Inorg

How many milligrams are in 0.2 decigrams?
(a) 20 milligrams 0.2dg x g/10dg x 1000mg/g = 20 mg
(b) 2000 milligrams
(c) 0.002 milligram
(d) 0.00002 milligram
2. What would be the volume in liters of 640 g of oil if the density of the oil is 0.8 g/mL?
(a) 800 liters
(b) 0.8 liter b
(c) 512 liters
(d) 0.5 liters
3. Five 1 peseta coins from Spain were dropped into a graduated cylinder containing 20.20
mL of water. The volume of the water increased to 22.05 mL. A single coin had a mass of
0.99 gram. What is the identity of the metal used for the Spanish 1 peseta coins?
density of aluminum = 2.7 g/mL
density of zinc = 7.1 g/mL
density of copper = 9.0 g/mL
density of silver = 10.0 g/mL
(a a) aluminum
(b) zinc
(c) copper
(d) silver
4. The mass of a metal cylinder was determined on an analytical balance to be 50.208 g. The
volume of the cylinder was measured and determined to be 5.6 mL. The density of the metal
cylinder, expressed to the proper number of significant figures, is...
(a) 8.9657 g/mL
1
(b
9.0 g/mL
b)
(c) 0.11153 g/mL
(d) 0.11 g/mL
5. Two students, Garrison and Isabella, determined the mass of an object on two different
balances. The accepted mass of the object was 2.355 g. Garrison obtained values of 2.531 g,
2.537 g, 2.535 g and 2.533 g. Isabella obtained values of 2.350 g, 2.404 g, 2.296 g and 2.370
g. Which statement best describes the results that were obtained by Garrison and Isabella.
(a) Garrison obtained the better accuracy.
(b b) Isabella obtained the better accuracy.
(c) Garrison obtained the better precision.
(d) Isabella obtained the better precision.
You are correct! Although her values were scattered widely, the average value she obtained
had a 0% error. Percent error is calculated by...% error = (accepted value - experimental
value)/accepted value x 100%. Isabella's percent error was 0%.
1. The probability area that best represents the shape of one of the atomic 3d orbitals is... option d is
correct
2. The common isotopes of carbon are 12C and 13C. The average mass of carbon is 12.01115 amu.
What is the abundance of the 13C isotope?
2
(a a) 1.115%
(b) 98.885%
(c) 0.480%
(d) 99.52%
3. If the abundance of 6Li (6.015121 amu) is 7.500% and the abundance of 7Li (7.016003 amu) is
92.500%, what is the average atomic mass?
(a) 6.0750 amu
(b) 6.0902 amu
(c) 6.9250 amu
(d
6.9409 amu
d)
4. What do the following have in common?

20 19 - 24
Ne F Mg2+
(a) They are isotopes of each other.
(b) They are isomers of each other.
(c c) They are isoelectronic with each other.
(d) They are different elements so they have nothing in common.
5. How many valence electrons does an oxygen atom have?
(a) 2
(b
6
b)
(c) 8
(d) 16
6. Fluorine atoms tend to...?...when they form chemical compounds with metals.
(a) lose electrons
3
(b
gain electrons
b)
(c) neither lose nor gain electrons...they usually share electrons equally with metals.
(d) Fluorine atoms do not form compounds with other atoms...fluorine is an inert gas.
7. The identity of an element is determined by...
You are correct! Protons cannot be lost or gained by an atom and therefore they do determine the
element's identity.
(a a) the number of its protons.
(b) the number of its neutrons.
(c) the number of its electrons.
(d) its atomic mass.
8. The probability area that best represents the shape of an atomic 3p orbital is... option b is correct
coz p orbital has 2 identical lobes.
9. Which of the following electron configurations represents the electron configuration for a
magnesium cation...Mg2+?
(a) 1s22s22p63s2
(b) 1s22s22p63s23p2
(c c) 1s22s22p6
(d) 1s22s22p4
10. Which of the following orbital box diagrams represents silicon, which has 14 electrons?
4
Option
c is
correct
11. The half-life of francium-212 is 19 minutes. How many minutes will it take for 1 gram of this
isotope to decay to 0.125 grams?
(a) 4.75 minutes
(b) 9.5 minutes
5
(c) 38 minutes
(d
57 minutes
d)
12. The atom formed by the beta decay of carbon-14 is...
(a) oxygen-18
(b) beryllium-10
(c) boron-14
(d
nitrogen-14
d)
Chemical periodicity
Chemical periodicity :
JUN- DEC- JUN- DEC- JUN- DEC- JUN- DEC- JUN- DEC- JUN-
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 1 2 2 1 2 2 1
1.The size of the d orbitals in Si, P, S and Cl follows the order.
(a) Cl> S > P > Si
(b) Cl> P > S > Si
(c) P > S > Si >Cl
(d) Si > P > S >Cl
6
Hide Answer
Ans (d)
Soln:
Size of d-orbitals decrease with decrease in size of element. The decreasing order of size is
Si > P > S >Cl.
Therefore decreasing order of size of d-orbitals is Si > P > S >Cl
2.The least basic among the following is:
(a) Al (OH)3
(b) La (OH)3
(c) Ce (OH)3
(d) Lu (OH)3
Hide Answer
Ans (a)
Soln:
Al (OH)3Amphoteric whereas hydroxides of lanthanoids are all base.
3.For an odd nucleon in g nuclear orbital and parallel to I, spin and parity are
(a) 9/2 and (+)
(b) 7/2 and (+)
(c) 9/2 and ()
(d) 7/2 and ()
Hide Answer
Ans (a)
Soln:
In g nuclear orbital total subshell is nine.
7
+
One odd nucleon finding in g-subshell
Total spin = 9/2
Parity=(-1)l= (-1)4 = (+)
4.The electronegativity differences is the highest for the pair
(1) Li, Cl
(b) K, F
(c) Na, Cl
(d) Li, F
Hide Answer
Ans (b)
Soln.
Among these elements K is least electronegative and F is most electronegative. Therefore

electronegativitydifference is highest for the pair K, F.
5.Among F, Na+, O2-and Mg2+ions, those having the highest and the lowest ionic radii
respectively are
(a) O2-andNa+
(b) F and Mg2+
(c) O2-andMg2+
(d) Mg2+andO2-
Hide Answer
Ans (c)
Soln:
All the given species are isoelectronic. Hence greater the nuclear charge, smaller will be the
ionic radii.
8
6. 12-Crown-4 binds with the alkali metal ions in the following order:Li+>> Na+> K+>
Cs+ .It is due to the
(a) Right size of cation
(b) Change in entropy being positive
(c) Conformational flexibility of crown ether
(d) Hydrophobicity of crown ether
Hide Answer
Ans (a)
Soln:
Each crown ether binds different ions, depending on the size of the cavity.
(Reference: Advance Organic Cheimistry, Jerry March, M. Smith)
Chemical periodicity
7. The correct order of decreasing electronegativity of the following atoms is,
(a) As > Al > Ca > S
(b) S > As > Al > Ca
(c) Al > Ca > S > As
(d) S > Ca > As > Al
Hide Answer
Ans (b)
Soln:
The electronegativities of elements are
Ca Al As S
9
1.0 1.5 2.0 2.5
8.The correct order of the size of S, S2, S2+ and S4+ species is,
(a) S>S2>S2+> S4+
(b) S2+>S4+>S> S2
(c) S2- >S>S2+> S4+
(d) S4+>S2>S> S2+
Hide Answer
Ans (c)
Soln:
As positive charge increases the size decreases while with increase in negative charge
increase the size. This is due to increase in Zeff in former case while decrease in Zeff in later
case.
Hence, order of size is S2- >S> S2+ > S4+
9. Which of the following pairs has the highest difference in their first ionization
energy?
(a) Xe, Cs
(b) Kr, Rb
(c) Ar, K
(d) Ne, Na
Hide Answer
Ans (d)
Soln:
First ionization potential of Ne 2080
First ionization potential of Na 495
I.E. (NeNa) 1585 eV
10
So, 1585 eV is the largest difference in given pairs. The reason being as we move down the
group number of electrons and proton increases simultaneously with addition of new energy
shells so increase in distance from Nucleus to electron is more pronounced as that of
increases in electron and proton resultantly Zeff (effective
nuclear charge) decreases and first ionization potential also decreases down the group.
10. Among the following pairs
(1) oxygen-sulfur (2) nitrogen -phosphorus
(3) phosphorus arsenic (4) chlorine- iodine
Those in which the first ionization energies differ by more than 300kJ mole-1are :
(a) (1) and (3) only
(b) (1) and (2) only
(c) (2) and (3) only
(d) (3) and (4) only
Hide Answer
Ans (b)
11.The formation constant for the complexation of M+(M = Li, Na, K and Cs) with
cryptant, C222 follows the order
(1.) Li+< Cs+< Na+< K+
(2.) Li+< Na+< K+< Cs+
(3.) K+< Cs+< Li+< Na+
(4.) Cs+< K+< Li+< Na+
Hide Answer
Ans (2)
Soln:
11
The ability of cryptant to trap an alkali metal cation depends on size of both cage and metal
ion, the better the math between these; the more effectively the ions can be trapped.
12
Structure and bonding
12
Structure and bonding : in homo- and heteronuclear molecules, including shapes of
molecules (VSEPR Theory).
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 3 4 1 1 2 2 3 1 3 3 4
1. The total number of lone pairs of electrons in I3is:
(a) Zero
(b) Three
(c) Six
(d) Nine
Hide Answer
Ans (d)
Soln:
Number of lone pair of electrons = 9
2. The strength of p-d bonding in EO (E = Si, P, S and C) follows the order
(a) Si O > P O > S O >Cl O
(b) P O > Si O > S O >Cl O
(c) S O >Cl O > P O > Si O
(d) Cl O > S O > P O > Si O
13
Hide Answer
Ans(d)
Soln:
Smaller the inter nuclear distance between two atoms, stronger will be -the bonds. The
increasing or due of inter nuclear distance is Cl O < S O < P O < Si 0
Therefore strength of pnd
bonding is Cl O > S O > P O > Si O
3.The decreasing order of dipole moment of molecules is
(a) NF3 > NH3 > H2O
(b) NH3 > NF3 > H2O
(c) H2O > NH3 > NF3
(d) H2O > NF3 > NH3
Hide Answer
Ans(c)
Soln:
Therefore, order of dipole moment is H2O > NH3 > NF3.
14
4.Which ones among CO32-, SO3, XeO3 and NO3 have planar structure?
(1) CO32, SO3 and XeO3
(b) NO3, SO3 and XeO3
(c) CO32- , NO3 and XeO3
(d) CO32- , SO3 and NO3
Hide Answer
Ans (d)
Soln
sp2-hybridization sp2-hybridization sp3-

hybridization Sp3-hybridization
(Trigonal planar) (Trigonal planar) (Trigonal

pyramidal) (Trigonal pyramidal)
NO3,CO32- and SO3have planar structure.
5.The correct schematic molecular energy diagram for SF6 molecule is
15
Hide Answer
Ans (a)
Soln:
Consider SF6, which has six S-F bonds and hence 12 electrons involved in forming bonds and
is therefore hypervalent. The simple basis set of atomic orbitals that are used to construct the
molecular orbitals consists of the valence shell s and p orbitals of the S atom and one p orbital
16
of each of the six F atoms and pointing towards the S atom. We use the F2p orbitals rather
than the F2s orbitals because they match the S orbitals more closely in energy. From these ten
atomic orbitals it is possible to construct ten molecular orbitals. Calculations indicate that
four of the orbitals are bonding and four are antibonding; the two remaining orbitals are
nonbonding.
(Reference : Inorganic Chemistry, Shriver Atkin)
6.The correct non-linear and iso-structural pair is
(a) SCl2and I3
(b) SCl2and I3
(c) SCl2and ClF2
(d) I3+and ClF2
Hide Answer
Ans (b)
7.The oxidation state of Ni and the number of metal-metal bonds in [Ni CO6]2-that are
consistent with the18 electron rule are
(a) Ni(II), 1 bond
(b) Ni(IV), 2 bonds
(c) Ni(I), 1 bond
(d) Ni(IV), 3 bonds
Hide Answer
Ans (c)
Soln:
17
8.In metal-olefin interaction, the extent of increase in metal olefin p-back-donation
would
(a) lead to a decrease in C = C bond length
(b) change the formal oxidation state of the metal
(c) change the hybridisation of the olefin carbon from sp2to sp3.
(d) increase with the presence of electron donating substituent on the olefin.
Hide Answer
Ans (c)
Soln:
9.The compound that will behave as an acid in H2SO4 is
(a) CH3COOH
(b) HNO3
(c) HClO4
(d) H2O
18
Hide Answer
Ans (c)
Soln:
HClO4behave as an acid in H2SO4. Because HClO4contain higher dissociation constant than

that of H2SO4.HClO4pKa value 9,
H2SO4pKa value 3, HNO3pKa value 1, CH3COOH pKa value 4.7.pKa value of HClO4>
pKa value of H2SO4.
10.Electron change in reduction of Ce(SO4)2, KMnO4, HNO2 and I2 with hydrazine in

acidic medium, respectively is
(a) 1e, 1e, 2e and 4e
(b) 1e, 3e, 2e and 4e
(c) 2e, 3e, 1e and 4e
(d) 2e, 4e, 1e and 3e
Hide Answer
Ans (a)
Soln:
Ce(SO4)2and KMnO4gives one electron on reduction with hydrazine in acidic medium and
HNO2 and I2gives
two electron and four electron on reduction with hydrazine in acidic medium.
11.The reason for the chemical inertness of gaseous nitrogen at room temperature is
best given by its
(a) high bonding energy only
(b) electronic configuration
(c) HOMO-LUMO gap only
(d) high bond energy and HOMO-LUMO gap
19
Hide Answer
Ans (d)
Soln:
High bond energy and HOMO-LUMO gap.
12.The orbital interactions shown below represent
(a) CH3Al interactions in Al2(CH3)6
(b) BH interactions in B2H6
(c) CH3Li interaction in Li4(CH3)4
(d) CH3CH2Mg interactions in EtMgBr.(OEt2)2
Hide Answer
20
Ans (c)
Soln
The diagram clearly indicates the four centered-two electron interaction (4c-2e). This takes
place in Liu(CH3)4.
The sp3 hybrid orbital is of carbon while the three s-orbitals are of three surrounding lithium
atoms.
13.Correct combination for and * orbitals in B2 molecules is..
(1) Gerade Ungerade
(2) Ungerade Gerade
(3) Gerade Gerade
(4) Ungerade Ungerade
Hide Answer
Ans (2)
Soln:
Molecular orbital energy level for molecule Li2 to N2are
Energy levels
21
14.The correct shape of [TeF5]ion on the basis of VSEPR theory is
(1) trigonalbipyramidal
(2) square pyramidal
(3) pentagonal planar
(4) see-saw
Hide Answer
Ans (2)
Soln:
Shape of [TeF5]ion on the basis of VSEPR theory is square pyramidal, as shown in the
figure.
15.Choose the correct option for carbonyl fluoride with respect to bond angle and bond
length
(1) F-C-F >F-C-O and C-F > C-O
(2) F-C-F >F-C-O and C-F < C-O
22
(3) F-C-F <F-C-O and C-F > C-O
(4) F-C-F <F-C-O and C-F < C-O
Hide Answer
Ans (3)
Soln:
Carbonyl flouride is written in the following form
From the structure it is clear that q1 is greater than q2 due to more bp-bp repulsion in q1So,
F-C-O is greater than F-C-F and bond length of C-F is greater than C-O bond.
16.In the molecules H2O, NH3 and CH4.
(a) The bond angles are same
(b) The bond distances are same.
(c) The hybridizations are same
(d) The shapes are same.
Hide Answer
Ans (c)
Soln:
All are sp3 hybradized molecules.
23
17.According to VSEPR theory, the molecule/ion having ideal tetrahedral shape is:
(a) SF4
(b) SO3-2
(c) S2Cl2
(d) SO2Cl2
Hide Answer
Ans (b)
18.The highest occupied MO in N2 and O2+respectively are (take x-axis as internuclear

axis)
(a) 2px, *2py
(b) 2py ,2pz
(c) *2px , 2px
(d) *2pz , *2py
Hide Answer
Ans (a)
24
19.The molecule with highest number of lone-pairs and has a linear shape based on
VSEPR theory is:
(a) CO2
(b) I3
(c) N02
(d) N02+
Hide Answer
Ans (b)
20.The number of antibonding electrons in NO and CO according to MO theory are

respectively.
(a) 1, 0
(b) 2, 2
(c) 3, 2
(d) 2, 3
Hide Answer
Ans (a)
21.Among the following pairs, those in which both species have similar structures are:
(A) N3,XeF2 (B)[ICl4] , [PtCl4]2- (C)[ClF2]+ , [ICl] (D) XeO3 , SO3
(a) (A) and (B) only
(b) (A) and (C) only
(c) (A), (B) and (C) only
(d) (B), (C) and (D) only
Hide Answer
Ans (b)
25
22.Match list I (compounds) with list II (structures), and select the correct answer using
the codes given below.
List-I List-II
(A) XeO4 (i) square planar
(B) BrF4 (ii) tetrahedral
(C) SeCl4 (iii) distorted tetrahedral.
(a) (Aii) (Biii) (Ci)
(b) (Aiii) (Bi) (Cii)
(c) (Aii) (Bi) (Ciii)
(d) (Ai) (Bii) (Ciii)
Hide Answer
Ans (c)
23. The molecule C3O2 has a linear structure. This compound has
(1) 4 and 4 bonds
(2) 3 and 2 bonds
(3) 2 and 3 bonds bonds
(4) 3 and 4 bonds
Hide Answer
Ans (1)
Soln:
Structure of carbon sub oxide C3O2
24.The structures of XeF2 and XeO2F2respectively are
26
(a) bent, tetrahedral
(b) linear, square planar
(c) linear, see-saw
(d) bent, see-saw
Hide Answer
Ans (c)
Soln:
XeF2 : linear molecule in vapor state
The three 5p electrons are promoted to higher energy 5d sub-level. The 5s three 5p and one
5d orbitals hybridize to give five sp3d hybrid orbitals. The four singly occupied orbitals are
used for bond formation to two fluorine and two oxygen atoms. The fifth hybrid orbital
contains the lone pair. The other 5d electrons of xenon which do not take part in the
hybridization scheme are involved in -bond formation to two oxygen atoms. The structure of
XeO2F2is represented in Fig.
27
25.The number of lone pair(s) of electrons on the central atom in [BrF4], XeF6and
[SbCl6]3-are, respectively,
(a) 2, 0 and 1
(b) 1, 0 and 0
(c) 2, 1 and 1
(d) 2, 1 and 0
Hide Answer
Ans (c)
Soln:
Formula to calculate Bond Pair and Lone Pair
calculate TVE (total valence electron)
Divide TVE by 8 if 8 < TVE < 56
The quotient will give number of bond pair
while dividing the remainder by 2 will give lone pair on central atom
26.The ground state electronic configuration of C2 using all electrons is
28
Hide Answer
Ans (4)
Soln:
C 1s22s2p2
MOT diagram for C2
1s22s2has been omitted for clarity
Concepts of acids and bases
Concepts of acids and bases : Hard-Soft acid base concept, Non-aqueous solvents.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
1 4 1 2 7 1 1 2 2 1
questions
29
appeared
1.In the reactions (A) and (B),
nH2O + Cl [Cl(H2O)n] (A)
6H2O + Mg2+ [Mg (H2O)6] 2+ (B)
water behaves as
(a) An acid in both (A) and (B)
(b) An acid in (A) and a base in (B)
(c) A base in (A) an acid in (B)
(d) A base in both (A) and (B)
Hide Answer
Ans (b)
Soln:
nH2O + Cl [Cl(H2O)n]
If negative end of O- H+dipole approaches the Clion, then there well be repulsion
ion dipole interaction positive and of O- H+dipole approaches the Clion and form
[Cl(BO)n]
Not stabilized. Thus H2O does not behave as a base
6H2O + Mg2+ [Mg (H2O)6] 2+
In this reaction Mg2+behave as lewis acid and H2O behave as a ligand or lewis base.
2.In the following reactions carried out in liquid NH3.
Zn(NH2)2+ 2KNH2 K2[Zn( NH2)4]
K2[Zn( NH2)4]+ 2NH4NO3 Zn(NH2)2 + 2KNO3+4NH3
KNH2 and NH4NO3 act respectively as
(a) Solvo-acid and solvo-base
(b) Solvo-base and solvo-acid
(c) Conjugate acid and conjugate base
30
(d) Conjugate base and conjugate acid
Hide Answer
Ans(a)
3.Match each item from the List-I (compound in solvent) with that from the List-II (its
behaviour) and select thecorrect combination using the codes given below.
List-I List-II
CH3COOH in pyridine (i) strong acid.
CH3COOH in H2SO4 (ii) weak acid
HClO4in H2SO4 (iii) strong base
SbF5 in HF (iv) weak base
(1) (Ai), (Bii), (Ciii), (Div)
(b) (Aii), (Bi), (Ciii), (Div)
(c) (Aiii), (Biv), (Cii), (Di)
(d) (Aiv), (Bii), (Ciii), (Di)
Hide Answer
Ans (c)
Soln:
CH3COOH + C5H5N : CH3COO+ C5H5NH+ (solvocation)
CH3COOH + H2SO4 CH3COOH2++ HSO4 (solvent anion)
HClO4 + H2SO4ClO4 + H3SO4 (solventcation weak acid)
SbF5 +2HF[SbF6]H2F (strong acid)
4.The reaction between SbF5 and two equivalents of HF leads to the formation of
(a) H2SbF3+ 2F2
(b) HSbF2+ 3F2
(c) SbF3+ H2 + 2F2
31
(d) [SbF6 ]+[H2F]+
Hide Answer
Ans (d)
Soln:
This is a reaction for the production of fluoroantimonic acid.
2HF H2F+ + F
SbF5 + F SbF6
Overall reaction is
SbF5 + 2 HF SbF6 + H2F+
5.Among the following species, (A) Ni(II) as dimethylglyoximate, (B) Al(III) as oxinate,
(C) Ag(I) as chloride,those that precipitate with the urea hydrolysis method are
(a) A, B and C
(b) A and B
(c) A and C
(d) B and C
Hide Answer
Ans (b)
6.The particles postulated to always accompany the positron emission among
(A) neutrino, (B) anti-neutrino, (C) electron,are
(a) A, B and C
(b) A and B
(c) A and C
(d) B and C
Hide Answer
Ans (c)
32
Soln:
Particles that are always to emit during position emission
1P + 1e0 + v (antineutrino)
1 1
0n
7.Among the compounds A-D, those which hydrolyse easily are
(a) NCl3
(b) NF3
(c) BiCl3
(d) PCl3
Hide Answer
Ans (c)
Soln:
BiCl3is readily hydrolysed by water to give BiOCl
BiCl3+H2O > BiOCl
But BiOCl redissolve in conc. HCl to produce BCl3 after evaporation. It has quasi molecular
structure. SbCl3 has similar behaviour to BCl3.
8.The reaction of FeCl3.6H2O with SOCl2yields.
(a) FeCl2(s), SO2(g) and HCl (g)
(b) FeCl3(s), SO2(g) and HCl(l)
(c) FeCl2(s), SO3(s) and HCl (g)
(d) FeCl3(s), SO2(g) and HCl(g)
Hide Answer
Ans (d)
9.Among the following, the correct acid strength trend is represented by
(a) [Al(H2O)6]3+<[Fe(H2O)6]3+<[Fe(H2O)6]2+
33
(b) [Fe(H2O)6]3+<[Al(H2O)6]3+<[Fe(H2O)6]2+
(c) [Fe(H2O)6]2+<[Fe(H2O)6]3+<[Al(H2O)6]3+
(d) [Fe(H2O)6]2+<[Al(H2O)6]3+<[Fe(H2O)6]3+
Hide Answer
Ans (c)
Soln
As the size of metal ion decreases, acidic character increases.
Order of size is Fe2+>Al3+>Fe3+
[Fe(H2O)6]2+<[Fe(H2O)6]3+<[Al(H2O)6]3+
Reference Shriver Atkin (P.No. 123, Bronsted axis base concept)
10.Among the following, an example of a hypervalent species is
(a) BF3.OEt2
(b) SF4
(c) [PF6]
(d) Sb2S3
Hide Answer
Ans (c)
Soln
More than 8 electrons in the valence shell of P in [PF6]
11.Two tautomeric forms of phosphorus acid are
34
Hide Answer
Ans (a)
Soln
H3PO3 is a dibasic and reducing in nature.
12.Xenon forms several fluorides and oxofluorides which exihibit acidic behaviour. The
correct sequence of descending Lewis acidity among the given species is represented by
(a) XeF6> XeOF4> XeF4> XeO2F2
(b) XeOF4 > XeO2F2> XeOF4 > XeF6
(c) XeF4> XeO2F2> XeOF4> XeF6
(d) XeF4 > XeF6> XeOF4> XeO2F2
Hide Answer
Ans (a)
Soln
Relative acidic strength of xenon fluorides follows order
XeF6> XeO3> F2> XeOF4> XeF4 > XeO2F2 > XeO3> XeF2
This order depends upon
(i) number of lone pair (ii) number of F atoms
35
13.The gases SO2 and SO3 were reacted separately with ClF gas under ambient
conditions. The major products expected from the two reactions respectively, are
(a) SOF2 and ClOSO2F
(b) SOF2and SO2F2
(c) SO2ClF and SO2F2
(d) SO2ClF and ClOSO2F
Hide Answer
Ans (d)
Soln
SO2+ClF >SO2ClF
ClF+SO3 >ClOSO2 F
14.Among KF, SnF4 and SbF5, solute(s) that increases(s) the concentration of BrF4
in BrF3,is are
(1) KF only
(2) KF and SnF4
(3) SnF4 and SbF5
(4) KF, SnF4 and SbF5
Hide Answer
Ans (1)
Soln:
The cation resulting formautodissociation of the solvent in the acid and the anion is the base
solutes that increase the concentration of cation of the solvent are considered acids and
solutes that increases the concentration of the anion are considered base. BrF3 also undergoes
autodissociation
2BF3> BrF2+ + BrF4
36
Solutes such as KF that increase the concentration BrF4are considered bases.
F+ BrF3>BrF4
15.Among SF4 ,BF4,XeF4 and ICl4the number of species having two lone pair of
electrons on the central atom according to VSEPR theory is:
(a) 2
(b) 3
(c) 4
(d) 0
Hide Answer
Ans (a)
16.Lewis acidity of BCl3, BPh3 ad BMe3 with respect to pyridine follows the order
(a) BCl3>BPh3>BMe3
(b) BPh3> BMe3>BCl3
(c) BCl3>BPh3>BMe3
(d) BCl3>BMe3>BPh3
Hide Answer
Ans (b)
17.The acid-base indicator (HIn) shows a colour change at pH 6.40 when 20% of it is
ionized. The dissociationonstant of the indicator is
(a) 9.95 x 10-8
(b) 3.95x 10-6
(c) 4.5x 10-8
(d) 6.0x 10-8
Hide Answer
Ans (a)
37
Main group elements and their compounds
Main group elements and their compounds: Allotropy, synthesis, structure and bonding,
industrial importance of the compounds.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 5 4 6 3 2 7 5 2 3 4 5
1.Among the halides, NCl3(A), PCl3(B) and AsCl3(C), those which produce two different
acids.
(a) A and B
(b) A and C
(c) B and C
(d) A, B and C
Hide Answer
Ans(c)
Soln:
NCl3+4H2 O > NH 4OH+3HOCl ; PCl3+ 3H2O >H PO3+3HCl (two different Acids)
AsCl3+ 3H2 O > H3 AsO3+3H3 (two different acids)
2.The correct structure of P4 S3 is:
38
Hide Answer
Ans(a)
Soln:
Structure of P4 S3.
3.The reaction that yields Li AlH4 is:
(a) HCl( excess)+ AlCl3+ Li>
(b) H2+ Al+ Li>
(c) LiH (excess)+ AlCl3>
(d) LiH(excess) +Al>
Hide Answer
Ans(c)
Soln:
LiH(exless)+AlCl3>Li (AlH4)+3HCl
4.Boric acid is a weak acid in aqueous solution. But its acidity increases significantly in
the presence of ethyleneglycol, because
(a) ethylene glycol releases additional H+
(b) B(OH)4- is consumed in forming a compound with ethylene glycol.
(c) ethylene glycol neutralizes H+ released by boric acid.
(d) Boric acid dissociates better in the mixed-solvent.
Hide Answer
39
Ans (b)
Soln:
5.For the deposition of Pb by electroplating, the best suited compound among the
following is
(a) PbCl2
(b) PbSO4
(c) Pb(Et)4
(d) Pb(BF4)2
Hide Answer
Ans (d)
Soln.
PbCl2 and PbSO4 are ionic compounds and insoluble in cold water. Therefore, cannot be used
for depositionof Pb and Pb(Et4) is toxic.
6.The correct order of the retention of cations on a sulfonated cation exchange resin
column is
(a) Ag+> K+> Na+> Li+
(b) K+> Na+> Ag+> Li+
(c) Li+> Na+> K+> Ag+
(d) Li+> Na+> Ag+> K+
Hide Answer
Ans (a)
Soln:
The retention of cation is measured in term of distribution constant K. In general, where K for
an ion is large,
there is strong tendency for the resin phase to retain that ion. Therefore, for a typically
sulphonated cation exchange resin ,
40
value of K for a univalent ion decreases in the order
Ag+
> Cs+> Rb+> K+>NH4+> Na+> H+> Li +
7.The reaction between diphenyldichlorosilane and water in 1:2 molar ratio gives
product A which on heating above 100C yields a cyclic or polymeric product B. The
products A and B respectively, are
Hide Answer
Ans (c)
Soln:
Diphenyl dichlorosilanes, Ph2SiCl2, which, like other halosilanes, are easily hydrolyzed,
initially to silanediols, R2Si(OH)2.
This on heating eliminate water molecule to form polymeric structure
41
8.The main products of the reaction of equimolar quantities of XeF6 with NaNO3 are
(a) XeOF4, NaF and NO2F
(b) Xe2O2 F2, NaF, NOF and F
(c) XeOF4, NaNO2 and F2
(d) XeF4, NaNO2 and F2O
Hide Answer
Ans (a)
Soln:
Nitrates react with XeF6to form XeOF4with stoichiometric deficiency of NaNO3
XeF6+NaNO3 > NaF+XeoF4+FNO2
9.Ozone present in upper atmosphere protects people on the earth
(a) due to its diamagnetic nature
(b) due to its blue colour
(c) due to absorption of radiation of wavelength at 255nm
(d) by destroying chlorofluoro carbons
Hide Answer
Ans (c)
Soln:
Ozone is a diamagnetic gas which is of dark blue coloured due to absorption of red light.
( =557 and 602 nm)
Ozone depliction discovered by J.C. Farman over Halley Bay in Antarctica.
Ozone also show strong absorption in =255 UV which is good for earth and living beings as
this UV-b is
most dangerous
= 557= UV- b
42
10.Amongst organolithium (A), Grignard (B) and organoaluminium (C) compounds,
those react with SiCl4 to give compound containing Si-C bond are
(a) A and B
(b) B and C
(c) A and C
(d) A, B and C
Hide Answer
Ans (d)
Soln:
11.Which of the following is used as propellant for whipping creams?
(a) N2O
(b) NO
(c) N2O3
(d) N2O5
Hide Answer
Ans (a)
Soln:
Nitrous acid (N2O) which is commonly known as laughing gas used as a propellent in
whipping cream.So, also known as whippits or nangs.
43
12.Flame proof fabrices contain
(a) H2NC(O)NH2 .Na2SO4
(b) H2NC(S)NH2 .Na2SO4
(c) H2NC (O) NH2 .H3PO4
(d) H2NC(S) NH2 .H3PO4
Hide Answer
Ans (c)
Soln:
The Flame proof fabrices contain urea and phosphoric acid (H2NC(O)NH2.H3PO4)
13.Among the compounds A-D, those which hydrolyse easily are
(a) NCl3
(b) NF3
(c) BiCl3
(d) PCl3
Hide Answer
Ans (c)
Soln:
BiCl3is readily hydrolysed by water to give BiOCl
BiCl3+H2O > BiOCl
But BiOCl redissolve in conc. HCl to produce BCl3 after evaporation. It has quasi molecular
structure. SbCl3 has similar behaviour to BCl3.
14.The number of lone-pairs are identical in the pairs
(a) XeF4, ClF3
(b) XeO4, ICl4
44
(c) XeO2F2, ICl4
(d) XeO4, ClF3
Hide Answer
Ans (a)
Soln:
15.Among the oxides of nitrogen, N2O3, N2O4 and N2O5, the compound(s) having NN
bond is/are
(a) N2O4 and N2O5
(b) N2O3 and N2O5
(c) N2O3 and N2O4
(d) N2O5 only
Hide Answer
Ans (c)
Soln:
(A) N2O3: HNO2+HNO2> N2O3
-H2O
45
(B) N2O4: HNO3+HNO2 > N2O
-H2O
16.Among the molten alkali metals, the example of an immiscible pair (in all
proportions) is
(a) K and Na
(b) K and Cs
(c) Li and Cs
(d) Rb and Cs
Hide Answer
Ans (c)
Soln
Large difference between the size of Li and Cs. So, it is difficult to get a solid solution of
these two metals.
17.Among the following, an example of a hypervalent species is
(a) BF3.OEt2
(b) SF4
(c) [PF6]
(d) Sb2S3
Hide Answer
Ans (c)
46
Soln
More than 8 electrons in the valence shell of P in [PF6]
18.Two tautomeric forms of phosphorus acid are
Hide Answer
Ans (a)
Soln
H3PO3 is a dibasic and reducing in nature.
19.In a specific reaction, hexachlorocyclophazene, N3P3Cl6 was reacted with a metal

