CHEMACADEMY 1

TIFR PREVIOUS YEAR QUESTIONS WITH SOLUTION

(2014 TO 2019)
INORGANIC CHEMISTRY
1. In isoelectronic ions VO 34 , CrO 24  and MnO4 , all members have intense charge transfer transistion. The
INCORRECT statement is
(a) The charge on the metal nucleus increase in the order VO34  CrO 24  MnO 4 .

(b) The wavelengths of transitions increase in the order VO34  CrO 24  MnO 4 .
(c) Charge transfer transitions are attributed to excitations of electrons from ligand to metal
(d) MnO4 exhibits charge transfer at shortest wavelength amongst the three.

Soln. In MnO4 , Mn is in +7 oxidation state and a dº system. Oxido ligand is  donar which stablises higher
oxidation state of Manganese through  donation 3d orbitals in Mn (+7) is relatively most stablised and
lowest in energy compared with CrO24  and VO34 ions and the energy gap between 3d of Mn (+7) and
2p donor orbital of O2– ligand is smallest. Therefore to effect charge transfer from O2–(2p)  Mn+7 (3d)
we need lowest energy or say highest wavelength photon compared with other two oxoions.

2.
CHEM ACADEMY
Option (d) is incorrect.
Identify the high-spin complex amongst the choice given below:
(a) [Co(NH3)6]3+ (b) [Co(CN)6]3– (c) [CoF6]3– (d) None of above
Ans. (c)
Soln. In all three complexs Co is in +3 oxidation state which is a d6 system. In octahedral complex electronic
configration can be either t 42 g e g2 or t 62g depending upon strength of ligand field. As CN–, NH3 are strong
ligand suggested by spectrochemical series where as F– is weak field towards Co3+ ions, therefore with 6F–
ligand Co+3 tends to form high spin complete therefore [CoF6]3– is high spin with t 42 g e g2 configuration.
3. The acidity of molecules is usually measured by a parameter called the pK3. Metal ions (Mn+) solubilized in
water form solvated aqua complexes commonly denoted by [M(H2O)m]n+ or Maqn+. It is known that the
pK3 of coordinated water in such metal-aqua complexes will be different from that of bulk water. For the
following set of metal-aqua complexs: Ca aq 2 , Feaq 2 , Mn aq 2 , Feaq 3 ; arrange the complexes with de-
creasing value of expected pK3 of the coordinated water molecule.

(a) Feaq 2  Mn aq 2  Ca aq 2  Feaq3 (b) Ca aq 2  Mn aq 2  Feaq 2  Feaq 3

(c) Feaq 2  Feaq3  Mn aq 2  Ca aq 2 (d) Mn aq 2  Ca aq 2  Feaq 2  Feaq3

Ans. (b)

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CHEM ACADEMY 2

Soln. Pka values of water coordinated complexes suggests about the acidity of aqua complexes. When water as
a lewis base coordinates to metal ion (lewis acid) there occurs a partial positive charge on electronegative
oxygen which makes it highly unstable and consequently O–H bonding electrons shifts towards oxygen
and tendency to lose H as proton increases. Extent of deficiency on oxygen depends upon charge density
or oxidation state of metal ions and also bond strength of M–OH2 bond. Strength of this bonds is also
influenced by cfse of octahedral metal aqua complex.
Among the given aqua metel ion complexes Fe+3 (aq) has highest oxidation state so most acidic and hence
lowest value of Pka .
On comparing Ca2+ (aq) and Mn+2 (aq), crystal field stablization effects are absent for both and now
acidity depends on charge density.
since Mn2+ has smaller size than Ca2+ and so Mn+2 possess higher charge density therefore Mn+2 (aq) is
more acidic than Ca2+ (aq).
On comparing Mn+2 (aq) and Fe+2 (aq)
Metal ion–OH2 bond for Fe+2 ion is more stable due to cfse contribution of –0.4 o and hence H2O ligands
form more stable complex with Fe+2 ion (more favourable interaction) and hence Fe+2 (aq) is more acidic
than Mn+2 (aq)
 Correct acidity order is
Ca2+ (aq) < Mn2+ (aq) < Fe+2(aq) < Fe+3 < (aq)
least acidicCHEM ACADEMY
so pka order is reverse of acidity sequence
most acidic

