Some Basic Concepts of Chemistry: Corporate Office: Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456

Chapter 1
Some Basic Concepts of Chemistry

1. Answer (B)
We will have to take weighted average
54  5  90  56  5  57
= 55.95
100
2. Answer (3)
25.2  25.25  25
Average titre value = = 25.15
3
Siginificant figure is 3.
3. Answer (4)
6.023 × 1023 × 1.380 × 10–23 = 8.312
It has four significant figure.
4. Answer (8)
w 2  1000
m
m2  w 1
1 mL solvent having mass 0.4 g.
1000 mL solvent having mass 400 g
1000 mL solution contain 3.2 × 80 g solute = 256 g
256  1000
 m 8
80  400
5. Answer (6.00 to 6.20)
2Al(s)  3H2SO4 (aq)  Al2 (SO 4 )3 (aq)  3H2 (g)
5.4 50  5
Moles taken
27 1000
= 0.2 moles 0.25 moles
H2SO4 is limiting reagent
 Moles of H2(g) produced = 0.25 moles
Using ideal gas equation : PV = nRT
0.25  0.082  300

 V
1
V = 6.15 L

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
Chapter 2
Structure of Atom
1. Answer (C)
Centripetal force = Coulombic force of attraction
mV 2 KZe2
=
r r2
KZe2
V2 =
mr
nh
V=
2mr
n2h2
V2 =
42m2r 2
KZe 2 n2h2
 
mr 4 2m2r 2
 h2  n 2 a0 n 2
 r  2 2 

 4 mKe  Z Z
hZ
Vn =
2ma0n
1 h2 Z 2 h2
K.E. = mv n2  2 2 2 ; K.E. (for x = 2 and Z = 1) =
2 8 ma0n 32 2ma02
2. Answer (A)
Radial probability function curve for 1s is
r
Here ‘P’ is 4 r 2  r2 dr
3. Answer (A, C)
Z2
En = –13.6 × eV
n2
22
 3.4 eV = –13.6 ×
n2
 n=4
ARCHIVE - JEE (Advanced) (Solutions) CHEMISTRY
n = 4, l = 2, m = 0 belongs to 4d orbital
no. of angular nodes in an orbital = value of l
no. of radial node in 4d = 1
Since it is a unielectronic species, there will be no shielding and the nuclear charge felt will be 2e.
4. Answer (B)
S1 state is 2s
In 2s, one radial node is present.
5. Answer (C)
Energy in S1 state
–13.6  3 2 9
E 2
 – 13.6 eV
2 4
E( H1 ) = –13.6 eV [Ground state]

1
So, energy = 2.25 × energy of e– in ground state in 1H1
6. Answer (B)
S2 state is 3p orbital.
Orbital angular momentum of 3p is 1.

7. Answer A(q, r); B(p, q, r, s); C(p, q, r), D(p, q)
8. Answer (D)
1s orbital is nondirectional so  will not depend upon cos.
Hence, 'D' is incorrect.
9. Answer (D)
For H-like species only D is correct, because
in (A), 1s orbital has no radial node.
In (B) for 3dz2 , xy plane is not nodal plane.
In (C), 2pz orbital has no radial node.

10. Answer (D)
For H-atom,
3  Zr 
 Z  2  a 
1s-orbital     e  0 
 a0 
3
Also, E 4  E2 
16
2
E6  E2 
9
27
Hence, (E6  E2 )   E4  E2
32
CHEMISTRY ARCHIVE - JEE (Advanced) (Solutions)
11. Answer (A)

1
Kinetic energy 
n2
1
Potential energy 
n2
 Correct match : (III), P ; (IV), P
12. Answer (D)
In Bohr’s model
Radius  n2
Angular momentum  n
1
Kinetic energy 
n2
1
Potential energy 
n2
 Correct match : (I), (T) ; (II), (S)
13. Answer (4)
Energy of incident photon should be higher than work function to slow photoelectric effect.
6.62  10 34  3  108

Energy of photon =  4.14 eV
300  109  1.6  1019
14. Answer (9)
3s 3p 3d
Out of 18 electrons present in 3rd shells.
1
Will have s  
2
15. Answer (5)
3RTNe TNe
MNe MNe
He MNe VNe MNe MNe MNe TNe
    205  1000
Ne MHe VHe 3RTHe 
MHe THe MHe THe 4  200
MHe
MHe MHe
He  5Ne
16. Answer (6)
|ml| = 1
means ml can be +1 and –1
1
So, for n = 4 six orbitals are possible and bear six electrons with s  –
2
17. Answer (3)
Ground state configuration:
H–:
1s 2s 2p
in second excited state, electron will jump from 1s to 2p, so degeneracy of second excited state of H– is 3.

18. Answer (30)
h 6.6  10 –27
Momentum of photon   gm cm s –1
 330  10 –7
Momentum of 1 mole of He-atoms = mv
 h
m v  NA 

6  1023  6.6  10 –27

4  v 
330  10 –7
6  6.6  102
v   30 cm s –1
33  4
 Change in velocity of He-atoms = 30 cm s–1


Chapter 3
Chemical Bonding and Molecular Structure

1. Answer (A)
Bond order of CO = 3 & NO– = 2.5
2. Answer (D)
3. Answer (C)
4. Answer (A)
Molecular orbital diagram for B2 where Hund’s rule is violated.

2p2X
1s 2  * 1s 2 2s 2 * 2s 2
2p0Y
 Bond order = 1 and diamagnetic.
5. Answer (D)
Pyramidal
S
O F
F
6. Answer (D)
F O
Xe  See saw..
F O
7. Answer (C)
Be2 = 1s2*1s22s2*2s2
B2 = 1s2*1s22s2*2s22pz2
C2 = 1s2*1s22s2*2s22pz22px12py1
N2 = 1s2*1s22s2*2s22pz22px22py2
8. Answer (B, C)
Compound Number of lone pairs on central atom
BrF5  1
ClF3  2
XeF4  2
SF4  1

9. Answer (A, C)
By MOT, C22– is diamagnetic as it is isoelectronic with N2.
By MOT, O22+ has bond order 3 and O2 has bond order 2. So, bond length of O22+ is shorter than O2.
N2+ and N2– have bond order 2.5
He2+, since has bond order 0.5 it has lower energy than He atoms.
10. Answer (B, C)
For symmetrical molecule  = 0
For unsymmetrical molecule   0
B  = 0, O = C = O  = 0, 0
:
S
F F sp
2 O O
sp
Cl
:
F F
:
  0, H — Se , Br  0
F F
91°
H 0 F Square Pyramidal
O
:
.
N   0, N   0, P 0
O O H H Cl Cl
H Cl
Cl
C   0,
H H
H
11. Answer (A, B, C)

H2O(l), K4[Fe(CN)6](s) and C6H6(l) are diamagnetic compounds. These compounds will be deflected upwards
from the magnetic field.
O2(g) is paramagnetic in nature. It will be attracted towards the magnetic field (downward).
12. Answer A(p, q, r, t); B(q, r, s, t); C(p, q, r); D(p, q, r, s)
Electronic configuration as
2p1x
B2  1s2 * 1s2 2s2 * 2s2
2p1y
 It is paramagnetic, as highest occupied orbital is partially filled and it is of bonding nature, therefore it will
readily undergo reduction.
When Zeff is less like B and N, then energy difference between 2s and 2pz is very small. Due to their same
symmetry mixing of s and p orbital take place.
Similarly in N2 b.o. is 3, it is diamagnetic, Neither it will undergo oxidation nor reduction.
O2 and O2 are paramagnetic.

13. Answer (C)
P. d – d ( bonding)
Q. p – d ( bonding)
R. p – d ( antibonding)
S. d – d ( antibonding)
14. Answer (4)
In CuSO4.5H2O, one molecule of water is H-bonded and other four molecules are bonded to metal centre.
15. Answer (0 or 8)
Fa
Feq Feq
Feq Feq
Br
Presence of lone pair will distort all the bond angles and none of the bond angle is exactly equal to 90º
FaBrFeq = 84°
FeqBrFeq = 89°
16. Answer (4)
Cl – Be – Cl N3–
Hybridization sp Hybridisation sp
Structure linear structure linear
..
+ O
O=N O ..
O O
..
..
..
..
Hybridisation sp Hybridisation sp2

Structure linear Structure Trigonal planar
..
S ..
..
[Cl –..I – Cl]–

..
Cl Cl 3
Hybridisation sp
3
Hybridisation sp d
Structure Angular Structure linear
.. – ..
[I –..I – I]
.. F –..Xe – F
..
3
Hybridisation sp d Hybridisation sp d
3
Structure linear Structure linear

 
NNO
Hybridisation sp
Structure linear

Only BeCl2, N3–, N2O and NO2 are linear with sp-hybridisation.

17. Answer (6)
H2 12s Diamagnetic
He 2 12s 1*s1 Paramagnetic
Li2 12s 1*s 2 22s Diamagnetic
Be2 12s 1*s2 22s 2*s2 Diamagnetic
B2 12s 1*s 2 22s 2*s 2 12 px  12 py Paramagnetic
C2 12s 1*s 2 22s 2*s 2 22 px  22 py Diamagnetic
N2 12s 1*s 2 22s 2*s 2 22 px  22 py 22 pz Diamagnetic
O2 12s 1*s2 22s 2*s2 22 pz 22 px  22 py *2 p1  2* p1 Paramagnetic
x y
F2 12s 1*s2 22s *2s2 22 pz 22 px  22 py , 2* p2  2* p2 Diamagnetic
x y
18. Answer (6)
Br
Br Br
Te It has one lone pair
Br Br
Br
Br It has two lone pairs

F
F
F
SN It has no lone pair
F
F
F
F
Xe It has three lone pairs
F
19. Answer (6)

Polar liquid will be attracted towards charged comb. Hence liquid showing deflection are HF, H2O, NH3, H2O2,
CHCl3, C6H5Cl.

20. Answer (–2640.00 to –2620.00) or (–5280.00 to –5240.00)
Potential energy of H-atom is taken as zero when electron and nucleus are at infinite distance (given).
 P.E. of a H-atom with electron in its ground state
= – 27.2 eV (from Bohr's Model)
At internuclear distance 'd0; electron-electron repulsion and nucleus-nucleus repulsion are absent.
 P.E. of two H-atom = – 2 × 27.2 eV = – 54.4 eV
54.4  1.6  10 19  6.023  10 23

=  kJ/mol
1000
= – 5242.42 kJ/mol


Chapter 4
States of Matter
1. Answer (B)
Correction factor in pressure is directly proportional to square of density.
an2
 It is .
V2
2. Answer (C)
 a 
 P  2  V = RT
 V 
a
PV + = RT
V
a
PV = RT –
V
 1
So, plot of (PV) vs   has slope – a.
V
20.1  24.6
 Slope =  – 1.5
3
 a = 1.5 atm L2 mol–2
3. Answer (B)
Due to symmetrical graph given, the average value of velocity will be at the middle, which is also most probable
velocity.
While calculating rms speed, we have to take average of square of speeds and its root. In square of speeds,
higher speeds will give more contribution. So the value will be more than the average value.
4. Answer (A, C, D) or (A, C)

 a  a
Because V is very large, so in Van der Waal’s equation  P  2  (V – b) = RT, 2 and b are neglected and
 V  V
equation becomes PV = RT. Coefficients depends on the identity of the gas but are independent of the temperature.
Real gas exert lower pressure than the same gas behaving ideally due to intermolecular force of attraction.
5. Answer (A, C, D)
According to Kinetic theory of gases,

(i) Collisions are always elastic

Fraction of
(iii) molecule
Velocity
(iv) Between collisions the molecules move in straight lines with constant velocity.
6. Answer (C)
V(r)
0
r
As per given conditions atoms have no interaction at long range but repell at short range.
7. Answer (A, C, D)
3
EK  KT Average kinetic energy depends only on absolute temperature
2
K = Boltzmann constant
Urms  T
3RT
Urms  1
M Urms 
M
Using above formulae, correct statements are (A, C, D).
8. Answer (C)
x 40

24 – x 10
x
2
24 – x
x = 16
9. Answer (D)
Increased collision frequency of X with the inert gas as compared to that of y with the inert gas. Therefore,
the experimental value of d is found to be smaller than the estimate obtained using Graham's law.
10. Answer A(p, s); B(r); C(p, q); D(p, s)
11. Answer (4)
3RT
Urms( X ) 
M
2RT
Vmp( Y ) 
M
Equating both, we get
3R(400) 2R(60)

40 X
X=4

12. Answer (7)

1 atm PT = 1 atm
1 atm vapour pressure of compound = 0.68 atm
 PHe = 0.32
PHeV = nHeRT
0.1 0.082  273

V= = 7 litre
0.32
13. Answer (4)
Diffusion coefficient 
Here  = mean free path
 = mean speed
T
since  
P
and   T
T T
 Diffusion coefficient 
P
As per question, 'T' is increased four times and 'P' is increased two times.
Hence, diffusion coefficient becomes four times.
14. Answer (2.20 to 2.23)
From figure - 1,
51 5
nA = 
R  400 400 R
1 3 3 1
nB =  
R  300 300 R 100 R
From figure. 2,
After the system attains equilibrium,
PA = PB and TA = TB = T
n A RT nBRT
 
VA VB
5 1
 
400 R.VA 100 R.VB
VA 5 4
   VB  VA
VB 4 5
4
 VA + VB = 4 m3  VA + VA  4
5
20
 VA = = 2.22 m3
9

Chapter 5
Thermodynamics
1. Answer (B)
G° = H° – TS° = –2.303 RT log10K
= – 54.07 × 103 – 298 × 10 = – 57050 JK–1mol–1
G° = – 2.303 RT log10K
– 57050 = –2.303 × 8.314 × 298 log10K
 10 = log10K
2. Answer (A)
At 373 K H2O(l) is in equilibrium with H2O(g).
3. Answer (B)
Cl2 is considered as standard state of chlorine and enthalpy of formation in standard state is zero (assumed).
4. Answer (C)
Bond energy of C—C is considered to be 100 kcal mol–1 approximately.
5. Answer (D)
H = Bond energy in reactant – Bond energy in product
 225 = (1410 + 330) – (700 + HCC)
 HCC = 1740 – 925 = 815 kJ/mol
6. Answer (C)
C6H12O6(s) + 6O2(g)  6CO2(g) + 6H2O(l)
H° = 6 (–400) + 6(–300) – (–1300)
H° = –2900 kJ/mol
2900
H    16.11 kJ/gm
180
7. Answer (B)
Given conditions are boiling conditions for water due to which
Stotal = 0
Ssystem + Ssurroundings = 0
Ssystem = –Ssurroundings
For process, Ssystem > 0
Ssurroundings < 0

8. Answer (C)
For isothermal change U = 0
 q = – w = PexU
= 3 × (2 – 1)
= 3 L atm
= 3  101.3 J
Heat released from surrounding = –3 × 101.3 J
–3  101.3
So, Ssurrounding   –1.013 JK –1
300
9. Answer (A)
Gº = V·P
 2900  2  10 –6 P
2900  106
 P  Pa
2
PF–1 = 14500 bar
 PF = 14501 bar
10. Answer (A, D)
Internal energy and Molar enthalpy are state functions.
11. Answer (A, B)
Molar conductivity and electromotive force are intensive properties.
12. Answer (A, C)
Entropy is a state function. In this diagram initial state is X and final state is Z.
Therefore, SX  Z = SX  Y + SY  Z
Work is a path function. Therefore W X  Y  Z = W X  Y
13. Answer (A, C, D)
Obviously here T1 > T3 from the graph and T 1 = T2 as process curve is isothermal. Uisothermal = 0 and that
for an adiabatic process is negative so option (D) is correct. Now W isothermal > W adiabatic also hence answer
is (A, C, D).
Work against zero external pressure is zero q = 0 due to insulated boundary
So, q = 0
U = 0
T = 0
 T2 = T 1
and P2V2 = P1V1
(A) In free expansion, Pex = 0  w = 0
For isothermal free expansion of an ideal gas,
U = 0  q = 0
 Adiabatic also.

(B)
WIsothermal > WAdiabatic

Isothermal
P
Adiabatic
V1 V V2
(C) Area under irreversible P v/s V graph in compression is more than that under P-V graph of reversible
compression.
(P1, V1 )
P1 (P1, V2)
Irreversible
P
Reversible
P2 (P2, V2)
V1 V V2
16. Answer (B, C)
A – C (Isochoric process)  wAC = 0 and UAC = qAC
B – C (Isobaric process)  UBC = qBC + wBC
wBC = –P2(V1 – V2) = P2(V2 – V1)
qBC = HBC
 (T)A–C = (T)B–C
 UBC = UAC = qAC
HBC = HAC = qBC
 T2 > T 1
HCA and UCA are negative
HCA = UCA + VP

(–ve)
 HCA < UCA

A – B (Isothermal process)
UAB = HAB = 0
V2
wAB = –nRT1 ln
V1
17. Answer (A, D)
Since standard enthalpy of formation of a compound is the change in the standard enthalpy when one mole
of the compound is formed starting from requisite amount of constituent elements in standard state.
Hence only (A) and (D) options are correct.
The following expression of P-V work done
W    Pext dV
is applicable for reversible isobaric as well as isothermal and adiabatic process. If Pext is substituted for a Vander
Waals equation then it becomes
 RT a 
W     2  dV
 V  b V 
But it is not applicable for irreversible process which are carried out very fast. So work done is calculated
assuming final pressure remains constant throughout the process.
19. Answer (A, B, D)
I  II  reversible, isothermal expansion,
T  constant, V  +ve, S  +ve H  0
II  III  Reversible, adiabatic expansion
Q = 0, V  +ve, S  0
p II –ve slope - isothemal < adi a batic

I  II  Isothermal
(A) II  III  Adiab atic
III
I
p
I  II  T constant
(B) II II  III  adiab atic
III
III
H
I  II   S  +ve, H  0
(C) II  III  S  0, H  –ve
I II
I II
T
I  II  S  +ve, T = 0
(D) II  III  S  0
III
20. Answer (C)

21. Answer (B)

Pressure K L
N M
Volume
As PV product increases temperature increases as PV product decreases temperature decreases.