fluoride to obtain mixed halo derivatives namely N3P3Cl5F(A), N3P3Cl4F2(B),
N3P3Cl3F3(C), N3P3Cl2F4(D), N3P3ClF5(E). Compositions among these
which can give isomeric products are
(a) A, B and C
(b) B, C and D
(c) C, D and E
(d) E, A and B
Hide Answer
Ans (b)
Soln
(A) N3P3Cl5F = only one isomer
47
(B) N3P3Cl3F3= three isomer
(C) N3P3Cl3F4 = three isomer
(D)N3P3Cl2F4 = one isomer
20.Xenon forms several fluorides and oxofluorides which exihibit acidic behaviour. The
correct sequence of descending Lewis acidity among the given species is represented by
(a) XeF6> XeOF4> XeF4> XeO2F2
(b) XeOF4 > XeO2F2> XeOF4 > XeF6
(c) XeF4> XeO2F2> XeOF4> XeF6
(d) XeF4 > XeF6> XeOF4> XeO2F2
Hide Answer
Ans (a)
48
Soln
Relative acidic strength of xenon fluorides follows order
XeF6> XeO3> F2> XeOF4> XeF4 > XeO2F2 > XeO3> XeF2
This order depends upon
(i) number of lone pair (ii) number of F atoms
21.The correct statement for ozone is
(a) It absorbs radiations in wavelength region 290-320 nm.
(b) It is mostly destroyed by NO radical in atmosphere
(c) It is non toxic even at 100 ppm level
(d) Its concentration near poles is high due to its paramagnetic nature.
Hide Answer
Ans (a)
Soln
(i) Ozone is diamagnetic in nature
(ii) It is non toxic even at 1PPm level
(iii) It is not destroyed by no radial in atmosphere
(iv) It absorbs radiations in wave length region 290-320 nm
22.The orbital interactions shown below represent
49
(a) CH3Al interactions in Al2(CH3)6
(b) BH interactions in B2H6
(c) CH3Li interaction in Li4(CH3)4
(d) CH3CH2Mg interactions in EtMgBr.(OEt2)2
Hide Answer
Ans (c)
Soln
The diagram clearly indicates the four centered-two electron interaction (4c-2e). This takes
place in Liu(CH3)4. The sp3 hybrid orbital is of carbon while the three s-orbitals are of three
surrounding lithium atoms.
23.The numbers of P-S and P-P bonds in the compounds P4S3are, respectively
(a)6 and 3
(b) 4 and 3
(c) 3 and 6
50
(d) 6 and 2
Hide Answer
Ans (a)
Soln:
P4S3is a derivative of tetrahedral (P4) unit form insertion of sulphur into three P-P bonds. The
P-S and P-P bond distance are 2.235 and 2.090 respectively. P4S3is called
phosphrousesquisulfide. Number of P-S bond is 6 and number of P-P is 3
Point group C3V signal = 2
24.Choose the correct option for carbonyl fluoride with respect to bond angle and bond
length
(a) <F-C-F > <F-C-O and C-F > C-O
(b) <F-C-F > <F-C-O and C-F < C-O
(c) <F-C-F < <F-C-O and C-F > C-O
(d) <F-C-F ><F-C-O and C-F < C-O
Hide Answer
Ans (c)
Soln:
Carbonyl flouride is written in the following form
51
From the structure it is clear that q1 is greater than q2 due to more bp-bp repulsion in q1So,
F-C-O is greater than F-C-F and bond length of C-F is greater than C-O bond.
25.Which of the following react(s) with AsF5 in liquid BrF3
(a) XeF6 only
(b) XeF6 and XeF4
(c) XeF6 and XeF2
(d) XeF4 and XeF2
Hide Answer
Ans(c)
Soln
XeF6 is flouride donor and react with PF5,AsF5&SbF5 in the presence of covalent solvent
such as BrF3
26.Consider the following reactions:
Hide Answer
Ans (2)
Soln:
For C: Bromintrifluoride is a strong fluorinating agent that is able to convert a metal to its
associated fluoride compound. The reaction of NOCl with BrF3 yields the monofluoride. If
the reaction is combined in BrF3 solution a mixed metal fluoride salt is formed.
NOCl+ BrF3 >[NO]+[BrF4Cl]
52
For D: NOCl behave as an electrophilic and an oxidant in most of its reactions with halide
acceptor
NOCl+ SbCl5 >[NO]+[SbCl6]
27.The number of 3c-2e bonds present in Al(BH4)3 is
(a) four
(b) three
(c) six
(d) zero
Hide Answer
Ans (c)
Soln:
Aluminium borohydride contain six bond which is shown in figure
3c-2e bonds are BHAl which is 6.
28.The correct order of stability of difluorides is:
(a) GeF2 > SiF2 > CF2
(b) CF2 > SiF2 >GeF2
(c) SiF2 >GeF2 >CF2
(d) CF2 >GeF2 >SiF2
53
Hide Answer
Ans (a)
29.Alkali metal superoxides are obtained by the reaction of
(a) Oxygen with alkali metals in liquid ammonia.
(b) Water with alkali metals in liquid ammonia
(c) H2O2 with alkali metals.
(d) H2O2 with alkali metals in liquid ammonia.
Hide Answer
Ans (a)
30.H2O2reduces
(A) [Fe (CN)6]4- (B) KIO4 (C) Ce (SO4)3 (D) S032-
(a) A and B only
(b) B and C only
(c) C and D only
(d) B and D only
Hide Answer
Ans (a)
31.Match List-I (compounds) with List-II (application) and select the correct answer
using the codes given below the lists.
List-I List-II
54
(A) Trisodium phosphate (i) Plasticizer
(B) Triarylphosphates (ii) Water softener
(C) Triethylphosphate (iii) Toothpaste
(D) Calcium hydrogen phosphate (iv) Insecticides
(a) (A)-ii (B)-i (C)-iv (D)-iii
(b) (A)-i (B)-ii (C)-iv (D)-iii
(c) (A)-ii (B)-iii (C)-iv (D)-i
(d) (A)-iii (B)-i (C)-ii (D)-iv
Hide Answer
Ans (a)
Soln:
32.Among the following, the number of anhydrides of acids are CO, NO, N2O, B2O3,
N2O5, SO3 and P4O10.
(a) 3
(b) 4
(c) 5
(d) 6
Hide Answer
Ans (b)
33.Lewis acidity of BCl3, BPh3 ad BMe3 with respect to pyridine follows the order
55
(a) BCl3>BPh3>BMe3
(b) BPh3> BMe3>BCl3
(c) BCl3>BPh3>BMe3
(d) BCl3>BMe3>BPh3
Hide Answer
Ans (b)
34.The reaction between NH4Br and Na metal in liquid ammonia (solvent) results in the
products
(a) NaBr,HBr
(b) NaBr, H2
(c) H2 ,HBr
(d) HBr, H2
Hide Answer
Ans (b)
35.The material that exhibits the highest electrical conductivity among the following
sulfur- nitrogen compounds is
(a) S4N4
(b) S7NH
(c) S2N2
(d)(SN)x
Hide Answer
Ans (d)
36.The final product (s) of the reaction P(OR)3+ RX is/are
(a) RPO (OR)2 and RX
(b) [RPO (OR)2]X
56
(c) [RRPO2 (OR)]X
(d) ROR and P(OR)2X
Hide Answer
Ans (a)
Main group elements and their

compounds
37.The structures of XeF2 and XeO2F2respectively are
(1.) bent, tetrahedral
(2.) linear, square planar
(3.) linear, see-saw
(4.) bent, see-saw
Hide Answer
Ans (3)
Soln:
XeF2 : linear molecule in vapor state
The three 5p electrons are promoted to higher energy 5d sub-level. The 5s three 5p and one 5d orbitals
hybridize to give five sp3d hybrid orbitals. The four singly occupied orbitals are used for
bond formation to two fluorine and two oxygen atoms. The fifth hybrid orbital contains the lone pair.
The other 5d electrons of xenon which do not take part in the hybridization scheme are involved in -
bond formation to two oxygen atoms. The structure of XeO2F2is represented in Fig.
57
38.The formation constant for the complexation of M+(M = Li, Na, K and Cs) with cryptant,
C222 follows the order
(1.) Li+< Cs+< Na+< K+
(2.) Li+< Na+< K+< Cs+
(3.) K+< Cs+< Li+< Na+
(4.) Cs+< K+< Li+< Na+
Hide Answer
Ans (2)
Soln:
The ability of cryptant to trap an alkali metal cation depends on size of both cage and metal ion, the
better the math between these; the more effectively the ions can be trapped.
58
39.The number of lone pair(s) of electrons on the central atom in [BrF4], XeF6and [SbCl6]3-are,
rzspectively,
(1.) 2, 0 and 1
(2.) 1, 0 and 0
(3.) 2, 1 and 1
(4.) 2, 1 and 0
Hide Answer
Ans (3)
Soln:
Formula to calculate Bond Pair and Lone Pair
1. calculate TVE (total valence electron)

2. Divide TVE by 8 if 8 < TVE < 56
3. The quotient will give number of bond pair
4. while dividing the remainder by 2 will give lone pair on central atom
40.Consider the following reaction:
N3P3Cl6 + 6 HNMe2 N3P3Cl3(NMe2)3 + 3Me2NH.HCl
[A]
The number of possible isomers for [A] is
(1.) 4
(2.) 3
(3.) 2
(4.) 5
59
Hide Answer
Ans (2)
Soln:
The cyclophosphazenes, first discovered by Liebig in 1834, have aroused great interest and, especially
within the last twenty years, have been intensively investigated. Much has been discovered about their
chemical and physical properties.
Two opposite points of view were put forward, one based on a completely delocalized molecular
orbital covering the whole of the cycle , the other based on the three-centered P-N-P islands with little
or no interaction between them.
Transition elements
Transition elements and coordination compounds: structure, bonding theories, spectral and
magnetic properties, reaction mechanisms.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 4 8 3 7 10 6 5 6 1 7 10
60
1.The number of microstates for d5 electron configuration is:
(a) 2163
(b) 1463
(c) 762
(d) 2863
Hide Answer
Ans(c)
Soln:
2.The number of possible isomers of [Ru(PPh3)2(acac)2] (acac=acetylacetonate) is:
(1) 2
(b) 3
(c) 4
(d) 5
Hide Answer
Ans (b)
Soln:
61
3.The correct spinel structure of Co3O4 is:
Hide Answer
Ans (a)
Soln:
Co3O4 is a normal spinel. In normal spinel the Co2+ ions occupy tetrahedral voids and Co3+ ions
occupy octahedral voids. Therefore, spinel structure of Co3O4 is (Co2+)t(2Co3+)oO4.
4.In the solid state, the CuCl53-ion has two types of bonds. These are
(1) Three long and two short
(b) Two long and three short
(c) One long and four short
(d) Four long and one short
Hide Answer
Ans (a)
62
Soln:
In trigonalbipyramidal complexes, the two ligands lie on z-axis and the three in xy plane somewhere
in between the axes. In xy plane, there are four electrons and on z-axis there is only one electron in
dz2 orbital
(E.C.
5.The platinum complex of NH3 and Cl ligands is an anti-tumour agent. The correct isomeric
formula of the complex and its precursor are
(1) cis-Pt(NH3)2Cl2 and PtCl42-
(b) trans-Pt(NH3)2Cl2 and PtCl42-
(c) cis-Pt(NH3)2Cl2 and Pt(NH3)42+
(d) trans-Pt(NH3)2Cl2 and Pt(NH3)42-
Hide Answer
Ans (a)
Soln:
Trans effect of Cl> NH3Antitumer agent is cis-[Pt(NH3)2Cl]
The precursor of this complex is [PtCl4]2-
6.Successive addition of NaCl, H3PO4, KSCN and NaF to a solutin of Fe(NO3)3.9H2O gives
yellow, colourless, red and again colorless solutions due to the respective formation of:
(1) [Fe (H2O)5Cl]2+ , [Fe (H2O)5 (PO4)] , [Fe (H2O)5 (SCN)]2+, [Fe (H2O)5 F]2+
(b) [Fe (H2O)5Cl(OH)]+ , [Fe (H2O)5 (PO4)] , [Fe (H2O)5 (SCN)]2-, [Fe (H2O)5 F]2+
(c) [Fe (H2O)5Cl]2+, [Fe (H2O)6 ]3+, [Fe (H2O)5 (SCN)]2+, [Fe (H2O)5 F]2+
(d) [Fe (H2O)5Cl]2+ , [Fe (H2O)5 (PO4)] , [Fe (H2O)5 (SCN)]2+, [Fe (H2O)4(SCN)F]+
63
Hide Answer
Ans (a)
Soln:
When Fe (NO3)3.9H2O is dissolved in water, the complex ion [Fe (H2O)6 ]3+is formed.
Transition elements
7. The rate of exchange of OH2 present in the coordination sphere by 18OH2 of,
(i) [Cu(OH)2)6]2+, (ii) [Mn(OH2)6]2+, (iii) Fe(OH2)6]2+, (iv) [Ni(OH2)6]2+, follows an order
(1) (i) > (ii) > (iii) > (iv)
(b) (i) > (iv) > (iii) > (ii)
(c) (ii) > (iii) > (iv) > (i)
(d) (iii) > (i) > (iv) > (ii)
Hide Answer
Ans (a)
Soln:
The rate of water exchange in [Cu(H2O)6]2+ is fastest due to John Teller distortion. For other three
complexes of 3d-series dipositive metal cation. The rate of water exchange decreases with increase in
effective nuclear charge and decrease in size.
64
8.The -bond is formed via the overlap of
(a) dx2-y and dx2-y 2orbitals
(b) dxz and dxz orbitals
(c) dxy and dxy orbitals
(d) dyz and dyz orbitals
Hide Answer
Ans (a)
Soln:
If the molecular orbital has two nodal planes passing through both the atomic nuclei , it is called
bond. Two bond can be formed per pair of atom one using twoand the other using two
22 which overlap in four region. Hence, (1) and (3) both seems to be correct.
9.In the following reaction compound B is
(a) trans-[PtCl2 (NO2 )(NH3)]
(b) cis-[PtCl2 (NO2 )(NH3)]
(c) trans-[PtCl2 (NH3)2]
(d) cis-[PtCl2 (NO2)2]2-
Hide Answer
Ans (a)
Soln:
This is an example of trans effect.
In 1st step addition substitution of NO2 take place at any place since all are equivalent.
In 2nd Trans effect of NO2 > Cl hence it will direct NH3 trans to itself leading to the formation of (A).
65
10.The number of stereoisomers of trans-[CoCl2(triethylenetetramine)]Br is
(a) One
(b) Two
(c) Three
(d) Four
Hide Answer
Ans (c)
11.Base hydrolysis of [CoCl3(NH3)5] 2+is an overall second order reaction, whereas that
of [Co(CN)6 ]3- is of first order. The rates depend in both cases solely on the concentrations of
the cobalt complex. This may be dueto
(A) Presence of ionizable proton in [CoCl2 (NH3) 5] 2+but not in [Co(CN)6]3-
(B)SN 1CBmechanism in the case of [CoCl2 (NH3) 5] 2+only
(C) S N 1CBmechanism in the case of [Co(CN)6]3- only
(D) S N 1CBmechanism in both the complexes
Correct explanation(s) is/are
(a)A and B
(b) A and C
(c) B only
(d) A and D
Hide Answer
Ans (a)
Soln:
Base Hydrolysis mechanism follows as
[CoCl3(NH3)5] 2+ + OH [CoCl(NH2)(NH3)4]+ + H2O
[CoCl(NH2)(NH3)4]+ [Co (NH2)(NH3)4]2+ + Cl (slow)
[Co (NH2)(NH3)4]2++ H2O [Co(OH)(NH3)5] 2+ (fast)
66
In the first step, an NH3 ligand acts as a Brnsted acid, resulting in the formation of its conjugate base,
the NH2ion, as a ligand. Because the deprotonated form of the complex has a lower charge, it will be
able to lose a Cl ion more readily than the protonated form, thus accelerating the reaction. In addition,
according to the conjugate base mechanism, loss of a proton from an NH3 ligand changes it from a
pure -donor ligand to a strong and donor (as NH2) and so helps to stabilize the five-coordinate
transition state, greatly accelerating the loss of the Cl ion.
12.The spin-only magnetic moment and the spectroscopic ground state term symbol of
manganese center in[MnF6]3-ion respectively, are
(a) 4.9 BM and 5D
(b) 4.9 BM and 4F
(c) 3.9 BM and 3D
(d) 4.9 BM and 3F
Hide Answer
Ans (A)
Soln:
[MnF6]3- = 3+= 40 34 n=4
S = 2 2S+1 = 5
L=2 D
Term symbol :5D
= ( + 2)
= = .
Transition elements
13.The three dimensional structure of compound [Co(Co(NH3) 4 (OH)2)3]Br 6 has
(a) Twelve CoO and twelve CoN bonds
(b) Ten CoO and ten CoN bonds
67
(c) Fourteen CoO and ten CoN bonds
(d) Twelve CoO and ten CoN bonds
Hide Answer
Ans (a)
Soln:
Werner first resolve this compound which was totally inorganic optically active compound.
14.The spin-only (S) and spin plus orbital (S+L) magnetic moments of [CrCl6]3- are
(a) 3.87 BM and 5.20 BM
(b) 2.84 BM and 5.20 BM
(c) 3.87 BM and 6.34 BM
(d) 2.84 BM and 6.34 BM
Hide Answer
Ans (a)
Soln:
Spin only magnetic moment is given by
= (n + 2)
For [CrCl63]
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n=3
= 3.87
Spin plus orbital magnetic moment is given by
= (n + 2) + n(n + 1)
Value of L is 3
Hence
eff =5.2
15.In bis(dimethylglyoximato)nickel(II), the number of NiN, NiO and intramolecular

