Вы находитесь на странице: 1из 26

PART B

(21) 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
Soln (3)
All the complex are d6 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)
(22) 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
Soln (1)
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.
(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
(4.) 3 and 4
bonds
Soln (1)
Structure of carbon sub oxide C3O2

(24) 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, 10phenathroline)
(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]4Soln (1)
The color changes observed with redox indicators at
the equivalence point is due to structural changes in
the indicator molecules. The redox indicators used
are organic molecules; they undergo structural

changes upon being oxidized or reduced. This can he


illustrated with ferroin indicator which is the iron(II)
complex of the organic compound 1,10phananthroline (Fig. 4.8}.

Each of the two nitrogen atoms in 1, 10phenanthroline 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 he
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, 10phananthroline. 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.
(25) 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
Soln (1)
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 exemplied by the
mineral 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.

(26) The W-W bond order in [W(5-C5H5)(Cl)(CO)2]2 is


(1.) three
(2.) two
(3.) one
(4.) zero
Soln (4)
To calculate bond order
(a) Calculate TVE
:a
(b) Calculate n x 18
: b [n = number of metal]
(c) Calculate

= [number of M-M bond]

[W( C5H5)(y Cl)(CO)2]2


(a) TVE = 36 [12 + 10 + 6 + 8] = a
(b) n x 18 = 2 x 8 = 36
=b

Fig : Mechanism of Berry Pseudorotation

(c)

3636
2

= 0 [Ans]

(27) 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]Soln (1)
Mn aqua complex do not allow any distortion
because of symmetrical d5 distribution.

(29) The oxidizing power of [CrO4]2-, [MnO4]2-, and


[FeO4]2- follows the order
(1.) [CrO4]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]2Soln (1)
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.
(31) The structures of XeF2 and XeO2F2 respectively
are
(1.) bent, tetrahedral
(2.) linear, square planar
(3.) linear, see-saw
(4.) bent, see-saw
Soln (3)
XeF2 : linear molecule in vapor state

All Mn-O bond are equal.


(28) 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
Soln (2)
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

Structure of XeF2

The three 5p electrons are promoted to higher energy


5d sub-level.
The 5s three 5p and one 5d orbitals hybridize to give
ve sp3d hybrid orbitals. The four singly occupied
orbitals are used for bond formation to two uorine
and two oxygen atoms. The fth 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 XeO2F2 is
represented in Fig.

(32)The biological functions of the cytochrome P450


and myoglobin are, respectively
(1.) Oxidation of alkene and O2 storage
(2.) O2 transport and O2 storage
(3.) O2 storage and electron carrier
(4.) Electron carrier and O2 transport
Soln (1)
The biological function of cytochrome P450 is to act
in a mono oxygenase reaction.e.g insertion of one
atom of oxygen into aliphatic position of organic
substrates.
RH +O2
R-O-H
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)
(33) 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
Soln (4)
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.
(Reference : P.W. Atkins, Quanta: A handbook of
concepts. Oxford University)
(34) The metallic radii are abnormally high for which
of the following pairs?
(1.) Eu, Yb
(2.) Sm, Tm
(3.) Gd, Lu
(4.) Nd, Ho
Soln (1)
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 oxidation

states 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 congurations 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
congurations 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 llings, 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
(35) 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
Soln (1)
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.
(36) Deoxy Hemocyanin is
(1.) heme protein and paramagnetic
(2.) Colorless and diamagnetic
(3.) O2 transport and paramagnetic
(4.) Blue colored and diamagnetic
Soln (2)

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.
(37) The major product formed in the following
reaction is

(1.) A =
and the reaction proceeds
through carbine intermediate

(2.) A =
and the reaction proceeds
through nitrene intermediate

Soln (2)

(3.) A =
and the reaction proceeds
through Norrish type II path

(4.) A =
and the reaction proceeds through
Norrish type I path
Soln (1)

Step 1 : Removal of nitrogen to form carbene


Step 2 : attack of Oxygen lone pair to form 5
membered cyclic adduct
Step 3 : 1,2 alkyl shift to form rearranged product
(38) In the mass spectrum of 1, 2-dichloroeth-ane,
approximate ratio of peaks at m/z values 98, 100, 102
will be
(1.) 3 : 1 : 1
(2.) 9 : 6 : 1
(3.) 1 : 1 :2
(4.) 1 : 2 : 1
Soln (2)
When chlorine is present, the M + 2 peak becomes
very significant. The heavy isotope these elements is
two mass units heavier than the lighter isotope. The
natural abundance of 37Cl is 32.5% that of 35Cl.
When Chlorine is present, the M + 2 peak becomes
quite intense. If a compound contains two chlorine
atoms, a distinct M + 4 peak, as well as an intense M
+ 2 peak, should be observed.

This reaction is an example of wolff rearrangement


in which cyclic diazoketone , on rearrangement leads
to ring contraction.
The R group migrates with retention of configuration
and the resulting ketene can be trapped by methanol
to give the corresponding ester.
(40) The major product formed in the following
reaction is

The M : M+2 : M+4 peaks for two chlorine atom is


in the ratio of 100 : 65.3 : 10.6 which on
simplification gives 9 : 6 : 1
(39) The correct statement about the following
reaction is that

Soln (3)

(42) The number of Chemical shift non equivalent


protons expected 1H NMR spectrum of -pinene is

-pinene
1. 7
Soln (4)

2. 8

3. 9

4. 10

All the protons are different and hence give 10


distinct signals in 1H NMR.

Step 1 : The rst step is an acetal exchange in which


the allylic alcohol displaces methanol.
Step 2 : . A second molecule of methanol is now lost
in an acid-catalysed elimination reaction to give the
vinyl group.
Step 3 : It is simple example of [3,3] sigmatropic
known as Claisen rearrangement
(41) The major products A and B in the following
reactions are

(43) Correctly matched structure and carbonyl


stretching frequency set is
Column A
Column B
P.
X.
1750 cm-1

Q.

