CHEMISTRY JEE SOLUTIONS

Part-1
Mole Concept
Atomic Structure
Periodic Properties
Chemical Bonding
Redox Reactions
Gaseous State
Thermodynamics
Chemical Equilibrium
Ionic Equilibrium
IUPAC Nomenclature
Isomerism
General Organic Chemistry
Hydrocarbons
Aromatic Compounds
Environmental Chemistry
Hydrogen and Its Compounds
s-Block Elements
p-Block (Part I)
  Mole Concept

Chapter 1 Mole Concept

INTEXT EXERCISE: 1
1. Chemical formula is a representation of the number N
7. a) No. of atoms = 14 # 58A = 0.24 N A
of atoms present in a molecule.
N
46 b) No. of atoms = 2 # 28A = 0.07 N A
2. Moles of Na = 23 = 2.
NA
1.4 1 c) No. of atoms = 108 = 0.009 N A
3. Moles of N 2 = 28 = 20
N
1 d) No. of atoms = 3 # 18A = 0.166 N A

\ No. of molecules of N 2 = 20 N A
8. M.W. = 12 # 60 + 122 amu
\ No. of atoms = 2 # b 20 N A l = 6.02 # 10 22
1
= 842 amu
54 = 842 × 1.67 × 10-24g
4. n Al = 27 = 2
9. Let masses be 2x, 5x
\ No. of Al atoms = 2NA
2x
\ No. of CO2 molecules = 44 # N A

\ No. of Mg atoms = 2NA
5x
\ n mg = 2 & m Mg = 48g No. of N2O molecules = 44 # N A
m H SO \ Ratio = 2 : 5
5. 0.25 = 98 2 4

10. m H O = VH O # t = 36g
m & H SO = 24.5g
2 4
2 2

36
VSTP (L) \ n H O = 18 = 2
2

6. n gas =
22.4 \ No. of H2O molecules = 2 NA
0.224 1 H2O molecule has (2+8) protons

\ n H = 22.4 = 0.01
2

\ No. of protons = 20 NA
INTEXT EXERCISE: 2
1. Empirical formula wt. = 30 \ x = 1 or 2 as MW = 100
n
M.W. 120 35.5 # x
` = Emp. wt. = 30 = 4 Also, MW # 100 = 71.

\ Mol. formula = (CH2O)4 = C4H8O1 \ x=2

\ At wt. of M = 100 - 71 = 29.
X Y
t gas1 MWgas1
2.
50 50
⇒ X2Y 6. t gas2 = MW
50 = 5 5 0 = 2 .5 gas2
10 20
to3 48
5 =2
2 .5
2 .5 = 1
2 .5
\ to 2 = 32 = 1.5
7. Vol. of gold + vol. of quartz = total volume
C H y x+y
x
\ d +d = d
92.3 7.7
3. ⇒ CH
1 2
9 2 .3 = 7 .7 7 .7 = 7 .7 8. n N + n NO + n N O = 1
2 2 2 4
12 1
7 .7 = 1 7.7 = 1 Suppose x + y + z = 1
7 .7 7.7
Total mass
` Mean M.W. = 1 & m tot = 55.4g
I O Now, N 2 O 4 " 2NO 2 z " 2z
4. 2 5 .4 = 0 .2
127
8 = 0 .5
16 ⇒ I2O5 Now total moles = x + (y + 2z) + O
2 5 Total mass remains constant
55.4 55.4
` x + y + 2z = 39.6 & 39.6 = 1 + z
5. V.D. = 50 ⇒ M.W. = 100
Let formula be MClx \ z = 0.4 ⇒ Ans = a
Chemistry
9. Let no. of ion atoms in one molecule of Haemoglobin 10.
be x. 12% H2O → 50g silica 7g water 43g others
56x Wet Clay Dried Clay
` 89600 # 100 = 0.25
\ x = 4. Mass of silica and other substances does not change
on drying.
(50 + 43)
` wt. of wet clay # 100 = 88

\ wt. of wet clay = 105.6 g
50

\ % of silica = 105.6 # 100 = 47.3%
INTEXT EXERCISE: 3
56000 7. n NaCl = n AgNO = 0.01
1. nCaO =
56 = 1000
3

m ` NaCl = 0.01 # 58.5 = 0.585g

n
` CaCO needed = 1000 3

\ mCaCO needed = 105 g = 102 kg 3
8. Ag + HNO3 AgNO3
AgCl
1.12 1
2. n Na w = n CO = 22.4 = 20
2 3 2
NaCl
1
n AgCl = n AgNO = n Ag in coin
m
3

` Na CO = 20 # 106 = 5.3g
n
` Ag in coin = 0.1
2 3

3. 2H 2 + O 2 " 2H 2 O(,)
(g) (g)
m
` Ag in coin = 10.8 g
nH O
2 = nO & n H O = 2nO = 0.2
2
2 2 2
%
` purity = 50%
m ` H O = 3.6g & VH O(,) = 3.6 mL
2 2
9. CaCO3
9
CaO + CO 2
4. 2SO 2 + O 2 " 2SO3
(g) (g) (g)
nCaO = n CaCO 3

VSO VSO Since 90% pure sample & mCaCO = 9 kg

` 2 = 2 & VSO = VSO = 5L
2 3
3 2
3

9000
5. nSO = nSO
3 2
n` CaO = nCaCO = 100 = 90 3

mSO 2
` 80 = 64 & mSO = 2.5g 3 m` CaO = 90 # 56g = 5.04 kg
3

6. AgNO3 + NaCl " AgCl . + NaNO3 10. 4Fe + 3O 2 " 2Fe 2 O3

n Fe n Fe O
4 = 2
2 3
1.7
n AgCl = n AgNO = 170 = 0.01 3

m 16
` AgCl = 1.435g N Fe O = 160 = 0.1 & n Fe = 0.2
2 3

m ` Fe = 11.2g
INTEXT EXERCISE: 4
1.
nA nB 4. Zn + Fe + 2S " ZnFeS 2
1 = 5 and 2 = 4 n Zn n Fe nS
n n 1 = 2, 1 = 3, 2 = 2.5
\ B is the LR ⇒ 3D = 2B ⇒ nD = 12
n \ Zn is the L.R.
Also, nC = 2B ⇒ nC = 4
n
` ZnFeS = 2 2
n nQ
2. 2P = 4 and 1 = 5 5. 3BaCl 2 + 2Na3 PO 4 " Ba3 (PO 4) 2 + 6NaCl
n
P ` is the LR & N R = 2P = 4 n BaCl 0.5
3 = 3 and 2 = 0.1
2 n Na PO 3 4

3. 2X + 3Y → X2Y3 \ Na3PO4 is L.R.

Let, wt. of X = wt. of y = a n Na PO
n ` Ba (PO ) = [ 2 = 0.1
3 4
3 4

a a
n
` X = 36 and n Y = 24 6. n H = 4 and N O = 0.5
2 2

n a n a nH NO

` 2X = 72 and 3Y = 72 2 = 2 and 1 = 0.5
2 2

\ Neither is in excess and by conserving mass we \ O2 is the LR & n H used = 1 2

have mass of X2Y3 produced = a + a = 2a n

` H left = 3 & m H left = 6g
2 2
  Mole Concept
7. P4 + 3O 2 " P4 O6 9. TiCl 4 + 2Mg " 2MgCl 2 + Ti

1
n P taken = 4 ; n O taken = 1
4 2

n TiCl taken = 1088; n Mg = 4
4

3 1 TiCl
` 4 is the LR
n ` O used = 4 & n O left = 4
2 2

1 n
` Ti that can form = 1. 88
n ` P O produced = 4
mass Ti that can form = 90.24 g
4 6
`
Now, P4 O6 + 2O 2 " P4 O10 32
% ` yield = 90.24 # 100 = 35.4%
ini tmoles = 1 1
4 4 10. 2C + O2 " 2CO
Now,O
` 2 is L.R.

initial 1 0.75 -
n
` P O used = 1/8

final 0.25 1
4 6

-
n
` P O left = 1/8
2CO + O2 " 2CO2
4 6

and n P O produced = 1/8

initial 1 0.25
4 10

-
m
` P O = 27.5g, m P O = 35.5g

final 0.5 0.5
4 6 4 10

-
8. 4Fe + 3O 2 " 2Fe 2 O3

nCO = 0.5

n Fe taken = 0.01
nCO = 0.5
2
0.56

nO taken = 22.4 = 0.025
2

n tot = 1
Fe
` is the L.R.
Vtot = 22.4 L
1
n
` FeO = 2 n Fe = 0.005
3

m
` Fe O = 0.005 # 160 = 0.8g
2 3

INTEXT EXERCISE: 5
1. mmol of H 2 SO 4 = 100 # 0.001 = 0.1 8. Al 2 (SO 4) 3 + BaCl 2 " 3BaSO 4 . + 2AlCl3
mmol
` of H = 0.2 +
mmol of Al2(SO4)3 taken = 4
no.
` of H ions = 0.2 # 10 # N A + -3

\ mmol. of Al3+ in solution = 8
= 1.2 # 10 20 Final volume = 40 mL.
2. n glucose = 0.5, V = 0.5 L 8
\ [Al3+] final = 40 = 0.2 M
0.5
M ` = 0.5 = 1 9. H 2 SO 4 + 2NaOH " Na 2 SO 4 + H 2 O
1000 X 1000 # 0.2
3. m = (1 - X) 18 = 0.8 # 18 = 13.8
first H2SO4 shall neutralize the NaOH and only
excess acid remains in solution
4. mass of solution = 1500 × 1.052 = 1578 g
mmol of NaOH = 5
\ mass of solvent = 1578 - 18 = 1560
Let, Vol. of H2SO4 add = V mL
(18/60) (0.1
5
V - 2 ) = 0.05 (V + 50)
\ molality = 1.56 = 0.192 `
5. 0.2 mole H2SO4 = 19.6 g
\ 0.05 V = 5 ⇒ V = 100 mL

\ 19.6 g solute in 1000g solvent 10. CuCl2 + H2S → CuS + 2 HCl

\ mass of solution = 1019.6 g
\ nCus = nCuCl 2

250 x 0.6 + 750 x 0.2

\ mCuS = 0.1 x (MW)CuS
6. Mmix = 1000 = 0.3 M
= 0.1 x 95.5

\ 0.3 × 1000 = 0.25 (1000 + V)
= 9.55 g

\ V = 200 mL
2.65/106
7. initial M = 0.25 = 0.1
initial V = 10 mL
Final V = 1000 mL
0.1 # 10
\ final M = 1000 = 10 -3 M
Chemistry
EXERCISE - 1
1. Traditionally it was H1 and then O16. But modern 10. 18 gm = NA molecules
atomic weight scale is based on C12. 18
1 molecule = N g
1 A
2. As, it is defined on carbon scale and 12 of mass 18
or 1 molecule = N cm3
of C-12 isotope gives absolute value of relative A
18
masses. So, molecules = 3 # 10 -23 cm3
6 # 10 23
3. 1 mole means 6.023 x 1023 molecules of CH4 1
11. No. of moles = 22400
1 mole molecule contains 1 mole C and 4 moles H 1
= Thus, no. of molecules = 22400 # N A
i.e. 1 g-atoms of C and 4 g-atoms of H. 1
= 22400 # 6 # 10 23
4. 1 NH3 molecule contains 1N atom 3H atoms = 2.7 × 1019
4.25 given mass
moles of NH3 = 17 = molecular mass 12. Weight of a molecule of a compound C60H122 is
1 Molecular W.t./ Avogardro’s No
= 4 moles 842
g = weight of one molecule
Since, 1 molecule contains 4 atoms Therefore 6 # 10 23

1 = 1.4 x 10-21 g
4 mole molecules contain 1 mole atoms
5. NA molecules of water weighs 18 g 13. 1 molecule contains = 6 O atoms,
18 0.3 mole molecules contains = 6 × 0.3 O atoms
1 molecule weigh = g = 1.8 moles O atoms
6.023 # 1023
Roughly = 3 # 10 -23 g or 3 # 10 -26 kg 14. If they are in equi molecular proportion means their
moles are same.
given mass 4.2 0.6
6. No. of moles = atomic mass = 14 = 2 Now, 1 mole of mixture will weigh
No. of moles = 0.3 moles 10 # 0.5 + 30 # 0.5
1 = 23 g
1 nitride ion (N3-) contains 8 valance electrons volume at STP
No. of moles =
0.3 mole N3- ions contain = 8 × 0.3 × NA 22.4 (g)
= 2.4 NA 2.24
= 22.4 = 0.1 moles
given mass So, mass = number of moles × M.W. of mixture
7. No. of moles = molecular mass
= 23 × 0.1 = 2.3 g
given no of moleculer
= Avogadro's No 15. By applying law, equal no of molecules have equal
Let given mass = X gm no of volume at constant pressure and temperature.
X 10 Thus, As, volume is 1 L in both the case. Thus, no of
250 = 6 # 10 molecules in P and q are some
X c 4.159 g
16. 22.4 L at STP weight as much as M.W.
7
8. Mass of II = N g 5.6 L at STP weigh 7.5 g
A
3d 1
Then, I = N g 4 M.W= 7.5 Thus, M.W. = 30
A
Then, III = 32 # 10 -10 g 17. 1 mole contains Na atoms i.e. 6.023 × 1023 C atoms
Then III = 53.5 # 10 -10 g 18. a) 22.4 × 103 mL CO2 gas ⇒ 22.4 L CO2
So, correct order is II < I < III < IV
1 mole CO2 molecules = 6.023 × 1023 molecules
9. 1 CH4 molecule contains 6 e- from C and 1 e- from 22 1
H = Total 10e- b) 22 g of CO2 gas = 44 = 2 mole.
1 i.e. 3.011 × 1023 molecules
No of moles of CH4 = 16 moles
1 10 c) 11.2 L of CO2 gas = 3.011 × 1023 molecules
16 moles CH 4 $ 16 # N A d) 0.1 mole CO2 = 0.1 NA = 6 × 1022 molecules
5
= # 6 # 10 = 3.75 # 10
23 23
  Mole Concept
19. Mass of Au recovered = 19.7 kg = 19700g 29. Vapour density = 50
Atomic mass of Au = 197 Now, Vapour density x 2 = MW.

19700
\ Moles of Au recovered = 197 = 100 moles MW = 100

\ No. of Au atoms recovered = 100 NA = 6.02×1025 Now, if total mass 100. Then chlorine = 71 g
These rest mass of metal = 100 - 71 = 29
20. (b) is wrong as Molar mass is mass of 1 mole
30. Given ; x = E by equating moles
molecules in grams. y
40 NA
21. Here, 1 element of definite mass is combining with
2x x y
two different masses of another element to form two Now, 80 = 40 = N
A
different compounds. This it follows law of multiple
proportion. Thus, it also contains y atoms
22. H2S contains 5.88% hydrogen, H2O contains 11.11% 31. If molecular wt is 200
Then, wt of Ca= 40 g b 20 # 100 l
hydrogen while SO2 contains 50% sulphur. These 200
figures illustrates law of reciprocal propotion as,
three elements are given wt of Br = 160 g

23. Irrespective of source the compound has fixed b80 # 200 l = 160g
100
propotion of atom by mass. he law of constant 40 160
propotion. Thus, atomic mass (Ca) = atomic mass (Br)

24. They must have equal volume 40 160

40 : 80 = 1 : 2. So, CaBr2
25. Under same conditions of temperature and pressure
they have someone of molecules M.W. of gas
32. Now, VD wrt (CH4) = M.W. of CH
But atoms may be different in all cases
4

M.W. of gas
H2 = 2 He = 1 O2 = 2 O3 = 3 4= 16 = 64
So, ratio 2:1:2:3 64
V.D = M.W. of H = 2 = 32
64
2
26. Avagadro’s constant, m = mass of 1 molecule, v =
33. 194 # b 100 l = n # 14
28.9
no of molecules
N
Now, N = no of moles n = 4
A
34. M.W = 170
N = NA x n
Given mass
No of moles =
27. 3g of hydrocarbon on combustion in 11.2 g of M.W
oxygen to produce 8.8 g of CO2 and 5.4 g of H2O.
100 10
= 170 = 17 milimoles
This data illustrates-
Now, 1 ferrous furmrate contains 1 Fe atom
Here, mass of reactant 3 + 11.2 = 14.2 g
10
mass of products = 8.8 + 5.4 = 14.2 g So, no of moles of Fe atom2 17 milimoles
mass of reactant = mass of product 10
Now, Mass of Fe = 17 # 56 = 17
560
Law of conservation no of mass
560
1 age composition = 17 # 100
28. The hydrated salt Na2SO4.10H2O undergoes x %
loss in weight on heating and becomes anhydrous.
140
= 17 = 8.19 % = 8%
The value of X will be-
(46 + 32 + 64 + 180) 100
Y 35. V.D. = 11.2
= 46 + 32 + 64 M.W = 11.2 × 2 = 22.4 g/mol
Volume of gas (STP)
Y
(322) × 100 = 142 Now, Given Mass
M.W. = moles = 22.4
Y
100 = 4 Y = 44 % 11.2 Volume
⇒ 22.4 = 22.4 ⇒ Volume = 11.2 L
So, loss in weight
X = 100 - 44 = 56 %
Chemistry
36. Let mass of (M.W.) compound is M
\ mass of Al needed = 2 × 27g
Now, as per given situation = 54g

8 42. From the given reaction
100 # M = 32 # n
M = 400 # n 2Al + 2NaOH + 2H2O → 2NaAlO2 + 3H2↑
Now, for least M.W., n should be = 1 3
moles of H2 evolved = 2 × moles of Al used.
M = 400 Given, mass of Al used = 27g
37. Mass of H in 0.0835 moles of compound = 1g 27
\ moles of Al used = 27 = 1
1

\ moles of H in 0.0835 moles of compound = 1 =1 \ moles of H2 evolved = 1.5
1
\ Vol. of H2 evolved at STP = 1.5 × 22.4 L

\ moles of H in 1 mole compound = 0.0835
= 11.97 . 12 = 33.6 L.

\ 1 molecule of given compound should contain 43. S + O 2 $ SO 2
12 atoms of H
1 mole of 5 reacts with 1 mole of O2

\ Molecular formula = C6H12O6.
Thus, 5 moles react with 5 moles of SO2
38. Molecular Formula can only be a whole number Given mass
multiple of the empirical formula. Now, 32 + 32 = 5
39.Let total given mass = 100 g Given mass = 64 × 5 = 320 g
Then, carbon = 49.3 44. Na2CO3 + H2O + CO2 → 2NaHCO3
Hydrogen = 6.84
\ moles of CO2 needed = moles of Na2CO3 used
Now, C H mass of Na2CO3 used = 21.2 kg = 21200g
49.3 6.84
12 1
21200
\ moles of Na2CO3 used = 106 = 200 moles
4.11 6.84
\ moles of CO2 needed = 200
Now, oxygen left
Now, CaCO3 CaO + CO2
3

= 100 - (49.3 + 6.84)= 43.86 %

\ Moles of CO2 produced = moles of CaCO3 used
43.86
16 = 0
\ moles of CaCO3 needed = 200
0 = 2.74
\ mass of CaCO3 = 200 × 100g
C H O = 20 kg
4.11 6.84 2.75
2.75 2.75 2.75 45. 3Mg(OH)2 + 2H3PO4 → Mg3(PO4) + 6H2O
1.5 2.5 1
2
moles of H3PO4 needed = 3 × moles of Mg(OH)2
3 5 2 mass of Mg(OH)2 taken = 100 g
C3 H5 O2 = emperical formula. 100
Empharical weight = 36 + 32 + 5 = 73 \ moles of Mg(OH)2 taken = 58
\ moles of H3PO4 needed = b 3 # 58 l
2 100
Now, weight (MW) = 73 × 2 = 146
143
y factor = 73 = 2 \ mass of H3PO4 needed = b 3 × 58 l × 98
2 100

(C3 H5 O2) × 2 = 112.64g

C6 H10 O4 2.76
46. Moles of Ag2CO3 taken = ]
0.33 1 M.W.gAg CO
40. 100 # 100 # 67200 2 3

2.76
56= #n = 276 = 0.01
672 # 0.33 From the given reaction,
n= 56
moles of Ag formed = 2 × moles of Ag2CO3
n = 4
3 = 0.02
41. 2Al + 2 O 2 $ Al 2 O3

\ mass of Ag formed (residue) = 0.02 × 108g
∵ moles of O2 taken = 1.5
= 2.16 g.

\ moles of Al needed = 2
  Mole Concept
47. 1 mole of C2H5O4 gives 2 mole of CO2. Thus ASG is limitng here,
2 Thus, option (a) is wrong
2 × 44 = 132 g × 3 = 88 g
48. Now, By using stoichiometry 54. (d)
n1 18/18
I 2 + Cl 2 $ 2ICl
2 = 3
I 2 + 3Cl 2 $ 2ICl3
2 2.54
n1 = 3
moles = 197 = 0.2
Given mass
Molecular mass = no of moles
14.2
35.5 = 0.4
2

= 3 # 56
Now, 0.1 mole of I 2 reacts with 0.1 mole Cl 2 to

= 37.3 g yield = 0.2 mole ICl and 0.1 mole I2 reacts with 0.3
mole Cl2 to gives 0.2 moles ICl3.
49. 2CH3OH + 3O2 → 2CO2 + 4H2O

Thus moles formed 0.2, 0.2
From the above reaction:-
55. KI + I 2 + 16HNO3 $
2 moles of CH3OH forms 4 moles of H2O
KIO3 + 2HIO3 + 16NO 2 + 7H 2 O

\ mass of H2O formed = 4 × 18g

I2 is the limiting reagent
= 72g.
From the above equation, 2 moles I2 will gives 32
7
50. 2 mole of CrO5 reacts with 2 mole of O2 moles NO2.

Thus, Volume at
7
1 mole of CrO5 reacts with 4 moles of O2
STP = 22.4 × 32
= 1.75 moles = 716.8 L
51. Zn + Fe + 2S $ Zn (FeS 2) 56. 2AgNO3 + Na 2 CrO 4 $ Ag 2 CrO 4 + 2NaNO3
moles taken 2 3 5
Now, here 2 moles AgNO3 forms 1 mole Ag2CrO4
` Zn is the limitng reagent. while reacting with 1 mole Na2CrO4.
n n Zn(FeS )
` 1Zn = 1
2

Thus, 0.6 moles forms 0.3 while reacting with 0.3
So, moles of Zn (FeS2) formed = 2 moles of Na2 CrO4
52. Let 509 kgm of M is required
Thus, Ans = 0.3 moles.
Now, By applying POAC from M to M3 × 8 57. Now, 2 moles reacts with 1 mole to given 2 mole
x H2O.
56 # 1 # N A = n # 3 # N A By Gay Lussac’s Law of combining volumes.

x 2 L H2 reacts with 1 L O2
56 = 3n ...(i)
\ 12 L H2 reacts with 6L O2
Now, \ Volume of O2 unreacted = 8 - 6 = 2 L
1 mole M3 X8 gives 8 mole NX
58. 1 mole H2 reacts with 1 mole Cl2 to give 2 mole HCl
Thus, n moles gives = 8 n moles
Similarly, 10 ml H2 + 10 ml Cl2 gives 20 ml HCl
206
8 x (3 × n)= 103 Thus, Volume of Cl2 Left = 12.5 - 10 = 2.5 mL
x
But, 3 × n = 56 from Eq. (i) above Ans = 20 ml HCl, 2.5 ml Cl2 in final mixture.
x 59. Now, CO 2 + C $ 2CO
n = 56 # 3
44 g 6 g
x 1
Now, 22 g CO2 reacts with 6 g to give 28 g CO
56 # 3 # 8 = 2
x = 42 g Now, 1 mole Ni reacts with 4 mole CO. Thus, 1
1
mole CO reacts with 4 mole Ni
53. 3 moles A reacts with
2 moles B to form 1 mole A3B2 1 Given mass
4 = molecular mass
1
Thus, here A is limiting 2 mole A3B2 reacts with 1 1
1 Given mass = 4 # M.M
mole C to form 2 mole A3B2C2
= 14.75 g
Chemistry
M1 V1 + M 2 V2 0.25 # 10 + 1 # 20 65. Let mass of solution = 100 gm
60. Using = =0.75 m
V1 + V2 30 Then mass of H2SO4 = 98 g
I) is true. moles of H2SO4 = 1
1 # 100 + 0.25 # 50 mass of solution 100
II) 150 = 0.75 M volume = density = 1.84 = 54.34 ml
Second is also true no of moles
100 25 Now, Molarity = volume (L)
40 # 100 + 100 # 20
III) 60
1
= 54.34 # 1000 = 18.4 M
45 3 66. Let volume = 100 ml
= 60 = 4 = 0.75 M
(III) is also correct Thus, weight of solute = 2.8
2.8 1
1 # 50 + 25 # 0.25 Moles of solute = 12.39 = 20
(IV) 75 = 0.75 M
(IV) is correct no of moles of solute
Now, molarity = volume of solutiion (L)
So, Ans I, II, III, IV
1/20 #
no of moles of isolute 100 1000 = 0.5 M
61. Now molarity = Volume of isolution
M V +M V 1 # 500 + 1 # 500
1/98 67. & 1 V1 + V 2 2 =
= 1 = 0.0102 M 1 2 500 + 500
= 1000 mM = 1 M
62. Now, here M1V1 × 5 = M2V2
0.01 × V × 5 = 0.01 × 50 68. Ba (OH) 2 $ Ba 2+ + 2OH -
V = 10 mL NaOH $ Na + + OH -
63.Let mass of solvent = 1 kg 2 # V # 0.4 + 0.3 # 50
V + 50 = 0.5
So, no. of moles = 3 0.8 V + 15 = 0.5 V + 25
given mass of NaOH 0.3 V = 10
= 40 × 3 = 120 g ` V = 33.33 mL
Mass of solution - 1120 g
Volume of solution 69. M1V1 = M2V2
1120 ⇒ 0.6 x V = 0.4 x 30
= 1.11 mL V = 20 ml ar
= 1009 mL 20 cm3
Now, molarity
70. H 2 SO 4 + BaCl 2 " BaSO 4 + 2HCl
3
= 1009 # 1000 = 2.97 M
1 mole H2SO4 + 1 mole BaCl2 $ 1 mole BaSO4
64. Moles of NaCl = 1
H2SO4 = n = M1V1
1000
Moles of water = 18 = 55.55

2.5 moles
= 1000
n
Mole fraction, XNaCl = n NaCl
+n
10
BaCl2 = n = 1000
NaCl H2 O
1 1

= 55.55 + 1 = 56.55 = 0.017
So, H2SO4 is a limiting reagent.

Thus, moles formed = 0.0025
EXERCISE - 2
1. Number of atom in 52 amu 0.5 mole molecule contains = 6 × 0.5 = 3 mole
1 atom = 4 amu atoms of carbon mass = 3 × 12 = 36 g
1 3. 180 gm of water
1 amu = 4 atoms
1
52 amu = 4 # 52 = 13 amu 1 molecule contains = 10 electrons
given mass
Now, no of moles = molecular mass
2. 0.5 moles of K 4 [Fe(N) 6]
180
1 molecule contains = 6 carbon atoms = 18 = 10 moles
1 mole molecule contains = 6 mole atom of carbon 10 mole molecules
= 10 × 10 = 100 mole electrons.
  Mole Concept
4. The total no of electrons or protons mg CO3 & 2
& # 75 + 3 # 32 = 246
molecular moss 24 + 12 + 48 = 84 g/mol Weight of 5 mole = 246 × 5 = 1230 = 1.23 Kg
GM
moles = MW = 0.1 mole 10. 9.2 g of NO2
1 mg 103 contains = 42 protons 9.2
means, no of moles = 46 = 0.2 mole
0.1 mole contains = 42 × 0.1 = 42 mg
No of moles of oxygen atom

& 4.2 moles
= 0.2 × 2 = 0.4 atom of oxygen
no of protons = 4.2 NA
No of moles of O atoms = 0.4 moles
= 4.2 x 6.02 × 1023 = 2.52 x 1024
0.4 moles O atoms has 0.4 No molecule
5. Atomic weight=a Mass of NO = 0.4 × 30 = 12 gms.
molecular weigth = 3a
11. 28 % N 72 % M
(Triatomic)
given mass Now, Le + the atomic weight = m
Now, no of moles = molecular mass 28 % N(14) 72% m(m)
Given mass = wg Now, Le + Total mass = 100 gm
w
& 3a = no of moles 28 72

14 = 2 m
6. mg3 (PO4)2

Now, Given they are in 2 : 3 ratio
8 atoms of O = 1 molecule
2 2 72
1
0.25 moles O atom = 8 # 0.25 72 = 3 m = 3, m = 24
m
= 3.125 × 10-2 moles
12. Nitrogen in organic compound = 0.014 %
7. (a) 16 g CH4
14 1
16 g = 1000 # 100
16 = 1 mole molecular
Now, 1 molecule contain = 2 nitrogen
= 4 mole atoms of H
4
(b) 31.2 g of C6H6 5 # x = 14 # 2 x = 2 × 105
10
31.2
78 = 0.4 mole molecules 13. 20X, 21X, 22X
= 0.4 × 6 = 2.4 moles atoms of H Average atomic mass = 20/11
(c) 34.2 g of Cl2H22O11 20 # 90 + 21 # x + 22/10 -
100 = 20.11
34.2
342 = 0.1 mole molecules 211 = 21 x + 22 O - 22 x
= 0.1 × 22 = 2.2 moles atom of H 14. 18O in meteorites is greater than 18O on earth
(d) 36 g of C6H12O6 Thus, Average atomic mass of oxygen in meteorites
must be greater than terrestrial oxygen atoms
36
180 = 0.2 moles molecules
15. Let total mass = 100 g
0.2 × 12 = 2.4 mole atoms of H mass of X = 20 g
mass of Y = 80 g
8. = 0.05 × NA = 3 × 1022 atoms
20 80
Now, This is very large. 10 : 20 2 : 4 1 : 2 (X Y2)
Thus, others are ignored 16. The percentage yield of arean’ n can be described as
amount of product orbital
Thus, Atoms (total) = 3x 1022 aproximately the Total maximum possible product × 100
9. A + W + of A = 75
& (d)
A + W + of B = 32 17. The sp heat is 0.16 Ca 11g

2A + 3B $ X By dulong - petit 2a

X = A2B3 6.4
= sp Heat = Atomic wt

Weight of 1 mole = molecules weight
6.4
= 0.16 = 40 g
Chemistry
18. Now, C 2 H 4 + 3O 2 $ 2CO 2 + 2H 2 O 130

C 4 H10 + 2 $ 4CO H 2 O
Now, 1 mole of C2H4 combines with 3 mole of O2 to
5000
form 2 moles each of CO2 and H2O
no of moles = 5 D = 86.2 moles
So, Ans. = (b) 13
Now, moles of O2 needed = 86.2 # 2
19. 2Z + 5O2 $ Z2 O5
= 560.34 moles

2 moles of Z 560.34 # 32
5 Mass of O2 needed = 1000 = 17.9 kg.

combines with 2 moles of O2 means
25. Now, under some condition, volume can be treated
5

1 Z $ 4 O2 as moles

b 0.346 l # 5 = 0.552 - 0.346

1
CO + 2 O 2 $ CO 2
m 4 32
1

m = 67.4 g/mol 1 mole CO + 2 mole O 2 $ 1 mole CO 2
20. Zn5 + 3O 2 $ 2ZnO + 2SO 2 2 mole CO + 1 mole O2 $ 1 mole CO 2
2 L CO2 is formed

2nO + C $ Zn + CO
3

10 tons = 10,000 Hg 26. 2Fe + 2 O 2 $ Fe 2 O3

2Zns $ 2ZnO $ 2Zn 3
2 moles Fe reacts with 2 moles O2
10000

Now, 32 + 65.5 2nS No of moles of Fe = 0.1

yeild some moles of Zn 1
No. of moles of O2= 4 = 0.25
10000

moles of Zn = 97.5 So, Fe is L.R. here
10000 Thus, moles of Fe2O3 formed

mass of Zn = 97.5 # 65

= 6718 Kg. But yield is 75% 0.1
= 2 = 0.05 moles
75

6718 # 100 = 5038 kg = 5 tons. 27. NO +
1
2 O 2 $ NO 2
20 ml 10 ml K
21. C7 H8 + 3HNO3 $ C7 H5 (NO 2) 3 + 3H 2 O
Now, 20 moles combines with 10 moles $

1 mole C7H8 needed 3HNO3
10 moles NO2 under STP
276 g x 20
92 = 3 moles
20 10
22.4 $ 22.4 $ 22.4 which of 22.4

requires = 9 moles HNO3
x = 20 ml

So, mass = 9 × 63 = 567 g. 28. C n H 2n + 2 + O 2 $ nCO 2 + H 2 O
1
22. Now, 2Fe3 O 4 + 2 O 2 $ 3Fe 2 O3 1 $ n moles
2 moles Fe3O4 gives 3 moles Fe2O3
0.2 $ 0.2 # n
26.4
3 Now, No of moles = 44 = 0.4
1 mole Fe3O4 gives 2 moles of Fe2O3
0.2 × n = 0.4
Now, 2 b 64 + 168 l = 160
3 x 0.498 n = 2

x = 0.4814 g 29. Na2CO3 + CaCl2 → CaCO3 + 2NaCl
0.4814 1
Now, % age yeild = 0.5 # 100 = 96.3 % = 100 = 0.01 moles
12.6 means 0.01 moles Na2CO3 = 0.01 × 106
23. 63 = 0.2 moles
= 1.06 gms
HNO3 + KOH $ KNO3 + H 2 O 92
Now, 1.06 = 100 # x

0.2 × 56 = 112 g
As only pure compound will react
24. C 4 H10 & Isobutane 92
100 # x = 1.06

C 4 H10 & n-butane x = 1.1529
  Mole Concept
30. MgCO3 $ MgO + CO 2 contains so MeCaCNO3
60g of 70 % pure MgCO3 i.e.,
2.35 # 5
106 4
20
60 # 100 = 42g 2.35 # 5 #
mass = 4 16
42 1 106
Now, 84 = 2 mole 481.75
= g
1 mole Mg CO3 gives1 mole CO2 106
1 481.75 # 3

1 1 in Mg = 10
2 mole 2 mole MgCO3 $ 2 mole CO 2 106
481.75

1 #
2 22.4 = 11.2 L at STP
=
103
31. NaCO3 $ CO 2
= 0.481.75 mg
NOHCO3 $ CO 2 34. First assume volume to be 1L
x 4-x
106 # 1 # N A + 84 Now, average Conc. 3.5 (3-4)
3.5
N
498
Y A = 22400 # 1 # XY Now, 23 = No of moles
X 4-X = 0.15 moles
106 + 84 = 0.02 0.15
84 X + 424 - 106 X = 178. Thus, Molarity = 1 = 0.15 M
245 a2 = 22 [ means wrong] 35. Ethanol + water = 0.1 mf of C2H5O4
But if
Weight of ethanol 0.1 x 46 = 4.6 g

2NaHCO3
9
NO 2 O3 + H 2 O + CO 2
Weight of water = 0.9 x 18 = 16.2 g
9

NO 2 CO 2 X weight of solution
W/W= Weight of solution # 100

b4-X l
84 4.6
20.8 # 100 = 22.11%
4 - X = 0.04
4 - X = 3.36 1
36. H 2 O 2 $ H 2 O + 2 O 2
X = 0.64 1.68
Now, 22.40 volume of O2 product = 0.075 moles
0.64
4 # 100 = 16% Volume of H2O2 formed = 0.075 x 0.15 moles
32. Let volume = 100 mL mass of H2O2 formed = 5.1g
5.1 1
Wt = 10 g of Glucose % age composition = 5.5 = 5 = 20
M.W. of Glucose = 180 g/mol 37. Urea solution
10 g contains 100 mL
A B

1g $ 10 mL
2 m 4m

180g $ 180 # 10 = 1800 mL = 1.8 L
1 kg 2 kg
33. 10 solution contains
6

No. of moles in A = 2 moles
Ca = 2.35
No. of moles in B = 4 x 2 = 8 moles
2.35
1 g solution contains =
106
Total moles = 10
2.35 # Mass = 3 kg
So, g solution contains = 50
106
moles of Ca =
10
Molality = 3 = 3.33m
2.35 # 5 38. HCl + NaOH

= 4
106
(CaCnO3)2 contains 0.1 m 0.1 m

1 Ca atom 50 ml 50 ml
2.35 5 0.1 HCl + 0.1 NaOH
6 # 4
10 0.1 # 50 + 0.1 # 50

Gives, 100 = 0.05M
Chemistry
39. Let it will be in ratio X = 1 moles of solvent = 0.8
10.9
Now, No of moles of HNO3 =- 63 = 0.3 Aq. solution Thus, 0.08 × 18 = Total mass
No. of moles of NaOH = 14.44 g
0.2

3.2
= 40 = 0.08 Now, Molality = 14.4 # 1000
Now, M1V1 = M2V2 13.88m
=
0.3 x X = 0.08 x 1 45. 100 ml H2SO4
X = 15
4
m H SO 2 4 = 100 # 0.9 = 90
X : 1 = 4 : 15 mass of 100 ml H2O = 100g
Weight of solute
40. 0.66 g of H3PO2 Now, % (w/W) = Weight of solution
0.66
66 = 0.01 90
= 190 # 100
Now, n factor = 1
= 47.36 %
Thus, 0.01 = 0.1 x n
x = 0.1 L 46. Z 2 O3 + 3H 2 $ 3H 2 O + 2Z
x = 0.1 x 1000 ml = 100 ml Now, 1 mole Z2O3requires = 3 mole H
0.2
41. Now, 1.5 x 1 = 1 x 2 x X M moles Z 2 O3
X = .75 b 0.2 l mole H 2
3
M
X = 75 %
b 0.2 l =
3
12
Slope of this curve M 1000 # 2

-1 M = 100
7.5%, -1 M = Z2O3 = 100
42. H 2 SO 4 + 2H 2 O —→ 2H3 O + SO + 2-
4 2 Z = 52, Z = 26
No of moles of H2SO4 = 0.1 × 0.1 = 10 milimoles 47. H2 g

1 H2SO4 molecule gives 2 H3O ions and 1 SO4
+ 2-
2% 6HCl $ 2YCl3 + 3H 2
ions
Now, 1 moles of Y reacts with 6 moles of
Thus 1 molecule gives 3 ions HCl $ 2YCl3 and 3H3
Total no. of ions = 30 milimoles = 0.18 × 1023 So, molar ratio
2
3
43. N1 + 2 O 2 $ N 2 O3 = 3 = 2: 3
7 gm of N2 means 48. Now, C2H5OH + H2O

7 1 10 ml 20 ml
28 = 4 moles

Mass of C2H5OH = 7.893 gm
But 80 % is convert

Mass of H2O = 19.942 gm
1 # 80 1
4 100 = 5 moles
Total mass = 27.835
3
Density of solution = 0.957
1 mole N 2 $ 2 O 2
27.835

1
= 0.9571
5 mole N 2 = 0.3 O 2
0.3 × 6 × 1023 molecules
Volume = 29.08 ml
Atoms = 0.6 × 6 × 1023 atoms
Expected volume = 30 ml
= 3.6 × 1023
Actual volume = 29.08 ml
30 - 29.08 # 100
44. Mole fraction = 0.2
percentage change = 30
Let total moles = 1
0.92
= 30 # 100 = 3.1 %
moles of solute = 0.2
  Mole Concept
49. Initial Solution = NaOH + Na2SO4
\ Moles of CuCl2 in 0.6g mixture = 1.106 × 10-3

H2SO4 only nutrilise NaOH \ mass of CuCl2 in 0.6 mixture = 0.15g

Thus, equivalents of H2SO4 and NaOH and same
0.15
\ % CuCl2 in mixture = 0.6 × 100

10 × 004 × d = 10 milimoles = 25% (Ans)
10 Putting the value of x in Eq(i) we get:

Now, 1000 # 40 = Given mass

= 0.4 g 143.5 × 2 × 1.106 × 10-3 + 188 × 2y = 0.9065
0.074 ⇒ 376y = 0.9065 - 0.3174
50. Here, N1 V1 = N 2 V2 = 2X 74 = ⇒ y = 1.56 × 10-3
4 = 2 \ Moles of CuBr2 in 0.6g mixture = 1.57 × 10-3
No of equivalent is are same \ mass of CuBr2 in 0.6g mixture
51. Mf C2H5OH = 0.25 = 1.57 × 10-3 × 188g
Let total moles = 1 = 0.2952g
moles C2H5O4 = 0.25 0.2952
\ % of CuBr2 in mixture = 0.6 × 100
Moles = H2O = 0.75 = 49.2%
0.25 × 46 = 1150 g 54. Let molar mass = X gm
C2H5O4
X $ XH 4
Total mass = 25 g
X $ X 2 H6
46 By POAC
% age mass = 100 = 46 %
5 X
52. 2H 2 O 2 $ 2H 2 O + O 2 m # 1 # NA = X + 4 # 1 # NA
1 mole of O2 gas 24 dm3 5 X 5.628 - X
X = X+4 = X+3
24 dm3 $ 1
But second
1
3dm3 $ 8 moles X
X+4 = d
Now, Volume of H2O2 = 100 cm3 5.628 - X
1 or X + 2H 2 $ XH 4
1/4 X+3
Now, Molarity 100 # 1000 = 2.5 M
2X + 3H 2 $ X 2 H6
53. 6g mixture was dissolved in 100mL and 10mL was Let one in n1 moles
taken second in n2 moles

⇒ mass of mixture in 10 mL solution = 0.6 g. Now, N1 moles of XH4 is formed
Suppose, in the 0.6g mixture:
N2
2 moles of X2H6 is formed
moles of CuCl2 = x and moles of CuBr2 = y n1 2
n2 # 2 = 1

\ moles of Cl- = 2x and moles of Br- = 2y
n1=n2

\ moles of AgCl ppt. = 2x and moles AgBr ppt.=2y
Now,

\ Adding masses of AgCl and AgBr:
(n1 + n2) x = 5
143.5 × 2x + 188 × 2y = 0.9065 (Eq(i))
2n1 x = 5

When the precipitate is shaken with NaBr, the AgCl Also,
is also converted to AgBr. n
n1 (X + 4) + 22 (2X + 6) = 56
Thus, total moles of AgBr formed = (2x + 2y) n1X + n2 X + 4n1 + 3n2 = 5

\ total mass of ppt. = (2x + 2y) × 188 7 n1 = 0.628

\ 188 × 2x + 188 × 2y = 1.005 (Eq(ii)) 0.628
n1 = 7
Eq(ii) - Eq(i) gives us
5#7
44.5 × 2x = 0.0985 Now, X = 2 # 0.628

⇒ x = 1.106 × 10-3 = 27.86
Chemistry
55. Now, mili equivalents of Barium Now, MW of on in
= M eq of solt H 2 SO 4 = 121.3
4.290 # 2 Now, As acid is monobasic
M = 2 # 21.64
So, M.W of Acid
# 0.477
M = 415.6 = 121.3 + 1
= 122.3
EXERCISE - 3
1. Moles of He taken = 3 7. M.W. of CaCl2.6H2O = 40 + 71 + 6 × 18 = 219
moles of N2 taken = 1 mass of water of crystallization = 108
108

3
⇒ mole fraction of He = 4 ⇒ % of water of crystallization = 219 × 100
1 = 49.31%
mole fraction of N2 = 4
Total moles removed = 2 8. Let volume of water needed V mL
3
\ Final volume = (V + 16) mL
⇒ moles of He removed = 2 × 4 = 1.5
Mi = 0.5 M Mf = 0.2 M
1
moles of N2 removed = 2 × 4 = 0.5

\ 0.5 × 16 = 0.2 × (V + 16)
\ Gases remaining are : 1.5 mole He and 0.5 mole

⇒ V + 16 = 40
N2

⇒ V = 24 mL

\ mass of He remaining = 1.5 × 4 = 6g
mass of N2 remaining = 0.5 × 28 = 14g 9. The compound must contain at least one oxygen
atom.

\ % by mass of He in remaining gases So, a minimum of 1 g atom of oxygen will be present
6
= 6 + 14 ×100 = 30% in 1 g molecule, i.e., 1 mol of the compound.
If M is the molecular weight of compound, then
2. Molarity = molality if density = 1g/mL since 16 is the atomic mass of oxygen, so minimum
At 4oC, density of water is 1 gm/mL ⇒ 277 K of 16 g of oxygen will be present in M gram of the
x
3. Let the moles of CO2 = x, then moles of SO2 = 2 compound.
16
moles of carbon in sample = x and moles of sulphur Thus, % of oxygen = M # 100
x 16 # 100
in a sample = 2 or 3.2 = or M = 500
M
x 12
12x + 2 # 32 = 12 & x = 28 = 3/7 10 ×1.18 × 49
10. M1 = 18

3 36
mass of carbon in sample = 7 # 12 = 7 = 5.14 M1V1 = M2V2
1.18 × 49 ×10
54 98 × 75 = M 2 × 590
4. moles of Al = 27 = 2 moles = moles of Mg
\ M2 = 0.75
mass of Mg = 2 × 24 = 48 g x # 5 + 20 # 2
11. x + 20 = 2.6
5. 3H3PO2 → PH3 + 2H3PO3
Solving, we get x = 5 mL

3 moles H3PO2 forms 1 mole PH3
12. Mass of 10 mole liquid - 2800g.

⇒ 6 moles H3PO2 forms 2 mole PH3

⇒ mass of PH3 formed = 2 × 34 = 68g density = 1.4 g/cc.
2800
240 \ volume = 1.4 = 2000 cc = 2L
6. Moles of C taken = 12 = 20
280 13. N has 7 electrons. So, each N3- ion has 10 electrons
moles of CO formed = 28 = 10

\ 0.5 mole N3- will have 0.5 x 10 mole electrons
⇒ moles of C used to form CO2 = 10
10 14. mass = 1.44 kg = 1440 g
\ % yield of CO2 = 20 × 100 = 50%

M.w. = 60 x 12
1440

\ No. of moles = 60 # 12 = 2
  Mole Concept
15. N2 + H2 $ N2 H2 3.78
(g) (g) (l)
21. Moles of SO2 taken = 64 = 0.06.

initial 5L 3L ` Applying POAC for S atoms.

final 2L - liquid nCaSO = nSO = 0.06
4 4

\ Contraction in volume = 8 - 2 = 6 L
` M CaSO = 0.06 + 136 = 8.16g
4

Note thas since N2 is in excess, therefore only first 22. Molarity = 3.2
reaction takes place. Density of solution = 0.4 g/mL
4
` 1 L of solution weight 400 g and contains 3.2
16. S 4 N 4 $ x S X + 2N 2 (g) (g)

moles of solute which weights 3.2 × 75g

Since volume of gaseous products = 4
` Mass of solvent = 400 - 3.2 × 75 = 160g
4
` x +2 = 4 3.2
` Molality = 0.16 = 20
4
or x = 2 & x = 2 23. Mass of algac initially = 1g
17. mNaCl needed = 0.3 g
` To double its mass, it must increase mass by 1g
0.3
` msolution # 100 = 5 & msolution = 6g

Now, this mass is due to formation of (C6 H10 O5) n
18. H x A + xNaOH $ Na x A + xH 2 O
6n CO 2 + 5n H 2 O $ (C6 H10 O5) n + 6n O 2
nH A n 1 0.1 1
` 1 = NaOH
x

x & n H A = 6 # x = 60x
1
` Moles of starch weighing 1g = (72 + 10 + 80) # n

x

2 1
` 600 = 60x & x = 5 1

= 162n
19. Number of electrons in 102- ion = 8 + 2 = 10
` N CO absorbed = 162
2
6
8
Number of O moles of ions in 9 g = 16
2-

` time needed =
6/162 6 # 103
-3 = # 4.7
4.7 # 10 162
8
` Number of electrons = 16 # 10 = 5
7.88 hours . 8 hours
20. From Dulong Petit Law we get 16
24. nSO = 32 + 16x = 22.4
x
5.6
6.4
Approx. Atomic Wt. = sp.heat (cal/g)
1 1
` 2+x = 4 & x = 2

6.4
= 0.057 = 114 25. Total mass of coal sample = 102.49g.