Ca2+ (aq) > Mn+2 (aq) > Fe+2 (aq) > Fe+3 (aq)
option (b) is correct.
4. The complex showing a spin-only magnetic moment of 2.82 B.M. is
(a) [Ni(CO)4] (b) [NiCl4]2– (c) [Ni(NH3)4]2+ (d) [Ni(CN)4]2–
Ans. (b)
Soln. (A) In Ni (CO)4 , Ni is in 0 oxidation state so it is a d8s2 system which in the presence of strong  acceptor
CO ligands undergoes electron pairing means d8s2 converts to d10 system. so it has 0 unpaired electron
 Ni (CO)4 is diamagnetic.
(B) In [NiCl4]2– complex Ni is in +2 oxidation state so it is d8 system. Cl– is a weak field ligand and hence
it forms tetrahedral complex to give e2 t 42 configuration in which these are 2 unpaired electrons accounting

for paramagnetism of this complex. Value of magnetic susceptibility is given by S.O = n(n  2) where n
is number of unpaired electron.
In (C) and (D) complexes, the Nickel metal is in +2 oxidation state which is d8 system. such d8 systems in
the presence of strong field CN– and NH3 ligands tends to form square planar complex due to appreciably
larger electronic stablization called cfse and are diamagnetic in nature, therefore S.O = 0
option (b) is correct

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CHEMACADEMY 3
5. Given the molecular formula of the hexa-coordinated complexes
(I) CoCl3(NH3)6 (II) CoCl3(NH3)5 (III) CoCl3(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
Ans. (d)
Soln. (I) CoCl3 (NH3)6
Since 6NH3 ligands are directly connected to Co+3 ion and NH3 ligands are neutral in nature therefore
this +3 charge in I complex appears on coordination sphere as
[Co (NH3)6]3+. 3Cl–
(II) As 5 NH3 and 1Cl– ligands are directly coordinated to Co+3 ion in coordination sphere to give
[Co (NH3)5Cl]+2. 2Cl–. NH3
Charge an coordination sphere is +2 whereas oxidation state of cobolt is still +3.
Similarly for complex III in which 4NH3 directly connects to Co+3 ion to give
[Co(NH3)4Cl2]+ . 2Cl– . 2NH3
In this complex cobalt metal is still in +3 oxidation state so in all complexes cobalt metal is in +3
oxidation state.

6.
CHEM ACADEMY
option (d) is correct.
Predict the products of the following reactions:
[Pt(PPh3)4]2+ + 2Cl–  X
[PtCl4]2– + 2PPh3  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]
Ans. (b)
2+ +
Ph3P PPh3 Ph3P PPh3
Soln. Pt + Cl- Pt
Ph3P PPh3 Ph3P Cl
–
Since trans effect of PR3 is greater than that of Cl ligand as suggested by trans directing series. So PPh3
trans to PPh3 is replaced to give
Ph3P PPh3
Cl - Pt
Cl Cl
cis chloro complex.
(X)

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CHEM ACADEMY 4

2- -
Cl Cl PPh3 Cl Cl PPh3
Pt Pt
Cl Cl Cl PPh3

since trans effect of PPh3 is larger than Cl– so Cl– trans to PR3 is replaced relatively easily and we get

Ph3P Cl
(trans product)
Pt
Cl PPh3
(Y)

Option (B) is correct

7. Which of the following cannot act as a chelating agent?
(a) HC (CH2CH2NH2)3 (b) CH3NHCH2CH2CH3
(c) N(CH2CH2NH2)3 (d) H2NCH2CH2CH2NH2
Ans. (b)
Soln. For any ligand to behave as a chelating ligand (to form a ring), it must have atleast two donar sites to give
chelate ring.
CHEM ACADEMY (CH2) n

