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 1
Solid State Chemistry
CSIR JUNE 2011

1. A one-dimensional crystal of lattice dimension 'a' is metallic. If the structure is distorted in such a way
that the lattice dimension is enhanced to ‘2a’.
(a) The electronic structure remains unchanged.
(b) The width of conduction band decreases and a band gap is generated.
(c) The width of conduction band increases
(d) The width of the conduction band remains unchanged

CSIR DEC 2011

2. The value of d111 in a cubic crystal is 325.6 pm. The value of d333 is
(a) 325.6 pm (b) 976.8 pm (c) 108.5 pm (d) 625.6 pm

3. Consider a n-type semiconductor whose E, = 0, EC = 2.0eV and ED -1.98eV. The correct

statement among the following is
(a) EF =leV and is independent of T
(b) EF = 1.99 eV and remains independent of T
(c) EF= 1.99 eV and increases towards 2.0 eV with increase of T
(d) EF = 1.99 eV and decreases with increase of T.

CSIR JUNE 2012

4. How many atoms are there in an element packed in a fcc structure

(a) 1 (b) 2 (c) 4 (d) 8
5. The structure obtained when all the tetrahedral holes are occupied in a fee structure is of the
type
(a) NaCl (b) CsCl (c) CaF2 (d) ZnS

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6. The lattice parameter of an element stabilized in a fcc structure is 4.04 Å. The atomic radius
of the element is:
(a) 2.86 Å (b) 1.43 Å (c) 4.29 Å (d) 5.72 Å
7. The wavelength and the spectral region for a single electron transfer across the band gap in
a semi-conductor (Ex -1.98 × 10-19) are [h = 6.626 × 10-34 Js, c = 3 × 108 ms-1]
(a) 1000 nm, UV (b) 1000 nm, IR
(c) 500 nm, visible (d) 500 nm, FAR IR

CSIR DEC 2012

8. The angle between the two planes represented by the Miller indices (110) and (111) in a
simple cubic lattice is:
(a) 30° (b) 45° (c) 60° (d) 90°
9. A metal crystallizes in fcc structure with a unit cell side of 500 pm. If the density of the
crystal is 1.33 g/cc, the molar mass of the metal is close to
(a) 23 (b) 24 (c) 25 (d) 26
10. The packing fraction of a simple cubic lattice is close to
(a) 0.94 (b) 0.76 (c) 0.52 (d) 0.45
11. Crystal A diffracts from (111) and (2 0 0) planes but not from (110) plane, while the crystal
B diffracts from (110) and (200) planes but not from the (1 1 1) plane. From the above, we may
conclude that
(a) A has fcc lattice while B has bcc lattice (b) A has bcc lattice while B has fee lattice
(c) A and B both have fcc lattice (d) A and B both have bcc lattice.

CSIR JUNE 2013

12. The coordinates for the atoms in a body centred cubic unit cell are
(a) (0, 0, 0) and (1/2, 0, 0) (b) (0, 0, 0) and (1/2, 1/2, 1/2)
(c) (0, 0, 0) and (0, 1/2, 0) (d) (0, 0, 0) and (0, 0, 1/2)

13. The inter planar distance (Å) for a (100) plane in a cubic structure with the lattice parameter of 4Å is:
(a) 1 (b) 2 (c) 4 (d) 8

14. A plane of spacing 'd' shows first order Bragg diffraction at angle . A plane of spacing 2d
(a) shows Bragg diffraction at 2 (b) shows Bragg diffraction at /2
(c) shows Bragg diffraction at sin-1 (sin/2) (d) shows Bragg diffraction at sin-1(sin2/2)

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CSIR DEC 2013

15. When Frenkel defects are created in an otherwise perfect ionic crystal, the density of the
ionic crystal
(a) increases (b) decreases
(c) remains same (d) oscillates with the number of defects
16. A compound of M and X atoms has a cubic unit cell. M atoms are at the corners and body centre position
and X atoms are at face centre positions of the cube. The molecular formula of the compound is

(a) MX (b) MX2 (c) M3X2 (d) M2X3

17. The angle at which the first order Bragg reflection is observed from (110) plane in a simple cubic unit
cell of side 3.238 Å, when chromium K radiation of wavelength 2.29 Å is used, is
(a) 30° (b) 45° (c) 60° (d) 90°

18. Both NaCl and KCl crystallize with the fcc structure. However, the X-ray powder diffraction pattern of
NaCl corresponds to the fcc structure whereas, that of KC corresponds
to simple cubic structure. This is because
(a) K+ and Cl- are isoelctronic
(b) Na+ and Cl- are isoelctronic
(c) K+ and Cl- are disordered in the lattice crystal
(d) KCl has anti-site defects
19. An element exists in two crystallographic - modifications with FCC and BCC structures. The ratio of
the densities of the FCC and BCC modifications in terms of the volumes of their unit cells (VFCCand
VBCC) is
(a) VBCC: VFCC (b) VBCC: 2VFCC (c) 2VBCC: VFCC (d) VBCC: 2 VFCC

20. Metallic gold crystallizes in fcc structure with unit cell dimension of 4.00 Å. The atomic radius of gold is
(a) 0.866 Å (b) 1.414 Å (c) 1.732 Å (d) 2.000 Å

CSIR JUNE 2014

21. When Si is doped with a Group V element

(a) Donor levels are created close to the valence band
(b) Donor levels are created close to the conduction band
(c) Acceptor levels are created close to the valence band
(d) Acceptor levels are created close to the conduction band

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22. The interplanar spacing of (110) planes in a cubic unit cell with lattice parameter a = 4.242 Å is
(a) 3 Å (b) 6 Å (c) 7.35 Å (d) 2.45 Å
23. A compound AxByhas a cubic structure with A atoms occupying all the corners of the cube as well as all
the face center positions. The B atoms occupy four tetrahedral voids. The values of x and y respectively,
are

(a) 4, 4 (b) 4, 8 (c) 8, 4 (d) 4, 2

CSIR DEC 2014

24. X-ray diffraction does not give any structural information for

(a) metallic solids (b) ionic solids (c) molecular solids (d) amorphous solids

25. A solid consisting of only X-atoms has a close-packed structure with X-X distance of 160
pm. Assuming it to be a closed packed structure of hard spheres with radius equal to half of
the X-X bond length, the number of atoms in 1 cm3 would be

(a) 6.023 × 1027 (b) 3.45 × 1023 (c) 6.02 × 1021 (d) 3.8 × 1021

CSIR JUNE 2015

26. Silver crystallizes in face-cantered cubic structure. The 2nd order diffraction angle of a
beam of X-ray (λ = 1Å) of (111) plane of the crystal is 30°. Therefore, the unit cell length of the
crystal would be

(a) a = 3.151 Å (b) a = 3.273 Å (c) a = 3.034 Å (d) a = 3.46 Å

CSIR DEC 2015

27. For a simple cubic crystal lattice, the angle between the [2 0 1] plane and the xy plane is
(a) less than 30°
(b) between 30° and 45°
(c) between 45° and 60°
(d) greater than 60°
28. For a simple cubic crystal, X-ray diffraction shows intense reflections for angles 1and 2
which are assigned to [1 0 1] and [1 1 1] planes, respectively. The ratio sin 1/sin2is
(a) 1.5 (b) 1.22 (c) 0.82 (d) 0.67

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CSIR JUNE 2016

29. In a cubic crystal, the plane [100] is equally inclined to the planes
(a) [010] and [011] (b) [010] and [110] (c) [001] and [101] (d) [110] and [011]
30. For a simple cubic lattice, the ratio between the unit cell length and the separation of two
adjacent parallel crystal planes can NOT have a value o
(a) 51/2 (b) 71/2 (c) 1111/2 (d) 1311/2

CSIR DEC 2016

31. Each void in a two dimensional hexagonal close-packed layer of circles is surrounded by
(a) six circles (b) three circles (c) four circles (d) twelve circles

32. The sin 2 values obtained from X-ray powder diffraction pattern of a solid are 2x, 4x,
6x, 8x where x is equal to 0.06. The wavelength of X-ray used to obtain this pattern is 1.54Å.
The unit cell and the unit cell length, respectively are
(a) BCC, 3.146 Å (b) FCC, 3.146Å (c) SCC, 6.281 Å (d) BCC, 1.544Å

CSIR JUNE 2017

33. Metallic silver crystallizes in face-centred-cubic lattice structure with a unit cell of length
40 nm. The first order diffraction angle of X-ray beam from (2, 1, 0) plane of silver is 30°. The
wavelength of X-ray used is close to
(a) 11 nm (b) 18 nm (c) 25 nm (d) 32 nm
34. Polonium is the only metal known to exist in a simple cubic lattice form. The density of
polonium at 0°C is measured to be 10.00 g/cm³. The atomic radius of polonium would then be
(assume the mass of a polonium atom = 2.7 × 10-22g)
(a) 1.1 Å (b) 1.9 Å (c) 1.5 Å (d) 2.3 Å

CSIR DEC 2017

35. If the atoms/ions in the crystal are taken to be hard spheres touching each other in the unit
cell, then the fraction of volume occupied in the body cantered cubic structure is
2 2
(a) 3 (b) (c)  (d)
6 6
36. The separation of the (123) planes of an orthorhombic unit cell is 3.12 nm. The separation
of (246) and (369) planes are, respectively,
(a) 1.56 nm and 1.04 nm (b) 1.04 nm and 1.56 nm
(c)3.12 m and 1.50nm (d) 1.04 nm and 3.12 nm
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CSIR JUNE 2018

37. If all the lattice points of an FCC structure are occupied by uniform hard spheres that
touch each other, the fraction of volume occupied is

 2  3  2
(a) (b) (c) (d)
6 6 6 6

38. The (002) plane of an elemental FCC crystal diffracts X-rays (λ = 0.154 nm) at Bragg angle90°. the density
of the crystal is 4 × 104 kg m-3. The atomic weight of the elemental solid is

(a) 22 (b) 44 (c) 88 (d) 66

CSIR DEC 2018

39. In a cubic crystal, the (111) and (222) reflections are observed, but not the (001) reflection.
The Bravais lattice is

(a) body centred cubic (b) face centred cubic

(c) simple cubic (d) side centred cubic

40. A metal crystallizes with cubic close-packed structure. The sin2values of Bragg
reflections of Miller Planes (200) and (111) are 0.18 and 0.14, respectively. The unit cell length
is

(a) λ/2 (b) λ/0.3 (c) λ/0.4 (d) 0.4 λ

CSIR JUNE 2019

41. The correct relationship among the following, for a tetragonal (a=b ≠c ,===90°)
crystal system, is
2 2
 
(a) sin 2   2 c2 h 2  k 2  a 2l2 
4a
(b) sin 2   2 2 c2 h 2  k 2  a 2l2 
4a c
 
2 2 2 2 2
(c) sin 2   a  h  k 2   c 2 l2 
2  2 
h  k 2   l2 ]
(d) sin 2  
4c  4a
a
42. Nearest neighbour distance in a crystal system of side length a is in
2
(a) Face-centered cube
(b) Body-centered cube
(c) Trigonal primitive
(d) Primitive cube

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CSIR DEC 2019

43. The Miller index for the plane as shown in the figure and parallel to the c-axis, is

(a) 110 (b) 120 (c) 210 (d )220

44. X-rays of 173 pm wavelength are reflected by the (111) plane of a cubic primitive crystal at
= 30°. The unit cell length (in pm) is closest to
(a) 173 (b) 300 (c) 346 (d) 600

CSIR 2020
45. Iron belongs to the BCC lattice. The Miller indices of the second allowed reflection in the
powder diffraction pattern of iron would be
(a) (100) (b) (111) (c) (200) (d) (210)
46. In the ccp packing, the number of lattice points per unit area in the planes is in the order
(a) (100)> (110)> (111) (b) (100)> (111) > (110)
(c) (111) > (100)> (110) (d) (111) > (110) > (100)

CSIR JUNE 2021

47. Plutonium (atomic mass = 244 g mol-1) crystallizes in monoclinic lattice (a = 620pm,
b =480pm, c = 1100pm; ß = 1020) with 16 atoms per unit cell. The density in g cm-3 will be close to
(Use sinß = 0.98 ; sinß/2 = 0.78)
(a) 25.38 (b) 16.12 (c) 12.69 (d) 20.26
48. The miller indices of the planes parallel to the b axis and intersecting the a and c axis, as
shown in the figure, are

(a) (i) 101, (ii) 102 (b) (i) 102, (ii) 101
(c) (i) 100, (ii) 101 (d) (i) 100, (ii) 102

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ANSWER KEY
SOLID STATE CHEMISTRY

1. (b) 2. (b) 3. (d) 4. (c) 5. (c) 6. (b) 7. (b)

8. (abcd) 9. (c) 10. (c) 11. (a) 12. (c) 13. (c) 14. (c)
15. (c) 16. (d) 17. (a) 18. (a) 19. (a) 20. (b) 21. (b)
22. (a) 23. (a) 24. (d) 25. (b) 26. (c) 27. (d) 28. (c)
29. (a) 30. (b) 31. (b) 32. (a) 33. (b) 34. (c) 35. (d)
36. (a) 37. (a) 38. (a) 39. (b) 40. (a) 41. (b) 42 (a)
43. (b) 44. (b) 45. (c) 46. (c) 47. (d) 48. (d)

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 2
Chemical Kinetics
CSIR DEC 2011
1. The rate constant of a unimolecular reaction was 2.66 × 10-1 and 2.2×10-1 at T=120K and 360K
respectively. The rate constant (in 1 s-1 units ) at 240 K would be
(a) 2.4 ×10-2 (b) 2.4 ×10-1 (c) 4.8 ×10-2 (d) 1.8 ×10-3
2. The overall rate of the following complex reaction,

by steady state approximation would be

(a) K1K2k3[A]3[B] (b) K2K1k3[A][B]3 (c) K1K2k3[A][B]2 (d) K1K2k3[A][B]
3. The concentration of a reactant undergoing decomposition was 0.1, 0.08 and 0.067 mol L-1 after
1.0, 2.0 and 3.0 hr respectively. The order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
4. At any temperature for the following reaction (D and T are deuterium and tritium respectively)
correct statement is:
(A) HCI + F → HF + Cl, (B) DCI + F → DF + CI (C) TCI + F → TF + Cl
(a) (A) is fastest
(b) (B) is fastest
(c) (C) is fastest
(d) All the above reactions have the same rate constant
5. An example of a relaxation method of measuring rates is:
(a) Spectroscopic monitoring of product concentration.
(b) Stopped flow technique
(c) Temperature jump experiments.
(d) Measurement of spectral line widths.

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CSIR JUNE 2011

6. The half-life of a zero order reaction (A → P) is given by (k = rate constant):

 A 0 2.303 A0  1
(a) t1/ 2  (b) t1/2  (c) t1/ 2  (d) t1/2 
2k k k k  A0 

7. The decomposition of gaseous acetaldehyde at T(K) follows second order kinetics. The half-life
of this reaction is 400 s when the initial pressure is 250 Torr. What will be the rate constant (in
Torr-1s-1) and half-life (in s) respectively, if the initial pressure of the acetaldehyde is 200 Torr at
the same temperature?
(a) 105and 500 (b) 10-5and 400 (c) 10-4and 400 (d) 10-5and 500
8. For an enzyme catalyzed reaction, a Lineweaver-Burk plot gave the following data:
slope = 40 s , intercept = 4 (mmol dm-3s-1)-1.
If the initial concentration of enzyme is 2.5 × 10-9mol dm-3, what is the catalytic efficiency (in dm-3
mol-1s-1) of the reaction?
(a) 105 (b) 106 (c) 107 (d) 104
9. Observe the following aqueous solutions of same compound. All the measurements are made at
same wavelength and same temperature.
Solution A: The transmittance of 0.1 mol dm-3using 1 cm cell is 0.5.
Solution B: The optical density 0.5 mol dm-3is measured using 1 mm cell.
Solution C: The transmittance of this solution is 0.1.
The optical density of these solutions follow the order. (log 20 = 1.3010; log 30 = 1.4771, log 50 =
1.6990
(a) A > B > C (b) B > C > A (c) B >A > C (d) C > A > B

CSIR JUNE 2012

10. For a reaction, the rate constant k at 27°C was found to be k =5.4 × 10 11e-50.The activation
energy of the reaction is:
(a) 1 50 J mol-1 (b) 1 415 J mol-1 (c) 1 15,000 J mol-1 (d) 1 125,000 J mol-1
11. The rate law for one of the mechanism of the pyrolysis of CH3CHO at 520°C and 0.2 bar is
1/2
 k 
Rate   k 2  1  CH3CHO 
3/2

 2k1 

The overall activation energy E, in terms of the rate law is:

1
(a) Ea(2) + Ea(1) + 2Ea(4) (b) Ea(2)  Ea(1)  Ea(4)
2
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1 1 1 1
(c) Ea(2)  Ea(1)  Ea(4) (d) Ea(2)  Ea(1)  Ea(4)
2 2 2 2
12. In the Michaelis-Menten mechanism for enzyme kinetics, the expression obtained is:
v 104 v
 1.4 1012 
 E0 S  E0
The values of k3(Kems, mol L-1s-1) and K (Michaelis constant, mol L-1), respectively are
(a) 1.4 × 1012, 104 (b) 1.4 × 108, 104 (c) 1.4 × 108, 10-4 (d) 1.4 × 1012, 10-4
13. One of the assumptions made in the conventional activated complex theory is:
(a) Equilibrium is maintained between reactants and the activated complex
(b) Equilibrium is maintained between the reactants and the products.
(c) Equilibrium is maintained between the products and the activated complex
(d) Equilibrium is maintained between the reactants, the activated complex and the products.
14. The quantitative determination of N2H4 with KIO3 proceeds in a mixture of H2O/CCI4as
Follows
N2H4+ KIO3+ 2HCI → N2+KCI+ICI+ 3H2O
The end point for the titrimetric reaction is:
(a) Consumption of
(b) ICI formation
(c) Disappearance of the Yellow colour due to Cl2in CCI4layer.
(d) Displacement of the Red colour due to I2in CCl4layer
15. The carbon-14 activity of an old wood sample is found to be 14.2 disintegrations min-1 g-1.Calculate age
of old wood sample, if for a fresh wood sample carbon-14 activity is 15.3disintegrations min-1g-
1
(t1/2carbon-14 is 5730 years), is:
(a) 5,000 years (b) 4,000 years (c) 877 years (d) 617 years
16. "Phosphorescence" is represented as
(a) T1→ S0+ hv (b) T1 → S0+ ∆ (c) S1→ S0+ hv (d) S1→ T1+ ∆
17. Using cuvettes of 0.5 cm path length, a 10-4 M solution of a chromophore shows 50%
transmittance at certain wave length. The molar extinction coefficient of the chromophore at this
wave length is (log 2 = 0.301)
(a) 1500 M-1cm-1
(b) 3010 M-1cm-1
(c) 5000 M-1cm-1
(d) 6020 M-1cm-1

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CSIR DEC 2012

18. If the concept of half-life is generalized to quarter-life of a first order chemical reaction, it will
be equal to
ln 2 ln 4 4 1
(a) (b) (c) (d)
k k k 4k
19. The activation energy for the bimolecular reaction A+ BC → AB + C is E0 in the gas phase. If
the reaction is carried out in a confined volume of λ3, the activation energy is expected to:
(a) Remain unchanged (b) Increase with decreasing
(c) Decrease with decreasing (d) Oscillate with decreasing 
20. The decomposition of NH3on Mo surface follows Langmuir-Hinshelwood mechanism. The
decomposition was carried out at low pressures. The initial pressure of NH3was 10-2torr. The
pressure of NH3was reduced to 10-4torr in 10 minutes. The rate constant of decomposition of NH3
is:
(a) 9.9 × 10-4torr min-1 (b) 0.4606 min-1
(c) 9.9 × 10-3 torr min-1 (d) 0.693 min-1

CSIR JUNE 2013

21. In atom recombination reactions

(a) Ea= 0, ∆S#= +ve, ∆H#= +ve (b) Ea= 0, ∆S#= -ve, ∆H#= = -ve
(c) Ea= +ve, ∆S#= -ve, ∆H#= -ve (d) Ea= +ve, ∆S#= +ve, ∆H#= +ve
22. A radioisotope 41Ar initially decays at the rate of 34, 500 disintegrations/minute, but decay rate
falls to 21, 500 disintegrations/minute after 75 minutes. The t1/2for 41Ar is:
(a) 90 minutes (b) 110 minutes (c) 180 minutes (d) 220 minutes
23. Observe the following statements
(I) In the H2–O2 reaction, explosion occurs when the rate of chain branching exceeds that of chain
termination.

(II) The order of the reaction, nA → products, is 2.5. For this reaction, t1/2   A0
3/2

(III) Unimolecular gas phase reactions are second order at low pressure but become first order at
high pressure.
Which of the following is correct?
(a) I, II and III are correct (b) Only II is correct
(c) Only III is correct (d) I and II are correct

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24. The concentrations of a species A undergoing the reaction A → P is 1.0, 0.5, 0.33, 0.25 mol dm–3
at t = 0, 1, 2 and 3 seconds, respectively. The order of the reaction is:
(a) two (b) one (c) zero (d) three
25. In the Lindemann mechanism of unimolecular reactions, the observed order at lowconcentration is:
(a) 0.5 (b) 1 (c) 1.5 (d) 2
26. A bacterial colony grows most commonly by cell division. The change in the population due to
cell division in an actively growing colony is dN=AN dt. The population of bacterial colony at time
't' is [N0= N(t=0)]
(a) N t (b) N0 exp[-] (c) N0 exp[21] (d) N0 (21)2
27. The rate equation for the reaction 2AB+B2 → 2AB2is given byrate = k[AB] [B2]
A possible mechanism consistent with this rate law is
(a) 2AB  B2 
slow
 2AB2

(b) AB+AB⇋A2B2 (fast) ; A2 B2  B2 

slow
 2AB2

(c) AB  B2 
slow
 AB3 ; AB3  AB 
fast
 2AB2

(d) AB+B2 ⇋AB3 (fast) ; AB3  AB 

slow
 2AB2

28. A 0.1 M solution of compound A shows 50% transmittance when a cell of 1cm width is used at
 nm. Another 0.1 M solution of compound B gives the optical density value of 0.1761 using 1 cm
cell at λ1 nm .What will be the transmittance of a solution that is simultaneously 0.1 M in A and 0.1 M in
B using the same cell and at the same wave length? [log 20= 1.301; log 30=1.4771; log 50 =1.699]
(a) 33.3% (b) 50% (c) 66.7% (d) 70%
29. A chemical reaction involving nonlinear molecule + nonlinear molecule ⇋nonlinear activated
complex .The number of vibrational degrees of freedom in the activated complex, containing N
atoms, is
(a) 3N-5 (b) 3N-6 (c) 3N-7 (d) 3N-8

CSIR DEC 2013

30. According to Arrhenius equation (k = rate constant and T = temperature)
(a) ln k decreases linearly with 1/T
(b) ln k decreases linearly with T
(c) ln k increases linearly with 1/T
(d) ln k increases linearly with T
31. A first order gaseous reaction is 25% complete in 30 minutes at 227oC and in 10 minutes at
237‫ۥ‬°C. The activation energy of the reaction is closest to (R = 2 cal K-1mol-1)
(a) 27 kcal mol-1 (b) 110 kcal mol-1 (c) 55 kcal mol-1 (d) 5.5 kcal mol-1

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32. In the reaction between NO and H2the following data are obtained
Experiment I: PH2constant

PNO (mm of Hg) 359 300 152

dPNO 1.59 1.03 0.25
dt
Experiment II : PNO= constant

PH 2 (mm of Hg) 289 205 147

dPH2 1.60 1.10 0.79
dt
The orders with respect to H2and NO are
(a) 1 with respect to NO and 2 with respect to H2
(b) 2 with respect to NO and 1 with respect to H2
(c) 1 with respect to NO and 3 with respect to H2
(d) 2 with respect to NO and 2 with respect to H2

CSIR JUNE 2014

33. Examine the following first order consecutive reactions. The rate constant (in s –1 units) for
each step is given above the arrow mark

(A) P   Q  R (B) P   Q  R
5 3 5 3
10 10 10 10

(C) P   Q  R (D) P   Q  R
7 7 2 5
10 10 10 10

Steady-state approximation can be applied to

(a) A only (b) C only (c) B and C only (d) A and D only
34. In the Lineweaver-Burk plot of (initial rate)-1vs. (initial substrate concentration)-1for an
enzyme catalysed reaction following Michaelis-Menten mechanism, they-intercept is 5000 M-1s. If
the initial enzyme concentration is 1×10-9M, the turnover number
(a) 2.5 × 103 (b) 1.0 × 104 (c) 2.5 × 104 (d) 2.0 × 105
35. The fluorescence lifetime of a molecule in a solution is 5 × 10-9s. The sum of all the noradiative
rate constants (knr) for the decay of excited state is 1.2 × 108s-1. The fluorescence quantum yield
of the molecule is
(a) 0.1 (b) 0.2 (c) 0.4 (d) 0.6
  A t 
36. For a first order reaction A→ products, the plot of ln 
  A  
vs time , where [A]0and [A]t
 0 

to concentration at time = 0 and t respectively, is

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(a) A straight line with a positive slope passing through origin

(b) A straight line with a negative slope passing through origin.
(c) An exponential curve asymptotic to the time axis
  A t 
(d) A curve asymptotic to the ln 
  A  
 0 

CSIR DEC 2014

37. For an enzyme-substrate reaction, a plot between 1/v and 1/[S0] yields a slope of 40s. If the enzyme
concentration is 2.5 µM, then the catalytic efficiency of the enzyme is
(a) 40 Lmol-1s-1 (b) 10-4Lmol-1s-1 (c) 107Lmol-1s-1 (d) 104Lmol-1s-1
38. For a gaseous reaction, 2NO(g) + Cl2(g)  Non-linear T.S.  2NOCl
the pre-exponential factor in the rate constant is proportional to
(a) T1/2 (b) T-1/2 (c) T-5/2 (d) T-7/2

39. The rate constant for a reaction A3+ + Bn+1 P is measured in two different aqueous solutions of ionic
strengths 0.01 M and 0.04 M. If log K0.04/K0.01 = 0.3, the charge n on B is closest to
(a) 1 (b) 2 (c) 3 (d) 6
40. A reaction A + B + C D follows the mechanism
A + B ⇋AB
AB + C → D
in which first step remains essentially in equilibrium. If ∆H is the enthalpy change for the first
reaction and E0is the activation energy for the second reaction, the activation energy of the
overall reaction will be given by
(a) E0 (b) E0– ΔH (c) E0+ ΔΗ (d) E0+ 2ΔH
41. Which of the following will result in deviation from Beer's law ?
1. Change in refractive index or medium.
2. Dissociation of analyte on dilution.
3. Polychromatic light.
4. Path length of cuvette.
(a) 1, 2 and 3 (b) 2, 3 and 4 (c) 1,3 and 4 (d) 1, 2 and 4

CSIR JUNE 2015

42. The temperature-dependence of a reaction is given by k= AT2exp(-E0/RT)
The activation energy Ea of the reaction is given by:
(a) E0 + ½ RT (b)E0 (c) E0+ 2RT (d)2E0+ RT
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43. For a reaction, 2A + B → 3Z, if the rate of consumption of A is 2 ×10-4mol dm-3s-1 the rate of formation
of Z (in mol dm-3s-1) will be
(a) 3×10-4 (b) 2×10-4 (c) 4/3 ×10-4 (d) 4×10-4
44 The equilibrium constants for the reactions CH4(g) + 2H2O(g) ⇌CO2(g) + 4H2(g) and CO(g) +
H2O(g) ⇌CO2(g) + H2(g) are K1and K2, respectively. The equilibrium constant for the reaction
CH4(g) + H2O(g) ⇌CO2(g) + 3H2(g) is
(a) K1.K2 (b) K1– K2 (c) K1/K2 (d) K2– K1
k
45. For a given ionic strength, (I) rate of reaction is given by log  4  0.51 I1/2 . Which of the
k0

following reactions follows the above equation?