Let molecular formula be MClx
When it is dried, mass remaining = 100g.
7.14
Molecular
` weight = (114 + 35.5x) ` % ash = 100 # 100 = 7.14%
0.22

` moles of MCl x = 114 + 35.5x

Now, moles of

Cl - = x # moles of MCl x = moles of AgNO3
0.22x 0.51

` 114 + 35.5x = 170 & x = 3

EXERCISE - 4
1. If mass of N2 taken = 14 g then mass of H2 = 3 g 2x x

= 2 - 2x = 1 - x
14

` moles of N 2 = 28 = 0.5 and moles of
Given mole fraction of NH3 = 40 %
3 x
H 2 = 2 = 1.5
` 1 - x # 100 = 40

N 2 + 3H 2 $ 2NH3
100
` x = 40 - 40x.

initial 0.5 1.5 0
40 2

final 0.5-x 1.5-3x 2x
` x = 140 = 7
2x

Fraction of NH3 = (0.5 - x) + (1.5 - 3x) + 2x X
0.5 - 2/7 3
` N = 2 - 4/7 = 0 = 0.15
2
Chemistry
2. Since P, T and V are same for both the flasks 9. 2 # I3 + 3Cl 2 $ 2 # Cl3 + 3I 2
therefore the number of moles must also be equal. n xI = n xCl
3 3

0.8 1.4 ` If atomic weight of x = M, we get

n ` A = nB & M = M
A B
0.5 0.236
1.4 M + 3 # 127 = M + 3 # 35.5
M ` B = 0.8 M A & M B = 1.75M A
Solving, we get M = 140
3. Suppose moles of FeSO4=x and moles of Fe2(SO4)3=y
500
n
` Fe = x and n Fe = 2y
2+ 3+ 10. No. of molecules of acid needed =
0.21 # 10 -14
Sulphate from FeSO 4 = x moles and from = 2.38 # 1017
Fe 2 (SO 4) 3 = 3y from given information x = 3y. 2.4 # 1017
` moles of acid needed . = 4 # 10 -7
n x 3y 3 6 # 1023

2+

` n Fe = 2y = 2y = 2 4.24
Fe 3+
Now, Molarity of acid solution = 256
4. Let volumes of the two acids taken be V and xV
4.24
` 256 # V = 4 # 10 -7
0.36V + 0.15 # V V
0.24
` = V + xV ` = 2.41 # 10 -5 L
36 + 15x 11. X + 2H 2 $ XH 4
or, 24 = 14x
2X + 3H 2 $ X 2 H6
or, 24 + 24 = 36 + 15x
4 Let moles of XH 4 = a and X 2 H6 = b
` 9x = 12 & x = 3 ` Total moles of X taken = a + 2 b
5. No. of atoms of Fe = 3 and that of C = 6 per molecule. Equating mass of X : (a + 2b) M = 5 ... (i)
` m Fe = 3 # 56 and mC = 6 # 12 Equating mass of compounds
m 3 # 56 7 (M + 4) a + (2M + 6) b = 5.628 ... (ii)
` mFe = 6 # 12 = 3
C a 2
Also given b = 1 ... (iii)
3
6. KClO3 $ KCl + 2 O 2 Solving, we get M = 28.

2.24
N O = 22.4 = 0.1
2
12. X CH COOH = 0.15 and msolution = 30 g
3

2 1 Suppose moles of acetic acid in solution = X

n ` KClO = 3 # 0.1 = 15 .85 17
` moles of water = .15 X = 3 X
3

1
m ` KClO = 15 # 122.5 = 8.166g
3
17
` Mass of solution “ = X # 60 + 3 X # 18 = 162 X
8.166
% ` purity = 10 # 100 = 81.66%
30 5
` 162 X = 30 & X = 162 = 27
11.5
7. Moles of C6 h5 COOK to be produced = 160
5
11.5 Thus, n NaOH needed = 27

If yield was 100%, moles of toluene needed = 160
5
0.01V
` = 27 & V = 18.51 L .

` When yield = 71%, moles of toluene needed
100 11.5 13.

= 71 # 160 = 0.101
K S Al O

` mass of toluene needed = 0.101 # 92 15.1 24.8 10.5 49.6

= 9.3g 39 32 27 16
= 0.38 = 0.775x = 0.388 = 3.1
8. C1 H6 O3 + C 4 H6 O3 $ C9 H8 O 4 + C 2 H 4 O 2
$ 38 $ 775 $ 388 3.1
2 1

nC H O taken = 138 = 69
7 6 3 $ 38 $ 38 $ 38 $ 38
4 2 =1 =2 =1 =8

nC H O takne = 102 = 51
4 6 3

` Anhydrous salt = KAlSO2O8
C
` 7 H6 O3 is the limiting Reagent.
Now, H 2 O = 45.6 in hydrate a salt
1 8X
n
` aspirin theoretical = 69
` 18X + (39 + 27 + 64 + 128) # 100 = 45.6
1
Solving, we get X = 12.
n
` aspirin = 69 # 180 = 2.6 g

` Salt is KAlS 2 O8 $ 12 H 2 O
2.1
%
` yield = 2.6 # 100 = 80.76%
  Mole Concept
29.4 17. Let moles of NH3 NO3 = a
14. M acid = 98 = 0.3 and V = 0.1 L

` Moles of N in it = 2a
20/40
M NaOH = 0.5 = 1 and V = 0.09 L mass of NH3 NO3 = 80a
H X A + X NaOH $ Na X A + X H 2 O Let moles of (NH 4) 2 HPO 4 = b

` If basicity of acid = X
` Moles of N in it = 2b
n Mass of (NH 4) 2 HPO 4 = 132 b

nacid = NaOH
X
1 # 0.09 14 $ (2a) + 14 $ (2b)

` 0.3 # 0.1 =
` = 0.3040
X 80 a + 132 b

` X = 3.
a
Solving we get b = 3.3
3 m NH NO 80 a
15. Vol. of 1 molecule = 4 a 2 # h
` m(NH ) HPO = 132 b = 1.99
4 3

4 2 4

3
` 2 :1.
= 4 # (10 -6) 2 # 3 # 10 -6
18. Let V mL of alcohol be required
3 3
= 4 # 10 -18 cm3
a mass of alcohol is same in both solutions
(M.w.) 75 30
` = 1.2
` 100 # 0.8 # V = 100 # 0.9 # 150
3 3 -18
# 10 # 10 23
4
V = 67.5 mL

18 3 19. Moles of NO 2 required
Mw = 1.2 ` # 4 # 10 g mol
5

= b 63 l # 2 # 0.8 = 46.875
9.35 # 105 g mol 1575 3 1
=
935
= # 103 46.875
Moles of NO required = 0.60
16. Let molarity of H2O2 be M and the volume in the
46.875 1
two parts be V mL and (150 - V) mL Moles of NH3 required = 0.60 # 0.50

` for first reaction: = 156.25
n Volume of NH3 at STP required

n H O # 0.4 = KOH
2 2
2 156.25
= # 22.4 = 3500 L

Now for KOH + H 2 SO 4 reaction
20. Let wt. of sample is x g; wt. of MnO 2 is 0.75 x g
n KOH = 2n H SO and n H SO = 0.1
2 4 2 4
0.75x
0.2 moles of MnO 2 = 87
n` H O = 0.8 2 2

0.75x
MV
`
2000
= 8 = 250 ...(i) wt. of Mn = 87 # 55 = 0.474x

For second reaction: 3MnO 2 $ Mn3 O 4 + O 2

6.74
N O = 22.4 = 0.3 wt. of Mn3 O 4 produced
2

0.75x 1
nO = 87 # 2 # 229 = 0.658x g
and n H O # 0.5 = 3 2 2
3

300 Total wt. of residue = 0.658x + 0.2x

M
` (150 - V) # 0.5 = 3
(wt.of impurities)
M
` (150 - V) = 200 ...(ii)
0.474x

% of Mn in residue = 0.858x # 100 = 55.24
V 250 5

` 150 - V = 200 = 4
5 # 150 250
V
` = 9 = 3

Also, MV = 250 & M = 3
Chemistry
21. Let x g is wt. of CaC 2 O 4 and (0.6 - x) g wt. of
1
` Y2 O3 : BaO 2 : CuO : : 2 : 2 : 3
MgC 2 O 4
9 : : 1 : 4 : 6

CaC 2 O 4 CaCO3 + CO 2
9 27. 35 drops = 2 mL

MgC 2 O 4 MgCO3 + CO 2
2 2
x ` 1 drops = 35 mL = 35 # 1.2 g

wt. of CaCO3 produced = 128 # 100
N # 2 # 1.2
(0.6 - x) ` No. of molecules = A35 # 70

wt. of MgCO3 produced = 112 # 84
1.2
(0.6 - x) = $ NA
x (35) 2

` 128 # 100 + 112 # 84 = 0.465
60

x = 0.48 g 28. g-atom of metal = 24 ;
40

Due to further heating g-atom of oxygen = 16 ; simple ratio os

9
CaO + CO 2 \ 60 40
CaCO3 24 : 16 or 1 : 1 .
x
- 15
128 29. m = (100 # 1.1 - 15) = 1.6

MgCO3
9
MgO + CO 2 98 # 1000

- b 0.6 - x l 30. 18 mL H2O or 18 g H2O has 10 NA electrons, as each

112 H2O molecules has 10 electrons

wt. of CaO and MgO produced
0.48 0.12 31. r = 1.25 g/mL M = 3 Mww = 158

= 128 # 56 + 112 # 40 = 0.252g
10 # % (w/w) # 1.25
3
` = 158 & % (w/w) = 37.92
1.22 1
22. Moles of BaSO 4 = 233.3 # 3

37.92 g Na 2 S 2 O3 is present in 62.08 g of H 2 O
= 1.743 # 10 -3
37.92 62.08
n
` Na S O = 158 = 0.24 n H O = 18 = 3.45

wt. of M 2 (SO 4) 3 = 0.596 2 2 3 2

0.24
1.743
` # 10 -3 (2M + 96 # 3) = 0.596 X
` Na S O = 0.24 + 3.45 = 0.065
2 2 3

M = 26.9 1000 X 1000 # 0.065

m = (1 - X) 18 & 0.935 # 18 = 3.866
23. 2NaOH + H 2 SO 4 $ Na 2 SO 4 + 2H 2 O
1 m
` N = 7.732 and mS O = 3.866.
+
a 2
2-
3

n H SO = 2 n NaOH = 0.5
32. a. 1 mole O2 = 32 g
2 4

m ` H SO needed = 0.5 # 98 = 49g.

2 4
b. 3.011 x 1023 molecules = 0.5 moles SO2 = 32 g
m H SO
` msolution # 100 = 70
2 4

c. 0.5 moles SO2 = 32 g

m
49
` solution = 70 # 100 = 70g. d. 1 g atom of S = 1 mole S atoms = 32 g
9
aV + bV bV + aV 33. CaCl 2 $ CaCO3 CaO
24. V1 + V 2 = M1 and V1 + V 2 = M2
1 2 1 2
x moles x moles x moles
\ bV1 + aV2 = M1 = 4 b given M1 = 54 l
aV + bV M 5 M 1.12

mCaO = 1.12 g = 56 = 0.02 moles
1 2 2 2

a + b ^V2 /V1h 5 a2 + b2 5 m
` CaCl in mixture = 0.02 × 111 g = 2.22 g
2

or,
b + a ^V2 /V1h
= 4 & 2ab = 4
m
` NaCl in mixture = 2.22 g
Solving we get a = 2 and b = 1 as given a > b. 34. a. 16g CH4 = 1 mole CH4 ⇒ 4 mole H atoms
2
25. 6 mole HCl / 3 mole H 2 = 3 # 22.4 litre H 2 . b. 52 g C6H6 = 3 mole C6H6 ⇒ 4 mole H atoms
1
26. 1 mole Y Ba 2 Cu3 O 7 requires 2 mole Y2 O3 c. 34.2g C12H22O11=0.1 mole C12H22O11 ⇒ 2.2 mole
2 mole BaO 2 H atoms

3 mole CuO d. 36g H2O = 2 mole H2O ⇒ 4 mole H atoms
  Mole Concept
35. 1g molecule of V2O5 means 1 mole molecules of
⇒ H2SO4 gives [SO42-] = 0.025 M
V2O5.

\ total [SO42-] = 0.05 M
36. All such units of concentration which do not
depend on volume of solution are independent of
m Na SO = 0.1 # 142 = 14.2gm
2 4

temperature e.g. molefraction, molality, %(w/w) 14.2

Strength of Na2SO4 in g/L = 4 = 3.55 g/L
N
37. N = no. of moles = n
0.754
45. n Na = 23 = 0.0328
A

Molar mass (amu) x NA = total mass = m

n n
38. 11.2 L of gas at STP ⇒ 0.5 moles given mass of 0.5 n ` f = 3Na = n p = 4o = ncompound
moles = 149 ⇒ (Mw)gas = 28
0.0328
(M.w.) n
` f= 3 & 6.58 # 10 21 ions
39. V.D. = M.w. of H & dimensionless
2
0.0328 0.0328 #
density
ncompound = 3 & mcompound = 3 183
Specific gravity = density of H O & dimensionless
2 m
` compound = 2g
mass
mass fraction = total mass & dimensionless 0.0328/3

[Na3 PO 4 F] = 0.1 = 0.011M
molality has units of moles /kg.
48. Even if we assume it to be 100% CaCO3, Maximum
40. All such units of concentration which do not
weight loss from CaCO3 only is 4.4 g. Thus because
depend on volume of solution are independent of
actual weight loss is more the 4.4g impurity must be
temperature e.g. molefraction, molality, %(w/w)
volatile (B). Also 4.48 g is weight of CaO only.
46
41. a. Volume of solution = 1.4 = 32.85 mL
⇒ % weight of CaCO3
` mass of solute = 0.7 # 32.85 = 23g
100 100
= 56 # 4.48 # 10 = 90 %

b. Volume of solutions 49. Reactions with HCl:
= 50 mL & moles of solute = 0.5
Na3 PO 4 + 3HCl $ 3NaCl + H3 PO 4
` mass solute = 0.5 # 46 = 23g
NaH 2 PO 4 + HCl $ NaCl + H3 PO 4
42. 3S 2n+ + Cr2 O 72- + 14H + $ 3Sn 4+ + 2Cr3+ + 7H 2 O
Reactions with NaOH:
43. Mass of 35 drops = 2.4 g ⇒ mass of 1 drop = 0.068g
NaH 2 PO 4 + 2NaOH $ Na3 PO 4 + 2H 2 O
m
\ Volume of 1 drop = p = 0.057 mL.
Since Na3PO4 is a basic salt so PH > 7
$ 068
\ No. of moles in 1 drop = 70
Let Molarity of NaOH and HCl used be M.

\ No. of molecules in 1 drop 5M

mmol of NaOH used = 10 M & n NaH PO = 1000 2 4

$ 068

= 70 # N A = 5.85 # 10 20
mmol of HCl used = 20 M

\ No. of molecules in 35 drops = 2.047 x 1022 3n
20M
& Na PO + n NaH PO = 1000
3 4 2 4

44. 2NaOH + H 2 SO 4 $ Na 2 SO 4 + 2H 2 O 1 15M 5M

0.2 moles 0.2 moles n
` Na PO = 3 # 1000 = 1000
3 4

- 0.1 moles 0.1 moles 0.2 moles

n Na PO = n NaH PO
3 4 2 4

0.1
\ [Na 2 SO 4] = 4 = 0.025M
⇒ Na2SO4 gives [SO42-] = 0.025 M
0.1

[H 2 SO 4] left = 4 = 0.025M
Chemistry
50. a. CaO + 3C $ CaC2 + CO c. [Mw P4 O10 = 284]
1 mole 3 mol (1 mol = 64 g) 0.01 mol of P4 produces = 0.01 mol of P4O10
16 1
= (0.01 mol P4) b mol P 4O 10 lc
Moles of CaC 2 = 64 = 4 mol
m
1 mol P O 284 g P4 O10

1 4 10 mol P4 O10
Weight of C = 3 # 4 # 12 = 9.0g
= 0.01 # 284 = 2.84 g

b. Weight of C2H4=(32. kg) d kg n c

3
10 g 1 mol CaC Hence (c) is wrong.
2
m
64 g d. [Mw of P4 O6 = 220]
b 1 mol C 2 H 4 l Weight of P4 O6 produced
mol CaC 2
= (0.01 mol P4) b mol P 4O 6 lc m
1 mol P O 220g P4 O6

c m
28g C 2 H 4 4 6 mol P4 O6
mol C 2 H 4 = 0.01 # 220 = 2.2g
32 # 103 # 1 # 1 # 28 Hence, (d) is wrong.
= 64
108
= 14 # 10 g = 14.0 kg 3
52. moles of Al = 27 = 4.0 mol
c. [Mw of [Ag (NH3) 2] Cl = 177.5, 213
moles of MnO = 71 = 3.0 mol
Mw of AgCl = 143.5g mol -1
a. Since 2 mol of Al requires 3 mol of MnO,
Weight of AgCl = [17.75 g Ag ( NH3) 2 Cl] therefore Al is in excess.
d n b. Wrong.
1 mol Ag (NH3) 2 Cl
177.5 g Ag (NH3) 2 Cl
c. Weight of Al required
d nd n = (3.0 mol MnO) b 3 mol MnO l c m
1 mol AgCl 143.5 g AgCl 2 mol Al 27g Al
mol Ag (NH3) 2 Cl mol AgCl mol Al
17.75 # 143.5 3 # 2 # 27
= = 14.35g = 3 = 54.0 g of Al
177.5
d. Weight of Al in excess = (108 - 54) = 54.0 g.
Hence (c) is wrong.
21
d. (Atomic weight of Zn = 65.4g, 53. Moles of Li = 7 = 3.0 mol
Mw of Na2S2O4=174) 32
Moles of O 2 = 32 = 3.0 mol
Weight of pure Na2S2O4 = (65.4 x 106g Zn)
a. since (3.0 mol Li) b 4 mol Li2 l = 4 = 0.75 mol
1 mol O 3
c 1 mol Zn m b 1 mol Na 2 S 2 O 4 l
65.4g Zn mol Zn
of O2 is required, therefore (1.0 - 0.75) = 0.25
c m mol of O2 is in excess. Hence, Li is the limiting
174g Na 2 S 2 O 4

mol Na 2 S 2 O 4 reagent.
65.4 # 106 # 1 # 1 # 74 b. Weight of Li2O formed
= 65.4
1 mol Li 2 O l c 30g Li 2 O m
= (3.0 mol Li) b 2 mol Li
6
= 174 # 10 g
mol Li 2 O
= 174 metric ton 3 # 1 # 30
174 # 100 = 2 = 45.0g Li 2 O
Weight of 50% pure Na 2 S 2 O 4 = 50 3.9
= 343 metric ton c. Moles of K = 39 = 0.1 mol
Hence, (d) is wrong. 4.26
Moles of Cl 2 = 71 = 0.06 mol
1.24 8
Since b 2 l = 0.05
51. n P = 31 # 4 = 0.01 mol, nO = 32 = 0.25 moles 0.1
4 2
mol of Cl2 is
In reaction (i), moles of O2 required
required. Therefore (0.06-0.05)=0.01 mol of
mol P4) b mol P 2 l
5 mol O
(0.01
= Cl2 is in excess.
4

= 0.01 # 5 = 0.05 mol Hence, K is the limiting reagent.

Since there is more O2 present than required d. Weight of KCl formed
= (0.1 mol K) b mol K lc
1 mol KCl 74.5g KCl m
a. Therefore, P4 is the limiting quantity
mol KCl
b. Wrong. = 0.1 # 1 # 74.5 = 7.45g of KCl
  Mole Concept
54. 1 mol Cl 2 / 2 mol KOH / 1 mol KClO / 13 KClO3 62. n He = 1 & no. of atoms = n A
4 1
1 nO = 32 & No. of atoms = 8 # N A # 2
/ 4 mol KClO 4 2

4 1
277 nO = 48 & No. of atoms = 12 # N A # 3
Moles of KClO 4 = 138.5 = 2
3

4 2
n H O = 34 & No. of atoms = 17 # N A # 4
> H
Moles of Cl 2 = 2 # 4 = 8 2 2

mass of Cl 2 = 8 # 71 = 568g 63. 1.12 L / 6.2g

Moles of KOH = 2 # 8 = 16 6.2 # 22.4
22.4 L = 1.12 = 124
16
VKOH = 1.5 = 10.67 L 124
` Atomicity = 31 = 4
55. (Let ‘a’ g of X and Y taken)
64. It is fact
2X + 3Y $ X 2 Y3
a a 65. Mass number of isotope of O with 9 neutrons = 16
Initial moles] & 36 24 and is 90%.
a

Final moles] & - -
72 Mass number of isotope of O with 9 neutrons = 17

Since both X and Y are completely consumed, there Let a%.
is no limiting reagent. Mass number of isotope of O with 10 neutrons = 18

a
Moles of X 2 Y3 = 72, (10
` - a) %
` Average atomic mass of O
(Mw of X 2 Y3 = 2 # 36 + 24 # 3 = 144)
%O16 ×16 + %O17 ×17 + %O18 ×18
=

Weight of 100
a

X 2 Y3 = 72 # 144 = 2a = 2 # Weight of X 90 16 + 17 (a) + 18 (10 - a)
#
\ 16.12 = 100
56. Cl - + AgNO3 $ AgCl + NO3- \ a=8
14.35
\ % of O17 = 8 %

Mass of AgCl produced = 143.5 = 0.1

and n AgCl = n AgNO 3 % of O18 = 10 - 8 = 2 %
135 ` # M AgNO = 0.1 # 10
3
3
66. NaCl + AgNO3 $ AgCl . + NaNO3
100
M ` AgNO = 135 = 0.74M
3

4.77
n NaCl = 58.5 and N AgNO = 170
5.77
3

57. Cu (NH3) x Cl 2 + HCl $ Cu 24 + xNH +4 + (x + 2) Cl - AgNO

` 3 is the limiting reagent
n

-

` x +Cl 2 = nCu(NH )Cl 5.77

n
` AgCl precipitated = 170 # 143.5
3 2

0.1 3.7
n ` Cu(NH ) Cl = x + 2 = 63.5 + 17x + 71
3 x 2

= 4.87g
Solving, we get x = 3 67. n H SO = 0.1 # 1.2 = 0.12

2 4

NH3 Cl + NaOH $ NH 4 OH + NaCl

x 3 m
` H SO = 0.12 # 98 = 11.76g
moles of NH 4 Cl = x + 2 # 0.1 = 5 # 0.1 = 0.06
2 4

68. a. n Al = 20 n H = 40 Final volume = 500

3+ +

n ` NaOH = 0.06 = 0.5V 20 + 40 60

600 ` [cation] = 500 = 500 = 0.12M
V ` = 5 mL = 120 mL
100
nCl = 3 # 20 + 40 = 100 & [Cl -] = 500 = 0.2M
-

58. Molar mass of complex = 63.5 + 17 × 3 + 71

= 185.5
20
b. n K = 20 ` [cations] = 100 = 0.2M
+

59. Mass of 1 water molecule = 18 amu nCl = 20 ` [Cl -] = 0.2M

-

= 18 × 1.64 × 10-24g
= 3 × 10-23g
c. n K = 2 # 30 # 0.2 = 12, nSO = 6
+ 2-
4

12
60. Avogadro’s Law, If P, T are same then equal volmes ` [K +] = 100 = 0.12M ` [SO 24-] = 0.06M
will have same no. of moles of molecules. 10 # 24.5

d. M = 98 = 2.5 ` [SO 24-] = 2.5M
61. Mass of ‘O’ atom is independent of NA.

[H +] = 5M
Chemistry
1 70. a. 0.5 mole SO2 & 11.2 L at STP
69. a. m H O = 1.8g & n H O = 0.1 & 10 N A molecules
2 2

& 1.5 mole atoms (1 mole O and 0.5 moles S)

` vol. of vapours at STP = 0.1 # 22.4L

b. 1g H2 & 0.5 moles & 11.2 L
1.8

b. 1.8 mL vapours at STP & 22400 moles
c. 0.5 moles O3 & 11.2L & 1.5 mole atoms

c. 8. # 10 -5 mole H 2 O(v) is same as (b) above.
d. 1g molecule of O2 & 1 mole O2 molecules
71. 32g SO2 & 0.5 mole SO2 & 1.5 mole atoms

& 11.2 L at STP

1. M.W. of C7H5N3O6 = 84 + 5 + 42 + 96 = 227 g/mol 90

% of carbon = 120 × 100 = 75%
681

nC H N O = 227 = 3
7 5 3 6

mass of hydrogen = n H O × 22

nN = nC H N O × 3 = 9 mol 270
7 5 3 6

= 18 × 2 = 30g

no. of N atoms = 9 × 6.02 × 1023
30

% of hydrogen = 120 × 100 = 25%

= 5418 × 1021
\ The answer is 5418 7. mass of Na+ present in 1 kg water = 92g
92
2. 100 molal aqueous solution means there is 100 mole moles of Na+ present in 1kg water = 23 = 4
solute in 1 kg = 1000 gm water.
moles of Na +
n solute \ molality of Na+ = mass of water (kg)
Now, mole-fraction of solute =
n solute + n soluvent
100 1800 4
=
1000
= =
2800 0.6428 = 1 = 4.
100 +
18 8. From given reaction
= 64.28 × 10–2
moles of H2O formed = 55 × moles of C57H110O6
3. Na+ present in 50 ml mass of C57H110O6 taken = 445 g.
70 mg
= 1 ml # 50 ml = 3500 mg = 3.5 gm 445
moles of C57H110O6 taken = 57 ×12 + 110 ×1 + 6 ×16
3.5
moles of Na+ = 23 = moles of NaNO3
445
= 890 = 0.5
weight of NaNO3 3.5 23 # 85 = 12.993 gm
⇒ moles of H2O = 55 × 0.5
Mass qf Fe ^in gh
⇒ mass of H2O = 27.5 × 18 g
4. 10 = # 106
= 495 g.
100 # 1000
or, mass Fe = 1 g 9. Mass% Atomic ratio
FeSO4.7H2O (M = 277.85) C 6.K% 6/12 = 1/2
55.85 g Fe in 277.85 gm of compound. H 1 K% 1/1 = 1
277.85 O (100-7K)%
so 1 gm Fe in 55.85 = 4.95 gm

x:y=1:2
5. 63% w/w → HNO3 solution
C
` x H y = C n H 2n
63 # 1.4
M= # 1000 mole/L = 14 mole/L
Cx Hy Oz + c x + m O $ xCO2 + H2 O
y z y
63 # 100
4-2 2 2
6. Given mass of organic compound = 120
C x H y + c x + m O2 $ xCO2 + 2 H2 O
y y

mass of CO2(g) = 330 g
4

x + 4 - 2 = 2 ;x + E
mass of H2O (l) = 270 g y z 1 y


mass of carbon = nCO × 12 4
2
x 2

330
= 44 × 12 = 90g z =3
Thus, Empirical Formula : C2H4O3
  Mole Concept
10. Mass of the adult = 75 kg (mO ) 2

% Hydrogen = 10% nO (MO )

13. n N = (m )
2 2

\ Mass of Hydrogen = 7.5 kg 2 N 2

(M N )
Now, if each 1H atom is replaced by 2H atom then
2

effectively the mass of each H atom doubles.

Where, mO = given mass of O2, m N = given mass
2 2

\ Mass of Hydrogen after replacement = 15 kg of N2, M O = molecular mass of O2, M N = number

2 2

Also, mass of other atoms remain same.

of moles of N2
\ Gain in mass = 7.5 kg.
= ; m O E 32 = 4 # 32 = 32
m 28 1 28 7
11. initial m. moles of CH3COOH = 50 × 0.06 = 3 2

N 2

final m. moles of CH3COOH = 50 × 0.042 = 2.1

M1 V1 + M 2 V2
\ m. moles of CH3COOH adsorbed by 3g charcoal 14. From the formula, M f =V1 + V2
= 0.9
Given, V1 = 750 mL, M1 = 0.5 M
\ m. moles of CH3COOH adsorbed by 1g charcoal
V2 = 250 mL, M2 = 2 M
= 0.3
\ mass of CH3COOH adsorbed per g of charcoal = 750 # 0.5 + 250 # 2 875
= 750 + 250 = 1000 = 0.875M
0.3 × 60 = 18 mg.
12. We know the molecular weight of C8H7SO3Na 15. Heavy water has 2 atoms of 12H and one atom of 168O
12
= # 8 + 1 # 7 + 32 + 16 # 3 + 23 = 206
\ Number of protons = 2 × 1 + 1 × 8 = 10

we have to find, mole per gram of resin.
\ Number of electrons = number of protons = 10

` 1 g of C8H7SO3Na has number of mole Number of neutrons = 2 × 1 + 1 × 8 = 10
weight of given resin 1 16. molality and Molarity of a solution are related by the

= Molecular, weight of resin = 206 mol
formulae given in Section 6.2 of theory.

Now, reaction looks like
17. moles of Urea = 2

2C8 H 7 SO3 Na + Ca 2+ $ (C8 H 7 SO3) 2 Ca + 2Na

Total mass of solution = 1120 g.

a 2 moles of C8H7SO3Na combines with 1 mol Ca2+

Total Volume of Solution = 973.9 mL
1

` 206 mole of C8H7SO3Na will combine with

So, Molarity = 2/0.9739 = 2.05M
1 1 1
2 # 206 mol Ca 2+ = 412 mol Ca 2+ 18. 24g C has 2 mole atoms rest all have 1 mole atoms

(120 + 1000) For option (a)

1. VSol = 1.15 mL Let atomic mass of P be MP and atomic mass of Q be MQ
W2 # 1000 120 # 1000 Molar ratio of atoms P : Q in compound 3 is
M = Mw = 60 # 1120/1.15
2 # Vsol 40 60
M P : M Q = 3: 4
2 # 115
= 112 = 2.05 M
2M Q 3
2. The atomic mass of iron is 3M P = 4 & 9M P = 8M Q
(5 # 54) + (90 # 56) + (5 # 57) Molar ratio of atoms P : Q in compound 2 is

= 100 = 55.95 44.4 55.6
M P : M Q = 44.4 MQ : 55.6 MP
3.
8M Q
= 44.4 MQ : 55.6 × 9
Compound Weight % of P Weight % of Q
8
1 50 50 = 44.4 : 55.6 # 9 = 9 : 10
2 44.4 55.6
⇒ Empirical formula of compound 2 is therefore
3 40 60 P9Q10

⇒ Option (a) in incorrect
Chemistry
For option (b) 1584
Number of Moles of (NH4)2SO4 = 132 = 12 moles
Molar Ratio of atoms P : Q in compound 3 is
40 60 Moles of NH3 released = 24 moles
M : M = 3:2
P Q 952
Moles of moles of NiCl2.6H2O = 238 = 4 moles
2M Q 3 Number of moles of Gypsum (CaSO4.2H2O) formed
3M P = 2 & 9M P = 4M Q = 12 moles
9 # 20 Mass of Gypsum formed = 12 × 172 = 2064

If MP = 20 & MQ = 4 = 45
Number of moles of complex formed [Ni(NH3)6]Cl2

⇒ Option (b) is correct 24
= 6 = 4 moles
For option (c)
Mass of complex formed = 4 × 232 = 928 g
Molar ratio of atoms P : Q in compound 2 is
44.4 55.6 Total Mass = 2064 + 928 = 2992 g
M : M = 44.4M Q: 55.6M P = 1: 1
P Q
nsolute
7. n = 0.1
M 44.4 solute + n solvent

& M P = 55.6
nsolute 1

Q
` nsolvent =9

Molar ratio of atoms P : Q in compound 1 is
\ If nsolute = 1, then nsolvent = 9
50 50
M P : M Q = M Q: M P \ mass of solute (MW)solute and
Msolvent = (M.W.)Solvent × 9

= 55.6 : 44.4 - 5 : 4 1000

Hence, empirical formula of compound 1 is P5Q4 \ Molality = 9 (M.W.)
solvent

Hence, option (c) is correct mass of (solute + solvent)
Volume of solution = 2000 L
For option (d) 2000
Molar ratio of atoms P : Q in compound 1 is \ Molarity = (MW) + 9 (MW)
solute solvent
50 50 a molality = Molarity
M : M = M Q: M P
P Q 1000 2000
\ 9 (MW) = (MW)

= 35 : 70 = 1 : 2 solvent solute + 9 (MW) solvent

Hence, empirical formula of compound 1 is PQ2 (MW)solute + 9 (MW)solvent = 18 (MW)Solvent

Hence, option (d) is incorrect (MW) solute
\ (MW) =9
solvent
4. 2Al + 3H2SO4 → Al2(SO4)3 + 3H2
5.4 8. If Molarity = 3.2
Moles of Al takes = 27 = 0.25
\ 3.2 moles of solute are present in 1 L solution
0.2 0.25
As 2 > 3 , H2 SO4 is limiting reagent Given, no change in volume ⇒ Vsolution = Vsolvent
Now, moles of H2 formed = P
nRT \ If Vsolution = 1L ⇒ Vsolvent = 1L ⇒ masssolvent=400g
3.2
=
0.25×0.082×300
= 6.15 L \ molality = 400 ×1000
1
\ molality = 8.
5. Let mole of urea = x
x 50 9. BenAl2Si6 O18
900 = 0.05, x = 19 (2n) + (3 × 2) + (4 × 6) + (-2 × 18) = 0
x + 18
or 2n + 30 - 36 = 0or 2n = 6 or n = 3
50 20100
Mass of solution = 19 × 60 + 900 = 19 10. Density = 10.5 g cc-1
This means 10.5 g silver is present in 1 cm3.
20100
Volume of solution = 19 # 1.2 ml
10.5
108 mol silver is present in 1 cm .
3

20.1 10.5
= 19 # 1.2 litre 108 N silvel atoms present in 1 cm .
3

50 3 10.5
19 60 108 N silvel atoms present in 1 cm
Molarity = 20.1 = 20.1 @ 2.985
b 10.5 N l silvel atoms present is 1 cm2.
1/2
3
19 # 1.2 108
6. Ca(OH)2 + (NH4)2SO4 2NH4 + CaSO4.2H2O 10-12 m2 is equal to 10-8 cm2.
b 10.5 N l # 10 -8 silver atoms present in
1/2
3
1584 g [Ni(H2O)6]Cl2
108
Complex Compound 10-12 m2.
On solving, we get 1.5 x 10 = Y x 10-x ` x = 7
-7
 Atomic Structure

Chapter 2 Atomic Structure

INTEXT EXERCISE: 1
1. Hydrogen atom contains 1 proton, 1 electron and no m
8.
e = 1.5 × 10 e = 1.6 × 10-19
-8
neutrons.

\ m = 1.5 × 10-8 × 1.6 × 10-19 = 2.4 × 10-27 kg
2. Cathode Rays have constant b m
e l ratio.

\ m = 2.4 × 10-24 g
(e/m) e e/me
3. (e/m) = 2e/(4 # 1836m
3672
= 1 9. Charge on oil drop = - 6.39 × 10-19 C
a e)

a -1.602 × 10-19 C is charge on one electron
4. Factual.

\ - 6.39 × 10-19 C is charge on
5. rN + 10 -13 cm and ratom + 10 -8 cm
- 6.39 # 10 -19
Volume of nucleus
= = 4 electrons.

Volume fraction = Total vol. of atom - 1.602 # 10 -19
10. From a particle scattering experiment, distance of
(4/3) r (10 -13) 3

= = 10 -15 closest approach of a particle with nucleus came out
(4/3) r (10 -8) 3 to be of the order of 10-14 m. This scattering followed
6. R = RoA1/3 = 1.3 × 641/3 = 5.2 fm Coulomb’s law and gave the size of the nucleus to
7. Speed of cathode rays is less than speed of light. be < 10-14m.

INTEXT EXERCISE: 2
c 3 # 10 8 7. According to Planck’s Quantum Theory the
1. m = y = = 0.75 m minimum energy which can be absorbed from an
400 # 106
EM wave
2. Violet colour has minimum wavelength so maximum
energy. hc
=
m
hc
3. I.E. of one sodium atom = 8. E \
1
m m
& I.E. of one mole Na atom \ l1 = 2000 and l2 = 4000
hc 6.62 # 1034 # 3 # 108 # 6.02 # 10 23
N A = m
m 242 # 10 -9
E
\ E1 = 2 = 2
m1
= 494.65 kJ. mol.
2

9. u = 6 × 1014 Hz
4. Energy absorbed = 40 J/s
Now, c = ul

\ Energy released (as EM waves) =0.8×40= 32 J/s 1 y
\ y= = c

\ 32 × 20 =
nhc m
m
6×1014

⇒ n = 2 × 1021
\ y= = 2×106 m -1
3×108
1
5. y =
m hc
10. Eabsorbed = 500 = Ereleased
1

\ y= = 2 × 106 m-1 hc hc
500×10 -9 m Now, Ereleased = 800 +
m
6. 4 waves are passing through a given point in 2s. 1 1 1
= 500 - 800
a Frequence = no. of waves / sec. m
\ Frequency = 4/2 = 2 Hz ⇒
1
=
3
m 4000
\ l = 1333.3 nm
Chemistry
INTEXT EXERCISE: 3
6. S1 : Potential energy of the two opposite charge
1. r a b nZ l As Z increases, radius of 1st orbit decreases.
2

system decreases with decrease in distance,

n2 c S4 : The energy of 1st excited state of He+ ion
2. Radius = 0.529 z A = 10 # 10 -9 m
= –3.4 Z 2 = –3.4×2 2 = –13.6 eV
So, n2 = 189 or n . 14 S2 and S3 are correct statement.
12 T n3 13 1
3. E1 (H) =- 13.6 # =- 13.6 eV ; 7. T1 = 13 = 3 = 8 . (for same Z)
12 2 n2 2
a bT = v l
22 2rr n3

E 2 (He +) =- 13.6 # =- 13.6 eV so, T \ 2
22 Z
32 r n2 R

E3 (Li 2+) =- 13.6 =- 13.6 eV ; 8. r \ n2 and r \ n3 for same Z r12 = 12 = 4R
32 n2
n 1
42 ⇒ n12 = 2

E 4 (Be3+) =- 13.6 # =- 13.6 eV
42 T n3 1
\ T1 = 13 = 8 .

\ E1 (H) = E 2 (He +) = E3 (Li 2+) = E 4 (Be3+) 2 n2
9. Angular momentum J = mvr
Z
4. v = 2.188 # 106 n m/s J2 = m2 v2 r2
or 2 = b 2 mv 2 l mr 2 or K.E. =
Z Z /n 3/3 J2 1 J2
Now, v \ n So, = Z 1 /n1 = 1/1 = 1
2 2 2mr 2
v3(Li2+) = v1 (H) 10. a) Energy of ground state of He +

= –13.6×2 2 = –54.4eV (iv)

5. rn - rn = 24 # (r1) H
1 2 b) Potential energy of 1 orbit of H-atom
st

= –27.2×1 2 = –27.2eV (ii)

0.529 # n12 0.529 # n 22
1 - 1 = 24 # 0.529 c) Kinetic energy of 2 excited state of He+
nd

22

\ (n12 - n 22) = 24 = 13.6× 2 = 6.04 eV (i)
3
So, n1 = 5 and n2 = 1 d) Ionisation potential of He+
= 13.6×2 2 = 54.4 V (iii)

INTEXT EXERCISE: 4
Z2 (1) 2 For last line of Pachen series
1. E n = E1 E5 =- 13.6 # =- 0.54 eV
y 2 = R H (3) 2 < 2 - F= R
n2 (5) 2 1 1

(3) (3) 2
hc 1
2. m = 9E ` ma 9E R
Thus, difference = 4
3. Infrared lines = total lines – visible lines – UV lines
6 (6 - 1) 8. (He+)2 → 4 = (Li 2+) n 4 " n3
Total lines = 2 = 15 Z n n 2 2 4
\ Z1 = n 24 = n13 or 3 = n 4 = n3
visible lines = 4 (6 → 2, 5 → 2, 4 → 2, 3 → 2) 2

UV lines = 5 (6 → 1, 5 → 1, 4 → 1, 3 → 1, 2 → 1) \ n4 = 3 and n3 = 6.
\ Transition in Li2+ ion = 3 → 6
4. When electron falls from n to 1, total possible
9. y1 = Rc Z 2 c 2 - 2 m = Rc Z 2 ,
1 1
number of lines = n – 1.
n1 3
5. Visible lines ⇒ Balmer series (5 → 2, 4 → 2, 3 → 2)
y 2 = Rc Z 2 c 2 - 2 m = 4 Rc Z 2 .
1 1 3
So, 3 lines.
1 2
y3 = Rc Z 2 c 2 - 2 m = 4 Rc Z 2
6. According to energy, E 4 " 1 > E3 " 1 > E 2 " 1 > E3 " 2 . 1 1 1

2 3

According to energy, Violet > Blue > Green > Red. \ u1 - u2 = u3.

\ Red line ⇒ 3 → 2 transition.
10. Visible lines ⇒ Balmer series ⇒ only in H atoms.
7. For 1st line of Balmer series In H like species, e.g. He+, we cannot make
generalizations of certain lines lying in the visible
y1 = R H (3) 2 < 2 - F = 9R b 5 l = 5 R
1 1

(2) (3) 2 36 4 region.
 Atomic Structure
INTEXT EXERCISE: 5
1. For photoelectric effect to take place, 6. P.E.E. occurs only if uin > uo
Elight > f K.E. ∝ uin not velocity of photoelectron.
hc hc 7. K.E.max = huin - f
\ $ or m # m 0 .
m m0
2. Photoelectric effect is a random phenomena. So, 8. uincident = u1
electron may come out with a kinetic energy less K. E. =
hc
-z
than or equal to (hu – w) as some energy is lost m1
hc z
while escaping out. \ stopping potential = -
m1 e e
3. If u > u0, emission takes place with a maximum K.E. when uincident = u2
of hu-huo. The K.E. is independent of the intensity hc z
but the number of photoelectrons increases with stopping potential = -
m2 e e
intensity.
\ stopping potential increase by e c
hc 1 - 1 m

hc m 2 m1
4. = 1 + z ...(1)
m
hc 9. | Max K.E. | = | stopping potential |
3# = 4 + z ...(2)
m
\ K.E.max = 1.5 eV also f = 2.5 eV
from, e.q., (1) and (2) z = 0.5 eV
\ Eincident = 1.5 + 2.5 = 4 eV
5. Number of lines in Balmer series = 2 10. K.E.mzx = Ein - f = 6 - 2.1 eV

\ n = 4 (lines will be 4 → 2, 3 → 2). = 3.9 eV
KE of ejected photoelectrons
\ stopping potential = - 3.9 eV
13.6
= Ephoton - En = 13 - 2 = 13 - 0.85 = 12.15 eV.
4
INTEXT EXERCISE: 6
-34
h 6.625 # 10 # h
7. 9p $ 9x = 4r
1. m = mv = 0.2 # 5 3600 . 10 -30 m.
6.62 # 10 -34
2.
m1
= V2 =
V 200 2 ⇒ 9x = = 5.27 # 10 -30 m.
m2 1 50 = 1 . 4 3.14 # 1 # 10 -5
#

3. r1 = 0.529 A c my mx vx my m vx 16
8. = & 1 = (0.25m )x (0.75v = 3 .
r3 = 0.529 # (3) 2 Ac = 9x mx my vy x x)

2rr 2r (9x)
So, m = n = 3 = 6rx. h
9. m = mv
o
12.3
4. m = A gives the De-Broglie wavelength of an mp m v
V = map vap m = 4mp
ma
electron accelerated by V volts.
mp 4m v 1 va vp 8
n n n 2 4 = m pav pa 2 = 4 # vp va = 1
5. m \ Z ` Z1 = Z2 or 3 = 6 (n = 4 of C5+ ion) ma
1 2

h 10. l = v
6. For a charged particle m = h h
2mqV
then m = mv or m2 = m
1

\ m\ . h
V
So, m= m
INTEXT EXERCISE: 7
h
\ No. of unpaired electron = 4.
1. Orbital angular momentum = , (, + 1) 2r = 0.
X26 : 1s22s22p63s23p63d84s2.

\ l = 0 (s orbital).
To get 4 unpaired electrons, outermost configuration
2. Cu:1s 2 2s 2 2p6 3s 2 3p6 3d10 4s1 . will be 3d6.
\ Cu 2+:1s 2 2s 2 2p6 3s 2 3p6 3d9 or 6Ar@ 3d9 .

\ No. of electrons lost = 2 (from 4s2).
3. Magnetic moment = n (n + 2) = 24 B.M.
\ n = 2.
Chemistry
4. Zn2+ : [Ar]3d10 (0 unpaired electrons). h
8. Orbital angular momentum = , (, + 1) 2r
Fe 2+
: [Ar]3d (4 unpaired electrons) maximum.
6
Now for 2s orbitals, l = 0
Ni 3+
: [Ar]3d7 (3 unpaired electrons). \ Orbital angular momentum = 0
Cu+ : [Ar]3d10 (0 unpaired electrons). 9. 17
Cl- : [Ne]3s23p6
5. d7 : 3 unpaired electrons Last electron enters 3p orbital.

n
\ Total spin = ! 2 = ! 2 .
3
\ , = 1 and m = 1, 0, - 1.
10. n = 3 can have l= 0, 1, 2
6. X23 : 1s22s22p63s23p63d34s2.
if l = 0 ⇒ orbital angular momentum = 0
No. of electron with , = 2 are 3 (3d3) .
2h
if l= 1 ⇒ orbital angular momentum = 2r
7. Cr (Zn = 24)
electronic configuration is :1s 2 2s 2 2p6 3s 2 3p6 4s1 3d5 6h
if l= 2 ⇒ orbital angular momentum = 2r
So, no. of electron in , = 1 i.e., p subshell is 12 and
no. of electron in , = 2 i.e., d subshell is 5.
INTEXT EXERCISE: 8
1. For 6g orbitals, n = 6 and l = 4. 6. Spherical node = n -l- 1

\ Radial nodes = n -l- 1 = 6 - 4 - 1 = 1 and non spherical =l.
Angular nodes =l= 4 7. The dual nature of electrons is the premise on which

\ Total 5 nodes. this model is based.
2. The radius of maximum probability of 1s orbital of 8. i) Electron density in the XY plane in 3d x - y 2 2

H atom has a value of 0.529Å. orbital is not zero

ii) Electron density in the XY plane in 3d z orbital
3. A has 0 radial nodes and B has 1 radial node
2

is not zero

\ A is 1s and B is 2s iii) 2s orbital has one nodal surface-it is a spherical
4. Dumbell lies at 45o to x & y axis represents dxy node.
orbital. iv) For 2pz orbital, XY is the nodal plane
5. XZ is the nodal plane of px orbital 9. Factual.
10. n, l and m, are obtained from y.

EXERCISE - 1

1. Cathode rays are made up of electrons and have 8. Urea - CO (NH2)2

mass and charge both
Atomic no. of C=6
2. It is average isotropic weight
O=8
3. Isotones ⇒ same value of A - Z i.e. same number of
2N = 7 x 2 = 14
neutrons.
2H2 = 4

\ 6 + 8 + 14 + 4 = 32
4. A nucleus has a much smaller volume than that of an
atom, hence only small fraction get deflected. 9. In the equation E = hu, E is the energy of a packet
which discribes the particle nature and u is the
5. The fraction of a particles undergoing a deviation
frequency of the EM wave and describes the wave
of ~ 180o is proportional to the ratio of volume of
nature.
nucleus to that of the atom.
10. Photons denote the particle nature of light.
6. They are deflected more as the experience stronger
electrostatic forces of repulsion. 11. Red has the largest wavelength and hence smallest
frequency among the visible light.
7. Nucleon are the particles in the nucleus.
12. A packet of energy of EM waves is called quantum.
 Atomic Structure
13. l = 600 nm 29. Lyman series emits highest energy lines and 2nd line
c of any series has more energy than 1st line. So 3 → 1
u=
m has highest energy and lowest l.
3 ×108
\ =u 30. Max number of spectral lines
600 ×10 -9
\ u = 5 × 1014 Hz
(n 2 - n1) (n 2 - n1 + 1) ]4 - 1g]4g
= 2 = 2 =6
n2 31. As atom is excited so energy of electron >
14. rn = 0.529 × Z ⇒ rn \ n2
\ r1 : r2 : r3 = 1 : 4 : 9 - 13.6 eV

1 32. When electron is in excited state in H atom,

15. K.E. = - T.E. = - 2 P.E.
E > - 3.4 eV. Thus, I.E. < 3.4 eV
For n = 3 and Z = 1
33. A quantum having energy equal to the difference
T.E. = - 1.51 eV of energy between the two energy levels is emitted

\ K.E. = + 1.51 eV and P.E. = - 3.02 eV during de-excitation.

