SOLUTIONS

1. (8) Molarity = 3.2 M 4. (6.47 kg) The equations of chemical Total number of electrons having
Let volume of solution = 1000 mL reactions occurring during the process 1
{| m l | = 1 and m s = − } = 6
= Volume of solvent are 2
Mass of solvent = 1000 × 0.4 = 400 g In the presence of oxygen 7. (9) In an one electron (hydrogenic)
Since, molarity of solution is 3.2 molar 2 PbS + 3O 2 → 2PbO + 2SO 2 …(i) system, all orbitals of a shell remains
By self reduction degenerate, hence in second excited
∴ n solute = 3.2 mol
2PbO + PbS → 3Pb + SO 2 state, the degeneracy of H-atom is nine
3.2
Molality (m) = = 8 Thus 3 moles of O 2 produces 3 moles of
400 / 1000 Second excited state of H-atom
Pb i.e.
3s 3p 3d
Hence, correct integer is (8). 32 × 3 = 96 g of O 2 produces
H(1s1)
w
2. (9) Moles of solute, n1 = 1 ; 3 × 207 = 621 g of Pb Ground state
m1 So, 1000 g (1kg) of oxygen will produce All are degenerate
w 621 degeneracy = 9
Moles of solvent, n2 = 2 × 1000 = 646815
. g
m2 96 In case of many electrons system,
χ1 (solute) = 01
. and χ 2 (solvent) = 0.9 = 6.4687 kg ≈ 6.47 kg different orbitals of a shell are
Alternatively non-degenerate. Hence,
χ1 n1 w m 1
∴ = = 1 ⋅ 2 = From the direct equation, 1s 1s 2s 2p
χ 2 n2 m1 w2 9
PbS + O 2 → Pb + SO 2 H
–
Solute (moles) w1 × 1000 × 2 32 g 207 g
Molarity = =
Volume (L) m1 ( w1 + w2 ) So, 32 g of O 2 gives 207 g of Pb Ground state First excited state

Total mass of solution 207 1s 2s 2p

Note Volume = 1 g of O 2 will give g of Pb
Density 32
1000g of O 2 will give Second excited
 w + w2  state only three p-orbitals
= 1  mL 207
× 1000 =6468.75 g = 6.46875 kg
 2  (2px, 2py, 2pz) are
32
Solute (moles) w1 × 1000 ≈ 6.47kg
degenerate.
Molality = =
Solvent (kg) m1 × w2 5. (126 mg) 8. (c) In the wave function ( ψ ) expression for
Given, molarity = molality Mn2+ → MnO –4 + 5 e − 1s-orbital of He + , there should be no
−
hence,
2000 w1
=
1000 w1 S 2O 82– + 2e → 2SO 24− angular part. Hence (iii) can’t be true for
m1 ( w1 + w2 ) m1 w2 ψ1 s of He + .
∴ 2Mn 2+
+ 5S 2O 2–
8 → 2MnO –4 + 10SO 2–
4
w2 1
∴ = ⇒ w1 = w2 = 1 Also, 9. (a) Correct : 2s orbital has one radial
w1+ w2 2
2MnO –4 + 5C 2O 42− → 2Mn2+ + 10CO 2 node.
w1 m2 1 m1(solute) Hence, 2Mn 2+
≡ 5C 2O 2– No of radial node = n − l − 1
∴ = ⇒ =9 4
= 2 − 0 − 1= 1
m1 w2 9 m2 (solvent) 1 MnCl 2 ≡ 2.5 H 2C 2O 4
Also, when radial part of wave function ( ψ )
Oxalic acid taken = 225 mg
3. (2992) Ca (OH 2 ) + (NH 4 )2 SO 4 → 225 is plotted against ‘‘r’’, wave function
1584 g = = 2.5 millimoles changes its sign at node.
[Ni(H 2O)6 ]Cl 2 90
2NH 3 + CaSO 4 2H 2O  
→ Hence, MnCl 2 = 1 millimole 10. (a) i is the correct expression of wave
Complex compound = ( 55 + 71) = 126 mg function for 1s-orbital of hydrogenic
Number of moles of 6. (6) For n = 4, the total number of possible system.
1584
(NH 4 )2SO 4 = = 12 mol orbitals are 11. (c,d) (a) is incorrect because NO is
132
4s 4p neutral oxide.
Moles of NH 3 released = 24 mol 4d
952 0 –1 0 +1 –2 –1 0 +1 +2 (b) is incorrect because CrO is neutral oxide.
Moles of NiCl 2 ⋅ 6H 2O = = 4 mol
238 4f 12. (c) PLAN
Number of moles of gypsum –3 –2 –1 0 +1 +2 +3 This problem can be solved by
(CaSO 4 ⋅ 2H 2O) formed = 12 mol using the concept involved in
Mass of gypsum formed = 12 × 172 According to question| m l | = 1 , i.e. there molecular orbital theory. Write the
= 2064 are two possible values of m l , i.e. +1 and molecular orbital electronic
Number of moles of complex formed –1 and one orbital can contain maximum configuration keeping in mind that
24 1
[Ni(NH 3 )6 ] Cl 2 = = 4 mol two electrons one having s = + and there is no 2s-2p mixing, then if
6 2 highest occupied molecular orbital
Mass of complex formed = 4 × 232 other having s = − 1 / 2 . contain unpaired electron then
= 928 g So, total number of orbitals having molecule is paramagnetic
Total mass = 2064 + 928 = 2992 g {| m l | = 1} = 6 otherwise diamagnetic.
 Assuming that no 2s-2p mixing takes When two same phase overlap with each
place the molecular orbital electronic other, it forms bonding molecular orbital
configuration can be written in the otherwise antibonding.
following sequence of energy levels of σ-bond
molecular orbitals

σ 1s, *σ 1s, σ 2 s, *σ 2 s, σ 2 pz , π2 px ≡ π2 py ,
*π 2 p ≡ *π 2 p , *σ 2 p
x y z π-bond
2 * * 2 s2
(a) Be → σ 1s , σ 1s , σ 2 s 2, σ
2
2

(diamagnetic)
* 1s 2, σ 2 s 2, σ
(b) B2 → σ 1s , σ 2 * 2 s 2, σ 2 p2,
z On the basis of above two concepts,
π2 px0 (diamagnetic) 14. (a,b,d) (a) Ice floates in water due to low correct matching can be done as shown
π2 py0 density of ice as compare to water which below:
is due to open cage like structure (formed
(c) C2 → σ 1s , *σ 1s 2, σ 2 s 2, *σ 2 s 2, σ 2 pz2,
2
by intermolecular hydrogen bonding).
π2 p1x A.
, (b) R NH 2 + H OH s
π2 p1y r
R NH 3 + OH − d-d σ bonding
*π 2 p0 (I )
* 2 p0 (paramagnetic)
x, σ
z
p-d π bonding
r
*π 2 p0 R 3N + H OH s R NH + OH − B.
y ( II )

(d) N2 → σ 1s 2, *σ 1s 2, σ 2 s 2, *σ 2 s 2, σ 2 pz2, The cation (I) in more stabilised through

more hydrogen bonding than ( R )3N in
π2 p 2
, x
aqueous solution.
π2 p 2
y C. p-d π antibonding
(c) HCOOH is stronger acid than
*π 2 p0 CH 3 COOH
x , σ * 2 pz0 (diamagnetic)
*π 2 p0 (d) Acetic acid dimerises in benzene
y through intermolecular hydrogen D.
Hence, (c) is the correct choice. bonding.
13. (4) PLAN O H O d-d σ antibonding
This problem includes concept of H 3C C C CH3 ∴ A → 2, B → 3, C → 1, D → 4
hybridisation using VBT, VSEPR O H O Hence, (c) is the correct option.
theory, etc., •• –
15. (c) PLAN 16. (4) Cl Be Cl N ≡≡ N → N •• ;
XeF4 , BrF4− , [Cu(NH 3 )4 ]2 + , [PtCl 4 ]2− are ↑ ↑ ••
This problem includes basic sp
square planar as shown below: sp
concept of bonding. It can be solved
•• +
F F
s by using the concept of molecular N ≡≡ N → O •• O == N == O
F F orbital theory. ↑ •• ↑
Xe Br sp sp
+ ve phase
F F F F All the above mentioned molecules/ions
have sp-hybridised central atom and no
2+
one pair at central atom, hence linear also.
H 3N NH3
– ve phase Others are :
Cu
O S
H 3N NH3 Any orbital has two phase +ve and –ve.
In the following diagram, +ve phase is O O Cl Cl
2– sp2-bent sp3-V-shaped
Cl Cl shown by darkening the lobes and –ve by
without darkening the lobes.
[Cl  I  Cl] [I  I  I]
–
Pt
Cl Cl
sp3d-linear sp3d-linear
SF4 (See-saw) as shown below:
F F  Xe  F
F Bonding MO
S
F sp3d-linear
–
F [Although ICl 2 , I–3 and XeF2 all also are
SiF4 , BF4− ,
[FeCl 4 ]2− , [CoCl 4 ]2− are linear but in them d-orbital contribute in
tetrahedral as shown below: hybridisation.]
Antibonding MO
JEE Main~Practice Set 1 03

17. (a,c) 21. (d) X is a lighter gas than Y, hence X has greater molecular speed. Due
Species Electrons MOEC N B N A BO Magnetic to greater molecular speed of X, it will have smaller mean free path
character and greater collision frequency with the inert gas molecules. As a
result X will take more time to travel a given distance along a straight
C 2−
2 14 σ1s 2 , σ * 1s 2 , 10 4 3 Diamagnetic line. Hence X and Y will meet at a distance smaller than one calculated
σ 2 s2, σ * 2 s2, from Graham’s law.
Hence, (d) is the correct choice.
π 2 p2x ≈ − π2 py2 ,
22. (c) PLAN
σ 2 pz2 This problem can be solved by using the concept of
O 2+
2 14 As above 10 4 3 Diamagnetic Graham’s law of diffusion according to which rate of
according to diffusion of non-reactive gases under similar conditions of
O2 16 10 6 2 Paramagnetic temperature and pressure are inversely proportional to
number of
N+2 13 electrons 9 4 2.5 Paramagnetic square root of their density.
1
N −2 15 10 5 2.5 Paramagnetic Rate of diffusion ∝
molar weight of gas
He +2 3 2 1 0.5 Paramagnetic
rx dy my
Thus, (a) is correct. = =
ry dx mx
(b) Bond order O 22 + > O 2 thus, Bond length of O 2+
2 < O 2 thus,
incorrect. d = density, m = molecular weight
(c) N+2 and N −2 have same bond order thus correct. rx d 40
= = =2
(d) He 2+ with bond order = 0.5 is more stable thus, less energy than ry 24 − d 10
isolated He atoms. Thus, (d) is incorrect. d
= 2 ⇒ d = 48 − 2d
18. (6) H 2 – σ 12s Diamagnetic 24 − d

