CENTRAL UNIVERSITY OF RAJASTHAN

DEPARTMENT OF CHEMISTRY
M.Sc-I
END-SEMESTER EXAMINATION, 06.12.2010
PAPER: CHT-101 (ANALYTICAL CHEMISTRY)

Time allowed: 3 hrs

M. Marks: 100

PART-A
Compulsory Question
1. (i)

The result of an analysis is 36.97g compared with the accepted value of 37.06g.
What is the relative error in parts per thousand?
3

(ii)

How does batch extraction differ from continuous extraction? Explain.

(iii)

Define distribution coefficient.

(iv)

What are ion-exchange resins? Name some commonly used ion- exchange
resins in chromatography.
3

(v)

Indicate the order in which the following compounds would be eluted from an
HPLC column containing reversed phase packing:
Benzene, diethylether, n-hexane
3

(vi)

Aniline absorbs at 280 nm (max 8600). However in acidic solution the main
absorption band is seen at 203 nm. Explain.
3

(vii)

Explain why absorption spectra for atomic species consist of discrete lines at
specific wavelengths rather than broad bands for molecular species.
3

(viii) What is paper electrophoresis? Explain.

(ix)

Discuss the principle of differential thermal analysis.

(x)

What are the different factors on which thermogravimetric analysis depends? 3

PART-B
Answer any three questions
2. A 50 ml volume of water containing 0.1 g of analyte is to undergo liquid-liquid
extraction by shaking with 25 ml of an organic phase. Analyte is 85 times more
soluble in the organic layer than in water. Compare the result of (a) one extraction
using all 25 ml of organic phase and (b) three extractions each using 8.33 ml of
organic phase.
7, 7
3. Following the Woodward Fieser rules, calculate the absorption maximum for each of
the following compounds:
53

(iii)

(ii)

(i)

(iv)

(v)

4. Discuss the principle of flame photometry. What are the different components of a
flame photometer and what are their uses?
5, 10
5. What is thermogravimetric analysis? What information can be obtained from the
pyrolysis curves? Describe the construction of a simple thermobalance.
3, 5, 7

PART-C
Answer any one question
6. (i)

(ii)

A soda ash sample is analysed in the analytical chemistry laboratory by

titration with standard hydrochloric acid. The analysis is performed in
triplicate with the following results: 93.50, 93.58 and 93.43 % Na2CO3. Within
what range are you 95% confident that the true values lies (at 95% confidence
level and two degrees of freedom, t = 4.303)?
7
Discuss in detail the chemical and spectral interferences occurring in atomic
absorption spectroscopy.
5, 4

(iii)

7. (i)
(ii)

(iii)

What are the various classifications of activation analysis? Discuss destructive

method of activation analysis.
3, 6
Describe two principle solvent extraction systems for metal ions. Give
examples of each.
4, 4
Give the principles of the following types of chromatography:
52
(a) Paper chromatography
(b) Thin layer chromatography
(c) Ion-exchange chromatography
(d) Affinity chromatography
(e) Gel-permeation chromatography
Write an explanatory note on dropping mercury electrode.
7

CENTRAL UNIVERSITY OF RAJASTHAN

DEPARTMENT OF CHEMISTRY
M.Sc-I
END-SEMESTER EXAMINATION, 08.12.2010
PAPER: CHT-102 (CHEMISTRY OF MAIN GROUP ELEMENTS)

Time allowed: 3 hrs

M. Marks: 100

PART-A
Compulsory Question
1. (i)
3

Write balanced equations for the hydrolysis of XeF 2 , XeF 4 and XeF 6 .

(ii)

Discuss Bents rule with example.

(iii)

Describe the difference in the structure of H 3 SiN=C=S and H 3 CN=C=S.

(iv)

How does diborane react with ammonia under different experimental

conditions?
3

(v)

Discuss the role of crown ethers in the extraction of alkali metals.

(vi)

Describe structure and bonding in borazine.