(a) S2O82  I (b) Co  NH3 5 Br 2  OH 

(c) CH3COOC2H5  OH (d) H  Br   H2O2

46. The intensity of a light beam decreases by 50% when it passes through a sample of 1.0 cm path
length. The percentage of transmission of the light passing through the same sample, but of 3.0 cm
path length, would be
(a) 50.0 (b) 25.0 (c) 16.67 (d) 12.5
47 .Considering the following parameters with reference to the fluorescence of a solution:
1. Molar absorptivity of fluorescent molecule.
2. Intensity of light source used for excitation.
3. Dissolved oxygen
The correct answer for the enhancement of fluorescence with the increase in these parameters
is/are
(a) 1 and 2 (b) 2 and 3 (c) 1 and 3 (d) 3 only
48. According to transition state theory, the temperature-dependence of pre-exponential factor (A)
for a reaction between a linear and a non-linear molecule, that forms products through a nonlinear
transition state, is given by
(a) T (b) T2 (c) T-2 (d) T-1.5
49. In a photochemical reaction, radicals formed according to the equation
C4H10+ hv ⇋ 2C2H5
C2 H5  C2 H5 
k2
 C2 H6  C2 H4
If I is the intensity of light absorbed, the rate of the overall reaction is proportional to-
(a) I (b) I1/2 (c) I[C4H10] (d) I1/2[C4H10]1/2

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50. For the following reaction,

d  B
is given by
dt
(a) k1[A] – k-1[B]2– 2k2[B] (b) 2k1[A] – k-1[B]2– k2[B]
(c) 1/2 k1[A] –1/2 k-1[B]2– k2[B] (d) 2k1[A] – 2k-1[B]1/2– k2[B]

CSIR DEC 2015

51. According to the transition state theory, one of the vibrations in the activated complex is a
loose vibration. The partition function for this loose vibration is equal to (kBis the Boltzmann’s
constant and h is the Planck’s constant)
(a) kBT/h (b)hv/kBT (c) kBT (d) kBT/hv
52. νmax and Kmfor an enzyme catalyzed reaction are 2.0 × 10-3Ms-1and 1.0 × 10-6M, respectively.
The rate of the reaction when the substrate concentration is 1.0 ×10-6M is
(a) 3.0 × 10-3s-1 (b) 1.0×10-3s-1 (c) 2.0×10-3s-1 (d) 0.5 s-1
53. The first order rate constant for a unimolecular gas phase reaction A → products that follows indemann
mechanism is 2.0 s-1at pA= 1 atm and 4.0 s-1at pA= 2 atm. The rate constant for the activation step is
(a) 1.0 atm-1s-1 (b) 2.0 atm-1s-1 (c) 4.0 atm-1s-1 (d) 8.0 atm-1s-1
54. The concentration of a reactant R varies with time for two different reactions as shown in the
following plots :
The orders of these two reactions I and II, respectively, are –
(a) zero and one (b) one and zero (c) zero and two (d) two and zero
55. If the rates of a reaction are R1 and R2 at concentrations C1and C2of a reactant respectively,
the order of reaction, ‘n’ (assuming that the concentrations of all other reactants and T remain
constant) with respect to that reactant is given by
log R1  log R 2 log C1  log C 2
(a) n  (b) n 
log C1  log C 2 log R1  log R 2

log C1  log R 1 log C 2  log R 2

(c) n  (d) n 
log C 2  log R 2 log C1  log R 1

CSIR JUNE 2016

Q56. Experimentally determined rate law for the chemical reaction,

2NO2F  2NO2+ F2is R = k[NO2F]

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The rate determining step consistent with the rate law is

(a) 2NO2F  2NO2 + F2 (b) NO2F + F  NO2+ F2
(c) NO2F  NO2+ F (d) NO2+ F  NO2F
Q57. For the chemical reaction in aqueous solution,
CH2ClCOO+ OH CH2OHCOO+ Clthe correct statement is
(a) increase of pressure increases the rate constant
(b) increase of dielectric constant increases the rate constant
(c) increase of ionic strength decreases the rate constant
(d) the entropy of activation is positive
Q58.If experimentally observed rate constant is greater than the maximum value of rate constant
obtained using hard-sphere model of collision theory, then relation between the impact parameter
(b) and sum of the radii of two reactants is
(a) b = r1+ r2 (b) b < r1+ r2 (c) b > r1+ r2 (d) b ≤ r1+ r2
Q59. Half-life t½ for a third order reaction 3C  products, where C0 is the initial concentration of C,
will be
3 3 3 2
(a) (b) (c) (d)
2kC02 kC 0 2kC0 3kC 02

CSIR DEC 2016

Q60.For a reaction with an activation energy of 49.8 kJ mol-1, the ratio of the rate constants at
600 K and 300 K, (k600/k300), is approximately (R = 8.3 J mol-1K-1)
(a)ln 10 (b) 10 (c) 10+e (d) e10
H 
Q61. According to the transition state theory, the plot with slope equal to is
R
k k 1 1
(a) ln k vs. T (b) ln vs T (c) ln vs (d) ln k vs.
T T T T
Q62. A reaction goes through the following elementary steps

Assuming that steady state approximation can be applied to C, on doubling the concentration of
A, the rate of production of D will increase by (assume K2[A] << K-1[C])
(a) 2 times (b) 4 times (c) 8 times (d) 2√2 times

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Q63. For two reactions

X (g) + Y(g)  Z(g) (1)

M (g) + N(g)  P(g) (2)

according to the collision theory, the ratio of squares of pre-exponential factors of reactions 2 (A2) and 1
2
A 
(A1) at the same temperature  2 
 A1 
Species Mass (g/mol) Diameter (mm)
X 5 0.3
Y 20 0.5
M 10 0.4
N 10 0.4
(a) 4/5 (b) 5/5 (c) 5/3 (d) 3/5
Q64.The rate of an acid-catalyzed reaction in aqueous solution follows the rate equation
r = k[X+][Y2-][H+]
If k16 and k4are rate constants for the reaction at ionic strength of 16 mol L-1and 4 mol L-1, respectively
k4
ln , in terms of Debye-Huckel constant (B = 0.51) , is
k16

(a) 4B (b) 8B (c) 10B (d) 12B

CSIR JUNE 2017

Q65.If the pre-exponential factor in Arrhenius equation is 1.6 × 1012s-1, the value of the rate constant at
extremely high temperature will be close to
(a) 1.6 × 1012s-1 (b) 4.2 × 1012s-1 (c) 2.4 × 109s-1 (d) 1.2 ´× 106s-1
Q66.In kinetic study of a chemical reaction, slopes are drawn at different times in the plot of
concentration of reactants versus time. The magnitude of slopes with increase of time
(a) remains unchanged (b) increases
(c) decreases (d) increases and decreases periodically
Q67. Photochemical decomposition of HI takes place with the following mechanism
HI + hv (Ia)  H + I
H + HI 
k1
 H2 + I
I + I + M 
k2
 I2 + M
Considering hydrogen (H) and iodine (I) atoms as intermediates, the rate of removal of HI is
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(a) Ia/2 (b) Ia (c) 2Ia (d) Ia2

Q68. In a enzyme catalyzed reaction:

k 2  3.42 104 s1 . If [E]0= 1.0 × 10-2 mol dm-3, the magnitude of maximum velocity andturn over number
using Michaelis-Menten kinetics are
(a) 3.42 102 moldm3s1;3.42 104 s1

(b) 3.42 106 moldm3s1;3.42 104 s1

(c) 3.42 104 moldm3s1;3.42 106 s1

(d) 3.42 104 moldm3s1;3.42 102 s1

Q69.Arrhenius equations for two chemical reactions are: k1  A1e E1 /RT , k 2  A2e E2 /RT . If
E1> E2then at a given temperature T
k 1 A1 k2 A2
(a)  (b)  (c) k1k 2  A1A2 (d) k1  k 2  A1  A2
k2 A2 k 1 A1

CSIR DEC 2017

Q70. For a sequence of consecutive reactions, A 

k1
 I 
k2
 P , the concentration of I would be, by steady
state approximation.

(a) k1  A  (b)  k1  k 2   A  (c) k1k 2  A 

k1
(d) A
k2

Q71. The slope and intercept obtained from (1/Rate) against (1/substrate concentration) of an
enzyme catalyzed reaction are 300 and 2 × 105, respectively. The Michaelis-Menten constants ofthe
enzyme in this reaction is
(a) 5 × 106M (b) 5 × 10-6M (c) 1.5 × 103M (d) 1.5 × 10-3M
Q72. Reaction between A and B is carried out for different initial concentrations and the
corresponding half-life times are measured. The data listed in the table:
Entry [A0] (µM) [B0] (µM) t1/2 (sec)
1 500 10 60
2 500 20 60
3 10 500 60
4 20 500 30

(a) k[A][B]2 (b) k[A]2 (c) k[A]2[B] (d) k[A][B]2

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CSIR JUNE 2018

Q73. Elementary steps of a reaction are as follows

If steady state approximation is applicable to C, the rate of product formation in the reaction is
(a) proportional to [A][B] (b) proportional to [A]2[B]2
(c) proportional to [A]1/2[B]1/2 (d) independent of [A][B]
Q74. For an enzyme-substrate reaction,

the slope and intercept of plot between 1/r and 1/[S] are 10-2 s and 102 M-1s, respectively, If E0 = 10-6M
k 1
and  1000 , the value of k1will be close to (in units of M-1s-1) [ ris the rate of reaction and E0
k2

is initial concentration of enzyme

(a) 1 × 1011 (b) 1 × 104 (c) 1 × 108 (d) 1 × 106
Q75. Difference between-activation energies of the reverse and forward steps of a reversible
reaction is 9.212RT. If the pre-exponential factor of the forward reaction is double that of the
reverse reaction at the same temperature, the equilibrium constant for the reaction at that
temperature will be (ln 10 = 2.303)
(a) 1 × 104 (b) 2 × 104 (c) 1 × 10-4 (d) 2 × 10-4
76. For a second-order reaction, the straight line among the following plots is
(a) [X] versus time (b) 1/[X] versus time
(c) log [X] versus 1/time (d) log [X] versus time

CSIR JUNE 2019

77. If the half-life of a reaction is inversely proportional to the square of the concentration of the
reactant, the order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
78. The gas phase decomposition of A at 1000K follows two decomposition paths.

Elementary Process Rate Constant

(i) AB+C 3 s-1
(ii) AP+Q 5 s-1

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The maximum theoretical percentage yield of P at 1000K is
(a) 62.5 (b) 60 (c) 166 (d) 37.5
79. Photochemistry of a molecule, M, is described as by the mechanism
Elementary Process Rate Constant
(i) M + hv  M Iabs
(ii) M + Q  M + Q kQ[Q][M]
(iii) M M + hvF 0.2[M]

 I
The intercept at [Q] = 0 is 4 for the inverse of fluorescence intensity   vs [Q] plot.
 IF 
The value of Iabsis
(a) 4 (b) 0.25 (c) 20 (d) 0.8

CSIR DEC 2019

80. If the rate constant for a base catalyzed ester hydrolysis reaction is 0.20 L mol-1s-1, half-life (in s) of the
ester (Given [ester]0= [base]0= 0.05 mol L-1) would be closest to
(a) 40 (b) 100 (c) 140 (d) 200
81. The rate constant of a second order reaction 2A Z is k2. If the initial concentration of the
reactant is a0 and the concentration of the product at time t is x, then a linear function of t with the
slope k2a0is
 x  x x  x 
(a) ln   (b) (c) (d) ln  
 a0  x  a0 a0  x  2(a 0  x)  a0 a0  x  
82. The oxidation of NO to NO2occurs via the mechanism given below

d  NO2 
in the presence of large excess of O2can be written as
dt
k1
(a) 2k1(NO)2 (b) 2k1k2(NO)2(O2) (c) (NO) 2 (d) 2k 2 (NO)2
k2

CSIR NOV 2020

83. Substance 'A' is exposed to 600 nm, 100 W light source for 6626 s, with 50% of the incident
light being absorbed. 'A' decomposes according to the reaction A 2B. As a result of irradiation,
0.2 mol B is produced. The quantum yield of the reaction is closest to

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Options:
(a) 6 × 106 (b) 6 × 10-4 (c) 6 × 10-2 (d) 6
84. The concentration (C) of a compound undergoing decomposition as a function of time (t) is
given below:
t/min 0 1 2 4 6
C/M 1.00 0.80 0.67 0.50 0.40
The order of the reaction is
Options:
(a) 0 (b) 1 (c) 2 (d) 3
85. For a reaction, raising the temperature from 200 K to 300 K results in the increase of rate
constant by a factor of 2. The activation energy for this reaction in kJ mol -1 is closest to
(ln 2 = 0.69)
Options:
(a) 7.0 (b) 3.5 (c) 14.0 (d) 0.83

CSIR JUNE 2021

86. The rate constant for the reaction A2B4O AB4 + AO, is described as,
10000 K
log k  14.1 
T
the activation energy (in kJ mol-1) is closest to
(a) 191.4 (b) 83.14 (c) 382.8 (d) 166.28
87. The rate of decomposition of a gas is 10 mM s-1when 10% is reacted and it is 5 mM s-1when
40% is reacted. The order of the reaction is:
(a) 2 (b) 1.71 (c) 0 (d) 2.15
88. For a person weighing 70 kg the minimal volume (in mL) of a fatal dose of a compound with
LD50= 80 mg. kg-1, and density = 1.45 g. mL-1is
(a) 5.6 (b) 3.9 (c) 0.8 (d) 0.4
89. For the reaction,

the equilibrium constant is 0.16 and k1is3.3×10-4𝑠-1. The experiment is started with pure cis
form. The time taken for half the equilibrium amount of trans isomer to be formed is about
(a) 290 s (b) 580 s (c) 190 s (d) 480 s

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ANSWER KEY
CHEMCIAL KINETICS

1. (a) 2. (a) 3. (c) 4. (a) 5. (c) 6. (a) 7. (d)

8. (c) 9. (d) 10. (d) 11. (c) 12. (c) 13. (a) 14. (d)
15. (d) 16. (a) 17. (d) 18. (b) 19. (c) 20. (b) 21. (b)
22. (b) 23. (a) 24. (a) 25. (d) 26. (a) 27. (c) 28. (a)
29. (c) 30. (a) 31. (c) 32. (b) 33. (d) 34. (d) 35. (c)
36. (b) 37. (d) 38. (d) 39. (c) 40. (c) 41. (a) 42 (c)
43. (a) 44. (c) 45. (b) 46. (d) 47. (d) 48. (d) 49. (d)
50. (d) 51. (d) 52. (b) 53. (b) 54. (c) 55. (a) 56. (c)
57. (b) 58. (c) 59. (a) 60. (d) 61. (c) 62. (d) 63. (a)
64. (d) 65. (a) 66. (c) 67. (c) 68. (a) 69. (a) 70. (d)
71. (d) 72. (c) 73. (a) 74. (a) 75. (b) 76. (b) 77. (a)
78. (a) 79. (b) 80. (b) 81. (c) 82. (a) 83. (c) 84. (c)
85. (b) 86. (a) 87. (b) 88. (b) 89. (a)

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 3
Electrochemistry
CSIRJUNE 2011

1. For an aqueous solution at 25ºC, the Debye-Huckel limiting law is given by

(a) log    0.509 Z Z  (b) log    0.509 Z Z 

(c) log    0.509 Z Z  (d) log    0.509 Z Z 

2

2. Debey-Hückel screening length (𝜅 −1 ) is a measure of size of diffuse ion cloud around an ion, provided
−1
2𝑒 2 𝑁𝐴 −1
√𝜀 ≈ 30 ( nm√ molkg ) at 298 K, which of the following values of 𝜅 −1 is true for a 0.03 molal
0 𝑘𝐵 𝑇

solution for Na2 SO4 in water (𝜀𝑟 ≈ 100) ?

10 9 10√2 9
(a) nm (b) 10 nm (c) nm (d) 10√2 nm
9 9
[0]
3. If the ratio of composition of oxidized and reduced species in electrochemical cell, is given as = 𝑒2
[𝑅]

the correct potential difference will be

2𝑅𝑇 2𝑅𝑇
(a) 𝐸 − 𝐸 𝑜 = (b) 𝐸 − 𝐸 𝑜 = −
𝑛𝐹 𝑛𝐹
𝑅𝑇 𝑅𝑇
(c) 𝐸 − 𝐸 𝑜 = 𝑛𝐹 (d) 𝐸 − 𝐸 𝑜 = − 𝑛𝐹

CSIR DEC 2011

4. Which one of the following conductometric titrations will show a linear increase of the conductance
with volume of the titrant added up to the break point and an almost constant conductance afterwards.
(a) A strong acid with a strong base
(b) A strong acid with a weak base
(c) A weak acid with a strong base
(d) A weak acid a weak base.
5. For a potentiometric titration, in the curve of emf (E) vs volume (V) of the titrant added, the
equivalence point is indicated by
(a) |dE/dV| = 0 ; |d2/d2V| = 0 (b) |dE/dV| = 0 ; |d2E/d2V| > 0
(c) |dE/dV| > 0 ; |d2E/d2V| = 0 (d) |dE/dV| > 0 ; |d2E/d2V| > 0

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3+ 2+ 2+
6. The standrad electrode potentials (E°) of Fe / Fe and Fe / Fe electrodes are + 0.77V and
-0.44 V respectively at 300 K. The E° of Fe3+ / Fe electrode at the same temperature is
(a) 1.21 V (b) 0.33 V (c) -0.11V (d) -0.04 V
7. The overall reaction for the passage of 1.0 faraday of charge in the following cell
Ag (s) ˗ AgCl (s) |KCl (a1) | KCl (a2) |AgCl (s) ˗ Ag (s) is given by (t denotes the transport numbers)
(a) t+ KCl(a1) → t+ KCl(a2) (b) t+ KCl(a2) → t+ KCl(a1)
(c) t- KCl(a1) → t- KCl(a2) (d) t- KCl(a2) → t- KCl(a1)

CSIR JUNE 2012

8. The molar conductivities at infinite dilution 𝛬OS for Na2SO4, K2SO4, KCl, HCl and HCOONa at 300 K
are 260, 308, 150, 426 and 105 S cm-1 mol-2 respectively. Hence  0m for formic acid in the same unit
and at the same temperature is
(a) 381 (b) 405 (c) 429 (d) 531
9. The correct value of Eº, of a half cell in the following graph of E vs log m(molality) is:

(a) CC/ AC (b) AB (c) BB (d) CC

10. The correct Nernst equation for the concentration cell:
Pt|H2 (p)|HCl(𝑎± )1 |AgCl(s)|Ag ∥ Ag|AgCl(s)|HCl(𝑎± )2 |H(p)|Pt
without liquid junction would be
2𝑅𝑇 (𝑎 )1 2𝑅𝑇 (𝑎 )2
(a) E = ln⁡(𝑎± )2 (b) E = ln⁡(𝑎± )1
𝐹 ± 𝐹 ±

𝑅𝑇 (𝑎 )2 𝑅𝑇 (𝑎 )2
(c) E = ln⁡(𝑎± )1 (d) E = ln⁡(𝑎± )1
𝐹 ± 2𝐹 ±

CSIR DEC 2012

11. The Daniel cell is
(a) PtI (s) | Zn (s) | Zn2+(aq) || Cu2+ (aq) | Cu(s) |PtII
(b) PtI (s) | Zn (s) | Zn2+ (aq) || Ag2+ (aq) | Ag(s) |PtII
(c) PtI (s) | Fe (s) | Fe2+ (aq) || Cu2+ (aq) | Cu(s) |PtII
(d) PtI (s) | H2 (s) | H2SO4(aq) || Cu2+ (aq) | Cu(s) |PtII
12. Kohlrausch’s law is applicable to a dilute solution of
(a) Potassium chloride in hexane (b) Acetic acid in water
(c) Hydrochloric acid in water (d) Benzoic acid in benzene
13. The equilibrium constant for an electrochemical reaction, is

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2Fe + Sn 2Fe + Sn
3+ 2+ 2+ 4+

𝑂 𝑜 2.303𝑅𝑇
[𝐸𝐹𝑒 +3 /Fe+2 = 0.75V, 𝐸𝑆𝑛+4 /𝑆𝑛 +2 = 0.15V; = 0.06V]
𝐹

(a) 1010 (b) 1020 (c) 1030 (d) 1040

14. The potential in Debye-Huckel theory is proportional to
(a) 1/κr (b) exp [-κr] (c) exp[-κr]/r (d) κr

CSIR JUNE 2013

15. If the concentration (c) is increased to 4 times its original value (c), the change in molar
conductivity for strong electrolytes is (where b is Kohlrausch constant)
(a) 0 (b) b√c (c)⁡2b√c (d) 4𝑏√𝑐
16. In complexometric titration
S (substrate) + T(titrant) → P(product)
The end point is estimated spectrophotometrically. If S and P have ε = 0 , the shape of the titrationcurve
would look like
(a) (b) (c) (d)

17. Which is correct Nernst equation for redox reaction 𝑂 + 𝑛𝑒 ⇌ ?

𝑛𝐹
𝑅𝑇 [𝑂] [𝑂] (𝐸−𝐸 𝑜 )
(a) 𝐸 = 𝐸 𝑜 − ln [𝑅] (b) = 𝑒 𝑅𝑇
𝑛𝐹 [𝑅]
𝑛𝐹 𝑅𝑇
[𝑂] (𝐸−𝐸 𝑜 ) [𝑂] (𝐸−𝐸 𝑜 )
(c) [𝑅] = 𝑒 −𝑅𝑇 (d) [𝑅] = 𝑒 𝑛𝐹

CSIR DEC 2013

18. In a potentiometric titration, the end point is obtained by observing
(a) change in colour (b) jump in potential
(c) increase in current (d) increase in turbidity

19. Electrolysis of an aqueous solution of 1.0 M NaOH results in

(a) Na at the cathode and O2 at the anode.
(b) H2 at the cathode and O2 at the anode.
(c) Na and H2 at the cathode, and O2 at the anode.
(d) O2 at the cathode and H2 at the anode.
20. The cell voltage of Daniel cell [ Zn | ZnSO4 (aq) || CuSO4 (aq) | Cu ] is 1.07 V. If reduced potential of Cu2+
| Cu is 0.34 V, the reduction potential of Zn2+|Zn is
(a) 1.141 V (b) –1.41 V (c) 0.73 V (d) –0.73 V
21. Consider the cell:

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2+ +2 +3
Zn | Zn (a = 0.01) || Fe (a = 0.001) , Fe (a = 0.01) | Pt Ecell = 1.71V at 25ºC for the above cell. The
equilibrium constant for the reaction:
𝑍𝑛 + 2𝐹𝑒+3 ⇌ 𝑍𝑛2+ + 2𝐹𝑒+2 at 25ºC would be close to
(a) 1027 (b) 1054 (c) 1081 (d) 1040
22. The limiting molar conductivities of NaCl, NaI and RbI are 12.7, 10.8 and 9.1 mS m 2 mol-1,
respectively. The limiting molar conductivity of RbCl would be
(a) 32.6 mS m2 mol-1 (b) 7.2 mS m2 mol-1
(c) 14.4 mS m2 mol-1 (d) 11.0 mS m2 mol-1

CSIR JUNE 2014

23. In the graph below, the correct option, according to Kohlrausch law, is

(a) A is a weak electrolyte and B is a strong electrolyte

(b) A is a strong electrolyte and B is a weak electrolyte
(c) C is a strong electrolyte and D is a weak electrolyte
(d) C is weak electrolyte and D is a strong electrolyte
24. Solutions of three electrolytes have the same ionic strength and different dielectric constants as 4,
25 and 81. The corresponding relative magnitude of Debye-Huckel screening, lengths of the three
solutions are
(a) 4, 25 and 81 (b) 2, 5 and 9 (c) 1/2, 1/5 and 1/9 (d) 1, 1 and 1
25. Given;
A. Fe(OH)2 (s) + 2e-  Fe (s) + 2OH- (aq) ; E0 = -0.877V
B. Al+3 (aq) + 3e-  Al (s) ; E0 = 1.66V
C. AgBr (aq) + e-  Ag (s) + Br- (aq) ; E0 = 0.071V
The overall reaction for the cells in the direction of spontaneous change would be
(a) Cell with A and B : Fe reduced ; Cell with A and C : Fe reduced
(b) Cell with A and B : Fe reduced ; Cell with A and C : Fe oxidized
(c) Cell with A and B : Fe oxidized ; Cell with A and C : Fe oxidized
(d) Cell with A and B : Fe oxidized ; Cell with A and C : Fe reduced

CSIR DEC 2014

26. For the cell reaction, Sn(s) + Sn4+ (aq) 2Sn2+ (aq), separate electrode reactions could be written with the
respective standard electrode potential data at 25°C as

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Sn4+ (aq) + 2e  Sn (aq),
2+
Eo = 0.15V
Sn2+ (aq) + 2e  Sn (s), Eo = 0.14V
When RT/F is given as 25.7 mV, logarithm of the equilibrium constant (ln K) is
(a) 22.6 (b) 226
(c) 2.26 (d) 2.26 × 10-1
27. Fuel cells provide clean electrical energy to a variety of applications including automobiles and
stationary power sources. Normally hydrogen combines with oxygen to give electrical energy and water.
13
⁡C4 H10 (g) +
O (g) → 4CO2 (g)5H2 O(𝑙)
2 2
If we use butane instead of hydrogen at 1.0 bar and 298 K, the following reaction occurs :

CSIR JUNE 2015

28. The correct ∆G for the cell reaction involving steps
Zn (s)  Zn+2 (aq) + 2e
Cu2+ (aq) + 2e  Cu (s)
𝑎 2+ 𝑎 2+
(a) Δ𝐺 𝑜 − 𝑅𝑇ln⁡𝑎𝑍𝑛 (b) Δ𝐺 𝑜 − 𝑅𝑇⁡ln⁡𝑎𝑍𝑛
𝐶𝑢2+ 𝐶𝑢(𝑠)

𝑎 𝑎 2+
(c) Δ𝐺 𝑜 − 𝑅𝑇⁡ln⁡ a𝑍𝑛(𝑠) (d) Δ𝐺 𝑜 + 𝑅𝑇⁡ln⁡a𝑍𝑛
Cu2+ Cu2+

29. For a given ionic strength, (I) rate of reaction is given by

k
log  4  0.51 I
k9

Which of the following reactions follows the above equation?