He 2+ – σ 12s σ 1*1s Paramagnetic ⇒ 3d = 48

Li 2 – σ 12s σ 1*2s, σ 22 s Diamagnetic ∴ d = 16

23. (9) 238
92 U → 206
82 Pb + 8 42 He + 6 − 1β 0
Be 2 – σ 12s σ 1*2s, σ 22 s σ 2*2s Diamagnetic
Initial no. of moles of gas = 1
B2 – σ 12s σ 1*2s , σ 22 s σ 2*2s , π12p x = π12p y Paramagnetic
Final no. of moles of gas = 1 + 8 = 9
C2 – σ 12s σ 1*2s σ 22 s σ 2*2s π 22p x = π 22p y Diamagnetic ⇒ At constant temperature and volume; p ∝ n.
pf n 9
N2 – σ 12s σ 1*2s σ 22 s σ *22s π 22p r = π 22p y σ 22p z Diamagnetic So, = f = =9
pi ni 1
O −2 – σ 12s σ 1*2s, σ 22 s σ *22s σ 22p π 22p x = π 22p y π *22p x = π *21p y
24. (c) p( V − b ) = RT
Paramagnetic
⇒ pV − pb = RT
F2 – σ 12s σ 1*2s, σ 22 s σ *22s σ 22p z π 22p x = π 22p y , π *22p x = π 2*2p y
pV pb pb
Diamagnetic ⇒ = + 1 ⇒ Z = 1+
RT RT RT
19. (6) Hence Z > 1 at all pressures
S.N. Species No. of σ-bonds with No. of L.P at central
This means, repulsive tendencies will be dominant when
central atom atom
interatomic distance are small.
(i) In [TeBr6 ]2− 6 1
This means, interatomic potential is never negative but becomes
+
(ii) In [BrF2 ] 2 2 positive at small interatomic distances.
(iii) In SNF3 4 0 Hence, answer is (c).
−
(iv) In [XeF3 ] 3 3 25. (d) I (CH 3OH) : Surface tension decreases as concentration
increases.
20. (4) PLAN II (KCl) : Surface tension increases with concentration for ionic salt.
This problem can be solved by using the concept III [CH 3(CH 2 )11OSO 3− Na + ] : It is an anionic detergent.
involved in calculation of significant figure. There is decrease in surface tension before micelle formation, and
Universal gas constant, R = kNA after CMC (Critical Micelle Concentration) is attained, no change in
where, k = Boltzmann constant surface tension.
and NA = Avogadro’s number
Surface tension

KCl (II)
∴ R = 1.380 × 10 −23 × 6.023 × 10 23 J/Kmol = 8.31174 ~ = 8.312
Since, k and NA both have four significant figures, so the value of R CH3OH (I)
is also rounded off upto 4 significant figures.
[When number is rounded off, the number of significant figure is -
CH3(CH2)11OSO3 Na + (III)
reduced, the last digit is increased by 1 if following digits≥ 5 and is
left as such if following digits is ≤ 4.]
Hence, correct integer is (4).
Concentration
26. (4) (DC) Diffusion coefficient ∝ λ (mean 31. (b) X 2( g ) 2 2 X(g ) y
= 10 5
free path) ∝ U mean At t =0 1 0 x− y
Thus (DC) ∝ λ Umean 1 − x  x − y = 10 −5 y …(ii)
At equilibrium   x
RT T  2 From Eqs. (i) and (ii),
But, λ= ⇒ λ∝ (where, x = βeq )
2 N0 σ p p 2 × 10 −10 = x 2 − 2 × 10 −6
Total moles =  1 +  and Mole fraction,
x
 x 2 = 2 × 10 −6
and U mean =
8RT
, U mean ∝ T 2
πM 1 − x    x = 20 × 10 −3
   x 
(T )3/ 2  2, = 4.47 × 10 −3
∴ DC ∝ X 2( g ) = X(g ) =  
1 + x  1+ x 
p    34. (d) For P, i.e. (10 mL of 0.1 M NaOH + 20
3/ 2  2 2
(DC)2  p  T  mL of 0.1 M acetic acid) is diluted to 60
( x) =  1   2  and p = 2 bar
(DC)1  p2   T1   1− x  mL
3/ 2   The correct match is 1, i.e. the value of
 p   4T  Partial pressure, pX 2 =  2 . p
=   ( 8) = 4
1 [H+ ] does not change on dilution due to
=  1   1 1+  x
 2 p1   T1  2
 2 the formation of following buffer.
27. (2.22) pA = pB also TA = TB p⋅ x
and pX =
1 + x  NaOH + CH 3COOH -
nA V
= A  
So,  2 CH 3COO −Na + + H 2O
nB VB 2
  x 
 px /  1 + 2  
5 V V 5 Initial millimol 1 2
= A⇒ A =
400R VB VB 4 ∴ K p = pX2 / pX 2 =   Final millimol 1 1
3 (1 − x / 2 ) Final volume – 30 mL (20 + 10) in which
p
300R 1 + x  millimoles of CH 3COOH and
 