PV product increases (K  L, N  K)
PV product decreases (M  N, L  M)
Isochoric process are (L  M, N  K)
22. Answer A(p, r, s); B(r, s); C(t); D(p, q, t)
Phase is the part which is physically and chemically uniform throughout. During phase transition from solid to
liquid or gas, S = +ve.
In 2H  H2, S is –ve because no. of entities decreases.
23. Answer A(R, T); B(P, Q, S); C(P, Q, S); D(P, Q, S, T)

(A)  R, T


H2O(  ) 
 H2O(S)
It is at equilibrium at 273 K and 1 atm
So Ssys is negative
As it is equilibrium process so G = 0
(B)  P, Q, S
Expansion of 1 mole of an ideal gas in vacuum under isolated condition
Hence, w = 0
and qp = CpdT ( dT = 0)
 q=0
U = CvdT ( dT = 0)
U = 0
(C)  P, Q, S
Mixing of two ideal gases at constant temperature
Hence, T = 0
 q=0
U = 0
also w = 0 (U = q + w)
(D)  P, Q, S, T
Reversible heating and cooling of gas follows same path also initial and final position is same.

q0 
Hence,  Path same
w  0
U  0 
 State function
G  0 
24. Answer (9)
q = heat capacity × T
1.125 kJ for 3.5 g
for 1 mole = 9 kJ
25. Answer (2)
Solid line path work done (W s) is isothermal beacuse PV is constant at each point & dash line path work
done (W d) is isobaric.
V2
Total work done on solid line path (W s) = 2.303nRT log
V1
V2
= 2.303PV log
V1
5.5
= 2.303 × 2log
0.5
 4.6 l atm
Total work done on dash line path (W d) = 4 × 1.5 + 1 × 1 + 0.5 × 2.5
= 8.255 l atm.
Wd 8.25
  2 (closest integer)
Ws 4.6
26. Answer (935)
SnO2(s) + C(s)  Sn(s) + CO2(g)
 r Ho  394  581  187 kJ/mol
 r So  52  210  56  6  200 J / K  mol
 r Ho
Tmin (at which reduction will take place) =  935 K
 r So
27. Answer (10)

Process I is adiabatic reversible
Process II is reversible isothermal process
Process I - (Adiabatic Reversible)
U
 450 – 2250
R
U = –1800R
W I = U = –1800R

Process II - (Reversible Isothermal Process)

T1 = 900 K
Calculation of T2 after reversible adiabatic process
–1800R = nCv(T2 – T1)
5
–1800R  1 R(T2 – 900)
2
T2 = 180 K
v3
WII  –nRT2 ln  WI
v2
v3
 –1 R  180ln  –1800R
v2
v3
ln  10
v2


Chapter 6
Equilibrium
1. Answer (D)
At equivalence point
N1V1  N2 V2
(base) (acid)
2 2
2.5 × = ×V
5 15
V = 7.5 ml
 Milli equivalents of salt = 1
Ch2 K w 10 –14
Kh =    10–2
1– h K b 10–12
0.1h2
10 –2 
1– h
h = 0.27
[H+] = Ch = 0.1 × 0.27
Hence [H+] = 2.7 × 10–2 M
2. Answer (D)
(MX) S2 = 4.0 × 10–8
S = 2.0 × 10–4
(MX2) 4S3 = 3.2 × 10–14
S3 = 0.8 × 10–14
S3 = 8 × 10–15
S = 2 × 10–5
(M3X) 27S4 = 2.7 × 10–15
S = 1 × 10–4
 Order is MX > M3X > MX2
3. Answer (C, D)
Solution of weak acid and its salt with strong base behave like buffer.
4. Answer (A)

Rate with respect to weak acid
R1 = K[H+]WA[ester]
and rate with respect to strong acid
R2 = K[H+]SA[ester]
R1 [H+ ]WA 1
 = + =
R 2 [H ]SA 100
[H ]SA 1
 H     0.01M  C
WA 100 100
 = 0.01
Ka for weak acid = C2
= 1(0.01)2 = 1 × 10–4
5. Answer (A, B, D)
CaCO3 (s)  CaO(s)  CO2 (g)
K  PCO2
K is only dependent on temperature and it is independent of the amount of reactant or product.
H is dependent on temperature according to Kirchoff's equation but independent of addition of catalyst.
6. Answer (B)
The solubility of Ag2CrO4 = CrO –2 

 4 
K sp 1.1  10 –12
  –2 
 1.1  10 –10 mol L1
CrO 4    2

(0.1) 2
 Ag
 
7. Answer (B)
On increasing temperature forward as well as backward reaction rate increases due to which initially %yield of
NH3 is higher at T2 K but equilibrium attain at lower time at T 2 K hence its yield at equilibrium is low at T2 K.
8. Answer (A, D)
With increase in temperature, the value of rate constant for exothermic reaction decreases because favourable
change in entropy of surroundings decreases.
9. Answer (A, C)
ln K1 T2

ln K 2 T 1
 On increasing temperature, K decreases.
 H° < 0
From graph K > 1  G° < 0
– H S

ln K1 T1R R T
  2
ln K 2 H S T1

T2R R
( H  T1S) T2 T2

( H  T2 S) T1 T1
–H° + T1S° > –H° + T2S°

 S° < 0
10. Answer (A)
Exp-1
Energy released = 5.7 kJ
Heat absorber by temperature rise = 200 × 4.2 × 5.7 = 2 × 42 × 57 = 4.788 kJ
Calorimetric constant = 5.7 – 4.788 = 0.912 J
Exp-2
Q = 200 × 4.2 × 5.6 = 4.704 kJ
Net energy = 4.704 + 0.912 = 5.616 kJ
Per mole of neutralization energy released = 56.16 kJ
Dissociation energy = 57 – 56.16 = 0.84 kJ  1 kJ
11. Answer (B)
Buffer is formed.
CH3COO  
pH  pK a  log  
CH3COOH
As per given question concentration of CH3COO– and CH3COOH is equal.
pH = pKa = –log2 + 5 = 4.7
12. Answer (B)
X2(g) 


 2X(g)
Initial mole: 1 0
  eqbm 
Moles at equilibrium : 1   eqbm
2 
eqbm
1 eqbm
2 P P
Partial pressure :
 eqbm   eqbm 
1   1  
2  2 
2
(Px )2 eqbmP
 Kp = 
Px2   2eqbm 
1  
4 
42eqbm × P
 Kp =
4   2
eqbm 
Since P = 2 bar
82eqbm
So, K p 
4   2
eqbm 
13. Answer (C)
Since, G°, is positive

It means Kp < 1.
Kp = –2.303 RT log Kp
So,  eqbm = 0.7
8  (0.7)2
Kp = 1
4  (0.7)2
Hence, eqbm  0.7
14. Answer (D)
20  0.1– 10  0.1 1
(P) CH3 COOHold  30

30
CH COO –  = 1
 3  old 30
Buffer with [Salt] = [Acid]
pH does not change on dilution (P)  (1)
20 × 0.1 2
(Q) [ CH 3COO– ] old = =
40 40
2
[ CH 3COO– ] new = 80
–
 CH3 COOH+ OH–
CH 3COO + H2O 
c x x
x 2 [OH– ]old
2
[OH– ]new
2
Kh = = =
c 2 / 40 2 / 80
– 2
 [OH ] new = [OH ]old
– 2
[OH– ]old
 [OH– ]new =
2
 [H+ ]new = 2[H+ ]old

(Q)  (5)
20 × 0.1 2
(R) [NH+4 ]old = =
40 40
2
[NH +4 ]new =
80
 NH4 OH + H+
NH+4 + H2 O 
c y y
+ 2 + 2
y 2 [H ]old [Hnew ]
Kh = = =
c  2 / 40   2 / 80 
+ [H+old ]2
 [Hnew ]2 =
2
+ [H+ ]old
[Hnew ]=
2
(R)  (4)
–
(S) For a saturated solution, [OH ] = 3 2K sp
irrespective of volume of solution. [H+] remains constant.

(S)  (1)
15. Answer (8)
pK a 4 2
pH = 7   log C = 7   8
2 2 2
16. Answer (3)
In basic medium, red litmus paper turn blue


(1) CN  H2O 
 HCN  OH



(2) CO32  H2 O  
 HCO 3  OH



(3) CN  H2O 
 HCN  OH

17. Answer (6)

H2SO4, H3PO3, H2CO3, H2CrO4 and H2SO3 and H2S2O7 will behave as dibasic acid.
18. Answer (7)
 Ag  Cl
AgCl 
x xy
K sp1 = 1.6 × 10–10 = x(x + y) ...(i)
 Cu  Cl
CuCl 
y yx
K sp2  1 10 –6  y(x  y) ...(ii)
From equation (i) and (ii),

K sp1 x
 1.6  10 –4  ...(iii)
K sp2 y
 x = 1.6 × 10–4 y
 K sp1  1.6  10 –10  1.6  10 –4 y(1.6  10 –4 y  y)
 10–6 = y2(1.6 × 10–4 + 1)

 y = 10–3  x = 1.6 × 10–7
 [Ag+] = x = 1.6 × 10–7
19. Answer (4.30 – 4.60)
AB(s)  A  (aq)  B  (aq)

s s x
B   H3  HB
s x 10
Ka of HB = 1 × 10–8
H  B   s  x   103

Ka      
HB x

sx
 105 s  x  x  10 5
x
Ksp = [A+] [B–] = s(s–x) = 2 × 10–10
Sx = 2 × 10–5 s2–sx = 2 × 10–10
s2 = 2 × 10–10 + 2 × 10–5
s2 = 2 × 10–5
s  20  103  4.47  103

20. Answer [(–14.7) – (–14.5)]
1
(i) 2Cu(s)  O2 (g)  Cu2O(s), G  –78 kJ / mole
2
1
(ii) H2 (g)  O2 (g)  H2O(g), G  –178 kJ / mole
2
(i) – (ii)
2Cu(s)  H2O(g)  Cu2O(s)  H2 (g), G  100 kJ
G  G  RT ln K  0
 pH 
 105  8  1250 ln  2 0
 pH O 
 2 
 pH 
10 4 ln  2   105  0
 pH O 
 2 
ln pH2 – ln pH2O  –10
–2
Now, pH2O  XH2O  PTotal  0.01 1  10
 ln pH2  2 ln10  –10
ln pH2  4.6  –10
ln pH2  –14.60
21. Answer (8.70 – 9.10)

2+ 2– 17
Fe (aq) + S (aq) FeS(s), K = 1.6 × 10
t0 0.03 0.1 –
t eq x 0.1 – 0.03 –
 0.07
1
 x(0.07)   10 17
1.6
 x  8.93  10 17 M
 Y = 8.93
22. Answer (0.25)
A B
pA = 1 bar (maintained throughout the experiment)

From diagram:
PB
K eq 1000 K 
PA
 10
 (rG°)1000 K = –RTlnKeq = – 1000Rln10
PB'
(Keq)2000 =  100
PA
(rG°)2000 K = –2000 Rln100
( r G)1000 K 1000 Rln10

 
( r G)2000 K 2000Rln100
1
  0.25
4
23. Answer (2.80 to 3.20)
B + HA  BH+ + A–
Volume of HA used till equivalence point = 6 mL (from given diagram)
At half of equivalence point, solution will be basic buffer with B and BH+.
[BH ]
 pOH  pK b  log
[B]
At half equivalence point : [BH+] = [B]
 pOH = pKb = 14 – 11 = 3
 pK b  3
24. Answer (0.2)
ZnS(s) Zn2  (aq)  S 2  (aq)
[Zn2+] = 0.05 M
K sp (ZnS)
 [S2–]max (to prevent precipitation) =
[Zn2  ]
1.25  1022
=  2.5  10 21 M
0.05
H2S 2H+ + S2–
[H ]2 [S 2  ]
K1  K 2 
[H2 S]
[H ]2  2.5  1021
 1 1021 
0.1
1
 [H ]2 
25
1
 [H ]   0.2 M
5
Ans  0.20

25. Answer (166.28)


X(s) 
 Y(s)  Z(g)
pz
Given K 
po
Hº
lnK  lnA –
RT
pz H
 ln o
 ln A –
p RT
 p 
d ln  oz 
pz 1  p   – Hº
Slope of ln vs is  
po T  1 R
d 
T
– Hº
From the graph, we have  –2  104
R
4
  Hº  2  10  8.314 J
Hº = 166.28 kJ mol–1
26. Answer (141.34)
–RTln K = Gº = Hº – TSº
Hº Sº
lnk  – 
RT R
Sº
 17
R
Sº = 17R
= 141.338 J K–1


Chapter 7
Redox Reactions and Volumetric Analysis

1. Answer (D)
2. Answer (B)
( 5) ( 2) (0) ( 3)
HNO3 , NO, N2 , NH4Cl
3. Answer (A)
H2O2 acting as a reducing agent with KIO4 and H2O2 acting as an oxidising agent with NH2OH.
4. Answer (A)
Oxidation state
H3PO4 P=+5
H4P2O6 P=+4
H3PO3 P=+3
H3PO2 P=+1
H3PO4 > H4P2O6 > H3PO3 > H3PO2
5. Answer (A, C, D)
MnO4 
aq
 MnO2
–
acidic
MnO4   Mn2 
Therefore in aqueous and in acidic mediums 3 and 5 electrons will transfer respecitvely.
6. Answer (A, B, D) or (A, D)
Balanced chemical equation is 6I  ClO3  6H2SO 4 
 Cl  6HSO 4  3I2  3H2O
Here, H2O is produced and I– is oxidized.
7. Answer (C)
25  N  45  0.25
N  48  0.25
25
 N = 0.48 M
0.48
 M  0.24 M
2
8. Answer (A)
Oxoacid is HOCl. The anhydride of oxoacid is Cl2O.
9. Answer (2)
F will only exhibit –1 oxidation state except zero.
and Na will exhibit +1 oxidation state.

10. Answer (5)
Br2  2Br – 
  5 Br2  2Br  10e 
5 –

2 e 
Br2 + 5Br2  10NaBr + 2NaBrO3 + 6CO2 + 6Na2CO3

3Br2 + 3Na2CO3  5NaBr + NaBrO3 + 3CO2
11. Answer (8)
1.25  29.2  1000

Molarity of HCl =  10(M)
100  1 36.5
V × 10 = 200 × 0.4
V = 8 mL
12. Answer (7)
K2Cr2O7 + I– + H+  I2
CuSO4 + I–  I2
H2O2 + I–  I2
Cl2 + I–  I2
O 3 + I–  I 2
FeCl3 + I–  I2
HNO3 + I–  I2
13. Answer (6)
3S2O3– + 8MnO4–  6SO42– + 8MnO2
 8 moles of MnO4– form 6 moles of SO42–
14. Answer (120 – 130)
From POAC,
m moles of MnCl2 = m moles of KMnO4 = x((let)
and, meq of KMnO4 = meq of oxalic acid
 225 
x5   2
 90 
x=1
 m moles of MnCl2 = 1
mg of MnCl2 = (55 + 71) = 126 mg
15. Answer (0.11)
Titration of oxalic acid solution with NaOH solution using phenolphthalein as an indicator.
H2C2O4 + NaOH  Na2C2O4 + H2O
At end point when phenolphthalein shows permanent faint pink colour, solution will have Na 2C2O4.
 Equivalent of H2C2O4 reacted = Equivalent of NaOH reacted
 5 × 0.1 × 2 = VNaOH × MNaOH

Using average of the NaOH volume used in five experiments.
(VNaOH)avg = 9 mL
52
 MNaOH =  0.11 mol/L
10  9
16. Answer (0)
2MnO 4  H2 O  I  2MnO2  2OH  IO3
17. Answer (1.875)

18. Answer (18.75)
Solution of Question Nos. 17 and 18
8H+ + 5Fe2+ + MnO4–  5Fe3+ + Mn2+ + 4H2O
For 25 ml,
meq of Fe2+ = meq of MnO4–
= 12.5 × 0.03 × 5
For 250 ml,
12.5  0.03  5  250

mmoles of Fe2+ 
25
18.75
moles of Fe2+  mol
1000
= 18.75 × 10–3 mol

= 1.875 × 10–2 mol
x = 1.875
Weight of Fe2+ = 1.875 × 10–2 × 56 = 1.05 g
1.05
% purity of Fe2+   100 = 18.75%
5.6
y = 18.75%


Chapter 8
The Solid State

1. Answer (D)
Area covered by particle

Packing efficiency =
Total area
2  r 2
=
a2
2  r 2
=
(2 2 r)2

=
4
2. Answer (B)
1 1
Number of X atoms/ ions per unit cell = 8   6  4
8 2
1
Number of M atoms/ions per unit cell = 1  4  2
4
 Empirical formula of the compound is MX2.
3. Answer (A)
Cation A + occupies octahedral void formed by anions X –. The maximum radius ratio for a cation to
accommodate a octahedral void without distortion is 0.414. Radius of anion X– is 250 pm.
RA
 0.414
R X
 R A   0.414  250  103.50  104 pm

4. Answer (B)
a = edge length of unit cell
2ry = a

2 rx  ry  2a 
2rx  a  2a
2rx  a  
2 –1
rx = 0.207 a
3  vol. of x  vol. of y
Packing fraction = vol. of unit cell
4 4
3  rx3     ry3
 3 3
a3
4
4    (0.207a)3     (0.5 a)3
 3
a3
 0.63
5. Answer (B, C)
ASchottky defect are favoured by small difference in sizes of cation and anion.
BIn Frenkel defect cations are dislocated therefore. (True)
CElectron trapped in lattice are called F-centre. (True)
DSchottky defect decrease density.
6. Answer (A)
The formula will be MgAl2O4
Total tetrahedral voids = 8
Total octahedral voids = 4
1
as only one Mg atom is present hence, n =
8
2 1
as there are two Al atoms are present hence, m = =
4 2
1 1
 m, n =,
2 8
7. Answer (B, C, D)
In CCP, the coordination number for atom in top-most layer is 9.
8. Answer (A, C)
1
Contribution of M = 21
2
1
Contribution of X =  4  1
4
Formula = MX
a2 a 2 3 3
Distance between M and X =   a a = 0.866 a
4 2 4 2
Both cation and anion have same co-ordination number, i.e., 8.
Assuming, anions are in contact, the ratio of ionic radii of cation M to anion X is 0.732, the minimum radius
ratio for a cubical void.
9. Answer (B)
1 1
The number of effective atom in a unit cell = 12   2   3 1 = 6
6 2  no of atoms in 
corner   Face   hexagonal primitive 
 Centre   
10. Answer (A)  unit cell 
Volume of HCP unit cell = Base area × height
 3 2  2 
= 6  a  4r
 4  3 
 
3  2 
= 6 2r 2   4r = 24 2 r 3
4  3 

11. Answer (D)

4 3
r 6
3
Packing fraction =
Base area  Height
4 3
6 r
3
= = 0.74
 
 6  3 a 2   4r 2
 4  3
 
% of empty space = (1 – 0.74) × 100 = 26%
12. Answer A(p, s); B(p, q); C(q); D(q, r)
13. Answer (7)
4 3
Volume of 1 Ag atom = r
3
4 3 108
 r  cm3
3 6.023  1023  10.5
 r = 1.6 × 10–8 cm
r = 1.6 × 10–10 m
 Number of Ag atoms in 10–12 m2
r2 × n = 10–12 m2
10 –12
n
3.14  (1.6  10 –10 )2
10  107
n
8
n = 1.25 × 107
 The value of x = 7
14. Answer (8)
Truncated octahedron contain 14 faces out of that eight are hexagonal and six are square.
15. Answer (2)
a = 4  10–8 cm (a = edge length)
d=8g cm–3 (density)
ZM
d M = molecular mass (g/mol)
NA a3
Z  number of atom in 1 unit cell

3
dNA a 8  6  10  64  10–24
23
M   76.8 g/mol
Z 4
Mole of solid in 256 g = 3.33 moles
No. of atom = 3.33  NA = 20  1023 = 2  1024

16. Answer (2.9 – 3.1)

MX has NaCl type structure.
From instructions, it is clear that in MX ionic solid.
Cation M - undergoes CCP
anion X - occupies all octahedral voids
(i) No. of anions left = 1
(ii) No. of anions added = 3
No. of cations left = 1
(iii) No. of cations left = 0
(iv) No. of cations added = 1
No. of anions left = 3
Final no. of cations in an unit cell = 1
Final no. of anions in an unit cell = 3
3
 ratio = = 3.00
1


Chapter 9
Solutions
1. Answer (A)
Tf = i × kf × m
20 1000
2 = i × 1.72 × 
172 50
i = 0.5
2. Answer (A)
As the mole fraction of N2 gas is 0.8 and total pressure is 5 atm. Therefore the partial pressure of N2 will be 4 atm.
Now, Pa = KH Ha
n
4 = 1 × 105  ( n is much less than 10)
n  10
n = 4 × 10–4 moles
3. Answer (C)
wt. of solute 1000

M 
mol. wt. of solute volume of solution
120 1000
M   2.05
60 1120
1.15
4. Answer (A)
0.1
329
Tf – Tf = 0 – Tf = 4 × 1.86 ×
100
1000
0.1 1000
Tf  4  1.86    0.023
329 100
5. Answer (A)
Tb = 1 × Kb × m
 2 = 1 × 0.76 × m
2
 m=  2.63
0.76
760  PS 18
  2.63 
760 1000
 Ps = 724 mmHg

6. Answer (C)
 W  1000 
Tf = iK f  2 
 M2  W1 
 34.5  1000 
= 1 2  =3K
 46  500 
273 (K) – Tf = 3 (K)
 Tf = 270 K
Also, with decrease in temperature, V.P. decreases.
 Graph (C) is correct.
7. Answer (B, C, D)
Benzene and naphthalene form an ideal solution. For an ideal solution, H = 0, Ssystem > 0 and Ssurroundings
= 0 because there is no exchange of heat energy between system and surroundings.
8. Answer (A, B)
Mixture Nature of deviation from Raoult's Law
Carbon tetrachloride + methanol +ve
Carbon disulphide + acetone +ve
Benzene + toluene Ideal solution
Phenol + aniline –ve deviation
9. Answer (A, D)
pL
xM = 1 xM  xM = 0
Pure M xL = 1
Pure L
Point Z represents v.p. of pure liquid L
At xL  1, solution is very dilute, L becomes solvent. Very dilute solution of M in L is nearly ideal and obey
Raoults law (pL = xLpL°)
Also, there is positive deviation indicated by graph above dotted line (expected for ideal solution)
 L-M interaction < L - L & M - M Interactions.