(b) Co  NH3 5 Br  OH
2 
(a) S2O82  I

(c) CH3COOC2H5  OH (d) H  Br   H2O2

30. The temperature-dependence of an electrochemical cell potential is
G H
(a) (b)
nFT nF
S S
(c) (d)
nF nFT
31. Conductometric titration of a strong acid with a strong alkali (MOH) shows linear fall of conductance up
to neutralization point because of
(a) formation of water
(b) increase in alkali concentration
(c) faster moving H+ being replaced by slower moving M+.
(d) neutralization of acid
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CSIR DEC 2015

32. In Kohlrausch law,  m   0m   c,  om and 

(a) depend only on stoichiometry

(b) depend only on specific identify of the electrolyte
(c) are independent of specific identify of the electrolyte
(d) are mainly dependent on specific identity of the electrolyte and stoichiometry, respectively
33. The concentration of a MgSO4 solution having the same ionic strength as that of a 0.1 M Na2SO4
solution is
(a) 0.05 M (b) 0.067 M (c) 0.075 M (d) 0.133 M
10
34. Given that E(Cl2 / Cl )  1.35V and K sp (AgCl)  10 at 25ºC, E0 corresponding to the electrode

1
reaction Cl 2 (g)  Ag  (Soln.)  e   AgCl(s)
2
(a) 0.75V (b) 1.05V (c) 1.65V (d) 1.95V
35. The standard EMF of the cell Pt, H.g HCl soln. AgCls, Ag(s)
(a) increases with T (b) decreases with T
(c) remains unchanged with T (d) decreases with [HCl]

CSIR JUNE 2016

36. In a potentiometric titration, the end point is characterised by
dE d2E
(a)  0; 0
dV d2V
dE d2E
(b)  0; 2  0
dV dV
dE d2E
(c)  0; 2  0
dV dV
dE d2E
(d)  0; 2  0
dV dV

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37. On titrating conductometrically a NaOH solution with a mixture of HCl and CH3CO2H solutions, plot of
the volume of mixed acid added (b) in y-axis against the conductance (a) in x-axis is expected to look like
(a) (b) (c) (d)

38. The standard electrode potential E0 at a fixed temperature and in a given medium is dependent on
(a) only the electrode composition
(b) the electrode composition and the extent of the reaction
(c) the extent of the electrode reaction only
(d) the electrode reaction and the electrode composition
39. Two aqueous 1 : 1 electrolyte systems A and B are at different temperatures T A and TB and CA and
CB concentrations, respectively. Their Debye lengths will be equal if
(a) TA = 2TB and CA = 2CB (b) TA = 2TB and CA = CB/2

(c) TA  2TB and CA  2CB (d) TA  2TB and CA  2CB

CSIR DEC 2016

40. The ionic mobilities of NH 4 and HCO3 are 6 × 10-4 V-1 s-1 and 5 × 10-4 V-1s-1, respectively. The transport

numbers of NH 4 and HCO3 are, respectively

(a) 0.545 and 0.455 (b) 0.455 and 0.545
(c) 0.090 and 0.910 (d) 0.910 and 0.090
41. The ionic strength of a solution containing 0.008 M AlCl3 and 0.005 M KCl is
(a) 0.134 M (b) 0.053 M
(c) 0.106 M (d) 0.086 M
42. If the specific conductance’s of a sparingly soluble (1 : 1) salt (MW = 200 g mol -1) in its saturated
aqueous solution at 25°C and that of water are 1.5 × 10-3 ohm-1 dm-1 and 1.5 × 10-5 ohm-1 dm-1,
respectively, and the ionic conductance’s for its cation and anion at infinite dilution are 0.485 and
1.0 ohm-1 dm2 mol-1, respectively, the solubility (in g L-1) of the salt in water at 25°C is
(a) 1 × 10-6 (b) 1 × 10-3 (c) 2 × 10-1 (d) 2 × 10-4
43. Given :
(i) Zn + 4NH3  Zn(NH3)42+ + 2e, E0 = 1.03 V
(ii) Zn  Zn+2 + 2e, E° = 0.763 V
the formation of the complex Zn(NH3)42+ is approximately
(a) 1 × 105 (b) 1 × 107 (c) 1 × 109 (d) 1 × 1012

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44. The molar conductivity Λ vs. concentration (c) plot of sodium dodecylsulfate in water is expected to look
like
(a) (b) (c) (d)

CSIR JUNE 2017

45. The electrochemical cell potential (E), after the reactants and products reach equilibrium, is (E0 is
the standard cell potential and n is the number of electrons involved)
nF nF
(a) E  E  (b) E  E 
RT RT
(c) E = E° (d) E = 0
46. The specific conductance of a solution is 0.176 W-11 cm-1. If the cell constant is 0.255 cm-1, the
conductance (-1) of that solution is
(a) 1.449 (b) 0.690 (c) 0.045 (d) 0.431
47. The standard cell potential for the reaction Zn(s) + Cu2+ (aq)  Zn2+ (aq) + Cu(s) is +1.10 V. The Gibbs
free energy change during the reaction is (F = 96500 coulomb mol-1)
(a) -21.2 kJ mol-1 (b) +212 kJ mol-1 (c) -212 kJ mol-1 (d) -212 J mol-1
48. A solution of Fe3+ is titrated potentiometrically using Ce3+ solution at 25°C. The emf (in V) of the redox
system thus formed when, (i) 50 % of Fe3+ and (ii) 80% of Fe3+ are titrated, would respectively be (Given
E oFe3 Fe2  0.77V, log 2  0.301 )
(a) 0.734 and 0.77 (b) 0.77 and 0.385 (c) 0.77 and 0.734 (d) 0.385 and 0.367
49. The standard cell potential of cell, Pt | H2(g) | HBr(aq) | AgBr(s) |Ag(s), was measured over a range
of temperatures, and the data was fitted as E0(Volt) = 0.01 - 1 × 10-4 (T - 298) - 2 ×10-6(T - 298)2. The
standard reaction entropy (JK-1mol-1) and enthalpy (kJmol-1) at 298 K are
(a) -9.65 and -3.84 (b) -3.84 and -9.65 (c) -18.3 and-7.68 (d) -7.68 and -18.3

CSIR DEC 2017

50. The correct statement among the following is
(a) Salt bridge is required for the mixing of the solutions in the two half cells.
(b) Salt bridge allows current to flow between the half cells without mixing the solutions
(c) Salt bridge enhances the rate of the reaction
(d) Salt bridge consists of a non-electrolyte in a gel.

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51. The standard free energy of the reaction
AgBr(s)  Ag+ (aq) + Br (aq)
Is closest to.
[E°(AgBr/Ag,Br) = 0.07V ; E°(Ag/Ag+) = 0.80 V; F = 96500 C mol-1]
(a) 7 kJ mol-1 (b) 70 J mol-1 (c) 70 kJ mol-1 (d) 7 J mol-1
52. Conductivities of water and a saturated solution of a sparingly soluble salt AB2 are 7 and 21 S m-1,
1 1
respectively. Given  A2  12.72 mS m mol and  B2  7.64 mS m mol , the solubility of AB2, in mol
0 2 0 2

m-1, is
(a) 5.0 × 104 (b) 5.0 × 103 (c) 5.0 × 105 (d) 5.0 × 106

CSIR JUNE 2018

53. The equilibrium constant of the following reaction:
Sn(s) + Sn4+(aq)  2Sn2+(aq)
1 1
At 300K is closest to, (Given : ESn 4 /Sn2  0.15V and ESn2 /Sn  0.15V, R  8.314 JK mol )
o o

(a) 106.08 (b) 108.08 (c) 1010.08 (d) 1012.08

CSIR JUNE 2019

54. The mobility of a divalent cation in water is 8×108m2V-1S-1. The effective radius of the ion is
(viscosity of water = 1cP; e =1.6 × 10-19 C)
(a) 106 pm (b) 212 pm (c) 424 pm (d) 318 pm
55. If the over potential of an electrolysis process is increased from 0.5V to 0.6V, then the ratio of current
 J 
densities  ln 0.6  of the electrolysis will be equal to (given transfer coefficient = 0.5)
 J 0.5 
F F
(a) 0.5 (b) 0.05
RT RT
F F
(c) 0.1 (d) 0.01
RT RT

CSIR DEC 2019

56. The cell potential (in V) of a Ag/AgCl/KCl electrode connected to the standard hydrogen electrodeat
298K is closest to (Given E0(AgCl/Ag.Cl )  0.222 V and assume that the activity of KCl is 0.01)

(a) 0.197 (b) 0.297 (c) 0.340 (d) 0.440

57. In common glass electrode, alkaline error caused at pH > 10 is least for
(a) 0.01M NaCl (b) 1.0M NaCl (c) 1.0M LiCl (d) 1.0M KCl
58. For the electrochemical cell Ag |AgCl | MCl(0.01M) | MCl (0.02M) | AgCl | Ag, the junction potential is
the highest when M+ is
(a) H+ (b) Li+ (c) Na+ (d) K+

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59. The electrolyte solution that has the smallest Debye-length at 298 K is
(a) 0.01M NaCl (b) 0.01M Na2SO4
(c) 0.01M CuCl2 (d) 0.01M LaCl3

CSIR 2020
60. The E0(M+ / M) of the cell, SHE || MX | M can be obtained from the plot of (Ecell is the cell potential
and m is molality of ideal dilute solution of MX)
1 
(a) Ecell vs (T log m) (b) E cell vs  log m 
T 
 m
(d) E cell vs 
 T 
(c) Ecell vs T m
 
61. An aqueous solution contains 0.02 mol kg NaCl and 0.03 mol kg-1 Ca(NO3)2. The logarithm of
-1

mean ionic activity coefficient (log 𝛾±) of this solution at 25°C is

(a)  0.095 (b) 0.154 (c)  0.033 (d)  0.11

CSIR JUNE 2021

62. For the cell Cd | CdCl2 || AgCl | Ag; Eocell  0.675 V and dEcell
o
/ dT  -6.5 × 10-4 VK-1 at 27°C. The

H(kJ mol1 ) value for the reaction Cd + 2AgCl  2Ag + CdCl2 is closest to
(a) -168 (b) -123 (c) -95 (d) -234
63. For weak electrolyte like acetic acid, the relation among conductance (), equilibrium constant (K)
and concentration (C) can be expressed as: (0 is conductance at infinite dilution)
1 1 C 1 1 C 1 1 C 1 C
(a)   (b)  o (c)  o (d) 
  o k o   K o   K o2  K o 2
64. The amount of Ba(NO3)2 (molecular weight 261.32 amu) required to be added to 500 g of a 0.11 mol
kg-1 solution of KNO3 in order to raise its ionic strength to 1.00 is approximately
(a) 38.8 g (b) 19.4 g (c) 76.2 g (d) 126.5 g
65. Consider following terms. Identify those which are relevant to d.c. polarography
A. Thermal current B. Supporting electrolyte
C. Depolarization D. Gelatin
Correct answer is
(a) A, B and C (b) A, B and D (c) B, C and D (d) C and D only



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ANSWER KEY
ELECTROCHEMISTRY

1. (c) 2. (a) 3. (a) 4. (d) 5. (c) 6. (d) 7. (?)

8. (b) 9. (c) 10. (c) 11. (a) 12. (c) 13. (b) 14. (c)
15. (b) 16. (c) 17. (b) 18. (b) 19. (b) 20. (d) 21. (b)
22. (d) 23. (c) 24. (b) 25. (b) 26. (a) 27. (b) 28. (d)
29. (b) 30. (c) 31. (c) 32. (d) 33. (c) 34. (d) 35. (b)
36. (b) 37. (d) 38. (d) 39. (a) 40. (a) 41. (b) 42 (c)
43. (c) 44. (d) 45. (d) 46. (b) 47. (c) 48. (c) 49. (a)
50. (b) 51. (c) 52. (a) 53. (c) 54. (b) 55. (b) 56. (c)
57. (d) 58. (a) 59. (d) 60. (a) 61. (d) 62. (a) 63. (b)
64. (a) 65. (c)

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 4
Surface Chemistry
CSIRJUNE 2011

1. The adsorption of a gas on a solid surface exhibits the following isotherm. Which one of the
following statements is true?

(a) Heat of adsoprtion is independent of coverage

(b) Adsorption is multilayer
(c) Heat of adsorption varies monotonically with coverage
(d) Heat of adsorption varies exponentially with coverage
2. Isothermal which has fractional coverage, linearly, dependent1 on pressure at low pressures but almost
independent at high pressure is called
(a) BET isotherm (b) Langmuir isotherm
(c) Freundlich isotherm (d) Temkin isotherm

CSIR DEC 2011

3. Flocculation value of K2SO4 is much less than that of KBr for Sol A. Floccultion value of CaCl2
is much less than that of NaCl for Sol B. Which of the following statements is correct?
(a) Sol A is negatively charged and Sol B is positively charged
(b) Both the sols are negatively charged.
(c) Sol A is positively charged and sol B is negatively charged
(d) Both the sols are positively charged.
kp
4. The Langmuir adsorption isotherm is given by , where P is the pressure of the
1  kp
adsorabate gas. The Langmuir adsorption isotherm for a diatomic gas A2 undergoing dissociative
adsorption is:

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(a)  = Kp /(1 + Kp) (b)  = 2Kp/(1 + 2Kp)
(c)  = (Kp)2/ ( 1 + (Kp)2) (d)  = (Kp)1/2 (1+(Kp))1/2

CSIR JUNE 2012

5. Dispersion of a solid in a liquid, a liquid in a gas and a liquid in a liquid are respectively known as
(a) Aerosol, emulsion, sol (c) Emulsion, sol, aerosol
(b) Sol, Aerosol, emulsion (d) Aerosol, sol, emulsion
6. A dilute silver nitrate solution is added to a slight excess iodide solution. A solution of AgI is formed
whose surface adsorbs.
(a) I (b) NO3 (c) Na+ (d) Ag+

7. The correct representation of the variation of molar conductivity (y-axis) with surfactant concentration
(x-axis) is [CMC = critical micelle concentration].

(a) (b)

(c) (d)

8. The adsorption of a gas is described by the Langmuir isotherm with the equilibrium constant K
= 0.9 kPa-1 at 25°C. The pressure (in kPa) at which the fractional surface coverage is 0.95, is
(a) 1/11.1 (b) 21.1
(c) 11.1 (d) 42.2

CSIR JUNE 2013

9. The aggregation of surfactant molecules is known as

(a) micelles (b) clusters (c) gel (d) colloid

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10. "Colloids are thermodynamically unstable with reference to bulk but kinetically stable".
Identify the correct pair
Statements Reasons
(A) thermodynamically unstable (C) interfacial
surface tension
(B) kinetically stable (D) electrical double layer
(a) (A)  (D) and (B)  (C) (c) (A)  (C) and (B)  (C)
(b) (A)  (C) and (B)  (D) (d) (A)  (D) and (B)  (D)

CSIR DEC 2013

11. The volume of a gas adsorbed on a solid surface is 10.0 mL, 11.0 mL, 11.2 mL, 14.5 mL and
22.5 mL at 1.0, 2.0, 3.0, 4.0 and 5.0 atm. pressure, respectively. These data are best represented by
(a) Gibbs's isotherm (b) Langmuir isotherm
(c) Freundlich isotherm (d) BET isotherm
12. Michael Faraday observed that the colour of colloidal suspensions of gold nanoparticles
changes with the size of the nano particles. This is because
(a) gold forms complex with the solvent
(b) band gap of gold changes with size of the nanoparticle
(c) gold in nanocrystalline form undergoes transmutation to other elements
(d) colloidal suspensions diffract light
13. The molecule that has the smallest diffusion coefficient in water is
(a) glucose (b) fructose (c) ribose (d) surcrose

CSIR JUNE 2014

14. For the non dissociative Langmuir type adsorption of a gas on a solid surface at a particular
temperature, the fraction of surface coverage is 0.6 at 30 bar. The Langmuir isotherm constant (in
bar-1 units) at this temperature is
(a) 0.05 (b) 0.20 (c) 2.0 (d) 5.0

CSIR DEC 2011

15. Hydrogen is adsorbed on many metal surfaces by dissociation (S represents a surface site)—

If the pressure of H₂ (p) is small, the fraction of the surface covered by hydrogen is proportional to
(a) p (b) p2 (c) p1/2 (d) p1/2

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CSIR JUNE 2015

16. For a reaction on a surface

At low pressure of H, the rate is proportional to

(a) H2 (b) 1/H2 (c) H21/2 (d) 1/[H2]1/2
17. Energy of interaction of colloidal particles as a function of distance of separation can be
identified as (1) Vander Waals, (2) double layer, (3) Vander Waals and double layer. The correct
order of interactions in the figure corresponding to curves (a), (b) and (c), respectively, is

(a) 1, 2, 3 (b) 2, 3, 1 (c) 3, 1, 2 (d) 1.3, 2

CSIR DEC 2015

18. Stability of lyophobic dispersions is determined by

(a) inter-particle electric double layer repulsion and intra-particle van der Waals attraction
(b) inter-particle electric double layer attraction and intra-particle van der Waals repulsion
(c) inter-particle excluded volume repulsion and intra-particle van der Waals attraction
(d) inter-particle excluded volume attraction and intra-particle van der Waals repulsion

CSIR JUNE 2016

19. Adsorbtion isotherm of three gases A,B ,C are shown in the following figure, where  is the
percentage of surface coverage. The correct order of the extent of adsorbtion of three gases is

(a) A > B > C (b) B > A > C (c) C > A>B (d) C > B > A

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CSIR DEC 2016

20. When 1 x 10-5 g of a fatty acid (M = 602.3 g/mol) was placed on water as a surface film, a
monomolecular layer of area 100 cm2 was formed on compression. The cross-sectional area (in Å 2 )
of the acid molecule is
(a) 50 (b) 100 (c) 150 (d) 200
21. Mark-Houwink equation ([n] = KMa) is used for the determination of
(a) number-average molar mass (b) weight-average molar mass
(c) viscosity-average molar mass (d) z-average molar mass
22. Many properties of nanoparticles are significantly different than the corresponding bulk
materials due to
(a) smaller band gap of ano-particles compared to bulk
(b) higher heterogeneity of the nano-particle solutions
(c) larger ratio of surface area to volume of the nano-particles compared to the bulk
(d) smaller ratio of surface area to volume of the nano-particles compared to the bulk

CSIR JUNE 2016

23. When river water containing colloidal clay flows into the sea, the major cause of silting is
(a) accumulation of sand at the bottom (b) flocculation and coagulation
(c) decreased salinity of sea water (d) micellization

CSIR JUNE 2017

24. An intense purple colour (Plasmon band) is exhibited by a colloid consisting of spherical
(a) silver particles of 10 mm diameter (b) silicon particles of 5 mm diameter
(c) gold particles of 5 nm diameter (d) iron particles of 3 mm diameter
25. The figure below depicts an adsorption isotherm of O2, on charcoal at 90 K.At a pressure 25 torr, only
10% of charcoal sites are occupied by O2. Therefore, the ratio of adsorption to desorption rate constants
(in torr-1) is close to

(a) 0.003 (b) 0.004 (c) 0.006 (d) 0.015

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CSIR JUNE 2019

26. Above the critical micelle concentration (CMC), the option which correctly describes the
variation of molar conductivity with increase in concentration of sodium dodecylsulphate in
aqueous solution is
(a) molar conductivity increases sharply, but the solution does not remain colloidal
(b) molar conductivity decreases sharply, but the solution remains colloidal
(c) molar conductivity decreases sharply and dissociation into monomers also occurs sharply
(d) molar conductivity increases sharply with large loss of entropy

CSIR DEC 2019

27. A liquid of density 1.1 g cm-3 climbs to a height of 5.0 cm when a capillary with internal radius
of 0.2 mm is dipped into it. The surface tension (in Nm-1) of the liquid is closest to
(a) 0.05 (b) 0.108 (c) 0.018 (d) 0.005
28. The order of a surface catalyzed unimolecular reaction, at very low and very high pressures of
the reactant, would be, respectively
(a) 0,0 (b) 1,0 (c) 0,1 (d) 1,1

CSIR NOV 2020

29. The correct statement about chemisorption is
(a) Chemisorption results in multi molecular layer adsorption.
(b) Chemisorption is reversible in nature.
(c) Chemisorption has lower specificity than physisorption.
(d) Chemisorption occurs due to formation of chemical bonds
30. A gas is known to satisfy Langmuir isotherm when adsorbed on a certain metal surface. If the
fractional coverage of the gas is 0.5 when the gas pressure is 1.0 Pa, the fractional coverage at 3.0
Pa would be closest to
(a) 0.67 (b) 0.75
(c) 0.80 (d) 1.0
31. The surface tension of dilute soap solution is lower than that of pure water because
(a) soap molecules accumulate more at the surface than in the bulk solution.
(b) soap molecules accumulate more in the bulk than on the surface.
(c) the soap molecules aggregate uniformly in the bulk and the surface.
(d) soap molecules form micellar structures at low concentration.

