TIFR Chemistry Questions 2010-18 PDF

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TIFR-2010
1. What is [H+] in 1.0 L solution that contains 0.2 M of NH4Cl?
(a) 1.1 × 10–5 M (b) 1.9 × 10–3 M
(c) 1.8 × 10–5 M (d) Not solvable with the information given
2. It is not easy to locate H atoms in the structure of proteins obtained by X-ray diffraction due to which of the
following reasons:
(a) H atoms are transparent to the X-rays (b) H-bonding interaction present in protein structures
(c) interaction of H with solvent molecules (d) Very low levels of scattering of X-rays by H
3. Glucose and galactose (found in the human body) are related to each other as :
(a) Enantiomers (b) Anomers (c) Epimers (d) L-sugars
4. ° °
Consider the formation of MgO(s). Assume that Hr and Sr are independent of temperature.
Mg(s) + 1/2 O2(g)  MgO(s)
Hr° = – 602 kJ/mol
Sr° = – 108 J/Kmol
Calculate Gr° for the formation of MgO(s) at 0°C and is the reaction spontaneous or non-spontaneous at
0°C?
(a) –573 kJ/mol, non-spontaneous (b) –573 kJ/mol, spontaneous
(c) 632 kJ/mol, non-spontaneous (d) –632 kJ/mol, spontaneous
5. Rank the following molecules in order of electrophillicity (from most to least electrophillic):
O O O O
CH3 CH3 CH3
Me N Me Cl Me S Me O
CH3
(i) (ii) (iii) (iv)
(a) ii > iii > iv > i (b) i > iv > iii > ii (c) ii > iv > iii > i (d) i > iii > iv > ii
6. Which of the following transitions is the highest energy transition in any given organic molecule?
(a) n to * (b) n to * (c)  to * (d)  to *
7. How many absorption lines will the following naturally occurring compound have in its proton-decoupled
13C NMR spectrum?
H3C
H
C C
H3C CH2CH3
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(a) 3 (b) 4 (c) 5 (d) 6
8. What would be the final major product of the following chemical reaction if it is carried out twice, once at
5°C and the second time at 45°C?
O
H3C CH + OH ?
(a) H2C CH at both the temperatures.

CH
OH O O
(b) H3C C CH2 CH at 5°C and H3C C CH CH at 45°C and

H H
O OH O
(c) H3C C CH CH at 5ºC and H3C C CH2 CH at 45ºC

H H
O OH O
O
(d) H3C C CH2 CH at 5ºC and H3C C C CH at 45ºC

H
H H
9. 0.1 M solution of a compound transmits 10% of the incident light. Another solution of the same compound
transmits 1% of the incident light of the same wavelength in the same container. Calculate concentration of
the solution.
(a) 0.02 M (b) 0.20 M (c) 0.21 M (d) 0.11 M
10. A polypeptide chain has six-SH groups. Any two SH groups can combine to give a disulphide (-S-S-) bond.
If such combinations are allowed to take place randomly, how many different protein structures can be formed?
(a) 12 (b) 15 (c) 30 (d) 36
11. Consider the following reaction carried out in presence of catalyst, C :
aA + bB  dD + eE
The rate law for this reaction is, rate = k[A]q[B]r[C]s
Which of the following statements is false ?
(a) The exponents q, r and s are often integers
(b) The overall reaction order is q + r + s.
(c) The exponents q and r are always equal to the coefficients a and b, respectively.
(d) The exponents must be determined experimentally.
12. The crystal lattice structure of sodium, vanadium and molybdenum is BCC (Body centered cubic). Which of
the following metallic mixtures are most likely to form a solid solution?
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(a) V and Mo (b) V and Na (c) Mo and Na (d) Na, V, Mo

13. FBCE is a rectangle. ABCD is a square in it with length of each side being of unit length. If AX has length of
x units then the length of FA is given by
A B
F
x
X
1
E D 1 C
x 1 2x 2
(a) 2(1  x) (b) (c) (d)
1 x 4x 2 (1  x)
14. At 1000°K for the following two equilibria, the representative Kp values are given :
(i) CaCO3  CaO + CO2 Kp = 4.0 × 10–2 atm
(ii) C + CO2  2 CO Kp = 2.0 atm
Solid Carbon (C), CaO, CaCO3 are mixed and allowed to attain equilibrium at 1000°K. What is the pressure
of CO achieved at equilibrium?
(a) 0.56 atm (b) 0.08 atm (c) 2.8 atm (d) 0.28 atm
15. Assume that a carnot engine is working in reverse in a refrigerator, with perfect thermodynamic efficiency.
Calculate the amount of work needed (i) to freeze 100 g of water at 0°C, the temperature of the surrounding
being 25°C; (ii) to withdraw the same amount of heat from a body at 10–5 K, the surrounding being at 1 K.
(Hmelt = 0.01 kJ/mol)
(a) (i) 601 kJ; (ii) 601 kJ (b) (i) 33.4 kJ; (ii) 33.4 kJ
(c) (i) 3.06 kJ; (ii) 33.4 kJ (d) (i) 3.06 kJ; (ii) 33.4 × 105 kJ
16. What is the empirical formula for the following unit cell:
Ti
(a) CaTi12O8 (b) CaTi8O12 (c) CaTiO3 (d) CaTi2O3

17. Which of the parallelogram in the figure below are viable unit cells?
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ii iii
(a) i (b) ii (c) iii (d) all of the above
18. The following reaction is at equilibrium in a cylinder fitted with a movable plunger.
N2O4(g)  NO2(g)
If the volume is decreased at constant temperature by moving the plunger, will the concentration of NO2(g)
be higher or lower than the original concentration when the equilibrium is reestablished?
(a) The concentration of NO2 will decrease, as Le Chatelier principle predicts that the equilibrium must
shift so as to oppose/minimize/relieve the total pressure.
(b) The concentration of NO2 will increase.
(c) The concentration of NO2 will decrease. If the volume is decreased, the equilibrium must shift to produce
fewer molecules. Thus the equilibrium must shift to produce fewer molecules. Thus the equilibrium must
shift to the left.
(d) The change in the concentration of NO2 is not certain. Le chatelier principle predicts that the equilibrium
must shift to the left to minimize the total pressure. However, the volume has decreased, so the number
of NO2 molecules must also decrease, making it difficult to say whether the concentration of NO2 would
decrease or increase.
19. To a green solution of Ni(H2O)62+, a small quantity of ammonia was added, which turned the solution blue
through formation of Ni(NH3)62+. The value of the equilibrium constant K for this reactions is ~109. To this
blue solution, the same number of moles of a chelating ligand ethylenediamine (en) were added, turning the
solution violet through formation of Ni(en)32+. The value of K for this reaction is also ~109. Using these
same quantities, what would happens if en was added first, then ammonia was added ?
(a) The violet solution would turn blue.
(b) The violet solution would stay violet.
(c) There will be an equimolar mixture of Ni(NH3)62+, giving the solution a colour which is an intermediate
between blue and violet.
(d) The question cannot be answered without knowing the concentrations and the volumes of all the reactants.
20. In a mass spectrum of bromine molecule shows three peaks due to the species Br2+ with the mass numbers
158, 160 and 162. Which isotopes of bromine occur in nature?
(a) 79Br and 80Br (b) 80Br and 81 Br (c) 79Br and 81Br (d) 79Br, 80Br and 81Br
21. Two 120-cm long test tubes are filled with mercury and then placed in a mercury reservoir in an inverted
position, as shown below. The height of the test tubes above the mercury pool is 100 cm. Syringes are used
to bring drops of H2O and ethanol to the top of columns of Hg, as shown below. Drops are added till a
small amount of water or alcohol is seen at the top of the Hg column. What will happen to the heights of the
Hg columns after the addition? The experiment is done at normal temperature and pressure.
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H 2O EtOH
H2O drops drops
100 cm
Syringe
Hg
(a) Both column heights will be the same (b) The column below H2O is shorter.
(c) The column below EtOH is shorter. (d) The column that has more number of drops will be shorter.
22. Scanning tunneling microscopy depends upon the flow of electricity (current) between a surface and an
atomically-sharp probe tip. Two plots of current vs. Tip-to-surface distance are shown below. Which one is
correct?
A
B
Current
Tip-to-surface distance
(a) A (b) B
(c) If the tip is more conducting than the surface, then the answer is A. Otherwise, the answer is B.
(d) Insufficient information is given to answer the question.
23. For each set of compounds below, choose the one in which the indicated hydrogen is farthest upfield in a
proton NMR spectrum :
NO2 OMe NMe2
H H H H
(A)
1 2 3 4
O O
(B) CH3OCH3 CH3OCH2OCH3 H3C

O O CH3
1 2 3 4
O O
(C) H2C CH2 H H O H

1 2 3
(a) A3 or A4, B4, C1 (b) A1, B2, C3 (c) A2, B3, C2 (d) A4, B1, C1
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24. Consider the following two infinite series:

n  2n 1 n  2n
n x n x
A=  ( 1)
(2n  1)! B=  ( 1)
(2n)! , where x is real
n 0 n 0
What is the value of A2 + B2 ?

(a) 0 (b) + (c) 1
(d) Its value cannot be defined, as the series A and B are divergent.
25. Four separate solutions are present in separate containers: HCl, NaOH, CH3COOH, and CH3COOK. What
possible pars can be used to make a buffer solution?
(a) HCl and CH3COOK (b) NaOH and CH3COOH
(c) CH3COOH and CH3COOK (d) All of the above
26. It is well known that the structure of ethylene (CH2 = CH2) is planar. Hence, what would be the structure of
allene (CH2=C=CH2) and cumulene (CH2=C=C=CH2)?
(a) Both will be planar
(b) Both will be staggered
(c) Allene will be planar, and cumulene will be staggered
(d) Allene will be staggered, and cumulene will be planar
27. In the Td molecule MX4, the A1 vibrational mode corresponds to all the M-X bonds stretching the same
distance simultaneously. With which spectroscopic technique is this vibrational mode observable?
M
X
X X
(a) IR (b) Raman (c) Neither (d) Both
28. An organic molecule A on photoexcitation goes to 1A*. Its various decay channels are shown below. you
measure the concentration of 3A* as a function of time using a fast-response spectrometer, in order to
determine the intersystem crossing rate constant kISC. Assume that the lifetime of 3A* is very long compared
to the other kinetic processes shown there. Which of the following statements would be true for this
experiment? 1 *
A
kISC
3
A*
hv
kFL
kNR
1
A
(a) The decay of 1A* will be multi-exponential

(b) The formation of 3A* will be single exponential.
(c) Plotting the concentration of [3A*] as a function of time, and fitting it to a single exponential will not give kISC.
(d) Both (b) and (c) above.
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29. Consider the four sulphates FeSO4, MnSO4, ZnSO4. Four separate capsules of these materials have been
made containing 0.1 mole of the substance and are suspended separately by a thread. Then a strong magnet
is brought close to each capsule. Order these sulphates according to the strength of the response that the
magnet will produce on these capsules.
(a) MnSO4 > FeSO4 > CoSO4 > ZnSO4 (b) FeSO4 > MnSO4 > CoSO4 > ZnSO4
(c) ZnSO4 > CoSO4 > FeSO4 > MnSO4 (d) CoSO4 > FeSO4 > MnSO4 > ZnSO4
30. N2O5(g) and NO(g) react to form NO2 according to the stoichiometric equation
N2O5(g) + NO(g)  3NO2(g) (R1)
at a given temperature and pressure. A possible mechanism for this overall reaction is:
k1
N 2O5   NO2  NO3 (M1)
k2
NO 2  NO3   N 2O 5 (M2)
k3
NO3  NO   2NO 2 (M3)
where NO3 is an unstable intermediate. What would be the rate expression of the disappearance of N2O5 in
terms of the concentrations of the stable species and the rate constants given above?
(a) The mechanism given above is not correct since the resultant of the reaction M1 + M2 + M3 is not the
original reaction R1.
d  k 2[NO 2 ] 
(b)  [N 2O5 ]  k1[N 2O5 ] 1  
dt  k 2[NO 2 ]  k 3[NO] 
d
(c)  [N 2O5 ]  k eff [N 2O5 ][NO], where keff is some function of k1, k2 and k3.
dt
d  k 2[NO 2 ] 
(d) dt [N 2O5 ]  k1[N 2O5 ] 1  k [NO ]  k [NO] 
 2 2 3 
31. For a cell constructed with a Cu(s) | Cu2+(aq) anode and Ag+ | Ag(s) cathode at 25.0°C, Calculate the cell
potential at 25.0°C under non-standard conditions: [CU2+] = 0.300 M and [Ag+] = 0.0500 M.
(a) 0.44 V (b) 0.41 V (c) 0.40 V (d) 0.34 V
32. Photo-exciation promotes an electron from the HOMO (highest occupied molecular orbital) to the LUMO
(lowest unoccupied molecular orbital) of a molecule. Between a molecule in its ground state and its excited
state, which would be the stronger oxidant and the stronger reductant?
(a) The molecule in its ground state would be a stronger oxidant and also a stronger reductant.
(b) The molecule in its excited state would be stronger oxidant and also a stronger reductant.
(c) The molecule in its ground would be a stronger oxidant, and in the excited state, a stronger reductant.
(d) The molecule in its ground state would be a stronger reductant, and in the excited state, a stronger oxidant.
33. The stretching frequency of the O–H is about 3600 cm–1. Compared to that, the stretching frequencies of
O–D and S–H bonds are very similar and appear at about 2500 cm–1. What can you conclude from these
data?
(a) The electronic structure of O–D and O–H are same, and that S–H is different.
(b) The force constant of the bonds O–D and O–H is same.
(c) S–H is a weaker bond than O–H or O–D bond.
(d) All of the above.
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34. Read the following two statements carefully:

1. The change in total angular momentum that occurs when a diatomic molecule (i.e. a rigid rotor) changes
rotational level from J = 2 to J = 3 is the same as the change in total angular momentum that occurs when
an electron on a H atom changes from a d to an f orbital, i.e. from l = 2 to l = 3.
2. The change in energy that occurs when a diatomic molecule (i.e. a rigid rotor) changes rotational level
from J = 2 to J = 3 is the same as the change in energy that occurs when an electron on a H atom
changes from a d to an f orbital, i.e. from l = 2 to l = 3.
Based on the above, which of the following is the correct statement:
(a) Both statements 1 and 2 are true (b) Both statements 1 and 2 are false
(c) Statement 1 is true, statement 2 is false (d) Statement 1 is false, and statement 2 is true
35. At room temperature, which of the molecules are expected to give five NMR lines in the proton-decoupled
13C NMR spectrum?
OCH3 OCH3
CH3 CH3
CH3
OCH3 H3C
(i) (ii) (iii) (iv) OCH (v) (vi)
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(a) Only 1 and 3 (b) Only 2 and 6 (c) Only 3 and 6 (d) All of the above
36. Do you expect that the minimum energy necessary to eject a 3s electron from phosphorus in a photoelectron
spectroscopy experiment for the process.
[Ne]3s23p3 [Ne] 3s13p3+ e–,
be larger than, smaller than, or the same as the 4th ionization energy (IE4) of phosphorus?
(a) Smaller (b) Larger
(b) The same (d) cannot be answered from the given information
37. 8
An average human DNA molecule has 5 × 10 base pairs, with four different kinds of bases. If the DNA
sequence was completely random, what would be the residual entropy associated with this typical DNA molecule?
(a) 9.57 × 10–15 JK–1 (b) 4.15 × 10–15 JK–1 (c) 6.90 × 10–15 JK–1 (d) 1.38 × 10–14 JK–1
38. Consider the two diatomic molecules CN and CN–, and the potential energy diagram shown below.
Energy
Inter nuclear
distance, (r)
Y
which of the following is the correct statement?
(a) Bond order of CN is 2.5 and the curve Y corresponds to CN.
(b) Bond order of CN is 3 and the curve X corresponds to CN.
(c) Bond order of CN– is 3 and the curve Y corresponds to CN–.
(d) Bond order of CN– is 2.5 and the curve X corresponds to CN–.
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39. Consider the following two matrices:
 7 0 0 1 0 3
   
A   0 1 i  and B   0 2i 0
 0 i 1  i 0 5i 
   
(a) 0
(b) The trace will be a real number, less than 0
(c) The trace will be a real number, greater than 0
(d) The trace will be a complex number
40. In valence-bond calculations, contributions of various resonance structures are used to calculate the total
energy of a molecule. Given below are four resonance structures of the cyanate ion. Which one contributes
least to the total energy.
 :
(a) : N  C  O (b) 2
:N  
  C  O  
(c)  N=C=O   :
(d) N—C—O
     
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TIFR-2011 (CHEMISTRY)
1. The following curve is obtained when a solution of glycine hydrochloride  HOOC – CH 2  NH 4  Cl  is
titrated with a strong base. What are the predominant species present at point 1 shown on the curve?
12
10
8 1
pH 6
4
2
0
0 0.5 1 1.5 2
–
OH (equivalents)
(a) H 3 N   CH 2  COO  and H 2 N  CH 2  COO 

(b) H 3 N   CH 2  COO 
(c) H 3 N   CH 2  COOH and H 3 N   CH 2  COO 
(d) H 2 N  CH 2  COO 
2. If the following probabilities were arranged in ascending order, which one would come third?
(a) The probability that a fair die will produce an even number
(b) A random digit from 1 to 9 (inclusive) is chosen, with all digits being equally probable. The probability that
its square will end in 1.
(c) The probability that a letter choosen randomly from the English alphabet (all letters being equallyprobable)
will be vowel.
(d) A random number between 1 and 20 (inclusive) is chosen. The probability that its square root will not be
an integer.
3. What is the major product if HBr (in excess) is added to H 2 C  CH  CH 2  OH