10. Answer (D)
0 .1 1000
Tf = kfm = 2 × × = 4.83
0 .9 46
Tf =T°f – Tf
Tf =155.7 – 4.83  150.9

11. Answer (B)
Water is solute
Po  PS
= Xsolute
Po
40  PS
= 0.1
40
PS =36 mm of Hg
Here ethanol is considered as non-volalite solute as given in statement of paragraph.
12. Answer (B)
Here, water is solvent and ethanol is solute.
Tb = kb × m
0.1 1000
= 0.52 ×
0.9  18
= 3.2084
Now, B.P. of solution = 373 + 3.2084
= 376.2084
13. Answer (2)
 = 0.5


MX2 
 M
2
 2X 
(1 )  2
1      2
i
1
i = 1 + 2
i = 1 + 2 × 0.5 = 2
14. Answer (9)
0.1 1000
Molality (m) = ...(i)
0.9  MWsolvent
0.1 2  1000
Molarity (M) = ...(ii)
 0.9  MWsolvent  0.1 MWsolute 
Equating (i) & (ii),
0.1 1000 0.1 2  1000


0.9  MWsolvent  0.9  MWsolvent  0.1 MWsolute 
MWsolute
So, 9
MWsolvent
15. Answer (18.5 – 19.5)

P°A = 20 Torr
1
For equimolar binary solution : xA = xB =
2

PA° + PB°
 = 45
2
 P°B = 70 Torr
If mole fractions are xA & xB
P°B + (P°A – P°B)xA = 22.5
 70 + (20 – 70)xA = 22.5
47.5 2.5
 xA = and xB =
50 50
x A 47.5
= = 19.00
xB 2.5
16. Answer (0.04 – 0.06)

When NaCl as solute is used
For solvent X For solvent Y
2 = 2Kb m 1 = 2 × Kb m
Kb
 =2
K b
When solute S is used then molality in both solvent is equal.
For solvent X For solvent Y
a 0.7
i = 1– i = 1– = 0.65
2 2
 a
Tb =  1 –  K b m Tb = (0.65)Kbm
 2
 a
1– × 2
Tb  2
3= =
Tb 0.65
 3
1– = × 0.65
2 2
 3
= 1 – × 0.65
2 2
 = 0.05
17. Answer (0.97 – 1.06)
P° – P nsolute
 = x solute =
P° nsolute + nsolvent
10 nsolute
 =  nsolute + 0.5 = 65 nsolute
650 nsolute + 0.5
0.5 1
 nsolute = =
64 2 × 64
Tf = Kf  m
1
= 5.12 ×1000 ×
2 × 64 × 39
= 1.02 K

18. Answer (2.80 – 3.05)

nurea
urea = 0.05 =
nwater  nurea
nurea
0.05 = 900
+ nurea
18
 nurea = 2.63 mol
Mass of urea = 2.63 × 60 g/mol Molar Mass (urea) = 60 g/mol
= 157.8 g
Mass of Solution = 157.8 + 900 = 1057.8 g
1057.8
Volume of Solution = = 881.5 ml
1.2
2.63
Molarity of Solution =  1000 = 2.98 M
881.5
19. Answer (0.2)
Using Raoult's law
PT  x A PAo  xB  PBo
 0.3  0.25  PAo  0.75  PBo ... (i)
0.4  0.5  PAo  0.5  PBo ... (ii)
From (i) and (ii)
PAo  0.6 bar
PBo  0.2 bar
 Ans  0.20
20. Answer (100.1)
21. Answer (2.5)

Sol. of Q. No. 20 and 21
Given molality of AgNO3 solution is 0.1 molal (solution-A)
Tb = ikbm
AgNO3  Ag+ + NO3–
van't Hoff factor (i) for AgNO3 = 2
Tb = 2 × 0.5 × 0.1
(Ts – Tº) = 0.1
(Ts)A = 100.1ºC, so x = 100.1
Now solution-A of equal volume is mixed with 0.1 molal BaCl2 solution to get solution-B. AgNO3 reacts with
BaCl2 to form AgCl(s).
0.1 mole of AgNO3 present in 1000 gram solvent or 1017 gram or 1017 mL solution,
milli moles of AgNO3 in V ml 0.1 molal solution is nearly 0.1 V. Similarly in BaCl2.

2AgNO3(aq) + BaCl2(aq)  2AgCl(s) + Ba(NO3)2 (aq)

0.1 V 0.1 V 0 0
0 0.05 V 0.1 V 0.05 V
 0.05V  3 0.05V  3 
Tb     0.5  0.075
 2V 2V 
 Ts B  100.075º C
(Ts)A – (Ts)B = 100.1 – 100.075 = 0.025ºC

= 2.5 × 10–2 ºC
So x = 100.1 and |y| = 2.5


Chapter 10
Electrochemistry
1. Answer (B)
W it

E F
W 10  10 3  t
 0.01 2 
E 96500
t = 19.3 × 104 s
2. Answer (D)
Ag+ and K+ have nearly same ionic mobility.
AgNO3 + KCl  AgCl(s) + KNO3
conc. of KCl
3. Answer (D)
0.0591 [Fe2 ]2
Ecell  1.67  log
4 pO2  [H ]4
0.0581 (10 3 )2
 1.67  log
4 0.1 (103 )4
0.0591 10 6
 1.67  log
4 1013
0.0591
 1.67  log107
4
0.0591
 1.67   7  1.57
4
4. Answer (D)
H2 (g)  2H  2e –
M4   2e –  M2
H2 (g)  M4   2H  M2 
H 2  M2 
Qx 
M4 
(1)2  M2  M2  , º

  Ecell  Eº 4 – Eº 
/M2 
M4   M4  M H /H2
= 0.151 – 0
= 0.151 V
0.059
E  0.151– log10 x
2
0.059
0.092  0.151– log10 x
2
On solving, we get x = 2
5. Answer (A)
Zn | ZnSO4 || CuSO4 | Cu
(aq) (aq)
G =G° + RT In Q
 [Zn2 ] 10 
G = G° + 2.303 RT log Q  Q   
 [Cu2 ] 1 
G° = – nFE°Cell
= – 2F  1.1
= – 2.2 F
10
G = – 2.2 F + 2.303 RT log
1
G  2.303 RT – 2.2 F
6. Answer (B)
Sodium stearate  CH3(CH2)16COO–Na+
At normal or low concentration, it behaves as strong electrolyte and for strong electrolyte, molar conductance
(m) decreases with increase in concentration.
But only above particular concentration sodium stearate forms aggregates that concentration is called as CMC.
Since number of ions decreases, hence m decreases.
CMC
m
7. Answer (A, B, D)
Oxidation of V
E° = 0.96 – (–1.19) = 2.15 V
For Fe,
E° = 0.96 – (–0.04) = 1.0 V

For Au,
E° = 0.96 – 1.4 = – 0.044 V (not feasible)
For Hg
E° = 0.96 – 0.86 = 0.1 V
8. Answer (A, C) or (A)
In a galvanic cell, the salt bridge does not participate in the cell reaction, stops diffusion of ions from one
electrode to another and is not necessary for the occurrence of the cell reaction.
9. Answer (A, B, C)
X + Y2+  X2+ + Y
0.06  10 –3 
E  E – log10  
2  10 –1 
 
E = E° + 0.06
(A) E° = –(– .4) + (– .24) = .16 > 0
(B) E° = –(– .4) + (– .44) = –.04 < 0 and Ecell = –0.04 + 0.06 = +0.02 > 0
(C) E° = –(– .24) + (– .13) = .11 > 0
(D) E° = –(– .24) + (– .44) = –.2 < 0
 Ecell = –0.2 + 0.06 = –0.14 < 0
 If Ecell > 0 then the cell construction is possible.
10. Answer (B)
4  500
nNaCl = 2
1000
 n Cl2  1 .
11. Answer (D)

nNa deposited = 2
 nNa–Hg formed = 2
 Mass = 2 × 223 = 446.
12. Answer (D)
Total charge required = 2 F
= 2 × 96500 = 193000 C.
13. Answer (B)
Cell reaction M 
 M
(1 M) (0.05 M)
Apply Nernst equation,
0.059 0.05
E  Eº – log
1 1
0.059
E–
1

log 5  10 –2 
0.059
E–  –2   log5 
1 
14. Answer (C)

E1 log0.05

E2 log0.0025
E1 log5  10 –2

E 2 log25  10 –4
E1  70(given)
70 –1.3 1
 
E2 –2.6 2
15. Answer (B)
0.059 0.001
0.059   log 2
2 (M )
0.001
log 2
[M 2  ]
0.001
 100 Ksp = 4 × (10–5)3 = 4 × 10–15
[M 2 ]
[M2+] = 10–5
16. Answer (D)
G = –nFE = –2 × 96500 × 0.059
= –11387 joule mol–1
 –11.4 kJ mol–1
17. Answer (A)
(P)
Conductivity
(C2H5)3 N
+
Firstly it decreases due to nutrilization of CH3COOH and replacement of H+ by (C2H5)3NH but thereafter buffer
+
formation takes place and [H+] becomes constant and (C2H5)3NH increases hence conductivity increases but
+
after equivalence point (C2H5)3N is not ionized due to much higher concentration of (C2H5)3N in solution.
(Q)
Conductivity
VKI
AgNO 3 + KI 
 AgI(S) + KNO 3

Initially only Ag+ is replaced by K+ hence conductivity remain the same thereafter equivalence point [K+]
increases hence conducitity increases.
(R)
Conductivity
VCH3COOH
Initially conducitity decreases due to replacement of OH– by CH3COO– and then almost constant due to
buffer formation
(S)
Conductivity
VNaOH
Decreases due to removal of H+ by Na+ then increases due to OH–.
18. Answer (D)
+3 +2
(P) Fe + e Fe ºG1 = – 1F × 0.77
+2
Fe + 2e Fe ºG2 = + 2F × 0.77
+3
Fe + 3e Fe ºG3 = – 3F × EºFe+3/Fe
ºG 3 = ºG1 + ºG2
– 3F × EºFe+3 /Fe = – 0.77 F + 0.88 F
– 3EºFe+3 /Fe = 0.11 (V)
0.11 (V)
EºFe+3 /Fe = – = – 0.036 (V)
3
+
(Q) 2H2O O2 + 4H + 4e Eº = – 1.23 V
–
4e + O2 + 2H2O OH Eº = + 0.40 V
+ –
4 H2O 4H + 4OH Eº = – 0.83 V
2+
(R) Cu + 2e Cu Eº = + 0.34 V
2+
2Cu Cu + 2eu Eº = – 0.52 V
2+ +
Cu + Cu 2Cu Eº = – 0.18 V
+3
(S) Cr + 3e Cr ºG1 = + 3 × F × 0.74
+2
Cr Cr + 2e ºG2 = + 2 × F ×0.91
+3 +2
Cr + e Cr
EºCr+3 /Cr+2 = – 0.4 V

19. Answer (4)

X  Y; rG° = – 193 kJ mol–1
M+  M3+ + 2e– E° = – 0.25 V
Hence G° for oxidation will be
G° = – nFE°
= –2× 96500 × (–0.25)
= 48250 J = 48.25 kJ
48.25 kJ energy oxidises one mole M+
193
 193 kJ energy oxidises mole M  4 mole M
48.25
20. Answer (3)
1  HX 2  HY
( m )HX ( m )HY
1  o
2  o
m m
K a1  C112 K a2  C2 22
2 2
( m )HX (m )HY
 0.01 o 2
 0.1 o 2
( m ) ( m )
2
K a1 2
0.01( m )HX  ( ) 
   0.1 m HX 
 ( m )HY 
2
K a2 0.1(m )HY
2
 1
 0.1  = 10–3
 10 
K a1
pK a (HX)  pK a (HY)   log   log10 3
K a2
=3
21. Answer (6)
 l  120
  C    5  10 7 
A
  1
= 6 × 10–5 S cm–1
  1000 6  105  1000

M  
M 15  10 4
 M = 40 S cm 2 mol–1
[H+] = C = 10–4
10 4 1
 4

15  10 15
M
  º
M

 M = 40 × 15 = 600 = 6 × 102 S cm–1 mol–1

22. Answer (9.9 – 10.1)

Cell reaction :
Mg(s)  Cu2 (1 M)  Cu(s)  Mg2 (xM)
2.303T
Ecell  Ecell  log x
F/R
2.303  300
2.67  2.70  log x
11500  2
2.303  3
0.03  log x
115  2
0.03  115  2
log x  1
2.303  3
x = 10.00
23. Answer [(–11.82) – (–11.42)]
A  A n  ne –
B2n  2ne –  B
2A  B2n  2A n  B
H° = 2G°, Ecell = 0
G° = H° – TS°
G
 G° = TS°  S 
T
– RTln K [A n ]2 22
S   – R ln 2n  – 8.3  ln
T [B ] 1
 S° = – 11.62 JK–1 mol–1
24. Answer (13.00 to 13.60)
1
H2 (g)  O 2 (g)  H2 O(l)
2
Eocell  1.23 V (from given data)
 Go  nFEocell
= –2 × 96500 × 1.23 J/mol
Work derived using 70% efficiency and on consumption of 1.0 × 10–3 mol of H2(g)
W = 2 × 96500 × 1.23 × 0.7 × 1 × 10–3
= 166.17 J
This work done = Change in internal energy of monoatomic gas.
 166.17 = nCv,m T
166.17  2
 T 
1 3R
T  13.32 K
25. Answer (0.215)
26. Answer (0.86)


Molar conductivity of HX at infinite dilution
 = 4 × 102 S cm2 mol–1
m
Molar conductivity of HX at conc. c1 = y × 102 S cm2 mol–1
c
m1 y  102 y
1   
 2 4
m 4  10
On 20 times dilution of the solution of HX
c
m2 3y  102 3y  c1 
2    c 2  20 
 2 4
m 4  10  
1 1
  2 = 31
2 3
HX 



 H  X
–
c1(1– 1) c11 c11
c112 c 2 c (3 )2
Ka   2 2  1 1
1– 1 1– 2 20(1– 31)
1 9

1– 1 20(1– 31)
11
20 – 601 = 9 – 91  1   0.215
51
y = 41 = 0.86


Chapter 11
Chemical Kinetics and Nuclear Chemistry

1. Answer (C)
23
11 Na  10
23
X  01e
2. Answer (D)
r = K[G] [H]
8r = K[2G] [2H]
2r = K[2G] [H]
 =1=2
 order of reaction = 3
3. Answer (A)
0.693
k1 = t1/2
0.693
k1 = (first order kinetics) ....(1)
40
1.386
k0 = 2  20 (zero order kinetics) ....(2)
k1
–1 3
k 0 = 0.5 mol dm .
4. Answer (D)
1
log k = – (2000) + 6.0
7
Ea
Comparing this equation with log k = log A – , we get
2.303 RT
log A = 6
 A = 106 s–1
Ea 2000
and – =–
2.303 RT T
Ea = 2000 × 2.303 × 8.314
Ea = 38.3 kJ mol–1

5. Answer (A)
Ea

k  A e RT
Ea
ln k = ln A –
RT
6. Answer (A)
He4
27
13 Al 
2
 30
14 Si  1H1
(X)
He4
27
13 Al 
2
 30
15 P  10 n
(Y)

14 Si 
30 1
1 e
(Z)
7. Answer (D)
The order of reaction with respect to P is one since t3/4 is twice of t1/2. From the given graph the order of
reaction with respect to Q is zero. Therefore, overall order of reaction is one.
8. Answer (B)

r2  [M]2 
 
r1  [M]1 
8 = (2)
=3
So, order of reaction is 3.
9. Answer (A, B, D)
2.303 A
t log
m 0.4  10 2  Α
8  0.693 2.303
  log250
k k
103
 2.303log
4
 2.303  (3  2  0.3010)
10. Answer (A, B)
9
4 Be    84Be  10n
9
4 Be  1
1 H  84Be  12H
11. Answer (B, C, D)
 A high activation energy usually implies a slow reaction.
 Rate constant of a reaction increases with increasing temperature due to the increase in greater number
of collisions whose energy exceeds the activation energy.
–E /RT
 k  P Ze a
So, pre-exponential factor (A) = P × Z and it is independent of activation energy or energy of molecules.