16. E = - 13.6
Z2 34. E in L shell (n = 2) = - 3.4 ev. If it loses 10.2 eV then
n2 new energy = (- 3.4 - 10.2) eV
1
= - 13.6 × 9 = - 1.51 eV
= 13.6 eV.
17. rn = ron2 ⇒ r3 = 9ro 35.
E1 = - 54.4 eV
18. E at n = 1 = - 13.6 eV - 54.4

\ E2 = 4 =- 13.6 eV

E at n = 2 = - 3.4 eV
\ I. E. = 13.6 eV.
E at n 3 = - 1.51 eV 36. Theoretical.
1st excitation potential = 10.2 37. Free electron at rest has 0 energy. When the electron
2nd excitation potential = 12.09 eV is bound to an atom, its energy is therefore negative.
19. I.E. from n = 3 is 1.51 eV 38. Shortest line of Paschen ⇒ n = 3 $ n = 3

\ E3 = - 1.51 eV = R3 2 : 9 - 3 D
1 1 1
m
\ E1 = - 1.51 × 9 = - 13.6 eV
1
13.6 \ m= R
\ E2 = - 4 = - 3.4 eV
39. Z = 2
20. L shell —→ n = 2
n = 2 → n = 1 (Longest l for lowest DE)
E = -3.4 eV
= R × 4 :1 - 4 D = R × 4 : 4 D
1 1 3
P.E. = 2 × -3.4 eV = -6.8 eV m
- P.E.
1
\ m = 3R (b)
21. K.E. =- T.E. = 2
22. K.E. decreases and total energy increases. 40. Z = 1
23. The charge on the nucleus of atomic no. Z n = 3 $ n = 1 (Shortest l for highest DE)
1
24. -3.4 eV (When n = 2). The possible value of energy = R x 1[1] = R
m
13.6
are - 2 eV where ‘n’ is an integer.
1
\ m= R =x
n
25. Bohr said that electrons neither gain nor lose energy Z = 2
when they are at particular orbits and hence these
n = 3 → n = 2
orbits are called stationary states.
= x × 4 : 4 - 9 D
1 1 1 1
26. Emission spectra is diserect, unequally spaced with m
varying intensity.
= x × 4 : 36 D
1 1 5
m
27. Electrons reaching n = 4 from any state emits EM
1 1 5
waves in the Brackett series. = x × 9
m
28. The energy of the orbits keep changing with Z. Thus m= 5
9x
line spectra of no two elements are indetical.
Chemistry
41. Photo electric emission occurs when u > uo 61. spin Q.N. is not obtained from y.
42. Refer Q. 41 above 62. Theoretical

43.
V I B G Y OR 63. Degenerate orbitals are such orbitals which have
decreasing frequency same energy.

So only V, I, B, G can cause emission
64. For m = 2, l can be from - 2 to 2.
44. It establishes the existence of quantum of energy,
65. If n = 2 then l can be 0 or 1.
which is a packet of energy.
66. An orbital can have maximum 2 electrons.
45. h (u1 - u0) = K.E.

u1 then K.E. - 67. For principal Q.N. n, number of possible values of
l is also n. Hence, number of subshells = n.
1242
46. E =
m (nm) 68. No. of subshells = n = 3.

4=
1242
No. of orbitals in 3s, 3p, 3d = 1 + 3 + 5 = 9.
m (nm) o
69. d x - y orbitals are double dumbbell shaped with its
2 2

l (nm) = 310.5 nm = 3105 A
two lobes lying along the x and y axes.
47. KE1 = E1 - f 70. Since m = -1, therefore it cannot be s-orbital
KE2 = 2E1 - f becuase for s-orbital m = 0.

\ K.E.2 = 2K.E.1 + f 71. Orbital anular momentum = 2r , ], + 1g
h
48. Changing frequency changes the K.E. of the 72. m can be -lto +l. So no. of values possible
photoelectron, not the number of electrons ejected.
= 2l+ 1.
Photocurrent increases on increasing intensity to
and attains a maximum value. 73. 19th electron goes to 4s orbital in Chromium.
49. Theoretical. 74. Fe3+ : [Ar] 3d5
50. Definition of work function. Co2+ : [Ar] 3d7
0.101 c
51. For an a particle (a), m = A. n = n (n + 2)
V
52. r1 = x ⇒ r4 = 42 x = 16 x. n Fe3+
5×7

\ nCo =
2+
3×5

\ circumference = 2p (16x) = 4 l3

\ l3 = 8 p x = 35 : 15

53. According to Heisenberg it is impossible to 75. For g-subshell l = 4

determine both the position as well as the momentum \ No. of e- = 2 ( 2 × 4 + 1) = 18.
of a particle simultaneously and accurately. 76. Two spectral lines of an element cannot have the
54. d orbital has l = 2 same wave number.

55. For 2 electrons in same orbital, n, l, m are same but
s is different.
56. No. of orbitals in a subshell = 2l+ 1. Since each
orbital can have a maximum of 2 electrons therefore,
maximum no. of electrons = 2 (2l+ 1).
57. n = 2 may have one s and 3 p orbitals with a maximum
of 8 electrons.
58. n = 2 l= 1 for 2 p orbitals.
59. f-subshell has 7 orbitals and can accomodate a
maximum of 14 electrons.
60. p orbital is dumbell shaped.
77. s-orbital is spherically symmetric. The probability
distribution is uniform in all directions independent
of the angle.
78. No. of radial nodes = 4 - 2 - 1 = 1.
Thus (d) is correct.
79. Radial nodes = 5 - 3 - 1 = 1
Node at infinity = 1
Angular node = 3
\ Total number of nodes = 5
80. No. of radial nodes for 5d orbitals = 5 - 2 - 1 = 2
Number of maxima in graph = no. of nodes + 1 = 3.
 Atomic Structure
EXERCISE - 2
1. Isotopes have same atomic number and different 13. N shell ⇒ n = 4
mass number. - 13.6 × 4 2
\ E4 (Bi3+) = = - 13.6 eV
2. The a-particles (He2+ ions) get deflected by the 42
Now, P.E. = 2 T.E. = - 27.2 eV
positively charged nucleus due to the electrostatic
forces of repulsion. - 13.6
14. P.E. of n = 2 of H atom = 2 × 4 = - 6.8 eV
3. Rutherford discoverd the nucleus by this experiment.
6.8
Now, for He+ if K.E. = 2 , T.E. = - 3.4
4. rnu = 1.25 × 10-13 × 641/3 cm = 5 × 10-13 cm \
- 13.6×4
=- 3.4 & n = 4
n2
ratom = 10-8 cm
0.529×9 o 0.529×16 o
V r3 125×10 -39 15. r3 (He+) = A and r4 (He+) = A
\ V Nu = 3nu = = 1.25 × 10-13 2 2
atom r atom 10 -24 0.529 o o
\ r4 - r3 = 2 (16 - 9) A = 1.851 A
5. A = 39 ⇒ n + p = 39 and n = (p+1)
\ (p + 1) + p = 39 ⇒ p = 19 0.529×16
16. r4 (Z) = Z
Also, e = 19 r1 (H) = 0.529
Now, n = (p + 1) = 20.

\ Z = 25 from the given options
6. In an element ZA X ,
Note: for Z = 16 it overlaps and doesn’t fit inside
no. of protons = electrons = Z the 1st Bohr orbit of H.
no. of neutrons = A - Z ro $ 4 RZ
28×60 + 29×30 + 30×20 17. r2 = R =
Z & ro - 4
Mavg = 110 RZ 9 9
= 28.64.
\ r3 = 4 × Z = 4 R = 2.25R
7. Atomic electrically neutral as well as nucleus n2
18. 0.529× 4 = 0.529
contains neutrons but neutrality is due toequal
number of protons and electrons. n ` =2
hc
8. Eabsorbed =
Ereleased =
hc hc
+ 19. rn \ n 2
^n 22 - n12h
m m1 m 2

\ Spacing is maximum when is
hc hc hc mm maximum.

\ = + &m= 1 2
m m1 m 2 m1 + m 2
1
9. Let no. of quanta absorbed and emitted be na and ne 20. E n \
n2
respectively.
\ spacing in terms of energy is maximum when
n a hc n e hc 1 1
\ Ea = 4500 and Ee = 5000 - is maximum.
n12 n 22
ne 1 na
Now, Ee = 0.5 Ea & 5000 = 2 × 4500 21. r \ n 2 and time period \ n3
n 5000 5
\ nea = 9000 = 9 = 0.55 r 1 T
since r12 = 4 & T1 = 8
1
2
10. Rest mass is not property of photons as they never 22. Bohr’s model cannot explain emission spectrum of
come to rest. multi electron species.
hc
11. E of quanta able to ionize Na = 23. More the energy of an electron, for ther a way from
2414 ×10 -10
the nucleus it can stay.
hc 6.02×10 23

\ I. E. of Na = -10 × kJ/mol
2414×10 103 24. E3 - E1 = 12.09 eV for H atoms.
. 497 kJ/mol.

Other permissible values of energy absorbed may be:
12. P.E. = 2 T.E. ⇒ T.E. = - 3.4 eV. Z = 2 : 12.09 × 4 = 48.36 eV
- 13.6
\ - 3.4 = Z = 3 : 12.09 × 9 = 108.81 eV
n2
⇒ n=2 and so on.

\ 1 excited state.
st
Chemistry
25. From III to I,
= R ×1 : 9 - 16 D
1 1 1

\
hc m
2 E - E = E = .....(1)
m 1 7R
From II to I =
m 144
4E E hc 144
3 - E = 3 = m1 ..... (2) m = 7R

Divide (1) and (2) 36. I.E. = x ⇒ E1 = - x

m x x
3= 1 \ E2 = - 4 and E3 = - 9
m
` m1 = 3m (d) x x 5x
\ E2 → 3 = 4 - 9 = 36
Z
26. v \ n & lower the value of n, higher the speed. 37. K.E.1 = hui = f and K.E.2 = 2hui - f
27. Since EC→B + EB→A = E C→A
\ K.E.2 = 2 K.E.1 + f
hc hc hc
Now, as intensity is doubled, the number of ejected

\ + =
m1 m 2 m3 electrons increases and hence photo current increases
m1 + m 2 1 but it might not necessarily double.
=
m1 m 2 m3 38. As l is doubled, Eincident is halved and hence stopping

mm
\ m3 = 1 2 potential decreases provided Eincident > f.
m1 + m 2
39. The number of photons emitted per unit time
28. I.E. of He+ = (I.E. of H) Z2 = 13.6 × 4 eV increases incident as higher intensity EM waves of

= 54. 4 eV suitable l are
29. He(g) —→ H(g)+ + e- 24.5 eV (given) 40. As intensity remains constant, the number of
electrons emitted are constant. But as l increases
He (g)
+
—→ H(g)2+ + e- 54.4 eV (Bohr’s Model)
Ein decreases and hence K.E.max and magnitude of

\ He(g) —→ H +
(g)
+ 2e-
78.9 eV (Adding the 2) stopping potential decrease.
30. Second series is Balmer series (n1 = 2) fourth line 41. ui = 4 × 1015 Hz
would be 6 → 2.
K.E. = 10.33 eV
31. 4 excited state is n = 5. So, 5 → 3 and 4 → 3 i.e., 2
th

\ f = hui - K.E.
lines in the Paschen sereis.
4×1015 ×6.6×10 -34
f = - 10.33 +
32. n2 - n1 = 2 and n2 + n1 = 4 1.6×10 -19

\ f = 6.2 eV

\ n2 = 3 and n1 = 1
hc
42. = f + 3qVo
= R4 ; 2 - 2 E & = 9
1 1 1 1 32R

\ m
m 1 3 m hc
= f + qVo
= RZ 2 ; 2 - ]n + 1g2 E
1 1 1 2m
33. hc
m n Solving we get f = ⇒ lo = 4l
4m
or y = = RcZ 2 c 2 ]n + 1g2 m
c 2n + 1
hc
m n 43. E = mc2 and also E =
m

if n > > 1 then (n + 1) . n and (2n + 1) . 2n \ mc =2 hc
m
2RcZ 2

\ y= h
n3 \ m=
cm
= R ;1 - 2 E & 2 = 1 -
1 1 1 1 1
34. 44. m =
h
& more the charge lesser the l
m n n Rm
2mqV
=b l& n =
1 Rm - 1 Rm

or, m1 q2 2
n2 Rm Rm - 1
\ = q = 1
m2 1
nh 2h
35. 2r = r ⇒ n = 4
\ l1 = 1.414 l2
n = 4
\ n2 = 4 → n1 = 3 is the transition that takes place.
 Atomic Structure
h
45. Dp = Dx ⇒ (Dp)2 = 4r n
` 2 + 2n - 15 = 0 ⇒ n = 3 or - 5
n
` =3
h

\ Dp = m Dv =
Mn +x = 1s 2 2s 2 2p6 3s 2 3p6 3d3
2 r
1 h x = + 4.

\ Dv = 2m r
56. By Aufbau Principle. {(n+l) rule}
h
46. 0.1 × 10 = p
-9
1 1
57. The quantum numbers + 2 and - 2 for electron
6.6 ×10 -34 spin represent two quantum mechanical spin states
` p =
0.1×10 -9 which have no classical analogue.
p = 6.6 × 10-24 kg m/s 58. By convention d z and pz are the orbitals which are
2

h assigned m = 0 for l= 2 and l= 1 respectively.

47. m = p . Hence l is inversely proportional to p.
59. No. of values of m is the no. of orbtials present in a
48. Eabsorbed = 1.5 × 13.6 eV given subshell. Thus, m = 2l+1 ⇒ l = 2
m-1

\ K.E. of emitted electron = 6.8 eV
60. Hund’s Rule says that pairing of electrons in an
h 6.625×10 -34
\l=
= atomic orbital will take place only after all the
2m ]K.E.g 2×9.1×10 -31 ×6.8×1.6×10 -19 degenerate orbitals have been singly occupied.
o

\ l = 4.70 A 61. Greater the atomic number smaller is the size of the
species. Thus, the graph with the highest probability
h 6.625 × 10 -34 at the least value of ‘r’ represents Li­2+ while the one
49. m = =
2m ]KEg 2×9.1×10 -31 ×4.55×10 -25 with the peak at largest value of ‘r’ represents H.

= 7.28 × 10 -7 m 62. For radial node, y = 0
50. E A - WA = K A ` E A - 2 = 4K B 6 ! 36 - 24
E A - 2 = K A E A + 0.5 - 4 = K B
⇒ 6 - 6s + s2 = 0 ⇒ s = 2
E B - 4 = K B E A - 3.5 = K B 2rZ
2

\ s = 3 ! 3 ⇒ 3a = 3 ! 3
o
h
m a2 = 2m × K ` E A - 2 = 4E A - 14
\ r1 = 2Z 3 + 3 h and r2 = 2Zo ^3 - 3 h
3a o ^ 3a
A

h2
4m 2A = m 2B = 2m × K ` E A = 4eV 3 3 ao
3a

\ (r1 - r2) = 2Zo ×2 3 = Z
B
EB = 4.5eV
1 K
` 4 = K B ` K A = 4K B \ VA = 2V, VB 0.5 V 1 :ZD 2
3
v
A 63. } = [(v - 1) (v 2 - 8v + 12)] e - 2
16 4 a o
h
51. Orbital angular momentum = , (, + 1) 2r
\ (v - 1) (v 2 - 8v + 12) = 0

for d-orbital l= 2
\ v = 1 or v 2 - v6 - 2v + 12 = 0
h
⇒ Orbital angular momentum = 2r 6
v (v - 6) - 2 (v - 6) = 0
52. No. of electrons for given value of l= 2 (2l+ 1) \ v = 2 or v = 6

and l can very from 0 to (n-1)
\ smin = 1
, = n-1

\ No. of electrons = / 2 (2, + 1)
a
& rmin = 2Z0
,=0

53. All p orbitals and d x - y , d z are located along the

2 2 2 and smax = 6
axis. 3a
& rmax = Z0
54. s-orbitals are spherically symmetric hence the
probability of finding an electron at a given distance 64. Since y becomes 0 for one value of r, therefore
is same in all directions. number of radial nodes = 1.
65. The probability of finding on electron in nucleus is
55. Mn = 1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d5
zero.

3.873 = n (n + 2)
15 = n2 + 2n
Chemistry
EXERCISE - 3
h k h k 11. 13.6 Z2 = 217.6 ⇒ Z2 = 16
1. m1 = = , m2 = =9
2mq (100) 10 2mq (81)
\ Z=4
h k
m3 = =7 12. No. of radial nodes = (n -l- 1) = 1
2mq (49)
m3 - m 2 ]1/7g - ]9/4g 10 × 2 13. Any d subshell can have maximum of 5 unpaired
\
m1
= ]1/10g = 63 = 0.317
electrons. so the maximum spin possible
1240 1
2. 3 E = 1282.5 eV = 0.96 eV = 5× ! 2 = S
This is the difference in levels 5 and 3 of atomic
5
\ Spin multiplicity = 2 | s | + 1 = 2 × 2 + 1 = 6.
hydrogen.
14. Longest wavelength of any series is the lowest
Now series limit means 3 → ∞ energy line of that series and has the lowest energy.
= (912) -1 c 2 m & = (912) -1 b 9 l & m For Lyman it is 2 → 1.
1 1 1 1
m n1 m
= 8208 Å 15. P.E. = - 6.8 eV = 2 × T.E.
- 13.6
3. 5th excited state ⇒ n2 = 6 \ T.E. = - 3.4 eV ⇒ = 3.4 ⇒ n2 = 4.
n2
For H-atoms: if n1 = 1 ⇒ UV region \ n = 2 ⇒ 1st excited sate.
if n1 = 2 ⇒ visible region h
16. 3 x = 3 p & 3 p =
if n1 = 3, 4, 5..... ⇒ IR region 4r
⇒ Maximum possible transitions are :- h
` m 3 v = 4r
6→5, 6→4, 6→3, 5→4, 5→3, 4→3
1 6.625×10 -34
⇒ Ans = 6. ` 3 v = -31 × 4×3.14
9.1×10

= 7.98 × 10+12 ⇒ y = 8
4. m1 = d n & V1 = 150
150 1/2
V1 m12 17. No. of volues of m = 2l+ 1
150 150 7-1
]1.41g2 ]1.73g2
V
& 1= = 75 V and V2 = = 50 V ⇒ l= 2 = 3

Hence, potential should be dropped by 25 V. 18. 3 → 2, 2 → 1, 3 → 1.
19. 5.27 = f + 0.27 ⇒ f = 5
12400
5. 3 E = 6200 = 2 eV.
20. Cu+ has 3d10 configuration. So, no. of electrons with
bs =- 1 l = 5
2 × 1.6 × 10-19 × n = 40 × 60 × 0.5
n = 3.75 × 1021 2
6. n = 2, l= 0, 1, 2, 3 = 1.09677×10 +7 ×Z 2 :1 - 4 D
1 1 1
21.
\ for last subshell, n = 2 and l= 3. 3×10 -8
4
\ n + l= 5
or, Z 2 =
3×3×1.09677×10 -8 ×10 +7
7. 2nd line of Balmer series ⇒ 4 → 2
⇒ Z2 = 4 ⇒ Z =2
1st line of Lyman series ⇒ 2 → 1 22. Maximum m = + 3 ⇒ l= 3 ⇒ n = 4
= R : 4 - 16 D & m B = 3R \ No. of waves by the electron in the fourth orbit = 4
1 1 1 16
\
mB
23. n l = 2 p r ⇒ n 200 = 400 ⇒ n =2
= R :1 - 4 D & m L = 3R
1 1 4

mL R R
24. E =- 9H =- 2H & n = 3 .
m n
\ B =4
mL No. of electrons that can be accomodated in n = 3 is
8. 4d orbital has 1 radial node, as (n -l- 1) = 1 2 × 32 = 18.

\ No. of peaks = no. of radial nodes + 1 = 2
\ No. of orbitals presents in n = 3 is 9. All these
9. b ro n4 l = ]rogH & n = 2
2 orbitals are degenerate as of single electron
Be 3+ species E3s = E3p = E3d and so on.
]5 - 2g]5 - 2 - 1g 25. 4→2 in He+ has same energy difference as 2→1 of H.
10. No. of lines = 2 =6
 Atomic Structure
EXERCISE - 4

10.
1. For He+ : x = R $ 4 ; - E & Rc 2 - 2 m = x
1 1 1 1 C contains 6 protons and 6 neutrons and weighs
12
6
n12 n 22 n1 n 2 4 12 amu. Mass of electron is negligible.

Now, if mass of neutrons is halved, total mass = 9
= R $ 16 ; 2 - 2 E & = 16× 4 = 4x
1 1 1 1 x

For Be3+ : amu.
m n1 n 2 m
3
2. Note that the question states that there is a single H
\ reduction in mass = 3 amu ⇒ 12 × 100 = 25%
atom. Thus, the maximum number of spectral lines 11. Factual.
emitted may be 3 for the transitions 5 → 4, 4 → 3
and 3 → 2. 12. Red end ⇒ we are talking about visible region of the
EM spectrum ⇒ Balmer series in an H atom.
3. The lowest value of ‘n’ for which d-orbital exists Thus, 3rd line from red end ⇒ 5 → 2
is 3.
13. Balmer series lines of only H atoms lies in the visible

\ Electronic configuration given is 3d6 4s2
region of the spectrum

⇒ 4th period.
14. K shell ⇒ n = 1
4. DE2→1=13.6 b 1 - 4 l eV and DE3→2=13.6× b 4 - 9 l eV
1 1 1 1
L shell ⇒ n = 2
3 5 M shell ⇒ n = 3 and so on
= 13.6× 4 eV = 13.6× 36 eV

Since electron makes transition into n = 2, therefore
\
3 E2 " 1 3/4 27 it is Balmer series.
3 E3 " 2 = 5/36 = 5
15. Lyman series is in UV region and Balmer series is in
5. Factural : K. E.max = huincident - f visible region in H atom.
6. Orbital angular momentum = 2r , ], + 1g = 2r
The 4 lines in uv region are : 2→1, 3→1, 4→1, 5→1
h 6h

3h
In the visible region we will have: 3→2, 4→2, 5→2
angular momentum in 3rd Bohr orbit = 2r

\ In the IR region: 5→4, 5→3, 4→3 ⇒ 3 lines
6 2
\ ratio = 3 = 3 16. Rest mass of photon =
h
cm
7. m = 1.73 = 3 = n ]n + 2g
= R :1 - 4 D = 4 R
1 1 3

For 1st line of Lyman:
\ no. of unpaired electrons, n = 1. m1
= R : 4 - 9 D = 36 R
Now Vanadium has Z = 23 and E.C. of [Ar] 4s23d3 1 1 1 5

For 1st line of Balmer:
m2
\ for 1 unpaired electron V must be in + 4 state
m m m 3 36 27
with an E.C. of [Ar] 3d1.
\ m12 = 2 & m12 = 4 × 5 = 5
m1
1
8. 4.25 - fA = TA and lA \ 17. Series limit of any series & 3 $ n1
TA
= R :1 - 3 D &
1 1 1 1
1 \ For Lyman series: =R

4.2 - fB = TB and lB \ mL mL
TB
= R; 2 - 3 E &
1 1 1 1 R

a lB = 2 lA For Balmer series: = 4
mB 2 mB

\ TA = 4 TB \ lL = 4 lB
Now, TB = TA - 1.5 ⇒ 3 TB = 1.5 18. Theoretical

⇒ TB = 0.5 eV and TA = 2 eV
19. Spectral lines of an element are unique and no 2

\ fA = 4.25 - TA = 2.25 eV lines of an element can have the same wavelength.
and fB = 4.2 - TB = 3.7 eV 20. y2 is the probability density i.e. probability per unit
9. 2.1 g ion of Cl- ⇒ 2.1 mole Cl- ions volume.
Now, 1 Cl- ion has 18 electrons 21. In H atom

\ 2.1 mole Cl contains 18 × 2.1 × NA electrons
- Elyman > Ebalmer > Epaschen ..........

\ llyman < lbalmer < lpaschen

\ l1 < l2 < l3 < l4
Chemistry
o o 36. In H atom, or any other H like species, the energy of
22. For n = 10, r = 0.529 × 102 A = 52.9 A
the electron depends only on the value of ‘n’. Thus,

\ 2 × p × 52.9 = 10 l we can say that for such species (E4s = E4p = E4d =

\ l = 33.22 A
o
E4f) > E3s = E3p = E3d and so on.

23. I : 1 radial node ⇒ 3p 37. Factual.

II : Zero radial nodes ⇒ 3d 38. Heisenberg’s uncertainty principle is valid for both
microscopic and macroscopic moving objects.

III : 2 radial nodes ⇒ 3s
However, it is significant only for microscopic
24. Longest wavelength of Paschen series ⇒ 4 → 3 objects.
\ R $ 1 2 $ : 9 - 16 D = R $ 2 2 $ ; 2 - 2 E
1 1 1 1 h
39. 3 x $3 p $ 4r : by definition.
n1 n 2
⇒ n1 = 6 and n2 = 8. dp
Now, dt = dF⇒ dp = dF.dt
25. y2 is maximum at nucleus and 3p r2 y2 is zero.
dE
hc And dF $ dx = dE & dx = dF
26. E = hu = = hc y
m dE
hc \ dp $ dx = dF $ dt $ dF

Also, Etot = n , but energy of 1 quantum is
m
= dE $ dt
independent of n.
27. \ -particles being much heavier than the electrons \ Heisenberg’s principle may be written as
have a high penetrating power, which is also because h
3 E $3 t $ 4r
of the high speed of \ -particles.
40. In option (c) if l= 2 then ‘m’ cannot be - 3.
28. All 4 statements were conclusions drawn from the
\ -scattering experiment. 41. a) s-orbital is spherically symmetric
29. Bohr’s model doesn’t talk about probabilities. Hence b) shape of orbital is given by ‘l’ not ‘m’.
statement (a) is incorrect. c) Since l= 0, therefore orbital angular momentum
30. Bohr derived that = 0 for 1s, 2s, 3s etc.
n2 Z Z2 d) Electrons in different orbitals have different
rn \ Z , v n \ n and freq \ 3 velocities.
n
Kq q KZe 2 Z3 42. For 3d orbitals: n = 3, l= 2, m = -2, -1, 0, 1, 2 and
]n /Zg
Now, Force = 2 & F \ 2 2 F \ 4
1 2

r n s = + 0.5
31. 2nd I.E. of He = 13.6 × 22 eV 43. If ‘l’ of two orbitals are same, then their orbital

3rd I.E. of Li = 13.6 × 32 eV angular momentum is also same.

1st I.E. of H = 13.6 eV 44. b) if n = 3 then l can be 0 or 1 or 2.
o o

9
r3 of H = 0.529 × 9 A and r3 of Li2+ = 0.529 × 3 A
d) if l= 2 then m can be 0 or + 1 or + 2.

n,land m are the 3 Q.N. which can define an orbital. 45. All 3 statements are correct.
Z2 Z2 46. All 3 statements are correct.
32. K.E. K.E. \2 , P.E. \ - 2 , rn = ro $ n
2
n n
47. electron cloud density of px orbital

Energy levels or orbits are not equally spaced. The
distance between the orbits keeps increasing with n. 48. (2) is the excited state electronic configuration of (1)
33. Bohr’s model can be applied to all single electron 49. (b) For n = 2 we can have 4 orbitals but they all do
species. not have different energy levels. Out of the 4, 3
are degenerate and have different energy from
n3
34. Frequency \ the 4th.
Z2
(c) M ⇒ n = 3 and can accommodate a maximum
35. For electronic transition from n → 1, no. of spectral
n ]n - 1g
of 18 electrons.
lines is given by 1 + 2 + 3 + ..... (n - 1) = 2
 Atomic Structure
50. Quantum numbers are derived by solving the 2.178×10 -11
Schroedinger’s wave equation. For a multi-electron 62. T.E.3 = - 9 ergs
species, the energy of an electron can be estimated a P.E. = 2 T.E.
by the value of (n +l). Azimuthal Q.N. does not 2
\ P.E. = - 9 ×2.18×10 -11 ergs
tell us anything about the motion of the electron.
= - 4.84 × 10-12 erts
51. Shape of orbital is given by azimuthal Q.N. Also,
h
electrons in an atom move with different velocities. 63. m =
2m ]K.E.g
52. Due to the presence of electrons in them the orbital
h
ex-orient themselves to minimize the energy in a 64. m =
2m qV
magnetic field.
6.625×10 -34
53. Spin of electron does not affect the angular 5 × 10-12 =
2×1.67×10 -27 ×1.6×10 -19 ×V
momentum and can be represented as clockwise and
Solving we get V = 32.8 V
anticlockwise.
65. m = 75 × 10-3 kg
54. Factual.
h 6.625×10 -34
55. E4s < E3d. If n = 2 the there are 4 orbitals which can Dx = l = mv ⇒ Dx =
75×10 -3 ×4
accommodate a maximum of 8 electrons. If n = 5 h 6.625×10 -34
then maximum no. of electrons in it is 2n2 = 50. \ Dv = 4rm 3 x =
4×3.14×75×10 -3 ×2.2×10 -33
56. If n = 4 and m = - 2, it may be a 4d or 4f orbital. The = 0.32 m/s
1 1
spin of the electron may be + 2 or - 2 . 66. No. of electrons possible in an orbital = 4
57.
l= 1 to (n + 1)
, ,
electron p q x y z
m = - 2 to + 2
n 3 3 3 3 3
For n = 1 ⇒ l= 1, 2 i.e. 1A, 1B
m 0 0 1 1 1
For n = 2 ⇒ l= 1, 2, 3 i.e. 2A, 2B, 2C
l 0 0 -1 +1 0
For n = 3 ⇒ l= 1, 2, 3, 4 i.e. 3A, 3B, 3C, 3D
s - 1
2 + 1
2 + 1
2 + 1
2 + 1
2
Now, for l= 1 : m = - 1 2 , + 1 2
58. K.E. of photo electron varies with u and l but is
l= 2 : m = -1, 0, 1
constant with intensity.

3 1 1 3
l= 3 : m = - 2 , - 2 , + 2 , + 2
59. A1 = p r12 An = p rn2 and rn = r1n2
l= 4 : m = -2, -1, 0, 1, 2

\ A subshell has 2 orbitals
\ b An l = & ln b An l = 4ln (n)
2 4
A rr n A
1
1 rr12 1 B subshell has 3 orbitals
\ Graph of ln b An l vs ln (n) is a straight line with
A
\ E.C. would be as follows:

1
1A 8
1B 12
2A 8
2B 12
3A 8
.....
slope = 4 and this line passes through the origin. 14444244443 14444244443
1st period 2 nd period

60. Energy of electron depends on (n + 1) in case

Therefore, number of elements in 2nd period are 20.
of multi electron species while in case of single
67. No. of elements in 1st period = 20
electron species, it depends on only the value of ‘n’.

\ 2nd period beings with Z = 21. i.e. Sc.

P.E.1 = - 2 K.E.1 and P.E.2 = - 2 K.E.2 ⇒ |DP.E.|=
2|DK.E.| 68. For Z = 100

It is practically not possible for an electron in an
excited state to absorb another photon.
o
61. r3 = 0.529 × 9 A

\ 2 p r3 = 3 l ⇒ 2 p 0.529 × 9 = 3 l

\ l = 9.96 × 10-10 m . = 10-9 m


\ outermost configuration = 4A8 3C16
Chemistry
69. For E subshell, l= 5 Z2
74. T.E. =- 13.6eV ⇒ as n increases, T.E. increases.
\ No. of orbitals = 6 n2
Z2
\ No. of electrons = 24 (as 4 electrons in each
Frequency of revolution \ 3 ⇒ as n increases,
n
orbital) frequency decreases.
70. Shortest wavelength is emitted for highest energy. Z3

Acceleration \ 4 ⇒ as n increases, acceleration
n
\ D has shortest wave length emitted decreases
71. Ionization potential is the amount of energy absorbed
n2
radius \ Z ⇒ as n increases, radius increases
by a gaseous atom to lose the aoutermost electron.
75. a) 3 radial nodes ⇒ 4s / 5p but for p orbitals, y < 0
72. B = 4 → 3 ⇒ EB = 13.6 b 9 - 16 l eV
1 1
at r = 0
= 13.6 × 9×16 eV
7
b) 3 radial node ⇒ 4s and 5 p
c) For p and d orbitals angular probability
= 1.983 eV
distribution depends on q and f
\ EB = 1.983 × 1.6 × 10-19 J
d) S - orbital is spherically symmetric, hence no
= 3.18 × 10-19 J energy is released.
planar node.
22
73. a) U1, 2 = - 2 × 13.6 × = - 13.6 × 8 eV 76. a) Orbital angular momentum
12
K1, 1 = + 13.6 eV = 2r , ], + 1g = 2 2r & , = 1 & p orbital.
h h
\ Ratio = - 8 : 1 b) Bohr’s model ⇒ classical mechanical

22
b) r2, 1 = ro 1 = 4 ro
12 r
and r1, 2 = ro 2 = 2o c) 5 degenerate orbitals ⇒ d-orbitals

\ Ratio = 8 : 1 d) N shell ⇒ n = 4 ⇒ no. of waves made by the

electron = 4
2 4

c) V1, 2 = Vo 1 = 2 Vo and V2, 4 = Vo 2 = 2 Vo
\ Ratio = 1 : 1
n3 T1,2 1

d) T \ 2 & T = 8
z 2,2

5 5. Number of radial nodes = n – l – 1

1. Tv = 90× 100
= 3 – 0 – 1 = 2
= 4.5 m/s
h Therefor corresponding graph is (IV)
Tv $ Tx = 4rm
Hence answer is (c)
h 6.63×10 -34
Tx = 4rm $ Tv = 4×3.14×0.01×4.5 6. 2 pr = nl
= 1.17 × 10-33 n2

2p × a = nl
2. E = W + K.Emax Z 0
K.Emax = E - W 42

2p × a = 4l
hc 1 0
= - 4.41 × 10-19 l = 8pa0
m
6.63 ×10 -34 × 3 ×108
= - 4.41 × 10-19
7. v = R H c- m cm -1
1 1
300 ×10 -9
82 n2
= 222 × 10-21 joule
R R R R
= 64H - 2H = 2H + 64H
3. Based on “n + l” rule only (II) has pair of electron in n n
degenerate orbitals. Comparing it with general straight line equation,
hc y = mx + c, we get
4. Energy of one mole of photons = × NA
m R
-34 Slope (m) = – RH, Intercept (c) = 64H
6.63 # 10 ×3×10 8
= × 6.02 × 1023
300×10 -9

= 399.13 × 103 Joule/mole ≈ 399 kJ mol-1
 Atomic Structure
8. (i) Higher the value of ‘l’, lesser is the penetration
13. Given, in the question E = - 2.178 × 10-18 J ; 2 E
Z2
of the orbital. Thus, given statement is correct. n
For hydrogen Z = 1,
(ii) Size of orbit depends on value of ‘n’. Thus,
So, E1 = - 2.178 ×10-18 J ; 2 E
incorrect. 1
1
nh
(iii) Angular momentum = 2r and for ground state
E2 = - 2.178 ×10-18 J ; 2 E
1
n=1. Thus, given statement is correct. 2
Now, E1 - E2
(iv) As value of azimuthal Q.N. increases, y vs r
i.e. DE = 2.178 ×10-18 c 2 - 2 m =
1 1 hc
graph has more number of peaks and hence 1 2 m
shift towards lower value of r. Thus, incorrect
2.178 ×10-18 c 2 - 2 m =
-34
1 1 6.62×10 ×3.0×108
statement.
1 2 m
9. The graph given in option (c) is incorrect as the m . 1.21×10 m -7

emission will begin only once n > n0. The graph for
(c) should look similar to that of (a) because E a n. 14. According to Bohr’s model,
nh n2 h2
10. Radius of nth Bohr orbit in H-atom = 0.53 n2 Ao mvr = 2r & (mv) 2 =
4r 2 r 2
Radius of 2nd Bohr orbit = 0.53 × (2)2 = 2.12 Ao 1 n2 h2
⇒ KE = 2 mv2 = ...(i)
13.6 8r 2 r 2 m
11. \ E n =- eV Where, n = 1, 2, 3...
n2 Also, Bohr’s radius for H-atom is, r = n2a0
- 13.6
In excited states, E2 = 4 =- 3.4 eV Substituting ‘r’ in Eq. (i) gives
h2 h2
12. Given, atomic number of Rb, Z = 37 KE = 2 2 2 When n = 2, KE =
8r n a0 m 32r 2 a02 m
Thus, its electronic configuration is [Kr]5s1.
So, the quantum numbers are n = 5, l = 0, (for
s-orbital) m = 0 ( a m = + l to - l), s = + 1 /2 or - 1/2.

- 13.6 # 22 3. At d = d0, nucleus-nucleus & electron-electron

1. - 3.4 = repulsion is absent.
n2
n = 4 Hence potential energy will be calculated for 2 H
 = 2 atoms. (P.E. due to attraction of proton & electron)
Subshell = 4d - Kq1 q 2 ]9 ×109g^1.6 ×10 -19h2
P.E. = =
Angular nodes =  = 2 r
]Bohr radiusg
0.529 ×10 -10
Radial nodes = n -- 1 = 4 - 2 -1 = 1 = -4.355 × 10-21 kJ
h 6.6×10 -27
For 1 mol = -4.355 × 10-21 × 6.023 × 1023
2. Momentum of photon = = gm cm s-1
m 330×10 -7 = -2623.249 kJ/mol
Momentum of 1 mole of He-atoms = mDv
For 2 H atoms = -5246.49 kJ/mol
h
\ mDv = NA ×
m r r
6×10 23 ×6.6×10 -27
4×Tv = e
 
e
330×10 -7
6×6.6×10 2 do
Tv = 33×4 = 30 cm s-1
\ Change in velocity of He-atoms = 30 cm s-1
Chemistry
4. n = 4 13.6Z2
| m | = 1 ⇒ l may be 1 | 2 | 3 and m = +1 or -1 7. & 8. KE = eV / atom
n2
\ 2 electrons each of 4p, 4d and 4f can have 2 # 13.6Z2
PE = eV / atom

1
n = 4, | m | = 1 and s = + 2 n2
⇒ Total 6 electrons n2 %
Radius 0.529 Z A
1242 nh
5. z = 300 = 4.14 eV Angular momentum of electron (mvr) = 2r
\ Li, Na, K, Mg show P.E.E. 9. 2s orbital has are radial node and y(r) = 0 once
6. n = 3 can accommodate maximum of 18 electrons of 10. 1s has zero radial nodes
1 1
which 9 will have s = + 2 and 9 will have s = - 2 11. E2 → 4 = 2.55 eV E2 → 6 = 3.022
 Periodic Properties

Chapter 3 Periodic Properties

INTEXT EXERCISE: 1
1. Li, Na, K were found to be triads. 6. Li, Na, K were triads suggested by Dobereines not
Mendeleev
2. 2 and 3 periods were called short periods. 1
nd rd st

period is very short period and not short period. 7. 3rd Period of group IV(A) ⇒ Si.
3. Previously valency of Be was thought to be 3 but 8. Mendeleev did not give any reason for the periodicity
Mendeleev corrected the valency as 2 and atomic in properties. So, both statements are true but they
weight was corrected from 13.5 to 9. are independent.
4. Eka-Silicon ⇒ Germanium and Eka-Aluminum ⇒ 9. Refer Periodic Table.
Gallium
10. Refer Periodic Table.
5. Factual. Mendeleev corrected the atomic weights of
Be and In.
INTEXT EXERCISE: 2
1. Chemical properties are similar due to similar 6. Only Lanthanoids are referred to as Rare Earth
valence shell configuration. Elements.
2. Modern P.T. has 7 periods and 18 groups. 7. He has 1s2 configuration. Others have ns2 np6
configuration.
3. By definition
8. All non-metals are present in the p-block. Also all
4. Representative elements constitute groups 1, 2 and
the matalloids are in the p-block.
13 to 17. They may gain, lose or share electrons to
attain noble gas configuration. 9. By definition.
5. Transition elements are d-block elements except 10. Fe : [Ar] 4s2 3d6 ⇒ [Fe3+] : [Ar] 3d5
group 12 (Zn, Cd, Hg).

Mn : [Ar] 4s2 3d5 ⇒ [Mn2+] : [Ar] 3d5
INTEXT EXERCISE: 3
-
1. More the number of bonds, stronger the bonds and 4. Ionic Radii order N3- > O2- >F . (Isoelectronic)
hence shorter the bond length.
5. Fe3+ should be smaller than Fe2+.
We know that
-
Vand. Radius > Met. Radius > Cov. Radius. 6. Order : S2- > O2- > Cl > Na+
Greater the positive charge on the ion, smaller is the 7. Covalent radius should be smaller than metallic
ion and greater the negative charge on the ion, larger radius.
is the ion.
8. Lanthanoid contraction causes similarity in
2. By definition, Vanderwaal’s radius is estimated in properties of La and Hf.
the solid state.
9. Anion is larger than neutral atom and cation is
3. Covalent Radius should be much smaller than smaller.
Vanderwaal’s Radius.
10. Lanthanoid Contraction causes reduction in size.
Chemistry
INTEXT EXERCISE: 4
1. Since K is below Na in the same group of the period
table therefore I.P. of K < I.P. of Na.
2. For a sudden jumb between 2nd and 3rd I.P., the element
should be attaining a noble gas configuration after 2
electrons. Thus, outermost configuration should be
ns2.
3. I.E. increases from Group 1 to Group 2 in the same
period.
4. By the same logic of Q.2 above, this element should
have ns2np1 configuration in the valence shell.
5. I.E. increases from Group 1 to Group 2 in the same
period.
6. Ca, Al and Si belong to the same period and their
I.E. order is Al < Ca < Si. Now Mg belongs to the 2nd
period and hence will have higher I.E. value than Ca.
The order of I.E. is Al < Ca < Mg < Si: Remember
INTEXT EXERCISE: 5
1. 1 and 3 processes are exothermic while the other
st rd
two processes are endothermic.
Since (EA)S > (EA) O, Therefore maximum energy
- -
released for S + e → S .
-
2. | I.E. (F ) | = EA of F |
3. Adding the 1st electron is endothermic for noble
gases alkaline earth metals and nitrogen.
4. The EA of group 16 follows the order S > Se > Te > O.
+
5. | IP (X) | = | EA of (X ) |
INTEXT EXERCISE: 6
1. According to Pauling
D l = 0.208 ! AB - ! AA . ! BB
2. More the D l greater the polarity bonds.
3. l P = 1.35 l M - 1.37
or, 1.35 l M = l P + 1.37
or, l M = b
l P + 1.37 l2
1.35
4. F and H are the two elements used as reference to
calculate EN values in Pauling Scale.
5. By definition of Mullikan’s Scale Electronegativity.
7. N has 2s2 2p3 configuration and is extra stable due to
half filled p orbitals.
8. Iron is the largest of the given atoms having high
electropositive character. Thus, Fe has the lowest
I.E.
9. O+ : 1s2 2s2 2p3
F+ : 1s2 2s2 2p4.
Thus I.E.2 of O will be higher than IE2 of F, as O+
attains half filled configuration.
Note: I.E.2 of O is greater than I.E.2 of N although
I.E.1 of N > I.E. 1 of O.
10. Z = 9 ⇒ 1s2 2s2 2p5 ⇒ F (A)
Z = 10 ⇒ 1s2 2s2 2p6 ⇒ Ne (B)
Z = 11 ⇒ 1s2 2s2 2p6 3s1 ⇒ Na (C)
Z = 12 ⇒ 1s2 2s2 2p6 3s2 ⇒ Mg (D)
\ I.E.1 order is B > A > D > C.
6. Adding first electron to a neutral atom is generally
an exothermic process while adding subsequent
electrons or removing electron from neutral atom is
endothermic.
7. EA is general decreases down the group except from
2nd period to 3rd period.
8. By definition of electron affinity.
9. EA by definition is at absolute zero temperature and
hence cannot be measured directly.
10. EA has units of energy per mole.
6. The relation given in Q.3 above is approximated as
l M = 2.8 l P
7. Mullikan’s scale only accounts for the first I.E. and
E.G.E. or E.A.
I+E
8. l M = 2 when I and E are taken in eV. If these
I+E
are taken in kJ/mol then l M = 544
9. As we more across a period EN increases.
10. Highly electronegative elements (eg F, Cl, O etc)
easily get reduced and form anions. Hence, they are
good oxidants.

INTEXT EXERCISE: 7
1. The oxide is CO2 and the elements is C.
2. Acidic character of oxides increases from left to
right across a period.
3. Oxide of Al is amphoteric while N2O5 on dissolving
in water forms HNO3.
4. Basic character decreases across a period and
increasess down a group.
5. Only 2nd period elements of first 3 groups show
diagonal relationship with 3rd period elements of
subsequent groups.
6. Li and Mg are diagonally related, hence Li+ and
Mg2+ have similar polarizing powers.
7. N has half filled configuration. Thus I.P.1 of N is
greater than that of oxygen.
8. X = K, Y = Rb, Z = Cs, IE1 decreases as we move
down group 1.
EXERCISE - 1
1. Ce-58 is an f-block element (lanthanide).
2. Modern Periodic Table contains 7 Horizontal and 18
vertical series.
3. It does not help to predict the stable valency states of
the elements.
4. Elements (a), (b) and (d) belong to the same group
since each one of them has two electrons in the valence
shell. In contrast, element (c) has seven electrons in
the valence shell and hence does not lie in the same
group in which elements (a) (b) and (d) lie.
5. Germanium is a metalloid.
6. The element with Z = 43 lies in the 5th period.
Therefore, the atomic number of the element which
lies just above it in the 4th period should be 43 – 18
= 25. As such, its electronic configuration is (a).
7. For transition elements, d-sub shells are not filled
with electrons monotonically (one at a time ) because
of extra stability of d5 and d10 configurations. Besides
these, there are many other exceptions, e.g. Nb, Mo,
Ru, Rh, Pd etc.
8. Element with Z= 33 lies in VA or 15th group.
9. Within a period from left to right, atomic volume
first decreases and then increases for noble gases.
10. Cerium is the most common lanthanide.
Periodic Properties
1
9. Moles of Mg = 24 = 0.04166
Mg —→ Mg+ + e- 740 kJ/mol.
1
\ Energy required for this step = 24 # 740 kJ
= 30.833 kJ.
Amount of energy left = 50 - 30.83 = 19.16 kJ
M g+ $ Mg 2+ + e - 1540 kJ/mol .
\ Number of moles of Mg+ that can be ionized by
19.16
the remaining energy = 1540 = 0.0124.
\ Moles of Mg2+ formed = 0.0124
0.0124
\ % of Mg 2+ = 0.04166 # 100 = 29.76%
\ % of Mg+ = 70 %
10. Factual.
11. The atomic number of the element with electronic
configuration 1s2 2s2 2p6 3s2 3p3 is 15. It belongs to
the 3rd period. Therefore, the atomic number of the
element which lies just below it in the 4th period is
15+ 18 = 33
12. If the configuration of a transition element X is [Ar]
d4 in its +3 oxidation state, then the configuration
of the neutral metal X is [Ar] 3d5 4s2 and hence its
atomic number must be 18 + 5 + 2 = 25.
13. [Ar]4s23d4 ⇒ Element with Z = 24, i.e. Chromium.
Its correct electronic configuration is [Ar]4s13d5.
14. In accordance with aufbau principle, gadolinium
with Z = 64 must have configuration (c).
15. Both As and Bi belongs to group 15 of the periodic
table and therefore, posses five electrons in the
outermost orbit.
16. Anion is larger than parent atom and that of cation is
smaller than parent atom.
17. Atomic radius of neon being Vanderwaal’s radius
is much higher than that of fluorine which is its
covalent radius.
18. Atomic size decreases along a period, but noble
gases have much larger size than other elements of
the same period.
19. Amongst isoelectronic ions, cations are smaller than
anions.
Chemistry
- -
20. Na+ and F ions are isoelectronic, therefore, F has
the largest and Na+ has the lowest size. Further, Al
with higher nuclear charge has lower size than Mg.
Thus the overall order is : Na+ < Al < Mg < F-.
21. Na- > Na > Na+. Refer Q.16 above.
22. Amongst isoelectronic ions, the size of the cation
decreases as the magnitude of the charge increases.
23. The atomic radii of C, O, F which lie in the second
period increase in the order: F, O, C. Further, the
atomic radii of F, Cl, Br which lie in the same group
(group17) increase in the order : F, Cl, Br. Thus, the
overall increasing order is F, O, C, Cl, Br.
24. Since atomic radii increase down a group, therefore,
the atomic radii of Na, K and Rb follow the sequence
Na < K < Rb.
Further, the atomic radii decrease along a period.
Since the atomic number of Mg is 12 and that of Na
is 11, therefore, the atomic radius of Mg is lower
than that of Na because of increased nuclear charge.
Thus, the over all sequence is : Mg < Na < K < Rb.
25. K+, Ca2+ and Ti4+ have all argon gas configuration i.e.
they have three shells. On the other hand, Al3+ has
neon gas configuration, i.e. it has only two shells.
Since the increase in size due to the addition of an
extra shell is not compensated by the contractive
effect of an additional positive charge, therefore, the
ionic radius of Al3+ (0.51Ǻ) is smaller than that of
Ti4+ (0.68Å).
-
26. C1 and S are isoelectronic with Ar while Na and
2- +
F- are isoelectronic with Ne. Therefore, S2- has the
largest size.
-
27. Na+, Mg2+, F are isoelectronic ions. Amongst
isoelectronic ions,the ion with the highest positive
charge has the smallest size, i.e. Mg2+.
28. H belongs to first period while Li belongs to second
period. Therefore, size of Li+ > H+. Both Li+ and H
- 40. Metallic character decreases in a period and
are isoelectronic. Thus the sequence of decreasing
-
order of the size is H > Li+ > H+.
29. P5+ has more effective nuclear charge than P3+ and is
smaller in size than P3+.
30. Atomic radius decreases on going from left to right
in a period.
-
Thus, size of O > F. As O2- and F are isoelectronic,
-
therefore, size of O2- > F .
31. Among the isoelectronic species, the size increases
as the negative charge increases.
32. Like covalent radii, Vanderwaal’s radii also
decreases along a period from left to right due to
increasing nuclear charge. Now N, O, F and Ne
belong to the same (2nd) period. Therefore, their
Vanderwaal’s radii will increase in the order: Ne,
F, O, N, Further, since Cl lies in third period, its
Vanderwaal’s radius would be largest. Thus the
overall increasing sequence is: Ne, F, O, N, Cl.
33. Rb (2.11Å) is much larger than O(0.73Å). since the
size of cation is smaller while that of the anion is
larger than the parent atom, therefore, the sizes of
Rb+(1.48Å) and O2- (1.45Å) coincidently match
each other.
The sizes of Li+ (0.68Å) and Mg2+ (0.65Å) being
diagonally related are nearly the same. The sizes
of Fe (1.17Å) and Co (1.16Å) are nearly the same
because the contractive effect of the increased
nuclear charge is counter balanced by increase in
size due to increased shielding effect of the inner
electrons.
34. Amongst halogens the outermost electron of I is
most loosely bound and hence can be lost most
readily.
35. Extra stability of the exactly half-filled p-orbitals.
36. Just sufficient to cause an electron to escape from
isolated gaseous atom.
37. With increase in atomic number, the atomic size
increases both in 1st (group 1) and VII group (group
17).
38. IE1 of N is higher than that of O.
39. IE1 of Mg is higher than that of Na because of
increased nuclear charge and also that of Al because
in Mg a 3s-electron has to be removed while in
Al it is the 3p-electron. The IE1 of Si is, however,
higher than those of Mg and Al because of increased
nuclear charge, Thus, the overall order is Na < Mg >
Al < Si.
increases in a group.
41. H (g)
IE
H + (g) + e - . H+ nothing but a proton.
42. IE of element with electronic configuration (d)
is lowest because of its biggest size. Among the
remaining three elements of the same period (3rd),
IE of element with electronic configuration (b) is the
highest due to greater stability of the exactly half-
filled 3p- subshell.
43. Bigger the size of the atom smaller will be its IE.
44. Within a group, IE decreases from top to bottom.
45. IE3 > IE2 > IE1.

