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Solved Paper
2007
IITJAM Chemistry
MM : 300 Time : 3 hrs

n
In this question paper, there are total of 44 questions carrying 300 marks of 3 hours duration.
n
Questions 1-30 (Objective questions) carry 3 marks each and questions 31-44 (Subjective questions) carry
15 marks each.
n Each objective question has four choices for its answer i.e. (a), (b), (c) and (d). Only one of them is the
correct answer.
n There will be negative marking for wrong answers to objective questions. The following marking scheme
for objective questions shall be used:
(a) For each correct answer, you will be awarded 3 (three) marks.
(b) For each wrong answer, you will be awarded –1 (Negative one) mark.
(c) Multiple answers to a question will be treated as a wrong answer.
(d) For each un-attempted question, you will be awarded 0 (Zero) mark.
(e) Negative marks for objective part will be carried over to total marks.
n Do not write more than one answer for the same question. In case you attempt a subjective question
more than once, please cancel the answer(s) you consider wrong. Otherwise, the answer appearing last
only will be evaluated.
n
Clip board, log tables, slide rule, calculator, cellular phone and electronic gadgets in any form are not
allowed.

1. In the extraction of metals from their ores, which one of the following reduction methods can
bring about an non-spontaneous reduction?
(a) Electrolytic reduction
(b) Reduction by carbon
(c) Reduction by another metal
(d) Reduction by hydrogen
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2. The solid-liquid phase diagram for the Mg − Zn system is shown in the figure below where the
vertical line at X (Mg) = 0.33 represents the formation of a congruent melting compound
MgZn 2 . The figure is divided into seven regions depending upon the physical state of the
system. The composition of the region # 6 represents
700

600
#1
500
#3
400 #2
#5 #7

300
#4 #6
200
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
Zn X(Mg) Mg
(a) single phase of a solution of Mg and Zn
(b) two phase regions between the solid Zn and solid MgZn2
(c) two phase regions between the liquid and solid MgZn2
(d) two phase regions between solid Mg and solid MgZn2

3. Which one of the following species is the conjugate base of HO − ?

(a) H2O (b) O 2− (c) O −2 (d) O 2−
2

4. The plot of Gibbs free energy G and the extent of a reaction ξ is given below for the reaction
A s B. If µ A and µ B are the chemical potentials of A and B respectively, the incorrect
statement is
Gibbs free energy

X
Z

Y
O
Extent of reaction
(a) at point X , µ A > µ B
(b) at point Y , ∆ G= 0
(c) at point Z , µ A < µ B
(d) at equilibrium, the composition of the reaction mixture can be identified

5. For a cyclic process performed by an ideal gas, changes in some thermodynamic functions
are zero. Indicate the set in which all the functions are zero.
(a) w, ∆ E, ∆ H, ∆G (b) q , ∆ S, ∆ H, ∆A
(c) q , ∆ E, ∆ S, ∆G (d) ∆ E, ∆S ∆ H, ∆ A

6. For a reaction with rate equation − dC / dt = kC 2 ,C 0 and C are the concentrations of the
reactant at time 0 and t respectively. If 10 minutes were required for C 0 to become C 0 / 2, the
time required for C o to become C o / 4 is
(a) 10 min (b) 20 min (c) 30 min (d) 40 min
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7. Which of the following compounds is optically active?

Cl Cl Cl Cl

Cl Cl Cl Cl
(1) (2) (3) (4)

(a) 1 (b) 2 (c) 3 (d) 4

8. Which one of the following compounds gives positive test for both nitrogen and halogen with
its Lassaigne’s extract?
(a) CH3NH2 ⋅ HCl (b) NH2OH ⋅ HCl (c) NH4Cl (d) H2NNH2 ⋅ HCl

9. The correct order of dipole moments (µ) of the following compounds is

1. CH3 CH2 CH2 CHO
2. CH3 CH == CHCHO
3. CH3 CH2 CH == CH2
(a) µ 1 > µ 2 > µ 3 (b) µ 2 > µ 3 > µ 1 (c) µ 3 > µ 1 > µ 2 (d) µ 2 > µ 1 > µ 3

10. An aqueous solution containing 0.01 M FeCl 3 and 0.06 M HClO 4 has the same ionic strength
as a solution of
(a) 0.09 M NaCl (b) 0.04 M Na 2SO 4
(c) 0.06 M CuSO 4 (d) 0.03 M H3PO 4

11. Which one of the following figures, showing kinetic energy of the ejected electron versus the
frequency (ν) of the incident photon, represents the Einstein’s photoelectric effect?

