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HINTS AND SOLUTIONS

1. Basic Concepts of Chemistry


11. (B) 28. (C)

o 9 Mass of 6.022 × 1023 O2 molecules = 32 gram


F = (oC) + 32
5 \ 3.01 × 1021 O2 molecules

\ x=
9x
5
+ 32
=
3.01 s 1021 s 32
= 0.16 gram
6.021 s 1023
\ 5x = 9x + (32 × 5)
\ – 4x = 160
29. (D)

\ x = – 40
Avg. at. mass =
10 s 19 11 s 81
12. (B) 19 81
1 Å = 10–8 cm = 10.81
10 Å = 10–7 cm = 1 nm 30 (C)
14. (B) 4.2
No. of moles of N31– = = 0.1
V = l × b × h = 0.6 m × 10 × 10–2 42
m × 150 × 10–3 m 1 mol N31– ions = 6.022 × 1023 = NA
= 9 × 10–3 m3 ions
=9L \ 0.1 mol N31– ions = 0.1 × NA ions
15. (A)
Now, number of valence electrons in one N31–ion
12.6 s 10 kg3
= 3 × 5 + 1 = 16
= 12.6 kg/L
10-3 L
Then no. of e–s in 0.1 × NA ions = 1. 6 NA
16. (B)
31. (B)
1.8 × 10–2 km
At STP, 22.4 L = 1 mol
= 18 m
= 1800 cm 1 21
1L= mol ×
17. (A) 22.4 100
= 0.009375 mol
o
9 s 40
D F= = 72 oF 32. (C)
5
19. (B) n × 56 × 100
0.33 = where
67200
D
o
F=
9
5
(C2 – C1) \ n = 3.96 » 4
n = No. of Fe atoms
9 36. (A)
18 = (111 – C1)
5
p
Vol. of virus = r2l =
C1 = 101
24. (B) 22
× (7 × 10–8)2 × (10 × 10–8)
7
KCl + AgNO3 ® AgCl + KNO3
7.45 g ‘x’ g 14.35 g 10.1 g = 154 × 10–23 cc
\ x = 14.35 + 10.1 – 7.45 = 17 Mass of virus particle

779
Vol 154 s 1023 1031
= = =
Sp. Vol. 6.02 s 1023 9.108 s 6.023 s 1023
\ M.W. of virus = Vol. of NA virus particles 1
= × 108 mol e– s
154 s 10 23 9.108 s 6.023
= × 6.02 × 1023
6.02 s 102 43. (B)
= 15400 gram/mol density of H2O = 1.0 gram/mL
= 15. 4 kg/mol
38. (A) \ Number of moles of H2O =
18
18
=1
Number of molecules in 15 L H2 at STP
6.023 s 1023 s 15 = 6.02 × 1023 molecules
=
22.4 Number of e– s in H2O molecule
= 4.033 × 1023 = 2 (1) + 8 = 10
Number of molecules in 5L N2 at STP \ Total number of e– s = 10 × 6.02 × 1023
6.023 s 1023 s 5 = 6.02 × 1024
=
22.4 44. (C)
23
= 1.344 × 10 mass of 6.023 × 1023 CuSO4.5H2O molecules
Number of molecules in 0.5 gram H2 = 249 gram

=
0.5 s 6.023 s 1023 \ 1 × 1022 CuSO4.5H2O molecules weigh
2
249 s 1022
= 1.505 × 1023 =
6.023 s 1023
Number of molecules in 10 gram O2
= 4.14 gram
10 s 6.023 s 1023 45. (B)
=
32
F69.94 O 30.06
= 1.882 × 1023 56 16

40. (C)
F1.2489 O1.8787
Mass of 6.02 × 1023 molecules = 18 gram =
\
1.2489 1.2489
Mass of one water molecule
= Fe O1.50
18
= gram Molecular Formula = Fe2O3
6.02 s 1023
48. (A)
mass 18
vol = density = 44 gram CO2 = 12 gram ‘C’
6.02 s 1023 s 1
2.64 s 12
» 3.0 × 10–23 cm3 \ 2.64 gram CO2 =
44
gram
41. (C)
1
\ 1.8 gram Organic Substance =
nO
2
= 32 = 7 2.64 s 12
nN 4 32 gram carbon
2
28 44
42. (D) \ 100 gram Organic Substance =
–31
9.108 × 10 kg = 1 electron
12 s 2.64 s 100
= 40 %
44 s 1.8
\ 1 kg =
1
9.108 s 1031
electrons
Similarly, H = 6.66 %
780
\ % O = 100 – (40 + 6.66) 62. (B)
= 53.33 2MnO4– + 6H+ + 5 SO32–
® 2Mn2+ + 5 SO42– + 3H2O
C 40 H 6.66 O 53.33
12 1 16 5 mol SO32– ion = 2 mol MnO4– ion

= C 3.33 H 6.66 O 3.33


3.33
\ 1 mol SO32– ion =
2
5
mol MnO4– ion
3.33 3.33
64. (D)
= CH2O
PbO + 2HCl ® PbCl2 + H2O
51. (A)
6.5
Zn + H2SO4 ® ZnSO4 + H2 Number of moles of PbO = = 0.029
22.3
Zn + 2NaOH + 2H2O ®
3.2
Na2 [Zn(OH)4] + H2 Number of moles of HCl = = 0.087
36.5
52. (A) PbO is Limiting Reagent

1 \ 1 mol PbO = 1 mol PbCl2


Ag2CO3(s) 2Ag(s) + CO2(g) + O
2 2(g) \ 0.029 mol PbO = 0.029 mol PbCl2
65. (B)
276 gram 108 × 2 gram
\ 2.76 gram = 2.16 gram
2MnO4– + 5C2O42– + 16H+
® 2Mn2+ + 10CO2 + 8H2O
53. (A)
5 mol C2O42– = 2 mol MnO4–
– 2–
There are 0.02 mol Br and 0.02 mol SO4 ions
in 2L solution. \ 1 mol C2O42– =
2
mol MnO4–
\ In 1 L mixture of X, contains 0.01 mol Br–
5
= 0.4 mol MnO4–
and 0.01 mol SO42– ions
\
70. (D)
Y = 0.01 mol AgBr
98 s 1.8 s 10
Z = 0.01 mol BaSO4 molarity = = 18 M
98
54. (C) M1V1 = M2V2
C2H4 + 3O2 ® 2CO2 + 2H2O 18 V1 = 0.1 × 1
28 gram 96 gram
\ 2.8 kg (?) \ V1 =
0.1
18
L
= 9.6 kg = 5.55 mL
55. (D) 71. (D)
2 mol = 15 mol O2 3BaCl2 + 2Na3PO4 ® Ba3 (PO4)2 + 6NaCl

\ 0.5 mol = 3.75 mol O2


Na3PO4 is L.R.
2 mol Na3PO4 = 1 mol Ba3 (PO4)2
At. STP 1 mol = 22.4 L
0.2 mol Na3PO4 = 0.1 mol Ba3 (PO4)2
3.75 mol = 84 L
73. (B)
60. (D)
M.W. of mixture = 2 × 38.3 = 76.6
1.2 mol NaCl = 70.2 gram NaCl
100
70.2 s 100 Number of moles of mixture = (i)
% w/w = 76.6
1070.2
Let in 100 gram mixture ‘x’ gram be NO2
= 6.56
781
123.5 gram 98 gram
\ Number of moles of NO2 =
x
46
(ii)
Thus, 123.5 gram CuCO3 = 98 gram H2SO4

Number of moles of N2O4 =


100 - x
92
(iii) \ 0.5 gram CuCO3 = 0.3967 gram H2SO4

From (i), (ii) and (iii) 0.3967 s 1000


Volume = = 8.097 mL
98 s 0.5
x + 100 - x = 100
46 92 76.6 78. (C)

\ x = 20.1 gram 3Pb(NO3)2 + Cr2(SO4)3


® 3PbSO4(s) + 2Cr(NO3)3
\ Number of moles of NO2 =
20.1
46
= 0.437 m mol of Pb(NO3)2 = 45 × 0.25 = 11.25

mol m mol of Cr2(SO4)3 = 25 × 0.1 = 2.5


75. (C) Cr2(SO4)3 is L.R.

Formula of compound = M3 N2 2.5mmol Cr2(SO4)3 give 7.5mmol of PbSO4

Valency of N = 3 \ Moles of PbSO 4


precipitated = 7.5 × 10–3
m moles of Pb(NO3)2 unreacted
\ Equivalent weight of N =
14
3
= 11.25 – 7.50 = 3.75

28 gram nitrogen combines with 72 gram metal \ Molarity of Pb(NO3)2 =


3.75
70
\ 14
3
gram nitrogen combine with = 0.0536 M
81. (A)
14 s 72 Mg2+ + Na2CO3 ® MgCO3 + 2Na+
= 12 gram metal
3 s 28 1 g. eq 1 g. eg.
\ Equivalent weight of M = 12 2+
1 g.eq. Mg = 12 g.Mg = 2+

\ Equivalent weight of M = 12000 mg Mg2+


Equivalent weight × valency º
12000 mg Mg2+ 1000 m.eq. Na2CO3
= 12 × 2 \ 1 mg Mg 2+
º 1 m.eq. Na CO2 3
= 24 82. (A)
76. (D) m.eq. H2SO4 = m.eq. NaOH

molarity×1000 \ Normality of H2SO4 = 32.96


molality = (1000d)-(M.W.×molarity) \ Mass of H2SO4 = 8.0752 gram

3×1000
= (1000 × 1.25)-(158 × 3)
\ density =
8.0752
5
= 1.615 g/mL

= 3.865m \ purity =
1.615
1.8
× 100 = 89.72%
Na2S2O3 ® 2Na+ + S2O32–
85. (B)
\ molality of Na+ = 2 × 3.865 = 7.73
n N
= 0.2 Q = 0.8
and molality of S2O32– = 3.865 n+N n+N

77. (A)
\ n
N
= 0.25
CuCO3 + H2SO4 ® CuSO4 + H2O + CO2
782
n × MC
\ 3V + 4(3 – V) = 10
\ WC
6H6
= 0.25 \ V=2L
6H6

1
% of C4H10 = ´ 100 = 33.33%
\ WC H
n = 0.25
78
3
6 6
90. (D)
Let the mass of hydrogen = 1 gram
\ n × 1000 = 1000 × 0.25
WC H 78 = 3.2
\ mass of carbon = 10.5 gram
6 6

86. (C) 10.5 1


mol of C : mol of H = :
12 1
64 + 34V
Normality of mixture = ,
1000 = 0.875 : 1
where, V = Vol of H2SO4 = 0.875 × 8 : 1 × 8
=7:8
10
Normality of Na2CO3.10H2O = Emperical Formula : (C7H8)n
143
N1VI = N2V2 mRT
From, PV =
M

64 + 34V 10 M = 91.8
× 30 = × 42.9
1000 143
MW 91.8
n= = » 1
\ V=
68 EFW 92
17
\ MF = C7H8
\ more equivalence of 17 M H2SO4 = •

68
34 × = 136
17 2. States of Matter
\ Equivalence of H2SO4 =
136
1000
= 0.136 27. Density of a solid crystal 19.3 gm/cm3, if

\ Equivalence of SO42– = 0.136


molecular mass of metal is 197 gm/mole

\ mass of SO42– = 0.136 × 48


and metal crystalises as fcc which of
following will be its atomic radius ?
= 6.528 gram
89. (C) For Fcc or ccp a = 2 2·r Q a3 =
Let the volume of C3H8 = V litre
\ Volume of C4H10 = (3 – V) litre 16 2·r3 and Z = 4

C3H6 + 5O2 ® 3CO2 + 4H2O


V 5V 3V 4V Z× M
Density d = 3
N×a
13
C4H10 + O ® 4CO2 + 5H2O
2 2

13 \ 19.3 =
4 × 197
23
6.022 × 10 × 16 2 × r
3
3–V (3 – V) 4(3 –V) 5(3 –V)
2

783
32.
4 s 197
\ r3 =
19.3 s 6.022 s 1023 s 16 2 P

Q
= 3.0 × 10–24

\ r = 1.44 × 10–8 cm

= 144 pm

28. For bcc unit cell Z = 2, a = 288 pm


R
= 2.88 × 10–8 cm

Z× M In a diamond crystal, carbon atoms are arranged


density d = 3 melecular mass of element
N×a in Fcc arrangement the four body diagonals of
the unit cell possess eight telrahedral voids. Out
3 of which alernate four voids (each body
M = d× N×a
Z diagonal has two tetrahedral voids out of which
one) carbon at atom is arranged.

=
7.2 s 6.022 s 1023 s (2.88 s 108 )3
2
\ Number of atoms (Z) per unit cell of
diamond Z = length of the body diagonal PR of
= 51.787 gm/mole the unit cell = 3·a

51.787 gm of element contains number of atom C – C bond length = PQ


= 1 mole
3·a
= 6.022 × 1024 = 154.48 pm
4

208 gm of element contains


154.48 s 4
Q a=
208 s 6.022 s 10 23
gm 3
= =
51.787 cm 3
= 356.75 pm
= 2.418 × 1023 33. Volume of any solid crystaline unit cell

29. V = abc[1 – cos2a – cos2b – cos2y

zM + 2cosa . cosb . cosy]1/2


density d =
Na 3
= a3 [1 – cos260o – cos260o – cos260o

dNa
3 + 2cos60o . cos60o . cos60o]1/2
Z= M
= a3 [1 – 3cos260o + 2cos360o]1/2

2.7 s 6.022 s 1023 s (405 s 10 10 )3 1 1


= = 4.0
27 = a3 [1 – 3 × + 2 × ]1/2
4 8
As unit cell of Al contains 4 atoms it is as fcc
3
unit cell a
=
2
784
34. In a diamond unit cell, length of body
diagonal is
M
PR = 3·a

S c

P
P
Q R
G X
120o
a Q

\ PX = PQsin 60o = 2r ⋅
3
= 3r
2
R

2PX = 2 3r = 2r
PG = 3 3 3
3·a
C – C bond length = PQ = = 2r (Right angle D SGP) in SP = 2r and
4

\ a=
8r
3
(in hcp unit cell C = m A = 2
3
Ð 2

\ Volume of unit cell, v = a3 SG2 + PG2 = SP2

3 2
512r
=
3 3 \ SG2 = SP2 – PG2 = 4r2 – 
 2r 
 3

Number of atoms in a diamond unit cell Z = 8


2 2
= 4r2 – 4r = 8r
\ Packing efficiency 3 3

100 Z 4π r 100 × 8 × 4π r \
3 3 2 2r
SG =
3 = 3 3
= a3  512r3 
 
 3 3  Now, HCP c = MG = 2SG

= 33.99 » 34.0 % 2 2·r 2


=2× =4 r
3 3
36. If centres of spheres P, Q, R, S are joined
they form a square planar structure.
40. If height of cylinder is l then c = 2l and
D PQR is an equilateral triangle and a = b = 2r.

PQ = OR = RP = 2r \ Volume of a cylinder X = pr l 2

In equilateral triangle D PQR, PX is its Now for 1 hcp arrangement of unit cell number
median and vertices and G is the centre. In of cylinder (atoms) is z = 6
right angle D PQX, mÐPQR = 60o and volume of unit cell of hcp
785
\ r
3 2 2
a - AD
V = 3a2c sin60o = 3 × 4r2 × c × – sin ( ) = 2
2 2 3a
2
= 6 3r × c = 6 3r 2 × 2l = 12 3r 2 l now mathematically (as explained in theory)
hcp arrangement packing efficiency
1-cos 2 FRV 2 FRV 2 FRV FRV FRV
100 Z x cos 2  
= sin 2
V

1  cos 2 600  cos 2 600  cos 2 600 2cos 600 ·cos 600 ·cos 600
100 × 6 × π r l
2
= sin 2 600
= 2
12 3r l

100 s 6 s 3.14 1  3cos 2 600 2cos3 600


 
= sin 2 600
12 3
= 90.64 %
2 3
42. ¥ 1µ ¥ 1µ
1  3¦ ¶ 2 ¦ ¶ 3 1
§ 2· § 2· 1
=  4 4  2
2
D ¥ 3µ 3 3
¦§ 2 ¶· 4

6a

\ r = 1 – cos p = 1 – 23
a
1
sin2 2 
3
( ) ( + 90o )

r=
o
(90 ) 3a
120o a
C 1
A a B
Therefore, sin
3

Now, r
– sin ( ) =
4a 2 - AD2
2 3a 2
As mentioned in the figure, the longest
body diagonal of Triangle crystal = AD. 2 2
Therefore, – 1 = 4a - AD
In D ABC AB = BC = a and mÐABC = 120 o
3 2 3a 2
According to the laws of Trigonometry
cosines cos 120o 2a2 = 4a2 – AD2

2
a + a − AC
2 2
1 2a - AC
2 2 \ AD2 = 6a2
= Q - 2= 2
\ AD =
2a a 2a
6a

\ – a2 = 2a2 – AC2 43. Metal oxide formula =


A B
1× 1 2× 1 O = A2B2O6
3 4

\ AC2 = 3a2 Q AC = 3a
A B
D ACD{kt AC = 3a , CD = a and 45. Formula of metal oxide = 1× 1 2× 1 O
3 4

mÐACD = (p + 90o)
= A2B2O6
According to the laws of Trigonometry
2 2 2
2(a) + 3(b) + 6(–2) = 0
a × ( 3a) − AD
r
cosines cos ( + 90 ) = o
2 3a a 2a + 3b = 12 solving it option (d) + 3, + 2
786
49. Number of O2– ions arranged in ccp unit cell = 4 \ 2(R + r) = 3a and a = 2R
Number of ions of metal A arranged in
tetrahedral void = 8
\ 2(R + r) = 3 (2R)

Number of ions of metal B arranged in \ R+r= 3R


octahedral void = 4
Hence components are occupying 100 % lattice \ r = ( 3 – 1) R
sites will have A8B4O4 as its common formula
of the compound. \ r
R
= 3 – 1 = 1.732 – 1
given formula for compound is A3BO3. to make


number of O ion 4 dividing it by
4
obtained
\ r
R
= 0.732
3
formula : A4 B 4 O4
3
\ radii ratio for body centred void Rr = 0.732
Now, out of 8 tetrahedral voids, ions of metal
A is occupying = 4 \ radii ratio for body centred void radius =
\ Percentage occupancy of tetrahedral void r = 0.732 × R
100 s 4 = 0.732 × 180
by ions of metal A = = 50 %
8
= 131.76 pm
and out of 4 octahedral viods, ions of meta
51. Spheres arranged in body centred arrangement
4
B is occupying = and the void created between them the ratio of
3
radius of sphere in lattice site is theoretically
\ Percentage occupancy of octahedral void explanied as

100 s 4 r
by ions of metal B = = 33.33 % = 0.291
4s3 R

50. edge length of unit cell = a, r = 0.291 × R


radius of body contred void = r
= 0.291 × 180
bond length of unit cell = 3a .
= 52.38 pm

r r +
K+ Na
58. r = 0.74 and r = 0.55
- -
a Cl Cl

Crystal structure of NaCl and KCl have fcc


2 (R + r) structure.

In both the cases the negative ions are filled

In fcc arrangement hence their edge length of


their unit cell a = 2(r+ + r–).

Ratio of edge length of their unit cell


787
The tetrahedral void created by cations having
a KCl
= a can be P, R, M and N is occupied by anion X.
NaCl
In the same tetrahedral void created by four
cation is occupied by anion Y.
2(r + +r - )
K Cl
= 2(r + r ) D XRP and D QYP are isociate triangle and
Na -
Cl
PQR will RP = PQ = m
RX = PX = PY + YQ = r+ + r–
r +
K
+1
r ¥ 1µ
= r
Cl-
Ð
m Ð R ´ P = m PYQ = 1090 28’ = cos–1 ¦§  ¶·
3
Na +
+1
´ P) =
r -
Cl
According to cosine rule, cos(mÐ R
2 2 2
RX + PX − PR
0.74 + 1
= 2 RX PX
0.55 + 1

1.74 ¥ 1µ
\
2 2
= 2XR - m
1.55 cos (cos–1 ¦§  ¶· ) = 2
3 2XR
= 1.226
60. anions are in a unit cell of fcc arrangement and 2XR 2 - m 2
Hence
2XR 2
4(r + + r - )
their edge length a =
3 \ – 2XR2 = 6XR2 – 3m2

For two ions in a fcc arrangement the distance \ 8XR2 = 3m2 \m


2
=
8
3
XR2. ... (1)
between their centres = half of the length of
the diagonal of its unit cell D PQR RQ = c, RP = PQ = m

¥ 1µ
=
2a =
+ −
a = 4(r + r ) = 4 × 205 Ð
and m RPQ = 109028’ = cos–1 ¦§  ¶·
3
2 2 6 6
Cosine Law of cos (m RPQ) Ð
= 334.76 pm
RP2 + PQ2 − RQ2
62. 2–
O = anion (S ) and O = cation (Zn ) 2+ =
2 RP PQ

N
¥ 1µ 2
2m - c
2
cos (cos–1 ¦§  ¶· ) =
R
\ 2
M 3 2m
m Y
1 2 2
2m - c
\  = 2
3 2m
c P

\ –2m2 = 6m2 – 3c2. Hence, 8m2 = 3c2


Y
m
8 2
\ c2 = m ... (2)
Q
3
b
a

788
8 8 Gaseous state
From result (1) and (2) c2 = s XR2
3 3

8 1. According to Boyle’s law P1V1 = P2V2


\ c= XR but XR = r+ + r–
3
P1 = 200 millibar

8 + – P2 = ?
c= (r + r )
3 V1 = 100 ml
V1 = 1 litre = 1000 ml
8 8 s 103.7
\ c = (74 + 29.7) = P1V1
3 3
∴ P2 = V
2
= 276.53 pm
71. Due to metal defficiency defect FexO is mostly 200 s 100
=
Fe0.92O calculate the percentage of Fe 2+
and 1000
3+
Fe ions in them ? = 20 millibar
OR
Suppose Fraction of Fe2+ ion = x
d1 d 2
\ Fraction of Fe3+ ion = 0.95 – x 2. = P1 = 1 bar d1 = 2.5
P1 P2
2+ 3+ 2–
\ metal oxide formula : Fex Fe (0.95–x)
O
P2 = 0.5 bar d2 = ?
Compound by charge is neutral hence some
of the oxidation state of ions in it is zero d1P2
d2 =
\ 2x + 3 (0.95 – x) + (– 2) – 0 P1
\ x = 0.85
2.5 s 0.5
= = 1.25
100 s 0.85 1
\ % Fe2+ ion =
0.95 3. T1 = 400 K V1 = 4 litre
= 89.47 T2 = ? V2 = 2 litre
% » 89.5 and
V1 T1 T1V2
% of Fe3+ ion = 100 – 89.5 =
V2 T2 ∴ T2 = V
1
= 10.5 %
400 s 2
72. Metal oxide has formula is M0.98O, when M is = = 200 K
4
M2+ and M3+ form.
T2 = – 73oC
3+ 2+
If M ion is x mole and M ion is (0.98 – x)
4. T1 = 27oC = 300 K
mole
\ Metal oxide formula (stochiometrically)
T2 = 77oC = 350 K

Fex3+M2+(0.98-x)O2– T1 P1
=
Compound by charge is neutral hence some of T2 P2
the oxidation state of ions in it is zero P1 = 1 bar
\ 3x + 2(0.98 – x) – 2 = 0 Hence 0.04 M3+
P2 = ?
0.04 s 100
% ions =
0.98 P1T2 1 s 350
∴ P2 = T1 = 300 = 1.17 bar
= 4.08 %