(a) CH3  CH  Br   CH 2  Br (b) H 2 C  CH  CH 2  Br
(c) CH3  CH  Br   CH 2  OH (d) CH3  CH  OH   CH 2  OH
4. Arrange the characteristic timescalses of the following set of dynamical spectroscopic techniques in decreasing
order of time (longest to shortest): NMR (Nuclear Magnetic Resonance), ESR (Electron Spin Resonance),
Fluorescence, Raman and Absorption.
(a) Absorption > NMR > Fluorescence > ESR > Raman
(b) NMR > ESR > Fluorescence > Raman > Absorption
(c) Fluorescence > Absorption > ESR > NMR > Raman
(d) All have similar characteristic timescales.
5. A segment of a protein under physiological conditions has a tendency to bury itself in the biological cell membrance.
Which of the following is this segment more likely to be?
(a) Valine rich (b) Lysine rich (c) Glutamatic rich (d) Alanine rich
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6. Light of wavelength 500 nm is transmitted through a 10–4 M dye solution which is contained in a glass cuvette
of path length 1 cm. The extinction coefficient of the dye at 500 nm is 3010 M–1 cm–1. Due to reflection, 4% of
light is reflected in the front face of the cuvette (at the air/glass interface) and 4% at the back face before exiting
the cuvette (at the glass/air interface). The percentage of the intensity of light transmitted through the dye and
cuvette is
(a) 42.6% (b) 27.74% (c) 30.1% (d) 46.08%
7. A 19th century iron bridge is protected from corrosion by connecting it to a block of metal (sacritificial anode),
which is replaced annually. The corrosion of iron, represented by the chemical equation:
2Fe  s   2H 2O     O2  g  
 2Fe  OH  2
Which of the following metals is best suited as sacrificial anode?
(a) Ag : Ag   e  
 Ag  s  , E 0  0.80 V
(b) Cd : Cd 2  2e 
 Cd  s  , E 0  0.40 V
(c) Cu : Cu 2   2e  
 Cu  s  , E 0  0.34V
(d) Mg : Mg 2  2e 
 Mg  s  , E 0  2.36V
8. An atom diffuses in one dimension on a x-axis. At t = 0, its position is x = x0. After a sufficiently long time, the
probability of finding the atom is maximum at:
(a) x = plus infinity or minus infinity (b) x = 0
(c) x = x0 (d) Indeterminate
9. Proton tunneling process has been implicated to be important part of many enzyme reaction mechanisms like in
Aromatic Amine Dehydrogenase (AADH) which does oxidative deamination of substrates to aldehydes via a
protein derived Asparate residue (shown below)
Classical
Potential Energy
h
2a
Reaction Coordinate
Picture reproduced from Masgrau et al. Science (2006)
Typically in such a reaction, the probaility of a tunneling event should depend on:
(a) Only the height (h) of the barrier
(b) Only the width (2a) of the barrier
(c) Both height (h) and width (2a) of the barrier
(d) None of the above.
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10. Structure of 1, 2-dimethylcyclohexane is show below. Which of the following is an enantiomer to the given
conformer?
CH3
?
CH3
Mirror
CH3 CH3
(a) H C (b) CH3
3
CH3
(c) H3C (d)
CH3
CH3
11. The pressure of a gas inside a spherical container is maintained at 2 atm. If the average velocity of the gas
molecules inside the container is increased by a factor of two, keeping the pressure the same, by how much
would the surface area of the container increase?
(a) 22/3 (b) 24/3 (c) 2–1/3 (d) 1
12. A molecule normally absorbs in the green wavelength (ca. 500 nm). At some temperature, it is measured that
for every 10 molecules in the excited state, there are about 27 molecules in the ground state. What is the
approximate temperature of the molecules?
(a) 270K (b) 1000K (c) 500K (d) 30000K
13. The half-life for a chemical reaction: A  B is 2.3 sec. When a single molecule of A is observed during its
conversion to B, what is the predicted time for this conversion to occur?
(a) e–2.3 (b) 4.6 sec (c) log 2.3 sec (d) undefined.
14. The molar absorption coefficient of a compound in water at 532 nm is 2200 L mol–1cm–1. When light at that
wavelength passes through an aqueous solution of this compound (kept in a 5 cm long cell), 50% of the light
was absorbed. What is the concentration of the solution?
(a) 2.7×10–5 M (b) 4.5×10–5 M (c) 1.1 M (d) Insufficient data.
15. A semi-permeable membrane, that is permeable only to cations, separates two compartments A and B. A
solution of a monovalent electrolyte (of the type X+Y–) is contained in both the compartments. The concentrations
are 0.1 M and 0.01 M in A and B respectively. When the voltage across the two compartments are measure,
we find:
(a) No potential difference across the two solutions
(b) Compartment B shows + 59mV with respect to A
(c) Compartment A shows +10mV with respect to B
(d) Compartment B shows-110 mV with respect to A
16. In an NMR experiment, the relative population difference  N/N  for 13C nuclei in the magnetic fields of (a)
0.5 T, (b) 2.5 T and (c) 15.0T at a temperature of 298K are in the ratio:
(a) 1 : 5 : 30 (b) e–1 : e–5 : e–30
–0.5/298 –2.5/298 –15/298
(c) e :e :e (d) 30 : 5 : 1
17. A polymer chain has 500 segments. The length of each segment is 1.2 nm. If the polymer chain is totally flexible
when dissolved in water, what would be the root mean square separation of the ends of the chain?
(a) 600 nm (b) 417 nm (c) 27 nm (d) 300 nm
4
18. An electronic state of a hydrogen atom is prepared to be a superposition energy of the eigenstates of the
hydrogen atom, and for which the normalized wavefunction is written as
1 1
 1s  2s  C3s 3s
2 4
here 1s , 2s and 3s are the exact eigenstates of the hydrogen atom, and C3s is a constant. What would be
the average value of energy, associated with this wavefunction  , in a.u.?
(a) –0.2951 a.u. (b) –0.4161 a.u. (c) –0.2269 a.u. (d) –0.3929 a.u.
19. For the reaction given below, activation energy is 271 kJ/mol. What is the value of k at 250ºC? Note that
A(frequency factor) = 1×1015 sec–1.
H H
H H (g) kr
H2C CH CH3 (g)
H H
11 1
(a) 8.568 10 12 s 1 (b) 8.568  10 s
(c) 5.141 1011 min 1 (d) 5.141 10 12 min 1
20. In a polyatomic molecule the radiative lifetime of an allowed electronic transition is typically in the range of a
few tens of nanoseconds. What will be the lifetimes of the allowed vibrationally excited states of the same
molecule?
(a) nanoseconds (b) picoseconds (c) femtoseconds (d) milliseconds
21. Vapour pressure of Cs(liq) contained in a cell of 1 litre volume is 80 Torr. IF the Cs atoms are excited to an
electronically excited state with a lifetime of 192 ns, how many collisions would the excited atoms suffer before
they deactive radiatively?
(a) ~100 (b) ~200 (c) 2.83×1018 (d) 5.48×108
22. Arrange the pKas of the hydroxy groups of methanol, trifluoroacetic acid, phenol and benzyl alcohol in ascending
order:
(a) Trifluoroacetic acid < phenol < benzyl alcohol < methanol
(b) Trifluoroacetic acid < benzyl alcohol < pehnol < methanol
(c) Phenol < trifluoroacetic acid < benzyl alcohol < methanol
(d) Trifluoroacetic acid < methanol < phenol < benzyl alcohol
23. Heme is a versatile molecule present in a large number of metalloproteins and enzymes. The absorption spectrum
of heme is characterized by sharp band at near 400 nm and weaker bands at 520–550 nm. The origin of these
absorption bands are
(a) MLCT transitions (b) LMCT transitions
(c) d-d transitions (d) pi-pi* transitions
24. The proton NMR spectrum of a saturated hydrocarbon shows a single absorption line at 1.42 ppm with
respect to TMS at room temperature. The area of the line is equivalent to 12 protons. Solely based on this
observation, what are the tentative inferences you can draw about the nature of the hydrocarbon?
(a) It is a pure compound i.e., there are no impurities present.
(b) More than one conformation of the molecules may be present and they are undergoing rapid interconversion.
(c) The hydrocarbon is cyclohexane.
5
25. Below is a diagram by Maurits Cornelis Escher (198-1972), A Dutch graphic artist. What elements of symmetry
are present in this Escher diagram generated by tessellation of fish images?
(a) no symmetry
(b) 2 fold rotation axis perpendicular to plane of paper
(c) mirror plane and 2-fold rotation axis perpendicular to plane of paper
(d) mirror plane
26. Imagine the world famous Koh-i-Noor diamond (mass 21.6g) is completely burnt in the presence of oxygen,
the amount of which is carefully controlled. After the completion of the burning process, the mass of the
gaseous product is measured. What would you expect the amount of this gas to be?
(a) Less than 50 g
(b) More than 50g but less than 80g
(c) More than 80g
(d) Diamond will not decompose under the given conditions.
27. IrCl(CO)[P(C6 H5 )3]2 (trans-chlorocarbonylbis(triphosphine)iridium(I)) also known as Vaska’s complex
can undergo oxidative addition with dihydrogen. Which of the following structures is a correct depicition
of the geometry and oxidation state of the ensuing product?
H H H H
(a) (C6H5)3P Ir P(C6H5)3 (b) (C6H5)3P Ir P(C6H5)3
CO Cl CO Cl
Ir(I) Ir(III)
H H Cl
Cl
(c) (C6H5)3P Ir P(C6H5)3 (d) (C6H5)3P Ir P(C6H5)3
CO H CO H
Ir(I) Ir(III)
6
28. ‘Click’ reactions can be used to join two molecular units with minimal side products, high chemical yield
and stereospecifiy. One such reaction is a thiol-yne reaction which is used in polymerization especially for
dendrimer synthesis. Predict the final product of the following thiol-yne reaction between L-cysteine and
1-butyne.
OH
H
sunlight
+ 2O SH
NH2
OH
H
O S
NH2
OH
H
S
(a) H (b) O S
HO NH2
NH2
O
OH
H
O S
NH2
OH
H
S
(c) H (d) O S
HO NH2
NH2
O
29. Two compartments X and Y are separated by an impermeable partition P. In the compartment X, the
following reaction is going on: A 2  B2  2AB in a solvent S, while compartment Y contains only the
solvent S. Contents of both the compartments are continuosly and vigorously stirred. After the reaction in
the compartment X has reached equilibrium, the concentrations of A2, B2 and AB are measured and the
equilibrium constant calculated. Then the partition is equickly removed. After waiting for a very long time,
all the concentrations are measured again, and the new value of the equilibrium calculated. What is the
most appropriate statement you can make about the result of this experiment? Assume that the chemicals
are behaving ideally and the temperature is kept constant.
X Y
P
(a) The concentrations of all the chemicals and the equilibrium constants will be less than their values
before the partition was removed.
(b) After removing the partition, the concentrations of A2, B2 will increase and that of AB will decrease,
leading to a lower value of the equilibrium constant.
(c) After removing the partition, the concentrations of A2, B2 will decrease and that of AB will increase,
leading to a higher value of the equilibrium constant.
(d) After removing the partition, the concentrations of all the chemicals will decrease, but value of the
equilibrium constant will not change.
7
30. What is the value of this continued fraction?

1 1

2 1 1

2 1 1
2 1 1

2 1  .....
2
(a) 1/2 (b) 1 (c) 2 (d) 
31. A rectangle with size given below is cut as shown. The two pieces are combined together to form a
square. Determine the perimeter of the square.
12m
27m
(a) 60 m (b) 48 m (c) 72 m (d) 78 m
32. The reaction of nitric oxide with ozone takes place according to the following stoichemistry:
NO  O 3   NO 2  O 2
The observed rate law for the reaction is found to be
d  NO 
    NO3  NO     NO 2 
dt
where  and  are constants. To explain the above rate law, the following reaction scheme has been
proposed.
k1
NO  O 3   NO 2  O 2
k2
NO 2  O3   NO3  O 2
k3
NO  NO3   2NO 2
Determine an expression for 
(a) a unique expression of  cannot be determined from the given information.
(b) k2 /k1
(c) k3 /k2
(d) k1 /k3
3
33. Given cos   ,     , find cos   /2 
2
1  1  2 1  1  2
(a)  (b)  (c) (d)
2 2 2 2
8
34. A student has measured the standard free energy change of a certain chemical reaction as a function of
temperature. The data and a linear fit to them are shown below. From this diagram, determine approximately
the standard entropy of the reaction. (Assume that the standard entropy of the reaction is independent of
temperature.)
–25
G/(kJ/mol)
–26
–27
280 290 300 310

Temperature/k
(a) +50J.mol–1.K–1 (b) +75J.mol–1.K–1
(c) +100 J.mol–1.K–1 (d) –100 J.mol–1.K–1
35. Consider the following electrochemical cell, from which current is drawn through an external resistor of
10 Ohms. During this process, the concentration of CuSO4 in the left and the right half-cells were measured,
and the value of K   CuSO 4 left /  CuSO 4 right was calculated. From the initial value of K  10 , predict
the value of K after a very long time when the cell stopped giving any current.
Cu | CuSO4(aq, 10M) || CuSO4(aq, 1M) | Cu
10
(a) An exact value cannot be predicted since CuSO4 solutions of such high concentrations, as used
above, would not behave ideally.
(b) K  0.1
(c) K = 1.0
(d) K will be very small, possibly < 0.00001.
36. Which of the following reaction sequence is the correct one for synthesis of t-butyl alcohol?
CH3
H3C C OH
CH3
O
Et2O H3O+
(a) CH3CH2MgBr + H2C CH2
CO2 H3O+
(b) CH3CH2MgBr
Et2O
O
Et2O H3O+
(c) CH3MgBr + H3C C CH3
O
Et2O H3O+
(d) CH3CH2MgBr + H3C C CH3
9
37. The 13 C NMR spectrum of a compound shows 6 peaks and the 1 H NMR spectrum shows 5 peaks.
Which of the following is this compound?
(a) CH3  CH  CH3   CH  CH3   CH  CH3   CH3
(b) CH3  C  CH3  2  CH 2  CH 2  CH3
(c) CH3  CH  CH3   CH 2  CH 2  C  CH3 2  CH 3
(d) CH3  CH  CH3   CH 2  CH 2  CH3
38. It is known that pKa of water is 15.7. Based on this water pKa benchmark, arrange the following solvated
metal-aqua ions in order of their increasing acidity:
2
Mn  H 2O 6 , Fe3  H 2 O 6 , Cu 2  H 2O 6 , and Ca 2  H 2O 8
(a) All have same acidities. (b) Fe 3  Cu 2   Mn 2   Ca 2
(c) Ca 2   Cu 2   Mn 2   Fe 3 (d) Ca 2   Mn 2  Cu 2   Fe 3
39. The n×n matrix P is idempotent if P2 = P and orthogonal if PTP = I. Which of the following is false?
(a) If P and Q are idempotent n×n matrices and PQ = QP = O, then P + Q is idempotent.
(c) If P is idempotent, then –P is idempotent.
 
(d) P   1 / 2  3 / 2  is orthogonal.
 3/2 1/ 2 

40. Which of the following statements is true for liquid crystals:
(a) These are self-assembled structures of amphiphillic molecules, solely formed upon heating the
amphiphillic solid above its melting point.
(b) These are solid crystals of ionic solids which have been exposed to temperaures above their melting
point.
(c) These are a mixture of liquid and solid phase of the same compound
(d) These are a state of matter having properties between that of a conventional liquid and a crystalline
solid.
1
1. A quantum mechanical state Q is a superposition of two normalized enregy eigenstates A and B in an amplitude
ratio 2:1. If the two states are degenerate with a common eigenvalue E, what is the energy of the state Q?
(a) 0 (b) 3E (c) 5E (d) E
2. For the above, if the states were non-degenerate and with energy eigenvalues E and –E respectively, then what
would be the expectation value of the energy?
(a) 3E (b) 5E (c) E (d) None of the above.
3. Suppose we inscribe a circle inside an equilateral triangle, and then inscribe a square inside this circle. What is
the ratio of the side of the square to the side of the triangle?
(a) 1: 3 (b) 2 : 5 (c) 1: 6 (d) 1 : 2
4. The reversible reaction S   P is catalyzed by a catalyst. The equilibrium constant Keq = [P]/[S] is 2×103.
The forward rate constant was found to be 5×104 sec–1 and 4×10–6 sec–1 in the presence and in the absence of
the catalyst respectively. What is the expected rate constant for the reverse reaction in the absence of the
catalyst?
(a) 5×108 sec–1 (b) 2×10–9 sec–1 (c) 0.8×10–10 sec–1 (d) 5×10–9 sec–1
5. The molar extinction coefficient (at 550 nm) of compounds A and B are 1×104 M–1 cm–1 and 1×105 M–1 cm 1
respectively. Solutions of A and B are made at concentrations of 1×10–4 M and 2×10–5 M respectively. In a
spectrophotometer set at 550 nm, the percentage of light transmitted by solution A and B (in two separate
experiments) will be
(a) The same
(b) B will transmit 10 times less light compared to A
(c) B will transmit 5 times less light compared to A
(d) B will transmit 2 times light compared to A
6. What are the configurations (R or S) of the chiral centers in the following molecules.
H OH
NH2
HOOC NH2
SH H OH
(1) (2) (3)
(a) Compound 1 = R; Compound 2 = R; Compound 3 = 1S, 2S
(b) Compound 1 = R; Compound 2 = S; Compound 3 = 1R, 2S
(c) Compound 1 = S; Compound 2 = S; Compound 3 = 1S, 2R
(d) Compound 1 = R; Compound 2 = S; Compound 3 = 1S, 2R
7. What are the oxidation states of the metal ion in the following compounds
(1) PdCl2 (2) Pd(PPh3)4 (3) Pd(OAc)2 (4) ArPdBr where Ar is Aryl
(a) 2, 4, 2, 2 (b) 2, 0, 2, 1 (c) 2, 0, 2, 2 (d) 0, 0, 0, 2
2
8. Methanesulfonyl chloride is used commonly to form methanesulfonates upon reaction with alcohols.
Methanesulfonates are good leaving groups in nucleophilic substitution reaction. In the following reaction calculate
the volumes of methanesulfonyl chloride and triethylamine required in µL. The amount of starting material and
the number of equivalents of each reagent is given.
O S O O S O
HO OH O O
N O N
Ethyl Acetate
+ S Cl + N
O
solid solid
Amount (mg) 100

equivalents 1 2 3
Density (g/mL) 1.48 0.73
µL D E
(a) D = 126, E = 167 (b) D = 0.085, E = 0.229

(c) D = 85, E = 229 (d) D = 1.1, E = 1.65
9. The vibrational Raman effect, a considerably weak scattering phenomena, was first reported by Late Sir CV
Raman in 1928. The intensity of the individual vibrational resonances observed in a Raman spectrum is proportional
to
(a) Number of molecules (b) Polarizibility of the bond
(c) Wavelength of radiation used (d) All of the above.
10. The Wittig reaction is a reaction with an aldehyde or ketone with a phosphonium yield. Predict the product of
the following reaction.
O
PPh3 +
H
(a) (b)
(c) (d)
11. The standard redox potential of water oxidation to dioxygen is –1.23 V.