(vii)

Give an example of deprotonation reactions of closo-carboranes.

(viii) How are the following prepared?

(Any Three):
NaOCl, NaClO 2 , NaClO 3 , HIO 4

(ix)

What structure do you predict for the compounds: B 4 H 10 , C 2 B 7 H 11 and

B 10 H 14 2 ?
3

(x)

Arrange the following in decreasing order of their reactivity:

IF 5 , ClF 3 , BrF, IF, ClF, IF 7 , BrF 3 , IF 3 , BrF 5

PART-B
Answer any three questions
2. (i)

(ii)

Draw the Lewis structure for the following molecules and predict the molecular
geometry including expected distortions:
52
+
TeCl 4 , ICl 2 , ClF 3 , SO 2 , XeF 4
Write a short note on atomic inversion in amines and phosphines.
5

3. Describe the structures of different types of silicates and give the name and formula of
one example of each type.
15
4. Comment on each of the following observations:
53
+

o
o
o
(i)
Bond angles for NO 2 , NO 2 and NO 2 are 180 , 134 and 115 , respectively.
(ii)
Mg 2 C 3 liberates alkyne, CH 3 CCH on treatment with water.
(iii) The chemistry of the fullerenes is dominated by the reactions of C=C bonds.
(iv)
Urea is weakly basic in aqueous solution but shows acidic property in liquid
ammonia.
(v)
Iodine is almost insoluble in water, but it dissolves readily in an aqueous
solution of KI.
5. Discuss in detail the chemical properties of the following non-aqueous solvents:
(Any two)
7, 7
(i)
liquid ammonia
(ii)
liquid sulphur dioxide.
(iii) dimethyl sulfoxide
(iv)
dimethyl formamide
PART-C
Answer any one question
6. (i)

Discuss the concept of molecular hydride. Classify and highlight the

characteristic features of various types of molecular hydrides.
3, 6
(ii)
Describe the preparation, properties, structure and applications of carbon nanotubes.
2, 2, 2, 2
(iii) Write an explanatory note on nitrogen activation.
8

7. (i)
(ii)
(iii)

Consult the Walsh diagram of BeH 2 and predict whether it will be linear or
bent.
10
Write a short note on intercalation compounds of graphite.
7
Describe what happens:
42

(a)
(b)
(c)
(d)

When metallic potassium is dissolved in ammonia to form a dilute

solution.
When more potassium is added to form a concentrated solution.
When solution (a) and (b) are evaporated carefully in vacuo.
When (a) is treated with Fe 2 O 3

CENTRAL UNIVERSITY OF RAJASTHAN

DEPARTMENT OF CHEMISTRY
M.Sc-I
END-SEMESTER EXAMINATION, 14.12.2010
PAPER: CHT-104 (ELECTROCHEMISTRY AND KINETICS)

Time allowed: 3 hrs

M. Marks: 100

PART-A
Compulsory Question
1. (i)

State Rice-Ramsperger-Kassel (RRK) theory.

(ii)

Put forward distinguishing features of chain reactions.

(iii)

Why flash photolysis is preferred over relaxation technique?

(iv)

What are the basic postulates and test of transition state theory? Highlight the
reasons for failure of the transition state theory.
3

(v)

A sample of milk kept at 25oC is found to sour 40 times as rapidly as when

kept at 4oC. Estimate the activation energy for the souring process.
3

(vi)

Discuss the mechanism of catalyst and co-catalyst action in ionic

polymerisation.

(vii)

Write the cell reactions involved in charging and discharging of batteries. 3

(viii) Identify the chain initiation, propagation and termination steps in H 2 and Cl 2
combination reaction in presence of oxygen and state the overall expression
for the rate of formation of HCl photo-chemically.
3
(ix)

Discuss the principle of molecular beam technique.

(x)

Explain the process and kinetics of corrosion.

PART-B
Answer any three questions
2. a. Discuss in detail the statistical approach to rate theory by Hinselwood.
b. What are fuel cells? Explain with suitable examples.