5 20  2 CH 3COO −Na + are counted.
VA = × 4 = = 2.22
9 9 4 px 2 8 βeq
2
For Q, i.e. (20 mL of 0.1 M NaOH + 20
= =
28. (2) MX 2 → M 2 + + 2 X − (4 − x2 ) ( 4 − βeq
2
) mL of 0.1 M CH 3COOH) is diluted to 80
mL
van’t Hoff factor for any salt can be 4 px 2
calculated by using equation 32. (c) (a) K p = = px 2 (Q 4 > > > x) The correct match is 5, i.e. the value of
(4 − x2 ) [H+ ] changes to 2 times of its initial
i = 1 + α ( n − 1)
1 value on dilution.
where, n = number of constituent ions ∴ x∝
p As per the condition given in Q the
∴ i ( MX 2 ) = 1 + α ( 3 − 1) = 1 + 2α
If p decreases, x increases. Equilibrium is resultant solution before dilution contain 2
( ∆Tf )observed
= i = 1 + 2α shifted in the forward side. Thus, millimoles of CH 3COO −Na + is 40 mL
( ∆Tf )theoretical
statement (a) is correct. solution. Hence, it is the salt of weak acid
∴ i = 1 + 2 × 0.5 ⇒ i = 2 (b) At the start of the reaction, Q = 0 and strong base. So,
29. (b) Since, the reaction is exothermic, where, Q is the reaction quotient Kw Ka
[H + ] initial =
these will be less ammonia at equilibrium ∆G = ∆G ° + 2.303 RT log Q C
at higher temperature. However, rate of Since, ∆G°> 0, thus ∆G is −ve. After dilution to 80 mL, the new ‘ C ’
reaction increases with rise in Hence, dissociation takes place C
becomes , So,
temperature, NH3 will be formed at faster spontaneously. 2
rate in the initial stage when the Thus, (b) is correct. K wK a
temperature is high. [H ] new =
+
(c) If we use x = 07 . and p = 2 bar then C /2
^m 4 × 2( 07
. )2
30. (3) Degree of ionisation (α) = Kp = = 1.16 > 1 or [H+ ] initial × 2
^∞ [4 − ( 07
. )2 ]
[H +
][ X−] For R, i.e. (20 mL of 0.1 M HCl + 20 mL of
HX s H + + X − , K a = Thus, (c) is incorrect. 0.1 M NH 3) is diluted to 80 mL
[HX ]
(d) At equilibrium, ∆G = 0 The correct match is 4, i.e. the value of
[H + ][Y − ]
HY s H + + Y −, Ka = ∴ ∆G ° = − 2.303RT log K p [H+ ] changes to
1
times of its initial
[HY ] 2
Since, ∆G° = + ve
^m for HX =^m1 K value of dilution.
^m for HY =^m 2 Hence, K p < 1, KC = p
( RT ) As per the condition given in R the
1
^m1 = ^m 2 resultant solution before dilution contains
10 Then KC < 1. Thus, (d) is correct.
2
2 millimoles of NH 4Cl in 40 mL of solution.
 ^m1  33. (4.47) AB - A + + B− Hence, a salt of strong acid and weak
K a = C ∝ 2, K a = C1 ×  
 ^° m 2  x x x− y base is formed.
2
 ^m 2  2 × 10 −10 = x ( x − y) …(i) For this,
K a2 = C 2 ×  
 ^° m 2  Kw × C
B− + H+ - HB [H+ ] initial =
2 2
x−y 10− 3 y Kb
K a1 C1  ^m1  0.01  1 
= ×  = ×  10 = 8 y
Now on dilution upto 80 mL new conc.
K a2 C 2  ^° m 2  01
.  10 
( x − y)10 −3 becomes C /2.
pK a1 − pK a2 = 3
 Kw ×
C 38. (c) G = H − TS = U + pV − TS 41. (b,c) AC → isochoric process
So, [H ] new =
+ 2 ⇒ dG = dU + pdV + Vdp − TdS − SdT AB→ isothermide process
Kb = Vdp − SdT [QdU + pdV = dq = TdS ] BC → isobaric process
or
1
[H+ ] new = [H + ] initial × ⇒ dG = Vdp if isothermal process (dT = 0) q AC = ∆ U AC = n C V . m (T2 − T1) = ∆ U BC
2 ⇒ ∆ G = V∆ p V 
W AB = − nRT1 ln  2 
For S , i.e. 10 mL saturated solution of Now taking initial state as standard state  V1 
Ni(OH)2 in equilibrium with excess solid G gr − G gr ° = Vgr ∆p …(i)
W BC = − p2 ( V1 − V2 ) = p2( V2 − V1 )
Ni(OH)2 is diluted to 20 mL and solid Gd − Gd ° = Vd ∆p …(ii)
Ni(OH)2 is still present after dilution. q BC = ∆ HBC = n C p1 m (T2 − T1 ) = ∆ HAC
Now (ii)-(i) gives,
∆ HCA = C p. m( T1 − T2 )
The correct match is 1. ° − G°
( Vd − Vgr )∆p = Gd − G gr + (G gr
Ni(OH)2( s ) - Ni 2+ + 2OH −
d ∆UCA = nC V . m(T1 − T2 )
At equilibrium, Gd = G gr ∆ HCA < ∆ UCA , since both are negative
as per the condition given it is a sparingly ⇒ ( Vgr − Vd )∆p = Gd ° − G gr ° = 2.9 × 10 3 J (T1 < T2 )
soluble salt. Hence, on dilution the
2.9 × 10 3
concentration of OH − ions remains ⇒ ∆p = Pa 42. (a,c) For the reaction,
constant in saturated solution. 2 × 10 −6 A = P
29 29000 Given, T1 < T2
So for this solution, = × 10 8Pa = bar
[H+ ] new = [H+ ] initial 2 2 ln K1 T2
29000 29000 > …(i)
p = p0 + = 1+ = 14501 bar ln K 2 T1
35. (b) PLAN 2 2
It shows,
This problem is based on 39. (a) On increasing the temperature, K
P1
assumption that total entropy decreases so reaction is exothermic i.e.,
change of universe is zero. –Wirr ∆H o < 0
At 100°C and 1 atmosphere pressure, P2 P2
Besides, graph shows
H2O ( l) rH2O( g)is at equilibrium. K >1
For equilibrium, ∆Stotal = 0 V1 V2 So ∆ Gº < 0
and ∆Ssystem + ∆Ssurrounding = 0 Irreversible compression Now from equation (i)
As we know during conversion of liquid to P1 T1 ln K1 > T2 ln K 2
gas entropy of system increases, in a − ∆G º1 > − ∆G º 2
similar manner entropy of surrounding P2 Likewise
P2 –Wrev
decreases. ( − ∆H º + T1∆S º ) > ( − ∆H º + T2 ∆S º )
∴ ∆Ssystem > 0 or simply
and ∆Ssurrounding < 0 V1 V2 T1 ∆S º> T2∆S º
36. (a,b,c) PLAN Reversible compression So, (T2 − T1 ) ∆S ° < 0
This problem includes concept of Maximum work is done on the system ∴ ∆S º< 0
isothermal adiabatic irreversible expansion. when compression occur irreversibly and In other words, increase of ∆G with
Process is adiabatic because of the use minimum work is done is reversible increase in temperature is possible only
of thermal insolution therefore, q = 0 compression. when ∆S °< 0.
Q pext = 0 (b) P1 A Hence, options (a) and (c) are correct.
w = pext ⋅ ∆V = 0 × ∆V = 0 43. (–14.6) Given,
Internal energy can be written as 1
∆U = q + W = 0
B (i) 2Cu( s )+ O 2( g ) → Cu2O( s );
2
The change in internal energy of an ideal C
∆Gº= −78000 J mol −1 =−78 kJ mol −1
gas depends only on temperature and
1
change in internal energy( ∆U ) = 0 therefore, V1 V2 (ii) H 2( g ) + O 2( g ) → H 2O( g );
2
∆T = 0 hence, process is isothermal and AB is isathermal and AC is adiabatic ∆Gº= −178000 J mol −1
T2 = T1 and p2V2 = p1V1 path. Work done is area Under the curve-
= −178 kJ mol −1
(d) p2V2γ = p1V1γ is incorrect, it is valid for Hence, less work is obtained in adiabatic
process than in isothemal. So, net reaction is (By (i)-(ii))
adiabatic reversible process. Hence, only
(a), (b) and (c) are correct choices. (c) It is incorrect. In adiabatic expansion 2Cu( s )+ H 2O( g ) → Cu2O( s )+ H 2( g );
cooling is observed, hence ∆G = 100000 J / mol or 10 5 J/mol
37. (c) By first law, ∆E = Q + W ∆U = nC v ∆T < 0. = 100 kJ mol −1
For isothermal expansion, ∆E = 0 (d) q = 0 (adiabatic), Now , for the above reaction
∴ Q= −W W = 0 (Free expansion)  p H2 
− Qirrev = Wirrev = p∆V = 3(2 − 1) Hence, ∆U = 0, ∆T = 0 (Isothermal) ∆G = ∆G º+ RT ln  
= 3 L atm  p H 2O 
− ∆H
Q ( − 3 × 101.3) J 40. (a,b,d) ∆S surr = and to prevent above reaction,
Also, ∆Ssurr = irrev = Tsurr
T 300 K ∆G ≥ 0
303.9 For endothermic reaction, if Tsurr  pH 2 
=− increases, ∆Ssurr will increase. For So, ∆G º + RT ln  ≥ 0
300  p H 2O 
exothermic reaction, if Tsurr increases,
= − 1.013 JK −1
∆Ssurr will decrease.
 After putting the values, Total volume of unit cell = a 3 = (2 2 r )3 is decreased. Mixture is more
 pH 2  vaporised thus, positive deviation
10 + 8 × 1250 ln  % of packing efficiency
≥ 0
5
from Raoult’s law.
4  πr 3 
4
 p H 2O  (b) Acetone molecules have higher
Volume of 4 s pheres 3 
 pH 2  = = × 100 intermolecular attraction due to
or 10 5 + 10 4 ln  ≥ 0
Volume of unit cell [2( 2 r )]3
dipole-dipole interaction. With CS 2,
 p H 2O  = 74.05% ~
− 74% this interaction is decreased thus,
or 10 4 (ln p H 2 − ln p H 2O ) ≥ −10 5 46. (2) fcc, a = 400 pm positive deviation.
or ln p H 2O ≥ −10 + ln p H 2O Z fcc × GMM (c) Mixture of benzene and toluene forms
d fcc = ideal solution.
or ln p H 2 ≥ −10 + 2.3 log (0.01) NA × a 3
(as p H 2O = 1%) (d) Phenol and aniline have higher
4 × GMM interaction due to intermolecular
≥ −10 − 4.6 8g/ml =
NA × 64 × 10 −24 H-bonding. Hence, negative
so ln p H 2 ≥ −14.6 deviation.
GMM = 128 × NA × 10 −24
44. (a) PLAN 50. (b,c) The graph shown indicates that
NA
Oxide ions are at ccp positions, = × 256 there is positive deviation because the
128 × N × 10 −24
hence 4O2– ions. Also, there are observed vapour pressure of L is greater
four octahedral voids and eight ∴ N=2 than the ideal pressure
tetrahedral voids. Since ‘m’ 47. (3) As per given information cation from
fraction of octahedral voids fcc Lattice and anion occupy all the Z
contain Al 3+ and ‘n’ fraction of octahedral void. So, Real
pL
tetrahedral voids contain Mg2+ Formula
M+ X−
ions, to maintain etectroneutrality MX al
Ide
2(2Al 3+ = + 6charge) and 4 ion
(Mg2+ = + 2charge), will make unit After step I 4 ion 1 ion 1 xM 0
cell neutral
After step II 1 ion 4 ion Since, deviation is positive, the
2 1 1
Hence, m = = , n=
4 2 8 After step III 0 ion 4 ion intermolecular force between L and M is
smaller than the same in pure L and
45. (b, c, d) After step IV 1 ion 3 ion
pure M.
(a) Nearest neighbour in the topmost Number of anion 3
So ratio of = Also as xL → 1, xM → 0, the real curve
layer of ccp structure is 9 thus, incorrect. Number of cation 1 approaching ideal curve where Raoult’s
(b) Packing efficiency is 74% thus, correct.
48. (1) ∆Tf = iK f m law will be obeyed.
(c) Tetrahedral voids = 2
∆Tf = 0 – (–0 . 0558° C ) = 0.0558° C 51. (19) pT = pA° X A + pB° X B
Octahedral voids = 1 per atom thus,
correct. 0.0558 45 = 20 ( 0.5) + pB° ( 0.5)
⇒ i (vant Hoff’s factor) = =3
4 . × 0.01
186 pB° = 70
(d) Edge length, a = r = 2 2r
2 This indicates that complex upon 22.5 = 20 X A + 70 (1 − X A )
ionisation produces three ions as: 50 X A = 47.5
[Co(NH 3 )5Cl]Cl 2 → 475
.
A XA = = 0.95
[Co(NH 3 )5Cl]2+ ( aq ) + 2Cl − ( aq ) 5
X B = 0.05
Thus, only one Cl is inside the XA
a coordination sphere. = 19
XB
49. (a,b) (a) When intermolecular attraction
between two components A and B in the 52. (0.05) 2 = 2 ( K b )x m
a C
B mixture is same as between A and A or B 1 = 2( K b )y m
and B, hence it is a case of ideal solution. ( K b )x
=2
thus, correct explanation When intermolecular attraction between A ( K b )y
and B in a mixture is smaller than that β
Edge length = a, Radius = r
between A and A or B and B, then mixture ∆ (Tb )x =  1 −  ( K b )x m … (i)
AC 2 = AB2 + BC 2  2
is more vaporised, bp is lowered. It is a
∆ (Tb )y =  1 −
( 4r )2 = a 2 + a 2 = 2 a 2 . 
07
case of positive deviation from Raoult’s law.  ( K b )y m … (ii)
 2 
4r = 2 a When intermolecular attraction between A
and B is higher than that between A and A On taking the ratio of Eqs. (i) and (ii),
2 a β
⇒ r= a= ⇒a=2 2 r or B and B, then mixture is less vaporised, 1−
4 2 2 2 ×2
bp is increased. It is a case of negative 3=
In ccp structure, number of spheres is 4. deviation. 0.65
β
Hence, volume of 4 spheres = 4 πr 3 
4 (a) Methanol molecules (CH 3OH) are 1 − = 15 . × 0.65
3  hydrogen bonded. In a mixture of 2
CCl 4 and CH 3OH, extent of H-bonding β = 0.05
53. (a,b) PLAN 0.059 RT [2 ]2 RT
0.059 = log 10 x or E° = ln = ln 4 …(i)
This problem is based on 2 2 nF [1] 2 nF
characteristics of salt-bridge. ∴ log10 x = 2
Further from the formula,
Functions of salt-bridge are ∴ x=2 ∆G ° = − nFE °
(i) It connects the two half-cells and 56. (c) The redox reaction is : ∆G ° = − 2 nFE °
completes the cell circuit. Zn( s ) + Cu2+ → Zn2+ + Cu Now putting the value of E° from eq. (i)
(ii) It keeps the solutions of two The Nernst equation is RT
∆G ° = − 2 nF × ln 4 …(ii)
half-cells and complete the cell 2.303 RT 2 nF
E = E° − log 10
circuit but does not participate 2F ∆G ° = − RT ln 4
chemically in the cell reaction. 2.303RT Finally, using the formula
= 1.1 − ∆G ° = ∆H ° − T∆S °
(iii) It maintains the diffusion of ions 2F
from one electrode to another ∆G ° = 2 ∆G ° − T∆S ° (as
Also, ∆G = − nEF = −2 F  1.1 −
2.303 RT 
electrode.  ∆H ° = 2 ∆G °, given)
 2F 
(iv) A cell reaction may also occur in ∆G ° = T∆S °
= − 2 .2 F + 2 .303RT ∆G ° − RT ln 4
the absence of salt-bridge. or ∆S ° = =
Sometimes, both the electrodes dip = 2.303RT − 2 .2 F T T
in the same electrolyte solution −4 10 −4 (from eq. (ii), ∆G ° = − RT ln 4)
57. (6) pH = Cα = 10 ⇒ α = = − R ln 4 = − 8.3 × 2 × 07
.
and in such cases we do not 0.0015
require a salt-bridge.” So, option (as all values given)
Also, conductance (G ) = κ  
A
(c) is incorrect.  l = − 1162
. J/K-mol
(v) This prevent mixing of two 60. (b) For the elementary reaction, M → N
κ = G   = 5 × 10 −7 ×
l 120
electrolytic solutions hence, option ⇒
 A 1 Rate law can be written as
(d) is incorrect choice.
= 6 × 10 −5 Rate ∝ [M ] n
Hence, correct choices are (a), (b).
κ × 1000 6 × 10 −5 × 1000 Rate = k [M ] n …(i)
54. (4) Energy obtained as one mole X is ⇒ Λc = =
C 0.0015 When we double the concentration of [M ] ,
converted into Y is 193 kJ.
∞ Λc rate becomes 8 times, hence new rate law
H(1s1) ⇒ Λ =
Ground state α can be written as
3s 3p 3d 6 × 10 −5 × 1000 0.0015 8 × Rate = k [2 M ] n …(ii)
= ×
Second excited 0.0015 10 −4 Rate k [M ] n 1 1
state of H-atom = ⇒ =
= 600 = 6 × 10 S cm mol −1
2 −1
8 × Rate k [2 M ] n 8 [2 ] n
All are degenerate
degeneracy = 9 58. (10) Mg → Mg 2 + + 2 e − ⇒ [2 ] n = 8 = [2 ] 3 ⇒ n = 3
2+
Energy consumed in converting one mole Cu + 2e − → Cu 61. (b,c,d )Rate constant, k = Ae − Ea / RT
of M + to M 3 + Mg + Cu 2+
→ Mg + Cu 2+ where, E a = activation energy and A =
= − nE ° F = 2 × 96500 × 025
. J RT x pre-exponential factor
96500 E = 2.67 = 2.7 − ln (a) If E a is high, it means lower value of k
= J nF 1
2 300 hence, slow reaction. Thus, incorrect.
0.03 = ln x
⇒ 193 × 10 3 = n 
96500  (b ) On increasing temperature, molecules
 2 × 11500
 2  are raised to higher energy (greater
2.3 = ln x
⇒ n = 4 mol than E a), hence number of collisions
x = 10
55. (d) Oxidation at anode increases. Thus, correct.
59. (– 11.62) E
H 2( g ) → 2H+ ( aq )+ 2e −; (c) log k = log A − a
Given,
° = 0.00 V
E SHE RT
A( s )| A n + ( aq , 2 M)|| B2n + ( aq , 1 M)| B( s ) d (log k ) E
Reduction at cathode ⇒ = a2
So, reactions at respective electrode will dT RT
M 4+ ( aq ) + 2e − → M 2+ ( aq ) ;
be Thus, when E a is high, stronger is the
E M° 4+ / M 2+ = 0.151 V Anode A( s )→ A n + + ne − × 2 temperature dependence of the rate
Net: M 4 + (aq ) + H 2( g ) → Cathode B2n + + 2 ne − → B( s ) constant. Thus, correct.
(d) Pre-exponential factor (A) is a
M 2 + (aq ) + 2H + ( aq ); Overall reaction
2 A( s ) + B2n + ( aq ) → 2 A n + ( aq ) + B( s ) measure of rate at which collisions
[M 2+ ] [H + ] 2 occur. Thus, correct.
K= ° = 0.151V)
(Ecell Further, ∆H ° = 2 ∆G ° and E cell = 0 is
[M 4+ ] pH 2 62. (a) If steric factor is considered, the
also given
corrected Arrhenius equation will be
[M 2+ ] Now by using the Nernst equation − Ea
=
[M ]4+
Ecell = E°cell −
RT [Product]
ln k = pAe RT where A = frequency factor
nF [Reactant]
° − 0.059 log K
Ecell = Ecell by Arrhenius.
2 After putting the values Q p > 1, pA > A hence, (a) is correct.
0.059 [M 2 + ] RT [ A n + ]2 Activation energy is not related to steric
0.092 = 0151. − log 4 + 0 = E cell
° − ln
2 [M ] 2 nF [B2n + ] factor.
 − E a f / RT
63. (a, d) Given for the reaction (at T= 300 K A fe involves some bonding between
so keq = −E
and constant volume=V) A be a b
/ RT adsorbent and adsorbate, hence
A( g ) → 2 B( g ) + C ( g ) A −( E − E a b )/ RT
exothermic. The last occupied
at t = 0 p0 – – = f e af molecular orbital in O2 is π *2 p. Hence,
Ab
at t = t p0 − x 2x x electron transfer from metal to oxygen
After putting the given values
at t = t1/ 3  p0 −
2 p0  p0 4 p0 2 p0 will increase occupancy of π *2 p
= keq = 4 e 2
 3  3 3 3 molecular orbitals. Also increase in
Af
We can calculate, (as E ab − E af = 2 RT and = 4) occupancy of π *2 p orbitals will
pt = p0 − x + 2 x + x = p0 + 2 x Ab
decrease bond order and hence
p t − p0 Now, ∆G ° = − RT ln K eq increase bond length of O2.
or 2 x = pt − p0 or x =
2 = − 2500 ln( 4e 2 )
67. (a,c) Higher the critical temperature,
Now for first order reaction, = − 2500 (ln 4 + lne 2 ) greater the extent of adsorption.
1 p0 (c) P( s ) + Q( g ) → PQ( s )
t = ln = − 2500 (1.4 + 2)
k ( p0 − x ) Adsorbent Adsorbate
= − 2500 × 3.4
As gaseous adsorbate is adsorbed on
Putting the value of x in the equation, = − 8500 J/mol
1 p0 solid surface, entropy decreases. Also
t = ln Absolute value = 8500 J/mol
k  p t − p0  formation of bond between P and Q results
p0 −   65. (b,d) For the elements with atomic in release of energy, hence ∆H < 0.
 2  number (Z ) larger than 20,
1 2 p0 68. (a) PLAN
= ln Neutrons (n) > Protons (p); Thus, n / p > 1
k 2 p0 − p t + p0 Thus, there is upward deviation from linearity.
This problem can be solved by
2 p0 If n < p, Thus n / p < 1, then
using concept of oxidant and
or kt = ln reductant.
( 3 p0 − p t ) (a) By β − - decay, 10 n → 11 p + 0
−1e
Oxidant Oxidant increases the oxidation
or kt = ln 2 p0 − ln ( 3 p0 − pt ) neutron changes to proton. Thus,
number of the species with which it is
or ln ( 3 p0 − p t ) = − kt + ln 2 p0 ( n / p) ratio further decreases below 1.
reacted.
It indicates graph between ln ( 3 p0 − pt ) vs Thus, this decay is not allowed.
Reductant Reductant decreases the
‘t ’ will be a straight line with negative (b) By orbital or K- electron capture, oxidation number of the species with
1 p + −1e → 0n
slope , so option (a) is correct 1 0 1
which it is reacted.
1 p0 1
t 1 /3 = ln = ln 3 proton changes to neutron, hence, H 2O 2 reacts with KIO 4 in the following
k p0 / 3 k ( n / p) ratio increases. Thus stability manner:
It indicates t 1/ 3 is independent of initial increases. Thus correct. +7 +5
concentration so, option (b) is incorrect. KIO 4 + H 2O 2 → KIO 3 + H 2O + O 2
(c) Neutron emission further decreases
Likewise, rate constant also does not n/p ratio. On reaction of KIO 4 with H 2O 2, oxidation
show its dependence over initial (d) By β + -emission, 1
→ 10n + 0 state of I varies from +7 to +5, i.e.
1p +1e
concentration. Thus, graph between rate decreases. Thus, KIO 4 gets reduced
proton changes to neutron.
constant and [ A ]0 will be a straight line hence, H 2O 2 is a reducing agent here.
Hence, n / p ratio increases. Thus correct.
parallel to X-axis . With NH 2OH, it given following reaction:
yp i − p t 120 −1 +3
( a − x ) at time t = N H 2OH + H 2O 2 → N 2 O 3 + H 2O
( y − 1) Neutron-rich
100 nuclei 1.5 In the above reaction, oxidation state of N
Number of neutrons