789
5. T1 = 400 K T2 = ? 14 1
12. moles of N2 = =
P1 = 4 bar P2 = 5 bar 28 2

T1P2 400 s 5 moles of O3 =


36
=
3
T2 = = = 500 K = 227 = C 48 4
4 4
6. T1 = 300 K T2 = 273 K 1
VN moles of N2 
V1 = 200 ml P2 = 1 bar 2
= moles of O  = 23 =
2
VO 3 3
P1 = 1.75 bar V2 = P 3
4
T1V1 TV T1V1T2
= 2 2 ∴ V2 = VN
T1 T2 T1P2 2 2
VO = ∴ 3 VN2 = 2VO3
= 1.23 bar 3 3
7. V = 2 litre 13. Pressure of the leaked N2 gas = 4 – 2.36
n = 0.1
= 1.64 atm
T = 300 K
PV = nRT
R = 0.08314 litre bar mole–1K–1
Pr = nRT PV W PV
n= OR =
RT M RT
nRT 0.1 s 0.08314 s 300
P= = = 1.23 bar ∴ W=
MPV
V 2 RT
8. T = 350 K
n=? 28 s 1.64 s 10
W= = 18.7 gm
V = 500 ml 0.082 s 300
P = 125 bar dRT
14. P= P = 2 atm
M
PV 125 s 0.5
n= = = 2.15
RT 0.08314 s 350 PM
∴ d= T = 300 K
RT
9. T = 400 K
0.8 s 0.0831 s 400 2 s 16
P=
dRT
= d= = 1.3 S/L M = 16
M 20 0.082 s 300
d = 0.8 g/litre 24. Suppose mass of H2 is 2 gm CH4 = 16 gm
M = 20 u = 1.33 bar
10. 6.022 × 1021 molecule = 0.01 mole = n \ moles of H2 =
16
2
=8
T = 273 K
P = 1 bar 16
moles of CH4 = =1
PV = nRT 16

V = nRT = 0.01× 0.0831× 273 mole of H 2


P 1 mole fraction of H2 =
Total number of mole
= 0.224 litre
11. P1 = 1 bar V1 = V 8
=
9
V
P2 = ? V2 = Total mole = 9
4
Partial pressure of H2
P1V1 = P2V2
= molefraction of H2× Total pressure
P1V1 1× V 8
∴ P2 = V = V 4 bar = P
2 4 9
790
RT
25. P = (nA + NB + nC) 3. Structure of atom
r
0.082 × 300 7. Reflection and refraction can explain both wave
= (4 + 4 + 2) ×
5 nature and particle nature of light, interference
= 50 bar diffraction and polarisation can explain only
27. More the moles, higher the mole fraction wave nature of light, while photoelectric effect
and partial pressure. of light can explain only particls nature of light.
\ H2 has more moles
\ partial pressure of H2 is more
6.
Answer : (B) Photoelectric effect
Reflection and refraction can explain both wave
30. VN = 50 ml MN = 28
2 2 nature and particle nature of light, interference,
Vx = 70 ml Mx = ? diffraction and polarisation can explain only
MN wave nature of light, while photoelectric effect
Vx = 2
of light can explain only particle nature of light.
VN Mx
2
Answer : (B) interference
70  28 17. molar mass of pure H2O = 18 gm mole–1
50 Mx

\ Mx = 14.3 gm / mole
18 gm pure water (H2O) = 1 mole H2O,
Number of electrons = 2 + 8 = 10 mole
35. Molecular mass of CaCO3 = 100 gm / mole
50
\ In 36 gm pure water (H2O) number of
moles of CaCO3 = 100 = 0.5 electrons
no. of molecules of CaCO3 = 2 × 10
23
= 0.5 × 6.022 × 10 = 20 mole
23
= 3.011 × 10
= 20 × 6.022 × 1023
One molecule CaCO3 has total five atoms
\ total atoms = 3.011 × 1023 × 5
= 1.2044 × 1025

= 15.055 × 1023 21. Wave length of moving particle of matter wave


37. T = 273 K W=? h
is l = mv
P = 1 bar M = 2 gm mole–1
V = 2.24 litre Kinetic energy of particle E = 2 × mv2
1

PV = W
M
RT
2E
\ v2 = m
\ PVM
W = RT =
1 × 2.24 × 2
0.0831 × 273
N = 0.2 gm \ V = 2E
m
Substituting the value in the equation
14
38. mole of N2 = 0.5 h m
28 \ l =
at STP volume of 1 mole gas = 22.4 litre m 2E
\ 0.5 mole has volume = 11.2 litre
h
40. PV = nRT If value of n is higher volume is \ l = 2mE
RT
more V = n P . Here mass is same so the
h 6.626 × 10 –34
one with higher molecular mass will have =
28. 2mE =
\
l
2 × 9.109 × 10 –31 × 1.64 × 10 –17
less mole and less volume HI has more
molecular mass so has less volume = 1.2 × 10–10 m
•
= 1.2 Å
791
34. 400 nm = 400 × 10–9 m, photon energy 41. According to Heisenberg’s principle,

hc  6.626 s 10 3.0 s 10 h
–34 8
Dx × Dp ³
DE = 4p
M 400 s 10 –9
Now Dx = Dp is given.
= 4.97 × 10–19 joule-photons–1
h
To absorb 4.97 × 10–19 joule energy 1 photon is \ (Dp)2 = (Dx)2 ³
4p
required
\ number of 1 joule energy photons h
\ D v = Dx ³
2 p
1
= According to Heisenberg’s principle,
4.97 s 10–19 42.

= 2.01 ×1018 h
Dx × Dp ³ and Dp = m × Dv
4p
35. Calculate wave number in cm–1 for photon hav-
h
ing 1.5 × 10–16 joule energy ? \ D x × m × Dv ³
4p

hc  6.626 s 10 3.0 s 10
–34 8
Now D v = 16Dx is given
=
l
%E 1.5 s 10 –16

h
\ 16(Dx)2 × m ³
= 1.3252 × 10 m –9 4p

= 1.3250 ×10–7 cm \ (Dx)2 ³


h
64 pm
wave number (number of waves travelling 1
cm distance on emission)
h
\ D x³
1 1 8 pm
v 
M 1.3252 s 10 –7
2 h
= 7546030 cm–1 \ D v = 16Dx ³
pm
40. If value of uncertainty in position and veocity
\ D p = m × Dv
is equal for a microscopic particle having mass
m, then calculate minimum possible value of m´ 2 h
uncertainity. \ D p³
pm
Heisenberg’s uncertainty principle
2 hm
x × Dp ³
h
and Dp = m × Dv \ D p
D
4p p

h
43. According to Heisenberg’s principle,
hence D x × m × Dv ³
4p
h
x × Dp ³ yLku Dp = m × Dv
4Q
D
h
Now Dx = Dv is given, (Dx)2 × m ³
4p
h
\ D x × m × Dv ³
h 4p
(Dv)2 = (Dx)2 ³
4pm Now D v = 4Dx is given
h
h \ 4(Dx)2 × m ³
\ D v = Dx × ³ 4p
2 Qm

792
h 53. angluar momentum of electron of Hydrogen
\ (Dx) ³
16pm nh
atom moving in nth orbit is mvr =
2p
h
\ D x³
4 pm \ Velocity of Hydrogen electron in nth orbit

h nh
v=
\ D v = 4Dx ³ 2π mr
pm
\ D p = m × Dv \ P (n = 6) orbit electron of Hydrogen atom
m h 6h 3h
p³ has velocity v = =
\ D
pm 2π mr PU

hm 54. For nth orbit electron of hydrogen atom has an-


\ D p=
4 p
gular momentum mvr = nh
47. Angular momentium : Angular momentum of 2π
an electron in nth orbit of H atom
\ Velocity of electron of nth orbit in Hydro
nh
mvr = nh
2 gen atom v =
2π mr
= 4.22 × 10–34 joule second
–34 \ For n = 2 orbit of electron in Hydrogen
n = 4.22 × 10 × 2 × a t o m
h
nh
4.22 × 10 –34 × 2 × 3.14 v=
= 2pmr
6.626 × 10 –34
= 3.99 » 4 h
=
\ electron will be in Nth orbit pmr
50. radius of first orbit in Bohr’s model is x.
\ a = x
6.626 × 10 –34
o = 3.14×9.11×10 –31 ×2.12×10 –10
radius of any orbit (nth orbit) in Bohr’s model
= a 0 × n2
\ v = 1.1 × 106 ms–1
\ radius of third orbit (n = 3) in Bohr’s model
= a0 × 32 = x × 9 = 9x 55. l = 3.6 Å = 3.6 × 10–10 m, velocity of photon
Wavelength (l) at an electron moving in any or- v = c = 3.0 × 108 ms–1
bit (nth orbit) in Bohr’s model and radius (r) of
its rotational path are related as h
l =
2pr = nl mv

\ l = 2π r . h
n \ m=
lv
\ de Broglie wavelength of electron
revolving in 3rd orbit (n = 3)
6.626 × 10 –34
2 ×π × 9 x \ mass of photon = 3.6×10 –10 ×3.0×108
l =
3
= 6px = 6.135 × 10–33 kg
h
51. l = mv and l = v 56. Ionization enthalpy of potassium is DE

\ v2 =
h = 416 KJ mole–1
m
416 × 1000
h = 6.022×1023
\ v=
m
793
= 6.91 × 10–19 Jmole–1 \ Ionization enthalpy of sodium Atom

\ The minimum amount of energy required 6.626 × 10 –34 × 3.0 × 108


to remove electron from potassium atom is DE = hc
l
=
242 s 10 –9
6.91 × 10–19 joule electron–1
= 8.21 × 10–19 joule-electron–1
\ The energy bombouded on a potassium atom
to remove an electron DE ³ 6.91 × 10–19 joule \ Ionization enthalpy of sodium Atom
electron–1 8.21 × 10 –19 × 6.022 × 1023
DE =
1000
hc
\ ³ 6.91 × 10–19 joule electron–1
l = 494 K joule-mole–1
hc 73. For transition of 2 ® 1
\ l £
6.91 s 10 –19
1 – 1  1 – 1 1– 1  3
–34
6.626 × 10 × 3.0 × 10 8 n12 n 22 12 22 1 4 4 = 0.75
\ l £
6.91 s 10 –19
(maximum value)
\ l £ 2.877 × 10–7 m = 287.7 nm For transition of 3 ® 2
58. Ionization enthalphy of zi DE = 520 K J mole– 1 – 1  1 – 1 1–1 5
520 × 1000 n12 n 22 22 32 4 9 36 = 0.139
1
= 6.022 s 1023
For transition of 4 ® 3
–19 –1
= 8.635 × 10 J
1 – 1  1 – 1  1– 1  7
\ The minimum amount of energy required to n12 n 22 32 42 9 16 44 = 0.0486
remove electron from Lithium atom is
For transition of 5 ® 4
8.635 × 10–19 joule electron–1
\ Energy given to Lithium atom 1 – 1  1 –1 1 – 1  9
n12 n22 42 52 16 25 400 = 0.0225
If DE ³ 8.635 × 10–19 joule electron–1 then
electron is removed. 74. Electron of Hydrogen atom in an electrically
discharged tube undergoes transition of
\ hv ³ 8.635 × 10–19 joule electron–1
1 1
n2 ® n1 (n2 > n1) for which as value of n 2 – n 2
\ 8.635 × 10 –19 1 2
8.635 × 10 –19
v³ \ v³ decreases the value of wavelength of emitted
h 6.626 × 10 –34
photon increases.
v ³ 1.30 × 1015 s–1
For transition of 2 ® 1
\

60. Minimum frequency of photon required to emit


1 – 1  1 – 1 1– 1  3
electron is v0 = 7.0 × 1014 s–1
n12 n 22 12 22 1 4 4 = 0.75
Frequency of photon bomborded on the metal For transition of 4 ® 2
surface v = 1.0 × 1015 s–1
1 – 1  1 – 1 1– 1  3
Kinetic energy of emitted electron K = h (v – v0) n12 n22 22 42 4 16 16 = 0.1875
= 6.626 × 10–34 × (1.0 × 1015 – 7.0 × 1014) For transition of 7 ® 5
1 – 1  1 – 1  1 – 1  24
\ K = 1.99 × 10–19 Joule
n12 n22 52 72 25 49 1176
61. For ionization of sodium atom = 242 nm = 0.0204 (minimum value)
= 242 × 10–9 m is the required wavelength. For transition of 6 ® 4

794
1 – 1  1 – 1  1 – 1  5 6.626 × 10–34 × 3.0 × 108
n12 n22 42 62 16 36 144 = 0.0347 = 7.57 × 10 –20
77. Electron of Hydrogen atom in an electrically
= 2.63 × 103 nm
discharge tube undergoes transition of n2® n1
(n2 > n1) 80. Change in energy for transition of ni ® nf of
an electron of single electron system (H, He+)
Energy of emitted photon DE = 2.18 × 10–18 ×
is
¨1 ¸ 1 1
© 2 – 12 ¹ = 2.18 × 10–18 × ¨ 1 – 2 ¸  
ª n1 n2 º ©ª1 4 º¹ 1 1
DE = Enf – Eni × Z2  2 – 2 
n n f 
 i
–18 15
= 2.18 × 10 ×
16 To calculate ionization enthalpy ni = 1, nf = ¥
–18
= 2.044 × 10 joule \ Ionization enthalpy of 1H atom
78. Electron of Hydrogen atom in an electrically
discharge tube undergoes transition of n2 ® n1
¨ 12 – 12 ¸ = R
D Ea – E1 = RH × (1)2 ©ª1 d ¹º H
(n2 > n1)
Energy to remove electron from nth orbit
Frequency of emitted photon DE = hv = 2.18 ×
(nth quantum state) of 2He+ and ionization en-
¨1 1¸ ¨1 1¸ thalpy of Hydrogen atom is same and for He+
10–18 × © n 2 – n 2 ¹ = 2.18 × 10–18 × © 2 – 2 ¹
ª 1 2º ª2 5º z=2
\ Energy to remove electron from nth orbit (nth
\ v=
2.18 × 10 –18
h
×
21
100 quantum state) of 2He+ is

2.18 × 10–18 × 21
= 6.626 × 10 –34 × 100
DE = E¥ – En = RH × (2)2 ¨ª© n12 – d12 ¸º¹ = RH \
4 × RH
= 6.91 × 1014 Hz = RH
n2
79. Electron of Hydrogen atom in an electrically
\ n2 = 4
discharge tube undergoes transition of n2 ® n1
(n2 > n1)
\n=2
82. In Balmer series for maximum emitted
Energy of emitted photon DE = 2.18 × 10–18 ×
wave length n1 = 2, n2 = 3
¨ 1 ¸ 1 1
© 2 – 12 ¹ = 2.18 × 10–18 × ¨ 2 – 2 ¸ h × c× 36
©ª 4 6 ¹º
ª n1 n2 º
lmax = RH ×5
5
= 2.18 × 10–18 × 6.626 × 10 –34 × 3.0 × 108 × 36
144 =
2.18 × 10 –18 × 5
= 7.57 × 10–20 joule
= 6.565 × 10–7 m
hc = 656.5 nm
Now D E=
M
83. In Paschen series for minimum emitted wave-
=
hc length n1 = 3, n2 = ¥
\ l
%E
hc × c×9
lmin = RH

795
6.626 × 10 –34 × 3.0 × 108 × 9 ¨ ¸ joule
=
2.18 × 10 –18
DE = En1 – En2 = RH × Z2 × ©ª n1 2
2
– 12 ¹
n1 º electron
= 8.206 × 10–7 m n1 = 2, n2 = 5 and Z = 1
= 820.6 nm
1 1 joule
84. In lyman series for minimum emitted frequency D E = 2.18 × 10–18 × 12 × ¨ª© 52 – 22 ¸º¹
electron
n1 = 1, n2 = 2
2.18 × 10 –18 × (–21) joule
=
R H ×3 100 electron
vmin =
h×4
joule
= – 4.578 × 10–19
electron
2.18 × 10 –18 × 3
=
6.626 × 10 –34 × 4
91. For electron of Hydrogen atom moving from
= 2.4675 × 10 s 15 –1 4th exited state to lower energy state then
85. In Brackett series for minimum emitted calculate the number of lines of in U.V. region
visible region and Infrared region.
frequency n1 = 4, n2 = 5
Fourth exited state = fifth orbit (fifth energy
R ×9
vmin = H level)
h × 400
(Fourth exited state n = 5)
2.18 × 10 –18 × 9
=
6.626 × 10 –34 × 400
n=5
13 –1 n=4
= 7.40 × 10 s Infrared : 3 lines
n=3
86. In pfand series the minimum emitted frequency n=2 Visible region : 3 lines

for n1 = 5, n2 = 6
n=1 Ultraviolet region : 4 lines
R H ×11 Total number of lines = 10
vmin =
h × 36 × 25

2.18 × 10 –18 × 11 106. All orbits between nuclear atom and P orbit
= possess one (l = 0) orbital.
6.626 × 10 –34 × 36 × 25

= 4.02 × 1013 s–1 Orbits between nucleus and P orbit is K(n =


1), L(n = 2), M(n = 3), N(n = 4) and O(n = 5),
87. In Lyman series the maximum emitted fre-
in this way total 5 orbits each having one or-
quency for n1 = 1, n2 = ¥
b i t a l
RH (l = 0). Therefore total five orbitals have l = 0
vmax =
h ×1 Now each orbital can have maximum 2
electron so electron having l = 0 = 5 × 2 = 10
2.18 × 10 –18
=
6.626 × 10 –34 109. For multi electron system (atom or ion)
= 3.29 × 1015 s–1 possible pair of quantum number n and l with
88. In a Hydrogen spectrum classification based on 2 £ n + l £ 5 as follows :
Bohr’s assumption, energy changes during tran- n = 5, l = 0 ® 5s orbital
sition of n2 ® n1
® number of orbitals = 1
n = 4, l = 0 ® 4s orbital

796
® number of orbitals = 1 pletely fill all orbitals between Nucleus and
O orbit is = 60
n = 4, l = 1 ® 4p orbital
® number of orbitals 113. Orbits between nucleus and P orbit is K(n = 1),
L (n = 2), M(n = 3) and N(n = 4) total four
= (4px, 4py, 4pz)
orbits. There are 2n2 number of electrons in any
n = 3, l = 0 ® 3s orbital
nth orbit
® number of orbitals = 1
For K (n =1) possible number of electrons to
n = 3, l = 1 ® 3p orbital
be filled ® 2(1)2 = 2
® number of orbitals
For L (n = 2) possible number of electrons to
= 3(3px, 3py, 3pz)
be filled ® 2(2)2 = 8
n = 3, l = 2 ® 3d orbital
For M (n = 3) possible number of electrons to
® number of orbitals be filled ® 2 (3)2 = 18
= 5(3dxy, 3dyz, 3dxz, 3dx2–y2, 3dz2) For N (n = 4) possible number of electrons to
n = 2, l = 0 ® 2s orbital be filled ® 2 (4)2 = 32

® number of orbitals = 1 \ The total number of electron which com-


pletely fill all orbitals between Nucleus and or-
n = 2, l = 1 ® 2p orbital
bit O is 60.
® number of orbitals
From this half the number that is 30 e– will have
=3 (2px, 2py, 2pz)
1
\ Total number of orbitals = 18 and each con- s=+
2
taining 2 electrons, for 2 < n + l < 5 have
total electron, 18 × 2 = 36 114. Orbits between nucleus and P orbit is K(n = 1),
L (n = 2), M(n = 3) and N(n = 4) total four
112. Orbits between nucleus and P orbit is
K(n = 1), L (n = 2), M(n = 3) and N(n = 4) orbits. For nth energy level there are n types of
Total four orbits orbital and in each type of orbital there is one
orbital of m = 0.
There are 2n2 number of electrons in any nth
orbit K (n = 1) Number of Types of orbital = 1

For K (n =1) possible number of electrons to L (n = 2) Number of Types of orbital = 2


2
be filled ® 2(1) = 2
M (n = 3) Number of Types of orbital = 3
For L (n = 2) possible number of electrons to
N (n = 4) Number of Types of orbital = 4
be filled ® 2(2)2 = 8
\ Total number of orbitals between nucleus
For M (n = 3) possible number of electrons to
and orbit O having m = 0 is 10
be filled ® 2 (3)2 = 18
\ Total number of electrons having m = 0,
For N (n = 4) possible number of electrons to
which completely fill all orbitals between
be filled ® 2 (4)2 = 32
Nucleus and O orbit = 2 × 10 = 20.
\ The total number of electrons which com-
115. Orbits between Nucleus and P orbit is
797
K(n = 1), L (n = 2), M(n = 3) and N(n = 4). Total four M He h m ×V
M= × × Ne Ne
orbits. For nth energy level there are n types of M Ne m He ×VHe h
orbital and in each type of orbital there is one
orbital of m = O 20
= =5
4
K (n = 1) Number of Types of orbital = 1 128. Ionization enthalpy of metal.
L (n = 2) Number of Types of orbital = 2 DE0 = 416 K J-mole–1
416 × 1000
M (n = 3) Number of Types of orbital = 3 = 6.022 × 1023
N (n = 4) Number of Types of orbital = 4 = 6.908 × 10–19 joule electron–1
\ Total number of orbitals between nucleus metal is bamborded with a radiation of wave-
and orbit O 10 length is 4.0 × 10–8 m.
s-orbitals do not have m = –1 and each Energy of a photon emitted from the metal
rbit has one s-orbitals.
Out of 10 orbitals, 4 orbitals are s-orbitals from hc 6.626 × 10 –34 × 3.0 × 108
E= = = 4.9695 ×
D
M 4.0 × 10 –8
the remaining 6 type of orbitals (2p, 3p, 3d, 4p,
4d, 4f) each type of orbitals has one orbital with 10–18 joule photon–1
m = –1 Kinetic energy of emitted electron
Therefore there are 6 orbitals with m = –1 K = (DE – DE0) = (4.9695 × 10–18 – 6.908 ×10–
and each orbital can acomodate maximum 19
)
2 electron each.
1
\ Total number of electrons having \ K= × mv2
2
m = –1,which completely fill all orbitals
= 4.2787 × 10–18 joule photon–1
between Nucleus and orbit O is 2 × 6 = 12
16
125. O is isotopic to 0.5 kg Neutron, then calcu- –18
8 \ v2 = 2 × 4.2787 × 10
late mass of Oxygen gas. m
Oxygen (168O) atom contains 8 Neutrons. 2 × 4.2787 × 10 –18
–27 = = 9.394 × 1012
Mass of one neutron = 1.67493 × 10 kg. 9.109 × 10 –11
\ Mass of 8 mole Neutron is v = 9.394 ×1012 = 3.065×106 ms–1
23 –27
= 8 × 6.022 × 10 × 1.67493 × 10 kg
129. Z = 16 is Sulphur and its ground state
–3
= 8.07 × 10 kg configuration :
\ Mass of Dioxygen having 8.07 × 10–3 kg
Neutrons is16 gm. [Ne]
\ Mass of Dioxygen having 0.5 kg Neutron 3s 3p
0.5 × 16 If second last filled electron has quantum
is = 8.07 × 10–3
1
= 991.3 gm number n = 3, l = 1, ms= 0, s = + then
2
126. de-Broglies wavelength l =
h
mv
and v d T
M
the quantum number of last filled electron
i s
n = 3, l = 1, ms = +1 OR –1 OR 0 and s = –
VHe THe M
s Ne 1
\
VNe = M He TNe 2
Hence the quantum number of last filled

200 s 20
= =1
4 1000
798
1 nh nh
electron is n = 3, l = 1, ms =–1, s = – . mvr =
2p
. OR r =
2 pmv
2
130. wavelength l of electron in nth orbit, nl = 2pr Now
h
mv
= l (de-Broglie wavelength)
2
\ l = 2p × 52.9 × n = 2p × 52.9 × n
n
\ r=
nl
2p
\ For 2nd orbit (n = 2) wavelength of
electron :
\ Now de-Broglie wavelength for nth orbit
2 pr
l = 2 × 3.14 × 52.9 × 2 = 664.424 pm l = and raduis of nth orbit
n
\ l = 664.424 × 10–12 m = 6.64 × 10–10 m r = 5.29 × 10–11 × n2 m
131. Wave length of an electron moving in nth orbit
of the single electron system is n = 2 r l p \ l
–11

n
2
= 2p × 5.29 × 10 × n m

\ nl = 2p × 52.9
Z
×n
2
\ l = 2p × 5.29 × 10–11 × n m
For transition of electron 4 ® 2 the
\ n=
Z× l
2p × 52.9
decrease in de-Broglie wavelength is

Now l = 1 nm = 1000 pm and Z = 1 l


4
– l2 = 2p × 5.29 × 10–11 (4 – 2)
– l2 = 2 × 3.14 × 5.29 × 10–11 × 2
\
\ l
1 × 1000 4
n= = 3.0 = 6.644 × 10–10 m = 6.644 Ao
2 × 3.14 × 52.9
132. radius of nth orbit in the Hydrogen atom, •
r = 5.29 × 10–11 × n2 m.
l = 486.3 nm = 4.863 × 10–7 m
4. Chemical Bonding and
Energy of a photon E =
h×c Molecular Structure
M
6.626 × 10 –34 × 3 × 108 2. (a) Bond formation is an exothermic reaction
= = 4.0876 × 10–19 joule
4.863 × 10 –7 during which free energy is released.