7
3

c.
Calculate
the
rate
constant
for
the
dissociation
reaction,
#
CH 3 CH 2 Cl
CH 2 =CH 2 + HCl at 640K. Given H = 202 KJ/mol and
#
S = -5.5J/K/mol.
5
3. a. Derive the rate law for the complex formation mechanism for I 2 formation,
assuming validity of steady state hypothesis.
5
b. Suppose initial concentration of iodine atoms is 3.2x10-6M and that of chaperon is
5.9x10-6M. How long does it take for half of iodine atoms to combine when
chaperon is Helium?
5
c. How are different flow techniques helpful in studying kinetics of reactions?
4.

Discuss the principle of cyclic voltametry. What are the characteristic features of
reversible and irreversible cyclic voltametry?
5, 10

5. a. Differentiate kinetics of gas phase and solution phase reactions.

b. Evaluate rate constant of diffusion controlled reactions.

5
5

NH 4 + + OH- , 0.1 mol/litre of NH 4 OH

c. For decomposition reaction of NH 4 OH
is subjected to temperature jump method. The equilibrium constant K=1.8x10-5 and
x e = 4.1x10-4 mol/litre . Find k 1 , k -1 and kr
5
PART-C
Answer any one question
6. a. Discuss in detail the kinetics of gas-phase polymerisation of styrene

b. State steady state hypothesis and apply it to determine rate constant for
decomposition of ozone.
9
c. What are different theories of corrosion? Recommend methods for the prevention
of corrosion
8

7.

a. Suggest the role of external impurity in chain termination step for anionic
polymerisation and discuss the kinetics of copolymerisation reactions.
7
b. Explain the structure of double layer by the following models: (any two)
i. Gouy Chapmann Model
ii. Stern Model
iii. Bockris, Devanathan and Muller Model
iv. Helmoltz Model

5 x2

c. What are composite reactions? How will you derive (k 1 +k 2 ) for interconversion of
-D glucose to -D glucose.
8

CENTRAL UNIVERSITY OF RAJASTHAN

DEPARTMENT OF CHEMISTRY
M.Sc-I
END-SEMESTER EXAMINATION, 16.12.2010
PAPER: CHT-105 (THERMODYNAMICS)

Time allowed: 3 hrs

M. Marks: 100

PART-A
Compulsory Question
1) (i)

Helium is compressed isothermally and reversibly at 100oC from a pressure of

2 to 10 bar. Calculate (a) q per mole, (b) w per mole, (c) G, (d)H, (e) U,
and (f) S , assuming that helium is an ideal gas.
3

(ii)

Prove (V/T) p = (S/P) T

(iii)

What are excess functions for non-ideal solutions?

(iv)

Explain the statistical interpretation of entropy.

(v)

Calculate entropy of mixing of 1 mole of oxygen and 2 moles of hydrogen

assuming no reaction occurs and gases behave ideally.
3

(vi)

Suggest significance of chemical potential.

(vii)

Comment on drawbacks of Clausius- Clapeyron equation.

(viii) Identify the systems for which it is essential to include the factor of 1/N!
in going from Q to q.
(i) a sample of nitrogen gas
(iii) sodium chloride crystals

(ii) a sample of solid CO

(iv) water vapors

(ix)

What are thermodynamic potentials and how are they generated?

(x)

State Raoults Law and give limitations of Henrys law.

PART-B
Answer any three questions
2) a. Derive S by non-ideal treatment.

b. Verify JT = 1/Cp[T(V/T) P -V]

c. Express the variation of activity with temperature and pressure.