hydrogen bond(s),respectively are
(a) 4, 0 and 2
(b) 2, 2 and 2
(c) 2, 2 and 0
(d) 4, 0 and 1
Hide Answer
Ans (a)
Soln:
Ni2+is tested by dmg.
Ni2++ 2dmg [Ni(dmg)2] (Tschugaeff test)
(Red)
The structure of complex is
69
Therefore,
Ni N bonds 4
Ni O Zero
Hydrogen bonds two
16.NiBr2reacts with (Et)(Ph2)P at 78C in CS2to give red compound A, which upon standing
at room temperatureturns green to give compound, B of the same formula. The measured
magnetic moments of A andB are 0.0 and 3.2 BM, respectively. The geometries of A and
B are
(a) square planar and tetrahedral
(b) tetrahedral and square planar
(c) square planar and octahedral
(d) tetrahedral and octahedral
Hide Answer
Ans (b)
Soln:
Therefore,
70
17.If L is a neutral monodentate ligand, the species,[AgL4]2+, [AgL6]2+and [AgL4]3+, respectively
are
(a) paramagnetic, paramagnetic and dimagnetic
(b) paramagnetic, diamagnetic and paramagnetic
(c) diamagnetic, paramagnetic and diamagnetic
(d) paramagnetic, diamagnetic and diamagnetic
Hide Answer
Ans (a)
Soln:
In ,[AgL4]2+ and [AgL6]2,Ag2+ has d9 configuration, hence have unpaired electron.
Hence paramagnetic.
[AgL4]3+ =>Ag3+ has d8 configuration and dsp2 hybridization (square planar so pairing of electron).
Hence,diamagnetic in nature.
18.Chromite ore on fusion with sodium carbonate gives
(a) Na2CrO4and Fe2O3
(b) Na2Cr2O7and Fe2O3
(c) Cr2(CO)3 and Fe(OH)3
(d)Na2CrO4andFe2(CO)3
71
Hide Answer
Ans (a)
Soln:
Chromium is extracted from chromite ore:
(I) 4FeCr2O4+ 8Na2CO3+ 7O2 8Na2CrO4+ 2Fe2O3+ 8CO2
(II) 2Na2CrO4+ H2SO4 Na2SO4 + Na2Cr2O7+ H2O
(III) Na2Cr2O7+2C Cr2O7+ Na2CO3+ CO
(IV) Cr2O3+ 2Al Al2O3+ 2Cr
Transition elements
19.[CoL6]2+is red in colour whereas [CoL6]2+is green. L and L respectively corresponds to,
(a) NH3and H2O
(b) NH3and 1, 10-phenanthroline
(c) NH3and 1, 10-phenanthroline
(d) H2O and NH3
Hide Answer
Ans (a)
Soln:
[CoL6]3+red colour absorbs green radiations.
[CoL6]2+ green colour absorbs red radiations.
Energy of green radiations > enegy of red radiations.
Therefore, L will be stronger ligand and than L. Thus, L and L are NH3 and H2O respectively.
72
20.The typical electronic configurations of the transition metal centre for oxidative addition
(a) d0and d8
(b) d6and d8
(c) d8and d10
(d) d5and d10
Hide Answer
Ans (c)
Soln:
Most commonly the metal in the complexes in their low oxidation state with d8 or d10 configuration
undergooxidative addition.
21.Reaction of [Ru(NH3)5(isonicotinamide)]3+ with [Cr(H2O)6]2+ occurs by inner sphere

mechanism and rate of the reaction is determined by dissociation of the successor complex. It is
due to the
(a) Inert ruthenium birdged to inert chromium centre
(b) Inert ruthenium bridged to labile chromium centre
(c) Labile ruthenium bridged to inert chromium centre
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(d) Labile ruthenium bridged to labile chromium centre
Hide Answer
Ans (a)
Soln:
In the successor complex inert rutherm bridged to inert chromium.
22.Consider the second order rate constants for the following outer-sphere electron transfer
reactions:
[Fe (H2O)6]3+ / [Fe (H2O)6]2+4.0 M1sec1
[Fe (phen)3]3+/ [Fe (phen)3]2+3.0107 M1sec1
(phen = 1, 10-phenanthroline)
The enhanced rate constant for the second reaction is due to the fact that
74
(a) The phen is a -acceptor ligand that allows mixing of electron donor and acceptor orbitals that
enhancesthe rate of electron transfer
(b) The phen is a -donor ligand that enhances the rate of electron transfer
(c) The phen forms charge transfer complex with iron and facilitates the eletron transfer
(d) The phen forms kinetically labile complex with iron and facilitates the electron transfer.
Hide Answer
Ans (a)
Soln:
(Phen) is an-accepter ligands hence there is mixing of donor and acceptor orbital having similar
symmetry this leads to fast transfer of electron leading to enhance rate of reaction.
23.Identify the correct statement about
[Ni(H2O)6]2+and [Cu(H2O)6]2+
(a) All Ni-O and Cu-O bond lengths of individual species are equal
(b) Ni-O(equatorial) and Cu-O(equatorial)
(c) All Ni-O bond lengths are equal whereas Cu-O (equatorial) bonds are shorter than Cu-O(axial)
bonds
(d) All Cu-O bond lengths are equal whereas Ni-O(equatorial) bonds are shorter than Ni-O(axial)
bonds.
Hide Answer
Ans (c)
75
Soln:
24.A 1 : 2 mixture of Me2NCH2CH2CH2PPh2 and KSCN with K2[PdCl4] gives a square planar
complex A.Identify the correct pairs of donor atoms trans to each other in complex A from the
following combinations.
(a) P, N
(b) N, S
(c) P, S
(d) N, N
Hide Answer
Ans (a)
Soln:
76
s and p both form -bonding with complex and -bonding capacity of sulphur is greater than
phosphorus due to smaller size of d-orbital of sulphur. Hence, in presence of sulphur trans to
phosphorus donor atom phosphorus- metal bond will be weak hence they do not lie trans to each other
in the complex. As nitrogen does not involvent in -bonding with complex hence when nitrogen atom
is trans to phosphorus, phosphorus become able to form efficient -bond with metal hence become
stable thats why P and N are trans to each other
Transition elements
25.The reaction of [PtCl4]2- with two equivalents of NH3 produces
(a) cis-[Pt(NH3)2Cl2]
(b)trans-[Pt(NH3)2Cl2]
(c)both cis-[Pt(NH3)2Cl2] and trans-[Pt(NH3)2Cl2]
(d) cis-[Pt(NH3)2Cl4]2-
Show Answer
Ans (a)
Soln:
Trans effect Cl has larger trans effect than NH3.
77
26.Which of the pairs will generally result in tetrahedral coordination complexes, when ligands
are Cl or OH
(A) Be(II), Ba(II) (B) Ba(II), Co(II) (C) Co(II), Zn(II) (D) Be(II), Zn(II)
(a) A and B
(b) B and C
(c) C and D
(d) A and D
Show Answer
Ans (c)
Soln:
Co(II), Zn(II) and Be(II) form tetrahedral complexes with Clor OH.
Be(II) has no d-orbitals, therefore it form tetrahedral complexes.
Co(II) and Zn(II) form tetrahedral complexes with halides and OH.
27.Silica gel contains [CoCl4]2as an indicator. When activated, silica gel becomes dark blue
while upon absorption of moisture, its colour changes to pale pink. This is because,
(a) Co(II) changes its coordination from tetrahedral to octahedral.
(b) Co(II) changes its oxidation state to Co(III)
(c) Tetrahedral crystal field splitting is NOT equal to octahedral crystal field splitting.
(d) Co(II) forms kinetically labile while Co(III) forms kinetically inert complexes
Hide Answer
Ans (a)
Soln:
28.The t of the following complexes
78
(A) [CoCl4]2 (B) [CoBr4]2 (C) [Co(NCS)4]2
(a) C > A > B
(b) A > B > C
(c) B > A > C
(d) C > B > A
Hide Answer
Ans (a)
Soln:
From spectro chemical series order, Br<Cl<NCS
Order of t
[Co(NCS)4]2> [CoCl4]2> [CoBr4]2
29.Identify the chiral complexes from the following
(A) [Cr (EDTA)](B) [Ru (bipy)3]3+(C) [PtCl(diene)]+
(a) A only
(b) A and B only
(c) A and C only
(d) B and C only
Hide Answer
Ans (b)
Soln:
[Cr (EDTA)] and [Ru (bipy)3]3+are octahedral and have no plane of symmetry. Therefore these
arechiral complex [PtCl(diene)]+is square planar and has plane of symmetry. Therefore, it is achiral
30.Among the following, the correct acid strength trend is represented by
(a) [Al(H2O)6]3+<[Fe(H2O)6]3+<[Fe(H2O)6]2+
79
(b) [Fe(H2O)6]3+<[Al(H2O)6]3+<[Fe(H2O)6]2+
(c) [Fe(H2O)6]2+<[Fe(H2O)6]3+<[Al(H2O)6]3+
(d) [Fe(H2O)6]2+<[Al(H2O)6]3+<[Fe(H2O)6]3+
Hide Answer
Ans (c)
Soln
As the size of metal ion decreases, acidic character increases.
Order of size is Fe2+>Al3+>Fe3+
[Fe(H2O)6]2+<[Fe(H2O)6]3+<[Al(H2O)6]3+
Reference Shriver Atkin (P.No. 123,Bronsted axis base concept)
Transition elements
31.An octahedral metal ion M2+has magnetic moment of 4.0 B.M. The correct combination of
metal ion and delectronconfiguration is given by
(a) Co2+, t2g5e g 2
(b) Cr2+,t2g4eg2
(c) Mn2+, t2g3eg1
(d) Fe2+,t2g4eg2
Hide Answer
Ans (a)
Soln
Co2+, t2g5e g 2 =3.89 B.M.
Cr2+,t2g4eg2 =4.9 B.M.
Mn2+, t2g3eg1=4.9 B.M.

Fe2+,t2g4eg2 =4.9 B.M.
80
32.According to VSEPR theory, the geometry (with lone pair) around the central iodine in
I3+ and I3ions respectivelyare
(a) tetrahedral and tetrahedal
(b) trigonalbipyramidal and trigonalbipyramidal
(c) tetrahedral and trigonalbipyramidal
(d) tetrahedral and octahedral
Hide Answer
Ans (c)
Soln
Number of valence electrons in I3+central atom are 8 while in I3are 10 and hence the geometries.
33.Among the following, the correct combination of complex and its color is
Hide Answer
Ans (c)
Soln
Order of ligand is spectro chemical series
SCN<Cl< F< CN
From above it is clear that CNwill produce highest energy difference, followed by F, Cl, SCN.As
colour of complex is complementary colour of absorbed light.
Thus,
81
[Co(CN)4] 2
absorbs orange colour radiation which complementary colour is blue therefore
colour of [Co(CN)4] 2 is blue.
The other combination according to energyare mismatched. Hence, only option (c) is correct.
34.MnCr2O4 is likely to have a normal spinel structure because
(a) Mn2+will have a LFSE in the octahedral site whereas the Cr3+will not
(b) Mn is +2 oxidation state and both the Cr are in +3 oxidation state.
(c) Mn is +3 oxidation state and 1 Cr is in +2 and the other is in +3 state.
(d) Cr3+will have a LFSE in the octahedral site whereas the Mn2+ion will not.
Hide Answer
Ans (d)
Soln
->
Mn2+ 3d5 ->t32geeg(high spin octahedral)
CFSE in oh fluid = (0.43 + 0.62) = 0
Cr 3+ >3d3 >t32geg0(octahedral )
CFSE in octahedral field. = 0.43D0 = -(0.43)0=-1.20
35.Compounds K2Ba[Cu(NO2)6] (A) and Cs2Ba[Cu(NO2)6] (B) exhibit tetragonal elongation and
tetragonal compression, respectively. The unpaired electron in A and B are found respectively,
in orbitals,
(a) dz2 and dx2-y2
(b) dx2-y2 and dz2
(c) dz2 and dz2
(d) dx2-y2 and dx2-y2
Hide Answer
Ans (b)
82
Soln:
36.Formonoionic complex [UO2(NO3)3],the correct coordination number and geometry

respectively are
(1) 8 and hexagonal bipyr90amidal
(2) 5 and square pyramidal
(3) 8 and squareantiprism
(4) 5 and trigonalbipyramidal
Hide Answer
Ans (1)
Soln:
[UO2(NO3)3]
NO3 =bidented ligand
U= Coordination number = 8
Geometry = Hexagonal bipyramidal
Transition elements
37.The complex that shows orbital contribution to the magnetic moment, is
83
(1) [Cu(H2O)6]2+
(2) [Ni(H2O)6]2+
(3) [Co(H2O)6]2+
(4) [Cr(H2O)6]2+
Hide Answer
Ans (3)
Soln:
If the electron is present in the t2g orbitals are unsymmetrical field then the orbital contribution to the
magnetic moment is large.
The electronsare present in eg orbitals they do not contribute.

Symmetrically field (t32g t62g ) they do not contribute.
38.Paramagnetic susceptibility of the order of 106 cm3mol1 observed for KMnO4 is due to
(1) random spin alignment
(2) antiferromagnetic exchange interaction
(3) paramagnetic impurity
(4) temperature independent paramagnetism
Hide Answer
Ans (4)
84
Soln:
KMnO4 show the temperature independent paramagnetion due to Mn in O.S. +7 then they are show
d0 orbital. They are diamagnetic in nature and magnetic moment is zero then they are show
temperature independent paramagnetism.
39.According to crystal field theory, N+2can have two unpaired electrons in
(a) Octahedral geometry only
(b) Square-planar geometry only
(c) Tetrahedral geometry only
(d) Both octahedral and tetrahedral geometry.
Hide Answer
Ans (d)
40.[Ni(CN)4]-2 and [NiCl4]-24complex ions are
(a) Both diamagnetic
(b) Both paramagnetic
(c) Diamagnetic and paramagnetic respectively
(d) Antiferromagnetic and diamagnetic respectively
Hide Answer
Ans (c)
41.The number of possible isomers for [Ru (bpy)2 Cl2] is (bpy = 2,2 bipyridine )
(a) 2
(b) 3
(c) 4
(d) 5
Hide Answer
85
Ans (d)
42.Cis and trans complexes of the type [PtA2X2] are distinguished by
(a) Chromyl chloride test
(b) Carbylamine test
(c) Kurnakov test
(d) Ring test
Hide Answer
Ans (c)
Transition elements
43.In the H2Ru6( CO)18 cluster, containing 8-coordinated Ru centers, the hydrogen atoms are
(a) Both terminal
(b) One terminal and the other bridging
(c) Both bridging between two Ru centers
(d) Both bridging between three Ru centers.
Hide Answer
Ans (b)
44.The correct order of LMCT energies is:
(a) MnO4< CrO42- < VO43-
(b) MnO4>CrO42- > VO43-
(c) MnO4> CrO42- < VO43-
(d) MnO4< CrO42- > VO43-
Hide Answer
Ans (a)
86
45.The complex [Mn (H2O)6] +2 has very light pink colour. The best reason for it is
(a) The complex does not have a charge transfer transition.
(b) d-d transitions here are orbital forbidden but spin allowed.
(c) d-d transitions here are orbital allowed but spin forbidden.
(d) d-d transitions here are both orbital forbidden and spin forbidden
Hide Answer
Ans (d)
46.Consider the compounds, (A) SnF4, (B) SnCl4and (C) R3SnCl. The nuclaerquadrupole
splitting are observed for
(a) (A), (B) and (C)
(b) (A) and (B) only
(c) (B) an d (C) only
(d) (A) and (C) only
Hide Answer
Ans (d)
47.Consider two redox pairs
(1) Cr(II)/Ru(III) (2) Cr(II)/Co(III)
The rate of acceleration in going from a outer-sphere to a inner-sphere mechanism is lower for
(1) relative to (2). Its correct explanation is:
(a) HOMO/LUMO are * and * respectively.
(b) HOMO/LUMO are * and * respectively.
(c) HOMO/LUMO are * and * respectively.
(d) HOMO/LUMO are * and * respectively.
Hide Answer
87
Ans (a)
48.For the complexes
(A) [Ni (H2O)6]2+ ,(B) [Mn (H2O)6]2+ ,(C) [Cr (H2O)6]3+ ,(D) [Ti (H2O)6]3+, the ideal octahedral
geometry will not be observed in
(a) (A) and (D)
(b) (C) and (D)
(c) (B) only
(d) (D) only
Hide Answer
Ans (d)
Soln:
Transition elements
49.The actual magnetic moment shows a large deviation from the spin-only formula in the case
of
(a) Ti3+
(b) V3+
(c) Gd3+
(d) Sm3+
Hide Answer
Ans (d)
50.The complex that absorbs light of shortest wavelength is
(a) [CoF6]3-
(b) [Co(H2O)6]3+
88
(c) [Co(NH3)6]3+
(d) [Co(OX)3]3-(OX = C2O42-)
Hide Answer
Ans (c)
51.Green colouredNi(PPh2Et)2 Br2 , has a magnetic moment of 3.20 B.M. The geometry and the
number of isomers possible for the complex respectively, are
(a) square planar and one
(b) tatrahedral and one
(c) Square planer and two
(d) tetrahedral and two
Hide Answer
Ans (b)
52.The correct order of acidity among the following species is
(a) [Na (H2O6)]+> [Ni (H2O6)]2+> [Mn (H2O6)] 2+> [Sc (H2O6)]3+
(b) [Sc (H2O6)]3+> [Ni (H2O6)]2+> [Mn (H2O6)] 2+> [Na (H2O6)]+
(c) [Mn (H2O6)] 2+> [Ni (H2O6)]2+> [Sc (H2O6)]3+> [Na (H2O6)]+
(d) [Sc (H2O6)]3+> [Na (H2O6)]+> [Ni (H2O6)]2+> [Mn (H2O6)] 2+
Hide Answer
Ans (a)
53.A true statement about base hydrolysis of [Co (NH3)5Cl]2+ is:
(a) It is a first order reaction
(b) The rate determining step involves the dissociation of chloride in [Co (NH3)4(NH2)Cl]+
(c) The rate is independent of the concentration of the base
89
(d) The rate determining step involves the abstraction of a proton from [Co (NH3)5Cl]2+
Hide Answer
Ans (b)
54.The correct order of d-orbital splitting in a trigonal bipyramidal geometry is:
Hide Answer
Ans (d)
ansition elements
55.For the following outer sphere electron transfer reactions.
[Co(NH3)6]2+ + [Co*(NH3)6]3+ [Co(NH3)6]3+ + [Co*(NH3)6]2+
[Ru(NH3)6]2+ + [Co*(NH3)6]3+ [Co(NH3)6]3+ + [Co*(NH3)6]2+
the rate constants are 106 M1 s1 and 8.2102 M1s1 respectively. This difference in the rate
constants is due to
(a) A change from high spin to low spin in Co* and high spin to low spin in Ru.
(b) A change from high spin to low spin in Co* and low spin to high spin Ru*.
(c) A change from low spin to high spin in Co* and the low spin state remains unchanged in Ru.
(d) A change from low spin to high spin in Co* and high spin to low spin in Ru*.
Hide Answer
Ans (c)
90
56.Using crystal field theory, identify from the following complex ions that shows the same
eff(spin only) values
(A) [CoF6]3-
(B) [IrCl6] 3-
(C) [Fe(H2O) 6] 2+
(1) A and B
(2) B and C
(3) A and C
(4) A, B and C
Hide Answer
Ans (3)
Soln:
All the complexes are d6 configured and contain weak field ligand but except Ir all form high spin
complex
*[4d and 5d metals never form high spin complex]
Hence spin only magnetic moment will be same for Co(III) and Fe(II).
57.Identify the complex ions in the sequential order when ferroin is used as an indicator in the
titration of iron(II) with potassium dichromate. (phen = 1, 10- phenathroline)
(1) [Fe(phen)3]2+and [Fe(phen)3]3+
(2) [Fe(phen)3] 3+and [Fe(phen)3] 2+
(3) [Fe(CN)6]4-and [Fe(CN)6]3-
(4) [Fe(CN)6]3-and [Fe(CN)6]4-
Hide Answer
Ans (1)
Soln:
91
The color changes observed with redox indicators at the equivalence point is due to structural changes
in changes upon being oxidized or reduced. This can be illustrated with ferroin indicator which is the
iron(II) complex of the organic compound 1,10-phananthroline .
Each of the two nitrogen atoms in 1, 10-phenanthroline has an unshared pair of electrons that
can be shared with the Fe(II) ion. Three such ligand molecules get attached to one Fe(II) ion
to form a blood red complex ion. This complex can be oxidized to the corresponding light blue
Fe(III) complex with the same structure. Therefore, a sharp colour change from red to blue occurs on
oxidation of the complex.
[Ph3Fe]2+ [Ph3Fe]3++ e E0 = -1.06 V
The indicator is prepared by mixing equivalent quantities of iron(II) sulphate and 1, 10-
phananthroline. The resulting Fe(II) complex sulphate is called Ferroin. The Fe(III) complex
sulphate is called ferrin. The colour changes occur at about -1.11 V (not at -1.06), since the color of
ferroin is so much more intense than that of ferrin.
58.The correct statement for Mn-O bond lengths in [Mn(H2O)6] 2+ is
(1.) All bonds are equal
(2.) Four bonds are longer than two others
(3.) Two bonds are longer than four others
(4.) They are shorter than the Mn-O bond in [MnO4]-
Hide Answer
Ans (1)
Soln:
Mn aqua complex do not allow any distortion because of symmetrical d5distribution.
92
59.Among the following, species expected to show fluxional behavior are
(A) [NiCl4]2- (tetrahedral), (B) IF7(pentagonal bipyramidal),
(C) [CoF6] 3- (octahedral), (D) Fe(CO)5(trigonal, bipyramidal)
(1.) B and C
(2.) B and D
(3.) C and D
(4.) A and D
Hide Answer
Ans (2)
Soln:
Fe(CO)5 show fluxional behavior by process called berry pseudo rotation. And molecule IF7 shows
similar mechanism called Bartell mechanism which exchanges the axial atoms with one pair of the
equatorial atoms with an energy requirement of about 2.7 kcal/mol.
93
60.The oxidizing power of [CrO4]2-, [MnO4]2-, and [FeO4]2-follows the order
(1.) [MnO4]2- < [MnO4]2-<[FeO4]2-
(2.) [FeO4]2-<[MnO4]2- < [CrO4]2-
(3.) [MnO4]2-<[FeO4]2-< [CrO4]2-
(4.) [CrO4]2-< [FeO4]2-<[MnO4]2-
Hide Answer
Ans (1)
Soln:
Since oxidation number is same (VI) in all three metals. Hence, in going from Cr to Mn to Fe, size
decrease due to which oxidizing power increase.
61.Aqueous Cr2+effects one electron reduction of [Co(NH3)5Cl]2+giving compound Y. compound