2H 2 O   O 2  4H   4e 
3
The redox potential of the same reaction at pH = 7 would be

(a) –0.41 V (b) –1V (c) –0.82 V (d) –1.64 V
12. Amino acid side-chains in proteins have hydrogen bonds for structural and catalytic reasons. One such
combination of H-bonding partners is Histidine associated with a partnering residue such as Tyrosine (X–H ...
N–His, where X is the partnering amino acid). If the pKa of Histidine is 6.1, estimate the pKa of the partnering
residue (X–H) such that protonation of His at pH 6.5 is a favorable process
(a) pKa > 10 (b) pKa < 1 (c) pKa < 6 (d) pKa > 6.5
13. The total energy expended to charge (total charge = +q) a sphere of radius ‘r’ in a dielectric medium    is
given by (in SI units)
(a) q 2 /4r (b) q 2 /16r (c) q 2 /4r 2 (d) q 2 /8r
14. A substance A is consumed by a reaction of unknown order. The initial concentration is 1mM, and concentrations
at later times are as shown
Time  min   A   mM 
1 0.83
2 0.72
4 0.56
8 0.38
16 0.24
What is the order of the reaction?
(a) Zero (b) First-order (c) Second-order (d) Pseudo-first order
15. G 0 values for the hydrolysis of glucose-1-phosphate and glucose-6-phosphate are –21 kJ/mol and –14 kJ/
mol, respectively. What is the equilibrium constant for the following equilibrium at 25ºC?

 Glu cos e  6  phosphate
Glucose-1-phosphate 

(a) 0.06 (b) 16.9 (c) 4798 (d) 284
16. In a double stranded DNA, if the sequence 5’AGATCC3’ appears on one strand of DNA, what sequence in
the complementary strand?
(a) 5’ AGATCC3’ (b) 5’ CCTAGA3’ (c) 5’ GGATCT3’ (d) 5’ TCTAGG3’
17. One sequence of amino acids repeats for long distances in silk protein. Complete hydrolysis of one mole of a
fragment with this sequence gives 2 mol alanine, 3 mol glycine, and 1 mol serine. Partial hydrolysi yields Ala-
Gly-Ala, Gly-Ala-Gly, Gly-Ser-Gly, and Ser-Gly-Ala peptides. What is the amino acid repeat?
(a) Gly-Gly-Ser-Ala-Gly-Ala (b) Gly-Gly-Gly-Ala-Ala-Ser
(c) Ser-Ala-Ala-Gly-Gly-Gly (d) Gly-Ser-Gly-Ala-Gly-Ala
18. Which of the following compounds would give the 1 H NMR spectrum shown below
(a) CH3CH  CH3  CH 2 X (b) CH3C  CH3 2 CH 2 CH 2X
4
(c) CH3CH 2  CH3  CH 2 X (d) CH3CH 2CH  CH 3  X
19. Which of the following compounds will react with R-SH in aqueous solutions between pH 6.5 and 8.5?
O O
O O
R N R C O N R C
RS S N
O O
R1 R2 R3 R4
(a) R1, R2 and R3 (b) R2, R3 and R4 (c) R4, R2 and R1 (d) R1, R3 and R4
20. In a spherical polar coordinate system, a point A at (x, y, z) in the Cartesian coordinate system can be de-
scribed by  r, ,   where r,  and  have their usual meaning. Expression for the volume of an infinitesimally
small cube confined by dx, dy and dz in terms of the spherical coordinate system is given by
(a) drdd (b) r sin drdd (c) r 2 sin 2 drdd (d) r 2 sin drdd
21. Rotational energy of a diatomic molecule is given by E rot  J  J  1 hBe , where E rot is in Joules. If the rota-
tional constant for H2 molecules is given as
Be  1.8324  1012 Hz , the rotational period of the H2 molecule in J = 10 level will be
19
(a) 1.33  10 sec (b) 5.0  1015 sec
7
(c) 5.46  1013 sec (d) 7.39 10 sec
22. Tyrosine, at pH 12, has the following structure
COO COO
(a) HO CH2 CH (b) O CH2 CH

NH3 NH2
COO COO
(c) HO CH2 CH (d) O CH2 CH

NH2 NH3
23. Quartz crystal watches lose or gain about a second a week. What is accuracy of these watches in ppm?
(a) 1 (b) 1000 (c) 0.605 (d) 1.653
24. The reaction of sodium ethoxide with ethyliodide to form diethyl ether is termed
(a) electrophilic substitution (b) nucleophilic substitution
(c) electrophilic addition (d) radical substitution
25. Of the following metal ions, which has the largest magnetic moment in its low-spin octahedral complexes?
(a) Fe3+ (b) Co3+ (c) Co2+ (d) Cr2+
26. In a certain axis of quantization, the z-component of the spin angular momentum, Sz, has the following matrix
representation.
5
1 0 0 
Sz   0 0 0 
0 0 1
What would be the trace of the matrix of S x 2 (square of the x-component) in the same representation?
(a) 0  2 (b) 1 2 (c) 2 2 (d) None of the above.
27. X-rays of CuK  (wavelength 154 pm) are diffracted by a set of atomic planes in a crystal in the following
manner. The separation of the layers in the crystal is 404 pm. Find the angle  along which the first-order
reflection will occur.
(a) 79º (b) 45º (c) 11º (d) None of the above.
28. How many molecules of cetanol (of cross-sectional area 2.58×10–19 m2) can be adsorbed on the surface of
a spherical drop of dodecane of radius 7.8 nm?
(a) 3.90×103 (b) 1.54×104 (c) 1.54×102 (d) 6.5×10–5.
29. The velocity of Li+ ion in water is 2×10–2 cm/sec when 100V is applied between two electrodes separated by
2 cm. The mobility of Li+ ion in water is,
(a) 4 104 cm 2s 1V 1 (b) 1 10 4 s 1V 1
(c) 4V cm 2s 1 (d) 2.5  105 V s cm 2
30. The melting point of lithium metal is 454K, and that of sodium is 371K. Which of the following statements can
explain this difference in their melting points?
(I) Metallic bonding in lithium is stronger than metallic bonding in sodium.
(II) The delocalised electrons are more strongly attracted to the metal cation of lithium.
(III) The lithium cations have a greater charge density than sodium cation.
(IV) Li+ cations are smaller than Na+ cations.
(a) Only I and II (b) Only II and III (c) Only IV (d) I, II, III, IV
31. What is the final product after the following reaction has gone to completion?
Benzene  liquid   Chlorine  gas  
Sunlight
?
?
(a) Benzene (b) Benzenehexachloride
(c) Chlorobenzene (d) Dichlorobenzene
32. The transition probability for spontaneous emission from state ‘m’ to state ‘n’ is given by an expression.
 644 Vmn3
 ˆn 
2
A m n   3  .  m d 
 3hc   
where, Vmn is the frequency of transition, and the term in the parenthesis is the transition dipole. Assuming that
the magnitude of the transition dipole is same for all types of transitions, arrange the average lifetimes for the
electronic, vibrational, and rotational transitions in the proper order.
(a) electronic < vibrational < rotational (b) vibrational < rotational < electronic
(c) rotational < vibrational < electronc (d) electronic < rotational = vibrational
6
33. At 20ºC, the standard EMF of a certain cell is +0.2699V, and at 30ºC it is +0.2669V. What can you say about
the standard entropy of this reaction? Assume that the standard H 0 and S0 are independent of tempera-
ture.
(a) S0  0 (b) S0   ve (c) S0   ve (d) Not enough information is given
34. Which of the following most closely resembles the 13 C NMR spectrum of ethanol? Assume a scalar coupling
of 150Hz among the 1 H and the 13 C nuclei within a functional group, a scalar coupling of 50 Hz between the
13
C nuclei, a static magnetic field of 11.7 T and a temperature of 300 K.
(a) (b)
(c) (d)
35. The roots of the equation x 3  ax 2  bx  c  0 are three consecutive integers. What is the maximum value of
b?
(a) –2 (b) 0 (c) 1 (d) 2
36. The corrosion of iron in contact with an acidic aqueous solution undergoes the following reaction
Fe  s   2H   aq   Fe2   aq   H 2  g  (1)
in the anaerobic condition, and the following reaction
2Fe  s   O 2  aq   4H   aq   Fe 2  aq   2H 2O    (2)
in the aerobic condition. During the corrosion, Fe (II) ions are formed in both conditions. If the water is
polluted with Cr(IV), the following reaction may take place.
7H  aq  3Fe2  aq  HCrO4  aq 3Fe3  aq  Cr3  aq  4H2O I (3)
Reaction (3) be broken down to the following redox half-reactions:
3Fe3  3e  3Fe2   aq  E 0  0.77 V (4)
7H   aq   HCrO4  aq   3e  Cr 3  aq   4H 2O    E 0  1.38V (5)
The standard potentials of these reactions are with respect to the normal hydrogen electrode. What would be
the approximate value of the equilibrium constant of reaction 3 at 298K ?
(a) 1011 (b) 1031 (c) 1031 (d) 1011
37. Consider a container of volume 5.0 L that is divided into two compartments of equal size. In the left
compartment there is nitrogen at 1.0 atm and 25ºC; in the right compartment there is hydrogen at the same
temperature and pressure. What will happen when the partition is removed?
(a) The entropy increases, and the free energy decreases.
(b) The entropy decreases, and the free energy decreases.
(c) The entropy increases, and the free energy increases.
(d) The entropy decreases, and the free energy increases.
38. Each of the following flasks contains 25ml of 1M HCl solution in water. To them a certain amount of sodium
bicarbonate is added and, as shown the picture, then the mouths of the flasks are quickly closed by rubber
7
balloons of identical size. The masses of NaHCO3 added to the flask 1 through the flask 5 are 0.70 g, 1.00g,
2.10 g, 4.20 g and 6.30 g, respectively. After waiting for a sufficiently long time, predict the relative size of the
5 balloons.
(a) The Size of Balloon 1 = Balloon 2 = Balloon 3 = Balloon 4 = Balloon 5.

(b) The Size of Balloon 1 < Balloon 2 < Balloon 3 < Balloon 4 < Balloon 5.
(c) The Size of Balloon 1 < Balloon 2 < Balloon 3 = Balloon 4 = Balloon 5.
(d) The Size of Balloon 1 < Balloon 2 < Balloon 3 < Balloon 4 = Balloon 5.
39. The degeneracy of the energy level 12h 2 / 8ma 2 of a particle in a three dimensional cube of length “a” is
(a) 1 (b) 3 (c) 6 (d) 12
40. Compound A is more soluble in solvent X when compared to solvent Y. X and Y are immiscible. The partitition
coefficient of A between the two solvents is 10. 10 mL of a 2×10–5M solution of A in solvent Y is mixed
vigorously with 100 mL of solvent X and the two phases are allowed to separate out. The concentration of A
in phase Y after the separation would be
(a) 2  10 9 M (b) 1.98 107 M (c) 2  10 6 M (d) 1.8 10 7 M
1
1. Which of the following will be strongest acid in pure liquid HF :
(a) H2O (b) SbF5 (c) CH3COOH (d) NaF
2. Which of the following experimental observations best demonstrate the wave like character of electrons?
(a) the photoelectric effect
(b) The flow of electrons in a metal wire
(c) The diffraction pattern of electrons scattered from a crystalline solid
(d) The deflection of an electron beam by electrical plates
3. What terms can arise from the configuration 2p1 3p1?
(a) 3D, 1D, 3P, 1P, 3S, 1S (b) 3D, 3P, 3S
(c) 1D, 1P, 1S (d) 1D, 3P, 3S
4. What is the degeneracy of the energy level with n = 6 (n being the principal quantum number) in a hydrogenic
atom or ion?
(a) 16 (b) 9 (c) 36 (d) 25
5. Compare the equilibrium bond lengths of AB-type of diatomic molecules N2 , NO, O2 , Cl2 and CN
with their cations (AB+) and anions (AB– ). Which of the following statements is correct in general?
(a) The equilibrium bond lengths of all AB + species will be shorter, and that of all AB– species will be
longer than that of the corresponding AB species.
(b) The equilibrium bond lengths of all AB– species will be shorter, and that of all AB+ species will be
longer than that of the corresponding AB species.
(c) The equilibrium bond lengths of O2+, Cl2+ and CN– ions will be shorter than the corresponding neutral
species. The equilibrium bond lengths of N2+, NO+ and Cl2– ions will be longer than the corresponding
neutral species.
(d) The equilibrium bond lengths of O2+, Cl2+ and CN– ions will be longer than the corresponding neutral
species. The equilibrium bond lengths of N2 + , NO+ and Cl2 – ions will be shorter than the
corresponding neutral species.
6. The method of initial rates is used to determine the rate law for the reaction given below.
2NO(g) + 2H2(g)  N2(g) + 2H2O(g)
The following initial rates were determined at the given partial pressures (p) of reactants.
pNO(mmHg) p H2 (mmHg) Initial rate (M/min)

200 400 0.46
400 200 0.92
400 400 1.85
These data imply which of the following rate laws?
2
2 2
(a) rate = k pNO p H2 (b) rate = k pNO p 2H2 (c) rate  k p 2NO p H2 (d) rate  k p NO p H2
7. Which of the following molecular species are expected to be paramagnetic ? O2+, O2– and O22–?
(a) All of them (b) Only O2+ and O2–
(c) Only O2+ and O22– (d) Only O2– and O22–
8. What are the elements of symmetry present in the following molecules and which of them is chiral?
A B
(a) A has a 2-fold rotation axis and B has a plane of symmetry, A is chiral.
(b) A has a plane of symmetry and B has a centre of inversion; B is chiral.
(c) A has a plane of symmetry and B has a 2-fold rotation axis; A is chiral
(d) A has a plane of symmetry and B has a 2-fold rotation axis; B is chiral.
9. The speed of a reaction that involves an enzyme increases as

(a) Temperature decreases (b) pH becomes less than optimal
(c) Substrate concentration increases (d) All of the above
10. The product of the following reaction will be able to couple with which amino acids?
NH2
acid
+ NaNO2
NO2
O O O O
H2N CHC OH H2N CHC OH H2N CHC OH H2N CHC OH
CH2 CH2 CH2 CH2

CH2 OH
CH2
CH2
OH NH2
Tyrosine Phenylalanine Lysine Serine
(a) Tyrosine and Phenylalanine (b) Tyrosine and Serine
(c) Lysine and Serine (d) Phenylalanine and Lysine
11. If the CO stretching frequency of Ni (CO)3(P(OMe)3) is A, and that of Ni(CO)2(PMe3)2 is , then

(a) A > B (b) A = B (c) A < B (d) None of these
12. Predict the products of the following condensation reaction where y:x could be either 1 or 2.
3
H
CHO N
acid
X + Y
Argon
N HN NH HN
NH HN N HN
NH N NH HN
A B C D
(a) A and D (b) A and B (c) C and D (d) C and B
13. The Friedel-Crafts reactions are common in organic chemistry. Which of the following is expected to be a
better catalyst?
(a) AlBr3 (b) AlI3 (c) AlCl3 (d) MgCl2
14. Which of the following statements is always true regarding conductors and semi-conductors?
(a) Semi-conductors are half as good as conductors when comparing their electron mobility.
(b) Conductors have large band gaps and semi-conductors have small band gaps.
(c) Conductors and semi-conductors do not conducts electricity at high temperatures.
(d) None of the above statements are true.
15. The standard Gibbs free energies of the following reactions, G0, have been determined at various
temperatures.
(i) C(s) + O2(g)  CO2(g) (ii) C(s) + 1/2O2(g)  CO(g) (iii) CO(g) + 1/2O2(g)  CO2(g)
Which of the following plots would represent most likely the temperature dependence of G0?
(iii)
(iii)
(i)
(i)
(a) (ii) (b)
0
G 0
G (ii)
T
T
4
(i) (ii)
(ii) (iii)
(c) (d)
0 0
G (iii) G (i)
T T
16. The reaction of sodium ethoxide with ethyliodide to form diethyl ether is termed
(a) electrophilic substitution (b) nucleophilic substitution
(c) electrophilic addition (d) radical substitution
17. Compound 1 reacts with vinyl Grignard reagent to give two compounds A and B after hydrolysis. A gives
compound 2 upon heating. Predict the structure of A.
H 2O
+ MgBr A + B
1
O
H
heat
A
O
H
2
OH O
(a) (b) (c) (d)
O OH
18. Point of group 1, 2-propadiene is

(a) C2h (b) C2v (c) D2h (d) D2d
19. Which of the following statements is true regarding amphiphilic molecules?