3) a. Evaluate the effect of temperature on the chemical potential.

b. Prove that H = -T2 G/T

5
5

T P,N

c. Calculate the change in entropy when 1 mole of helium (ideal gas) is heated from
temperature 298K to 1000K at constant pressure, Cv =3/2R
5
4) a. What are partial molar quantities? Discuss the methods for the determination of
partial molar enthalpy and partial molar volume.
5
b. What should be the partial pressure of CO 2 gas to achieve 30mg of CO 2 gas
dissolved in 250ml of water at 25oC? Given that Henrys Law constant for CO 2 gas
in water is 1.25x 106 torr at 25oC.
5
c. Prove G mixing for an ideal gases = RTxlnx

5) a. Derive an expression for the translational partition function of a molecule which is

free to move in three dimensions.
5
b. A certain atom has 2 fold degenerate ground level, a non degenerate electronically
excited level at 3000 cm-1, and a 2-fold degenerate level at 5000cm-1. Calculate the
partition function of these electronic states at 2000K.
5
c. State Stirlings Approximation.

PART-C
Answer any one question
6. a. What are Ellingham diagrams? Discuss the effect of temperature and pressure on
Gibbs energy. Show that (A/V) T,N = P and (G/T) T,N = V
5,5
b. Write short note on regular solution model.
5
c. What is fugacity and discuss methods to determine fugacity. The boiling point of
benzene at 101.3 kPa is 353.2K. Find out the boiling point of benzene at 60 kPa.
The enthalpy of vaporisation of benzene at its boiling point is 31.8KJ/mol.
6,4

7. a. Write an expression for the molecular partition function and explain meaning of each
term involved in it. Show that the molecular partition function gives an indication
of the average number of states that are thermally accessible to a molecule at the
temperature of the system.
5
b. Derive Gibbs-Duhem Equation. A 10 gm of naphthalene is dissolved in 100g of
benzene at 25oC.Calculate the chemical potentials of the two components
5x2
c. Explain the positive and negative deviations from Raoults law. The vapour
pressures of benzene and toluene are 400 and 139 mm Hg, respectively at 60.6oC
Calculate the vapour pressure of a solution consisting of 40.0gm of toluene and
60.0g of benzene.
5x2

Central University of Rajasthan

End-Semester Examination, December 2010
Dynamic of Communication Skills and Technical Writing (DCSTW)
Department of English (for M.Sc. Chemistry)
DATE: 18-12-2010; TIME: 3 Hrs

[MM100 marks]

SECTION I Short Answer Type Questions; Attempt all the questions.

i.
ii.

Which method should be adopted for vocabulary building?

(3 Marks)
You are a new admission in your class. How would you introduce yourself to your
classmates.
(3 Marks)
Make a list of all the tenses.
(3 Marks)
Rectify the spelling errors in the following words:
(3 Marks)
a. Loughter
b. Trustwarthy
c. Assamble
d. Dissappear
e. Revael
f. Liberary
Fill in the blanks with appropriate forms of verbs.
(3 Marks)

iii.
iv.

v.

a. They_____(try) to help me.

b. I ________never______(see) such a building.
c. He________(run) to catch the ball.
d. A stitch in time______(save) nine.
e. War_______(break) out in Africa.
f. _____you alright?
vi.

Identify errors in the following sentences, if there are any, and rewrite them.
a. Nobody doesnt care for me.
b. How long have you standing here.
c. I speak to him last night.
d. The train has arrive late night.
If you have a headache how would you define it to a doctor?
Give two examples of polite requests.

vii
viii

(2 Marks)

(2 Marks)
(1 Mark)

SECTION II Long Answer Type Questions. Each question carries 20 marks

II. Write a letter to the editor of The Times of India informing him about the traffic hazards at
Kishangarh.
OR
Write a letter of advice to your sister informing her about the ways in which she should
prepare for her interviews in the corporate sector.