12. Answer (B, D)

When N/P ratio is less than one, then proton changes into neutron.
Positron emission : 11 H  10n  01 
Capture : 11 H  0
1 e  10 n  X-rays
13. Answer (A, D)

A exp erimental
Steric factor =
A calculated
Steric factor = 4.5
It means Aexperimental > Acalculated
[This seems that reaction occurs more quickly than particles collide, thus concept of steric factor was
introduced]
14. Answer (A, D)
A  2B + C
P0 – –
P0 – P 2P P
Pt = P0 + 2P
Pt  P0
P=
2
 P0  2P0
Kt  ln   ln
 Pt  P0   3P0  Pt
 P0   
  2  
Kt  ln 2P0  ln(3P0  Pt )
ln (3P0 – P)t
Time
Rate constant of reaction is independent of initial concentration.
92U
238  90Th
234 + 2He4
90Th
234  91Pa
234 + –1e
0
91Pa
234  92Z
234 + –1e
0
92Z
234  90Th230 + 2He4
 x1 =  ; x2 = x3 = –1
0 ; x4 = 
Z has atomic number 92.

d[P]
rate   k[X]
dt
2X  Y  P
2 mole 1 mole
1 mole 0.5 mole 0.5 mole
d[X]
– = k1[X] = 2k[X]  2k = k1
dt
d[Y]
– = k2[X] = k[X]  k2 = k
dt
1
2k  ln 2
50
1 0.693
k ln 2   6.93  10 –3 s –1
100 100
ln 2 ln2  100
 t1/2 x    50 sec
k1 2  0.693
At 50 sec
d[X] 0.693
–  2k[X]  2  1
dt 100
= 13.86 × 10–3 mol L–1 s–1

At 100 sec
d[Y] 0.693 1
–  k 2 [X]  k[X]  
dt 100 2
1
( Concentration of X after 2 half lives = M)
2
= 3.46 × 10–3 mol L–1 s–1
17. Answer (8)
238 214
92 U 
 82 Pb  X24 He  y 01 e
24 = 4x; x=6
10 = 2x – y
y= 2
 x +y=8
18. Answer (0)
For zero order reaction,
dx
k
dt
From 1 to 0.75 (M),
0.25
5
0.05
From 0.75 to 0.40,
0.35
5
0.07
From 0.40 to 0.10,
0.30
5
0.06
It mean order of this reaction is zero.
19. Answer (3)
142
92 U235  54 Xe + 38
90
Sr +3 10n
20. Answer (8)
63
29 Cu  11H  610 n  ( 24 He)  211H  X( 52
26 Fe)
Fe belongs to group-8.
21. Answer (9)
2.303 1
t1/8  log10 ...(i)
k 18
2.303 1
t1/10  log10 ...(ii)
k 1 10
[t1/8 ] log8
 10   10  3  0.3  10  9
[t1/10 ] log10
22. Answer (9)
238 206 4 0
92 U  82 Pb  8 2He  6 – 
Now, number of moles in gas phase = 1 + 8 = 9 mole

At constant temperature and pressure
PF nF 9
  9
Pin nin 1
23. Answer (8)
8H  5 Fe(H2O)2 (OX)2   MnO4  Mn2  5 Fe(H2O)2 (OX)2   4H2O

2 
1 d[H ] d[MnO4 ]
Rate   
8 dt dt
rate of [H ] decay

Hence, 8
rate of [MnO 4 ] decay
24. Answer (8430 – 8570)
A(g) + B(g)  AB(g)
Eab – Eaf = 2RT

Af
=4
Ab
Kf
K=
Kb
–E a f /RT
Kf = Afe
K b = A b e –Eab /RT
Kf A (E –E )/RT
= f e ab af
Kb Ab
 K = 4e2RT/RT
K = 4e2
G° = – RT In K
= – RT (2 + ln 4)
= – 2500 (2 + 2 × 0.7)
= – 8500 J mol–1
Absolute value is 8500.00.
25. Answer (6.70 – 6.80)
A + B + C  Product
Rate  [A]x [B]y [C]z
R1 (0.2)x (0.1)y (0.1)z 6 ×10 –5

= =
R2 (0.2)x (0.2)y (0.1)z 6 ×10 –5
 y= 0
Similarly x and z are calculated, x = 1, z = 1
6 ×10 –5
Rate constant K = = 3 ×10 –3
0.2× 0.1
 Rate at given concentrations = 3 × 10–3 × (0.15)1(0.25)0(0.15)1
= 6.75 × 10–5 mol dm–3 S–1
Y = 6.75
26. Answer (2.3)

2N2O5   2N2O4  O2 ; K  5  10  4 sec 1
Initial pressure (in atm) 1 – –
Pressure after time t sec 1 – 2x 2x x
 1 – 2x + 2x + x = 1.45 atm
 x = 0.45 atm
For 1st order reaction (taking into account of reaction stoichiometry)
a
2Kt  ln 0
a0  x
 a0  1 and a0 – x  0.1
1 1
 t 4
ln  2.3  103 s
2  5  10 0.1

27. Answer (1.19 to 1.21)
238
92 U 206
82 Pb
Number of -particles emitted per nucleii of
238  206
238
92 U 8
4
238
68  10 6
Moles of U present initially =
92
238
7 68  10 6
After three half lives, moles of 238
U decayed = 
92
8 238
7 68  106
 Number of -particles emitted = 8    6.02  1023
8 238
= 12.04 × 1017
= 1.2 × 1018
 Z = 1.2


Chapter 12
Surface Chemistry
1. Answer (C)
Coagulating power of a electrolyte is dependent on the valency of effective ion and Sb2S3 is negatively charged
sol.
 Answer is Al2(SO4)3.
2. Answer (B)
The adsorption of methylene blue on activated charcoal is physiosorption which is exothermic, multilayer and
does not have energy barrier.
3. Answer (D)
 A solution of CH 3OH and water shows positive deviation from Raoult's law, it means by adding
intermolecular force of attraction decreases and hence surface tension decreases.
 By adding KCl in water, intermolecular force of attraction bit increases, so surface tension increases by
small value.
 By adding surfactant like CH3(CH2)11OSO3–Na+, surface tension decreases rapidly and after forming micelle
it slightly increases.
4. Answer (A, B, D)
At high temperature, sufficient activation energy for chemical adsorption is provided.
Hadsorption for chemical lies between 200-400 kJ/mole.
5. Answer (A, D)
Lyophobic colloids carry either +ve or –ve charge. In order to acquire stability the colloidal particles attract
oppositely charged ions forming a diffused layer. A potential is developed between fixed layer and diffused layer
called zeta potential. Higher the value of zeta potential higher will be the stability of lyophobic colloid.
6. Answer (A, C)
Under mild conditions of temperatures extent of physisorption decreases with increasing temperature so
graph (I) is correct. As initial temperature provided meets the necessary activation energy needed for chemical
bond formation for chemisorption so graph (II) is also correct. Finally graph (IV) is correct for chemisorption
as plot is now of potential energy vs distance of molecule from surface. Hence, answer is (A, C).
7. Answer (B, C, D)
Reaction on metal surface
M  M  e 
O2  e   O2
This is an example of chemisorption.
8. Answer (A, C)
Adsorption is an exothermic process and is accompanied by decrease is entropy,
H  0, S  0
sys sys

More is critical temperature (Tc), more are intermolecular forces of attraction.

 More is extent of adsorption.
9. Answer (B, C)
Select the correct statements.
(A) The process of precipitating colloidal sol by an electrolyte is called peptization - False, (It is process of
converting precipitate into colloid)
(B) Colloidal solution freezes at a higher temperature than the true solution at the same concentration - True
(colligative properties)
(C) Surfactants form miscelle above critical miscelle concentration (CMC). CMC depends on temperature -
True
(D) Miscelles are macromolecular colloids - False, As misceles are associated colloids.


Chapter 13
Hydrogen
1. Answer (B)
Ca(OH)2 is used to remove hardness of water. Which is used in Clark's method.
2. Answer (A, B, D)
In ice water molecules are excessively H-bonded giving a cage-like structure which is lighter than water. Primary
amines are more basic than tertiary amines in aqueous solution mainly due to H-bonding with water molecules.
Dimerisation of acetic acid in benzene is due to intermolecular H-bonding.
3. Answer (A, B)
Fe3+ is reduced to Fe2+ by H2O2 and Na2O2 in water.
Na2O2 + 2H2O  2NaOH + H2O2
2Fe3+ + H2O2  2OH– 2Fe2+ + 2H2O + O2


Chapter 14
The s-Block Elements

1. Answer (B)
2KO2 + 2H2O 
 2KOH + H2O2 + O2
2. Answer (A, B) or (A)


Chapter 15
The p-Block Elements (Group 13 to Group 18)

1. Answer (D)
P4, hybridisation of P = sp3
P character = 75%
2. Answer (A)
3. Answer (A) or (B)
4. Answer (C)
5. Answer (B)
Na2S2O3 + 4Cl2 + 5H2O  2NaHSO4 + 8HCl
6. Answer (B)
P4  O2  P4 O6
(air )
(78% N2  21% O2 )
7. Answer (D)
Ba(N3)2  Ba(s) + 3N2 
8. Answer (B)
Conc. HNO3 slowly decomposes as
4HNO3  4NO2 + 2H2O + O2
It acquires yellow-brown colour due to the formation of NO2.
9. Answer (A)
P4  8SOCl2  4PCl3  4SO2  2S2 Cl2

(White)
10. Answer (C)

Complete
XeF6 Hydrolysis
XeO3 + H2F2
OH–/H2O
–
HXeO4
Slow disproportionation in OH–/H2O
–4
XeO6 + Xe(g) + H2O + O2(g)

11. Answer (B)

The increasing order of atomic radii is
Ga < Al < In < Tl
r
(pm) 135 145 167 170

Small bases (NH3 and 1º amine) are able to break the bond of bridged hydrogen in a unsymmetrical manner.

O O O O
N  N—O , N—N , N—N
O O O

14. Answer (B, D)
Property-wise graphite is softer than diamond. However electrical conductivity of graphite is higher than that
of diamond. Bond order (C–C) in graphite is 1.5 and higher than C–C bond order in diamond. Hence, answer
is (B, D).

 
O O
O O O O
Ozone is diamagnetic in nature and both the O – O bond length are equal. It has a bent structure.
Dilute solution of Na in liquid ammonia is paramagnetic
K O2  KO2
(excess)
O2– is paramagnetic due to unpaired electron in antibonding orbital
3Cu  8HNO3  3Cu(NO3 )2  2NO  4H2O

(diluted)
NO is paramagnetic due to unpaired electrons on "N".
17. Answer (B, D)


H3BO3  H2 O 
 B(OH)4  H

CH2 OH CH2 O O CH2

B(OH)4 + B
CH2 OH CH2 O O CH2
OH
B
HO OH
In boric acid, planar H3BO3 units are joined by hydrogen bonds to give layered structure.
18. Answer (B)
(CH3)2 SiCl2 form linear polymer on hydrolysis and (CH3)3 SiCl is a chain terminator.

19. Answer (B, C)

HClO HClO2 HClO3 HClO4
Cl O 0 1 2 3
lone pair on Cl 3 2 1 0
Hybridization sp3 sp3 sp3 sp3
HClO4 is strongest acid.
Borax formula is Na2[B4O5(OH)4].8H2O
[B4O5(OH)4]2– has following structure
O H
(–)
B(I)
OO O
H
(IV) O
H B (–) B(II) B(III)
O O
O O H
B(I) and B(II) are sp3 hybridized
B(III) and B(IV) are sp2 hybridized.
21. Answer (B, D)
P4O10 is dehydrating agent and dehydrate HNO3.
PO
2HNO3 
4 10
 N2O5
N2O5 is dia magnetic


N2O5 
 NO2+ + NO3–
Na  Na+ + e–
NO2+ + e–  NO2
(brown)
22. Answer (B, C)
The colours arise from the absorption of light on promoting an electron from the ground state to higher
state. On descending the group, the energy levels become closer and gap between HOMO – LUMO
decreases.
HOMO is *
LUMO is *
(A) HClO4 > H2O Acidic character
ClO4– < OH– Conjugate Base
Strong acids have weak conjugate base
(B) Both HCIO4 and HClO central atom is sp3 hybridised
(D) HClO4 > HClO Acidic strength
 H+ + ClO4
HClO 4 

 H+ + ClO 
HClO 
O– O O O
CI O CI O CI O CI O–
O O O– O O
O O– O
In ClO4 , nagative charge is dispersed on four oxygen, so better resonance stabilised.

24. Answer (A, C)
ZnO, Al2O3, PbO, PbO2, Cr2O3, BeO, SnO and SnO2 are amphoteric oxides.
NO is neutral oxide.
CrO is basic oxide.
B2O3 is acidic oxide.
H e– H e
– H
B – B It has two 3c-2e bonds.
e– e
H H H
Cl Cl Cl
2AlCl3  Al Al No 3c-2e bond
Cl Cl Cl
CH3 CH3 CH3
Al Al Has two 3c-2e bonds.
CH3 CH3 CH3
Also, BCl3 is stronger lewis acid than AlCl3.
26. Answer (B, C)
NH4NO3 on heating at 250°C decomposes to nitrous oxide and water
NH4NO3  N2O + H2O
Nitrous oxide above 600°C decomposes to dinitrogen and dioxygen gas
2N2O  2N2 + O2
Ammonium dichromate on heating decomposes to give dinitrogen and chromium (III) oxide

(NH4)2Cr2O7  N2 + Cr2O3 + 4H2O
Barium azide on heating around 180°C decomposes to give dinitrogen gas and barium
Ba(N3)2  3N2 + Ba
Magnesium nitride decomposes above 700°C to give magnesium and dinitrogen gas
Mg3N2  3Mg + N2
So, below 300°C only (NH4)2Cr2O7 and Ba(N3)2 can provide N2 gas only heating.
Basic character of oxide decreases as we move down the group.
 Bi2O5 is more basic than N2O5
- Covalent nature depends on the electronegativity difference between bonded atoms.
 NF3 is more covalent than BiF3
- Boiling point of NH3 is more (due to H-bonding) than PH3
- P–P single bond is stronger than N–N single bond (as in N, due to smaller size of atoms lone pair-
lone pair repulsion will be more)

28. Answer (B, D)

Compound Q is SnCl2. The given reactions are
SnCl2 + Cl–  SnCl3–

(X)
+ –
SnCl2 + Me3N  Me3 N – SnCl2
(Y)
SnCl2 + 2CuCl2 
 SnCl4 + 2CuCl
(Z)
Hybridisation of Sn in SnCl3– is sp3
(–)
Sn
Cl Cl
Cl
Trimethylamine forms a co-ordinate bond with Sn in SnCl2.
There is no lone pair on central atom of SnCl4(Z).
(A) HNO3 + 3HCl 
 NOCl + Cl2 + 2H2O
The nitrosyl chloride and chlorine impart yellow color to aqua regia.
(B) Aqua regia is a 3 : 1 mixture of conc. HCl and conc. HNO3.
(C) Gold dissolves in aqua regia to form [AuCl4]–.
Au  4H  NO3–  4Cl–  [AuCl4 ]–  NO  2H2O
(D) Air oxidises NO to NO2.
Hence in absence of air, possibility of formation of NO2 is less.

HClO 4  HClO3  HOCl
most acidic least acidic
Conjugate ClO4  ClO3  OCl Cl

most O O
base least
basic basic –
O
 2  2
ClO  SO 3  Cl  SO 4
3ClO   2Cl  ClO3
4ClO3  Cl  3ClO 4

31. Answer (A, B)
Sn4+ > Sn2+ ... stability order
 Sn2+ acts as a reducing agent.
SnO2 + 2KOH + 2H2O  K2[Sn(OH)6]
In conc. HCl, PbCl2 exists as chloroplumbous acid, H2[PbCl4]
PbCl2 + 2HCl  H2[PbCl4]
Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 2H2O
(2PbO + PbO2)


4H3PO3  PH3  3H3PO 4
In H3PO4, phosphorous is present in highest oxidation state, i.e., +5. So H 3PO4 cannot acts as reducing
agent.
Structure of H3PO3,
O
P
HO OH H
It is a dibasic acid.
H atom present in P–H bond is not ionizable.
These P-H bonds are not ionisable to give H+ and do not play any role in basicity. Only those H atoms which
are attached with oxygen in P-OH form are ionisable and cause the basicity. Thus, H 3PO3 and H3PO4 are
dibasic and tribasic, respectively as the structure of H3PO3 has two P–OH bonds and H3PO4 three.
33. Answer (C)
Since nitrates are more soluble in water.
Nitrates are less abundant in earth’s crust.
34. Answer (C)
NH3 is strong Lewis base than PH3 because in NH3, lone pair of electron present in more directional sp3 hybrid
orbital while lone pair of e– in PH3 reside in s orbital which is non-directional.
35. Answer (B)
Oxidation
0 –3 +1
P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2
Reduction
36. Answer (A)
cold
Cl2  2NaOH(dil.)   NaOCl NaCl  H2O
(P)
hot
3Cl2  6NaOH(conc.)   NaClO3  5NaCl  3H2O
(Q)
(P) and (Q) are salts of HOCl and HClO3 respectively.
37. Answer (A)

Charcoal
SO2  Cl2 
Catalyst
SO2Cl2
(R)
10SO2 Cl2  P4  4PCl5  10SO2

(R) (S)
PCl5  4H2 O  H3PO 4  5HCl

(S) (T)
38. Answer (C)

39. Answer (A)

Solutions of Q. Nos. 38 and 39

[MnO ]
2KClO3 
2
 2KCl  3O2
(W )
5O2  P4  P4O10
( X)
P4 O10  4HNO3  2N2O5  4HPO3

(Y) (Z)
40. Answer A(p, s); B(q, s); C(r, t); D(q, t)
3Cu  8HNO3 

 3Cu(NO3 )2  2NO  4H2O
(dil.)
Cu  4HNO3 
 Cu(NO3 )2  2NO2  2H2O
(conc.)
4Zn  10HNO3 

 4Zn(NO3 )2  N2O  5H2O
(dil.)
Zn  4HNO3 
 Zn(NO3 )2  2NO2  2H2O
(conc.)
41. Answer A(p, s); B(p, q, r, t); C(p, q); D(p)

CH3
CH3
Polymerise Si
(A) (CH3)2SiCl2 + H2O Si—OH O O
OH CH3 CH3
n
(B) 6XeF4  12H2O  4Xe  2XeO3  24HF  3O 2

(C) Cl2  H2 O  HCl  HOCl
(D) VCl5  H2O  VOCl3  HCl
Note : Vanadium in (+V) oxidation state from only fluoride. Existence of VCl5 is doubtful.
42. Answer (D)
Warm
(P) 2PbO2 + 2H2SO 4   2PbSO 4 + 2H2O + O 2
(Q) Na 2S 2 O3 + 5H2 O + 4Cl2 

 2NaHSO 4 + 8HCl
(R) N 2H 4 + 2I2 
 N 2 + 4HI
(S) XeF2 + 2NO 

 Xe + 2NOF
43. Answer (6)
Al
Cl
Cl Cl
Al Al
Cl Cl
Cl
Al
44. Answer (3)

Be3Al2Si6O18

45. Answer (5)
Structure of S4O62– is
O O
0
+5
O–S–S–S–S–O
O O
 Difference in oxidation state is +5 – 0 = +5.
46. Answer (4)
SO2, H2O, H2SO4 and P4O10 convert PCl5 to POCl3.
47. Answer (8)

..
O
..
.. .. ..
N – N =O
..
O
..
..
Number of lone pair = 8
48. Answer (6)
3B2H6 + 18CH3OH  6B(OCH3)3 + 18H2
49. Answer (5) or (6)

N2O 3 N 2O5
O O O O
O
N—N N N
O O O
P4O 6 P4O7 H4P2O5

O O O
P O P P O P P P
HO O OH
O OO O O OO O H
H
P O P P O P
H5P3O10 H2S2O3 H2S2O5

O O O S O O
P P P S S S
HO O O OH HO O HO OH
OH OH OH OH O
50. Answer (4.00)
O O
N 2O : – +
N2O4 : N N N N O
O O
S O O
H 2S2O3 : S H 2S2O8 : S O O S
O O OH OH O
HO
OH
 Number of compounds having bond between same type of atoms = 4

51. Answer (19.00)
XeF4  O2F2 

143 K
 XeF6  O2
(Y)
XeF6 F F
Xe Total number of lone pairs = 19
(Y)
F F
F
52. Answer (288 – 288.30)
Conc. HNO3 oxidises rhombic sulphur (S8) to H2SO4 and itself gets reduced to NO2.
0 5 6 4
S8  48HNO3  8H2SO4  48NO 2  16H2O
1 mole of S8 gives 16 moles of H2O.
Mass of H2O = 16 × 18 = 288 gm
53. Answer (6)
ClO2 contains an odd electron and is paramagnetic. It reacts with ozone to give O2 and Cl2O6.
2ClO2 + 2O3  Cl2O6 + 2O2
In Cl2O6, the average oxidation state of Cl is +6.


