1.(a) The mean speed of the molecules of an ideal gas is 2.0x 10^3ms^-1 .

The radius of a gas

molecule is 1.5 x10^-10 m.Calculate the (i) collision frequency, and (ii) mean free path. It is
given that n = 4 x10^24 m−3

1.(B) Write van der Waals’ equation of state for one mole of a gas. What do the symbols a
and b signify? Under what conditions does this equation reduce to ideal gas equation?

Van der waal's equation for gas; (P+V2n2a)(V−nb)=nRT

For 1 mole of gas, the equation is:- (P+V2a)(V−b)=RT

The constant 'a' gives the idea of the magnitude of attractive forces between
the molecules of the gas and 'b' is the measure of effective volume occupied
by the gas molecules in the van der Waals equation. It is also called co-
volume or excluded volume
At low pressure , the distance between the molecules is large. At high temperatures , these
molecules are moving wit great speeds. Under these conditions , intermolecular interactions are
minimum. Thus , a real gas behaves like an ideal gas and the van der Waals equation reduces
itself to the ideal gas equation.
1.(c) The expression for the number of molecules in a Maxwellian gas having speeds in
the range v to v + dv asdNv = 4πN (m/2πkBT)3/2 v2 exp [-(mv2/2kBT)] dv
Using this relation, obtain an expression for average speed. Also, plot Maxwellian
distribution function versus speed at three different temperatures.

Maxwellian gas having speeds in the range v to v + dv as

dNv = 4πN (m/2πkBT)3/2 v2 exp [-(mv2/2kBT)] dv

Using this relation, obtain an expression for average speed. Also, plot
Maxwellian distribution function versus speed at three different
temperatures.
1.(d) What is Brownian motion? State four significant characteristics of
Brownian motion
Brownian motion is the random movement of small particles suspended in a liquid or
a gas.

Significance of Brownian motion

It tells us that particles are tiny nature and the particles of a matter are constantly
moving.
Particles of matter have spaces between them.
Particles of matter are in continuous movement.
Vital evidence on the existence of atoms and molecules.
The kinetic theory of gases which explains that pressure, temperature and volume of
gases are based on the Brownian motion.

2.(a) Explain the five types of boundaries with one example each (other than the
ones discussed in the study material) encountered in the thermodynamic
systems
1. Fixed boundary:

A boundary incapable of movement during flow of energy between the system and surrounding.

E.g. Fixed boundary is like filled in Gas cylinders.

2. Movable boundary:
A boundary capable to move during energy transfer between the system and surrounding by
expanding or compressing the system inside.

E.g. piston cylinder arrangement in a engine.

3. Real boundary:

A well defined margin between system and surrounding .

E.g. If a room is a thermodynamics system then the boundary around it is a real boundary if
windows and doors are closed

4. Imaginary boundary:

A imaginary line is considered during study of a system that is not precisely separated from the
surrounding.

E.g. If a room is a thermodynamics system then the boundary around it is a real boundary if
windows and doors are open.

5. Adiabatic boundary:

A type of boundary that don't allow any exchange of heat and mass between system and
surrounding.

2.(b) For a thermodynamic system, isobaric coefficient of volume expansion ()

and isothermal compressibility () are defined as
Change the a value into alfa and B value into Bita (see the quaestion on print out copy)
2.(c) What is meant by internal energy of a system? State the first law of
thermodynamics in its differential form. Write it for isothermal, adiabatic and
isochoric changes.
The internal energy of a body is understood as the sum of the kinetic energy of the
chaotic movement of molecules and the potential energy of interaction of the
molecules that make up this body. When calculating the internal energy, the kinetic
energy of the movement of the whole body and the potential energy of the body in
the external force field should not be taken into account. Also, the internal energy
does not include intra-atomic energy.
2.(d) Air in an enclosure is compressed isothermally until its pressure is doubled. It is then
expanded adiabatically until its original volume is restored. Its pressure is then recorded as
0.75 of its initial value. Determine the value of 

2.(e) One mole of oxygen at 273 K and atmospheric pressure is adiabatically compressed to 5
atm. Calculate the final temperature. Also calculate the work done on the gas. Take  = 1.4
and R = 8.31 J mol−1 K−1.