Y.

1770 cm-1

R.

Z.

1800 cm-1

(1.) P-Y, Q-Z, R-X


(3.) P-Z, Q-Y, R-X
Soln (1)

(2.) P-Y, Q-X, R-Z


(4.) P-X, Q-Z, R-Y

-lactone has very peculiar IR stretching frequency at


around ~ 1770 cm-1.
Soln (3)

Next, Conjugation lowers IR stretching frequency.


Therefore structure R must correspond to ~ 1750 cm1
.
Hence , the correct option is (1)
(44) the major product formed by photochemical
reaction of (2E, 4Z, 6E)-decatriene is

Heating dimethylmenthyl amine oxide gave a


mixture of 2- and 3menthene, whereas isomeric neo
menthylamine oxide gave only 2menthene. This is
an example of pyrolytic syn elimination

Soln (1)

radical species. The reaction occurs at a rate that is


faster remarkably even than 5-exo-trig cyclization.
Hence, the eight-membered lactone 92 was formed,
rather than a ve-, six- or seven-membered lactone,
on treatment
Of the bromide with tributyltin hydride

This is an example of electrocyclic ring closing


reaction of 4n + 2 electron system by Conrotatory
photochemical mode.
(45) The major product formed in the following
reaction is

(47) D-Mannose upon fluxing in acetone with CuSO4


and H2SO4 gives

D-mannose

Soln (3)
This is an example of favorskii rearrangement of
-dibromoketone

(46) The major product formed in the following


reaction is

Soln (2)
The formation of eight-membered rings by radical
cyclization has been found to occur using -acyl

Soln (3)
This is an example of protection of 1,2 diol by
acetone in the presence of acid. For the protection of
1,2 diol the two hydroxyl group must be in cisorientation. Hence only anomeric OH group remain
unaffected rest all OH will form 5-membered cyclic
acetal as thermodynamic product.
(48) The structure of the compound that matches the
1
H NMR data given below is
1
H NMR (DMSO-D6): 7.75 (dd, J = 8.8, 2.4 Hz,
1H), 7.58 (d J = 2.4 Hz, 1H), 6.70 (d J = 8.8 Hz, 1H),
6.50 (broad s, 2H), 3.80 (s, 3H).

Soln (2)

Steps to Analyze NMR Spectra


a. First we know that delta value of aromatic protons
comes at 7.2 . So the first delta value 7.75 indicates
the proton is deshielded . so it must be adjacent to
EWG. Further since it is doublet of doublet hence
there must be meta and ortho coupling based on their
J values.
So 1 and 4th option are straight away ruled out since
the above condition is not followed.
Further in 3rd , all the three aromatic protons will give
doublet of doublet which is clearly not the case.
(49) The major product formed in the following
reaction is
(51) The major product formed in the following
reaction is

Soln (1)
This is an example of intramolecular Diels alder
reaction.

Soln (4)
This is an example of Swern Oxidation in which last
step is the intermolecular SN2 displacement by
chloride ion in the absence of base

(50) The major product formed in the following


reaction is

Soln (4)

(52) Identify two enantiomers among the following


compounds.

(1.) A and B

(2.) A and C

(3.) B and D
Soln (4)

(4.) C and D

(55) .) sp hybrid orbitals are of the form C12s + C22pz


(2s and 2pz are normalized individually). The
coefficients of the normalized form of the above sp
hybrid orbitals are
(1.) C1 =
(3.) C1 =
1
2

1
,
2
1
,
2

1
2
1
2

C2 =

(2.) C1 = 2,

C2 = 2

C2 =

(4.) C1 = 2,

C2 =

Soln (1)

Condition for normalization = 1


= C12s + C22pz
12 (2)2 + 22 (2)2 + 21 2 2 2 = 1
The last two terms cancel out each other because
they are orthogonal
A and B are homomers ; A and C are diastereomers
B and D are diastereomers ; C and D are enantiomer

(53) The correct expression for the product


). (
)) [Mn and Mw are the number-average
((
and weight average molar masses, respectively, of a
polymer] is
(1.) N-1 i Ni Mi
(2.) N-1 i Ni Mi2
(3.) N / N M
(4.) N / N M2
Soln (2)
Number average and weight average molar mass is
given by the expression
=

x
=

= 1 2

(54) The concentration of a reactant K varies with


time for two different reactions as shown in the
following plots:

The order of these two reactions I and II,


respectively, are
(1.) zero and one
(2.) one and zero
(3.) zero and two
(4.) two and zero
Soln (3)
For the zero order reaction
x = kT
(a x) = -RT (linear with negative slope)
For 2nd order reaction
1
[]

= [ ] + (linear with intercept [


0

0]

Also |2 |2 = 1
|2 | = 1 [condition of
normalization]
C12 + C22 = 1
Since Sp orbital have equal contribution toward
atomic orbital C1 = C2
2C12 = 1
C2 =

1
2

C1 =

1
2

(56) For a single cubic crystal lattice, the angle


between the [2 0 1] plane and the xy plane is
(1.) less than 300
(2.) between 300 and
0
45
(3.) between 450 and 600
(4.) greater than 600
Soln (4)
The expression for finding the angle between the two
plane is given by
1 2 + 1 2 + 1 2
=
12 + 12 + 12 . 22 + 22 + 22
For the XY Plane , miller indices are [001]
1 = 2 1 = 0 1 = 1 ; 2 = 0 , 2 = 0 , 2 = 1
On solving
2.0 + 0.0 + 1.1
=
22 + 02 + 12 . 02 + 02 + 12
1
1
=
=
= 0.44
5 2.23
Therefore = cos-1 (0.44) = 63.89
(57) The concentration of a MgSO4 solution having
the same ionic strength as that of a 0.1 M Na2SO4
solution is
(1.) 0.05 M
(2.) 0.067 M
(3.) 0.075 M
(4.) 0.133 M
Soln (3)
Ionic strength of 0.1M Na2SO4
1