Y undergoes rapid hydrolysis. Y is,
(1.) [Co(NH3) 5Co] 2+
(2.) [Co(NH3) 5Co(OH)] 2+
(3.) [Co(NH3)4Co (OH) 2]
(4.) [Cr(H2O)5Cl] 2+
Hide Answer
94
Ans (1)
Soln:
The reduction of cobalt(III) (in [Co(NH3)5Cl] 2+) by chromium(II) (in [Cr(H2O)6] 2+) and was
specifically chosen because (I) both CO(III) and Cr(III) form inert complexes and (2) the complexes
of Co(II) and Cr(III) are labile.
Under these circumstances the chlorine atom, while remaining firmly attached to the inert Co(III) ion,
can displace a water molecule from the labile Cr(III) complex to form a bridged intermediate:
[Co(NH3)3Cl] 2++ [Cr(H2O)6] 2+ [(NH3)5Co-Cl-Cr(H2O) 5]4++ H2O
The redox reaction now takes place within this dinuclear complex with formation of reduced Co(II)
and oxidized Cr(III). The latter species forms an inert chloroaqua complex, but the cobalt(II) is labile,
so the intermediate dissociates with the chlorine atom remaining with the chromium:
[(NH3)5Co-Cl-Cr(OH2) 5] 4+ [(NH3) 5Co] 2++ [ClCr(H2O)5]2+
62.The correct statement about the substitution reaction of [Co(CN) 5 (Cl)]3-with OH to give
[Co(CN) 5(OH)] 3-is,
(1.) it obeys first order kinetics
(2.) its rate is proportional to the concentration of both the reactants
(3.) it follows the SN1 CB mechanism
(4.) its rate is dependent only on the concentration of [OH]
Hide Answer
Ans (1)
Soln:
Complexes such as [Co(CN) 5 (Cl)]3-[Co(py) 4Cl2] + would not be expected typical base hydrolysis and
reaction proceeds slowly without dependence of OH ion.
(Reference : Inorganic Chemistry , Huheey)
63.Among the following complexes[Co(ox) 3] 3-, B. trans-[CoCl2 (en) 2] +, C. [Cr(EDTA)] the

chiral one(s) is/are
(1.) A and B
(2.) C and B
95
(3.) C only
(4.) A and C
Hide Answer
Ans (4)
Soln:
The essential condition to show the chirality is the lack of any symmetry element and it show have
handedness
Chiral complex is able to show handedness properly (right or left handedness) by and
designation
However the complex trans-[CoCl2(en)2]+ contains plane of symmetry and hence are achiral
64.The room temperature magnetic moment (eff in BM) for a monomeric Cu(II) complex is
greater than 1.73. This may be explained using the expression:
Hide Answer
Ans (1)
96
CSIR-NET CHEMICAL SCIENCES | Inner
transition elements
Inner transition elements: spectral and magnetic properties, redox chemistry, analytical applications.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 2 2 2 2 1 1 2 2 3 3 2
(a) Al (OH)3
97
(b) La (OH)3
(c) Ce (OH)3
(d) Lu (OH)3
Hide Answer
Ans (a)
Soln:
Al (OH)3 Amphoteric whereas hydroxides of lanthanoids are all base.
2.The pair of lanthanides with the highest third-ionization energy is:
(a) Eu, Gd
(b) Eu, Yb
(c) Dy, Yb
(d) Lu, Yb
Hide Answer
Ans(b)
Soln:
Eu2+4f 7Half filled stable; Yb2+4f14Computely filled stable
3.The lanthanide(III) ion having the highest partition coefficient between tri-n-butylphosphate
and concentrated HNO3 is:
(a) La(III)
(b) Eu(III)
(c) Nd(III)
(d) Lu(III)
Hide Answer
Ans(d)
98
Soln:
Smaller the size of Ln3+ion, higher will be the higher be the partition coefficient.
4.Consider the ions Eu(III), Gd(III), Sm(II) and Lu(III). The observed and calculated magnetic
moment values are closest for the pair
(1) Gd(III), Lu(III)
(b) Eu(III), Lu(III)
(c) Sm(III), Gd(III)
(d) Sm(III), Eu(III)
Hide Answer
Ans (a)
Soln:
The electronic configuration of Gd3+ and Lu5+ are 4f7 and 4f14, for this ions total angular momentumis
zero i.e.there is no orbital contribution. Therefore, calculated and observed values of magnetic
moment are closest for this pair.
5.Which one of the following shows the highest solubility in hot concentrated aqueous NaOH?
(1) La(OH)3
(b) Nd(OH)3
(c) Sm(OH)3
(d) Lu(OH)3.
Hide Answer
Ans (d)
Soln
Since size of Lu3+ is smallest, therefore Lu(OH)3 complex most easily formed with NaOH and
dissolves.
Lu(OH)3 + 3OH [Lu(OH)6]3-
99
6.Hindered diketonates like dpmH (dpmH = dipivaloylmethane) are used for the separation
of lanthanidesbecause complexes formed with dpmH can be separated by
(a) Gel permeantion chromatography
(b) Gas chromatography
(c) Gel filtration chromatography
(d) Ion exchange chromatography
Hide Answer
Ans (b)
Soln:

transition elements
7.Gel permeantion chromatography can be used to separate which of the following
(A) Lanthanides
(B) Alkaline earths
(C) Fatty acids
(D) Low molecular weight peptides
The correct answer is
(a) A and B
(b) B and C
(c) C and D
(d) A and D
Hide Answer
Ans (c)
Soln:
100
Gel permeation chromatography (GPC) is a type of size exclusion chromatography (SEC), that
separates analytes on the basis of size. The technique is often used for the analysis of polymer.
8.The cooperative binding of O2 in hemoglobin is due to
(a) a decrease in size of iron followed by changes in the protein conformation
(b) an increase in size of iron followed by changes in the protein conformation
(c) a decrease in size of iron that is NOT accompanied by the protein conformational changes
(d) an increase in size of iron that is NOT accompanied by the protein conformational changes
Hide Answer
Ans (a)
Soln:
The movement of iron atom and imidazole side chain of histidine F8 toward the porphyrin
plane results inbreaking of some of the salt bridges. The breaking of these salt bridges reduces
the strain in haemoglobin molecule. Therefore, the oxyform of hemoglobin is called relaxed
state (i.e., R state). The T form of deoxyhemoglobin discourages the addition of first
dioxygen molecule.
The bonding of one dioxygen molecule to a subunit of hemoglobin reduces the steric
hindrance in the other subunits (due to breaking of salt bridges) and therefore encourages the
third as well as fourth subunits.This is called cooperative mechanism.
9.Identify the pairs in which the covalent radii of elements are almost similar
(A) Nb , Ta (B) Mo, W (C) La, Lu (D) Sc, Y
(a) A and B only
(b) A and C only
(c) B and C only
(d) A, B and C only
Hide Answer
Ans (a)
Soln:
101
As we move from NbTa and MoW there is introduction of electron into f-orbital. As the shielding
power of f-orbital is very less. Therefore, as we move from LaLu in 4f series the size decreases, this
is termed as Lanthanide contraction. This leads to slight increase in size of 5d metal than 4d. Due to
this size of d and 5d metals are nearly similar. Hence MbTa nad MoW have similar covalent radii.
10.Consider following lanthanide (III) ions
(A) Nd(III) (B) Gd(III) (C) Dy(III)
The magnetic moment closest to the spin only h value is(are) for
(a) B only
(b) A and B only
(c) A and C only
(d) B and C only
Hide Answer
Ans (b)
Soln:
11.The ground state forms of Sm3+ and Eu3+ respectively, are
(a) 7F0 and 6H5/2
(b) 6H5/2 and 7F0
(c) 2F5/2 and 5I4
(d) 7F6 and 2F7/2
Hide Answer
102
Ans (b)
Soln
12.In the absence of bound globin chain, heme group on exposure to O2 gives the iron-oxygen
species
Hide Answer
Ans (1)
Soln:
103
When aqueous solution of free Heme is exposes to O2 then it is immediately convert into -oxo-dimer
which is also called Hematin.

transition elements
13.The g values for Ce3+ (4f1) and Pr3+ (4f2) are, respectively
(1) 3/7 and 2/5
(2) 5/7 and 4/5
(3) 6/7 and 3/5
(4) 6/7 and 4/5
Hide Answer
Ans (4)
Soln:
The g values for Ce3+ (4f1) and Pr3+ (4f2) are give below
104
14.Among the following statements, identify the correct ones for complexes of lanthanide (III)
ion.
(A) Metal-ligand bond is significantly ionic.
(B) Complexes rarely show isomerism.
(C) The coordination number is not more than 8.
(D) The magnetic moments are not accounted even approximately by spin only value for majority of
lanthanides.
(a) A, B and D only
(b) A, B and C only
(c) B and C only
(d) A and D only.
Hide Answer
Ans (d)
15.Statement I: The sizes of Zr and Hf are similar
Statement II: Size of Hf is affected by lanthanide contraction.
(a) Statement I and II are correct and II is correct explanation of I.
(b) Statement I and II are correct but II is not a correct explanation of I.
(c) Statement I is correct and II is incorrect
(d) Statements I and II both are incorrect.
Hide Answer
Ans (a)
16.Uranium fluorides co-precipitate with
(a) CaF2
(b) AgF
105
(c) LiF
(d) MgF2
Hide Answer
Ans (a)
17.The coordination number and geometry of cerium in [Ce(NO)6]2-are respectively,
(a) 6 and octahedron
(b) 6 and trigonal prism
(c) 8 and cubic
(d) 12 and icosahedrons
Hide Answer
Ans (d)
18.Statement I. U(VI) is more stable than Nd(VI).
Statement II.The valence electrons in U are in 5f, 6d and 7s orbitals.
(a) Statements I and II are correct and Statement II is correct explanation of I.
(b) Statements I and II are correct but Statement II is not an explanation for Statement I.
(c) Statements I is correct and Statement II is incorrect.
(d) Statements I and II both are incorrect.
Hide Answer
Ans (b)
19.The metallic radii are abnormally high for which of the following pairs?
(1.) Eu, Yb
(2.) Sm, Tm
(3.) Gd, Lu
106
(4.) Nd, Ho
Hide Answer
Ans (1)
Soln:
The lanthanide and actinide elements are all metallic and are formally members of Group 3 of the
Periodic Table. They all form 3+ ions in their compounds and in aqueous solution, with few
exceptions. The actinide elements form a larger range of oxidationstates than the lanthanides, but the
3+ ions are used in this section for comparison purposes. Figure shows the lanthanides metallic and
3+ ionic radii. There is an almost regular decrease in metallic radius along the lanthanide series, with
discontinuities at Eu and Yb. Most of the Lanthanide metals contribute three electrons to bands of
molecular orbitals constructed from the 5d and 6s atomic orbitals, their other valency shell electrons
remaining as 4fn configurations that do not interact with those on neighboring atoms. In the cases of
Eu and Yb, the atoms only contribute two electrons to the 5d/6s bands and retain the configurations
4f7and 4F14, respectively, and so maximize their exchange energies of stabilization. The
contributions of only two electrons each to the bonding bands makes the Eu and Yb metallic radii
larger than those of their neighbors that contribute three electrons.
The 3+ ions have regular 4f orbital fillings, and there is an almost linear decrease in their ionic radii
along the series. This is known as the Lanthanide contraction, and has consequences for the transition
elements
20.Which of the following statements are TRUE for the lanthanides?
(1.) The observed magnetic moment of Eu3+ at room temperature is higher than that calculated
from spin-orbit coupling
(2.) Lanthanide oxides are predominantly acidic in nature
(3.) The stability of Sm(II) is due to its half-filled sub-shell
(4.) Lanthanide(III) ions can be separated by ion exchange chromatography
Correct answer is
(1.) A and D
107
(2.) A and B
(3.) A and C
(4.) B and C
Hide Answer
Ans (1)
Soln:
Oxides of lanthanides are generally basic in nature.
Sm: [Xe]6s24f6
Sm: [Xe]6s24f6Sm(II) is not stable because of half-filled subshell
Rest all statement are correct above Lanthanides (for detailed description on above statement of
lanthanides, refer, inorganic chemistry, Shriver & Atkins)
Organometallic compounds
Organometallic compounds: synthesis, bonding and structure, and reactivity. Organometallics in
homogeneous catalysis.
108
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 8 8 11 10 5 10 12 10 10 8 7
1.The reactions of Ni(CO)4with the ligand (L = PMe3or P(OMe)3)L yields 3 Ni(CO)3L . The
reaction is
(a) Associative
(b) Dissociative
(c) Interchange (Ia)
(d) Interchange (Id)
Hide Answer
Ans (b)
Soln:
Ni(CO)4 [L = PMe3,P(OMe)3]
Ni(CO)4 Total valence electron around
Ni = 10 + 4 x 2 = 18 electron
Substitution reactions at coordinatively saturated tetrahedral complexes with a 18 electron count

likeNi(CO)4 or Ni(CO)2(PR3)2 follows a simple first order kinetics.
Since rate does not depend upon the concentration and nature of the ligand suggesting a dissociative
mechanism.
2.The correct statement for the aggregating nature of alkyl lithium (RLi) reagent is:
(a) The carbanionnucleophilicity increases with aggregation.
109
(b) The observed aggregation arises from its electron deficient nature.
(c) Carbanionnucleophilicity does not depend on aggregation.
(d) The extent of aggregation is maximum in polar dative solvents.
Hide Answer
Ans (b)
Soln:
CH3Li the tendency of organolithium compounds to associate in the solid state as well as in
solution is due to the fact that in a single molecule (LiR), the number of valence electrons is too low
to use all the available Li valence orbitals for 2e2c bonding. This electron deficiency is compensated
by the formation of multicentre bonds e.g. (2e 4c) bonding.
In this structure methyl group of one (LiCH3)4unit interacts with the Li atoms of neighbouring
(Li)4tetrahedron.
3.For the reaction, trans-[IrCl (CO) (PPh3)2] + Cl2 trans-[IrCl3(CO) (PPh3)2], the correct
observation
(a) VCO(product) > VCO(reactant)
(b) VCO(product) < VCO(reactant)
(c) VCO(product) = VCO(reactant)
(d) VCO(product) = VCO(free CO)
Hide Answer
Ans (a)
Soln:
110
Since in product metal Ir is present in the higher oxidation state.So, there is less back bonding to
*orbital of CO.
Hence, V(CO) product >V(CO) reactant
4.The nucleophilic attack on olefins under mild conditions:
(a) Is always facile
(b) Is more facile than electrophilic attack on olefins
(c) Is facile for electron-rich olefins
(d) Requires activation by coordination to metal.
111
Hide Answer
Ans (d)
Soln:
Nucleophilic attack on olefins under mild conditions
So, it requires activation by coordination to metal.
5.The cluster having arachno type structure is:
(a) Os5(CO)16
(b) Os3(CO)12
(c) Ir4(CO)12
(d) Rh6(CO)16
Hide Answer
Ans(b)
Soln:
Step-I: Calculate T.V.E. (total valency electron)
= 83 + 2 12 = 48
Step-II: Polyhedral electron count
= T.V. E. (n12) = 4836=12 n = number of the metal atom
Step-III: = P.E.C./2 = 12/2 = 6 = (n + 3) = Archano.
112
6.The carbonyl resonance in 13C NMR spectrum of [(h5 C5 H5)Rh(CO)]3 (103Rh, nuclear spin,
I=1/2, 100%) shows a triplet at 65 C owing to the presence of
(a) Terminal CO
(b) 2 CO
(c) 3 CO
(d) 5-C5H5
Hide Answer
Ans(b)
Soln:
Doublet of carbonyl carbon indicates the each CO is attached with chemically equivalent two Rh-
atomsthat means 2-CO complex.
Actual structure is:
7.Low oxidation state complexes are often air-sensitive, but are rarely water sensitive because
113
(a) Air is reducing in nature while water is inert
(b) Both air and water are oxidizing in nature
(c) Both air and water are not -acceptors
(d) Complexes with low oxidation states will easily lose electrons to O2but will not bind to p-donor
molecule like H2O.
Hide Answer
Ans(d)
8.The complex that DOES NOT obey 18- electron rule is:
(a) [(5-C5 H5) RuCl (CO) (PPh)3]
(b) [W(CO)3(SiMe3) (Cl) (NCMe)2]
(c) [IrCl3(PPh3)2(AsPh2)]
(d) [Os(N) Br2 (PMe3)NMe2]
Hide Answer
Ans(d)
Soln:
[5C5 H5Ru+2Cl 1 (CO)(PPh)3]
T.V.E=6+6+2+2+2=18
[W+2(CO)3(Si1Me3) Cl1 (NCMe)2]
Total valence electron = 4 + 6 + 2 + 2 + 4 = 18
[IrCl33(PPh3)2(AsPh2)]1
Total valence elecatron = 6 + 6 + 4 + 2 = 18
[Os+5(N-3) Br-22 (PMe3)N-1Me2]
Total valence electron = 3 + 2 + 4 + 2 + 2 = 13
9.The final product of the reaction [Mn (CO)6]++M eLi > is:
114
(a) [Mn(CO)6]+ Me
(b) [Mn(CO)5 Me]
(c) [Mn(CO)6]
(d) [(MeCO)Mn(CO)5]
Hide Answer
Ans(d)
Soln:
[Mn(CO)6]+ + MeLi
10.The reaction 3 [Rh4(CO)12] > 2[Rh6(CO)16]+ 4CO [25C, 500 atm CO] is:
(a) Exothermic as more metal-metal bonds are formed.
(b) Endothermic as stronger metal-carbonyl bonds are cleaved while weaker metal-metal bonds are
formed.
(c) Is entropicallyfavorable but enthalpicallyunfavorable such that G= 0
(d) Thermodynamically unfavourable G >0
Hide Answer
Ans(b)
Soln:
Because metal carbonyls are stronger bond then break this bond huge amount of energy are required.
But metal-metal bonds are weaker bond. So, reaction is endothermic and enthalpy predominant and
entropy unfavorable.
115
11.The substitution of 5Cp group with nitric oxide is the easiest for
(a) 5-Cp2Fe
(b)5-Cp2CoCl
(c)5 Cp2Ni
(d) 5-Cp2Co
Hide Answer
Ans (c)
Soln:
12.The molecule (OC)5M=C(OCH3)(C6H5)obeys 18 e rule. The two M satisfying the condition

are
(a) Cr, Re+
(b) Mo, V
(c) V, Re+
(d) Cr, V
Hide Answer
Ans (a)
116
Soln:
2 5 + M + 2 = 18, M = 1812 = 6
So, M = Cr, and Re+.
13.Complexes of general formula, fac-[Mo(CO)3(phosphite)3] have the CO stretching bands as

given below.
Phosphines: PF3(A); PCl3(B); P(Cl)Ph2(C); PMe3(D)
v(CO), cm-1: 2090(i); 2040(ii); 1977(iii); 1945(iv)
The correct comibination of the phsphine and the streching frequency is,
(b) (Aii), (Bi), (Civ), (Diii)
(c) (Aiv), (Biii), (Cii), (Di)
(d) (Aiii), (Biv), (Ci), (Dii)
Hide Answer
Ans (a)
Soln:
As the -accepting abilities of phosphine increases vCO stretching frequency of the complex
increases.So,the order of -accepting abilities among the given phosphine is:
PF3> PCl3> PClPh2> PMe3.
i.e. A > B > C > D.
117
So, the correct combination for vCO streching is:
A 2090 C 1977
B 2040 D 1945
14.For the molecule below,
consider the following statements about its room temperature spectral data.
(1) 1H NMR has singlets at 5.48 and 3.18 ppm
(B) 1H NMR has multiplet at 5.48 and singlet at 3.18 ppm
(C) IR has CO stretching bands at 1950 and 1860 cm-1
(D) IR has only one CO stretching band at 1900 cm-1.
The correct pair of statement is,
(a) A and C
(b) B and C
(c) A and D
(d) B and D
Hide Answer
Ans (a)
Soln:
118
all 5H proton gives on signal in
1
H NMR at 5.48
Since, the molecule is C2symmetric. So, two COs will give two absorption band in IR spectrum.
15.In the cluster [Co3(CH)(CO) 9] obeying 18e rule, the number of metal-metal bonds and the
bridgind ligands respectively, are
(a) 3 and 1 CH
(b) 0 and 3 CO
(c) 3 and 1 CO
(d) 6 and 1 CH
Hide Answer
Ans (a)
Soln:
The structure of cluster [Co3(CH)(CO)9]
119
So, the number of MM bond = 3 and bridging ligand = 1CH
16.Consider the catalyst in column-I and reactin in column-II
Column-I Column-II
1. [(R)-BINAP]Ru2- (i) hydroformylation

2. [Rh(CO)2I2] (ii) asymmetric hydrogenation.
3. Pd(PPh3)4 (iii) asymmetric hydrogen transfer
(iv) heck coupling.
The best match of a catalyst of column-I with the reaction nuclear column-II is
(a) (Aii), (Bi), (Civ), (Diii)
(b) (Ai), (Bii), (Ciii), (Div)
(c) (Aiii), (Bi), (Civ), (Dii)
(d) (Aiv), (Biii), (Cii), (Di)
Hide Answer
Ans (a)
Soln:
[Rh(CO)2I2] Hydroformylation.
[Pd(PPh3)4] Heck coupling (It is a catalyst for Heck coupling)
120
Asymmetry hydrogen transfer.
17.Which one of the following will NOT undergo oxidative addition by methyl iodide?
(1) [Rh (CO)2I2]
(b) [Ir (PPh3) 2 (CO) Cl]
(c) [2 CpRh (CO)2]
(d) [5 Cp2Ti (Me) Cl]
Hide Answer
Ans (d)
Soln:
[Rh (CO)2I2] 16e and a better cordidate for O.A.
[Ir (PPh3) 2 (CO) Cl] 16e species (Vaskas complex) O.A. is possible.
5 Cp2Ti (Me) Cl] d0 system O.A. is not possible.
[5 Cp2Ti (Me) Cl] 18e species as such O.A. is not possible but after the dissociation
ofligand CO O.A. is possible.
18.In hydrofomylation reaction using [Rh (PPh3)3 (CO) (H)]as the catalyst, addition of excess
PPh3 would
(1) increase the rate of reaction
(b) decrease the rate of reaction.
(c) not influence of the rate of reaction
(d) stop the reaction.
Hide Answer
Ans (b)
Soln:
121
18e species in excess PPh3 it becomes 20e species but the active catalyst is 16e species. So, in
presence of excess PPh3. The rate of hydroformylation will be decreases.
19.Reactions A and B are, termed as respectively.
(1) Insertion, Metathesis
(b) Metathesis, insertion
(c) Oxidative, addition, metathesis
(d) Oxidative addition, insertion
Hide Answer
Ans (a)
Soln:
Since SnCl2 will behaves as a carbene and it insert into the MM bond. So, it is a kind of insertion
reaction.
122
20.Consider the following reaction mechanism. The steps A, B and C, respectively, are
(1) Oxidative addition; transmetallation; reductive elimination.
(b) Oxidative addition; carbopalladation; -hydride elimination.
(c) Carbopalladation; transmetallation; reductive elimination.
(d) Metal halogen exchange; transmetallation; metal extrusion.
Hide Answer
Ans (a)
Soln:
Step (1) is O.A. because the oxidation state of the metal is increased by two units.
123
Step(B) is transmetallation because the ligand is transferring from one metal to another metal.
Step(C) is reductive elimination because the oxidation state of the metal is increased by two units.
21.The hapticities x and y of the arene moieties in the diamagnetic complex
[(x C6H6 )Ru(yC6H6)]respectively are
(a) 6 and 6
(b) 4 and 4
(c) 4 and 6
(d) 6 and 2
Hide Answer
Ans (c)
Soln:
In the compound [66 66]
, 18 .
TVE = 8 + x + y = 18
& 6 & 4.
22.The rate of the reaction depends on
124
(a) Concentration of both the reactants
(b) Concentration of Ni(CO)4only
(c) Concentration of PPh3only
(d) The steric bulk of PPh3
Hide Answer
Ans (b)
Soln:
Ni(CO)4: This is 18 electron complex hence stable. In order to undergo substitution, it must follow
dissociative mechanism (SN1). Hence, it depends only on concentration of reactant.
23.The product of the reaction of propene, CO and H2in the presence of CO2(CO) 8as a catalyst
is
(a) Butanoic acid
(b) Butanal
(c) 2-butanone
(d) Methylpropanoate
Hide Answer
Ans (b)
Soln:
This is an example of Hydroformylation reaction (oxo) process. Conversion of alkene to aldehyde.
24.Reductive elimination step in hydrogenation of alkenes by Wilkinson catalyst results in

