CEMA-UG-S4-ES-C8-19

RAMARRISHNA Mission VIVEKANANDA CENTENARY COLLEGE, RAHARA, KoLKATA

End Semester Examination 2019
Ivth Semester B.Sc. Chemistry Honours
Core Course VIII
Full Marks: 50 Time: 2 hours
(Symbols and notations have their usual meanings)
Answer three questions taking one from each Group

Group-A
1. a) Deduce Van't Hoff relation for osmotic pressure using the concept of equality of
chemical potential at equilibrium. Mention the assumptions and approximations
involved.
b) "Sulphur melts but iodine sublimes"- Explain.
c) State and explain the phase rule. Discuss phase diagram of a ternary system:
CHCOOHH,0/CHCl; with use of phase rule. 5
d) A solution containing 11g urea in litre water was found to be isotonic with a
decinormal solution of NaCl calculate degree of dissociation, 'a. 3

. a) Establish 'Konowallof's rule' to obtain the effect of alteration of composition over

the total vapour pressure of a two-component volatile mixture and hence justify the
concept of azeotropic mixture using phase rule. 4+2
b) Calculate the number of components for (i) an aqueous solution of FeCl; considering
its hydrolysis. (ii) A mixture of ammonium gas and ammonium chloride (solid) being
heated in a sealed container till equilibrium. 4
c) State whether colligative properties are extensive properties or not with justification.
2
d) Describe a phase diagram of a simple eutectic system following thermal analysis
principle. 4

Group-B

AH
a) Show that , where the symbols have their usual significance.

3
b) For the following cell, write down the cell reaction and calculate e.m.f (Ecel). free
energy change (aG) and equilibrium constant for the cell reaction:
H ,(g.latm )|H ,S0 (m = 0.05.Y, = 0,340 , Hg ,SO ,(s)| Hg (liq )

Given: E (He ,So, /so lg) = 0.6141 volt 4

c)Write down the cell where the following chemical reaction takes place:
H ) Of H,0 (liq) 2
d) Molar polarisabilities of O and CHs are independent of temperature while those of
HCI gas and CHCl decrease with temperature. Explain with proper physical reasoning
and also from relevant equation. 4
e) Estimate the mean activity coefficient and the mean activity of 0.005 mol.kg"
aqueous KCI at 298 K. 4

a) A potentiometer equipped with glass electrode and saturated calomel electrode gave
a reading of 0.0232 volt at 25° C for a pH of 2.5 buffer solution. What is the pH of

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 CEMA-UG-S4-ES-C8-19

another buffer solution for which the same potentiometer reads 0.11| volt

b) What is concentration cell1? For the concentration cell with transference,

Ag(s)| AgC(s). HCla1) HC(a). AgCHS)| Ag(s):
i) Write the various processes at the two electrodes and at the liquid junction.
4
ii) Derive the expression of the e.m.fof the cell.
C w r i t e the clausius-Mosottii equation in S.I. form mentioning all the terms involved n

it. 2

d) Activity solubility product of AgCl is 1.56 10 at 298K. Estimate the solubility of

AgCl in 0.001M and 0.0IM Ca(NO)> solution at 298K. 3

e) Explain how the e.m.f. of a quinhydrone half-cell depends on the pH of aqueous

solution.
) Calculate the E° for the Fe"/ Fe couple using the data given below.
Fe" (aq)+e-Fe"(aq) E=0.771V
Fe (aq)+ 2e-Fe(s) E=-0.447V

Group-C
5. a) Calculate the commutators: [L ,L-] and [x , L]
b) What is atomic unit? How are the atomic unit of length and energy related to the Sl

unit of the parameters? 3

c) What is meant by 1s configuration of the atom? Write the total wave function for the
configuration. 3
d) Arrange the following systems, viz. H, Ha and H2 in order of increasing degree of
complexity in regard of solving their respective Schrodinger equations. Explain your
answer Also mention for which system one gets an exact wave function and why this
is not possible for the other systems.

e) Prove that the energy eigen states of the H-atom are also eigen states of the L

operator L, =ih | . 3

6. a)the electronic wave function, for a H atom is given by

100 exp(-/a.) Showthatthe function is normalised. Calculate the most

probable value of r for this state. 4

b) Write the operator i, in the Cartian coordinates. Show that e is an eigenfunction
of the operator. Find the eigenvalue. 3
c) Arrive at the Hartree-Fock equation for a He atom. 3
d) Discuss the relative merits and demerits of VB method as compared to the LCAO-
MO method. 4
e) Explain whether or not the E values for J f 0 for H°Cl and D 5 CI will be the same

or not when both considered as rigid rotors with the same inter-nuclear separation.
3

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 CEMA UG-S4-MS-CC 8-19

RAMAKRISHNA M1ssION VIVEKANANDA (CENTENARY CoLLEGE, RaHara, KoLKATA

MID SEMESTER EXAMINATION 2019
FOURTH SEMESTER
B.Se. CHEMISTRY HONOURS
CORE COURSE VII
Full Marks: 25 Time: 1 hour

Group- A
1. a) Derive "phase rule' thermodynamically. 4
b) Explain the 'triple point' in phase diagram of water system.
c) Calculate 'degrees of frecdom' of unsaturated and saturated solutions of NaCi
that remain in equilibrium with vapour. 2
OR
2 a) Draw and explain the phase diagram of phenol-water system.
b) What is Plait Point' of a ternary system - explain. 2

c)What do you mean by first order phase transition ? Explain. 2

Group-B
a) Write down the Debye-Huckel limiting law and explain the terms.
b) The solubility of KHTa in water is increased in presence of NaNO1. Justity or
criticize. 3
Calculate the ionic of solution containing 0.2M KCI, 0.IM MgSO, and 0.05
c) strength
M NazPO4
d) Why Debye-Huckel law is called the limiting law?
OR
a) Plot log y: Vs. Vi for 1-1 type and 2-2 type electrolyte (in the same graph) as per
4.
Debye-Huckel limiting law. 2

b) Extent of dissociation of acetic acid in water in presence of KNO; is increased.

3
Justify.
M solution of K[Fe(CN)«] at 298 K.
c) Calculate mean activity coefficient of 0.001
2
[Given =0.509].
d) Plot y VS. m (molality) for HCI
e) Name the factors on which A' depends.

Group-C
a) Write the operator L, in Cartesian coordinate. Express L, in the spherical
5.
1+2+
polar coordinate and hence derive the eigenfunetion of L,.
2x2 4
b)Findthe commutators: [L,,L,1.Ix,L,
OR
Find [L, L, ] and. L,L I+2+2
6. a) What are L, and IL_ operators. ,
.

Write
b) Explain why L'and L, have simultaneous eigenfunction ( ) .
I+I+
the eigenvalues of L'and L,.

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