64. (+ 8500 J/mol) varies from –1 to +3. Here, oxidation

For the reaction, 80 1.4 number increases, hence H 2O 2 is acting
A( g ) + B( g ) AB( g )
- as an oxidising agent here.
Given E ab = E af + 2 RT 60 1.2 Hence, (a) is the correct choice.
or E ab − E af = 2 RT 69. (b,d)
40
Further
Af (a) It does not undergo self ionisation in
A f = 4 A b or =4 20 1.1 ratio
Ab water but accepts an electron pair
Neutron poor nuclei from water, so it behaves as weak
Now, rate constant for forward reaction, 0
− E a f / RT monobasic acid.
k f = A fe 20 40 60 80
Number of protons H 3BO 3 + H 2O r B(OH)−4 + H +
Likewise, rate constant for backward Hence, (a) is incorrect.
reaction, Plot of the number of neutrons against the
− E a b / RT number of protons in stable nuclei (shown (b) When treated with 1, 2-dihydroxy or
k b = A be
by dots). polyhydroxy compounds, they form
At equilibrium, chelate (ring complex) which effectively
Rate of forward reaction 66. (b, c, d) Since, adsorption involves
electron transfer from metal to O2, it is remove [B(OH)4 ]− species from
= Rate of backward reaction
chemical adsorption not physical solution and thereby produce
i.e., k f = k b
kf adsorption, hence (a) is incorrect. maximum number of H 3O + or H + ions,
or = keq Adsorption is spontaneous which
kb i.e. results in increased acidity.
 (c) Boric acid crystallises in a layer structure in which planar 74. (a) PLAN
triangular BO 3−
3 ions are bonded together through hydrogen This problem is based on chemical properties of
bonds. phosphorus.
One trigonal planar White phosphorus on reaction with thionyl chloride (SOCl 2 )
B(OH)3 unit produces phosphorus trichloride. P4 ( s ) + 8SOCl 2( l ) → 4PCl 3( l )
H H + 4SO 2( g ) + 2S 2Cl 2( g )
H H But if amount of thionyl chloride (SOCl 2 ) is in excess then it
H H produces phosphorus pentachloride.
B
H P4 + 10SOCl 2( l ) → 4PCl 5 + 10SO 2
H B H
H H
B H 75. (c) PLAN
H H H This problem can be solved by using concept involved in
H
H H H chemical properties of xenon oxide and xenon fluoride.
B B
H H XeF6 on complete hydrolysis produces XeO 3.
H
B XeO 3 on reaction with OH− produces HXeO −4 which on further
H
H H treatment with OH− undergo slow disproportionation reaction and
H H
produces XeO 46 − along with Xe( g ), H 2O( l ) and O2( g ) as a
H H by-product.
(d) In water the pK a value of H 3BO 3 is 9.25. Oxidation half-cell in basic aqueous solution
H 3BO 3 + H 2O r B(OH)4− + H + ; pKa = 9.25 HXeO − + 5OH − →
4
So, it is a weak electrolyte in water. XeO 46 − + 3H 2O + 2e –
70. (6) B 2H 6 + 6 CH 3OH → 2[B(OCH 3 )3 ] + 6H 2 Reduction half-cell in basic aqueous solution
Therefore, from 3 moles of B 2H 6, 6 moles of B(OCH 3 )3 will be HXeO − + 3H O + 6e − → Xe + 7OH −
4 2

71. (b) Due to poor shielding of d-orbital in Ga, atomic radius of Ga is Balanced overall disproportionation reaction is
smaller than that of Al. Thus, Ga < Al < In < Tl. 4HXeO −4 + 8OH − →
72. (a, c, d) Na 2B 4O 7 ⋅ 10H 2O (borax) is actually made of two 3XeO 46 − + Xe + 6H 2O
1442 44 3
tetrahedral and two triangular units, and is actually written as 2 products
Na 2[B 4O 5(OH)4 ] ⋅ 5H 2O. Complete sequence of reaction can be shown as
OH XeF6+3H2O XeO3+ 3H2F2
s sp3
O—B O sp2 OH
–

HO—B O B—OH
O HXeO4–
O—B
sp2 s –
OH /H2O (disproportionation)
sp3 OH
(a) Thus, correct. XeO64-(s) + Xe(g) + H2O(l ) + O2(g)
(b) Boron atoms are in different planes thus, incorrect.
Thus, (c) is the correct answer.
(c) Two sp2 and two sp3-hybridised B atoms thus, correct.
(d) Each boron has one  OH group thus, correct.
76. (b,c)

73. (a, b, d) Three centre two Compounds Hydridisation Structures Lone pair on
H H H electron bond central atom
CH3 CH3 BrF5 sp3d 2 F F 1
C
Al Al Br
CH3 C CH3 F F
H H H F
ClF3 sp3d F 2
(b) BCl 3 is stronger Lewis acid than AlCl 3 due to greater extent of F
pπ − pπ back bonding in AlCl 3. Cl
(c) Three centre four
electron bond F
Cl Cl Cl XeF4 sp3d 2 F F 2
Al Al Xe
Cl Cl Cl F F
3
(d) Three centre two SF4 sp d 1
electron bond
H H 77. (b,d) P4O10 is a dehydrating agent and converts HNO3 into N 2O 5
H
B B 2HNO 3 → N 2O 5 + H 2O
H H H P4O10 + 6H 2O → 4H 3PO 4
 (a) P4 + 20HNO 3 → 4H 3PO 4 + 20NO 2 + 4H 2O 2. N2O 5 It has following structure.
Thus, (a) is incorrect. O O O
N N
(b) N 2O 5 has no unpaired electron and is thus, diamagnetic
O O
thus, (b) is correct. Bridging oxo
(c) O O group
N O N Conclusion 1 bridging oxo group is present in the compound.
O O where, pi = initial pressure, pt = total pressure
There is no N—N bond, thus, (c) is incorrect. y = number of gaseous products per mole of reactant
3. P4 O 6
(d) N 2O 5 + Na → NaNO 3 + NO 2
N 2O 5 vapours are of brownish colour. Thus, (d) is correct. P
O O
+5 +4 +3 +1
78. (b) H 3 P O 4 > H 4 P2 O 6 > H 3 P O 3 > H 3 P O 2 O
P P
79. (a,c,d) O
O O O
P
HO Cl O HO Cl
Conclusion 6 bridging oxo groups are present in the compound.
sp3 sp3
O 4. P4 O 7
(b) Incorrect : Cl 2 + H 2O → HCl + HOCl P
(c) HClO 4 is stronger acid than H 2O. O O
(d) ClO −4 is more stable than ClO . −
O
P P O
80. (d) Colour of halogen arises due to transition from HOMO to O
LUMO in the visible region. On moving down a group, the O O
difference in energy between HOMO and LUMO decreases P
electronic transition occur more easily and colour intensity
Conclusion 6 bridging oxo groups are present in the compound.
increases.
5. H4 P2O 5
O O
Passage
MnO 2 P P
KClO 3 → KCl + O 2 H O H
∆ W OH OH
∆ HNO 3
O 2 + P4 → P4O 10 → N2O 5 + HPO 3 Conclusion 1 bridging oxo group is present in the compound.
X Y Z 6. H5P3O 10
81. (d) O O O