(neglecting solvent incoordination sphere of Rh)
(a) T-shaped [Rh(PPh3)2 Cl]
(b) Trigonal-planar [Rh(PPh3)2 Cl]2+
125
(c) T-shaped [Rh(H)(PPh3)2 Cl]+
(d) Trigonal-planar [Rh(H)(PPh3)2]
Hide Answer
Ans (a)
Soln:
Structure is T- shape.
25.Na[(5 C5H5)Fe(CO)2 ] reacts with Br2 to give A. Reaction of A with LiAlH4 results in B. The
protonNMR spectrum of B consists of two singlets of relative intensity 5:1. Compounds A and
B, respectively, are
(a) (5 C5H5)Fe(CO)2Br and (5 C5H5)Fe(CO)2H
(b) (4 C5H5)Fe(CO)2Br2 and (4 C5H5)Fe(CO)2HBr
(c) (5 C5H5)Fe(CO)2Br and (4 C5H5)Fe(CO)2(H)2
(d) (5 C5H5)Fe(CO)2Br and (5 C5H5)Fe(CO)2HBr
Hide Answer
Ans (a)
Soln:
First bromination occurs at Fe center to form stable 18 ecomplex. Then reaction with LAH will
substitute Br with H. In 1H NMR singlet appears for Cp ring and 1H in the ratio of 5:1 (5 protons in
Cp and for 1H in Fe)
26.The compound that undergoes oxidative addition reaction in presence of H2is
(a) [Mn(CO)5]
(b) [(5 C5H5)Mo(CO)]
126
(c) [IrCl(CO)(PPh3)2]
(d) [(5 C5H5)2 ReH]
Hide Answer
Ans (c)
Soln:
Oxidative addition is possible only in case of Iridium complex, commonly known as vaskas
complex. Rest all are 18e complex hence stable.
27.1
H NMR spectrum of free benzene shows a peak at ~ 7.2 ppm. The expected chemical shift (in
ppm) of C6H6ligand in 1H NMR spectrum of [(6 C6H6)Cr(CO)3 ] and the reason for it, if an,
is/are
(a) 4.5 ; disruption of ring current
(b) 9.0 ; inductive effect
(c) 7.2
(d) 2.5 ; combination of inductive effect and disruption of ring current
Hide Answer
Ans (a)
Soln:
There is change in chemical shift experience by particular proton on the formation of complex, bt still
depends on number of other factors including change in ring current brought about by complex
formation.
The calculated value experimentally obtained is 4.43. this work was carried out by Strohmeier and
Helhnanni which differ substantially for those in free ligand
(Ref : J. organometal. Chem, 5, 1966, 147-154)
28.The reaction of phosphorus trichloride with phenyllithium in 1:3 molar ratio yields product
A, which on furthertreatment with methyl iodide produces B. The reaction of B with n-BuLi
gives product C. The products A, Band C, respectively, are
(a) [PPh4]Cl, [Ph2P=CH2]I, Ph2P(nBu)
127
(b) PPh3, [Ph3PI]Me, Ph2P(nBu)3
(c) PPh3, [Ph3PMe]I, Ph3P=CH2
(d) [PPh4]Cl, [Ph3P=CH2]I, [Ph3P(nBu)]Li
Hide Answer
Ans (c)
Soln:
PCl3is the precursor for the formation of PPh3
PCl3+ 3PhCl + 6Na PPh3+ 6NaCl
PPh3combines with most alkyl halides to give phosphonium salts. The facility of the reaction follows
the usual pattern whereby alkyl iodides and benzylic and allylic halides are particularly efficient
reactants:
PPh3+ CH3I [CH3PPh3]+I
These salts, which are readily isolated as crystalline solids, react with strong bases to form ylides:
Such ylides are key reagents in the Wittig reactions, used to convert aldehydes and ketones into
alkenes. Nickel salts are required to react PPh3 with PhBr to give [PPh4]Br. The
tetraphenylphosphonium cation is widely used to prepare crystallizable lipophilic salts.
(References : Elschenbroich, C.; Salzer, Organometallic Chemsitry)
29.The final product in the reaction of [Cp2* ThH] with CO in an equimolar ratio is
128
Hide Answer
Ans (d)
Soln:
In Lanthanides and Actinides, reaction with CO , the initial product undergoes a facile conversion in
which the acyl ligands appear to be dihapto bonded due to special affinity of these metals towards
oxygen
(555)2 () 3 + (5 55)2 3
(Ref : Organometallic Chemistry By R. C. Mehrotra)
30.Complexes HM(CO)5 and[(5-C5H5 )M(CO)3]2 obey the 18-electron rule. Identify M and M
and their1H NMR chemical shifts relative to TMS.
(a) M =Mn, -7.5; M=Cr, 4.10
(b) M =Cr, 4.10; M=Mn, -7.5
(c) M =V, -7.5; M=Cr, 4.10
129
(d) M =Mn,10.22; M=Fe, 2.80
Hide Answer
Ans (a)
31.The ligand(s) that is (are) fluxional in [(5 C5H5) (1 C5H5)Fe(CO)2] in the temperature
range 221298K, is (are)
(a) 5 C5H5
(b) 1 C5H5
(c) 5 C5H5 and CO
(d) 1 C5H5 and CO
Hide Answer
Ans (b)
Soln:
32.The oxidation state of Ni and the number of metal-metal bonds in [Ni CO6]2-that are
consistent with the18 electron rule are
(a) Ni(II), 1 bond
(b) Ni(IV), 2 bonds
(c) Ni(I), 1 bond
(d) Ni(IV), 3 bonds
Hide Answer
Ans (c)
Soln:
130
33.The compound [Re2(Me2PPh)4Cl4] (M) having a configuration of 242*2 can be oxidized to
M+ and M2+.The formal metal-metal order in M, M+ and M2+ respectively, are
(a) 3.0, 3.5 and 4.0
(b) 3.5, 4.0 and 3.0
(c) 4.0, 3.5 and 3.0
(d) 3.0, 4.0 and 3.5
Hide Answer
Ans (a)
Soln:
131
34.Reaction of nitrosyl tetrafluoroborate to Vaskas complex gives complex A with <M-N-O =
124 . Thecomplex A and its N-O stretching frequency are, respectively
(a) [IrCl(CO)(NO)(PPh3)2]BF4, 1620 cm1
(b) [IrCl(CO)(NO)2(PPh3)](BF4)2, 1730 cm1
(c) [IrCl(CO)(NO)2(PPh3)](BF4)2, 1520 cm1
(d) [IrCl(CO)(NO)(PPh3)2], 1820 cm1
Hide Answer
132
Ans (a)
Soln:
NO = 1650 cm1Bent
NO = 1520 cm1Linear
35.Amongst the following which is not isolobal pairs
(a) Mn(CO)5, CH3
(b) Fe(CO)4, O
(c) Co(CO)3, R2Si
(d) Mn(CO)5, RS
Hide Answer
Ans (c)
Soln:
Total number of electrons
Co(CO)3 15 electrons not isolobal
R2Si 6 electrons
Mn(CO)5 17 electrons isolobal
CH3 7 electrons
Fe(CO)4 16 electrons isolobal
133
O 6 electrons
RS 7 electrons
36.The ligand in uranocene is:
(a) C8 H82-
(b) C5 H52-
(c) C6 H6
(d) C4H42-
Hide Answer
Ans (a)
Soln:
Uranocene U(C8H8)2 is the most notable cyclo octatetraenidl
of f-block elements and first organouranium compounds.
2K+C8H8 > K2(C8H8)
2K2(C8H8) + UCl4> U(C8H8)2+ 4KCl
rganometallic compounds
134
37.In metal-olefin interaction, the extent of increase in metal > olefin p-back-donation would
(a) lead to a decrease in C = C bond length
(b) change the formal oxidation state of the metal
(c) change the hybridisation of the olefin carbon from sp2to sp3.
(d) increase with the presence of electron donating substituent on the olefin.
Hide Answer
Ans (c)
Soln:
38.The oxidation state of molybdenum in [(7tropylium) Mo (CO)3]is :
(a) +2
(b) +1
(c) 0
(d) 1
Hide Answer
Ans (c)
Soln:
135
Mo in zero oxidation state.
39.The number of metal-metal bonds in [W2(OPh)6] is:
(a) 1
(b) 2
(c) 3
(d) 4
Hide Answer
Ans (c)
Soln:
Total valency electron = 12 + 18 = 30 (A) [ (OPh) in bridging donate 3 electron]
B = (n18A) = 3630 = 6
Metal-metal bond = B/2 = 6/2 = 3
40.The reaction,
[(CO)5 Mn( Me)+CO [(CO)5 Mn{ C(O )Me}]is an example for
(a) oxidative addition
(b) electrophilic substitution
136
(c) nucleophilic substitution
(d) migratory insertion
Hide Answer
Ans (d)
Soln:
41.The orders of reactivity of ligands, NMe3, PMe3and CO with complexes MeTiCl3and
(CO)5Mo(thf) are
(a) CO > PMe3> NMe3 and CO > NMe3> PMe3
(b) PMe3 > CO > NMe3 and NMe3> CO > PMe3
(c) NMe3 > PMe3> CO and CO > PMe3> NMe3
(d) NMe3 > CO > PMe3 and PMe3> NMe3> CO
Hide Answer
Ans (c)
Soln:
137
42.Intense band at 15000 cm1in the UV-visible spectrum of [Bu4N]2Re2Cl8is due to the
transition
(a) p-p*
(b) d-d*
(c) d-p*
(d) p-d*
Hide Answer
Ans (b)
Soln:
138
43.The treatment of PhBr with n-BuLi yields:
(a) 2 n-BuPh + Br2 + Li2
(b) PhPh + octane + 2 LiBr
(c) n-BuPh + LiBr
(d) PhLi + n-BuBr
Hide Answer
Ans (d)
Soln:
This follows electron transfer (radical) process
139
Hence, formation of 4-membered transition state model.
44.Though cyclobutadiene (C4H4) is highly unstable and readily polymerizes in its free stae, its
transition metal complexes could be isolated because
(a) it engages in long-range interaction with transition metals.
(b) it gains stability due to formation of C4H42 on binding to transition metals.
(c) its polymerization ability reduces in presence of transition metal.
(d) it becomes stable in presence of transition metals due to formation of C4H42+.
Hide Answer
Ans (c)
Soln:
Cyclobutadiene is
which is antiaromatic and unstable due to this reasons it dimerizes, but when it attached with metal
such as
140
The back p-bonding occurs from metal to cyclobutadienes due to this it gain electro from the metal
and converted, into cyclobutadiene anion which aromatic and hence stables.
45. Identify the order representing increasing p acidity of the following ligands C2F4, NEt3, CO
and C2H4
(a) CO < C2F4< C2H4< NEt3
(b) C2F4< C2H4< NEt3< CO
(c) C2H4< NEt3< CO < C2F4
(d) NEt3< C2H4< C2F4< CO
Hide Answer
Ans (d)
Soln:
Increasing p-acidity
NEt3< C2H4< C2F4< CO
Where, NEt3=Neitherp-donor nor p-acceptor
C2H4< C2F4< CO=Increasing order of p-acceptor ability (on the bases of LFT)
46.The species with highest magnetic moment (spin only value) is
(a) VCl64
(b)[(h5-C5H5)2Cr
(c) [Co (NO2)6]3
(d)[Ni(EDTA)]2
141
Hide Answer
Ans (a)
Soln:
47.The number of metal-metal bonds in Ir4(CO)12is
(a) 4
(b) 6
(c) 10
(d) 12
Hide Answer
Ans (b)
Soln:
142
A = TVE = 60
B = (n 18)TVE = 7260 = 14
Metal metal bond = B/2 = 12/2 = 6
48.The bond order of the metal-metal bond in the dimericcomplex [Re2Cl4(PMe2)Ph4]+is
(a) 4.0
(b) 3.5
(c) 3.0
(d) 2.5
Hide Answer
Ans (b)
Soln
143
49.Which of the following in NOT suitable as catalyst for hydroformylation?
(a) HCo(CO)4
(b) HCo(CO)3PBu3
(c) HRh(CO)(PPh3)3
(d) H2Rh(PPh3)2Cl
Hide Answer
Ans (d)
Soln
HCo(CO)4, HCo(CO)3PBu3and HRb(CO)(PPh3)3. These all are the catalyst for hydroformylation
process.
50.In a cluster, H3CoRu3(CO)12, total number of electrons considered to be involved in its

formation is
(a) 57
(b) 60
144
(c) 63
(d) 72
Hide Answer
Ans (b)
Soln
H3CoRu3(CO)12
3+a+83 + 122 = 60 electron.
51.The correct statement regarding terminal/bridging CO groups in solid Co4(CO)12 and

Ir4(CO)12 is
(a) both have equal number of bridging CO groups
(b) number of bridging CO groups in Co4(CO)12is 4
(c) the number of terminal CO groups in Co4(CO)12is 8
(d) the number of bridging CO groups in Ir4(CO)12is zero.
Hide Answer
Ans (d)
Soln
145
52.On reducing Fe3(CO)12 with an excess of sodium, a carbonylate ion is formed. The iron is
isoelectronic with
(a) [Mn(CO)5]
(b) [Ni(CO)4]
(c) [Mn(CO)5]+
(d) [V(CO)6]
Hide Answer
Ans (b)
Soln
53.Among the following clusters,
H is encapsulated in
(a) A only
(b) B only
(c) B and C only
(d) A and B only
Hide Answer
Ans (a)
146
Soln
54.The electrophile Ph3C+ reacts with [(h5 C5H5)Fe(CO)2(CDMe)2]+
to give a product A. The productA is formed because
(a) Fe is oxidised
(b) alkyl is susbtituted with Ph3C
(c) Fe-Ph bond is formed
(d) Alkyl is converted to alkene
Hide Answer
Ans (d)
Soln
55.Subsitution of L with other ligands will be easiest for the species
147
Hide Answer
Ans (c)
Soln
In case of (c) the chances of conversion of haptacityfrom h5h3is more due to partial bond fixation.
56.Among the following, the correct statement is
(a) CH is isolobal to Co(CO)3
(b) CH2 is isolobal to Ni(CO)2
(c) CH is isolobal to Fe(CO)4
(d) CH2 is isolobal to Mn(CO)4
Hide Answer
Ans (a)
Soln
CH4 +1=5 e-
148
Co (CO )39+ 6 =15 e-
But,
CH24+2 =6e-
Ni (CO) 210+4= 14 e-
i.eand so on
57.The most appropriate structure for the [Pt2(NH3)2(NCS)2(PPh3)2] is
Hide Answer
Ans (c)
Soln
Pt -Sd, -d, bonding in weaker than that of Pt-P bonding. When Pt-S and Pt-P bond are trans to
each other then Pt-S become weaker therefore in such a situation SCM ligand tends to form bonding
through M atoms of ligand as M do not form d, -p, bonding.Hence the most propable structure will
be
149
58.CpM[Cpis (5-C5H5)]fragmentisolobal with a BH fragment is..
(1) CpGe
(2) CpMn
(3) CpRu
(4) CpCO
Hide Answer
Ans (4)
Soln:
CpCoThe species which have same difference of electron to complete their valence shell electronic
configuration called isolobal fragment or electrochemical equivalent species
Total number of electron in BH = 4e
Electron deficiency = 4e
Total electron in M-Cp
x + 5 = 18
x = 13
For isolobal fragment, edeficiency = 4
So, number of electrons present in metal=13 4 = 9e
Then electronic configuration of valence shell of metal is 3d74s2, which is configuration of Co
Metal, therefore CpCo is isolobal fragment of BH
59.The number of metal-metal bonds in [Co2Fe2(CO)11(4-PPh)2] is
(1) 3
(2) 4
(3) 5
150
(4) 6
Hide Answer
Ans (2)
Soln:
Number of metal-metal bond is calculated by following formula
Number of M-M bond = [18 x No.of metals Totalvalenceshellelectron]
Here, Number of M-M = [18 x 4 (2 x 9 + 2 x 8 + 2 x 11 + 2 x 4)]
= [72 64]
= x 8
=4
Number of M-M bond = 4
60.Correct order of M-C bond length of metallocenes (a-c)
1. [Fe(5-Cp)2]
2. [Ni(5-Cp)2]
3. [Co(5-Cp)2] is
(1) a> b > c
(2) b> c > a
(3) c> b > a
(4) a > c > b
Hide Answer
Ans (2)
Soln:
The value of M-C bond length of metallocenes are
Cp2Fe Cp2Co Cp2Ni
M-C Distance in ( ) 2.06 2.12 2.20
151
61.For fluxional Fe(CO)5 (structure given below) in solution, the exchange of numbered CO
groups will be between
(1) 2 and 5; 3 and 4
(2) 2 and 3; 4 and 5
(3) 2 and 3; 1 and 5
(4) 1 and 2; 4 and 5
Hide Answer
Ans (1)
Soln:
Fluxional molecules that undergo dynamics such that some or all of their atoms interchange between
symmetry equivalent positions. In Fe(CO)5 is the archetypal fluxional molecule due to rapid
interchange of the axial and equatorial CO group.
62.In the following reaction sequence
152
Hide Answer
Ans (1)
Soln:
In the following reaction sequence the product is given below
63.Reaction of Cr(CO)6 with LiC6H5 gives A which reacts with [Me3O][BF4] to give B. The
structures of A and B respectively, are
Hide Answer
153
Ans (1)
Soln:
Reaction of Cr(CO)6 with LiC6H5 gives A which react with [Me3O] [BF4] to give B. The structure of
A and B in the following reaction sequence are given below
64.Heating a sample of [(5-C5H5)Mo(CO)3]2 results in the formation of [(5-

C5H5)Mo(CO)2]2with elimination of 2 equivalents of CO. The MoMo bond order in this
reaction changes from
(1) 2 to 3
(2) 1 to 2
(3) 1 to 3
(4) 2 to 4
Hide Answer
Ans (3)
Soln:
65.A plausible intermediate involved in the self metathesis reaction of C6H5CC-C6H4-p-Me

catalyzed by [(tBuO)3WCtBu] is
154
Hide Answer
Ans (2)
Soln:
66.In Ziegler-Natta catalysis the commonly used catalyst system is:
(a) TiCl4 ,Al (C2 H5)3
(b) 5 Cp2TiCl2 ,Al (OEt)3
(c) VO(acac) , Al2 (CH3) 6
(d) TiCl4 ,BF3
Hide Answer
Ans (a)
67.Oxidation occurs very easily in case of
(a)5-( C5H5)2 Fe
(b)5-( C5H5)2 Co
(c) 5-( C5H5)2 Ru
155
(d)5-( C5H5)2 Co+
Hide Answer
Ans (b)
68.Complex in which organic ligand is having only sbond with metal is:
(a) W (CH3)6
(b) 5 ( C5H5)2Fe Ru
(c) K [PtCl3(C2H4 )]
(d) 6-( C6H6)2Ru
Hide Answer
Ans (a)
69.The oxidative addition and reductive elimination steps are favoured by
(a) Electron rich metal centres.
(b) Electron deficient metal centers
(c) Electron deficient and electron rich metal centers respectively.
(d) Electron rich and electron deficient metal centers respectively
Hide Answer
Ans (d)
70.Identify the order according to increasing stability of the following organometallic

compounds, TiMe4, Ti(CH2Ph)4, Ti(i-Pr)4and TiEt4.
(Me = methyl, Ph = phenyl, i-Pr = isopropyl, Et = ethyl)
(a) Ti(CH2Ph)4 < Ti(i-Pr)4< TiEt4 <TiMe4
(b) TiEt4 < TiMe4 < Ti(i-Pr)4 < Ti(CH2Ph)4
(c) Ti(i-Pr)4 < TiEt4< TiMe4 < Ti(CH2Ph)4
156
(d) TiMe4 < TiEt4 <Ti(i-Pr)4 < Ti(CH2Ph)4
Hide Answer
Ans (c)
71.Among the metals, Mn, Fe, Co and Ni, the ones those would react in its native form directly
with CO givingmetal carbonyl compounds are:
(a) Co and Mn
(b) Mn and Fe
(c) Fe and Ni
(d) Ni and Co
Hide Answer
Ans (c)
72.In the hydroformylation reaction, the intermediate CH3CH2CH2Co(CO)4:
(a) Forms are acyl intermediate CH3CH2CH2CO Co(CO)3
(b) Forms an adduct with an olefin reactant.
(c) Reacts with H2.
(d) Eliminates propane.
Hide Answer
Ans (a)
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73.The correct combination of metal, number of carbonyl ligands and the charge for a metal
carbonyl complex [M(CO)x]z-that satisfies the 18 electron rule is
(a) M = Ti, x = 6, z =1
(b) M = V, x = 6, z =1
(c) M = Co, x = 4, z=2
(d) M = Mo, x = 5, z = 1
Hide Answer
Ans (b)
74.The stable cyclopentadienyl complex of beryllium is
(a) [Be(2-C5H5)2]
(b) [Be(2-C5H5)(3-C5H5)]
(c) [Be(1-C5H5)(3-C5H5)]
(d) [Be(1-C5H5)(5-C5H5)]
Hide Answer
Ans (d)
75.Reaction of Fe (CO)5with OH leads to complex A which on oxidation with MnO2gives B.

Compounds A and B respectively are
(a) [HFe(CO 4 ] and Fe3(CO)12
(b) [Fe(CO)5(OH)] and Fe2(CO)9
(c) [Fe(CO)4 ]2- and Mn2(CO)10
158
(d) [HFe(CO)4 ] and Fe2O3
Hide Answer
Ans (a)
76.The number of metal-metal bonds in the dimers, [CpFe (CO) (NO)]2 and
[CpMo(CO)3]2respectively, are
(a) two and two
(b) two and three
(c) one and two
(d) zero and one
Hide Answer
Ans (d)
77.In the trans-PtCl2L(CO) complex, the CO stretching frequency for L = NH3, pyridine,
NMe3 decreases in theorder.
(a) pyridine>NH3> NMe3
(b) NH3> pyridine> NMe3
(c) NMe3>NH3> pyridine
(d) pyridine>NMe3> NH3
Hide Answer
Ans (a)
78.The catalyst involved in carrying out the metathesis of 1-butene to give ethylene and 3-
hexene is:
159
(b) Na2 PdCl4
(c) Co2(CO)8 , H2
(d) RhCl(PPh3)3
Hide Answer
Ans (a)
79.The greater stability of (( CH3)3C CH2 )4 Ti (A) compared to that of (( CH3)3C CH2
)4 Ti (B)is due to
(a) Hyperconjugation present in complex (A)(b) -hydride elimination is not possible in complex (A)
(c) Steric protection of titanium from reactive species in complex (A)
(d) The stronger nature of TiC bond in complex (A)
Hide Answer
Ans (b)
80.A compound A having the composition 9 8 3 Fe C H O shows one signal at 2.5 ppm and
another one around 5.0ppm in its 1H NMR spectrum. The IR spectrum of this compound shows
two bands around and 1680 cm1.The compound follows the 18 electron rule of the following
statements for A, the correct one is/are
(A) It has 5 Cp group. (B) It has a terminal CO ligand.
(C) It has a CH3ligand (D) It has FeH bond.
160
(b) (C) only
(c) (A) and (C) only
(d) (B) and (D) only.
Hide Answer
Ans (a)
81.The W-W bond order in [W(5-C5H5)(- Cl)(CO)2]2 is .
(1.) three
(2.) two
(3.) one
(4.) zero
Hide Answer
Ans (4)
Soln:
To calculate bond order
(a) Calculate TVE :a
(b) Calculate n x 18 : b [n = number of metal]
82.[(3-C3H5)Mn(CO)4] shows fluxional behaviour. The 1H NMR spectrum of this compound

when it is in the non-fluxional state shows
(1.) one signal
(2.) two signals in the intensity ratio of 4 : 1
161
(3.) three signals in the intensity ratio of 2 : 2 : 1
(4.) five signals of equal intensity
Hide Answer
Ans (3)
Soln:
Non fluxional behavior can be observed if NMR is carried out at low temperature. For this complex, 3
signals are observed
one for H3
two for H1and H4
third for H2and H5
In the intensity ratio 2 : 2 : 1
83.Reaction of [Mn2(CO)10] with I2 results in A without loss of CO. Compound A, on heating

to 1200C loses a CO ligand to give B, which does not have a Mn-Mn bond. Compound B reacts
with pyridine to give 2 equivalents of C. Compounds A, B and C from the following respectively,
are
162
(1.) II, V and IV
(2.) II, III and IV
(3.) V, III and IV
(4.) II, V and III
Hide Answer
Ans (1)
Soln:
(a) Dimanganesedecacarbonyl reacts with halogens to form carbonyl halides.
Mn2CO10+ I2 2Mn(Co)5I
84.The final product of the reaction of carbonyl metalates [V(CO)6]and [Co(CO)4] with H3PO4,
respectively, are
(1.) V(CO)6and HCo(CO)4
(2.) HV(CO)6and Co2(CO)8
(3.) [H2V(CO)6]+ and HCo(CO)4
(4.) V(CO)6and Co2(CO)8
Hide Answer
Ans ()
Soln:
163
85.For, uranocene, the correct statement(s) is/are:
(1.) Oxidation use of uranium is +4.
(2.) it has cyclocotatetraenide ligands
(3.) it is a bend sandwich compound
(4.) it has -2 charge.
Correct answer is
(1.) A and B
(2.) B and C
(3.) A and D
(4.) B only
Hide Answer
Ans (1)
Soln:
Uranium compound was the 1st metallocene of Cot2- to be synthesized
UCl2- + 2Cot2- U(Cot)2
From the given reaction, it is concluded that among the following option (A) and (B) are correct.
86.The approximate positions of vco band (cm-1) in the solid-state infrared spectrum and the
Fe-Fe bond order in [Fe(5 C5H5)( CO)(CO)]2(non-centro-symmetric) respectively, are
(1.) (2020, 1980, 1800) and one
164
(2.) (2020, 1980, 1800) and two
(3.) (2020, 1980) and one
(4.) (2143) and one
Hide Answer
Ans (1)
Soln:
Three bands are expected in CO in the complex [Fe(5-C5H5)(-Co)(CO)]2 since it is non Centro-
symmetric.
One band for bridging CO around 1800
Two bands (one symm, one asymm) around 2020 (asymm) and 1980 (symm)
Total valence electrons = 34
nx18 36 (there are 2 Fe atoms)
M.M bond = 36 34 /2 = 1
87.Protonated form of ZSM-5 catalyzes the reaction of ethene with benzene to produce
ethylbenzene. The correct statement for this catalyst process is
(1.) alkyl carbocation is formed
(2.) carbanion is formed
(3.) benzene is converted to (C6H5)+group
(4.) vinyl radical is formed
Hide Answer
Ans (1)
Soln:
165
ZSM-5 is an acid catalyst and is typically used for Alkylation of aromatic compounds.
88.The intermediate and final major product of photolysis of Z
From the following:
Are
(1.) A and D
(2.) B and D
(3.) B and C
(4.) A and C
Hide Answer
166
Ans (2)
Soln:
In the following photolysis reaction, first the removal of CO takes place to form 16e- complex and
then the change in hapticity from 1to 3. Hence correct option is (2)
Cages and metal clusters