46. IE2 of K is much higher than those of Ca and Ba
because in case of K, the second electron has to be
removed from noble gas (argon) core while this is
not so in case of Ca and Ba. Out of Ca and Ba the IE2
of Ca is higher than that of Ba due to smaller size.
The overall sequence is K > Ca > Ba.
47. The four elements (Li, Be, B and C) belong to the
2nd period. As we go form Li → Be, IE1 increases
due to smaller size and increased nuclear charge.
The IE1 of B is, however, lower than that of Be
because in B a 2p-electron is to be removed while
in Be a 2s-electron is to be removed. The IE1 of C
is however, higher than those of B and Be due to
increased nuclear charge. Thus, the overall order is :
C > Be > B > Li.
48. Argon has the highest ionization potential as it is a
noble gas.
49. After the removal of an electron from C, N, O and F,
their electronic configurations are:
C + (1s 2 2s 2 2p1), N + (1s 2 2s 2 2p1x 2p1y)
O (1s 2s 2p 2p 2p ) and
+ 2 2 1
x
1
y
1
z 59. Ionization energy decreases, all others increase.
+ 2
F (1s 2s 2p 2p p ) 2 2
x
1 1
y z
Since O gives a stable electronic configuration with
+
exactly half- filled 2p-subshell, therefore, IE2 of O
is higher than that of F. The IE2 of C because of the
larger size is lower than that of N. Thus, the overall
order is O >F > N > C.
50. Argon (3s2 3p6 ) is most stable and has least tendency
to add on electron.
-
51. Molecules F2, Cl2 and anion F (due to inert gas Ne
configuration) have almost zero electron affinity.
52. Cl has the highest E.A. value among halogens. EA
is general decreases down the group except for 2nd to
3rd periods in the p-Block.
53. Amongst O, S and Te the EA of O is the smallest due
to inter-electronic repulsions present in its relatively
compact 2p-subshell. EA of Te is,however, smaller
than S due to its greater size. Thus, the overall
sequence is S > Te > O.
EXERCISE - 2
1. The highest principal quantum number of an element
is its period number.
2. The d-block has 10 columns, because a maximum
of 10 electrons can occupy all the orbitals (5) in a
d-subshell.
3. Three complete subshells ( 1s2 2s2 2p6).
Periodic Properties
54. O(g)
+ -
$ O(g)
Z=8 Z=8
- -
e =7 e =9
55. Elements (a) and (b) are alkali metals whereas (c)
and (d) are alkaline earth metals. Amongst alkali and
alkaline earth metals, alkali metal with the biggest
size is the most electropositive element.
56. ns2 np5 i.e. halogens are most electronegative in
respective periods.
57. Pauling Scale is based on bond energies and
Mullikan Scale is based on Ionization Potential and
electron Affinity.
58. 9 = EC - H - E H - H × EC - C
1
98.8
= - (104.2) ×83.1) 2
= 5.75 k cal.
1
X C - X H = 0.18 9 = 0.18 (5.75) 2 = 0.43.
\ X C = 0.43 + X H = 0.43 + 2.1 = 2.53
60. Ionic radius increases.
61. Same number of electrons in the outermost shell of
their atoms.
62. Transition elements generally show atleast 2
valencies.
63. Ionic radius of Fe3+ (0.64Å) is < that of Mn3+ (0.66Å).
Other properties vary as indicated.
64. On descending a group, valence electrons remain
the same.
65. Size of an anion is larger than the corresponding
atom and the ionization energy generally increases
as the size decreases with increasing atomic number
in a period. EN is tendency to attract a shared pair of
electrons.
66. IE1 of Li < Be > B < C or IE1 of Li < B < Be < C.
4. 4f orbitals are filled for Lanthanoids and 5f for
actinoids.
5. Due to stability of the [Rn] core, the filling of 5f
orbitals does not begin until there are two electrons
in the 6d-orbital and similarly, due to stability of the
[Xe] core, the filling of 4f-orbitals does not occur
until there is one electron in the 5 d-orbital. As such,
the only true d-block element is (d).
Chemistry
6. Yes, hydrogen can be placed in 1st group on the basis
of its valency +1 (H+).
7. The exceptional outer electronic configuration of Pd
suggests that, in principle its configuration should
have been 4d8 5s2. As such it lies in 5th period and
group 10.
8. Silver belongs to Vth period. So the atomic number
of elements placed above and below will be 47 – 18
= 29 and 47 + 32 = 79 respectively.
9. Une stands for unnilennium which is the IUPAC
name for 109.
10. Z = 118 [Rn]86 5f14 6d10 7s2 7p6 ; as last electron
enters in p-subshell, it belongs to p-block. Thus its
group number will be 10 + 2 + 6 = 18. Hence the
element is a noble gas.
11. More compact an orbital greater is its screening
effect.
12. For isoelectronic species, as Z increases, Zeff
increases (and vice versa).
13. The atomic sizes of Li Na, Ca, S and Xe are 1.34Å,
1.54Å, 1.74Å, 1.02Å and 2.09Å respectively Thus,
the atomic size of S (1.02Å) is approx. half than that
of Xe (2.09Å). (Factual)
14. Sn4+ > In+ > Sn > In. Higher cationic charge ⇒ more
Zeff.
15. For isoelectronic species, as Z increases, Zeff
increases (and vice versa).
16. For a given element rcovalent < rmetallic < rvanderwaal
17. The size of K will be higher than that of K+ while
-
size of F will be lower than that of F .
18. On moving left to right in a period, atomic radii
decreases due to increase in Zeff and addition of
electrons to the same outermost shell.
19.
V >S Cl -3 > W
- 2-
Br 14444>
24444 N 3-
4th period 3rd period 2nd period
(isoelectronic)
20. Vanderwaal’s radius is considered in case of neon,
which normally has a large value. So, atomic radii
of neon is greater than that of fluorine.
21. Ionic radii in aqueous solution is equal to size of
hydrated ion.
Hydration is highest in smaller ion if charge is same.
22. Isoelectronic species how the same valence principal
quantum number. for such species more the Z,
smaller the size.
- - -
23. I > Se2- > Br > O2- > F . I is in 5th period and Se is
in 4th period.
24. Atomic radius increases on moving top to bottom in
a group due to increasing number of shells. However,
it decreasing on moving left to right in a period due to
increasing Zeff and addition of electrons to the same
shell. Nb (4d) ≈ Ta (5d) (Lanthanoid Contraction).
For isoelectronic species, ionic radius
1
\ nuclear charge
So correct order is Y3+ < Sr2+ < Rb+.
25. Orbitals bearing lower value of n will be more closer
to the nucleus and thus electrons will experience
greater attraction from nucleus and so its removal
will be difficult, not easier.
7
26. No. of moles of Li = 1000×7 = 10-3
23
No. of moles of Na = 1000×23 = 10-3
\ The amounts of energies required for 10-3 mole each Li
and Na are 520 kJ × 10-3 or 520 J and 495 J respectively.
27. Due to stable half filled electronic configuration of
outer most shell of N, it has higher ionization energy
than O.
28. IE2 of Mg is lower than that of Na because in case
of Mg3+ 3s-electron has to be removed while in
case of Na+, an electron from the stable inert gas
configuration (Neon) has to be removed.
29. Across the period (i.e. 3rd period) the size of atom
decreases and nuclear charge increases. So generally
the ionization energy increases. However the
ionization energy of Mg is greater than Al because of
more penetration power of 2s sub-shell electrons of
Mg as compared to that of the 2p sub-shell electron
of Al. Also, Mg has fully filled configuration.
-
30. Mg(g) + IE1 → Mg+(g) + e ; IE1 = 750 kJ mol-1 ....(i)
-
Mg+(g) + IE2 → Mg2+(g) + e ; IE2 1450 kJ mol-1 ..(ii)
First of all, all Mg (g) atoms will get converted
into Mg+ (g) and then some of these will finally get
converted into Mg2+(g).
Amount of energy supplied = 1779.5 kJ mol-1
Amount of energy needed for the conversion of 1
mole of Mg (g) atoms into Mg+(g) =750 mol-1
Amount of energy left for the conversion of
Mg+(g) → Mg2+(g) =1779.5 - 450 = 1029.5 kJ.
From Eq. (ii), 1450 kJ energy converts Mg+(g) to
Mg2+(g) = 1mole
\ 1029.5 kJ energy will converty Mg+(g) to Mg2+(g)
1
= 1450 x1029.5 = 0.71 moles
Thus, Mg2+ (g) = 0.71 moles and Mg+(g) = 1.0 – 0.71
= 0.29 moles.

31. Removal of Ist electron is easier because of bigger
size but 2nd electron is to be removed from ns2 np6
configuration i.e. stable noble gas configuration. So
IE2 > IE1.
32. Second ionization energy of potassium is greater
than that of Ca. In case of potassium ion (i.e. K+)
the electron removal from the stable inert gas
configuration (1s2 2s2 2p63s23p6) requires much
higher energy.
33. EA of 2nd period elements is less than 3rd period
elements.
34. In chlorine, the addition of additional electron
to larger 3p-subshell experiences less electron-
electron repulsion than smaller 2p-subshell of
fluorine. Phosphorus has very low electron affinity
because there is high electron repulsion when the
incoming electron enters an orbital that is already
half filled.
35. O has exceptionally smaller value of electron affinity
(minimum in family) due to greater electron-
electron repulsion in larger 3p-subshell).
36. i: Ne, ii: O, iii: Na; iv:F. so EA order is i < iii < ii < i
37. All are facts.
38. The addition of extra electron is difficult to the atom
having stable configuration and so electron gain
enthalpy will be positive. Similarly the removal of
electron is quite difficult from stable configuration
and so ionisation enthalpy is higher. However EN
remains unaffected because it neither involves gain
nor loss of electron.
39. As size of atom decreases across the period, the
attraction between the nucleus and shared pair of
electrons increases. So electronegativity increases
across the period.
EXERCISE - 3
1. H, C, N, O, F
2. Chlorine has maximum electron affinity.
3. A + e
–
→ A + 3 eV
–
Number of moles of A = 10/30.
As 1 mole of A releases = 3 × 23 kcal.
\ Energy released for conversion of 10/30 mole
– 3×23
gaseous A into A ions 30 ×10 = 23 kCal.
– –
4. A (g) + e → A (g) DH = + E.G.E ...(1)
–
A (g) → A (g) + 2e DH = 1200 KJ/mol
2+
...(2)
– –
A (g) → A2+ (g) + 3e DH = 1100 KJ/mol ...(3)
Periodic Properties
40. Electronegativity of elements generally increases
across the period (less increase) and decreases down
the group (more decrease).
Si = 1.8, P = 2.1, C = 2.5, N = 3.0. So, the correct
increasing order is Si < P < C < N.
41. Electronegativity of elements generally increases
across the period (less increase) and decreases down
the group (more decrease).
42. Non metals are more electronegative than metals.
43. Z = 32 & Ge . It can show +2 and +4 oxidation
states.
44. Group 16 has -2 as the most common O.S.
45. Gold is a noble metal.
46. I can show -1, +3, +5 and +7 oxidation sates.
47. Maximum O.S. = Group No. and min, O.S. = Group
No. 8.
48. Transition metals can show variable oxidation states
49. Inert pair effect is seen post the f-block elements.
50. Tl+ and Tl3+ are possible of which Tl+ is more stable
51. Due to inert pair effect.
-
52. BiI5 does not exists because of I being very strong
reducing agent. So it reduces Bi5+ to Bi3+ and forms
BiI3.
53. Be has fully filled 2s-subshell (2s2) and therefore,
shows least tendency to accept an electron. Thus,
Be- is least stable.
54. None. Review the definitions of ionization enthalpy,
electron gain enthalpy and electronegativity.
55. In the isoelectronic series all isoelectronic anions
belongs to the same period and cations to the next
period.
Eq. (3) = (2) – (1)
– E.G.E + 1200 = 1100
– E.G.E = –100 kJ/mol
P = 1.
5. Since large jump from IE2 to IE3, therefore element
belongs to 2nd group.
6. a is Na, b is Mg, c is Al, d is Si, e is P, f is S, g is Cl,
h is Ar,
x = 3, y = 3
x–y=0
7. Be, N
Chemistry
8. Size decreases from Ni to Cu and then increases
from Cu to Zn.
9. rA + rA = 10Å ...(i)
rB + rB = 6Å ...(ii)
(i) + (ii)
2(rA + rB) = 16Å
rA + rB = 8Å
10. +6, +7
6 + 7 = 13.
–
11. The 4f e in the antepenultimate shell are very
effectively shielded from their chemical environment
–
outside the atom by 5s and 5pe . Consequently the
–
4f e do not take part in bonding.
12. BiF5, TlI3, PbO2, SnCl2, Tl2O3, As2O3
13. Of the many O.S. of Chromium, +3 O.S. is most
stable.
EXERCISE - 4
1. For transition elements, the 3d-orbitals are filled with
electrons after 4s-orbitals and before 4p-orbitals.
2. Electron configuration is [Ar]18 3d10 4s2 4p3. As last
electron enters in p-subshell it is p-block element
and thus its group number is equal to 10 + 5 = 15. As
principal quantum number of valence shell is 4, so it
is 4th period element.
3. Atomic No. of Group 1 Elements : 3, 11, 19, 37, 55
Atomic No. of Group 2 Elements : 2, 4, 12, 20, 38,
56.
4. He+, 1s1 ; Li2+, 1s1 ; Be3+, 1s1. All these ions have only
one electron. So they do not have any inner orbital
and thus do not experience any screening effect.
5. O is larger than F and has lesser no. of protons. F- is
negatively changed and hence has lower Zeff. Cl is
below F and its Zeff is not higher than F.
6. Fe exhibits +1 oxidation state only in rare cases like
brown ring complex.
7. Maximum possible oxidation state is group number
which for Mn is VII.
- and decreases across a period. (K > Mg > Al)
8. TlI3 exists as Tl+ and I3 while PbF4 exists because of
F- being very weak reducing agent.
9. Inert pair effects seen in the p-block elements of 6th
period.
10. Across the period ionic size decreases as nuclear
charge increases for successive addition of an
electron but down the group increases due to
14. N, O, F, P, C, S, Cl
15. x = 4 Period
y = 11 Group
8 + 11 = 19.
16. m = 5.92 = 35 ⇒ 5 unpaired electrons ⇒ Fe3+
\ Z = 26.
17. In c, d, f and j processes energy will be released. The
remaining processes are endothermic.
18. In HNO3 and N2O5, nitrogen exhibits maximum
oxidation sate 5.
19. In 1000 kJ of energy 600 kJ is consumed to convert
one mole of M to M+. The remaining 400 kJ can
convert only 0.25 mole of M+ to M2+.
20. Form the electronic config. the atomic number of
element is 90 and it is Th. It belongs to f-block.
increase in the number of atomic shells (effective
nuclear charge remains nearly same).
-
O2– = 140 pm, Se2– = 198 pm, F = 133 pm,
- -
Br = 196 pm, I = 220 pm.
So, the correct decreasing order of ionic
radii.
- - -
I > Se2– > Br > O2– > F .
11. Mn is in +2 oxidation state in MnO while in other
compounds, it is in higher oxidation state. As number
of electrons per proton decreases, the size decreases.
12. (1) Be has completely filled stable valence shell
configuration i.e. 2s2 while in Be+ because of
positive charge, the removal of electron requires
much higher energy. So, ionisation energy of
Be+ is greater than Be.
(3) Across the period, atomic size decreases and
nuclear charge increases and thus valence shell
electron(s) is/are tightly held by nucleus. So,
ionisation energy of C is greater than Be.
13. Metallic character increases down a group (Al > B)
14. There is more interelectronic repulsion in
2p-subshell of fluorine than chlorine (3p). So extra
electron will be added easily in 3p-subshell of
chlorine as compared to 2p-subshell of fluorine.
15. Correct order of electron gain enthalpy is O < S <
F < Cl Since F and O have more electron electron
density with respect to Cl and S.

16. The tendency to attract bonded pair of electron in
case of hybrid orbitals increases with increase in %
s-character and so the order : sp > sp2 > sp3
The electron affinity values for 2p-series elements
is less than that for 3p-series elements on account
of small size and high inter electronic repulsions.
Statements (b) and (c) are facts. Every cation
releases more energy than neutral atom upon gain of
an electron.
17. X is non-metal since its hydroxy compound is
acidic. Y is metalloid as its hydroxy compound react
with both acid and base. Z is metal.
18. Metal when react with water gives H2 and the
solution becomes alkaline.
19. From Bohr’s model size is inversly proportional to
the neuclear charge.
20. First gas is CO2, second one is H2O and third one
must be SO2.
21. Z must be divalent alkaline earth metal and W must
be halogen.
22. Q is SCl2, R in RCl2 is divalent metal.
23. The effective nuclear charge in Ar is less due to
shielding by more number of inner electrons and the
atomic size of Ar is greater than Ne.
24. O2-, Mg2+ and Na+ are isoelectronic.
25. If X0 - XB is greater than X0 - XH, B - O bond ionizes
more easily than O - H bond.
26. In isoelectronic species ionic radii decrease with
increase in nuclear charge.
40. Group no. e in outermost shell
27. IE values are increasing gradually and suddenly
decreased in the E5 value indicating a change from
noble gas to alkali metal.
28. In the formation of ionic bond the cation forming
element should have lesser IE and EA values than
the anion forming element.
29. Formation of ion means cation or anion. So, it may
be endothermic or exothermic. More the charge on
ion lesser is the stability. Electron gain enthalpy may
be positive or negative.
30. IE = 10x ; EA = 3x
10x + 3x
2.8 = 544 `x=
2.8×544
= 117 kJ
13
EA = 3x = 117 × 3 = 351
31. Increase in s character increases electronegativity.
More the number of bonds also increases the
attractive power of atom M bonded electrons
increases due to decreases in bond length. Higher
the oxidation state, more is the electronegativity.
Periodic Properties
32. Increase in effective charge increase the acidic
character and decreases the basic character of the
elements.
33. Due to inrt pair effet Tl3+ and Pb4+ are unstable and
act as oxidizing agents. Ga+ is less stable so it can
act as a reducing agent.
34. All the factors influence the bond length and thus
covalent radius of the an atom.
5 5
35. 9H eg =- A e - 2 RT and 9H ie = E o + 2 RT
36. Due to the absence of d-subshell in valence shell,
second period element do not exhibit maximum
covalence beyond 4. 2nd period elements form
strong pp-pp bonds not pp-dp bonds. Anomalous
behaviour is due to small size, high electronegativity.
Diagonal relationship is exist only up to IVth group.
37. With increase in oxidation state electronegativity
(attraction towards electrons) increases. As
the s-character of hybrid orbital increases,
electonegativity increases. EN of Cu is greater than
Zn. The EN of Al is less than Ga.
38. 6th period contain mercury (liquid), Xenon (gas) and
other solid elements
VII A group contain gases (F2 and Cl2) liquid (Br2)
and solids (I2 and At)
4th period contains liquid (Br2), Kr (gas) and solid
(other elements).
39. As the number of positive charges on an ion increases
the radius decreases. Other statements are correct.
-
13th 3
11th 1
9th 2 or 1
18th 2 or 8
41. Z = 19 is Potassium which is an s-block element.
42. Higher cationic charge in general results in greater
Zeff.
43. 1st group elements show 1+ oxidation state and 2nd
group elements show 2+ oxidation state.
44. Fact. Se shows only +3 oxidation state and the most
common O.S. of Al is +3.
45. Cuprous chloride exists as a dimer KO2 is speroxide
of potassium.
46. Zn have only 2+ or zero oxidation state.
Chemistry
47. O16, O18 : –2, –1, +1, +2
Na, K : +1
C : +4 to –4 Be :+2
Zn : +2 Rb : +1
48. -2 O.S. of oxygen is most stable due to it high
electonegativity and the lower O.S. of Tl, Pb, Bi are
more stable due to inert pair effect.
49. Atomic radii decreases from Group 1 to Group 17
across a period for representative elements.
50. Sc 2 Ti 2 V 2 Cr 2 Mn . Fe . Cq
Ni. . Cu 1 Zn
51. (b) Isoelectronic series of ions; all have the xenon
electron configuration.
1
Ionic radius \ nuclear charge
Atomic number : Te = 52; I = 53;
Cs = 55; Ba = 56.
(d) Due to poor shielding of nuclear charge by 4f
electrons.
52. Ionic radii depends on all the given factors.
53. (a) As removal of second electron takes place from
half filled valence shell electron configuration of
O+ i.e. 2s2 2p3.
(b) I.E (III) of 13Al is 2744 kJ mol–1 where as that of
15
P is 2910 kJ mol–1. This is because of higher
nuclear charge in phosphorus.
(c) I.E (I) of Al is 577 kJ mol–1 and that of Ga is 579
kJ mol–1. This may be because of their similar
sizes i.e. 1.25Å in both.
(d) 5B+ = 1s2 2s2 ; 6C+ = 1s2 2s2 2p1 ; As s-sub shell
electron has high penetration power than p-sub
shell electron. In addition B+ has completely
filled 2s sub shell. So I.E (II) of B is 2427 and
that of C is 2354 kJ mol–1.
54. Alkali metals and alkaline earth metals import
characteristic colour to Bunsen flame.
55. (C) : EA order P < Si (D) : N < C
56. Z = 57 is La, It is a d-block element.
57. 6th period, p-block, last element should have 6s 2 6p6
valence shows configuration.
58. Current periodic table can accommodate 118
elements.
59. Element just above Z = 43 will be Z = 43 – 18
= 25 and will have electronic configuration
1s22s22p63s23p63d54s2.
60. All these elements have outermost configuration ns2
np5. So they belong to Group (12 + 5 = 17) means
halogen family.
61. For same element, rVander > rMet. > rCov
1
62. Ionic size \ nuclear charge for isoelectronic
species.
63. Both N3– and Al3+ are isoelectronic species, but Al3+ has
greater nuclear charge. So, it will have smaller size
Zr (4d) ≈ Hf(5d), because of Lanthanide contraction.
Zn > Cu, their occur greater inter electronic repulsions
in completely filled electronic configuration of 12th
group elements.
64. The metallic character of the elements is highest
at the extremely left (low ionization energies) and
then decreases across the period from left to right
(ionization energies increases across the period).
65. The non-metallic character of the elements is
highest at the extreme right and then decreases from
right to left across the period. Also it decreases more
on moving top to bottom.
66. (a) Ionization enthalpies of elements generally
decrease along a group and increase along a
period in Modern periodic table.
(b) In the 3rd period of Modern periodic table, the
two most reactive elements are sodium and
chlorine.
(c) Iodine has the least negative electron gain
enthalpy among all halogens.
(d) Ionization enthalpy of Pb is greater than that of
Sn, because of poor shielding of nuclear charge
by 4f-electrons.
67. Z = 57 & La ; Z = 17 & Cl ; Z = 19 & K ;
Z = 29 & Cu
68. a, b are electron gain enthalpies in which b is
endothermic and hence positive c and d are not
electron gain enthalpy.
69. IE1: Be > B; B < C; C < N; N > O
Be2+ : 1s2 Be2+ : 1s22s1 C2+ : 1s22s2
N2+ : 1s22s22p1 O2+ : 1s22s22p2
\ IE3 : Be > B; B < C; C > N; N < O
 Periodic Properties

1. Isoelectronic species have same no. of electrons 8. Second electron gain enthalpy of oxygen is +850 kJ
Al+3, O2-, Mg+2 all have 10 electrons. mol–1.
2. As Cl has maximum electron affinity among all 9. Both Beryllium and Aluminum have similar
elements. electronegativity thus they show diagonal
Element DegH (kJ/mol) relationship.
-
F –328 10. Ions O-2 F Na+ Mg+2
Atomic number = 8 9 11 12
Cl –349
No. of e- = 10 10 10 10
Te –190
-
Therefore O2-, F , Na+, Mg+2 are isoelectronic
Po –174
11. These are isoelectronic species.
3. Na → [Ne] 3s1 IE1 is very low but IE2 is very high As negative charge increases, ionic radius increases.
due to stable noble gas configuration of Na+. -
12. Na Na+ + e → Ist I.E. = 5.1 eV
-
Mg → [Ne] 3s IE1 & IE2 → Low
2
Na+ + e → Na Electron gain enthalpy of Na+
IE3 is very high. Because reaction is reverse, so DegH = – 5.1 eV.

4. correct order of electron gain enthalpy is :- 13. Order of increasing 9H IE Ba < Ca < Se < S < Ar
1

Ba < Ca ; Se < S : On moving top to bottom in

O < S > Se > Te a group, size increases. So ionization enthalpy

⇒ S > Se > Te > O decreases.

(Oxygen shows least electron gain enthalpy due to Ar : Maximum value of ionization enthalpy, since it
is an inert gas.
small size of atom)
14. Order of ionic radii Ca2+ < K+ < Cl– < S2–
5. B → 1s2, 2s2, 2p1
In isoelectronic species, as Z increases, size
Be → 1s2, 2s2 decreases.
In Boron 4e- of 1s2 & 2s2 shield nuclear charge 15. As we move in a group from top to bottom, electron
In Berillium 2e of 1s
- 2
shield nuclear charge gain enthalpy becomes less negative because the
size of the atom increases and the added electron
C N O F would be at larger distance from the nucleus.
6. Size decreases
Negative electron gain enthalpy of F is less than Cl.
Cl This is due to the fact that when an electron is added
to F, the added electron goes to the smaller n = 2
Br energy level and experiences significant repulsion
from the other electrons present in this level. In Cl,
Size increases
the electron goes to the larger n = 3 energy level
7. In general in the periodic table, it can be said that: and consequently occupies a larger region of space
Electronegativity decreases down a group and leading to much less electron-electron repulsion. So
Atomic radius increases down a group. the correct order is Cl > F > Br > I.

1. Be has 1s22s2 configuration. Adding another electron 4.

implies filling a completely vacant subshell. Hence Atomic Ionization Enthalpy (kJ/mol)
it is least stable. Number I1 I2 I3
2. I.E. order: Be > Mg > Ca as I.E. decreases on moving n 1681 3374 6050
down Group 2.
n+1 2081 3952 6122
3. All are isoelectronic species having 10 electrons in n+2 496 4562 6910
each species but different nuclear charge and thus
1 n+3 738 1451 7733
ionic radius \ nuclear charge .

By observing the values of I1, I2 & I3 for atomic
-

So correct order is 9F < 8O2– < 7N3–. number (n+2), it is observed that I2 >>I1.
Chemistry
This indicates that number of valence shell electrons
is 1 and atomic number (n+2) should be an alkali
metal.
Also for atomic number (n+3), I3 >> I2.
This indicates that it will be an alkaline earth metal
which suggests that atomic number (n+1) should be
a noble gas & atomic number (n) should belong to
Halogen family. Since n < 10; hence n = 9 (F atom)
Note : n = 1 (H atom) cannot be the answer because
it does not have I2 & I3 values.
5. F and Na can show only -1 and +1 O.S. respectively
in their compounds. All others can show multiple
O.S.
 Chemical Bonding

Chapter 4 Chemical Bonding

INTEXT EXERCISE: 1
1. Non-metals readily form diatomic molecules by 6. NH4Cl has covalent as well as ionic bonds.
sharing of electrons. Element M(1s22s22p5) has RS V+
SS H WWW The bond between NH4+ and
seven electrons in its valence shell and thus needs SS W
| W Cl- is an ionic bond. The
one more electron to complete its octet. Therefore, SS +WW
WW Cl bonds between N atom and H
-
SS H - N " H
two atoms share one electron each to form a diatomic SS WW
| atoms in the ammonium ion is
molecule (M2) SS WW
S H W covalent bond.
T X
M + M  M M
7. Molecule X is nitrogen because nitrogen molecule
has triple bond. It’s configuration will be 1s2, 2s22p3.
2. In a covalent bond between similar atoms the elecron
pair is equally shared. This is called a covalent bond. 8. PCl5 does not follow octet rule, it has 10 electrons in
3. An ionic bond can never be formed between two its valence shell. It is said to have a super octet.
atoms of the same element. 9. Each nitrogen share 3 electrons to form triple bond.
4. BCl3 is electron deficient compound because B has So, total number of shared electrons is 6.
only 6 electrons after forming 3 covalent bonds. 10. HCl has ionic character although it is a covalent
5. Electropositive tendency increases down the group. compound because electronegativity of chlorine is
Thus, Be has the least tendency to form cations greater than that of hydrogen. E.N. of Cl = 3 and that
among the given options and hence has the highest of H = 2.1
tendency to form covalent bonds.

INTEXT EXERCISE: 2
1. Number of bonds do not change in resonating 7. In resonance structure there should be the same
structures. Also, Carbon cannot have 5 bonds. number of electron pairs. Only the location of these
electron pairs vary between the different atoms.
2. In NH3 nitrogen has one lone pair of electron.
8. There are three resonance structure of CO32- ion.
3. During resonance the electrons of the second or third
bond between two atoms (called p bonds) change
their position i.e. get delocalized. C C C

4. During resonance electrons in p bonds get

delocalized. Position of atoms and functional groups
remain unchanged.
5. In CN- ion formal negative charge is on nitrogen 9.
atom due to lone pair of electrons.

6.
3
\ B.O. = 2 10. All bonds of CO32- are of equal length due to
Resonance.
Chemistry
INTEXT EXERCISE: 3
1. In fluorine molecule formation p-orbitals take part
in bond formation. There is p-p s bond.
8. S 2s, 2p bond and one lone pair.
2. p-bond is formed by lateral overlapping of
unhybridised p or d orbitals. O O
O
3. In a double bond connecting two atom sharing of 4
electrons take place as in H 2 C = CH 2 , 2 for s and 2 9. S O
NO3-, PO43- and CO32- have one p bond
for p bonds. O
each.
 
4. C≡≡C is a multiple bond so it is strongest.
5. Greater the extent of overlap, stronger are the bonds 10. N N.


6. Each Phosphorus is attached to 4 Oxygen atoms.
First bond between any two atoms is s bond, all
Remember coordinate bonds are also s bonds. subsequent bonds are p bonds.
H

C
7. H C C -H Number of s bonds = 12
Number of p bonds = 3
C C
H C H \ Ratio = 4 : 1

INTEXT EXERCISE: 4
1. H2O is not linear because oxygen is sp3 hybridised in 3 2 1

H2O. 7. In compound CH 2 = C = CH 2 the second carbon

sp-hybridised.
2. In sp3–hybridisation each sp3 hybridised orbital has
1/4 s-character and 3/4 p-chracter. 8. T.V.E. = 8 + 4 × 7 = 36.
Now 36/8 = 4, remainder = 4
3. sp3d hybrid orbitals have bond angles 120o, 90o.
4
\ n = 4+ 2 = 6 \ Hybridization sp3d2
4. In BeF3-, Be is not sp3–hybridised it is sp2-hybridised.
9. As p-character increases the bond angle decreases.
5. T.V.E. = 20. Now 20/8 gives quotient = 2 and
remainder = 4
1
In sp-p-character 2 , bond angle -180o
4
\ n = 2+ 2 = 4
2
In sp2-p-character 3 , bond angle -120o
6. Hybridization of C in C2H2, C2H4 and C2H4Br2 is 3
sp, sp2 and sp3 respectively. As the % p character of In sp3-p-character 4 , bond angle -109o
the hybrid orbital of C increases the hybrid orbital 10. Structure of N2O is similar to CO2 both have linear
becomes more elongated. Thus the C-H bond structure and also 22 e- each.
length is maximum for C2H4Br2 which has C in sp3
hybridization.
INTEXT EXERCISE: 5
1. sp3d2 hybridization corresponds to octahedral
Hybridization of ICl3 is sp3d with two L.P. Thus,
geometry. its geometry is trigonal bipyramidal and shape is
T-shaped
2. IF7 is shows sp3d3 hybridization. Hence the bond
angles are is about 72o and 90o. Thus, among the 4. PF5 has sp3d hybridization with zero L.P. of electrons.
given options IF7 has the smallest bond angle. Hence it has trigonal bipyramidal structure.
3. BCl3 is sp2 hybrid, geometry and shape both are 5. In SO3 sulphur is sp2 hybridized so its shape will be
trigonal planar. PCl3 is sp3 hybrid with one L.P. Thus trigonal planar.
its geometry is tetrahedral and shape is pyramidal.
6. Benzene has all carbons sp2 hybridised and planar in
shape.

7. CO2 has sp-hybridization and is linear.
8. Boron is sp2 hybridized in BF3 with 3 bond
pairs and 0 lone pair of electrons. Thus, it
has trigonal planar geometry.
INTEXT EXERCISE: 6
1. H2S show bond angle nearly 90 as there is no
0
hybridization due to Drago’s rule
2. Bond angle decreases from H2O to H2Te. Note that
there is no hybridization in H2S, H2Se or H2Te. Hence
the bond angle keeps decreasing marginally due to
the increase in the bond length with increasing size
of central atom and decreasing E.N. of central atom.
3. BCl3, BBr3 and BF3 all of these have same structure
i.e. trigonal planar (sp2 hybridization). Hence bond
angle is same for all of them (i.e. equal to 120o)
4. There are 2 lone pair of electrons on O in H2O and
only 1 lone pair on N in NH3 and both are sp3 hybrid.
Thus, bond angle of NH3 is greater than H2O.
In case of PH3, AsH3 bond angle is nearly 90o as there
is no hybridization due to Drago’s Rule. Therefore,
NH3 has the largest bond angle.
5. In NH3, sp3 hybridization is present but bond angle
is 107o because Nitrogen has lone pair of electrons.
According to VSEPR theory due to bp-lp repulsion
bond angle decreases from 109o45` to 107o.
6. The bond angle in PH3 would be expected to be
close to 90o due to Drago’s Rule.
INTEXT EXERCISE: 7
1. CO2 is symmetrical molecule so its net dipole
moment is zero.
2. Chloroform has 3 chlorine atoms and one hydrogen
atom attached to the carbon so it is polarised and it
will show a net dipole moment.
3. Net dipole moment is a vector addition of all the
dipoles in a molecule
$
\ | n net | = n12 + n 22 + 2n1 n 2 cosi
Greater the value of q, lesser is the | mnet|
4. CCl4 has no net dipole moment because of its regular
tetrahedral structure, as all the dipoles cancel out.
5. CH4 has regular tetrahedral structure so its dipole
moment is zero, same reason as above.
6. HF has largest dipole moment because
electronegativity difference between H and F is
highest so it is highly polar.
7. Polarity is created due to the difference in
electronegativity of both atom in a molecule. Except
Chemical Bonding
9. Structure of sp3d hybridized compound is Trigonal
bipyramidal.
10. XeF4 molecule has ‘Xe’ sp3d2 hybridised and its
shape is square planar as it has 2 lone pairs.
7. Since it is a 2nd period central atom, thus it cannot
have d orbitals involved in hybridization.
sp hybrid central atom will always have angle of
180o sp2 hybrid central atom with 0 L.P. = 120o
1 L.P. ≈ 115o
sp3 hybrid central atom with 0 L.P. = 109.5o,
1 L.P. ≈ 107o and 2 L.P. = 105o.
8. BF3 contain 6 electron so it is lewis acid. Species
that can accept a lone pair of electrons are called
Lewis Acid.
9. s-character increases with increase in bond angle.
Hybridization s% Angle
sp 50 1800
sp2 33.33 1200
sp3 25 109.280
sp3d 20 900 and 1200
10. s-orbitals are short and bulky. As % s character
decreases, the hybrid orbital becomes more
elongated and hence bond length increases.
H2 all other molecule have the different atom so they
will have the polarity while H2 will be non polar.
8. :dipole moments cancel off.
cis isomer shows dipole moment while that of trans
is zero or very low value.
: mnet = 0 as dipoles cancel off.
9. Given ionic charge = 4.8 × 10-10 e.s.u. and ionic
distance = 1Å = 10-8 cm we know that dipole
moment = ionic charge × ionic distance
= 4.8 × 10-10 × 10-8 = 4.8 × 10-18 esu cm.
\ m = 4.8 D.
10. % of ionic character
Experiment al value of diple moment
= Expected value of dipole moment
1.03
= 6.12 ×100 = 16.83% . 17%
Chemistry
INTEXT EXERCISE: 8
1. s1s s 1s s2s s 2s p2px p2py p2pz
* *
n b - na 8 - 3 5
6. B.O. of O2+ = = 2 = 2 = 2.5 .
2 2 2 2 2 2 2

2

nb = 10 and na = 4
7. p2py has two nodal planes.
10 - 4
B.O.
` = 2 =3 8. Correct Sequence of bond order is
1
2. H has the bond order = 2 , it has only one electron
+
2
O +2 > O 2 > O -2
v1s 1
B.O. - 2.5 2 1.5
3. Helium molecule does not exist as bond order of 9. In the conversion of O 2 into O -2 bond order
He2 = 0. decreases, from 2 to 1.5.
n b - na 8 - 4 10. O 22-: v1s v1s pairs
4. B.O. of C2 = = 2 = 2. v 2s v*2s v 2p r 2px r 2py r*2px r*2py & 4
2
* 2 2 2 2 2 2 2 2

2
of anti-bonding electrons.
n -n 10 - 4
5. B.O. = b 2 a = 2 = 3 .
INTEXT EXERCISE: 9
1. Valencies of L, Q, P and R is - 2, - 1, + 1 and + 2 6. Cations with high charge and small size have high
respectively so they will from P2L, RL, PQ and RQ2 polarizing power. Anions with larger magnitude of
charge and larger size show greater polarizibility.
2. All ionic compounds are good conductors of
electricity only in the molten or aqueous states, as 7. Smaller cation with higher charge causes maximum
the ions can move freely in these states and act as polarization. Larger anions are more polarizable.
carriers of charge.
8. Smaller cation with high charge and large anion
3. Since high charge on ions, smaller size of cation an favours most covalent compound
arge size of anion all favour covalent character as
9. Larger the anion, greater is the polarisibility.
per Fajan’s Rules.
10. I—Cl bond is polar due to difference in E.N. between
4. Ionic bond is the strongest bond so bond between
I and Cl. Since Cl is more E.N., thus negative end is
Na - Cl is the strongest bond.
on Cl.
5. Water is a polar solvent so it decreases the interionic
attraction in the crystal lattice due to salvation.
INTEXT EXERCISE: 10
1. Hydrogen bond strength will be maximum in F—H 7. Water is denser than ice because of hydrogen
bond due to greater electronegativity difference. bonding interaction and structure of ice, which has
air trapped inside cage like structures.
2. HF has highest boiling point because it has
intermolecular hydrogen bonding. 8. Ethanol: CH3—CH2—OH
3. Intermolecular hydrogen bonding increases the
Dimethyl ether: CH3—O—CH3 Ethanol has
boiling point of compounds like water, HF etc. hydrogen bonding so its boiling point is higher than
its isomer dimethyl ether.
4. o-Nitrophenol has intramolecular hydrogen bonding
but p-Nitrophenol has intermolecular hydrogen 9. The H atom covalently bonded to a higher E.N. atom
bonding so boiling point of p-Nitrophenol is more will have more acidic character (partial positive
than o-Nitrophenol. charge) and hence will form stronger H-bonds.
5. H2O can form hydrogen bonds rest CH4 and CHCl3
Also, a higher E.N. atom is able to form stronger
do not have any acidic hydrogen. NaCl does not have H-bonds.
any H atom, so there is no question of H-bonding. 10. C2H5OH will dissolve in water because it forms
6. Due to highest E.N. difference between H and F, the hydrogen bond with water molecule.
strength of intermolecular H bonds is maximum in
HF.
 Chemical Bonding
INTEXT EXERCISE: 11
1. Since Mercury is a liquid at room temperature, it 6. In NaOH covalent bond is present in O - H bond
must have very weak interatomic forces. while ionic bond is formed between OH - and Na + .
2. The melting and boiling points of argon is low 7. Bond formation is an exothermic reaction so there is
hence, in solid argon, atoms are held together by decrease in energy of product.
weak Vanderwaal’s forces. Also, as Argon is a noble 8. The bond formation take place when forces of
gas, it can only have Vanderwaal’s forces between attraction and repulsion balance off each other.
particles. RS
H
VW+
SS WW
3. Diamond is one of the hardest substances. Its melting SS | WW
SS W
point would be high, as it is difficult to break its 9. SH - N " HWW Cl -
SS WW
structure. SS | WW
4. Generally zero group elements are linked together SS H WW
T X
by Vanderwaal’s forces. Hence, these show weakest
ionic bond = 1, Covalent bond = 3
intermolecular forces.
Co-ordinate bond = 1.
5. Glycerol has a three OH group hence it is viscous in
10. Fact.
nature, as there are 3-H bonds between 2 glycerol
molecules.

EXERCISE - 1

1. Covalent substances have lower MP, BP and are also

O O
generally insoluble in water.
2. The monothiocarbonate is CSO 2- 2 and has a 8. H O C O H O C=O
structure similar to carbonate ion.
There is Resonance between the bonds y and z.
Cl Cl Thus, they both have partial double bond character.
3. BCl3:- B
. There are only 6 electrons in the The bond x is purely single bond.

Cl

\ x>y=z
valence shell of Boron and hence it is an electron 1
9. Bond length \ Bond order
deficient species.
Bond order of CO = 3 (as isoelectronic with N2)
4. In BCl3 and PCl5, B and P contain 6 and 10 electrons No. of bonds in all possible sides
respectively in their valence shell. Therefore they Bond order = No. of resonating structures
violate octet rule.
4

Bond order of CO 2 = 2 = 2
5. N3-, (CNO) - and (NCN) 2- all have same number
of electrons i.e., 22; so all are isoelectronic with CO2 4
which also has 22 electrons.
Bond order of CO32- = 3 = 1.33

6. (a) BrF5:Br contains 10 electrons in place of eight.

So, order of bond length of C-O is CO < CO2 < CO32-

(b) SF6:S contains 12 electrons in place of eight. 10.

(c) IF7:I contains 14 electrons in place of eight.

\ Bond order = 1.5 as 3 double bonds are
O
distributed among 6 possible locations.
O O
11. Bond orders:
7. I -5 charge is distributed on 6O
(a) CO2 = 2 (b) CH3COO- = 1.5
O O atoms. So, average charge =
-5/6 (c) CO = 3 (d) CO32- = 1.33
O

1
Average B.O.=1 + 6 = 1.167 Lesser the bond order, weaker the bond.
Chemistry

21.
12. (a)


22. (i) (ii) [N  N  N]2
sp

(b) (iii) PCl5 (s) exists as [PCl 4] + and [PCl6] - ,

(c)

(iv) I 2 Cl6 (,) ? [ICl 2] + + [ICl 4] - self ionisation

23. sp3d : see - saw shape

(d) zero overlap

sp3d : see - saw shape

24. (A) BF3 (sp 2) + F - $ BF 4- (sp3)

13. (a) and (b) have negative overlap while (c) has
positive overlap. Thus (c) will show effective (B) NH3 (sp3) + H + $ NH +4 (sp3)
overlapping. (C) 2SO 2 (sp 2) + O 2 $ 2SO3 (sp 2)
14. p-orbital can have both axial and side ways over lapping (D) H 2 O (sp3) + H + $ H3 O + (sp3)
- -
2 2
15. Structure of C34- is (C = C = C)
16. Sigma bond is stronger than pi bond as in case of pi 25. (A)
bonds there is straining of orbitals.
17. C having 4 single bonds is sp3
(B) Number of bond pairs around

C having 2 single, 1 double bond is sp2

C having 1 single, 1 triple bond is sp
I = 2. Number of lone pairs around I = 3.

C having 2 double bonds is also sp
6 5
18. N36:[N = N = N -]; NOCl:O = N - Cl and
- +
(C)

N 2 O:N = N = 0

19.

20. XeF 7+ sp3 d3 (D)

PCl +
4 sp 3

SF6 sp3 d 2

PF 4+ sp3

26. (A) XeO3 is trigonal pyramid.
(B) IOF 4+ is trigonal bipyramidal
(C) PCl5 is pyramidal.
(D) and square pyramidal.
27. (B) Bond angle is 180o because of sp
hybridisation of nitrogen. In all others N is sp2
hybrid.
28. Central atom is sp hybridized and it is linear
molecule.
29. As the electronegativity of central atom increases
the bond angle increases due to repulsion between
bond pair and bond pair as bond pairs are more close
to the central atom. Also there is no hybridization in
case of H2S, H2Se and H2Te as per Drago’s Rule
30. Due to absence of lone pair on N in
NH +4 , lp - lp or lp - bp repulsion is not there.
31. As per Drago’s rule
Chemical Bonding
Decrease in B–F bond length is due to delocalized
pp-pp bonding between filled p-orbital of F atom
and vacant p-orbital of B atom.
39. In SOCl2, sulphur atom is sp3 hybridized. Due to the
presence of one lone pair of electrons on ‘S’ atom,
the molecule has distorted tetrahedral shape. i.e.,
trigonal pyramidal shape. This shape contains two
chlorine and one oxygen atom in a triangle. The S –
O – p bond is pp-dp back bond.
40. Back bonding is more effective when size of donor
and acceptor orbitals are similar. Also, greater the
extent of back bonding, lesser is the Lewis Acid
character.
41. BF3 has pp-pp back bonds
O
O
S
O O
42. O O
S S
O
O O
1
43. Dipole moment \ bond angle

32. 44. n ! 0; SiF4, BF3 and PF5

2+
(H2O) (H2O)
33. Cu SO 24- - H 2 O
are symmetrical molecules thus m = 0
(H2O) (H2O)

Ionic bond between Cu2+ and SO42- coordinate bonds 45. The values of C = O bond dipoles are
between H2O and Cu2+ covalent bonds within H2O same but acting in opposite directions, so cancel out.
and SO42-. Thus diple moment of CO2 is zero.
34. B2H6 is electron deficient and hence has banana 46. Symmetrical molecules have zero dipole moment.
bonding
plannar, q = 120o, m = 0
35. B is sp3 hybrid.
4s and 2 bridging bonds.
36. O2 and N2O4 contain even number of electrons but
O2 is paramagnetic.
37. B has 2s22p1 configuration. Since it is forming 2v
and 2 banana bonds therefore it must be in excited
state.
47. S Bond angle ≈ 90o. mnet ! 0
H
H
38.
48. Dipole moment depends on the electronegativity of
the elements as it is the product of charge on one
of the ions and the distance between them. Dipole
moment of CH3Cl is greater than CH3F due to more
charge separation. (fact)
Chemistry
Cl 62. Be2+ has highest polarizing power and Rb+ has least
polarizing power.
49. net = 0 63. The stability of the ionic bond depends upon the
lattice energy which is expected to be more between
Cl Mg and F due to +2 charge on Mg atom.