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

KE (J)

KE (J)

KE (J)

KE (J)

0 0 0 0
ν (s–1) ν (s–1) ν (s–1) ν (s–1)

12. The standard potential of a Daniell cell is + 1.10V and the equilibrium constant for the cell
reaction is 1 .5 × 10 37 . It can be concluded that
(a) zinc oxidises copper
(b) displacement of copper by zinc goes to near completion
(c) copper oxidises zinc
(d) displacement of zinc by copper goes to completion
13. The main product obtained in the following reaction is
O O

(i) MeMgBr/dry ether

+ [ ?]
(ii) H /H2O

O O O O OH
OH O O
(a) (b) (c) (d)
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14. Which one of the following compounds reacts with nitrous acid to give the product [P ]?
O

[P] = H
H
OH OH

(a) (b) OH (c) NH2 (d) OH

NH2 NH2 NH2

CHO CH2OH
H OH H OH
15. H Cl H Cl
CH2OH CHO
1 2

The given compounds 1 and 2 are

(a) identical (b) diastereomeric
(c) enantiomeric (d) constitutionally isomeric

16. The compound, which

(i) reacts rapidly with acetyl chloride
(ii) does not react with 2,4-dinitrophenylhydrazine and
(iii) does not form a yellow precipitate with excess of iodine in aqueous alkali
is called
(a) acetone (b) diethyl ether
(c) 2-methyl-2-propanol (d) ethanol

17. During Wittig reaction, a phosphorus ylide gets converted to

(a) R 3 P (b) R 3 P == O (c) R 3P+HOH− (d) R2P  PR2

18. Which one of the following species is not isoelectronic with CO ?

(a) N 2 (b) CN − (c) NO+ (d) O+2

19. The ligand with only sigma (σ) bonding character is

(a) CN − (b) CH3− (c) CO (d) NO

20. The correct valence shell electronic configuration of the element with atomic number 22 is
(a) [Ar]4s 2 3 d 2 (b) [Ar]3d 4
(c) [Ar]3 d 2 4s 2 (d) [Ar]4s 2 4 p2

21. The correct order of the ionic radii is

(a) In3+ > Sn4+ > Sr 2+ > Rb+ (b) Sn4+ > In3+ > Sr 2+ > Rb+
+ 3+ 2+ 4+
(c) Rb > In > Sr > Sn (d) Rb+ > Sr 2+ > In3+ > Sn4+

22. The normalisation constant ‘A’ for the wave function ψ ( φ) = Ae (im φ) where, 0 ≤ φ ≤ 2 π is
1 1
(a) (b) 2π (c) 2 π (d)
2π 2π

23. The pH of a 1.0 × 10 −3 M solution of weak acid HA is 4.0. The acid dissociation constant K a is
(a) 1.0 × 10−3 (b) 1.0 × 10−4 (c) 1.0 × 10−5 (d) 2.0 × 10−5
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24. The overlap between the atomic orbitals sketched below is

Z Z
Y Y
– + +

X + X
+
– –

(a) positive (b) negative (c) zero (d) no overlap

25. The value of ‘n’ for the following molecule according to Huckel’s rule is

(a) 16 (b) 4 (c) 3 (d) 14

26. The shape of CH3− ion is

(a) trigonal planar (b) tetrahedral (c) trigonal pyramidal (d) linear

27. The complementary strand of DNA for the following single stranded DNA sequence,
5'-A - T - C - A - T - G - C - 3' is
(a) 5′-A - T - C - A - T - G - C - 3′ (b) 5′-T - A - G - T - A - C - G - 3′
(c) 5′-G - C - A - T - G - A - T - 3′ (d) 5′-C - G - T - A - C - T - A - 3′