\ DE = – 4.0876 × 10–19 joule Cl


6Electron
Third excited state means n = 4 and 7. (b) BCl3 ×
transi- tion for electron will be 4 nf ® B×
×
Cl

¨1 ¸
Cl
DE = 2.18 × 10 –18
× © 2 – 12 ¹
ª4 nf º
F
× 12 electron
4.0876 × 10 –19 ¨1 1¸ F × × F
=– = © 2 –
2.18 × 10 –18 ª4 n f2 ¹º 8. (c) SF6 ×
S
×
F × F
¨ F

\ – 0.1875 = ©0.0625 – n 2 ¹
ª f º
9. (b) Hydrazine : NH2 – NH2
1
\ n f2 = 0.1875 + 0.0625 = 0.25 H H
N–N
\ nf2 =
1
0.25
= 4 and nf = 2 H H
Transition of electron will be 4 2 ®
angular momentum of n electronth 10. (b) Aceta ion : CH3COO–
799
valence electron :
26. (c) (i) P = 1s2 2s2 2p6 3s1, L = 1s2 2s2 2p4:
= 2 (C) + 3 (H) + 2 (O) + 1 P = 1s2 2s2 2p6 3s1 do
= 2 (4) + 3 (1) + 2 (6) + 1 = 24 natir y 2 e –
(a) Peroxide ion : O22–
11.
no. of electrons = 2 (O) + 2
\ formed compound P L 2
(ii) R = 1s 2s 2p 3s , L = 1s 2s 2p 4
2 2 6 2 2 2
= 2 (8) + 2 = 18
don
13. (a) Nuclear charge of K+ is more than K, atir y 2e –
has nucleur charge increase size formed compound RL
decreases hence size of K+ is smaller
(iii) P = 1s2 2s2 2p6 3s1, Q = 1s2 2s2 2p6 3s2 3p5:
than K.
d on a t i
15. (a) In NaCl Bond is formed due to transfer r y 1e –
formed compound PQ
of electron which is known as ionic
electro valent bond. (iv) R = 1s2 2s2 2p6 3s2 : Q = 1s2 2s2 2p6 3s2 3p5
16. (b) x : 1s2 2s2 2p6 3s2 2 electron in valence Q =1s2 2s22p6 3s2 3p5
d on
orbit. atir y –
2e
\ x ® x+2 + 2e– formed compound RQ2
*There are 7e– in valence orbit of chlorine. 28. (c) In LiF electronegativity of F is more and
– – hence attraction between Li and F is strong.
\ 2Cl + 2e ® 2Cl
Hence solubility of LiF is more.
\ x+2 + 2Cl– ® xCl2 is formed.
29. (b) In CsF size of Cs+ is large so attraction
17. (c) Z : 1s 2s 2p5 posses 7e– in valence
2 2
between Cs+ and F– is weak, so CsF has
orbit bond has a strong tendency to
high solubility.
gain one electron. Hence produces bond
by transfer of electron hence has a 31. (d) According to Fajan’s rule as size of
cation increases covalent characteristics
higher tendency to form ionic bond.
decreases and melting pt increases.
18. (d) Molecular formula of metal phosphate
} Li} }< K} <}R}b }< C}}m size increases
+
MPO4 + s + +

MPO4
+3 3–
\ }}}}}}}}}}}}}}}
Li CO < K CO < Rb CO < Cs CO
2 3
}m 2 3 2 3 2 3

M PO 4
Melting point increases
Metal nitrate formula of same metal
33. (a) According to Fajan’s rule as size of anion
M+3 + 3(NO3–) ® M (NO3)3 decreases their covalent characteristic de-
19. (d) Metal oxide formula : MO creases.
MO
}}}}}}}} m size decreases
– – – –
I > Br > Cl > F
2+ 2–
M O
Metal phosphate formula of the same \ }}}}}}}}}}}}
SnI >SnBr >SnCl > CnF
4
m 4 4 4

metal is as follows. Covalent characters decreases


3(M2+) + 2(PO43–) ® M3 (PO4)2 34. (d) According to Fajan’s rule as size of cat-
20. (b) Z = 20 atomic number element has ion/anion increases, the eovalent charac-
electronic configuration 2, 8, 8, 2. This ele- teristics Increases due to which melting
point decreases.
ment has tendency to loose two electrons.
Hence can easily form ionic bond. There \ Out of Na+, Pb+2, Mg+2 and Sn+4 charge
are 6 electrons in valence orbit of element of Sn+4 is maximum melting point of SnCl4 is
having atomic number of 16. least.
800
36. (c) According to Fajan’s rule as charge on 60. (b) In x2 molecule x º x covalent orbital 3
cation/anion increases the solubility of electron shared.
solute in solvent decreases.
\ x = electron configuration 1s2 2s2 2p3
\ }}}}}}}m size increases
Rb+ < Cd +2 < Pb+4
61. (b) H F

\ }}}}}}}m
H N B F Co-ordinate covalent bond
RbI > CdI > PbO solubility
2 de-2 H F
creases 74. (a) In the same group moving from top to bot-
37. (c) According to Fajaan’s rule as charge of cat- tom attraction of nucleus towards electron
ion/anion is less their covalent character- decreases. Hence according to VSEPR
istics decreases. Therefore (·) stability in- principle, compounds of element have re-
creases and does not undergo dissociation pulsion between them and decrease bond
easily (·) Na2CO3 (Na+) angle.
38. (c) As size of positive ion is more covalent
characteristics is less and ionic character
\ }}}}}}}}}}}
NH > PH > AsH > SbH
3
m 3 3 3

increases. bond angle decreases


\ From Be+2, Li+, Sn+2, Mg+2 size of Sn+2 is
76. (b) XeF2 : F – Xe – F
largest hence SnCl2 has highest ionic char- linear
acteristics. CO2 : O = C = O
41. (c) According to Fajaan’s rule as charge on
cation/anion increases the solubility of 77. (a) F
solute in solvent decreases.
\ AlN < MgO < NaF
F F
distorted octahedral
42. (b) According to Fajaan’s rule as size of an-
Hybridisation= Sp d
3 3
Xe
ion is small and solubility of solute in sol-
vent increases. Oxidation state of Xe = + 6
\ AgF will have maximum solubility. F F

43. (d) According to Fajaan’s rule as size of F


cation increases the covalent characteristic
decreases and stability increases. Hence Angular
80. (b) H2S S
from the given BaCO3 will have maximum angle
stability. H H
44. (a) According to Fajaan’s rule as the size of
BeCl2 : Cl – Be – Cl
cation is small the solubility product
increases. CS2 : S = C = S
46. (c) Electron taking part C2H2 : H – C º C – H
×N × × N× in bond formation = 6
× × × × 180°
82. (a) : CO2 : O C O
× ×
H
O Two lone pair
51. (a) Two bonded pair electron pair C 109.281
H H : CH4 :
H H
H H
+ –
52. (b) H N H Cl
N 107°
H : NH3 : H H
54. (a) As Boron has small size and large ioniza- H
tion enthalpy it cannot loose electron eas-
O 104.5°
ily. Hence forms covalent bond) : H2O :
H H
801
s bond : P – O = 08
F2Atom Over lap
(P-P) 04
O–H=
12
2p 2p
85. (b) 2s dp – pp bond = P – O : 02
2s
96. (a) Acetate ion
1s 1s H O

O O
H – C – C – O– C–O:1
87. (b)
O O O O C=O:1
2 sigma and one pie bond H
90. (b) Calcium Carbide : CaC2 100. (a) XeO3 :
Xe dQ - pQ bond
Ca O O xe - O : 03
O
C C Calcium carbide
XeO4 :

92. (d) O O dQ – pQ bond


Xe xe – O : 04
CH3 O O
101. (a) SF6 :
P- Xylene = Tbond  = 18 SF 6 six valence electron in sulphur and 7
C – C :Tbond 8 valence electron in chlorine.
C – H :Tbond 10 \ 1(S) + 6(F)
3
= 1(6) + 6(7)
94. (d) P4O10 Phosphorous = 48
48
O = 6 : hybridisation : sP3d2
8
P ® Characteristics of d-orbital
O O Total Tbond = 16 Number of d orbital in SF 6
O =
Total Qbond= 04 Total number of orbitals
O P O P O 2 s 100
= 33.3 %
6
O O
102. (a) CH3 – CH = CH2
P
3 2 2
O Sp Sp Sp

95. (d) Pyrophosphoric acid 103. (b) SP SP


[H4P2O7]
N C C N
O O
C=C
H–O–P–O–P–O–H N C C N
SP2
O O SP SP
H H C2 (CN)4
802
111. (b) : sp hybridisation ® bond angle = 180 o

: sp hybridisation ® bond angle = 120


Cl
2 o

: sp hybridisation ® bond angle = 109.28


3 o 128. (b)
: dsp hybridisation ® bond angle = 90
2 o
Cl
112. (d) But –1, 2– diene
® P – dichloro benzene, dipole moment = zero
CH=
2 C = CH – C H3

2 2 3
H
Sp Sp Sp Sp
+
133. (a) H–N H ® Cl–
..
114. (b) distorted tetrahedral H
N
3
H H hybridisation : SP NH4Cl possess polar and non polar bond.
H 135. (b) CO 3 2– :

116. (c) O O O

B C C C
Trigonal pyramidal O O O O O O
2
Sp hybridisation
Cl Cl
Cl 141. (b) Li2– < Li2+ < Li2
¯ ¯ ¯
119. (c) CCl4 : It is regular tetrahedral structure.
® linear, planar triangle, tetrahedral,
bond order :
1 1
1
Triagonal bipyramidal, definite actahedral, 2 2
as well as pentagonal bipyramidal have Nuclear charge bond order
their dipole moment zero. increases and increases
122. (c) 4.8 D stability increases stability increases
® Ionic charge : 4.8 × 10–10 esu 142. (c)

® Ionic distance : 1A0 = 10–8 esu/cm


Bond order for H2+2 = 0
Bond order for He2 = 0
Dipole moment
Components having bond zero cannot
= ionic charge × ionic distance exist
= (4.8 × 10–10) esu × (10–8) esu/cm 143. (b)
= (4.8 × 10–10) esu × (10–10) esu/mm Bond order of N2+ = 2.5
Bond order of O2+ = 2.5
= 4.8 D
145. (a)
123. (a) 17 %
NO– : Bond order = 2
% ionic character
NO+ : Bond order = 3 CO Bond order = 3
Experimental value of dipolement
= 100 CN– : Bond order = 3
Theoretical value of dipole moment
N2 : Bond order = 3
1.03 146. (a)
= × 100
6.12 Peroxide ion : O22–
.. .. 2–
= 17 % –( O
.. – O
.. )–

803
147. (a) Bond order 156. (b) electron
C1O2 : 33
O2+2 : 3
ClO2– : 34 paired electron
® O2 + : 2.5 \ NO2 : 23
O2 – : 1.5 Bond order a
1 NO : 15
Bond length 162. (d) : Bond order

O2 : 1.0 CN– : 03
+
\ O2 < O2+ < O2– < O22–
+2 NO : 03
164. (b) : O2+ > O2 > O2– > O22–

Bond length increases


¯ ¯ ¯ ¯
Bond order : 2.5 2 1.5 1.0
Bond order a stability a Bond strength
Bond length decreases a Bond energy
165. (c) In N2 molecule,
\ Least bond length is of O2+2
151. (b) :NO ® NO+ Bond order = ( Nb -2 Na )
Bond order : ¯ ¯

3 2.5 \ 3= ( Nb2- 4 )
¯ ¯
\ 6 = Nb – 4
O: Diamagnetic paramagnetic \ Nb (BMO electron) = 10
152. (b) : O2+ bond order = 2.5 paramagnetic 166. (c) : Bond order in PO43–
property Number of Bonds in PO4 –3
154. (c) N2 electronic configuration Number of resonating structure in PO4 –3
( s 1s ) 2 ( s * 1s ) 2 ( s 2s ) 2 ( s * 2s ) 2 ( p 2 px) 2
5
= (p2py)2 (s2pz)2 = = 1.25
4
N2+ electronic configuration 167. (d) : Bond order in perchlorate ion [ClO4–]

( s 1s ) 2 ( s * 1s ) 2 ( s 2s ) 2 ( s * 2s ) 2 ( p 2 px) Number of Bonds in ClO4
= 
= (p2py)2 (s2pz)1 Number of resonating structure of ClO 4

So when N2+ is formed N2 electron is re- 7


= = 1.75
4
p2
moved from s
2
168. s s s s
(b) : O2 : ( 1s)2 ( * 1s) ( 2s)2 ( * 2s)2 ( 2p )2 s
§ electronic configuration of O2
p p p
( 2P )2 = ( 2p )2 ( * 2p )1 = ( * 2p )1 p z

(s1s)2 (s*1s)2 (s2s)2 (s* 2s)2 (s2pz)2 = (p2px)2 ® x y


ABMO electrons = 06
x y

= (p2py)2 (p2px)1 = (p2py)1 s s s s s


O22– = ( 1s)2 ( *1s)2 ( 2s)2 ( * 2s)2 ( 2p )2 ( 2p )2 p
§ electronic configuration of O2+ p p
= ( 2p )2 ( 2p )2 = ( * 2p )2
y x y
p z x

ABMO electrons = 8
( s 1s ) 2 ( s * 1s ) ( s 2s ) 2 ( s * 2s ) 2 ( s 2s ) 2 ( s 2p ) 2
z s s s s s
O2– : ( 1s)2 ( * 1s)2 ( 2s)2 ( *2s)2 ( 2s)2 ( 2P )2 = s
= (p2p )2 = (p2p )2 = (p*2p )1 = (p* 2p )0
p
( *2p )1
x

®
x y x y
y
So when O2+ is formed from O2 electron is ABMO electrons : 07
removed from (p *
2py
) or (p *
2px
). O2+ : (s1s)2 (s* 1s)2 (s2s)2 (s* 2s)2 (s2p )2
z
155. (c) NO +
> NO > NO– (p* 2p )2 = (p2p )1 (p*2p )1
x y x
® ABMO electrons : 05
¯ ¯ ¯
169. (b) : Ne2
Bond order 3 2.5 2.0 (s1s)2 ( s* 1s)2 (s2s)2 (s* 2s)2 (s2p2)2 (p2p )2 =
x
Bond order a stability (p2p )2 (p*2p )2 = (p*2p )2 (s*2p )2
y x y z
stability a Bond order ® Total number of electron pair = 10
804
(373 – 273) = – 831.4 Joule
177. (c) H–C–O–H
14. D H = 38880 Cal,
O Hydrogen bond D H = DU + Dn(g)RT
CH3 – C – O – H \ D U = DH – Dn(g)RT
= 38880 – (4 × 2 × 373)
O
= 38880 – 2984
181. (c) O O intramolecular H–Bond = 35896 K cal mol–1
N H = 35.89 K cal
O 25. CH3COOH CH3COO– + H+
D H = 0.30 K cal mol–1
\ 2CH3COOH 2CH3COO– + 2H+
(O – nitrophenol) DH = 0.60 K cal

189. (b) F2 < Cl2 < Br2 < I2 Ca(OH)2 Ca2+ + 2OH–
DH = O
as Nuclear charge increases altration
increases. 2H + 2OH– ® 2H2O
+

DH = –13.7 × 2 = – 27.4
198. (a) as charge of cation increases, attraction
\ DH = – 27.4 + 0. 60
increases and bond strength increases. = – 26.80 K cal
199. (b) In a diamond, one carbon is attached to four 28. D H = Dso1H1 + Dso1H2
hyd
other carbon atoms by tetrahedral. Three = – 91.21 – 13.81
dimensional rigid network structure due to = – 105.02
which it becomes hard. 29. D H = [4((BH))
C–H
+ (BH)C=C + (BH)H–H] –
200. (b) Based. on metallic bond. [6(BH)C–H + (BH)C–C]
Note : assume BH = Bond enthalpy
• Heat conductivity
41.75 joule
• Electrical conductivity 31. Cv = 0.1mole×20° = 20.875 JK–1 mol–1
• ductileability
\ Cp = Cv + R = 20.875 + 8.314 = 29.189
• Maleability like properties can be ex- JK–1 mol–1
plained.
C P 29.189
\  = 1.4
C V 20.875
• \ Gas is diatomic.
3
32. Monoatomic gas Cv = R and T = 10
5. Chemical Thermodynamics 2
D

3 3
607.8 \ D U = Cv DT = R × T = × 2 = 3 cal
9. W=– = – 6 litre atm, P = 20 atm 2 2
101.3 41. For the process DU = O
\ W = – PDV \ – 6 litre atm = – 20 \ q=–w
0 –1
atm × DV 42. DrG = – 702.6 K J mole

\ D V = 1.2 litre D H0 = – 726 K J mole–1


10. W = – P D V = – 1.0 atm × (500 – 250) 3
Reduction : CH3OH(l) + O2(g) ® CO2(g) +
= 0.25 litre atm = 25.32 Joule 2
2H2O(l)
\ DU = q + W = – 10 – 25.32 = – 35.32 Joule
702.6 s 100
12. W = – PDV = – nR (T2 – T1) = – 1 × 8.314 × efficiency = = 97 %
726
805
51. Using Hess’s law
2.303 R T1 T2 P2
52. Using Hess’s law 68. DH = T2 - T1 log P
1

55. D H = S DfHo(Lke) – S DfHo(«)


r
1 1  2.303 R P2
\ – 265 = 4x + 6x – 26 \ T −T  = ∆H log P1
 1 2
\ x = – 23.9
 1 1  2.303 × 2 10
\ D HoSO2 = 3x \ DfHoSO2 = – 71.7 \  50 − T  = 460.6 log
f  2 1
56. DrH = Bond enthalpy – Bond enthalpy \ T2 = 100K
of reactant of product

(x
– 200 = 2 + 2
0.5x
) – (x) 6. Solution
\ x = 800 1. 98 % H 2 SO 4 means 980 gm H 2SO 4 is
dissolved in 1000 solution. Now density of
62.
P
V
=1 \ P=V ... (i) solution = Mass

® Based on first law dq = CvdT + Pdv


\ Volumevolume
of 1000 gm solution =Mass
density
® 1 mole gas PV = RT 1000
= = 543.4 ml
\ PdV VdP = RdT 1.84

\ from equation (i) PdV = VdP ... (ii)


Molarity (M) =
W
MW
´ 1000
Vml
2Pdv = RdT
980 1000
\ PdV = R
2
dt =
98
×
543.4
= 18.4 M
2. 1 molal aqueous solution means, 1 mole solute
\ R is dissolved in 1000 gm of solvent.
dq = CvdT +
2
dT
\ moles of solute = 1

\
dq
dT
= Cv +
R
2
3
= R+
2
R
2
= 2R \ moles of solvent =
1000
18
= 55.56 mole

66. DH = [DcombustionH(cycloHexane)] – Now, molefraction of solute =


1
1 55.56
[DcombustionHcycloHexene + DcombustionHH2]
= 0. 0177
7 3. 6.022 × 1023 molecules of urea = 1 mole urea
67. C2H6 + O ® 2CO2 + 3H2
2 2 \ 6.022 × 1020 molecules of urea = (?)
6.022 s 1020 s 1
DH = – 368 K cal \ Moles of urea =
6.022 s 1023
= 10–3
CH4 + 2O2 ® CO2 + 2H2O
mole
DH = – 210 K cal Now, molarity = Volumeof solution (in litre)

3
\ CH2 + O ® CO2 + H2O 10 3
2 2 = = 0.01 M
0.1
DH = – 158 K cal 4. For an aqueous solution of a given substance If
x molar solution is more concentrated than x
\ DcombustionH (C H ) = DcombustionH(CH ) molal solution. Then the value of molarity of the
10 22 4
+ [9 × DcombustionH(CH )] solution is less than the molarity of the
2 solution.
806
molarity molarity \ glucose = 18 gm, solution = 100 gm, sol-
\
molarity
< 1, Now,
molarity
= vent (water) = 82 gm

M × Wo
= 1000 × W
18
´
M×V 1000 × W
\ Glucose = 180
18 82
molarity W (gm)
\ = Vo (m) 180 18
molarity

Wo 0.1 0.1
\ < 1 gram ml–1 =  = 0.021
V 0.1 4.56 4.66
Wo W +W - W Wo + W
Now, = o = - W 8. • 2 litre of 3 M AgNO3 solution contains 6
V V V V
mole of AgNO3
W
=d– • 3 litre of 1 M BaCl2 solution contains 3
V
mole of BaCl2.
= d + 1000 × W × ® 2 AgCl + Ba(NO )
Wo W M
\ =d+ •
V V M×V 1000 2 AgNO3 + BaCl2 3 2

Wo (gm) gm Molarity × M.W. That is 6 mole of AgNO3 will react with 3 mole
\
V (ml)
=d + of BaCl2 .
ml 1000

gm Molarity × M.W. gm Hence after the complete reaction it produces


\ d + <1 3 moles of Ba(NO3)2
ml 1000 ml

\ d
gm
<1
gm
+
Molarity × M.W. \ 2 + 3 = 5 litre solution contains 6 moles of
ml ml 1000 NO3–1 ion.
Now, for 0.5 M H2SO4 aqueous solution.