Chapter 16
General Principles and Processes of
Isolation of Elements
1. Answer (B)
2ZnS + 3O2 2ZnO + 2SO2

+ carbon
Zn + CO
2. Answer (D)
Haematite Fe2O3 Fe+3
Magnetite Fe3O4 Fe+2 and Fe+3
3. Answer (B)


Ag2S  4NaCN 
 2Na[Ag(CN)2 ]  Na2 S
Na 2 S 2  2O2  Na 26 SO 4
2Na[Ag1(CN)2 ]  Zn  Na2 [Zn(CN)4 ]  2Ag0 

4. Answer (A)
Silver, copper and lead are commonly found in earth's crust as Ag2S (silver glance), CuFeS2 (Copper pyrites)
and PbS (Galena).
5. Answer (C)
CuCO3Cu(OH)2  Malachite
Fe3O4  Magnetite
ZnCO3  Calamine
Na3AlF6  Cryolite
6. Answer (A, D)
12001300C
SnO2  2C Sn  2CO
if after contain Fe and Cu as impurity.

7. Answer (C, D)
Al2O3 and MgCO3.CaCO3 are separately reduced by electrolytic reduction.
8. Answer (B, C, D)

Cu2S  2Cu2O  6Cu  SO2
Since, CuSO4 as well as CuO both on heating produces Cu2O as shown below so, they also produce Cu on
heating with Cu2S.
 1
2CuO  Cu2O  O2
2

 1
CuSO 4  CuO  SO2  O2
2
9. Answer (B, C, D)
In electrolytic refining of blister Cu, acidified CuSO4 is used as electrolyte, pure Cu deposits at Cathode and
impurities sattle as anode mud.
Extraction of Cu from copper pyrite (CuFeS2) involves following steps:
Step 1: Pulverisation or crushing of copper pyrite ore.
Step 2: Concentration of the ore by froth-flotation method.
Step 3: Self-reduction during partial roasting.
CuFeS2 + O2  Cu2S + FeS + SO2
Cu2S + O2  Cu2O + SO2
2Cu2O + Cu2S  6Cu  SO2
(blister copper )
FeS + O2  FeO + SO2
FeO + SiO2 
 FeSiO3
(flux) (slag)
Step 4: Refining of blister copper : Refining is done by electrolytic refining method.

Extraction of gold is done by leaching with dil. solution of NaCN in the presence of air (O 2).
Au + NaCN + O2   Au(CN)2  + OH–

–
(Q) (R)
[Au(CN)2 ]– + Zn   Zn(CN)4  + Au

2–
(R) (T) (Z) (S)
R is [Au(CN)2]–.
Q is O2.
Z is [Zn(CN)4]2–.
12. Answer (A, B, C, D)
Al2O3 + 2NaOH + 3H2O  2Na[Al(OH)4]
2Na[Al(OH)4] + 2CO2  Al2O3xH2O + 2NaHCO3
Al2O3xH2O  Al2O3(s) + xH2O

1473K
PbS  2PbO  3Pb  SO2

Self reduction is taking place between PbS and PbO.
In the Bessemer converter : The raw material for the Bessemer converter is matte, i.e., Cu2S + FeS (little).
Here air blasting is initially done for slag formation and SiO2 is added from external source.
3
FeS  O2  FeO  SO2 
2
SiO2  FeO  FeSiO3 (slag)

During slag formation, the characteristic green flame is observed at the mouth of the Bessemer converter which
indicates the presence of iron in the form of FeO. Disappearance of this green flame indicates that the slag
formation is complete. Then air blasting is stopped and slag is removed.
Again air blasting is restarted for partial roasting before self reduction, until two-thirds of Cu 2S is converted
into Cu2O. After this, only heating is continued for the self reduction process.
3
Cu2S  O2  Cu2O  SO2 
2
Cu2 S  2Cu2 O  6Cu(l)  SO 2  (self reduction)
and Cu2S  2O2  Cu2SO4
Cu2 S  Cu2SO 4  4Cu  2SO 2  (self reduction)
Thus the molten Cu obtained is poured into large container and allowed to cool and during cooling the dissolved
SO2 comes up to the surface and forms blisters. It is known as blister copper.
2Na[Au(CN)2 ]  Zn  Na2 [Zn(CN)4 ]  2Au 
14. Answer (A)

Partial roasting of chalcopyrite
O2 / 
CuFeS2   Cu2 S  FeO
15. Answer (D)
FeO  SiO2  FeSiO3

gauge flux slag
16. Answer (C)
Cu2S + Cu2O  6Cu + SO2

17. Answer A(p); B(q); C(p, r); D(p, s)
18. Answer A(P, Q, S); B(T); C(Q, R); D(R)
Siderite  FeCO3
Malachite  CuCO3
Cu(OH)2
Bauxite  Al2O3·xH2O or
AlOx(OH)3 – 2x 0 < x < 1
Calamine  ZnCO3
Argentite  Ag2S
19. Answer (6.40 – 6.50)
2PbS + 3O2  2PbO + 2SO2
2PbO + PbS  3Pb + SO2
3 moles of O2 produce 3 moles of lead
96 kg of oxygen produce 621 kg of lead.
621
1 kg of oxygen produce = 6.468 = 6.47 kg
96

Chapter 17
The d & f - Block Elements

1. Answer (D)
2. Answer (B)
4Ag + 8NaCN + 2H2O + O2

4Na [Ag (CN)2] + 4NaOH
3. Answer (C)
In CuF2, copper is in +2 oxidation state
 Coloured. In other options copper is in +1 oxidation state therefore colourless.

4. Answer (A)
Complementary colour of blue is (Orange-red)
5. Answer (B)
Zn + 2NaOH  Na2ZnO2 + H2
Iron become passive with conc. HNO3.
Copper liberate NO2 with HNO3
6. Answer (A, B, C)
Cr2+ is a reducing agent and Mn3+ is an oxidizing agent and both have electronic configuration d4.
E  0.41 V E  1.51 V
Cr 3  /Cr 2 Mn3  /Mn2
Above E° values explains reducing nature of Cr2+ and oxidizing behaviour of Mn3+.
7. Answer (B, D)
(A) Manganese show pale purple colour in flame test.

H2S
(B) Cu2 
HCl
 CuS 
Black ppt.
(C) Both Cu+2 and Mn+2 form precipitate with H2S in basic medium.
(D) ECu2 /Cu  0.34
EMn2  /Mn  1.18 V
8. Answer (A, B, D)
Fusion
2MnO2  4KOH  O2   2K 2MnO 4  2H2O
W 
Electrolysis of aq K2MnO4 oxidises MnO2– –
4 to MnO 4

Electrolysis
2K 2MnO 4  2H2O   2KMnO 4  2KOH  H2
W  X
K2MnO4 in acidic medium undergoes disproportionation


3MnO2–
4  4H  2MnO 4–  MnO2  2H2O
Y Z 
K2MnO4 is green in colour and KMnO4 is in purple colour. Both are tetrahedral in shape involving p – d bond.
– –
O O O O
Mn Mn
O O –
O O
MnO–4 MnO2–
4
Z Y
9. Answer (6)
KOH
MnO2 
fuse
 MnO24
Oxidation state = 6.


Chapter 18
Co-ordination Compounds
1. Answer (D)
2. Answer (B)
[Ni(CO)4] --------- sp3 hybridization
[Ni(CN)4]–2 --------- dsp2 hybridization
3. Answer (A)
Cr(CO)6
Cr in G.S.
Under the influence
of strong ligand
2 3
d sp hybridization
Diamagnetic  = 0
4. Answer (B)
Cr(H2O)4Cl(NO2)]Cl and [Cr(H2O)4Cl2](NO2) have same molecular formula but they give different ions on
ionization.
5. Answer (C)
HOOC CH2 CH2 COOH

N CH2 CH2 N
HOOC CH2 CH2 COOH
6. Answer (B)
Ni2+ is sp3 hybridized and metal ion is connected with weak ligands.
 Ni2+  d 8
two unpaired electrons sp3
 s = 2 (2  2) B.M.
= 8 B.M. = 2.83 B.M.

7. Answer (B)
Ni+2 + 4Cl–  [NiCl4]–2 (tetrahedral)
Ni+2 + 4CN–  Ni(CN)4–2 (square planar)
Ni+2 + H2O  Ni(H2O)6+2 (octahedral)
8. Answer (C)
[Co(NH3)6]Cl3 d 2sp3 diamagnetic
Na3[Co(OX)3] d 2sp3 diamagnetic
K2[Pt(CN)4] dsp2 diamagnetic
[Zn(H2O)6](NO3)2 sp3d2 diamagnetic
9. Answer (D)
10. Answer (C)
The hybridisation of Ni2+ in paramagnetic complex is sp3 and hence the complex is tetrahedral. The diamagnetic
complex is square planar as the hybridisation of Ni2+ is dsp2.
11. Answer (B)
The electronic configuration of central metal ion in complex ions P, Q and R are
P  [FeF6 ]3  ; Fe3  :
3d
Q = [V(H2O)6]2+; V2+:
3d
R = [Fe(H2O)6]2+; Fe2+
3d
The correct order of spin only magnetic moment is Q < R < P
12. Answer (B)
[NiCl4]2– and Na3[CoF6] are paramagnetic since involve weak field ligand. CsO2 is paramagnetic due to
paramagnetism by O2–.
13. Answer (A)

2
Ni2   6NH3  Ni  NH3 6 
octahedral
2
Pt 2   4NH3  Pt NH3 4 
(square planar )
2
Zn2   4NH3   Zn NH3 4 
tetrahedral

14. Answer (A)

[Cr(NH3)6]3+ = Cr3+
Cr3+ = 3d3 4s0
It has 3 unpaired electrons
  n(n  2) BM
 3(3  2) BM
= 3.87 BM
[CuF6]3– = Cu+3
Cu+3 = 3d8 4s0
It has 2 unpaired electrons
  2(2  2) BM
= 2.84 BM
15. Answer (C, D)
Cl
en
Cl
(C) en Pt en &
Cl
en
Cl
Cl NH3 Cl NH3
(D) Pt & Pt
NH3 Cl Cl NH3
16. Answer (B, D)
The pair of complex ions [Co(NH3)4Cl2]+ and [Pt(NH3)2(H2O)Cl]+ show geometrical isomerism. The pair of
complexes [Pt(NH3)3(NO3)]Cl and [Pt(NH3)3Cl]Br show ionisation isomerism. The other pairs given do not have
same type of isomerism.
(X) = CoCl26H2O, or, [Co(H2O)6]Cl2 (Pink)
Co2+ = [Ar]
3d
H2O is weak field ligand, therefore No pairing of electron
 Number of unpaired electron, n = 3
 s  n(n  2) B.M.
= 15 B.M.
= 3.87 B.M.


[Co(H2O)6 ]2   6NH3(aq)  2
 [Co(NH3 )6 ]  6H2O
O2 will oxidise [Co(NH3)6]2+ to [Co(NH3)6]3+, therefore shift in forward.
 Y = [Co(NH3)6]3+Cl3 [1 : 3 complex]
Co(III) = [Ar]
3d
NH3 is strong field ligand
 Forces electrons to pair up.
 n=0
 = 0 B.M.
[Co(NH3)6]3+ = [Ar]
3d 4s 4p
d2sp3
+ 6H2O; H = +ve
2+ – 2–
Also, [Co(H2O)6] + 4Cl [CoCl4] (aq)
(X) (Z)
(Pink) Blue
At 0°C, equilibrium shifts in backward, therefore pink colour.
18. Answer (B, C)
(A) Valence shell electrons in iron in compound Fe(CO)5.
Fe(26) – 1s2, 2s2, 2p6, 3s2, 3p6, 3d8 (after pairing of electrons)
3d 4s 4p
3
dsp Hybridization
Valence = 2 + 6 + 8 = 16
Electrons (3rd shell)
Valence shell electrons in nickel in compound Ni(CO)4
Ni(28) - 1s2, 2s2, 3s2, 3p6 ,3d10
3d
3
sp Hybridization
Valence electrons (3rd shell) = 2 + 6 + 10 = 18
(B) Both complexes are formed in low spin condition due to strong field ligand 'CO'.
(C) Metal carbon bond strengthens when complex is formed in lower oxidation number of metal. Since in lower
oxidation number; number of electrons in d-subshell are higher, so it can donate more electrons in ABMO
of ligands and increases the double bond character between metal and carbon.
(D) In higher oxidation number, metal may have less number of electrons in d-orbitals, which decreases the
extent of synergic bonding.
(A) [Co(en)(NH3)3(H2O)]3+
3+ 3+
OH2 NH3
CH 2 H2N NH3 CH2 NH 2 OH2

Co Co
CH 2 NH2 NH3 CH2 NH 2 NH 3
NH3 NH3
(B) [Co(CN)2(NH3)3(H2O)]1+
1+ 1+ 1+
OH2 NH3 CN
NC NH3 NC OH2 H3N OH 2

Co Co Co
NC NH3 NC NH3 H 3N NH3
NH3 NH3 CN
(C) Co3+ = [Ar]3d6

in presence of en and NH3 it form low spin complex.
(D) [Co(en)(NH3)4]3+ has larger gap between eg and t2g than [Co(en)(NH3)3(H2O)]3+. So [Co(en)(NH3)3(H2O)3+
absorb longer wavelength than [Co(en)(NH3)4]3+.
20. Answer (A, C)
[FeCl4]–
+3 5
Fe = 3d
x x x x
x x x x
Cl Cl Cl Cl
3
sp hybridization
tetrahedral
[Co(en)(NH3)2Cl2]+ has 3 geometrical isomers, one of them is optically active. So, it has 4 stereoisomers.
Cl Cl en en
NH3 H 3N Cl H3N
en Co Co en Co Co
Cl Cl H3N Cl Cl NH 3
NH 3 NH3 NH3 Cl
(I) (II) (III) (IV)
I and II are enantiomers.
Co+3 = 3d6
d2sp3 hybridization
[FeCl4]–  Fe3+, 3d5 (weak field ligand) = sp3
[Fe(CO)4]–2  Fe2–, 3d10  sp3
[Co(CO)4]–  Co–, 3d10  sp3
[CoCl4]2–  Co2+, 3d7 (weak field ligand)  sp3
[Ni(CO)4]  Ni, 3d10  sp3
[Ni(CN)4]2–  Ni2+, 3d8 (strong field ligand)  dsp2

[Cu(py)4]+  Cu+, 3d10  sp3

[Cu(CN)4]3–  Cu+, 3d10  sp3
In 3d10 electronic configuration only sp3 hybridisation and tetrahedral geometry is possible.
22. Answer (B)
23. Answer (A)
24. Answer (C)
Solution of Q. Nos. 22 to 24
Cu  Ag  Cu2  Ag
Ag  NaCl  AgCl

White ppt
AgCl  NH3 [Ag(NH3 )2 ] Cl
Cu2  NH3  Cu(NH3 )24

(Blue)
M - Cu
N - Solution of AgNO3
O - AgCl
25. Answer (B)
Ni+2 + HCl  [NiCl4]–2
Ni+2 + KCN  [Ni(CN)4]–2
26. Answer (D)

Zn2   OH  Zn(OH)2 
OH
 [Zn(OH)4 ]2 
white ppt Soluble
27. Answer A(p, q, s); B(p, r, s); C(q, s); D(q, s)
28. Answer (B)
Hint : Magnetic character Isomerism
P. [Cr(NH3)4Cl2]Cl Paramagnetic cis/trans
Q. [Ti(H2O)5Cl](NO3)2 Paramagnetic ionization
R. [Pt(en)(NH3)Cl]NO3 Diamagnetic ionization
S. [Co(NH3)4(NO3)2]NO3 Diamagnetic cis/trans
29. Answer (C)
1. [FeF6]4–
3d 4s 4p
+2
Fe
High spin complex because F– is weak field ligand.
sp3d2
2. [Ti(H2O)3Cl3]
Ti3+ d2 sp3
d2 sp3
3. [Cr(NH3)6]3+
2 3
Cr3+ d sp
d 2sp3

4. [FeCl4]2–
Fe+2 : 3d6, Cl– is weak field ligand.
3d 4s 4p
sp 3
5. Ni(CO)4
Ni0 – 3d84s2, CO is strong field ligand
Ni
sp 3
6. [Ni(CN)4]2–
+2
Ni
dsp2
CN– is strong field ligand.
30. Answer (3)
Rh Cl(CO)(PPh3)(NH3)] is a square planar complex with four different ligands and hence it will have three
geometrical isomers
a b a b a c
Rh Rh Rh
d c c d d b
31. Answer (6)
Applying equation,
N1V1 = N2V2
0.1 × V = 2 × 0.01 × 30
2  30  10
V 6
100  1
32. Answer (8)
I
O O–C=O
C CH2 CH2
I
II O N
CH2
Co
II CH2
III O N
C CH2
CH2
O O–C=O
IV
So, bond angles are

(1) NI CoOI
(2) NI CoOII
(3) NI CoOIII
(4) NI CoOIV
(5) NII CoOI
(6) NII CoOII
(7) NII CoOIII
(8) NII CoOIV
So, total asked bond angles are 8.

33. Answer (4)
F F
F
F F F
Xe S Si B
F F F F F F F
F F
F 2–
Cl
F F NH3 NH3
Br Cu Fe
F F NH3 NH3 Cl Cl
Cl
2–
Cl 2–
Cl Cl
Co Pt
Cl Cl Cl Cl
Cl
34. Answer (1)
Given Tf = 0.0558°C
as we know, Tf = i × Kf × m
 0.0558 = i × 1.86 × 0.01
 i3
Therefore, the complex will be [Co(NH3)5Cl]Cl2.
Hence, number of chloride in co-ordination sphere is 1.
35. Answer (4)
Fe(26)  [Ar]18 3d64s2
Fe3+  [Ar]18 3d54s0

SCN– is weak field ligand hence pairing will not occur.
3+
 Fe
Unpaired electrons = 5
Magnetic moment  5(5  2) B.M.  35 B.M.  5.92 B.M.

