B.Sc./Part-I/Hons.

/CEMA-II/2018

WEST BENGAL STATE UNIVERSITY

B.Sc. Honours PART-I Examinations, 2018

CHEMISTRY-HONOURS
PAPER-CEMA-II
Time Allotted: 2 Hours Full Marks: 50
The figures in the margin indicate full marks.
Candidates should answer in their own words and adhere to the word limit as practicable.
All symbols are of usual significance.

CEMAT-12-PA
Answer any two questions taking one from each Unit
Unit-I
1. (a) The number of gas molecules of mass m having speed in the range c and 3
mc 2
−
c + dc is given as dN = Ac e 2 2k BT
dc .
Obtain an expression for ‘A’. What is the unit of ‘A’?
∞
1⎛ π ⎞
1/ 2

∫ x e dx = 4 ⎜⎝ a 3 ⎟⎠
2 − ax 2
Given: .
0

−23
(b) The mass of each molecule of a Maxwellian gas is 5.18 ×10 g. Find the 2
average momentum of the gas molecules at 27°C.
(c) Calculate the frequency of nitrogen-nitrogen collisions in one cubic 4
centimeter of air at 1 bar and 20°C. Assume that 80% of the molecules are
nitrogen molecules.
The collision cross section of nitrogen molecule is 4.5 ×10 −19 m 2 .
(d) The principle of equipartition of energy predicts the value of heat capacity 2
ratio γ (γ = C p CV ) for H2(g) more accurately at 110 K compared to that at
10 K. The Boyle temperature of H2(g) is 110 K. Comment on the result.
(e) The mean free path of an ideal gas at 27°C and 1.0 atm is 10 −5 cm . Suppose 2
the gas is taken to a high altitude where the pressure is only 100 mm of Hg.
Calculate the temperature at which the gas will have the same mean free
path at the high altitude.

2. (a) Write down Maxwell’s expression for the distribution of molecular speeds 5
in three dimensions and derive the expression for the number of molecules
with translational kinetic energies greater than ε ′ , assuming ε ′ >> kT.

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B.Sc./Part-I/Hons./CEMA-II/2018

(b) Find the dimension of 1 /(σ 2 nc ) where σ, n and c are the collision 2
diameter, number of molecules per unit volume and mean speed of
molecules respectively.
(c) Show schematically the Maxwellian distribution of speed of gas molecules. 4
Indicate on the plot the following.
(i) most probable, rms and average speed (relative values)
(ii) fraction of molecules having speed greater than a certain value (c say)
How will be the plot be different for CO2 and He at the same value of
temperature?
(d) Find an expression for the number of molecules striking the unit area of wall 2
of container per unit time.

Unit-II
⎡ σ 12 σ 6 ⎤
3. (a) The Lennard-Jones potential is expressed as U (r ) = 4ε ⎢⎛⎜ ⎞⎟ − ⎛⎜ ⎞⎟ ⎥ , 3
⎣⎢⎝ r ⎠ ⎝ r ⎠ ⎦⎥
where r is the internuclear separation. Find an expression for the minimum
value of the internuclear separation (rmin ) in terms of σ and hence show that
the minimum value of the potential energy is U (rmin ) = −ε .
(b) Calculate the change in surface energy when two identical mercury droplets 3
of diameter 2 mm merge to form one drop (assume the process to be
isothermal). Surface tension of mercury = 490 dyne cm −1 .
(c) For the He gas, Pc = 2.24 atm and Tc = 5.2 K. Calculate the radius of the 3
molecule of helium gas.
(d) The virial equation in terms of V ( V is molar volume) is given as: 3
B (T ) B3V (T )
Z = 1 + 2V + + .....
V V2
Where, Z is the compressibility factor. Express the van-der Waals equation
for a gas in terms of the virial equation and hence justify that in the limit of
every low pressure or very high temperature the behavior of the gas
approaches ideality.

4. (a) Draw schematically the PV vs P isotherms for N2 stating the characteristic 3

features at temperatures below, above and at TB.
(b) The second virial coefficient of methane can be approximated by the 3
−c /T 2 −1
empirical equation B(T ) = a + be , where a = −0.1993 bar ,
−1
b = 0.2002 bar and c = 1131 K .
2

What is the Boyle temperature for methane?