¥ 0.5 s 98 µ
\ molarity of NO3– ion =
6
5
= 1.2
d < ¦§1 ¶
1000 · 9. M1V1 + M2V2 = M3 (V1 + V2)

5.
\ d < 1.049 gram/ml
For a given substance of two different concen-
\ 6 × 250 + 3 × 650 = M3 (250 + 650)
trated solution are mixed the concentration of ob- \ 1500 + 1950 = 900 M3
tained concentration of the mixture of the solu-
tion. Concentration of dilute soultion < Concen- \ M3 =
3450
900
M
tration of mixed solution < concentration of con-
centrated solution. that is molarity of mixed solution will be
6. 25% of NH4NO3 in 300 gm solution
3450
25 M.
900
= × 300 = 75 gm
100 ® Before dilution After dilution
• 40% of NH4NO3 150 gm solution
M1 V1 = M2 V2
40
= × 150 = 60 gm 3450
100 × 900 = 3 × V'2
900
• Total mass of the solution = (300 + 150)
= 450 gm \ V'2 = 1150 ml
• Total mass of solute = (75 + 60) gm • Amount of volume of water to be added
= 135 gm
= 1150 – 900 = 250 ml
• Percentage by mass (concentration)
10. • Molarity of a solution is 11.5. Which means
135
= × 100 = 30 % 11.5 moles of H2SO4 is disolved in 1 litre.
450
7. 18 % W/W glucose solution means 18 gm • Suppose density of 1 litre solution is d
glucose dissolved in 100 gm solution. gm/ml then 1000 ml solution = 1000 d gm.
807
\ 1000 d gm solution of H2SO4 = 11.5 mole 16. millimole = 500 × 0.2 = 100
\ 11.5 × 98 gm = 1127 gm
\ mass of water = (1000 d – 1127) gm \ Molarity of dilute solution = 100 = 0.1428
700
\ molarity =
11.5
1000 d - 1127
× 1000 = 94.5 m M
OR moles of solute
15500 = 94.5 × 1000 d – 94.5 × 1127 17. Molarity =
volume of solution in litre
OR
94500 d = 11500 + 106501.5 = 118001.5 120 s 1.15
=× 1000 = 2.05 M
60 s 1120
\ d=
118001.5
94500
= 1.2487 gm litre–1 Normality molecular mass
Molarity = Equivalent mass = n
18.
W 5.85
11. Molarity (M) = M.W. × V = For 2N HCl For 4N H2SO4
lit 58.5 s 0.5
= 0.2 M
M = N × E.W. M = N × E.W.
12. Decimolar solution means 0.1 M M.W. M.W.
Now, molarity = Mole
vol. in 2 s 36.5 4 s 49
1 = =
× li- × 1000 = 0.1
W 36.5 98
=
200 tre
100
=2M =2M
\ 0.1 =
W
20
\ W = 2 gm 21. According to Raoult’s law

13. 20 % FeCl 3 solution means 20 gm FeCl 3 P = Po .X + Po .X


A A B B
dissolved in 100 gm solution. UR = QY.VU + VW.QU

\ Volume of 100 gm solution =


100
= 90.91
\ UR – QY.VU = VW.QU
1.1 W
R
ml
Y
20
Now, moles of 20 gm FeCl3 =
vap press

162 S
= 0.1234 mole
\ molar concentration of solution
T

0.1234 U
= × 1000 Q V
90.91 mole fraction
= 1.357 M
mass of solute (mg) 22. YA = 0.4 and PA = 400 mm
14. PPm = × 106
mass of solvent (kg)
Now, PA = PTotal . YA

=
0.025
× 106 = 25 PPm \ 400 = PTotalX0.4
103
15. 2 litre solution = 2000 ml solution
\ PTotal = 400/0.4

100×mass of solute (gm)


\ PTotal = 1000 mm
%
W
V
=
Volume of solution (ml) \ PB = 1000 – 400 = 600 mm

100×massof solution (sugar) 23. Molecular mass of Benzene = 78 gm/mole


5 =
2000 Molecular mass of Toluene = 92 gm/mole

\ mass of solute (sugar) = 5 s100


2000
= 100 gm moles of Toluene =
7.8
= 0.1 mole
78
808
180
moles of Toluene = = 1.956 mole W2
92 o
\
P1 - P1 M2
Total number of moles of solution =
0.1+1.956 = 2.056 mole
\ P1
o
=
W1
M1
® Molefraction of Benzene (X1) =
0.1
2.056 where,W2 = mass of solute = 0.5 gm
= 0.0486 W1= mass of solvent (Benzene)
= 39.0 gm
® Molefraction of Toluene (X2) =
1.956
2.056 M1 = molecular mass of Benzene = 78u
= 0.9514 M2 = (?)
® P10 = 0.9 Bar, P20 = 0.85 Bar
0.5
PTotal vappour pressure = P20 + (P10 – P20) × X1 0.850 - 0.845 = M 2
= 0.85 + (0.9 – 0.85) × \ 0.850 39
0.0486 78
= 0.85 + 0.00243
= 0.8524 Bar
\ M2 = 170 gm
24. Based on figure, partial pressure of A 30. According to Raoult’s law,
P0A = 60 mm o
P1 - P1 WA MB
partial pressure of B P0A = 80 mm o = M × W
P1 A B
Now, Total pressure P = P0A.XA + P0B.XB
according to lowering of vapour pressure
¥ 1µ ¥ 3µ
= 60 × ¦ ¶
§ 4·
+ 80 × ¦ ¶
§ 4· o
P1 - P1 10
= 15 + 60 = 15 mm o =
P1 100
25. According to Raoult’s law
o
P1 - P1 n2 x

P1
o
=
n1 \ 10
100
60
= 180
18
0.5
143 - P1
\ \
= 65 x
143 158
154
P1 = 141.93 mm
\ 1
10
=
60
10
26. Suppose in a solution XA = x and XB = 2x \ x = 60 gmmole –1
and PAo = P and PBo = 2P 31. P = PAXA + PBXB
\ PA = X × P and PB = 2x × 2P = 4x × P = PAXA + PB (1 – XA)
\ PTotal = 5xP
\ molefraction in vapour state
= PAXA + PB – PBXA
= PB + XA (PA – PB)
PA xp 1
YA = P1o - P1
PTotal = 5x p = 5 = 0.2
32. According toRaoult’s Raw :
n2
= n
o
27. According to Raoult’s law for volatile sub- P1 1

stances. • How, 4 % W/W urea solution means 4 gm


PTotal = PAo.XA + PBo.XB urea in 96 gm water and P1o = 0.025 bar
\ 290 = 200 × 0.4 + PBo × 0.6
\ PBo = 350 mm
W1
n1 = M =
96
= 5.33 mole
28. According to Raoult’s law 1 18

P1o - P1 n W2 4
= 2 where, P1o = 0.850 bar n2 = M = 0.0667 mole
P1 n1 2 60
P1 = 0.845 bar • Substituting the value in equation of

809
Raoult’s law \ D Vmix = –Ve (negative) DHmix – Ve
0.025 - P1 0.0667 \ Total volume of solution = < (30 + 50) ml
= = < 80 ml
0.025 5.33
50. Due to H-bond formation between Butyl Al-
0.0667 s 0.025 cohol (C4H9OH) and H2O (water)
0.025 – P1 =
5.33 52. According to Henrry’s law : PH S = K .XH S 2 H 2

0.025 – P1 = 0.000313 PH S 3 s 108

\ P1 = 0.025 – 0.000313
\ XH2S = K
2

H
=
5.6 s 10 4
= 0.5357 ×

\ P1 = 0.02469 bar 10–4


33. Relative lowering in vapour pressure = 5.357 × 10–5
= mole fraction of solute 1 litre water = 1000 ml water = 1000 gm water
(Q density of water = 1 gm/ml)
\
n2
n1 + n 2 = 0.0125 where n2 = molarity 1000
Moles of water (n1) = = 55.55 mole
18
n1 + n 2 1 1000
= n2 = n2
n2 0.0125 18 XH2S = n n
1 2

\
n1 + n 2
\
n2
n2 = 80 = 55.55 mole XH2S = n 55.55
2

\ \
n1 n2
n 2 + 1 = 80 5.357 × 10–5 =
55.55
\ n2 = 5.357 × 10–5 × 55.55
\
n1 n1 55.55
n2 = 297.58 × 10–5 mole
n 2 = 79 and n2 = 79 = 79 = 0.70
n2 = 2.9798 ml mole
where, (n2) = 0.70 M 55. PN2 = KH.XN2
34. Pvappressure = 80 torr, and Qvappressure = 60 torr
\ PTotal press = [Pvap press × Xp] + [Qvap press × XQ] \ XN2 =
1
105
× 0.8 × 5

¨ 3¸ ¨ 2¸ = 4 × 10–5 Solubility in 1 mole


= ©80 s ¹ + © 60 s ¹ Solubility in 10 mole = 4 × 10–4
ª 5º ª 5º \

56. as value of Henry’s constant (KH) decreses solu-


= [16 × 3] + [12 × 2]
bility increases. From the given gases, CO2 dis-
= 48 + 24
= 72 torr solves in water fastest. Hence KH value for CO2
gas will be lowest
35. A solution of ethanol in acetone shows posi-
tive deviation in Raoult’s law because ethanol 1 4
57. PO = ×1 × 0.2 bar, PN = × 1 = 0.8 bar
molecules aer joined to each other by strong 2 5 2 5
H-bond. But when acetone is added. it breaks PO
the H-bonds between the molecules and etha- Now, PO = KH(O ) · XO OR XO = K
2

2 2 2 2 H(O 2)
nol becomes more volatile and its vapour pres-
sure increases. PN
38. Chloroform and acetene form a non ideal PN = KH(N ) · XN OR XN = K
2

2 2 2 2 H(N 2)
solution where due to H-bond formation
attraction between A–B is more attrection XO PO K H(N )
between A – A and B – B as result they show \
2
= 2
× 2
XN PN K H(O )
negative deviation in Raoult’s law. 2 2 2

810
XO 7
70. (ii) 0.1 M glucose, p = CRT = 0.1 RT
2 0.2 bar 6.60 ×10 torr 1 (iii) 100 ml solution has 0.6 gm urea dissolved
\
XN = 0.8bar × 7 =
2 3.3×10 torr 2 in it.
\ XO : XN = 1 : 2 0.6
63.
2 2
According to DTb = i.Kb.m more the number of
W s 1000
n M 60
p= RT = V RT = × RT
particles in the solution higher is its boiling V 100
point.
= 0.1RT
Here, KNO3= 2, Na3PO4 = 4, (iv) 1.0 gm nonvolatile solute (x) disolved in
BaCl2 = 3, K2SO4 = 3 50 ml solution.(x)
64. According to DTb = iKf.m more the number of
particles in the solution lower is its freezing 0.1
point. p =
200 × 1000 RT = 0.1 RT
50
K4[Fe(CN)6]=5, C6H12O6=1, KCl = 2 NaCl = 2
Hecen, (ii), (iii) and (iv) will have equal os-
DTf 0.186
65. D Tf = kf.m \ m = K = = 0.1 motic pressure.
f 1.86 71. For sugar cane (sugar) solution :
\ D Tb = kb m WB = 5 gm, WA (water) = (100 – 5) = gm 95
= 0.512 × 0.1 MB (sugar) = 342 gm mole–1,
= 0.05120 C DTf = 273.15 – 271 = 2.15K

66. P V = nRT K f × WB
500 V1 Now, DTf = M × W
nR × 283 B A
105.3 V2 = nR × 298
Kf × 5
2.15 = (1)
V1 1 180 × 95
\
V2 = 5 \ V2 = 5V1
• For glucose solution :
67. D Tb = kb.m WB (glucose) = 5 gm,
DTb WA (water) = (100 – 5) gm = 95 gm
0.128
\ m= K = = 0.25 MB (glucose) = 180 gm mole–1, DTf = (?)
b 0.512
Now, Kf = 1.860 C and m = 0.25 Kf × 5
® D Tf = (2)
180 × 95
\ Tf = kf × m
D

= 1.86 × 0.25 Divide equation (2) by (1),


= 0.465o C DTf K ×5 342 × 95
= f × K ×5
Now, freezing point of solution 2.15 180 × 95 f

(Tb) = T0b – DTf DTf 342


= 0 – 0.465 \ =
2.15 180
= – 0.4650 C
342 s 2.15
68. Mass of water (WA) = 500 gm = 0.5 kg \ D Tf = = 4.085 K
180
® Increase in boiling point
® Freezing point of 5% glucose solution
0
DT = 100 – 99.63 = 0.37 C
b = (273.15 – 4.085) = 269.07K
Kb = 0.52 K kg mole–1
72. ethylene glycol (C2H6O2) used as a coolant in
Molecular mass of sucrose (MB) = 342 gm mole–1 a radiator is a non electrolyte.
o
DT = 2.8 C
M B × ∆Tb × WA 342 s 0.37 s 0.5 f
\ WB = Kb =
0.52 1000 × K f × W1
\ D Tf = M1 × W2
= 121.7 gm

811
78. According to p = CRT
1000 ×1.86 × W1
\ 2.8 =
62 ×1000 36
C1 = RT, p1 = 4.98 bar
180
\ W1 = 93.33 gm
C2 = (?); p2 = 1.76 bar
73. Boiling point (Tb) = 100 + DTb
36
= 100 + kb m \ 4.98 = ... (1)
180
Freezing point (Tf) = 0 – DTf \ 1.76 = C2RT ... (2)
Now, dividing equation (2) by (1),
= kf m
1.76 C2
Now, Tb – Tf = (100 + kbm) – (– kf m) = × 180
4.98 36
\ 105 = 100 + 0.151 m + 1.86 m
1.76 36
\ 2.37 m = 5 \ C2 = × = 0.071 M
4.98 180
5
\ m= = 2.11 79. Osmotic pressure p = CRT OR C =
p
2.37 RT
® mass of sucrose soluble in 100 gm water
2.0
C= = 0.0812 mole litre –1
2.11 s 342
\
0.0821 s 300
= × 100 = 72 gm –3
1000 ® Now, density of water is 1.0 gm cm mo-
74. D Tb = i × kbm larity and molality of aqueous solution can be
considered same.
13.44 \ DT = K m = 1.86 × 0.0812 = 0.151
o
= 3 × 0.52 = 0.16 gm f f
134.4 Freezing point of solution = 0 – 0.151
W WRT 1 = – 0.151o C
75. P= RT where, is constant P a
MV V M 80. DT = K m ... (i)
f f
\ P2 > P1 > P3 DT = K m . ... (ii)
b b
76. According to p = iCRT dividing equation (ii) by (i)
(A) p = 4 × 0.01 RT = 0.04 RT DTf K f ·m DTf Kf
(B) p = 2 × 0.01 RT = 0.02 RT DTb = K b ·m \
DTb = Kb
(C) p = 1 × 0.1 RT = 0.1 RT
Kf
(D) p = 3 × 0.1 RT = 0.3 RT \ D Tf = K × DTb
® Concentration is more
b

\ more osmotic pressure Where, D Tb = 100.18 – 100 = 0.18o C


Hence a hypertonic solution 1.86
\ D Tf = × 0.18 = 0.654o C
K b × 1000 × W2 0.152
77. D Tb = W1 × M 2 Hence, Freezing point of solution
= 0–0.654 = – 0.654o C
1.72 s 1000 s 0.456 81. solution : I mass of solute
= = 0.16 C
31.4 s 152 25
= × 300 = 75 gm
\ Boiling point of solution 100
= 56.30 + 0.16 = 56.46 C solution : II mass of solute
M2 = 152 gm mole–1 40
= × 400 = 160 gm
W1 = 31.4 gm 100
W2 = 0.456 gm mole–1 On mixing both the solution mass of the solute
in the mixture solution = 75 + 160 = 235 gm
36 Total mass of the solution = 300 + 400 = 700 gm
kb = 17.2 K mole per 100 gm
180 \Final percentage of solute in solution

= 1.72 K mole–1 235


= × 100 = 33.57 %
700
812
82. For isotonic solution C1RT = C2RT Hence M1 = Molecular mass of Benzene
C1 = C2 = 78 gm mole–1
density of the solution is assumbed to be
1.0 gm cm–3, W2
o
molality = molarity = 5.25 P1 - P1 n2 M2
= =
o n1 W1
Hence 5.25 gm solute is dissolved in 100 gm P1
M1
solution so 52.5 gm solute is dissolved in 1000
gm solution.
0.5
52.5 15 0.850 - 0.845 = M
= 2
M 60 \
0.850 39
78
52.5 s 60
\ M=
15
= 210 gm mole–1 \ M2 = 170 gm mole–1
87. D Tf = 0.372o C
Hence, molecular mass = 1200 gm mole–1
Now, D Tf = Kf.m
W
83. p =
n
V
RT = MRT
V \
∆Tf
m= K =
0.372
= 0.2 m
f 1.86

\ 600 = 20 × 0.0821 × 288 × 1000


760 500 × M \ W2 =
m × M × 8000
1000
\ M = 1200 gm mole–1
0.2 s 60 s 8000
Hence, molecular mass = 1200 gm mole–1 \ W2 =
1000
= 96 gm

W2 88. As concentration of isotonic solution is same,


5
P1
o
- P1 M2 M2 34.2 gm/litre sucrose = 0.1 M
3000 - 2985
84. P1o
=
W1
=
3000
=
100 \ \ 18.0 gm/litre glucose = 0.1 M
M1 18
89. Tb – Tf = 105o C
M2 = 180 gm mole–1 \ D Tb = Kb m

K b × W2 × 1000 105 = (Kb + Kf) m + 100


85. M2 = W1 × ∆Tb \ To – 100 = Kb m
where, D Tb = 0.323 K \ 5 = (0.512 + 1.86) m

W2 = 0.5143 gm \ To = Kb m + 100

Kb = 3.9 K.kg mole–1 \ m = 2.107


gm
W1 = 35 K.kg mole –1 mole 1000
W
DT = K m Now,
\
f f M
´
Wo = 2.107
3.9 s 0.5143 s 1000
M1 =
35 s 0.323 \ To – Tf = Kf m
–1
M2 = 177.42 gm mole
W 1000
86. P1o = 0.850 bar \ ´ = 2.107
342 100
P1 = 0.845 bar
\ 0 – Tf = Kf m
W2 = 0.5 gm
\ W = 72.09 gm
M2 = (?)
\ Tf = Kf.m
W1 = 39.0 gm
813
90. According to Raolut’s law
2.8 = M B - 6
\ P1o = 0.0335 gm OR o MB ... (1)
P1

P1o − P1 W2 × M1 ® dividing equation (1) by (2)


=
P1o M 2 × W1 2.8 = M B - 6
2.9 MB - 5
Where, P1o = 0.033 bar
2.8 MB – 14 = 2.9 MB – 17.4
0.0335 − 0.033 = 10 × 18 2.9 MB – 2.8 MB = 17.4 – 14
0.033 M 2 × 540
0.1 MB = 3.4
W1=540 gm \ MB = 34 gm mole–1
0.0005 = 1 92. Molecular mass of sulphur,
0.033 3× M2
Where, Kb = 2.53 K kg mole–1
M1 = 18 gm and M2 = (?) W2 = 3.24 gm,

0.033 W1 = 40 gm
\ M2 = = 22.0 gm mole–1
3 s 0.0005 D Tb = 0.81K
K b × 1000 × W2
WB \ M2 = ∆Tb × W1
o MB
P1 - P1
91. o
= xB = W W 2.53 s 1000 s 3.24
P1 A
+ B = = 253 gm
MA MB 0.81 s 40
® Suppose formula of sulphur = Sx
Now, WB = 30 gm, PA = 2.9 k Pa
atomic mass of sulphur = 32
WB × M A atomic mass = 32x
»
M B × WB \ 32x = 253
\ x = 791 » 8
WA = (90 gm + 18 gm) = 108 gm
\ molecular formula = S8
P1o − 2.8 30 × 18 0.52 s 12.5 s 1000
\
= 93. MB = = 53.06 gm
P1o MB 90 0.70 s 175
94. For compound AB2 and compound AB4
1 - 2.9 = 5
o MB K f × WB × 1000
P1
MB = WA × ∆Tf

1 - 2.8 = 6 K f × WB × 1000
o MB
P1 MB = WA × ∆Tf

2.9 = 1 - 5 = M B - 5 5.1 s 10 s 1000 5.1 s 10 s 1000


= =
P1
o MB MB 20.0 s 2.3 20.0 s 1.3
MAB = 110.87 MAB = 196.15 gm
MB - 6 2 4
2.8
=1– 6 = M ® Suppose molecular mass of A = a and
P1
o MB B
molecular mass of B = b,
MAB = a + 2b = 110.87 ... (1)
2.9 = M B - 5 2
\ o MB ... (2) MAB = a + 4b = 196.15 ... (2)
P1
4

814
Subtracting equation (2) from equation (1), 100. D Tf = i × Kf × m,
– 2b = – 85.28 \ b = 42.64 gm
∆Tf × WA 3.82 s 45
Substituting value of b in equation, i = K × n ×1000 =
¥ 5 µ
f B
1.86 s ¦ s 1000
a + 2 × 42.64 = 110.87 § 142 ¶·
\ a = 110.87 – 85.28 = 25.59
= 2.63
\ a = 25.59
101. Van’t Hoff factor based on osmotic pressure
95. p (blood) = p (glucose solution) = 8.21 atm. pV = inRT

\ PV = nRT OR n=
PV K f × WB ×1000
RT 102. MB = ∆Tf × WA
8.21 s 1.0 10 Where, WB = 0.5 gm,
\ n= 
0.0821 s 310 31 WA = 100 gm
10 DTf = 0 – (– 0.24)
\ mass of glucose = × 180 = 58.06 gm
31 = 0.240 C

K f ×1000 × WB
1.86 s 0.5 s 1000
96. MB = = 1.86 × 1000 ×15 \ MB =
0.24 s 100
= 38.75 gm
∆Tf × WA 0.34 × 450
• molecular mass of KCl = 39 + 35.5
= 182. 35 gm mole–1 = 74.5 gm mole–1
where, D Tf = 0 – (– 0.34) • Van’t Hoff factor (i)
Normal molecular mass
= 0.340 C =
Abnormal molecular mass
97. Napthoic acid (C11H8O2) molecular mass
74.5
= = 1.92
= 172 gm mole–1 38.75
K f ×1000 × W2 • KCl K+ + Cl–
M2 = = 1000 × 1.72 × 20
∆Tf × W1 50 × 2 Initial mole 1 0 0
moles after dissociation 1–a a a
= 344
Total moles after dissociation
Actul molecular mass
Van’t Hoff factor (i) = =1– a + a + a + a = 1 + a
Abnormal molecular mass
number of moles of solute after dissociation
172 i= normal moles of solute
= = 0.5
344 1 2
=
98. AxBy XAy+ + YBx– 1
After dissociation (1 – a) xa ya 1 B
• \ = 1.92 Hence 1 + a = 1.92
y+
i = n (AxBy) + n(A ) + n(B ) x– 1
\ a = 1.92 – 1 = 0.92
i = 1 – a + ax + ya
• \ Percentage iconization = 92 %
i = 1 + a (x + y – 1)
K f ×1000 × WB
i- 1 103. D Tf = i × WA × M B
\ a =
(x + y - 1)
1.86 ×1000 × WB
99. Na2SO4 2Na+ + SO4–2 7.50 = 1.87 ×
65.0 × 58.5
Before dissociation 1 0 0
7.50 s 65.0 s 58.5
After dissociation 1–a 2a 1a \ WB = = 8.2 gm
1.87 s 1.86 s 1000
Now, i = 1 – a + 2a + a = 1 + 2 a
815
104. Molecualr mass of CH2FCOOH = 78 gm mole–1 C2 0.01
\ i= C = = 2.5
19.5 1 0.004
moles of CH2FCOOH = 0.25 mole
78 Now, number of particles in Na2SO4 n = 3
\ i = 1 + (n – 1) a
0.25 s 1000
\ molality (m) =
500
= 0.50 m 2.5 = 1 + 2a
\ 1.5 = 2a
• \ D Tf = Kf m = 1.86 × 0.50 = 0.93 K \ a = 0.75

• Van’t Hoff factor \ 75%


107. Depression in freezing point
measured depression in freezing point
(i) = calculated freezing point D Tf Kf m = 1.86 × 0.01 = 0.0186 K
\ Van’t Hoff factor (i) =
1.0
= = 1.0753 Practical depression freezing point
0.93 (i) = Theoretical freezing point
\ i = 1.0753 0.062
– + = = 3.33
CH2FCOOH CH2FCOO H 0.0186
Initial mole m 0 0 \ Number of particles of K3 [Fe(CN)6] = 4
after dissociation m(1–a) ma ma
Total mole = m (1–a) + ma + ma i 1
\ degree of dissociation (a) =
= (1 + a) n 1

m(1 + a ) 3.33  1
i= = 1 + a = 1.0753 = = 0.778
m 4 1
\ a = 1.0753 – 1 = 0.0753
108. Molecular mass of phenol (C6H5OH)
[CH2FCOO–] = ma
= 94 gm mole–1
= 0.50 × 0.0753 = 0.03765 Practical molecular mass of phenol
[H+] = ma = 0.50 × 0.0753 = 0.03765
1000 × K f × W2
[CH2FCOOH] = m (1 – a) = 0.50 M2 = ∆Tf × W1
(1 – 0.0753) = 0.462
1000 s 4.0 s 1.5
CH FCOO−   H+  M2 =
 2   = (0.03765)× (0.03765) 0.56 s 100
Ka=
CH2 FCOOH  0.462 M2 = 107.14 gm
= 3.07 × 10–3 Now, Van’t Hoff factor
105. i = 2.47 p = iCRT Actual molecular mass
(i) = Practical molecualr mass
nB
p =i RT 94
V = = 0.879
10.7.14
2.47 × n B × 0.082 × 300 Now,
\ 0.75 =
2.47 × 0.082 × 300
¥ n µ
0.75 s 2.5 degree of association (x) = (1 – i) ¦§ ¶
nB = = 0.03 mole n  1·
2.47 s 0.082 s 300
106. Osmotic pressure, p = iCRT ¥ 2 µ
= (1 – 0.879) ¦§ ¶ = 0.121 × 2 = 0.242
Here, C1 = 0.004 M and C2 = 0.01 M 2  1·
p
1
= p2 109. When solute undergoes association in a
iC1RT = iC2RT solution i < 1 (less than 1) when dissociation
i > 1 (more than)
816
110. 50% dissociation 134. As sucrose undergoes association it possesses
\degree of dissociation a = 0.5 least number of particles and highest freezing
point.
K4[Fe(CN)6](ag) 4K+(ag) +[Fe(CN)6]4–(ag)
135. K4[Fe(CN)6] 4K+ + [Fe(CN)6)]4–
Initial mole 1 0 0
moles at \ i=5
equilibrium 1–a 4a a D Tf = i Kf m = 5 × 0.52 × 0.1 = 0.260
Total moles of solution = 1 – a. + 4a +a
Tb = 100.260 C
= 1 + 4a
136. Ba(NO3)2 Ba2+ + 2NO3–
1 4B 1 4(0.5)
Van’t Hoff factor (i) = = =3 Initial 1 0 0
1 1
p = iCRT = 3 × 0.1 × 0.082 × 300
after dissociation 1 – a a 2a
= 7.38 atm Total mole = 1 – a + a + 2 a
P1 T1 V2 = 1 + 2a
111. According P = V × T \ i=1+2a
2 1 2