= 2 2

= 2 [0.2 x 12 + 0.1 x 22 ]
= 0.3
MgSO4 will have ionic strength equal to 0.3
1
2

0.3 = [m x 22 + m x 22]
0.3 = 4m
m = 0.3/4 = 0.075
(58) H of a reaction is equal to slope of the plot of
(1.) G versus (1/T)
(2.) G versus T
(3.) (G/T) versus T
(4.) (G/T) versus (1/T)
Soln (1)
H = U + PV .. (1st Law of thermodynamics)
H = U + ngRT
U - H = -ngRT
Fe2O3(s) + 3C(s) 2Fe(s) + 3(CO)
Ans = -(3-0)= -3RT
(59) Two different non-zero operators and (A
B) satisfy the relation
(A + B) (A - B) = A2 - B2, when
(1.) AB = A2 and BA = B2
(2.) AB + BA = 0
(3.) A and B are arbitrary
(4.) AB - BA = 0
Soln (4)
Expanding and simplifying the expression gives the
option (4) as answer
(A + B) (A B) = A2 AB + BA B2
= A2 B2 (only when AB BA = 0)

(61) The standard deviation of speed (c) for


Maxwells distribution satisfies the relation
(1.) c T
(2.) c
(3.) c 1/T
(4.) c 1/
Soln (2)
Standard deviation for the velocity of Maxwell
distribution is given by
=

(62) In Kohlrausch law m = 0m - , 0m and


(1.) depends only on stoichiometry
(2.) depends only on specific identity of the
electrolyte
(3.) are independent on specific identity of the
electrolyte
(4.) are mainly dependent on specific identity of the
electrolyte and stoichiometry, respectively
Soln (1)
The justification of Kohlrauschs law on theoretical
grounds cannot be obtained within the framework of
a macroscopic description of conduction. It requires
an intimate view of ions in motion. A clue to the type
of theory required emerges from the empirical
findings by Kohlrausch: (l) the c1/2 dependence and
(2) the intercepts 0 and slopes A of the versus c1/2
curves depend not so much on the particular
electrolyte (whether it is KCI or NaCl) as on the type
of electrolyte (whether it is a l:l or 2:2 electrolyte)

(60) For the following reaction,

[]

is given by

(1.)1 [] 1 []2 22 []
(2.) 21 [] 21 []2 2 []
1

(3.) 2 1 [] 2 1 []2 2 []

(4.) 21 [] 21 []12 2 []
Soln (2)

Rate of formation of B is given by

1
= 1 [] 1 []2 (1)
2
[]
= 21 [] 21 []2 (2)

Also = 2 []

overall rate is given by

= 22 [] 21 []2 1 []

(63) If the reduced mass of the diatomic molecule is


doubled without changing its force constant, the
vibrational frequency of the molecule will be
(1.) 2 times the original frequency
(2.)
2 times the original frequency
(3.) twice the original frequency
(4.) unchanged
Soln (2)

Vibrational frequency of molecule is given by


1

Intercept = -S

= 2

if reduced mass is doubled, then will become

1
2

times the original frequency.


(64) The degeneracy of an excited state of a particle
in 3-dimensional cubic box with energy three times
its ground state energy is
(1.) 3
(2.) 2
(3.) 1
(4.)
4
Soln (1)
For particle in 3D box
2

= 22 [12 + 22 + 32 ]
In the ground state n1 = n2 = n3 = 1
2
3

= 22
Energy when it wil be 3 times to its ground state will
2
3

2
9

be 3 x 22 = 22
It is possible when m1 = n2 = 2, n3 = 1
Total degeneracy is 3 (221), (122) and (212)
(65) If the pressure p system is greater than the p
(surroundings), then
(1.) work is done on the system by the surroundings.
(2.) work is done on the surroundings by the system.
(3.) work done on the system by the surroundings is
equal to the work done on the surroundings by the
system.
(4.) internal energy of the system increases
Soln (2)
When the pressure of the system is greater than
pressure of surrounding, expansion will take place.
Hence, during expansion work is done by the system
on the surrounding
(66) H of a reaction is equal to slope of the plot of
(1.) G versus (1/T)
(2.) G versus T
(3.) (G/T) versus T
(4.) (G/T) versus (1/T)
Soln (4)
G = H TS
Dividing the whole equation be T brought out

Equation of straight line


y = mx + c
y=

x=

Slope = H

(67) The correct statement among the following is


(1.) N2 has higher bond other than N2+ and hence has
larger bond length compared to N2+
(2.) N2+ has higher bond other than N2 and hence has
larger bond length compared to N2
(3.) N2 has higher bond other than N2+ and hence has
higher dissociation energy compared to N2+
(4.) N2 has lower bond other than N2+ and hence has
lower dissociation energy compared to N2+ energy
Soln (3)
N2 = KK (2S)2 *(2S)2 (2px)2 (2py)2 6(2pz)2
B.O =

82
2

= 3 (most stable, diamagnetic)

72
2

= 2.5 (less stable, paramagnetic)

2
2 2
2
N2+ = KK 2
2
2 2
612

B.O =

(68) The correct form for the simple Langmuir


isotherm is
(1.) = Kp
(2.) = (Kp)1/2
(3.) = Kp / (1 + Kp) (4.) = (1 + Kp) / Kp
Soln (3)
The concentration of vacant sites on the surface of an
adsorbent will be directly proportional to the fraction
of the surface that remains uncovered and hence will
be directly proportional to the factor (1 - ). Thus we
can write,
Rate of absorption p(l )
i.e. Rate of adsorption = ka p(l - )
Now since at equilibrium
Rate of absorption = rate of desorption,
it follows that
ka (1 - )p = kd
i.e. =

( )

= 1+( ) = 1+1

(69) The correct match of the compound in column A


with the description in column B is
Column A
Column B
P.