One mole of oxygen at STP is adiabatically compressed to 5 atm. Calculate the final
temperature. Also, calculate the work done on the gas. Take = 1.4 and R = 8.31 J mol−1 K−1.
Solution:
Given:
Standard temperature and pressure (informally abbreviated as STP) is
T1 = 273.15 K
p1 = 100 kPa
p2 = 5 atm =5· 101325 Pa = 506.625 kPa
T1 = ?
An adiabatic process is one in which no heat is gained or lost by the system.
The adiabatic condition
𝑝𝑉𝛾 = 𝑐𝑜𝑛𝑠𝑡
where p is pressure, V is volume, and 𝛾 = 1.4 is the adiabatic index.
An ideal gas can be characterized by three state variables: absolute pressure (P), volume (V),
and absolute temperature (T). The relationship between them may be deduced from kinetic
theory and is called the ideal gas law:
𝑝𝑉 = 𝑛𝑅𝑇
where n = number of moles, R = universal gas constant = 8.31 J/mol K.
Hence:
𝑉 =𝑛𝑅𝑇/𝑝
𝑝 (𝑛𝑅𝑇/𝑝)𝛾= 𝑐𝑜𝑛𝑠𝑡
𝑝1−𝛾𝑇𝛾 = 𝑐𝑜𝑛𝑠𝑡
Hence
𝑝1^1−𝛾𝑇^𝛾 = 𝑝2^1−𝑇2^y

𝑇2 = 𝑇1 (𝑝1^1−𝛾/𝑝2^1−𝛾)1/𝛾
𝑇2 = 273.15 ∙ (1001−1.4/506.6251−1.4)1/1.4= 434.25 K

The work, done by the gas in adiabatic process is

𝑊𝑏 = −𝛼𝑛𝑅𝑇1 ((𝑝2/𝑝1)𝛾−1/𝛾− 1)
where α is the number of degrees of freedom divided by two.
α is 5/2 for diatomic gas such as oxygen.
Thus,
𝑊𝑏 = −5/2∙ 1 ∙ 8.31 ∙ 273.15 ∙ ((506.625/100)1.4−1/1.4− 1) = −3346.86 J
And work done on the gas
𝑊 = −𝑊𝑏 = 3.35 kJ
Answer. 𝑇2 = 434.25 K, 𝑊 = 3.35 kJ.

3.(a) Derive Planck’s law of black body radiation

3.(b) Derive the expression for the efficiency of a Carnot cycle for an ideal gas.
Hence, obtain its value for a heat engine operating between fixed temperatures
600 K and 300K

The Carnot cycle consists of the following four processes:

A reversible isothermal gas expansion process. In this process, the

ideal gas in the system absorbs qin amount heat from a heat source at
a high temperature Th, expands and does work on surroundings.
A reversible adiabatic gas expansion process. In this process, the
system is thermally insulated. The gas continues to expand and do
work on surroundings, which causes the system to cool to a lower
temperature, Tl.
A reversible isothermal gas compression process. In this process,
surroundings do work to the gas at Tl, and causes a loss of heat, qout.
A reversible adiabatic gas compression process. In this process, the
system is thermally insulated. Surroundings continue to do work to the
gas, which causes the temperature to rise back to Th.
#####
Efficiency

The Carnot cycle is the most efficient engine possible based on the
assumption of the absence of incidental wasteful processes such as
friction, and the assumption of no conduction of heat between
different parts of the engine at different temperatures. The efficiency
of the carnot engine is defined as the ratio of the energy output to the
energy input.

efficiency=net work done by heat engineheat absorbed by heat

engine=−wsysqh(1.1)

=nRThln(V2V1)+nRTlln(V4V3)nRThln(V2V1)(1.2)

Since processes II (2-3) and IV (4-1) are adiabatic,

(T2T3)CV/R=V3V2(1.3)

and

(T1T4)CV/R=V4V1(1.4)

And since T1 = T2 and T3 = T4,

V3V4=V2V1(1.5)

Therefore,

efficiency=nRThln(V2V1)−nRTlln(V2V1)nRThln(V2V1)(1.6)
efficiency=Th−TlTh(1.7)

Given : For Carnot engine,

⇒T1=600K T2=300K
⇒W=800J
We know,
Efficiency (n)=1−T1T2=QW
⇒QW=1−600300
⇒Q=1−21W
⇒21800
⇒Q=1600J
i.e, heat given to system is 1600J.
Hence, the answer is 1600.
3.(c) Two separate containers are filled with different gases. If these gases are
allowed to mix, obtain an expression for entropy of mixing per mole of the
mixture
To calculate the entropy change, let us treat this mixing as two separate gas
expansions, one for gas A and another for B. From the statistical definition of
entropy, we know that
ΔS=nRlnV1/V2
Now, for each gas, the volume V1 is the initial volume of the gas, and V2 is the final
volume, which is both the gases combined, VA+VB. So for the two separate gas
expansions,
ΔSA=nARln *VA+VB/VA //

ΔSB=nBRln*VA+VB/ VB
So to find the total entropy change for both these processes, because they are
happening at the same time, we simply add the two changes in entropy together.