500 / 760 283 V2 V2 i- 1 2.74  1


= V × 298 = = = 0.87 = 87 %
V1 = 5
\ a
\ 2
105.3/ 760 1 2
\ V1 = 5V2 137. mole fraction of ethanol = 0.9
127. PA = XA.PAo = 0.5 × 108 = 54 torr \ molefraction of water = 0.1
\ molality of water in solution (m) =
PB = XB.PBo = 0.5 × 36 = 18 torr
0.1
PTotal = 54 + 18 = 72 torr = × 1000 = 2.415
0.9 s 46
PB
128. Molefraction of B in gasseous state = P + P \ D Tf = kf.(ethanol) m = 2.0 × 2.415
A B
= 4.83 K
18 \ Freesing point of ethanol in solution =
= = 0.25
72 = Tfo(ethanol) – DTf
∆P 10 = 155.7 – 4.83
129. o
= X2\ o = 0.2 \ P0 = 50 mm
P P = 150.87K = 150.9K
20 20 138. Psolution = X1.Po1 + X2Po2
\ o = X2 \ = X2 \ X2 = 0.4
P 50 = 0.9 × 40 + 0.1 × 32.8
\ X1 = 1 – 0.4 = 0.6 = 36 + 3.28 = 39.28 » 39.3 mm
139. Ethanol = solvent and water = solute
W2
o \ Molaity of ethanol in the solution
P1 - P1 M2
130. =
o W1 W2 0.1
P1 + = × 1000 = 6.17 m
M1 M2 0.9 s 18

1
\ D Tb = Kb(water) × m = 0.52 × 6.17 = 3.2 K
10 - 9 = M2 \ Boiling point of solution = Tob(water) + DTb
10 20 + 1 = 373 + 3.2 = 376.2K
200 M2
10.6 1000
140. (A) Molarity (M) = s = 1M
1  1 × 1  = 1 106 100
10  10 M 2  M2
34.2gm litre –1
9  1 = 1
(B) Molarity (M) = = 0.1M
342gm mole –1
\
10  M 2  100 \ M2 = 90 gm mole–1
817
(C) 9.8 % H 2SO 4 means 9.8 gm H 2SO 4 in 151. K4[Fe(CH)6] ® 4K+ + [Fe(CN)6]4–
100 gm solution 1 mole 0 0
\ Volume of solution = 100/1.25 = 80 ml
1–a 4a a

9.8 1 Total mole = 1 – a + 4 a + a = 1 + 4a


molarity (M) = × × 1000 = 1.25M
98 80
1 4B
(D) 20 % ethanol means 20 ml ethanol in 100 \ i= = 1 + 4a = 1 + 4 × (0.75)
1
ml solution
\ Volume of solution = 100 × 0.938 = 93.8 =1+3=4
gm 153. For m mole [Cr(H2O)5Cl]Cl2 = 0.01 × 30 =
\ Volume of water = 100 – 20 = 80 ml = 80 0.3 m moles of Cl– ion = 0.3 × 2 = 0.6
gm
m mol of Ag+ ion = m moles of Cl– ion
\ ethanol = 93.8 – 80 = 13.8 gm
0.1 × V = 0.6
13.8 1
\ molarity (M) = × × 1000 = 3.0 M V = 6 ml
46 100
157. Molarity =
141. 0.91 % NaCl in contact of Red blood cell is
> 0.91 % Hypertonic; 3M= \ mole = 9
< 0.91 % Hypotonic 158. D Tb = 1.50 C M = 176 gm mole–1
and 5.85 % NaCl solution = 1N solution
K f ×1000 × WB
147. PN = XN .PTotal M=
2 2 WA × ∆Tf
= 0.78 × 1
= 0.78 × 760 = 592.8 mm
3.9×1000×WB
Concentration of solution = KH.PN \ 176 =
2 75×1.5
= 8.42 × 10–7 × 592.8
= 4.99 × 10–4 M 176 s 75 s 1.5
\ WB = = 5.08 » 5 gm
» 5.0 × 10
–4
M 3.9 s 1000
\ x=5 •
150. Volume of mixture = 200 ml
1.4gm
Concentration of urea solution =
200 ml
7. Equilibrium
= 7.0 gm litre–1 1. 2NO + Br2 2NOBr
7.0 Initial moles 0.087 0.0437 –
= mole litre–1 Moles at
60
equilibrium 0.087–2x 0.0437–x 2x
7.0 Number of moles of NOBr at equilibrium
p
(urea)
= CRT = × 0.0821 × 293
60 = 0.0518
= 2.80 atm \ 2x = 0.0518
3.42gm \ x = 0.0259
% of sugar cane in solution = Moles of No at equilibrium = 0.087 – 2x
200 ml
= 17.10 gm/litre = 0.087 – 0.0518 = 0.0352
Moles of Br2 at equilibrium = 0.0437 – x
17.10
= mole/litre = 0.0437 – 0.0259 = 0.0178
342
3. 3O2(g) 2O3(g)
17.10
p = CRT = × 0.0821 × 293 [O3] = 2.0 × 10–50 × (1.6 × 10–2)3
2
(sugarcane) 342
= 8.192 × 10–56
= 1.20 atm
Total osmotic pressure = 2.80 + 1.20 = 4.0 atm \ [O3] = 2.86 × 10–28 M

818
5. CO(g) +H2O(g) CO2(g)+H2(g) 16. I2(g) 2I(g)
Initial pressure 4 bar 4 bar – – partial pressure of I atom,
pressure at
105 s 40
equilibrium 4–P bar4–P bar P P PI = = 0.4 × 105 Pa
100
PCO ·PH
\ kp = P ·P
CO H
2

2O
2
partial pressure of I2 molecule PI2 =
105 s 60
100
= 0.6 × 105 Pa
1
6. K’c = 2
(K C ) 2 2
PI
s 105

7. C2H6C(g) C2H4(g) + H2(g) \ Kp = P


I2

=
0.4

0.6 s 105
= 2.67 × 104
Initial pressure 4.0 atm – –
18. From the formula Kp = Kc (RT)Dn(g)
pressure at
equilibrium 4.0–P atm P P 90.55
20. mole of CO = 3.234
28
PC H ·PH
2 4 2
Kp = P 9.45
C H mole of CO2 = = 0.215
2 6 44
2
¥2 µ ¥ Pµ 3.234
10. Kp = ¦ P¶ ¦ ¶
PCO = Xco PTotal XCO =
§3 · § 3· 3.234 + 0.215
= 0.938 × 1 = 0.938)
4p3 = 0.938 atm
p = 3.0 atm substituting in Kp =
27
PCO = Xco2 PTotal XCO = 1 – 0.938
2 2
11. PCl5 PCl3 + Cl2 = 0.62 × 1 = 0.062)
Initial 1 – – = 0.062 atm.
at equilibrium 1–0.4 0.4 0.4
= 0.6 \ P 2co
Kp = Pco
® Total mole = 0.6 + 0.4 + 0.4 = 1.4
2

Obtain KC from Kp = KC (RT)Dn(g)


1.4 s 0.082 s 400
® V=
nRT
P
=
1
22. adding the first two reactions the third reaction
is obtained from that K3 = K1 K2
= 45.92 litre
25. using equation DGo = – 2.303 RT log ke

\ Density =
208.5
45.92
27. D Go = SDfGfao(m) – SD Gaof(g)
& Do = – 2.30 3 RT log Kp
–1
= 4.54 gm litre
K2 %H  T2 - T1 
15. CO2(g) + C(s) 2CO(g) 31. log K = R T T 
1  1 2
Initial pressure 0.48 bar – –
pressure at 9.25  %H s 75
log
18.5 2.303× 8.3114 9.25 s 1000
\
(bar) equilibrium 0.48–x bar 2x
2 \ H = – 71.08 K joule mole–1
( PCO ) 4x
2
Kp = P = 32. On comparing QC and KC
CO 0.48 - x
2
33. Based on Lechatelier’s principle

\ 34. Based on Lechatelier’s principle


2
3= 4x
0.48 - x 35. Based on Lechatelier’s principle
36. [H3O+] = a&

819
[H3O+] = µ c pKa = – log ka
= – log 1.8 × 10–5 = 4.745
\ a C= a&
[H k ]
\ 4 = 4.745 + log [0.1] moles of salt can be
Ka
\ a =
C calculated
1 68. ksp = 2754
44. Na + H2O ® NaOH + H
2 2
ksp
23 gm Na produces 1 mole NaOH. \ S= 4
27
0.023 gm Na produces 10–3 mole NaOH.
\ S = 1 × 10–3 M
–3
10 × 1000
\ [NaOH] = _ = 10–2 M \ Solubility (S) = 1 × 10–3 × 78
100
= 7.8 × 10–2 gm litre–1
[OH–] = 10–2 M \ pOH = 2 so pH = 12
\
\

_ Now conc of [OH–] in the solution


10 –pH × 200
52. moles of H+ = _ = 2 × 10–3 = 3S = 3×(1 × 10–3 M) M
1000
= 3 × 10–3 M
–
moles of OH =
10
_
_
–pOH
× 300
= 3 × 10–3 \ pH = 14 + log [OH–]
1000
= 14 + log 3 × 10–3
–3
\ = 1 × 10 = 14 + 0.4771 – 3
1 × 10 × 10 –3 3
= 11.4771
\ [OH–] = = 2 × 10–3
500 71. Mg (OH)2 ksp = [Mg2+] [OH–]2
\ pOH = 3 – log 2 = 3 – 0.3010 = 2.7
\ pH = 11.3
\ ksp 10–11
[OH–] = [Mg 2+ ] = 10–3 = 10–4M
53. Cocaine (C18H21NO3) is base.
C18H22NO3 + H2O C18H22N+O3H + + OH– \ poH = 4 \ pH = 10
Find pOH from pH and from that calculate 73. ksp of BaCO3 = [Ba2+] [CO32–]
[OH–]
5.1×10 –9
[OH – ]2 \ 2+
[Ba ]=
ksp
2– =
[CO 3 ] 1×10
–5
–4 = 5.1 × 10 M
Using equation Kb =
C
54. NH3 + H2O NH4+ + OH– 19.23
75. Solution of Sr (OH)2 = = 0.1581 M
121.6
Initial 5.8 – –
at equilibrium 5.8 – x x x \ [OH–] = 2 × 0.1581
= 0.3162 M
( x) ( x) x2
\ kb = »
5.8 – x 5.8 – x
... (i) \ pH = 14 – log [OH–] = 14 – log 0.3162
= 13.50
Kw 10 –14
kb = Ka  5 s10 –10 = 2 × 10–5 ... (ii) 76. [Ba2+] = 0.05 M (For BaCl2)

Comparing (i) and (ii)


\ [Ba2+] = xm (For BaSO4)
x = (OH–) = 1.078 × 10–2 M \ [Ba2+] = 0.05 M + xm » 0.005 M
Kw \ ksp = [Ba ] 2+
[SO42–]
\
+
From [H ] = [OH – ] , [H+] is obtained \ 1.1 × 10–10 = (0.05) (x)

60. Using equation : pH = 7 –


pKb logC
2

2 \ x=
1.1× 10 –10
5 × 10 –2
= 2.2 × 10–9 M

[salt] 96. 2AB2 2AB + B2


65. pH = pKa + log [Acid]

820
x
initial 1–x 4x 4 P1 x 2 P2
2
\ Kp1 =
(1 – x 2 )
Kp2 =
(1 – x 2 )
\ Total mole = 1–x + x +
x
2

x
\ KP1 1 4P1
KP2 = 9 = P2
=1+
2

(PAB )2 (PB2 )
\ P1 1
P2 = 36
\ Kp = (P ) 2
AB2 104. AB(g) A(g) + B(g)
initialt 1 – –
2
   x  equilibrium1–033 0.33 0.33
 x   
 × P  2 P
1+ x   1+ x 
\ Kp =  2   2  0.33 P 0.33 P
\
2 1.33

1.33

  Kp =
1– x  0.67
 P 1.33 P

1+ x 
 2 

0.33×0.33×P
=
x x 0.67×1.33
Now, 1+
2
»1 1–
2
»1

1
\ P = 8 Kp

\ x3p
\ 2Kp µ 3
¥
Kp = x= § P · 1
2 107. pH = (Pkw + Pka + log C)
2
97. A + 3B 4C \ 8.9 × 2 = 14 + pka + log 0.1
initial cane a b –
\ 17.8 = 14 + pka – 1
At equilibrium a–x b–3x 4x
initial a = b and at equilibrium a – x = 4x
\ pka = 4.8

\ a = b = 5x \ ka = antilog ( 5 .2)

(4x)4 = 1.585 × 10–5


\ Kc =
(a – x) (b – 3x)3 •

(4x)4 (4x)4
= = =8
(5x – x) (5x – 3x)3 (4n ) (2x)3 8. Redox Reactions and
100. X 2Y Z P + Q
initial 1 – 1 – –
Electro Chemistry
equilibrium1–x 2x 1–x x x 19. Aq. solution salt Y can be filled in container X.
Reation :
 2x 
2 x 2 P22
 1+ x P1  2 X(s) + Yn+(aq) Xn+(aq) + Y is not spontane-
  (1+ x)
Kp1 =  1– x  Kp2 =  1– x  ous in forward direction.
 1+ x P1   1+ x P2 
    (EoYn+/y < Eoxn+/x )
Aq. solution of salt Z can be filled in container
of Y.
821
Reaction : 42.
2+ +
For the cell, Zn | Zn (0.04M) | Ag (c2 ) | Ag
Y (s) + Z n+ (aq) Y n+ (aq) + Z (s) is not
Ecell = E ocell , Q = 1
spmteneous in forward direction.
(EoYn+/y < EoYn+/y) [Zn 2+ ]
\
[Ag + ]2 = 1
EoZn+/z < Eoyn+|y < EoXn+/x
Decreasing strength as reducing agent is 0.04
C22 = 1\ C2 = 0.2 M
\
\

Z>Y>X
43. Fe | Fe2+(C ) || Cl–(C ) | Cl2(1)| Pt For the given cell,
31. Cell regn for cell Co | Co2+(C1) || Ag+(C2) | Ag is 1 2

2+ –
Co(s) + 2Ag+(aq) Co2+(aq) + 2Ag(s) reaction is Fe(s) + Cl2(l) Fe(aq) + 2Cl(aq)
\ n=2 n = 2 and Q = [ Fe(aq) ] [Cl–]2.
2+

[Co 2+ ] \ On increasing concentration of cathode


Q = [Ag + ]2 By dividing equation by 2 solution, the value of Q increase.
Hence at a definite temperature, the value
1 1 2+ 2.303 RT
Co(s) + Ag+(aq) Co (aq) + Ag(s) – log Q will decrease i.e. the value
2 2 2F
1 2.303 RT 2+
[Co 2+ ] 2 – log [ Fe (aq) ] [Cl–]2 decrease.
\ n = 1 and Q =
2F
[Ag + ] 2+ 2+
44. In a cell Mg | Mg (C1) || Fe(0.5 M) | Fe. On equal
2+
1 decrease of conc. of both solutions at definite
RT [Co ] 2
Nemst equation, Ecell = E o
– ln temperature, cell potential increases.
cell F [Ag + ]
\ On equal decrease in conc of both solutions,

1
RT [Co 2 + ] 2 C1
E o
= Ecell + ln \ Q= decrease. \ C1 < 0.5.
\
cell F [Ag + ] 0.5
2+
45. For cell Co | Co (C1 ) ||Sn2+(C )| Sn, cell reation :
35. Equation const. Kc for cell reaction of cell : 2

2+ 2+ o Co(s) + Sn2+(aq) Co2+(aq) + Sn(s)


Zn | ZN || Cu
(C1) (C 2 ) | Cu at 25 C is
[Co 2+ ] C1
n×E 0 Q = [Sn 2+ ] = C (C2 > C1 is given)
\ logKc = cell 2
0.059
Therefore if same decrease in conc. of
Calculate by this formula.
solutions at both electrodes is made then as
36. For, Pt | H2(g.1.0 bar) | H+(pOH = 11)
C2 < C1, increase will be there in C1 and Q
Eoox = 0.059 × pH = 0.059 × 3 = 0.177 V will increase and potential will decrease.
37.
o
EZn2+/zn < E Zn 2+ |Zn | Zn is given. 49. Calculation of ECell at 25o C for
2+ 2+
Sn | Sn (0.1M) || Pb (0.01M) | Pb gives negative value.
0.059
log ( 1x )
o
Now EZn2+/Zn = E Zn 2+ |Zn –
2 51. By increasing temperature in a cell,

\ E 0Zn 2+|Zn – 0.059 log ( 1 ) < E oZn 2+ |Zn RT [Ni 2+ ] RT1 [Ni 2+ ]
2 x T < T1 \ log [Ag + ]2 < log [Ag + ]2
2F 2F
0.059 1 0.059
\ – log < 0 \ log ( 1x ) > 0 RT [Ni 2+ ] RT1
2 2 2 As Q > 1, log [Ag + ]2 > –
2F 2F
\ log ( 1x ) > 0 \ x < 1 \ x = 0.2 M
[Ni 2+ ]
log [Ag + ]2
822
56. For reaction – 2+
71. For the forward reaction : 2I(aq.0.1 M) + Cu (aq.0.05 M)
+ –
2H2O(l) O2(g.1 bar) + 4H (aq)
+ 4e
n = 4, at 25o C [H+] = 10–7 M and I°2(s) + Cu(s) Calculation of cell poten-
standard cell potential = – 1.23 V tial gives positive value. Whereas for other cells
it will be negative.
0.059
Ox. pot. of water = – 1.23 – log [H+]4
4 72. E 0ox for Fe | Fe2+ and Fe2+ | Fe3+ will be + 0.44V
= – 1.23 – 0.059 × log 10–7 and – 0.77 V respectively.
= – 0.817 V (1) Fe(s) Fe2+(aq) + 2e–
65. EH + = 0.059 × pH (25° C, 1.0 bar) n1 = 2 and E10 = + 0.44 V
2/H
\ 0.118 = 0.059 × pH 2+
(2) Fe(aq) Fe3+
(aq) + 2e
–

0.118 n1 = 2 and E02 = – 0.77 V


\ pH = =2
0.059
(3) Fe(s) Fe3+
(aq) + 3e
–

\ pOH = 14 – pH = 14 – 2 = 12
n3 = 3 and E 03 = ?
E cell – E ocell log [M n+ ] 0.635 – 0.34 Reaction (3) = (1) + (2) \ D G3o = D G1o + D Go2
66. pH = – =
0.059 n 0.059
\ – n3 FE3o = – n1 FE1o – n2 FEo2
log (0.01)
– = 6.0
2 n1E1o + E o2 2×0.44+1×(–0.77)
\ Eo3 = n3
=
3
E ocell – E cell log [M n+ ] 2.36 – 2.09 = 0.037 V
67. pH = – = –
0.059 n 0.059
73. E 0Cu|Cu 2+ = – 0.34 V and E 0Cu 2+|Cu + = + 0.16
log (0.01)
= 5.58 Cu ® Cu2+ + 2e–, n1 = 2, E1o = – 0.34 V
2
Cu2+ + e– ® Cu+, n2 = 1, Eo2 = – 0.16 V
68. Pt | H2(g.1.0 bar) | HCl(XM) ||| Au3+(0.001 M) | Au
Cu ® Cu+ + e–, n3 = 1, E3o = ?
E cell – E 0cell log [M n+ ] 1.6655 – 14
pH = – = – \ n3 E3o = n1 E1o + n2 Eo2 \ Eo2 = – 0.52 V
0.059 n 0.059
– +
–3
75. Pt/H2(g.1.0 bar) | OH (aq) ||| H (aq) | H2(g.1.0 bar) | Pt
log (10 )
= 5.5
3 1 –
anode : H2(g) + OH (aq) H2O(l) + e–
2
69. Ecell = E(OX.)(anode) – E(Ox)(cathode)
E 0ox = + 0.83
= 0.59 × (pH(anode)– pH(cathodes)
+ 1
cathode : H (aq) + e– H E o = 0.0
= 0.059 × (4.5 – 2.5) 2 2(g) red
= 0.118 V D G0 = nF E ocell = – 2.303 RT log K

70. Ecell = E(OX.)(anode) – E(OX.)(cathode) 0


nFEcell
\ log K =
2.303 RT
= 0.059 × (pH(anode)– pH(cathode)
1 1
= 0.059 × (3.5 – 2.0) Here, K = [H + ][OH – ]  K
w

= 0.0885 V 1
\ log K = log K
w

823
3+
+ 1 78. Initial concentration of Fe (aq) is 1.0 × 10–3 M
Cathode : H (aq) + e– H E o = 0.0V
2 2(g) red
and equation 5% of it remains.
+ –
Total : H (aq) + OH (aq) –3
At eqn. 1.0 × 10 × 5 = 5.0 × 10–5 M Fe (aq) is
3+
H2O(l) E o
cell
= + 0.83 100

1 0 left and 1.0 × 10–3 – 5.0 × 10–5


nFEcell
\ log K =
w 2.303 RT = 95 × 10–5 M is consumed.
nFEocell 2Hg(l) + 2Fe (aq)
3+
Hg 2+ 2+
2(aq) + 2Fe (aq)
\ – log Kw =
2.303 RT
conc. initially 1.0 ×10–3 M – –
R = 8.314 joule-mole–1 K–1 F = 96500mole
n=1, Conc. at
equilibrium 5.0 ×10–5 M
1 × 96500 × 0.83
\ – log Kw =
2.303 × 8.314 × T
95 × 10 –5 × M 95 × 10–5 M
4183.13083 2
\ log Kw = now, T = 323 K
T
= 47.5 × 10–5 M
4183.13083
\ – log Kw = = 12.9509 2 2
323  Hg 2 +   Fe 2 + 
 2(aq)   aq 
\ K w = antilog (– 12.9509) = Antilog Kc = 2
 Fe3+ 
( 13 .049) and Kw = 1.12 × 10 –13  aq 

77. E oCo2+ |Co = – 0.28 V and EoNi2+ |Ni = – 0.23 V


[48.5 × 10 –5 ][95 s10 –5 ]2
= = 0.171475
o o [5.0 × 10 –5 ]2
E 0cell = E Ni2+ |Ni – E Co2+ |Co
M = 0.1713 M
= – 0.23 – (– 0.28)
= 0.05 V and n = 2 At 25o C according to Nernst equation
0 0.059
n × E cell 2 × 0.05 Ecell = E ocell – log Qc
log Kc = = = 1.6949 2
0.059 0.059
Kc = antilog (1.6949) = 49.5336 At equilibrium, Ecell = 0.0 V, Qc = Kc
2+
Let the decrease in conc of Ni (aq) at equilibrium 0.059
\ 0 = E ocell – logKc
2
be xM.
2+ 2+ 2 × E ocell
Co(s) + Ni(aq.0.1M) Co (aq.0.01M) +Ni(s) \ logKc =
0.059
Initial conc. 0.1 M 0.01 –
Conc. at E 0cell
\ log0.1715 =
equilibrium (0.1 – x)M (0.01 + x)M 0.0295
0.01 + x E ocell
Kc = = 49.5336 = 4.95336 – – 0.7657 =
0.1 – x \
0.0295
49.5336x = 0.01 + x
50.5336x = 4.94336 \ E ocell = 0.0295 × (– 0.7657) = – 0.02259 V
4.94336 now E ocell = EoFe3+|Fe2+– E ocell
x=
50.5336
x = 0.09782 M = 0.77 – (– 0.02259)

100 × 0.09782 \ E Hg2+|Hg = 0.793 V


0
2+
Decrease in conc of Ni (aq) =
0.1 79.
2+ 2+
In cell Fe| Fe (0.1M) || Cd (0.5M) | Cd at 298 K, if
= 97.82 %
equilibrium constant is K,

824
nE ocell o o
SO2(g) +
1
O SO3(g)
logK = Here, E ocell = E Cd2+ |Cd – E Fe2+ |Fe 2 2(g)
0.059