(a) An amphiphilic molecule consist of both a positive charge and a negative charge.
(b) Amphiphilic molecules show spontaneous aggregation behaviour in any solvent and at all concentrations.
(c) Amphiphilic molecules are insoluble in water.
(d) Amphiphilic molecules are known to form liquid crystals.
20. Using crystal field theory, determine the type of d-orbital(s) which will have the lowest energy in the complex
shown below. Based on the above, determine the comparative rates of reduction of the Mn(V) to Mn(V)
versus Mn(IV) to Mn(III) states.
5
N N
Mn
N N
OH
(a) (dxy); Mn(V) to Mn(IV) is slower than Mn(IV) to Mn(III)

(b) (dxy, dyz, dzx); Mn(V) to Mn(IV) is slower than Mn(IV) to Mn(III)
 
(c) d z2 , d x 2  y2 Mn(V) to Mn(IV) is faster than Mn(IV) to Mn(III)
(d) (dxy); Mn(V) to Mn(IV) is faster than Mn(IV) to Mn(III)

21. Which statement is true of the ground state of the Co2+ ion?
(a) The number of unpaired electrons is 0 and the Co2+ ion is paramagnetic
(b) The number of unpaired electrons is 0 and the Co2+ ion is not paramagnetic
(c) The number of unpaired electrons is 3 and the Co2+ ion is paramagnetic
(d) The number of unpaired electrons is 3 and the Co2+ ion is not paramagnetic.
22. How many molecules of cetanol (of cross-sectional area 2.58 × 10–19 m2) can be adsorbed on the surface
of a spherical drop of dodecane of diameter 35.6 nm?
(a) 6.16 × 104 (b) 1.23 × 103 (c) 1.54 × 104 (d) 4.90 × 103
23. In a chemistry lab, the aim of an experiment was to generate well structured, 5 nm sized gold nanoparticles.
A student experimented with the following synthesis:
1-nonanethiol (C9H19SH) and HAuCl4 were first mixed (in a molar ratio of 10:1), and then gold ions
were reduced by slowly adding NaBH4. In this synthesis, after 2 hours no precipitate was observed
and only a very faint pink colloidal solution was obtained. This solution was then evaporated onto a
glass slide and the sample characterized by X-ray diffraction.
Given below are three XRD patterns. One out of these three patterns was obtained by the student when he/
she characterized the sample on the glass slides. Which statement below is true?
(111)
Intensity (a.u.)
(200) (220) (311) a
b
c
30 40 50 60 70 80 90
Diffraction Angle (2)
(a) The synthesis did not yield gold nanoparticles as there was no precipitate. Therefore, the XRD pattern
that will be obtained is that shown as curve (c)—It is almost a flat baseline indicating no product.
(b) 5 nm gold nanoparticles were formed and XRD pattern shown as (a) represents the product. It signifies
6
that the nanoparticles are crystalline and the face-centered cubic (fcc) crystal structure can be clearly
used to index the peaks.
(c) 5 nm gold nanoparticles will show size-dependent line broadening and therefore if the product consisted
of such particles, then curve (b) will be obtained.
(d) None of the above statements are true.
24. Consider a classical harmonic oscillator with a mass m and a force constant k oscillating with a frequency v.
Which of the following statements is NOT true for this system?
(a) v increases if m decreases
(b) The oscillator is most likely to be found at its equilibrium position
(c) The acceleration is maximum at its turning points
(d) v does not depend on how large the amplitude of the oscillation is
25. Photosynthesis is a process by which light energy gets funnelled into creating chemical potential for generation
of proton gradients across membranes. Suppose photosynthesis is only 0.5% efficient in creating such gradients,
calculate how many 530 nm photons will be required to create a pH gradient (per mole) as shown below
across a cellular membrane under ambient temperature of 300 K?
(a) 1000 photons (b) 1010 photons (c) 10 photons (d) 6 × 1023 photons
26. What is the result of the following reaction?
OMe
+ R2B PdP(Ph 3)4
Br Bu 2M Na 2 CO 3
MeO
THF, 65ºC
7
OMe OMe
Bu
(a) MeO (b) MeO

Br
(c) Reaction is unfavourable under given reagents

(d) (a) and (b) both are plausible.
27. What are the limits of detection of the following common analytical methods used with capillary separations:
fluorescence, mass spectrometry, UV-Vis absorbance, and NMR, respectively, in mol?
(a) 10–18-10–23, 10–13-10–21, 10–13-10–16, 10–9-10–11
(b) 10–13-10–21, 10–18-10–23, 10–13-10–16, 10–9-10–11
(c) 10–18-10–23, 10–13-10–21, 10–9-10–11, 10–13-10–16
(d) 10–13-10–21, 10–13-10–16, 10–18-10–23, 10–9-10–11
28. Shown below in solid-line is the harmonic potential of a quantum oscillator for a diatomic molecule. If the
harmonic potential is suddenly transformed into Morse potential shown in dashed-line how would the zero
point energy and shape of wavefunctions change?
5
Energy
0
Q
(a) Zero-point energy remains the same and wavefunctions do not change.
(b) Zero-point energy remains the same but wavefunction reflects a change on the high Q side.
(c) Zero-point energy changes and wavefunction reflects a change on the high Q side.
(d) Potentials never reflect any change in the shape of the wavefunction.
29. The cell potential for the following electrochemical system at 25°C is:
Al(s) | Al3+ (0.01 M) || Fe2+ (0.1 M) | Fe(s)
(a) 1.23 V (b) 1.21 V (c) 1.22 V (d) –2.10 V
30. Given three system, A, B and C what could be they if the spacing between the neighbouring energy levels in
A decreases with increasing energy, while that for B is constant, and that for C increases with increasing
energy?
(a) A = particle in a one-dimensional box, B = harmonic oscillator, C = electron in hydrogen atom
(b) A = electron in hydrogen atom, B = harmonic oscillator, C = particle in a one-dimensional box
8
(c) A = particle in a one-dimensional box, B = electron in hydrogen atom, C = harmonic oscillator
(d) A = electron in hydrogen atom, B = particle in a one-dimensional box, C = harmonic oscillator
31. Sodium metal crystallizes in a cubic unit cell. From X-ray diffraction, the unit cell parameter was determined
to be 4.29 A. If the density of the element is known to be 0.968 g/cm3, how many atoms are present in each
unit cell?
(a) Not enough information is given to calculate the value.
(b) 1 (c) 2 (c) 3
32. Electrospray ionization mass spectroscopy produces multiply charged ions of proteins. On application of this
technique to hemeprotein it gave a large number of peaks corresponding to different charge-states of the
protein. The three consecutive peaks are observed at the m/z values:
2061, 1767, 1546
The approximate m/z value of the consecutive fourth peak in the series would be:
(a) 1252 (b) 1374 (c) 1498 (d) 1325
33. A is a 5 × 5 matrix with elements aij = aji. Its eigenvalues are 0, ±1 and ±2. Which of the following statements
best describes the properties of the matrix A?
(a) A can be diagonalized by a unitary transformation.
(b) A can be diagonalized by an orthogonal transformation.
(c) A cannot be inverted.
(d) All of the above
34. Real gases behave differently from ideal gases because:

1. the molecules of real gases are in constant motion
2. molecules of real gases collide with the walls of the container.
3. molecules of real gases have volume
4. molecules of real gases attract each other.
(a) 1 and 2 (b) 3 only (c) 3 and 4 (d) all of the above
35. The following reaction, conducted reaction, conducted in a vessel of capacity 10 litre, has reached equilibrium
at 330 K.
 CO 2 (g)  H 2 (g)

CO(g)  H 2O(g)  H   41.2 kJ
The temperature of the vessel is then increased to 350 K. Which of the following statement is correct before
the reaction reaches a new equilibrium at this elevated temperature?
(a) The rate constant of the forward reaction will decrease, and the rate constant of the reverse reaction will
increase.
(b) Concentrations of all the species will increase, but increase will be more for the reactants than that for
the products.
(c) Both A and B
(d) None of the above
36. Global warming is due to increase of

(a) Methane in atmosphere (b) CO2 in atmosphere
(c) Water vapour (d) Methane and CO2
9
37. The state of 2 moles of an ideal gas is changed from the point A to the point B along three different paths, as
shown in the following P-V diagram. If the change of entropy of the gas in changing its state from sate A to
B along the path i is denoted Si, then which of the following statements is correct?
A 1
1
2
B
P 3 3
(a) S1 > S2 > S3 (b) S1 < S2 < S3
(c) S1  S2  S3 (d) S1 = S2 = S3
38. A reaction has a negative (and approximately temperature independent) enthalpy change. It does not proceed
spontaneously at room temperature (25°C). At which of the following temperatures is the reaction more likely
to become spontaneous?
(a) –50°C (b) 50°C (c) 100°C (d)1000°C
39. In a Huckel tight binding representation with a single orbital per site and nearest neighbour interactions between
sites, the Hamiltonian for a cluster of three Na atoms in linear and triangular forms is written as
Assuming the nearest neighbour coupling < 0, which form (linear or triangular) of the cluster is more probable
for neutral Na3 and for the anion Na3– ?
(a) Linear for Na3 and triangular for Na3– (b) Linear for both
–
(c) Triangular for Na3 and linear for Na3 (d) Triangular for both
40. 1
The H NMR spectrum of a compound with molecular formula C3H7NO shows the following features:
Chemical shift (ppm) 6.50 2.25 1.10
Shape broad singlet quartet triplet
which of the following is in agreement with this information?
(a) (CH3)2C = NOH (b) CH3COCH2NH2 (c) CH3CH2CONH2 (d) HCON(CH3)2
1
1. For the following reaction,

CO2  H 2 O 
 H 2 CO3
the entropy change  Ssystem  was calculated to be –96 JK–1 mol–1. The enthalpy change  H  was measured
to be –45 kJ K–1 mol–1. This reaction is expected to be a spontaneous process. the total change in entropy
 S system  surroundings is:
–1 –1
(a) +54 JK mol (b) –96 J K–1 mol–1
(c) –45096 J K–1 mol–1 (d) –44004 J K–1 mol–1
2. What is the product of the following electrocyclic ring-closing reaction?

X
(a) (b) (c) both (a) and (b) (d) none of the above
3. For the following chemical reaction

k1
A  B
k2
A  C
k3
B  C
k4
C  B
The rate constants k1 and k2 are at least 1000 times slower than either k3 or k4. During the course of the above
reactions the ratio of the products B and C will be
(a)  B /  C  k 3 / k 4 (b)  B /  C  k 4 / k 3
(c)  B /  C  k 2 /k 3 /k1k 4 (d)  B /  C  k1 / k 2
4. Transition states in chemical reactions are generally not directly observed in experiments because
(a) Their structures are different from reactants and products
(b) They have the highest kinetic energy and hence difficult to capture
(c) They have the highest potential energy and their lifetimes are short
5. A single-stranded RNA has 1200 bases. The total base content of this RNA was found to have the following
ratio A:U:G:C = 0.2: 0.3:0.3:0.2. The probability of a randomly chosen 5 nucleotide long sequence as GAUGA
is:
(a) 0.00098 (b) 0.00243 (c) 0.00032 (d) 0.00108
2
6. Phosphorescence is a slower process than fluorescence because

(a) Phosphorescence occurs at longer wavelengths than fluorescence
(b) Spin angular momentum is not conserved in phosphorescence process
(c) Both (a) and (b)
7. The partition constant of a compound between two immiscible solvents A and B is 10. Solvent A is preferred
over solvent B. You are given 10ml of 0.1M solution of the compound in solvent B. This solution is vigorously
shaken and equilibrated with 10ml of solvent A. After phase separation, the concentration of the compound in
solvent B is
(a) 0.09 M (b) 0.099 M (c) 0.009 M (d) 0.05 M
8. A molecule has a ground state and two excited electronic energy levels, all of which are nondegenerate with the
energies: E 0  0, E1  1 10 20 J , and E 2  3  10 20 J . If P0, P1 and P3 are fractions of molecules occupied in
ground, first and second excited states, respectively, at 298K, then, P0 : P1 : P2 = ?
(a) 0.919 : 0.081 : 0.001 (b) 0.900 : 0.098 : 0.002
(c) 0.666 : 0.333 : 0.111 (d) 0.880 : 0.088 : 0.022
9. While carrying out the titration of a weak acid with a strong base, the pH of the solution is measured as a
function of the added titrant. The result is shown below.
pH3
pH2
pH
pH1
O V0/2 V0 3V0/2
Volume of base added
Three pH values have been marked, corresponding to 3 different volumes of the added base. V0 corresponds
to the ‘end point’ or the ‘stoichiometric point’ of neutralization. What is the pKa of the acid?
(a) pH1 (b) pH2 (c) pH3
(d) cannot be answered because of insufficient information
10. Although both NF3 and NCl3 are covalent, NCl3 undergoes hydrolysis whereas NF3 does not because
(a) NF3 is more stable than NCl3 (b) dipole moment of NF3 is more than NCl3
(c) electronegativity of F > Cl (d) Cl can expand its octet by using d-orbitals.
11. The pontential energy of a diatomic molecule, as a function of the internuclear separation r, is approximated as
A B
Ur  a  b
r r
where A and B are postive constants and a > b
3
r0
r
As shown in the above figure, r0 is the equilibrium bond length. What is the energy necessary to break the bond
from its equilibrium position?
A B B C Aa 
(a) r a  r b (b) r b  r a (c)   1 (d) both (b) and (c)
0 0 0 0 r0a  b 
12. The heme is present at the active site of many proteins and enzymes including hemoglobin, cytochromes etc. It
is an iron complex of a cyclic aromatic ligand named porphyrin. Several metal complexes of porphyrin synthesized
in the laboratory have similar absorption spectra, except that the most intense absorption band position is either
red shifted or blue shifted around 400 nm depending on the nature of the metal ion. The origin of this most
intense absorption band in these porphyrin complexes is:
(a) MLCT transitions (b) LMCT transitions
(c) d-d transitions (d)   * transitions.
13. Which of the following statements is true about ferromagnets?
(a) In the presence of a magnetic field, the unpaired spins of a ferromagnet all align with the external field. In the
absence of external magnetic field, spins then revert back immediately to their original state.
(b) The origin of magnetism in a ferromagnet arises from randomly arranged paired spins in a lattice.
(c) A ferromagnetic material is weaker (in its attraction to an external magnetic field) than a paramagnetic
material.
14. An electron can be transferred between two molecules X and Y either directly with a rate kXY = k1 or through
an intermediate molecule Z with rates kXZ = kZY = k2. If at time t = 0 the electron is situated at X then average
time ‘t’ it will take to reach Y is given by
Z
k2 k2
X Y
k2
(a) t  1/  k1  k 2 /2  (b) t  1/k1  1/k 2

(c) t  1/  k1  2k 2  (d) t   k1  k 2  /  k1k 2 
15. For a conservative force field (e.g., gravity) F, work done in moving a particle by distance dr is W = F.dr which
of the following is true.
(a) W.around a closed path is zero and W is path independent
(b) W around a closed path is zero and W is path dependent
(c) W around a closed path is non-zero and W is path indendent
(d) W around a closed path is non-zero and W is path dependent.
4
16. 0.050 mol of acetic acid and 0.20 mol of sodium acetate are mixed and total volume is adjusted to 500 ml in
water. The pKa for acetic acid (CH3COOH) is 4.75. If now 0.010 mol of NaOH is added to the above
mixture, what will be the final pH of the solution be?
(a) > pH 7
(b) pH will stay at 4.75 because it is a buffered solution
(c) > pH 4.75
(d) not sufficient information has been given
17. Given below is a figure showing three X-ray diffraction patterns for (a)
(along with lattice planes) and (b) nanoparticles of gold that were synthesized in a research lab. These were
deposited on the same flat polymeric substrate and (c) is a blank polymeric substrate.
Which of the following statements is true regarding structural-quality of the gold nanoparticles that have been
synthesized?
(a) The gold nanoparticles that have been synthesized are amorphous in natural and not crystalline. As such
they do not belong to the FCC lattice.
(b) There are many impurities present in the sample containing gold nanoparticles.
(c) Insufficient information is given to make a conclusive statement
18. An artificial soft drink contains 11.0 g/L of tartaric acid C4H6O6, and 20 g/L of its potassium salt C4H5O6K.
What is the pH of the drink?
(Given: Ka tartaric acid = 1.0×10–3)
(a) 4.24 (b) 5.21 (c) 3.82 (d) 3.16
19. Which of the catalytic protocols listed below demonstrate a homogeneous catalysis?
(I) Pt(s) catalyzing the reaction of O2(g) with CO (g)
(II) Cl(g) catalyzing the decomposition of O3(g)
(III) H2O2(aq) decomposition catalyzed by Br–(aq)
(a) I only (b) II only (c) I and III only (d) II and III only
20. FAD is a redox-active molecule which takes part in many important biological reactions. The redox potential of
FAD at pH 7.0 is given below
 FADH 2
FAD  2H   2e 
E 0FADH 2 /FAD  0.180V
Calculate the redox potential when the media is acidified to pH 0
(a) 0V (b) 0.24 V (c) 0.12V (d) none of the above.
21. What is ii ? (Given, i2 = –1)

(a) a real number (b) a complex number
(c) an imaginary number (d) none of the above
22. The two fine-structure components of a nuclear magnetic resonance tranistion are observed at chemical shifts
of 2.142 and 2.208 ppm in a 300 MHz NMR spectrometer. Calculate the coupling constant
5
(a) 19.8 Hz (b) 0.066 Hz (c) 6.6 Hz (d) data is insufficient

23. The concentration of a molecule in aqueous solution is (C/1000)L–1, where C is the number of molecules.
Assuming the molecule is a sphere of radius r0 Angstrom, one can estimate the intermolecular (centre-to-
centre) separation by
1 1
(a) 3  2  r0 metre (b) 3 metre
C C
1
(c) 3
– 2  10 10  r0 metre (d) cannot be estimated based on the information above.
C
24. Paraformaldehyde (4% by wt), acrylamide (4% wt/vol), and an azo initiator (0.25%) were added to a protein.
What are the expected products X and Y?
O O 4ºC Heat
+ X Y
azo initiator
+ H H H2N
(a) (b)
(c)
(d)
25. Raman scattering is often seen overlapping with fluorescence emanating from the sample. However, fundamentally
Raman process is different from fluorescence. This is because
(a) Raman scattering is a two-photon process and fluorescence is not
(b) Raman process is a scattering process while fluorescence is not
(c) Raman process need not be Stokes shifted
6
26. Predict the products X and Y for the following de-protection reactions:
KOH, MeOH/H2O
X
OMe
COOMe Pg Liver Esterase

Y
pH 6.8
OMe OH
(a) COOH COOMe
X Y
OH OMe
(b) COOMe COOH
X Y
OH OMe
(c) COOH COOH
X Y
OMe OMe
(d) COOH COOH
X Y
27. Calculate the change in entropy when 1 mol of solid iodine, I2, at a temperature of 360 K is heated at constant
pressure to produce liquid iodine at a temperature of 410 K. The constant pressure molar heat capacity of
solid iodine is 54.44 K–1 mol–1 and of liquid iodine is 80.67 J K–1 mol–1. The melting temperature of iodine is
387 K, and hte molar enthalpy of fusion of iodine is 7.87 kJ mol–1.
(a) 8.6 J K–1 mol–1 (b) 28.9 JK–1 mol–1
–1 –1
(c) 20.3 J K mol (d) 11.7 J K–1 mol–1
28. What is the product X in the following reaction?
+
NH3
oxygen
Cu water X
H3N NH3
NH3
2+ +
NH3 OH2
H3N NH3
Cu Cu
(a) tetrahedral NH3 (b) octahedral H3N
H3N NH3
NH3 OH2
7
3+
OH2
H3N NH3
Cu
(c) distorted octahedral H3N NH3
OH2
+
OH2
H3N NH3
(d) square pyramid Cu
H3N NH3
29. How many molecular orbitals may be constructed from the valence shell orbitals of the constitutent atoms in
CH4 ?
(a) 2 (b) 4 (c) 6 (d) 8
30. Write down the matrix representing a two-step transformation of a general point (x, y, z): rotation through 180º
(about the z-axis) followed by reflection in an yz mirror plane
1 0 0   1 0 0  1 0 0   1 0 0 
0 1 0  0 1 0  0 1 0  0 1 0 
(a)   (b)   (c)   (d)  
0 0 1  0 0 1  0 0 1 0 0 1
31. What is the side product (X) of the following ring closing metathesis reaction?
O O O
O Ru catalyst
O +X
O O
H H H H
(a) (b) O (c) H (d) H H
C O H
H H H H
32. What is the nature of silicon-oxygen bonds in silica (SiO2)?