82. (a) P P P
HO O O OH
83. (b,c) OH OH OH
(a) NH 4NO 3 (decompose below 300° C to produce N 2O and
Conclusion 2 bridging oxo groups are present in the compound.
H 2O, but to produce N 2, it should be heated above 300°C)
∆ 7. H2S2O 3
(b) (NH 4 )2 Cr2 O 7  → N 2 + Cr2O 3 + H 2O
∆ S
(c) Ba(N 3 )2 → Ba + N 2
(d) Mg 3N 2 (an ionic compound, will not decompose below S
300° C) HO OH
O
84. (a,b, c)
(a) Bi 2O 5 is more basic than N 2O 5 Conclusion This compound does not contain any bridging oxo
group.
(b) NF3 is more covalent than BiF3
8. H2S2O 5
(c) NH 3 boiling point is higher than PH 3.
O O
(d) p − p single bond is stronger than n  n single bond.
85. (6) The structures of various molecules given in problem are S S
discussed below— HO OH
O
1. N2O 3 It is the tautomeric mixture of following two structures—
O N N Conclusion This compound also does not contain any bridging
O N N O O O oxo group.
O
Bridging 86. (7) Acidified K 2Cr2O 7, CuSO 4 , H 2O 2, Cl 2, O3 , FeCl 3 and HNO 3 oxidise
oxo group aq. iodide to iodine. Alkaline KMnO 4 oxidise aq. iodide
Conclusion 1 bridging oxo group is present in the to IO −3 .
compound.
 Na 2S 2O 3 is a strong reducing agent which on reaction with I 2 Number of unpaired electrons ( n) = 3
produces I − . Magnetic properties = paramagnetic
Na 2S 2O 3 + I 2 → 2I − + Na 2S 4O 6 Geometrical isomers of [Cr(NH 3 )4 Cl 2 ]+ are
Therefore, no reaction takes place betweenNa 2S 2O 3 and iodide ion. Cl Cl
Hence, correct integer is (7). + +
87. (a, b, c) In aqueous solution Cr 2 + (3d 4 ) acts as a reducing agent, H 3N Cl H 3N NH3
oxidising itself to Cr 3 + (3d 3 ) that gives a completely half-field t 2g Cr and Cr
level in octahedral ligand field of H 2O H 3N NH3 H3 N NH3
(b) Mn3 + (3d 4 ) is an oxidising agent as it is reduced to Mn2 + (3d 5 ) , a
NH3 Cl
completely half-filled stable configuration.
(c) Both Cr 2+
and Mn 3+
have d configuration. 4 Cis Trans

(d) 3d Cr ( aq )  
4 2+
→ Cr 3+ (aq ) +e –
R. A B. n = 1
Hence (d) is wrong statement. Magnetic properties = paramagnetic
Ionisation isomers of [Ti(H 2O)5Cl](NO 3 )2 are
88. (a, b) H 2O 2 in alkaline medium acts as reducing agent, reduces
[Ti(H 2O)5Cl](NO 3 )2 and [Ti(H 2O)5(NO 3 )]Cl(NO 3 )
Fe 3+ to Fe 2+. In acidic medium the same H 2O 2 oxidises Fe 2+ to
Fe 3+. C. MOEC of [Pt(en)(NH 3 )Cl]NO 3 is
89. (8) The balanced redox reaction is ×× ×× ×× ××
××
MnO −4 + [Fe(H 2O)2 (C 2O 4 )2 ]2 − + 8H+ → Mn2 + + Fe 3 + en en NH3 Cl
+ 4CO 2 + 6H 2O
+
r [H ] 8 (d) n=0
⇒ = =8
r [MnO –4 ] 1 Magnetic property = diamagnetic
90. (6) In neutral or faintly alkaline solution, MnO −4 is reduced to MnO 2 Ionisation isomers are [Pt(en)2(NH 3 )Cl]NO 3
and S 2O 32− is oxidised to SO 2− and [Pt(en)2NH 3(NO 3 )]Cl
4 .
D.MOEC of [Co(NH 3 )4 (NO 3 )2 ]NO 3
Change in ON = 4 units
2– 2– +
MnO4
– + 1/2 S2 O3 SO 4 MnO2 ×× ×× ×× ×× ×× ××
+6 +4
+7 +2 NH3NH3 NH3 NH3NO3NO3
Change in ON = 3 units
D. n=0
3
Thus, 4MnO 4− + S 2O 32− → 3SO 24− + 4MnO 2 Magnetic property = Diamagnetic
2
Geometrical isomers are
or 8MnO −4 + 3S 2O 32− → 6SO 24− + 8MnO 2
−
NO3 NH3
4 formed by 8 moles of MnO 4 = 6
Thus, moles of SO2−
H3 N NH3 NO3 NH3
91. (d) Zn + 2NaOH → Na 2ZnO 2 + H 2
Amphoteric CO and CO
92. (b,c) Fe(CO)5 → Total number of valence is electrons 18, low H3 N NH3 NO3 NH3
spin complex.
NO3 NH3
Ni(CO)4 → Total number of valence is electrons 18, low spin
complex. Trans Cis
Metalcarbonyl bond strengthes other when oxidation state of metal
Thus, magnetic property and isomerism in given coordination
is lowered.
compound can be summarised as
The carbonyl C O bond is stronger in case of increased oxidation
state of metal. (P) [Cr(NH 3 )4 Cl 2 ]Cl → Paramagnetic and exhibits cis-trans
isomerism (3)
93. (a) Paramagnetic → Mn3O 4 , (NH 4 )2 [FeCl 4 ], (NH 4 )2 [NiCl 4 ],
(Q) [Ti(H 2O)5Cl](NO 3 )2 → Paramagnetic and exhibits ionisation
K 2MnO 4 isomerism (1)
Diamagentic → K 2CrO 4
(R) [Pt(en)(NH 3 )Cl]NO 3 → Diamagnetic and exhibits ionisation
94. (b) PLAN
isomerism (4)
This problem is based on concept of VBT and magnetic
(S) Diamagnetic and exhibits cis-trans isomerism (2)
properties of coordination compound.
∴ P → 3, Q → 1, R → 4, S → 2
Draw VBT for each coordination compound.
Hence, (b) is the correct choice.
If unpaired electron is present then coordination compound will be
paramagnetic otherwise diamagnetic. 95. (4) When S is donor atom of SCN− , it produces weak ligand field
Coordination compounds of [MA 4 B2 ] type show geometrical and forms high spin complex as
isomerism. Molecular orbital electronic configuration (MOEC) for [Fe(SCN)6 ]3− : Fe 3+ ( 3d 5 ) =
various coordination compound can be drawn using VBT as
A. MO EC for [Cr(NH 3 )4 Cl 2 ]Cl is 4s 4p 4d

3d 4s 4p
3d 5(n-5) sp3d2
×× ×× ×× ×× ×× ××
NH3NH3 NH3 NH3Cl Cl Spin only magnetic moment (µ s ) = 5 ( 5 + 2 ) BM = 35 BM
 In case of CN − ligand, carbon is the donor atom , it produces 98. (b)
strong ligand field and forms low spin complex as Compounds Hybridisation Unpaired Magnetic
[Fe(CN)6 ]3− : Fe 3+ ( 3d 5 ) electron(s) character
3d 4s 4p Ni(CO)4 sp3 No Diamagnetic
2− 3
[NiCl 4 ] sp two Paramagnetic
d2sp3
3 2
[Co(NH3 )4 Cl 2 ] Cl sp d No Diamagnetic
Spin only magnetic moment (µ s ) = 1 (1 + 2 ) BM 3 2
= 3 BM
Na 3 [CoF6 ] sp d three Paramagnetic
Hence, difference in spin only magnetic moment Na 2O 2 — No Diamagnetic (O 22 − )
= 35 − 3 CsO 2 — One Paramagnetic
≈ 4 BM
O −2 (superoxide ion
96. (3) C O
Br O
is paramagnetic)
==

(II)
Et3P Fe C  CH 3 99. (5) Ligand is CH 2 — NH 2
acetylbromidodicarbonylbis 
Et3P CH 2O
C O (triethylphosphine)iron (II)
Geometrical isomers are
97. (6) All six complex will show cis-trans isomerism
Cl NH2
en + +
NH2 NH2
Cl Cl Cl NH2 O
3+
Co3+ O Co O Co3+
Co3+ and en Co3+ en
O NH2 O Cl
Cl Cl O
NH2
Cl
Cl
en
Cis Trans Cis
Cis Cl
Trans (I) (II) (III)
O
O
O 3–
Cl 3–
O Cl O O
O O

Cr3+ and Cr3+

Cl O O O Cis Trans
O O
O Cl
(IV) (V)
Trans
O O
Excess NH 4OH /NH 4Cl
– 100. (a,c,d) [Co(H 2O) 6 ] Cl 2 → Co(NH 3 ) 6 ]Cl 3
+ + O 2 (Air) Y
OH2 OH CN Pink ( X )

OH H 2O OH2 NC NH3 [Co(H 2O) 6 ]2+ + 4Cl − → [CoCl 4 ]2−

H 2O (Excess)
X blue Z
Fe3+ and Fe3+ Fe3+ and
(a) Since NH 3 is moderately strong ligand,hybridisation of cobalt in
NC NH3
H2O OH H2 O OH2 Y is d 2sp3.
OH2 OH CN
Trans (b) [Co(NH 3 ) 6 ]Cl 3 + 3AgNO 3( aq ) → 3AgCl ↓
Cis Cis
(c) [CoCl 4 ]Y 2− + 6H 2O q[Co(H 2O)6 ] 2+ + 4Cl − ; ∆H < 0
Blue Pink
– 2+ 2+
NH3 en Cl (d) Cobalt is sp3-hybridised in [CoCl 4 ] 2− .
NC CN NH3 101. (a, b, d) Statement wise explanation is
Co3+ and en Co3+ en
Fe3+ Statement (a)
Cl
NC CN
en
[Co(en)(NH 3 )3H 2O]3 + have following 2 geometrical isomers.
NH3 NH3 NH3 NH3
Cis Trans
Trans NH3 H2O
2+
2+
Cl
en Co en Co
NH3
H3N
H3N NH3 NH3 NH3
Cl
Co3+ and Co3+ H2O NH3
H 3N H3N NH3 Fac Mer
OH2
NH3 OH2 [ M( AA )b3c ] type complex
Cis Trans
Hence, this is correct statement.
 Statement (b) Structure : Square planar
If bidentate ligand ‘en’ is replaced by two cyanide ligands then So correct match for P is 6.
[Co(NH 3 )3(H 2O) (CN)2 ] + is formed. For Q i.e., sp3
It is [Ma3 b2c ] type complex which has following 3 geometrical It is seen in [FeCl 4 ]2− and Ni(CO)4
isomers. Fe − [Ar]3d 6 4s 2
NH3 NH3
Fe 2+ − [Ar]3d 6
N C NH3 N C NH3
3d 4s 4p
Co Co Fe2+
N C NH3 H2O NH3
H2O CN As Cl − is a weak ligand so when it approaches towards central
metal pairing of unpaired electrons does not take place.
(Fac) (Mer)
NH3 Thus, in [FeCl 4 ]2−
N C H2O sp3 hybridisation
Co
NH3 3d 4s 4p
N C
Fe2+
NH3
Cl– Cl– Cl– Cl–
(Mer)
Hence, this statement is also correct. Structure-Tetrahedral
Statement (c) Likewise in Ni(CO)4
Co metal has [Ar]3d 7 4s 2 configuration while in Ni [Ar]3d 8 4s 2
3d 4s 4p
[Co(en)(NH 3 )3(H 2O)]3 + it is in +3 oxidation state. Thus, Co 3+ has
6 2 3
Ni
[Ar]3d configuration, and d sp in complex.
3d 4s As CO is a strong ligand, hence when it approaches towards
central metal atom pairing of unpaired electron of central atom
takes place.
As en is a strong ligand, so pairing will occur
Thus, in Ni(CO)4
sp3 hybridisation