CN– is strong field ligand hence pairing will take place.
3+
 Fe
Unpaired electrons = 1
Magnetic moment  1(1  2) B.M.  3 B.M.  1.732
Difference = 5.92 – 1.732 = 4.188

Hence answer is (4).
36. Answer (3)
Et3P CO
O
– +2 –
CH3 – C Fe Br
Et3P CO
37. Answer (6)
Cl N
N N N Cl
Co Co
N N N Cl
Cl N
Cl O
O O O Cl
Cr Cr
O O O Cl
Cl O
NH3 NH3
NC CN NC NH3
Fe Fe
NC CN NC CN
NH3 CN
NH3 NH3
NH2 NH2 NH2 Cl
Co Co
NH2 NH2 NH2 NH2
Cl NH2
OH2 OH2
H3N NH3 H3N Cl
Co Co
H3N NH3 H3N NH3
Cl NH3
H2O OH
H2O OH H2O OH2
Fe Fe
H2O OH H2O OH2
H2O OH
(All the six complexes will show cis-trans isomerism)

38. Answer (5)

– –
Cl Cl
O O NH2 O
Co Co
NH2 NH2 O NH2
Cl Cl
– –
O NH2
NH2 Cl O Cl
Co Co
NH2 Cl O Cl
O NH2
–
O
H2N Cl
Co
O Cl
NH2
39. Answer (1)
H atom :
NO2 Monomer :
2p2x  * 2p2x
O2– (Superoxide) : 1s2, *1s2, 2s2, *2s2, 2pz2,
2p2y  * 2p1y
One unpaired electron is present in either *2px or *2py. So, it is paramagnetic in nature.
Dimeric sulphur in vapor phase : It is similar as O2 in vapor state, paramagnetic in nature.
Mn3O4 : It is combined form of MnO and Mn2O3
Mn+2 has 5 unpaired electrons (d5 electronic configuration)
Mn+3 has 4 unpaired electrons (d4 electronic configuration)
So, it is paramagnetic in nature.
(NH4)2[FeCl4] : Consist [Fe+2Cl4]–2 ion.
[FeCl4]–2 : Tetrahedral, sp3 Hybridized, has configuration eg3, t2g3. (Paramagnetic in nature)
(NH4)2[NiCl4] : Consist [Ni+2Cl4]–2 ion.
[NiCl4]–2 : Tetrahedral, sp3 Hybridized, has configuration eg4, t2g3. (Paramagnetic in nature)
K2MnO4 : Mn+6 is present in compound which has one unpaired electron in 3d subshell. Mn+6 - [Ar]3d1
Paramagnetic in nature.
K2CrO4 : Cr+6 is present in compound which has zero unpaired electron, diamagnetic in nature.
40. Answer (2989 – 2995)
12(NH4)2SO4 + 12Ca(OH)2 + 4NiCl2  6H2O

12CaSO4  2H2O + 4[Ni(NH3)6]Cl2 + 24H2O

952
nNiCl 2  6H2O = = 4 mol
238
Mass = 12  MCaSO4 2H2O  4M[Ni(NH3 )6 ]Cl2
= (12 × 172) + (4 × 232) = 2992 g
41. Answer (6)
cis-[Mn(en)2Cl2]
Cl
H 2N
CH 2
Cl
CH 2
NH 2 Mn
NH 2
H 2N CH 2
CH 2
No. of N-Mn-Cl bonds (in which N-Mn bond is cis to Mn-Cl bonds) = 6
(Two N-Mn-Cl bonds have N-Mn bond trans to Mn-Cl bonds)
42. Answer (6)
The given complex [Pt(NH3)4Cl2]Br2 has three ionisation isomers and each of them has two geometrical isomers.
Cl Cl Cl Cl
H3N Cl H3N NH3 H3N Br H3N NH3
Pt Pt Pt Pt
H3N NH3 H3N NH3 H3N NH3 H3N NH3

NH3 Cl NH3 Br
(cis) (trans) (cis) (trans)
Br Br
H3N NH3 H3N Br
Pt Pt
H3N NH3 H3N NH3

Br NH3
(trans) (cis)


Chapter 19
Qualitative Analysis
1. Answer (B)
Hg2+ + 2I–  HgI2
red ppt
HgI2 + 2I–  [HgI4]2–
soluble complex
Hg2+ + Co2+ + 4SCN–  CO[Hg(SCN)4]
blue ppt
2. Answer (A)
Cu+2 and Hg+2 belong with 2nd group of basic radical.
3. Answer (D)
Upon treatment with ammoniacal H2S, Zn2+ ion gets precipitated as ZnS. Fe3+ ion and Al3+ ions also get
precipitated as hydroxides but not as sulphide.
4. Answer (A)
+ +
Ag Ag with time
S2O32– [Ag(S2O3)2]3– Ag2S2O3 Ag2S
Clear solution white ppt (black ppt)
5. Answer (C)
In borax bead test, metal oxide reacts with glassy bead to form metaborates.
 
Na2B 4O7  10H2O   Na2B 4O7   NaBO2  B2O3
Borax

glassy bead
NaBO2  Cr2O3  Cr(BO2 )3

green
6. Answer (A)
X = Ag, Y = Pb
Residue
NaCl
AgCl
AgNO3 AgCl  (P)
NaCl
Pb(NO3 )2 PbCl2 Q
PbCl 2
 [Ag(NH3 )2 ]
AgCl  aq(NH3 ) 
(P) Soluble
PbCl2  KI 
 PbI2
(Q) Yellow ppt
hot

7. Answer (A, B)
All ammonium salt evolves NH3 with NaOH but only NO 3 and NO 2 ions restarts evolution of NH3 again with
zinc dust.
(A)  NH4NO 3  NaOH  NaNO 3  NH3  H2 O
Zn / NaOH
NaNO 3  8[H]    NaOH  NH3  2H2O
(B)  NH4NO 2  NaOH  NaNO 2  NH3  H2 O
Zn / NaOH
NaNO 2  6[H]    NaOH  NH3  H2 O
8. Answer (A, C, D)
2Na S O
Na2S2O3 + AgX  Ag2S2O3 
2 2 3
 Na2[Ag(S2O3)3]
[X = Cl and Br]
9. Answer (A, C, D)
2[Excess KI] + 2K3[Fe(CN)6] 2K4[Fe(CN)6] + I2
ZnSO4
I2 + K2Zn3[Fe(CN)6]2
Brown-yellow (white ppt)
filtrate
Zn+2 + 4NaOH
2– +
[Zn(OH)4] + 4Na
Soluble
2Na2S2O3 + I2 Na2S4O6 + 2NaI

colourless solution
So, answer is (A, C, D).
10. Answer (C, D)
Only group II cations precipitate as sulphide with H2S in acidic medium that is (Cu2+, Pb2+) and (Hg2+, Bi3+)
11. Answer (A or A, C)
S2– SO42–
Cu2+ CuS (ppt) CuSO4 (Soluble)
Ba2+ BaS (Soluble) BaSO4 (ppt)

Pb(OAc)2 PbS (ppt) PbSO4 (ppt)
Na2[Fe(CN)5NO] Na4[Fe(CN)5(NOS)] ______
Colour (not a ppt)
Zn + H2SO4 ZnSO4 + SO2 + H2O

conc. (G) (R) (X)
Zn + NaOH Na2[ZnO2] + H2
conc. (T) (Q)
ZnSO4 + H2S + NH4OH ZnS + (NH4)2SO4 + H2O

(G)   (Z)
group-IV (Y) (X)
reagent

SO2 (R) is V-shaped.
ZnS (Z) is dirty white gelatinous ppt.
Bond order in H2 (Q) is 1.
13. Answer (A, B)
Pb NO3 2 
dil HCl
Room temp.
PbCl2
 white ppt 
Dilute NaOH  aq 
Pb NO3 2 
Room temperature
Pb  OH2
 white ppt 
Zn NO3 2 
dil HCl
Room temperature
Zn2  2Cl–
 solub le 
dil NaOH aq 
Zn NO3 2 
Room temperature
Zn  OH 2
 white ppt 
dil HCl aq

Bi NO3 3 
Room temperature
BiOCl
 White ppt 
dil NaOH aq

Bi NO3 3 
Room temperature
Bi  OH3
 White ppt 
dil HCl
AgNO3 
Room temperature
AgCl
(White ppt)
dilute NaOH aq

AgNO3 
Room temperature
Ag2O
Brownish black ppt 
Hg NO3 2 
dil HCl
Room temperature
Hg2   2Cl–
 so lub le 
dilute NaOH aq 
Hg NO3 2 
Room temperature
HgO
 Yellow precipitate 
14. Answer (D)

N(CH3)2 N(CH3)2
Cl–
+
(CH3)2N S N(CH3)2
+3
+ H2S + + 6 Fe 6Fe2  NH4  4H 
N
NH2 NH2 Methylene blue
15. Answer (C)
Fe3  [Fe(CN)6 ]4 

 Fe 4 [Fe(CN)6 ]3
Prussian blue ppt.
16. Answer (B)
Fe 3  [Fe(CN)6 ]3 

 Fe[Fe(CN)6 ]
Brown colouration

17. Answer (A)

Lead salts give white precipitate of PbCl2 with dil. HCl which is soluble in hot water.
18. Answer (D)
The filtrate on treatment with ammonical H2S gives a precipitate which dissolves in aqueous NaOH containing
H2O2 giving a coloured solution. It contains Cr3+ ion.
Cr 3  3NH4OH  Cr(OH)3   3NH
4
(Green)
2Cr(OH)3  3H2O2  4NaOH  2Na2CrO 4  8H2O

(yellow colour )
19. Answer (C)

20. Answer (D)
Fe2  K 3 [Fe(CN)6 ]  Fe3 [Fe(CN)6 ]2 

Turnbull's blue ppt.
in absence
Fe2  K 4 [Fe(CN)6 ]  K 2Fe[Fe(CN)6 ] 
of air
White ppt. (X)
In air Fe2+ gets oxidised to Fe3+
Fe3   [Fe(CN)6 ]4–  Fe4 [Fe(CN)6 ]3 

Prussian blue
2NO3– + 4H2SO4 + 6Fe2+  6Fe3+ + 2NO + 4SO42– + 4H2O
[Fe(H2 O)6 ]2  NO  [Fe(H2O)5 NO]2  H2O

Compound responsible
for brown ring
 X = K2Fe[Fe(CN)6]
Brown ring is due to [Fe(H2O)5NO]2+
21. Answer A(p, s); B(r); C(p, q); D(p)

22. Answer (7) or (6)
Black sulphides are
PbS, CuS, HgS, NiS, CoS, Bi2S3 and Ag2S
MnS is buff
SnS2 is yellow
23. Answer (4)
CrO24   2H  2H2O 2  CrO5  3H2 O

X is CrO5
O
O O
Cr
O O
Number of oxygen atoms bonded to chromium through only single bond is 4.
The blue colour is attributed to the presence of chromium pentaoxide.

Chapter 20
Organic Chemistry : Some Basic Principles
and Techniques
1. Answer (C)
2. Answer (A)
3. Answer (A)
4. Answer (B)
Hyperconjugation involves -p conjugation.

5. Answer (D)
I & III are stabilized by resonance, hyperconjugation and + inductive effect.
 Order (I) > (III) > (II) > (IV)
6. Answer (A)
COOH COOH OH OH
> > >
CH3 Cl
(+I effect) (–I effect)
7. Answer (B)
OH
CN
Br
2-Bromo-5-hydroxy benzonitrile
8. Answer (D)
H H H H
1 + 5 +
2 4
H3C—C —C—C
3
—CH3 CH3—C—C—C—CH3
HO H CH3 :OH H CH3

More stable resonance
stabilized carbocation
9. Answer (B)
Resonating structures having maximum number of covalent bonds are more contributing. Among
charge separated resonating structures, structures where opposite charge are close enough are more
contributing.

10. Answer (D)
OH
3 2 COOH
1
4
5
6
3-ethynyl-2-hydroxy-4-methylhex-3-en-5-ynoic acid
11. Answer (B)
Meso compounds have plane of symmetry. In case of butan-2, 3-diol, gauche form is the most stable due to
intra-molecular H-bonding.
H H-bonding
O
H O H
H Me
Me
Compound E, F and E, G are keto-enol tautomers.
(F) & (G) show cis trans isomerism and these are also diastereomers.
13. Answer (B, C)
H
C H
H
C
C sp2 C C C O
H sp2 H
H
All atoms lie in one Planar

plane in all conformation
H
H
C C C is nonplanar
H
H
H
H
C C H
H C C
H H
Non-planar in many conformations due to rotation along.

C2 — C3 bond.

14. Answer (B, C)
The compound is antiaromatic and hence unstable at room temperature. The other compound
–
O O
+
is also unstable at room temperature due to partial positive charge at carbonyl

C-atom
15. Answer (A)
In hyperconjugation   p (empty) electron delocalization for tert-butyl carbocation and   * electron
delocalization for 2-butene will take place.
16. Answer (A, B)
IUPAC name
Cl
1
2
(A) 1-chloro-4-methylbenzene
3
4
CH3
CH3
1
2
(B) 4-chlorotoluene
3
4
Cl
H
| H
C H
H – CH 3 H– CºC– H
(I) (II) (III) (IV) (V)
Triphenylmethane (I) is acidic because its conjugate base is stabilised by resonance.

Cyclopentadiene (IV) is acidic because its conjugate base is aromatic.
Nitrobenzene is more acidic than benzene because nitro group is electron withdrawing. It will stabilise the
conjugate base of benzene by - I effect.
The correct order of acidity of the given compounds is IV > V > I > II > III.
18. Answer (7)
, , ,
d, l d, l, meso
19. Answer (5)
Index of hydrogen deficiency in the compound C4H6 is 2. Therefore either bicyclic compound or cycloalkenes
are possible as cyclic isomers.
 Possible isomers are

, , , ,
20. Answer (6)
H3C CH2CH3
It contains 6 alpha hydrogen atoms.
 6 contributing structures are possible.
21. Answer (9)
OH O
NaOH
–H2O
O O O O
II III IV V
O O O
III VI VII
O O
VIII IX
22. Answer (5)
, , , and are aromatic.

+
and are non-aromatic while and + are antiaromatic compounds.


Chapter 21
Hydrocarbons
1. Answer (B)
2. Answer (D)
Br
CH2—CH2 —CH2 —CH3

NH2
CH3—CH2—C C—H CH3—CH2—CC CH 3—CH2—CC—CH2—CH2—CH2—CH3
3-octyne
3. Answer (C)
COOH COOH
HNO3/H2SO4
HO HO
NO2
OCH3 HNO3/H2SO4 OCH3
H3C H3C NO2

O O NO2
C HNO3/H2SO4
C
O O
4. Answer (B)
H (sp) H
C=C=C
H H
(sp2) (sp2)
(Allene)
5. Answer (A)
Ozonolysis produces CH3CHO and CH3–CH(CHO)2.
6. Answer (B)
As branching increases boiling point decreases, so order of boiling point is III > II > I.
7. Answer (B)
It is a case of Birch reduction. Alkynes on reaction with alkali metal in liq. NH3 gives trans-alkene. But terminal
alkynes do not get reduced.
NaNH 2
Na
liq. NH3
8. Answer (B, D)
X H3C CH3
H3C CH3
X C
C
H H H HY
Y
When X = H & Y = C2H5
H3C CH3
H C
2
C C2H5
H 1 H
2, 2- dimethyl butane
When X = CH3 and Y = CH3
H3C CH3
C2
4CH3
C CH3
H 3 H 1
2, 2-dimethyl butane
9. Answer (D)
CH3
CH2 1 equiv. HBr
H2C H
+
H3C 
 Br
–
Br
(Major)
Br
+
NaOEt
–
AlCl3 + 1, 2 H +
Shift
Cl
+
H +

BF3 1, 2 H– +
+
O–H Shift
H
11. Answer (B, D)
HC
3
H CH3 CH3
(i) C=C (ii) C=C
H CH 3
H Cis H
Trans
Br2
Br2 /CHCl3
CH3 CH3
CH CH
3 3
H Br Br H
H Br Br H +
Br H H Br
+
H Br Br H CH3 CH3
CH CH
3 3
O P
Meso (M and N) Pair of enantiomers
Cis anti Racemic
M and N are meso (identical)
O and P are pair of enantiomers
(B) Bromination proceeds through anti addition.
(D) (M and O) and (N and P) are two pairs of diastereomer.
12. Answer (B, D)
Br
EtO
(A) (Anti Aromatic)
H
Me
(i) Alc. KOH
(B) Br Br (ii) NaNH2 Me — C º CH
Red hot Fe tube, 873 K
Cl
Cl Cl
UV
(C) + 3Cl2
500 K Cl Cl
Cl
H
(D) MeO
+ MeOH

13. Answer (B, C)
Me
(A) Zn
CH3—CH == CH2
Br Br
NaOH–CaO
(B) COOH 
(C) Zn
Cl +
H
(D) 2 COONa + 2H2O

Electrolysis
+ 2CO2 + H2 + 2NaOH
14. Answer (B, C)
X Pd-C/Quinoline/H2
*
R
(P)
(ii) KMnO4/H2SO4/
*COOH
COOH
COOH
(Q)
15. Answer (D)
16. Answer (B)
Solution of Q. Nos. 15 and 16
O (i) NaBH4 OH
H3C 2+ + H3C H3C
Hg /H3O (ii) dil H
+
H3C C – C C–H H3C C – C H3C C – C – H

H3C H3C CH3 H3C CH3
H3C H H3C H 
–H
   H
C – C – CH3 H3C C – C
H3C CH3 H3C CH3
(i) O3
H3C CH3 CH3
(ii) Zn–H2O
C C 2 C O
H3C CH3 CH3

17. Answer (A)
NaNH2 – + CH3 CH2 I

H C Na C
+ – (1 eq) + –
HO Na O Na O
CH3 I
CH3
H2
CH3 O
O Lindlar's
H H catalyst
18. Answer (C)
1. NaNH2 (2 eq ) O
2. OH
Br
H +
3. H3O (mild)
4. H2, Pd/C
5. CrO3
19. Answer (C)
OH
Pd-BaSO4 i. B2H6
C8H6
H2 ii. H2O 2, NaOH, H2O
20. Answer (D)
H2O
C8H6
HgSO4
H2SO4
i. Et MgBr, H2O
+
ii. H , Heat
21. Answer (A)
H – C H(CH3)2 HC – CH3
CH 3
H – C H2Ph CH2 – Ph
Benzyl radical
H – CH = CH2  CH = CH2

H – C  CH  C  CH
Order of stability of free radical
Q>P>R>S
1
Stability of free radical  Bond energy
 Order of bond energy :

S>R>P>Q
22. Answer (D)
(1) Cl2  2Cl (Initiation step) H = 58 kcal/mol
(2) CH4 + Cl  CH3 + HCl 
CH
 Propagation step
(3) 3 + Cl2  CH3Cl + Cl 
Step (1)  Endothermic (bond breaking)

Step (2)  H = 105 – 103
= 2 kcal/mol (Endothermic)
Step (3)  H = 58 – 85
= –27 kcal/mol (Exothermic)
For complete reaction
light
CH4 (g)  Cl2 (g)  CH3 Cl(g)  HCl(g)
H = 58 + 105 – 85 – 103
= –25 kcal/mol
23. Answer (A)
NaOEt
(P) Cl
(Q) ONa + Et-Br OEt
(1) Hg(OAc)2 OH
(R)
(2) NaBH4
(1) BH3
(S) (2) H2O2/NaOH
OH
24. Answer (4)
Aqueous dilute
OH
+
H H KMnO4 (excess)
Heat
HO OH
HO
(P) OH
25. Answer (6)
(i) H2, Pd-BaSO4, quinoline
HO
(ii) dil. KMnO4 (excess)
OH
273 K
HO OH
OH
OH
26. Answer (8) or (12)
O O
O O
+ +
OH OH OH OH
N N N N
2. NH 2OH (–) (–)

(–) (–)
(excess)
N N N N
+ +
OH OH OH OH
(P)
The total number of atoms having sp2 hybridisation in the major product (P) = 12
This includes 4 C-atoms, 4 N-atoms and 4 O-atoms.
If only 4 C-atoms and 4 N-atoms are considered, then only 8 sp2 -hybridised atoms will be present in the
final product. Officially JEE gave 8 and 12 as the correct answer.


