PG, 1 Sem, Apc, CC-3, Question Paper - Jan 23

RAMAKRISHNA MISSION VIDYAMANDIRA
(Residential Autonomous College affiliated to University of Calcutta)

M.A./M.Sc. FIRST SEMESTER EXAMINATION, JANUARY 2023
FIRST YEAR [BATCH 2022-24]
Date : 20/01/2023 APPLIED CHEMISTRY
Time : 11.00 am – 1.00 pm Paper : CC 3 Full Marks : 50
[Use a separate Answer Book for each group]

Group - A
Answer any five questions: [55]
h  
1. Show that the compton shift is given by   2 Sin 2   , where  is the scattering angle
meC 2
and Me is the mass of the electron. Then find the maximum value of compton shift. [4+1]
2. Derive the expression for energy of a particle in a one dimensional box using the de Broglie
quantization rule. [5]
3. a) State the condition of ''acceptablity of wavefunction'' in quantum mechanics.
b) Determine, citing reasons, whether each the following functions are acceptable or not as a
wavefunction over the indicated intervals.
(i) xe x  , (ii) Sin1 x  1,1 (iii)  x 2  1 e x   , 
2
[2+3]
4. Show that uncertainty in the measurement of a classical observable A in the eigen state of A is
the quantum mechanical operator corresponding to the classical observable A. [5]
5. Consider a free particle of mass, m, confined in a 1D box of length L having walls at x =0 and
x=L. Set up the time independent Schrodinger equation and hence solve this equation to get the
energy eigenvalues. [5]
6. Show that the Eigen functions of a free particle of mass m confined in a one-dimensional box of
length L form an ortho normal set. [5]
d2
Show that the function   xe  ax is an eigenfunction of the operator  4 x 2 . Find the
2
7.
dx 2
possible values of α so that eigen value become independent of x. [5]
8. Estimate the wavefunction of light absorbed when a π electron of butadiene is excited from the
highest occupied energy level to the lowest unoccupied energy level. For the sake of simplicity
assume that π electrons of butadiene move in a 1D box of length 7.0Å [me = 9.1110-31 kg] [5]
Group - B
Unit - I
Answer any one question: [115]
9. a) Derive an expression for Langmuir adsorption isotherm stating the assumptions clearly.
b) For low partial pressure of ozone (O3), the adsorption of ozone on graphite surface is fully
dissociative in nature, and follows Langmuir Isotherm. Under these conditions, if the dependence
of the surface coverage of graphite () on partial pressure of ozone (𝑃𝑂3 ) is given by  α (𝑃𝑂3 )x .
Find out the value of x.
c) Micelle formation is entropically favourable. Justify or criticize.
d) The surface tension (γ ) of a solution, prepared by mixing 0.02 mol of an organic acid in 1L of
pure water, is represented as  0   = A log (1+ BC) where γo denotes the surface tension of the
pure water, A = 0.03 Nm-1, B = 50 mol-1L and C is concentration in mol L-1. The excess
concentration of the organic acid at the liquid, determined by Gibbs adsorption equation at 300K
is n x 10-6 mol m-2. Find out the value of ‘n‘. [Given R= 8.314 J mol-1K-1]
e) Define surface excess concentration. [5+3+2+3+2]
10. a) Write down BET equation for multi-layer adsorption and derive Langmuir adsorption isotherm
from it.
(1)
b) Adsorption of N2 on TiO2 was carried out at 75K. A plot of Z / (1-Z)V versus Z (Z=P/Po) gives a
straight line with an intercept 4 x 10-6 mm-3 and slope 1 x 10-3 mm-3. Find out volume (in mm3)
corresponding to the monolayer coverage.
c) Find the surface area occupied by a single molecule of a fatty acid at 300K. Assuming that fatty
acid molecules are oriented vertically and they form a surface film of one molecule thickness.
Given a = 0.179, γo = 72.5 dyn/ cm.
d) A bimolecular surface reaction involves the following elementary process.
Considering Langmuir – Hinshelwood mechanism, derive rate equation if reactant A is much

preferentially adsorbed than B. [(1+3)+3+3+5]
11. a) For SO2 (g), at STP, the dielectric constant is 1.00993. This molecule has a permanent dipole
moment 1.63 D. Assuming SO2 (g) to behave ideally. Find out induced Polarisation or distortion
polarisation (Pind or Pd ) in cm 3 mol -1 unit.
b) Write down Clausius- Mossotti- Debye equation defining each term.
c) Explain why the polarizability of a molecule decreases at high frequency.
d) The dipole moment of water is 1.47 D. The H-O-H angle is 97°. Calculate the S-H bond moment.
If the bond distance of S-H bond is 133.4 pm, calculate the % of ionic character of the S-H bond.
e) Write down SI unit of µ2/ 3KT.
f) What is orientation polarization? [3+3+3+3+1+2]
Unit - II
Answer any one question: [110]
12. a) Write down the simple Butler-volmer equation. Using High field approximation, derive Tafel
equation.
b) At 25 °C, the current density and transfer co-efficient of hydrogen evolution on Pt are 0.84 mA
cm-2 and 0.5, respectively. What will be the exchange current density at -1 mV activation over
potential.
c) The diffusion limiting current (Id) at a dropping mercury electrode for an aqueous Mg (III)
solution of concentration ‘C’ (mol L-1) is 300 µA. If ‘C’ is increased by 0.1 mol L-1, Id is
increased to 900 µA. Find out the value of ‘C’ (mol L-1). [(1+3)+3+3]
13. a) ‘Efficiency of an ideally fuel cell can be greater than one’-justify or criticize.
b) What is activation over potential?
c) Why a corroding metal is called a short-circuited galvanic cell.
d) The reaction I3- + 2e- = 3I- occurs in steps like
i) I3- = I- + I2
ii) I2 = I + I
iii) (I + e- = I-) x 2
Considering 3rd step be the rds, show that the electrochemical reaction orders are
𝑃𝑎𝑛 ,𝐼− = 1, 𝑃𝑐𝑎𝑡ℎ ,𝐼− = - 1/2
𝑃𝑎𝑛 ,𝐼3− = 0, 𝑃𝑐𝑎𝑡ℎ ,𝐼3− =1/2. [3+2+3+2]

———— × ————
(2)

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RAMAKRISHNA MISSION VIDYAMANDIRA

(Residential Autonomous College affiliated to University of Calcutta)

[Use a separate Answer Book for each group]

Considering Langmuir – Hinshelwood mechanism, derive rate equation if reactant A is much

𝑃𝑎𝑛 ,𝐼3− = 0, 𝑃𝑐𝑎𝑡ℎ ,𝐼3− =1/2. [3+2+3+2]

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