Cages and metal clusters.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 5 2 2 1 4 1 4 1 4
1.The correct structure of basic beryllium nitrate is:
167
Hide Answer
Ans (a)
2.In [Mo2(S2)6]2-cluster the number of birdgingS22- and coordination number of Mo respectively,

are
(1) 2 and 8
(b) 2 and 6
(c) 1 and 8
(d) 1 and 6
Hide Answer
168
Ans (a)
Soln.
[Mo2(S2)6]2-
The structure of [Mo2(S2)6]2-cluster is:
So, the bridging S22- is two and co-ordination number of Mo is 8.
3.The total number of CuO bonds present in the crystalline copper(II) acetate monohydrate is:
(1) 10
(b) 6
(c) 8
(d) 4
Hide Answer
Ans (a)
Soln
169
4.Structure of a carborane with formula, C2B4H8 is formally derived from
(1) Closo-borane
(b) Nido-borane
(c) Arachno-borane
(d) Conjuncto-borane
Hide Answer
Ans (b)
Soln:
C2B4H8
(BH) 2B4H8; B2H2B4H8
Or,
5.Silicates with continuous 3D frame work are
(1) Neso-silicates
(b) Soro-silicates
170
(c) Phyllo-silicates
(d) Tecto-silicates
Hide Answer
Ans (d)
6.Co4(CO)12 adopts the
(a) closo-structure
(b) nido-structure
(c) arachno-structure
(d) hypho-structure
Hide Answer
Ans (b)
Soln:
Co4(CO)12
Calculating TVE = 9 4 + 2 12 = 60
For transition metals; according to Wades rule,
14n + 2 = closo, 14n + 6 = arachno, 14n + 4 = nido
Putting n = 4, 14 4 + 4 = 60 .
7.According to Wades rule, anion C2 B9H 12adopts
(a) closo-structure
(b) nido-structure
(c) arachno-sturcture
(d) hypho-structure
Hide Answer
Ans (b)
Soln:
171
According to Wade Rule, each C is equivalent to B-H bond
Hence, C2B9H12= B11H14
One negative charge is equivalent to one H hence its equivalent structure is B11H15. This corresponds
to nido structure.
8.The total valence electron count and the structure type adopted by the complex [Fe5(CO)15C)]
respectively,are
(a) 74 and nido
(b) 60 and closo
(c) 84 and arachno
(d) 62 and nido
Hide Answer
Ans (a)
Soln:
[Fe5(CO)15C)]
Total valency electron = 85 + 152 + 4 = 74
PEC = TEC n 12
PEC = 74512 = 7460 = 14
PEC /2 = 14/2 = 7
7=n+2 where, n = number of metal in electron.
= 5 + 2 = (n + 2) Nido
9.The correct equilibrium order for the interconversion of different forms of SiO2 is
(a) Tridymitequartzcristobaliteliquid SiO2
(b) quartzTridymitecristobalite liquid SiO2
(c) quartzcristobalitet tridymiteliquid SiO2
(d) Cristobalitetridymitequartzliquid SiO2
172
Hide Answer
Ans (b)
Soln:
10.Number of isomeric derivatives possible for the neutral closo-carborane, C2B10H12 is
(a) three
(b) two
(c) four
(d) six
Hide Answer
Ans (a)
Soln
C2B10H12is show three isomeric derivative which is depend on the temperature.
173
11.In a specific reaction, hexachlorocyclotriphosphazene, N3P3Cl6 was reacted with a metal
fluoride to obtain mixed halo derivatives namely N3P3Cl5F(A), N3P3Cl4F2(B), N3P3Cl3F3(C),
N3P3Cl2F4(D), N3P3ClF5(E). Compositions among these which can give isomeric products are
(a) A, B and C
(b) B, C and D
(c) C, D and E
(d) E, A and B
Hide Answer
Ans (b)
Soln
(A) N3P3Cl5F = only one isomer
(B) N3P3Cl3F3= three isomer
(C) N3P3Cl3F4 = three isomer
174
(D)N3P3Cl2F4 = one isomer
12.For higher boranes 3c-2e BBB bond may be a part of their structures. In B5H9, the number
of such electron deficient bond(s) present is/are
(a) four
(b) two
(c) zero
(d) one
Hide Answer
Ans (d)
Soln:
175
13.The solid state structure of aluminum fluoride is
176
Hide Answer
Ans (c)
Soln:
AlF3has octahedral arrangement in 3-dimethyl structure which causes high methyl point of AlF3in
comparison to AlCl3, AlBr3and AlI3. AlCl3dimer has layered structure.
14.The number of 3c-2e bonds present in Al(BH4)3 is
(1) four
(2) three
(3) six
(4) zero
Hide Answer
177
Ans (3)
Soln:
Aluminium borohydride contain six bond which is shown in figure
3c-2e bonds are BHAl which is 6.
15.The numbers of skeletal electrons present in the compounds C2B3H5, C2B4H6, and B5H9are,
respectively,
(1) 10, 12 and 12
(2) 12, 14 and 14
(3) 10, 12 and 14
(4) 12, 14 and 12
Hide Answer
Ans (2)
Soln:
The number of skeletal electron present in the following compound are given below
(a) C2B3H5 = (CH) X 2 + (BH) X 3
= 3 X 2 + 2 X 3 = 12
(b) C2B4H6 = (CH) X 2 + (BH) X 4
178
= 3 X 2 + 2 X 4 = 14
(c) B5H9 = (BH) X 5 + 4H
= 2 X 5 + 4 X 1 = 14
BH can donate 2e electron, CH can donate 3 e electron& hydrogen (H) can donate one electron
16.A Sodalite cage in zeolites is
(a) a truncated tetrahedron
(b) an icosahedron
(c) a truncated octahedron
(d) a dodecahedron
Hide Answer
Ans (c)
17.The STYX code of B4H10 is:
(a) 4120
(b) 4220
(c) 4012
(d) 3203
Hide Answer
Ans (c)
18.Bayers process involves.
(a) Synthesis of B2H6from NaBH4
(b) Synthesis of NaBH4from borax
(c) Synthesis of NaBH4from B2H6
179
(d) Synthesis of B3N3H6from B2H6
Hide Answer
Ans (a)

19.The order of increasing bronsted acidity for boron hydrides is
(1) B5H9< B6H10< B10H14
(2) B10H14< B5H9< B6H10
(3) B6H10< B10H14< B5H9
(4) B10H14< B6H10< B5H9
Hide Answer
Ans (1)
Soln:
Acidity of boron hydride depends on the size of borane greater the sizes higher will be the
acidity. This is because the negative charge, formed upon deprotonation, can be better delocalized
over a large anion with many boron atoms than over a small one.
20.The ring size and the numbers of linked tetrahedral present in [Si6O18]12-are,respectively,
(1) 6 and 6
(2) 12 and 6
(3) 12 and 12
(4) 6 and 12
Hide Answer
Ans (1)
Soln:
Cyclic metasilicates [SiO3)n]2n- having 3, 4, 6 or S linked tetrahedra are known, though 3 and 6 are the
most common. These anions are shown schematically in Fig. and are exemplified by the mineral
180
benitoite [BaTi{Si3O9}], the synthetic compound [K4{Si4O8(OH)4}], and beryl [Be3Al2{Si6O8}] and
murite [Ba,0(Ca, Mn, Ti]4{Si8O24}(Cl, OH, O)2].4H2O.
21.The reaction of BCl3awith NH4Cl gives product A which upon reduction by NaBH4 gives
product B. product B upon reacting with HCl affords compound C, which is
(1.) Cl3B3N3H9
(2.) [ClBNH]3
(3.) [HBNH]3
(4.) (ClH)3B3N3(ClH)3
Hide Answer
Ans (1)
Soln:
Ammonium chloride reacts with Boron chloride to produce trichloridoborazine and hydrogen
chloride. This reaction takes place at temperature 140 150 0C. catalyst C6H6, C6H5Cl.
22.Using wades rules predict the structure type of [C2B5H7].
(1.) nido
(2.) closo
(3.) arachno
181
(4.) hypho
Hide Answer
Ans (2)
Soln:
Wades rule
1 carbon is equal to BH fragment as both are isolobal
C2B5H11= B7H9 B7H72 (hence closo)
23.The number of valence electrons provided by [Ru(CO) 3] fragment towards cluster bonding
is
(1.) 1
(2.) 14
(3.) 6
(4.) 2
Hide Answer
Ans (4)
Soln:
For transition metal, number of electrons available per building block for cluster bonding
L = d + y2 12
d = number of valence shell electron
y = number of ligands
L = number of e- contributed by each ligand
RuCO3
Ru(d8) = 8 + 6 12
=2
182
Analytical chemistry
Analytical chemistry: separation, spectroscopic, electro- and thermoanalytical methods.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 3 2 3 2 4 3 3 3 2 1 1
1.The spectrophotometric response for the titration of a mixture of Fe3+and Cu2+ions against
EDTA is given below.
The correct statment is:
(a) Volume ab [Fe3+]and volume cd [Cu2+]
(b) Volume ab [Cu2+]and volume cd [Fe3+]
(c) Volume ab [Fe3+]and volume abexcess EDTA
(d) Volume ab [Cu2+]and volume cd excess EDTA
Hide Answer
Ans (c)
2.The quantitative determination of N2H4 with KIO3 proceeds in a mixture of H2O/CCl4 as

follows
183
N2 H4 +KIO3+2HCl -> N2 +KCl+ICl+3H2O
The end point for the titrimetric reaction is:
(a) Consumption of N2H4
(b) ICI formation
(c) Disappearance of the yellow color due to Cl2 in CCl4 layer.
(d) Displacement of the rod color due to I2 in CCl4 layer.
Hide Answer
Ans(d)
3.Appropriate reasons for the deviation form the Beers law among the following are
(a) Monochromaticity of light
(C) Very high concentration of analyte
(B) Association of analyte
(D) Dissociation of analyte.
(1) A, B and D
(b) B, C and D
(c) A, C and D
(d) A, B and C
Hide Answer
Ans (b)
Soln
Beers law is subjected to certain real and apparent deviation.

Real deviations are most usually encountered in relatively concentrated solutions of the
absorbing compound(> 0.01 M). These deviations are due to interactions between the
absorbing species and to atterations of the refractive index of the medium.
Most common are the apparent deviations and these deviations are due to Chemical reasons
arising when the absorbing compound dissociates, associates or reacts with a solvent to
produce a product having a different absorption spectrum.
Strict adherence to Beers law is observed only with truly monochromatic radiation.
184
4.On subjecting 9.5 ml solution of Pb2+of X M to polorographic measurements, Id was found to
be 1 A. When0.5 mL of 0.04 M Pb2+was added before the measurement, the Idwas found to be
1.25 A.
(1) 0.0035
(b) 0.0400
(c) 0.0067
(d) 0.0080
Hide Answer
Ans (c)
5.A solution of 2.0 g of brass was analysed for Cu electrogravimetrically using Pt-gauze as
electrode. The weight of Pt-gauze changed from 14.5g to 16.0 g. The percentage weight of Cu in
brass is
(a) 50
(b) 55
(c) 60
(d) 75
Hide Answer
Ans (d)
Soln:
The weight of Pt-gauze as electrode increases by 1614.5 = 1.5 g because 1.5 g of Cu is deposited on
Ptgauze.
Therefore, weight of Cu in 2.0 gram brass is 1.5g.
Therefore, percentage weight of Cu in brass =1.5/2.0 x100 = 75
6.In a polarographic measurement, (aqueous KCl solution used as supporting electrolyte)

anapplied potentialmore than +0.4 V, results mainly in the formation of
(a) HgI
185
(b) HgII
(c) Cl2
(d) O2
Hide Answer
Ans (a)
Soln:
The major drawback of polarographic measurement is that when the applied potential exceed more
than 0.4, oxidation of mercury takes place in mercurous ion (Hg22+).
7.Gel permeantion chromatography can be used to separate which of the following
(A) Lanthanides
(B) Alkaline earths
(C) Fatty acids
(D) Low molecular weight peptides
A and B
B and C
C and D
A and D
Hide Answer
Ans (c)
Soln:
Gel permeation chromatography (GPC) is a type of size exclusion chromatography (SEC), that
separates analytes on the basis of size. The technique is often used for the analysis of polymer.
8.Among the following species, (A) Ni(II) as dimethylglyoximate, (B) Al(III) as oxinate, (C)
Ag(I) as chloride,those that precipitate with the urea hydrolysis method are
(a) A, B and C
(b) A and B
(c) A and C
186
(d) B and C
Hide Answer
Ans (b)
9.Gelatin added during the polarographic measurement carried out using dropping mercury
electrode
(a) reduces streaming motion of Hg drop
(b) decreases viscosity of the solution
(c) eliminates migrating current
(d) prevents oxidation of Hg
Hide Answer
Ans (a)
10.The use of dynamic inert atmosphere in thermogravimetric analysis (TGA)

(a) decreases decomposition temperature
(b) decrease weight loss
(c) reducds rate of decomposition
(d) increases weight loss
Hide Answer
Ans (a)
Soln:
In thermogravimetric analysis (TGA) use of dynamic innert atmosphere is decrease decomposition
with respect to temperature.
11.The correct statements for hollow cathode lamp (HCL) from the following are
(A) HCL is suitable for atomic absorption spectroscopy (AAS)
(B) lines emitted from HCL are very narrow
(C) the hardening of lamp makes it unsuitbale for AAS
(D) transition elements used in lamps have short life
(a) A, B and C
(b) B, C and D
(c) C, D and A
(d) D, A and B
Hide Answer
Ans (a)
12.In complexometric titration

S(substrate)+T(titrant)P(product)
The end point is estimated spectro photometrically. If S and P have =0 , the shape of the
titration curve would look like
187
Hide Answer
Ans (c)
Soln:
If S and P have e= 0, then titrant shows parallely and after end point goes increasingly with respect
to substate.
13.Distribution ratio of A between CHCl3 and water is 9.0. It is extracted with several, 5 mL
aliquots of CHCl3. The number of aliquots needed to extract 99.9% of A from its 5 mL
aqueous solution are
(a) 2
(b) 3
(c) 4
(d) 5
showhide type=post13]
Ans (c)
[/showhide]
188
14.For neutron activation analysis of an element, the favourable characteristics of both the
target and the product are from the following
(A) high neutron cross-section area of target
(B) long half-life of the product
(C) low neutron cross-section area of target
(D) low half-life time of the product.
The correct characteristics from the above are
(a) A and B
(b) C and D
(c) B and C
(d) A and D
Hide Answer
Ans (a)
Soln:
For an element the favourable characteristics both the target and the product in neutron activation is
high neutron cross-section area of the target and long half-life of the product
15.Commonly used scintillator for measuring radiation is
(a) NaI(AI)
(b) NaI(TI)
(c) CsI (TI)
(d) CsI(AI)
Hide Answer
Ans (b)
Soln
189
16.A sample of aluminium ore (having no other metal) is dissolved in 50 mL of 0.05 M EDTA.
For the titration ofunreacted EDTA, 4 mL of 0.05 M MgSO4 is required. The percentage of AI
in the sample is:
(a) 27
(b) 31
(c) 35
(d) 40
Hide Answer
Ans (?)
17.In a polarographic estimation, the limiting currents (A) were 0.15, 4.65, 9.15 and 27.15
when concentration (mM) of Pb(II) were 0, 0.5, 1.0 and 3.0 respectively. An unknown solution of
Pb(II) gives a limiting current of 13.65A. Cocentration of Pb(II) in the unknown is
(a) 1.355 mM
(b) 1.408 mM
(c) 1.468 mM
(d) 1.500 mM
Hide Answer
Ans (d)
Soln
190
18.In the iodometric titration of sodium thiosulfate (Na2S2O3) with acidic dichromate solution,
25 mL of 0.1 M dichromate requires 25 mL of x M thiosulfate. The value of x is
(1) 0.2
(2) 0.1
(3) 0.6
(4) 0.4
Hide Answer
Ans (3)
Soln:
We know that N = n x M, where n = number of eexchange in the reaction
ForK2Cr2O7, n = 6
191
So, for 0.1M, 25mLK2Cr2O7solution requiredNa2S2O3 is 0.6 M, 25mL.
1234
19.Decomposition temperature of CaCO3 in thermogravimetric analysis will be highest in

dynamic atmosphere of
(1) nitrogen
(2) synthesis gas
(3) 1:1 mixture of O2 and CO
(4) water gas
Hide Answer
Ans (3)
Soln:
In thermal decomposition of CaCO3 the thermal temperature is highest, when mixture of O2and CO is
present in 1:1 ratio
20.A 100 mL solution of 2.5 X 103 M in Bi(III) and Cu(II) each, is photometrically titrated at
745 nm with 0.1 M EDTA solution. Identify correct statements for this titration.
1. Total volume of EDTA solution used is 5 mL

2. B. 3 mL of EDTA is required to complex Bi(III) and 2 mL for Cu(II)
3. 2.5 mL of EDTA is used for each metal ion
4. First break in titration curve is for Cu(II)
Correct statements are
(1) A and B
(2) A and C
(3) A, B and C
(4) B, C and D
192
Hide Answer
Ans (2)
Soln:
In photometric Titration metal ion is titrated with EDTA
Since 1mol EDTA = mol of Cu(II)
and 1mol EDTA = 1mol of Bi(III)
Therefore volume of EDTA for Titration of Cu(II) is obtained 5ml of volume and Volume of EDTA
for Titration of Bi(III) is 2-5ml of volume
Calculated by M1V1= M2V2
21.The FALSE staement for a polarographic measurement procedure is:
(a) O2 is removed
(b) Dropping mercury electrode is working electrode.
(c) Id is proportionaal to concentation of electroactive species.
(d) Residual current is made zero by adding supporting electrolyte.
Hide Answer
Ans (d)
22.In the titration of 50 mL of 0.1 M HCl with 0.1 M NaOH using methyl orange as an
indicator, the end point (color change) occurs as pH reaches 4.0. The titration error is:
(a) 0.2%
(b) 84.7%
(c) + 0.2%
(d) + 84.2%
Hide Answer
Ans (b)
193
23.Correct statement for coulometry is
(1.) it is based on faradays law of electrolysis
(2.) it is a type of voltammetry
(3.) it is based on Ohms law
(4.) it uses ion selective electrode
Hide Answer
Ans (1)
Soln:
Coulometry is an analytical in which we measure amount of amount of water transferred during an

electrolysis reaction by measuring the amount of electricity consumed/produced.
24.The calibration curve in spectrofluorimetric analysis becomes non-linear when
(1.) Molecular weight of analyte is high
(2.) Intensity of light source is high
(3.) Concentration of analyte is high
(4.) Molar absorptivity of analyte is high
Hide Answer
Ans (3)
Soln:
According to Lambert-Beer law
A = C.l
When A is plotted v/s conc. Curve should nearly be of straight line. However, only limitation is that
conc. Of analytes should be low.
Bioinorganic chemistry
Bioinorganic chemistry: photosystems, porphyrins, metalloenzymes, oxygen transport,
electron- transfer reactions; nitrogen fixation, metal complexes in medicine.
194
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 3 6 8 7 4 5 7 8 9 5 6
1.The actual base pairs present in the double helical structure of DNA containing adenine (A),
thymine (T), cytosine (C) and guanine (G), are
(a) AG and CT
(b) AC and GT
(c) AG and AC
(d) AT and GC
Hide Answer
Ans (d)
Soln:
195
2.The oxidation state of iron in met-hemoglobin is
(a) Three
(b) Two
(c) Four
(d) Zero
Hide Answer
Ans (a)
3.The changes (from A-D given below) which occur when O2 binds to hemerythrin are
(A) One iron atoms is oxidized
(B) Both the iron atoms are oxidized
(C) O2 binds to one iron atom and is also hydrogen bonded.
(D) O2 binds to both the iron atoms and is also hydrogen bonded.
196
(a) B and C
(b) B and D
(c) A and D
(d) A and C
Hide Answer
Ans(a)
Soln:
4.In photosynthetic systems the redox metalloproteins involved in electron transfer are
cytochrome (cyt, b),cytochrome bf complex (cyt bf) and plastocyamin (PC). The pathway of
electron flow is
(a) PC> cyt b > cyt bf
(b) cyt bf > cyt b >PC
(c) cyt b> cyt bf > PC
(d) PC> cyt bf > cyt b
Hide Answer
Ans(c)
5.The correct set of the biologically essential elements is,
(1) Fe, Mo, Cu, Zn
(b) Fe, Cu, Co, Ru
(c) Cu, Mn, Zn, Ag
(d) Fe, Ru, Zn, Mg
Hide Answer
Ans (a)
Soln:
197
6.Degradation of penicillin G
givespenicillamine that can utilize nitrogen, oxygen or sulfur atoms as donors to bind with lead(II),
mercury (II) or copper(II). The structure of penicillamine is
198
Hide Answer
Ans (a)
Soln:
199
7.In metalloenzymes, the metal centres are covalently linked through the side chains of the
amino acid residues.The correct set of amino acids which are involved in the primary
coordinates spheres of metalloenzymes is
(a) Ala, Leu, His
(b) Glu, His, Cys
(c) Leu, Glu, Cys
(d) Ala, His, Glu
Hide Answer
Ans (b)
Soln:
So, it creat chiral environment across the catalyst.
8.Based on the behaviour of the metalloenzymes, consider the following statements
(A) In the enzymes, the zinc activates O2 to form peroxide species.
(B) In the enzymes, the zinc activates H2O and provides a zinc boud hydroxide.
(C) In the oxidases, the iron activates O2 to break the bonding between the two oxygens
(D) Zinc ion acts as a nucleophile and attacks at the peptide carbonyl
The set of correct statements is,
(a) A and B
(b) B and C
(c) C and D
(d) A and D
Hide Answer
Ans (b)
Soln:
Because zinc is a Lewis acid and hence,
200
However, oxidase are enzyme that catalyse the reduction of O2 H2O or H2O2.
O2(g)+ 4e+ 8H+(inside) 2H2O(l)+ 4H+(outside)
9.Fe2+-porphyrins fail to exhibit reversible oxygen transport and cannot differentiate CO from
O2. However, the hemoglobin is free from both these pit falls. Among the following
(A) Fe2+ porphyrins undergo -oxodimer formation and the same is prevented in case of the
hemoglobin.
(B) FeCO bond strength is much low in case of hemoglobin when compared to the Fe2+
porphyrins.
(C) While FeCO is linear, FeO2 is bent and is recognized by hemoglobin
(D) The interlinked four monomeric units in the hemoglobin are responsible to overcome the pitfalls.
The correct set of statements is
(a) A and B
(b) A and C
(c) C and D
(d) B and D
Hide Answer
Ans (b)
Soln:
Free heme (i.e. without globular protein chain) it foms -oxodimer) i.e.
201
oxo-dimer (hematin).
Which is unable to bind O2.
10.The extent of -electron conjugation in macrocyclic rings of (1) heme, (2) coenzyme B12 and
(3) chlorophyllfollows the order
(a) (1) > (3) > (2)
(b) (1) > (2) > (3)
(c) (3) > (1) > (2)
(d) (2) (1) > (3)
Hide Answer
Ans (a)
Soln:
Least conjugation is present in Vitamin B12 as one side of the corrin ring doesnt have methylene
linkages. In Heme, there is extensive conjugation of electron (11 ) as compared to that of
chlorophyll.( 10 )
202
11.The number of histidine amino acid nitrogen atoms coordinated to bimetallic active site of
oxyhemocyanin, andoxyhemerythrin, respectively, are
(a) 2, 3 and 3, 3
(b) 3, 3 and 2, 3
(c) 3, 3 and 2, 2
(d) 2, 4 and 3, 2
Hide Answer
Ans (b)
Soln:
203
12.Identify correct statements for mercury as an environment pollutant.
1. Carbanionic biomethylation converts it to MeHg+