X.

Oil
Wintergreen

Q.

Y.

Aspirin

R.

Z.

Ibuprofen

(1.) P-Y, Q-Z, R-X


(3.) P-Z, Q-Y, R-X
Soln (2)
Aspirin : acetyl salicylic acid

of

(2.) P-Z, Q-X, R-Y


(4.) P-X, Q-Z, R-Y

Ibuprofen :
ISO butyl phenyl propanoic acid
Oil of winter green : methyl salicylate

(c.)

Vitamin B12

(d.) Hemocyanin
(70) 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+
Soln (2)
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.

(iii.) O2 transport and


copper
(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
Soln (1) Self explanatory
(73) [(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
(3.) three signals in the intensity ratio of 2 : 2 : 1
(4.) five signals of equal intensity
Soln (3)

PART C
(71) Identify radioactive capture from the following
nuclear reactions
(1.) 9Be(, n) 8Be
(2.) 23Na(n, ) 24Na
(3.) 63Cu (p, p 3n 9) 24Na
(4.) 107Ag (n, n)
107
Ag
Soln (2)
Radioactive capture reactions are described as
follows Parent Nucleus, Projectile Daughter
nucleus, ejectile
23
Na11 + 0n6 11Na24 + 0n6 (y rays)
Rest all examples do not follow this trend.
(72) Match the metalloproteins in column A with its
biological function and metal center in column B
Column A
Column B
(a.) Hemoglobin
(i.)
Electron carrier
and iron
(b.) Cytochrome b
(ii.) Electron carrier
and copper

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 H1 and H4
third for H2 and H5
In the intensity ratio 2 : 2 : 1
(74) 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

(1.) II, V and IV


(2.) II, III and IV
(3.) V, III and IV
(4.) II, V and III
Soln (1)
(a) Dimanganese decacarbonyl reacts with halogens
to form carbonyl halides.
Mn2CO10 + l2 2Mn(Co)5 I

(75) The final product of the reaction of carbonyl


metalates [V(CO)6]- and [Co(CO)4]- with H3PO4,
respectively, are
(1.) V(CO)6 and HCo(CO)4
(2.) HV(CO)6 and Co2(CO)8
(3.) [H2V(CO)6]+ and HCo(CO)4
(4.) V(CO)6 and Co2(CO)8
Soln (4)
[V(CO)6]- + H3PO4 [H V(CO)6]
2[Co(CO)4]-

2+

2[HCo(CO)4]

V(CO)6
Co2(CO)8

(76) 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
Soln (1)
Uranium compound was the 1st metallocene of Cot2to be synthesized

BrF4XeF6SbCl63-

36
4
= 4 + 2 = 4 + 2 (lp)
8
50
2
: 4 + 42 = 8 = 6 + 2 = 6 + 1 (lp)
50
2
: 5 + 6 x 7 + 3 = 8 = 6 +2 = 6 + 1 (lp)

: TVE = 5 x 7 +1 =

(78) 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
Soln (2)
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.

UCl2- + 2Cot2- U(Cot)2


From the given reaction, it is concluded that among
the following option (A) and (B) are correct.
(77) The number of lone pair(s) of electrons on the
central atom in [BrF4]-, XeF6 and [SbCl6]3- are,
respectively,
(1.) 2, 0 and 1
(2.) 1, 0 and 0
(3.) 2, 1 and 1
(4.) 2, 1 and 0
Soln (3)
Formula to calculate Bond Pair and Lone Pair
A. calculate TVE (total valence electron)
B. Divide TVE by 8 if 8 < TVE < 56
C. The quotient will give number of bond pair
D. while dividing the remainder by 2 will give lone
pair on central atom

(79) 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)
Soln (2)
C6H63-: d3 electronic configuration orgel diagram for
d3 electronic transition are-

TV E = 34
nx18 36 (there are 2 Fe atoms)
M.M bond =

4A2g 4A2g corresponds to the transition of lowest


energy.
(80) 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
Soln (3)
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
(81) The reaction of BCl3 awith 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
Soln (1)
Ammonium chloride reacts with Boron chloride to
produce trichloridoborazine and hydrogen chloride.
This reaction takes place at temperature 140 150
0
C. catalyst C6H6, C6H5Cl.
(82) 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-centrosymmetric) respectively, are
(1.) (2020, 1980, 1800) and one
(2.) (2020, 1980, 1800) and two
(3.) (2020, 1980) and one
(4.) (2143) and one
Soln (1)
Three bands are expected in CO in the complex
[Fe(5-C5H5)(-Co)(CO)]2 since it is non Centrosymmetric.
One band for bridging CO around 1800
Two bands (one symm, one asymm) around 2020
(asymm) and 1980 (symm)
To calculate bond order

36 34
2

=1

(83) 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
Soln (1)
ZSM-5 is an acid catalyst and is typically used for
Alkylation of aromatic He

(84) [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
Soln (3)
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.
(85) The resonance Raman stretching frequency (vo-o,
in cm-1) of O2 is 1580. The vo-o for O2 in bound oxyhemoglobin is close to
(1.) 1600
(2.) 1900
(3.) 800
(4.) 1100
Soln (4)
It is known fact that stretching frequency of any
molecule in the Free State is always higher that the
same in bound state