50. The electron density is zero in the nodal plane during 64. The solubility order is:
the formation of a molecular orbital from atomic
BeF2 > MgF 2 > CaF2 > SrF2 So, SrF2 is least soluble.
orbitals of the same atom by definition 65. NaF has maximum melting point. Melting point
51. Pi molecular orbitals are formed by orebitals that are decreases of sodium halides with incease in size of
perpendicular to the bonding axis. halide as their lattice energy get lower.
52. Bond order for species which can exist must be 66. Electrovalent bond is formed by losing electrons
positive but may be integral or fractional. from one atom and gaining electron by other atom
i.e. redox reaction.
53. (a) Bond order of N2+ = 2.5 The bond order of O2+
1/2(10-5) = 2.5 67. CaCl has ionic bonding.
(b) Bond order of F2 = 1; The bond order of Ne2 = 0 68. As charge on cations increases, their polarising
(c) Bond order of O2 = 2; The bond order B2 = 1 power increases and thus covalent character
increases.
(d) Bond order of C2 = 2; The bond order of N2 = 3 + 2+ 3+ 4+

54. Homodiatomic species with total number of

LiCl < BeCl 2 < BCl3 < CCl 4
electrons < 14 in the neutral specie can show s-p 69. Increase in oxidation state (Ni 4+) increases the
mixing. polarizing power of cation.
55. N 22-: v1s v1s
*
v 2s v*2s r 2p r 2p v 2p r 2p r*2p
2 2 2 2 2
x
2
y
2
z
1
x
1
y 70. Because of high charge density on Sn 4+ it has
10 - 6 high polarizing power and thus leads to greater
B.O. N 22- = 2 = 2; polarization of anion i.e., greater distortion of
10 - 6 electron clouds of the Cl - ions. So SnCl4 is most
B.O. O 2 = 2 = 2
covalent.
10 - 6
NO - isoelectronic with O 2 so B.O. = 2 = 2 71. All molecules have London dispersion force
All have same number of electrons (i.e. 16) so because of number of polarizable electrons. Non
isoelectronic. polar molecules have only London dispersion force
56. B2 bond order =1; C2 bond order = 2, F2 bond order = because of polarisable electron. Benzene is non
1 polar molecule. Polar molecules have dipole-dipole
1; O -2 bond order = 1.5 bond length # bond order
attraction in addition to London dispersion force.
57. NO– is derivative of O2 and isoelectronic with O2.

So v1s v1s
*
v 2s v*2s v 2p r p r p r p r p and 2 unpaired
2 2 2 2 2
z
2
x
2
y
1
x
1
x and so on
electrons.

Molecules with, O–H, N–H, or F – H bond have

O22– : v1s v1s
*
v 2s v*2s v 2p r 2p r 2p r*2p r*2p and no unpaired
2 2 2 2 2
z
2
x
2
y
2
x
2
y
hydrogen bonding in addition to London dispersion
electrons.. force.
58. O2 O2- O22- O2+
Molecule ICl is polar, so in addition to London

Bond order 2 1.5 1 2.5 dispersion force it also has dipole-dipole attraction.
59. O and NO both have odd number of electrons and
-
2 72. All statements are true.
must be paramagnetic
73. London forces are extremely short range in action
60. From MOT and bond order values. In case of N +2 and the weakest of all attractive forces.
and N -2 both same B.O. So, the one with less

The order of strength of bonds/ forces is :
number of antibonding electrons has stronger bond.

Ionic Bond > Covalent Bond > Hydrogen Bond >
61. F 2- HOMO: v*2pz . Due to the additional electron
London Dispersion Force.
2

B.O. of O -2 = 1.5 and that of O +2 = 2.5 . Hence, S1,

S2 are false.
 Chemical Bonding
76. As molecular weight increases, magnitude of
Vanderwaal’s force of attraction increases.
74. (a) Hydroxy benzaldehyde : can form 6 Therefore, boiling point increases. Though NH3
has strong H-bonding but boiling point of SbH3 is
membered ring by intramolecular H-bonding. highest due to highest molecular weight. Boiling
point NH3 = 238.5 K and SbH3 = 254.6 K.
(b) o-nitrophenol forms 6 membered ring by
intramolecular H-bonding. 77. (i) H2O has highest boiling point because of
H-bonding.
(c) Chloral hydrate can form 5 (ii) Boiling point also depends on the magnitude
of Vanderwaal’s force of attraction, which
in turns depends on molecular weight of
membered ring by intramolecular H-bonding. the compounds. Thus the correct order is
(d) B(OH)3 cannot show intramolecular H-bonding H 2 O 2 H 2 Te 2 H 2 Se 2 H 2 S .
75. Nitrogen is less electronegative than oxygen so 78. The presence of two OH groups in H2SO4 lead to
electron pair is easily available for bonding, thus P significant H-bonding.
has stronger H-bonding than Q. As oxygen is more 79. The strength of metallic bonds depends upon the
electronegative so H-bond strength of Q is greater number of mobile electron(s) per atom. Sodium has
than S. The same explanation is given for R and S as only one mobile electron per atom where as iron has
that of P and Q. 8 mobile electrons per atom.
80. Electron sea model of metallic bonding.
EXERCISE - 2
O O-
1. Number of bond pairs on N = 4 9. CaC 2 exists as Ca 2+ and C 2-
2
N
Number of lone pairs on N = 0 10. : N / C - C / N:
O

2. IF7 is sp3d3 with 7 B.P. and 0 L.P. 11. Both PO34- & SO32- have hybridization sp3

3. There are only 4 electrons in the valence shell of Be 12. (a) Electronic configuration of boron in ground
in Be Cl2 (g) state is 1s 2 2s 2 2p1 .

4. BF3 : Sub-octet. 6e - on B

XeF6 : Super octet. 14e - on Xe

ClO3 : Super octet. 13e - on Cl

SiH4 follows octet rule (b) Electronic configuration of nitrogen in ground
O state is 1s2 2s2 2p3
5. has no formal charge on any atom and
S
hence is the most stable. NH3 :
O O

6. ; there is positive charge on two (c) Electronic configuration of phosphorus in
adjacent nitrogen atoms. This ground state is 1s 2 2s 2 2p6 3s 2 3p3
leads to repulsion and thus
increases the energy of the molecule.
PCl3 :
7
7. ClO -4 Bond order = 4 = 1.75

5
ClO3- Bond order = 3 = 1.66 (d) Electronic configuration of beryllium in ground

3
ClO -2 Bond order = 2 = 1.5 state is 1s 2 2s 2
1
ClO - Bond order = 1 = 1 BeF2 :
8. Since p bond is weaker than s bond, energy of s

bond should be more than that of p bond
Chemistry
13. sp3 with 2 lone pairs has a bent shape and sp2 with a participate in sp2 hybridization.
lone pair is also bent shape.
14. The 3 equatorial bonds are taken to be formed by
sp2 and the two axial bonds in sp3d are formed by pd
hybrid orbitals.
H

15. C C H

H
Since for the cationic C, steric No. = 2
27. ; Hybridisation of Cl is sp3 and

\ Hybridization sp.
molecule is polar.
16. The axial bonds will be formed by orbitals
perpendicular to the equatorial plane (XY in the 28. Polarity depend on net diple moment. If dipole
case) moment m = 0 it is nonpolar.
17. T shape geometry is possible in sp3d hybridization
In XeF4 m = 0 non polar; SO3 m = 0 non polar
which indicates presence of two lone pairs in MX3.
XeF4 m ! 0 polar; ICl -4 n = 0 non polar

18. 29. ; Dipole moment of

NH3 is greater than NF3
as in case of NH3 the m
due to B.P. and L.P. are additive but not in NF3.

19. a) b) c) 30. (a) (b)

≈ 104o 90o 90o

20. H2S - No hybridisation bond angle ≈ 90o

NH3 - Pyramidal bond angle = 104.5o

CH4 - Tetrahedral bond angle = 109o28` (c) (d)

BF3 - Triangular planar bond angle = 120o
21. In sp3 d hybridisation (trigonal bipyramidal) the
axial and equatorial bonds are of different lengths. 31. MX3 has 3 B.P. and m = 0 which is possible in case of
5 sp2 only. In sp3 with 1 L.P. m ! 0. For sp3d with 2 L.P.
22. O = N = O Bond order = 2 m ! 0 as L.P. are in equatorial positions. Similarly

K
O - N = O Bond order = 1.5 (due to Resonance) for sp3d2 etc.
23. Due to small size of nitrogen, the LP-LP repulsion 32. (a) Fact
of the unbonded electrons in N is more than that in P. (b) Fact
(c) Symmetrical molecule so dipole moment = 0
24.
(d) Fact
25. Partial double bond character is developed in B–F 33. v1s v1s
* 2
v 2s v*2s r 2p r 2p v 2p
2 2 2 2 2 2

bond of BF3 (due to formation of dative p bond)

x y z

number of anti bonding electrons in N2 is 4.

In other case B is sp3 hybridized (tetrahedral * represents antibonding molecular orbitals.
molecule or ion) and the possibility for p
10 - 4 6
bonding no longer exists. 34. B.O. = 2 = 2 = 3
26. There is pr - dr delocalization of lone pair of 35. He2+ = v1s v1*s
2 1

electron on nitrogen atom and empty d-orbital

2-1 1
of silicon but not pr - pr , one of the 2s-orbital
B.O. = 2 = 2
electrons jumps to the last p orbital and does not
 Chemical Bonding
36. B 2: v1s v v v r 2p r 2p
2
* * *
1s 2 2s 2 2s 2 1
x
1
y
42. N 2 O 4
5-4 1 O O

B.O. = 2 = 2 >0 N N

Rest all have zero B.O. O O

37. (a) O : B.O. = 1
-
2
1
2 (b) O2 : B.O. = 2
O -2 NO 2 and ClO 2 are odd electron species.
(c) O +2 : B.O. = 2 1 2 (d) O 22-: B.O. = 1 43. This X element is second group element so its

1
Bond length \ bond length chloride will be XCl2.
44. When electronegativity difference is more than 1.7
38. O2 O3 O 2-
2 the bond formed is ionic bond.
B.O.: 2 1.5 1 45. Generally MgCl 2 , SrCl 2 , BaCl 2 are ionic
39. NO > NO > NO (bond length)
- + compounds so they conduct electricity in fused state.

Bond order 2.0 2.5 3
BeCl2 has significant covalent character due to high

H2 > H2+ > He2+ (bond energy) polarizing power to Be2+.

Bond order 1 0.5 0.5 46. Ionic bond between Na+ and NO3- and covalent
bonds between N and O in nitrate ion.

NO- > NO > NO+ (bond angle)
47. As size of cations increase, their polarizing power

Bond angle 180o 133o 115o
decrease and thus ionic character increase.

O22- < O2+ < O2
48. Sn4+ has highest polarizing power amongst Na+,
(paramagnetic moment) Pb2+, Sn4+ and Al3+ because of smaller size and

Unpaired e- 0 1 2 higher charge. So SnCl4 is most covalent and thus
2-1 1
40. He +2 bond order = has least melting point.
2 = 2;
10 - 7 49. As DEN (difference in electronegativities between

O -2 bond order = 2 = 1.5 element and oxygen) decreases, the acidic character

8-4
C2 bond order = 2 2 ; increases.
10 - 5
Acidic character of oxides increases on moving left

NO bond order = 2 = 2.5 to right and decreases on moving top to bottom.

Bond order ∝ bond dissociation energy
So, order : SiO 2 < CO 2 < N 2 O5 < SO3 .
41. N2: s1s2 s *
1s2
s2s2 s *
2s2
p2p2 p2p2 s2p2 50. Polarisation of the I - by the Cu2+ results in the
x y z

The bond order of N2 is 1/2(10 – 4) = 3.
N2+ : s1s2 s*1s2 s2s2 s*2s2 p2p2 p2p2 s2p1
x y
The bond order of N2+ is 1/2(9 – 4) = 2.5.
O2 : s1s2 s*1s2 s2s2 s*2s2 s2p2 p2p2 p2p2 p*2p1p*2p1
z x
The bond order of O2 1/2(10 – 6) = 2.
O2– : s1s2 s*1s2 s2s2 s*2s2 s2p2 p2p2 p2p2 p*2p2 p*2p1
z x
transference of an electron towards Cu2+ makes it as
oxidising agent and I - as a reducing agent, reduces
z
Cu2+ to Cu+ and is itself oxidised to I2.
51. Metallic bond results from the electrical attractions
y x y among positively charged metal ions and mobile,
delocalised electrons belonging to the crystal as a
whole. These bonds are non-directional
y x y

The bond order of O2 1/2(10 – 7) = 1.5. 52. H-bonding shown by -COOH group is stonger than
that shown by -OH group.

NO+ derivative of O2 and isoelectronic with O22+ ; so
s1s2 s*1s2 s2s2 s*2s2 s2p2 p2p2 p2p2
z x y 53. It has intramolecular H-bonding

The bond order of NO+ 1/2(10 – 4) = 3.

Hence, it cannot show

NO derivative of O2 and isoelectronic with O2+ ; intermolecular H-bonding.

s1s2 s*1s2 s2s2 s*2s2 s2p2 p2p2 p2p2 p*2p1
z x y x

The bond order of NO is 1/2(10 – 5) = 2.5.
1

Bond length \ Bond order

Bond dissociation energy ∝ Bond order
Chemistry
54. S1:Due to intermolecular H-bonding in HF it boils
at higher temperature than HCl 60.
S2: Mol. wt. of HBr < Mol. wt. of HI
S3: Bond order of N2 is more than N2+
S4: Molecular mass of F2 is less than that of Cl2

55. HCl is the most covalent species.

56. (I)

As a result of H-bonding, number of sulphuric

acid molecules are associated to form cluster.
Hence it has high boiling point and viscosity.

(II) All S—O bond lengths are equal due to
resonance.
[B4O5(OH)4]2- is the anion of borax and does not
contain any peroxide in it.
61. All are nonconductors.
(III)

62.

(IV)

63. Hybridisation is sp3.

57. HF is least volatile (i.e. highest boiling point) due to

strong intermolcular hydrogen bonding.
58. Boiling point SbH3 is greater than NH3. The higher
boiling point of SbH3 is due to higher Vanderwaal’s
forces because of its higher molecular weight despite
the presence of H-bonding in NH3.
59. Diamond (1.54Å). In graphite, perpendicular to the
sheets there is no covalent bonding
C60 (1.54Å and 1.38Å)
Benzene (1.36Å).
EXERCISE - 3
64. Hybridization of 2px and 2py does not take place
without s-orbital as 2px and 2py are degenerate
orbitals.
65. Oxidation no. of N in N2O5 is + 5
Anhydride of HOCl is Cl2O.
Bond angle : CH4 > NH3 > H2O all sp3 with same
terminal atoms and increasing E.N. of central atom.
The bond length decreases with increase in difference
of electronegativity as ionic character increases.

1. ClO2 = 11 e- 2. HClO2, H2O, NH2–1, XeF2, XeF4, I3–1, ClF3, ICl4–,

NO3- = 8 e- ICl2+, XeF5–1.
O3 = 8e- 3. s bond formation : (i)
PCl5 = 10e- p bond formation : (ii), (iii), (iv), (v), (vi)
SO3 = 12 e- No bond formation : (vii)
SO42 = 12 e- d bond formation : (viii)

CO2 = 8e-
N3- = 8e-
I3- = 10e-
 Chemical Bonding
4. Only pp– pp Only pp– dp
The 4 double bonded P-O bonds are shorter than the
other single bonded P-O bonds.

CO3–2, NO2–, NO3–2 SO3–2

SO4–2

R3PO
13.

S2O3–2

S2O8–2

PO4–3

ClO4.–

There are no pp-dp back bonds possible in NO3-.

ClO3– Hence, Ans = 5.

SO3 : (pp – dp & pp-pp )
14. PF3Cl2, SF4, BF2Cl, are polar

SO2 : (pp-pp & pp– pp)
15. C3O2, BF3, XeF4 are all non polar and entirely lie on
5. (BF3, BCl3, CO32–, SO3, XeF4) one plane.
6. H2S, NH3, PH3, PF3, H2O, NH -2 16. Only NH3, H2O, HF, HCOOH, B(OH)3, CH3COOH,
7. No. of p bond HCO3– ion. CH4 and HI cannot show H-bonding as
the H atoms are not acidic enough because they are

XeOF2 1 not bonded to highly E.N. atoms.

XeO2F4 2
17. Statement is incorrect as it depends an number of

XeO3 3 valence electrons

XeO4 4
18. Mn2O7, SO2, NO2, CrO3, SiO2 are acidic oxides.

XeO3F2 3
19. (i), (ii), (vi) are correct.

XeOF4 1
20. H3PO4, H3PO3, H3PO2, HClO4, HClO3, HClO2,

XeO2F2 2
H2SO3, H2SO4, H2SO5, H2S2O8, SO3, SO2, P4O10
All Xe-O bonds contain 1s and 1p bond.

8. 21. 1. ⇒ x=1

LP of N can be delocalised back bonding (pp–dp)
Total 9 bonds and hence 18 bonding electrons.
2. ⇒ y=4
9. N , N , O , C have fractional bond order.
+
2
-
2
+
2
+
2

1
10. Bond length \ Bond order

3. ⇒ z=1
11. (ii, iv, vii)

Bond order decreases in (ii) and (iv), hence bond
length increases.

In (vii) there is partial double bond character in BF3
4. ⇒w=0
but not so in BF4-, hence bond length is more. Also,
hybridization charges from sp2 to sp3 hence bond
length increases with the increase in the p-character
of the hybrid orbital.

22. and will have non-zero

dipole moment.
12. P4 O10
Chemistry
23. m cal = q × d = 1.6 × 10-29 C × 150 × 10-12m
= 2.4 × 10-29 Cm
mobs = 1.8 × 10-29 Cm 24. Non polar: BF3, CO2, PCl5, CH4, ; ⇒x=5
n obs
% ionic character = nCaL ×100
1.8
= 2.4 ×100
= 75 %
Planar BF3, CO2, SO2, ClF3, ⇒y=5

\ (x × y) = 25

25. (1, 2, 5, 6, 7, 8) are correct.

EXERCISE - 4

1. Bond energy ∝ Bond order

Species Bond order (b) pyramidal
CO 3
CO2 2
(c) pyramidal
CO3 2-
1.33
2. Across a period, effective nuclear charge increases.
As a result the size of atom, and therefore, the size of
d-orbital deceases leading to progressively stronger 6. (a) (b)
pp-dp bonds. Stronger the bond, shorter it is.
3. (D) Position of atoms are different.
(E) Has unpaired electrons and this is not possible
since the molecule is diamagnetic. Also, N and
O have only 4 orbitals and hence cannot have
double bond (2 orbitals), one lone pair (1 orbital)
and 2 unpaired electrons (2 orbitals) (c) (d)

+ + +

4. (a) x (b) + x

– – – 7. Steric No = 4
pz pz pz Hybridization = sp3
 bond zero overlap
8. (a) Both are sp3d
y
(b) Both are sp3d
(c) [ClF2O]+ is sp3 but [ClF4O]- is sp3d2
(c) – + + x (d)
px
s (d) Both are sp3d2
 bond
9. AsF4- has sp3d hybridization with 1L.P. and a see-

Overlap is not sufficient saw shape. Since in sp3d hybridization the axial
so, such s bond orbitals are longer than the equitorial orbitals hence
do not exist. all the bond lengths in AsF4- are not identical.
10. PH3- No Hybridisation
:

3
sp
NH3 and H2O bond angle is less than 109o28` due to
5. Se pyramidal
F O F LP-BP repulsion.
CH4 bond angle is 109o28`
(a) trigonal planar
 Chemical Bonding
11. (i) Negative charge is more stable on ‘S’ than on N
(size factor is dominant over EN factor). (c) N2O5 Dinitrogen pentoxide
(ii) Less formal charge provides more stability.
12. px-px over lap will result in s bond. Also, s-s s
overlap is weaker than p-p s overlap as the extent
of overlap is greater in case of p-p overlap due to (d) N2O4 Dinitrogen tetroxide
the longitudinal nature of p-orbitals.

22. (a) Stability O 2+ > O 2 > O 2-

13. Bond order 2.5 2 1.5
(b) Bond order of He2 is 0
(c) In all these molecules all electrons are paired in
14. I and III are sp3 hybridised while II and IV are sp2 molecular orbitals
hybridised. In II due to double bond and in IV due to
(d) There is no s - p mixing for species containing
coordinate bond from N to O.
> 14 electrons.
23. (I) O2+ : s1s2 s*1s2 s2s2 s*2s2 s2p2 p2p2 = p2p2 p*2p1 = p*2p0
z x y x y
15. Bond order = 1/2(10 – 5) = 2.5.
(II) NO is derivative of O2 and isoelectronic with
16. P4 bond angle = 60 o O2+:
PH3 bond angle ≈ 90o (Drago’s rule) so s1s2 s*1s2 s2s2 s*2s2 s2p2 (p2p2 = p2p2) (p*2p1 = p*2p0)
z x y x y

H2O bond angle = 104.5o Bond order = 1/2(10 – 5) = 2.5.

17.
18. (a) According to Bent’s rule the increase in
p-character of the O - F bond is greater in case
of O2F2.
(b) In O2F2 each O atom is in +1 while each F atom
is in -1 O.S.
(c) By Bent’s rule as the O - F bond length increases
due to high E.N. of F, it results in the decrease in
O - O bond length in O2F2.
19. Banana bond is present when bridging atom does
not have any lone pair of electrons.
20. By definition
21. (a) N2O2 Dinitrogen trioxide
(b) N2O22- Hyponitrite ion
(III)N2+ : s1s2 s*1s2 s2s2 s*2s2 p2p2 = p2p2 s2p1
x y z
Bond order = 1/2(9 – 4) = 2.5.
O2+ , NO and N2+ have same bond order i.e. 2.5 and
have same magnetic property having one unpaired
electron.
24. SO2: O ! S = O HNO2: H – O – N = O
H2SO3: HNO3:
25. S1: as it does not have d-orbitals.
S2: ClF3 2 Lone pairs, present at
equitorial positions
S3: In B2 mixing of the sg(2s) orbital with the sg(2p)
orbital lowers the energy of the sg(2s) orbital
and increases the energy of the sg(2p) orbital to
a higher level than the p orbitals. As a result, the
last two electrons are unpaired in the degenerate
(having the same energy) porbitals, and the
molecule is paramagnetic.
In N2 the sg(2s) and sg(2p) levels of N2 interact
(mix) less than the B2 and C2 levels, and the sg(2p)
and pu(2p) are very close in energy.
Chemistry
26. Bond order of N2 = 3 bond order of N2+ = 2.5 33. B2H6 has 12 bonding electrons, 3 form each B atom
B.O. of O2 = 2. and 1 form each H atom.
H
B
B.O. of O2+ = 2.5
B3N3H6 is inorganic benzene. NH NH

27. MO for C2= s1s2 < s*1s2 < s2s2 < s*2s2 < r 2p = r 2p < v 2p
1444442444443 V It is not electron deficient.
2 2
y z x
BH BH
HOMO LUMO N
H

It is important to note that double bond in C2 consists
of both p bonds because of the presence of four 34.
electrons in two p molecular orbitals C 2-
2

28. (a) H2O2 = 1.48 Å due to repulsions between non-

bonded pairs of electron on O-atoms and O2F2
= 1.217 Å. 35. Hypophosphoric Acid : H4P2O6
(b) In O very slightly increases due to charge
2-
2
O O

(-ve) on two O atoms. The oxidation states of both P

(c) O2+ : B.O. = 1.5, 1 unpaired electron
O2- : B.O. = 2.5, 1 unpaired electron
29. OF is derivative of O2 and isoelectronic with O2–.
So s1s2 s*1s2 s2s2 s2p2 = p2p2 = p2p2 p*2p2 = p*2p1
]10 - 7g
z x y x
The bond order of OF = = 1.5.
2
30. ClO2 has odd number of electrons add hence must
contain unpaired electron.
31. (a) NO : B.O. = 3, triple bond.
O = N – Cl there is a double bond between N
and ‘O’ atom, hence its B.O. = 2. Thus, bond
length of NOCl is greagter.
(b) CaC 2 / Ca 2+ + C 22- (- C / C -) B.O. = 3
C2 H4 / B.O. = 2
OH P P OH
atoms is +4.
OH OH
36. Dipole moment of compound if it would have been
completely ionic
= (4.8 × 10-10 esu) (2.67 × 10-8cm) = 12.8 D
y
4
So % ionic character = 12.8 × 100% = 31.25 %
37. Graphite has layered structure. Layers are held by
Vanderwaal’s forces and distance between two
layers is 340 pm. Each layer is composed of planar
hexagonal rings of carbon atoms. C – C bond length
within the layer is 141.5 pm Each carbon atom in
hexagonal ring undergoes sp2 hybridization and
make three sigma bonds with three neighbouring
carbon atoms. Fourth electron forms a dangling
bond. The electrons are delocalised over the whole
sheet.

(c) KO 2 / O -2 B.O. = 1.5

Na 2 / O 2-
2 B.O. = 1

(d)

32. (i) [PCl 4] + " sp3

(ii) has < 109.5o bond angle due to lp-lp

repulsion.

(iii) all have sp3 hybridisation and one lone pair.

(iv)

38. (a) A fact
(b) In the solid state and in liquid HF, the HF2– ion is
held together by hydrogen bonding. In aqueous
solutions there is hydrogen bonding but each HF
molecule forms hydrogen bonds with the much
more prevalent H2O present, instead of with
other HF molecules and H3O+ and F – are much
more likely to be formed.
(c) H3BO3 (solid) has inter molecular hydrogen
bonding.
H power of cations.
H B H H
H B H H B BaCl2 has higher melting point due to more ionic
H H H H
H B H H B H
B electrons. And if number of valence electrons are
H H
H same, then strength of metallic bond ∝ size
H
39. D is less electronegative than H-atom so the results
40. N2 is a non-polar molecule with zero dipole moment.
41. (a) As d+ charge on central atom increases, the
attraction between d+ and d- increases and thus
Xe–F bond length decreases. The correct order
is XeF2 > XeF4 > XeF6
(b) PH5 cannot exist as according to Drago’s rule
the electronegativity of terminal atoms should
be more than 2.5 to cause hybridization of
central atom belonging to 3rd or higher period.
(c) Dipole moment of CH3Cl is greater than CH3F
due to greater charge sepration on carbon and
chlorine atoms in CH3Cl.
(d) It is a correct order.
The strength of hydrogen bond depends upon :
(i) size (ii) electronegativity and (iii) ease of donation
of electron pair by electronegative element.
Higher the value of electronegativity and smaller
the size of the covalently bonded atom to H atom
stronger is the hydrogen bonding.
42. Fact based.
Chemical Bonding
43. NaCl is most ionic compound as polarizing power of
Na+ is the least among the given options.
44. The element present in short period will be of 13th
group (group no = 10 + 3 = 13) i.e. aluminium
and its oxide will be Al2O3 which is amphoteric in
nature; as react with acids as well as bases froming
salts and water.
45. As Pb2+ has low polarising power. So, PbCl2 is ionic.
CCl4 is covalent due to low E.N. difference while
PbCl4 and SnCl4 are covalent due to high polarizing
46. Solubility BaCO3 and MgCO3 can be explained on
the basis of their hydration and lattice energies.
47. AgI is less soluble than AgF due to covalent nature.
character compared to BeCl2 which has significant
covalent character due to high polarizing power of
Be2+.
Higher the charge density, larger will be the hydrated
radii.
48. Strength of metallic bond ∝ number of valence
1
49. (i) Alkali metal, potassium forms K+ (number of
electrons = 18) which is isoelectronic with P3–
(number of electrons = 18) → Q.
(ii) Transition element, chromium show maximum
oxidation state of +6 in Cr2 O 72- and CrO 2-
4 and
they are coloured → S.
(iii) Noble gas, Kr has largest atomic radius because
radius is expressed as Vanderwaal’s radius
and there is interelectronic repulsions due to
completely filled outer most shell. Inert gas has
highest first ionisation energy in the respective
period because of stable valence shell electron
configuration → T.
(iv) Element (Z = 13), aluminium has intermediate
value of electronegativity and therefore its oxide
is amphoteric in nature → R.
50. Greater the charge on the cation, more is the extent
of hydrolysis. CCl4 is a non-polar molecule.
O
51. S B.O. = 1.5, all bonds are identical due to
O - resonance.
O
O-
It is a superoctet as S has 12 valence
electrons according to the structure.
Chemistry
52. Bond order =
Total no. of bonds between twoatoms in all the structure 59. The species in which the central atom has expanded
Total no. of resonating structure
octet, are called hypervalent compounds.
 
O O O
has 4 bond pairs and 1 lone pair.

CO32- C C C
    Hence there are 10e- on S.
O O O O O O
60. If x axis is inter nuclear axis, then:

NO3- (i) 2py + 2py ⇒ p
(ii) 2pz + 2pz ⇒ p not s
2+1+1
BO = = 1.33
3 (iii) 2px + 2px ⇒ s not p
53. H 2 C = CH - C / CH (iv) 1s + 2p ⇒ non bonding

sp 2 sp 2 sp sp (v) 2py + 2pz ⇒ non bonding
(vi) 1s + 2s ⇒ s
54. b and c ⇒ Drago’s rule

Thus, (i) and (vi) are correct rest all are incorrect in
the given question.
ICl3 61. PCl6- : sp3d2 hybrid but Phosphorus has d orbitals as
vacant in ground state.

BF4- : sp3 hybrid but B has 2 vacant p orbitals which
55. (b) B2H6 is electron deficient compound as boron have participated in hybridization. Similarly, BF3
has only six electron in its valence shell. is sp2 hybrid, so 1 vacant orbital has participated in
(c) AlCl3 is a electron deficient compound as hybridization.
aluminium has only six electron in its valence
62. Bigger atoms, LP and double bond occupy equatorial
shell.
positions in trigonal bipyramidal structure.
56. In FO+ total no. of electrons = 16, so bond order will O
F
be 2. O¯
O¯
In FO- total number of electrons = 18, so bond order Xe
will be 1. 63. (a) Xe
(b)
57. Fullerene are cage like molecules. C60 molecule O¯ O¯
F
has a shape like soccer ball and called Buckminster O
Perxenate ion [XeO]6
4-
XeF2(Linear)

fullerene.
O F

It contains twenty ‘six-membered rings’ and twelve F
F
‘five membered rings’. A six membered ring is fused
(c) (d)
Xe O Xe
with six or five membered rings but a five membered
ring can only fuse with six membered rings. All F F O
F
the carbon atoms are equal and they undergo sp2 XeOF4(one l.p.) XeOF(one
22 l.p.)
hybridisation. Each carbon atom forms three sigma
bonds with other three carbon atoms. The remaining 64. (a) Due to the presence of lone pair bond angle
electron at each carbon atom is delocalised in decreases.
molecular orbitals, which in turn give aromatic CH3
|
character to molecule. This ball shaped molecule (b) B
has 60 verticles and each one is occupied by one H3C CH3
carbon atom and it also contains both single and sp2hyb.
double bonds with C–C distance of 143.5 pm and (c) NH4Cl is an ionic compound and ‘N’ is in sp3
138.3 pm respectively. hybridisation.
58. Cl 2 O > F2 O and F2 O < H 2 O (d) S8 molecule has 16
111 o
102 o
102 o
104 o electron pairs left behind
after the bonding.

NO > NO +
2
-
2

sp sp 2

AsI3 > AsBr3 > AsCl3 (due to size of halogen)
 Chemical Bonding

69.
65.

Valence shell electron configuration of Cl, 3s23p5

To obtain effective pp-dp overlap the size of the d
orbital must be similar to size of the p orbital. Hence
in chlorine, pp-dp bonding is so strong that no
polymerization of oxoanions occurs.
66. There must be vacant orbitals with acceptor atom
and the donor atom should have a lone pair of
electron. Also the size of orbitals play a role.
..
67. (CH3 )2 O : can act as lewis base but (SiH 3) 2 O &
(SiH 3) 3 N can not, as lone pairs on O & N are
70. P4 O10
The P–O bond lengths shows that the bridging
bonds on the edges are 1.60Å but the P=O bonds
on the corners are 1.43Å and this P=O is formed by
pp-dp back bonding. A full p-orbital on the oxygen
atom overlaps sideway with an empty d-orbital on
the phosphorus atom. The bond angle POP is 127º
and there is no P–P bonds.
F

delocalised in to empty orbitals of Si. 71. (a) N N Both sp2, planar.

68. (a) Nitrogen is
phosphorus.
more electronegative than F F
(b) F2 :- v1s < v1s
*
< v 2s < v*2s < v 2pz < r 2px = r 2py

(c) H2O2 :- O 22- & B.O. = 2

O2F2 :- O 22+ & B.O. = 3

(d) F2 is diamagnetic
So, dipole moment of trimethylamine is greater +2 0 +2
than trimethy phosphine. 72. C3 O 2 O=C=C=C=0

(b)

Br3 O8
In trisilyl ether the lone pair of electron on
oxygen atom is less easily available for donation
because of pp-dp delocalisation due to presence
of the vacant d-orbital with Si. This however is
S 4 O62-
not possible with carbon in CH3-O-CH3 due to
the absence of d-orbital making it more basic.
(c) Bond order of C2 and O2 are same i.e., 2. In C2
P2 O 74-
molecules both bonds are p-bonds whereas,
there is one s and one p-bond in O2 molecule
73. o-hydroxy benzaldehyde is a liquid at room
C 2 = 131 pm ; O 2 = 121 pm temperature but it is not due to intramolecular
H-bonding. It is liquid due to other reasons. It is
when intermolecular H-bonding is strong that
(d) boiling point becomes abnormally high.
74. All the given specices contain H-bonded to O, and
so are capable of intermolecular H-bonding as none
of them can form intramolecular H-bonds.

Chemistry
75. Borazine is B3N3H6. It is a non polar molecule with Cl Cl Cl
polar bonds. Thus, it can have dipole-dipole type 82. Al Al has its octet complete
interactions but benzene cannot. Cl Cl Cl

The charge on O2 in O2[AsF4] is O +2 , B.O. = 2.5 and
in KO2 it is O -2 , B.O. = 1.5. 83.
O

As halogen becomes bulkier, bond

S
angle increases. Hybridization of all atoms remain same
X X 84. I2Cl6 is still electron deficient. Hence, octet
76. The critical temperature depends on the magnitude completion is not the driving force.
(of strength) of intermolecular force of attraction BeCl2 (solid) is a polymer in which Be has its octet
between the molecules. If a molecule has dipole complete.
moment it means there is dipole dipole attraction 85. C2H6 doesn’t have any banana bonding.
between the molecules and thus it will affect the
critical temperature. 86. A = Ne
77. According to Fajan’s rule, larger the anion and 87. B 4 = P4
greater the charge density on cation more is the 88. BC3 = PCl3
covalent character. BC5 = PCl5
78. Group1 elements have lesser strength of metallic 89. B and C are both non-metals. Hence the bond
bonding than corresponding group 2 elements between them will be covalent.
due to only one electron per atom participating in 90. Small gap between V.B. and C.B. is necessary for
metallic bonding in group 1. In group 2 elements, conducting behaviour and V.B. should be occupied.
two electrons per metal atom participate in metallic
91. Fact.
bonding.
92. AlH -4 , BH -4 , AlCl -4 are not iso electronic
79. (a) due to decreasing strength of metallic bond with
increasing size of atoms.
(b) Fact
(c) Elements having half-filled stable configurations
have lesser strength of metallic bonding.
93.
(d) Electron delocalisation is the main reason for
electricity conduction in both.
80. (a) It results from the electrical attractions among
positively charged metal ions and mobile,
delocalised electrons belonging to the crystal as 94. Refer diagram above. All terminal B-H bonds are
a whole. 2c-2e bonds. Hence total 6. All B-H-Al bonds are
(b) In general, greater the number of (n–1)d and ns 3c-2e bonds. Hence 6.
electrons, stronger is the resultant bonding.
(c) Strength of metallic bond depends on the 95.
number of hybrid orbitals participating in
Same logic as Q.94 above.
metallic bonding.
(d) As the size of atom increases the attraction
between the positive part of the atom and 96. (a)
delocalised electrons decreases and thus the
strength of the metallic bond decreases.

81. B 2 H6 =

(b)

Be 2 H 4 =
 Chemical Bonding

(d)
(c)
sp3d, polar; EF-S-F ! 180o due to repulsions
from the lone pair; one lone pair.
99. Steric no. of I3– = 5, sp3d; (2B.P., 3L.P.)
(d) Steric no. of XeO3 = 4, sp3; (3B.P., 1L.P.)
Steric no. of ClOF3 = 4 + 1 = 5, sp3d;(4B.P., 1L.P.)
Steric no. of XeF5+ = 5 + 1 = 6, sp3d2 (5B.P., 1L.P.)
97. BF3 has pp-pp back bond.
(SiH3)3N has pp-dp back bond. 100. (a) non-polar, both pp-pp and pp-dp
B2H6 is sp hybrid and has banana (3c-2e) bonding.
3 bonds present. All S-O bonds are
identical
SiO2 is sp3 hybrid and has pp-dp back bond.
No lone pair.

98. (a) sp3 d; +F - I - F = 180 o; n = 0

(b) polar, pp-dp bonds present.
No lone pair.

(b)
(c) " polar
" pp-pp bonds present.
sp3d, polar; EF-Cl-F ! 180o due to repulsions " Due to resonance identical
from the lone pair. S-O bond length

(c) (d) " polar

" pp-dp bonds present.
sp3d, non-polar; EF-Xe-F = 180o " lone pair present.

1. BeF2, BF3 and CCl4 ⇒ mnet = 0 5. Ethyl acetate (CH3COOC2H5) is polar molecule so
H2O, NH3 and HCl ⇒ mnet ! 0 dipole-dipole interaction will be present in it.

2. AX is a covalent diatomic molecule. 6.

O 2 = v1s 2 v* 1s 2 v2s 2 v* 2s 2 v2p z2 r2p x2 = r2p y2 r* 2p x1
The molecule is NO.
= r* 2p y1
Total no. of electrons is 15.
O -2 = v1s 2 v* 1s 2 v2s 2 v* 2s 2 v2p z2 r2p x2 = r2p y2 r* 2p x2
3. = r* 2p y1
Species Bond order
O +2 = v1s 2 v* 1s 2 v2s 2 v* 2s 2 v2p z2 r2p x2 = r2p y2 r* 2p x1
C 2- 3 = r* 2p y0
2

O 2- 2 both O2- & O2+ have 1 unpaired e-

2

N 2- 1
2 7. Li2+ : v1s v1s
*2 v1s ⇒ B.O. = 0.5 ⇒ Stable
2 1

I

Li2- : v1s v1s
*
v 2s v*2s ⇒ B.O. = 0.5 ⇒ Stable
2 2 2 1

4. I
I

Shape : Linear, I–I–I Bond angle ⇒ 180°
Chemistry
8.
O2 → O2+ O2 → O22–
Bond order 2 2.5 2 1
Magnetic nature Paramagnetic Paramagnetic Paramagnetic Diamagnetic
N2 → N2+ NO → NO+
Bond order 3 2.5 2.5 3
Magnetic nature Diamagnetic Paramagnetic Paramagnetic Diamagnetic
9. Bond order of N2+ is 2.5, which signifies, two pi and 15. NO -2 = sp 2
half sigma bonds.

NO3- = sp 2
1
10. H = 2 (V +M −C + a)
NO 2 = sp 2
where, H = Hybridisation
NO +2 = sp
a = Anionic charge 16. There is extensive intermolecular hydrogen bonding
V = No. of valence electrons in the condensed phase not intramolecular.
M = No. of monovalent atoms 17. London dispersion forces increase from He to Xe
C = Cationic charge because molecular mass increases. So boiling point
1 will also increase from He to Xe.
∴H = 2 (8 + 4) = 6
18. Fact
i.e., sp3d2
19. Fact

From structure, it is clear that
it has five bond pairs and one 20. Decreasing order of strength of oxoacids:
lone pair. HClO 4 > HClO3 > HClO 2 > HOCl
Reason:
11. KCl is ionic compound. Consider the structures of conjugate bases
While PH3, O2, B2H6 & H2SO4 are covalent
compounds.
12. ⇒ total 9 lone pairs of electrons.

13. H 2-
2 total e = 4
-

Negative charge is more delocalized on ClO -4 due
2-2 to resonance, hence ClO -4 is more stable (& less

σ1s σ1s
* 2 2
B.O. = 2 =0 basic).
2 total e = 2
He 2+ -

2-0 21. Silicon exists as covalent crystal in solid state.

σ1s B.O. = 2 = 1
2
(Network like structure, like diamond).

He +2 total e - = 3 22. H 2+
2 : Bond order = 0
2-1

σ1s σ1s
* 2
B.O. = 2 = 0.5
1

2-2
He 2 : Bond order = 2 = 0

H -2 total e - = 3 So, both H 2+
2 & He 2 do not exist.
2-1

σ1s σ1s* 2
B.O. = 2 = 0.5
1

23. Li 2 v1s 2 v* 1s 2 v2s 2 Bond order = 1

14. NO ⇒ One unpaired electron is present in p *

Li +2 v1s2 v* 1s 2 v2s1 Bond order = 0.5
molecular orbital.
CO ⇒ No unpaired electron is present. Hence,
Li -2 v1s2 v* 1s 2 v2s 2 v* 2s1 Bond order = 0.5
paramagnetic.
Stability order Li 2 > Li2+ > Li -2
O2 ⇒ Two unpaired electrons are present in p*

molecular orbitals. 24. As electronegativity of central atom decreases, bond
B2 ⇒ Two unpaired electrons are presents in p
angle decreases. (Hybridisation and number of lone
bonding molecular orbitals. pair on central atom are same in all options)
 Chemical Bonding

1. XeO2F2 has trigonal bipyramidal geometry. Due Nodal plane

to presence of lone pair on equatorial position, the    
shape is see-saw. (+)
F x-axis
   
O (d)
Xe pz pz * molecular orbital
O
F
One node in xy plane containing
2. → It is d–d axial overlap in same the molecular axis
phase, so d–d s bonding.
→ It is p & d lateral overlap in
same phase, so it is p–d p bonding. 5.
→ It is p and d lateral overlap in
opposite phase, so it is p–d p
antibonding.
→ It is d–d axial overlap in
opposite phase, so it is d–d s
antibonding.

All above molecules have permanent dipole
3. If 2s-2p mixing is not operative, the increasing moments
order of Molecular orbitals will be :
6. Colour is imparted to the compounds when the
, v 2s , v*2s , v 2P > H
r 2p 1
amount of energy liberated by the de-excitation of

y
*
v1s , v1s 2 2 2 2 2

electrons from the excited state to the ground state

x
r 2p 1
z

Considering this Be2 & B2 become diamagnetic, releases quanta having wavelength in the visible
so does N2. Only C2 would be paramagnatic with region of the spectrum.
electronic configuration as above 7. AlCl3 does not have 3c-2e bonds in its dimer because
4. the bridging atom (Cl) has lone pair of electrons and
Nodal plane can form coordinate bond.
O

(+) Cl Cl Cl
(a)       z-axis
+ Cl O H O OH O OH
8. O OH O O
pz pz  molecular  Total 2 (i) (ii) (iii) (iv)
orbital nodal plane
Nodal plane
Number of lone pairs on Cl in (ii) & (iii) together is 3
Hybridisation of Cl in (iv) is sp3
   
(+)   + z-axis Strongest acid is HClO4 (iv)
(b) +
pz pz 9. Here polar molecules in the liquid form will be
* molecular  zero node attracted/deflected near charged comb.
orbital in the xz plane
Polar molecules : HF, H2O, NH3, H2O2, CHCl3,
+ 
(+) +
Nodal plane
C6H5Cl (6-polar molecules)
x-axis
 Nonpolar molecules : O2, CCl4, C6H6
 
(c) -molecular orbital O O
O O O
pz pz - +
Zero nodes in the plane which is 10. N = N = O, N N , S S OH , HO S O O S
perpendicular to the molecular axis O O OH O O
and goes through the center of the molecule O O O
O O
N N S
S
OH HO
S
O O
S
OH
O O OH O O
Chemistry
11. He2+, B2 and O2- are paramagnetic. The rest are 13. N2O3
diamagnetic. XX
O XX
O

XX

XX
12. [TeBr6] 2-
:- 1 L.P. N
XX
N
XX
O
[BrF2]+ :- 2 L.P.

XX
XX
- + -
[SNF3] :- 0 L.P. 14. Cl - Be - Cl N=N=N N/N$O
sp sp sp
[XeF3]- :- 3 L.P. Total 6 L.P. +

O=N=O
sp
 Redox Reactions

Chapter 5 Redox Reactions

INTEXT EXERCISE: 1
x +1 -2 6. a) O.N. of N in NH3 =- 3
1. C12 H 22 O11
b) O.N. of N in NH 2 OH = x + 2 x 1 - 2 + 1 = 0
` 12x + 22× ^+ 1h + 11 # ^- 2h = 0 or x = 0.

or x =- 1
+1 +2 -3
2. H - C / N c) O.N. of N in (N 2 H5) 22+ = 2 x (2x + 5) =+ 2 or
x =- 5/2
3. O.N of C in CO2 = x + 2 × (-2) = 0 or x = + 4.
d) O.N. of N in mg3 N 2 = 3 x (+ 2) + 2x = 0 or
4. In metal carbonyls, the O.N. of metal is always zero. x =- 3
a) O.N. of Fe in Fe(CO)5 is x + 5 × 0 = 0 or x = 0 Thus, option (d) is correct.
b) O.N. of Fe in Fe2O3 is 2x + 3x (-2) = 0 or x = +3 7. O.N. of metals in metal carbonyls is zero.
c) O.N. of Fe in K4[Fe(CN)6] is +4 +4
8. a) NO 2 and N 2 O 4 ; Difference = 0
4 × (+1) + x + 6 × (-1) = 0 or x = + 12 +5 +5
b) P2 O5 and P4 O10 ; Difference = 0
d) O.N. of Fe in FeSO 4 . ^ NH 4h2 SO 4 .6H 2 O
+x -2
+1 +2
c) N 2 O and NO ; Difference = + 2 - 1 = +1
= x + 1 × -2 = 0 or x = + 2 +4 +6
Thus, option (a) is correct. d) SO 2 and SO3 ; Difference = +6 - 4 = +2
+2 +1 X -2 x +1 -2 +1
5. Ba (H 2 P O 2) 2 9. NH 2 OH ` x + 2 # 1 - 2 + 1 = 0 or x =- 1
` 2 + 2 62× ^+ 1h + x + 2× ^- 2h@ = 0 or
10. The O.N. of metal in metal carbonyls is zero.

2 + 4 + 2x - 8 = 0 or x =+ 1
INTEXT EXERCISE: 2
+4 -2 -1 +1 -2 +2 -1 5. The balanced redox reaction equation is
1. Pb O 2 + (Cl) -1 " (Cl O) -1 + Pb (OH) 3-
4Fe + 10HNO3 " 4Fe (NO3) 2 + NH 4 NO3 + 3H 2 O
Change O.N. of Pb =+ 2 - 4 =- 2
Thus the correct ratio of coefficients of HNO3 ,
Change in O.N. of Cl =+ 1 - (- 1) =+ 2
Fe (NO3) 2 and NH 4 NO3 respectively are 10, 4, 1
Hence option (b) is correct. and hence option (b) is correct.
0 -1 +2 +1
2. a) Br2 " HBr b) HgCl 2 " HgCl 2 6. Zn + Cu 2+ " Zn 2+ + Cu
-1 0 +1 Here Zn is oxidized to Zn 2+ as its O.N. increases.
c) 2KI " I 2 d) 2Cu 2+ " Cu 2 I 2
2+4-2 +2 - 2 +4 - 2

3. a)
+2
CO " CO 2
+4
b) 2Cu 2+
+2
" CuCl 2 7. CaCO3 " CaO + CO 2
+1 0 0 +4 This is not a redox reaction since no element
c) H2 O " H2 d) C " CO 2 undergoes a change in O.N.
4. In all these reactions the same substance is reduced +3 -2 +2 0

as well as oxidised. Therefore, option (d) is correct. 8. FeCl3 + H 2 S " 2FeCl 2 + 2HCl + S
Here FeCl3 acts as an oxidising agent and oxidises
H 2 S to S . Hence option (a) is correct.
Chemistry
9. a) H 2 SO 4 + 2NaOH " Na 2 SO 4 + 2H 2 O is a d) H 2 O (l) " H 2 O (g)
neutralization reaction. Only state of matter changes and hence there is
o o
b) 2O3 " 3O 2 no change in O.N.
O.N. of O in both O3 and O2 is zero, therefore, Thus option (c) is correct.
it is not a redox reaction but is actually a 10. 2MnO -4 + 5C 2 O 24- + 16H +
decomposition reaction. " 2Mn 2+ + 10CO 2 + 8H 2 O
0 0 +2 -2
c) 2N 2 + O 2 " 2NO
From the above balanced equation is clear than
Here O.N of N increases from 0 in N2 to +2 in coefficient of oxalate ion, C 2 O 2-
4 is 5.

NO, and that of O decreases from 0 in O2 to -2

in NO. Therefore, it is a redox reaction.
INTEXT EXERCISE: 3
0 -3
8. NaOH + H3 PO 4 " NaH 2 PO 4 + H 2 O
1. N 2 + 6e - " 2NH3
Here reduction of N2 (28g) requires 6 moles Here 1 mole of NaOH reacts with 1 mole of H3PO4
of electrons, therefore, equivalent weight of Since during the reaction the acid loses only one H+
N2 =
mol.wt. 28
= 6 ion per molecule, so n-factor of acid = 1. Therefore,
6 equivalent weight of H3PO4 in this reaction is 98.
+7 +6
2. For the given reaction MnO -4 " MnO 24- 9. SO 2 + 2H 2 S " 3S + 2H 2 O
Change in O.N. of Mn = 1
In this reaction, SO2 acts as the oxidising agent.
Mol.wt.
Eq.wt.
` of KMnO 4 = = 158 +4 0
1 Reduction: SO 2 " S
3. For the given reaction I 2 " 2IO3- + 10e -
To balance O.N., add 4e- to L.H.S. we have
n-factor of I2 = 10 0
\ Eq. wt. of I2 = M/10 SO 2 + 3e - " S
+7 +2 Therefore, n-factor of SO2 in this reaction = 4
4. KMnO 4 " MnSO 4 change in O.N. of Mn = 5 1 1
\ Eq. wt. = M/5 Eq. wt. of SO 2 = 4 # Mol.wt. = 4 # 64 = 16.