28. The ionic radii of Ca 2+ and F − are 100 pm and 133 pm respectively. The coordination number
of Ca 2+ in the ionic solid will be
(a) 8 (b) 6 (c) 4 (d) 2
29. The compounds that react with aqueous NaHCO 3 to release CO 2 are
O
H 3C
OH NH
HO
HO O HO O
N O
O HOH2C O

HO O
OH HO OH
HO OH
(1) (2) (3) (4)
(a) 1 and 3 (b) 2 and 4 (c) 2 and 3 (d) 1 and 4

30. Which of the following reactions does not give H3 PO 4 ?

(a) Ca 3(PO 4 )2 + H2SO 4 
→ (b) P4O 6 + H2O 
→
(c) PCl 5 + H2O  → (d) P4S10 + H2O →

(i) KMnO4 (i) NaOH

31. [Q ] C11H12O2 [R ] C11H12O2
(ii) NaIO4 (ii) H+
(i) CH3MgBr
[P ] (excess)
(ii) HBr
O NaH
[S ] C13H19BrO

[T ]

Identify the structures of the intermediate compounds Q, R and S. Show the transformation for
each step.
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32. a. For the following scheme of transformations, draw the structures of A, B, C and D.
CHO
H OH Phenylhydrazine Benzaldehyde
HO H (3 eq) (excess)
[A ] [B ]
H OH H+
Acid catalysed
H OH rearrangement
CH2OH OH
O OH
Br2/H2O HIO4 HO
[D ] [C ]
HO O
b. Complete hydrolysis of a pentapeptide with 6 N HCl at 110°C in a sealed tube gave
two equivalents of glycine, one equivalent each of tyrosine, leucine and phenylalanine.
Reaction of the pentapeptide with Sanger’s reagent ( 2, 4-dinitrofluorobenzene, DNFB)
and subsequent hydrolysis gave the DNFB derivative of tyrosine. Chymotrypsin
cleavage of this peptide yielded tyrosine, leucine and a tripeptide. Deduce the
sequence of the pentapeptide.

33. a. Complete the following reactions with appropriate structures for E, F, G, H and I.
O CO2Et
NaNO2/HCl Zn/AcOH Heat
COOEt [E ] [F ] + [G ]
O
Alkaline Heat,
KMnO4 acetophenone
b. [H] [I ]
N
34. a. Account for the following transformation with an appropriate mechanism. Give the structure
of the Hofmann exhaustive methylation product of 1,2-dihydro derivative of [X ].
OH
N
MeO MeO
H PCl5
N
MeO MeO
[X ]
b. The optically pure ester [J ] is hydrolysed in aqueous acetic acid to form a racemic
mixture of cis -4, 4-dimethyl 1, 2-acetoxycyclopentanol [K ]. Give a mechanistic explanation
to account for the formation of [K ] and the observed change in the optical activity.
O
O S
O AcOH/H2O
O [K ]

O
[J ]
35. a. M is a first row transition metal. MCl 2 on treatment with aqueous ammonia gives a
blue coloured solution of complex N. A solution of MCl 2 also gives a bright red
precipitate of complex O with ethanolic dimethylglyoxime.
(i) Identify M and draw the structure of O.
(ii) Determine the hybridisation of M in complex N.
(iii) Identify the paramagnetic complex.
b. [Cr(H2 O) 6 ] 3+ gave an absorption at 208 kJ/ mol which corresponds to ∆ o . Calculate the
crystal field stabilisation energy of this complex in kJ/ mol.
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36. a. Consider the ethers H3 SiOSiH3 and H3 COCH3 .

(i) Which ether has more Lewis base character?
(ii) Which angle [Si  O  Si and C  O  C] is greater ? Justify your answer.
b. Starting from SiO 2 , show how the following polymer is prepared industrially?
CH3

Si O

CH3 n
2+
37. a. A solution of metal ion (M ) when treated with H2 S gas gives a black precipitate A.
Precipitate A dissolves in hot concentrated nitric acid to give B along with elemental
sulphur. The metal iron solution also gives a white precipitate C with an excess of KI.
Write the chemical formulae of A, B and C.
b. Why are potassium permanganate solutions unstable in the presence of Mn 2+ ions?
In the quantitative estimation of iron present in iron ores dissolved in dilute HCl,
titrations with dichromate are preferred over titrations with permanganate. Rationalise.