III. Choose a section and answer all questions in that section:

a. How do you define a Group Discussion (GD)? How can an individual lead in a GD?
b. Write a paragraph on Modern Trends in Science. (300 words)
OR
a. Write a paragraph on Indian performance in the Asian Games 2010. (200 words)
b. Compose a paragraph on Modern Means of Education.
IV Discuss in detail the rural life in Rajasthan. (300 words)
OR
a. Discuss in detail the ways of agreeing, disagreeing and presenting an argument in a
group discussion.
b. Discuss the effective ways of vocabulary building.
V. Create an imaginary dialogue between a doctor and a patient. (Word limit 300 words)
OR
Write a paragraph on The life in a University. (Word limit 300 words)

CENTRAL UNIVERSITY OF RAJASTHAN

End Semester Examination (December 2010)
First Semester M. Sc. Chemistry 2010-11
Subject: CHT 107(Mathematics for Chemists)
Time Allowed: Three Hour

Maximum Marks: 100

PART-I

Q.1 Attempt all questions. Each question having 4 marks.

(a) Find the distance between the points P1 (3, 4) and P2 (4, 6).
(b) Find

dy
dx

for y = e2x tan1 x.

(c) Find the derivative of the function (sinx)x .

(d) Given that x = t3 + 3t, y = t3 3t, compute

d2 y
.
dx2

(e) Solve the differential equation 2y 00 (x) + 6y 0 (x) + 2y(x) = 0.

(f) Integrate
Z

etan x
dx
1 + x2

(g) Integrate
Z

2x
dx
(x 1)(x + 3)

(h) Evaluate
Z

v2

v1

nRT
n2 a
2
V nb
V


dV ;

a, b, n, R and T are constants.

(i) Solve
d2 8 2 mE
+
= 0.
dx2
h2
(j) Expand (x + 5)8 .
(k) Find the eleventh term in the expression of (2x + y 2 )13 .
(l) Fill the blanks
(a + b)4 = a4 +

a3 b +

a2 b2 +

ab3 + b4 .

(m) Find general solution of the equation

dy
2
+ 2xy = 2ex .
dx
Q.2 Attempt any five questions. Each question having 8 marks.
(a) The probability of a gas molecule having a speed c laying in a range between c and c + dc
is given by the Maxwell distribution law for molecular speed:
 m 3/2
2
Pc dc = 4
emc /2kT c2 dc
2kT
where m, k and T are constants. Find an expression for most probable speed.
1

(b) The vibrational potential energy of a diatomic molecule can be approximated by the Morse
function


2
U (r) = A 1 eB(rr0 )

where A, B and r0 are constants. Find the value of r for which U is maximum.
(c) The Kirchhoff equation for a chemical reaction relating the variation of H of a reaction
with absolute temperature is


(H)
T


= Cp
p

where Cp is the change in the heat capacity at constant pressure. If Cp is given by

Cp = a + b T + c T 2
drive an equation for H as a function of temperature.
(d) Find the expected value < x > for an electron in the 1st state of Hydrogen atom, given that
 3 Z
1
< x >= 4
e2r/a0 r3 dr.
a0
0
(e) In the consecutive reaction A k1 B k2 C, where k1 and k2 are rate constants, the
concentration of B, (B), follows the rate equation
d(B)
= k1 (A)0 ek1 t k2 (B)
dt
here (A)0 represents the concentration of A at t = 0. Find the concentration (B).
(f) If the fifth term of an arithmetic progression is 10 while 15th term is 40. Write down the
first 5 terms of A. P.
(g)If the sum of first eight terms of an arithmetic progression is 56 and the sum of the first 20
terms is 260. Find the first term and common difference of the A. P.

CENTRAL UNIVERSITY OF RAJASTHAN

DEPARTMENT OF CHEMISTRY
M.Sc. I-SEMESTER EXAMINATION
PAPER: CHP (CHEMISTRY PRACTICAL)

M. Marks: 90

1. Estimate gravimetrically barium ions as barium sulphate in the given solution.

30

2. Separate the given organic mixture by appropriate method and identify individual
compounds.
30

3. Study the kinetics of reaction between potassium persulphate and potassium iodide
and determine the rate constant when concentration of potassium persulphate and
potassium iodide are equal.
30
OR
Study kinetics of methylacetate in presence of mineral acid and evaluate the rate
constant.