5. MnO -4 + 8H + " Mn 2+ + 4H 2 O 10. Acidic medium:

+7 +2
To balance charge add 5e- to LHS
MnO -4 + 8H + + 5e - " Mn 2+ + 4H 2 O
MnO -4 + 8H + + 5e - " Mn 2+ + 4H 2 O Basic medium:
6. If a redox reaction involves two-electron change
MnO -4 + 2H 2 O + 3e - " MnO 2 + 4OH -
then the Eq. wt. of the substance is half the molecular Neutral medium:
+2 +4
weight, i.e., MnSO 4 " MnO 2
MnO -4 + 2H 2 O + 3e - " MnO 2 + 4OH -

7. FeSO 4 " Fe 2 ^SO 4h3 If M is the molecular weight of KMnO4, then its
+2 +3

equivalent weights in acidic, basic and neutral media

FeSO 4 present in Mohr’s salt gets converted into M M M
respectively are: 5 : 3 : 3 or 3 : 5 : 5.
Fe 2 (SO 4) 3 . This is a one-electron change and
hence Eq. wt. of Mohr’s salt is equal to its Mol. wt.
INTEXT EXERCISE: 4
1. Fe 2+ 3+
" Fe + e -
; n-factor = 1 5 moles of oxalicacid react with KMnO4 = 2 moles

Mn + Se " Mn ; n-factor = 5 in acidic medium. 2.70
7+ - 2+
2.70g oxalic acid = 90 mole = 0.03 moles
M
` 1 V1 n1 = M 2 V2 n 2 ` 0.03 moles of oxalic acid will react with =
1 2
10
` # 10 # 1 = M 2 V2 5 5 # 0.03 = 0.012 mole
M
1
` 2 V2 = 5 = 0.2 M` KMnO # VKMnO (mL) = 12
4 4

12
2. The balanced equations is V` KMnO = 0.05 = 240 mL
4

2KMnO 4 + 3H 2 SO 4 + 5H 2 C 2 O 4 "
K 2 SO 4 + 2MnSO 4 + 8H 2 O + 10CO 2
 Redox Reactions
3. According to the given reaction 7. The weight % of available Cl2 from the given sample
2S 2 O32- " S 4 O62- + 2e - of bleaching powder on reaction with dil acids or
` Eq. wt. of Na2S2O3 . 5H2O CO2 is called available chlorine.
Mol.wt. 248 CaOCl 2 + H 2 SO 4 " CaSO 4 + H 2 O + Cl 2
= 1 = 1 = 248
71
1000 cm of 1 N sol require Na 2 S 2 O3 .5H 2 O = 248g
3 Max. % of available of Cl 2 = 127 # 100 = 55.9% .
` 1000 cm3 of 0.2 N of require 8. 2 moles of Cu2+ = 1 mole of I2
248×0.2
Na 2 S 2 O3 .5H 2 O = 1000 ×100 = 4.96g = 2 moles of hypo.

4. Na2CO3 + H2SO4 → Na2SO4 + H2O + CO2 so moles of hypo used = 20 # 10- 3 # 0.1 = 2m
moles = moles of copper hence % of copper
0.125
Moles of of Na2CO3 = 106 2 # 10 -3 # 63.5 #
= 0.2 10% = 63.5%
0.1×V 0.125
\ 2 = 106 9. H2C2O4 readily participates in oxidation-reduction

\ V = 0.0236 L = 23.6 mL and acid-base reactions both (due to 2 acidic H and
5. n factor of KMnO4 = 5 C in + 3 oxidation state).
n factor of K2Cr2O7 = 6 10. Volume strength = N × 5.6
\ M × V × n-factor = no. of eq. of Fe2+ or 11.2 = N # 5.6
\oxidized greater n-factor means more Fe2+
or N = 2 eq/L
6. MnO -4 + 5e - $ Mn 2+ = 2 # 17 g/L

C62+ $ 2C 4+ + 2e - = 34 g/L

\ moles of KMnO4 × 5 = moles of oxalate × 2 34g
5 = 1000ml # 100 = 3.4% (wt/vol)

\ moles of oxalate = 2 × moles of KMnO4

EXERCISE - 1
1. O.N. of P in H3PO3 (phosphorous acid) 6. Fe : O, N : - 2, N : +3, Cr : +6

x 2-
3 x 1 + x + 3 x (- 2) = 0 or x =+ 3 7. O.N. of Os in OsO 4 , x - 4 # 2 = 0 or x =+ 8

In orthophosphoric acid (H3PO4), O.N. of P is +5, x -2 -1

In hypophosphorous acid (H3PO2) it is +1 8. O.N. of Cr in CrO 2 Cl 2 is

while in metaphosphoric acid (HPO3), it is +5. x + 2× ^- 2h + 2× ^- 1h = 0

2. Highest O.N. of Mn in K2MnO4 is 2 + x - 8 = 0 or
or x – 4 – 2 = 0 or x = + 6.
x = + 6 while in all other compounds O.N. of Mn is x -2

lower than 6, i.e., 9. The O.N. of Fe in Fe3 O 4 is 3x – 4 x 2 = 0

+4 +8/3 +2
or x = 8/3

MnO 2 , Mn3 O 4, MnSO 4 x -2

3. Which of the following elements has least oxidation 10. (SO3) 2-, x - 6 =- 2, x =+ 4

Ni ^CNh4 Ni ^COh4
+2 0 x -2

(S 2 O6) 2-, 2x - 8 =- 2, x =+ 3
+3 +6 x -2

Fe 2 O3, SF6
(S 2 O 4) 2-, 2x - 12 =- 2, x =+ 5

Here O.N of Ni is least, i.e., 0 in NiCO4 11. In case of Cl 2 O chlorine shows +1 oxidation state.
4. The O.N. of Fe in 9Fe(H 2 O) (NO) +1C SO 24- is
x 2+ 0 +5
12. Br2 " BrO3- , in this reaction oxidation state change
x + 0 + 1 = + 2 or x = + 1. from 0 to + 5.
0 +1 -1 +1 -2 13. HClO4 is perchloric acid
5. S8, S 2 F 2, H 2 S
1 + x - 2 # 4 = 0; 1 + x - 8 = 0

Here O.N. of S in S8, S2F2 and H2S respectively are

x = 8 - 1 =+ 7 oxidation state.
0, + 1 and -2.
Chemistry
14. The chemical structure of H2S2O8 is as follows: 0 +4 +1 -2 +5 +4

O O 26. 3Br2 + 6CO32- + 3H 2 O " 5Br - + BrO3- + 6HCO3-

|| || Here, O.N. of Br increases from 0 in Br2 to +5 in
H-O- S-O-O- S-O-H BrO3- and decreases to -1 in Br - therefore Br2 is
|| || both reduced and oxidised.
O O
2+
So the oxidation number of S should be : 27. MnO -4 + 8H + + 5e - " Mn + 4H 2 O] ×2
2 # (+ 1) + 2 # X + 6 # (- 2) + 2 # (- 1) = 0 C 2 O 24- " 2CO 2 + 2e -] ×5
(for H) (for S) (for O) (for O - O) 2+
or X = +6. 2MnO -4 + 5C 2 O 24- + 16H + " 2Mn + 10CO 2 + 8H 2 O

15. In hydrazoic acid (N3H) nitrogen shows -

1 Thus, the coefficients of MnO -4 , C 2 O 24- in the above
3 balanced equation respectively are 2, 5, 16.
oxidation state.
x +1
1 28. H 2 O 2 + 2OH - " O 2 + 2H 2 O + 2e -] ×5
N3 H:3x + 1 = 0, 3x =- 1, x =- 3
ClO 2 + 2H 2 O + 5e - " Cl - + 4OH -] ×2
16. Only in reaction (d), the O.N. of element changes.
5H 2 O 2 + 2ClO 2 + 2OH - " 2Cl - + 5O 2 + 6H 2 O
0 +1 2+ 0

Zn + 2HCl " ZnCl 2 + H 2 Thus x, the coefficient of ClO2 is 2 while y, the
coefficient of Cl - is 5.
17. Oxidation: Fe " Fe3 O 4
0 8/3 29. C is in + 4 O.S. and cannot get oxidized any further.
3Fe " Fe3 O 4
To balance O.N. on either side, add 8e- to R.H.S., 30. 2K 2 CrO 4 + 2HCl " K 2 Cr2 O 7 + 2KCl + H 2 O
we have 3Fe " Fe3 O 4 + 8e - 31. HNO3 has acidic H atom and also N is in + 5 O.S.
Thus eight electrons are lost. So, HNO3 is both an acid and an oxidizing agent.
18. 4Zn + NO3- + 7H 2 O " 4Zn 2+ + NH +4 + 10 OH - 32. Zn
Ox Red
Zn 2+ + 2e -, Ag + + e - Ag
Thus, the coefficients of Zn, and OH- respectively +7 -1 0 +2
are 4, 1, 10. Thus option (c) is correct. 33. KMnO 4 + HCl " Cl 2 + MnCl 2 + KCl + H 2 O
19. In basic medium, chromium salts form chromates. Thus KMnO4 has been reduced to MnCl2 (because
Therefore, the balanced equation is O.N. of Mn decreases). Hence the reduced product
Cr ^OHh3 + 2ClO - + OH - " CrO 24- + 2Cl - + 2H 2 O is MnCl2.
20. NO3- + 4H + " 2H 2 O + NO 34. In alkaline medium
In this equation, all the atoms are balanced.
2KMnO 4 + KI + H 2 O " 2MnO 2 + 2KOH + KIO3
To balance charge add 3e - to L.H.S., we have
NO3- + 4H + + 3e - " 2H 2 O + NO 35. In acidic medium BaCrO4 is converted into BaCr2O7

2CrO 24- + 2H + " Cr2 O 72- + H 2 O
21. O.N. of Ni changes from 0 to +2 and hence Ni acts
as a reducing agent.
Cr2 O 72- + 14H + + 6e - " 2Cr3+ + 7H 2 O
-2 0

2CrO 24- + 16H + + 6e - " 2Cr3+ + 8H 2 O
22. 2H 2 S + SO 2 3S + 2H 2 O
Here SO2 acts as an oxidising agent and thus oxidises Thus 2BaCrO 4 / 6e - or BaCrO 4 / 3e -
S from - 2 to 0.
1
\ Eq. of Ba 2+ / 3 # At.wt.
23. BaO 2 + H 2 SO 4 " BaSO 4 + H 2 O 2 1
= 3 ×137.34 = 45.78
Valency is the charge on an ion for ionic species and
the number of bonds for covalent species. 36. Let E.W. of metal be E
x y
+2 +5
` E = E+8
24. NO + 3I 2 + 4H 2 O " 2NO3- + 6I - + 8H +
Here, NO acts as a reducing agent and reduces I2 to E ` = y-x
8x
I- since the O.N. of nitrogen changes from +2 in NO
to +5 in NO3- . 37. n-factors if H3PO4 in the given reactions are 1, 2
98 98 98
25. In CO2, the O.N. of C, i.e., + 4 is already the and 3 respectively. Thus, E.W. are 1 , 2 , 3
maximum and it cannot increase its O.N. further and respectively
hence does not act as a reducing agent.
 Redox Reactions
38. Suppose E.W. of metal = E 1.12
49. No. of eq. of H 2 = 11.2 = 0.1 = no. of metal

\ E.W. of oxide = E + 8 and E.W. of chloride
E.W.
` of M = 12g
= E + 35.5

3 5
` E + 8 = E + 35.5 & E = 33.25 50. FeC 2 O 4 " Fe3+ + 2CO 2 + 3e -
Milli equivalents of FeC2O4 = 0.1 × 3 × 25 = 7.5
39. 6 × 1023 electrons / 1 equivalent
From option (D), milli equivalents of KMnO4
6 # 10 20
\ 6 # 10 20 electrons = = 0.001 equivalent = 0.1 × 5 × 15 = 7.5
6 # 10 23

\ m. eq. of FeC2O4 = m. eq. of KMnO4
40. 6e - + N 2 $ 2N3-
n` - factor = 6 51. 1.68 × 10-3 × 6 = 3.36 × 10-3 × x
mol.wt. 28 x = 3
Eq. wt. = n - factor = 6 = 4.67 .
So, oxidation number of A increases by 3.
41. 2Br5+ + 10e - " Br2
\ New oxidation number of A = –n + 3=3–n.
10
\ n-factor = 2 = 5 52. K 2 Cr2 O 7 + 4H 2 SO 4 + 3SO 2 "
+6
M
E.W.
` = 5 K 2 SO 4 + Cr2 (SO 4) 3 + 3SO3 + 4H 2 O
O.N. of S changes from + 4 in SO2 to + 6 in SO3.
42. In this reaction H2SO4 is providing only 1 H+
+5 -1
therefore, its n-factor = 1 and equivalent mass = 53. 3KIO3 + 3SO 2 " 3K I + 3SO3
98
1 During this reaction, O.N. of iodine changes from
43. eq HNO = eq NaOH
3
+5 in KIO3 to – 1 in KI.
18.9 3.2 54. Cr2 O 72- + 14H + + 6e - " 2Cr3+ + 7H 2 O
63 x 1 x V1 = 40 x 1 x V2
n-factor of K2Cr2O7 = 6
V1 4
V2 = 15 1
\ Eq. wt. of K 2 Cr2 O 7 = 6 (molecular weight)
+7 +6
44. KMnO 4
+1e-
(MnO 4) -2 55. N 2 H 4 - 10e - " Y (with two N atoms)
+7 +4 Total O.N. of two N atoms in N2H4 is - 4
+3e-

KMnO 4 MnO 2 Since it loses 10 moles of electrons, therefore, total
+7
+4e- 1 +3 O.N. of two N atoms increases by 10, i.e., the total

KMnO 4 2 Mn 2 O3 (2x-6=0 or x=3) O.N. of two N-atoms in
+7 +2

KMnO 4
+5e
Mn Y = - 4 + 10 = + 6

\ O.N. of each N atom in Y = + 3.
45. 2I 7+ + 14e - " I 2 +7

14 56. MnO -4 + 5e - " Mn 2+

n` - factor = 2 = 7
Since 1 mole of MnO -4 accepts 5 moles of electrons,
So eq. wt. = M/7. therefore, 5 moles of electrons are lost by 1.67 moles
of M x+
46. I 2 + 2e - " 2I - & n - factor = 2

\ 1 Mole of will lose electrons=5/1.67
M.W.
E.W.
` of I 2 = 2 = 3 moles (approx.)
Since M x+ changes to MO3-
47. I5+ + 6e - " I -
(where O.N. of M = +5) by accepting 3 electrons
n
` - factor of KIO3 = 6
x
` =+ 5 - 3 =+ 2 .
M.W.
E.W.
` = 6 57. CaCO3 " CaO + CO 2
0 Since oxides of metals are produced by burning.
48. H 2 S " S + 2e Therefore, option (d), is correct, i.e., statement is
Equivalent wt. =
Mol.wt. 34
= 2 = 17 . incorrect as there is no change in O.S. of any element
2
but the reason is correct.
Chemistry
58. BaO 2 + H 2 SO 4 " BaSO 4 + H 2 O 2 Thus 5FeC 2 O 4 / 3MnO -4
The most electronegative atom is O. It appears in 1FeC - -
` 2 O 4 / 3/5 MnO 4 = 0.6 MnO 4
SO 2-
4 where its O.N. is -2 and in H2O2 where it is
-1. Therefore, option (b) is correct. 60. HNO3 + 4e - " ?
59. Fe(C 2 O 4) E Fe 2+ + C 2 O 24- O.N. of N in HNO3 = + 5
Both Fe2+ and C 2 O 2- Electrons gained = 4
4 are oxidised by in acidic
medium. \ O.N. of N in new compound = + 5 – 4 = + 1
Fe 2+ " Fe3+ + e - Since O.N. of N in N2 = 0
C 2 O 24- " 2CO 2 + 2e - O.N. of N in N2O = + 1
FeC 2 O 4 " Fe3+ + 2CO 2 + 3e - O.N. of N in NO2 = + 4
Thus, the balanced equation for this redox reaction O.N. of N in NH3 = – 3
may be derived as follows:
Thus the product of reduction is N2O
MnO -4 + 8H + + 5e - " Mn 2+ + 4H 2 O] ×3
FeC 2 O 4 " Fe3+ + 2CO 2 + 3e -] ×5
Now 2HNO3 / N2O or HNO3 = 0.5 N2O
-
3MnO 4 + 24H + 5FeC 2 O 4 " 3Mn 2+ + 5Fe3+ + 10CO 2 + 12H 2 O
+
\ 0.5 mole of N2O is produced.

EXERCISE - 2
1. In HNO 2 oxidation number of N = + 3 7
12. 2CrO5 + 3H 2 SO 4 " Cr2 (SO 4 + 3H 2 O + 2 O 2
3

In HNO3 oxidation number of N = + 5.

13. O3 will oxidize H2O2 into oxygen
2. K [Co (CO) 4]
hence radioactive oxygen of H2O2 will go only in

1 + x += 0; x =- 1
oxygen not in water.
+6 +6
3. K 2 Cr2 O 7 " K 2 CrO 4 . In this reaction no change in 14.
oxidation state of chromium.
4. Hydrogen have oxidation no. + 1 and – 1.
5. Maximum oxi. state for Cr is + 6.
x y
6. FeS 2 FeS 2
x - 4 = 0 4 + 2y = 0
x = +4 2y = - 4 15. During oxidation of H2O2, O–O bond is not broken.
-4
y = 2 =- 2 +5
1 +1
16. HNO3 " 2 N 2 O
*
7. KIO 4 If HNO3 is converted into N2O then change in O.N.

1 + x - 2 # 4 = 0; x = 8 - 1 =+ 7 is 4. Hence 4 moles of electron will be involved per
mole of HNO3.
8. In all these three compounds
17. In FeO0.93 some Fe are in +2 while some in + 3 O.S.
H2SO4, H2SO5, H2S2O8, ‘S’ is in +6 state which is it’s
Let the Fe2+ ion be x mole and Fe3+ be (0.93 - x)
maximum oxidation state.
mole
9. C5H8 C5H12 As total charge on cations = anions
8 # 12
%H = 68 100 %H = 72 # 100 x × 2 + 3 (0.93 – x) = 2
= 11.76 % 2x + 0.93 × 3 – 3x = 2
% increases = 16.66 – 11.76 = 4.91% –x = 2 – 2.79
hence n = 5
x = 0.79 mole
10. Fe can show +8 highest state and it forms FeO42– in
Fe 2+ " Fe3+ + e -
which its oxidation state is +6.
Mn7+ + 5e - " Mn 2+ (acidic medium)
11. H2C2O4 readily participates in oxidation-reduction 0.79
and acid-base reactions both. \ KMnO4 needed = 5 = 0.158 mole.
 Redox Reactions
18. B 2 H6 + 2KOH + 2H 2 O " 2KBO 2 + 6H 2 +7
39 + 55 + 64
29. i) KMnO 4 $ Mn 2+ & E1 = 5
+5 -3
19. NO -3 $ NH +4 +6
39x2 + 52x2 + 16x7
ii) K 2 Cr2 O 7 $ Cr +3 & E 2

8e - + 10H + + NO -3 $ NH +4 + 3H 2 O 6
+5
39 + 35.5 + 48
+1 +3 -2 iii) KClO3 $ Cl - & E3 6
20. In HNO , ‘N’ is in +3 state but it’s O.N. can be – 3
to 5 hence it can act as both oxidising and reducing 30. 6e - + 10H + + V2 O5 $ 2V2 + + 5H 2 O
agent. Rest are facts. (Zn $ Zn 2+ + 2e -) # 3
1
21. N5+ + 5e - " 2 N 2 V2 O5 + 3Zn + 10H + $ 3Zn 2+ + 2V 2+ + 5H 2 O
If HNO3 is converted into N2 then change in O.N. Now H 2 O + V 2+ $ VO 2+ + 2H + + 2e -
is 5. Hence 5 moles of electron will be involved per 2e - + I 2 $ 2I -
1 V + I 2 + H 2 O $ 2I - + VO 2+ + 2H +
2+
mole of HNO3 when it forms 2 mole N2.
So, 1 mole of V2O5 will reduce 2 moles of iodine

so b 102 + 80 l # 2 moles of will be reduced by

22. H3PO2 H3PO3 H3PO4 10
V.f. 1 2 3
given amount of V2O5=0.11 moles of I2.
NaOH Ca(OH)2 Al(OH)3
V.f. 1 2 3 31. 2 moles of Cu2+ produces 1 moles of I2 which needs
2 moles of hypo.
m.eq. must be equal so x : y : z = 1 : 1 : 1
+5 0 +5 0
Now, moles of hypo used = 20 × 10-3 × 0.1 = 2 moles
23. 2KClO3 + I 2 $ 2KIO 3 + Cl 2 = moles of copper
24. May equations hence % of copper
Reduction : 2e - + Br2 $ 2Br - 2 # 10 -3 # 63.5 #
= 0.2 10% = 63.5%
Oxidation : 2H 2 O + SO 2 $ SO 2-4 + 4H + + 2e -
9
SO 2 + Br2 + 2H 2 O $ SO 2-4 + 2Br - + 4H + 32. Ni (CO) 4 Ni + 4CO

5CO + I 2 O5 " I 2 + 5CO 2
25. Equivalents of KMnO4 = equivalent of FeSO4 +
equivalent of FeC2O4
2S 2 O32- + I 2 " S 4 O62- + 2I -
n-factors: KMnO 4 = 5, FeSO 4 = 1, FeC 2 O 4 = 3 5 moles Ni(CO)4 will prodeuce 20 mole CO
x × 5 = 1 × 1 + 1 × 3 So, moles of I2 produced = 4 moles
4
x = 5 mole So moles of hypo used = 8 moles = (4 M) (2 litres).
33. Excess of Mohr’s salt = 30 × 0.1 × 5 meq. = 15 meq
26. Fe 2+ " Fe3+ + e -
Mohr’s salt consumed = [(35 × 1.0 × 1)-15] meq

S 22- " 2S 4+ + 10e - = 20 meq.

\ n-factor of FeS2 = 1 + 2 × 5 = 11 Now Cl 2 + 2Fe 2+ $ 2Fe + + 2Cl - (balanced

\ Equivalent weight = 11
M equation)
1
So moles of Cl 2 = 2 # moles of Fe 2+
27. As62+ $ 2As5+ + 4e -
1

S63- $ 3S6+ + 24e - = 2 # 20m moles = 10 mmole

As 2 S6 " 2As5+ + 3S6+ + 28e - 10
= # 10 -3 # 71gm = 0.71gm

` n - factor = 28 0.71
M So, % available Cl2 = 10 # 100 = 7.1%

E = 28
Na 2 S 2 O3 + 2AgNO3 $ Ag 2 S 2 O3 . + H 2 SO 4
28. Let Ca3 (PO4)2 is x-mole 34. White ppt.
H3PO3 is y-mole Ag 2 S 2 O3 + H 2 O $ Ag 2 S . + H 2 SO 4
x 1 black ppt.
2x
& =y& y = 2
OS
` of S =- 2
moles of 'O' Ca3 (PO 4) 2 8x 4
Moles of 'O' in H3 PO3 = 3y = 3
Chemistry
1 43. M. eq. of the substance = M. eq. of the solution
35. 30 # 12 = 20 # N '
Let x be the percentage purity of the substance hence
x

30 1
N ' = 12 # 12 = 8 normality will be 100
1 #
\ strength = N ' # equivalent mass = 8 # 17 # 2 x # x
⇒ 100 E # 100 = 25 100

= 2.12 g/L. 2 # 1000
⇒ E=
25
36. Valency factor of K 4 [(Fe (CN) 6] = 61

⇒ E = 80
so if molarity of H2O2 = xM then
44. MnO 2 " Mn3 O 4
2 x × 100 = 5 × 61 × 1 a
mole a
for KMnO4 and K4[Fe(CN)6] reaction 9 3
mass : a × 87 76.33 a
61 × y × 5 = 5 × 61 × 1 ⇒ y = 1M
% loss in weight is
305
so x = 200 = 1.525 87a - 76.33a #
= 87a 100 = 12%
so volume strength = 17.08
45. Moles of iodine = moles of chlorine
37. Volume strength = 11.2 Molarity
80 # 0.2 # -3

⇒ M = 1 mol/L = 2 10
Hence there are 34 g H2O2 in 1 litre 8 = # 10 -3

i.e. 3.4 g in 100 mL 8 # 71 # 10 -3 #

so required % = 3.55 100% = 16%
wt.
Hence 3.4 % vol.
46. Meq. of KMnO 4 = Meq. of Fe (NO3) 2
38. meq of meq of FeSO 4 = meq of KMnO 4 1
10 # 5 # V = 1 # 1
100 # 2 # 5
eq. of FeSO 4 = =1
1000 V = 2 ml
moles of FeSO 4 = 1
1 47. 5I - + IO3- + 6H + $ 3I 2 + 3H 2 O
Moles
` fraction of FeSO 4 = 3
moles of KI used
11.2 moles of KIO3 used = 5
39. N H O = 5.6 = 2N
2 2

valency factor of KIO3 = 5

KMnO 4 60 # 2 = VKMnO # 0.1 # 5 4

mol.wt.

VKMnO = 240 ml 4

` E KIO =3
5

K 2 Cr2 O 7 60 # 2 = VK Cr O # 0.1 # 6 2 2 7
48. Meq of titrate = Meq of KMnO4 (with H2SO4)

VK Cr O = 200 ml.
2 2 7
Meq of titrate = Meq of KMnO4 + Meq of HNO3
Vol. strength (with HNO3)
40. Normality = 5.6 Normality of resultant
solution 49. Iodine undergoes disproportionation in strongly
100 # 1 + 100 # 2 3 alkalie medium.
= 100 + 100 = 2 N = 1.5N
50. N 24- $ N 2 + 4e - & n - factor = 4
Strength in gm/L = 1.5 # 17 = 25.5 gm/L

Fe3+ + e - $ Fe 2+ & n - factor = 1
41. 6H + BrO + 6I " 3I 2 + 1Br + 3H 2 O
+
3
- -
Meq. of N2H4 = Meq. of K3[Fe(CN)6]
n
= KBrO # 3 and n Na S O = 2n I
3 2 2 3 2
m. moles x 4 = 30 × 1 × 1
V m. moles of N2H4 = 7.5

` 0.002 # 3 # 2 = 0.1 # 1000
7+ 2+ 4+

& V = 120 ml 51. KMnO 4 + MnSO 4 $ MnF4
n = 3 n=2
42. 8KMnO 4 + 3Na 2 S 2 O3 + H 2 O "
Meq. of KMnO4 = Meq. of MnSO4
2KOH + 8MnO 2 + 3Na 2 SO 4 + 3K 2 SO 4
3×x=2×y
So x < y
 Redox Reactions
52. Meq. of reductant in 25 mL = Meq. of KMnO4 35
wt. of SeO32- in mg = 36 × 127

` Meq. of reductant in 1 litre = 20 × 0.01 × 5
= 123.47 mg . 123 mg
Reductant shows the change A +32 $ 2A +b + 2e -

M.wt.
` Eq. wt. of reductant = 2 54. C 2 O 2-4 + K 2 Cr2 O 7 $ Cr +3 + CO 2

a Meq. of reductant = 40 n-factor of C 2 O 24- = 2

w 2.52 # 2 # 1000 n-factor of Cr2 O 72- = 6
` M/2 # 1000 = 40 ` = 40
M Meq. of C 2 O24- = Meq of K2Cr2O7
M = 126
1 1
M × 2 × 25 = 10 × 10 = 50
53. m.eq. of SeO32- = m.eq. of BrO3-
2 × m.mole of SeO32- = m.eq. of BrO3- × 5 55. Fe 2 (C 2 O 4) 3 + K 2 Cr2 O 7 $ Fe +3 + CO 2 + Cr +3
2 × m.mole of As2- = m.eq. of BrO3- × 6 n = 6 n=6
2 2
5 x m.mole of SeO3 + 6 m. mole of AsO2
2- - 1
meq. of Fe 2 (C 2 O 4) 3 reacted = 10× 10 = 1
1 meq. of FeCl3 required = 1
20= # 40
m. mole of SeO32- = b 2 - 3 l 2 = 36
1
1 1 5 35 millimole of FeCl3 = 3

EXERCISE - 3

Numerical Type m. eq. of H2SO4 = m. eq. of Na2CO3 + m. eq. of

NaOH
1. The relevant equations are
0.15 × 2 × V = (a × 2) + (a × 1)
2Cu2+ + 4I- → 2CuI + I2
V = 15 ml
I2 + 2S2O32- → 2I- + S4O62-
m.moles of Cu2+ = m.moles of I2 × 2 4. Mg - 2e - $ Mg 2+
1 equivalents = moles × n-factor
m.moles of I2 = 2 × m. moles of hypo
=2×2=4
1
m.moles of Cu2+ = 26.9 × 0.0847 × 2 × 2
5. 22400 mL volume contains = 1 mole gas
= 2.278 mmol.

` 224 mL volume contains
weight of Cu = 2.278 × 63.5 = 144.65 mg 1 1
144.65
= 22400 ×224 = 100 mole CO 2
% Cu = 220 × 100 = 65.75
Eq of CO2 = Eq of HCl
2. 2I- + O3 + H2O → 2OH- + I2 + O2
1 20
I2 + 2Na2S2O3 → Na2S4O6 + 2NaI 100 ×2 = 1000 ×N (n-factor of CO2 = 2)
From the above reaction: N = 1 N

2Na2S2O3 ≡ I2 ≡ O3 6. m. eq. of H3PO4 = m. eq. of Ba(OH)2

40 × 0.1 120 × 1.5 × 3 = V × 3 × 2
mol of Na2S2O3 = 1000 = 0.004
So, V = 90 mL
mol of I2 = mol of O3 = 0.002
volume of O3 at STP = 0.002 × 22.4 7. meq of Na2SO3 = meq of salt
= 0.0448 L present in 1 L mixture 25 × 0.1 × 2 = 50 × 0.1 × x & x = 1
Percentage of O3 = 4.48% (by volume) So, oxidation number of metal decreases by 1.
New oxidation number of metal = 3 - 1 = 2.
3. Suppose, no. of moles = a
9
In presence of phenolphthalein indicator 8. Ni(CO)4 Ni + 4CO
m. eq. of HCl = m. eq. of Na2CO3 + m.eq. of NaOH 5CO + I2O5 " I2 + 5CO2
30 × 0.1 = (a ×1) + (a × 1) 2S2O32– + I2 " 2I– + S4O62–

` a = 1.5 so moles of I2 produced = 4 moles
In presence of methyl orange indicator so moles of hypo used = 8 moles = (4 M) (2 litres).
Chemistry
9. 85 = Emetal + EOH -
13. Valency factor of
or 85 = Emetal + 17 K2C2O4. 3H2C2O4. 4H2O is 2 + 3 (2) = 8
or Emetal = 68 (as we now that KMnO4 oxidises only C2O42– to
CO2)
10. 40 g, O / 60 g metal Now equivalents of K2C2O4. 3H2C2O4. 4H2O =

` 8 g, O / 12 g metal equivalents of MnO4–
5.08 1
0 +8/3
11. 3Fe + 4H 2 O $ Fe3 O 4 + 4H 2 508 × 8 = 1 × 5 × V × 1000 , so V = 16 mL.
3Fe + 4H 2 O $ Fe3 O 4 + 8H + + 8e - 14. V.f. of SO2 = 1 (6 - 4) = 2
M 64

8
V.f. of Fe = 3 ` Eq. wt. = 2 = 2 = 32

E Fe =
Atomic mass 56
= 8/3 = 21 15. Species which are very good reducing agents are
V.F.
Na MnO46 Ce4+ Cr2O72-
12. meq Ca(OH) = meq H PO
CrO42- HNO3
2 3 4

0.05 × V × 2 = 10 × 0.1 × 1
V = 10 mL

EXERCISE - 4

1. m.eq of (NH4)2SO4 + m.eq of H2SO4 = m.eq of

NaOH
250 4.
(m.moles × 2) + (0.1 × 10 × 25 ) = 0.2 × 100
` m. mole of (NH4)2SO4 = 5
5
` v.f. of dichloroacetic acid
wt. of (NH4)2SO4 = 1000 × 132 = 0.66 g

0.66
` % of (NH4)2SO4= 0.7 × 100 = 94.28% . = 2 (4 - 2) +2 (0 - (-1)) = 6
94.3% m.eq. of dichloroacetic acid = m.eq. of oxidising
agent = 600
2. BrO + 6I $ 3I 2 + Br
-
3
- -
600
moles of I2 = 3 × moles of KBrO3 ` m.moles of dichloroacetic acid = 6 = 100

` moles of I2 = 0.05 × 3 = 0.015 CHCl 2 COOH + NH3 $ CHCl 2 COONH 4
Eq of I2 = Eq of Hypo From reaction, m.moles of NH3= m.moles of
0.015 × 2 = 0.1 × V dichloroacetic acid = 100
V = 3 L = 3000 mL. 100
` Moles of NH3 = 1000 = 0.1
3. meq of H2SO4 = meq of NaOH + meq of Na2CO3 5. C + O2 $ CO + CO2 ...(i)
0.265
N × 25 = 0.5 × 50 + × 103 t = 0 0.1 - -
106/2
or N = 1.2 t = t 0 x (0.1-x)
In original H2SO4 solution 5CO + I2O5 $ 5CO2 + I2 ...(ii)
N1V1 = N2V2 t = 0 x
or N1 × 10 = 1.2 × 100 t = t 0 x x/5
or N1 = 12 N I2 + 2Na2S2O3 $ Na2S4O6 + 2NaI
1
` moles of I2 liberated = 2 × moles of hypo
1
consumed = 2 × 120 × 10-3 × 0.1=60 × 10-4
So, x = 5 × 60 × 10-4 = 0.03 moles (from reaction
(ii): 5 × mole of I2 = moles of CO)
0.3 # 12
So, % of C forming CO = 1.2 x 100 = 30 %
 Redox Reactions
x
6. Mass of H2O2 = 100 g 2
10×63
12. M H C O = 126 ⇒ N = 10
2 4

x 10x
\ moles of H2O2 = 100 = 34 mmoles
10×40
\ MNaOH = 40 ⇒ N = 10
n-factor of H2O2 = 2 \ Resultant solution contains neither excess acid

10x
\ 34 × 2 = x × N nor excess base.
10 13. Let Z undergoes change in oxidation number from
\ N = 17 = 0.588 N n1 to n2 (n2 > n1) as a result of reaction with KMnO4.
7. Assuming new normality of original H2O2 solution =
` meq of Z = meq of KMnO4
X
0.1 × 25 × (n2 – n1) = 0.04 × 25 × 5
After dilution to 100 mL of 10 mL of this solution,
New normality will be (say X1)
` n2 – n1 = 2

` X × 10 = X1 × 100 Hence, the oxidation number of Z increases by 2.

X
` change = (Z2+ " Z4+).
X1 = 10 .........(i)
10
10 mL of this dilute solution is titrated with 25 mL, 14. No. of equivalents of KMnO4 = 158 × 5 = 0.3164
0.0245 M KMnO4 solution. \ No. of equivalents of Cl2 liberated = 0.3164
So, N1V1 = N2V2
\ Vol. of Cl2 liberated at STP = 3.54 L
X
10 × 10 = 0.0245 × 5 × 25 1
15. Mole of I2 = Mole of Na3AsO4 = 208
X = 3.0625 N Now, mole of Na2S2O3 = 2 × Mole of I2
So, volume strength of original H2O2 solution V 2
0.2 × 1000 = 208 So, V = 48.1 mL
= X × 5.6 = 3.0625 × 5.6 = 17.15 V
16. 3I2 + OH– $ IO3– + 5I– (balanced reaction)
8. Given Emetal = 2 × 8 = 16
So, ratio is 1 : 5.
Weight oxide
Weigth metal = ? 17. For KMnO4 with Fe2+
eqmetal = eqoxide KMnO4 + Fe+2 $ Fe+3 + Mn+2
Wmetal W milli equivalent of KMnO4 = milli equivalent of Fe2+
16 = 16 oxide
+8
140
W 24 3 1 × 5 × M = 1× 56
` Woxide = 16 = 2 = 1.5
metal
140 # 1
9. Equivalent of KMnO4 = Eq. of H2C2O4 M = 56 # 5 = 0.5 = 0.5
0.0162 × V × 5 = .022 × 2 × 25 For KHC2O4.H2C2O4 with KMnO4
0.022 # 2 # 25 = 2 C2O42– + KMnO4 $ Mn2+ + CO2
V = .0162 = 13.6 ml
N#V milli eq. of KMnO4 = milli eq. of
10. Moles of pure NaOH required = v.f. L
KH2 C2O4 . H2C2O4
0.5 # 70
= = 35
1 100 × 5 × 0.5 = 1 × 2 × 2 × M
Mass of pure NaOH required = 35 × 40 = 1400 g
M = 0.0625
= 1.4 kg.
KHC2O4.H2C2O4 + 3NaOH
Mass of wet NaOH required (containing 15% water) $ 3H2O+Na2C2O4+KNaC2O4
1.4 meq of KHC2O4 . KHC2O4 = meq of NaOH
= 0.85 1.4 × = 1.65 kg.
11. n-factor of Na2CO3 = 2 3 × 1 × 0.0625 = 0.20 × V
3 # 0.0625

1.06 25
\ 106 × 2 = 1000 × N V= 0.20 = 0.9375 mL
\ N = 0.8
Chemistry
18. a. Formula of silver chromate will be Ag2CrO4 6 # 90
1 g KIO3 = 2 # 214 = 1.262 g
b. Minimum mass of zinc required for reduction of
23. No. of equivalents of S2O32– = 40 × 0.3 × 10–3
0.1 mole of Cr3+ to Cr2+
No. of equivalents of I2 produced = 12 × 10–3 eq.
0.1
= 2 moles of Zn No. of equivalents of H2O2 used = 12 × 10–3 eq.
6.54 Wt of H2O2 present in 250 ml of solution
= 2 gm = 3.27 gm
= 12 × 10–3 × 17
c. 2-
CrO ? Cr2 O 2-
in both ions chromium is in
4 7 ( a Eq. wt H2O2 = 17) = 0.204g
+6 state
Statement (A) is correct.
d. Given reaction is correct.
0.102 # 1000
Wt of H2O2 in 1L of the solution = 250
19. CuSO4 . 5H2O is a blue coloured compound. Since
the liquid drops convert CuSO4 to CuSO4 . 5H2O = 0.816g
therefore the liquid is water. Thus, the evolved gas
24. N2 + 3NH2 ? 2NH3
mixture contained H2O vapours.
1 3 0 $ 4 mole total
Now, we know 5CO + I2O5 → 5CO2 + I2 1–x 3 (1– x) 2x $ 3 mole total
Since 50% of the dry gas undergoes this reaction 1 – x + 3 – 3x + 2x = 3
therefore the dry gas has 50% Co. Thus the while & x= 2
1
crystalline substance must have been H 2 C 2 O 4 .2H 2 O
11.2

H 2 C 2 O 4 .2H 2 O
H 2 SO 4
CO + CO 2 + 3H 2 O 25. N of H2O2 = 5.6 = 2.
Now, for reaction with KMnO4 n-factor of oxalate = milli equivalents Ba(MnO4)2 = milli eq of H2O2
2 and n-factor of KMnO4 = 5 = 2 × 100= 200 m eq = 0.2 eq
1` # 2 = moles of KMnO 4 # 5 + -
2 + 10e " 2Mn
Mn14 2+

` moles of KMnO 4 = 0.4 ` n-factor of Ba(MnO4)2 = 10
20. 2KClO3 $ 2KCl + 3O 2 0.2
` Moles of Ba(MnO4)2 & 10 = 0.02
9 ` wt. of Ba(MnO4)2 = 0.02 × 375
C3 H6 + 2 O 2 $ 3CO 2 + 3H 2 O
54 375 # 0.02
moles of H 2 O = 18 = 3 % purity of Ba(MnO4)2 = 15 × 100 = 50%

6For K 2 Cr2 O 7, n - factor = 6@

9
` moles of O2 needed for the reaction = 2 26. a) 6M1V1 = M2V2
2 9 c) N1V1 = N2V2 [Law of chemical equivalence]
` moles of KClO3 required = 3 × 2 = 3 mole
volume of CO2 at STP = 3 × 22.4 = 67.2 Ltr. b) and (d) are not possible.
mass of hydrocarbon combusted = 1 × 42 = 42 gm 27.
Reagent n-factors
21. Sulphur as sulphide $ – 2
MnO -
5
Total (–)ve change = – 16 4
Cr2 O 2-
7 6
(7 – x) × 2 + x × 3 = 16 FeSO 4 1
14 – 2x + 3 x = 16 Cu 2 S 8
+x=2
Eq MnO = Eq Fe -
4
2+

x=2
n MnO # 5 = n Fe # 1
-
4
2+

So Ratio 5 : 2
EqCr O = Eq Fe
2
2- 2+
7

22. 2KIO3+H2C2O4 $ K2C2O4+2HIO3

nCr O # 6 = n Fe # 1
2
2-
7
2+

(acid-base reaction)
Eq MnO = Eq Cu S-
4 2

2HIO3+5H2C2O4 $ I2+6H2O+10CO2
n MnO # 5 = nCu S # 8
-
4 2

(redox reaction)
EqCr O = EqCu S
2
2-
7 2

nCr O # 6 = nCu S # 8
Adding,
2-
2 7 2

2KIO3+6H2C2O4 $ K2C2O4+I2+6H2O+10CO2
2 × 214 g KIO3 / 6 × 90 g
 Redox Reactions
28. milli eq. of KMnO4 = 25 × 0.2 = 5 meq. 32. Cr 12+
2
-
+ 6e $ 2Cr 3+

(a) Fe $ Fe
2+ 3+

` n-factor = 6
milli eq. of FeSO4 = 25 × 0.2 × 1 = 0.2 × 25 = 5
` no. of m. eq. = 15 × 0.2 × 6 = 18
(same)
(b) H3AsO3 $ H3AsO4 a) Fe 2+ $ Fe3+ + e - & n - factor = 1
milli equivalent of H3AsO3 = 2 × 50 × 0.1 = 10 ` no. of m.eq. = 180 # 0.1 # 1 = 18
(not same)
b) As3+ $ As5+ + 2e - & n - factor = 2
(c) H2O2 $ 2H + O2 +

milli eq. of H2O2 = 25 × 0.1 × 2 = 5 (same) ` no.of m.eq. = 50 # 0.1 # 2 = 10

(d) Sn2+ $ Sn4+ c) H 2 O 2 $ 2H + + O 2 + 2e - & n - factor = 2
milli eq. of SnCl2 = 25 × 0.2 = 25 × 0.1 = 5 ` no. of m.eq = 25 # 1 # 2 = 50
(same)
29. No. of eq. of S2O32– = 20 × 0.3 × 10–3 = 6 × 10–3 eq. d) Sn 2+ $ Sn 4+ + 2e - & n - factor = 2

No. of eq. uivalents of I2 produced = 6 × 10–3 eq. ` no. of m.eq. = 60 # 0.15 # 2 = 18

No. of equivalents of H2O2 = 6 × 10–3 eq. 33. Please refer solution to previous question
Wt of H2O2 present in 25 ml of solution 34. Cu 2 O + 2e - $ 2Cu o + O 2-
= 6 × 10–3 × 17
Cu 2 S $ 2Cu o + s 4+ + 4e -
( a Eq. wt H2O2 = 17)= 0.102 g
` Although Cu is getting reduced in both Cu2S
Statement (a) is correct. and Cu2O but Cu2S is undergoing net oxidation
0.102 # 1000 due to increase in O.S. of sulphur.
Wt of H2O2 in 1L of the solution = 25 35. a. CH 2 O: x + 2 - 2 = 0 & x = 0 ;
= 4.08 g Oxidation state of C = 0.
Statement (c) is wrong. b. CH 2 Cl 2: x + 2 - 2 = 0 & x = 0
Oxidation state of C = 0.
30. For HCl N = M, as n-factor = 1
V # 1 + V2 # 0.25 c. C6 H12 O6: 6x + 12 - 12 = 0 & x = 0
Final molarity = 1 (V + V = 0.75 Oxidation state of C = 0.
1 2)

0.75 (V1 + V2) = V1 + V2 × 0.25 d. C12 H 22 O11:12x + 22 - 22 = 0 & x = 0

0.75 V1 + 0.75 V2 = V1 + V2 × 0.25 Oxidation state of C = 0.

0.5 V2 = 0.25 V1 36. a. H 2 S 2 O 7: 2 + 2x - 14 = 0 & x = 6 VWW

W
V1 Na 2 S 4 O6: 2 + 4x - 12 = 0 & x = 2.5WWWOxidation
V2 = 2 (All options are possible) W state of S
Na 2 S 2 O3: 2 + 2x - 6 = 0 & x = 2 WW
WW
31. n-factor of KHC 2 O 4 in redox = 2 S8 : 8x = 0 & x = 0 W
X
m.eq. of KMnO4 = m.eq. of KHC2O4 c. H2SO4
x Oxidation state of S = + 6
0.02 × 100 × 5 = M × 2 × 1000 ....(1)
H2SO3 : 2 + x - 6 = 0
n-factor of KHC 2 O 4 in neutralization = 1
Oxidation state of S = + 4
m eq. of Ca(OH)2 = m. eq of KHC2O4
SCl2 : x - 2 = 0
y
0.05 × 100 × 2 = M × 1 × 1000 Oxidation state of S = + 2
(M = Mol. wt. of KHC2O4) ....(2) H2S : 2 + x = 0
Divide (1) and (2) Oxidation state of S = - 2

0.02 # 100 # 5 2x
0.05 # 100 # 2 = y
2x 37. In tailing of Hg, it loses its meniscus and sticks to
& 1= y & 2x = y glass, due to solubility of Hg2O in Hg, when Hg
gets oxidised to Hg 2+
2 by O3. It is removed by H2O2.
(Fact)
Chemistry
38. c. 2e - + ClO K $ Cl 6 (Reduction) 48. meq of SnCl2 = meq of
x-2=-1 x=-1 W
K 2 Cr2 O 7 & 190 ×1000 = 2000 × 0.1 & W = 19 gm
x=+1 2
ClO 6 $ ClO 63 + 4e - (Oxidation) 4.9 1
× = 1N
49. Normality of K2Cr2O7 = M 0.1
x=1 x=5 6
d. In HCuCl2, Cu is in +1 oxidation state which & Meq. of K2Cr2O7 = Meq. of Sn4+
disproportionates to Cu2+ and Cu0.
& Meq. Sn4+ = 10 x 1 = 10
0 -3 +1 10
39. b. 3H 2 O + P + 3OH - $ PH3 + 3H 2 PO -2
` M. moles of Fe3+ = 2 × 2 = 10
+2
c. S 08 + 12OH - $ 4S 2- + 2S 2 O32- + 6H 2 O 50. (A) Eq. of base = N × V = 0.5 × 0.2 = 0.1
0 +1 4.1
d. Br2 + 2OH - $ B r O - + H 2 O + Br - Eq. of H2SO3 = 82 × 2 = 0.1
40. 2S 2 O32- $ S 4 O62- + 2e - (Oxidation) Millimoles of O-atoms = (Millimoles of H2SO3)
× 3 = b 82 ×1000l × 3 = 150
4.1

I 2 + 2e - $ 2I - (Reduction)
S is in + 4 oxidation state (Max = + 6)
41. 10 e– + 2MnO4– $ 2Mn2+; v.f. = 10
M It may react with an oxidising agent and S may
` Eq. mass of Ba(MnO4)2 = 10 get oxidised from + 4 to + 6.
4.9
42. Fe0.9
2+
$ 0.9Fe3+ + 0.7e - (B) Eq of H3PO4 = 98 × 3 = 0.15
n factore Fe0.9 O = 0.7 Millimoles of O-atoms = (Millimoles of H3PO4)
× 4 = b 98 �1000 l × 4 = 200
M 10M 4.9
` Eq mass = 0.7 = 7
P is in + 5 oxidation state (Max = + 5)
43. n factor is 2 (acid-base reaction)
M It will not react with an oxidising agent as P is
Eq. weight = 2 already in max O.S.
128
= 2 = 64. 4.5
(C) Eq of H2C2O4 = 90 × 2 = 0.1
44. Let V mL of H2O2 is taken Millimoles of O-atoms = (Millimoles of
H2C2O4) × 4 = b 90 �1000 l × 4 = 200
4.5
20
Normality = 5.6
meq. of H2O2 = meq of I2 liberated = meq of C is in + 3 oxidation state (Max = + 4).
Na 2 S 2 O3 It may react with an oxidising agent and C may
20 get oxidised from + 3 to + 4.
V × 5.6 = 200 × 0.1 & V = 5.6 mL
(D) Na2CO3 is itself basic in nature, so it will not
45. Meq of H2O2 = meq of K2Cr2O7 react with a base.
20 x Millimoles of O-atoms = (Millimoles of
5.6 × 5.6 = 294 × 6 ×1000
Na2CO3) × 3 = b 106 �1000 l × 3 = 150.
5.3
20 × 294
x = 6 ×1000 = 0.98 C is in + 4 oxidation state (Max = + 4).
` Mass of K2Cr2O7 needed It will not react with an oxidising agent as C is
x = 0.98 g. already in max oxidation state.
46. 1000 mL H2O2 $ liberates 20 L O2 at STP

` 1 mL H2O2 $ x 1000 mL O2

` 5.6 $ 20 × 5.6 mL of O2 = 112 mL of O2
47. Balanced reaction is

3Sn 2+ + 14H + + Cr2 O 72- $ 3Sn 4+ + 2Cr3+ + 7H 2 O
 Redox Reactions
0 0 +VI
9
51. (A) 5AgNO3(aq) + 3 I 2 (excess) (C) 2C + Na 2 Cr2 O 7
+ 3H2O $ + 5AgNO3 (aq) + 2CO 2 (g)
+III +IV +II
C r 2 O3 + Na 2 C O3 + CO -
+V -1
$ H I O3 + 5Ag l + 5HNO3 Redox reaction. Cr2O3 (green pigment) insoluble

disproportionation reaction. Agl insoluble in in water.
water. Redox reaction. +II 0 +I
(D) CuCl 2 (aq) + Cu (s) $ Cu 2 Cl 2 (s)
+VI
(B) 3K 2 MnO 4 (aq) + 2CO 2 (g) $ 52. (A) 3H3 PO 2
415K
2H3 PO3 + PH3 -
+VII +IV

435K
2KMnO 4 + MnO 2 + 2K 2 CO3 4H3 PO3 3H3 PO 4 + PH3
disproportionation reaction. MnO2 insoluble in (B) PCl3 3H 2 O
Hydrolysis
H3 PO3 + 3HCl
water. Redox reaction. 4H3 PO3
435K
3H3 PO 4 + PH3 -
(C) 2NO 2 + H 2 O $ HNO 2 + HNO3
(D) 4HNO3 + P4 O10 $ 4HPO3 + 2N 2 O5
PH3 and HNO 2 act as reducing agents.