Chapter 22
Haloalkanes and Haloarenes

1. Answer (A)
Trans alkene + anti addition  Meso compound
2. Answer (A)
SN 2 mechanism occurs in polar aprotic solvent hence inversion of configuration takes place.
3. Answer (B)
O
Cl
Compounds : CH3–Cl : : Cl
Cl
S P R Q
Relative reactivities 1,00,000 : 200 : 79 : 0.02

towards SN 2 reaction
4. Answer (A, D)
Since configuration is R, R.
 Optically active and possesses axis of symmetry.
5. Answer (A, D)
Given compound has three stereocentre with symmetrical substituents. It will form six stereoisomers out of
which 2 will be meso and one dl pair of cis and one dl pair of trans.
6. Answer (A, B, C)
With reference to structure (M), if the chiral carbon bearing the methyl group is C–1 and that bearing the
chlorine is C–2, then
Structure Configuration of C–1, C–2

respectively
M S, R
N R, R
O S, R
P R, S
Q R, R
Now from the above configurations we learn that

(A) M and N are diastereomers i.e., non-mirror image stereoisomers.
(B) M and O are surely identical as their configurations are same.
(C) M and P are also enantiomers due to opposite configurations.
But M and Q are again not identical but diastereomeric.
Hence answer is (A, B, C).

7. Answer (B, D)
H Br H Br
H2/Ni
(A) *
(Optically active)
H Br H Br
H2/Ni
(B)
(Optically inactive)
H Br H Br
H2C H2/Ni
H3C
(C) CH3 CH3
CH3 CH3
(Optically active)
Br H Br H
H2/Ni
(D) H2C CH3 H3C CH3
(Optically inactive)
8. Answer (A, B, D) or (A, B, C, D)

When medium is highly polar and protic I & III will follow SN1.
Hence, (A) is correct.
Option (B) is correct as
Nu–
Br Nu
SN2
Inversion in case of SN2.

(D) I & II will follow SN2 when medium is polar aprotic and nucleophile is strong in high concentration.
9. Answer (A)
Rate  [Substrate]1 (for SN1 reaction)
Rate = k[[P]0 – X]
Order of reaction = 1
For 1st order reaction Q = [P]0(1 – e–kt)
t1/2  Independent of initial concentration.
10. Answer (A, D)
F S – Ph
NO 2 NO2
+ PhSNa
NO 2 NO2

Cl S Ph
+ PhSNa
S Me S Me
NO 2 NO2
Answer should be (A) and (D)
Compounds given in option - (B) and (C) do not react with PhSNa.
11. Answer (B)
(P) ONa + Br + OH
with 3° halide, elimination predominates.
(Q) OMe + HBr Br + MeOH
(R) Br + NaOMe
(S) ONa + MeBr OMe
P  1, 4; Q  2; R  4; S  3.
12. Answer (5)
Alc. KOH
Br
+ +
3-bromo-3-cyclopentylhexane (E + Z) (E + Z)
1 + 2 + 2
Total =5
Note : Dehydrobromination of alkyl bromides in the presence of alc. KOH follows E2 mechanism. Hence no
rearrangement in alkylchain is possible
13. Answer (8)
Cl2
Cl
Cl Cl
* * *
Cl
Two + Four + One + One
Stereoisomers Stereoisomers
 Total Number = 8

14. Answer (3)

Following conformers are stable with non-zero dipole moment
CH3 CH3 CH3
Br Cl CH3 Br Cl CH3
Br Cl Br Cl Br Cl
CH3 Cl Br
15. Answer (2)
Possible stereoisomer are
and
16. Answer (5)
CH3 CH2 Br CH3 CH3

H H H H H * Br Br * H
Br2 (1 mole)
H H 300 ºC
H H + H H H H
H Br H * Br H * Br H * Br
*
CH3 CH3 CH3 CH3
(enantiomerically pure) Chiral Achiral Chiral
(1) (1)
CH3 CH3 CH3

H H H H H H
H * Br H H H H
H * Br Br Br H * Br
CH3 CH3 CH2 Br
Chiral Achiral Chiral
(2) (1)
17. Answer (7.00)
HO OH
HO OH
Only three streocentre are present.

 Total isomer = 23 = 8
But one is optically inactive.
OH OH
HO
OH
18. Answer (9, 13) or (14)
Br
CH3 CH2Br CH2 CH3 CH 3 CH3
UV *
+ Br 2 + + + + Br
*
Br *
(A) (B)() (C)()
Br E(±)
(D)()
Br CH 3
+ * +
*
Br
F(±) G(±)
Monobromination of 1-methylcyclohexene in presence of UV light proceeds by free radical mechanism. The
allyl radicals are formed which are stabilised by resonance. The secondary alkyl radicals are also formed which
are stabilised by hyperconjugation. Of the seven products formed, six of them are optically active. So, 13
possible isomers are formed.
If only allylic substituion is considered, then only 9 stereoisomers will be formed. Officially JEE gave 9, 13
and 14 as correct answer.


Chapter 23
Alcohols, Phenols and Ethers

1. Answer (D)

H
H—Br
O O – OH + CH3Br
Br
CH3 CH3
2. Answer (D)
OH O O
OH
O2N NO2 NH O–C–CH3
HN
HO O COOH
, O ,
O O H
NO2 (Barbituric acid) HO OH
(Picric acid) (Ascorbic acid) (Aspirin)
3. Answer (C)
–OCH3 group has +R effect. It increases the stability of the carbocation.
4. Answer (C)
H5 C2 H H H
2 OH CH 3 3
CH 3
C2 H5 H3C 1 CH3
3,4 4
HO 1 CH 3 H 2 C2 H5
(Q) (R)
Q and R represents identical molecules.

5. Answer (A, C)
(A) & (C) are usual products.

6. Answer (B)
OH OH
Br Br
aqueous
Br2 (3.0 equivalents)
SO3H Br
7. Answer (B, D)
OH OH O
CHO
CHCl3
– +
OH
CH3 CH3 H3C CHCl2

(S) (Q)
(Major product) (Minor product)

8. Answer (A, B, C)
O–H
(I) (III)
(II)
(I), (II) and (III) are probable positions as per electronic effect of OH group where electrophile can attack and
due to steric hindrance at (II) and (III) positions bulky electrophiles are not preferred like I only preferred at
position I, Bromine at positions II and I while chlorine at all three positions.
9. Answer (B)
O H
O
+
,H Radical, initiator, O2
High pressure, heat
'T' 'U'
10. Answer (B, C)
CH3 CH3
H3C – C – H H3C – C – O – O – H OH
O
(i) O2 H3O+
+ CH3 – C – CH3
(P)
H H
OH O O O
CH
CHCl3
+
NaOH
(P) (Q)
CH = O
(Major)
(R)
(i) NaOH (Minor)
(ii) PhCH2 – Br
O – CH2 – Ph
CH = O
(S)
 Q is steam volatile due to intramolecular hydrogen bonding but (R) is a high melting solid.
 Since, Q contains a phenotic group, it forms dark brown solution with 1% aqueous FeCl3 solution.
O – CH2 – Ph O – CH2 – Ph NO2
NO2
CH = O
H+ CH = N – NH NO2
 + H2N – NH NO2
2, 4 DNP (yellow precipitate)
 Since, (S) does not contain free phenolic group, therefore it will not form violet colour with FeCl3
solution.
11. Answer (B)
Me OH
The correct structure of X is

Me OH Me Br Me I
PBr3 NaI
Et2O(SN2) acetone(SN2 ) NaN3, HCONMe2
(SN2)
Me N3
enantiomerically pure
Enantiomerically pure product after several substitution reactions, is only possible when each reaction must
stereospecific in nature which confirms pathway used is SN2 in nature.
12. Answer (C, D)
O OH CH 3 CH 3 Cl
(i) MeMgBr conc. HCl

(ii) H2O
(C6H10O) (Q) S
(major)
20% H 3PO4, 360 K
CH3 Br CH3 CH 3
Br
(i) H 2 , Ni HBr, benzoyl peroxide
(ii) Br2 , h  
T R U
(major) (major) (major)
13. Answer A(r, s); B(p, q); C(p, q, r), D(p, s) or A(r); B(p, q); C(p, q, r), D(p)
14. Answer (10)
Cyclic ethers, including stereoisomers of formula C4H8O are
O O O O O O O
(±) (±)
(±)
Total number of cyclic ethers = 10
15. Answer (6)
OH OH OH
C* — CH 3
OH
H
C* — CH 3
OH H
HC* — CH 3
OH
Phenolic group gives positive test with neutral FeCl3 solution.

Chapter 24
Aldehydes, Ketones and Carboxylic Acids

1. Answer (A)
O3 CHO intramolecular
CHO
Zn, H2O CHO aldol condensation
E F
2. Answer (C)
O O O O
 I2 + NaOH
–CO2 C  C 
iodoform reaction
Ph  OH Ph CH3 Ph ONa + CHI3
-keto acid E G
3. Answer (C)
O H O
–
C C

O –H O
H H
O O
Most acidic Stabilized by strong
intramolecular hydrogen
bonding
4. Answer (B)
H
– H :O – CH2 – R
:
CH2
O O O O R
H

–H
CH2 – R
O O
An acetal
5. Answer (C)
CH2OH
|
OH + HCHO/OH
CH3 — CHO + H — CHO 
Aldol
 HOCH2 — CH2 — CHO 
Aldol
HOCH2 — CH — CHO

CH2OH CH2OH
| |
+ HCHO/OH + HCHO/OH

Aldol
HOCH2 — C — CHO 
Cannizzaro HOCH2 — C — CH2OH
| |
CH2OH CH2OH
 Number of aldol reactions = 3

6. Answer (B)
COOH
O
 -keto acid undergoes easy decarboxylation just by heating through the formation of six membered
transition state.
7. Answer (A)
O OH CN COOH
CN 95% H2SO4
CH3 – CH2 – C – CH3 CH3 – CH2 – C – CH3 
CH3 – CH = C – CH 3
8. Answer (D)
Carbolic acid (Phenol) is weaker acid than carbonic acid and hence does not liberate CO 2 on treatment with
aq. NaHCO3 solution. Benzoic acid, benzenesulphonic acid and salicylic are more acidic than carbonic acid
and hence will liberate CO2 with aq. NaHCO3 solution.
9. Answer (D)
O O– CH3
Cl Cl
CH3
CH3
O
CH3 – MgI
10. Answer (A)
COOH O
– O
H C H
HO OH
O O
(I)
(stabilizes by H-bonding)
COOH O O– H
OH O
(II) (stabilizes by H-bonding)
COOH COO–
OH OH
(III) (stabilizes by –I effect)

COOH COO–
OH OH
(IV) (destabilizes of +m effect)
 Acidity order is I > II > III > IV.

11. Answer (A)
O O
C C
H – CH = O, NaOH, 
(crossed aldol condensation)
CH2
OH
OH O O
H H
C=O C=O
H H
OH , 
–
H+
HO
12. Answer (B)

I. HC  C  COOH
sp
II. H2C  CH
2
 COOH
sp
III. MeO COOH

(EDG) 2
sp
IV. H3 C  CH2  COOH

sp3
+I effect decreases the acidic character of carboxylic acid and –I effect increases the acidic character.
Since the electronegativity order of 'C' attached to carboxylic acid is sp > sp2 > sp3, hence the order is
I > II > III > IV.
II is more acidic than III since the electron donating group is attached to benzene ring.
13. Answer (C, D)
X (CH2)4 X
In C and D diamine is obtained which will give polyamide with dicarboxylic acid.
14. Answer (B, D)
C6H5COOH + NaOH  C6H5COONa + H2O
C6H5COOH + NaHCO3  C6H5COONa + CO2 + H2O
C6H5CH2 – OH + NaOH  No reaction
C6H5CH2OH + NaHCO3  No reaction

C6H5CH2COOH + NaOH  C6H5CH2 – COONa + H2O
C6H5CH2COOH + NaHCO3  C6H5CH2COONa + CO2 + H2O
C6H5CH2OH + NaOH  No reaction
C6H5CH2OH + NaHCO3  No reaction

OCOCH 3
O
CH2OH CH2
O OH Excess (CHCO) OCOCH 3
LiAlH 4 3 2O
H3C H3C H3C

T Optically W
inactive (Molecular formula C10H18O4 )
(U)
COOH
+
CrO3/H
COOH
H3C
V
Hence answer is (A, C, D).

16. Answer (A, B, C, D)
AlCl3
(i) Cl AlCl4 (P)
(AROMATIC)
Na
NaH
(ii) (Q) + H2
(AROMATIC)
(NH4)2CO3
R
(iii) 100–115ºC
O O

(NH4)2CO3 2NH3 + CO2 + H2O
 IMPE
+ NH
O O O O NH O NH OH
H
H H H H
N N N
 IMPE
–2H2O
HO OH O OH
(R) AROMATIC

HCl
(iv) O OH Cl (S)
(AROMATIC)
17. Answer (C)

O
Reaction I : C Br2 (1.0 mol)

CHBr3 + CH3COONa
CH3 CH3 aqueous NaOH
(1.0 mol)
O O
Br2 (1.0 mol)
Reaction II : C CH3COOH
C
CH3 CH3 CH3 CH2Br
(1.0 mol)
18. Answer (A)

CH3 CH3
CH3 O OH
O H O O O +
O
KOH, H2O H
CH3
O
O O

+
(Minor) (Major)
All aldehydes gives Tollen's test as shown below
O
R – CH = O + [Ag(NH3)2 ]+ R – C – O– + Ag+ NH+4
(Silver mirror)
-hydroxy ketones are oxidised to 1, 2 diketones and Ag+ is reduced to Ag.
OH O O O
+
[Ag(NH3)2] +
Ph – CH – C – Ph Ph – C – C – Ph + Ag+ NH4
20. Answer (B, C)
O O
(i) O3/CH2Cl2
CH3 CH3 C–H+H–C–H
(ii) Zn/H2O
Undergoes
Cannizzaro's
reaction
CH2 O O
O3/CH2 Cl2
C C + H–C–H
Zn/H2O
CH3 CH3
Undergoes
Haloform reaction

O O
O3/CH2 Cl2
CH3 C – H + CH3 – C – H
Zn/H2O
CH3 CH3 Undergoes

Cannizzaro's reaction
CH3
CH3 O CH3 CH3
O3/CH2Cl2
C +
Zn/H2O
CH3 O
CH3
CH3 Undergoes
Haloform reaction
H
H
C
H O Me Me
Me C C Me Conc.H2SO4
+ 3H2O
(A) O C H 
H H H
H Me
C O
H C
Me
Me
|
C H Me Me
H C
C Heated iron tube
(B) 873K
C C
Me C Me
Me
|
H
O O
|| O Na
C—Me C
| |
(C)
Br2/NaOH
(Haloform reaction)
Me
Me—C C C C—O Na
|| || Na O || ||
O O O O
+
3H3O
COOH
Soda lime

(decarboxylation)
COOH COOH

CHO CH3
Zn/Hg,HCl
(D) (Clemmensen reduction)
OHC CHO CH3 CH3
22. Answer (B, D)
O
C C – CH2 – CHO C – CH2 – CH2 – CHO
HgSO4, H2SO4 (dil.)
OMe OMe AgNO3, NH4OH
O O
–
CH2 – CH2 – CH2 – COOH C – CH2 – CH2 – C – O
Zn-Hg
(Q)
HCl
OMe OMe
SOCl2 , Py
O
CH2 – CH2 – CH2 – C – Cl
AlCl3 O Zn-Hg
(S)
HCl
OMe OMe OMe

(R)
23. Answer (B, D)
O
CH3 H C CH3 CH3 H C CH 3
H3C 3 CH3 3
O (i) Zn - Hg/HCl
H 3C CH3
AlCl 3 (ii) H 3PO 4
(P) C=O
HOOC
(Q)
CH3 CH 3
H3C H 3C CH3 H 3C H3C CH3
(i) CH3 MgBr
H 3C + H3C
(ii) H 3O
H 3C
O (iii) H 2SO 4/D
(R) (S)

24. Answer (A, B)
CH 3 CH3
N2Cl CN
CuCN
(A)
273 K
DIBAL – H

then HO
3
O
N2H4 C H
KOH, 
CH 3 O O
Br (1) Mg/THF
C OH C Cl
SOCl2
(B) (2) CO2
+
(3) H /H2 O
H2 /Pd-BaSO4
Zn-Hg
C H
HCl
CH 3 CH 3 CH 3
(i) BH3 H 2O2/OH
–
(C)
BH 2 OH
PBr3
Zn
dil HCl
Br
O
C H
(D) O3 O N2H4
Zn/H2O C H KOH, 
25. Answer (C)
26. Answer (C)
27. Answer (B)
28. Answer (D)
29. Answer (A)
30. Answer (C)

O
(1) NaBH4
H3C CH2 C C CH2 C H CH3CH2 C C CH2 CH2Br
(2) PBr3
(I)
(1) Mg/Ether
(2) CO2
+
(3) H3O
Me Cl SOCl2
CH3 CH2 C C CH2 CH2COOH
O (J)
(K)
H2/Pd, BaSO4 , quinoline

(Lindlar’s calatyst)
CHO
(cis product) (L)
31. Answer (B)

32. Answer (A)
33. Answer (D)
O OH
Ph – C – CH3 + PhCH2MgBr Ph – C – CH2 – Ph
CH3 H
Conc. H2SO4 dehydration
Ph – C = CHPh Ph CH3
or
CH3 H Ph
I
Ozonolysis
O
Ph – C = O Ph – C – H
CH3 J
K Cannizzaro's
KOH reaction
Aldol followed
KOH
by dehydration
PhCH2OH + PhCOOK
O
H3C L
Ph Ph
H
M

34. Answer (B)
35. Answer (A)
36. Answer (B)
Me Me Me
(i) MeMgBr H2SO4 (i) O3
(ii) H3O
+ OH (ii) Zn-H2O
O Me Me Me Me Me
P Q
– Me
(i) OH/H2O O
O
(ii) H , 
+
C
O Me
Me Me Me Me
S R
37. Answer (B)
38. Answer (A)
39. Answer (D)
Solution of Q.Nos. 37 to 39
CH3 O
H3C
1. K2CO3 C
C H
2. H H C H
H3C C H3C
H C
(Q) CH2
(P) O 3. H+
O OH
(R)
HCN
OH
H3C CN
CH O
C C H3C
H3C CH
Hydrolysis
C OH
H2C HO H3C
O H CH2
 OH
(S)
OH
H3C
C O
H3C
H2C O
40. Answer (C)
41. Answer (A)

CHO CH = CH–COOH
(CH3CO)2 O (i) H2 , Pd/C

CH3 COONa (ii) SOCl2
(iii) Anhyd. AlCl3
O
42. Answer (B)
H COOH COOH
dil. alk. KMnO4 H OH
C
H OH
C
COOH
H COOH
(S)
(P)
H COOH
COOH COOH
C dil. alk. KMnO4 H OH HO H
C HO H + H OH
HOOC H COOH COOH
(Q) (T) (U)
43. Answer (A)
O
H COOH
C H2/Ni
O