Due to the presence of all paired electrons it show diamagnetic 3d 4s 4p

behaviour rather than paramagnetic. Ni
Hence, this statement is incorrect. CO CO CO CO
Statement (d)
Structure Tetrahedral
According to CFT, absorption of light by coordination complexes
depends upon CFSE i.e., crystal field splitting energy (∆ 0)as So, for Q-4 and 5 are correct match.
1 For R i.e., sp3 d2
∆0 ∝
λ It is seen in [FeF6 ]4 −
Among the complexes given [Co(en)(NH 3 )4 ]3 + has more ∆ 0 value Fe [Ar]3d 6 4s 2
3+
as compared to complex [Co(en)(NH 3 )3(H 2O)] . Thus, Fe 2+ [Ar]3d 6
3+
[Co(en)(NH 3 )3(H 2O)] absorbs the light at longer wavelength for d- 3d 4s 4p 4d
d transition. Fe2+
Hence, this statement is also correct.
As F − is a weak field ligand hence, when it approaches towards
Note : For any complex, the value of ∆ 0 can be calculated via the central metal atom, pairing of its electrons does not take place.
difference or gap between e g and t 2g values. Thus, in [FeF6 ]4 −
102. (c) For, P i.e. dsp2 , It is seen in [Ni(CN)4 ]2− sp3d2 hybridisation
Ni [Ar]3d 8 4s 2
3d 4s 4p 4d
Ni 2+ [Ar]3d 8 Fe2+
3d 4s 4p
F– F– F– F– F– F–
Ni2+
Structure : Octahedral
as CN − is a strong ligand so when it approaches towards central
So, 1 is the correct match for R.
metal pairing of unpaired electrons takes place.
For S i.e., d2 sp3
Thus, in [Ni(CN)4 ]2−
It is seen in [Ti(H 2O)3Cl 3 ] and [Cr(NH 3 )6 ]3+
dsp2-hybridisation
Ti [Ar]3d 2 4s 2

3d 4s 4p
Ti 3+ [Ar]3d 1
Ni2+ 3d 4s 4p
Ti3+
CN– CN– CN– CN–
 Here, both H 2O and Cl are weak ligands 105. (a,b,c) CuFeS 2 (copper pyrite) is converted into copper into following
So, in [Ti(H 2O)3Cl 3 ] steps:
d2sp3 hybridisation Step I Crushing (grinding ) followed by concentration by
3d 4s 4p froth-floatation process.
Ti3+ Step II Roasting of ore in the presence of SiO 2 which removes iron as
slag (FeSiO 3).
H2O H2O H2O Cl– Cl– Cl– 2CuFeS 2 + O 2 → Cu2S + 2FeS + SO 2
2FeS + 3O 2 → 2SO 2 + 2FeO
Structure Octahedral
FeO + SiO 2 → FeSiO 3(Slag)
Likewise in [Cr(NH 3 )6 ]3+
Step III Self-reduction in Bessemer converter
Cr [Ar]3d 5 4s1 2Cu2S + 3O 2 → 2Cu2O + 2SO 2
Cr 3+ [Ar]3d 3 4s 0 2Cu2O + Cu2S → 6Cu + SO 2
3d 4s 4p Copper obtained is blister copper (98% pure).
Step IV Refining of blister copper is done by electrolysis Impure
Cr3+
copper—Anode
Here, NH 3 is also a weak field ligand so due to its approach no Pure copper— Cathode
pairing takes place in Cr. At anode : Cu → Cu2+ + 2e −
Thus, In [Cr(NH 3 )6 ]3+ At cathode : Cu2+ + 2e − → Cu
Carbon-reduction method is not used. Thus, (d) is incorrect.
d2sp3 hybridisation
106. (*) Siderite = FeCO 3, Malachite = CuCO 3 ⋅ Cu(OH)2
Bauxite = Al 2O 3 ⋅ 2H 2O 2 consisting some Al(OH )3
3d 4s 4p
Calamine = ZnCO 3, Argentite = Ag 2S
Cr3+–
107. (6,7) From qualitative analysis of the different metal ions it is found
NH3 NH3 NH3 NH3 NH3 NH3 that PbS, CuS, HgS, Ag 2S, NiS, CoS are black coloured.
MnS — dirty pink/buff coloured, SnS2—yellow coloured.
So for, S-2 and 3 are the correct match.
1100°C Bi 2S3 — brown/black (brownish black) coloured.
103. (b,c,d) (b) 4CuO → 2Cu2O + O 2 Hence, correct integer is (6 or 7).
∆ 6Cu SO
2Cu2O + Cu2S → + 2
108. (c,d) Only radicals of I and II group of qualitative analysis get
precipitated with H 2S in the presence of dilute HCl.
∆
(c) Cu2S + 2Cu2O → 6Cu + SO 2 +
(c) Cu2+ + H 2S H→ CuS ↓
720°C
(d) CuSO 4 →
1
CuO + SO 2 + O 2 Black
2 +
Pb 2+ + H 2S H→ PbS ↓
1100°C
4CuO → 2Cu2O + O 2 Black
+
∆ 6Cu SO (d) Hg 2+ + H 2S H→ HgS ↓
2Cu2O + Cu2S → + 2
Black
Reaction is believed to proceed as +
Bi 3+ + H 2S H→ Bi 2S 3 ↓
Cu2S r 2Cu + + S 2−
Brown ppt
2Cu2O r 4 Cu + + 2O 2−
2−
Ba 2 + , Ζn2 + and Fe 3 + are not precipitated as sulphide.
S + 2O 2− → SO 2 + 6e −
6Cu + + 6e − → 6Cu ; E cell
o
= 0.52 109. (a) 2S 2O 32− + Ag + → [Ag(S 2O 3 )2 ] 3−
(Clear solution)
Here, copper sulphide is reduced to copper metal. Solidified
[Ag(S2O 3 ) 2 ]3− + 3Ag + → 2 Ag 2S 2O 3
copper has blistered appearance due to evolution of SO2 and thus (White ppt.)
obtained copper is known as blister copper.
Ag 2S 2O 3 + H 2O → Ag 2S + H 2SO 4
Other compounds which give Cu are (Black ppt.)
1100°C
(i) CuO as 4CuO → 2Cu2O + O 2 110. (a,c) S 2– + CuCl 2 → CuS ↓ (black ppt.)
∆ SO 24− + CuCl 2 → Soluble, Thus
2Cu2O + Cu2S → 6Cu + SO 2
(a) CuCl 2 selectively precipitates S2– .
720°C 1
(ii) CuSO 4 as CuSO 4 → CuO + SO 2 + O 2 (b) S 2– + BaCl 2 → BaS ↓ (soluble)
∆ 2
4CuO → 2Cu2O + O 2 SO 24− + BaCl 2 → BaSO 4 ↓ (white ppt.)
∆ (b) precipitates SO 2− 2−
4 and not S .
2Cu2O + Cu2S → 6Cu + SO 2 2+
(c) S + Pb → PbS ↓ (black ppt.)
2–
While CuFeS 2 will not give Cu on heating. The heating in the SO 24− + Pb 2+ → PbSO 4 ↓ (white ppt.)
presence of O 2 gives Cu 2S and FeS with the evolution of SO 2 S2− and SO2− 4 , both are precipitated.
104. (b,c,d) (a) is wrong statement. Impure copper is set as anode (d) S 2− +Na 2 [Fe (CN)] 5NO → Na 4 [Fe (CN)] 5NOS]
where copper is oxidised to Cu2+ and goes into electrolytic solutions. Sodium nitroprusside (Purple colour)
(b) CuSO 4 is used as an electrolyte in purification process. But no colour with SO2−
4 .
(c) Pure copper is deposited at cathode as:
Cu2+ + 2e – → Cu : (At cathode) 111. (b,d) Statement wise explanation is
(d) Less active metals like Ag, Au etc settle down as anode mud. Statement (a) Mn2+ produces yellow-green colour in flame test
while Cu2+ produces bluish-green colour in flame test.
 Thus, due to the presence of green colour in both the cases, flame Cl CH3 Br
test is not the suitable method to distinguish between nitrate salts Br Cl Br Cl Br Cl
of Cu2+ and Mn2+ . Hence this statement is wrong.
Statement (b) Cu2+ belong to group II of cationic or basic radicals.
It gives black ppt. of CuS if H 2S is passed through it in the presence
CH3 Br Br Cl Cl CH3
of acid (e.g HCl). Mn2 + does not show this property hence this can CH3 CH3 CH3
be considered as a suitable method to distinguish betweenMn2+ (Me-Me)gauche (Br-Me)gauche (Cl-Me)gauche
and Cu2+ . These three have non-zero dipole moment due to non-cancellation
Hence, this statement is correct. of all dipole moment created by C—Cl and C—Br bond.
Statement (c) In faintly basic medium when H 2S is passed both 114. (2) Although the compound has two chiral carbons (indicated by
Cu2+ and Mn2+ forms precipitates. Thus, it is not suitable method to stars), it does not has four optically active isomers as expected. It
distinguish between them. is due to its existence in cis-form only.
Hence, this statement is incorrect CH3
CH3 CH3
Statement (d) The standard reduction potential of Cu2+ /Cu is H 3C
+0.34 V while that of Mn2+ /Mn is –1.18V. This can be used to ∗
distinguish between Cu2+ and Mn2+ . In general less electropositive
metals have higher SRP. ∗
Hence, this statement is correct. H 3C
O CH3
112. (a,b,c,d) PLAN O
cis-form trans-form (only hypothetical)
This problem is based on structure and nomenclature of
organic compound. The above shown transformation does not exist due to restricted
Draw structure of each compound and write IUPAC rotation about the bridge head carbons, hence only cis-form and its
name of the given compound. mirror image exist.
Match the molecular formula of given compound with molecular 115. (a)  OH group displays both kinds of effect;
formula of compound given in choices.
an electron withdrawing acid-strengthening inductive effect from
The combination of names for possible isomeric alcohols with the meta-position and an electron-releasing acid weakening
molecular formula C 4H10O is/are resonance effect from the para-position (at this position, resonance
Formula Names effect overweighs the inductive effect). Thus, III > IV.
CH3CH2CH2CH2OH n-butyl alcohol / n-butanol o-hydroxybenzoic acid (II) is far stronger than the corresponding
/ butan-1-ol meta and para isomers as the carboxylate ion is stabilised by
intramolecular H-bonding.
CH3  CH  CH2 OH Iso-butyl alcohol / 2-methyl 2,6-dihydroxybenzoic acid (I) forms carboxylate ion which is further
 propan-1-ol
CH3 stabilised by intramolecular H-bonding, Thus, correct order is
I > II > III > IV
CH3  CH2  CH  OH Secondary butyl alcohol / δ−
 O δ− δ−
butan-2-ol O δ+
C δ+ O O δ+
CH3 H H C H
CH3 Tertiary butyl alcohol / O O O
 tert butanol / 2-methyl
CH3 C  OH
propan-2-ol