L L
M
H 2 H2
H3C C C CH3
Since N has only one donar atom so it is monodentate ligand and can never act as
H
polydentate to give chelate ring.
Option (b) is correct.
8. For Co in oxidation state II, predict the overall charges of the coordination complexes shown in the
reactions below:
x y
z OH2
OH Cl Cl
H2O OH 2
H2O OH 2 NaOH HCl Co
Co + 6H 2O
Co
Cl Cl
H 2O OH
H 2O OH2 OH2 2
OH

(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
Ans. (b)

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CHEMACADEMY 5
NaOH
Soln. [Co (H2O)6]+2 


OH 2
H 2O OH2
Co
H2O
OH
H
OH -

Here two H+ will be abstracted by base hydroxide and hence form [Co (H2O)4 (OH)2] and overall charge
on Co will remain as +2 and total charge on coordination sphere is zero.
If [Co(H2O)6] is treated with an acid like HCl then all the secondary water molecule will be replaced by
4Cl–, and hence [CoCl4]– is formed which will contain overall charge of –2.  [CoCl4]–2

ORGANOMETALLICS REACTION MECHANISM

9. The clusters Sn 52 , Ge94  and Rh6 (CO)16 have structure respectively:

Ans.
CHEM ACADEMY
(a) nido, closo and closo
(c) arachno, closo, and nido
(d)
(b) closo, nido and arachno
(d) closo, nido and closo

Sn 52 Apply un rule

Sol.   4  5  2  4n  2
TVE  4  5  2  22 closo shape

Ge 94 Apply un rule

  4  9  4  40
TVE  4  9  4  40 4n  4  nido

Rh 6  CO 16
 
TVE  9  6  2  16  54  32  86

TVE  12n 86  12  6
nx   6 x 
2 2

14
6x  7
2

x  7  6  1 closo

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CHEM ACADEMY 6

10. What is the product of the following reaction?

-
PhS SPh
Fe NO (g)
PhS NO
- 2-
PhS NO PhS NO
(a) Fe (b) Fe
PhS NO ON NO

3- 3-
NO SPh
PhS SPh PhS NO
(c) Fe (d) Fe
PhS NO PhS NO
NO NO
11. Predict the relative rates for the following reductive elimination for X = H, Cl, CH3, OCH3

L II H L 2Pt 0 + CH 4
L
Pt
CH 3
CHEM ACADEMY
L= P X
3

(a) Cl > H > CH3 > OCH3 (b) H > Cl > OCH3 > CH3
(c) OCH3 > CH3 > H > Cl (d) CH3 > H > Cl > OCH3
Ans. (a)
Sol. Reductive elimination is directly proportional to the oxidation state.
Secondary if oxidation state is same then it is directly proportional to EWG (–M or –I) and inversely
proportional to the EDG (+M, +I)

Hence, Cl   H  CH3   OCH 3  Rade order 

 I   I   M 
BIOINORGANIC
12. 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 uphill if the water oxidation reaction be
carried out at pH = 0 versus at pH = 7.0?
(a) 0.41 eV (b) -1.6eV
(c) -0.41eV (d) Cannot be calculated based on the data given
Ans. (a)

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CHEMACADEMY 7
CHEMICAL BONDING
13. The short-ranged mtermolecular interactions are often described by the Lennard-Jones potential V(r) =
4[/r)12 – (/r)6], which gives the internal energy of interaction between two molecules as a function of
intemolecular separation. Here  is the depth of the potential well,  is the finite distance at which the inter-
particle potential is zero, r is the distance between the particles, and rm is the distance at which the potential
reaches its minimum At rm, the potential functions has the value –.
If you would like to express the same potential energy function in terms of rm and , the function should be
5
V/
4
3
2
1
0
-1
0 1rm 2 r/

(a) V (r) = [rm/r)12 – 2(rm/r)6] (b) V(r) = [(rm/r)12]

(c) V(r) = 4[(rm/r)32– (rm/r)6] (d) V(r) = [2(rm/r)12– (rm/r)6]

CONDUCTORS/SEMICONDUCTORS
14.
CHEM ACADEMY
“Doping” and “Alloying” are two common terms used to describe the presence of two different element 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) Dopping 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.
Sol. Correct option is (b)
15. Solid inorganic material are commonly classified as conductors, semi-conductors or insulators as deter-
mined by their bandgap. Carbon has many allotropes such as diamond, graphite, carbon nanotubes and
graphene with distinct bandgaps. Considering the properties of diamond, what should be its bandgap.
(a) 7.0 eV (b) 1.0 eV (c) 0.01eV (d) 0 eV
Ans. (a)
Sol. Since, graphite is a insulation, so it must have high energy difference between its conduction and valance
bond.
Conduction
Band
Band
gap

Valance Band
So, correct option is 7.0 eV.