C
HOOC H
(Q) O
(V)
O O
Zn(Hg)
O+ AlCl3 H3PO3
anhydrous HCl
HO HO
O O O O
(V) (W)
44. Answer (A)

O O
NH2
KMnO4/H +
C OH NH3 C NH2 Br2/NaOH
 C OH  C NH2 (Hoffman bromamide)
NH2
O O
(P) (Q) (R)

45. Answer (B)

C
Br – C
C=O
O
O O O
CH2
C – NH2 C C C
 CH3
–NH3
N–H N–C
C=O
C – NH2 C C
(Q) (S)
O (Phthalimide) O O O
CH2
+
H3O
CH3
O
O C – OH
C – C – C – OH+
NH2 C – OH
(alanine)
(T) O
46. Answer (C)
47. Answer (C)

– +
O OMgBr
C(CH3)3 C – OEt CH3MgBr (excess)/(C2H5)2O C(CH3)3 CH3–C–CH3
(P)
H2O
H H
O O–H
C(CH3)3 C(CH3)2 H2SO4/ C(CH3)3 CH3–C–CH3
0°C
(Q)
–H2O (dehydration)
O CH3
CH3 CH3
CH3 CH3–C–Cl/AlCl3 C(CH3)3
C(CH3)3 C(CH3)2 C(CH3)3 (Acylation)
(alkylation)
(R) COCH3
(S)
48. Answer (C)
CHO O—H
COOH
Ac2O Br Moist
CO/HCl Br2/Na 2 CO3
AlCl3 AcONa COOH KOH
(anhy.) D
CuCl (X) (473 K) (Y)

49. Answer (A)

O
CO/HCl – C– H AC2O/NaOAC – CH = CH – COOH
AlCl3/CuCl
(X)
H2/Pd–C
– CH2 – CH 2 – COOH
H3PO4
O
(Z)
50. Answer (A)
CH2–CH2 O
(C11H12O2) dibasic acid OH OH O
oxidation C C (CH 2)2 O
(P must have O
P, Organic acid
multiple bond) O
dacron
dibasic acid must be terephthalic acid i.e.
COOH
to give dacron, compound must have benzene based structure
COOH
Ozonolysis
C11H12O2 ketone + oxidized products of benzene.
COOH
Possible structure of P is (C111H12O2)
COOH COOH
O
oxidation
+
COOH
(P)
COOH
ozonolysis
O
+ oxidized product
ketone
(P)
O O Me
COOH COOH C–Cl C–Me H–C–OH
H 2/Pd-C SOCl2 MeMgBr, CdCl2 NaBH 4
(P) (Q)

Me Me
– +2 –
CH–OH CH–Cl Me–CH Mg Cl Me–CH–COOMgCl Me–CH–COOH
+
HCl Mg, Et2 O CO2 H 3O
(Q) (R)
51. Answer (B)
 –
COOH COOH CONH 2 NH2 N C NH CH 3
H2 /Pd-C NH3 / Br2 /NaOH CHCl3/KOH H2 /Pd-C
52. Answer A(p, s); B(q); C(q, r, s); D(q, r)
53. Answer A(p, q, s, t), B(s, t), C(p), D(r)
(A) CH3CH2CH2CN will give mentioned reaction with other reagents.
(B) Esters will be reduced by DIBAL-H and it will be hydrolyzed by alkaline hydrolysis.
(C) Alkenes are only reduced by catalytic hydrogenation.
(D) Primary amines will give +ve carbyl amine test with NaOH and CHCl3.
 
O
NaOH
CH3CH2CH2CH2 — NH2 
CHCl
 CH3CH2CH2CH2 — N  C
3
Carbyl amine
54. Answer A(p, q, t); B(p, s, t); C(r, s); D(p)
NCl
SN2
Br
O
(A)
O E2
(B) OH ZnCl 2/HCl Cl [Nucleophilic substitution]
(RCO) 2O
O
C
O R
A and B can undergo dehydrogenation.

HO NCl
C
NCl H
O
OH
C
(C) H
O
OH O O
C
R C O C R H
O
O R
Br Nu
Nu
(D) (SNAr)
NO2 Mechanism NO2
55. Answer A(r, s); B(t); C(p, q); D(r)
(A) NN + O—H

Cl–
OH
N=N O
H
N=N O
 Coupling reaction and electrophilic substitution reaction.
OH OH OH OH2
+H
(B) CH3 — C — C — CH3 CH3 — C — C — CH3
CH3 CH3 CH3 CH3
O CH3 OH
CH3
CH3 — C — C — CH3 CH3 — C — C
CH3
CH3 CH3
Carbocation intermediate
O OH
O +
LiAlH4 H H3O
(C) C Nucleophilic addition
C H C H
CH3
CH3 CH3
Racemic mixture
Nucleophilic
H Base S substitution S
(D)
S Cl Cl
B

56. Answer A(r, s, t), B(p, s), C(r, s), D(q, r)
O O
H CH2 H2C
O O O O
OH Nucleophilic addition
A.
Carbanion
O OH O
Dehydration HO – H
–H2O
O Cl
Cl O O
B. CH3MgBr Nucleophilic
CH3 substitution CH3
Carbanion
Nucleophilic
addition
H
..
.O
. O H H
18 18 18
H–O H–O O H–O O O
–H
Nucleophilic +H Dehydration
C. addition
H
+H Electrophilic
D. OH Dehydration substitution
H
Me Me
57. Answer (A)
O O
(1) C6H5CH2 – C – O CH3 C6H5CH2 + CO2 + CH3 – O
O CH3 CH3
O
(3) C6H5CH2 – C – O C CH3 CO2 + C6H5CH2 + CH3 – C – O
CH2 – C6H5 CH2 – C6H5
O
C O CH3 O CH3
(4) C6H5 O C – CH3 C6H5 – C – O + O – C – CH3

CH3 CH3
O O
C O C
(2) C6H5 O CH3 C6H5 O + CH3 – O

58. Answer (D)

h
Br2 Br + Br
CH3 CH2
+ Br + HBr
CH2 CH2 – Br
+ Br2 + Br
59. Answer (C)
COO–Na+
NaOH
C CH3 Br2 + CHBr3
O
H2O/H+
COOH
It is haloform reaction.
60. Answer (C)
O
CH3 – C
O
CH3 – C
CH = O CH = CH – COOH
O
CH3 COOK
Cinnamic acid
It exists in two geometrical forms.
C –H C –H
H – C – COOH HOC – C – H
Trans O
isomer Cis isomer
It is basic example of Perkin's reaction.
61. Answer (D)
Ph Ph O O
Me Ph
I2/NaOH
(P) HO + H2SO4 Me Me C – OH
Ph HO Me Ph Me Ph
O
Ph
NaOBr
Me C – OH
Ph
P  1, 5

Ph Ph O Ph
H [Ag(NH3)2]OH
(Q) H2N OH + HNO2 Me Me COOH
Ph Me Ph H Ph
Ph
Fehling
Me COOH
Solution
Ph
Q  2, 3
Ph Ph O
Ph
(R) HO OH + H2SO4 Ph
Me Me Me Me
NaOBr I2/NaOH
Ph Ph
Me COOH Me COOH
Ph Ph
R  1, 5
Ph Ph
Ph
(S) Ph OH + AgNO3 Ph CHO
Br Me Me
Fehling [Ag(NH3)2]OH
solution
Ph Ph
Ph COOH Ph COOH
Me Me
S  2, 3
62. Answer (A)
Cl KCN CN +
H 3O / COOH LiA H 4
(III)
CO 2CH3 CO 2CH3 CO 2H
Conc.
CH2OH H 2SO 4 CH 2 OH –H 2 O
:
+ –H
+
O
CH2 OH CH2 OH2
(Q) (R)
CH2OH
CO2Me CH2OH Conc.
LiAH4 H2SO4
+
(IV)
CH2Me CH2OH CH2—OH2
(Q)
+ –H
+
O—H O
(R)
(III), (Q), (R) ; (IV), (Q), (R)

63. Answer (B)
CN DIBAL-H CHO dil. HCl CHO NaBH 4 CH 2OH

(I)
O O
CHO CH 2OH
O O
(Q)
+
Conc. CH2 OH2 –H
+
H2 SO 4 + O O
CH2 OH 2 H
(R)
OH Conc.
(i) O3 CHO NaBH4 H2SO4
(II)
(ii) Zn/H2O O
COOH COOH COOH
O
(P) (S) (U)
(I), (Q), (R); (II), (P), (S), (U)

64. Answer (1)
O
O
1. O3 1. NaOH(aq)
2. Zn–H2O 2. Heat
O
65. Answer (4)
Carboxylic acids and aromatic alcohols dissolves in aqueous NaOH.
COOH OH OH COOH
, , ,
N
H3C CH3
will be soluble in aqueous NaOH.
66. Answer (2)
O O O O O
+
OH
H3O OH *
O (–H2O, –CO2)
OH
O O O O O
O
HOOC (i) O3
HOOC (ii) H2O2
O (P)

So, final product (P) has two carboxylic acid

 Heating causes evaporation of water and due to which concentration of acid increases and in concentrated
acidic medium decarboxylation as well as dehydration will take place.
67. Answer (5)
O
1 2 3 4
(I) CH3 CH2 CH2 CH2 C CH3
5 6
(II) CH3 CH2 CH 2 C CH2 CH3
CH3 O
(III) CH3 CH2 CH C CH3

It has chiral centre
CH3 O
(IV) CH3 CH C CH3
CH3
CH3 O
(V) CH3 CH C CH2 CH3
(VI) CH3 CH CH2 C CH3
CH3
Only (III) form diastereomers on addition reaction so, desired ketones as per addition reaction is 5.
68. Answer (4)
CHO
CO, HCl
(Gatterman Koch Reaction)
Anhyd AlCl3/CuCl
OH
CHCl2 CH CHO
H2O OH
100°C –H2O
COCl CHO
H2
(Rosenmund Reduction)
Pd–BaSO4
COOMe CHO
DIBAL–H
Toluene, –78°C H2O

69. Answer (18.00)
Degree of unsaturation of Q = 18
70. Answer (1.62)
71. Answer (3.20)
Sol. of Q. No. 70 and 71
H 2O NaNH 2
Mg2C3 C3H 4 (P) CH3 C C CH 3
4g MeI
(Q)
Hg2+/H + Red hot

iron tube
O
CH3 C CH 3 (S)
Ba(OH)2/ (R)
O
CH 3 C CH C CH3
CH3
(T)
NaOCl
O
CH 3 C CH C OH (U) + CHCl 3
CH3
4 g of C3H4 = 0.1 mol
From 0.1 mol of P, 0.01 mol of R will be produced
 1.62 g of R is produced
From 0.1 mol of P, 0.032 mol of U is produced
= 3.2 g of U is produced


Chapter 25
Amines
1. Answer (B)
O
N
1
H 2
Ring 1 is activated by NH group .
2. Answer (C)
O
O C
O C
NaOH + Br2 Cl NH
H3C C H3C NH2
NH2
H 3C
3. Answer (A)
More reactive
site for SN2
O O
O
C C Br CH2 Cl
OH
N H N K N CH2 Br
C C
O
O O
4. Answer (C)
OH
HO
NH2 NaNO /HCl N N N N
2 –
Cl
H3C H3C H3C
Brilliant coloured dye
5. Answer (D)
N2+Cl– O H
O H O N N
NaOH

6. Answer (A)
NH2
H2N NH
IV
Resonance with two NH2 groups increases electron density on 'N' of NH
NH
Lesser increase of electron density on = NH due to
only one resonance with one –NH2.
CH3 NH2
2
sp
N
N This LPe– is not available as it is involve in aromatic Sextet.

H 'N' is bonded to sp2 C on both sides.
III
N This LPe– is not involve in aromaticity. So more available

H
Also, 'N' is bonded to sp3 C on one side.
II
 IV > I > II > III
7. Answer (B)
–
OH OH O
NaNO2 + HCl aq.NaOH

0°C
+
N  NCl NN
+ –
NH2
OH O
N=N N=N H
8. Answer (A)
H
+
NH2 N
O O
H O
O
+ CH3COO–
NH2 CH2Cl2
O
H
N
O
+ CH3COOH

9. Answer (C)
H H
O O
O
C O C O C O
NaNO2
aq. HCl (Inversion)
H – H
NH2 0°C +
Cl N2 H
(Diazotisation)
H
O
O
C O C O
(Inversion)
H OH2
OH H
(Retention Product)
(Major)
10. Answer (A)

+ –
N  NCl OH
N=N
NH2 , NaOH OH
NaNO2, HCl
0°C
(V) (W)
11. Answer (A)

O OH
H NH
(1) O3 H NH3
(2) Zn, H2O
O OH
–2H2O
12. Answer (B)

O O
NH2 NH – C – CH3 NH – C – CH3
Ac2O KBrO3/HBr
pyridine
acetamilide
Br
(major)
+ –
NH2 N  NCl Br
H3O+ NaNO2/HCl Cu
273 – 278 K HBr
(diazotisation)
Br Br Br

13. Answer (D)

NH2 NH 2 NH 2 NH 2
Conc. HNO3 NO 2
+ +
Conc. H2SO 4
NO 2
NO 2
51% 47% 2%
(P) (Q) (R)
O O
NH2 NH – C – CH 3 NH – C – CH 3
NO2 Ac 2 O, Pyridine NO2 Br2 NO 2
CH3COOH
(R) Br
+
H3 O
+ –
N2 Cl NH2
NO2 EtOH
NO 2 NaNO2, HCl
NO 2
 273-278 K
Br Br Br
(S)
Br
NO2 Sn/HCl
NH 2 Br 2
NH 2
H2 O (excess) Br Br
Br Br Br
(S)
NaNO2 , HCl
Br Br
+ –
H 3PO 2 N2 Cl
Br Br Br Br
Br Br
14. Answer (C, D)
Basicity order: II > I > IV > III
In IV, because of steric effect–N(Me)2 goes out of plane.
That's why resonance of N with the ring decreases and its basic nature increases.
15. Answer (C, D)
AgCN (V)
Br2 CHCl 3
Ph – CH3 light
Ph – CH2 – Br Ph – CH2 – NH2 Ph – CH 2 – N C
(ii) H 2/Pd – C KOH
(P) (S)
(i) KMnO4 OH, 
(ii) H 3O
O LiAlH4
O NH 2 (W)
C
C OH (i) NH 3
(ii) Heat
(T) (U)
 Correct option are

Q = AgNO2, R = phenylmethanamine
W = LiAlH4, V = AgCN
16. Answer (C)
NO2
Scheme I (S)
CH3
NO2
Scheme II (R)
Scheme III H – C  C – H (P)

OH
Scheme IV
OH
17. Answer (490 – 500)
O COOH CONH 2 NH2 NH2

Br Br
NaOBr NH 3 Br 2 KOH
+
H 3O D D
Acetophenone A B C
10 moles (60%) (50%) (50%) Br
D
(100%)
60 50 50
Yield of D in moles = 10     1.5 moles
100 100 100
Amount of D = 1.5 × 330 = 495.00
18. Answer (4.00)
+ –
NH2 NH2 N2Cl
Br Br Br Br
(i)Br2(excess) (ii) NaNO2
H 2O HCl
273 K
(P)
Br Br
COOH CN
Br Br Br Br
(iv ) H 2O (iii) CuCN
H, 
+ KCN
O
Br Br
C Cl
(iv) SOCl2
Br Br
Py
(Q)
Br

SO3H OH
OH
(i) Oleum (ii) NaOH (iv) Br 2

 CS2 , 273 K
(iii) H+
(R)
Br
O Cl (S)
C
–
Br Br
OH O
Br
O
NaOH
Br
Br O C Br
(Q)
Br
Br Br (T)
(S)
19. Answer (18.6)
+ –
NH2 N2Cl
(i) NaNO2 + HCl/0-5°C
(P)
OH
(ii) , NaOH
N
N
O
OH
CH 3CO2H/H2 O N=N
(Q)
M.M. = 248
9.3 mL of P  9.3 g of P
9.3
Moles of P =  0.1
93
Moles of Q obtained = 0.1 × 0.75 = 0.075
3
Mass of Q obtained = 248 × 0.1 × = 18.6 g
4
20. Answer (3.57)
21. Answer (1.23)
Sn + HCl  SnCl2
NO2 NH3Cl
SnCl 2/HCl
+ SnCl 4
y gm 1.29 gm
1.29
 Moles of ammonium salt = = 0.01
129
 Moles of nitrobenzene = 0.01

 y = 0.01 × Molar mass of nitrobenzene
= 0.01 × 123
y = 1.23
Also
No. of eq. of nitrobenzene = No. of eq. of SnCl2
6  (0.01)  2  nSnCl2
nSnCl2  0.03
 nSn = 0.03
wSn = 0.03 × 119
x = 3.57


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Chapter 1

Some Basic Concepts of Chemistry

2Al(s)  3H2SO4 (aq)  Al2 (SO 4 )3 (aq)  3H2 (g)

= 0.2 moles 0.25 moles

H2SO4 is limiting reagent

 Moles of H2(g) produced = 0.25 moles

Using ideal gas equation : PV = nRT

0.25  0.082  300

Radial probability function curve for 1s is

no. of angular nodes in an orbital = value of l

no. of radial node in 4d = 1

In 2s, one radial node is present.

E( H1 ) = –13.6 eV [Ground state]

So, energy = 2.25 × energy of e– in ground state in 1H1

Orbital angular momentum of 3p is 1.

In (B) for 3dz2 , xy plane is not nodal plane.

In (C), 2pz orbital has no radial node.

11. Answer (A)

6.62  10 34  3  108

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18. Answer (30)

Momentum of 1 mole of He-atoms = mv

6  1023  6.6  10 –27

 Change in velocity of He-atoms = 30 cm s–1

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Chemical Bonding and Molecular Structure

Molecular orbital diagram for B2 where Hund’s rule is violated.

Compound Number of lone pairs on central atom

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11. Answer (A, B, C)

Similarly in N2 b.o. is 3, it is diamagnetic, Neither it will undergo oxidation nor reduction.

O2 and O2 are paramagnetic.

13. Answer (C)

14. Answer (4)

Hybridisation sp Hybridisation sp2

[Cl –..I – Cl]–

Structure linear Structure linear

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17. Answer (6)

He 2 12s 1*s1 Paramagnetic

Li2 12s 1*s 2 22s Diamagnetic

Be2 12s 1*s2 22s 2*s2 Diamagnetic

B2 12s 1*s 2 22s 2*s 2 12 px  12 py Paramagnetic

C2 12s 1*s 2 22s 2*s 2 22 px  22 py Diamagnetic

N2 12s 1*s 2 22s 2*s 2 22 px  22 py 22 pz Diamagnetic

18. Answer (6)

Br It has two lone pairs

19. Answer (6)

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20. Answer (–2640.00 to –2620.00) or (–5280.00 to –5240.00)

54.4  1.6  10 19  6.023  10 23

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Correction factor in pressure is directly proportional to square of density.

 a = 1.5 atm L2 mol–2

4. Answer (A, C, D) or (A, C)

According to Kinetic theory of gases,

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11. Answer (4)

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Be2 12s 1s2 22s 2s2 Diamagnetic

B2 12s 1s 2 22s 2s 2 12 px  12 py Paramagnetic

C2 12s 1s 2 22s 2s 2 22 px  22 py Diamagnetic

N2 12s 1s 2 22s 2s 2 22 px  22 py 22 pz Diamagnetic