1. MnO 2-4
disproportionates in a neutral or acidic Reduction
solution to give MnO -4 and Mn+4 +6 2 +7 +4
4. 3 MnO4 + 4H+  2 MnO4 + MnO2 + 2H2O

3MnO + 3H → 2MnO + MnO 2 + 2H 2 O
2-
4
+ -
4

O.S. of Mn in MnO -4 =+ 7 Oxidation

O.S. of Mn in MnO 2 =+ 4 5. I– is oxidised to I2 by H2O2
difference = 3 Hence answer is (b)
2. neq Fe2+ = neq Cr2O72– 6. Oxalic acid is a primary standard solution while
H2SO4 is a secondary standard solution.
or, b
15×M Fe l
×1 = b 20×0.03 l ×6
2+

1000 1000 7. [Cr(H2O)6]Cl3 (Cr(C6H6)2)

` M Fe = 0.24 M = 24 × 10-2 M
2+
x + 0 – 3 = 0 x+0=0
3. K2Cr2O7 x = +3 x=0
2 (+1) + 2x + 7(-2) = 0 K2(Cr(CN)2(O)2(O2)(NH3))
x = +6 2+x–2–4–2=0
In K2Cr2O7, Transition metal (Cr) present in +6
(note that both oxide and peroxide are present
oxidation state.

x = 16
KMnO4
8. 1 equivalent of acid will provide 1 mole H+
(+1) + y + 4(-2) = 0
y = +7 ` no. of moles of H + = 0.1 # V.
In KMnO4, transition metal (Mn) present in +7 Now, H + + OH - $ H 2 O
oxidation state ` 0.1 # V = 0.04
K2FeO4 V
` = 0.4L = 400 mL
2(+1) + z + 4(-2) = 0
z = +6
In K2FeO4, transition metal (Fe) present in +6
oxidation state
So, x = +6
y = +7
z = +6
___________________
x + y + z = 19
Chemistry
9. Mass of organic compound = 1.4 g 10. MnO -4 + C 2 O 24- + H + $ Mn 2 + CO 2 + H 2 O
let it contain x mmole of N atom. vf = 1(7 –2) vf = 2(3–2)
organic compound $ NH3 = 5 =2
x m mole Balanced Equation : 2MnO -4 + 5C 2 O 24- + 16H +
2NH3 + H 2 SO 4 $ (NH 4) 2 SO 4 . (1st) $ 2Mn 2+ + 10CO 2 + 8H 2 O
6 mmole So, x = 2, y = 5 & z = 16.
initially taken.
H 2 SO 4 + 2NaOH $ Na 2 SO 4 + 2H 2 O ^2ndh 11. Weight of organic compound = 29.5 mg
2 mmole NH3 + HCl $ NH 4 Cl
reacted HCl (remaining) + NaOH NaCl + H2O
Hence m moles of H2SO4 reacted in 2nd equation = 1 (1.5 m mole)
& m moles of H2SO4 reacted from 1st equation Total milimole of HCl = 2
= 6 – 1 = 5 m moles
mili mole of HCl used by NH3 = 2 – 1.5 = 0.5
& m moles of NH3 in 1st equation
= 2 × 5 = 10 m moles mili mole of NH3 = 0.5
& m moles of N atom in the organic compound weight of NH3 = 0.5 × 17 mg = 8.5 mg
= 10 m moles 14
weight of nitrogen = 17 # 8.5 mg = 7 mg
& mass of N = 10 × 10–3 × 14 = 0.14 g 7
0.14 ` % of Nitrogen in compound = 29.5 ×100=
& % of N = 1.4 # 100 = 10%
23.7%.

2. 6I - + ClO3- + 6H 2 SO 4
In decay from U238 to Pb206, each U238 atom decays
" Cl - + 6HSO -4 + 3I 2 + 3H 2 O and produces 8 a-particles and hence, total number
Hence, I - is oxidised to I2 of a-particles emitted out
= b 8 x l × 8 × NA
7
Coefficient of HSO -4 = 6
and H2O is one of the product. 68 ×10 -6
7
= × 238 × 6.022 ×10 23
Hence (A), (B), (D)
= 1.204 × 1018
3. & 4.
8H+ + 5Fe2+ + MnO4– → 5Fe3+ + Mn2+ + 4H2O 6. No. of eq. of oxalic acid = No. of eq. of NaOH
[KMnO4] = 0.03 M and V = 12.5 mL 5.00 # 0.10 # 9.0 # M
or 1000 2 = 1000 # 1
Also, n-factor of KMnO4 = 5 1
Molarity of NaOH solution 9 = 0.11 M
\ m.eq. of KMnO4 used = 0.03 × 12.5 × 5 = 1.875
Now, n-factor of Fe2+ = 1 7. KMnO4 + KI → MnO2 + I2
m.eq. of Fe2+ in 25 mL solution = m.eq. of KMnO4
Eq of KMnO4 = Eq of I2
used
4×3=n×2
\ m.eq. of Fe2+ in 25 mL solution = 1.875
n=6
⇒ m.eq. of Fe2+ in 250 mL = 18.75 8. 2MnCl2 + 5K2S2O8 + 8H2O —→ 2KMnO4 + 4K2SO4
\ No. of m.moles of Fe2+ in 250 mL = 18.75 + 6H2SO4 + 4HCl .......(1)
\ moles of Fe2+ in 250 mL = 0.01875 = 1.875 × 10-2
2KMnO4 + 5H2C2O4 + 3H2SO4 —→ K2SO4 +
⇒ x = 1.875 2MnSO4 + 8H2O + 10CO2 .......(2)
\ Mass of Fe2+ in sample = 1.875 × 10-2 × 56g Mass of oxalic acid added = 225 mg
1.875×10 -2 ×56 225
\ % of Fe2+ in sample = ×100 Milimoles of oxalic acid added = 90 = 2.5
5.6
= 18.75% From equation (2)

\ y = 18.75
Milimoles of KMnO4 used to react with oxalic acid = 1
and milimoles of MnCl2 required initially = 1
68 ×10 -6
5. Initial moles of U238 =238 =x
\ Mass of MnCl2 required initially = 1 × 126
7
Moles of U238 decayed in three half-lives = 8 x = 126 mg
 Gaseous State

Chapter 6 Gaseous State

INTEXT EXERCISE: 1
1. At constant T, P1V1 = P2V2 number of moles remains constant because there is
20 neither addition nor removal of gas in the occurring.
1 # 20 = P2 # 50; P2 = 50 # 1
n P
6. PV = nRT ` V = RT
2. P.V = constant at constant temperature. As
temperature changes, the value of constant also nRT 2 # 0.0821 # 546
7. P = V = = 2atm.
changes. 44.8
PV m
3. T1 = 273oC = 273 + 273oK = 546oK 8. n = RT = M
T2 = 0oC = 273 + 0oC = 273oK MPV 34 # 2 # 100
m = RT = 0.082 # 293 = 282.4 gm
P1 = 1; P2 = ? PV PV PV m
9. n1 T1 = n2 T2 ` T2 = P2 V2 T1 m12
According to Gay-Lussac’s law 1 1 2 2 1 1
P1 T2 1 # 273 0.75 1 2

P1 P2 1
T1 = T2 ` P2 = T1 = 546 atm = 2 atm .
= 1 # 1 # 1 # 300 = 450

T 270 10. At constant pressure

4. V2 = T2 .V1 = 300 $ 400cm3 = 360cm3 m
1 V \ nT \ M T
contraction = V1 - V2 = 400 - 360 = 40cm3
V1 m1 T1 T1 V1 m 2 d 2
5. At constant V of a definite mass V2 = m 2 T2 ` T2 = m1 # V2 = d1
P1 P2 P1 300 1
T1 = T2 ` P2 = 600 = 2 i.e. pressure increases
300 0.75d
& T = d
2
and on increasing temperature energy of molecules
300
increases so the rate of collisions also increases and T & 2 = 0.75 = 400K

INTEXT EXERCISE: 2
P T 1 250 = (28 × 0.1) + (2 × 0.1) + (32 × 0.1) = 6.2 gm
1. V2 = P1 T2 .V1 = 0.5 # 300 # 12000 lit.
2 1
5. Since, P, V, T are same so N O = NSO
= 20000 lit. 2 2

MO MO
2. Because H2 & Cl2 gases may react with each other
\ M = M 2 2

SO SO
to produce HCl gas hence Dalton’s law is not
2 2

M.wt. of O M 32 1
applicable. M.wt. of SO2 & M1 & 64 = 2
2 2
m
3. No. of moles of lighter gas = 4 1
The weight of oxygen will be 2 that of SO2
m
No. of moles of heavier gas = 40 6. Since no. of molecules of gas is halved so pressure
m m 11m should also be halved.

Total no. of moles = 4 + 40 = 40
m 7. (a) Mixture of SO2 and Cl2 are reacted chemically

Mole fraction of lighter gas = 11m 4 = 10 and forms SO2Cl2. That is why Delton’s Law is not
11 applicable to mixture of these gases.
40
10 8. According to gas law

Partial pressure due to lighter gas = P0 # 11
PV
1.1
= # 10
11 = 1 atm.
PV = nRT, n = RT
PA VA
4. 6.02 × 1022 molecules of each N2 O2and H2 nA RTA n A PA VA TB
n B = PB VB ; n B = TA × PB VB
6.02 # 10 22
= moles of each RTB
6.02 # 10 23
Weight of mixture = weight of 0.1 mole N2 + weight
n A 2P # 2V T n A 2
of 0.1 mole H2 + weight of 0.1 mole of O2 nB = 2T × PV ; n B = 1
Chemistry
9. Given that 10. Boyle’s law:- PV = constant
P1 = 76 cm of Hg (Initial pressure at S.T.P.) On differentiating the equation,
P2 = ?, V1 = 5 litre, V2 = 30 + 5 = 35 litres. d(PV) = d(C) ⇒ PdV + VdP = 0
According to Boyle’s law dP dV
P1V1 = P2V2; 76 × 5 = P2 × 35 ⇒ VdP = - PdV ⇒ P =- V .
76 # 5
P2 = 35 & P2 = 10.8 cm of Hg
INTEXT EXERCISE: 3
rg 2 1
1. rHe =
M He
` M
r He
g = M He . 2
\ nO diffused = 4 2
Mg rg
. 2 = 2 6Note:1.4 . 2 @
32

=
4 4
\ mass of O2 diffused = 4 = 8g
(1.4) 2
1 a r = Volume effused = V
2. rg = 6 rH ; M g = M H . ; rH E
1 r 2 8. r ? t
2
g
2
2
M time taken

= 2 × 62 = 2 × 36 = 72
V? 1 ` for same volumes (V constant)
t M
3. ra = 5rb; d a = : rb D = b 5 l = 25
d r 2 1 2 1
b a

t \ M ` t12 = t M1
1 1
M2
tA = ; tA E ; ` DA = DB c tA m
D tB t B 2 tB 2
4. D A =
B

t He = t HM He = 5 4 = 5 2 s.
5. NH4Cl ring will first formed near the HCl bottle MH 2 2
2

because rate of diffusion of NH3 is more than that of tO = t = 5 32

HCl because M NH :M HCl = 17: 36.5) . So NH3 will
3
2
2 = 20s
reach farther towards the HCl bottle and will react
tCO = 5 28

2 = 5 14 s ;
there with HCl to form NH4Cl.

6. M A = b rB l a rA = 2rB & rAB = 2 tCO = 5 44

M r 2 r 1
B A 2 = 5 22 s
2

M 1 1 1
]2g2 4
& MA = = = 0.25 9. (a) Rate of diffusion \ that is
B Molecular Mass
rH 32 why H2 gas diffuse first
7. rO =2

2 =4
10. M1 = 32 for O2, M2 = 2 for H2
2

nH
\ nO = 4 (as time is same)
2

r1 M2 r1 2 1 1

2

2 r2 = M1 ; r2 = 32 = 16 = 4
n H diffused = 2 = 1
2

INTEXT EXERCISE: 4
1. According to K.T.G Total translational kinetic energy will also be same
3 because at same temperature & pressure number of
Average K.E. = 2 RT
molecules present in same volume would be same.
\ K.E \ T 1
But u RMS \
3 3 M
2. K.E. = 2 .RT = 2 .2.T a R . 2calK -1 mol -1 5. Average kinetic energy per molecule
K.E. = 3 T. 3 3
= 2 kT = 2 ×1.38×10 -23 ×300 J = 6.17 × 10-21 J
3 3
3. T.K.E. = 2 nRT = 2 PV UH TH M O 50 32
6. U = 2

M H . TH =
2 2

2 . 800 = 1
2 E O
\ P = 3 V for unit volume (V = 1)
2 2 2

` T1 = c
U T1 T 5 # 10 4 m2 1
2 7. U1 = = 4
⇒ P = 3 E 2 T2 2 10 # 10 4
4. Kinetic energies per molecule will be same because 8. Temperature is doubled and due to dissociation
it is proportional to absolute temperature only. M.W. is halved . So uRMS is doubled.
dN MN 28
dCO = M CO = 44 i.e. d N < dCO
2 2
2 2
2 2
 Gaseous State
2RT 3RT
Vmp M = r 10. Vrms = M
9. Vav = 2
8RT 3RT 3R×300
rM 30 R = 2
M & 30×30 R = M
3×300
M & = 30×30 = 1gm = 0.001 kg.

INTEXT EXERCISE: 5
PV 6. Real gas behaves as an ideal gas at very low pressure
1. Z = nRT < 1 at STP (as given)
and high temperature.
nRT > PV _b R = 0.821
bb 7. At Boyle temperature real gas gollows ideal gas
b T = 273K
n×0.0821×273 > 1Vm` bb most closely for a wide range of temperature.
22.41 litres > Vm bb P = 1
a n=1 8. At high temperature and low pressure, Vander
Waal’s equation is reduced to ideal gas equation.
2. c P - 2 m (V - nb) = nRT
n2 a
V PV = nRT
PV = RT (For 1 mole of gas)
eP - o (5 - 2×.03711) = 2×.0821×300
(2) 2 ×4.17
9. When pressure is low
(5) 2
c P - 2 m (V - b) = RT
a
2×.0821×300 4.7×2 2

P = 5 - 2×.03711 - V
52 a
or, PV = RT - V

⇒ 10 - 0.66 = 9.33 atm.
PV a
PV
3. Z = RT ; for ideal gas PV = RT; so Z = 1 or, RT =- VRT
a
Z = 1 - VRT
4. Because molecules of real gases have intermolecular
forces of attraction so the effective impact on the
10. c P + 2 m (V - nb) = nRT
n2 a
wall of container is diminished. Pressure of real gas V
a
is reduced by 2 factor hence behaviour of real gas
bP + 2.253 l
0.25 # 0.25 (0.25 - 0.0428)
v
deviate from ideal behaviour.
= 0.0821 × 300
5. By definition, Vanderwaals, equation of state is :
or (P + 36.048) (0.2072) = 24.63
c P + an2 m]V - nbg = nRT
2

⇒ P + 36.048 = 118.87 ⇒ P = 82.82 atm.
V
INTEXT EXERCISE: 6
a
1. Second Viral coefficient B = b - RT 6. Value of constant ‘a’ is highest than other for NH3
a that’s why NH3 can be most easily liquefied.
\ T = Rb .
7. The temperature below which the gas can be
This temperature is called Boyle’s temperature.
liquefied by the application of pressure alone is
2. An ideal gas can’t be liquefied because molecules of called critical temperature.
ideal gas have not force of attraction between them.
8. For Z critical temperature is highest as it has the
3. At above critical temperature, substances are existing highest value of a/b.
in gaseous state, since gas cannot be liquefied above 8a 8×12
Tc = 27Rb & Tc = 27×.0821×.027 = 1603.98 K
it.
9. All differences between liquid and gas phases vanish
4. Gases can be liquefied most easily at a low
at the critical temperature including surface tension.
temperature and high pressure.
10. Vol. of O2 at STP = 112 mL
5. Adiabatic demagnetisation is a technique
of liquefaction of gases in which temperature is
112 1
\ moles of O2 at STP = 22400 = 200
reduced.
1

\ mass of O2 = 200 ×32g = 0.16g
Chemistry
EXERCISE - 1
1. Gases do not have definite shape and volume. Their w PMV
20. PV = nRT = M RT or w = RT
volume is equal to the volume of the container.
2.46×10 -2 ×350×0.1×103
2. 1m3 = 103 dm3 = 103 L = 106 cm3 = 106 m2. = 0.082×300
3. Newton is unit of force. = 35 g (1m3 = 103L)

4. If DT = 1oC then DT = 1K. RT 1.61×8.314×298

21. m = d P = 101.325 g/mol.
5. The mass of gas can be determined by weighing 22. After mixing, volume is doubled, so pressures are
the container, filled with gas and again weighing halved. Hence total pressure after mixing = 50 + 200
the container after removing the gas. The difference = 250 mm.
between the two masses gives the mass of the gas. w w
23. n (C 2 H6) = 30 ; n (H 2) = 2 ,
6. In a closed flask, on heating the no. of moles does
w/2 1 15 PH
not change, as long as the gas doesn’t dissociate. (H 2) = w/2 + w/20 = 1 = 16 = Ptot
2

1 + 15
7. Molecules of a gas move with different speeds
which keep changing after they collide with other 4 2
24. nO = 32 , n H = 2 Total n = 8
9
molecules.
2 2

9 273
8. R = 0.0821 L-atm mol-1 K-1 PV = nRT, P = 8 ×0.0821× 1 = 25.215 atm

9. R = 0.0821 L atm mol-1 K-1. 25. The total pressure is sum of partial pressures
irrespective of the number of their moles.
10. R=0.0.082 litre atm K-1 mol-1.
26. Ptot = 10 atm and PHe = 2 atm
n
11. PV = nRT or P = V RT = CRT. 2
\ XHe = 10 = 0.2
1
Hence 1 = 1 × 0.082 × T is T = 0.082 = 12 K. \ X O = 1 - 0.2 = 0.8
2

12. Charles’ law deals with variation of volume with X N M 32

Now, XHe = NHe = 4He × M
temperature at constant pressure. O O 2 O2 2

0.2 M He
n P \ 0.8 = M ×8
13. PV = nRT or V = RT i.e. no of moles per litre O 2

= P / RT. MO
\ M = 32 2

He
14. Pressure is doubled, volume is halved (at const. 27. 3.2 g O2 = 0.1 mol, 0.2 g H2 = 0.1 mol,
temp.)
Total n = 0.2 mol,
V V 100 200
15. T1 = T2 , 373 = T , T2 = 746 K = 473 o C nRT 0.2×0.082×273
1 2 2 P= V = 1.12 = 4 atm.
PM 2 # 16 28. (751 - 21)mm = 730 mm Hg
16. d = RT = 0.082 # 300 = 1.30 gL-1
730
17. 2.8 g CO = 2.8 / 28 mol = 0.1 mol, \ PO = 760 = 0.96 atm
2

PV = nRT or 29. Suppose initially, the pressure of the gas in bulb

nRT 0.1×0.0821×300 A=P mm. Initial volume = 100 ml. After opening
V= P = 0.821 = 3 litre. the stop-cock, final volume =100+150 = 250 ml.
RT 1.8×0.082×300 Now P1V1 = P2V2 i.e., P × 100 = P2 × 250
18. M = d P = 760/760 . 44.
100
Hence the gas is CO2. Or P2 = 250 P = 0.40P = 40% of P.
4 3.2 30. Under similar conditions of temp. and pressure,
19. n i = 40 = 0.1 nf = 40 = 0.08
equal volumes contain equal no. of moles. Hence
Ti = TK Tf = (T + 50) K mole fraction of O2 = 0.21

\ 0.1 T = 0.08 (T + 50)
\ Partial pressure of O2 = 0.21 × 750 = 157.5 mm
or 10 T = 8 T + 400 of Hg.

\ T = 200 K. 31. Gases with same M.W. diffuse at the same rate under
similar conditions.
 Gaseous State

32. D A = c t B m
1/2
D t 44. u RMS \ M
1
by Graham’s law of diffusion.
B A
1 Molecular masses of H2, N2, O2 and HBr are 2, 28,
33. At constant temperature, rate of diffusion \ d or
32, and 81.
1
M and \ P Hence rA /rB = (PA /PB) (M B /M A)
1/2
45. u \ T where T is in Kelvin.
rO Mx 27 + 273
34.
rx = M O ,
2
u1 /u 2 = T1 /T2 = 927 + 273
2

As volumes are in the same ratio as the no. of moles. u1 300 1

u 2 = 1200 = 2 , u 2 = 2u1 .
n/18 Mx
n/45 = 32 , 46. K.E. \ T .
45 Mx
18 = 32 , Hence at the same temperature, KECO = KE N 2

45 2 3RT u (H 2) T (H 2) M (N 2)
M x = 2 ×32 47. u = ` u (N ) =
18 M 2 M (H 2) × T (N 2)
r M 50/t M
35. rAB = M B , 40/t = 64B , or 7=
T (H 2) 28
A
T (N 2) × 2
50 MB
40 = 64 or MB = 100 T (H 2) T (H 2) 1
or 7 = T (N ) ×14 or T (N ) = 2
2 2
rCH Mx
36. rx =
4

M CH , or T (N 2) = 2×T (H 2) i.e. T (N 2) > T (H 2) .

4

M
2 = 16x , 48. At a particular temp. the fraction of molecules
possessing a particular speed remains constant. As

⇒ Mx = 64. the total no. of molecules is doubled, to keep the
PM 2 ×16
37. d = RT = 0.082 × 300 = 1.30 gL-1 fraction same, no. of molecules possessing speed in
the same range is also doubled.
3RT
38. u RMS = 49. u AVG =
8 RT
M.W. rM = 3: 8/r
Now, PV = nRT
= 3r/8:1
PV
\ RT = n = 1.086 : 1
3 PV 3 PV 50. At constant temp., the K.E. of the molecules remains

\ u RMS = n $ (MW) = mass
MW $ MW the same.

\ u RMS =
3 PV 51. Gases deviate form ideal behaviour because of
mass intermolecular forces of attraction and repulsion and
also, u RMS =
3P 3P also the volume of thereal gas molecules are non-
mass = t zero.
Vol
3RT 52. Intermolecular forces of attraction are given by the
39. u RMS = M where M is the M.W. of the gas. term c P + 2 m
a
Thus, uRMS is independent of mass of the gas taken. V
Which is also called the pressure correction factor.

Hence, uRMS a mo where m is mass of gas taken.
53. ‘a’ is directly related to forces of attraction. Hence
40. Average kinetic energy depends only on temperature greater the value of ‘a’, more easily the gas is
and does not depend upon the nature of the gas. liquefied.
u T
41. u12 = T1 , 8a a
54. Tc = 27Rb Thus Tc \ b .
2
4
5×10 T T 1
= T1 or T1 = 4 55. Boiling point \ a
10×10 4 2 2

or T2 = 4 × Ti 56. We know, 6 = 4 b 3 rr3 l N O

4

n1 C12 + n 2 C 22 + .....
42. By definition, u = n1 + n 2 + .....
4
Now, if V = 3 rr3 then
b = 4 V No
43. a : o : u = 2 : 8/r : 3 .
Chemistry
57. The volume correction factor takes into account the or, 0.1 V2 - 0.02 V (20) + 1000 (0.02)2 = 0
forces of repulsion and the volume of the molecules. or, 0.1 V2 - 0.4 V + 0.4 = 0
58. As S8 decomposes to S2, the size of the molecules or, V2 - 4 V + 4 = 0
decrease. Thus, ‘b’ decreases. or, (V - 2)2 = 0 ⇒ V = 2
59. If volume correction factor is ignored, then attraction PV 0.1×2
\ Z = nRT = 0.02×20 = 0.5
dominates.
60. Vanderwaal’s equation can be written as
c P + an2 m V = nRT
2

Z = 1 + b b - RT l Vm
v a

PV + an2 = nVRT
2
a
So, by compassing coefficient of Vm = b - RT

EXERCISE - 2

1. For barometer t1 ,1 = t 2 , 2 PA 2M B 2 # 2M A
PB = M A = M A = 4 .
13.6×740
t 2 = 6.095 = 1651 mm . 165 cm 11. Since, P, V, T are same therefore number of moles
20×6.8 must also be the same
2. Pgas = 75 - 10 cos 60o - 13.6 × cos 60
o
15 75

= 60 cm of Hg 30 = M B
150
3. 2NH3 (g) → N2 (g) + 3H2 (g) MB = 150 ⇒ (V.D.)B = 2 = 75.
P

Before sparking 76 0 0 12. t \ T .
After sparking at eqm 76 - 2x x 3x n1 T1 n 2 T2 3×300 5×400 20
13. P = P & 3 = P P2 = 3 atm
Increase in pressure 2x = 6 x; x = 3 cm Hg 1 2 2

Partial pressure of H2 = 3 × 3 = 9 cm Hg 14. Since, P, T and V of both flasks are same therefore
no. of moles of gases (H2 and He) are also same.
1
4. For r 1g/cc. h' = 13.6 ×27.2 = 2 cm Hg However, He is monoatomic and H2 is diatomic.
3.4
for r = 3.4 gm/cc h' = 13.6 ×4 = 1 P 1.2 P
15. t + 273 = t + 273×2
\ pgas = 76 - (2 + 1 +10) = 63 cm Hg. 1.2 T + 273 × 1.2 = T + 273 × 2
5. \ When tube was out side pgas was 75 cm and
⇒ 0.2 T = 273 × 0.8
length of air column = h. Now, length of air t = 273 × 4 ⇒ t = 1092oC = 1365 K
column = 15 and pgas = 90

90 × 15 = h × 75
40 cm 5cm

⇒ h = 18 cm ....
16. .. . . . .
6. At constant temperature P \ 1/V ⇒ PV = constant 
I

\ log P + log V = log C.
II

\ log P + log V = log C
P1V1 = P2V2 (P2 = (75 + 5) cm Hg)
or, logm P = log b V l + log C
1
75 × 40 = (75 + 5) ×l
10 273
7. V = 373 ⇒ V2 = 13.66 L 75 × 40 = 80 ×l ⇒ l= 37.5 cm
Distance moved = 40 - 37.5 = 2.5 cm
2

100 T 100
8. 100.4 = T + 1 ⇒ T= 0.4 = 250 K PM
17. Density = d = RT
9. PV = nRT
3.1×0.0821×300
1 0.082 × 276 so, M = 1 g/mole
PV = M RT ⇒ M = 0.82 = 76.353 gm/mole
= 27.6 ⇒ B2H6 Hence molar mass shows that there should be cluster
3RT 1.5RT
10. PA = M ; PB = M of four HF molecules which must be bonded through
A B H-bonds.
 Gaseous State
n THe n NH $ TNH PT = 0.625 + 0.5 = 1.125 atm
18. HeVHe = VNH
3 3

3
3
4.8 400 3.4 360 25. Initially PO = 11 P (total pressure)
2

\ 4 × 2 = 17 × V
NH 3 after removal of one mole
0.2×360
or, VNH = 200×1.2 = 0.3 L 2 P
3
P' O = 10 P = 5
2

m 3 P
19.
PCH 16 P-
Ptot = X CH =
4
4 m
16 + m 30 % decreases = 11 3 5 ×100 = 26.66%
11 P
20. Weight of H2 = 20 g in 100g mixture;
26. The moles of the gas in the bubble remains constant,
Weight of O2 = 80 g.
so that n1 = n2. To calculate the final volume, V2:
20
\ Moles of H 2 = 2 = 10 ; PV 6×2 1×V
T = 281 = 2982 & V2 = 12.72 mL.
80 5
\ Moles of O 2 = 32 = 2
27. Mass of the filled balloon = 50 + 685 = 735 kg
5 25
\ Total moles = 10 + 2 = 2 Pay load = Mass of displaced air - Mass of balloon
\ PH = PT X H
2 2 = 5108 - 735 = 4373 kg
10
mole fraction of H 2 = 1× 25/2 = 0.8 bar nN Mx
28. nx =
2

M N .....(i)
21. Total weight = 96 g and extent of reaction is 50% so,
2

PT VT = n T RT .....(ii)
96 96
m A = 2 g and m A = 2 g 2.8×4

2
n T = 0.0821×273 = 0.5
96 1
moles of A = 2 × 48 = 1

n x + n N = 0.5
2

96 1 1
Moles of A 2 = 2 × 96 = 2
n x = 0.1
Total mole = 3/2 From (i)
3 0.0821×2×273 0.4 Mx
P = nRT/V = 2 × 33.6 = 2 atm 0.1 = 28 ; M x = 448.
22. Let, Pressure of H2 = PH 1
2
29. r \ if all other factors are same.
Pressure of O 2 = PO 2
M
given PH PO = 1 atm ......(1)
2 + 2 30. Molar ratio of He and CH4= 4 : 1
1 4
H2 + 2 O2 $ H2 O \ partial pressures PHe = 5 ×20 = 16 bar
initially PH PO 0 1
partial pressures PCH = 5 ×20 = 4
2 2

final PH - 2PO
4

2 2 0 -
Now PH - 2PO = 0.4 atm .......(2)
\ PHe : PCH = 16 : 4 4
2 2

From eq. (1) and (2)

a time of diffusion is same hence
rHe n He PHe M CH 16 16

PH = 0.8 atm & PO = 0.2 atm
2 2 rCH = nCH = PCH × M He = 4 ×
4

4
4 4 4

23. P1 V1 = Pf Vf 4×2
= = 8 :1
P × 100 = 0.4 P (100 + V)
31. Since radius of hole is 2 times larger thus area of

⇒ V = 150 ml the hole is 2 times larger.
24. In combined system volume of all gases is 400 ml rH AH M gas
Now, rgas = A 2

MH
2

Before any reaction occurs gas 2

X/5 AH M
1
partial pressure of O 2 = 4 = 0.25 atm
⇒ X/t = 2A 2

2
H 2

3 t 1 M
partial pressure of NO = 1.5× 4 = 1.125 atm
⇒ 5 =2 2
2NO (g) + O 2 (g) $ 2NO 2 (g) 8t 2

⇒ M = 25
initial P 1.125 0.25 -
final P 0.625 - 0.5 Putting t = 10 gives M = 32 ⇒ O2 gas.
Chemistry
r 1 w 2
32. r12 = 4 , w12 = 3 43. V \ T
3 8.314×300
r1 M2 M2 1 44. Average KE = 2 ×
r2 = M1 & M1 = 16
6.023×10 23
n W M 2 1 1 = 6.21 × 10-21 J/molecule.
mole ratio = n12 = W1 × M2 = 3 × 16 = 24 .
2 1
45. Average K.E. depends only on temperature while
1
33. r \ So, NH3 diffuses with faster rate. total K.E. depends on no. of moles also.
M
3
PV 5.6×3
34. n T = RT = 0.0821×273 46. K.E. = 2 nRT
nT = 0.75 47. Avg. K.E. depends only on temperature.
moles of unknown gas = 0.75 - 0.5 = 0.25 (Vrms) 1
48. (V ) =
M1 T2 2 800
ng t N rms 2 M 2 T1 = 32 × 50 = 1
MN 1 28
n N . tg = ⇒ 2 = M
2 2

2 Mg g 49. The pressure of real gas is lesser than the ideal gas

⇒ Mg = 112 g mol-1 due to intermolecular forces of attraction. Thus, if
these forces disappear, pressure will increase.
20 30 32
35. 60 × V = 64 ⇒ V = 10 2
50. The pressure of real gas is lesser than the ideal gas
36. When two vessels are connected then the partial due to intermolecular forces of attraction.
pressure of each gas in all vessels become equal at
51. Due to H-bonding water has a high value of ‘a’.
equilibrium. Hence, we can say that to tap pressure
Also, TC \ a.
also becomes equal.
1 1 1 52. A gas cannot be liquefied above TC no matter how
37. r N : r H : r He =
2 2 : : high a pressure is applied.
28 2 4
= 1: 14: 7 53. If a and b are negligibly small then the Vanderwaal’s
equation of state transforms to ideal gas equation.
T
38. u RMS \ M 54. For H2 and He repulsive forces dominate even at low

uO TO M
\ u Ne = T × MNe = 1 2 2 pressures. Thus, at high as well as low pressures

Ne O 2
VH > Videal gas

⇒ TO ×20 = 300×32
2
2

\ TO = 480 K 55. At moderate pressures attractive forces dominate and
hence pressure exerted by real gas is less than that
2

39. V =
3P exerted by an ideal gas under identical conditions.
d
40. mA = 2 mB uA = 2 uB PV 0.9×0.0821×273
56. Z = nRT ; V = 9
nA = nB VA = VB = 2.24 litre / mol
m A n A u 2A 2×1× ]2g2 8
\ Volume of 1 mili-mole of gas = 2.24 mL
1
PA VA 3
PB VB = 1 = =1
57. c P + 2 m V = nRT
2 1 an 2
3 mB nB uB V
41. PA = 20PB VA = 100 and VB = 150 an 2
\ PV = nRT - V
1 1

PA VA + PB VB

Final pressure P2 = (as the gas is
VA + VB 58. PV = Pb + RT as only repulsive force dominate in H2
same)
PV Rb
2150 RT = 1 + RT

\ P2 = 250 P
59. c P +
m (V) = RT
2150 a
\ DP = 20 P - P2 = 250 P V2
3P a
\ % change = 20P ×100 = 57%
PV + V = RT
PV a
3 N RT = 1 - VRT
2 × N ×R×150 x
42. K.E. O = 3 N'A
2 = 2x
× ×R×300 4
2 NA 60. 4× 3 rr3 ×N A = 24
N#1 1
⇒ K.EO = N' # 2 = 2 & N = N '
2
 Gaseous State
EXERCISE - 3
1. Pideal (V - b) = RT
7. b 1T 1 l = b 2T 2 l
PV PV
0.08 × 300 24
P & ideal = 0.075 - 0.025 = 0.05 = 480 atm
1 Inside cylinder 2 Outside cylinder

20×2.82 1×V
300 = 2732
& = : P real D = 480 = 2
P 960
Z
ideal T,V

V2 = 51.324 L
2. From Boyle’s Law
Volume of gas at STP in cylinder = 51.324 L
P1V1 = P2V2
Volume of gas left inside cylinder = 2.82 L
P1 × A × l1 = P2A × l2
Volume of gas available to be filled in balloon =
where A = cross sectional area 48.504 L
76 × 14.4 = (76 + 15.2) × l2 Let n balloons are filled

l2 = 12 cm.
` 3 r× b 2 l × 1000 = 48.504
4 21 3 n
& n = 10
Total weight
3. PV = nRT = ×RT
M molar 8. PV = n Total RT
Mass RT RT
⇒ P= V ×M & P=d M
105 ×0.02 = n Total ×8.314×300
molar

d M 8
⇒ p = RT = 49.26 (from graph)
n Total = 0.8
8×0.0821×300 m Ar m Ne
⇒ M= 49.26 =4 40 + 20 = 0.8
4. PV = nRT
m Ar + m Ne = 28
log P

m Ar = 24; m Ne = 4
nR
P= V T 2 log T
-2
9. P0= 76 cm P0= 76 cm
log10 P = log10 b V l + log10 T
nR
45 cm 10cm 45 cm

log P = log10 b 82.1 l + log10 T

10×0.0821 Initially : (A) 76 × 45 × A
= 76 × 45 × A (B)

log10 P =- 2 + log10 T (On comparing with A = Area of cross section
y = mx + c )
When tube is made vertical, let Hg
a = m = 1
column gets displaced by
b = 2 x cm towards A.
c = - 2 For A side: P1 ×(45 + x) ×A = 76×45×A
(a + b + c = 1) For B side: P2 ×(45 - x) ×A = 76×45×A
5. Pressure in lower half of gas = P0 = 75 cm of Hg Also P2 = P1 + 10
column
76×45 76×45 10 2x
Pressure in upper half of gas = 70 cm (45 - x) = (45 + x) + 10 ⇒ 76×45 = 45 2 - x 2

Pressure difference of gases in upper and lower half
& 76×45 ; (45 - x) - (45 + x) E = 10
1 1
of column = (75 - 70) = 5 cm of Hg.
6. At equilibrium pressure in each chamber is the same
76×45 ; (45 - x) (45 + x) E = 10 ⇒ x = 2.94 cm
45 + x - 45 + x
280×10 -3 200×10 -3
n1 = 28 = 10 -2
; n 2 =
4 = 5×10 -2
Let A = area of cross section of cylinder.
n1 RT n 2 RT L n

P = AL = AL & L2 = n2 = 5
1
1 2 1
Chemistry
10. Total number of moles 1
1×V = 2 ×0.0821×300
300 1 240 1 440 .5
= 760 × RT + 760 × RT + 760 × RT V = 12.32 litre
Let the pressure of the gases be P atm when all the For N2 PV = nRT
stopcocks are open. applying ideal gas equation,
0.5×12.32 = n×0.0821×300
P (1 + 1 + .5)
n = 0.25 mole
= b 760 × RT + 760 × RT 760 RT l RT;
300 1 240 1 440 .5
mass of N 2 = 0.25×28 = 7g
P = 0.4 atm 15. Patm = 75 cm of Hg
x = 0.4 P=
atm 75 cm of Hg

Therefore, 10x = 4. 10 cm  = 6.8g/m

(1)
10 cm Hg

11. (2)
60 cm

Converting the pressure due to the first liquid

10×6.8 = 13.6×h1
2500 × 2V + 1000 × V = Pf × 3V h
& 1 = 5 cm of Hg
5000 + 1000
(Pgas) 2 = 75 + 5 + 10 = 90 cm of Hg

\ Pf = 3 = 2000 mm
(2) x

\ Pf = 2 m
10 cm Hg
14000 (1)
12. Moles of N2 initially =28 = 500 10 cm  = 6.8 g/ml
1000

moles of H2 initially = 2 = 500 P atm

For pressure to fall to half moles diffused in bpoth '
(P gas ) 2 = 75 - 5 - 10 = 60 cm of Hg
balloons must be 250 P
& 1 V1 = P2 V2
250/t N 2
60 x = 90×60 & x = 90 cm

\ 250/t = 2

28 20
16. rH = 4 = 5 ml/sec
H 2
2
tH 1

or, 60 = 2

V
14 rO = 8 ml/sec
2

60 60

\ tH = = 3.74 min ro 2 PO MH
14
2
rH = PH MO
2 2

2 2 2

= 16.04 min. V/8 1 2 1
5 = 2 32 = 8
13. uA = 2uB and u \ T
V = 5ml.
1
\ TA 4TB. Also, VA = 2 VB
17. Given m A = 2m B
\ PA =
nR (4TB) nRT
PB = V B mA = 2mB Mol. w.t of A = 2× mol. wt. of B .....(i)
b VB l
1 B
Given, u rms of A = 2×u rms of B ....(ii)
2
1
nRT
or, PA = 8. V B & PA = 8PB For gas A PA VA = 3 M A u rmsA
2
B
1
For gas B PB VB = 3 M B u 2rmsB
14. N2 Total Pressure = 1.5 atm
Temperature = 27 + 273 = 300 K P V M u2
\ PA VA = M A × A2 .(iv)
CO2 B B B uB
PCO = 1 atm
2
Given VA = VB .....(v)
WCO = 22 g
2 \ By equation (i), (ii), (iv) and (v)
P

22 1
Moles of CO 2 = 44 = 2 mole PA = 2× (2) 2 = 8
B

For CO 2 PV = nRT
\ PA = 8PB & PA = 8 × 2 = 16 atm
 Gaseous State
0.20 112 excluded volume for 20 moles
18. M = 22400 & M = 40
nb = 20 x 0.2
n 2 = b 40 - 4 l
m m 1
now n1 = 40 , nb = 4

T1 = 300 K ,
T2 = 400 K 21. D = b3, C = b2
D b3 VC VC

3
V1 = V V2 = 4 V C = b =b= 3 = x
\ x=3
n1 T1 n 2 T2 160
V = V & m = 7 . 23 g . 4
1 2
22. 4N 3 rr3 = 3.2×r×10 -6
19. b = 4N A b 3 rr3 l
4
r3 = 10-10m
(4r×10 -4) ×103 = 4×6.0×10 23 b 3 rr3 l r = 0.1 nm
4

d = 2r = 0.2 nm ⇒ 10 d = 2 nm.
10 -8
r= 2 m
23. b dV l = 0 at critical point
dP

\ r = 5 # 10 -9 cm
m

3 3 x

\ z=5 \ ZC = 8 ; 8 = 24 ; x = 3×3; x = 9.
20. a Very high pressure \ neglect (a) 24. (a) Under low pressure region,
Z = RT = b1 - RTV l
Pb PV a
\ Z = 1 + RT ...(i)

comparing above equation with y = mx + c

20.39
\ Z = 1 - 0.0821×350×35 = 0.98

b
\ m = RT (b) Under high pressure region,
PV Pb
b Z = RT = 1 + RT
& RT = 0.01 (given m = 0.01)
b 0.1383
b = 0.01 RT ...(ii) \ Z = 1 + V = 1 + 35 = 1 + 0.004 = 1.004

by approximation b RT = 1, RT = V l
(PV) real PV P 1
Z = (PV)
ideal
9
25. CaCO3 (s) CaO (s) + CO 2 (g)
(PV) real
Z = nRT (given for n = 2, PV = 40) 25
Moles of CaCO3 used = 100
40
Z = 2RT 25
Moles of CaO formed = 100 = moles of CO2

20
Z = RT ...(iii) formed
25
Pb Mass of CaO formed = 100 ×56g = 14g
as, Z = 1 + RT from equation (iii)
14
20 Pb Valume occupied by CaO = 3.3 cc - 4.2 mL
Z = RT = 1 + RT ...(iv)

\ Volume available for
20 = RT + Pb
CO2 (g) = 504.2 - 4.2 mL = 0.5 L
Pb = 20 - RT ...(v)
Now applying the van der walls equation of state
(PV) real = 40 = ZnRT = b1 + 2RT l 2RT
Pb
c P + an2 m (V - nb) = nRT
2

V
40
& = b1 + 20 - RT l
2RT 2RT
=P + G[0.5 - 0.25×0.04]
4× (0.25) 2

40 = 2RT + 20 - RT (0.5) 2

20 = RT = 0.25 × 0.082 × 1500

From (ii) & (iv) 4× (0.25) 2
P& = 62.83 - = 61.83 atm.
b = 0.01 x 20 (0.5) 2

b = 0.2
Chemistry
EXERCISE - 4

1. Isotherms go further away from the origin on 6. Using the same logic as the previous question, if
increasing temperature. final pressure = Pf
2. H2 + 1 / 2O2 → H2O(l)
Pf V PV 0.5 V
300 R + 400 R = 300 R
a b 0
2×0.5×400
a-2b 0 b
\ Pf = 700 = 0.5714 atm
Reaction is studied at constant P & T. 7. Patm = 75 cm of Hg
a + b = 40 a - 2b = 10
a = 30 ml b = 10ml 10 cm  = 6.8 gm/ml
mole fraction of H2 = volume fraction of (1)
10 cm Hg
H2 = 30 / 40 = 0.75. (2) 30 cm

3. Max capacity of balloon = 600 ml
10 × 6.8 = 13.6 × h1
P1V1 = P2V2

⇒ h1 = 5 cm of Hg
500 × 1 = 600 × P2
5 (Pgas)2 = 75 + 5 + 10 = 90 cm of Hg
P2 = 6 ×760 mm = 633 mm
(2) x
Height above which balloon will burst
= (760 - 633) × 100 cm = 127 × 100 cm = 127 m 10 cm Hg
(1)
4. N2 → 2N 10 cm  = 6.8 g/ml
1.4 1

at t = 0 28 = 20 0 Patm

at t = tf
1 (P’gas)2 = 75 - 5 - 10 = 60 cm of Hg
20 - x 2x

⇒ P1V1 = P2V2
1 3
but, x = 30% of 20 = 200 60 × X = 90 × 30
Final number of moles
⇒ x = 45 cm

1
= 20 - x + 2x 8. In P vs h will be a straight line with negative slope.
1 1 3 13 9. The Centre of mass of A can not move freely in any
= 20 + x = 20 + 200 = 200
finite volume, it can only move on a circular path.
13 0.0821×1800 So for it volume available for free movement = 0.
\ P = 200 × 5 = 1.92 atm .
4
Hence excluded volume = 3 r (2r) 3 .
5. If volume of each flask = V then moles of gas
2PV 10. Finally in both vessels P, V will be same.

= RT

Therefore we can say that n1T1 = n2T2 (as PV are
1

Now, due to temperature difference the moles get same)
redistributed but total moles remain same and final
pressure in both vessels are also equal. n T 400 4

\ n12 = T2 = 300 = 3
1

Suppose final pressure of = Pf
Also, n1 + n2 = 0.7

+ RT = RT & Pf b 1T T 2 l = T
\ Moles in the vessels at 300 K = 0.4
Pf V Pf V 2PV T +T 2P

\ RT
and moles in the vessels at 400 K = 0.3.
1 2 1 1 2 1

2PT2

\ Pf = T + T rmixture 1
32
11.
1 2 311
rO =2
2
20×60
= M mix

⇒ Mmix = 8.59

⇒ V.D.mix = 4.32
 Gaseous State
a a
t
12. tmix
r
= rO = 2 M mix 19. Tc \ b , Pc \ 2 , vc \ b
O 2mix 32 b

234 M mix
224 = 32

M mix = 34.92
20.
From the rates of diffusion of O2 and the other gas in
mixture
1 X gas Xo
& = + 2

M mix M gas Mo 2
a) at T = 500 K, P = 40 at corresponds to ‘a’ substance
&
1
=
0.2
+
0.8 - gas
34.92 M gas 32 b) at T = 300 K, P = 50 at corresponds to ‘b’ substance
Mgas = 51.5 - liquid
c) at T < 300 K, P > 20 at corresponds to ‘c’ substance
13. - liquid
d) at T < 500 K, P > 50 at corresponds to ‘d’ substance
- liquid
rHCl 17 x 17
rNH = 36.5 & 200 - x =
3 36.5 21. High T, low P favours ideal behaviour in real gases.
x
& = 81.13 cm
PV 40×0.4
22. Z = nRT = 1×0.082×300 = 0.65
14. Let both gases meet at nth row
rNO x 179 23. It is factual question.
rC H Br = 12 - x =
2

44 = 2
6 10
24. At Boyle’s Temperature, attractive and repulsion
x = 24 - 2x
forces balance each other.
3x = 24
44
x = 8 = n - 1 25. 0.44 = V & VC = 100
C

n = 9th Row
4
\ 100 = 3N 3 rr3
V/45 M
15. V/60 = 40
25
⇒ r 3 = rN
⇒ M = 71.11
26. a V1 = V2 Suppose the cylinder will burst at T2K
16. Temperature to be taken in Kelvin.
P2 T1 14.9×300
17. VC H = 200×0.465 = 73
\ T2 = P = 12 = 372.5 K
3 8 1

VCH + CCO = 200 - 73 = 127
4 27. (c) from the first graph.