2. Thiol group of cysteine has strong affinity for mercury
3. Mercury containing industrial catalyst release caused Minamata disaster
(a) A and B
(b) A and C
(c) B and C
(d) A, B and C
Hide Answer
Ans (d)
Soln:
Methylmercury is a form of mercury (3+) that is most easily bio accumulated in organisms.
Transformation of Hg(II) to (3+) is brought about by sulphate reducing bacterial in lower lakes.
Mercury and its compound possess affinity for binding to reduced sulphydryl group of many thiol
compounds in the body such as glutathione, S containing amino acid cysteine
204
13.Under physiological condition, oxygen is binding to deoxyhemoglobin and deoxymyoglobin,
the binding curveand its pH dependence, respectively, are
(a) Sigmoidal and pH dependent;
(b) Hyperbolic and pH independent;hyperbolic and pH independent sigmoidal and pH dependent
(c) Sigmoidal and pH independent;
(d) Hyperbolic and pH dependent;hyperbolic and pH dependent sigmoidal and pH independent
Hide Answer
Ans (a)
Soln:
Oxygen binding curve for deoxyhaemoglobin is sigmoidal and pH dependent, this phenomenon is
known as Bohr effect. Whereas deoxymyoglobin is hyperbolic and pH independent.
(Reference : Biochemistry, Lippard)
14.Match the metalloproteins in columnA with their function in columnB
ColumnA ColumnB
I. Oxyhemocyanin A. hydrolysis of C-terminal peptide bond
II. Carbonic anhydrase B. methylation
III. Cytochrome P450 C. C. Conversion of CO2 to H2CO3
IV. Carboxy-peptidase A D. oxdiation of alkene
E. oxygen stroage
F. oxygen transport
(a) I F; II C; III D; IV A
(b) I E; II C; III A; IV F
205
(c) I F; II B; III C; IV A
(d) I E; II D; III C; IV A
Hide Answer
Ans (a)
Soln:
Oxyhaemocyanin : function is oxygen transport mainly in invertebrates.
Carbonic anhydrase :Carbonic anhydraseis an enzyme that balances the pH of the blood and enables
the breathing out of carbon dioxide. In red blood cells carbonic anhydrase catalyzes the reaction to
convert carbon dioxide into carbonic acid, which further breaks down into bicarbonate ions and
protons (H+).
Cytochrome p450: class of monooxygenases that catalyzes oxidation of alkene, are interesting
potential green catalyst.
15.If an enzyme fixes N2in plants by evolving H2, the number of electrons and protons associated
with that,respectively are
(a) 6 and 6
(b) 8 and 8
(c) 6 and 8
(d) 8 and 6
Hide Answer
Ans (b)
Soln:
N2 +8H+ +8e + 16 ATP 2NH3 + H2 + 16ADP + 16Pi
16.Toxicity of cadmium and mercury in the body is being reversed by proteins, mainly using the
amino acidresidue,
(a) Glycine
(b) Leucine
206
(c) Lysine
(d) Cysteine
Hide Answer
Ans (d)
Soln:
Toxicity of cadmium and mercury in the body is being reversed by cysteine amino acid.
17.In low chloride ion concentration, the anticancer drug cis-platin hydrolyses to give a diaqueo
complex and thisbinds to DNA via adjacent guanine
Soln:
The coordinating atom of guanine to Pt(II) is
(a) N1
(b) N3
(c) N7
(d) N9
Hide Answer
Ans (c)
Soln:
18.At pH 7, the zinc(II) ion in carbonic anhydrase reacts with CO2 to give
207
Hide Answer
Ans (a)
Soln:
208
19.Molybdoenzymes can both oxidize as well as reduce the substrates, because
(a) Mo(VI) is more stable than Mo(IV)
(b) Mo(IV) can transfer oxygen atom to the substrate and Mo(VI) can abstract oxygen atom from the
substrate
(c) Conversion of Mo(VI) to Mo(IV) is not favoured
(d) Mo(VI) can transfer oxygen atom to the substrate and Mo(IV) can abstract oxygen atom from the
substrate.
Hide Answer
Ans (d)
Soln:
209
20.Amongst the following which is not isolobal pairs
(a) Mn(CO)5, CH3
(b) Fe(CO)4, O
(c) Co(CO)3, R2Si
(d) Mn(CO)5, RS
Hide Answer
Ans (c)
Soln:
Total number of electrons
Co(CO)3 15 electrons not isolobal
R2Si 6 electrons
CH3 7 electrons
Fe(CO)4 16 electrons isolobal
O 6 electrons
RS 7 electrons
21.The coordination geometry of copper (II) in the type I copper protein plastocyanin is:
(a) square planar
(b) tetrahedral
(c) octahedral
(d) distorted tetrahedral
210
Hide Answer
Ans (d)
Soln:
The coordination Geometry of copper(II) in coper(I) protein plastocyanin is distorted tetrahedral.
22.The metal ions present in the active site of nitrogenase enzyme co-factor are
(a) Fe, Mo
(b) Fe, W
(c) Fe, Cu
(d) Fe, Ni
Hide Answer
Ans (a)
Soln:
Nitrogenase enzyme cofactor contains Fe, Mo also known as Iron-molebdenum cofactor.
23.For the metalloprotein hemerythrin, the statement that is NOT TRUE is
(a) there are two ion centres per active site.
(b) both iron centres are hexacoordinated in the active state.
(c) one iron is hexacoordinated while the other is pentacoordinated in the active state.
(d) it is found in marine invertebrates
Hide Answer
Ans (b)
Soln:
211
Deoxy hemerythrine
In Hemerythrin, one iron centre is pentacoordinated and is hexacoordinated. And iron exist at peractive site
found in mariene invertebrates.
24.Patients suffering from Wilsons disease have
(a) Low level of Cu-Zn superoxide dismutase
(b) High level of Cu-Zn superoxide dismutase
(c) Low level of copper-storage protein, ceruloplasmin
(d) High level of copper-storage protein, ceruloplasmin
Hide Answer
Ans (c)
Soln
Wilsons disease is caused by excess accomulation of Cu in the body.
25.High dose of dietary supplement ZnSO4 for the cure of Zn deficiency
(a) reduces myoglobin
(b) increases iron level in blood
212
(c) increases copper level in brain
(d) reduces copper, iron and calcium levels in body
Hide Answer
Ans (d)
26.Oxidised form of enzyme catalase (structure A); prepared by the reaction of [Fe(P)]+(P =
porphyrin) withH2O2, has green colorbecauase
A(substitutents on ring are removed for clarity)
(a) Oxidation state of iron changed from FeIII to FeIV.
(b) Porphyrin ring is oxidized by one electron
(c) p-p* transition appears in the visible region
(d) FeIV is coordinated with anionic tyrosinate ligand in axial position
Hide Answer
Ans (a)
Soln
Catalase is a tetrames of four polypeptide chains covering 500 amino acids.
It works as
H2O2+Fe (III) -E -> H2O+ O= Fe (IV) -E+0
H2O2+O =Fe(IV)-E+ -> H2O+Fe(III)-E +O2
213
The colour arises as Fe(III) changes into Fe(IV).
27.The reactive position of nicotinamide adenine dinucleotide (NAD) in biological redox

reactions is
(a) 2-position of the pyridine ring
(b) 6-position of the pyridine ring
(c) 4-position of the pyridine ring
(d) 5-position of the pyridine ring
Hide Answer
Ans (c)
Soln
Therefore, the 4-position of the pyridine ring is reactive position in the biological reaction.
28.The compound which dissolves in POCl3 to give a solution with highest chloride ion
concentration, is
(1) Et3N
(2) KCl
(3) FeCl3
(4) SbCl5
Hide Answer
214
Ans (2)
Soln:
When KCl dissolves in POCl3 to give a solution with highest concentration of Cl ion.
29.Correct combination of number and size of rings present in a metal ion-porphine complex
(including metal ion bearing chelate rings) is
(1) four 5-membered and four 6-membered
(2) two 5-membered and six 6-membered
(3) six 5-membered and two 6-membered
(4) five 5-membered and three 6-membered
Hide Answer
Ans (1)
Soln:
The combination of number and size of ring presence in a metal ion-porphine complex is four five
membered ring and four six membered ring which shown below
30.In human body cis-platinhydrolyzes to a diaqua complex and modifies the DNA structure by
binding to
215
(1) N-atom of guanine base
(2) O-atom of cytosine base
(3) N-atom of adenine base
(4) O-atom of thymine base
Hide Answer
Ans (1)
Soln:
In human body cis-platin hydrolysis to a diaqua complex and modifies the DNA structure by binding
to N-atom of guanine base
31.The ligand system present in vitamin B12 is:
(a) Porphyrin
(b) Corrin
(c) Phthalocyanine
(d) Crown ether
Hide Answer
Ans (b)
Soln:
216
32.Carboxypeptidase contains:
(a) Zn(II) and hydrolyses CO2.
(b) Zn(II) and hydrolyses peptide bonds.
(c) Mg(II) and hydrolyses CO2.
(d) Mg(II) and hydrolyses peptide bonds
Hide Answer
Ans (b)
33.Superoxide dismutase contains the metal ions
217
(a) Zn (II) and Ni(II)
(b) Cu(II) and Zn(II)
(c) Ni (II) and Co(III)
(d) Cu (II) and Fe(III)
Hide Answer
Ans (d)
34.The chemiluminescence method for determining NO in environmental samples is based on

formation of NO2* (excited) which is generally generated by reacting NO with
(a) O2
(b) O2
(c) O3
(d) O22-
Hide Answer
Ans (c)
35.The reduction of nitrogen to ammonia, carried out by the enzyme nitrogenase, needs,
(a) 2 electrons
(b) 4 electrons
(c) 6 electrons
(d) 8 elecrons
Hide Answer
Ans (c)
218
36.A metal ion that replace manganese (II) ion in mangano-proteins without changing its
function, is
(a) Fe (II)
(b) Zn (II)
(c) Mg (II)
(d) Cu (II)
Hide Answer
Ans (c)
37.In bacterial rubredoxin, the number of iron atoms, sulfur bridges and cysteine ligands areFe
atom sulfer bridge cysteine
(a) 4 4 4
(b) 2 2 4
(c) 2 2 2
(d) 1 0 4
Hide Answer
Ans (d)
38.The biological functions of the cytochrome P450and myoglobin are, respectively
(1.) Oxidation of alkene and O2storage
(2.) O2transport and O2storage
(3.) O2storage and electron carrier
(4.) Electron carrier and O2transport
Hide Answer
Ans (1)
Soln:
219
The biological function of cytochrome P450is to act in a mono oxygenasereaction.e.g insertion of one
atom of oxygen into aliphatic position of organic substrates.
The function of Mb is more subtle than Hb. Besides being a simple repository for dioxygen, it also
serve as dioxygen reserve against which organism can draw during increased metabolism
(O2 deprivation).
(Reference : Inorganic Chemistry , Huheey)
39.Deoxy Hemocyanin is
(1.) heme protein and paramagnetic
(2.) Colorless and diamagnetic
(3.) O2 transport and paramagnetic
(4.) Blue colored and diamagnetic
Hide Answer
Ans (2)
Soln:
Hemocyanin is blue pigment which contains Cu in (I) oxidation state.Since it is in deoxy form it is
colorless and also diamagnetic (d10) configuration.
40.Match the metalloproteins in column A with its biological function and metal center
in column B
Column A ColumnB
(a) Hemoglobin (i) Electron carrier and iron
(b) Cytochrome b (ii) Electron carrier and copper
220
(c) Vitamin B12 (iii) O2 transport and copper
(d) Hemocyanin (iv) Group transfer reactions and cobalt
(v) O2 storage and cobalt
(vi) O2 transport and iron
The correct match is
(1.) (a)-(vi); (b)-(i); (c)-(iv) and (d)-(iii)
(2.) (a)-(v); (b)-(i); (c)-(iv) and (d)-(iii)
(3.) (a)-(iv); (b)-(v); (c)-(i) and (d)-(ii)
(4.) (b)-(v); (b)-(vi); (c)-(ii) and (d)-(iv)
Hide Answer
Ans (1)
41.The resonance Raman stretching frequency (vo-o, in cm-1) of O2 is 1580. The vo-o for O2in
bound oxy-hemoglobin is close to
(1.) 1600
(2.) 1900
(3.) 800
(4.) 1100
Hide Answer
Ans (4)
Soln:
It is known fact that stretching frequency of any molecule in the Free State is always higher that the
same in bound stateHere it is given that o-o is 1580 of free O2. Hence in bound Hb it must be less
than that, so correct answer is 1100 (more precisely 1180 cm-1)
221
42.Pick the correct statements about Atomic Absorption Spectrometry (AAS) from the
following
(1.) Hg lamp is not suitable source for AAS
(2.) Graphite furnace is the best atomizer for AAS
(3.) Non-metals cannot be determined with AAS
(4.) AAS is better than ICP-AES for simultaneous determination of metal ions
Correct answer is
(1.) A, B and C
(2.) B, C and D
(3.) C, D and A
(4.) D, A and B
Hide Answer
Ans (1)
Soln:
Common source used in AAS is HCl (Hallow Cathode Lamp) and EDL (Electrodes Discharge Lamp)
Best atomizer is graphite tube

Since it is based on the principle of flame detection, generally non-metal cannot be detected
ICP-AES is better technique that trivial AAS.
Nuclear chemistry
222
Nuclear chemistry: nuclear reactions, fission and fusion, radio-analytical techniques and activation
analysis.
YEAR 2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 2 2 1 1 3 1 2 1 2
1.The carbon-14 activity of an old wood sample is found to be 14.2 disintegrations min-1g-1.
Calculate age of oldwood sample, if for a fresh wood sample carbon-14 activity is 15.3
disintegrations min-1g-1(t1/2 carbon-14 is5730 years), is:
(a) 5, 000 years
(b) 4, 000 years
(c) 877 years
(d) 617 years
Hide Answer
Ans(d)
Soln:
Because metal carbonyls are stronger bond then break this bond huge amount of energy are required.
But metal-metal bonds are weaker bond. So, reaction is endothermic and enthalpy predominant and
entropy unfavorable.
2.In carbon-dating application of radioisotopes, 14C emits
(a) -particle
(b) -particle
223
(c) -radiation
(d) Positron.
Hide Answer
Ans (a)
Soln:
Carbon dating
14
C6 undergoes ray decay;
14
C614N7 +
3.The geometric cross-section (in barn) of a nucleus A = 125, ro = 1.4 10-15 m approximately is
(a) 1.05
(b) 1.54
(c) 2.05
(d) 2.54
Hide Answer
Ans (b)
Soln:
According to the Fermi model of nuclear size and density, relation is given by
=01/3 where r is the radius of the nucleus of mass number A.
Geometric cross section area = 2
1 barn = 10-28m2
Solving the equation, we get 1.54
4.The particles postulated to always accompany the positron emission among
(A) neutrino, (B) anti-neutrino, (C) electron,are
(a) A, B and C
224
(b) A and B
(c) A and C
(d) B and C
Hide Answer
Ans (c)
Soln:
Particles that are always to emit during position emission
1P + 1e0 + v (antineutrino)
1 1
0n
5.The nuclides among the following, capable of undergoing fission by thermal neutrons,
are(A) 233U (B) 235U (C) 239Pu (D) 232Th
(a) A, B and D
(b) A, C and D
(c) B, C and D
(d) A, B and C
Hide Answer
Ans (d)
Soln:
6.For a low energy nuclear reaction, 24Mg (d,)22Na, the correct statements from the following
are
(A) Kinetic energy of d particle is not fully available for exciting 24Mg.
(B) Total number of protons and neutrons is conserved
(C) Q value of nuclear reaction is much higher in magnitude relative to heat of chemical reaction
(D) Threshold energy is Q value.
(a) A, B and C
(b) A, B and D
225
(c) B, C and D
(d) A, C and D
Hide Answer
Ans (a)
Soln:
Nuclear chemistry
7.A radioisotope 41Ar initially decays at the rate of 34, 500 disintegrations/minute, but decay
rate falls to 21, 500 disintegrations/minute after 75 minutes. The t1/2 for 41Ar is:
(a) 90 minutes
(b) 110 minutes
(c) 180 minutes
(d) 220 minutes
Hide Answer
Ans (b)
Soln:
8.Given g(H)@2.7C108T-1s-1 . The resonance frequency of a proton in magnetic field of
(a) 60 MHz
226
(b) 110 MHz
(c) 540 MHz
(d) 780 MHz
Hide Answer
Ans (c)
Soln:
Gyromagnetic ratio = 2.7108 T1S1 = 2.7108/23.14 Hz T1
= 42.5 106 Hz T1 = 42.5 MHz T1.
Frequency at 12.6 T = 42.5 12.6 MHz = 536 MHz.
9.In Mossbauer experiment, a source emitting at 14.4 KeV(3.48X1018 Hz) had to be moved
towards absorber at 2.2 mm s1 for resonance. The shift in the frequency between the source
and the absorber is
(a) 15.0 MHz
(b) 20.0 MHz
(c) 25.5 MHz
(d) 30.0 MHz
Hide Answer
Ans (c)
Soln:
10.Among the following, the correct combination of complex and its color is
227
Hide Answer
Ans (c)
Soln:
Order of ligand is spectro chemical series
SCN<Cl< F< CN
From above it is clear that CNwill produce highest energy difference, followed by F, Cl, SCN.As
colour of complex is complementary colour of absorbed light.
Thus,
[Co(CN)4] 2
absorbs orange colour radiation which complementary colour is blue therefore
colour of [Co(CN)4] 2 is blue.
The other combination according to energyare mismatched. Hence, only option (c) is correct.
11.absorbance decreases with the addition of
(a)CO2-3
(b) SO42
(c) EDTA
(d) Cl
228
Hide Answer
Ans (b)
Soln
Chemical reactions between analyte and matrix that prevent the atomization of the analyte. One
common one is that Sulfate or phosphates anions will form non-volitile salts with Fe+3, so its signal
decreases. Can be treated in two ways 1. Releasing agents can add to metal to prevent formation of
interference complexs. This this example EDTA or 8- hydroxyquinoline
12Reaction of Ph2PCH2CH2PPh2 with [RhCl(CO)2]2 in a 2:1 molar ratio gives a crystalline solid
A. The IR spectrum of complex A shows nCOat 1985 cm1. The 31P(1H) NMR spectrum of A
consists (103Rh is 100% abundant and I = ). The structure of complex A is
Hide Answer
Ans (a)
Soln:
229
IR band at 1985 cm1 indicates terminal CO. Both P atoms are non-equivalent. Each P atom will
show doublet of doublet with (1JPRh and 2JPP).
Nuclear chemistry
13.On continuous exposure of 10B sample to a slow neutron flux of 1016 m2s1, its 3 % weight
fraction disappears in 3 X 107 s. Cross section for neutron capture (in barns) by 10B is
(1) 1000
(2) 3000
(3) 10,000
(4) 30,000
Hide Answer
Ans (1)
Soln:
On continuous exposure of 10B sample to a slow neutron flux 1016 m2s1. The cross section for neutron
capture by 10B is found to be approx 1000 barns .
14.On two sequential electron capture,56Ba131 will give
(1) 54Xe131
(2) 54Xe130
(3) 56Ce131
(4) 56Ce130
230
Hide Answer
Ans (1)
Soln:
56Ba
131
+ 2e 54Xe131 + 2V
In this mode of decay two of the orbital electrons are capture by two protons in the nucleus forming
two neutrons. Two neutrinos are emitted in the process. Since the protons have changed to neutrons,
the number of neutrons increases by 2 the number of protons decreases by 2 and the atomic mass
number remain unchanged.
15.The species 19Ne and 14C emit a positron and bparticle respectively. The resulting species
formed arerespectively
(a) 19Na and 14B
(b) 19F and14 N
(c) 19Na and 14N
(d)19 F and 14B
Hide Answer
Ans (b)
16.For a given nuclear fission reaction of 235U
235
U92+1n0 142Ba56 +91Kr36+1n0
the amount of energy (in kJ/mol) released during this process is (given 235U = 235.0439 amu,142Ba =
141.9164amu, 91Kr = 90.9234 amu, neutron = 1.00866 amu)
(a) 3.121012
(b) 2.81011
(c) 1.0109
(d) 1.681010
Hide Answer
Ans (d)
231
17.For the nuclear reactions.
(A)8Bec 24He2 (B)80Kr36 240Ar18
(Given masses: 8Bev= 8.005300, 4He2= 4.002603 and 80Kr36 =79.81638, 40Ar18 =39.96238 )
The correct statement is:
(a) (A) and (B) are both spontaneous fission processes.
(b) (A) is spontaneous fission but (B) is not.
(c) (B) is spontaneous fission but (A) is not
(d) Both (A) and (B) are not spontaneous fission processes.
Hide Answer
Ans (b)
18.Spin motion of which of the following gives magnetic moment
(A) Electron (B) Proton (C) Neutron
Correct answer is
(1.) A and B
(2.) B and C
(3.) A and C
(4.) A, B and C
Hide Answer
Ans (4)
Soln:
Magnetic moment is induced by the spin of elementary particles (electron and quarks in the proton
and neutron of atomic nuclei).
* Neutron is electrically neutral but a non-zero magnetic moment because of its internal quark
structure.
232
(Reference : P.W. Atkins, Quanta: A handbook of concepts. Oxford University)
19.Identify radioactive capture from the following nuclear reactions
(1.) 9Be(, n) 28Be
(2.) 23Na(n, ) 24Na
(3.) 63Cu (p, p 3n 9) 24Na
(4.)107Ag (n, n) 107Ag
Hide Answer
Ans (2)
Soln:
Radioactive capture reactions are described as follows Parent Nucleus, Projectile Daughter
nucleus, ejectile
23
Na11+ 0n6 24Na11+ 0n6(y rays)
Rest all examples do not follow this trend.
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Characterisation of inorganic compounds

Characterisation of inorganic compounds: by IR, Raman, NMR, EPR, Mssbauer, UV-vis, NQR,
MS, electron spectroscopy and microscopic techniques.
YEAR
233
2016 2015 2015 2014 2014 2013 2013 2012 2012 2011 2011
No.of
questions
appeared 7 5 4 5 7 4 3 5 4 5 2
1.As a ligand Cl is:
(a) Only a donor
(b) Only a donor
(c) Both a donor and a donor
(d) A donor and a acceptor
Hide Answer
Ans (c)
Soln:
Ligand Cl is both donorand -donor
According to LFT, each ligand is always donor some ligands like : NH3which has only one lone
pair of electrons is only donor. Some ligands like F, Cl, Si, OH etc which hence two or more
lone pair of electrons are as well as donors Some ligands like CO, CN , SH4bpy, phenetc how
vacant * orbitals so these are donor but acceptors.
2.The correct d-electron configuration showing spin-orbit coupling is
(a) t2g4eg2
(b) t2g6eg0
(c) t2g4eg0
(d) t2g3eg2
Hide Answer
Ans (c)
Soln:
Spin-orbit coupling of d-electrons takes place in which t2gorbitals are unsymmetricaly filled.
234
3.For the reaction, trans-[IrCl (CO) (PPh3)2] + Cl2 trans-[IrCl3(CO) (PPh3)2], the correct
observation
(a) VCO(product) > VCO(reactant)
(b) VCO(product) < VCO(reactant)
(c) VCO(product) = VCO(reactant)
(d) VCO(product) = VCO(free CO)
Hide Answer
Ans (a)
Soln:
Since in product metal Ir is present in the higher oxidation state.So, there is less back bonding to
*orbital of CO.
Hence, V(CO) product >V(CO) reactant
235
4.Among the following the strongest oxidizing agent is:
(a) [WO]2-
(b) [CrO]2-
(c) [MoO]2-
(d) [ReO]1-
Hide Answer
Ans (b)
Soln:
In [WO]2-,[CrO]2-, [MoO]2-and [ReO]1-all the metals have same oxidation state but Cr6+is of smallest
size. Therefore it has strongest tendency to attract electrons. Therefore strongest oxidizing agent.
(a) Al (OH)3
(b) La (OH)3
(c) Ce (OH)3
(d) Lu (OH)3
Hide Answer
Ans (a)
Soln:
236
Al (OH)3Amphoteric whereas hydroxides of lanthanoids are all base.
6.The carbonyl resonance in13C NMR spectrum of [(h5 C5 H5)Rh(CO)]3 (103Rh, nuclear spin,
I=1/2, 100%) shows a triplet at 65 C owing to the presence of
(a) Terminal CO
(b) m2 CO
(c)m3 CO
(d) h5-C5H5
Hide Answer
Ans(b)
Soln:
Doublet of carbonyl carbon indicates the each CO is attached with chemically equivalent two Rh-
atomsthat means 2-CO complex.
Actual structure is:

7.The metal complex that exhibits a triplet as well as doublet in its 31P NMR spectrum is
237
(a) mer- [IrCl (Co) (PPh3)] 2
(b) trans-[IrCl (Co) (PPh3)] 2
(c) fac-[IrCl (Co) (PPh3)] 2
(d) [Ir (PPh3)4] +
Hide Answer
Ans (a)
Soln:
Indicates total three phosphorus atoms in the molecules in two sets 2P and 1P
2P doublet, 1P Triplet
That is possible in) mer- [IrCl (Co) (PPh3)] 2
fac-[IrCl (Co) (PPh3)] 2 will give siglet of 3P.
trans-[IrCl (Co) (PPh3)] 2will give siglet of 2P.
[Ir (PPh3)4] +will give siglet of 4P.
238
8.The number of spin-allowed ligand field transitions for octahedral Ni(II) complexes
with3A2gground state is:
(a) Two
(b) Three
(c) One
(d) Four
Show Answer
9.The total numbers of fine and hyperfine EPR lines expected for octahedral high-spin Mn(II)
complexes arerespectively (I = 5/2 for Mn)
(a) 3 and 30
(b) 5 and 33
(c) 5 and 30
(d) 4 and 24
Show Answer
10.The Mossbauer spectra of two iron complexes are shown below. They may arise from (i)
high-spin iron(III),(ii) high-spin iron(II) and (iii) low-spin iron(III)
The correct matches of spectra (A) and (B) with the iron complexes are
(a) A with (i) and B with (ii)
(b) A with (ii) and B with (i)
(c) A with (iii) and B with (ii)
(d) A with (ii) and B with (iii)
Show Answer
11.In the vibrational spectrum of CO2, the number of fundamental vibrational modes common
in both infraredand Raman are
(1) Three
239
(b) Two
(c) One
(d) Zero
Show Answer
12.The light pink color of [Co(H2O)6]2+and the deep blue color of [CoCl4]2-are due to
(1) MLCT transition in the first and d-d transition in the second
(b) LMCT transition in both
(c) d-d transitions in both
(d) d-d transition in the first and MLCT transition in the second.
Hide Answer
Ans (c)
Soln:

240
13. 1
H NMR spectrum of HD would show.
(a) a singlet
(b) a doublet
(c) a triplet with intensity ratio 1:2:1
(d) a triplet with intensity ratio 1:1:1
Show Answer
14.The number of lines exhibited by a high resolution EPR spectrum of the species,
[Cu(ethylenediamine)2]2+ is [Nuclear spin (I) of Cu = 3/2 and that of N = 1]
(1) 12
(b) 15
(c) 20
(d) 36
Show Answer
15.The recoil energy of a Mossabauer nuclide of mass 139 amu is 2.5 MeV. The energy emitted
by the nucleusin keV is:
(a) 12.5
(b) 15.0
(c) 20.5
(d) 25.0
Show Answer
16.Complexes of general formula, fac-[Mo(CO)3(phosphite)3] have the CO stretching bands as

given below.
Phosphines: PF3(A); PCl3(B); P(Cl)Ph2(C); PMe3(D)
v(CO), cm-1: 2090(i); 2040(ii); 1977(iii); 1945(iv)
241
The correct comibination of the phsphine and the streching frequency is,
(b) (Aii), (Bi), (Civ), (Diii)
(c) (Aiv), (Biii), (Cii), (Di)
(d) (Aiii), (Biv), (Ci), (Dii)
Show Answer
17.For the molecule below,
consider the following statements about its room temperature spectral data.
(1) 1H NMR has singlets at 5.48 and 3.18 ppm
(B) 1H NMR has multiplet at 5.48 and singlet at 3.18 ppm
(C) IR has CO stretching bands at 1950 and 1860 cm-1
(D) IR has only one CO stretching band at 1900 cm-1.
The correct pair of statement is,
(a) A and C
(b) B and C
(c) A and D
(d) B and D
Show Answer
242
18.Find out the number of lines in the 31P NMR signal for
(1) 3
(b) 6
(c) 18
(d) 90
Hide Answer
Ans (d)
Soln:
243
19.The correct order of the isomeric shift in Mossbauer spectra (57Fe source) of iron compounds
is
(a) Fe(II) > Fe(III) > Fe(IV)
(b) Fe(III) > Fe(II) > Fe(IV)
(c) Fe(IV) > Fe(III) > Fe(II)
(d) Fe(IV) > Fe(II) > Fe(III)
Hide Answer
Ans (c)
Soln:
Isomer shift is given by
=210 0 [ 22 ] [ 0 20 2]
244
[ 22 ]=
If the electron density at nucleus is shielded by other factor, then this term become negative.
2 .
FeIV < FeIII < FeII (increasing order of electron density)
( FeIV> FeIII > FeII ) .
20.The S and L values for 15N atom respectively, are
(a) 1/2 and 1
(b)1/2and 02
(c) 1 and 0
(d) 3/2 and 0
Hide Answer
Ans (d)
Soln:
Since the number of protons is same for N14and N15hence term symbol will be same as that for N14.
21.The point group symmetries for trans-[Cr(en)2 F2 ] +and [TiCl6]3-, respectively, are
(a) D4d and D3d
(b) D3d and D
(c) D4h and D3h
(d) D3h and D4h
Hide Answer
Ans (c)
Soln:
The point group of trans [Cr(en)2F2]+ is D2h. But for this case, we assume D2h D4h. Since,
chelating ligand have very little effect in geometry, hence it can be considered as trans [ML4X2]
type molecule.
245
22.Which of the following will result in deviation from Beers law:
(A) Change in refractive index of medium,
(B) Dissociation of analyte on dilution,
(C) Polychromatic light
(D) Path length of cuvette
(a) A, B and C
(b) B, C and D
(c) A, C and D
(d) A, B and D
Hide Answer
Ans (a)
Soln:
In Lambert Beer Law, Path length of cuvette do not cause any deviation from the ideal behaviour.
23.The gas commonly used in generating plasma in Inductively Coupled Plasma Atomic
Emission Spectroscopy(ICPAES) is
(a) Argon
(b) Carbon dioxide
(c) Nitrous oxide
(d) Hydrogen
Hide Answer
Ans (a)
Soln:
246
ICP is created by igniting plasma gas, typically argon, with a spark, and the plasma is sustained under
high radio frequency electromagnetic field.
24.An aqueous solution of [Mn(H2O)6]2+ complex is pale pink in colour. The probable reasons
for it are
(A) Presence of 6Alg ground state
(B) Disallowed transition by spin selection rule
(C) Presence of 2T2g ground state
(D) Charge transfer transition
(a) A and B
(b) A and C
(c) B and C
(c) C and D
Hide Answer
Ans (a)
Soln:
[Mn(H2O)6]2+= Mn2+ = 4s03d5
Total spin Value = 5/2 hence spin multiplicity (2S+1) = 6 hence 1st option is correct
Spin selection rule states that S = 0 i.e change in spin during transition is dis allowed as all electrons
are spin up hence spin selection rule is violated. Hence option 2 is also correct.
Rest all options are incorrect. (ground state is 6A1gand charge transfer is impossible)
25.A borane (X) is reacted with ammonia to give a salt of borohydride (Y). The 11B NMR
spectrum of Y consistsof a triplet and a quintet. The borane X is
(a) B2H6
(b) B3H9
(c) B4H8
(d) B5H9
247
Hide Answer
Ans (a)
Soln:
The free electron pair of the donor like NH3is added to the electron sextet of borane to complete its
octet. The compound amino borane (BH3:NH3) is thus formed by the symmetric cleavage of
dibborane on passing NH3.
This product is formed in 23%. The other major product formed is Borohydride salt.
[BH2(NH3)2][BH4]
11
B NMR gives triplet and quintet due to 2 and 4 H respectively.
26.[CoL6]2+is red in colour whereas [CoL6]2+is green. L and L respectively corresponds to,
(a) NH3and H2O
(b) NH3and 1, 10-phenanthroline
(c) NH3and 1, 10-phenanthroline
(d) H2O and NH3
Hide Answer
Ans (a)
Soln:
[CoL6]3+red colour absorbs green radiations.
[CoL6]2+ green colour absorbs red radiations.
Energy of green radiations > enegy of red radiations.
Therefore, L will be stronger ligand and than L. Thus, L and L are NH3 and H2O respectively.
248
27.The 19F NMR spectrum of ClF3 shows
(a) doublet and triplet for a T-shaped structure
(b) singlet for a trigonal planar structure
(c) singlet for a trigonal pyramidal structure
(d) doublet and singlet for a T-shaped structure.
Hide Answer
Ans (a)
Soln:
19
F 2F doublet
19
F 1F triplet
T shaped structure
28.The low temperature (98C) 19F NMR spectrum of SF4 shows doublet of triplets. It is
consistent with thepoint group symmetry.
(a) C3V
(b) C4V
249
(c) Td
(d) C2V
Hide Answer
Ans (a)
Soln:
29.In its electronic spectrum, [V(H2O)6]3+ exihibits two absorption bands, one at 17, 800 (v1) and
the secondat 25, 700 (v2) cm1. The correct assignment of these bands, respectively, is
(a) V1= 3T1g(F) 3T2g(F), V2 = 3T1g (F) 3T1g (F)
(b) V1 = 3T1g (F) 3T1g (P), V2 = 3A2g (F) 3T2g (P)
(c)V1 = 3A1g (F) 3T1g(F), V2 = 3A2g (F) 3T2g (F)
(d)V1 = 3A2g (F) 3T2g(F), V2 = 3A2g (F) 3T1g (F)
Hide Answer
Ans (a)
Soln:
250
251
H NMR spectrum of [(5 C5H5 Rh)(C2H4)2] at 20C shows a typical AA XXpattern in the
30.1
olefinicregion. On increasing the temperature to ~70C, the separate lines collapse into a single
line which is due to
(a) free rotation of the ethylene ligand about the metal-olefin bond
(b) interamolecular exchange between the ethylene ligands
(c) intermolecular exchange between the ethylene ligands
(d) change in hapticity of the cyclopentadienyl ligand
Hide Answer
Ans (a)
Soln:
31.The electronic transition responsible for the color of the transition metal ions is
(a) dp ds
(b) dp ds
(c)dp dp
(d) ds d p
Hide Answer
Ans (a)
Soln:
The electronic transition responsible for the colour of the transition metal ions is dp dswhich is in
according to LFT.
252
32.The Mulliken symbols for the spectroscopic states arising from the free-ion term F are
(a) T2g +Eg
(b) T1g+T2g+T1u
(c) T1g+T2g+ A2g
(d) A1g+T2g +T1g
Hide Answer
Ans (c)
Soln:
The mulliken symbols for the spectroscopic states arising from free ion term F are
T1g+T2g+A2g
33.The number of EPR signals observed for octahedral Ni(II) complexes is
253
(a) One
(b) Two
(c) Three
(d) Zero
Hide Answer
Ans (a)
Soln:
If the system has an even number of unpaired electrons then zero field splitting within the ground
state may result in the EPR transitions being undetectable and only one EPR signal is observed. Since
Ni(II) octahedral complex has two unpaired electrons, therefore, number EPR signals is one
34.Among the following, those can act as Mossbauer nuclei are
(A) 129I, (B)57CO (C) 57Fe (D) 121Sb
(a) A, B, C and D
(b) B, C and D only
(c) A, B, and D only
(d) A, C and D only.
Hide Answer
Ans (d)
Soln:
129
I, 57Fe and 121Sb
Mossbauer nuclei and they fulfuil all the properties for that 57CO is unstable nuclei which is used
as source in the Mossbauer spectro photometer for 57Fe study.
35.Silica gel contains [CoCl4]2as an indicator. When activated, silica gel becomes dark blue
while upon absorption of moisture, its colour changes to pale pink. This is because,
(a) Co(II) changes its coordination from tetrahedral to octahedral.
(b) Co(II) changes its oxidation state to Co(III)
(c) Tetrahedral crystal field splitting is NOT equal to octahedral crystal field splitting.
254
(d) Co(II) forms kinetically labile while Co(III) forms kinetically inert complexes
Hide Answer
Ans (a)
Soln:
36.For a tetragonally distorted Cr(III) complex, zero-field splitting results in the following
number of Kramers doublets:
(a) 1
(b) 2
(c) 3
(d) 4
Hide Answer
Ans (b)
Soln:
For systems with more than one unpaired electrons the ground state can be split in the
absence ofexternal magnetic field due to local site symmetry-the zero field splitting. For odd electrons
systems, this results in pairs of energy levels known as Kramers doublets. Since Cr(III) has three
unpaired electrons, therefore number of Kramers doublets in tetragonally disterted Cr(III) complex in
zero field splitting is 2.
37.Three bands in the electronic spectrum of [Cr(NH3)6]3+are due to the following transitions
(A) 4A2g 4T1g (B) 4A2g 4T2g (C) 4A2g 2Eg
Identify the correct statement about them
(a) Intensity of (A) is lowest
(b) Intensity of (C) is lowest
255
(c) Intensitites of (A), (B) and (C) are similar
(d) Intensities of (B) and (C) are similar
Hide Answer
Ans (b)
Soln:
Intensity of C (4A2g2Eg )is lowest, since it is spin forbidden.
38.Patients suffering from Wilsons disease have
(a) Low level of Cu-Zn superoxide dismutase
(b) High level of Cu-Zn superoxide dismutase
(c) Low level of copper-storage protein, ceruloplasmin
(d) High level of copper-storage protein, ceruloplasmin
Hide Answer
Ans (c)
Soln
Wilsons disease is caused by excess accomulation of Cu in the body.
39.High dose of dietary supplement ZnSO4 for the cure of Zn deficiency
(a) reduces myoglobin
(b) increases iron level in blood
(c) increases copper level in brain
(d) reduces copper, iron and calcium levels in body
Hide Answer
Ans (d)
256
40.Oxidised form of enzyme catalase (structure A); prepared by the reaction of [Fe(P)]+(P =
porphyrin) withH2O2, has green colorbecauase
A(substitutents on ring are removed for clarity)
(a) Oxidation state of iron changed from FeIII to FeIV.
(b) Porphyrin ring is oxidized by one electron
(c) p-p* transition appears in the visible region
(d) FeIV is coordinated with anionic tyrosinate ligand in axial position
Hide Answer
Ans (a)
Soln
Catalase is a tetrames of four polypeptide chains covering 500 amino acids.
It works as
H2O2+Fe (III) -E -> H2O + O= Fe (IV) -E+0
H2O2+O =Fe(IV)-E+ -> H2O+Fe(III)-E +O2
The colour arises as Fe(III) changes into Fe(IV).
41.The reactive position of nicotinamide adenine dinucleotide (NAD) in biological redox

reactions is
(a) 2-position of the pyridine ring
(b) 6-position of the pyridine ring
257
(c) 4-position of the pyridine ring
(d) 5-position of the pyridine ring
Hide Answer
Ans (c)
Soln:
Therefore, the 4-position of the pyridine ring is reactive position in the biological reaction.
42.[NiIIL6]n+orn-shows absorption bands at 8500, 15400 and 26000 cm-1whereas[NiIIL6]n+orn- ,

10750, 17500, 28200 cm-1. L and L are respectively
(a) OH and N3
(b) Cl and I
(c) NCS and RCO2
(d) H2O and NH3
Hide Answer
Ans (4)
Soln:
[NiIIL6]n+shows three absorption bond at 8500, 15400 and 26000 cm-1, corresponds to L = H2O
and [NiIIL6]n+shows three absorption bonds at 10750, 17500 and 28200. Which corresponds toL=
NH3, absorption bond is shown in the following plats
258
43.The number of microstates present in 3F term is
(1) 3
(2) 21
(3) 9
(4) 28
Hide Answer
Ans (2)
Soln:
Number of microstates in
3
F = (2S+1) (2L+1),here S = 1 and L = 3
= (2 X 1+1)(2 X 3+1)
= (3)(7)
= 21
259
44.Complex [Cr(bipyridyl)3]3+, shows red phosphorescence due to transition
(1) 4T2g 4
A2g
(2) 4T1g 4
A2g
(3) 4A2g 2
Eg
(4) 2Eg 2
A2g
Hide Answer
Ans (3)
Soln:
The mechanism of phosphorescence involves intersystem crossing (the non radiative conversion of
the initial excited state into another excited state of different multiplicity). This second excited state
act as an energy reservoir because radiative decay to the ground state is spin forbidden.
45.The1H NMR spectrum of [Ru(4-C8H8)(CO)3] at 23C consists of a sharp single line. The
number of signals observed at low temperature (140 C) in its spectrum is
(1) 8
(2) 6
(3) 4
(4) 2
Hide Answer
Ans (3)
260
Soln:
The 1H-NMR spectrum of [Ru( 4-C8H8)(CO)3] at low temperature (-140C ) is 4 different 1HNMR
signals from C8H8 ring broadened approximately equally. We have same fluxional processes possible
including random shift.
46.Identify correct statements for the EPR spectrum of VO(acac)2 [with square pyramidal
geometry at vanadium] at 77 K [ I (51V) = 7/2].
1. It has two g values.

2. It has 8 lines only.
3. It has one g value.
4. It has two patterns of 8 lines each.
Correct statements are
(1) A and D
(2) A and C
261
(3) B and C
(4) B and D
Hide Answer
Ans (1)
Soln:
Structure of VO(acac)2
47.The numbers of lines shown by the BH3 part of the molecule Ph3P.11BH3 in the 1H and11B
NMR spectra are, respectively [I (11B) = 3/2; I (31P) = ]
(1) 8 and 8.
(2) 4 and 8.
(3) 3 and 6.
(4) 6 and 3.
Hide Answer
Ans (1)
Soln:
The numbers of lines shown by the BH3 part of the molecule Ph3P is 8.
11
BH3 in the 1H &11B-NMR spectra are.
262
48.To record Mssbauer spectrum of Fe containing samples, a source X is used. X after a
nuclear transformation (Y), gives - radiation used in Mssbauer spectroscopy. X and Y
respectively, are
(1) 57Fe, -emission
(2) 57Co, -emission
(3) 57Co, e capture
(4) 57Fe, e capture
Hide Answer
263
Ans (3)
Soln:
To record mossbauer spectrum of Fe containing sample, a source 57Co is used. 57Co after a nuclear
transformation e -radiation used in mossbauer spectroscopy.capture give
49.Which of the following spectroscopic techniques will be useful to distinguish between M-SCN
and M-NCSbinding modes?
(a) NMR
(b) IR
(c) EPR
(d) Mass
Hide Answer
Ans (b)
50.Which of the following compounds show a charge-transfer band?
(a) Lanthanum nitrate
(b) Ceric ammonium nitrate
(c) Manganese (II) acetate
(d) Copper (II) sulphate pentahydrate
Hide Answer
Ans (b)
51.Which one of the following exhibits rotational spectra?
(a) H2
(b) N2
(c) CO
(d) CO2
Hide Answer
264
Ans (c)
Soln:
52.Which of the following spectroscopic techniques will be useful to distinguish between M-SCN
and M-NCSbinding modes?
(a) NMR
(b) IR
(c) EPR
(d) Mass
Hide Answer
Ans (b)
Soln:
53.Which of the following compounds show a charge-transfer band?
(a) Lanthanum nitrate
(b) Ceric ammonium nitrate
265
(c) Manganese (II) acetate
(d) Copper (II) sulphate pentahydrate
Hide Answer
Ans (b)
Soln:
54.In the EPR spectrum of tetragonal Cu(II) complex, when g || >g >ge the unpaired electron
resides in the orbital.
(a) dxy
(b) dx2-y2
(c)dz2
(d) dxz
Hide Answer
Ans (a)
Soln:

55.The correct value of isomer shift (in Mossbauer spectra) and its explanation for Fe(II)TPP
and Fe(III)TPPrespectively from the following are:
(TPP = tetraphenylporphyrinate)
(A) 0.52 mms1 (B) 0.45mms1
(C) Increase in s electron density (D) Decrease in s electron density.
266
(a) (A) and (D); (B) and (C)
(b) (A) and (C); (B) and (C)
(c) (B) and (D); (A) and (D)
(d) (B) and (D); (A) and (C)
Hide Answer
Ans (b)
56.In IR spectrum of [Co (CN)5 H]3- the CoH stretch is observed at 1840 cm1. The (CoI)
stretch in[Co (CN)5 H]3- will appear at nearly
(a) 1300 cm1
(b) 1400 cm1
(c) 1500 cm1
(d) 1600 cm1.
Hide Answer
Ans (a)
57.In the 19F NMR spectrum of PF5, the number of signals and multiplicity, at room
temperature are
(a) one, singlet
(b) one, doublet
(c) two, doublet
(d) two singlet
Hide Answer
Ans (b)
267
58.The electronic spectrum of [CrF6]3- shows three bands at 14, 900 cm1, 22400 cm1 and 34,
800 cm1. The value of 0 in this case is:
(a) 5,500 cm-1
(b) 14,900 cm-1
(c) 22,400 cm-1
(d) 34,800 cm-1
Hide Answer
Ans (b)
59.In the trans-PtCl2L(CO) complex, the CO stretching frequency for L = NH3, pyridine,
NMe3 decreases in theorder.
(a) pyridine>NH3> NMe3
(b) NH3> pyridine> NMe3
(c) NMe3>NH3> pyridine
(d) pyridine>NMe3> NH3
Hide Answer
Ans (a)
60.In 57Fe* Mossbauer experiment, source of 14.4 keV (equivalent to 3.481012 MHz) is moved
towards absorber at a velocity of 2.2 mm s1. The shift in frequency of the source for this sample
is:
(a) 35.5 MHz
(b) 25.5 MHz
(c) 20.2 MHz
(d) 15.5 MHz
Hide Answer
Ans (b)
268
61.A compound A having the composition 9 8 3 FeC H O shows one signal at 2.5 ppm and
another one around 5.0ppm in its 1H NMR spectrum. The IR spectrum of this compound shows
two bands around and 1680 cm1.The compound follows the 18 electron rule of the following
statements for A, the correct one is/are
(A) It has 5 Cp group. (B) It has a terminal CO ligand.
(C) It has a CH3ligand (D) It has FeH bond.
(b) (C) only
(c) (A) and (C) only
(d) (B) and (D) only.
Hide Answer
Ans (a)
62.Three electronic transitions at 14900, 22700 and 34400 cm-1 are observed in the absorption
spectrum of [CrF6]3- and the corresponding transition are
(1.) 7800 and 4A2g 4T2g
(2.) 14900 and 4A2g 4T2g
(3.) 14900 and 4T2g 4T1g (F)
(4.) 7800 and 4T2g 4T1g (F)
Hide Answer
Ans (2)
Soln:
C6H63-: d3electronic configuration orgel diagram for d3 electronic transition are-
269
4A2g 4A2g corresponds to the transition of lowest energy.
63.The approximate positions of vcoband (cm-1) in the solid-state infrared spectrum and the Fe-
Fe bond order in [Fe(5 C5H5)( CO)(CO)]2(non-centro-symmetric) respectively, are
(1.) (2020, 1980, 1800) and one
(2.) (2020, 1980, 1800) and two
(3.) (2020, 1980) and one
(4.) (2143) and one
Hide Answer
Ans (1)
Soln:
Three bands are expected in CO in the complex [Fe(5-C5H5)(-Co)(CO)]2 since it is non Centro-
symmetric.
One band for bridging CO around 1800
Two bands (one symm, one asymm) around 2020 (asymm) and 1980 (symm)
Total valence electrons = 34
nx18 36 (there are 2 Fe atoms)
M.M bond = 36 34 /2 = 1
270
64.[MnO4]is deep purple in color whereas [ReO4] is colorless. This is due to greater energy
require for
(1.) d-d transition in the Re compound compared to the Mn compound
(2.) d-d transition in the Mn compound compared to the Re compound
(3.) charge transfer from O to Re compared to O to Mn
(4.) charge transfer from O to Mn compared to O to Re
Hide Answer
Ans (3)
Soln:
The 5d orbitals of Re are higher in energy than the 3d orbitals of Mn, so an LMCT excitation requires
more energy for ReO-. In addition, since the molecular orbitals derived primarily from the 3d orbitals
of MnO4 are lower in energy than the corresponding MOs of [ReO4], [MnO4]is better able to
accept electrons; it is a better oxidizing agent.

65.The resonance Raman stretching frequency (vo-o, in cm-1) of O2 is 1580. The vo-o for O2in
bound oxy-hemoglobin is close to
(1.) 1600
(2.) 1900
(3.) 800
(4.) 1100
Hide Answer
Ans (4)
Soln:
It is known fact that stretching frequency of any molecule in the Free State is always higher that the
same in bound stateHere it is given that o-o is 1580 of free O2. Hence in bound Hb it must be less
than that, so correct answer is 1100 (more precisely 1180 cm-1)
66.Choose the correct statements about Tanabe- Sugano diagrams:
271
(1.) E/B is plotted against 0/B.
(2.) The zero energy is taken as that of the lowest term.
(3.) Terms of the same symmetry cross each other.
(4.) Two terms of the same symmetry upon increase of ligand field strength bend apart from each
other.
Correct answer is
(1.) A and B
(2.) A and C
(3.) A, B and D
(4.) A, B, C and D
Hide Answer
Ans (3)
Soln:
Self-explanatory.
Reference: Inorganic Chemistry, James Huheey
67.Mossbauer spectrum of a metal complex gives information about
(A) oxidation state and spin state of metal
(B) types of ligands coordinated of metal
(C) nuclear spin state of metal
(D) geometry of metal
Correct answer is
(1.) A and C
(2.) B and C
(3.) A, B and D
(4.) B and D
272
Hide Answer
Ans (3)
Soln:
Mssbauer spectroscopy is unique in its sensitivity to subtle changes in the chemical environment of
the nucleus including oxidation state changes, the effect of different ligands on a particular atom, and
the magnetic environment of the sample.
273

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How many milligrams are in 0.2 decigrams?

(a) 20 milligrams 0.2dg x g/10dg x 1000mg/g = 20 mg

(b) 2000 milligrams

(c) 0.002 milligram

(d) 0.00002 milligram

(a) 800 liters

(b) 0.8 liter b

(c) 512 liters

(d) 0.5 liters

density of aluminum = 2.7 g/mL

density of zinc = 7.1 g/mL

density of copper = 9.0 g/mL

density of silver = 10.0 g/mL

(a) 8.9657 g/mL

(c) 0.11153 g/mL

(d) 0.11 g/mL

(a) Garrison obtained the better accuracy.

(b b) Isabella obtained the better accuracy.

(c) Garrison obtained the better precision.

(d) Isabella obtained the better precision.

(a) 6.0750 amu

(b) 6.0902 amu

(c) 6.9250 amu

4. What do the following have in common?

(a) They are isotopes of each other.

(b) They are isomers of each other.

(c c) They are isoelectronic with each other.

(d) They are different elements so they have nothing in common.

5. How many valence electrons does an oxygen atom have?

(a) lose electrons

7. The identity of an element is determined by...

(a a) the number of its protons.

(b) the number of its neutrons.

(c) the number of its electrons.

(d) its atomic mass.

(a) 4.75 minutes

(b) 9.5 minutes

12. The atom formed by the beta decay of carbon-14 is...

1.The size of the d orbitals in Si, P, S and Cl follows the order.

(a) Cl> S > P > Si

(b) Cl> P > S > Si

(c) P > S > Si >Cl

(d) Si > P > S >Cl

Therefore decreasing order of size of d-orbitals is Si > P > S >Cl

2.The least basic among the following is:

Al (OH)3Amphoteric whereas hydroxides of lanthanoids are all base.

(a) 9/2 and (+)

(b) 7/2 and (+)

(c) 9/2 and ()

(d) 7/2 and ()

In g nuclear orbital total subshell is nine.

One odd nucleon finding in g-subshell

Total spin = 9/2

Parity=(-1)l= (-1)4 = (+)

4.The electronegativity differences is the highest for the pair

Among these elements K is least electronegative and F is most electronegative. Therefore

(b) F and Mg2+

(a) Right size of cation

(b) Change in entropy being positive

(c) Conformational flexibility of crown ether

(d) Hydrophobicity of crown ether

(Reference: Advance Organic Cheimistry, Jerry March, M. Smith)

7. The correct order of decreasing electronegativity of the following atoms is,