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CSIR JUNE 2021

32. The volume of nitrogen gas adsorbed at STP to form a monolayer on a porous solid surface is
22.4 cm3 g-1. If the area occupied by one nitrogen gas molecule is 16.2 Å2 , then the surface area
(in cm2 g-1) of the solid is close to:
(a) 1.2 × 107 (b) 9.8 × 105 (c) 1.2 × 105 (d) 9.8 × 10
33. In a Langmuir-type adsorption, a solid adsorbs 0.25 mg of a gas when the pressure of the gas is
50 bar and 0.2 mg of the gas at 20 bar pressure. The percentage of surface coverage at 50 bar is
close to:
(a) 75 (b) 38 (c) 57 (d) 83
34. Liquid A has half the surface tension and twice the density of liquid B at 30°C. The contact
angles of A and B are the same. If A rises 10 cm in a capillary, then the rise (in cm) of liquid B in
the same capillary at the same temperature will be equal to
(a) 60 (b) 10 (c) 40 (d) 20



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ANSWER KEY
ELECTROCHEMISTRY

1. (a) 2. (b) 3. (c) 4. (d) 5. (b) 6. (a) 7. (b)

8. (b) 9. (a) 10. (b) 11. (d) 12. (b) 13. (d) 14. (a)
15. (c) 16. (c) 17. (a) 18. (a) 19. (d) 20. (b) 21. (c)
22. (c) 23. (b) 24. (c) 25. (b) 26. (b) 27. (a) 28. (b)
29. (d) 30. (d) 31. (a) 32. (b) 33. (d) 34. (c)

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 5
Nuclear Chemistry
CSIRJUNE 2011

1. For a given nuclear fission reaction of U

235
92 U  10 n  142
56 Ba 
91
36 Kr  310 n
235 142
the amount of energy (in kJ/mol) released during this process is (given U = 235.0439 amu, Ba =
141.9164 amu, 91Kr = 90.9234 amu , neutron = 1.00866 amu)
(a) 3.12 × 1012 (b) 2.8 × 1011
(c) 1.0 × 109 (d) 1.68 × 1010
2. Saturation factor in neutron activation analysis is (A = induced radioactivity ,  = neutron flux ,
 = effective nuclear cross section , N = no. of target atoms ,  = decay constant )
A NA  N
(a) (b) (c) (d)
N  AN A
235 235
3. In fission of U atom the energy released is 200 MeV. In one day fission of 1 kg U will give
power (in MW) approximately
(a) 550 (b) 650 (c) 950 (d) 1250
4. The penetrating power (R) and ionizing power (I) of α, β, and γ rays follow the ordering
(a) R   R  R  and I  I   I (b) R   R   R  and I  I  I

(c) R   R   R  and I  I  I (d) R   R   R  and I  I  I

5. The reactive cross section is expected to be the largest for the reaction
(a) Li + Cl2  LiCl + Cl (b) Na + Cl2
(c) K + Cl2 (d) Rb + Cl2



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QUANTA CHEMISTRY CLASSES |Nuclear Chemistry

ANSWER KEY
NUCLEAR CHEMISTRY

1. (d) 2. (a) 3. (d) 4. (d) 5. (d)

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 6
Polymer Chemistry
CSIR JUNE 2011
1. There are several types of mean molar masses for polymer and they are dependent on
experimental methods like:
(1) Osmometry
(2) Light scattering
(3) Sedimentation.
Correct relation between mean molar masses and experimental method is:
(a) Mn  (3), Mw  (2), Mz  (1)

(b) Mn  (2), Mw  (3), Mz  (1)

(c) Mn  (1), Mw  (2), Mz  (3)

(d) Mn  (1), Mw  (3), Mz  (2)

CSIR DEC 2011

2. The osmotic pressure () of a polymer sample at different concentrations (c) was measured at
T(K). A plot of (/c) versus c gave a straight line with slope (m) and intercept (c'). The number
average molecular weight of the polymer is (R = gas constant).
Rt c
(a) (b) (c) RT (d) mRT
c RT
3. The addition polymerization of M (monomer) involves the following stages: (I = initiator, R = free radical)
The rate constant for free radical formation is 2 × 10-1s-1. The initial concentration of initiator is 10-3 mol
dm-3 . The overall rate of the reaction is 4 × 10-1 mol dm-1 s-1. Assuming steady state approximation for
free radical, the kinetic chain length is
(a) 2000 (b) 8 × 109 (c) 20 (d) 200

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CSIR JUNE 2012

4. A polymer sample has the following composition.

Number of Molecules Molecular Weight

10 1000
50 2000
40 4000

The polydispersity index (P.D.I) of the polymer is

(a) 85000/27 (b) 85/81 (c) 850/729 (d) 729/850
5. During the addition polymerization , the reaction proceeds via
(a) Step-growth process (b) Free-radical chain reaction
(c) Cascade process (d) Addition reaction
6. The number-average molar mass  MN  and weight-average molar mass  Mw  of a polymer are obtained

respectively by
(a) Osmometry and light scattering measurements
(b) Osmometry and viscosity measurements
(c) Light scattering and sedimentation measurements
(d) Viscosity and light scattering measurements

CSIR JUNE 2014

7. In radical chain polymerization the quantity given by the ‘rate of monomer depletion, divided by the rate
of propagating radical formation’ is called
(a) kinetic chain length (b) propagation efficiency
(c) propagation rate constant (d) polymerization time

CSIR DEC 2014

8. The fraction of groups condensed at time in any stepwise condensation polymerization (overall second
order) reaction is
(a) 1+ kt[A]0 (b) 1/ 1+ kt[A]0 (c) kt[A]0 / 1+ kt[A]0 (d) 1+ kt[A]0 /kt[A]0
9. For a polydispersed macromolecular colloid, osmometry gives
(a) weight-average molecular weight
(b) number-average molecular weight
(c) both weight-average and number average molecular weight
(d) viscosity-average molecular weight
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10. A sample experiment revealed that PVC formed in the medium has (Mn) = 13, and (Mw) = 16, where (Mn)
stands for the number average molar mass and (Mw) for the weight average molar
mass. The variance of Mn will then be
(a) 39 (b) 3 (c) 1 (d) 87
11. Among the following figures, the variations of mass adsorbs with pressure for a monolayer
and a multilayer are represented by

(a) A and C respectively (b) A and B respectively

(c) C and A respectively (d) B and A respectively

CSIR JUNE 2015

12. The intrinsic viscosity depends on the molar mass as [] = KMa. The empirical constants K and a are
dependent on
(a) solvent only (b) polymer only
(c) polymer-solvent pair (d) polymer-polymer interaction
13. The stability of a lyophobic colloid is the consequence of
(a) van der Waals attraction among the solute-solvent adducts
(b) Brownian motion of the colloidal particles
(c) insolubility of colloidal particles in solvent
(d) electrostatic repulsion among double layered colloidal particles
14. Find the probability of the link in polymers where average values of links are
(1) 10, (2) 50 and (3) 10
(a) (1) 0.99, (2) 0.98, (3) 0.90
(b) (1) 0.98, (2) 0.90, (3) 0.99
(c) (1) 0.90, (2) 0.98, (3) 0.99
(d) (1) 0.90, (2) 0.99, (3) 0.98

CSIR DEC 2015

15. The correct form for a simple Langmuir isotherm is
(a)  = Kp (b)  = (Kp)1/22 (c)  = Kp/(1+ Kp) (d)  = (1 + Kp)/Kp

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16. The correct expression for the product  M    M 

n w [(( M n and (( Mw are the number average

and weight average molar masses, respectively, of a polymer] is

(a) N-1i Ni Mi (b) N-1i Ni Mi2 (c) N/i Ni Mi (d) N/i Ni Mi2
17. The average end-to-end distance of a random coil polymer of 106 monomers (in units of segment length)
is
(a) 106 (b) 105 (c) 104 (d) 103

CSIR JUNE 2016

18. The condensation of hydroxy acid produces a polyster with the probability of linkage at both
ends being p . The mole fraction of k-mer chain formation is
(a) pk (b) p(1 - p)k-1 (c) pk-1(1 - p) (d) pk-1

CSIR DEC 2016

19. Distribution of molar masses in a typical polymer sample is shown below

The A, B and C represent

(a) Mw , Mv and Mn Respectively (b) Mn , Mv and M w Respectively

(c) Mv , Mw and Mn Respectively (d) Mn , Mw and M v Respectively

CSIR JUNE 2017

20. For a monodisperse polymer, the number-average molar mass  MN  and weight-average molar mass

 M  are related according to

w

(a) M w  M N (b) M w  M N (c) M w  M N (d) Mw  log M N

21. A polydisperse polymer sample has ten molecules of molar mass 20,000 g mol -1 and fifteen
molecules of molar mass 10,000 g mol-1. The number-average molar mass (g mol-1) M n of the

sample is
(a) 13,000 (b) 14,000 (c) 15,000 (d) 16,000

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CSIR DEC 2017

22. A polymer has the following molar mass distribution

Number of molecules Molar mass (g.mol-1)
50 5000
75 6000
The calculated number average molar mass  M n  of the polymer is

(a) 5200 (b) 5600 (c) 5800 (d) 6000

CSIR JUNE 2018

23. A 5 g/L polymer solution is prepared with a polymer whose molar mass is 25 kg the osmotic
pressure (in atm) of this solution at 25°C is (consider RT = 2500 J mol-1)
(a) 0.002 (b) 0.05 (c) 0.005 (d) 0.008

CSIR DEC 2018

24. The dispersity of a polymeric sample is
2 2
M2 M M M
(a) 2
(b) 2
(c) (d) 2
M M M M

25. The contour and root mean square length (in nm) of a polymer chain modelled as a random
coil, with N = 1000 and = 150 pm, are closest to
(a) 1.50 and 47.4 (b) 15.0 and 4.74 (c) 150 and 47.4 (d) 150 and 4.74

CSIR JUNE 2019

26.The degree of polymerisation (<N>) and the fraction of monomer consumed (P) for apolymerization
reaction are related as
1 1 1 1
(a) N  (b) N  (c) N  (d) N 
1 P 1 P P P2
27. The reaction rate of a self-catalyzed polyesterification reaction is given as
d  COOH 
  k  COOH   OH 
2

dt
If [M] is the initial concentration of hydroxyl and carboxyl monomers, then the degree of
polymerization, <N> is given by

(a) N  2  M0 kt (b) N  2  M0 kt (c) N  2  M0 kt  1 (d) N  2  M0 kt  1

2 2 2 2 2 2

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CSIR DEC 2019

28. In a polymer of N monomer units, the root mean square separation between the two ends is
proportional to
(a) N1/2 (b) N (c) N3/2 (d) N2

CSIR 2020
29. The degree of polymerization at t = 10 h of a polymer formed by a stepwise process with
polymerization rate constant of 3 × 10-2 M-1s-1 and an initial monomer concentration of 50 mM is
Options:
(a) 55 (b) 65 (c) 550 (d) 505

30. Using standard equation for intrinsic viscosity   K Mav for a solution of polymer and any

information from the graph identify viscosity average molar mass  M [given that a = 0.5,

K = 5 × 10-5 L g-1)

(a) 103 g/mol (b) 104 g/mol (c) 105 g/mol (d) 106 g/mol
31. A sample of polysterene is composed of three weight fractions: 0.20, 0.50 and 0.30. The molecular weight
of these fractions are 10,000, 40,000 and 60,000, respectively. The weight average molecular weight of
this sample is
(a) 40000 (b) 55000 (c) 50000 (d) 60000

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ANSWER KEY
POLYMER CHEMISTRY
1. (c) 2. (b) 3. (a) 4. (c) 5. (b) 6. (b) 7. (a)
8. (c) 9. (b) 10. (a) 11. (b) 12. (c) 13. (d) 14. (c)
15. (c) 16. (b) 17. (d) 18. (d) 19. (b) 20. (b) 21. (b)
22. (b) 23. (c) 24. (a) 25. (a) 26. (a) 27. (c) 28. (a)
29. (a) 30. (c) 31. (a)

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 7
Thermodynamics
CSIR JUNE 2011
1. A process is carried out at constant volume and at constant entropy. It will be spontaneous if:
(a) ∆G < 0 (b) ∆H < 0 (c) ∆U < 0 (d) ∆A < 0
2. The variation of equilibrium constant (K) of a certain reaction with temperature (T) is
2.0 104
ln k  3.0 
T
given R = 8.3 Jk-1mol-1, the values of ∆H0and ∆S0are.
(a) 166 kJ mol-1and 24.9 JK-1mol-1 (b) 166 kJ mol-1and -24.9 JK-1mol-1
(c) -166 kJ mol-1and 24.9 JK-1mol-1 (d) -166 kJ mol-1and -24.9 JK-1mol-1
3. The chemical potential of component 1 in a solution of binary mixture is 1  10  RT ln p1 , when p1is

the partial pressure of component 1 vapour phase. The standard state 10 is:
(a) Independent of temperature and pressure
(b) Depends on temperature and pressure both
(c) Depends on temperature only
(d) Depends on pressure only

CSIR DEC 2011

4. For a system of constant composition, the pressure (P) is given by.
 U   U   V   U 
(a)    (b)    (C)   (d)  
 S V  V S  S T  V T
5. For the reaction C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l), the value of ∆H-∆U (in kJ) at 300K
and 1bar is
(a) –5.0 (b) 0.0 (c) 2.5 (d) 5.0
6. 1 mol of CO2 , 1 mol of N2 and 2 mol of O2 were mixed at 300 K. The entropy of mixing is
(a) 6R ln 2 (b) 8R ln 2 (c) 8R ln 2/ 300 (d) 16R/ ln 2

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7. For the liquid ⇌vapour equilibrium of a substance dP/dT at 1 bar and 400 K is 8 × 10-3bar
K-1. If the molar volume in the vapour form is 200 Lmol-1and the molar volume in the liquid form is
negligible, the molar enthalpy of vapourisation is (1.0 bar L = 100 J)
(a) 640 kJ mol-1 (b) 100 kJ mol-1 (c) 80 kJ mol-1 (d) 64 kJ mol
8. For the reaction H2O(g) + C (graphite)⇋CO(g) + H2O(g), the variation of energy parameter
ΔG0, ΔH0and TΔS0of the reaction over a large temperature range is shown below. The correct
identification of the curves is given by

(a) A  ΔG, B  ΔH, C  TAS (b) A  ΔH, B  ΔG, C  TΔS

(c) A  ΔG. B  TΔS, C  ΔH (d) A  TAS, B  ΔH, C  ΔG

CSIR JUNE 2012

9. The vapour of a pure substance, when cooled under a pressure less than its triple-point
pressure,
(a) Liquefies (b) Liquefies first and then solidifies
(c) Solidifies directly (d) Remains unchanged
10. The quantities, which are held fixed in a canonical ensemble are
(a) N, T and P (b) V, T and N (c) N, V and E (d) µ, V and P
11. An ideal gas was subjected to a reversible, adiabatic, expansion and then its initial volume
was restored by a reversible, isothermal compression. If ‘q’ denotes the heat added to the system
and ‘w’ the work done by the system, then
(a) w < 0, q < 0 (b) w > 0, q < 0 (c) w < 0, q > 0 (d) w > 0, q > 0
12. Indicate which one of the following relations is NOT correct
 T   P   T   V   S   P   S   V 
(a)       (b)       (c)      (d)      
 V S  S V  P S  S P  V T  T V  P T  T P

CSIR DEC 2012

13. For water, ∆Hvap≈ 41 kJ mol-1. The molar entropy of vaporization at 1 atm pressure is
approximately
(a) 410 J K-1mol-1 (b) 110 J K-1mol-1 (c) 41 J K-1mol-1 (d) 11 J K-1mol-1

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14. A carnot takes up 90 J of heat from the source kept at 300K. The correct statement among
the following is
(a) It transfers 60 J of heat to the sink at 200K
(b) It transfers 50 J of heat to the sink at 200K
(c) It transfers 60 J of heat to the sink at 250 K
(d) It transfers 50 J of heat to the sink at 250 K
15. The fugacity of a gas depends on pressure and the compressibility factor Z( = p V /RT) through the
relation ( V is the molar volume). For most gases at temperature T and up to moderate pressure, this
equation shows that
(a) f <p, if T  0 (b) f <p, if T  ∞ (c) f >p, if T  0 (d) f = p, if T  0
16. The internal pressure (U / V)T of a real gas is related to the compressibility factor

Z = p V /RT by [ where, V is the molar volume]

(a) (U / V)T  RT(Z / V)T (b) (U / V)T  RT(VZ)

(c) (U / V)T  (RT2 / V)(Z / T) V (d) (U / V)T  (V / RT2 )(Z / T) V

CSIR JUNE 2013

17. The lowest pressure at which the liquid phase of a pure substance can exist is known as
(a) critical point pressure (b) super-incumbent pressure
(c) triple-point pressure (d) saturation vapour pressure.
18. A chemical reaction involving nonlinear molecule + nonlinear molecule ⇌nonlinear
activated complex, The number of vibrational degrees of freedom in the activated complex,
containing N atoms, is
(a) 3N–5 (b) 3N–6 (c) 3N–7 (d) 3N–8
19. A system consists of gaseous H2, O2, H2O and CO2where the amount of CO2is specified and
the equilibrium constant for the reaction 2H2(g) + O(g) ⇌2H2O(g) is known. The number of
degrees of freedom of the system is
(a) 2 (b) 3 (c) 4 (d) 5
20. Which of the following statements is true for a cyclic process?
(a) q = 0
(b) w= 0
(c) Heat can be completely converted into work
(d) Work can be completely converted into heat

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CSIR DEC 2013

21. The correct thermodynamics relation among the following is

 U   H   G   A 
(a)    P (b)    P (c)    P (d)    P
 V S  V S  V S  V S
22. The heat capacity of 10 mol of an ideal gas at a certain temperature is 300 JK -1at constant
pressure. The heat capacity of the same gas at the same temperature and at constant volume
would be
(a) 383 JK-1 (b) 217 JK-1 (c) 134 JK-1 (d) 466 JK-1
23. The Maxwell’s relationship derived from the equation dGVdP Å SdTis

 V   S   P   T   V   S   P   T 
(a)      (b)     (c)     (d)    
 T P  P T  V T  S P  T P  P T  V T  S P
24. The chemical potential (i) of the ithcomponent is defined as

 U   H   A   G 
(a) i    (b) i    (c) i    (d) i   
 n i T,P  n i T,P  n i T,P  n i T,P
25. Work (w) involved in isothermal reversible expansion from Vi to Vf of n moles of an ideal gas is
(a) w = -nRT ln (Vf/Vi) (b) w = nRT ln (Vf/Vi)
(c) w = -nRT (Vf/Vi) (d) w = -nRT log (Vf/Vi)
26. The boiling point of a solution of non-volatile solid is higher than that of the pure solvent. It
always indicates that
(a) the enthalpy of the solution is higher than that of the pure solvent
(b) the entropy of the solution is higher than that of the pure solvent
(c) the Gibbs free energy of the solution is higher than that of the pure solvent
(d) the internal energy of the solution is higher than that of the pure solvent

CSIR JUNE 2014

27. The figure below represents the path followed by a gas during expansion from A  B.
The work done is (L atm)

(a) 0 (b) 9 (c) 5 (d) 4

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28. Two phases α and β of a species are in equilibrium. The correct relations observed among the
variables, T, p and µ are
(a) T= T; p≠ p; µ= µ (b) T≠ T; p= p; µ= µ
(c) T= T; p= p; µ= µ (d) T= T; p≠ p; µ≠ µ
29. In a bomb calorimeter, the combustion of 0.5 g of compound A (molar mass = 50 g mol -1)
increased the temperature by 4K. If the heat capacity of the calorimeter along with that of the
material is 2.5 kJ K-1, the molar internal energy of combustion, in kJ, is
(a) 1000 (b) –1000 (c) 20 (d) –20
30. The number of phases, components and degrees of freedom, when Ar is added to an
equilibrium mixture of NO, O2 and NO2 in gas phase are, respectively,
(a) 1, 3, 5 (b) 1, 4, 5 (c) 1, 3, 4 (d) 1, 4, 4

CSIR DEC 2014

31. For a process in a closed system, temperature is equal to
 H   A   G   H 
(a)   (b)    (c)   (d)  
 P S  V T  P T  S P
32. The exact differential dfof a state function f(x, y), among the following is
x 1 x
(a) xdy (b) dx  dy (c) ydx  xdy (d) dx  2 dy
y y y
33. Given the following two relations,
x1d1  x 2d2  0

And x1dV1  x 2dV2  0

for a binary liquid mixture at constant temperature and pressure, the true statement is that,
(a) Both the relations are correct
(b) Relation A is correct, but B is not
(c) Relation B is correct, but A is not
(d) Both the relations are incorrect, except for very dilute solutions.
34. At high pressure, the fugacity coefficient of a real gas is greater than one, because
(a) Attractive term overweighs the repulsive term
(b) Repulsive term overweighs the attractive term
(c) Repulsive term is equal to the attractive term
(d) The system is independent of both the attractive and repulsive terms

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CSIR JUNE 2015

35. Heat capacity of a species is independent of temperature if it is
(a) tetratomic (b) triatomic (c) diatomic (d) monatomic
36. Consider the progress of a system along the path shown in the figure ∆S(B→C) for one
mole of an ideal gas is then given by

T1 T3 V2 V1
(a) R ln (b) R ln (c) R ln (d) R ln
T3 T1 V1 V2
37. A thermodynamic equation that relates the chemical potential to the composition of a
mixture isknown as
(a) Gibb’s-Helmholtz equation (b) Gibbs-Duhem equation
(c) Joule-Thomson equation (d) Debye-Huckel equation
38. The temperature-dependence of an electrochemical cell potential is
G H S S
(a) (b) (c) (d)
nFT nF nF nFT

CSIR DEC 2015

39. The value of ∆U - ∆H for the reaction Fe2O3(s) + 3C (s) → 2Fe (s) + 3CO (g) is
(a) –3RT (b) +3RT (c) +RT (d) –RT
40. If the pressure p(system) is greater than the p(surroundings), then
(a) work is done on the system by the surroundings
(b) work is down on the surroundings by the systems
(c) work done on the system by the surroundings is equal to the work done on the surroundings by
the system
(d) internal energy of the system increases
41. ∆H of a reaction is equal to slope of the plot of
(a) ∆G vs (1/T) (b) ∆G vs T (c) (∆G/T) vs T (d) (∆G/T) vs (1/T)
42. A reversible expansion of 1.0 mol of an ideal gas is carried out from 1.0 L to 4.0 L under
isothermal condition at 300 K. ∆G for this process is
(a) 300R.ln 2 (b) 600R.ln 2 (c) –600R.ln 2 (d) –300R.ln 2
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1800
43. The temperature-dependence of the vapour pressure of solid A can be represented by log p  10.0  ,
T
and that of liquid A by log p = 8.0 =  1400/T. The temperature of the triplepoint of A is
(a) 200 K (b) 300 K (c) 400 K (d) 500 K
44. The non-spontaneous process among the following is
(a) vapourisation of superhead water at 105ºC and 1 atm pressure
(b) expansion of a gas into vacuum freezing
(c) freezing of supercooled water at –10ºC and 1 atm pressure
(d) freezing of water at 0ºC and 1 atm pressure.

CSIR JUNE 2016

 H 
45.   has the dimension of
 P T

(a) pressure (b) volume (c) temperature (d) heat capacity

46. For an ideal gas at 300 K

 U   U   H   G 
(a)   0 (b)   0 (c)   0 (d)   0
 V T  T V  T P  T P

47. Phase diagram of a compound is shown below

  
The slopes of the lines OA, AC and AB are tan , tan and tan respectively. If melting point
4 6 3
and ∆H of melting are 300 K and 3 kJ mole-1respectively, the change in the volume on melting is
   
(a) 10 tan (b) 10 tan (c) 10 cot (d) 10 cot
3 4 3 4
48. The figure below describes how a Carnot engine works. It starts from the adiabatic compression step
denoted by

(a) AB (b) BC (c) DC (d) AD

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 U 
Q49. If U is a function of V and T,   is equal to ( and are the internal pressure and the coefficient of
 T P
thermal expansion, respectively)
(a) CP (b) CV (c) CP– παV (d) CP+ παV

CSIR DEC 2016

50. The parameter which always decreases during a spontaneous process at constant S and V, is
(a) U (b) H (c) Cp (d) q
51. Triple point pressure of substances A, B, C and D are 0.2, 0.5, 0.8 and 1.2 bar, respectively.
The substance which sublimes under standard conditions on increasing temperature is
(a) A (b) B (c) C (d) D
52. The equation of state for one mole of a gas is given by PV  b = RT, where b and Rareconstants. The value
 H 
of   is
 P T

(a) V  b (b) b (c) 0 (d) RT/P + b

53. The volume change in a phase transition is zero. From this, we may infer that the phase
boundary is represented by

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

 T 
54. The partial derivative   is equal to
 V P
 P   P   P   P 
(a)    (b)    (c)    (d)   
 S T  S V  S n  S H

CSIR JUNE 2017

55. A one-component system with the associated phase diagram (see the figure) is not possible
because

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(a) OB has a negative slops

(b) OC has a positive slope
(c) Both OB and OC are linear
(d) OB, OC and OD cannot all coexist, given OA
56. A phase transition process is always
(a) isothermal – isoentropic (b) isochoric – isothermal
(c) isobaric – isochoric (d) isothermal – isobaric
57. The correct statement for any cyclic thermodynamic process is
(a) dq = 0 (b) dw = 0 (c) dU = 0 (d) Vdq = 0
58. The fugacity of a real gas is less than the pressure (P) of an ideal gas at the same temperature
(T) only when (Tbis the Boyle temperature of the real gas)
(a) high P, T <Tb (b) low P, T <Tb (c) high P, T >Tb (d) low P, T > Tb
59. The minimum work required by an engine to transfer 5 J of heat from a reservoir at 100 K
to one at 300 K is
(a) 5 J (b) 10 J (c) 15 J (d) 20 J

CSIR DEC 2017

60. Enthalpy is equal to

(a) TS  PV  i ni (b) TS  i ni
(c) i ni (d) PV  i ni
61. In stretching of a rubber band, dG = VdpSdT + fdL. Which of the following relations in
true?
 S   f   S   f 
(a)       (b)      
 L p,T  T p,L  L p,T  V p,L
 S   V   S   f 
(c)       (d)      
 L p,T  T p,L  L p,T  p T,L
62. One mole of an ideal gas undergoes a cyclic process (ABCDA) starting from point A through
4 reversible steps as shown in the figure. Total work done in the process is
V V V V
(a) R  T1  T2  2 (b) R  T1  T2  2 (c) R  T1  T2  ln 2 (d) R  T1  T2  ln 2
V1 V1 V1 V1

CSIR JUNE 2018

63. The change in entropy for a reversible adiabatic process is
(a) Maximum
(b) Minimum
(c) Zero
(d) Positive
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64. In the phase diagram of water, the solid-liquid boundary has a negative slope. The reason for this unusual
behavior can be traced to decrease in
(a) Density of the system on melting (b) volume of the system on melting
(c) entropy of the system on melting (d) enthalpy of the system on melting
65. At 300K, the thermal expansion coefficient and isothermal compressibility of liquid water are
 U 
2 × 10-4 K-1 and 5 × 10-5 bar-1, respectively   (in k bar) for water at 320 K and 1 bar willbe.
 V T
(a) 2.4 (b) 1.2 (c) 0.6 (d) 12.0