(a) Polar covalent (b) Ionic (c) Nonpolar covalent (d) Coordinate covalent
33. The Sharpless epoxidation catalyst Ti(OiPr)4 converts allylic alcohols to epoxides stereoselectively. What is
the stereochemistry of the products obtained in the following oxidation reactions?
O
OH
s, s-Diethyltartrate
Ti(OiPr)4
t O
BuOOH
R, R-Diethyltartrate OH
Ti(OiPr)4
tBuOOH
(a) X: (2R, 3S)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol

Y: (2S, 3R)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
(b) X: (2S, 3R)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
Y: (2R, 3S)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
(c) X: (2S, 3R)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
Y: (2S, 3S)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
(d) X: (2R, 3S)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
Y: (2S, 3S)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol
8
34. When 10 mL of each liquid of liquid pairs listed below are mixed and then allowed to stand, which pair is most
likely to separate into two layers?
(a) carbon tetrachloride and hexane (b) ethanol and methanol
(c) carbon tetrachloride and methanol (d) hexane and pentane
35. The mathematical expression e i kx t  represents

(a) A wave stationary in space but oscillating in time
(b) A travelling wave moving in the positive x direction
(c) A wave stationary in time but periodically varying in space
(d) A travelling wave moving in the negative x direction
36. Blue copper proteins consist of mon-nuclear copper center bound to 2 imidazole groups (histidine), one thiol
group (cysteine) and one thioether group (methionine). The coordination geometry around the metal ion is
distorted tetrahedral. What will be the relative value of the redox potential of the metal centre  Cu 2 / Cu   in
the protein compared to that of CuSO4 in water?
(a) More positive (b) More negative
(c) Equal (d) Redox potential of the metal centre in the protein will be zero.
37. Vapor pressure of a liquid in a closed container depends upon
(a) The volume of the container (b) The volume of the liquid
(c) The temperature (d) Both (b) and (c)
38. Which of the following statements is/are true?
(i) HCl absorbs IR radiation (ii) CO2 absorbs IR radiation
(iii) H atom absorbs IR radiation (iv) H atom absorbs UV-vis and microwave radiation
(a) (i) only (b) (i) and (ii) only
(c) (i), (ii) and (iii) only (d) (i), (ii), (iii) and (iv)
39. N2 does not show pure vibrational spectra because
(a) triple bond in N2 is very strong (b) The dipole moment of N2 is zero
(c) Both (a) and (b) (d) None of the above.
40. What is the de-Broglie wavelength of an electron that has been accelerated through a potential difference of
100V?
(a) 0.123 nm (b) 0.123Å (c) 1.23×10–11 cm (d) none of the above
1
GS-2015 (CHEMISTRY)
TATA INSTITUTE OF FUNDAMENTAL RESEARCH
1. Predict the product for the following sugar functionalization reaction :

OR
O NaN3.DMF
RO SPh
H3CO
O
OR = O S CH3
N3 N3
O O
(a) N3 (b) N3 SPh
N3 SPh H3CO
N3 N3
O O
(c) N3 N3 (d) RO SPh
N3 N3
2. Which of the following cannot act as a chelating agent ?

(a) HC(CH 2CH 2 NH 2 )3 (b) CH 3 NHCH 2 CH 2CH 3
(c) N(CH 2 CH 2 NH 2 ) 3 (d) H 2 NCH 2CH 2 CH 2 NH 2
3. In the following setup, two chambers 1 and 2 are enclosed by a thermally insulated material. Chamber 1
contains an ideal gas at 100 atm. Chamber 2 is completely evacuated. The two chambers are separated
by a breakable seal. Before the seal is broken, the temperature of the chamber 1 is T1, initial. Then the seal
is broken, and the gas is allowed to rush to chamber 2. The volume of chamber 2 is 100 times the volume
of chamber 1. When the pressure in the two chambers becomes equal, their respective temperature is
T1,final and T2,final. Which of the following statements is true ?
1 2
Seal
(a) T1, final  T2, final  T1, initial (b) T2, final  T1, final  T1, initial
(c) T2, final  T1, initial , T1, final  T1, initial
(d) Only a very small drop in temperature is expected. So T1, final , T2, final will be approximately equal to T1, initial .
2
cos A  sin A  1
4. Consider the trigonometric function . It can be simplified as
cos A  sin A  1
1  sec A  tan A
(a) (b) cosec A + cot A
1  sec A  tan A
1
(c) (d) All of the above
(cosec A  cot A)
5. The combustion of ethane (C2H6) is represented by the following reaction :
2 C2 H 6 (g)  7 O 2 (g)  4 CO 2 (g)  6 H 2O(l)
Which of the following is TRUE for the above reaction ?
(a) The rate of consumption of ethane is seven times faster than the rate of consumption of oxygen
(b) Water is formed at a rate equal to two-thirds the rate of formation of CO2
(c) The rate of consumption of oxygen equals the rate of formation of water
(d) CO2 is formed twice as fast as ethane is consumed
6. Consider the following reaction : Au  O2  3F2  [O2 ]  [AuF6 ]

Which statement is correct about the redox changes in this reaction ?
(a) Au is oxidized; O is oxidized; F is reduced
(b) Au is reduced; O is oxidized; F is reduced
(c) Au is oxidized; O does not undergo a redox change; F is reduced
(d) Au is reduced; O is oxidized; F does not undergo a redox change
7. Formation of Z from X is theoretically expected to obey the following kinetic scheme.
k1 k2
X Y Z
k–1 k–2
An experimentalist wants to verify the above scheme, but can observe and measure the concentration of
only X or Z. Is it possible that under certain conditions, the measurements of [X] or [Z] as function of
time would lead the experimenter to conclude that the kinetic scheme is as given below, and that the
species Y is absent ?
kobs
X Z
k– obs
(a) No, that is not possible
(b) Yes, if k1  k1 and k 2  k2
k1 k
(c) Yes, if  2
k 1 k 2
(d) Yes, if [Y] attains a steady-state concentration during the experiment
8. NaCl, KCl, NaBr and KBr crystallize in FCC lattices. Their anoin and cation touch along the edge of the
unit cell. The dimensions of their unit cells are 562.8 pm, 627.7 pm, 596.2 pm and 658.6 pm, respec-
tively. From these data, what can you say about the size of the ionic radii (within an error of about 5%) ?
(a) Ionic radii of the cations depend on the nature of the anions
(b) Ionic radii of the anions depend on the nature of the cations
(c) Both (a) and (b)
(d) Ionic radii are independent of the ions
3
9. Indicate which of the following is/are “acceptable” wave function(s) in quantum mechanics in the range
 x
i.   x
ii.   x 2
iii.   sin x
iv.   exp(  x )
v.   exp (  x 2 )
(a) iii and v (b) iv only (c) iv and v (d) i and iii
1
10. For a harmonic oscillator in its ground state i.e. v = 0 state, the energy is given by E  h where  is the
2
vibrational frequency. This is due to its
(a) Kinetic energy (b) Potential energy
(c) Sum of kinetic and potential energy (d) Heat of formation
11. The state of a certain amount of a gas, not necessarily ideal, is changed from A to B in various hypotheti-
cal paths, as shown below. The total amount of the gas remains constant. Which of the following paths
are physically realizable ?
A A
A
(i) P (ii) P (iii) P
B B
B
V V V
A
A
(iv) P (v) P
B
B
V V
(a) All of them (b) Only (i), (ii) and (iii)
(c) Only (iii) and (v) (d) Only (i) and (iii)
12. Thiols are important molecular species present in cells and can mediate cell signaling processes. A
procedure for detecting thiols has been recently reported based on the following reaction. Predict the
structures of reaction products.
O N
pH 7.6
O
+
O S O SH
4
S O N O
O S
(a) O
O
N
O O O O
(b) O S S
O N
O
(c) O S O
O
N
S O O O O
(d) O S S
13. If the peak in the mass spectrum of C2F6 at mass number 138 is 100 units tall, what will be the heights of
the peak at mass numbers 139 and 140.
(Isotopic abundances :12C, 98.89%; 13C, 1.11%; 19F, 100%)
(a) 2.24 and 0.0126 (b) 1.12 and 0.0126 (c) 50 and 25 (d) 2.24 and 0.025
14. According to the Nernst equation, the potential of an electrode changes by 59.2 mV whenever the ratio of
the oxidized and the reduced species changes by a factor of 10 at 25°C. What would be the correspond-
ing change in the electrode potential if the experiment is carried out at 30°C ?
(a) 59.2 mV (b) 71.0 mV (c) 60.2 mV (d) None of the above
15. Degenerate C-C coupling reactions are very important for synthesizing supramolecular organic struc-
tures. Name the reagents X, Y and Z that would be necessary to make the C3 symmetric product ?
N
Br
Y
+ X
Z
Br Br
N N
H H
B
(a) X = Y = Pd(PPh3)3 Z = Na2CO3

N
5
H H
B
(b) X = Y = NiCl2(PPh3)2 Z = Na2CO3

N
HO OH
B
(c) X = Y = Pd(PPh3)4 Z = Na2CO3

N
HO OH
B
(d) X = Y = Pd(PPh3)4 Z =HCl

N
16. What is the point group of Fe2(CO)9 ?

(a) C3h (b) D3h (c) C3v (d) D3d
17. Which of the following is the curve x = y2.
30 30
20 20
10
10
Y 0
(i) (ii) Y 0
–10
–10
–20
–20
–30
–10 –5 0 5 10
X –30
–10 –5 0 5 10
X
–10 –10
–5 –5
(iii) Y 0 (iv) Y 0
5 5
10 10
–30 –20 –10 0 10 20 30 –30 –20 –10 0 10 20 30
X X
(a) i (b) ii (c) iii (d) iv
6
18. For a particle undergoing quantum tunneling through a barrier, which of the following is NOT true :
(a) The amplitude the particle wave function after passing the barrier decreases with an increase in tunneling
distance.
(b) The probability of finding the particle after passing the barrier decreases with increase in tunneling barrier
height.
(c) The energy of the particle after crossing the barrier decreases with increase in tunneling distance.
(d) The change in the phase of the particle wave function upon transmission is proportional to the tunneling
distance.
19. A magnetic resonance spectrum, recorded using a radiation of frequency 100 MHz, is shown below. What can
you say about the nature of this spectrum ?
Signal
Magnetic field
(a) It is a continuous-wave NMR spectrum
(b) It is a Fourier transform NMR spectrum
(c) It is an ESR spectrum
20. An electron can transfer from state D to state A with a rate kDA. The intrinsic (in the absence of any charge
transfer between states D and A) lifetimes of charge transfer states D and A are D and A, respectively.
Assuming that initially the electrons is in state D, under what conditions would kDA be completely deter-
mined in terms of the overall rate at which the electron leaves the combined D + A system.
1 1 1 1
(a) k DA   and k DA   (b) k DA   and k DA  
D A D A
1 1 1 1
(c) k DA   and k DA   (d) k DA   and k DA  
D A D A
21. A common characteristic of conducting polymers, such as polypyrrole and polythiophene, which make them
conduct electricity is
(a) The presence of stereogenic centers of the same configuration
(b) A monodisperse distribution in molecular weight
(c) Conjugation throughout the polymer chain
(d) A very low glass transition temperature
22. Which of the following plots represent(s) the Arrhenius rate equation, k  Ae  Ea /RT with
A  3  107 s 1 and Ea  3  104 J/mol.
1000 7
900
6.5
800
700 6
600 5.5
In (k)
k (s–1)
500
5
400
300 4.5
(i) 200
(ii)
4
100
0 3.5
280 290 300 310 320 330 340 350 0.0029 0.0031 0.0033 0.0035
T (K) 1/T (K–1)
7
30.5
30
29.5
In (k)
29
28.5
(iii)
28
27.5
0.0029 0.0031 0.0033 0.0035
1/T (K–1)
(a) (i) (b) (ii) (c) (iii) (d) (i) and (ii)
23. Which of the following monomers do you expect to find in a RNA molecule ?
NH2
N
O N
O O
NH3+ P N N
O O P O
(i) O HO (ii) O
O
O
O OH
NH2
R O
N C CH2
N
O O
N N O C H O CH3
(iii) O P O
O (iv) R C H2 CH3
O H2C P C N
O O O C CH3
H2
O O
(a) (i) (b) (ii) (c) (iii) (d) (iv)

24. How many normal modes does the CO2 molecule have ? What if the C and the O atoms were constrained
to move in one dimension ?
(a) 4 normal modes for free CO2 and 4 for constrained CO2
(b) 3 normal modes for free CO2 and 2 for constrained CO2
(c) 3 normal modes for free CO2 and 3 for constrained CO2
(d) 4 normal modes for free CO2 and 2 for constrained CO2
25. Two containers X and Y have equal fixed number of particles. Container X is maintained at constant
temperature while container Y is maintained at constant temperature and pressure. What statistical en-
semble will you use to best describe the properties of particles in the two containers ?
(a) Canonical ensemble for both X and Y
(b) Microcanonical ensemble for X and canonical for Y
(c) Canonical ensemble for X and grand canonical ensemble for Y
(d) Microcanonical ensemble for both X and Y
8
26. An aqueous solution contains 0.300 mole L –1 of KH2PO4 and 0.0150 mole L–1 of K2HPO4. Which of the
following statement(s) is/are true about this solution ?
(a) It can act as a buffer solution around pH  7.0
(b) It can act as a buffer solution around pH = 12
(c) Its pH will approximately equal to 6.9
(d) Both (a) and (c)
27. A catalyst :
(a) Participates in the reaction (b) Does not affect a reaction energy path
(c) Always decreases the rate for a reaction (d) Always increases the activation energy for a reaction
28. What would be the likely ratio of products X and Y for the following reaction on 2-methyl-cyclohex-
anone if we consider that torsional effects play a significant role in the reaction outcome ?
H O
LiAlH4 LiAlH4
O
O H
H H H
(X) (Y)
(a) X:Y = 80:20 (b) X:Y = 50:50 (c) X:Y = 20:80 (d) X:Y = 1:99
29. A pure substance can exist in several different phases A, B, C,..... Its partial phase diagram is shown
below.

E F
P D
C 
A  B

T
Which of the following statements is correct about the above diagram ?

