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DEPARTMENT OF CHEMISTRY
M.Sc-I
END-SEMESTER EXAMINATION, 06.12.2010
PAPER: CHT-101 (ANALYTICAL CHEMISTRY)
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)
(iii)
(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
(ix)
(x)
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)
(iii)
7. (i)
(ii)
(iii)
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)
(iii)
(iv)
(v)
(vi)
(vii)
(ix)
(x)
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)
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)
M. Marks: 100
PART-A
Compulsory Question
1. (i)
(ii)
(iii)
(iv)
What are the basic postulates and test of transition state theory? Highlight the
reasons for failure of the transition state theory.
3
(v)
(vi)
(vii)
(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)
(x)
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
5
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
M. Marks: 100
PART-A
Compulsory Question
1) (i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(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
(ix)
(x)
PART-B
Answer any three questions
2) a. Derive S by non-ideal treatment.
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
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
[MM100 marks]
iii.
iv.
v.
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)
dy
dx
d2 y
.
dx2
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 ;
(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 .
(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
M. Marks: 90
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.