CSIR DEC 2018

66. For a closed system in the absence of non-PV work, the correct statement is
(a) dU = TdS– PdV (b) dG= VdP+ SdT (c) dU= TdS+ PdV (d) dU = VdP– SdT
67. The volume change in a certain phase transition is 2.0 mL mol–1 at the transition point. From
this, we may conclude that the transition is most likely to
(a) First order phase transition (b) Second order phase transition
(c) Third order phase transition (d) l phase transition
68. Consider a phase transition between two incompressible phases. The correct statement among the
following is
(a) The transition is independent of pressure
(b) The transition is independent of temperature
(c) The entropy of such transition is always zero
(d) The enthalpy of such transition is always non-zero
69. Entropy of a perfect gas is
(a) independent of V (b) proportional to V
(c) proportional to ln V (d) proportional to V2

CSIR JUNE 2019

70. One mole of a mono-atomic ideal gas is transformed from 300 K and 2 atm to 600 K and 4 atm.
The entropy change for this process is
(a) 3/2 R ln 2
(b) 1/2 R ln 2
(c) 7/2 R ln 2
(d) 5/2 R ln 2

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71. A non-ideal gas, follows the equation

RT  B
P 1  
Vm  Vm 

where B is a function of temperature only. The deviation in internal energy from that of an ideal
gas, UUideal ideal is given by

RT  B  RT 2  B  RT 2 RT
(a)    (b)    (c)  B (d)  B
Vm  T V Vm  T V Vm Vm
72. When two moles of liquid A are mixed with two moles of liquid B at 300K, the excess molar
Gibbs energy of the solution is -1.5 kJ mol-1. The corresponding value of Gibbs energy of mixing
(in kJ) is closest to (R= 8.3 J K-1mol-1)
(a) -12.9 (b) -6.0 (c) -1.5 (d) -0.9
73. A sample of 2.0 moles of O2(g) (assumed ideal) at 500K is expanded from 5L to 50 L under
adiabatic and reversible conditions. The change in its internal energy (in kJ) is close to
5
R  8.3K 1 mol1 ;C V,m  R
2
(a) -22.5 (b) -12.5 (c) -19.1 (d) -7.5
74. The chemical potential () of a 2 molar Na2SO4solution is expressed in terms of mean ionic
activity co-efficient () as
(a) 0+ 5RTln 2 + 3RT ln (b) 0+ 53Tln 2 + 3RT ln
(c) 0+ +3RTln (d) 0+ +4RTln

CSIR DEC 2019

75. Consider the entropy changes in a system undergoing transformation, as depicted in the
diagram, below

The correct statement among the following is

(1)ΔS1= ΔS2and ΔS ≠ ΔS1+ ΔS2 (2) ΔS1> ΔS2and ΔS ≠ΔS1+ ΔS2
(3)ΔS1= ΔS2and ΔS = ΔS1+ ΔS2 (4) ΔS1> ΔS2and ΔS = ΔS1+ ΔS2
Options
(a) 1 (b) 2
(c) 3 (d) 4

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76. Molar composition of a mixture of P and Q at equilibrium is 3 : 1 (P : Q). A small disturbance in

composition results in change of chemical potential of P by 10Jmol -1 . The chemical potential of Q
will change (in J mol-1) by
(1) 30 (2) 3.3
(3) -30 (4) -3.3
Options
(a) 1 (b)2
(c) 3 (d) 4
77. 1.0 mol of a perfect monatomic gas is put through the cycle shown in the figure. The total work
(in J) done during the cycle is (use 1L-bar 100 J, R= 8.3 J K-1mol-1= 0.083 L-bar K-1mol-1, ln2 = 0.7)

(1)930 (2)-4183
(3)8831 (4)-5113
Options
(a) 1 (b)2
(c)3 (d)4
78. (Cp -Cv) for a non-ideal gas differs from (Cp - Cv) for a perfect gas by the expression
 P   U   V   U 
(a)     (b)    
 T V  P S  T P  V T
1  V   U   P   U 
(c)      (d)    
T  T P  V T  T V  T P
Options
(a) 1 (b) 2
(c) 3 (d) 4

CSIR 2020

79. A monatomic perfect gas undergoes expansion from (p1, V1) to (p2, V2) under isothermal or
adiabatic conditions. The pressure of the gas will fall more rapidly under adiabatic conditions because
Options:

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1 1 1 1
(a) p  (b) p  (c) p  (d) p 
V V 7/5 V 3/ 2 V 5/3
 U 
80. For a van der Waals gas, the partial derivative is  
 V T
Vm Vm2 a a
(a) (b) (c) (d)
a a Vm2 Vm
81. The excess molar entropy of mixing of liquid A with liquid B is -R ln 2. The experimentally
observed change in entropy upon mixing 1.0 mol of liquid A with 1.0 mol of liquid B is
Options:
(a) -2Rln 2 (b) +4Rln 2 (c) 0 (d) +R ln 2
82. The change in chemical potential (in J) of one mole of an ideal gas, when it is compressed
isothermally at 300 K from 1.0 atm to 2.0 atm, is closest to (ln 2 = 0.69)
Options:
(a) 1225 (b) 1725 (c) 2425 (d) 2725

CSIR JUNE 2021

83. The maximum number of phases that can be simultaneously in equilibrium for a one component system
is
(a) 1 (b) 2 (c) 3 (d) 4
84. When yellow phosphorous is converted to red phosphorous, the entropy and volume of the
system do not change. The order of this phase transition is most likely to be
(a) 3 (b) 2 (c) 1 (d) 0

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ANSWER KEY
THERMODYNAMICS

1. (c) 2. (c) 3. (c) 4. (b) 5. (a) 6. (a) 7. (d)

8. (d) 9. (c) 10. (b) 11. (b) 12. (b) 13. (b) 14. (a)

15. (a) 16. (c) 17. (c) 18. (c) 19. (b) 20. (d) 21. (a)

22. (b) 23. (c) 24. (d) 25. (a) 26. (b) 27. (d) 28. (a)

29. (b) 30. (c) 31. (d) 32. (d) 33. (a) 34. (b) 35. (d)

36. (c) 37. (b) 38. (c) 39. (a) 40. (b) 41. (d) 42 (c)

43. (a) 44. (d) 45. (b) 46. (a) 47. (c) 48. (b) 49. (d)

50. (a) 51. (d) 52. (b) 53. (a) 54. (a) 55. (d) 56. (d)

57. (c) 58. (b) 59. (b) 60. (b) 61. (a) 62. (d) 63. (c)

64. (b) 65. (b) 66. (a) 67. (a) 68. (a) 69. (c) 70. (a)

71. (b) 72. (a) 73. (b) 74. (a) 75. (d) 76. (c) 77. (b)

78. (b) 79. (d) 80. (c) 81. (c) 82. (c) 83. (c) 84. (b)

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 8
Statistical Thermodynamics
CSIR JUNE 2011
Tm
1. A certain system of non interacting particles has the single-particle partition function f  A where A is
V
some constant. The average energy per particle will be
(a) mkT (b) AkT (c) kT/m (d) kT/A

2. The virial expression for a real gas can be written I either of the following forms :
PV
 1  BP P  CP P 2  .....  1  Bv V  Cv V 2  .....
RT
If BV = BP, the value of α would be:
(a) PV/RT (b) RT/PV (c) PV (d) RT
3. For an assembly of molecules (molar mass = M) at temperature T, the standard deviation of Maxwell’s
speed is approximately :

RT RT M M
(a) 0.7 (b) 1.4 (c) 0.7   (d) 1.4
M M  RT  RT

CSIR DEC 2011

4. PA and PB denote the populations of two energy states EA and EB and EA > EB, The correct
statement when the temperature T1 > T2 is
(a) PA (T1) > PB (T1) , PA (T2) < PB (T2) and (PA/PB) T1 > (PA/PB)T2
(b) PA (T1) < PB (T1) , PA (T2) > PB (T2) and (PA/PB) T1 > (PA/PB)T2
(c) PA (T1) < PB (T1) , PA (T2) < PB (T2) and (PA/PB) T1 > (PA/PB)T2
(d) PA (T1) < PB (T1) , PA (T2) < PB (T2) and (PA/PB) T1 < (PA/PB)T2
5. If θr denotes the characteristic temperatures of rotation, then the magnitude of [r, H2. r(D2)] / [r HD]2
(assume the bond lengths to be the same for all the molecules) is:
(a) 2/3 (b) 3/2 (c) 8/9 (d) 9/8

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6. A system consisting of 4 identical and distinguishable particles, each possessing three available states of 1,
2 and 3 units, has 10 units of energy. The number of ways, W, in which these conditions are satisfied is :
(a) 2 (b) 4 (c) 6 (d) 10
7. Two  particles having speeds S1 and S2 have kinetic 1 and 2 MeV respectively; the relationship
between S1 and S2 is
(a) S1 =2S2 (b) S2 = 2S1 (c) S2  2S1 (d) S1  2S2

CSIR JUNE 2012

8. The relative population in two states with energies E1 and E2 satisfying Boltzmann distribution is given by
n1/n2 = (3/2) exp[-(E1 – E2)/kbT]. The relative degeneracy g2/g1 is:
(a) 2 (b) 2/3 (c) 3/2 (d) 3
9. The energy levels of the harmonic oscillator (neglecting zero point energy) are ϵ(n) = nhv and
n = 0,1,2,…. Assuming T partition function is :
(a) e (b) 1/e (c) 1  1/e (d) 1/1 – 1/e
10. The correct entropy for 6 identical particles with their occupation number 0,1,2,3 in for steps is
(a) kA ln 8 (b) kA ln 12 (c) kB ln 60 (d) kB ln 720

CSIR DEC 2012

11. The rotational partition function of H2 is :
(a)  J 0,1,2.....  2J  1 ehcBJ(J 1)

(b)  J 1,3,5.....  2J  1 ehcBJ(J 1)

(c) J  0,2,4.....  2J  1 ehcBJ(J 1)

1
(d)  J  0,2,4.....  2J  1 e hcBJ(J 1)  3 J 1,3,5.....  2J  1 e hcBJ(J 1) 
4

CSIR JUNE 2013

12. A system has 100 degenerate energy levels and 100 bosons are kept in it. Find the entropy of the system
at equilibrium
(a) 10-2 kb (b) 102 kb (c) 460.0 kb (d) 4.606 kb
13. Calculate the total number of microstates for 6 identical particles with their occupation numbers {1, 2,
and 3} in three states is
(a) 6 (b) 12 (c) 60 (d) 720
14. The equilibrium population ratio (nj/ni) of a doubly-degenerate energy level (Ej) lying at
energy 2 units higher than a lower non-degenerate energy level (Ej), assuming kBT = 1 unit, will be
(a) 2e-2 (b) 2e (c) e2 (d) e-2
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CSIR DEC 2013

15.The number of ways in which four molecules can be distributed in two different energy levels is :
(a) 6 (b) 3 (c) 16 (d) 8
16 The molecule with the smallest rotation partition function at any temperature among the following is :
(a) CH3 — C ≡ C — H
(b) H — C ≡ C — H
(c) H — C ≡ C — D
(d) D — C ≡ C — D

CSIR JUNE 2014

17. The translational, rotational and vibrational partition functions for a molecule are ftranslation =
1010 m-1, frotation = 10, fvibration = 1, (kBT/h) = 1013 at room temperature, NA = 6 × 1023. Using the
approximate data given above, the frequency factor (A) for a reaction of the type: atom + diatomic
molecule  nonlinear transition state  product, according to the conventional transition state
theory is
(a) 2 × 103 (b) 6 × 107 (c) 2 × 1012 (d) 6 × 1013
18. The number of configurations in the most probable state, according to Boltzmann formula, is
S S E G
kB kB k BT k BT
(a) e (b) e (c) e (d) e

CSIR DEC 2014

19. The low and high temperature limits of vibrational partition function are (θ =h/k) :



T  T 
2T
T  2T 

2T
T  T 

2T
  2T
(a) e T and e (b) e and e (c) e and e (d) e and e
   T
20. The number of microstates that are possible, when two particles are distributed in four states such that the
resulting wave functions are antisymmetric with respect to exchange of the particles, is :
(a) 16 (b) 12 (c) 8 (d) 6
21. When T ∞, value of the single-particle partition function will be (given : degeneracy of level j = gj) :
(a) 1 (b) g0 (c) jgj (d)1/ jgj

CSIR DEC 2014

22. The probability of finding the harmonic oscillator in the energy level n = 1 is (neglect zero
point energy and assume hv = kBT)
(a) e (b) e2 (c) 1 e2 (d) e-2(e  1)

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23. Identify the speed distribution functions of Ne, Ar and Kr with the curves in the figure above:

(a) Ne-A, Ar-B, Kr-C (b) Ne-B, Ar-C, Kr-A

(c) Ne-C, Ar-B, Kr-A (d) Ne-C, Ar-A, Kr-B

CSIR JUNE 2015

24.The single-particle partition function (f) for a certain system has the form f = Ave BT. The
average energy per particle will then be (k is the Boltzman constant)
(a) BkT (b) BkT2 (c) kT/B (d) kT/B2
25. The indistinguishability correction in the Boltzmann formulation is incorporated in the following way: (N
= total number of particles; f = single-particle partition function)
(a) Replace f by f/N! (b) Replace fN by fN/N! (c) Replace f by f/ln (N!) (d) Replace fN by fN/ln (N!)

CSIR DEC 2015

26. Though a constant shift of energy levels of a system changes the partition function, the properties that do
not change are
(a) average energy, entropy and heat capacity
(b) average energy and entropy
(c) average energy and heat capacity
(d) entropy and heat capacity
27. The standard deviation of speed (c) for Maxwell’s distribution satisfies the relation
1 1
(a) c  T (b) c  T (c)  c  (d) c 
T T
28. The vibrational frequency of a homonuclear diatomic molecule is 𝒗. The temperature at which
the population of the first excited state will be half that of the ground state is given by
(a) hv. Ln2/kb (b) hv/(ln2.kb) (c) ln2/(hv.kb) (d) hv.log2/kb

CSIR JUNE 2016

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29.The single – partition translational partition function (f) for an ideal gas in a fixed volume V depends on
the thermal Broglie wave function th as f ~ (th)n where :
(a) n =3 (b) n = 1 (c) n = -1 (d) n = -3

CSIR DEC 2016

30. The weight of configuration with two ups and three down spins in a system with five spin ½ particles is
(a) 120 (b) 60 (c) 20 (d) 10
31. Partition function of a one – dimensional oscillator having equispaced energy level with energy spacing
equal to kbT and zero ground energy is
(a) e (b) 1/(e  1) (c) e/(e 1) (d) 1/(e + 1)

CSIR JUNE 2017

32. Consider a system of three particles which can occupy energy levels with energy 0,  and 2 , such that
the total energy E = 4  . Cases A, B and C correspond to spin ½ fermions, spin 0 bosons, and classically
distinguishable particles, respectively. The correct ordering of entropy is
(a) SA > SB > SC (b) SB > SA >SC (c) SC > SB > SA (d) SC > SA > SB
33. The first excited state (2P1/2) of fluorine lies at an energy of 400 cm-1 above the ground state (2P3/2). The
fraction of Fluorine atoms in the first excited state at kBT = 420 cm-1 is close to
1 1 1 1
(a) (b) (c) (d)
1 e 2e 1  4e 1  2e

CSIR DEC 2017

34. The term symbol for the ground state of a metal ion is 3P2. The residual entropy of a crystal of a salt of
this metal ion at 0 K is :
(a) kB ln1 (b) kB ln3 (c) kB ln5 (d) kB ln7
35. Four distinguishable molecules are distributed in energy level E1 and E2 with degeneracy of 2 & 3
respectively. Number of microstates with 3 molecules in energy level E1 and E2 is
(a) 4 (b) 12 (c) 96 (d) 192

CSIR JUNE 2018

36. Translational partition function of a D2 molecule confined in 100 cm vessel at 25 C is

(a) 3.8×1022 (b) 5.8×1024 (c) 7.8×1026 (d) 9.8×1028

CSIR DEC 2018

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37. The free energy [A-A(0)] of a system with 10 non interacting spins (S = I) is
(a)  k b T ln(3)

(b) 10k bTln(3)

(c) k bTln(0.3)

(d) 10k bTln(0.3)

38. The translational partition function for Ar confined to a volume of 1L at 300 K, having thermal wavelength
of 1.60 × 1011 m, is closest to :
(a) 24.4 × 1029 (b) 2.44 ×1029 (c) 0.244 × 1029 (d) 244 × 1029

CSIR JUNE 2019

39. The rotational partition function is expected to be the smallest for the molecule, among the following
(a) H2 (b) Li2 (c) N2 (d) F2
40. For a linear molecule the mean energies for translation, rotation (T >> r) and vibration (T >> v) follow
ratio:
3 3 1 1
(a) 1: :1 (b) :1:1 (c) 1: :1 (d) :1:1
2 2 2 2
41. The populations of proton spins in the highest energy level of a sample in magnetic fields of
N
1.5T and 7.0 T are N and N, respectively. The value of ln in (,h,k,T are gyromagnetic ratio of the
N
proton, Planck's constant, Boltzmann constant and temperature of the sample, respectively, assume that
the partition functions for both systems can be approximated as 1)
h 3 h 14 h h
(a) 5.5 (b) (c) (d) 8.5
kT 14 kT 3 kT kT
42. The difference between standard molar entropies of two mono-atomic gases (A) and (B) S0m,A  S0m,B  at

a given temperature is (given that the molar mass of (A) is twice the molar mass of (B)
3 5 7
(a) R ln 2 (b) R ln 2 (c) R ln 2 (d) R ln 2
2 2 2

CSIR DEC 2019

43. Consider a two-level system in which the excited state, separated from the ground state by energy , is doubly
degenerate. The fraction of the molecules in the excited state, as T  ∞ is
1 1 2
(a) (b)  (c) (d) 1
2 2 3
44. The molar residual entropy (in J K-1) of solid OCS would be closest to
(a) 0 (b) 2.9 (c) 5.8 (d) 8.7

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CSIR 2020

45. The entropy in terms of internal energy {U-U(0)}, and canonical partition function (Q) is given
U  U(0)
by S   k ln Q . Assuming that T the atoms are distinguishable, the corresponding expression
T
for a monatomic perfect gas is [Here n, m, NA, k and h represent number of moles, mass of atom,
Avogadro constant,Boltzmann constant and Planck constant, respectively. U(0) is internal energy at
T = 0]. Options:
5  3
 3  3

(a) S  nR  n R ln V  2mkT  2 nN A h 3  (b) S  nR  n R ln V  2mkT  2 h 3 
2   2  
5  3
 3  3

(c) S  nR  n R ln V  2mkT  2 h 3  (d) S  nR  n R ln V  2mkT  2 nN A h 3 
2   2  

CSIR JUNE 2021

46. For a micro-canonical system, the correct probability distribution function for energy is given by
(a) Exponential distribution function
(b) Gaussian distribution function
(c) Poisson distribution function
(d) Uniform distribution function

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ANSWER KEY
STATISTICAL THERMODYNAMICS
1. (a) 2. (d) 3. (a) 4. (c) 5. (c) 6. (d) 7. (c)

8. (b) 9. (d) 10. (c) 11. (d) 12. (b) 13. (c) 14. (a)

15. (c) 16. (b) 17. (b) 18. (b) 19. (a) 20. (d) 21. (c)

22. (d) 23. (c) 24. (b) 25. (b) 26. (d) 27. (b) 28. (b)

29. (d) 30. (d) 31. (c) 32. (d) 33. (d) 34. (d) 35. (c)

36. (c) 37. (b) 38. (b) 39. (a) 40. (b) 41. (a) 42 (a)

43. (c) 44. (c) 45. (b) 46. (d)

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 9
Atomic & Molecular term symbols
CSIR JUNE 2011
1. The term symbol of a molecule with electronic configuration 1g  1u   2g   2u   2u   2u  is
2 2 2 2 1 1

(a) 1  g (b) 3  g (c) 1  g (d) 3

 g

2. The possible J values for 3D term symbol are

(a) 2 (b) 3 (c) 4 (d) 5

CSIR DEC 2011

3. The term symbol for the ground state of nitrogen atoms is

(a) 3P0 (b) 4P3/2 (c) 1P1 (d) 4S3/2
4. Observe the following electronic transition of a diatomic molecule.
(a) 1  g  3 g (b) 1 u  1g (c) 1  u  1 g (d) 1  g  1 u

The allowed transitions are

(a) (A) and (C) only (b) (B) and (D) only
(c) (A), (B) and (C) only (d) (A), (C) and (D) only

CSIR DEC 2012

5. The electric dipole allowed transition in a d2 atomic system is
(a) 3F  1D (b) 3F  1P (c) 3F  3D (d) 3F  3P

CSIR JUNE 2013

6. What is the atomic term symbol for helium atom with electronic configuration 1s2?
(a) 2S1/2 (b) 1P0 (c) 1S0 (d) 1S1

CSIR JUNE 2014

7. The term symbol that is NOT allowed for the np2 configuration is

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QUANTA CHEMISTRY CLASSES | Atomic and Molecular Term Symbols
1 3 1
(a) D (b) P (c) S (d) 3D

CSIR JUNE 2015

8. The lowest energy-state of an atom with electronic configuration ns1np1 has the term symbol
(a) 3P1 (b) 1P1 (c) 3P2 (d) 3P
9. The electric-dipole allowed transition among the following is
(a) 3S  3D (b) 3S  3P (c) 3S  1D (d) 3S  1F
10. The term symbol for the first excited state of Be with the electronic configuration 1s2 2s1 3s1 is
(a) 3S1 (b) 3S0 (c) 1S0 (d) 2S1/2

CSIR DEC 2016

11. The highest molecular orbital’s for an excited electronic configuration of the oxygen molecule are
[1g]1[3u]1. A possible molecular term symbol for oxygen with this electronic configuration is
(a) 1 (b) 3 (c) 1 (d) 1

CSIR JUNE 2017

12. for the electronic configuration 1s2 2s1 2p4 two of the possible term symbols are 1S and 3P. the remaining
term is
(a) 1D (b) 1F (c) 3D (d) 3F

CSIR JUNE 2018

13. The lowest energy state of 1s1 2s1 electronic configuration, according to Hund’s rule is
(a) 3S0 (b) 1S0 (c) 3S1 (d) 1S1

CSIR JUNE 2019

14. The allowed transition among the following is
(a) 3F4  3D3 (b) 3F4  1D3 (c) 3F4  3P4 (d) 3F4  3D2

CSIR 2020


15. The term symbol for ground state dinitrogen cation radical N2 _ , is 
(a) 2  u (b) 2 u (c) 2  g (d) 2  g

CSIR JUNE 2021

16. The Number of microstates corresponding to 4F atomic term?

(a) 7 (b) 12 (c) 28 (d) 42

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17. The stopping potential for photoelectrons emitted from a surface illuminated by light of
frequency 6.0 × 108 MHz is 0.72 V. When the incident frequency is changed, the stopping potential is
found to be 1.44 V. The new frequency is approximately (e/h = 2.4 × 1014 C J-1 𝑠-1)
(a) 7 × 108 (b) 4 × 108 (c) 2 × 109 (d) 7 × 1014

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ANSWER KEY
ATOMIC AND MOLECULAR TERM SYMBOLS

1. (b) 2. (b) 3. (d) 4. (b) 5. (c) 6. (c) 7. (d)

8. (d) 9. (b) 10. (a) 11. (a) 12. (a) 13. (c) 14. (a)

15. (b) 16. (c) 17. (a)

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 10
Kinetic Theory of Gases
CSIR JUNE 2011

1. An ideal gas expands by following an equation PVa = constant. In which case does one expect
heating?
(a) 3 > a > 2 (b) 2 > a > 1 (c) 0 < a < 1 (d) –1 < a < 0
2. For an assembly of molecules (molar mass = M) at temperature T, the standard deviation of Maxweller’s
speed is approximately

RT RT M M
(a) 0.7 (b) 1.4 (c) 0.7 (d) 1.4
M M RT RT
3. The virial expansion for a real gas can be written in either of the following forms:
PV
 1  BP P  CP P 2 
RT
 1  BV V  CV V2 
If B0 = B, the value of 𝛼 would be
(a) PV/RT (b) RT/PV (c) PV (d) RT

CSIR DEC 2011

4. Two α particles having speeds S1 and S2 have kinetic energies 1 and 2 MeV respectively; the relationship
between S1 and S2 is :
(a) S1 = 2S2
(b) S2 = 2S1

(c) S2  2S1

(d) S1  2S2

CSIR DEC 2014

5. Identify the speed distribution functions of Ne, Ar, and Kr with the curves in the figure below

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(a) Ne-A, Ar-B, Kr-C (b) Ne-B, Ar-C, Kr-A (c) Ne-C, Ar-B, Kr-A (d) Ne-C, Ar-A, Kr-B

CSIR DEC 2015

6. The standard deviation of speed (c) for Maxwell’s distribution satisfies the relation

(a) c  T (b) c  T (c) c 1/ T (d) c 1/ T

CSIR DEC 2018

7. Root mean square speed of the molecules of a perfect gas is proportional to
(a) 1/T1/2 (b) T (c) T1/2 (d) 1/T
8. Entropy of a perfect gas is
(a) independent of V (b) proportional to V
(c) proportional to lnV (d) proportional to V2

CSIR DEC 2019

9. The molar residual entropy (in J/K) for solid OCS is close to
(a) 0 (b) 2.9 (c) 5.8 (d) 8.7

CSIR 2020

10.A monoatomic perfect gas undergoes expansion from (p1,V1) to (p2, V2) under isothermal or adiabatic
conditions. The pressure of the gas will fall more rapidly under adiabatic conditions because
1 1 1 1
(a) p  (b) p  (c) p  (d) p 
V V 7/5 V 3/ 2 V 5/3

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ANSWER KEY
KINETIC THEORY OF GASES

1. (c) 2. (a) 3. (d) 4. (c) 5. (c) 6. (b) 7. (c)

8. (c) 9. (c) 10. (d)

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 11
Molecular Spectroscopy
CSIR JUNE 2011
Q1. A molecule, AX, has a vibrational energy of 1000 cm-1and rotational energy of 10 cm-1. Another
molecule, BX, has a vibrational energy of 400 cm–1 and rotational energy of 40 cm-1. Which one of the
following statements about the coupling of vibrational and rotational motion is true?
(a) The coupling is stronger in BX.
(b) The coupling is stronger in AX.
(c) Magnitude of coupling is same in both AX and BX.
(d) There is no coupling in both AX and BX
Q2. At room temperature, which molecule has the maximum rotational entropy?
(a) H2 (b) O2 (c) D2 (d) N2

Q3. The microwave spectrum of a molecule yields three rotational constants. The molecule is
(a) Prolate symmetric top (b) Spherical top
(c) Asymmetric top (d) Oblate symmetric top

Q4. The Q band in the vibrational spectrum of acetylene is observed in the

(a) C–C stretching mode (b) C-H symmetric stretching mode
(c) Bending mode (d) C-H antisymmetric stretching mode

Q5. In IR spectrum of [Co (CN)5H]3-the Co–H stretch is observed at 1840 cm-1. The (Co–D) stretch in
[Co (CN)5D]3-will appear at nearly
(a) 1300 cm-1 (b) 1400 cm-1 (c) 1500 cm-1 (d) 1600 cm-1

Q6. The Stark splitting for a given field is larger for a molecule AX as compared to BX. Which one of the
following is true? (𝜇is the dipole moment)
(a)𝜇AB= 𝜇BX (b) 𝜇AB>𝜇BX (c) 𝜇AB<𝜇BX (d) 𝜇BX= 2𝜇AX

Q7. The uncertainty in the NMR frequency of a compound in liquid state (relaxation time =1s) is 0.1 Hz.
The uncertainty in the frequency (in Hz) of same compound in solid state (relaxation time=10-4s)is
(a) 10 (b) 100 (c) 1000 (d) 10-3

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Q8. The sodium D lines are due to P1/2→ S1/2(ΔE1) and P1/2→ S1/2(ΔE2) transitions. The splitting
2 2 2 2

due to spin-orbit coupling in 2p state of the sodium atom is

(a) ΔE2+ΔE1 (b) ΔΕ2– ΔΕ1 (c) ΔΕ2– ΔΕ1/2 (d) ΔΕ2+ ΔΕ1/2

Q9. The NMR spectrum of AX, exhibits lines at = 2.1 and 2.3 ppm (for X type protons) and = 4.1, 4.3,
4.5 and 4.7 ppm (for A type protons), measured from TMS with an instrument operating at 100 MHz.
The chemical shift (in ppm) of A and X protons and coupling constant in (Hz) are respectively.