(a) The diagram is correct in all respects
(b) The diagram is wrong as it has more than one triple point
(c) A phase diagram cannot have an island, such as D
(d) The point  cannot be present in any phase diagram
30. Free water pKa is 15.7 at 25°C. Based on the free water pKa benchmark, arrange the acidity of the “bound”
water molecules in increasing order within the following metal aqua complexes:
[Mn(H 2O)6 ]2 , [Cu(H 2O)5 ]2 , [Ca(H 2O)8 ]2 , [Sr(H 2O)8 ]2
(a) Ca 2  Mn 2   Cu 2   Sr 2  (b) Mn 2  Cu 2   Sr 2   Ca 2 
(c) Sr 2   Ca 2   Mn 2  Cu 2  (d) All have same acidities
31. The number of peptide bonds in a protein consisting of a linear chain of 128 amino acids is
(a) 127 (b) 128 (c) 129 (d) None of the above
9
32. Which of the following statement(s) is/are true ?
(i) The state function (x, t) is always equal to a function of time multiplied by a function of the coordinates
(ii) If f1 and f2 are eigenfunctions of an operator B, then c1f1  c2 f 2 must always be an eigenfunction of B,
where c1 and c2 are constants
(iii) The operator L2 commutes with Lx + Ly
(a) i and ii (b) i and iii (c) ii and iii (d) Only iii
33. The restriction enzyme Alu1 recognizes four DNA base pairs and cuts right in the middle as shown below:
5 AGCT 3
3 TCGA 5
What fragments of DNA do you expect to recover from the reaction mixture if the following DNA sequence
5 CGACTAGCTACTGAGCTAAA 3
3 GCTGATCGATGACTCGATTT 5
is partially digested with Alu1. Partially digested means that the reaction is not allowed to proceed to comple-
tion, say only to 50%.
(i) 5 CGACTAG 3 and 5 CTACTGAGCTAAA 3
3 GCTGATC 5 and 3 GATGACTCGATTT 5
(ii) 5 CGACTAGCTACTGAG 3 and 5 CTAAA 3
3 GCTGATCGATGACTC 5 and 3 GATTT 5
(iii) 5 CGACTAG 3 and 5 CTACTGAG 3 and 5 CTAAA 3
3 GCTGATC 5 3 GATGACTC 5 3 GATTT 5
(iv) 5 CGACTAGCTACTGAGCTAAA 3
3 GCTGATCGATGACTCGATTT 5
(a) Only i and ii (b) Only i and iii (c) Only iii and iv (d) i, ii, iii and iv
34. Which of the following statement are true ?
(i) For a harmonic oscillattor potential, the spacing between adjacent energy levels remain constant with
increasing the quantum number.
(ii) For a Morse oscillator potential, the spacing between adjacent energy levels increases with increasing the
vibrational quantum number.
(iii) Harmonic oscillators are be used to explain the bond dissociation.
(iv) Morse oscillators can be used to explain the vibration of molecules.
(a) i, ii and iii only (b) i and iv only (c) i, ii and iv only (d) i, ii, iii and iv
35. Molecular knots have been observed in DNA and proteins. Although synthetically challenging, a few purely
organic molecular knots have also been reported in the literature. One such elusive knot is the trefoil knot. An
organic trefoil knot was prepared by reacting two structurally distinct components X and Y. The reaction
mixture contained four products as shown in the figure below:
Y Y Y X
X X X X
X X Y Y
X X X X
Y Y Y Y Y Y Y Y
C D E F
Which spectra will afford distinguishable spectral features for (1) C and D ? and (2) E and F ?
10
(a) Circular Dichroism Spectra for C and D; 1H-NMR for E and F
1
(b) H-NMR and 13C-NMR Spectra for C and D; Circular Dichroism for E and F
(c) Absorbance and Emission Spectra for C and D; Circular Dichroism for E and F
(d) Infra-Red Spectra for C and D; Circular Dichroism for E and F
36. The molar absorption coefficient of sea water in the visible region is 6.2  10  5 M 1cm 1 . What will be depth
from the sea surface at which intensity of light becomes one-tenth of that at the surface ?
(a) 2.9 m (b) 0.9 m (c) 1.1 m (d) 8.0 m
37. The electronic absorption spectra or two species A and B are shown below:
absorptivity
Molar
A B
A B
Frequency Frequency
In a solution, these two species are dissolved, and they are moving freely. Using a tunable laser, when the
solution is excited at A, a single fluorescence band is seen around frequency F1. When the laser frequency is
changed to B, two fluorescence bands are seen around frequencies F1 and F2. Which of the following figures
can qualitatively describe the correct relative positions of the frequencies A, B, F1 and F2? The continuous
line shows absorption and the dashed line shows fluorescence emission spectra.
emission intensity
Absorption or
A B
(a)
A F1 B F2
Frequency
emission intensity
Absorption or
(b)
A B
F1 A F2 B
Frequency
emission intensity
Absorption or
(c)
A B
F1 A F2 B
Frequency
11
emission intensity
(d) Absorption or B A
F2 B F1 A
Frequency
38. For Co in oxidation state II, predict the overall charges of the coordination complexes shown in the reactions
below:
OH z OH2 x y
H2O OH2 H2O OH2 Cl Cl
NaOH
Co Co Co
+ 6H2O
H2O OH2 H2O OH2 Cl Cl
OH OH2
(a) z = +2; x = –2; y = +2 (b) z = 0; x = +2; y = –2
(c) z = 0; x = +2; y = +2 (d) z = –2; x = +2; y = –2
39. If (x, t) can be expressed as a product of two functions f(t)g(x), where f(t) has the form exp   (iEt/) 
then it can be shown that the probability of finding the particle between x and (x + dx)
(a) Equal to 1
(b) Is independent of time
(c) Can be obtained by solving Time Dependent Schrodinger Equation
(d) Can be obtained by solving Time Independent Schrodinger Equation
40. Which of the following statements is TRUE regarding the electrical conductivity of HCl in aqueous solution,
HCl as a gas and HCl in benzene ?
(a) All three conduct electricity because HCl is a strong acid
(b) HCl in aqueous solution only conducts electricity because it is ionized but not HCl gas and HCl in benzene
(c) HCl in benzene is not conducting because benzene is a non-polar solvent and but HCl gas and HCl in
aqueous solution conduct electricity
(d) HCl in aqueous solution and HCl in benzene are conducting because they are solutions but not HCl gas
1
TIFR 2016 CHEMISTRY

1. In a 1g diamond crystal, a scientist wants to replace a few of the carbon atoms with nitrogen atoms. Which of
the following statements best describes the resulting material?
(a) This is not possible as nitrogen has a coordination number of 3 and carbon has a coordination number of 4
(b) The resulting material will NOT have a cubic diamond structure
(c) The resulting material will be a defective diamond as it will be p-doped
(d) The resulting material can be characterized as n-doped diamond.
2. What is the product of the following reaction?
O
(dioxane)
n O
GeCl4 + Bu3SnH
Diethyl ether/
n-hexane
(a) HGeCl3 (b) Cl2Ge : Dioxane (c) Cl3Ge–SnnBu3 (d) none of the above.
3. A long column of water in any transparent bottle appears slightly blue. However, if we replace water with heavy
water (D2O) it will look more transparent. This effect is due to
(a) Rayleigh scattering
(b) Kinetic isotope effects
(c) Absorption spectra of H2O and D2O are different
a
4. The integral  cos  x  sin  x  dx

a
(a) Equals to zero for any vlaue of a, and cos  x  is symmetric in the range of the integral.
(b) Is not equal to zero except for certain values of a, and sin  x  is antisymmetric in the range of the integral.
(c) Is not equal to zero except for certain values of a, and cos  x  is symmetric in the range of the intgegral.
(d) Has a non-zero value depending on a.
5. Which of the following statements is the best definition of the base peak in a mass spectrum?
(a) The molecular ion peak (b) The lowest m/z peak
(c) The highest mass rearrangement ion (d) The ion peak of greatest intensity
6. Shown below are the front and side views of the structure a molybdenum-based metal organic polygon. What
is the symmetry of the molecule?
Front view Side view
(a) D4h (b) C4h (c) C2v (d) C4

2
7. Which of the following is/are implied by the second law of thermodynamics?
B
(a) S   dq  irreversible  / T for an irreversible process A  B at temperature T.

A
(b) S  0 for an isolated system in the course of a spontaneous change

(c) Entropy of the universe always tends to maximum
8. A protein has three folded states F1, F2, F3 and three unfolded states U1, U2 and U3. Consider transitions
between configurations Ti  f where the initial (i) and (f) configurations each comprise of simple additive com-
binations of purely folded (e.g. F1, F1 + F2, F1+F2+F3) or unfolded states (e.g. U1, U1 + U2, U1+ U2+U3).
Transitions between folded (or unfolded) configurations are also allowed unless a state is part of both the initial
and final configurations. Assuming Ti  f  T f i the total number of distinct transitions are
(a) 61 (b) 49 (c) 73 (d) 9
PPh2 PPh2 DCM
+ PBr3 +
P Br
P
(a) Ph2P PPh2
+ (b) Ph2P PPh2
+
Br3 Br Br
Br
P
(c) Ph2P PPh2
+ (d) none of the above.
Br3 Br
10. The specific heat of a certain material monotonically increases with temperature. Two identical blocks of this
material are kept at 50ºC and 100ºC, respectively. The two blocks are now brought in contact with each other.
Assume that no heat is lost to the surrounding. When thermal equilibrium is reached after the two blocks are
kept in contact, what would be the final temperature of the two blocks?
(a) 75ºC (b) > 75ºC (c) < 75ºC
(d) Tf can be either more than or less than 75ºC, depending upon the precise variation of the specific heat with
temperature.
11. A carpenter claims to have made a rectangular parallelepiped (cuboid), the length of whose three face diago-
nals are 33, 56 and 65 meters. You are required to determine the length the main diagonal joining a pair of
opposite corners of this parallelepiped
(a) 65 2 meters (b) 65 / 2 meters (c) 65 meters
(d) It is not possible to make a rectangular parallelepiped with the claimed dimensions of the three faces.
12. For a canonical ensemble where each system has N, V, T fixed, which of the follwoing statements regarding
energy hold(s) true:
(a) Energy of the system does not fluctuate
(b) At thermodynamics limit (large N) the fluctuation in energy is extremely narrow
(c) At thermodynamics limit (large N), the fluctuation in energy is extremely broad
3
13. Predict the products X and Y of the following peptide ligation reaction.
SH
PPh2 H
O O
H H N
N3 H H
N N (i) N N
S O N
(X) H
O (ii) H2O O O
+ Y
SH O
O
H PPh2
N
S
(a) X = Y=
O PPh2
SH
PPh2
O
H O
N N H
S N
(b) X = Y= S
O O
O PPh2
O NH
SH
SH
PPh2 O PPh2 SH O
(c) PPh2
N N
S Y=
X=
O O
O O
H H
N N
S S
(d) X = Y=
O PPh2 O PPh2
O
14. Neopentyl chloride, (CH3)3CCH2Cl, reacts with a strong base (sodium amide) to produce a new compound.
This compound has two 1H NMR singlets at  0.20 ppm and  1.05 ppm (intensity ratio = 2 : 3). What is the
most probable structure of this compound?
(a) 2-methyl-2-butene (b) 1, 1-dimethylcyclopropane
(c) methylcyclobutane (d) cyclopentane
4
15. The 1H NMR of 1, 1-dibromoethane consists of two well-separated signals, one large and another one small.
Which one of the following statements is correct?
(a) the large signal is a quartet and the small signal is a doublet
(b) the large signal is a triplet and the small signal is a singlet
(c) the large signal is a singlet and the small signal is a triplet
(d) the large signal is a doublet and the small signal is a quartet
U H
16. For an ideal gas in a closed system at constant temperature T, what are the values of and ?
V p
U H U H
(a)  0 and 0 (b)  0 and 0
V p V p
U H U H
(c)  0 and 0 (d)  0 and 0
V p V p
17. The reaction of nitric oxide with oxygen gas is given by NO  O2 
 NO2 . When 25 g of NO is allowed to
react with 12g of oxygen gas, the maximum amount of NO2 formed will be
(a) 38.3 g (b) 17.3 g (c) 34.5 g (d) none of these
18. Proton pumps are ubiquitous in living organisms. They (shown in figure below) serve as an important regulator
of pH gradient across momebrances, which lead to ATP synthesis. Calculate the amount of CHEMICAL
workd one at temperature T by such a pump to maintain pH = 5 inside the cellular compartment against a
neutral pH outside the membrane?
(a) 2 RT (b) 2.303 RT (c) 4.606 RT (d) 23.3 RT

19. Which of the following observations reflect colligative properties?
(I) A 0.5 M NaCl solution has a higher vapour pressurse than a 0.5M BaCl2 solution.
(II) A 0.5M NaOH solution freezes at a lower temperature than pure water
(III) Pure water freezes at a higher temperture than pure methanol.
(a) I and II only (b) I and III only (c) II and III only (d) I, II and III
20. ABCD is a rectangle of area 50 m2. The mid-points AB, BC and AD are E, F and G, respectively. When EF
is extended, DC at H. Similarly, when EG is extended, it meets extended CD at J. What is the area of the
triangle EHJ?
(a) 50 m2 (b) 100 m2 (c) 200 m2
(d) the area cannot be determined without knowing the length and breadth of the rectangle.
5
21. Predict the products of the following reactions between cis-2-butene and singlet and triplet methylenes.
C
+ H H
singlet
C
+ H H
triplet
(a) singlet = triplet =
(b) singlet = triplet =
(c) singlet = triplet =
(d) singlet = triplet =
22. Consider an electron with energy E and mass M tunneling through a barrier of height V > E and width W. The
total time of the electron spends inside the barrier is
 2M 2M V  E  4M 2 V  E 
(a) (b) W  (c) (d)
V E E  E
ethyl acetate
N N + 1/n (HCHO)n + Me3SiCl
70ºC
Dip Dip
Dip = 2, 6-diisopropylphenyl
N N N N
(a) Dip C Dip Cl (b) Dip C Dip Me3Si
SiMe3 Cl
N N
(c) Dip C Dip Cl (d) none of the above
H
24. A doubly ionized lithium atom in an excited state (n = 6) emits a photon of energy 4.25 eV. What are the
quantum number (n) and the energy (E) of the final state?
(a) n = 2, E = –30.6 eV (b) n = 3, E = –13.6 eV
(c) n = 4, E = –7.65 eV (d) n = 5, E = – 4.90 eV
25. Which of the following can be labelled as a colloid?
(I) a mixture of water and ethanol (II) milk
(III) clouds (IV) gemstones
(a) I, II and III (b) II and III (c) II, III and IV (d) all of the above.
6
26. A beaker contains 10 mL of dilute buffer solution of pH 7. To this, dilute solution of HNO3 is added continu-
ously and the pH is measured. Which of the following graphs will be representative to show how the pH varies
on addition of HNO3?
7 7 7 pH
pH pH pH 7
(a) (b) (c) (d)
0 0 0 0
volume of HNO3 volume of HNO3 volume of HNO3 volume of HNO3

nBuLi
H3N BH3
THF/0ºC
(ammonia borane)
H2N BH3
(a) H3N BH3 (b) H3N BH2 (c) (d) no reaction
n Bu Li
Li
Li
28. Equal volumes of two metals of densties d1 and d2 are mixed together. The density of the resulting alloy is given
by
d1  d 2 2d1d 2 dd
(a) d1d 2 (b) (c) d  d (d) 1 2
2 1 2 2
29. A C5H12O2 compound has strong infrared absorption at 3300 to 3400 cm . The 1H NMR specrum has three
–1
singlets at  0.9,  3.45 and  3.2 ppm with relative areas 3 : 2 : 1. Addition of D2O to the sample eliminates
the lower field signal. The 13C NMR spectrum shows three signals all at higher field than  100 ppm. Which
of the following compounds best fits this data?
(a) 1, 5-pentanediol (b) 1, 3-dimethoxypropane
(c) 2, 2-dimethyl-1, 3-propanediol (d) 2, 4-pentanediol
1
30. The H NMR spectrum of a compound A shows a doublet and a septet. Which one of the following statements
is TRUE?
(a) The spectrum is consistent with A containing a CH3CH2CH2 group
(b) The spectrum is consistent with A being (CH3)2CHCl
(c) The spectrum is consistent with A containing a CH3CH2 group
(d) The spectrum is consistent with A being (CH3)2CCl2
31. What is the molecular mass (M) of a compound that has a concentration w = 1.2 g/L and an osmotic pressusre
of  = 0.20 atm at T = 300K?
(a) M = 576 g/mol (b) 3876 g/mol (c) M = 147 g/mol (d) M = 9818 g/mol
32. In a face centered arrangement of A and B atoms. Where A atoms are at the corners of the unit cell and B
atoms are at the face centres. For each unit cell, one A atom is missing from a corner position and one B atom
is missing from one face position. The simplest formula of the resulting compound will be
(a) A14B40 (b) A7B20 (c) A1-xB3-x (d) AB2
33. For a binary mixture of ideal gas, free energy of mixing is given by Gmix  nRT  x ln x  1  x  ln 1  x   ,
where x is the mole fraction of one of the components. what are the enthalpy and entropy of mixing of this
system?
(a) H mix  0 and Smix  0 (b) H mix  0 and Smix  0
(c) H mix  0 and Smix  0 (d) H mix  0 and Smix  0
7
34. Far infrared and microwave radiation is useful in studying the following process
(a) Transition of inner electrons of atoms
(b) Transitions of outer (or valence) electrons in atoms or molecules
(c) Changes in vibrational-rotational states of molecules
(d) Changes in molecular rotational states only
35. A compound of formula C5H12 gives one signal in the 1H NMR and two signals in the 13C NMR spectra. The
compound is
(a) pentane (b) 2-methylbutane
(c) 2, 2-dimethylpropane (d) cannot tell without more information
36. Predict the products of the following reactions:
2
 Pt  PPh3  
 4
 2Cl  
X
 PtCl4 2  2 PPh3 

Y
(a) X = trans-[PtCl2(PPh3)2] and Y = cis-[PtCl2(PPh3)2]
(b) X = cis-[PtCl2(PPh3)2] and Y = trans-[PtCl2(PPh3)2]
(c) X = Y = cis-[PtCl2(PPh3)2]
(d) X = Y = trans-[PtCl2(PPh3)2]
37. Predict the products of the following reaction
AgBF4
PhCl
Cl O
(a) (b) + AgCl

+ CO2
F2B
Cl
O Cl
(c) (d) + HF
+ BF3
  
38. A set of N vectors, X 1, X 2 ,..... X N satisfy the eigenvalue equation for an operator A with scalar eigenvalues
N  
  
1 , 2 ,......N  
i.e. , AX k  k X k . The linear combination vector X   Ck X k , where Ck ’s are non-zero
k 1
scalar coefficients.
(a) is not an eigenvector of A
(b) is an eigenvector of A only if the k ' s are all distinct (no two eigenvalue are equal)
(c) is an eigenvector of A only if the k ' s are all equal
(d) is an eigenvector of only if Ck ' s are equal
8
39. What is the value of i i 2  , where i  1