E ocell = – 0.40 – (– 0.44) = 0.44 V 1


D Go = D GoSO3(g) – [DfGo (SO2(g)) + D Go
f 2 f
and n = 2
(O2(g))]
2 × 0.44
logK = \ K = 22.6934 \ – 35126 = DfGoSO3(g) – [– 300370 + 0]
0.059
Cell reaction \ D Go = D
f
GoSO3(g) = – 335496 J mol–1
2+
Fe(s) + Cd (aq)
2+
Fe(aq) + Cd(s) = – 335.496 J mol–1
initial conc. – 0.5 M 0.1 M – 95. On passing 5F electricity through molten CaCl2
Conc. at theoretical no. of moles of Ca at cathode is
equilibrium (0.5 – x) M (0.1 + x) M electricity passed in farady
[Fe2+ Valency of Ca in CaCl2 . Now efficiency
(aq) ]
Eq. const K = [Cd 2+ ] of cell is never 100% therefore experimental
(aq)
value of product obtained < theoretical value.
0.1 + x
\ 22.6934 = 96. The mole proportion of the metals obtained at
0.5 – x
different electrodes when same quantity of
\ 11.3467 – 22.6934x = 0.1 + x
\ 23.6934x = 11.2457 \ x = 0.475 electricity is passed through electrolytic
2+ cell containing aqueos solution of CuSO4,
[ Fe (aq) ] = 0.1 + x = 0.1 + 0.475 = 0.575 M
AgNO3 and NiSO4.
2+
[ Cd (aq) ] = 0.5 – x = 0.475 = 0.25 M Cu2+ Ag+ Ni2+
At equilibrium, reduction potential of anode Valency : +2 +1 +2
2+ –
(LHS) ie potential of Fe (aq. 0.575 M) +2e Fe(s) 1 1
mole ratio : : 1 :
2 2
o 0.059 1
EFe2+|Fe = E Fe2+ |Fe – log 2+ = – 0.44 \ 1 : 2 : 1
2 [Fe(aq) ]
W1 Q1 W1
–
0.059
log
1
= – 0.447 V 97. W µQ\ W Q \  6 × 40
W2 4 × 2 × 60
2 0.575 2 2

At equilibrium reduction potential of half cell


m
at RHS (cathode side) is – 0.447 V. \ W1 = gram
2
88. At STP, 84 L Cl2(g) is obtained on passing
10 F electricita in electrolysis of molten 4.5
103. Quantity of electricity passed = ×3
NaCl experimentally. 27

10 = 0.5 F
Theoretical mole of Cl2(g) =5
2 = mole of H2 produced by this electri cal
\ Vol. of Cl2(g) produced theoretically at STP.
0.5
= 5 × 22.4 = 112 L charge = = 0.25
2
Cell efficiency =
\ Vol. of H2 at STP = 0.25 × 22.4 = 5.6 L
exp. amount of product
theoretical amount of product × 100 104. Cd–Hg amalgam is obtained by electrolysis of
CdCl2 using 2gm Hg cathode.
84
= × 100 = 75 % At cathode Cd–Hg amalgam containing 20%
112
Cd produce.
90. D G0 = – nFE0 n =
%G o = –35126 = 2.0
FE o 96500 × 0.182 20 × 2
\ Mass of Cd produced at Cathode =
80
Therefore reaction will be :
= 0.5 gram
825
0.5 93.93× 100
\ mol of Cd = = 0.004444 = = 104.37 seconds
112.5 90
\ Quantity of electricity passed through the 134. R = 50 W , k = 1.3 S m–1 = 0.013 S cm–1
cell = 0.004444 × 2 = 0.00889 F l
cell constant = = kR = 0.013 × 50
A
96500 × F = 0.65 cm–1
\ Electric current (I) =
time
Now for 0.4 M solution, R = 260 W given
96500 × 0.00889 1 l 1
= \ k= × = × 0.65 = 0.0025 S cm–1
100 R A 260
= 8.58 amp
Lm = 1000×K
C
\ L m
=
1000×0.0025
0.4
105. 5A current for 2.15 hr is passed in unknown
salt solution of Pd. = 6.25 S cm2 mol–1
\ Lm = 6.25 × 10–4 S m2 mol–1
I× t 137. The quantity of electric current passing
Quantity fo electricity F =
96500 through wire having resistance 10 W , when
applied a potential of 20 V can be calcu-
5 × 2.15 × 3600
= lated as follows:
96500
potential 20
= 0.4 F Electric current = = =2A
Resistants 10
Let ox. no. of Pd be + X Now, Q = I × t = 2 × 2 × 60 = 240 C
151. Value of Lom for A2B, X3Y2 and A3Y are 2.4,
Faraday 0.466
\ mole of Pd =
Oxi. no. of Pd
=
X 1.5 and 1.8 mho. cm2.mole–1 respectively.
(1) A2B ® 2A+ + B2– × 3 = 3A2B ® 6A+ + 3B2–
0.4  10.64 (2) X3Y2 ® 3X2+ + 2Y3– × 1 = X3Y2
\ \ X=+4
X 106.4 2+
® 3X + 2Y3–
125. Thickness of Ag layer = 0.01 mm = 1.0 × 10–3 (3) A3Y ® 3A+ + Y3– × 2 = 2A3Y ® 6A+ 2Y3–
cm. Vol. of Ag consumed for electro plating =
\ 3 × (1) + (2) – 2× (3) = 3X2+ + 3B2– = 3XB
surface area of statue × thickness of layer
= 150 × 10–3 cm3. \ 3Lo(XB) = 3 L o m(A B) + L o m(Y Y ) –
2Lom(A
2 2 2

Mass of Ag consumed for electroplating of 3Y)


= 3(2.4) + 1.5 –2(1.8)
statue = density of Ag × vol. of Ag
= 5.1 \ Lo(XB)
= 10.5 × 150 × 10–3 = 1.7 moh (cm)2 mole–1
= 1.575 gram 152. LoKCI – LoNaCl= 23.4 mho (cm)2 mol–1 and
LoNaBr – LoNaCI = mho (cm)2 mol–1
Ag + e– ® Ag
o o
From given date K+
± Na +
= 23.4 mho (cm)2
According to stoichiometry of reaction quan-
tity of electric change used for plating 0.01475 mol–1 and
o
Br –
± o
Cl –
= 1.8 mho (cm)2 mol–1
mol Ag = 0.0146 F
\ Value of LoKBr will maximum and that of
I× t  96500
faraday× LoNaCI will minimum.
Faraday = \ t=
Now, LoKCI–LoNaBr = (
96500 I o
o o o
K+ Cl–
) –( Na +
± Br –
)
0.0146× 96500
= = 93.93 seconds –(
o
± o
)–(
o
± o
)
15 K+ Na + Br + Cl –

Experimentaly required time = 23.4 – 1.8 = 21.6 > 0

Theoretical time× 100


= efficiency of current \ LoKCI>LoNaBr= % \
o
KBr
>LoKCI>LoNaBr>LoNaCl
\ NaCl < NaBr < KCl < KBr
826
155. Resistance of a
N
salt solution placed between uE
10 Where uT
= Temperature constant of emf
p
two Pt electrodes having area 5.4 cm2 and 1.8
cm apart is 32 W ¥ E 2  E1 µ
\ –nFEcell = DH – TnF ¦§ T – T ¶·
2 1

L= 1000 × K
Normality ¥ E 2  E1 µ
Where DH = nFEcell + TnF ¦§ T – T ¶·
2 1
1 l 1 1.8
Where K= × = × \ D H = (–2 × 96500 × 0.6753) + 298 × 2 ×
R A 32 5.4
¥ 0.6753 – 0.6915 µ
1 96500 ¦ Joule
=
96
mho (cm)–1 § 298 – 273 ¶·

– 0.0162
\ L = 100096×10 = 104.17 S m2 gmeq–1 \ D H = – 1303329 + 57514000 × 25

\ DH = – 167601.972 joule
159. MmAg
0
= 5.0 × 10–3 S cm2 mol–1 ionic mobility
DH = – 167.6 Kg joule
+
\

of Ag+ can be calculated by following formula •


Equivalent conductivity 9. Chemical Kinetics
Ionic mobility =
96500
d[A] d[B] d[C] d[D]
170. The resistance of a 0.2 M electrolytic solution 14. –1 =– =+ 1 +1
is 50 W. The specific conductivity of solution 2 dt dt 2 dt 4 dt
is 1.4 S m–1. The resistance of the 0.5 M solu- = 1.6 × 10–3 ms–1
tion of same electrolyte is 280 W. d[C]
\ +1 = 8.0 × 10–4 ms–1
2 dt
Resistance of 0.5 M electrolyte R1 = 50 W
d[N 2O5 ] 1 d[NO 2 ] d[O 2 ]
and its specific conductivity K1 = 1.4 Sm–1 15. –1 = =
2 dt 4 dt dt
= 0.014 Scm–1 1
k k k11
Resistance of 0.5 M electrolyte = R2 = 280 W
and its specific conductivity K2 = ? \ – 1 k = 1 k1 = k11
2 4
K1 × R 1 k
K 1 × R 1 = K 2 × R 2 and K 2 = \ k1 = 2k, k11 =
R2 2
d[Br] d[H + ] d[Br2 ]
0.014 × 50 16. –1 =–1 =+1
= = 0.0025 S cm2 mol–1 5 dt 6 dt 3 dt
280
d[Br – ] 6 d[H + ] 3 d[Br2 ]
Lm of 0.5 M electrolyte = 1000C× K \ –
dt
=
5 dt
=
5 dt
6 3
1000 × 0.0025 \ 1.5 × 10–2 = × 1.5 × 10–2 × 1.5 × 10–2
= = 5.0 S cm–2 mol–1 5 5
0.5
d[H 2 ]
= 5.0 × 10–4 S m2 mol–1 17. = – 0.3 × 10–4 MS–1
dt
198. The cell reaction for a call : Cd | CdCl2(0.1 M) ||
d[H 2 ] 1 d[NH 3 ]
AgCl(s)|Ag is Cd(s) + 2AgCl(s) ® 2Ag(s) + Cd2+(aq) –1 
3 dt 2 dt
+ 2Cl–(aq) . The voltage of this cell at 273 K and
d[NH 3 ] d[H 2 ]
298K temperature is 0.6915 V and 0.6753 V. \ – 2  – 2 (– 0.3 × 10–4)
dt 3 dt 3
Here, n = 2, T1 = 273 K, E1 = 0.6915 V and T2
d[N 2O 4 ] d[NO 2 ]
= 239 K, E2 = 0.6753 V. 18.   1
dt 2 dt
Now DG = DH – TDS, DG = – nFEcell
(0.32 – 0.50) d[NO 2 ]
uE ¥ E 2  E1 µ \ – = 0.006 = 1
30 2 dt
and DS = nF uT
= nF ¦§ T  T ¶·
p 2 1
827
d[NO 2 ] will be 42 = 16 times.
\ = 0.012 atm min–1
dt 34. Volume of vessel is halved º Conc. doubles
d[A] d[B] As reaction is of third order, rate of reaction
19. – – 1 will be 23 = 8 times.
dt 2 dt

d[B] d[A] 35. For reactant A, rate µ [A]1


\ – 2s – = 2 × 2.6 × 10–2 m sec–1
dt dt 1
–2
= 5.2 × 10 m sec –1 For reactant B, rate µ B 1
< >

K 2 ¨ A2 ¸
n
2K 1 ¨ 8A1 ¸
n
\ rate = 1 – 1 = 0
25. = \ =
K1 ©ª A1 ¹º K 1 ©ª A1 ¹º 1
36. rate = K [Y] <Z> 2 =r 1

1 r2 = 1.414 r1
\ (2) = (8)n .\ n = \
3
1
26. rate µ [B]2 \ doubling concentration of B will rate = K [Y] <2Z> 2 = r2
make rate 4 times. 1
r2 = 2 K [Y] <Z> 2
27. V1 = K [A]2 [B] = x V2 = [2A]2 [2B] = K [A]2
[B] × 8 = 8x 37. r = K [A]n .. 8r = K [4 A]n \ 8 = 4n \ N = 1.5
28. r = K [A]n 2r = K [16 A]n = K.[A]n (16)n 38. For zero order reaction, t = 1
{[A]0 – [A]} But
K

2r = K [A ] (16 )
n n
1 [A]0 = a and on completion of reaction [A] = 0.
2 = 16n \ n =
K [A ]
n \
r 4
\ t = aK
29. increase in conc. is 10 times.
<R >o
\ increase in rate 102 64. For zero order reaction, t 1 =
2 2K
\ n=2
2 <R >o 2
¨ B¸ 1
30. r = [A] [B]2, r1 = K [2A] = K [A] [B]2 \ K = 2 × t 1 = 2 × 1 = 1 m hr–1
©ª 2 ¹º 2 2

1 [ R ]o - [ R ]t
r1 = r
= 0.5 - 0.25 = 0.25 hr–1
\
2 t=
K 1
31. [A] is made four times and [B] is constant so
rate becomes four times. a0 a0
67. t 3 = 2.303 log =
2.303
log
\ w.r.t A, rate µ [A] K K
a0 – a0 3 a0
4
4 4
[B] is made double and [A] is constant so rate
becomes four times.
2.303
\ w.r.t B, rate µ [B]2 = log 4
K
rate = K [A] [B]2
}}m A2 }}m A4 }}m A8
\

32. On doubling [A], rate becomes four times. 68. A0 t1


0
t1
0
t1
0
2 2 2

\ rate µ [A]2
Rate does not change on doubling [B]. \ T = 3 × t 12 = 3 × 14 = 42 s

\ rate µ [B]0 69. 100% }}m 50% }}m 25%


t1
2
t1
2

\ rate = k [A]2 [B] = K [A]2


\ T = 2 × t 12 \
t 1 = T = 60
1 2 2 2
33. Conc. will be 4 times when volume is made
4
As reaction is of second order, rate of reaction 70. M
10
}}m 20M }}m 40M }}m 80M }}m 160
t1
2 Mt1
2
t1
2
t1
2

828
Approximate T = 3 × t 12 to 4 × t 12 N 0 2.303
log N  2 × 60 log
2.303 1  2.303
76. K=
t
\ T = » 450 to 600 second
t
1 – 3 120
4
\ Approximate 500 second log 4 = 0.01155 min –1

71. Amount left after ‘n’ half lives = a t 1 = 0.693  0.693 = 60 min
2n 2 K 0.01155
T = n t 12
77. K = 0.693  0.693 min–1
t1 120
2
T 60
\ n= = =4
t1 15 2.303 a
2 t= log
t a–a%
1 1 2.303 × 120 100
\ Amount left = t= log log
24 16 0.693 100 – 90

72. n=
T  96
=4  2.303 × 120 10 = 120 × 2.3036 = 398.8 min
t 1 24 0.693 0.693
2

<R >0 2.303


log R  40 log
2.303
Amount left = an = 104 = 0.63 78. K=
\ t < >t
2 2
0.1  2.303
2.303 a log 4 = 0.03466 min–1
73. K= log 0.025 40
t a–a %
100 rate = K [R] = 0.03466 × 0.01
= 3.466 × 10–4 M min–1
2.303 a
\ K= log 79. Original conc. = 100% = [R]0 25% consumed
1.386 × 60 × 60 a – 0.75 a
\ Left 75% = [R]t
2.303 a
\ K= log
1.386 × 60 × 60 0.25 a t 1 = 2.303 log 100  2.303 log 1.333
4 K 75 K
2.303
= log 4 = 2.8 × 10–4 s–1 0.29
1.386 × 60 × 60 =
K
74. K = 0.693  0.693  0.1 87. (3.2 × 10–3) × 2 = 6.4 × 10–3 Because rate
t1 6.93 doubles on increase of 10 K temperature
2

88. Rate doubles (2 1 ) on increase of 10 K


2.303 a 2.303 temperature.
t= log = log
K a–a% 0.1
100 – 10 = 90 K increase in temperature
a 2.303 \ Rate constant 29 = 512 times
a – a (0.99) = 0.1 log 100 = 46.06 min
K2 Ea s %T
log K  2.303 R s T s T
75. 1 }}m }}m
t1
2
1
2 t1
2
1 t1
4 min T = n 2
89.
1 1 2

0.0693
T 20 \ log = log 3 = 0.4771
\
t1 = = = 10 min 0.0231
2 n 2
0.4771 × 2.303 × 8.3 × 300 × 320
Ea =
}}m }}m }}m }}m
\
1 1 1 1 20
1 t1 t1 t1 t1
2 2 2 4 2 8 2 16 = 43.84
\ T = 4 × 10 = 40 min 92. Co-efficient of temperature m = 2 D T = 50

%T  K 2 50

K 2 K2
\ m
10 K1 \
m10 K \ 25 = K = 32
1 1

829
Ea 101. D H = Ea – Ear + 5 = + 15 – Ear \ Ear = + 10
93. log K = log A –
2.303 RT 102. D H = Ea – Ear –30 = + 70 – Ear \ Ear = + 100
K 2.303RT 110. From slow step, rate K = [A] [B2]
\ log A  – 2.303RT
= – 1.0
From reaction (1) Keq = [A]2 / [A2]
K 1 1
\ = Antilog – 1.0 = 0.1 \ [A] = K e q 2 <A 2 > 2 rate
A
1 1
Ea – %T
1
K2 K = [B2] K e q 2 <A 2 >
2
= K1 [B2] <A 2 > 2
94. log K  2.303 R T T
1 1 2
\ n = 1.5
2.303 × 1.987 × 303 × 333 6.735 111. For slow step, r = K1 [O3] [O] From eq. (1)
\ Ea = log
33 0.325 Keq = [O2] [O] / [O3]
\ Ea = 20260 cal \ [O] = Keq [O3] / [O2]
K2 Ea %T r = K1 = [O3] Keq [O3][O2]
log K  2.303 R T T
\
95. \
1 1 2 = K [O3]2 [O2]–1
9000 × 5 2
= = 0.1104 <NO>
2.303 × 2 × 295 × 300 112. N2(g) + O2(g) 2NO(g) K1 =
< N 2 ><O 2 >
K2
log K = 0.1104 2
1
< NO 2 >
2NO(g) + O2(g) 2NO2(g) K2 = 2
< NO> <O 2 >
K2
\
K1 = 1.289 \ K2 = K1 × 1.289
1
NO2(g) N + O2(g)
96. K1 = Al e –E1/RT
, K2 = A2e –E2/RT 2 2(g)

1
K1 A1 (E –Ei)

2
<N 2 > <O 2 >
K 2 A1 e
2
/RT = A.e(2E1–E1)/Rt K=
< NO 2 >
E1/RT
=A e
1 s 1
\ K1 = K2.A.eE1/RT \
K1 K 2
K1 E1 ¨ %T ¸
97. log K  2.303 R © T T ¹ But 1 1 1 1
ª º <N 2 >
2
<O 2 >
2
<NO><O 2 >
2
<N 2 >
2
<O 2 >
s 
1 1 2
=
<NO> < NO 2 > < NO 2 >
K12 E 2 ¨ %T ¸
log K  2.303 R © T T ¹ But E1 > E2
2 ª 1 2º b
m

113. r' = K an bm r'' = K (2a)n 2

K11 K12 K11 K12


log K ¸ log K > 1 OR K > K
r ′′ = K
1 2 1 2 n n m –m
/ =2 a b a
r′ K / n m = 2n – 2m = 2(n–m)
98. K1 = K2 \ 1016 e – 2000/T = 1015 e – 1000/T a b

\ 10.e–2000/T = e–1000/T 114. For zero order reactions

2000 1000 <A >0 2


\ In 10 –
T

T K = 2 – t 1  2 s 1 = 1 M litre–1 hr–1
2

2000 1000
\ 2.303 log 10 – =–
T T <A>0 – <A>t 0.50 – 0.25
t=  = 0.25 hr
K 1
1000
\ T=
2.303
830
P0
115. K=
2.303
t
log P 10. Surface Chemistry
t

500 7. Size of adsorbate molecule is effective because


2.303
\ 3.38 × 10–5 = log P by decreasing the size of adsorbate molecule,
600 t
effective surface area increases.
500 500
\ log P = 0.0088 \ P = 1.021 10. Physical and chemical adsorption both done at
t t
high pressure.
\ Pt = 490 atm
11. Value of entropy decreases for exothermic
Total time reaction.
116. t1 = No. of half lives.
2 12. Van-der-waal’s attraction is more in gases like
9.6 CO2 because those atoms contain high mass and
\ = 4 half lives.
2.4 size.
10.8 21. According to Langmuir adsorption isotherm to
Initial mol of N2O5 = = 0.1 mol.
108 form a unilayer of adsorbate molecules require
0.1 }}m 0.12 }}m 0.14 }}m 0.18 }}m 0.1
t1
1
2
t1
2
2

16
t1
3
2
t1
4
2
per gram weight of adsorbent molecules is

x ap
0.1 related with pressure, so = 1 + bp .
= 0.00625 mol Amount of N2O5 left. m
16
Moles of N2O5 consumed = 0.1 – 0.00625 = 43. P(N2) = 0.001 atm, V = 2.46 cm3 T = 298 K;
0.09375 mol R = 82.0 atm cm3 K–1.
0.09375
\ moles of O2 produced = = 0.04875 PV 0.001 × 2.46
2 Moles of N2 (n) = 
RT 82.0 × 298
\ Vol. of O2 at STP = 22.4 × 0.04875
= 1.05 L = 1.006 × 10–7
117. A(g) ® 2B(g) + C(g) Number of adsorbed N2 molecules
Initial Po 0 0
= 1.006 × 10–7 × 6.022 × 1023
At Eq. Po–P 2P P
Total pressure at a time = 6.022 × 1016
Po–P + 2P + P = P0 + 2P = Pt Total sides = sides in per cm2 × area
Pt – P0 = 6.023 × 1014 × 1000
Pt – Po = 2P \ P=
2
= 6.023 × 1017
2.303 P0
K= log P – P Side of surface on which N2 gas adsorbed
t 0

17
=
2.303
log
P0 = 6.023 × 10 × 20 = 12.046 × 1016
t ¥ Pt – P0 µ 100
P0 – ¦
§ 2 ¶·
12.046 × 1016
Side adsorbed by N2 gas = =2
2.303 2P0 6.023 × 1016
= log 2P – P + P
t 0 t 0
W × 1000
2P0 44. Molarity (M) = M W × V (ml)
2.303
= log 3P – P
t 0 t

• M × M W × V (ml)
initial (W) =
1000
831
Ea 101. DH = Ea – Ear + 5 = + 15 – Ear \ Ear = + 10
93. log K = log A –
2.303 RT 102. DH = Ea – Ear –30 = + 70 – Ear \ Ear = + 100

\ K 2.303RT
log A  – 2.303RT
= – 1.0
110. From slow step, rate K = [A] [B2]
From reaction (1) Keq = [A]2 / [A2]

\ KA = Antilog – 1.0 = 0.1 \ [A] =


1
K e q 2 <A 2 > 2 rate
1

1 1
Ea – %T
1
K2 K = [B2] K e q 2 <A 2 >
2
= K1 [B2] <A 2 > 2
94. log K  2.303 R T T
1 1 2
\ n = 1.5
\ Ea =
2.303 × 1.987 × 303 × 333
33
log
6.735
0.325
111. For slow step, r = K1 [O3] [O] From eq. (1)
Keq = [O2] [O] / [O3]
\ Ea = 20260 cal \ [O] = Keq [O3] / [O2]
95. \ log KK 2
 Ea %T \ r = K1 = [O3] Keq [O3][O2]
1 2.303 R T1T2 = K [O3]2 [O2]–1
9000 × 5 2
= = 0.1104 <NO>
2.303 × 2 × 295 × 300 112. N2(g) + O2(g) 2NO(g) K1 =
< N 2 ><O 2 >
K2
log K = 0.1104 2
1
< NO 2 >
2NO(g) + O2(g) 2NO2(g) K2 = 2
< NO> <O 2 >
\ K2
K1 = 1.289 \K 2
= K1 × 1.289
1
NO2(g) N + O2(g)
96. K1 = Al e –E1/RT
, K2 = A2e –E2/RT 2 2(g)

1
K1 A1 (E –Ei)

2
<N 2 > <O 2 >
K 2 A1 e
2
/RT = A.e(2E1–E1)/Rt K=
< NO 2 >
E1/RT
=A e
\ K1 = K2.A.eE1/RT \ 1 s 1
K1 K 2
K1 E1 ¨ %T ¸
97. log K  2.303 R © T T ¹ But 1 1 1 1
ª º <N 2 >
2
<O 2 >
2
<NO><O 2 >
2
<N 2 >
2
<O 2 >
s 
1 1 2
=
<NO> < NO 2 > < NO 2 >
K12 E 2 ¨ %T ¸
log K  2.303 R © T T ¹ But E1 > E2
2 ª 1 2º b
m

113. r' = K an bm r'' = K (2a)n 2

K11 K1 K1 K1
log K ¸ log K 2 > 1 OR K1 > K 2
r ′′ = K
1 2 1 2 n n m –m
/ =2 a b a
r′ K / n m = 2n – 2m = 2(n–m)
98. K1 = K2 \ 1016 e – 2000/T = 1015 e – 1000/T a b

\ 10.e–2000/T = e–1000/T 114. For zero order reactions

<A >0
\ In 10 – 2000
T

1000
T
2
K = 2 – t 1  2 s 1 = 1 M litre–1 hr–1
2

2000 1000
\ 2.303 log 10 –
T

T <A>0 – <A>t 0.50 – 0.25
t=  = 0.25 hr
K 1
1000
\ T = 2.303
832
P0
115. K=
2.303
t
log P 10. Surface Chemistry
t

