CBCS/B.Sc./Hons./4th Sem.

/CEMACOR08T/2020

WEST BENGAL STATE UNIVERSITY

B.Sc. Honours 4th Semester Examination, 2020

CEMACOR08T-CHEMISTRY (CC8)
PHYSICAL CHEMISTRY

Time Allotted: 2 Hours Full Marks: 40

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.

Answer any three questions taking one from each unit

Unit-I
1. (a) Using the concept of chemical potential (  ) derive thermodynamically a relation 4+2
between the osmotic pressure of a binary solution and its molar concentration.
Clearly mention the assumptions and approximations used in your derivation.
(b) Starting from a suitable form of Duhem-Margules equation, derive the condition 3
that for an azeotrope the mole fraction of each component in the liquid phase is
equal to that in the vapor phase.
(c) The vapor pressure of benzaldehyde is 400 torr at 154 ºC and its normal boiling 2+1
point is 179 ºC. Calculate the molar enthalpy of vaporization of benzaldehyde.
Mention the assumption(s), if any, in your calculation.
(d) The intermolecular attraction between the molecules of all components (solute and 2
solvent) in an ideal solution must be identical in nature. Justify or criticize.

2. (a) Draw the chemical potential versus temperature diagram at constant pressure for a 2+1+1
pure substance in the three states of matter with proper explanation. Comment on
the relative magnitudes of  Tf and  Tb from the plot. Mention the assumptions in
your answer (  Tf is the depression of freezing point,  Tb is the elevation of
boiling point).
(b) (i) For an ideal solution plot the variation of the quantity p1 p10 as a function of 1+2+2
x2.
(ii) Sketch the plot of p1 p10 as a function of molality of the solute if water is the
solvent.
(iii) How is the plot of p1 p10 with molality affected when the solvent is changed
to toluene?
(x2 = mole fraction of solute, p10 = vapor pressure of pure solvent, p1 = partial vapor
pressure of solvent in solution).
(c) Using the Clausius-Clapeyron equation show that the slope of the solid-gas 3
coexistence curve is greater than the slope of the liquid-gas coexistence curve at the
triple point.

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CBCS/B.Sc./Hons./4th Sem./CEMACOR08T/2020
(d) The vapor pressure of benzene is expressed by the following empirical relationship 2
3884 K
ln( p torr)  17.63  T . Find the boiling point of benzene when the
atmospheric pressure is 500 torr.

Unit-II

( E 0 T )
Derive the expression   (1 T )    nF
H 0 , where the terms have usual 3+1
3. (a) (i)
  p
significance.
(ii) Justify whether the standard emf (E0) of a cell is an intensive or extensive
property.
(b) A cell is represented by Pb | PbI2 (s) | KI (aq) | AgI (s) | Ag 4
Write down the cell reaction. If the cell has an e.m.f of 0.2078 V at 25 ºC and
( TE )  1.88 104 V/K , calculate G and S for the cell reaction.
P

(c) Write down the Debye Huckel Limiting Law explaining all the terms. Calculate the 1+2
mean ionic activity coefficient of a 2-1 electrolyte at a molality of 0.01 aqueous
solution at 15 ºC [A = 0.50 at 15 ºC]
(d) Why does Clausius-Mossoti equation fail in case of polar molecules? How is it 3
modified in the form of the Debye equation?

4. (a) For the concentration cell 2+2

Ag | AgCl (s) | HCl (a1) | HCl (a2) | AgCl (s) | Ag
(i) Write the various processes at the two electrodes and at the liquid junction
(ii) Derive the expression for G and e.m.f of the cell
(b) How does molar polarization vary with temperature? Explain using proper 2+1
2
equation. Find the C.G.S unit of kT .

(c) The thermodynamic dissociation constant for acetic acid, HAc, is 1.75 105 at 3
25 ºC.
Calculate using the Debye-Huckel theory, the degree of dissociation of 0.001 M
acid in 0.05 M Ca(NO3)2.
(d) The molar orientation polarization of chloroform decreases sharply with increasing 2
temperature but that of carbon tetrachloride remains almost invariant with
temperature. Explain with the help of an appropriate equation.
(e) Calculate the equilibrium constant for the formation of I 3 from I 2 (aq) and I  at 2
25 ºC using the following data
I 2 (aq )  2e  ⇌ 2I  E 0  0.619 Volt
I 3  2e  ⇌ 3I  E 0  0.536 Volt

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CBCS/B.Sc./Hons./4th Sem./CEMACOR08T/2020
Unit-III

5. (a) The operator for the z-component of angular momentum in spherical polar 1+3+2
coordinates is given as Lˆz  i  where 0    2 and Yl , m ( ,  ) is an eigen
function of the operator.
(i) Construct a suitable eigen value equation giving proper justification for your
answer.
(ii) Solve the eigen value equation applying the technique of separation of
variables to find a suitable solution for the  -part.
(iii) Verify if the solution gives quantized values for Lz.
(b) What are the relative merits and demerits of VB method as compared to the LCAO- 2
MO method?
(c) The radial wavefunctions for the 1s and 2s orbitals of H-atom are given below. 3+1
Without using any explicit formula justify the number and location of nodes in the
two wavefunctions and indicate the same graphically.
3 2
R1s  2a0 e r a0
R2 s  (2a0 )3 2 (2  ar )e r 2 a0
0
(a0 is Bohr radius).
Find the SI units of the functions R1s and R2s.

6. (a) Using the results Lˆ2Yl ,m   2Yl , m and LˆzYl , m  m 2Yl , m find the maximum allowed 3
limit for the value of m (m and  are pure integers).
(b) (i) If we measure Ly of a particle whose state function is an eigen function of L̂2 3+1
2
with eigen value 12 , what possible outcomes for the measurement do you
expect? Give proper justification for your answer.
(ii) What possible outcome do you expect if Lz is also measured at the same time?
Justify.
(c) (i) Using the expression for  1s find an expression for the average distance 3+(1+1)
( r ) of a 1s electron from the nucleus for a hydrogen-like atom.
(ii) Using your expression for  r  calculate the average distance of a 1s electron
from the nucleus for H-atom and He+ ion and state the significance of your
result.

Given:  1s  1 ( aZ )3 2 e  zr a0 ,
0 
0
x n e  axdx  nn!1 , Bohr radius, a0  0.529 Å,
a
Z = atomic number.

N.B. : Students have to complete submission of their Answer Scripts through E-mail / Whatsapp to
their own respective colleges on the same day / date of examination within 1 hour after end of
exam. University / College authorities will not be held responsible for wrong submission (at
in proper address). Students are strongly advised not to submit multiple copies of the same
answer script.

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