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CHEM ACADEMY 8

16. In a 1 g 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
Ans. (d)
Sol. Carbon is replaced by Nitrogen
2s22p2 2s22p3
extra electron
so, n-doped diamond
Correct answer is (d)
17. Which of the following statements is TRUE regarding the electrical conductivity of HCl in aqueous solu-
tion, HCl as a gas and HCl in benzene?
(a) All three conduct electricity because HCl is a strong acid

CHEM ACADEMY
(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
Ans. (b)
Sol. For conduction of electricity a species must produce ions.
Ionic solutions have capability to conduct electricity.
HCl in aqueous solution
HCl(aq.)  H+(aq.) + Cl–(aq.)
Ions thus formed are responsible for electrical conductivity of HCl in aqueous solution.
HCl in benzene
Benzene dissolves the HCl as molecular entity. no ions are present and have no electricity can be con-
ducted.
HCl is dissolved as molecular entity in benzene as benzene is a non-polar solvent.
Similarly HCl gas is also not ionised. So it also does not conduct electricity.

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CHEMACADEMY 9
ACID BASE/INORGANIC REACTIONS
18. What are the products of the following reaction?
LiAlH4 + Et3NHCl Toluene

(a) H2 + Et3N + LiCl + AlH3 (b) LiH + Et3N + HCl + 0.5 Al2H6
(c) LiCl + H3Al:NEt3 + H2 (d) LiCl + NEt3 + H2 + 0.5 Al2H6
Ans. (c)

 + Cl–
Sol. LiAlH3 H + El3 N H

LiCl + H2 + AlH3 + Et3N:

Co-ordinate bond
forms between them
H3Al  NEt3

19. What is the product of the following reaction?

CHEM ACADEMY
n
BuLi
H3 N :  BH 3 
THF/0ºC

(ammonia borane)

H 3N: BH 3
H 3N: BH 3
(a) nBu (b)
Li Li

H 2N: BH 3
(c) (d) No reaction
Li

Ans. (c)

 
Sol. H  H 2 N  BH 3 H  H 2 N  B H3
 
B u Li
more acidic less acidic

H 2 N  BH 3
Li

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CHEM ACADEMY 10

correct answer is (c)

20. What is the product of the following reaction?

O
(dioxane)
O
GeCl4 + nBu3SnH
Dietheyl Ether
\n-Hexane

(a) HGeCl3 (b) Cl2Ge:Dioxane

n
(c) Cl3Ge–Sn Bu3 (d) none of the above
Sol. Correct answer is (b)
21. Free water pKa is 15.7 at 25ºC. Based on the free water pKa benchmark, arrange the acidity of the
“bound” water molecules in increasing order within the following metalaqua complexes: [Mn(H2O)6]2+,
[Cu(H2O)5]2+, [Ca[H2O)8]2+, [Sr(H2O)8]2+
(a) Ca2+ < Mn2+ < Cu2+ < Sr2+
(b) Mn2+ < Cu2+ < Sr2+ < Ca2+
(c) Sr2+ < Ca2+ < Mn2+ < Cu2+

Ans. (c)
CHEM ACADEMY
(d) All have same acidities

Sol. For acidity of aqua complexes:

Non-transition metal complexes  More the oxiclation state of metal, more will be acidity.
Transition metal complexes  For M2+: Mn2+ < Ni2+ < Co2+ < Fe2+ <Cu2+ < V2+ < Cr2+ and M3+ > M2+
(acidity).
Also Acidity of Tm complexes > Non-Tm complexes
Based on above factors
Ans.: Sr2+ < Ca2+ < Mn2+ < Cu2+

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