ΔmixS=ΔSA+ΔSB= nARlnVA+VB/ VA + nBRln*VA+VB/ VB

///

Recalling the ideal gas law, PV=nRT, we see that the volume is directly proportional
to the number of moles (Avogadro's Law), and since we know the number of moles
we can substitute this for the volume:
ΔmixS=nARln*nA+nB/nA+nBRln*nA+nB/nB
Now we recognize that the inverse of the term nA+nB/nA is the mole fraction
/

χA= nA/ nA+nB

After substitution the equation of the entropy can be written as :
S=−R(nAlnχA+nBlnχB)
Entropy increases on mixing the two gases which can be justified by the above
expression which will be always as mole-fraction is always less than unity which will
make the whole term positive
3.(d) Using Maxwell’s relations, deduce first and second TdS equations
3.(E)
Derive Clausius-Clapeyron equation. Explain why the boiling point of
water increases with increasing pressure
The equilibrium between water and water vapor depends upon the
temperature of the system. If the temperature increases the saturation
pressure of the water vapor increases. The rate of increase in vapor
pressure per unit increase in temperature is given by the Clausius-
Clapeyron equation. Let p be the saturation vapor pressure and T the
temperature. The Clausius-Clapeyron equation for the equilibrium
between liquid and vapor is then

dp/dT = L/(T(Vv-Vl))

where L is the latent heat of evaporation, and Vv and Vl are the

specific volumes at temperature T of the vapor and liquid phases,
respectively.

More generally the Clausius-Clapeyron equation pertains to the

relationship between the pressure and temperature for conditions of
equilibrium between two phases. The two phases could be vapor and
solid for sublimation or solid and liquid for melting.

The material below is an examination of the application of the

Clausius-Clapeyron equation to meteorology where the most relevant
systems are water and water vapor and salt water and water vapor.
But the equation also applies to ice and water vapor and ice and
water. Finally there is a derivation of the Clausius-Clapeyron equation
from thermodynamic principles.

Note that Vv is much greater than Vl so that to a good approximation

dp/dT = L/(TVv)

Furthermore the ideal gas equation applies to the vapor; i.e.,

pVv = RT
and hence

Vv = RT/p

where R is the universal gas constant.

Thus

dp/dT = L/(RT²/p)

or, equivalently

(1/p)(dp/dT) = L/(RT²)

In differential form this is

dp/p = (L/R)(dT/T²)

or, equivalently

d(ln(p)) = (L/R)d(-1/T)

If L is independent of temperature then the solution to the differential

equation is

ln(p) = c0 - (L/RT)

or, equivalently

p = c1exp(-L/RT)

where c1 is a constant.

The shape of this function is given below:

The empirical curves have the opposite curvature but clearly the
equation dp/dT = L/(RT²/p) = Lp/T² indicates that as temperature
increases the slope (dp/dT) decreases. Of course, the empirical curves
take into account that the latent heat L can change with temperature,
but the change in L with T is relative small. There is a fundamental
discrepancy between the Clausius-Clapeyron Equation and the
empirical relationships and the published derivations of the equation
blithely show an empirical curve in which dp/dT increases with T and
an equation in which dp/dT is inversely proportional to T. However this
discrepancy will be left unresolved here and the implications of the
Clausius-Clapeyron equation will will be further explored.

For some purposes the density of the vapor is of more interest than the
pressure. By the ideal gas equation, the molecular density D is given
by

D(T) = 1/Vv = p/RT

which for the above

pressure-temperature

relationship is

D(T) = c1exp(-L/RT)/RT

The shape of this latter relationship for some arbitrary values of the
parameters is shown below:

It is a surprise that there would be a case such that as the

temperature goes up the density of decreases. This needs to be
checked for generality.

The ideal gas equation indicates that density would go down as

temperature increases if pressure remained constant. Even if pressure
increases with temperature the density will decrease if the increase in
pressure is not enough to offset the direct effect of the temperature
increase on density. In differential terms the ideal gas equation is

dD/D = dp/p - dT/T

The Clausius Clapeyron equation, when the specific volume of the

liquid is assumed to be zero, gives

dp/p = (LD/p)(dT/T) = (L/RT)(dT/T)

so

dD/D = [L/RT − 1](dT/T)

Thus the effect of a temperature increase on molecular density
depends upon the magnitude of the latent heat of vaporization
compared to RT.

The latent heat of vaporization for water is 2.257×106 J/kg. The gas
constant for water vapor in SI units is 461.5 J/(kg K) so at T=300 K,
RT=1.3845×105 J/kg. Thus L/RT=16.3 and hence dD/D=15.3(dT/T) so if
(dT/T)=1/300 then dD/D = 15.3/300=.051.

4. a) For a Bose-Einstein system, the expression for the thermodynamic

probability is
W=π{(gi+Ni–1)!/(Ni !(gi–1)!)}
Derive an expression for the Bose-Einstein distribution function
4.(B) A box of volume 1 cm3 contains electrons. Calculate their Fermi
momentum and Fermi energy. Take 21 5.2×10
−−−28 24 27 = 9.1×10 g, =1.67×10 g and = 6.62×10 ergs e n mmh
4.(C) Two indistinguishable particles are to be placed in five cells. Enumerate
the possible macrostates and the corresponding microstates .
4.(D) Calculate the partition function, free energy, entropy, CV and Cp of N
linear harmonic oscillators