. m.f at J1 at temperature T1

+1tA�B

The net electromotive force for the complete circuit is

(crA -crB) x (7; -T1)-1tA�B (T2)+ nA�B (I;).

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 If we consider a circuit with junction at temperatures T1 and T1 + dT, where dT is infinitely
small, the result is more simply expressed for the Peltier coefficients are n and n + dn where dn is the
increment or difference inn corresponding to dT, and crA and crB are the values of the Thomson
coefficients for the temperature T. Hence the four gains-of energy given above are respectively

- (n + dx), + n, cAdT, and- crBdT, and we therefore have for dE, the infinitely small electromotive
force in the circuit.

3.15 APPLICATION OF THERMODYNAMICS TO A THERMOCOUPLE

Several important relations may be deduced by applying the principle of thermodynamics to a

thermoelectric circuit. In such circuit, the operations are reversible provided we neglect the joule
heating effect in the conductor. When the electromotive force in the circuit is infinitely small, the
joule heating effect, being proportional to the square of the current, is negligible.

The Peltier and Thomson effects, being directly proportional to the current are reversible in the
above thermoelectric circuit withjunctions at absolute temperatures T and T + dT, since quantities of
energy - (n + dn), - n, oA dT and - oB dT are absorbed at temperatures T + dT, T, T and T, it follows
thermodynamically that

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 Conductivity ofMetals (Part II) 101

1t
or -d 1t + "f' dT + ( o A - o B) di' = 0
7t

or (o A -aB)dT = dn-- dT ... (26)

T

and substituting this value in the expression for dEviz.

dE = (o A - oB) dT - dn

1t

we obtain dE = --.di'
T
This relation indicates the only practicable method of measuring n. It means that for any two
substances, the Peltier coefficient at any temperature is given by the product of the temperature
gradient of the thermoelectric e. m.f at that temperature and the absolute temperature.

From (26), it follows that if for metal A, the value of o be zero (lead), then

dx 1t

-(jB = di' -T
This result expresses the Thomson coefficient at temperature T for metal B in terms of the
Peltier coefficient for metal B and a metal for which the Thomson effect is zero. Again, from equation
(3),

dx 1t

Now,

... (27)

And by differentiating

d2E

Hence,

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 2 d
i _ Td2E =-TP
-Td E _ dE ' dT2 ... (28)
.
ar? di' d
i
2 '
-(Td E + dEJ+ dE
ar?
where - is denoted by
sr: p.

That is, if o A is zero, cr = Td E =TJ).

B dT2 }--'

and if �: be denoted by a,

Equation (27) and (28) are the two fundamental relations which are valid for any pair of metals.
The metals usually employed for thermocouples are :

(a) high conductivity copper and a 60/40 copper nickel alloy (constantan) for temperatures
upto about 500°C.

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 102 An Introduction To Electrical Engineering Materials

(b) pure iron and constantan for temperatures upto about 800°C.

(c) a 90/10 Ni-Cr alloy and an alloy with 95% Ni with the balance of Al, Mn and Si for
temperatures upto about 1100°C.

(d) Pt and Pt-Rh alloy for temperatures upto 1500°C.

The experimental and calculated values of the thermo-e. mj for copper constantan thermocouple
assuming the cold junction to be at 0°C, are tabulated in Table 3. 5.

Table 3.5: Thermo-em/ of Cu constantan thermocouple

T°C E(mV) F(mV)

Experimental Calculated
100° 4.3 4.3
200° 9.2 9.1
300° 14.6 14.5
400° 20.5 20.3
500° 26.7 26.7
From the results for 100 and 500°C, a and pare found to be 40.7 µV/deg and 0.052 µV/(deg)2

respectively.

The thermo-e.mj for the iron constantan and Pt and Pt-Rh thermocouple are tabulated in Table

3.6 the cold junction being kept at 0°C.

Table 3.6: Thermo emf of some metal couples in millivolts

Te mperature Pt. Pt with Iron consta ntan

oc 10% Rhodium

-100 0 -4.75
-200 - -8.15
0 0 0
100 0.64 5.37
200 1.44 10.95
300 2.32 16.55
400 3.25 22.15
500 4.22 27.84
600 5.22 33.66
700 6.26 39.72
800 7.33 46.23
900 8.43 53.15
1000 9.57 58
llOO 10.74
1200 11.94
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1300 13.14
 Conductivity ofMetals (Part II) 103

(PROBLEMS)

1. Give a brief account ofthe temperature dependence of resistivity in a metal and indicate why the
increase in resistivity caused by an impurity is practically independent of temperature.

2. Explain superconductivity and its practical applications.

In case of metals the conductivity decreases with temperature whereas in case of semiconductors
it might decrease and increase as well. Explain qualitatively.

3. How would you interpret thermal conduction and specific heat of a solid in terms of its
microscopic structure ?

4. State the 'Law of emission' of electrons from heated metals. Explain briefly how you would
determine the 'emission equation constants'. Discuss briefly the importance of 'work function'
of the (emitter) metal.

Discuss the effect of space charge on voltage distribution in a diode. State Child Langmuir Law.

5. In copper, at temperatures of 0°C and 200°C the fractional number of free atoms are 1.88 x 10-

21and 1.313 x 10- 13 respectively. Calculate the energy required to move the atom into an
interstitial position. Then evaluate the number of vacancies at a temperature of 1000°C.

[Ans. 1 eV; 7.1462 x 1022 / m3]

6. Calculate the frequency ofvibration of an atom of copper at a temperature of 20°C if the average
amplitude of oscillation is 1.88 A. Calculate also the amplitude of oscillation at the melting

point.

[Ans. 6.42 x 10-11 Hz; 2.556 A]

7. What are the main differences between the gaseous, liquid and solid states ? Explain the motion
of atoms in a solid vi a the interstitial and vacancy mechanisms.

8. If the atomic radius of Aluminium is 1.431 A, calculate the frequency of vibration of the

Aluminium atoms if the melting point is 6660°C.

9. During semiconductor manufacture, a photographic glass plate with two narrow thin black lines
separated by 10.00 cm is used. If the separation of these lines is to remain constant to within

± 2 microns, deduce the types of glass that may be used for the photographic plate if the minimum

and maximum temperature the glass plate is subjected to are 14°C and 28°C. The separation of
the lines given above is that at 20°C. The thermal expansion coefficients of the plate glass,
Borosilicate glass, silica glass and Vycor glass are 9 x 10-6, 2.7 x 10-6, 0.54 x 10-6 and 0.63 x

10-9 °K-1 respectively.

10. The specific heat of a piece of Silicon is 310 Lkg' K-1 at a temperature of 25°C. Calculate its
specific heat an 800°C. Assume T3 dependence. Calculate the heat loss involved when one kg of
the above substance is cooled from 700°C to 500°C.

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 ( Hint: heat loss= J; c,
2
dT ).

11. Explain why the area under the Maxwell-Boltzmann velocity distribution is independent of
temperature. Calculate the change in mean and the most probable velocity when the temperature
of a monatomic gas of molecular weight 200.6 is changed from 400°C to 800°C.

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104 An Introduction To Electrical Engineering Materials

( SELF ASSESSMENT QUESTIONS)

1. Name the four variables which govern the number of gas atoms travelling at a particular velocity.

2. What is the mean free path of a gas related to ?

- Total number of atoms

- diameter of atom

- temperature

- velocity

- volume

-mass
- pressure

- concentration of atoms.