(c) Glycerol flows faster at higher temperatures. — Explain. 3
(d) Find the numerical value of compressibility factor (Z) of a gas that obeys the 3
equation of state P(V – nb) = nRT. The pressure and temperature are such
that V/n = 10b.

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B.Sc./Part-I/Hons./CEMA-II/2018

CEMAT-12-PB

Answer any two questions taking one from each Unit

Unit-I

5. (a) For a fixed change in volume, the reversible adiabatic expansion will 2
produce the maximum drop in temperature than the irreversible one. Justify
or criticize.
(b) The temperature of an ideal gas, with constant heat capacity, is changed 3
from T1 to T2 by a constant pressure process and by a constant volume
process, then ΔS P = ΔSV ( ΔS refers of the gas). Justify or criticize.

⎛ ∂P ⎞ ⎛ ∂V ⎞
(c) Prove that: C P − CV = T ⎜ ⎟ ⎜ ⎟ and hence find the condition when 4
⎝ ∂T ⎠V ⎝ ∂T ⎠ P
C P = CV . Give one example of such a system.

(d) Explain whether the heat of an uncatalysed reaction is different from that of 4
a catalysed reaction at a given temperature. When will be the heat of a
reaction independent of temperature?

6. (a) Justify or criticize any one of the following statements: 2

(i) ΔH = q for a process in which the initial and final pressures are same
but the pressure is not constant throughout.
(ii) Any adiabatic process must be isentropic.
⎛ δα ⎞ ⎛ δβ ⎞
(b) Show that ⎜⎜ ⎟⎟ + ⎜ ⎟ = 0 , where α is the coefficient of thermal 2
⎝ δp ⎠T ⎝ δT ⎠ p
expansion and β is the compressibility factor.
(c) Using a suitable thermodynamic equation of state evaluate the quantity 4
⎛ ∂U ⎞
⎜ ⎟ for an ideal gas and a van-der Waals gas. Comment on the results.
⎝ ∂V ⎠T
(d) 1 mole of an ideal gas is subject to undergo a reversible cycle involving the 5
following steps:
Step 1: Isothermal expansion at temperature T1 from p1, V1 → p2, V2
Step 2: Isochoric change of state from p2, T1 → p3, T2 (p3 < p2)
Step 3: Adiabatic compression from p3, V2, T2 → p1, V1, T1.
(i) Represent the cycle on a properly labeled p-V diagram.
(ii) Elucidate the expression for work-done for each step.
T1 − T2
(iii) Show that the efficiency of the cycle is η = 1 − .
T1 ln(T1 / T2 )

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B.Sc./Part-I/Hons./CEMA-II/2018

Unit-II

7. (a) A first order reaction is 20% complete in 15 minutes at 300 K. The same 4
reaction is 39% complete in 10 minutes at 320 K. Calculate the energy of
activation (EA). Will the result (the value of EA) differ if the reaction be of
second order?
(b) A catalyst increases the rate of the forward reaction by 10%. Calculate the 2
change of rate (increase / decrease) of the backward reaction.
(c) Consider the following process 4
A ⇌ B
t=0 a 0
t=t a–x x
Find x as a function of t and find also the value of x as t → 0 and t → ∞.
(d) It is customary, in the study of kinetics of a reaction, to “chill” the reaction 2
by adding an aliquot of the reaction mixture in a large volume of cold water.
Explain why these two conditions are used.

8. (a) Write the Arrhenius equation for the variation of rate constant with 2
temperature. Show plots of (i) k vs T and (ii) log k vs 1/T.
(b) Draw schematically the energy profile for an exothermic reaction and 3
indicate (i) the activation energy for the forward and the backward reactions,
(ii) ΔH of the reaction, (iii) effects of addition of a positive catalyst.
(c) (i) The rate constant (k) of a reaction is given as a function of temperature(T) 2
as follows.
2.5
log k = +2.1 − + 0.5 log T
T
Find the value of the activation energy of the reaction.
(ii) Find the time for completion for a second order reaction. 2
≠
(d) Explain the term entropy of activation (ΔS ) . Comment on the sign of 3
ΔS ≠ .

——×——

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