Here 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)
(86) 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
Soln (1)
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.
(87) Aqueous Cr2+ effects one electron reduction of
[Co(NH3)5Cl]2+ giving compound Y. compound Y
undergoes rapid hydrolysis. Y is,
(1.) [Co(NH3)5]2+
(2.)
+
[Co(NH3)5(OH)]
(3.) [Co(NH3)4(OH)2]
(4.) [Cr(H2O)5Cl]2+
Soln (1)
The reduction of cobalt(III) (in [Co(NH3)5Cl]2+) by
chromium(II) (in [Cr(H2O)6]2+) and was specically
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 rmly 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+ [(H3N)5Co-ClCr(OH2)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:
[(H3N)5Co-Cl-Cr(OH2)5]4+ [(H3N)5Co]2+ +
[ClCr(OH2)5]2+
(88) 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 spinorbit 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
(2.) A and B
(3.) A and C
(4.) B and C
Soln (1)
Oxides of lanthanides are generally basic in nature.
Sm: [Xe]6s24f6
Sm: [Xe]6s24f6 Sm(II) is not stable because of halffilled subshell
Rest all statement are correct above Lanthanides (for
detailed description on above statement of
lanthanides, refer, inorganic chemistry, Shriver &
Atkins)
(89) 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 SN1CB mechanism
(4.) its rate is dependent only on the concentration of
[OH]Soln (1)
Complexes such as [Co(CN)5Cl]3- [Co(py)4Cl2]+
would not be expected typical base hydrolysis and
reaction proceeds slowly without dependence of OHion.
(Reference : Inorganic Chemistry , Huheey)
(90) 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
Soln (3)
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.
(91) Using wades rules predict the structure type of
[C2B5H7].
(1.) nido
(2.) closo
(3.) arachno
(4.) hypho
Soln (2)
Wades rule
1 carbon is equal to BH fragment as both are isolobal
C2B5H11 = B7H9 B7H72- (hence closo)
(92) Among the following complexes
A.
[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
(3.) C only
(4.) A and C
Soln (4)
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
(93) Choose the correct statements about TanabeSugano diagrams:
(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
Soln (3)
Self-explanatory.
Reference: Inorganic Chemistry, James Huheey

Are
(1.) A and D
(2.) B and D
(3.) B and C
(4.) A and C
Soln (2)
In the following photolysis reaction, first the removal
of CO takes place to form 16e- complex and then the
change in hapticity from 1 to 3. Hence correct
option is (2)
(95) The number of valence electrons provided by
[Ru(CO)3] fragment towards cluster bonding is
(1.) 1
(2.) 14
(3.) 6
(4.)
2
Soln (4)
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
(96) The major products A and B in the following
reaction sequence are

Soln (1)
(94) The intermediate and final major product of
photolysis of Z

From the following:

A. The first step is


Borabicyclo[3.3.1] nonane

the

synthesis

of

9-

B. Second is the Boronic Suzuki coupling which is


highly stereospecific in which geometry of the
reactant is faithfully reproduced in the product.
(97) The major product A and B in the following
reaction sequence are

(99) The major product formed in the following


reaction is

Soln (3)
Mechanism :

Soln (2)
It is an example of light induced photo-isomerization
of benzene via Dewar benzene intermediate

(98) The major product A and B in the following


reaction sequence are

(100) The correct reagent combination to effect the


following transformation is

Soln (3)
Mechanism:

(1.) A = NaBH4, BF3.OEt2; B = MeMgBr (2.5


equiv.), THF then H3O+
(2.) A = BH3.THF; B = MeLi (2.5 equiv.), THF then
H3O+
(3.) A = BH3.THF; B = (i) aq. NaOH then H3O+ ,
(ii) MeLi (2.5 equiv.), THF then H3O+
(4.) A = (i) Me3Al, MeNHOMe, (ii) MeMgBr, THF
then H3O+; B = LiAlH4, THF

Soln (3)
Method of Analysis :
A. NaBH4 cannot be the reagent of choice since it
generally do not reduces amides.
B. reagent 2 and 4 results in the formation of tertiary
alchohol as resulting ketone is more reactive than
ester itself.
C. So the proper strategy should be (i) first reduce
the amide with borane (ii) then , convert ester to acid
which is usually less reactive and then perform
alkylation which will stop at ketone oxidation state
only.

a. First step is the metathesis ring closing reaction by


grubbs catalyst.
b. Second is the reduction of amide be lithium
aluminium hydride.
(103) A concerted [1,3]-sigmatropic rearrangement
took place in the reaction shown below. The structure
of the resulting product is

(101) The major product A and B in the following


reaction sequence are

Soln (3)
This is an example of 1,3 carbon shift and according
to woodward Hoffman rule it should be inversion.
Soln (2)
This is an example of Mannich reaction which will
take place prefentially at 2 and 5 position.

(104) The major product formed in the following


reaction is

(102) The major product A and B in the following


reaction sequence are

Soln (3)

Soln (3)
The ease of the anionic oxy-Cope rearrangement and
its high level of stereo-control make this reaction a
popular and valuable synthetic method. For example,
stereo-controlled rearrangement of the potassium salt
of the 3-hydroxy-1, 5-diene to give the
cyclohexanone. The diastereoselectivity across the
new carbon-carbon single bond reects the
preference for a chair-shaped transition state with the
methoxy group in the pseudo equatorial position.

then H2O2, yield aldehydes. This synthesis has been


made enantioselective, with high ee values (> 99%),
by the use of an optically pure boronic ester.