500 7. Size of adsorbate molecule is effective because


2.303
\ 3.38 × 10–5 = log P by decreasing the size of adsorbate molecule,
600 t
effective surface area increases.
500 500
\ log P = 0.0088 \ P = 1.021 10. Physical and chemical adsorption both done at
t t
high pressure.
\ Pt = 490 atm
11. Value of entropy decreases for exothermic
Total time reaction.
116. t1 = No. of half lives.
2 12. Van-der-waal’s attraction is more in gases like
9.6 CO2 because those atoms contain high mass and
\ = 4 half lives.
2.4 size.
10.8 21. According to Langmuir adsorption isotherm to
Initial mol of N2O5 = = 0.1 mol.
108 form a unilayer of adsorbate molecules require
0.1 }}m 0.12 }}m 0.14 }}m 0.18 }}m 0.1
t1
1
2
t1
2
2

16
t1
3
2
t1
4
2
per gram weight of adsorbent molecules is

x ap
0.1 related with pressure, so = 1 + bp .
= 0.00625 mol Amount of N2O5 left. m
16
Moles of N2O5 consumed = 0.1 – 0.00625 = 43. P(N2) = 0.001 atm, V = 2.46 cm3 T = 298 K;
0.09375 mol R = 82.0 atm cm3 K–1.
0.09375
\ moles of O2 produced = = 0.04875 PV 0.001 × 2.46
2 Moles of N2 (n) = 
RT 82.0 × 298
\ Vol. of O2 at STP = 22.4 × 0.04875
= 1.05 L = 1.006 × 10–7
117. A(g) ® 2B(g) + C(g) Number of adsorbed N2 molecules
Initial Po 0 0
= 1.006 × 10–7 × 6.022 × 1023
At Eq. Po–P 2P P
Total pressure at a time = 6.022 × 1016
Po–P + 2P + P = P0 + 2P = Pt Total sides = sides in per cm2 × area
Pt – P0 = 6.023 × 1014 × 1000
Pt – Po = 2P \ P=
2
= 6.023 × 1017
2.303 P0
K= log P – P Side of surface on which N2 gas adsorbed
t 0

17
=
2.303
log
P0 = 6.023 × 10 × 20 = 12.046 × 1016
t ¥ Pt – P0 µ 100
P0 – ¦
§ 2 ¶·
12.046 × 1016
Side adsorbed by N2 gas = =2
2.303 2P0 6.023 × 1016
= log 2P – P + P
t 0 t 0
W × 1000
2P0 44. Molarity (M) = M W × V (ml)
2.303
= log 3P – P
t 0 t

• M × M W × V (ml)
initial (W) =
1000
833
Surface area of every silver molecule = = 3.567
pr2 = p × (0.407 10–29 m3)2/3 gm/lit = N × E
= 3.567 × 17
10 12
= = 60.7
(0.407 s 1029 )2 / 3
38. H2O2 KMnO4
108 N1V1 = N2V2
= = 1.6 × 107
×2 N1 × 30 = 0.1 × 30
= y 10x N1 = 0.1, M = 0.05
\ x=7 gm/lit = N × E
203. Emulsion = Coldcream, Butter, Cod liver oil, = 1.7
Hair cream, milk, vanishing cream. Total = 6 Volume = 11.2 × M
• = 11.2 × 0.05
= 0.56
13. Hydrogen
W
39. M =
W M1 × V
33. Volume = 1 × 11.2
M ×V
284
=
40 34 × 10
= × 11.2
34 = 0.835
= 13.17 litre N = 2M
= 1.67
W
34. Volume = × 11.2 % /W/V = 3.4 × M
M1 × V
= 2.839
=
440
× 11.2 gm lit–1 = 28.39
34 × 6
Volume = 11.2 × M
= 24.156 litre = 9.352
35. Volume = M × 11.2 40. 400 × 1.25 + 350 × 2.1 + 250 × 2.65
= 2.823 × 11.2 = 1000 × %W/V
= 31.62 % W/V = 1.897
% /W/W = 2.823 × 3.4 gm litre–1 = 18.97
= 9.6 Volume = % W/V × 3.94
= 6.25
W
36. M= Volume = 11.2 × M
M1 × V
M = 0.558
W N=2M
3.72 =
34 × 8
= 1.116
W = 1011.8 gram
41. H2O2 KMnO4
% W/V = M × 3.4
1.5 × 30 = strength (Volume) × 10
= 12.648
Volume = 4.5
37. Volume = 11.2 × M
Volume = 11.2 × M
20 = 11.2 × M
M = 0.4
M = 1.785
N = 2M
N = 2M
M = 0.8
= 2 (1.785)
•
834
14. s-block elements Cl
91. Cl Be Be Cl Every Be attach with
5. Chilliesaltpeter NaNO3 Nitrate salt
Cl
time
7. Number of Half life (n) = Half life period
three Cl.
63 Down the group in (II) solubility of hydroxide
= =3 94.
21
increases.
Initial amount  500
leftout amount 97. BaO2 + O3 ® BaO + 2O2
2n 23
= 62.5 gram 102. MgSO4 + Na2HPO4 + NH4OH
12. As atomic size increases, strength of metallic
bond decreases and melting point decreases. ® Mg (MP4) PO4 + Na2SO4 + H2O

13. Due to small size of Li+ its hydration enthalpy 118. Hydration enthalpy of Be2+ and Mg2+ is more
is maximum and so Li is strong reducing agent. than lattice enthalpy. So, they are soluble in
22. % m Na O
2Na + O2 (Enough) }} water.
2 2
29. Lithium bicarbonate is not in solid state. 122. Mg3N2 + 6H2O ® 3Mg(OH)2 + 2NH3
30. As ionic size increases, nature of co-valent bond
strong. \ 1 mole 2 mole

32. Solution of sodium metal in liquid ammonial 2 mole 4 mole


is paramagnetic.
125. 2 Mg + O2® 2 MgO
35. Li2CO3 is not thermally stable due to its small
size. Its decomposes into Li2O and CO2. 2 × 24 2 × 16 2 (24 + 16) gram

45. % m 2Li O + 4NO + O


4LiNO3 }} Here 48 gram Mg combined with 32 gm O2
2 2 2
gives, 80 gm MgO. So, 30 gm Mg combine
46. % m 2Li N
6Li + N2 }} 3 with 20 gm O2 gives 50 gm MgO. At the end of
Li3N + 3H2O ® 3LiOH + NH3
reaction 10 gm O2 is left.
CuSO4 + 4NH3 ® [Cu(CH3)4] SO4
134. Na2CO3.10H2O(s)
Dark blue colour
48. All carbonates react with acid produce CO2 gas Na 2CO3 • H 2O(s)
but among these only Li2CO3 is thermally 
373K → + 9H2O(g)
unsatble produce CO2 gas.
286 gm 124 gm
% m Li O + CO
Li2CO3 }} 2 2
52. Except lithium other alkali metal nitrate heated % SiO 2 23
146. n = % Al O % Fe O  2 3 = 4.6
decompose in their respective nitrite. 2 3 2 3

54. 2 NaNO3 }}}m


800oC 2 NaNO2 + O2
152. Mg3N2 + 6H2O ® 3Mg(OH)2 + 2NH3
77. Electron of Be and Mg are strongly bonded that
1 mole 2 mole
they do not excited in flame test.
80. 2Sr(NO 3) 2 }}m 2SrO + O
%
2
+ 4NO 2 ®
2 mole 4 mole
Brown coloured gas Sr gives Crimson red in 154. CaC2 –C ≡ C– Ca2–1 1 s and 2p bond
flame test.
•
835
15. p-block elements 19. Purification of and
9. As we go down the group basicity of oxides Chracterisation of
increases.
10. Aluminium hydorxide reacts with acid and base
Organic Compounds
both. 49. (A)
13. %m
Ca2B6O11 + 2Na2CO3 }} 38.71 9.67 51.62
C= H= O=
2 CaCO3(S) + Na2B4O7 + 2NaBO2 12 1 16
17. Borazine (B3N 3H 6) is known as inorganic 3.2258 9.67 3.226
C= H= O=
benzene. 3.2258 3.2258 3.2258
21. % m H BO + 3HCl
BCl3 + 3H2O }} C1 H2.99 O1
3 3
% m SnO + CO + CO \ E.F. : CH3O
31. SnC2O4 }} 2
Tin oxalate 35.5 × 0.285 × 100
56. (B) % Cl = = 80.11
52. As we go down the group basicity of hydride 143.5 × 0.088
gradually decreases. 32 × 0.36 × 100
60. (A) % S = = 19.01 %
53. More is the oxidation state of N, it is most 233 × 0.26
acidic. 62. (B)
73. Molecular mass of H3PO 4 = 98. In given P1 = 715 – 15 = 700 mm P2 = 760 mm
reaction one atom substituted. V2 = ?
\ Equivalent weight = 981 = 98 V1 = 40 ml
T1 = 300 K T2 = 273 K
97. Na S O + 2AgNO ® Ag S O + 2NaNO
2 2 3 3 2 2 3 3
P1V1 P2V2
Ag2S2O3 }}}m
H 2O Ag2S + H2SO4
T1

T2 \ V2 = 33.52 ml
Black ppt
98. 2
­
% m SO + S + H O
S2O32– + 2H+ }} 2
¯ %N=
28 × 33.52
224 × 0.2
= 20.95
Foul odour yellow ppt

}}}}m
H O 1.4 × 2 × 10
135. HCOOH + H2SO4 2 CO 63. (C) % N = = 56
0.5
105. Cl2 reacts with CaO in presence of moisture 66. (C) Molecular weight of acid
gives bleaching powder. ¨ 108 × 0.38 ¸
®
CaO + H2O + Cl2 CaOCl2.H2O = 2 © 0.27
–107¹  90
ª º
142. 6 NaOH + 3I2 }} % m NaIO + 5NaI + 3H O
62 × 0.20 × 100
®
3 2
69. (C) % P = = 11.17
143. 2Na2S2O3 + I2 Na2S4O8 + 2NaI 222 × 0.5
148. Cl2 is weak oxidising agent than F2. So, it can’t
2 ¨ 195 × 0.984 ¸
remove F2 from NaF. 71 (D) M.w. of base = 2 © 0.39
– 410¹  82
ª º
149. Bleaching powder possess all the properties.
72. (C) M. eq. of H2SO4 for absorption of
151. I2 is dark purple coloured solid substance.
NH3 = 0.2 × 100 = 20
176. XeF4 + 2SF4 ® Xe + 2SF 6 M.eq. of H2SO4 left after absorption of NH3
F = M.eq. of NaOH
O 2°-Carbocation (more stable)
Xe : = 0.5 × 20 = 10
177.
\ M. eq. of H 2 SO 4 consumed for NH 3
O
= 20 – 10 = 10
178. XeF2 > XeF4 > XeF6
200 Pm 195 Pm 189 Pm 1.4 × 10
• %N= = 46.66
0.3
836
38.07 2.38
o
w O = 2.38 =2
P –P= m 16 1.19
73. (B) Po w+W \ E.F. = (C3H2NO2)n
m M
1000 × Kb × W
Now, M.W. = %Tb × W0
3
–2 m
1.306 × 10 = 3 100
+ 1000 × 2.53 × 5.5
m 78 = = 168
1.84× 45
\ m = 176.83 M.W.  168
n= =2
E.F. of hydrocarbon = (C7H5) × n E.F.w. 84
NO2

M.w.  176.83
\ n=
E.F.w. 89
» 2 \ M.W. : C6H4N2O4 i.e.
NO2

\ M.F. : C14H10 80. (B)


C 68.87 H 4.9 O 26.23 C18 H2 N7
74. (C) 12 1 14
12 1 16

C 5.7391 H C1.6393 C 1.5 H 2 N 0.5


\
4.9
1.6393 1.6393 1.6393 0.5 0.5 0.5

\ C3.5 H3 O1 \ C3H4N

\ (C7H6O2) × n \ Emperical Formula : = (C3H4N)n


M.W.  108
Now, no of eq. of acid =
0.1 × 25 n= =2
1000 E.F.W. 54
\ M.F = C6H8N2
0.305
\ Eq. wt of acid = = 122
0.0025 •
Acid, being monobasic, M.W. = 122

Now, n=
M.w.  122
E.F.w 122
=1 20. Some Basic Principles of
\ M.W. = C7H6O2
Organic Chemistry
NO2 2. Dicyanoethene : N ≡ C – CH = CH – C ≡ N

75. (A) }}}m


HNO 3
H 2SO3 + Minor product
3. But – 1 – en – 3 – yne : CH2 = CH – C ≡ CH
5. CH3 – CH = CH – C ≡ N
Calculation of empirical formula of minor Hybridisation can be decided on the basis of
product : number of s – bonds.
¯ ¯ ¯ ¯
42.86 3.57
C = 3.57 =3 4s 3s 3s 2s
12 1.19
3 2
sP sP sP2 sP

}}}m CH
2.40 2.40
H = 2.40 =2 8. P2O5
C N
1 1.19 CH3 C NH2 % 3

O
16.67 1.19 sp2 sp
N = 1.19 =1
14 1.19
21. Four isomers ® (i) Propan –1– amine
(ii) propan–2–amine (iii) Ethylmethylamine
(iv) Trimethyl amine

837
22. Three isomers ® But–1–en, But–2–en, 60. In C6H5CHCH3, + I effect of CH3 group and
2–Methyl propen resonance effect of C 6H 5 group increases
23. Because first number is given to carbon of
stability.
–CHO group.
79. –COOH is main functional group. So, the
25. Ether does not show isomerism with ketone.
lowest number is given to this carbon.
26. Four isomeric alcohols and 3 isomeric ethers.
So, total 7 isomers. 80. –COOCH3 is main functional group and other
_ groups are substituent groups.
28. NH 2  C  NH 2 NH  C _ NH 2
|| |
NC _ CH 2 _ CH _ CH 2 _ COO CH 3
4 3 2 1
O urea OH
|
31. Geometrical isomerism in alkene OCH 3
CH3 CH3 CH3 H 81. Carbonitrile suffix is used.
C C and C C 82. pent –3–en–1–yne is correct.
H H H CH3 83. R is correct ® longest chain should contain
Cis trans C = C – group.
33. and CH3 – CH2 – C ≡ CH 85. R is correct ® in styrene CH = CH2
Cyclobutene But–1–yne two H atoms at one end are identical.
_ _
34. CH3–CH2–CH2–OH and CH 3 CH CH 3 87. R is correct ® Due to more number of alkyl
|
OH groups, positive charge is more distributed, so
stability increases.
n–propylalcohol isopropylalcohol
37. C5H10O formula containing compound is ke- 90. R is correct ® In a compound if C = C (double
bond) may present or may not be present but
tone. So, it will show all the given isomerism.
rotation around C–C bond is not possible, then
CH3 _ CH 2 _ CH _ CH _ CH3 _ CH3
6 5 4 3 2 1
41. geometrical isomerism is possible.
| | •
CH 3 C2H5
42. Double bond should be involved in main hy-
drocarbon chain. 21. Hydrocarbons
4 3 2
CH3 - CH - C - CH2 - CH3
| || CH 3
CH3 1CH2 |
_ _
6. Neopentane CH 3 C CH 3
45. –CHO is main functional group according to |
CH 3
priority and –OH group becomes substituent.

CH3 _ CH _ CH = C _ CHO
5 4 3 2 1
CH 3
| | |
OH CH3 7. CH 3 _ C __ CH _ CH 2 _ CH 3
| |
CH 3 CH 3
2 _1
CH3 _ CH = CH _ C _ CH
5 4 3
47.
sum of position is 1 + 3 = 4 which is less. 8. CH 3 _ CH __ CH _ CH 3
| |
CH 3 CH 3
CH 2 _CH 3
|
50. c ® CH 3 _ CH 2 _ C ______ CH 2 _ CH 3 CH 3
| | 1°
CH 3 _ CH 2 _ C _ CH 3
1° 2°
CH 3 _ CH 2

9. |
CH 3
line structure Structural formula
(3o carbon is not present)
838
10. It should be alkyene according to CnH2n–2 59. Both steps are exothermic in a reaction of
_ __ _ alkene with HBr in presence of peroxide. So,
13. Isopentane CH 3 CH CH 2 CH 3 the reaction occurs easily. While one of step is
|
CH 3 endothermic in a reaction of alkene with HCl
and HI.
14. CH3 CH CH2 CH2 CH3 2Methylpentane 60. C6H5 – CH2 – CH = CH2 + H+ ®
CH3 C6H5 – CH2 – +CH – CH3
Isopropyl group
2o-carbocation (less stable)
15. Molecular mass is 72. i.e. three isomers are
possible for C5H12 1, 2 hydride shift

24. 2C2H5Cl + 2Na }}}}


ether m C6H5 – CH – CH2 – CH3

CH3–CH2–CH2–CH3 + 2NaCl 2o-carbocation (more stable)

25. CH3COONa }}}}}}


NaOH + CaO m
sodalime%
C6H5 – CH – CH2 – CH3
|
Br

CH4 + Na2CO3 Br
27. 2CH3COONa + 2H2O }}}}}}
Electrolysis
m 68. CH3 _ CH = C = CH 2
4 3 2 1

CH3–CH3+2CO2 + 2NaOH + H2
33. CH3CH2COOH + 6HI }}}}
Red P
m CH3
|
_ _
CH 3
|
_
CH3CH2CH3 + 2H2O + 3I2 70. CH 3 C C y C – C CH3
| |
1
CH3 CH 3
2 3 4 5 6
38. CH 3 – CH – CH = CH – CH = CH 3
| 7
| 72. CH3 – C ≡ CH and CH2
CH 3 CH – CH 3
8
| 9
CH 2 – CH 3 HC CH

CH 3
75. Br CH2= CH2Br + 2KOH }}}}
ethanolm
%
| CH ≡ CH + 2KBr + 2H2O
®
3 4 25
39. CH 3 – CH 2 – C – CH – C y CH
1||
78. HC ≡ C– Na+ + CH3Br
CH 2
HC ≡ C – CH3 + NaBr
42. CH2 = C = CH2 80. CH ≡ CH + CH3CH2Mg Br ®
CH3 – CH3 + CH ≡ C – MgBr
¯ ¯ ¯

sp2 sp sp2
43. CH2 = CH – CH = CH2 87. CnH2n–6m = C14H28–18 = C14H10
¯ ¯ ¯ ¯

2 2 2
sp sp sp sp2 88. Pyridine
N
Br
45. Three cis isomers, trans CH2 C
Br 93. Phenanthrene 4n + 2 = 4(3) + 2 = 14
54. According to Markovnikov rule.
55. According to Markovnikov rule. p e–
56. anti-Markovnikov CH 3 – C = CH 2 + HBr
| 95. Biphenyl
CH 3
O–H
}}}}}m CH – CH
peroxide
|
 CH – Br 3 2

CH 3 97. Phenol

839
108. Because, in toluene –CH3 is o/p directing group
(e– donating group) . So it will activate benzene H –*N – CH3

ring.
6. N–methyl aniline
109. Because, in acetophenone –COCH 3 is m
directing group ( e attractive group). So, it will
decreases reactivity of benzene ring. 8. Four (n–Butylamine, isobutylamine, secondary
126. Huckle rule is not obeyed due to 4 p e– butyl amine, ter. butylamine)
127. According to Huckle rule, 2, 6, 10,..... p 11. In 3o–amine three different alkyl groups are
electron containing cyclic system is aromatic. attached to nitrogen. So, during racemization
In the given options A, B, C, D no. of p e– are it will lost optical activity.
8, 6, 4, 4 respectively. So, (B) is aromatic. 16. Only primary aromatic amine gives dye test.
128 Because in the given three compounds 6pe– are 17. 3o amine does not give reaction. A. B, D are 3°
present. amines.
132. R is correct ® Benzene is more stable than alk- 23. Boiling Point order for same number of carbon
ene. is : alkane < amine < alcohol.
133. R is correct ® Cis is polar and trans is 28. Primary aromatic amine is not obtained by this
non-polar. reaction because
134. R is correct ® Benzene is more stable and less
reactive due to resonance. Cyclic p molecular 30. NH2 + ClCO
orbital is also formed.
135. R is correct ® Due to symmetrical structure of NHCO
neopentane, molecules of this compound are
Benzenilide
arranged nearer.
136. A is correct ® On dehydration Butan –1–ol O

137.
give main product which is but-2-en.
R is correct ® Benzene gives substitution reac-
34
C
NH2 }}}}
LiAlH
m4

tion easily than addition reaction, because


NH2
electrophile ion obtained during substitution re-
action is attracted towards 6pe– electron cloud hexanamide hexan–1–amine
of benzene. 36 –OCH 3 group is e – donating group, so,
138. A is correct ® In presence of peroxide, Hoffman reaction occurs easily.
propene reacts only with HBr. While with HCl,
according to Markovnikov rule 2-
39 NaN3 }}}}m R–NH
(i) R-X
– Nax 2

chloropropane is obtained. This reaction occurs o


(ii) LiAlH4 1 Amine
through carbocation. – N2
139. R is correct explanation of A. 40 1° amine is obtained by reduction of aldoxime.
140. R is correct explanation of A. 46. High value of Kb (low value of pkb) contain-
• ing amine show more basic nature pkb = 14 –
pka \pkb = 11.12. \less basic.
24. Organic Compounds 47. C 6 H 5 NH 2 is weak base than NH 3 and in
Containing Nitrogen aqueous solution basicity of amines is : 2o > 3o > 1o
48. In non aqueous solution with increase in + I
2. R – CH2 – NO2 }}}}m
HONO
– H2O R – C - NO2 effect basic strength increases 3o > 2o > 1o
49. Basic strength decrease due to steric hinderence
N·OH
basic strength decreases from (I) to (IV)
Nitrocompound Nitolic acid
IV < III < II < I.

840
53. CH3NH+Cl– is salt. It completely dissociate. So 110. R–NH2 + HNO2 ® R–OH + N2 + H2O
dissociation constant is high. aliphatic alcohol
amine
55. –NO2 group is e– attracting group.
70. nC4HqLi is strong base which gain proton from
114. CH 3 CH 2 CH 2
*
– CH – CH3
|
}}}}}m
HNO / H O
–N
2

2
2

– HCl
amine gives salt. NH3
[(CH3)2CH]2 NH + nC4H9Li ® [(CH3)2 CH]2 CH3CH2CH2 – CH – CH 3
|
NLi + n C4H10
OH
Lethiumdi isopropyl n–butane amine * Due to chiral carbon it is optically active.
73. CCl3 NO2 is known as “chloropcirin.” •

77. (CH3)4.N.OH }}
% m (CH ) N + CH OH
3 3 3 25. Polymers
81. 2CH3CH2NH2 + 2Na ® 2CH3CH2NHNa + H2 1. Resin : Phenolformaldehyde resin is known as
82. CH3CH2NH2 + CS2 + HgCl2 ® CH3CH2NCS bakelite, which is obtained on condensation.
+ HgS + 2HCl 22. CF2 = CF2 is monomer of teflon.
ethylisocyanate 28. Above reaction is an example of electrophilic
This reaction is known as “Hoffman mustard substitution reaction.
oil” reaction. 29. Use : In plastic pain and beaker.
O O 30. CF2 = CF2 (tetra floro ethene)
|| vv vv || v v 31. Terylene is an example of condensation reac-
94. R – C – CH – N y N }}}
–N2 m R – C – CH tion.
Carbene 32. Terylene is an example of condensation reac-
96. –OCH3 group is electron donating group. So, tion.
it gives Hoffman reaction easily. 33. • Polymer made from two different type of
103. Selective reduction reaction monomers is called co-polymer.
• Nylon-66 is obtained from hexamethelene
NO2 diamine (HMDA) and adipic acid.
36. Celofane is a natural polymer.