(a) 4.4, 2.2 and 20 (b) 2.2, 4.4 and 10 (c) 2.2, 4.4 and 5 (d) 4.3, 2.1 and 2
14
Q10.The rotational constant of N2is 2 cm-1. The wave number of incident radiation in a Raman
spectrometer is 20487 cm-1. What is the wave number of first scattered Stokes line (in cm-1) of 14N2?

(a) 20479 (b) 20475 (c) 20499 (d) 20495

Q11.The vibrational energy levels, ν" = 0 and ν' =1 of a diatomic molecule are separated by 2143 cm-1. Its
anharmonicity ωexe is 14 cm-1. The values of ωe (in cm-1) and first overtone (cm-1) of this molecule
are respectively.
(a) 2143 and 4286 (b) 2157 and 4286 (c) 2157 and 4314 (d) 2171 and 4258

CSIR JUNE 2012

Q12. For a diatomic molecule AB, the energy for the rotational transition from J = 0 to J = 1 state is
3.9 cm-1. The energy for the rotational transition from J = 3 to J = 4 state would be

(a) 3.9 cm-1 (b) 7.8 cm-1 (c) 11.7 cm-1 (d) 15.6 cm-1

Q13. For the vibrational Raman spectrum of a homonuclear diatomic molecule, the selection rule under
harmonic approximation is
(a) ∆v = 0 only (b) ∆v = ±1 only (c) ∆v = ±2 only (d) ∆v = 0, ±1

Q14. The following data were obtained from the vibrational fine structure in the vibronic spectrum of a
diatomic molecule:
ωe= 512cm-1, ωexe= 8 cm-1
where ωeis the energy associated with the natural frequency of vibration and xe is the anharmonicity
constant. The dissociation energy (De) of the molecule is:
(a) 4096 cm-1 (b) 6144 cm-1 (c) 8192 cm-1 (d) 16384 cm-1

Q15. In the 400 MHz 1H NMR spectrum, of organic compound exhibited a doublet. The two lines of the
doublet are at 8 2.35 and 2.38 ppm. The coupling constant (J) value is
(a) 3 Hz (b) 6 Hz (c) 9 Hz (d) 12 Hz

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CSIR DEC 2012

Q16. The absorption spectrum of O2 shows a vibrational structure that becomes continuum at 56875 cm-1. At
the continuum, it dissociates into one ground state atom (Og) and one excited state atom (Oe). The
energy difference between Oeand Ogis 15125 cm-1. The dissociation energy (in cm-1) of ground state of
O2is:
(a) 56875/15125 (b) 15125/56875 (c) 7200 (d) 41750
Q17. The vibrational frequency and anharmonicity constant of an alkali halide are 300 cm-1and 0.0025
respectively. The positions (in cm-1) of its fundamental mode and first overtone are respectively.
(a) 300, 600 (b) 298.5, 595.5 (c) 301.5, 604.5 (d) 290, 580

CSIR JUNE 2013

Q18. A triatomic molecule of the type AB2 shows two IR absorption lines and one IR-Raman line. The
structure of the molecule is:

(a)B-B-A (b) B-A-B (c) (d)

Q19. In NMR spectroscopy, the product of the nuclear 'g' factor (gN), the nuclear magneton (N) and the
magnetic field strength (B0) gives the
(a) energy of transition from to state (b) chemical shift

(c) spin-spin coupling constant (d) gyromagnetic ratio

Q20. An AX system gave 4 lines at 4.72, 4.6, 1.12 and 1.0 ppm away from the TMS using an nmr
spectrometer operating at 100 MHz. What are the values of JAX(in Hz) and Hz(in ppm), respectively
(a) 12 and 3.6 (b) 6 and 3.6 (c) 12 and 2.86 (d) 6 and 2.86

CSIR DEC 2013

Q21. The molecule with the smallest rotation partition function at any temperature among the following
is:
(a) CH3C ≡ C  H (b) H C ≡ C H
(c) H C ≡ CD (d) D C ≡ C  D

Q22. The atomic masses of fluorine and hydrogen are 19.0 and 1.0 amu, respectively (1 amu = 1.67 × 10-27
kg). The bond length of HF is 2.0 Å. The moment of inertia of HF is
(a) 3.2 × 10-47kg m² (b) 6-4 × 10-47kg m² (c) 9-6 × 10-47kg m² (d) 4.8 × 10-47kg m²

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Q23. The C = O bond length is 120 pm in CO2. The moment of inertia of CO2would be close to (masses
of C and O are 1.9 × 10-27kg and 2.5 × 10-27kg, respectively)
(a) 1.8 × 10-45kgm2 (b) 3.6 × 10-45kgm2 (c) 5.4 × 10-45kgm2 (d) 7.2 × 10-45kgm2

CSIR DEC 2014

Q24. Bond lengths of homonuclear diatomic molecules can be determined with the help of both
(a) Rotational and vibrational spectroscopy.
(b) Rotational and rotational Raman spectroscopy.
(c) Rotational Raman and electronic spectroscopy.
(d) Vibrational and electronic spectroscopy.

Q25. If the component of the orbital angular momentum along the molecular axis of a heteronuclear
diatomic molecule is non-zero, the rotational-vibrational spectrum will show
(a) P and R branches only. (b) P and Q branches only.
(c) Q and R branches only. (d) All the P, Q and R branches

Q26. If the bond length of a heteronuclear diatomic molecule is greater in the upper vibrational state, the
gap between the successive absorption lines of P-branch
(a) Increases non-linearly (b) Decreases non-linearly
(c) Increases linearly (d) Decreases linearly

CSIR JUNE 2015

Q27. The symmetric rotor among the following is

(a) CH4 (b) CH3Cl (c) CH2Cl2 (d) CCl4

Q28. The nuclear g-factors of 1H and 14N are 5.6 and 0.40 respectively. If the magnetic field in an NMR
spectrometer is set such that the proton resonates at 700 MHz, the 14N nucleus would resonate at
(a) 1750 MHz (b) 700 MHz (c) 125 MHz (d) 50 MHz

Q29. The spectroscopic technique, by which the ground state dissociation energies of diatomic
molecules can be estimated, is

(a) Microwave spectroscopy (b) Infrared spectroscopy

(c) UV-visible absorption spectroscopy (d) X-ray spectroscopy

CSIR DEC 2015

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Q30. If the reduced mass of a diatomic molecule is doubled without changing its force constant, the
vibrational frequency of the molecule will be

(a) 2 times the original frequency (b) 1/ 2 times the vibrational frequency
(c) twice the original frequency (d) unchanged

Q31. The molecule with the smallest rotational constant (in the microwave spectrum) among the
following is
(a) N ≡ CH (b) HC ≡ CCl (c) CCl ≡ CF (d) B ≡ CCl

Q32. The spectroscopic technique that can distinguish unambiguously between trans-1, 2-
dichloroethylene and cis-1, 2-dichloroethylene without any numerical calculation is

(a) microwave spectroscopy (b) UV-visible spectroscopy

(c) X-ray photoelectron spectroscopy (d) γ-ray spectroscopy

Q33. The vibrational frequency of a homo-nuclear diatomic molecule is v. The temperature at which the
population of the first excited state will be half that of the ground state is given by
(a) hv .ln 2 / kB (b) hv / (ln 2 .kB) (c) ln 2 / (hv . kB) (d) hv . log 2 / kB
1 1 13
Q34. The H NMR frequency at 1.0T is 42.4 MHz. If the gyromagnetic ratios of H and C
are 27 × 107and 6.75 ×107T-1S-1respectively, what will be the 13C frequency at 1.0 T ?

(a) 10.6 MHz (b) 169.6 MHz (c) 42.6 MHz (d) 21.3 MHz

CSIR JUNE 2016

Q35. In an NMR spectrometer containing a 2.5 T magnet, Larmor precession frequency of 1H is 100
MHz. The radiofrequency used in this spectrometer has an associated magnetic field strength of
2.5 ×10-4T. The duration of a 90º pulse in this instrument is

(a) 25×10-6s (b) 50×10-6s (c) 25×10-5 s (d) 50×10-5 s

Q36. Upon application of a weak magnetic field, a line in the microwave absorption spectrum of rigid
rotor splits into 3 lines. The quantum number (J) of the rotational energy level from which the transition
originates is
(a) 0 (b) 1 (c) 2 (d) 3

CSIR DEC 2016

Q37. 1H NMR spectrum of an organic compound recorded on a 500 MHz spectrometer showed a quartet
with line positions at 1759, 1753, 1747, 1741 Hz. Chemical shift and coupling constant (Hz) of the
quartet are

(a) 3.5 ppm, 6 Hz (b) 3.5 ppm, 12 Hz (c) 3.6 ppm, 6 Hz (d) 3.6 ppm, 12 Hz

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Q38. Vibrations of diatomic molecules are usually modelled by a harmonic potential. If the potential is
given by x2, the correct statement is
(a) Force is 2𝑥and force constant is 2 (b) Force is -2𝑥and force constant is 2
(c) Force is 2𝑥and force constant is -1 (d) Force is -2𝑥and force constant is -1
Q39. The transition that belongs to the Lyman series in the hydrogen-atom spectrum is
(a) 1𝑠 ← 4𝑠 (b) 1𝑠 ← 4𝑝 (c) 2𝑠 ← 4𝑠 (d) 2𝑠 ← 4𝑝
Q40. The rotational constant and the fundamental vibrational frequency of 𝐻𝐵𝑟are, respectively,
10 𝑐𝑚-1and 2000 𝑐𝑚-1. The corresponding values for 𝐷𝐵𝑟approximately are
(a) 20 𝑐𝑚-1𝑎𝑛𝑑 2000 𝑐𝑚-1 (b) 10 𝑐𝑚-1𝑎𝑛𝑑 1410 𝑐𝑚-1
(c) 5 𝑐𝑚-1𝑎𝑛𝑑 2000 𝑐𝑚-1 (d) 5 𝑐𝑚-1𝑎𝑛𝑑 1410 𝑐𝑚-1
Q41. Among the following, both microwave and rotational Raman active molecule is
(a) CH4 (b) N2O (c) C2H4 (d) CO2
Q42. In a 200 MHzNMR spectrometer, a molecule shows two doublets separated by 2 ppm. The
observed coupling constant is 10 Hz. The separation between these two signals and the coupling
constant in a 600 MHz spectrometer will be, respectively
(a) 600 Hzand 30 Hz (b) 1200 Hzand 30 Hz
(c) 600 Hzand 10 Hz (d) 1200 Hzand 10 Hz

CSIR JUNE 2017

Q43. The v = 0 to 1 vibration-rotation spectrum of a diatomic molecule exhibits transitions for R(0), R1,
P (1) and P(2) lines at 2241, 2254, 2216 and 2203 cm-1, respectively. From this data, we can conclude
that the molecule
(a) has rigid rotation and harmonic vibration
(b) has anharmonic vibration
(c) has rotational-vibrational interaction
(d) is affected by nuclear spin-statistics
Q44. For a certain magnetic field strength, a free proton spin transition occurs at 700 MHz. Keeping the
magnetic field strength constant the 14N nucleus will resonate at ( g(p) = 5.6 and g(N) = 0.4)
(a) 700 MHz (b) 400 MHz (c) 200 MHz (d) 50 MHz
Q45. The first electronic absorption band maximum of a polar and relatively rigid aromatic molecule
appears at 310 nm but its fluorescence maximum in acetonitrile solution appears with a large Stokes
shift at 450 nm. The most likely reason for the Stokes shift is
(a) Large change in molecular geometry in the excited state
(b) Increase in dipole moment of the molecule in the excited state
(c) Decrease in polarizability of the molecule in the excited state

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(d) Lowered interaction of the excited molecule with polar solvent

CSIR DEC 2017

Q46. The molecule that will show Raman spectrum, but not IR spectrum, among the following is

(a) H2 (b) HCl (c) BrCl (d) CS2

Q47. The normal mode of ethylene represented, by the figure below, is

(a) only IR active (b) only Raman active

(c) both IR and Raman active (d) neither IR nor Raman active

Q48. The pair that contains a spherical top and a symmetric top, among the following, is
(a) CH4, CH2Cl2 (b) CH2Cl2, CH3Cl (c) CH3Cl, CH4 (d) CH4,C(CH3)4
Q49. The g-factors of 1H and 13
C are 5.6 and 1.4 respectively. For the same value of the magnetic field
strength, if the 1H resonates at 600 MHz, the 13C would resonate at
(a) 2400 MHz (b) 600 MHz (c) 150 MHz (d) 38 MHz

CSIR JUNE 2018

Q50.In the pure Raman rotational spectrum of 16

O2, whose electronic ground state is 3∑g, transitions
between to/from
(a) Even J levels are missing (b) Odd J levels are missing
(c) All J levels appear (d) None of the J levels appear
Q51. A symmetric top molecule, among the following, is
(a) Ethylene (b) Allene
(c) butatriene (d) Hexatriene
Q52. Assuming harmonic approximation, the energy change for the reaction
HCl + D2 → DCl + HD in cm-1 is (the vibrational frequency data in cm-1 is given in the table below),

HCl D2 DCl HD

2885 2990 1990 3627

(a) -258 (b) +258 (c) -129 (d) +129

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CSIR DEC 2018

Q53. Arrange the following molecules in order of increasing fundamental vibrational frequencies

(a) O22  O2  O2  O2

(b) O2  O2  O2  O22

(c) O22  O2  O2  O2

(d) O22  O2  O2  O22

Q54.The third and fourth lines in the rotational Raman spectrum of CO are separated by 8 cm-1. The
CO bond length is given by

h 3h h 5h
(a) (b) (c) (d)
16 2C 322C 322C 322C

CSIR JUNE 2019

Q55.The correct statements about HCl and DCl, among the following is
(a) DCl has smaller Zero Point Energy than HCl
(b) HCl has smaller vibrational frequency than DCl
(c) The force constant k for HCl bond is half that of DCl
(d) The reduced mass of DCl is smaller than that of HCl

Q56. The Berge-Sponer plot between G 1    v1   v  and 𝜈 + 1 for CO in a straight line with
v
2

slope of 14 cm-1and intercept of 2170cm-1. The approximate value of dissociation energy of CO
(in 𝑐𝑚-1) is (Assume CO as an Anharmonic oscillator with energy expression.


2
 1  1
 v   v      v   x e ; D 
 2  2 4x e

(a) 42044 (b) 84088 (c) 168175 (d) 336350

CSIR DEC 2019

Q57.The frequency of O  H stretch occurs at ~3600 cm-1. The O  D stretch frequency (in cm-1) would be
closest to

(a)3000 (b)2600 (c)1800 (d)900

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Q58. In the pure rotational microwave spectrum of a XY molecule, the adjacent lines are separated by
4 cm-1. If the molecule is irradiated by a radiation of 30,000 cm-1 , the first Stokes line(in cm-1) appears at

(a) 29988 (b) 30012 (c)30004 (d)29996

CSIR 2020
Q59. The equilibrium dissociation energy of a diatomic molecule is 4.75 eV and its stretching frequency
corresponds to 0.5 eV. The minimum energy required to dissociate the molecule in eV is

(a) 4.75 (b) 4.25 (c) 4.50 (d) 5.00

Q60. The vibrational transition energies of a diatomic molecule corresponding to v = 1 ← v= 0 and v = 2

← v = 1 are 2143.1 cm-1and 2116.1 cm-1, respectively. The anharmonic constant (ee) of the
molecule in cm-1is

Options:

(a) 27 (b) 13.5 (c) 10 (d) 54

12 16
Q61. The energy separation of C O rotational energy levels between J" =3 and J" = 9 is 24 cm-1. The
rotational constant of 13C 16O in cm1 is closest to

Options:

(a) 2.98 (b) 0.88 (c) 1.90 (d) 2.08

CSIR JUNE 2021

Q62.The correct statement from the following set (i) to (iv) is
(i) if q is the displacement from equilibrium for harmonic motion, the potential energy is proportional to
q
(ii) if the vibrational frequency (𝜈) of HCl is 2990 cm-1, its zero point energy will be 1495 cm-1
(iii) the correct order of vibrational frequency of O-1H (X1), O-2H (X2) and O-3H (X3) is X1> X2> X3
(iv) the fundamental vibrational transition of a diatomic molecule appears at 1880 cm-1. Its first overtone
will be at 940 cm-1(assuming anharmonicity constant as zero)
(a) i, ii, iii only (b) i, ii, iii, iv (c) ii, iii only (d) i, ii, iv only

Q63. Match the following

Measurement Spectroscopic Technique

(a) Binding energy (i) NMR spectroscopy

(b) Quadrupole splitting (ii) Energy-dispersive X-ray spectroscopy

(EDS)

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(c) Contact shift (iii) X-ray photoelectron spectroscopy (XPS)

(d) Elemental analysis (iv) Mossbauer spectroscopy

(a) a-ii, b-i, c-iv, d-iii (b) a-iii, b-iv, c-i, d-ii

(c) a-iv, b-iii, c-i, d-ii (d) a-i, b-iv, c-ii, d-iii
Q64. The molecule that will not absorb in the microwave region, but will absorb in the infra-red region
(a) N2 (b) C2H2 (c) HCl (d) H2O
Q65. The following data is obtained for a light diatomic (AB) molecule from its rotational Raman
spectrum. (B = 2 cm-1 ; xe = 0.01; ve  1600 cm-1)

If the molecule is irradiated by a laser of 20,000 cm-1, the expected Stokes lines (in 𝑐𝑚-1) for this
molecule are
(a) 18348, 18356, 18368, 18380, 18388
(b) 18412, 18420, 18432, 18444, 18452
(c) 18380, 18388, 18400, 18412, 18420
(d) 18416, 18424, 18430, 18440, 18452

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ANSWER KEY
MOLECULAR SPECTROSCOPY
1. (a) 2. (b) 3. (c) 4. (c) 5. (a) 6. (b) 7. (c)
8. (b) 9. (a) 10. (b) 11. (a) 12. (d) 13. (b) 14. (c)
15. (d) 16. (d) 17. (b) 18. (b) 19. (b) 20. (a) 21. (b)
22. (b) 23. (d) 24. (c) 25. (d) 26. (a) 27. (b) 28. (d)
29. (b) 30. (b) 31. (c) 32. (a) 33. (b) 34. (a) 35. (a)
36. (a) 37. (a) 38. (b) 39. (b) 40. (d) 41. (b) 42 (d)
43. (c) 44. (d) 45. (b) 46. (a) 47. (b) 48. (c) 49. (c)
50. (a) 51. (b) 52. (c) 53. (a) 54. (a) 55. (a) 56. (c)
57. (b) 58. (a) 59. (c) 60. (b) 61. (b) 62. (c) 63. (a)
64. (b) 65. (b)

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Quantum Chemistry
CSIR JUNE 2011
3
r
1    2  a0
1. The normalized hydrogen atom 1s wave function is given by 1s    e where ζ = 1 and energy
  a0 

is – 0.5 au. If we use a normalized wave function of the above form with ζ  1, the average value of energy
of the ground state of hydrogen atom is:

(a) Greater than – 0.5 au (b) Equal to – 0.5 au

(c) Less than – 0.5 au (d) Equal to ζ times – 0.5 au.

2. A constant of motion is defined by the equation:

(d) A  A
†
(a) [H, A] = 0 (b) <[H, A] > =0 (c) A = f(H)

The Hermitian conjugate of operator d/dx, called  d / dx  , is actually equal to

†
3.

(a) –d /dx (b) d/dx (c) i(d/dx) (d) –i(d/dx)

4. The unperturbed energy levels of a system are ε0 = 0, ε1 = 2 and ε2 = 4. The second order correction to
energy for the ground state in pressure of the perturbation V for which V10 = 2, V20 = 4 and V12 = 6 has
been found to be

(a) –6 (b) 0 (c) +6 (d) –8

5. The energy levels for cyclobutadiene are  + 2, ,  and   2. The delocalization energy in this
molecule is:

(a) 0 (b) –4 (c) –8 (d) 4

6. For a certain particle encountering a barrier, the tunneling probability is approximately e-10. If the mass
is halved and width of the barrier (rectangular) doubled, approximate value of the tunnelling probability
will be

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10/ 2 10 2 20 2 10
(a) e (b) e (c) e (d) e

7. An operator A is defined as A = d/dx + x. Which one of the following statements is true?

(a) A is a Hermitian operator.

(b) A† is an antihermitian operator.

† †
(c) Both A A and A A are Hermitian.

† †
(d) A A is Hermitian, but A A is antihermitian

8. For a H2 molecule, the ground state wave function is  1, 2 =  1, 2 (1, 2) where ϕ refers to the space
part and  to the spin part. Given that  1, 2 =  2, 1 the form of (1, 2) would be

(a) (1) (2) (b) (2) (1)

(c) 12  (2)(1) (d) 12 + (2)(1)

9. A hydrogenic orbital with radial function of the form r  exp  r  and -part as exp[-3i] corresponds

to

(a) n > 4, l > 3, m = 3 (b) n = 4, l = 3, m = -3

(c) n = 4, l > 3, m = 3 (d) n > 4 , l = 3, m = -3

CSIR DEC 2011

10. Identify which of the following operators is not hermitian?

d d2 d2
(a) (b) i (c) (d) x2
i dx dx 2 dx 2
11. A particle is constrained in a one dimensional box of length 2a with potential V(x) = ; x < a, x > a and
V(x) = 0; a  x  a. Energy difference between levels n = 3 and n = 2 is

5h 2 9h 2 9h 2 5h 2
(a) (b) (c) (d)
8ma 2 8ma 2 32ma 2 32ma 2
12. For the eigen states of the hydrogen atom, which of the following relations between the
expectation value of kinetic energy (T) and potential (V) holds true?
(a)T = V (b) 2T = V (c) 2T = V (d) T = 2V
13. Which of the following is true for the radial part of the hydrogen atom wave functions Rnl(r) (n principal
quantum number) and the nodes associated with them?
(a) The radial part of only s function is non-zero at the origin and has (n – 1) nodes.

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(b) The radial part of s function is zero at the origin and has n number of nodes.
(c) All radial functions have values of zero at the origin and have (n –1) nodes.
(d) The radial parts of all s functions are zero at the origin and have no nodes.

14. For non-degenerate perturbation theory for ground state, with E(0) (1)
0 as zeroth order energy, E 0 as the

first-order perturbation correction and E0 as the exact energy, which of the following is true?


0  E0
(a) E(0) (1)

is always equal to E0 
0  E0
(b) E(0) (1)

 E0

(c) E (0)
0 0   E0
 E(1) 
(d) E0  E0(1)  E0 
15. An excited triplet state wave function of hydrogen molecule with the electronic configuration 1g 1u has

the following space part

(a) σg(1) σu(2) (b) σg (1) σu (2) + σu (1) σg(2)

(c) σg (1) σu (2)  σu (1) σg (2) (d) σg (1) σg (2) + σu (1) σu (2)

CSIR JUNE 2012

16. For any operator A and its adjoint A† , the INCORRECT statement is:

(a) AA† is Hermitian (b) AA† + A†A is hermitian.

(c) A + A† is Hermitian (d) A - A† is Hermitian

17. For hydrogen-like atom with a nuclear charge Z, the energy of orbital with principal quantum number
‘n’ follows the relation.