(105) The major product A and B in the following


reaction sequence are

(107) The major product of the following reaction is

Soln (1)
The diol 1 must first be protected/activated and this
can be achieved by selective acylation (or
mesylation) of the less hindered primary alcohol
group. For example, treatment with a carboxylic acid,
dicyclohexylcarbodiimide
(DCC)
and
4dimethylaminopyridine gives the required ester.
Oxidation of the secondary alcohol can be achieved
by using one of a number of oxidizing agents such as
pyridinium dichromate (PDC). Formation of the
ketone was followed by _-elimination on alumina
to give the unsaturated ketone

Soln (1)
This is an example of acid-catalyzed diels Alder
reaction

(108) The major products A and B in the following


reaction sequence are

(106) The major product formed in the following


reaction sequence is
Soln (1)

Soln (4)
Boronic
esters
RB(OR')2
react
with
methoxy(phenylthio)methyllithium LiCH(OMe)SPh
to give salts, which, after treatment with HgCl2 and

(109) The major product A and B in the following


reaction sequences are

Reference : Organic Mechanisms Reactions,


Stereochemistry and Synthesis , Reinhard Bruckner
(111) The major product of the following reaction is
(1.) A = D-threose;
B = D-glucose
(2.) A = D erythrose; B = D-glucose + D-mannose
(3.) A = D-threose;
B = D-glucose + D-mannose
(4.) A = D-tartaric acid; B = D-glucose
Soln (2)
Soln (3)
This is an example of chelation control felkin-Ahn
model

(112) The
sequential

following

transformation

involves

(110) The major product A and B in the following


reaction sequence are
(1.) Claisen rearrangement cope rearrangement
ene reaction
(2.) Cope rearrangement - Claisen rearrangement
ene reaction
(3.) Cope rearrangement ene reaction Claisen
rearrangement
(4.) ene reaction Claisen rearrangement - Cope
rearrangement
Soln (2)
Mechanism :

Soln (2)
This is an example of wolf-kischner reduction

(113) The mechanism and the product formed in the


following reaction, respectively, are

Soln (2)
Mechanism :

(115) The major product A and B in the following


reaction sequence are

Since Alkyl halide is tertiary in nature hence only


possibility of SN1 mechanism.
Moreover , Since in SN1 there is formation of
carbocation hence racemization take place hence
stereochemistry is not defined.
(Reference : Organic Chemistry , clayden)
(114)The major product A and B in the following
reaction sequence are

Soln (4)
Mechanism :

Soln (4)
This is an example of wittig reaction

(116) The major product formed in the following


reaction is

Soln (4)

This is an example of prins-pinacol cyclization

Subjection of ketal 1 to a Lewis acid gives the


corresponding oxacarbenium 2, which is poised to
undergo a Prins cyclization to furnish intermediate 3.
The empty p orbital in 3 (at C10) is aligned
periplanar to the C1-C2 bond thus allowing this bond
to migrate to form bicyclic ketone bearing a
quaternary center at C10.

Soln (2)
Mechanism:

(117) The major product formed in the following


reaction is

(119) The major product A and B in the following


reaction sequence are

Soln (2)
This is an example of intermolecular heck coupling

Palladium is very sensitive to steric effect and


generally forms less hindered complex
further migration of alkene by hydro palladation
are prevented by Ag2CO3 which rapidly removes
oxide re-addition of Pd-H to alkene
Overall elimination must be Syn.

Soln (3)

(118) The major product formed in the following


reaction is

(a) 1st step in the chlorination of anime with


hypochlorite
(b) 2nd step is the HLF reaction with retention in
stereochemistry

(120) The major product formed in the following


reaction is

Soln (3)
G = Wmax
WD = -RT In

= -R x 300 x ln22
= -600 R ln 2
(Reference : Physical chemistry , Atkins)

Soln (4)
Mechanism :

(121) The spectroscopic technique that can


distinguish unambiguously between trans-1, 2dichloroethynele and cis-1, 2-dichloroethynele
without any numerical calculation is
(1.) Microwave spectroscopy
(2.) UV Visible spectroscopy
(3.) X-ray photoelectron spectroscopy
(4.) -ray spectroscopy
Soln (1)
In microwave, only molecule possessing permanent
dipole moment can be distinguished
cis and trans have marked different in their dipole
moment.
UV is for conjugated system hence cannot be the
answer
(122) 10 mL aliquots of a mixture of HCl and HNO3
are titrated conductometrically using a 0.1M NaOH
and 0.1M AgNO3 separately. The titer volumes are
V1 and V2 mL, respectively. The concentration of
HNO3 in the mixture is obtained from the
combination
(1.) V1 - V2
(2.) 2V1 - V2
(3.) V2 - V1
(4.) 2V2 V1
Soln (3)
(123) A reversible expansion of 1.0 mol of an ideal
gas is carried out from 1.0 L to 4.0 L under
isothermal condition at 300 K. G for this process is
(1.) 300 R . ln2
(2.) 600 R .ln2
(3.) -600 R. ln2
(4.) -300 R . ln2

(124) The non-spontaneous process among the


following is
(1.) Vaporization of superheated water at 1050C and
1 atm pressure
(2.) Expansion of gas into vacuum
(3.) Freezing of super cooled water at -100C and 1
atm pressure
(4.) Freezing of water at 00C and 1 atm pressure
Soln (3)
Expansion of gas into vacuum and freezing of water
at 0 C is always a spontaneous process.
However , it is sometimes possible to cool liquid
water at low temperature without solidification. The
liquid below the freezing point is in the supercooled
state.This state is not quite stable and is known as
metastable state. The metastable state is
spontaneously converted into stable state by addition
of small amount of ice to the supercooled liquid ,
which will result in the solidification of water. This
indicates that former process is non-spontaneous at
the same temperature.
(125) The 1H NMR frequency at 1.0 T is 42.4 MHz.
If the gyromagnetic ratios of 1H and 13C are 27 x 107
and 6.75 x 107 T-1 s-1, respectively, what will be the
13
C frequency at 1.0 T?
(1.) 10.6 MHz
(2.) 169.6 MHz
(3.) 42.6 MHz
(4.) 21.3 MHz
Soln (1)
since we know that gyromagnetic ratio of C13 is
almost time to that of 1H hence even without
calculation, it can be inferred that
1
13 = 1
4
if 1H NMR frequency at 1.0T is 42.4 Mhz so the
C13 frequency at the same field strength would be
42.4/4 = 10.6 MHz
(126) The first order rate constant for a unimolecular
gas phase reaction A products that follows
Lindemann mechanism is 2.0 s-1 at pA = 1 atm and
4.0 s-1 at pA =2 atm. The rate constant for the
activation step is
(1.) 1.0 atm-1 s-1
(2.) 2.0 atm-1 s-1