38. a. Al 2 Cl 6 and Al 2 Me 6 are dimeric in gas phase. Draw their structures. Which compound
has more Lewis acid character ? Explain.
b. Arrange the halides SnCl 2 , PbCl 2 , SiCl 2 in the increasing order of their stability.
Give reasons for your answer.

39. a. Acidification of an aqueous solution of yellow sodium chromate gives an orange coloured
compound A. A saturated solution of A on treatment with concentrated H2 SO 4 gives a
bright orange solid B. Compound A in the presence of concentrated H2 SO 4 reacts with
anion C to give a deep red coloured liquid. Identify A, B and C.
215
b. 84 Po undergoes an a emission to give element X followed by a β emission to give
element Y.
(i) Write the valence shell electronic configuration of Y.
(ii) Indicate the groups of the periodic table to which X and Y belong.

40. a. When an ideal monoatomic gas is expanded from 1.5 bar, 24.8 L and 298 K into an
evacuated container, the final volume becomes 49.6 L. Calculate ∆H , ∆S, ∆G, for the
process.
b. The Maxwell distribution function for the distribution of speeds of molecules in gaseous
systems is given as,
3/ 2
 m   −mc 2 
f (c ) = 4 π   c 2 exp  
 2πkT   2 kT 
1/ 2
 2 kT 
Show that the most probable speed, c mps =  
 m 

41. a. At 600 K and 200 bar, a 1:3 (molar ratio) mixture of A2 and B 2 react to form an equilibrium
mixture containing χ AB3 = 0.60. Assuming ideal gas behaviour, calculate K p for the reaction
A2 ( g ) + 3B 2 ( g ) - 2AB (g )
3

b. A 50 mL 0.05 M solution of Fe (II) is titrated with 0.05 M solution of Ce(IV) in the presence
of dilute H2 SO 4 at 25°C. Calculate the equivalence point potential and the equilibrium
° 3+ 2+ = + 0.75 V,E ° 4+ 3+ = + 1.45 V]
constant K in terms of log K. [E (Fe / Fe ) (Ce / Ce )
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42. a. The vapour pressure of D2 O at 20° C is 745 mm of Hg. When 15 g of a non-volatile

compound is dissolved in 200 g of D2 O, the pressure changes to 730 mm of Hg.
Assuming the applicability of Raoult’s law, calculate the molecular weight of the
compound.
b. An enzyme following Michaelis- Menten kinetics was found to have highest activity at 37°C
and pH 7.0 . If the maximum velocity V max for this enzyme was 2.4 × 10 −4 mol L−1s −1 with
an initial enzyme concentration [E ] 0 = 2.4 nM, calculate the turn over frequency.

43. a. Consider the 4π electrons in cyclobutadiene to be free particles in a 2-dimensional square

box of length 2 Å. Calculate the wavelength of the electronic transition from the highest
occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO).
Also write down the normalised wavefunctions for the occupied degenerate states.
b. The reaction
k1
k –1
cis trans
is first order in both directions. At 25°C, the equilibrium constant (K ) of this reaction is
0.40. If 0.115 mol dm −3 of cis-isomer is allowed to equilibrate, calculate the equilibrium
concentration of each isomer.
→
44. a. With i , j and k as the unit vectors along X, Y and Z axes, express the vector P1P 2 in the
given figure in terms of the coordinates of P1 and P 2 . Also determine the dot products of
the unit vectors i , j , k. z

P2 (x2, y2, z2)

k
i j
O
x
y
P1 (x1, y1, z1)

b. Deduce whether the matrices A and B commute or not.

 2 1 1 1
A=  , B =  
 0 1 0 1

Answers
1. (a) 2. (d) 3. (b) 4. (c) 5. (d) 6. (c) 7. (d) 8. (a) 9. (d) 10. (b)
11. (a) 12. (b) 13. (a) 14. (a) 15. (d) 16. (c) 17. (b) 18. (d) 19. (b) 20. (c)
21. (d) 22. (d) 23. (c) 24. (a) 25. (c) 26. (c) 27. (c) 28. (a) 29. (b) 30. (b)