Z2 Z Z2
(a) En  n 2 Z2 (b) E n   (c) E n  (d) E n  
n n n2

18. The average value of the radius <r> in the 1s state of the hydrogen atom is (a0 is Bohr radius)

(a) a0 (b) 1.5 a0 (c) 0.75 a0 (d) 0.5 a0

19. The probability of finding the particle in a one dimensional box of length ‘L’ in the region between
L 3L
and for quantum number n = 1 is
4 4
1 1 1 1 1 2
(a) (b)  (c)  (d)
2 2  2  3

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2
14h
20. A particle in three dimensional cubic box of length L has energy of . The degeneracy of the state
8mL2
is
(a) 2 (b) 3 (c) 6 (d) 9
21. The following are the three statements about perturbation theory
(A) Second order perturbation correction to the ground state energy is ALWAYS negative.
(B) Sum of the zeroth order and the first order corrections to the ground state energy is ALWAYS
greater than the exact ground state energy.
(C) Sum of the zeroth order and first order corrections to the ground state energy is less than the exact
state energy.
From the following which one is correct?
(a) Only A is true (b) Both A and B are true
(c) Only C is true (d) Both B and C are true
22. Using Huckel molecular orbital approximation, the two roots of secular equation of ethane are

(a)   2 ,   2 (b)  + , 

(c)  + ,   (d)   2,   2

23. For H2 molecule in the excited state 1g 1u spin part of the triplet state with mS = 0 is proportional to

(a) (1)(2) (b) [(1)(2) - (1)(2)]

(c) (1)(2) (d) [(1)(2) + (1)(2)

CSIR DEC 2012

24. If A and B are non-commuting Hermitian operators, all eigenvalues of the operator given by the
commutator
[A, B] are

(a) complex (b) real (c) imaginary (d) zero

25. The value of commutator  x̂, pˆ 2x  is given by

(a) 2i (b) 2i (c) 2i x (d)

2i px

26. Combining two real wave functions ϕ1 and ϕ2 the following functions are constructed:

A= ϕ1 + ϕ2, B = ϕ1 + iϕ2, C= ϕ1 – iϕ2, D= i(ϕ1 + ϕ2)

The correct statement will then be

(a) A and B represent the same state (b) A and C represent the same state.
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(c) A and D represents the same state (d) B and D represent the same state

27. The trial wave function of a system is expanded as t = c11 + c22. The matrix elements of the
Hamiltonian are 1 H 1 = 0 ; 1 H 2 = 20 = 2 H 1 and 2 H 2 H 2 = 3.0. The approximate
ground-state energy of the system from the linear variational principle is
(a) –1.0 (b) –2.0 (c) +4.0 (d) +5.0

28. One molecular orbital of a polar molecule AB has the form cAA  cBB , where A and B are
normalized atomic orbital’s centred on A and B, respectively. The electron in this orbital is found on atom
B with a probability of 90% neglecting the overlap between A and B a possible set of cA and cB is:
(a) cA = 0.95, cB = 0.32 (b) cA = 0.10, cB = 0.90
(c) cA = -0.95, cB = 0.32 (d) cA = 0.32, cB = 0.95
29. Suppose, the ground stationary state of a harmonic oscillator with force constant 'k' is given by
0  exp Ax 2  Then, A should depend on K as

(a) A  k1/2 (b) A  k (c) A  k1/2 (d) A  k

1/3

30. The energy of a harmonic oscillator in its ground state is 1/ 2h . According to the virial theorem, the
average kinetic (T) and potential (V) energies of the above are
(a) T=1/4 h V =1/4 h (b) T=1/8 h V=3/8 h
(c) T= h V= 1/2 h (d) T =3/8 h V= 1/8 h
h C R H
31. The energy of a hydrogen atom in a state is (RH = Rydberg constant). The degeneracy of the
25
state will be
(a) 5 (b) 10 (c) 25 (d) 50
32. In a many-electron atom, the total orbital angular momentum (L) and spin (S) are good quantum
numbers instead of the individual orbital (I1 , I2) and spin (s1 , s2) angular momenta in the presence of
(a) inter-electron repulsion (b) spin-orbit interaction
(c) hyperfine coupling (d) external magnetic field
33. The difference in energy levels of n = 2 and n = 1 of a particle -in - a one dimensional box is 6 units of
energy. In the same units, what is the difference in energy levels of n = 3 and n = 2 for the above
system?
(a) 4 (b) 5 (c) 9 (d) 10

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1 3
34. The wave function ψ of a certain system is the linear combination   1   2 where 1 and 2
4 4
are energy eigen functions with eigen values (non-degenerate) E1 and E2 respectively. What is the
probability that the system energy will be observed to be E1 ?

3 3  1
(a) (b) (c) (d)
16 4 4 4

35. For the particle-in-a-box problem in (0,L) an approximate wave function is given as x(L/2-x)(L-x). The
average energy E for such a state will obey

h2 h2 h2
(a)  E  (b) E 
8mL2 2mL2 2mL2

h2 h2 h2
(c)  E  (d) 0  E 
4mL2 2mL2 8mL2

36. The hydrogenic orbital with the form of the radial function r 2  1  r   2  r  exp  r  where a1, a2

and b are constants, may be identified as a

(a) 3d orbital (b) 4f orbital (c) 5d orbital (d) 5f orbital

37. The operator  x, ˆ pˆ 2   is identical with

ˆ  x,


ˆ ˆ  x,
(a) px, ˆ pˆ  ˆ ˆ  x,
(b)  xp, ˆ pˆ  (c)   p,
ˆ  xˆ 2 , pˆ   (d)   x,
ˆ  xˆ 2 , pˆ  
 

38. For the particle -in-a-box problem in (0, L) the value of x̂ 3 in the n  ∞ limit would be

L3 L3 L3 L4
(a) (b) (c) (d)
6 3 4 4

39. Identify the Huckel determinant for cyclobutadiene

E  0 0 E  0 
 E  0  E  0
(a) (b)
0  E  0  E 
0 0  E   0 E

E  0  E  0 
 E  0  E  0
(c) (d)
0  E  0  E 
 0  E 0 0  E
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40. In the formation of H2 molecules from 2H atoms placed at positions A and B, and separated by a distance
rAB, a part of special wave function is A (1) A (2)  B (1) B (2)

(a) This is a covalent term and is important as rAB  

(b) This is a ionic term and is important as rAB  

(c) This is a covalent term and is important as rAB  

(d) This is a ionic term and is important as rAB  

CSIR DEC 2013

41. The orbital with two radial and two angular nodes is
(a) 3p (b) 5d (c) 5f (d) 8d
1 1
42. Consider a two-dimensional harmonic oscillator with potential energy V(x, y)  k x x 2  k y y 2 If
2 2
nx (x) and ny (y) are the eigensolutions and Enx and Eny are the eigenvalues of harmonic oscillator
1 1
problem in x and y direction with potential k x x 2 and k y y 2 respectively, the wave function and
2 2
eigenvalues of the above two-dimensional harmonic oscillator problem are
 nx,ny   nx (x)   ny (y)  nx,ny   nx (x) .  ny (y)
(a) (b)
E nx,ny  E nx  E ny E nx,ny  E nx . E ny
 nx,ny   nx (x) .  ny (y)  nx,ny   nx (x) .  ny (y)
(c) (d)
E nx,ny  E nx  E ny E nx,ny  E nx . E ny

43. The quantum mechanical virial theorem for a general potential V(x,y,z) is given by x v  y v  z v
x y z
where T is the kinetic energy operator and < > indicates expectation value. This leads to the following
relation between the expectation value of kinetic energy and potential energy for a quantum mechanical
harmonic oscillator problem with potential V  1 k x x 2  1 k y y 2  1 k z z 2
2 2 2
(a) <T> = <V> (b) <T> = -1/2<V> (c) <T> = 1/2 <V> (d) <T> =<V>
44. Consider a particle in a one dimensional box of length ‘a’ with the following potential
V(x) =  x<0
V(x) =  x>a
V(x) = 0 0  x  a/2
V(x) = V1 a/2  x  a
Starting with the standard particle in a box Hamiltonian as the zeroth order Hamiltonian and the potential
of V1 from ‘a/2’ to ‘a’ as a perturbation, the first order energy state is
(a) V1 (b) V1/4 (c) V1 (d) V1/2
45. The most probable value of ‘r’ for an electron in 1s orbital of hydrogen atom is

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(a) a0 / 2 (b) a0 (c) 2a0 (d) 3a0 / 2

46. The angular momentum operator L̂ y

       
(a)   y  z  (b) z  x 
i  z y  i  x z 

i     
(c) (d) z  y 
2m x i  x y 

47. The energy for a single electron excitation in cyclopropenium cation in Huckel theory is
(a)  (b) 2 (c) 3 (d) 4

CSIR JUNE 2014

48. The commutator of the kinetic energy operator, T̂x and the momentum operator, p̂ x for the one-
dimensional case is

(a) i (b) i d (c) 0 (d) i x

dx

49. Consider a particle confined in a cubic box. The degeneracy of the level, that has an energy twice that of
the lowest level, is

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

50. A particle in a one-dimensional box (potential zero between to a and infinite outside) has the ground state
2
energy E 0  0.1252h . The expectation value of the above Hamiltonian with yields an energy E1. Using a
ma

linear combination of two even functions x(x – a) and x2 (x – a)2 we obtain variational maximum to the
ground state energy as E2. Which of the following relations holds for E0, E1 and E2?

(a) E0 < E1 < E2 (b) E0 < E2 < E1

(c) E1 < E0 < E2 (d) E2 < E0 < E1

51. The ground state energy of hydrogen atom is –13.598 eV. The expectation values of kinetic energy, <T>
and potential energy, <V>, in units of eV, are
(a) <T> =13.598, <V> = -27.196 (b) <T> = -27.196, <V> = 13.598
(c) <T> = -6.799, <V> = -6.799 (d) <T> = 6.799, <V> = -20.397
52. If  = 0.8A + 0.4 B is a normalized molecular orbital of a diaotmic molecule AB, constructed from A
and B which are also normalized, the overlap between A and B is

(a) 0.11 (b) 0.31 (c) 0.51 (d) 0.71

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+2
53. If the ionization energy of H atom is x, the ionization energy of Li is
(a) 2x (b) 3x (c) 9x (d) 27x
54. Simple Huckel molecular orbital theory

(a) considers electron-electron repulsion explicitly

(b) distinguishes cis-butadiene and trans butadiene

(c) distinguishes cyclobutadiene cis-butadiene

(d) has different coulomb integrals for non equivalent carbons

55. A particle in a one dimensional harmonic oscillator in x-direction is perturbed by a potential  x( is
number). The first-order correction to the energy of the ground state

(a) is zero (b) is negative

(c) is positive (d) may be negative or positive but not zero

56. The spatial part of the wave function of the atom in its ground state is 1s (1)1s (2). The spin part would
be

(a) (1) (2) (b) (1) (2)

1 1
(c) [ (1) (2) (1) (2)] (d) [ (1) (2) (1) (2)]
2 2

57. For a particle of mass m confined in a box of length L, assume x = L. Assume further that p(min) =
<p2>1/2. Use the uncertainity principle to obtain an estimate of the energy of the particle. The value will
be

h2 2
(a) (b)
8mL2 8mL2

h2 h2
(c) (d)
32mL2 2mL2


58. The angular momentum operator Lz  i has eigen functions of the form exp (iA). The condition

that a full rotation leaves such an eigen function unchanged is satisfies for all the values of A

1 2 4
(a) 0,  ,  , 1,  , (b) 0,  1, 2, 3, 4,
3 3 3

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1 3 1 3 5 7
(c) 0,  , 1,  , (d) 0, , , , ,
2 2 2 2 2 2

59. A particle in a 1-dimensional box of length L is perturbed by a delta function potential, (x-L/2), in the
middle of the box. The first order energy correction to the ground state will be [Hint:


 f (x) (x  a)dx  f (a) ]



(a) 0 (b) 1 (c) L/2 (d) 2/L

60. The operators S are defined by S  Sx  iSy where Sx and Sy are components of the spin angular

momentum operator. The commutator Sx ,S  is

(a) S (b) S (c)  S (d)  S

61. A quantum particle with fixed initial energy E0 < V is allowed to strike the following four barriers
separately. The transmission probability is maximum in

(a) (b)

(c) (d)

62. For some one-electron system with l = 0 and m = 0, the functions N0e and N1  2    e refer

respectively to the ground (E0) and fist excited (E1) energy levels. If a variational wave function
N 2  3    e yields an average energy E , it will satisfy

(a) E  0 (b) 0  E  E0

(c) E  E1 (d) E0  E  E1

63. A Slater determinant corresponding to the ionic part of the ground state valence bond wave function of
H2 molecule is (1sa, 1sa, 1sb, 1sb are atomic spin-orbital’s of hydrogen atoms a and b of the hydrogen
molecule)

1sa (1) 1sa(1) 1sa (1) 1sb(1)

(a) (b)
1sa (2) 1sa(2) 1sa (2) 1s b(2)
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1sa (1) 1s b (1) 1sa (1) 1s b(1)
(c) (d)
1sa (2) 1s b (2) 1sa (1) 1s b(2)

64. An eigen state of energy satisfy H n  E n  n . In the presence of an extra constant potential V0

(a) both En and ψn will change

(b) both En and average kinetic energy will change
(c) only En will change, but not ψn
(d) only ψn will change, but not En
65. The simplest ground-state VB wave function of a diatomic molecule like HCl is written as
  H (1s,1) Cl (3pz ,2)  B where B stands for

(a) H (3pz ,2) Cl (1s,1) (b) H (1s,2) Cl (3pz ,1)

(c) Cl (1s, 2) Cl (3pz ,1) (d) Cl (1s,2) H (3pz ,1)

66. Which of the following statement is INCORRECT?

(a) A Slater determinant is an anti-symmetrized wave function
(b) Electronic wave function should be represented by Slater determinants
(c) A Slater determinant always corresponds to a particular spin state
(d) A Slater determinant obeys the Pauli exclusion principle
67. Compare the difference of energies of the first excited and ground states of a particle confined in (i) a
1-d box (∆1), (ii) a 2-d square box (∆2), and (iii) a 3-d cubic box (∆3). Assume the length of each of the
boxes is the same. The correct relation between the energy differences ∆1, ∆2 and ∆3 for the three states
is
(a) ∆1 > ∆2 > ∆3 (b) ∆1 = ∆2 = ∆3 (c) ∆3 > ∆2 > ∆1 (d) ∆3 > ∆1 > ∆2
68. The correct statement about both the average value of position x and momentum p of a 1-d harmonic
oscillator wave function is
(a)  x   0 and  p   0 (b) x  0 and p  0

(c) x = 0 and p = 0 (d) x  0 and p  0

69. The value of the commutator [x, [x, px]] is

(a) i x (b) i (c) 𝒊ℏ (d) 0
70. A particle is in a one-dimensional box with a potential Vo inside the box and infinite outside.
An energy state corresponding to n = 0 (n = quantum number) is not allowed because
(a) the total energy becomes zero
(b) the average momentum becomes zero
x(c) the wave function becomes zero everywhere
(d) the potential V0 ≠ 0
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ˆ and B
71. Two different non-zero operators A ˆ B
ˆ A   ˆ B
ˆ satisfy the relation A ˆ B
ˆ A ˆ 2 B
ˆ A ˆ2  
ˆ ˆ A
(a) AB ˆ 2 and BA
ˆ ˆ B
ˆ2 ˆ ˆ  BA
(b) AB ˆ ˆ 0

ˆ and B
(c) A ˆ are arbitrary ˆ ˆ  BA
(d) AB ˆ ˆ 0

72. The degeneracy of an excited state of a particle in 3-dimensional cubic box with energy 3 times its ground
state energy is
(a) 3 (b) 2 (c) 1 (d) 4
73. sp hybrid orbitals are of the form C12s + C22pz (2s and 2pz are normalised individually). The coefficients
of the normalized form of the above sp hybrid orbital’s are
1 1 1 1
(a) C1  , C2   (b) C1  , C 2  
2 2 2 2

1 1 1 1
(c) C1  , C2   (d) C1  , C2  
2 2 2 2
74. A certain 2-level system has stationary state energies E1 and E2 (E1 < E2) with normalized wave functions
1 and 2 respectively. In the presence of a perturbation V, the second-order correction to the energy for
the first state (1) will be

1 | V | 2 1 | V | 2 | 1 | V | 2 |2 | 1 | V | 2 |2
(a) (b) (c) (d)
E1  E 2 E 2  E1 E1  E 2  E1  E 2 
2

75. The radial part of a hydrogenic wave function is given as r(  r)er (,  are constants). This function
is then indentifiable as
(a) 2s (b) 3p (c) 4d (d) 5f
76. A normalised state  is constructed as a linear combination of the ground state (0) and the first excited
state (1) of some harmonic oscillator with energies 1/2 and 3/2 units, respectively. If the average energy
of the state  is 7/6, the probability of finding 0 in  will be
(a) 1/2 (b) 1/3 (c) 1/3 (d) 1/5

CSIR JUNE 2016

77. The eigenfunctions of the Hamiltonian H (H = T + V) of a harmonic oscillator are (where T and V are
kinetic energy and potential energy operators, respectively)
(a) eigenfunctions of T as well as V
(b) eigenfunctions of T, but not of V
(c) eigenfunctions of V, but not of T
(d) eigenfunctions of neither T nor V
78. For a particle of mass m confined in a rectangular box with sides 2a and a, the energy and degeneracy of
the first excited state, respectively, are

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h 2
2
h  17 
2
h  5 
2
h 5
2
(a)   ,1 (b)  ,2 (c)   ,1 (d)  ,2
8m  a 2  8m  4a 2  8m  4a 2  8m  a 2 
79. Choosing some Hamiltonian H and an orthonormal basis, a linear variation is carried out to
get approximately energies E j With 2 basis functions, one obtains E1(2) ≤ E2(2). Taking 3 basis

functions, similarly three ordered energies E1(3)  E2(3)  are found. The relation which holds from the
following is?
(a) E1 (2)  E1 (3) E2 (2)  E2 (3) (b) E1 (3)  E1 (2) E2 (2)  E2 (3)

(c) E1 (2)  E1 (3) E2 (3)  E2 (2) (d) E1 (3)  E1 (2) E2 (3)  E2 (2)
80. Average value of momentum for the ground state of a particle in a 1-d box is zero because
(a) [p, H] = 0 (b) V (potential) = 0
(c) H is Hermitian (d) the state is bound and stationary
81. For a hermitian operator A, which does NOT commute with the Hamiltonian H, let 1 be an eigenfunction
of A and ψ2 be an eigenfunction of H. The correct statement regarding the average of A and value of the
commutator of A with H ([A,H]) is
(a) both 1 [A, H] 1 and 2 [A, H] 2 are non-zero
(b) only 1 [A, H] 1 is zero , but 2 [A, H] 2 is non-zero
(c) only 2 [A, H] 2 is zero , but 1 [A, H] 1 is non-zero
(d) both 1 [A, H] 1 and 2 [A, H] 2 are zero
82. The simultaneous eigen functions of angular momentum operators L2 and LZ are
(a) all of 2s, 2px , 2py, and 2pz orbitals (b) only 2s, 2px and 2py orbital
(c) only 2s and 2pz orbitals (d) only 2pz orbital
83. The ionization energy of hydrogen atom in its ground state is approximately 13.6 eV. The potential energy
of He+, in its ground state is approximately
(a) -54.4 eV (b) -27.2 eV (c) -13.6 eV (d) -108.8 eV
84. In simple molecular orbital theory of hydrogen molecule, bonding g and anti-bonding u molecular
orbitals are constructed as linear combinations of atomic orbitals of two hydrogen atoms. The spatial part
of a purely covalent singlet wave function is obtained by
1
(a) g2   2u (b)  g2 (c) g2   2u (d)  g2   u2
2
85. The correct normalized wave function for one of the sp2 hybrid orbitals is
1 1 1 1 2 1
(a)  2s   2px   2py (b)  2s   2px   2py
3 3 3 3 3 6
1 1 1 1 1 1
(c)  2s   2px   2py (d)  2s   2px   2py
3 2 6 3 2 2 6

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86. The orbital degeneracy of the level of a one-electron atomic system with Z = 5 and energy = -13.6 eV, is
(a) 1 (b) 5 (c) 25 (d) 36

87. If we write a normalized wave function  = Â , then  is also normalized when

(a) Â is hermitian (b) Â is anti-hermitian

(c) Â is unitary (d) Â is any linear operators

88. The ground state of a certain system with energy 0 , is subjected to a perturbation V, yielding a first order

correction 1 . If E0 is the true ground-state energy of the perturbed system, the inequality that always
holds is
(a) 1  0 (b) 1  E 0 (c) 0 1  E i (d) 0 1  E i

89. The spatial part of an excited state b 3

u of hydrogen molecule is proportional to

1g (1) u (2)  1g (2)u (1)  . Using LCAO-MO expansion of 1g and 1u in terms of 1s-atomic orbitals,

one can infer that this wavefunction has

(a) only ionic parts (b) only covalent parts
(c) both ionic and covalent parts (d) neither ionic nor covalent parts
90. Consider a particle in its ground state confined to a one-dimensional box in the interval (0, ∞).
 
The probability of finding it between 4.0  and 4.0  is close to ( is sufficiently small so that the
2 2
wave function can be taken as a constant in this interval).
  
(a) (b) (c) (d) 
4 3 2

d d2
91. Which of the functions below is a common eigenfunction of and operators?
dx dx 2
(a) cos x (b) kx (c) eix (d) e - x²
92. The two limiting wave functions of the ground state of H2+ molecular ion, as the internuclear
separation R goes to (i) ∞ (infinity) and (ii) 0 (zero) are (1sa, 1sb are 1s-orbital wave functions of
hydrogen atoms a and b in H 2 , and 1s He is the wave function of the 1s orbital of He+)
(a) (i) 1sa (r); (ii) 1sb (r) (b) (i) 1sb (r); (ii) 1sa (r)
(c) (i) 1sa (r1) 1sb (r2) ; (ii) 1s He (r1) 1s He (r2) (d) (i) 1sa (r) + 1sb (r): (ii) 1s He (r)
93. The un-normalized radial wave function of a certain hydrogen atom eigenstate is (6Rr  r2) exp (r/3). A
possible angular part of the eigen state is
(a) 5cos   3cos  (b) 35cos2  1 (c) cos 
3
(d) 1

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94. Given a trial wave function  = C11 + C22 and the Hamiltonian matrix elements.   H dv  0,
*
1 1

  H dv  2.5,   H dv  12.0 the variationally determined ground state energy is

* *
1 2 2 2

(a) -0.52 (b) -0.50 (c) 12.50 (d) 12.52

95. The number of degenerate spatial orbitals of a hydrogen-like atom with principal quantum
number n = 6 is
(a) 12 (b) 6
(c) 72 (d) 36
ˆ B
96. If  A, ˆ ˆ
ˆ   0 and  A, ˆ B
, then which of the following necessarily holds:  A, ˆ are operators 
ˆ and C
  C  0 
ˆ0
(a)  B̂, C (b)  Â, BC   0 (c)  B̂, AC   0 (d)  Ĉ, AB   0


97. The correct statement among the following is ( Â is a hermitian operator)

(a) The eigenvalues of  2 can be negative (b) The eigenvalues of  2 are always positive

(c) No eigenvalues of  can be negative  2 (d) The eigenvalues of  2 can be complex.

98. The correct statement about the symmetry of the eigenfunctions of a quantum of 1-D harmonic
oscillator is
(a) All the eigenfunctions are only even functions, because the potential is an even function.
(b) All the eigenfunction are only odd functions, although the potential is an even function.
(c) The eigenfunctions have no odd-even symmetry.
(d) All the eigenfunctions are either odd or even functions, because the potential is an even function.
99. The correct statement about the difference of second and first excited state energies (E) of a
particle in 1-D, 2-D square and 3-D cubic boxes with same length for each, is
(a) E (1-D box) = E (2-D box) = E (3-D box)
(b) E (1-D box) > E (2-D box) > E (3-D box)
(c) E (1-D box) > E (2-D box) = E (3-D box)
(d) E (1-D box) < E (2-D box) < E (3-D box)
100.A one-dimensional quantum harmonic oscillator is perturbed by a potential. The first order correction to
the energy for the ground state (E(1)) is
(a) E(1) but < 1 (b) E(1) < 0
(c) E(1) = 0 (d) E(1) >2
101. The electronic transition energy from 1   2 in propenyl radical is 4.8 eV. Within the framework of

Huckel theory, the transitions energy from 1  3 would be

(a) 2.4 eV (b) 4.8 eV (c) 9.6 eV (d) 14.4 eV

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102.The transition moment integral for a rotational transition between J = 1; MJ = 0 and J = 2 ; MJ = 0 states
for a diatomic molecule along the z-axis is proportional to
 

(a)  cos (3cos   1) d

2 2
(b)  cos 2  (3cos 2   1) sin d
0 0

 

(c)  cos  (3cos   1) sin d

2
(d)  cos 2  (3cos 2   1) sin 2 d
0 0

103. One of the correct normalized sp2 hybridorbitals is

1 1 1 1 3 3
(a) 2s  2px  2py (b) 2s  2px  2py
3 3 3 2 8 8

1 3 1 2
(c) 2s  2px (d) 2s  2p
3 8 3 3
104.Which of these is not a suitable unnormalized wave function for the excited 1s 2s electron configuration
of the helium atom ?
(a) [1s (1) 2s (2) - 2s (1)1s (2)][(1)(2)]
(b) [1s(1) 2s(2) + 2s(1)1s(2)][(1)(2)-(1)(2)]
(c) [1s(1) 2s(2) - 2s(1)1s(2)][ (1) (2) + (l) (2)]
(d) [1s(1) 2s(2) + 2s (1)1s(2)][  (1)  (2)]
105. Two opposite sides (in the y direction) of a square box of side L are slightly stretched. Consider the
following four statements:
A. The point group changes from D4h to D2h
B. The (1,2) and (2,1) energy levels remain doubly degenerate
C. Both the energy levels are lowered and the energy of the (1, 2) level higher than that of (2, 1) level.
D. Both the energy levels are lowered and the energy of the (1, 2) level lower than that of (2, 1) level
The two correct statements are:
(a) A and B (b) A and C (c) B and C (d) B and D
106.Consider a model system of five non interacting fermions in a single 3-dimensional harmonic

oscillator. The Hamiltonian of a single particle is Ĥ 

1
2m
 p    p    p   12  x
2
x
2
y
2
z
2
 y 2  z 2  where m

is the mass of the particle, on is the angular frequency, Pˆ x , Pˆ y and Pˆ z are the momentum operators. The

ground state energy of the system of non-interacting fermions is

21 15 5 25
(a) h (b) h (c) h (d) h
2 2 2 2

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107.A particle is in a state   1  32 where 1 and  2 are eigenfunctions of the Hamiltonian of the particle

with eigenvalues E1 and E2, respectively. The average energy of the particle in the state  is
(a) (E1 + 9E2)/10 (b) (E1 + 3E2)
(c) (E1 + 9E2)/14 (d) (E1 + 3E2)/10
108.Which of the following statements on ground state perturbation theory, involving the zeroth order energy
E(0) (1) (2)
0 , first order energy correction E 0 and second order energy correction E0 , is false?