(3.) 4.0 atm-1 s-1


Soln (4)

(4.) 8.0 atm-1 s-1

1
`
1
=
+

Therefore, two different pressures we have
1
(1 )

1
(1

So, = (

=
)

) (

( )
2

(1 )

1 1

(2 )

=(1 ) x ( )
2
2
4
= 8 atm-1s-1

(127) Stability of lyophobic dispersions is


determined by
(1.) inner-particle electric double layer repulsion and
intra-particle van der Waals attraction
(2.) inner-particle electric double layer attraction and
intra-particle van der Waals repulsion
(3.) inner-particle excluded volume repulsion and
intra-particle van der Waals attraction
(4.) inner-particle excluded volume attraction and
intra-particle van der Waals repulsion
Soln (1)
The theory of the stability of lyophobic dispersions
was developed by B. Derjaguin and L. Landau and
independently by E. Verwey and J.T.G. Overbeek,
and is known as the DLVO theory. It assumes that
there is a balance between the repulsive interaction
between the charges of the electrical double layers on
neighboring particles and the attractive interactions
arising from van der Waals interactions between the
molecules in the particles. The potential energy
arising from the repulsion of double layers on
particles of radius a has the form
2 2

= +

(128) According to transition state theory, one of the


vibrations in the activated complex is a loose
vibration. The partition function for this loose
vibration is equal to (kB is the Boltzmanns constant
and h is the Plancks constant)
(1.)

(2.)

(3.) kBT

(4.)

Soln (4)
Reactants A and B have 3N-6 vibrational degrees of
freedom if non-linear, 3N-5 if linear. The same is
true of the activated complex, which has 3(NA + NB)6 vibrational modes if it is non-linear. One of these
modes is of a different character from the rest
corresponding to a very loose vibration that allows

the complex to dissociate into products. For this


degree of freedom we can use a vibrational partition
function q* in which the vibrational frequency v
tends to zero. i.e.
1
1

= lim
=
=

0 1
1 (1 /)
(129) The average end to end distance of a random
coil polymer of 106 monomers (in units of segment
length) is
(1.) 106
(2.) 105
(3.) 104
(4.)
3
10
Soln (4)
Average end to end distance of random coil polymer
is given by
R2 = l.N1/2, where N = no of monomer l = segment
length
R2 = 106 = 103
(130) The radial part of the hydrogenic wave
function is given as r( r)-r (, are constants).
This function is then identifiable as
(1.) 2s
(2.) 3p
(3.) 4d
(4.)
5f
Soln (2)
Radial part of hydrogenic wave function is given as
(L )-g. The corresponds to one radial node.
Number of radial nodes = n l 1 =1
n=3
l=1
Orbital wave function must be 3p
(131) A normalized state is constructed as the
linear combination of the ground state (0) and the
first excited state (1) of some harmonic oscillator
with energies and 3/2 units, respectively. If the
average energy of the state is 7/6, the probability of
finding 0 in will be
(1.) 1/2
(2.) 1/3
(3.) 1/4
(4.)
1/5
Soln (2)
According to Schrodinger Equation
H = E
i.e. Hamiltonian operated on a wave function will
give a same wave function back with an eigen value.
Here the eigen value for the 1st two state is given
and 3/2
Linear combination will give
= C10 + C21, where e1 and c2 are normalizable
constant
+

= 1

12 12 + 22 12 + 21 2 1 0 = 0

The last term in the integral vehicles due to ortho


genes
C12 + C12 = 1
Now its easy to find the expectation value of energy
H = | |2En = | |2(n + ) h
H = C12 (hw) + C12 (3/2hw)
C12 + C12 = 1.. (1)
1 2 3 2
C1 + 2C1
2
3 2
3
+ 2 21
2 1

C12

= 6 (given)
3

(2)
7

= 2 () 2 12 + 2 21 = 6

= 2/6

=1/3

(133) Given that E0 (Cl2/Cl-) = 1.35 V and Ksp


(AgCl) = 10-10 at 250C, E0 corresponding to the
() is
(1.) 0.75 V
(3.) 1.65 V
2.303
[

1
2 () +
2

+ (. ) +

(2.) 1.05 V
(4.) 1.95 V

= 0.06 ]

Soln (1)
According to the Nernst equation
Ecell = E0cell +

[]
2.303
log []

Since Ksp is given which is the condition for


equilibrium hence ECL will be zero
E0cell =

C2 = 61s261s262s261s22p4
(135) The temperature dependence of the vapor
pressure of solid A can be represented by log p =

(132) The symmetry-allowed atomic transition


among the following is
(1.) 3F 1D
(2.) 3F 3D
(3.) 3F 1P
(4.) 3F 3P
Soln (2)
Solution rule for the atomic transition is
l = 1 (parity should be changed by unity)
s = 0 (spin should not change)
Hence option 2 is correct

electrode reaction

1s2 2s2 has been omitted for clarity

2.303
log

= 0.06 log 10-10 since log10 = 1


E0cell = 0.6
E0cell = Eox + Ered
Eox = E0cell Ered = 0.6 1.35 = 0.75 V
(134) The ground state electronic configuration of C2
using all electrons is
2 2 2 2 2 2
(1.) 1
1 2 2 2 2
2 2 2 2 2 2
(2.) 1
1 2 2 2 2
2 2 2 2 2 1 1
(3.) 1
1 2 2 2 2 2
2 2 2 2 4
(4.) 1
1 2 2 2
Soln (4)
C 1s22s2p2
MOT diagram for C2

10.0 -

1800
,

and that of liquid A by log p = 8.0 -

1400
.