NO 2
+ 3 (NH4)2 S
41. (C2H5)3 Al + TiC14 ® Ziegler-Nata catalyst.
42. Nylon-66 is a polymer of adipic acid and
m–DNB hexamethylene diamine.
48. This bottle is made from polytheneterpthalate
NH2
(PET) plastic.
50. Nylon-66 i made from adipicacid and HMDA
+ 6 NH3 + 2H 2O + 3 S
53. Nylon-66
NO2
O
m–nitroaniline ||
105. Due to electron with drawing effect of –NO2 –[ NI + –(CH 2 )– Nl + CO –(CH 2 )–4 C ]–n

group, reactivity of –NH 2 group towards 55.


nucleophilic reaction decreases. So
CH 3
diazzotisation is difficult. CH 3 |
107. If electron donating group is present on O and
P position then diazzotisation occurs speediy
n – | – CH 2
CH 3 }}}}}}}
polymerisation
m – C – CH 2 –
|
CH 3
than aniline. While electron attracting group
is present then diazzotisation is difficult. Butyl rubber

841
57. Polyfeen is a double-bond containing 8a 8 × 0.1361
hydrocarbon. 2. Tc = 27bR 
27 × 3.85 × 10 –5 × 8.314
•
= 125.98 K
Sample Questionnaire (JEE) (1) 7. Solubility of Fe(OH)2 in 0.01 M NaOH is SM
then,
1. 312.5 gm metal carbonate in close container
2+ –
on decomposition gives 80% decomposition by Fe(OH)2(s) Fe(aq) + 2OH (aq)
mass. (S + 0.01) M
Mass of decomposed metal carbonate = 2+
Ksp = [ Fe(aq) ] [ OH (aq) ]2

312.5 × 80 S <<< 0.01 M


= 250 gm
100
\ 1.5 × 10–15 = S × (S + 0.01)2
Molar weight of carbonate 1.5 10–15 = S × (0.01)2

= 12 + 3(16) = 60 gm mole–1 \ S = 1.5 × 10–11 M


8. At 25o C temperature cell potential of given cell
Equivalent weight of carbonate = 30g
is 0.3245 V
\ In 60 gm carboante ion, wt. of carbon 2+ 2+
A | A (0.00001M) || B(0.0001M) | B
= 12 gm
2+ 2+
A(s) + B(aq) + B(s) (1) n = 2
\
A (aq)
In 30 gm carbonate ion, wt. of carbon
= 6 gm
2+
0.059 ¥ [Fe ] µ
Ecell = E o
– log ¦§
Cell 2 [Cu 2+ ]¶·
If equivalant weight of carbon = E gm
\ 30 gm carbonate combines with E gm metal \ 0.3245 = E 0
–
0.059 0.00001
log 0.0001
=
Cell 2
\ (E + 30) gm metal carbonate possess
weight of carbon = 6 gm E oCell – 0.0295 × log 10–1 = E oCell + 0.0295

\ 250 gm metal carbonate possess weight of \ E oCell = 0.3245 – 0.0295 = 0.295 V


6 × 250 At 25° C temperature,
carbon = gm ... (1)
E + 30 2+ +
for cell B | B(C1) || M (C2 ) | M equilibrium constant
\ At STP, volume of dry carbon dioxide – 12
liberated = 56 litre for reaction is 1.0 × 105 ( ) mole
litre
\ Moles of liberated dry carbon dioxide

liberated = mole =
56
= 2.5
\ 1
2 (s)
+
B + M (aq)
1 2+
B + M(s)
2 (aq)
224
Equilibrium constant for reaction is,
Moles of carbon in 2.5 mole of gas = 2.5 =
– 12
2.5(12) = 30 gm C (2) 1.0 × 1010 ( )
mole
litre
In result (1) and (2),
\ + 2+
B (s) + 2 M (aq) B(aq) + M (s) equilibrium
weight of carbon will be same = –1

6 × 250
constant for reaction is 1.0 × 1010 ( )
mole
litre
= 30 gm carbon E + 30 = 50
E + 30
2 s E oCell
\ equivalent weight of metal E = 20 gm
log(Kc) =
0.059
842
Metal oxide obtained by decomposition of
2 s E oCell
\ log (1.0 × 1010) = metal hydroxide possess equivalent weight
0.059
(E + 8) gm/equi.
0.059 s10 \ Mass of metal in (E + 8) gm metal oxide =
\ E oCell = 0.295 V E gm
\
2
Mass of metal in 1 gm metal oxide
At 25o C temperature, for cell,
E
= gm
A| A
2+
(XM) || M
+
(YM) |M E +8
Now, Mass of metal is equal in metal
cell reaction is, hydroxide which decomposes and metal oxide
+ 2+ which is obtained.
A(s) + M (aq) A (aq) + 2M(s) ... (3)
Now reaction (3) = reaction (1) + reaction (2)
\ E
20
=
E
E +8
\E + 8 = 20

\ standard cell potential for reaction (3) is, \ Equivalent weight of metal = 12 gm/equi.
2. Inverstion temperature of H2 and He is lower.
n3 E3o = n1 Eo3 + n2 Eo2 So, at room temperature such gases gets effect
of heating.
\ 2 × E3o = 2 × 0.295 + 2 × 0.295 4. What is minimum distance between two F–
centres in crystal lattice structure of CaF2?
\ E3o = 0.295 + 0.295 = 0.59 V
In calcium fluoride, Ca2+ posses Fec structure.
Equilibrium constant for reaction (3) is, and F– ions are situated in tetrahedral holes :

log(Kc) =
2 s E oCell
0.059
=
2 s 0.59
0.059
= 20 \ r+ + r– = 3a
4
–1
\ Minimum distance between centres of two
\ Kc = 10 20
( )mole
litre
+
a (r + r )
F– ions 2 

• 3
7. H2O(g) reacted by mass 40 %
Sample Questionnaire (JEE) (2) Moles which experienced reaction
1 × 40
1. Equivalent of N normality contained solution = = 0.4
100
=
V× N
, H2O(g) + CO(g) H2(g) + CO2(g)
1000 Initial mole : 1 1 0 0
Moles at
100 × 1 equilibrium : (1–0.4) 0.6 0.4 .04
1 3 1
100 ml N H2SO4 = 1000 = equivalent = 0.6
3 30
Equivalence of metal hydroxide which is Concentration
1 0.6
neutralised by acid = = 30% metal at equilibrium = = 0.06 M 0.06 M 0.0 M 0.04
30 10
hydroxide by mass. Equivalence of metal 0.04 × 0.04 4
hydroxide which decomposed 60 % by mass = Kc = = . As number of moles of
0.06 × 0.06 9
60 1 gaseous reactant and products are equal,
= .
40 × 30 20 4
Kc = Kp =
Suppose, equi. w. of metal = E gm/equivalent. 9
\ Equi. w. of metal hydroxide = 9. Ea1 = 41720 J/mol, T1 = 350 K, rate constant = K1
(E + 17) gm/equivalent. Ea2 = 35760 J/mol, T2 = ?, rate constant = K2
Mass of metal in l equivalent of metal Time required to complete 40 % of reaction is
hydroxide = E gm. equal,
\ K1 = K2
\ Mass of metal in
1
20
equivalent of metal \ According to Arrhenious equation,
E Ea1 Ea 2
hydroxide = gm 
20 T1 T2
843
7. Concentration of aqueous solution of
\ 41720  35760
350 T2 monobasic strong acid and monoacidic weak
\ T2 = 300 K
base is Co M.
\ Aqueous solution of salt obtained from
Sample Questionnaire (JEE) (3) monobasic strong acid and mono acidic weak
base posses,
N N
1. 50 ml NaOH ≡ 50 ml HCl ≡ 5 ml 1 N HCl K w [H 2O + ]2 Kw
10 10  and [H O +
] =
Kb C0 3 [OH – ]
\ To dissolve 1 gm alkaline earth metal
carbonate 25 – 5 = 20 ml 1 N HCl solution [K w ]2
is required. \ Kw

K b [OH – ]2 ×C0
20 ml 1 N HCl ≡ 1 gm metal carbonate
\ [OH–]2 =
Kb × Kw
\ 1000 ml 1 N HCl ≡
1000 × 1 × 1
20 × 1
= 50 gm
C0

1 gm equivalent of metal carbonate


\ Equivalent weight of Alkaline earth
\ [OH–]2 =
Kb × Kw
C0
metal carbonate = 50 gm 23. KA = Kc
\ Metal carbonate = 100 gm mole –1

\ 1015 e
– 2000
T
 1014 e
–1000
T
Weight of CO32– =12 + 3(16) = 60 gm mole–
1 –1000
–1000

\
T
10 = e – 2000  e T
Equivalent weight of CO32– 60 = 30 gm e T
2
\ Equivalent weight of alkaline earth
\ In(10) =
1000
= 50 – 30 = 20 gm T

Atomic weight of alkaline earth metal


\ 2.303 × log (10) =
1000
= 2 × 20 = 40 gm mole–1 T

3. For species having more than one electron


(atom or ion) if 2 < n + l < 4 then possible pairs
\ T = 2.303
1000
K

of n and 1 are as given below : •


n = 4, l = 0 ® 4s orbital ® no. of orbitals = 1 Sample Questionnaire (JEE) (4)
n = 3, l = 1 ® 3p orbital ® no. of orbitals
1. For hydrogen gas produced :
= 3 (3px, 3py, 3pz)
n = 3, l = 0 ® 3s orbital ® no. of orbitals = 1 T1 = 15 Co = 288 K To = 273 K

n = 2, l = 1 ® 2p orbital ® no. of orbitals


P1 = 740 mm Po = 760 mm
V1 =304 ml Vo = ? ml
= (2px, 2py , 2pz)
n = 2, l = 0 ® 2s orbital ® no. of orbitals = 1 Po × Vo P1 × V1
=
\ Total no. of orbitals = 9. Every orbital To T1
occupies two e– maximum.
Total no. of e–s having 2 < n + l < 4 \V = P T× V× P× T
o
1

1
1

o
o
=
740 × 304 × 273
288 × 760
= 9 × 2 = 18
= 2.88.53 ml
844
\ At STP, volume of hydrogen gas
produced = 288.53 ml \ 9.5 gm oxygen gives
9.5 × 40
16
= 23.75 gm
\ At STP, 22400 ml dihydrogen gas = 1 NaOH
mole H2 gas \ 25 gm NaOH sample actually contains
\ At STP, 288.53 ml dihydrogen gas 23.75 gm NaOH

=
288.53 s 1
22400
= 0.012526 mole H2 gas \ Purity of sample =
100 × 23.75
25
= 95 %

2HCl(aq) + Zn(s) ® H2(g) + ZnCl(aq) 2. Vmp : Vav = 1.414 : 1.595


mole : 2
(?)
1 1
0.012526
1
\ Vav =
Vmp × 1.595
1.414
= 2.7
cm
sec
\ moles of HCl in 50 ml aquous solution of 3. Fourth excited state = Fifth orbit (fifth energy
HCl (n) = 2 × 0.012526 = 0.02505 mole level)
Molarity of HCl in aquous solution, (Third excited state)
1000 × W  1000 × n  1000 × 0.02505
=
M×V V 50
= 0.501 M
Molecular weight of HCl and equivalent weight
of HCl are equal
\ Normality of HCl; in aqueous solution = \ Total lines = 6
0.501 N 4. Crystal structure of diamond is fcc and every
2. Compressibility factor (z) at critical temperature carbon is attached to four other carbon by
for real gas is = covalent bond.

 a 
  (3b)
» 0.375
PC × VC  27b2 
= =3
RTC
R (
8a
27bR
8
) P
Q
3. For, n = 4, l = 3, m = 0 only one orbital is
available and that is 4 d2z. For every orbital only
one wave function (ψ) is accepted.
5. W = 4 litrebar (work done on the system),
R
P = 1 bar, Vf = 10 litre, V1 = ?
W = – P (Vf – Vi)
\ 4 = –1 × (10 – Vi) In unit cell of diamond :
\ Vi = 14 litre length of body diagonal of diamond unit cell
20. Suppose, Initial concentration of A is C then = PR = 3 a
half reaction time of both reaction are equal.
C–C bond length = PR = 3 v a 2r
\ C
2K
=
1n (2)
K
4

\ C = 2ln(2) M \ a=
8r
• 3

\ 3 v a = 8r
Sample Questionnaire (JEE) (5) In unit cell of diamond on body diagonal three
carbon atoms are present. Out of which two
1. Molecular weight of NaOH = 40 gm mole–1 carbons are on corners of unit cell while one is
\ 16 gm oxygen is in 40 gm NaOH in tetrahedral void. Radius of two carbon
845
present on corner = (r + r) and diameter of carbon
1 ¥ [R]0 µ
present in tetrahedral void is 2r. K= × In ¦§ [R] ¶
\ Total 4r length is occupied by carbon atoms
t t ·

From 8r length of body diagonal 4r length


\ 50 % length is occupied by carbon atoms. \ 1
20
× In3 =
1
40
¥ 75
× ln ¦§ 75 × P
40
µ

·
6. (Assume 100% dissociotion of the given ionic
salts in solution) \ ¥ 75
ln 9 = ln ¦§ 75 × P
40
µ

·
(i) 0.08 M Na3PO4 0.32 M
(ii) 0.1 M FeCl3 0.4 i.C M \ 75
9 = 75 × P
40

(iii) 0.12 M CaCl2 0.36 M \ 676 – 9 × P40 = 75

(iv) 0.07 M K4[Fe(CN)6] 0.35 M


\ 9 × P40 = 600

pair of solution i–C difference \ P40 =


600
9
(i) and (ii)
(i) and (iii)
|0.32 – 0.40 | = 0.08 M
|0.32 – 0.36 | = 0.04 M
\ total gaseous pressure after 40 minutes
3 × 600
(i) and (iv) |0.32 – 0.35 | = 0.03 M = 3P40 = 200 mm
9
(ii) and (iii) |0.40 – 0.36 | = 0.04 M •
(ii) and (iv) |0.40 – 0.35 | = 0.05 M
(iii) andu (iv) |0.36 – 0.35 | = 0.01 M Sample Questionnaire (JEE) (6)
For solution (i) and (ii) pair, difference of iC is
maximum. So , it possess maximum 1. If 0.33 gram carbon dioxide gas is obtain on
osmotic pressure. complete combustion of 0.11 gm hydrocarbon
gas, then what would be the empirical formula
A(s) 2B(g) + C(g)
of that hydrocarbon gas ?
initial pressure / mole : a, 0, 0 M.W. of CO2 = 44 gm.mole–1 atomic wt of C =
mole/pres. after 20 minutes : a – x, 2P20 µ 2x, 12 gm mole–1
P20 µ x total pressure = 3P 20
= 150 mm 12 gm carbon is in 44 gm CO2 .
mole/pres. after long time : 0, 2P∞ µ 2a, P µ a

\ 0.33 gm CO2 contain weight of carbon
total pressure = 3P∞ = 225 mm 0.33 × 12
= = 0.09 gm
mole/pres. after 40 minutes : a – y, 2P40 µ 2y, 44
0.11 gm hydrocarbon gas contain 0.09 gm
µy
\

P40 total pressure = 3P40 carbon and remaining weight 0.02 gm of


\ P20 = 50 mm and P∞ = 75 a µP ∞
and
hydrogen.

(a – x) µ (P ∞
– P20) % of carbon (by weight) =
100 × 0.09
= 81.82
\ µP
0.11
P20 = 50 mm and P∞ = 75 a ∞
and
µ (P
100 × 0.02
(a – x) – P20) and % of hydrogen (by weight) =
∞ 0.11
= 18.18 %
[R]0 a Pd 75
after 20 minutes [R]  a – x  (P s P )  25 \ Empirial formula of hydro carbon gas = C H
t d d 3 8

d PA dA MB
1 ¥ [R]0 µ 1 2. Pµ \ = d × M
=3K= × In ¦ [R] ¶ K= × In3 M PB B A
t § t · 20
\ K = 0.05 × In3
2
=
1
×
2
1
=
4
1
=4:1
after 40 minutes
3. The radius of first orbit of Bohr’s model is ‘x’
[R]0 Pd \ a = x
 a   75
[R]t a – y (Pd  P40 ) (75 – P40 ) Now
o
radius of any orbit (nth orbit) of Bohr’s model
= a o × n2
\ radius of second orbit (n = 2) of Bohr’s
846
model is = ao × 22 = x × 4 = 4x for given reaction K, n and ([R]0)–1 are constant
Relation between the de-Broglie wave length
([R]0 ) n - 1 - ([R]t )n - 1
(l) of the electron rotating in any orbit (nth \ the group of ® t is
n- 1
orbit) of that atom and radius (r) : 2pr = nl l ([R]t )
2 pr
= [R]0 - [R]t
n straight line. \ for n = 2 graph of [R]t
\ It the de-Broglie wave length of the
electron rotating in second orbit (n= 2) of that ® t (time) is traight line.

atom 30. If a metal crystalizers in fcc pattern, then what


would be the minimum distance between two
l = 2× ×4x = 4pr centers of tetrahedral voids formed in it ? radius
2
of metal atom is r.
14. Suppose in Fe0.9S1.0 number of mole of Fe atoms
having oxidation no. + 3 and + 2 are
A B
respectively m and n.
\ m + n = 0.9 (i) and m(+ 3) + n(+ 2) C D
\ + 1 (– 2) = 0 3m + 2n = 2 (ii)

By solving equation (i) and (ii) we get ,


m = 0.2 and n = 0.7
\ the ratio of Fe atom having oxidation no.
+ 3 and + 2 are respectively in Fe0.9S1.0 is
7
0.2 6
= = 0.2857 » O.286
0.7
for fcc 4r = 2a \ a = 2 2r
21. If ratio of reaction R ® P is n than rate law : minimum distance between two centers of
d[R] tetrahedral voids =
– = K[R]n
dt AB a
CD = = = 2 2r = 2r
d[R] 2 2 2
\ = – K dt •
[R]n

d[R] JEE MAIN PAPER-1 (2013)


\ ∫ [R]
= – Kòdt
n

1
Answers
\
n - 1 = – Kt + C 1. : 1, Group 2 16 18
(1 - n)[R]
Ca S Ar
(integration constant) Ba Se
Now t = 0 than [R] = [R]0 2. In 0.72 gm H2O, 0.08 gm hydrogen is present.
1
While, 0.84 gram carbon is present in
\ C= n- 1 3.08 gm CO2
(1 - n)[R]0
0.84 0.08
1 1 \ C:H= : = 0.07 : 0.08 = 7 : 8
\
n- 1
= – Kt + n- 1
12 1
(1 - n)[R] (1 - n)[R]0
\ Empirical formula : C7H8
1 1 K2 1 1 
n - 1 = – Kt
- E
 −  . Apply above
\ a
(1 - n)([R]t )
n- 1
(1 - n)([R]0 ) 3. log K =
1 2.303R  T1 T2 

n- 1 n- 1
equation.
([R]0 ) - ([R]t ) 4. :3
\ n- 1
([R]t ) NH3
5. : 2, CH3CH2COOH
n–1.t
= –K (1 – n) ([R]0)
CH3CH2COONH4
847
Br2/KOH
CH3CH2CONH2 CH3CH2NH2 ¥1 1µ
27. : 3, E = 2.178 × 10–18 ¦§  ¶
22 ·
D
:2
2
6. 1
O
¥1 1µ
\
hc
= 2.178 × 10–18 ¦§  ¶·
7. : 4, R – NH2 + Cl – C – C – CH3 ®
λ 1 4
O \ = 1.24 × 10–7 m
l

28. : 3, 6CO2 + 12NADPH + 18ATP


R – NH – C – CH3 ® C6H12O6 + 12NADP + 18ATP
Molecular mass of 42 is increase in the 29. :2
reaction of one – NH2 group. 30. :2
Here, increase in total molecular mass is 210. •
210
\ Number of NH2 group =
42
=5 JEE MAIN PAPER-2 (2014)
8. : 3, 4
9. : 1, B.O. = 0 for both species Answers
10. : 1, It contains facial and meridional isomer- 1. : 4 Mole particles are same in all solutions.
ism. 2. :4
11. :4 3. :4
12. :1 4. :1
13. :4 5. :3
14. :1 6. :1
15. :4 7. : 4, Eocell = Eooxi + Eored
16. :2 = – 1.51 – 1.18 = – 2.69 V
17. :3 o
E cell is negative, so reaction will not oc-
18. : 3, DU = 0 Therefore, q = – W q = + 208J curs.
W = – 208J 8. : 1, write van der wall equation at low pres-
19. : 4, (0.98 – x) × 2 + 3x = 2 sure.
\ x = 0.04
 a 
0.04  P + 2  V = RT
\ % of M =3+
× 100 = 4.08 %  V 
0.98

20. : 1, C* =
2RT \ PV +
a
V
= RT
M

– 8RT
\ PV = RT –
a
V
C =
\
pM PV a
=1–
RT RTV
3RT
C=
M
\ Z=1–
a
RTV
4 3
\ C* : C– : C = 1 : : LiAlH4
p 2 9. : 2, CH 3 COOH CH 3 CH 3 OH
= 1 : 1.128 : 1.225 PCl5
21. :1 CH3CH2Cl CH2 = CH2
KOH
22. :2 10. :2
23. : 4, Electron gain is a reverse reaction of
Number of O 2 molecules 1 28
ionisation. 11. : 1 Number of N molecules = × = 7 : 32
24. :2 2 4 32
25. : 4, Bond order for Li2– and Li2+ is same. But 12. : 4, one unpaired electron is present in NO gas
in Li2– number of electron in antibonding 13. :3
molecular orbital is more. 14. :3
26. : All statements are correct, so no one is 15. : 2, Cs+ and Cl– touches eachother on
incorrect. boadydiagonal in unit cell of CsCl.
848
:4
\ rCs+ + rCl– = 2r, for bcc structure r =
4
3
a
1. CH3

+ O3
\ rCs+ + rCl– = 2 ×
4
3
a=
2
3
a CH3
16. :4 H3C O O
17. :3
Zn
18. : 4, From DH = DU + Dn(g) RT equation,
+ H3O
Here DU = – 1364.47, Dn(g) = (–1) C H3
19. : 1, L1 - red colour, L3 - yellow colours
L2 - green colour, L4 - blue colour H3C O
H
• Strength of ligand a energy of adsorb light O
1
a
Wavelength
+ H2O2
\ Order of energy : Blue > Green > Yellow 2. :3
> Red 3. :4
20. : 1, Ma Va Na = MbVbNb 5. : 1,
1 1 NH2
× Va × 2 = × 20 × 1
10 10 NaNO2 + 2 HCl
\ Va = 10 mL 0-5 oC
\ Used H2SO4 = 60 – 10 = 50 mL
C H3
– NaCl
–2H2O
\ % of N =
1.4 × N(H 2SO 4 ) × V(H 2SO4 )
W + –
N·Cl
2

1.4 s 0.2 s 50 CuCN + KCN


= = 10
1.4
21. :3
22. :1 C H3
23 :2
CN
24 :2
K1 1 R
25 : 4, K = R + K Cl + N 2
2 2

K1R1 CH3
1.4 ´ 50
\ K2 = R =
280
= 0.25
2 5. : 3, 4r = 3a
2
K 0.25 25 s 10
\ Dm = 1000 2× M = 1000 s 0.5 = 1.732 s 4.29
5 s 102 \ r= 3a
4
=
4
= 1.857 » 1.86Å
= 5 × 10–4
26. : 4, Salicylic acid by Kolbe-Smith and then 6. :3
aspirin
7. : 1, En = – 13.6 × 12 eV
27. :1 n
28. : 4, e– structure : [Kr] 5s1
: 3, rate a [A] from practical results.
\
29. 1
:1 E2 = – 13.6 × = – 3.4eV
30. (2) 2
•
8. :1
JEE MAIN PAPER-3 9. :3
10. :4
Answers
849
11. :2 20. :1
CH3 COOH 21. :2
22. :3
KMnO4 SOCl2
23. : 3, Mole of CH3COOH adsorbs by 3 gram
50 s 0.06 50 s 0.042
charcoal = –
COCl CHO 1000 100

H2/P = 0.0009
\ 1 gram charcoal CH3COOH = 0.0003
\ Weight of CH3COOH = 0.0003 × 60 ×
12. :3 1000
13. :3 = 18 mg
14. :4 24. :4
15. :4
1
16. : 2, From 2C8H7SO3Na + Ca2+ ® 25. : 4, From DGo = – RT In Kc, Kc =
2.718
(C8H2SO3)2 Ca + 2Na+
1
2 s 63.5 2×
17. : 4, weight of Cu = = 63.5 gm [13][C] 2
2 and QC = = 2 = 4
[A ]2 1
:4  
18. 2
19. : 3, Molecular mass of AgBr
\ For QC > Kc, reaction occurs in reverse
= 108 + 80 = 188 g/mole
direction
141 mg AgBr = 0.141 gm AgBr
26. :2
• Weight of Br in 180 g AgBr = 80 g
27. :4
• Weight of Br in 0.141 gm AgBr = 0.06 gm
28. :2
100 s 0.06 29. :3
\ % of Br = = 24 %
0.25 30. :3

• • •

850