CH3
II I
Hence, choices (a), (b), (c) and (d) are correct. (Most stable)

113. (3) PLAN 116. (7) As given in the question 3 stereocentres are visible, i.e.,
This problem can be solved by using concept of OH OH
conformational analysis of given organic compound. To
solve the question draw the stable conformational * *
structures of organic compound and determine the net
resultant dipole moment. *
The conformations of the given compound are as follows HO
OH
Cl
Br Cl Hence, the total number of stereoisomers = 2 3 = 8
Cl CH3 Br But out of these the following one is optically inactive due to
Br CH3 Cl Br
= = symmetry
Br Cl Br Cl OH OH
CH3 CH3
H3C CH3
H H H
1
   5
C H3 C *2  C *3  C *4  C H 3
HO
   OH
Cl Cl Cl Hence, total number of optically active stereoisomers=7
117. (b) PLAN (ii) H
r
H Br
This problem is based on boiling point of isomeric Br2 CH3
C C
alkanes. As we know more the branching in an H
CH3 CH3 H
alkane, lesser will be its surface area and lesser will be CH3
the boiling point H
Br CH3
Br
Br –
H CH3
+
and CH3 Br
H H
Br CH3
O P

⌠


 ⌠

III II
Enantiomers
Here (M + O) and (N + P) are pair of diastereomers.
and 121. (a) NBS
hv
I
On moving left to right (III to I)
• branching increases Br Br
• surface area decreases +
• boiling point decreases
Hence, correct choice is (b)
H2O/K2CO3
118. (c) The reaction condition indicates that starting compound is phenyl
acetylene.
 CH2
CH  HO OH
C≡≡C—H
Pd/BaSO4 (i) B2H6 +
H2 (ii) H2O2, NaOH, H2O

OH 122. (b,d) H Br H Br
H2/Ni – (optically active)
H 3C CH3
(2-phenyl ethanol)
(X)
H Br H Br
H2/Ni
119. (d) Hydroboration oxidation brings about anti-Markonikoff’s H 2C (optically inactive)
hydration of alkene.
O
C ≡≡ CH
H2O, HgSO4 CH3 H Br H Br
H2SO4 H 2C H2/Ni H 3C (optically active)
CH3 – CH3
CH3
CH3 CH3 CH3

H+/∆ CH3
C2H5 MgBr, H2O CH3 Br H Br H
OH H2/Ni (optically inactive)
H 2C CH3 H3 C CH3

120. (b,d) Addition of halogen at double bond occur in antiorientation via 123. (d) Since, there is no mention of temperature, room temperature
cyclic halonium ion intermediate. will be considered and thermodynamically controlled product
(i) r Br would be the major product as:
CH3 H Br CH3 H
Br2 CH3 Br – CH3 CH3
C C CH3 CH2 H+
H CH2
H trans CH3 H 3C H CH2 Br– CH3
H Br
Meso (M and N) 3º-carbocation

CH3 CH3
CH2
CH3 CH3 Br
124. (a, b, c) OH
C O

(a) I is Br (benzylic halide) and C C Br + CH3—C—CH3
 Acetone CHCl3/NaOH
C Phenol ∆ , Reimer-Tiemann
(P) reaction
(3° alkyl halide) follow SN 1
OH O O H O H
(b) I and II follow SN 2 also, as both are 1° halide.
(c) Compound (IV) undergoes inversion of configuration due to H CHO
presence of chiral carbon atom. , NaOH

125. (b) Me OH Me Br (Q) Major

(Q) Major
PBr3 NaI
CHO
(R) Minor
Et2O (SN2) Acetone (SN2)
O—Na Br CH2—Ph O—CH2Ph

Me I Me N3 CHO
Williamson's CHO
NaN3 (DMF) synthesis
(SN2)
(S)
126. (c) PLAN (a) R is not steam volatile, but Q is steam volatile thus, incorrect.
This problem can be solved by using the concept of (b) Q has enolic group thus, gives violet colour with 1% aqueous
stability of carbocation and SN 1 reaction. FeCl 3 solution thus, correct.
When two phenyl groups are replaced by two para methoxy group, (c) S has carbonyl group hence, gives yellow precipitate with 2,
carbocation formed will be more stable. As the stability of 4-DNP thus, correct.
carbocation formed increases, rate of acidic hydrolysis (d) S does not give colour with FeCl 3 thus, incorrect.
increases.
129. (b)
OCH3
For P, i.e. –+
ONa + Br
OCH3 group indicated
For this reaction 1 and 4 are probable products.
by arrow increases
C C the stability of
Product 1 i.e., is formed due to substitution while
carbocation OH
electronically (by + M effect)
product 4 i.e., is formed due to elimination. A tertiary

OCH3
More stable carbocation carbocation i.e, + formed during the reaction. Remember for 3°

Hence, (c) is the correct choice

carbocation ions elimination product predominates.
127. (4)
H+ 1, 2 Methyl shift
For Q, i.e. + HBr
H
Heat
⊕ OMe
–H2O
HO H 3C
H 3C CH3 H 3C CH3
CH3
Correctly matched product for this reaction is 2 i.e., .
Br
OH
The reaction proceeds as
–H KMnO4(dil)
P 0°C HO
Heat
(P) CH3
OH + HBr MeOH +
CH3
OH CH3 OMe Br
CH3
(Q) + NaOMe
For R i.e.,
128. (b,c) CH3 Br
CH3
CH CH3 O—O—CH Correctly matched product is 4 i.e., . It is a normal
CH3
O2 H3O + elimination reaction and proceeds as
+–
+ NaOMe
Br (Alkali in
alcohol)
3° alkyl halide preferes elimination.
 131. (a) CH3
For S i.e., + MeBr
O O O
ONa
HO–

The correct match is 3 i.e., . The reaction proceeds as CH3

OMe Aldol type
O Condensation
+ MeBr + NaBr CH3 CH3
– + O
ONa OMe O O
H+
130. (d) PLAN ∆
This problem includes concept of nucleophilic addition –H2O
reaction to carbonyl compound (ketone here) and α, β-unsaturated ketone
intramolecular nucleophilic substitution reaction. 132. (c,d) Only  CHO group is to be reduced to CH 2OH.
Complete reaction sequence is as shown below:
It can be done using NaBH4 in C 2H 5OH.
O
Cl CH3MgBr, dry ether, 0°C O IV O
CH3 Nucleophilic C O
addition reaction
O III H
II

OMgX COOH
aq. acid
CH3 I

Cl intramolecular + Mg X Cl (a) LiAlH 4 / (C 2H 5 )2O reduces I, II and III into CH 2OH, and IV into
CH3 CH3 diol.
CH3
nucleophilic O
substitution reaction (b) BH 3 / THF show same properties as (a).
3d 4s
(c) NaBH 4 / C 2H 5OH reduces III into CH 2OH.
(d) Raney nickel, same as (a) and (b), thus (c) is correct reagent.

133. (a) PLAN

This problem can be solved by using the stability of radical obtained after fragmentation of peroxyester.
Allylic radical are more stable than alkyl radical, so when there is a possibility of formation of allyl radical, it will undergo fragmentation through
formation of allyl radical. i.e. fragmentation produces stable radical.
On the basis of stability of radical, fragmentation can be done as

Column I Column II Explanation

O
O
P. 1. C6H5H2C CH3
O C6H5 — CH2+ CO2+ CH3O

O
O CH3
O CH3 C6H5 — CH2+ CO2+Ph—CH2 — C— CH3
Q. 3. C6H5H2C O
CH2C6H5 CH3

Ph —CH2+ CH3—CO—CH3

O O
CH3
O CH3 C6H5 — CO2+ CH3—C—CH3 Ph + CH3—CO—Ph + CH3
R. 4. C6H5 O
–CO2

C6H5 C6H5

O
C6H5 —CO2+ CH3O
O
S. 2. C6H5 O CH3 C6H5+ CO2

Codes
P → 1, Q → 3, R → 4, S → 2
Thus, (a) is the correct choice.
 Passage-1 NH
r
NH2 NH2 NH2
H+
OH r r
H 2N NH2 H 2N NH2 H 2N NH2 H2 N NH2
(I) CH3MgBr(ex)
OEt+ (ii) H2O III is least basic as
(Q )
H+ r
O H+/0°C H N N H N N H

CH3COCl Destablised by −I-effect of sp2-carbons.

AlCl3 139. (c)
R(F.C. Alkylation) PLAN This problem can be solved by using the various
O concepts synthesis of benzene, electrophilic
S(F.C. Acylation) substitution reaction and directive influence of
various substituents, including oxidation and
134. (b)
reduction.
135. (c) ⇒ —OH and —NH 2 are o/p-directing groups.
136. (a) ⇒ N-acetylation is more favourable than C-acylation.
137. (b) Explanation ⇒ N-sulphonation is more favourable than C-sulphonation.
⇒ NO 2 is a meta-directing group.

OH ⇒ H 2S ⋅ NH 3 reduces only one NO 2 group selectively in the

- NH3
MnO4 /H+
∆ presence of two NO 2 groups.
∆ OH
Using above concepts the correct sequence of reaction can be
written as
O OP
Red hot Fuming HNO3 / H2SO4
NH2 A. 3CH CH
iron 873K
NH2 ∆
Br2/NaOH
NH2 ∆
NH2 NO2 NH2
O R
Q O H2S .NH3
Selective reduction
∆ NO2
NH
KOH NO2
–
N+
2HSO4 OH
S O
NaNO2 Hydrolysis
O H2SO4
Here, N-sulphonation is NO2 NO2
Br COOC2H5 more favourable in
N—K comparisons to
–KBr
O C-sulphonation.

O OH OH
S1 N
+
COOC2H5 Conc. H2SO4 NO2
B.
60°C Here, nitration takes
O OH OH place at o-position of
S2 less hindered side.
O SO3H
NH2 OH
H3O+ OH OH

OH COOH O2N O2N

Dil.H2SO4

O (T ) D
(P) OH OH

138. (c) IV is most basic as conjugate acid is stabilised by resonance of SO3H

two  NH 2.
140. (b) CH3 Here, among two functional group NH2 and
CONH2 ,
+
+ CH2 — CH—CH3 H CH3 NH 2 is more nucleophilic, hence NH2 group will undergo reaction
faster than CONH 2.