The temperature of the triple point of A is


(1.) 200 K
(2.) 300 K
(3.) 400 K
(4.) 500 K
Soln (1)
Triple point correspondence of unique value of
pressure hence two equation for the pressure must
equate to the same value
1800
log = 10
(1)

1400
log = 8
(2)

(1) and (2) must be same


Hence
10

1800

10 8 =
2=

400

1400

1400
1800
+

=8

2T = 400

T = 200 K
(136) The molecule with the smallest rotational
constant(in the microwave spectrum) among the
following is
(1.) N CH
(2.) HC CCl
(3.) ClC CF
(4.) B CCl
Soln (3)
Expression for the rational constant is given by
= 2 /8 2
1/I ( is inversely proportional to reduced
mass)
i.e. heavier will be the molecule, lesser will be the
rotational constant. Hence 3 is the correct option
(137) vmax and Km for an enzyme catalyzed reaction
are 2.0 x 10-3 Ms-1 and 1.0 x 10-6 M, respectively.
The rate of the reaction when the substrate
concentration is 1.0 x 10-6 M is
(1.) 3.0 x 10-3 s-1
(2.) 1.0 x 10-3 s-1
(3.) 2.0 x 10-3 s-1
(4.) 0.5 s-1

Soln (2)
According to Michaelis Menten equation
=

[5]

= max
+[5]
3 [106 ]

2 10
2 109
2 109
=
=
[1 + 1]106 2 106
106 + 106

=10-3
(138)A certain 2 level system has stationary state
energies E1 and E2 (E1 < E2) with normalized wave
functions 1 and 2 respectively. In the presence of a
perturbation V, the second order correction to the
energy for the first state (1) will be
| |
| |
(1.) 1 2
(2.) 1 2
1

(3.)

|1 | |2 |

(4.)

1 2

|1 | |2 |
(1 2 )2

Soln (3)
Since we know that second order correction is always
hence it follows that expression should contain E1
E2 (since E1 < E2). Therefore correct option is 3
(139) The vibrational frequency of a homonuclear
diatomic molecule is v. The temperature at which the
population of the first excited state will be half that
of the ground state is given by
(1.) hv.In2/kB
(2.) hv/(In2.kB)
(3.) In2/(hv.kB)
(4.) hv.log2/kB
Soln (2)
Expression for the Boltzmann population is given by
2
1

= E/RT
1
2

According to given condition 2 = 1


1

2 = hv/kT
1

ln 2 = hv/kT

or

ln2 = hv/kT

T = hv/ln2.kB
(140) For a simple cubic crystal, X-ray diffraction
how intense reflections for angles 1 and 2 which are
assigned to [1 0 1] and [1 1 1] planes , respectively.
The ratio sin1/sin2 is
(1.) 1.5
(2.) 1.22
(3.) 0.82
(4.)
0.67
Soln (3)
According to Braggs law,
= 2dsin

sin = 2
1
2

= 0.85

sin 1/d where d =

12 +12 +12
12 +12 +12

2
3

2 + 2 + 2

(141) The standard EMF of the cell


Pt, H2(g)HCl (soln.) AgCl(s), Ag(s)
(1.) Increase with T
(2.) decrease with T
(3.) remains unchanged with T
(4.) decreases with HCl
Soln (3)
This cell is an example chemical cell without
transference. It consist of hydrogen electrode on the
left hand side and Ag|AgCl electrode on the right ,
dipping directly in hydrochloric acid giving cell with
no liquid junction. In the cell, the hydrogen electrode
is negative and reversible with respect to hydrogen
ion whereas the Ag|AgCl electrode is positive and
reversible with respect to chloride ions.
EMF of the cell is given by (without derivation)
||
Ecell =

ln

1
2
2

The cell reaction indicates that cell EMF results from


chemical reaction , namely , the reduction of silver
chloride by hydrogen gas to solid silver and
hydrochloric acid.
Furthermore , the EMF of the cell as given by above
equation depends on the activity of hydrochloric acid
and the pressure of hydrogen gas. If the pressure of
the gas is 1 atm equation becomes

||
=

ln

(142) The irreducible representations of C2h are Ag,


Bg, Au, and Bu. The Raman active modes of trans-1,
3-butadiene belongs to the irreducible representations
(1) Ag and Bg
(3) Ag and Au
(2) Au and Bg
(4) Bg and Bu
Soln (1)
The character table for C2h point group is given by
E C2
i
h Linear
quadratic
(z)
Rotation
Ag 1 1
1 1
Rz
2 , 2 , 2 ,
Bg 1 -1
1 -1 Rx , Ry
xz , yz
Au 1 1
-1 -1 z
Bu 1 -1
1 1
x,y
From above it is evident that Raman active modes
belong to Ag and Bg representation
(143) The molecule diborane belongs to the
symmetry point group
(1.) C2v
(2.) C2h
(3.) D2d
(4.)
D2h
Soln (4)
Diborane has three perpendicular C2 axes are 3
perpendicular mirror plane

(144) Possible term symbol(s) of the excited states of


Na atom with the electronic configuration
[1s22s22p63p1] is/are
(1.) 2S1/2
(2.) 2P3/2 and 2P1/2
(3.) 1S0 and 1P1
(4.) 3P0 and 3P1
Soln (2)
Excited state configuration of Na11 1s22s2p63p1
Term symbol: 2s + 1LJ
S = , 2s + 1 = 2, L = 1
J = |L - S|to|L + S|
1 + = 3/2 or
1=
Possible term symbol are: 2P3/2 and 2P1/2
(145) Though a constant shift of energy levels of a
system changes the partition function, the properties
that do not change are
(1.) average energy, entropy and heat capacity
(2.) average energy and entropy
(3.) average energy and heat capacity
(4.) entropy and heat capacity
Soln (2)
The expression for the average energy U in the
partition fn is given by the

1
( ) = ( ) exp() =

Similarly, for entropy we have expression ( )

where F = -RT[In Z]
Therefore both the terms depends only on
temperature but not on energy levels