(a) E(1)
0 is the average value of perturbation operator with respect to the ground state of the zeroth order

Hamiltonian.
(b) E(1)
0 is necessarily negative.

(c) E(2)
0 is necessarily negative.

(d) E(0) (1)

0 E0 is an upper bound to the exact ground state energy.

ˆ  x,
109.The commutator of x with the Hamiltonian H. ˆ ˆ
 H  is

h2 ih
(a) 0 (b) ih (c)  p̂x (d)  p̂x
2m m
110.The lowest energy unnormalized wave function of H 2 molecule is (r1 and r2 are the distances between
the electron and nuclei 1 and 2, respectively)
  r1  r2
   r1  r2

(a)    e a 0  e a 0  (b)    e a 0  e a 0 
   
   
 a r1   ar2 
(c)    e 0  (d)    e 0 
   
   
111.For a particle of mass m in a one-dimensional box of length 2L, the energy of the level corresponding to
n = 8 is
h2 h2
(a) (b)
8mL2 32mL2
4h 2 2h 2
(c) (d)
mL2 mL2
112.A physical observable, 'x', appears with the probability distribution e|2x 12| . The average of 'x' would be
(a) 0 (b) 3 (c) 6 (d) 12

 
113.The energy functional from a trial wave function is E()  3  3 / 6 . The variationally optimized

energy is
1 3 3 3
(a)  (b)  (c) (d)
2 8 2 8
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114.A satisfactory spin wave function for an excited helium atom is
1
(a) (1) (2)  (2) (1) (b) (1) (2)
2
1
(c) (1) (2)  (1) (2) (d) (2) (1)
2
115.The highest energy -molecular orbital for the allyl system is
1 1 1 1 1
(a) 1  1  3 (b) 1  3
2 2 2 2 2
1 1 1 1 1 1
(c) 1   2  3 (d) 1   2  3
2 2 2 2 2 2


116.An unnormalized wave function of the hydrogen atom is given by r 2er/3 3cos2   1 . The three quantum 
numbers, n, l and m, associated with this orbital are, respectively.
(a) 2, 2, 0 (b) 2, 1, 1 (c) 3, 2, 0 (d) 3, 1, 1
r

117. The hydrogen atomic orbital given by Nr e 2 3a 0

(3cos2  1) represents
(a) 2p orbital (b) 3p orbital
(c) 3d orbital (d) 4d orbital
27h 2
118.The degeneracy of the state having energy for a particle in a 3-D cubic box of length L is
8mL2
(a) 4 (b) 3 (c) 2 (d) 1
119.The spatial part of the dominant resonance structure of the LiH molecule is (only valance part of the wave
function is shown).
(a) 2sLi (r1 )2sLi (r2 ) (b) 2sLi (r1 )1sH (r2 )  2sLi (r2 )1sH (r1 )

(c) 2sLi (r1 )1sH (r2 )  2sLi (r2 )1sH (r1 ) (d) 1s H (r1 )1s H (r2 )
120.The function, which is NOT an eigenfunction of the indicated operator, is
Operator Function
 x2
d2
1. 2  x 2 e 2
dx
 x2
d2
2. 2  x 2 e 2
dx
d2 x
3. cos
dx 2 4

d2
4. e 4ix
dx 2

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Options
(a) 1 (b) 2 (c) 3 (d) 4
121.The Hückel molecular orbital of benzene that is degenerate with the molecular orbital
1
  2  3  5   6 
2
1
(a)  21  2  3  5  6  (b)
1
  2  3  3   6 
12 2

1 1
(c)  21  2  3  24  5  6  (d)  1  2  3  4  5  6 
12 6
122. In linear variation method using two orthogonal basis functions, the two roots obtained are
0 and 1 0 1  . The correct relation of these with exact ground and first excited state energies, E0 and

E1, respectively, is
(1) ∈0 ≥ E0 and ∈1 < E1 (2) ∈0 <E1 and ∈1 ≥ E1
(3) ∈0 < E0 and ∈1 < E1 (4) ∈0 ≥ E0 and ∈1 ≥ E1
Options
(a) 1 (b) 2 (c) 3 (d) 4
123. The expectation value of p2 of a particle in a cubic box of side l , having the wave function
3
 2 2 2x 2y 2z
 n x ,n y ,n z (x, y, z)    sin sin sin
l l l l
Options
17h 2 7h 2 3h 2 13h 2
(a) (b) (c) (d)
4l 2 4l2 4l2 4l 2
124.For a model system of three non-interacting electrons confined in a two dimensional square box of length
 h2 
L, the ground state energy in units of  2 
is
 8mL 
Options:
(a) 14 (b) 6 (c) 4 (d) 9
125.Consider a particle on a ring that is perturbed by interacting with an applied electric field (E) with the
perturbation being H  E cos E, where  is the dipole moment. The energy levels correct upto first
order are
Options
m l2 h 2 E m l2 h 2 E
(a)  (b) 
2  2I 2

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m h E
2 2 2
mh 2
(c) l
 (d) l
2I 2 2I

126.For an electron in 1s orbital of He+, the average value of r, <r> is

3 3 1
(a) a0 (b) a0 (c) 3a 0 (d) 3a 0
2 4 2

p 2x
127. Let the Hamiltonian H, in one-dimension, be H   V(x) . The commutator of H with x , [H, x], is
2m
Options:
ih ih 2 ih ih
(a) px (b) px (c) px (d) px
m 2m m 2m

128.The commutator,  x̂, pˆ 2x  is equivalent to

(a) 2ihpˆ x (b) 2ihpˆ x (c) ihpˆ x (d) ihpˆ x

129.The total -electron density on the four carbon atoms of trans butadiene are in the ratio

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

130.Consider an electron me  9.11031 kg having energy 13.6 eV, confined in an infinite potential well. If

the potential energy inside the well is zero, the expectation value for the square of the electron speed, v 2

, is
(a) 3 × 1012 m2 s-2 (b) 4.3 × 1018 m2 s-2 (c) 4.7 × 1012 m2 s-2 (d) 4.7 × 1031 m2 s-2
131.When a hydrogen atom is exposed to a perturbation V = E.z, the first order correction to the wave function
comes only from the orbital
(a) 2s (b) 2p z (c) 2p y (d) 3d 2z



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ANSWER KEY
QUANTUM CHEMISTRY

1. (c) 2. (b) 3. (a) 4. (a) 5. (b) 6. (c) 7. (c)

8. (c) 9. (b) 10. (b) 11. (d) 12. (b) 13. (a) 14. (c)
15. (c) 16. (d) 17. (d) 18. (b) 19. (b) 20. (c) 21. (b)
22. (c) 23. (d) 24. (c) 25. (d) 26. (c) 27. (a) 28. (d)
29. (c) 30. (a) 31. (c) 32. (a) 33. (d) 34. (c) 35. (b)
36. (c) 37. (c) 38. (c) 39. (c) 40. (d) 41. (b) 42 (c)
43. (a) 44. (d) 45. (b) 46. (b) 47. (c) 48. (c) 49. (a)
50. (b) 51. (a) 52. (b) 53. (c) 54. (b) 55. (a) 56. (d)
57. (b) 58. (b) 59. (d) 60. (a) 61. (b) 62. (c) 63. (a)
64. (c) 65. (b) 66. (c) 67. (b) 68. (c) 69. (d) 70. (d)
71. (c) 72. (d) 73. (a) 74. (c) 75. (b) 76. (b) 77. (d)
78. (a) 79. (d) 80. (d) 81. (d) 82. (c) 83. (d) 84. (c)
85. (c) 86. (c) 87. (c) 88. (b) 89. (b) 90. (a) 91. (c)
92. (b) 93. (c) 94. (b) 95. (d) 96. (b) 97. (b) 98. (d)
99. (c) 100. (c) 101. (c) 102. (b) 103. (b) 104. (d) 105. (d)
106. (a) 107. (a) 108. (b) 109. (d) 110. (a) 111. (d) 112. (d)
113. (d) 114. (a) 115. (c) 116. (c) 117. (c) 118. (a) 119. (d)
120. (b) 121. (a) 122. (d) 123. (a) 124. (d) 125. (d) 126. (b)
127. (a) 128. (b) 129. (a) 130. (c) 131. (b)

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 13
Group Theory
CSIR JUNE 2011

1. Given the character table of the point group C3V

E 2C3 3v
A1 1 1 1 Z
A2 1 1 -1
E 2 -1 0 (x,y)
Consider the reducible representation, Γ
E 2C3 3v
 6 3 0
Its irreducible components are
(a) E + 2A1 + 2A2 (b) 2E + A1 + A2 (c) 3A1 + 3A2 (d) 2E + 2A
2. Refer to the character table of the point group C3V given above. Find which of the following transition is
forbidden
(a) a1  a1 (b) a1  e (c) a2  e (d) a1  a2
3. The symmetry point group of ethane in its staggered conformation is
(a) C3V (b) D3d (c) D3h (d) S6
4. The character table of the C2v point group is given below:

C2V E C2 v v
A1 1 1 1 1
A2 1 1 -1 -1
B1 1 -1 1 -1
B2 1 -1 -1 1

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The two functions φ = p1 + 2p2 + 2p3 + p4 and φ = p1 - 2p2 - 2p3 + p4 (where pk is the p- orbital on the kth
atom of cis-butadiene and σv is the molecular plane) belong to
(a) A1 and A2 respectively (b) Both A2
(c) Both B2 (d) B1 and B2 respectively.
5. Among the following, the CORRECT statement is:
(a) The number of irreducible representations is equal to classes of symmetry operations.
(b) The number of irreducible representations is equal to the order of the symmetry point group.
(c) The irreducible representations contained in any point group are always of one dimension.
(d) A symmetry point group may not contain a totally symmetric irreducible representation.
6. A square pyramidal, MX4, molecule belongs to C4V point group. The symmetry operations are: E, 2C4,
C2, 2v and 2d. The trace for the reducible representation, when symmetry operations of C4v applied to
MX4, is:
(a) 5 1 1 1 3 (b) 1 1 1 1 1 (c) 5 1 1 1 1 (d) 4 1 1 1 3
7. Character table of C2V point group is:

If the initial and final states belong to A1 and B1 irreducible representation respectively, the allowed
electronic transition from A1 to B1 is:
(a) z-polarized (b) y-polarized (c) x-polarized (d) x, z-polarized
8. The molecular that has an S6 symmetry element is
(a) B2H6 (b) CH4 (c) PH5 (d) SF6
9. The number of IR active vibrational modes of pyridine is:

(a) 12 (b) 20 (c) 24 (d) 33

10. A molecules contains the following symmetry operations: E, 2C6, 2C3, C2, 3σd , 3σv. The number of classes
and order of the symmetry point group is:
(a) 3, 12 (b) 5, 12 (c) 6, 12 (d) 6, 6
11. Identify the Mulliken notation for the following irreducible representation

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
(a) A1u (b) A2u (c) B2u (d) A2u

12. Identify the point group symmetry of the following molecule (all C–C bond lengths are equal)

(a) C2v (b) S4 (c) D2d (d) D4d

13. The transition that is allowed by x-polarized light in trans-butadiene is (The character table for C2h is
given below)

(a) 1 Au  1Au (b) 1 A u  1Bg (c) 1 Bu  1Bg (d) 3 Bg  1Ag

14. The symmetry point group of propyne is

(a) C3 (b) C3v (c) D3 (d) D3d
15. Number of rotational symmetry axes for triclinic crystal system is
(a) 4 (b) 3 (c) 1 (d) 0
16. The low temperature (–98ºC) 19F NMR spectrum of SF4 shows doublet of triplets. It is consistent with the
point group symmetry.
(a) C3v (b) C4V (c) Td (d) C2V
17. The E × E direct product in D3 point group contains the irreducible representations

(a) A1 + A2 + E (b) 2A1 + E (c) 2A2 + E (d) 2A1 + 2A2

18. The result of the product C2(x)C2(y) is
(a) E (b) xy (c) C2(z) (d) i

CSIR DEC 2014

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3
19. The point group symmetries for trans-[Cr(en)2F2]+ and [TiCl6] , respectively, are
(a) D4d and D3d (b) D3d and D4d (c) D4h and D3h (d) D3h and D4h
20. The character table of C2v point group is given below. In cis-butadiene molecule the vibrational modes
belonging to A2 irreducible representation are IR inactive. The remaining IR active modes are
(a) 7A1 + 5B1 + 8B2 (b) 9A1 + 4B1 + 7B2 (c) 7A1 + 3B1 + 7B2 (d) 9A1 + 3B1 + 8B2

21. The product xy .Sz4 (Sz4 is the four fold improper axis of rotation around the z-axis, and xy is the reflection

in the xy plane) is

(a) Cz4 (b) Cz4 .i (c) C4y (d) Cz2

CSIR DEC 2015

22. The product C2x .xy ( C2x is the two-fold rotation axis around the x-axis and xy is the xy mirror plane) is

(a) xz (b) yz (c) C2y (d) Cz2

23. A molecular orbital of a diatomic molecule changes sign when it is rotated by 180º around the molecular
axis. This orbital is
(a)  (b)  (c)  (d) 
24. IR active normal modes of methane belong to the irreducible representation:

(a) E + A1 (b) E + A2 (c) T1 (d) T2

CSIR DEC 2011

25. The molecule diborane belongs to the symmetry point group
(a) C2v (b) C2h (c) D2d (d) D2h
26. The irreducible representations of C2h are Ag, Bg, Au and Bu . The Raman active modes of trans- 1, 3-
butadiene belong to the irreducible representations
(a) Ag and Bg (b) Ag and Au (c) Au and Bg (d) Bg and Bu
27. The symmetry point group of the most stable geometry of the following molecule Cl(H)C = C = C(H)Cl
is
(a) C2 (b) C1 (c) C2v (d) C2h
28. The point group obtained by adding symmetry operation h to the point group C4 is
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(a) S4 (b) C4h (c) D2h (d) D4
29. The character table for the D4 point group is provided below:

For this point group, the correct statement among the following is:
(a) it is possible to have a totally symmetric normal mode of vibration which is IR-active
(b) all IR-active normal modes are necessarily Raman inactive
(c) all Raman-active normal modes are necessarily IR-active
(d) it is possible to have a pair of IR-active normal modes that are degenerate.
30. The character table of C3v point group is provided below, along with an additional reducible
representation, Γ

Γ is given by
(a) A1 + A2 + E (b) 2A1 + 2E (c) 2A2 + 2E (d) 2A1 + 2A2 + E

CSIR DEC 2011

31. The molecule that possesses symmetry S4 element is
(a) ethylene (b) allene (c) benzene (d) 1,3-butadiene
32. For H2O molecule, the electronic transition from the ground state to an excited state of B1 symmetry is

(a) not allowed (b) allowed with 𝒙 polarization

(c) allowed with 𝒚 polarization (d) allowed with 𝒛 polarization
33. The pair of symmetry point groups that are associated with only polar molecules is
(a) C2v, DBh (b) C3v C2h (c) D2h, Td (d) C2v, CBv

CSIR DEC 2017

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34. The correct relation involving symmetry operations

(a) S24  S2 (b) (xz).(yz)  C2 (x)

(c) S34  C34 (d) S36  S2

35. For a point group, an incomplete character table is given below with one irreducible representation
missing

The Mulliken symbol and characters of the missing representation are

(a) A1 1  1 1 (b) B1  1 1  1 (c) A2 1 1  1 (d) B2 1  1 1

36. Given below is a specific vibrational mode of BCl3 with  and denoting movements of the respective
atoms above and below the plane of the molecule respectively. The irreducible representation of the
vibrational mode and its IR / Raman activity are

(a) A2 ; neither IR nor Raman active (b) E ; both IR and Raman active

(c) A1 ; Raman active (d) A2 ; IR active

37. The molecule with a C2 axis of symmetry among the following is

(a) BH2Cl (b) CH3Cl (c) NH2Cl (d) HOCl
38. A part of the character table of a point group (of order 4) is given below

The four characters of G4 are, respectively

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(a) 1, 1, –1, –1 (b) 2, 0, 0, 1 (c) 1, i, i, 1 (d) 1, –i, i, –1
39. N2O molecule belongs to the point group
(a) Dh (b) Ch (c) C 2v (d) S2

Table 1

40. The -orbital u of ethylene, when placed in the xy-plane with the C = C bond aligned to the x-axis,
transforms according to the irreducible representation (Use Table-1)
(a) au (b) b1u (c) b2u (d) b3u
41. The b1u  b2g transition in ethylene is (Use Table 1)

(a) not allowed (b) allowed by to x-polarized light

(c) allowed by y-polarized light (d) allowed by z-polarized light

CSIR JUNE 2019

42. The π-orbital p1 +p2  p3  p4 of cis-butadiene belongs to the irreducible representation

(a) A1 (b) A2 (c) B1 (d) B2

43. The number of times A1 representation appears in the representation Γ of the C2v point group given below
is

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

CSIR DEC 2019

44. A cube does not have the symmetry element

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(a) C2 (b) C3 (c) C4 (d) C6
45. The reducible representation Γ, in the table is equal to the following superposition of the irreducible
representation of C2v point group.
𝑪𝟐𝒗 𝑬 𝑪𝟐 𝝈𝒗 𝝈𝒗$
𝑨𝟏 1 1 1 1
𝑨𝟐 1 1 -1 -1
𝑩𝟏 1 -1 1 -1
𝑩𝟐 1 -1 -1 1
Γ 8 -2 -6 4

(a) A1 + 2A2 + 5B1 (b) A1 + 2A2 + 5B2 (c) 5A1 + A2 + 2B1 (d) A1 + 5A2 + 2B1

CSIR 2020
46. The following is the character table for the C2v point group

There are two functions f1 and f2 belonging to A2 and B1 representations, respectively. The correct
option for the product of two functions f1 abd f2 and the integral ∫ f1f2dt is
(a) The product belongs to A2 representation and the integral is non-zero
(b) The product belongs to B2 representation and the integral is zero
(c) The product belongs to A1 representation and the integral is zero
(d) The product belongs to B1 representation and the integral is non-zero
47. The observed IR spectrum of BCl3 exhibits three bands at 995, 480 and 244 cm-1, while the
Raman bands are observed at 995, 471 and 244 cm-1. Given that for BCl3 vib =A1 + 2E + A2,
the frequency of A1 mode in cm-1 is

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(a) 244 (b) 471 (c) 480 (d) 995
48. Given the matrices for C3 and h below

 1/ 2  3/ 2 0 1 0 0 
 
C3   3 / 2 1/ 2 0   h  0 1 0 
 0 0 1  0 0 1 
 

the trace of the matrix representing for S32 is

(a) 0 (b) 2 (c) 1 (d) 1

CSIR 2021

49. For every atom that is NOT shifted under C4 and  symmetry operations, the characters are respectively.
(a) -1,-1 (b) 0,0 (c) 1,1 (d) -1,1

50. The equivalent symmetry operations for S36 and S36 are, respectively

(a) C3 and C2 (b) h and I (c) h and E (d) i and E

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ANSWER KEY
GROUP THEORY
1. (a) 2. (d) 3. (b) 4. (c) 5. (a) 6. (a) 7. (c)
8. (d) 9. (c) 10. (c) 11. (b) 12. (c) 13. (b) 14. (b)
15. (d) 16. (d) 17. (a) 18. (c) 19. (a) 20. (d) 21. (a)
22. (a) 23. (b) 24. (d) 25. (d) 26. (a) 27. (a) 28. (b)
29. (d) 30. (b) 31. (b) 32. (b) 33. (d) 34. (d) 35. (c)
36. (d) 37. (a) 38. (a) 39. (b) 40. (b) 41. (d) 42 (b)
43. (b) 44. (d) 45. (b) 46. (b) 47. (b) 48. (a) 49. (c)
50. (d)

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Data Analysis
CSIR JUNE 2011

1. If y2 = 4x and 0.1% error is incurred for x, the percentage error involved in y will be
(a) 0.4 (b) 0.025 (c) 0.1 (d) 0.05

CSIR DEC 2011

2. In least square fitting of a data set {XiYi} to the equation Y = A.X, the regression coefficient
(A) is estimated by
(a) Yi2 / Xi2 (b) Xi Yi / Xi2 (c) Xi Yi / Yi2 (d) Xi2 / Yi2

CSIR JUNE 2012

3. The data obtained from two sets of experiments A and B have the following characteristics

Experiment A B
Mean 50 units 100 units
Standard deviation 2 units 2 units

It may be concluded that

(a) A is more precise than B
(b) A is less precise than B
(c) A and B are of the same precision
(d) Relative precision of A and B cannot be assessed
4. Two data sets involving the same variables X and Y are given below

X 4.1 4.2 4.3 4.4 4.5 4.6

Y(set A) 10.2 10.6 10.9 11.5 11.8 12.2
Y (set B) 10.2 10.6 11.1 11.3 11.8 12.2

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If the slopes and intercepts of the regression lines for the two sets are denoted by (m A, mB) and (CA,CB)
respectively are
(a) mA > mB, CA > CB (b) mA < mB, CA > CB
(c) mA > mB, CA < CB (d) mA < mB, CA < CB+

CSIR DEC 2012

5. The correlation coefficient between two arbitrary variables x and y is zero, if
(a) <xy> = <yx> (b) <x2> = <x>2 (c) <y2> = <y>2 (d) <xy> = <x> <y>

CSIR JUNE 2013

6. The correlation coefficient of two parameters is found to be –0.99. It may be concluded that
the two parameters are
(a) strongly correlated (b) almost uncorrelated
(c) connected by a cause-effect relationship (d) not connected by a cause-effect relationship
7. For two variables x and y, the following data set is given:
x y
-1 1
0 2
1 3
The correct statement for the covariance A and correlation coefficient B of x and y is
(a) A = 2/3, B = 1 (b) A = –2/3, B = 1
(c) A = –2/3, B = –1 (d) A = 0, B =0

CSIR DEC 2013

8. The masses recorded when a substance is weighed 4 times are 15.8, 15.4, 15.6 and 16.0 mg. The variance
(square of the standard deviation) is closest to
(a) 0.02 (b) 0.05 (c) 0.10 (d) 0.20

CSIR JUNE 2014

9. For a set of 10 observed data points, the mean is 8 and the variance is 0.04. The ‘standard deviation’ and
the ‘coefficient of variation’ of the data are, respectively
(a) 0.005, 0.1% (b) 0.02, 0.2% (c) 0.20, 2.5% (d) 0.32, 1.0%

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CSIR JUNE 2015

10. In a conductometric experiment for estimation of acid dissociation constant of acetic acid,
the following values were obtained in four sets of measurements. 1.71 × 10-5, 1.77 × 10-5, 1.79 × 10-5 and
1.73 × 10-5. The standard deviation of the data would be in the range of
(a) 0.01 × 10-5 – 0.019 × 10-5 (b) 0.02 × 10-5 – 0.029 × 10-5
(c) 0.03 × 10-5 – 0.039 × 10-5 (d) 0.04 × 10-5 – 0.049 × 10-5

CSIR JUNE 2016

11. In a titration, the percentage uncertainties in the measured aliquot volume and the measured
titre volume are ±x and ±y respectively. The percentage error in the calculated concentration of
aliquot is
(a) x + y (b) xy (c) xy1/2 (d) (x2 + y2)1/2

CSIR DEC 2016

12. Covariance is defined by the relation Cov (x, y) = <xy>  <x><y>. Given the arbitrary constants A, B
and C, Cov (x, y) will be zero if
(a) y = Ax2 (b) y = Ax2 + B (c) y = Ax + B (d) y = Ax2 + Bx + c

CSIR DEC 2017

13. Repeated measurement of Pb in a lake water sample gave 3.2, 5.2 and 7.2 ppb of Pb. Standard deviation
in the measurement of Pb is

(a) 2 ppb (b) 4 ppb (c) 0 ppb (d) 2 ppb

CSIR JUNE 2018

2
14. A Gaussian distribution has the functional form f (x)  e  (x  b)
2
/2a 2
. The variance of such distribution
2a 2 
is
(a) a (b) a2 (c) b (d) b2

CSIR JUNE 2019

15. A physical observable, ‘x’, appears with the probability distribution e |2x 12| the average of x would be
(a) 0 (b) 3 (c) 6 (d) 12

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QUANTA CHEMISTRY CLASSES | Data Analysis

ANSWER KEY
DATA ANALYSIS
1. (d) 2. (b) 3. (b) 4. (c) 5. (d) 6. (a) 7. (a)
8. (b) 9. (c) 10. (c) 11. (d) 12. (c) 13. (a) 14. (b)
15. (c)

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