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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.
(c)
3636
2
= 0 [Ans]
Structure of XeF2
(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)
Soln (3)
-pinene
1. 7
Soln (4)
2. 8
3. 9
4. 10
Q.
Y.
1770 cm-1
R.
Z.
1800 cm-1
Soln (1)
D-mannose
Soln (3)
This is an example of favorskii rearrangement of
-dibromoketone
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)
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
Soln (4)
(1.) A and B
(2.) A and C
(3.) B and D
Soln (4)
(4.) C and D
1
,
2
1
,
2
1
2
1
2
C2 =
(2.) C1 = 2,
C2 = 2
C2 =
(4.) C1 = 2,
C2 =
Soln (1)
x
=
= 1 2
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
= 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)
[]
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)
1
= 1 [] 1 []2 (1)
2
[]
= 21 [] 21 []2 (2)
Also = 2 []
= 22 [] 21 []2 1 []
Intercept = -S
= 2
1
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
x=
Slope = H
82
2
72
2
2
2 2
2
N2+ = KK 2
2
2 2
612
B.O =
( )
= 1+( ) = 1+1
X.
Oil
Wintergreen
Q.
Y.
Aspirin
R.
Z.
Ibuprofen
of
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.
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
2+
2[HCo(CO)4]
V(CO)6
Co2(CO)8
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 =
TV E = 34
nx18 36 (there are 2 Fe atoms)
M.M bond =
36 34
2
=1
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
the
synthesis
of
9-
Soln (3)
Mechanism :
Soln (2)
It is an example of light induced photo-isomerization
of benzene via Dewar benzene intermediate
Soln (3)
Mechanism:
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.
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.
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.
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
Soln (4)
Boronic
esters
RB(OR')2
react
with
methoxy(phenylthio)methyllithium LiCH(OMe)SPh
to give salts, which, after treatment with HgCl2 and
(112) The
sequential
following
transformation
involves
Soln (2)
This is an example of wolf-kischner reduction
Soln (2)
Mechanism :
Soln (4)
Mechanism :
Soln (4)
This is an example of wittig reaction
Soln (4)
Soln (2)
Mechanism:
Soln (2)
This is an example of intermolecular heck coupling
Soln (3)
Soln (3)
G = Wmax
WD = -RT In
= -R x 300 x ln22
= -600 R ln 2
(Reference : Physical chemistry , Atkins)
Soln (4)
Mechanism :
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
= +
(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
= 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
C12
= 6 (given)
3
(2)
7
= 2 () 2 12 + 2 21 = 6
= 2/6
=1/3
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 []
C2 = 61s261s262s261s22p4
(135) The temperature dependence of the vapor
pressure of solid A can be represented by log p =
electrode reaction
2.303
log
10.0 -
1800
,
1400
.
1400
log = 8
(2)
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
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
12 +12 +12
12 +12 +12
2
3
2 + 2 + 2
ln
1
2
2
||
=
ln
1
( ) = ( ) exp() =
where F = -RT[In Z]
Therefore both the terms depends only on
temperature but not on energy levels