(a) real number (b) complex number
(c) cannot be calculated (d) none of the above.
40. Chemical oxidation of water to produce O2 gas is an energy demanding reaction, done routinely by plants using
the process called photosynthesis. By how many eV will it be uphil if the water oxidation reaction be carried
out at pH = 0 versus at pH = 7.0?
(a) 0.41 eV (b) –1.6 eV
(c) –0.41 eV (d) cannot be calculated based on the data given.
1
TIFR-Chemistry 2017
1. All natural amino acids, except one, react with cold nitrous acid and produce nitrogen gas. Which one of the
following is that odd amino acid?
(a) Tryptophan (b) Glycine (c) Proline (d) Histidine
2. Predict the multiplicities for hydrogens on C1, C3, and C4 of butanone associated with the spin-spin coupling
in its 1H NMR spectrum.
(a) H’s on C1: Singlet; H’s on C3: Doublet; H’s on C4: Triplet
(b) H’s on C1: Singlet; H’s on C3: Triplet; H’s on C4: Quartet
(c) H’s on C1: Singlet; H’s on C3: Quartet; H’s on C4: Triplet
(d) H’s on C1: Triplet; H’s on C3: Doublet; H’s on C4, Triplet
0
3. If standard potential of the reaction 2H 2O  l   O 2 (g,1bar)  4H  (aq)  4e  is E  1.23V . At 25ºC and
pH = 7, what is the oxidation potential of pure water according to this reaction?
(a) 0.410 V (b) –2.620 V (c) –0.817 V (d) –0.410 V
4. An organic compound has the following spectroscopic properties: Mass Spectrometry: m/z 102 (very small),
87 and 43 are the largest ions; 1H NMR:  1.4 and 3.9 ppm (both singlets, intensity ratio 3:2); 13C NMR: 
108, 64 and 25 ppm; Infrared spectroscopy: several strong absorptions in the 1000 to 1300 cm–1 region.
Which of the following is the most likely formula of this compound?
O O
O O
(a) (b) O (c) O (d)
O O
5. Predict the relative rates for the following reductive elimination for X = H, Cl, CH3, OCH3
L H
Pt L2Pt0 + CH4
L CH3
L= P X
3
(a) Cl  H  CH3  OCH 3 (b) H  Cl  OCH 3  CH 3

(c) OCH 3  CH3  H  Cl (d) CH 3  H  Cl  OCH 3
6. A bio-conjugation reaction can be used to modify a specific residue on a protein to attach therapeutics and
diagnostic agents. Predict the major product of the following bio-conjugation reaction with Fluorescein.
2
HN
NH
C-terminal S
COOH NH
pH 7.9
N-terminal SH +
O
H2N
Protein O
HO O OH
HS
NH2
NH2
O C
O
NH
S
NH
(a) O
HO O OH
3
NH2
S NH2
NH
HOOC
S
NH
O
(b)
O
HO O OH
CO2H
NH2
SH
HN
NH
S
NH
O
(c)
O
HO O OH
4
(d)
HO2C
CO2H
NH2
NH2
HN S S NH
NH HN
S S
NH HN
O
O
O
O
HO O OH
HO O OH
7. For a hydrogen atom, which of the following orbital(s) have the lowest energy:
(a) 4s (b) 4p
(c) 4d (d) All of the above have same energy
8. An electron tunnels through a square barrier of width d and height h. If h is fixed and d is is normally distributed,
then the electron transfer probability distribution is:
(a) a normal distribution (b) a delta function
(c) a log normal distribution (d) a poisson distribution
9. In a cubic unit cell, identify the Miller plane (111)
(a) (b) (c) (d) None of the above
10. Zinc solid has hcp (hexagonal close packed) structure. In a unit cell of Zinc solid, the Zinc atoms occupy
(a) 74% of volume of unit cell. (b) 80% of volume of unit cell.
(c) 68% of volume of unit cell. (d) 90% of volume of unit cell.
11. The acidity of molecules is usually measured by a parameter called the pKa. Metal ions (M n  ) solubilized in
n n
water form solvated aqua complexes commonly denoted by  M  H 2 O  m  or M aq . it is known that the pKa
of coordinated water in such metal-aqua complexes will be different from that of bulk water. For the following
2 2 2
set of metal-aqua complexes: Ca aq , Feaq , Mn aq , Fe3aq ; arrange the complexes with decreasing value of ex-
pected pKa of the coordinated water molecule:
2 2 2
(a) Feaq  Mn aq  Ca aq  Fe3aq 2
(b) Ca aq 2
 Mn aq 2
 Feaq  Fe3aq
2
(c) Feaq  Fe3aq  Mn aq
2 2
 Ca aq 2
(d) Mn aq 2
 Ca aq 2
 Feaq  Fe3aq
12. Solid inorganic materials are commonly classified as conductors, semi-conductors or insulators as determined
by their bandgap. Carbon has many allotropes such as diamond, graphite, carbon nanotubes and graphene
5
with distinct bandgaps. Considering the properties of diamond, what should be its bandgap:
(a) 7.0 eV (b) 1.0 eV (c) 0.01 eV (d) 0 eV
13. Predict the major product of the following hydroboration reaction:
R heat
BH + CH3CH C(CH3)2
R
R=
R R
B R
R R
(a) B (b) (c) B (d) B
R R R
14. Given an operator A and a set of vectors X which obey the following relationship
AX  X ,
where  is the set of scalars. If A commutes with B and B  A, which of the following is correct:
(a) X are eigenvectors of A only if the  are all distinct (no two eigenvalues are equal)
(b) X are eigenvectors of B
(c) X are eigenvectors of B with set of eigenvalues 
(d) X need not be eigenvectors of A
15. Given the molecular formula of the hexa-coordinated complexes
(I) Co Cl3 (NH3)6
(II) Co Cl3 (NH3)5
(III) Co Cl3 (NH3)4
If the number of coordinated NH3 molecules in (I), (II), and (III) respectively are 6, 5 and 4 then the oxidation
state of Co in (I), (II) and (III) are respectively:
(a) 6,  5,  4 (b) 3,  2,  1 (c) 0,  1,  2 (d) 3,  3,  3
16. An aqueous solution contains 0.300 mole L–1 of KH2PO4 and 0.015 mole L–1 of K2HPO4. Which of the
following statements is true about this solution? [Data: For H3 PO 4 ,pK1  2.16, pK 2  7.21, pK 3  12.32 ]
(a) It can act as a buffer solution around pH = 2
(b) It can act as a buffer solution around pH = 12
(c) Its pH will approximately equal to 6.9
(d) Both B and C.
17. What is the value of the continued fraction given below?
2000
1
2000
2
2000
2
2  
(a) 1999 (b) 2000 (c) 2001 (d) None of them

18. For angular momentum vector operator L , which of the following relation is true:
          
(a) L  L  i L2 (b) L  L  i L (c) L  L  i L (d) L  L  0
6
19. The complex showing a spin-only magnetic moment of 2.82 B.M. is

2 2+ 2
(a)  Ni  CO 4  (b)  NiCl4  (c)  Ni  NH 3  4  (d)  Ni  CN  4 
20. What are the products of the following reaction?

LiAlH + Et NHCl  Toluene 
4 3
(a) H 2  Et 3 N  LiCl  AlH 3 (b) LiH  Et 3 N  HCl  0.5 Al2 H 6

(c) LiCl  H 3 Al : NEt 3  H 2 (d) LiCl  NEt 3  H 2  0.5 Al2 H 6
21. Isotopic substitution is an often-used procedure in assigning vibrational spectroscopic features but the differ-
ence in isotopic masses of the vibrating atoms has to be sufficiently large to make the vibrational shift observ-
able. In a double isotopic replacement experiment, a proline with a 13 C  18O carbonyl group is inserted in the
middle of the polypeptide using molecular recombinant techniques. Given that in the naturally found proline the
12
C  16 O group exhibits a narrow vibrational feature at 1,711 cm–1, what is the shift of the carbonyl stretching
vibration for the 13 C  18O proline isotopomer..
Assume:
(A) The force constant for different isotopes can be considered identical.
(B) The isotopic changes in the carbonyl group will have little effect on the vibrations of other atoms in proline.
(a) 80 cm 1 (b) 165cm 1 (c) 85cm 1 (d) 42.5cm 1

22. A compound with molecular formula C5 H12 O 2 , has strong infrared absorption at 3300 to 3400 cm–1. The 1H
NM R spectrum showed three singlets at  0.90,  3.45 and  3.20 ppm; with relative areas 3:2:1. Addition of
D2O to the sample eliminates the lower field signal. The 13C NMR spectrum shows three signals all higher than
 100 ppm. Which of the following compounds best fits this data?
(a) 1,5-pentanediol (b) 1,3-dimethoxypropane
(c) 2,2-dimethyl-1,3-propanediol (d) 2,4-pentanediol
23. The heat of formation  H f  for the reaction 2Cu  s   O  g   2CuO  s  is measured and plotted as a
2
function of temperature (T). Of the 4 possible graphs shown below, which one would most likely represent the
observed trend?
3
Hf
1
T
(a) 1 (b) 2 (c) 3 (d) 4

24. During isothermal expansion of an ideal gas which of the following happen:
(i) Temperature does not change
(ii) Process is spontaneous
(iii) The energy of the system does not change
(iv) Entropy increases
(a) (i) and (iii) only (b) (i), (ii), and (iv) only
(c) (i), (iii), and (iv) only (d) (i), (ii), (iii) and (iv)
7
kON
25. + H H
kOFF
Protein Drug Protein-Drug complex
NMR spectroscopy can be used to assay for drug binding to certain protein targets. One of the primary
objectives of any binding assay is the quantification of the free and the bound forms of a drug molecule at a
certain concentration of the protein target. Let us assume that the fully bound drug exhibits a 1H chemical shift
of A while that of the free form resonates at B for the same proton (see figure above). if the exchange
timescale (i.e. proportional to kOFF as kON is diffusion limited) between the free form of the drug and its bound
form is in microseconds, which of the following statements cannot be true assuming that the drug is only 50%
bound with its protein target?
(a) The NMR linewidth of the observed transition(s) will be different from the free form of the drug.
(b) There will be two resonances obtained in the NMR spectrum of the Protein-Drug complex: one for the free
form while other for the bound form.
(c) We will see a single resonance at a position eff which is in between A and B.
(d) Varying the concentration of the drug molecule while observing the NMR signatures will provide an esti-
mate of the binding constant.
26. What is the value of i log10 i 2 , where i  1 ?

(a) Real and positive number (b) Real and negative number
(c) Complex number (d) Purely imaginary
27. What are X and Y in the following reaction?
O
SiMe3 CsF
X Y
OS(O)2CF3
O
(a) (b) O
X Y X Y
(c) O (d) O
X Y X Y
28. At 25ºC, if the pKa value for a weak acid is smaller than its aqueous solution pH by 2, what is the fraction of the
acid in dissociated form?
(a) 1.10% (b) 99.01% (c) 0.99% (d) More information is needed
29. Cyclooctatetraene is
(a) aromatic, because it is planar and it follows Hückel’s rule
(b) antiaromatic, because it is not planar and it does not follow Hückel’s rule
(c) antiaromatic, because it is planar and it does not follow Hückel’s rule
(d) nonaromatic, because it is not planar and it does not follow Hückel’s rule
8
30. In an experiment measuring the weight of the object, 100 repeats were performed by one student. He found
the mean weight of 332 grams with standard error of the mean as 5 grams. A lazier student only performs 10
measurements on the same object. Which of the following values will her result be closest to?
(a) 330  50 grams (b) 400  15 grams (c) 330  15 grams (d) 330  5 grams
31. The graph below plots the progress of a dimerization reaction involving species A. it depicts a straight line with
slope k (the rate constant). What is the value of the intercept, c in the graph?
slope = k
f([A(t)])
c
0 time
2 1 2
(a)  A  0   (b)  A  0   (c)  A  0   (d) k x  A  0  
32. Two compartments X and Y are separated by an impermeable partition P. In the compartment X, the following
reaction is going on in a solvent S, while the compartment Y contains only the solvent S:
A 2  B2  2AB
Contents of both the compartments are continuously and vigorously stirred. After the reaction in the compart-
ment X has reached equilibrium, the concentrations of A2, B2 and AB are measured and the equilibrium con-
stant calculated. Then the partition is quickly removed. After waiting for a very long time, all the concentrations
are measured again, and the new value of the equilibrium calculated. What is the most appropriate statement
you can make about the result of this experiment? Assume that the chemicals are behaving ideally and the
temperature is kept constant.
X Y
P
(a) The concentrations of all the chemicals and the equilibrium constant will be less than their values before the
partition was removed.
(b) After removing the partition, the concentrations of A2 and B2 will increase, and that of AB will decrease.
(c) After removing the partition, the concentrations of A2 and B2 will decrease, and that of AB will increase.
(d) After removing the partition, the concentrations of all the chemicals will decrease.
33. Assume that the temperature (T) dependence of G for a chemical reaction can be represented by an equa-
tion of the form
G  x  yT  zT 2
What is the expression for the heat capacity change at constant pressure, C p ?
(a) x /T (b) –y (c) –2zT (d) Insufficient information
34. If the outer circle radius is ‘Z’, in the diagram given below, then what is the line segment AB? The ratio of inner
circles’ diameters is 2.
9
A B
4 2 5 2 5
(a) Z (b) close to 2 Z (c) Z (d) Z
3 2 3
35. A kid has been playing with an inflated balloon. suddenly, a reaction happens inside the balloon. This causes the
inside surface of the balloon to become sticky, so that some of the air molecules inside which collide against the
surface get stuck to it. As a result, immediately after the reaction, the balloon will
(a) Inflate (b) Deflate
(c) Remain unaltered (d) Will change its shape without changing its volume
36. The non-bonded interactions between two molecules consist of electrostatic (El) and van der Waals (vdW)
forces. Which of the following is a correct description of the distance dependence intermolecular interactions
between two molecules?
(a) At large distances, El interactions decay faster than the vdW interactions
(b) At large distances, vdW interactions decrease faster than the El interactions
(c) Which force drops faster depends on the net charge of the molecules
(d) Both interactions have same distance dependence
37. “Doping” and “Alloying” are two common terms used to describe the presence of two different elements in one
material. Which one of the following statements is false?
(a) Doping is the process of intentionally introducing impurities into an semiconductor in order to change its
electrical properties.
(b) Doping means making one solid solution.
(c) Alloying is a homogeneous mixture of two or more elements, at least one of which is a metal.
(d) In an alloy, the combined mixture has different properties from those of its component elements.
38. What major products are obtained in the following Mitsunobu reaction?
OH
Ph3P
X + Y
O EtO2C N N CO2Et
H H
CO2Me PhCO2H
CO2Ph
and Ph3P O
(a) O
H H
CO2Me
CO2Ph
and Ph3P O
(b) O
H H
CO2Me
10
OH
and Ph3P O
(c) O
H H
CO2Ph
CO2Ph
and Ph3P O
(d) O
H H
CO2Ph
39. A particle in a 1-D box of length L has eigenstates  n  x  with energies En . Consider two initial states of the
particle at time t = 0: case (1)   x, t  0    n (arbitrary n) , and case (2)   x, t  0    n   m (arbitrary

n and m; n  m ). The probability to find the particle at a specific position within the box:
(a) Varies with time for case 1 but not for case 2
(b) Is time dependent for both cases
(c) Is time independent for both cases
(d) Varies with time for case 2 but for case 1
40. In a rotational microwave spectrum of C12 O16 lines were equally spaced by 3.863 cm–1. In a rotational Raman
spectrum of N2 (normal isotope) the lines were equally spaced by 8.04 cm–1. Assuming that the force constant
for the two molecules is inversely proportional to their bond lengths, the ratio of the vibrational frequency of
CO to that of N2 will be:
(a) 0.8368 (b) 0.9952 (c) 1.0258 (d) 1.2198
The following question does NOT carry any marks and is given to collect information only:
41. How much time did you take to complete this chemistry exam?
(a) Less than 1 hour (b) Between 1 to 2 hours
(c) Between 2 to 3 hours (d) Insufficient time was given
1
TIFR - 2018 CHEMISTRY
1. X-ray diffraction (XRD) is a widely used technique to analyse the structure of slids. In an XRD experiment, a
solid crystal is irradiated with monochromatic X-rays and the resulting data consists of diffraction spots. These
bright spots occur due to the explanation given by which ONE of the following statements?
(a) X-rays are being absorbed by the crystal and the structure in turn emits radiation at specific wavelengths
(b) X-rays are being refracted through the crystal and the rays bend at specific angles
(c) X-rays are being scattered by individual atoms in the solid
2. Which of the following is not correct with regard to the uncertainty principle?
(a) An electron in an atom cannot be defined by a well-defined orbit
(b) The momentum of an electron cannot be measured exactly
(c) A harmonic oscillator possesses a zero-point energy
(d) Measurement of one variable in an atomic system can affect subsequent measurements of certain other
variables
3. Which of the following belong to the same symmetry group as NH3?
(a) BF3 (b) CH4 (c) CH3O (d) CHCl3
PhS SPh NO(g)

Fe
NO
PhS
2
PhS NO PhS NO
(a) Fe (b) Fe
NO NO
PhS ON
NO 3 SPh 3
PhS SPh PhS NO
(c) Fe (d) Fe
PhS NO PhS NO
NO NO
5. Using the data given below, find out the strongest reducing agent:

E0 Cr2O72 / Cr 3  1.33 V  
E0 Cl2 / Cl  1.36 V 
E0  MnO 4 / Mn 2   1.51 V E0  Cr 3
/ Cr   0.74 V
(a) C1- (b) Mn04- (c) Cr (d) Mn2+
6. For electronic transitions in organic molecules, the expected energy ordering of the transitions is:
(a)  to * < n to * < * < n to * (b)  to * < n to * < n to* <  to *
(c) n to * <  to * < n* <  to * (d) n to * <  to * < n to* <  to *
2
7. The volume of a parallelepiped formed by three polar vectors: A = 1i + 2j , B = 4k , and C = 2i + 4j is
(a) 20 cubic units (b) 40 cubic units (c) 12 cubic units (d) 0 cubic units
8. For an one-dimensional quantum-mechanical harmonic oscillator
(a) Average linear momentum is nonzero but average displacement is zero.
(b) Average linear momentum is zero and average displacement is zero.
(c) Average linear momentum is zero but average displacement is nonzero
(d) Average linear momentum and average displacement both are non-zero.
9. Suppose you are carrying out an experiment measuring the Raman spectrum of N2 gas in the outdoor air.
Where would you find a higher strength of the anti-Stokes line:
(a) In Kanyakumari (b) On top of Mt. Everest
(c) The strength will be the same in both the places
(d) Nitrogen would not have an anti-Stokes Raman line
10. If two identical vessels (placed at the same horizontal level) containing water at two different levels are connected
by a pipe at time zero by opening the valve slightly, how would the water levels equalize with time (t)?
h
g
Fig.
opened at t = 0
(a) Linearly with t (b) Exponentially with t

n
(c) As t , where t is time and n is an integer (d) Proportional to t*sin(t)
11. Predict the feasible product/products of the following bio-conjugation reaction.
O
pH 7.4
N + R1 SH
Fig. HEPES Buffer
R
O
O
O
N N R
1. R 2. H
R1 S
O CO2H
3
O O
R
N R N
3. H 4. R S
1
R1 S CO2H
O
(a) 1, 2, and, 3 (b) 1 only (c) 2, 3 and 4 (d) 1 and 2
12. An organic compound (C9H10O3) exhibited the following spectral data: IR: 3400, 1680 cm-I; 'H-NMR: 7.8
(1 H, doublet, J =8 Hz), 7.0 (1 H, doublet, J = 8 Hz), 6.5 (1 H, singlet), 5.8 (1 H, singlet, D2O exchangeable),
3.9 (3 H, singlet), 2.3 (3 H, singlet). The compound is,
O HO
HO
OMe O
(a) (b)
Me Me OMe
O HO
MeO
H O
(c) (d)
OMe OMe OMe
13. The restriction enzyme EcoRI recognizes and cuts a six basepair long DNA sequence (GAATTC). You are
given a bacterial genome which is 5 × 106 basepairs long of unknown sequence. Estimate the number of
EcorRI cut sites that you would expect:
(a) 1220 (b) 10037 (c) 124 (d) 102874
14. The rotational constant for a diatomic molecule is 1.9225 cm-1. In general (within the rigid rotor approximation),
at T = 600 K, for rotation state with maximum population (Jmax) and the position of maximum intensity of pure
rotational absorption spectrum (Imax), which of the following holds True ?
(a) Jmax = 7, while Imax position is near transitions originating from J = 7
(b) Jmax = 10, while Imax position is near transitions originating from J = 7
(c) Jmax = 7, while Imax position cannot be determined from this information alone
(d) Jmax = 10, while Imax position cannot be determined from this information alone
15. Based on the behaviour of the metalloenzymes, consider the following statements
(i) In the enzymes, Zinc activates O2 to form peroxide species
(ii) In the enzymes, Zinc activates H2O and provides a Zinc-bound hydroxide
(iii) In the oxidases, Iron activates O2 to break the bonding between the two oxygen atoms
(iv) Zinc ion acts as a nucleophile and attacks at the peptide carbonyl
Which combination of statements is the correct one:
(a) i and ii (b) ii and iii (c) iii and iv (d) None of the above
16. For a gas that obeys following equation of state P(V-b)= RT , where b is a constant and R is an universal gas
constant, which of the following is right:
 U   U   U   U 
(a)   b (b)   R (c)   P (d)   0
 V T  V T  V T  V T
17. If a cylindrical box with a lid of cross-sectional area 0.01m2 containing air at 1 atmosphere is transferred into a
vacuum chamber, how much of a weight would we have to put on the lid of the box in order to maintain the
internal pressure? Assume that the lid is loosely put on the box and it is massless.
4
(a) ~1 kg (b) ~10 kg (c) ~100 kg (d) insufficient data
18. Phosphite esters undergo nucleophilic substitution with alkyl halides. Predict the final stable product of the
following reaction.
O
P +
O O
O
P O
+
(a) O O (b) P
O O
OH
O O
+ +
P P
(c) O O (d) O O
19. Which amongst the following molecules is chiral?

H OH
O O
COOH OH
OH
O H
I II III
(a) I (b) II (c) III (d) None of the above
20. Thermal desorption rate of adsorbates from a surface can be estimated by using the Arrhenius equation of the
following form:
k = A × exp (–Edes/ kBTs)
Where, k is the rate constant, A is the usual pre-exponential factor, Edes is the desorption energy, kB is the
Boltzmann constant, Ts is the surface temperature. If none of the adsorbates stick permanently to the surface,
which of the following best represents a typical value of A?
(a) 103 sec (b) 1010 sec (c) 10-7 sec–1 (d) 1013 sec-1
21. A unimolecular reaction of chemical species A interconverting with B is studied over a small temperature range
(15 to 25 °C). It is found that reaction proceeds rapidly and that the kAB reaction rate has a strong temperature
dependence, increasing rapidly (by a factor 5 over the range studied) with increasing temperature. However,
the activation free energy AG* is known to be quite small ~5RT. What can you conclude about the reaction:
5
(a) H* and S* are positive and H* is large compared to RT.
(b) H* and S* are positive and H* is small compared to RT.
(c) H* is positive and S* is negative and H* is large compared to RT.
(d) H* is positive and S* is negative and H* is small compared to RT.
22. Which of the following equations meaningfully represents the change of concentration of a non-ribosomal
protein (P) inside a cell. Here  is rate at which proteins are synthesized by the ribosomes from constituent
amino acids, and  is the rate of degradation+dilution of the protein due to proteases and cell growth.
dP dP dP dP
(a)  P   P (b)    P (c)  P   (d)    P
dt dt dt dt
23. Mr. Bhatt has two children; the older child is a boy. Mrs. Ghose also has two children; at least one of them is
a girl. Let Pa be the probability that both children of Mr. Bhatt are boys, and Pa be the probability that both
children of Mrs. Ghose are girls. Assume the following: (1) Birth of boys and girls are independent; (2) no
identical twins are born; (3) neither parent followed sex-selective birth of their offsprings, and (4) none of the
children was transgcnder. What would be values of PB and PG?
(a) PB = PG (b) PB < PG (c) PB > PG (d) PB = PG = 1/2
24. The lattice energy of solid NaC1 is 180 kcal/mole. The dissolution of the solid in water in the form of ions is
endothermic to the extent of 1 kcal/mole. If the hydration energies of Na+ and CC– ions are in the ratio 6:5,
what is the enthalpy of hydration of sodium ion?
(a) –85.6 kcal/mole (b) –97.6 kcal/mole (c) 82.6 kcal/mole (d) none of the above
25. A particle can occupy either of two energy levels: The ground state with energy zero and an excited state with
energy > 0. At a finite temperature T, the probability of occupying the excited level will be if kB is the
Boltzmann constant:
(a) 0 (b) 1+ exp(-/kBT)
(c) exp(–/kBT) / (1 + exp(–/kBT)) (d) 1 / (1 + exp(–/kBT))
26. The Haber process is commonly known as the reaction of Hydrogen gas with Nitrogen gas to prodcue ammonia
in the presence of a catalyst such as iron. Which of hte following statements is true regarding the Haber
process:
(a) Iron serves as a homogenous catalyst for this reaction
(b) Increasing the temperature increases the amount of ammonia formed
(c) Increasing the pressure increases the amount of ammonia formed
(d) All of the above
27. Predict the final product of the following reaction:
Me
1. Heat
?
2. Maleic anhydride, AlCl3
Me
H Me H Me
H H O
Me Me
O
(a) O (b)
O O O
6
H Me H Me
Me Me O
H H
O
(c) O (d)
O O O
28. The fully symmetric C-H stretching mode (a1) of CH4 was detected to be at 3025 cm–1. The C–H bending
mode (t2) on the other hand was detected to be at 1380 cm–1. If complete H/D exchange labeling was done to
produce the moelcule CD4, and the frequency ratio RD is defined as = [Vbend/Vstretch] for CD4 while RH =
[Vbend/Vstretch] for methane; which of the following statement is TRUE about RH?RD and the vibrational technique
used for detection:
(a) RH/RD= 1.4 while IR spectroscopy can be used to detect both the symmetric stretch and the bending
mode.
(b) RH/RD= 1.0 while Raman spectroscopy can be used to detect both the symmetric stretch and the bending
mode.
(c) RH/RD= 1.0 while IR can detect the symmetric stretch and Raman the bending mode.
(d) RH/RD = 1.4 while Raman can detect the symmetric stretch and IR the bending mode.
29. You want to purify a DNA binding protein (pI ~ 9.0) from other cellular proteins (pI ~ 5.5) by ion exchange
chromatography. You have the choice of choosing high pH (9.0) or low pH (5.5) buffers and anion and cation
exchange columns. Anion exchange columns are positively charged and cation exchange columns are negatively
charged. To purify the protein you will use:
(a) Anion exchange column with a low pH (5.5) buffer.
(b) Anion exchange column with a high pH (9.0) buffer.
(c) Cation exchange column with a low pH (5.5) buffer.
(d) Cation exchange column with a high pH (9.0) buffer.
30. The position of a particle in space has a Gaussian probability distribution function. This implies that the underlying
potential energy surface for the particle
(a) Is flat in space
(b) Has a linear dependence on spatial coordinates
(c) Has a quadratic dependence on spatial coordinates
(d) Has a cubic dependence on spatial coordinates
31. A reaction involving chemical species "R", "G", "P" and "H" has the observed stoichiometry:
2R + G  P + H
The experimentally observed rate equation for this reaction is rate = k[R]2. Which of the following is a possible
mechanism for the above reaction?
(a) R + G  I (fast); I + R  P + H (slow)
(b) R + R  I (fast); I + G  P + H (slow)
(c) R + R  I (slow); I + G  P + H (fast)
(d) R + G  I (slow); I + R  P + H (fast)
32. If R and r are the radii of outer and inner circles, respectively, the hat is R/r?
[Hint: the triangle is equilateral]
7
(a) 0.5 (b) 2 (c) 2 3 (d) 4

33. Where on a given protein are you more likely to find a Leucine residue whose structure is given below:
NH2
O
OH
(a) In the interior part of the protein
(b) In the exterior part
(c) Equally likely in the exterior or the interior parts
(d) Depends on whether the protein is water-soluble or is a membrane protein
34. A bottle contains hydrogen molecule in gaseous state. The nuclear wavefunction of this hydrogen gas is given
by:
1
  1   2    1   2  
2
What would be the NMR spectrum of this hydrogen gas, assuming that the wavefunction does not change
during recording of the NMR spectrum?
(a) A single NMR peak
(b) Two NMR peaks, each is a doublet
(c) Three NMR peaks, with relative intensities 1:2:1
(d) No NMR lines
35. Suppose a reaction A  B is slowly progressing in a closed vessel (no energy or material in supplied from the
outside). To speed it up, you have the option of simultaneously carrying out a separate reaction in the same
vessel, which can be either be i) C  D, or ii) E  F . The free energy diagram of the reactions i) and ii) are
given below in the Figure below respectively. Which reaction would you chose to carry out to speed up A 
B? Assume that the individual reactants C and E as well as products D and F do not interact in any way with A
or B.
(i) (ii)
Free Energy
Free energy
D
C E F
Reaction co-ordinate Reaction co-ordinate
(a) E  F (b) C  D
(c) Neither will affect the rate (d) Both can help equally
8
36. Identify the high-spin complex amongst the choices given below:
3 3 3
(a)  Co  NH3 6  (b)  Co  CN3 6  (c)  CoF6  (d) None of the above
37. What is the role of reagent A in the macrocyclization reaction based on the nucleophilic attack of 2 on 1?
N
N
S O O S water/toluene
LiOH NH
+ NH
N
O O
S C16H33P+)C4H9)3
S O
NH HN (reagent A)
O
N 80°C, 6th
(a) Reagent A is transferred to the toluene layer and pulls hydroxyl ions to toluene to deprotonate 2.
(b) Reagent A acts as a catalyst for the macrocyclization reaction by forming coordinate covalent bonds with
1 and 2.
(c) Reagent A is transferred to water and hydroXyl ions are transferred to toluene to deprotonate 2.
(d) Reagent A reacts with LiOH to form a lithiated intermediate that catalyzes the reaction.
38. Consider a polar diatomic molecule (with bond along the x-axis) whose internuclear potential, near the equilibrium

geometry is well described by a harmonic oscillator. Suppose a weak electric field  E  is turned on such that

the system is perturbed by an amount H' = —k x E × x (k is a proportionality constant). Using first order
perturbation theory, the shift in the ground state energy level is equal to:
 
(a) 1 2   q  E  x (b) 0 (c)  1 2   q  E  x (d) None of the above
39. The following bio-conjugation reaction is known as native chemical ligation (NCL) and is used to stitch to
peptides together. The intermediate for this reaction has been shown. Predict the product of the following NCL
reaction.
9
HS
S +
O H2N
O
= amino acid in a peptide chain
H2N
O Intermediate
O
(a)
N N
H H
SH
O
(b) N
H
O
HS
(c)
N
H
O O
S S
(d) ;
N
H
O O
40. Identify the products A and B in the following reaction scheme
10
CHO
1. PPh3
2. NaH OH
Br
Br I P
NaH
C
(a) I = Br Ph3P P=
PPh3
(b) I = Ph3P P=
OH
OH
PPh3
(c) I = Ph3P P=
OH
OH
(d) I = Br Ph3P P=
O
41. How much time did you take to complete this chemistry exam?
(a) Less than 1 hour (b) Between 1 to 2 hours
(c) Between 2 to 3 hours (d) Insufficient time was given

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1

(a) H2C CH at both the temperatures.

(b) H3C C CH2 CH at 5°C and H3C C CH CH at 45°C and

(c) H3C C CH CH at 5ºC and H3C C CH2 CH at 45ºC

(d) H3C C CH2 CH at 5ºC and H3C C C CH at 45ºC

(a) V and Mo (b) V and Na (c) Mo and Na (d) Na, V, Mo

(a) CaTi12O8 (b) CaTi8O12 (c) CaTiO3 (d) CaTi2O3

(a) i (b) ii (c) iii (d) all of the above

(B) CH3OCH3 CH3OCH2OCH3 H3C

(C) H2C CH2 H H O H

24. Consider the following two infinite series:

What is the value of A2 + B2 ?

(a) The decay of 1A* will be multi-exponential

34. Read the following two statements carefully:

39. Consider the following two matrices:

(a) H 3 N   CH 2  COO  and H 2 N  CH 2  COO 

3. What is the major product if HBr (in excess) is added to H 2 C  CH  CH 2  OH

Picture reproduced from Masgrau et al. Science (2006)

(a) (C6H5)3P Ir P(C6H5)3 (b) (C6H5)3P Ir P(C6H5)3

(c) (C6H5)3P Ir P(C6H5)3 (d) (C6H5)3P Ir P(C6H5)3

30. What is the value of this continued fraction?

280 290 300 310

Amount (mg) 100

(a) D = 126, E = 167 (b) D = 0.085, E = 0.229

11. The standard redox potential of water oxidation to dioxygen is –1.23 V.

The redox potential of the same reaction at pH = 7 would be

(a) CH3CH  CH3  CH 2 X (b) CH3C  CH3 2 CH 2 CH 2X

(c) CH3CH 2  CH3  CH 2 X (d) CH3CH 2CH  CH 3  X

(a) HO CH2 CH (b) O CH2 CH

(c) HO CH2 CH (d) O CH2 CH

(a) The Size of Balloon 1 = Balloon 2 = Balloon 3 = Balloon 4 = Balloon 5.

(a) 2  10 9 M (b) 1.98 107 M (c) 2  10 6 M (d) 1.8 10 7 M

pNO(mmHg) p H2 (mmHg) Initial rate (M/min)

9. The speed of a reaction that involves an enzyme increases as

H2N CHC OH H2N CHC OH H2N CHC OH H2N CHC OH

CH2 CH2 CH2 CH2

11. If the CO stretching frequency of Ni (CO)3(P(OMe)3) is A, and that of Ni(CO)2(PMe3)2 is , then

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

18. Point of group 1, 2-propadiene is

19. Which of the following statements is true regarding amphiphilic molecules?

(a) (dxy); Mn(V) to Mn(IV) is slower than Mn(IV) to Mn(III)

(d) (dxy); Mn(V) to Mn(IV) is faster than Mn(IV) to Mn(III)

(200) (220) (311) a

(a) MeO (b) MeO

(c) Reaction is unfavourable under given reagents

34. Real gases behave differently from ideal gases because:

 CO 2 (g)  H 2 (g)

36. Global warming is due to increase of

1. For the following reaction,

3. For the following chemical reaction

6. Phosphorescence is a slower process than fluorescence because

(a) t  1/  k1  k 2 /2  (b) t  1/k1  1/k 2

21. What is ii ? (Given, i2 = –1)

(a) 19.8 Hz (b) 0.066 Hz (c) 6.6 Hz (d) data is insufficient

COOMe Pg Liver Esterase

(a) COOH COOMe

(b) COOMe COOH

(c) COOH COOH

(d) COOH COOH

32. What is the nature of silicon-oxygen bonds in silica (SiO2)?

(a) X: (2R, 3S)-3-benzyl-2, 3-dimethyloxiran-2-yl)methanol

35. The mathematical expression e i kx t  represents

1. Predict the product for the following sugar functionalization reaction :