Cumene
CH2—NH2 O O
CH3 CH2Cl2
O + CH3—C—O—C—CH3
OH
O2 CH3 C—NH2

O O
Cumene hydroperoxide

Cumene hydroperoxide formed above is an intermediate in the

CH2—NH—C—CH3
synthesis of phenol.
141. (b,c,d)
NaOC2H5
Br C—NH2

C 2H 5O − (a strong nucleophile) causes E1 reaction to form

O
isobutene as the major product.
—CH2—NH2 is more nucleophilic than —C—NH2

O
(b) Cl AlCl3 1, 2-hydride Hence, correct choice is (a).
shift 3° carbocation
1° carbocation (Major)
144. (a) Diazo coupling occur at para-position of phenol.
OH OH

(i) NaNO2/HCl/0°C
(ii) NaOH

SE Tertiary butyl benzene(X) NH2

+
N2Cl–

+
H
(c) (X) OH

BF3,Et2O
OH + N N
(d)
145. (b) NH 2 NHAc
142. (a,b,d) CH3

Conc.H2SO4 Ac2O/Pyridine
(a) H3C—C—CH3 ∆
H 3C CH3
CH3 KBrO 3 + HBr → Br2
Ac is CH 3CO (acetyl), it protects NH 2 group from being oxidised.
— CH Heated iron tube NHAc NHAc NH2
(b) H3C —
— 873 K
H 3C CH3
Br2 water H3O+
+ CH3COOH
CHO CH3

Zn/Hg, HCl Br Br
(d)
OHC CHO H 3C CH3 NH2 N2Cl Br

143. (a) PLAN NaNO2/HCl CuBr/HBr

This problem includes concept of acetylation reaction 273-278 K (Sandmeyer
(Diazotisation) reaction)
and regioselectivity of chemical reaction.
Regioselectivity means which group will react Br Br Br
selectivity in the presence of two or more than two
functional groups.
 HNO 3 +
146. (d) Given, Aniline Conc.
 → P + Q + R 147. (495 g) Given,
Conc. H2SO 4 (51%) O
(47%) (2%)
Then P, Q and R will be
NH2 NH2 NH2 NH2 NaOBr NH3/∆ Br2/KOH Br2(3-eqiv.)
A B C D
NO2 H3O+ (60%) AcOH
(50%) (50%) (100%)
Conc. HNO3+
+ +
Conc. H2SO4
The products formed are
NO2 O HO O H2N O
NO2
P (51%) Q (47%) R (2%) NH3/∆
NaOBr
Its given H3O+
(i) Ac 2O, pyridine
(ii) Br2, CH3COOH Acetophenone Benzoic acid Benzamide
R           → S (60%) (50%) Br2(3-eqiv.)
10 mol
(iii) H3O + i.e., i.e., AcOH
6 mol 3 mol
(iv) NaNO 2, HCl/273-278 K (A) (B)
(v) EtOH, ∆
O O
NH2 NH2
NH2 HN C CH3 HN C CH3 Br Br
Br2/KOH
NO2 NO2 NO2
Ac2O Br2
Pyridine CH3COOH Aniline
Br (50%)
(R ) i.e.,
Br 2,4,6-tribromo aniline 1.5 mol
H3O+ (100%) (C)
–CH3COOH i.e.,
(Hydrolysis)
1.5 mol
+ –
N2Cl NH2 (D)

NO2 NO2 NO2 NH2

EtOH NaNO2/HCl
Br Br
∆ 273-278K
(Diazotisation) So, 1.5 mol of are produced from
Br Br Br
(S)
Br
Now from S to major products its given.
(i) Sn / HCl 10 moles of acetophenone.
(ii) Br2 /H 2O (Excess)
S         → Major product NH2
(iii) NaNO 2, HCl / 273-278K Br Br
(iv) H 3PO 2
So, Molar mass of = 240 + 14 + 4 + 72 = 330
Br
NO2 NH2 NH2 Br
Sn/HCl Br2
H2O (Excess) NH2
Br Br
Br Br
Br Br Br
(S) NaNO2+HCl Hence, amount of produced
273-278K
Br Br
– Br
N2+Cl is 330 × 1.5 = 495 g
H3PO2
148. (d)PLAN
Br Br Br Br This problem can be solved by using the concept of
Br Br synthesis of dye using electrophilic aromatic
Major product
substitution reaction.
1, 3, 4, 5-tetrabromobenzene
In basic (alkaline) solution naphthol exists as naphthoxide ion which
Hence, only (d) is the correct answer. is a strong o, p-directing group.
 OH O III. Rosenmund’s reduction.
KOH IV. Acid chloride, anhydride and ester undergo controlled reduction
with di-iso-butylaluminium hydride (DIBAL-H) at − 78°C to give
III aldehydes.
−δ −δ
O 152. (a) O O
−δ
–
−δ OH
H
Thus, formation of dye can be shown as
N N—Ph H-atom at α carbon Carbanion
OH OH O
[Ph—N N]Cl– O
O
Alkaline solution

H—C—H H—C—H
Thus, (d) is the correct choice.
149. (9)
OH O O O O
NaOH

Crossed – H 2O
aldol CH2O CH2OH
N (I) (II)
a-carbon has no H-atom
O O O O hence, next reaction with HCHO is
crossed Cannizzaro reaction
-
HCHO, OH
(VI) (V) (IV)
(III) OH
O O
O O O
HCHO
Acetal CH2OH + HCOO–
formation
VII IX (VIII) (By reduction) (By oxidation)

All the above shown nine resonance structures are different. 153. (b,c)
150. (a) O
(b) CH3 CH CH2
O3
CH3 CHO+H2CO
Zn–H2O
H 3C H3C (R)
C—H
(i) O3 (P) Gives Cannizzaro
CHO but not haloform reaction
(ii) Zn– H2O
R
H 3C CHO O
NH3 CH NH O3
Zn–H2O
C CH3+H2CO
(X) (S)
(Q) Gives haloform reaction
In the above reaction, NH 3 prefer to attack at aliphatic aldehyde but not Cannizzaro reaction
group than an less reactive aromatic aldehyde group.
O3
O OH (c) CH CH CH3 Zn–H2O
CHO+CH3CHO
(R)
H3 C P
H3 C C N—H
H CH3 CH3
Tautomerism
Xs NH2 Gives Cannizzaro
but not haloform reaction
CH3 O O
– H 2O
CH3 O3
Zn–H2O
C CH3+CH3 C CH3
O CH3
Q (S)
H3 C Gives haloform reaction
N but not Cannizzaro reaction

154. (a,b,c)
A
OH −
151. (4) I. Gattermann-Koch reaction. RCHO + Ag 2O   → RCOOH + 2Ag
(Tollen's reagent) Silver mirror
II. CHCl2 CH(OH)2
Tollen’s test is given by all aldehydes and all reducing sugars as
H 2O
glucose, fructose and α-hydroxy ketones.
100°C (S N1) OH O
CHO
gem-diol
–H2O — CH— C —
α
 H O 161. (b) COOH COOH CONH2
having an aldehyde group gives Tollen's test.
H H2/Ni NH3 /∆ KOH/Br2
H Hoffmann
bromide
Br
O CH CH2 CH2
CHO (c)
CH C C CH CH
H3C CH3 H3C CH3 H 3C CH3

OH NH2 NO NH—CH3
Aldehyde α-hydroxy ketone
give positive tollen's test. CHCl2/KOH LiAlH4/Et2O
Carbylamine
Br
155. (d) C 6H 5  CH 3 →
2
C 6H 5  CH 2Br + HBr reaction
hv (Free radical bromination) CH2 CH2 CH2
O CH CH CH
|| NaOH /Br 2
H 3C CH3 H3C CH3 H 3C CH3
156. (a) C 6H 5  C  CH 3 → C 6H 5COONa + CHBr3( P )
(i ) Ph
(II) Bromoform 162. (d)
O O HO Me
|| || For P i.e.,
157. (d) C 6H 5CHO + CH 3  C  O  C  CH 3 Ph OH + H2SO4
CH COOK
→
3
C 6H 5  CH == CH  COOH Me
Perkin's condensation (Cinnamic acid) The correct match is 1 i.e., I 2, NaOH and 5 i.e., NaOBr
Cinnamic acid shows cis-trans isomerism. The reactions proceed as
158. (c) O Ph Me Ph O
O Pinacol
OH
+ H2SO4
HO OH Pinacolone Me
rearrangement Ph Me
Ph Me
CO/HCl (CH3CO)2O (Methyl shift)
AlCl3/CuCl CH3COONa

H
aO
Both

/N
Br haloform

I2
HO reactions
OH
OH NaOBr
Br3/Na2CO3 Moist KOH/ Ph O
473K
Me OH
Ph
159. (a) O O ‘ X’
C CH==CH—C Ph H
H CH3COONa H
(CH3CO)2O For Q i.e., + HNO2
NH2 OH
Ph Me
O The correct match is 2 i.e. [Ag(NH 3 )2 ]OH and 3 i.e. Fehling’s
CH2==CH2—C CH2 solution.
H2/Pd H H3 /PO4/∆ The reactions proceed as
CH2
Ph H Ph O
Deamination
+ HNO2
H2N rearrangement Me H
Ph Me OH (Methyl shift) Ph
160. (a) O n
O OH HO tio
CH3 H 3C
OH s olu
1. HCl g's
1. H2/Pd-C in
2. SOCl2 2. Mg/Et2O e hl Both
F oxidation
3. MeMgBr, CdCl2 3. CO2 (dry ice) Reactions
4. NaBH4 4. H3O+ [Ag(NH3)2]OH
H3C H 3C H 3C (Tollens's
O reagent)
CH3 CH3 CH3 Ph
(P) (Q) (R) Me
OH
Ph
‘ X’
 Ph Ph O
For R i.e., HO + H2SO4 H
OH H O H O N
Me Me O O
N N
The correct match is 1, 5 again. NH—C NH N
N
The reaction proceed as O CH2
N CH2 O H O
Ph Ph Ph O H
Pinacol
+ H2SO4 Pinacolone O
HO OH Me Me H3O+
Me Me rearrangement Ph CMe3
(Phenyl shift)
+ + – +
H3N—CH2—CO2 + O2C—CH—NH3
H Both (A) (B)
aO haloform
/N +
I2 reactions H 3N CO2
HO—C—CHNH—CH2—C—OH

Ph O NaOBr O CH2 O
CH2 +
Me
OH
Ph
X
(C ) (D)
Ph (A) is glycine which is only naturally occurring amino acid. While (B),
For S i.e., Br H (C) and (D) are not the naturally occurring amino acids.
+ AgNO3 Hence, correct integer is (1).
Ph OH
164. (a,b,c) If there is inversion of specific rotation from( + ) to ( − ), then
Me
invert sugar is formed.
The correct match is 2, 3.
(a ) C12H 22O11 + H 2O → Glucose
The reaction proceed as D( + )
( + )Maltose
Ph 140° 52°
(b) C 12H 22O11 + H 2O → Glucose +Fructose
Br H D( + ) L( − )
dibromination ( + )Sucrose
rearrangement + 66° 52° −92°
Ph OH + AgNO3 −40°for 2 moles mixture
−20°for 1 mole mixture
Me There is formation of invert sugar. Thus, correct.
Ph (c) Specific rotation of invert sugar is −20 ° per mole. Thus, correct.
O (d) Br2 water is a weak oxidising agent. It oxidises CHO to
Me COOH. CH 2OH group is not affected.
Ph H
COOH CHO COOH
Rest procedure is same as seen for Q above i.e., via oxidation.   Br water 
(CHOH)4 ← HNO 3
 (CHOH)4 →2
(CHOH)4
163. (1) PLAN
  
This problem can be solved by performing hydrolysis COOH CH 2OH CH 2OH
of peptide and deciding the nature of product. Saccharic acid Gluconic acid
Chemical reaction and product formed after (one of the products)
hydrolysis of given peptide can be represented as HNO 3 (a strong oxidising agent) oxidises invert sugar to
saccharic acid. Thus, incorrect.
165. (a) Natural rubber is formed by polymerisation of isoprene. So, β-L glucopyranose is formed as
H
CH2 C—CH CH2 CH2—C CH—CH2 5
O H

—
CH3 CH3 HO 6 CH2OH
Polymerise 4 1C O
Ethylene
H H OH H
Propylene

—CH2—CH— CH2—CH2— —CH2—C CH—CH2— 3 2 H

H2/Pt
OH H 5
CH3 CH3 O
n n HO CH2OH H
Natural rubber 6
Ethylene-propylene copolymer 4 1
This co-polymer is formed from propylene and ethylene. H H OH OH
3 2
n CH 2 == C H + nCH 2 == CH 2 →—CH2—CH CH2—CH2—
 OH H
CH 3 CH3 β-L-glucopyranose
n
166. (d) H H The α-L-glucopyranose has configurational change at C1 only and
O O
looks like
C1 C1
H
H C2 OH HO C2 H O
HO CH2OH HO Configuration at
HO C3 H H C3 OH this carbon atom
1
is opposite in α
H H OH H and β-forms
H C4 OH HO C4 H

H C5 OH HO C5 H OH H
α-L-glucopyranose
6CH2OH 6CH2OH
D-glucose L-glucose