VCO = 3VC H + (VCH + VCO)
2 3 8 4

(a) from the second graph.
3×73
= + 127 = 346 ml
28. PT = (1 + 3x) =1 + 3 × 0.1 = 1.3 atm
18. I - Slope of isotherm below critical point < 0.
9P = 0.3 atm or; 76×0.3 cm of Hg = 228 Mn of Hg
Slope of isotherm above critical point < 0.
760 # 0.3 mm of Hg
Slope of isotherm at critical point = 0.
So slope of isotherm at critical point is maximum.
8a
II - Tc = 27Rb
Tc \ a
Larger value of Tc It means less decreases in
temperature is required to liquefy the gas. Gas
will liquify at higher temperature. So, easier’ll be
liquefication.
III - When gas is below critical temperature. It is
‘liquid’ at a high pressure so Vanderwaal’s equation
of state is not valid.
Chemistry
29. At constant V, n PV 16×3
33. nCO = RT = 0.08×300 = 2
PT = KT & y = kx & Straight line
2

PV 48×1
At constant P, n n o = RT = 0.08×300 = 2
2

VT = KT & y = kx & Parabola

2 2

2CO + O 2 $ 2CO 2 (g)
V B ⇒ CO is limiting Reagent so no. of moles of CO2
A
formed = 2 and no. of moles of O2 left = 1
I II nRT
Partial Pressure O 2 = V
T
Slope of line (I) > Slope of line (II) 1×0.08×300
= 4 = 6 atm

b nR l > b nR l
34. r \
1
P I P II
M

\ P B > Pa r 16 w 2
35. Given rAB = 3 ; w AB = 3
At constant V and n
P = KT r n
we have rAB = nAB
MB
MA
P
T = K
16 wA MB MB
3 = MA wB MA
P
\ T v/s T 2 will be straight line.
16 2 b M B l3/2 b MB l = 8 & M
3/2
MB
3 = 3 MA & =4
30. Let pressure in vessel B = P ⇒ PA = 20 P MA A

After they are connected, let final pressure be P2
\ mole ratio = 8 : 3

\ 20 P (100) + P (150) = P2 (250) ⇒ P2 = 8.6 P 36. PT = PA + PB and PB XB PT = (1 - xA) PT

\ For A :- DP = 20P - 8.6 P = 11.4 P
\ PT = PA + (1 - xA) PT
1
11.4
uRMS \ , So if M.W. are different, uRMS is not
⇒ 20 × 100 = 57 % equal M

For B :- DP = 8.6 P - P = 7.6 P (C) Since it is an equimolar mixture at the same T.

7.6
⇒ 1 × 100 = 760 % 37. K.E. is a function of temperature. If temperature is
constant, K.E. will be constant.
31. At constant T and mols, PV = constant
38. Helium gas has lower molecular mass and hence it

\ PV vs anything is a straight line moves faster than neon and strikes the wall more

c 1
Also, as PV = c ⇒ P = v ⇒ P vs v is a st. line frequently.
passing through the origin. U av = rM ⇒ U av \ b M l
8RT 1 1/2

32. nA = 3, nB = 1, nC = 1 Hence, He has higher speed than neon.
(3 + 1) RT 5RT Although frequency of collision of Ne is less but

(PT) i = & (PT) f = V
V force imparted per collision is more. Hence pressure

(PT) i
& (P ) = 5
4 exerted by He and Ne are equal.
T f

1 39. n N = nCO p, V, T = constant

2 2

Partial pressure of C = X c ×PT = 5 ×25 = 5 atm

MW of N2 < MW of CO2.
40. yM x " xM y
20x
y = 8
x 2
y =5
 Gaseous State
a Patm
41. Tb = 540 K = Rb 52. P1 = 75 cm of Hg, V1 = 24×A
8 a 8 20.4×10
\ TC = 27 Rb = 27 ×540 = 160 K = -113oC
P2 = 75 + 10 +13.6

\ Gas can be liquified at -113oC 100
= cm of Hg
T1 > 540 K and T2, T3 < 540 K
& 75×24 = 100×x
P2
x = 18 cm
42. It is a factual question.
53. Case I Case II
43. All properties of gas and liquid phases coincide at
the critical point.
P1 = (P0 + h)
P2 = (P0 - h)
44. PC =
a
TC2 =
64 a 2 P1 V1 = P2 V2
Now in both the cases, the gas is the same and
2
27b 27×27R 2 b 2
TC2 64 a 2 27b 2 temperature is also constant, hence boyles law can
VC = 3b = ×
PC 27×27R b 2 2 a be applied.

2 2

8a
TC = 27Rb a=
27R TC
= 3PCVC2 ,1 A (P0 + h) = , 2 A (P0 - h)
PC
h (,1 + , 2)
45. Area under the graph = 1 and remains constant
P0 = (, - , ) cm of Hg column.
1 1
(b), (c) are evident from the graph. n /t P MB n1 M1 + n 2 M 2
54. nA /t = PA = M mix
(d) we cannot compare uMPS (T2) an uRMS (T1) without B B MA x1 + x 2
values. X1 M1 + (1 - X1) M 2 = M mix
2 3
46. Clearly from the sketch at temperature T4 & T5 & X1 = 5 , X 2 = 5
liquefaction of gas is not possible at any pressures x A 2 72 1
because T4 and T5 is greater than TC. & x B = 3 128 = 2
But in case of T1 and T2 liquefaction can take place
1
& xA = 3 , xB = 3
2
hence there can be liquid vapour equilibrium
1000 - 900
47. It is a factual question. 55. Initially rA = 5 = 20 torr/s
48. At TB real gas behaves as ideal gas. In the initial mixture
112 2 3
27 X A = 280 = 5 , X B = 5

TB = 8 TC ⇒ above TC real gas may behave as
ideal gas. Due to difference in the hole

At high pressure, repulsive forces dominate. rA PA .' A1'
' =
rA P A' A 2
49. Lt (PVm) = RT Lt (PVm) = RT as it behaves as ideal r 1 x2 1
P"0
rA'A = 2 × 3x = 3
gas at high T x× 2
hence, Lt b RTm l = 1
PV
P"0
r A = 3rA = 3×20 = 60 torr/s
'

50. (a) Real gases may not occupy 22.4 L at STP per Now for the diffusing mixture
mole r' P' M 2 72 1
A' = A' M B = 3 × 128 = 2
o

rB o
PB A
3
(b) ZC = 8 r B' = 120 torr/s
(d) At absolute zero, K.E. = 0 as molcular motion After 10 sec
cases. P A" = 2000 - 60×10 = 1400 torr
51. P1 = 70 + 20 = 90 cm of Hg P B" = 3000 - 120×10 = 1800 torr
n"A 7

P2 = (70 + 5) cm of Hg =
n"B 9

⇒ 90 × 20 = 75 × (5 + x) 56.2000 - 60t = 3000 - 120t

⇒ x = 19 cm. 60t = 1000 & t = 3 sec.
50
Chemistry
57. Area under the curve PC R 300×1/12 1
TC = 8b & b = 8×50 = 16
4 1

4× 3 rr3 . N A = 16

r = b 256rNa l
1/3

3
N N
b 1 dN l dv = 1
x

= # ydx =
# N dv N # dN = 1 64. From the graph it is evident that below 20 atm at 100
0 0 0 K it will be liquid.
2RT
58. vMPS = M , vMPS is the speed which is possessed 65. (A) PV = nRT
by maximum number of molecules. Hence in the
At constant temperature
d b N dv l
1 dN
above curves = 0; vav =
8KT PV = K (T = constant)
dv rm

Higher the value of PV, higher the temperature.

So, T3 > T2 > T1
59.
Since, P 1 = P2 = P3

So, V \ T ⇒ V3 > V2 > V1

From the figure it is shown that plot is symmetrical

d = RT
PM
about vMPS clearly total no. of molecules between the

Since, P 1 = P2 = P3
v 3v MPS

speed MPS
2 and 2 is 2 N.

1
d \ T ⇒ d1 > d2 > d3
2N 1
Hence fraction of molecules = 4N = 2 .
(B) From Graph,
60. If two gases haves identical Max wellian plot then
V 3 > V2 > V1 and T1 = T2 = T3
their all the speeds will also be identical
Higher the volume, lesser the pressure because
T
Hence MA = MB
T temperature is same for all.

P 1 > P2 > P3
A B
T
Since all the speeds are proportional to M for
PM
SO 2 : - M1 = 64, T1 = 600 K
d = RT

O2 :- M 2 = 32, T2 = 300 K
Since, T1 = T2 = T3

⇒
T1 T2
So, d \ P ⇒ d1 > d2 > d3
M1 = M 2

(C) From the graph,
61. Clearly from the diagram

P 3 > P2 > P1 and T1 = T2 = T3

(v MPS) B > (v MPS) A

Higher the pressure, lesser the volume because
T2 T1 T2 M B temperature is same for all.

& MB > MA & T1 > M A

Hence if T1 > T2 . M A is necessarily greater than
V 1 > V2 > V3
PM
MB
d = RT
62. At critical point
Since, T1 = T2 = T3
2P RTC 2B 3C
So, d \ P ⇒ d3 > d2 > d1
2Vm = 0 & - V m2 + V m3 - V m4 = 0

(D) From the graph,
2B 3C

& - RTC + V - 2 = 0
d3 > d2 > d1 and P1 = P2 = P3
m Vm
PM 1

d = RT ⇒ d \T

& RTC V 2 - 2BV + 3C = 0
as equation will have repeated root so
So, T1> T2 > T3
B2
PV = nRT
Discriminant = 0 & TC = 3RC

Since, P 1 = P2 = P3
a 8a
63. PC = , TC = 27Rb
V\T
27b 2

So, V 1 > V2 > V3
 Gaseous State
66. (A) For H2 : Z is always > 1 (C) Refer part B

10
(B) Assuming O2 to be ideal PSTP = 7 g/L. Given (D) Like H2, for He also, Z is always > 1
67. At low P attraction dominates, Z < 1. At high P
10
PO > 7 & Vreal < Videal & Z < 1
2
repulsion dominates Z > 1.
For H2 and He Z is always > 1

1. Given : Ideal gas A and H2 gas at same pressure 2RT

and volume. 8. C* = most probable speed = M
From ideal gas equation PV = nRT C = average speed = rM
8RT
n1T1 = n2T2 3RT
3 0.2 C = Mean square speed corrected as rms = M
GMM of A × 300 = 2 × 200

C* < C < C
GMM of A = 45 g/mole 4 3

C*: C: C = 1: r : 2 = 1: 1.128: 1.225
2. P \ T
Note: As no option correspond to mean square

P2 T 40 T
= 2 & = 2 speed, it is understood as misprint. It should be root
P1 T1 35 300
T2 = 342.854 K means square speed.
= 69.70oC - 70oC 9. 18g H2O contains 2g H
Hence answer is (70) \ 0.72g H2O contains 0.08 H.
3. Given Mass = 4.75 g ⇒ C2H2(g) 44g CO2 contains 12g C
4.75 \ 3.08g CO2 contains 12g C
⇒ Moles = 26 mol
0.84 0.08
Temp = 50 + 273 = 323 K \ C : H = 12 : 1 = 0.07: 0.08 = 7: 8
740 \ Empirical formula = C7H8
P = 760 atm
10. cP + m (V - b) = RT
, atm a
R = 0.0826 mol K V2
a

&V=
nRT
=
4.75 0.0826×323 at high pressure 2 can be neglected.
b 740 l
P 26 × V
PV - Pb = RT
760
96314.078 PV = RT + Pb

& V = 19240 = 5.0059 , - 5,
PV Pb
RT = 1 + RT
4. Mass of liquid = 135 – 40 = 95 g
Pb
mass 95
Volume of liquid = density = .95 mL Z = 1 + RT ; Z = 1at high pressure
= 100 mL = 0.1 L 8RT
11. V = rM & V \ T
mass of ideal gas = 40.5 – 40 g = 0.5 g
PV = nRT t r tA M
12. r \ & rAB = t B M B
0.82 × 0.1 = b M l × 0.082 × 250
0.5 M A

M = 125 13. Cl2 has higher MW, more Vanderwaal’s forces hence
larger value of ‘a’.
5. Statement ‘A’ is Gay-Lussac’s Law C26 is a bulkier molecule hence higher ‘b’
6. Total number of moles (nT) = (0.5 + x) 14. Let the mass of methane and oxygen be m gm. Mole
PV = nRT f reaction of oxygen.
200 × 10 = (0.5 + x) R × 1000 m
m 32 1

2 2 1 X O = m 32 m = 32 × 3m = 3
R = 0.5 + x & R = 2 + x 2

2 1 4-R 32 + 16
& R - 2 = x & x = 2R
Let the total pressure be P.
7. In low pressure region, vanderwall equation
\ Partial pressure of O 2, P0 = P # X 0
becomes. 2 2

a 1 1
Z = 1 - RTV P× 3 = 3 P.
m
Chemistry

1. Graph represents symmetrical distribution of speed

The curve IV is applicable provided temperature of
and hence, the most probable and the average speed the gas is near but larger than it’s critical temperature
should be same. But the root mean square speed Hence, the choice (A), (B) and (C) are correct.
must be greater than the average speed.
7. According to Graham’s law, if all conditions are
2. P (V - b) = RT identical,
PV
& - Pb = RT
r\
1
PV Pb M

& RT = RT + 1

As in this question, all conditions are identical for X
Z
& = 1 + RT
Pb and Y, it will be followed

Hence Z > 1 at all pressures.
r
Hence rxy = M
My
x

This means, repulsive tendencies will be dominant d 40
when interatomic distance are small. 24 - d = 10
d

This means, interatomic potential is never negative 24 - d = 2
but becomes positive at small interatomic distances.
d = 48 - 2d

3. c P +
m (V) = RT
a 3d = 48
V2

PV + a/V = RT
d = 16 cm .

PV = RT - a (V) 8. The general formula of mean free path ( m ) is

RT
y = RT - a(x)
m= (d=diameter of molecule,
2 rd 2 N A P
21.6 - 20.1 1.5
p = pressure inside the vessel).

So, slope = a = 3-2 = 1 = 1.5
3 3RT
a d & p are some for both gases, ideally their l are
4. Eav = 2 RT Urms = M same. Hence it must be the higher drift speed of X
Eav does not depend on its molecular mass but due to which it is seeing more collisions per second,
depends upon absolute temperature. with the inert gas in comparison to gas Y. So X see
comparably more resistance from noble gas than Y
5. (A) Fact
and hence covers lesser distance than that predicted
M 3RT 3MRT by Graham’s Law.
(B) p = mv = N A M = NA
(C) Max well distribution 9. K " L & V - at constant P
(D) Fact Hence T - (Heating)
6. The Vanderwaal’s equation of state is : (for 1 mole
L " M & P . at constant V
of gas) Hence T - (Cooling)
c P + 2 m (Vm - b) = RT
a

M " N & V . at constant P
Vm

When a is negligible, then Hence T - (Cooling)

PV
Z = RTm = 1 + RT P
b
N " K & P - at constant V

that is Z increases with increaser in P. Hence T - (Heating)

When b is negligible, then 10. L " M
PV a
M"K
Z = RTm = 1 - VRT

Both are having constant volume therefore these

increasing P implies decrease in V, which is turn, processes are isochloric.
implies increase in the value of a/VRT and hence
decrease in the value of Z.
 Gaseous State
11. Initial moles of gases = 1 h
12. m = KE \ T
238 2m (KE)
92 U $ 82 Pb + 8 2 He + 6 -1 e
206 4 o

Initial moles1 moles m m Ne KE Ne 20×1000
He = m He KE He = 4×200 = 5
m Ne

Moles after 8 mole
13. PHe = 1 - 0.68 = 0.32 atm

decomposition

V=?

Total gaseous mole after decomposition = 8 + 1 = 9

n = 0.1
moles
nRT 0.1×0.0821×273
P n
V= P = =7

Ratio of pressures Pf = nfi = 9 0.32
i
 Thermodynamics

Chapter 7 Thermodynamics
INTEXT EXERCISE: 1
1. Properties, which are amount independent, are 7. P × 1 = RT
intensive properties and others which are amount 3
Also, internal energy U = 2 RT
dependent are extensive properties.
3
\ U= 2P
2. An isolated system neither shows exchange of heat
nor matter with surroundings. or P = 3 U
2
3. KE = (3/2) RT. Since T is same, hence K.E. is same. 8. Temperature is a measure of intensity of energy,
Force extensive
4. Pressure = Area i.e. extensive whereas heat is a measure of quantity of energy.

\ Pressure is an intensive property. Specific heat 9. Follow Zeroth law of thermodynamics.
capacity is intensive not heat capacity. 10. The water in beaker will be heated to 100oC but
5. During reversible process, the internal equilibrium will not boil as for boiling it requires latent heat of
is disturbed only infinitesimally. Thus, the system evaporation. Water can be made to boil by lowering
always remains in the equilibrium state during this the external pressure. Regulation involves melting
process. of ice under pressure and resolidification on releasing
pressure. Ice can be sublimed by reducing external
6. At constant temperature DU = 0. pressure to its vapour pressure.
INTEXT EXERCISE: 2
3. At constant volume P9V = 0, ` q = 9U
1. 9W =- # P9V = Area under PV curve
4. WAB = P9V =- 10 J; WBC = 0;
q = 9U + (- WT)

a 9U = 0 ⇒ WT = -q = -2.5J
- 2.5 = [WAB + WBC + WCA]

-2.5 = [-10 + 0 + WCA]

=- [4 + V]
1 or WCA = 7.5 J

=- [P0 (V1 - V0) + 2 (P1 - P0) × (V1 - V0)]
PV 1×22.44
5. At A : T1 = nR = 1×0.0821 = 273 K
1 1

=- [P0 (V1 - V0) + 2 P1 (V1 - V0) - 2 P0 (V1 - V0)] PV 1×44.88

At B : T2 = nR = 1×0.0821 = 546 K
=- : 2 P0 (V1 - V0) + 2 P1 (V1 - V0)D
1 1
PV 0.5×44.88

At C : T3 = nR = 1×0.0821 = 273 K
1 1
=- 2 [P0 + P1] [V1 - V0] =- 2 [(1 + 4)) ×105] ×[4 - 1]
Y -Y

=- 7.5×105 J 6. Equation of line AB is Y - Y1 = X1 - X2 (X - X1)
1 2
3Po - Po
2. P - 3P0 = V - 3V (V - V0) ...(i)
o o
nRT P
V - 3P0 =- V0 (V - V0)
0
P0 2
or nRT = 3P0 V - V V + P0 V ...(ii)

Net work done = Area covered by the cycle 0

(clockwise) Differentiating w.r.t. V

1 nRdT 2P 2P

=- 2 [(4P - P) ×(3V - V)] dV = 3P0 - V 0 V + P0 = 4P0 - V 0 V
0 0
1 dT
=- 2 ×6PV For max. value of T, dV = 0
=- 3PV
Chemistry

\ P 01 :4 - V D = 0 or V = 2V0
2V CP 5R # n + 7R # n
` C = 1.50 = 3R # n1 + 5R # n 2
m

0 V m 1 2

Now from (ii) or 4.50 Rn1 + 7.5Rn 2 = 5Rn1 + 7Rn 2

P
nRTmax = 6P0 V0 - V0 4V 02 + P0 2V0 = 4P0 V0 0.5 Rn 2 = 0.5 Rn1
0 n
4P0 V0
\ n12 = 1

\ Tmax = nR
8. 9H = 9U + P9V
3R 5R
n1 × 2 + n 2 × 2 9H - 9U 50 - 113
7. C V =
3Rn + 5Rn
= 2 (n1 + n ) 2 \ P= 9V = - 10 = 6.3 K Nm -2
m
n1 + n 2 1 2

5 7R 9. In a cyclic process 9U = 0.
n1 × 2 + n 2 × 2 5Rn + 7Rn
CP =m
n1 + n 2 = 2 (n1 + n ) 2 5
10. 9U = n×C V ×9T = 1× 2 ×8.314×15 = 311.75J
1 2

INTEXT EXERCISE: 3
1. For isothermal process DU = 0. or T3 - 2c = constant
dP
2. Slope of an isotherm in P-V curve : dV =- V
P \ 3 - 2c = 0
3
dP P or c = 2
Slope of an adiabat in P-V curve : dV =- c V
8. The work done by the gas during isothermal and
\ Slope of adiabat = g slope of isotherm adiabatic expansions are shown schematically by
3. For adiabatic process TVg-1 = constant the corresponding P - V lines.
Given T(V)1/2 = constant
Obviously, W2 > W1 > W3 since we are only talking
1 about the magnitude of work here.
\ g-1= 2
3
or c = 2 = 1.5
4. The given process is isothermal, hence DU = 0

\ q=-w

a q = 208 J

\ w = - 208 J (i.e., work done by the system)
u rms T T1
5. u rms T = T2
1

2×u T1
u = T2 b u rms T = u rms T l
1

2
2

T1 9. Let volume after compression be XV

or T = 4
P1Vg = P2 (XV)g
2
T
i.e., T2 = 41 1.01 × 105 × Vg = 1.122 × 105 (XV)g
\ X = b 1.122 l = b 1.122 l
From TV c - 1 = constant fro adiabatic expansion 1.01 1/c 1.01 1/1.667
= 0.94
T1 V1c - 1 = T2 V 2c - 1
\ Reduction in volume = V - 0.94 V = 0.06 V
or : V1 D = T2 = 4
V c-1 T 1 0.06 V
2 1 \ % = V ×100 = 6

\ b V1 l
V 1.4 - 1 1 b V2 l 10. CP - CV = R

5

= 4 & V =4 2

2 1 R
\ CP - CV = M
V2
or V = 32
C
Also, C P = c
1

6. q = m $ s $ 9T if 9T = 0, S = 3, As during melting V

or boiling there is no change in T.

C
\ C P - cP = M
R
if q = 0, S = 0, As q = 0 in adiabatic processes. R$c
\ C P = M (c - 1)
7. For adiabatic process Tc P(1 - c) = constant
CP here is the molar specific heat capacity at constant
or Tc (T) 3(1 - c) = constant (a P \ T3)
pressure.
 Thermodynamics
INTEXT EXERCISE: 4
1. For free expansion, Pext = 0
w = - P D V = 0; For adiabatic process q = 0

Dv = q + w

\ q = 0, w = 0 \ DT = 0
2. Work done by gas = - Pext × change in volume
= - 105 (10-2 - 10-3)
= - 105 × 0.009 = - 900 J
Hence, Wirreversible > Wreversible
3. Assuming P, T to be constant, V remains constant as
the no. of moles of gas remains unchanged. 7. q = n $ C p 3 T
100
4. T = KP0.4 = KP2/5 1000 = 18 ×75×9T

a PV = RT \ DT = 2.4 K
or PV = R $ K $ P 2/5 8. The colling shows fusion process for 30 minute
P =K
3/5 I (40 - 10) at 400 K
PV5/3 = KII q = 0 0.4 × 103 × 30 = 12 kJ

5
PVg = constant g - 1.66 = 3 for He 9. w = P (Vg - Vl) = PVg = nRT
Thus, process is adiabatic \ DH = 0 103
= 18 ×8.314×373 = 172284.56 J
5. Wexp =- P×9V 172.28
= kJ
=- 1×(13 - 3) =- 10 atm dm3 70
10. Q P = C P $ 9T ` C P = 5 = 14 cal o C -1
6. In both the curves, work done on the gas is C P - C V = nR
represented by the shaded area and the area under the

\ C V = 14 - 2×2 = 10 cal K -1
curve is always more in irreversible compression.

Q V = C V $ 9T = 10×5 = 50 cal
INTEXT EXERCISE: 5
1. 9Ssyst =- ve 9SSurr =+ ve , as system loses heat Tsurr = 300 K
and surrounding gains heat. - 3×101.3
\ DSsurr = 300 = -1.013 J/K
9S T =- ve
q rev 8. At 100 C and 1 atmosphere pressure, water shows
o
2. Entropy change 9S = T
equilibrium in two phases as H 2 O (l) ? H 2 O (g)

` Unit of S is J K -1 mol -1 . and thus for equilibrium 9S total = 0 and
3. An exothermic reaction in which entropy of system 9Ssystem + 9SSurrounding = 0 For change of liquid to
is increasing is spontaneous at all temperatures. gases state, 9Ssys is + ve and therefore 9Ssurr. will
be - ve.
\ DH < 0, DS > 0 ⇒ always spontaneous.
\ 9Ssystem > 0 and 9Ssurrounding < 0
4. 9S total = 9Ssys + 9Ssurr =+ ve for irreversible
process. 9. During compression for isothermal process
9S = nR ln V2 =- R ln 2 b V2 = 21 l
V V
T1 - T2 500 - 400 1
5. h = T1 = 500 =5 1
During heating for isochloric process
1
\ w = h×Q = 5 ×6×10 4 = 1.2×10 4
T
9S = nC V ln T2 = C V ln 2 (T2 = 2T1)
1
dq Work done by the gas (W)
6. - 9S = T = Thus, total change in entropy
T C = V ln 2 - R ln 2 = (C V - R) ln 2
- 9S×PV
W =- 9S×T = nR Q rev
10. 9S = T
7. W = - 3(2 - 1) = - 3 L atm
a Q rev = 0 for adiabatic process
\ q = - W = 3 L atm ( a Du = 0 for isothermal)
Thus, 9S = 0
\ qsurr = - 3 L atm = - 3 × 101.3 J
Reversible Adiabatic processes are isoentropic.
Chemistry
INTEXT EXERCISE: 6
9H 540×18 6. For spontaneous change (work is being done by the
1. 9S = T = 373 cal mol -1
system)
= 26.06 cal K -1 mol -1
\ (dG)T, P - ve and (dS)V, U be + ve
2. All are acid and thus reaction will go in forward 7. - 9G o = RT In K C (Theoretical)
direction. However maximum for HI as their K
values are 10-3, 108, 1010 and 1017 for HF, HCl, HBr 8. DG = DH - T D S, since DG = + ve at T = 273 K
and HI respectively. and DH = + ve and at high temperature 373 K it
becomes spontaneous (DG = - ve) even if DH = +
3. 9G = 9H - T9S ve. This is possible only, if DS = + ve because at
at equilibrium 9G = 0 high temperature T D S > DH to give DG = - ve.
9H 30×103 9. On adding more product, reaction will tend to move
\ T = 9S = 75 = 400 K
backward
4. 9G o = 9H o - T9S o
10. Given DH = +ve; DS = +ve
=- 382.64 - 298× (- 145.6×10 -3)
Thus, DG is -ve only when |DH| < |TDS|.
=- 339.3 kJ mol -1
9H 6×103
5. 9S f = T f = 273 = 21.98 J
INTEXT EXERCISE: 7
1. CH 4(g) + 2O 2(g) $ CO 2(g) + 2H 2 O(l) 5. 9H 2 - 9H1 = 9C P (T2 - T1)

9n g = 1 - 3 =- 2 9H 2 - 9H1 = 0×100
\ 9H 2 = 9H1

9H o = 9U o + 9n g RT
6. Cgraphite → Cdiamond DHreaction = DfH(diamond) - DfH(graphite)

9H o =- 393 + (- 2) RT
= 1.896 - 0.23 = 1.666 kJ/ mol.

\ 9H o =- 393 - 2×8.314×10 -3 ×T
7. 9C P = C P of products - C P of reactants.

\ 9H o < 9U o
100
2. No doubt (a) and (b) both represent heat of 8. 9H 2 = 9H1 + # 9C P $ dT
formations but standard heat of formation (91 H fo) 10
for CO2 will be from C(graphite) + O2 → CO2 as C(graphite) 100

is most stable form of carbon.

=- 142 + # [2.0 + 0.2T] $ dT
10
3. Subtracting (ii) from (i)
=- 14.2×103 + ;2.0× [100 - 10] + 0.2 :100 10 2 DE
2

1 2 - 2
CO + 2 O 2 $ CO 2; 9H = X - Y
=- 14.2×10 + [180 + 1000 - 10]
3
\ Z=X-Y

=- 14.2×103 + 1170 =- 13.03 kcal .

\ X=Y+Z
9. 9H = H G - H D =- ve , i.e., Graphite has lower
4. 9H = 9U + 9nRT
energy and thus more stable.
for (a), (b), (c) 9n = 0 and for (d) 9n =- 2
10. Br2 has 9f H o = 0 in liquid state.
INTEXT EXERCISE: 8
3 4. 9Hsol = 9H lattice + 9H hyd
1. S + 2 O 2 $ SO3; 9H =- 2x ...(i)
1 1 = 180 + 9H h
SO 2 + 2 O 2 $ SO3; 9H =- y ...(ii)

\ 9H h =- 179 kcal
By eqs. [(i) - (ii)]
9H Na (h) + 9H Cl (h) =- 179 kcal
+ -

S + O 2 $ SO 2; 9H = (y - 2x)
5
2. Two equivalents of each are used.
\ 9H Na (h) + 6 9H Na (h) =- 179 kcal
+ +

3. H + + OH - ? H 2 O; 9H =- 57.46 kJ 6× (- 179)

\ 9H Na (h) = +
11 =- 97.64 kcal

` H 2 O ? H + OH ;
+ -
9H =+ 57.46 kJ
 Thermodynamics
5. C6 H12 O6 (s) + 6O 2 (g) $ 6CO 2 (g) + 6H 2 O (l) 8. 9C H = 9C U + 9n(g) RT

9c H Co H 6 12 O6 = 69f H CO
o
+ 69f H oH O(l) - 9f H Co H
2 2 6 12 O6 (s) 9C U =- 1364.47 kJ mol -1, 9n(g) = 2 - 3 = - 1
= 6×(- 400) + 6× (- 300) - (- 1300)
\ 9C H =- 1364.47×103 + (- 1) ×8.314×298
=- 2900 kJ/mol =- 1364470 - 2477.57 =- 1366.95 kJ
\ Standard enthalpy of combution per gram of =- 1366.95 kJ mol -1
glucose
9. Heat required to dissociate 90% of the undissociated
- 2900 acid = 0.90 × 400 = 360 cal.
= 180 =- 16.11 kJ
6. 9Hsub
o
= 9H fusion
o
+ 9H ovap = 0.36 kcal.

9H cond
o
=- 9H ovap
\ DHneut with strong base = - 13.7 + 0.36

57.5 = 9H fusion
o
+ 42 = - 13.34 kcal

\ 9H fusion
o
= 15.5 kJ mol -1, 10. H B > H A H B - H A = 24

\ 9H o
freezing =- 15.5 kJ mol -1

H C > H B
H C - H B =- 18
7. q = 1.23×103 ×6.12 = 7.5×103 J
\ H B > HC > H A

\ Du = - 7.5 kJ
3×8.314×343
DH = - 7.5 - 1000
= - 16.08 kJ
INTEXT EXERCISE: 9
1. Bond energy is the amount of heat required to break Given: 9H fCO =- 393 kJ
2

1 mole bond to give isolated gaseous atoms. \ Resonance energy of CO2 = -393-538 kJ
= -931 kJ
2. Shorter is bond, more is bond energy.
8. A + O 2 $ Oxide of A or B; 9H =- 17 kJ
3. PH3 $ P + 3H; 9H = 228
228
B + O 2 $ Oxide of A or B; 9H =- 12 kJ
\ EP-H = 3

A$B ; 9H =- 5 kJ
H2P - PH2 → 2P + 4H; DH = 355;
Thus A has higher energy than B and is less stable.
E P - P + 4×E P - H = 355
228 9. 9H =- [2 × EC - H + EC - C + [EC = C + E H - H]
E P - P + 4× 3 = 355
and EH-H = 2 × heat of formation of H-atom
\ E P - P = 51

=- [2 × 413 + 346] + 611 + 2 × 218
4. 9H =- [EC - C + 6×EC - H] + [EC = C + 4EC - H] + E H - H
=- 125 kJ
5. EA-A = a 10. 3C (s) + 3H 2 (g) $ C3 H6; 9H = 53.0 kJ mol -1 ..(i)
EA-B = a
C (s) $ C (g); 9H = 715 ...(ii)
EB-B = 0.5 a 1
1 1 2 H 2 (g) $ H (g); 9H = 218 ...(iii)
Also, 2 A 2 + 2 B 2 $ AB;
By eqs. 3×(ii) + 6×(iii)
9H =- 100 kJ mol -1

3C (s) + 3H 2 (g) $ 3C (g) + 6H (g);
1
\ 9H =- [E A - B] + 2 [E A - A + E B - B]
9H = 2145 + 1308 = 3453 kJ mol -1 ..(iv)
1
=- a + 2 [a + 0.5a] By (iv) - (i)
- 100 =- 0.25 a
3C (g) + 6H (g) $ C3 H6; 9H = 3400 kJ mol -1
a = 400 kJ mol -1
3C (g) + 3H 2 (g) $ CH2
6. Average bond energy of C - H bond is
H2C CH2
Dissociation energy of CH 4 X1
No. of bond broken = 4
\ 9H = 3×EC - C + 6×C - H = 3×356 + 6×408
7. C + O 2 $ CO 2 = 1068 + 2448 = 3516 kJ mol -1
H f ]CO 2g = 3 Hsub ]Cg + EO = O - 2×EC = O Thus strain = 3516 - 3400 = 116 kJ
= 718 + 498 - 2 × 339 = 538 kJ
Chemistry
EXERCISE - 1
1. U ∝ T for ideal gases Heat capacity at constant volume (Cv)=20 J/k
2. By definition 1 cal = 4.184 J We know that work done
W =- nC V (T2 - T1); 3000 =- 1×20 (T2 - 300)
3. Thermos flask is an isolated system.
3000 =- 20T2 + 6000
4. 1 cal = 4.184 J and 1 J = 107 erg. 3000
20T2 = 3000; T2 = 20 = 150 K
5. Lower the energy more stable it is.
20. Given that
6. u = K.E. and hence u \ T. Thus u is a state function.

P1 = 10 atm, P2 = 1 atm, T = 300 K, n = 1
7. Density tension is an intensive property which do

R = 8.314 J/K/mol
not depend upon the quantity of matter present in the
system. Now, by using
P
8. No exchange of mass or heat takes place in an
W = 2.303 nRT log10 P2
1
isolated system. 1
2.303×1×8.314×300
= log10 10
9. Surface tension is an intensive property which do
not depend upon the quantity of matter present in the
W = 5744.1 Joule
system. 21. At constant volume, w = 0
10. First Law : Du = Q + W
\ Du = q
11. Du increases with temperature. 22. Enthalpy (H) is defined as H = u + PV.
12. q = Du - W if q = 0 for adiabatic process, than DE =W. 23. 9H = 9u - W or 9H = 9u + P9V .
13. As the system is closed and insulated no heat enter 24. W =- P9V =- 1×105 (1×10 -2 - 1×10 -3)
or leave the system, i.e. q = 0;

=- 1×105 ×9×10 -3 =- 900 J
\ Du = Q + W = W.
25. W =- P9V; W =- 3×(6 - 4) = - 6 L atm
14. We know that Du = Q + W = 600 + (-300)

W =- 6×101.32 (` 1 L atm = 101.32 J)
= 600 + (-300) = 300 J

W =- 608 J
W = 300, because the work done by the system.
26. DV ! 0 but w = - Pext DV = 0 as Pext = 0
15. A monoatomic gas has only three translational
degrees of freedom. Energy associated with each 27. When DStot = + ve the change is spontaneous.
1
degree of freedom = 2 kT . Hence internal energy 28. Heat is always flows from the higher to lower
3 3 temperature.
of 1 mole of gas - 2 kT × N 0 2 RT .
29. Mixing of non-reacting gases increases randomness
16. DU is a state function but w and q are not state
and so increase entropy.
functions.
p1 30. DStot > 0 as process is irreversible. Since the system
17. - W =+ 2.303 nRT log p 2 is isolated so DSsurr = 0 ⇒ DSsys > 0
10 31. For the same suibstance in solid, liquid and gas, Ssolid
- W = 2.303×1×2×300 log 1 = 1381.8 cal
P2 < Sliquid < Sgas.
18. W = 2.303 nRT log P1
32. For adiabatic expansion q = 0 than according to the
10 q
2.303×1×2×300
= log 2 = 965.84 definition DS = T ⇒ DS = 0.
at constant temperature, Du = 0. 33. If DH > 0 and DS < 0 then the process will be non-

Du = q + w; q = - w = - 965.84 cal. spontaneous at all temperatures.
19. Given number of moles = 1 34. There are the assumptions in deriring the relation
Initial temperature = 27oC = 300 K DH - T D S < 0 for spontaneous reaction.
Work done by the system = 3 KJ = 3000 K 35. Solid → Liquid, DS increases.
It will be (-) because work is done by the system. q rev
36. 9S = T ` unit of S is JK-1mol-1.
 Thermodynamics
37. Both melting of ice and evaporation are spontaneous 57. DH = DU + DngRT
at room temperature. Since Dng = - 2
(900×18)
38. 9S vap = 373 = 43.4 JK -1 mol -1 . Then DH = DU - 2RT.
9H 9.2 58. If Dn = - ve than DH < DE.
39. Tm = 9S fusion = 0.008 = 1150 K.
59. It is a combustion reaction, DH = - ve.
fusion

40. Formation of CO2 is,

C(s) + O2(g) → CO2(g) 60. The enthalpies of all elements in their standard state
at 25oC or 298 K are zero.

DSo = 213.5 - 5.690 - 205 = 2.81 JK-1.
61. DE = DH if Dng = 0
41. Because solid → solid, DS is same and DH is -ve.
62. For this reaction Dn = 0 hence DE = DH.
3 H 2257×18
42. 3 S = T = 373 (As DH is given in kJ/g)
63. Since DH is a state function, therefore its value is the
= 108.91 JK mol
-1 -1
same when Reactants get converted into products
43. It does not violates the first law of thermodynamics irrespective of the path followed by the reaction.
but violates the II law of thermodynamics. 64. 9H - 9E = 9n g RT; 9n g =- 3
44. Given that, T1 = 500 K, T2 = 300 K so, 9H - 9E =- 3RT .
T -T 500 - 300 200
By using, h = 1 T 2 = 500 = 500 = 0.4 65. 9H - 9E = 9n g RT
1

45. Since gas gets attached on solid surface therefore also, 2NH3(g) " N 2(g) + 3H 2(g)
entropy decreases.
9n g = 2 and T = 300 K
46. G is a measure of the Chemical Potential. 66. PCl5 (g) → PCl3 (g) + Cl2 (g)
47. At equilibrium, DG = 0. For this reaction Dng = 2 - 1 = 1
48. 9G o =- 2.303 RT log K
Dng = is positive, i.e., there is an increase in the
number of gaseous moles then DH > DE.

- 4.606 =- 2.303×0.002×500 log K
1

log K = 2, K = 100. 67. H 2 + 2 O 2 " H 2 O 9H =- 188kJ/mole ...(i)
49. 9G = 9H - T9S, T = 25 + 273 = 298 K
H 2 + O 2 " H 2 O 2; 9H =- 286kJ/mole ...(ii)
11.7×10
= - 298× (- 105)
3
By 2 × (i) and (ii)
19590
= J = 19.59 kJ
2H 2 + O 2 " 2H 2 O; 9H =- 376kJ/mole ...(iii)
50. If 9G =- ve reaction is spontaneous.
2H 2 + 2O 2 " 2H 2 O 2 H =- 572kJ/mole ...(iv)
51. 9G = 9H - T9S By (iii) - (iv)

9G =- 382.64 - (- 145.6) ×10 -3 ×298
2H 2 O 2 " 2H 2 O + O 2 9H =+ 196kJ .

=- 339.3 KJmol -1 68. DH for C2H6 = - 341.1 kcal.
- 341.1
52. 9G = 9H - T9S = 31400 - 1273×32 its calorific value = 30 =- 11.37 kcal/g.
31400
= - 40736 =- 9336 cal
DH for C2H2 = - 310.0 kcal
53. 9G = 9H - T9S - 310.0
its Calorific value = 26 =- 11.92,
0 =+ 30.558 - T×0.066
30.558 hence C2H2 is a better fuel.
or T = 0.066 = 463 K
69. For the decomposition of 9gm of water heat required
54. dG = VdP - SdT by definition. =142.5 kJ
55. 2CO(g) + O2(g) → 2CO2(g)
We know H2O = 2 + 16 = 18

Dng = 2 - 3 = - 1
Therefore heat required for decomposition of 18gm
18
Now, DH = Du + DngRT. Since Dng < 0 water = 9 ×142.5 = 285 KJ

\ DH > Du
Than, enthalpy of formation of water is reverse of
heat required =- 285 kj.
56. By definition exothermic reaction means DH < 0.
Chemistry
70. C(s) + 2H 2(g) " CH 4(g) ...(i)
C(s) + O 2(g) " CO 2(g) 9H =- 94 kcalmol ... (ii)
-1
1 & - 890.4 =- 395.5 + 2 (- 285.5) - 9Hf (CH 4) - 2 # 0
H 2(g) + 2 O 2(g) " H 2 O(l) 9H =- 68kcal mol -1 ..(iii)
CH 4 + 3/2 O 2 " CO 2 + 2H 2 O DH
= - 213 kcalmol-1 ...(iv)
to obtain equation (i) operate-(ii) + 2 x (iii) - (iv).
⇒ DH of equation (i) = - 94 + 2 ( - 68) - ( - 213)
= - 17 kcal/mol.
71. C(s) + O2(g) → CO2(g) DH = - 393.5 KJmol-1 ...(i)
CO(g)+1/2O2(g)→CO2(g) DH =-393.5 KJmol-1..(ii)
On substracting equation (ii) from equation (i)
We get
C(s) + O2(g) → CO2(g); DH = -110.5 KJmol-1
The enthalpy of formation of carbon monoxide per
mole = -110.5 KJmol-1
72. C + O 2 " CO 2; 9H = q
C + 1/2O 2 " CO; 9H =- 12 ...(i)
CO + 1/2O 2 " CO 2; 9H =- 10 ...(ii)
additing equation (i) and (ii) we can get
9H =- 12 + (- 10) =- 22
25
73. C8 H18 + 2 O 2 " 8CO 2 + 9H 2 O
H 3 orxn = 8H fo ]CO 2g + 9H fo ]H 2 Og - H fo ]C8 H18g
= 8 ( - 490) + 9 ( - 240) - 160
\ 3 H orxn = - 3920 - 2160 - 160 = 6240 KJ/mol
\ 3 H orxn = for 6 moles of octane = 6240 × 6
= 37440 KJ /mol = - 37.4 KJ
3 80. XY $ X(g) + Y(g); 9H =+ a kJ/mol ...(i)
74. 2Fe + 2 O 2 " Fe 2 O3; 9H =- 193.4 kJ ...(i)
1
Mg + 2 O 2 " MgO; 9H =- 140.2 kJ ...(ii)
On multiplying eq. (ii) by 3
3
3Mg + 2 O 2 " 3MgO; 9H =- 420.6 kJ ...(iii)
Resulting equation can be obtained by subtracting
eq. (i) from (iii)
3
3Mg + 2 O 2 " 3MgO; 9H =- 420.6 kJ
3
2Fe + 2 O 2 " Fe 2 O3; 9H =- 193.4 KJ
Subtraction:
3Mg + Fe 2 O3 " 2Fe + 3MgO; 9H =- 227.2 KJ
75. CH 4 + 2O 2 " CO 2 + 2H 2 O, 9H =- 890.4 kJ .(i)
C + O 2 " CO 2, 9H =- 395.5 kJ ...(ii)
1
H 2 + 2 O 2 " H 2 O, 9H =- 285.8 kJ ...(iii)
from (i), (ii), (iii).
9H comb. (CH 4)
= 9H f (CO 2) + 29H f (H 2 O) - 9H f (CH 4) - 29H f (O 2)
9H f (CH 4) =- 76.7 kJ mol -1 .
76. S + O 2 " SO 2, 9H f =- 4.6 kJ
a 0.5 gm of sulphu on burning produce 1gm of
SO2
\ 32 gm of sulphur on burning produce 64gm of
SO2
\ 9H = (- 4.6 kJ) ×64 =- 294.4 kJ .
77. No doubt heat evolved during neutralization of
250 cm3 of each acid and base is five time the heat
evolved during neutralization of 50 cm3 of each acid
and base but the quantity of solution taking heat is
also five time thus same temperature rise is noticed.
78. Given: Weight of iron burnt = 4g; Heat liberated =
29.28 KJ and atomic weight of iron (Fe) = 56. We
know that in ferric oxide (Fe2O3), 2 moles of iron
or 2 × 56 = 112 gram of iron are burnt. We also
know that when 4 grams of iron are burnt, then
heat liberated = 29.28 KJ, therefore when 112
grams of the iron are burnt, then heat liberated
29.28×112
= =- 819.8 kJ (Minus sign due to
4
liberation of heat).
79. C + O 2 " CO 2(g), 9H fo =- 393.5 kJ mol1 ...(i)
1
C + 2 O 2 " CO(g), 9Hfo =- 110.5 kJ mol -1 ...(ii)
1
H 2 + 2 O 2 " H 2 O(g), 9Hfo =- 241.8 kJ mol -1 ...(iii)
By (ii) + (iii) - (i)
CO 2(g) + H 2(g) " CO(g) + H 2 O(g), 9H =+ 41.2 .
X 2 $ 2X; 9H =+ a kJ/mol ...(ii)
Y2 $ 2Y; 9H =+ 0.5 a kJ/mole ...(iii)
1
1
2 ×(ii) + 2 ×(iii) - (i), gives
1 1
2 X 2 + 2 Y2 $ XY ;
9H = b + 2 + 2 a - a l kJ/mole
a 0.5
a 0.5 a
+ 2 + 2 - a =- 200
a = 800 .
81. 4g H2 = 2 moles, Bond energy for 1 mole of
H2 = 208 / 2 = 104 kcal.
82. is resonance stabilized and hence the
:
C - H bond is easier to break than CH4 to form CH3
83. N ≡ N is the strongest bond among the given options.
 Thermodynamics
1 1 - 166
84. Aim: 2 H 2 + 2 Cl 2 " HCl 86. 4 =- 41.5 kJ/mole ⇒ EC-H = 41.5 kJ/mol.
9H = /B.E.(Products) - /B.E.(Reactants) 1 1
87. 2 H 2 + 2 Cl 2 " HCl, 9H =- 90 KJ
(HCl) - : 2 B.E. (H 2) + 2 B.E. (Cl 2)D
1 1
B.E
=
1 1
\ 9H = 2 f H - H + 2 fCl - Cl
=- 103 - : 2 (- 104) + 2 (- 58)D
1 1 1 1
or - 90 = 2 ×430 + 2 ×240 - f HCl
=- 103 - (- 52 - 29) =- 22 kcal . \ f H - Cl = 425 kJmol -1 .

85. First ionization potential of Li = 5.4 eV 88. CH 4 " C + 4H, 9H = 320

Electron affinity of Cl = 3.61 eV
fC - H = 80 cal
We have DH = I.P. - E.A.
C 2 H6 " 2C + 6H, 9H = 520
= 5.4 - 3.61 = 1.80 eV = 1.80 × 1.6 × 10-22 kJ
\ 520 = fC - C + 6fC - H
DH = 2.86 × 10-22 kJ,
\ fC - C = 520 - 480 = 40 cal.
for 1 mol
89. H - H + Br - Br " 2H - Br
DH = 2.86 × 10-22 × 6.02 × 1023 = 170 kJ/mole.
\ DH = 625 - 728 = - 103 kJ
EXERCISE - 2
1. Test tube is open to atmosphere. 14. From graph we know that VB > VA, so expansion has
2. (i), (ii), (iii), (iv) taken place so w will be with –ve sign and DH will
be +ve as T has increased.
3. (ii), (iii), (iv), (v), (vi), (vii), (viii)
15. If system returns to initial state after multiple
4. Insulated container of rigid walls will not show any processes then it is a cyclic process.
change in temperature.
5. A ideal thermos flask is an isolated system. 16. Work done by the gas in the

6. Case (i) 9V = 0, W = 0
cyclic process = Area bounded
Case (ii) P = constant, W =- P (2V1 - V1) =- PV1
(ABCA) = 5P1V1
7. W = +ve because work done on system.

Since Vol. is in X axis and loop is clockwise
q = 0 because thermally insulated container.

\ Sign of W is negative
8. Freezing of liquid is always an exothermic process
in which the system loses heat. 17. At constant vol. or decreasing volume, T is increasing
thus pressure must be increasing.
9. DU = Q + W = 600 + (-300) = 300 J

When V, T both increasing, P is decreasing as slope
W = -300, because the work done by the system.
is greater than 45o.
10. DU = q + 2 = q - Pext (V2 - V1)
300 = 500 - 1 (DV) × 100 18.
500 - 300
9V = 100 = 2 lit.
11. Formation of bonds results from attractive forces i.e.
decrease in potential energy. Since u = P.E. + K.E.
PV = const = K
therefore as P.E. decreases, u also decreases. log P + log V = log K
12. A → B, volume is not changing (Isochoric)
⇒ Y + X = K as T - K -
B → C Isobaric Hence intercept on co-ordinate axes will increase
C → A Temperature is constant (Isothermal)
⇒ T2 > T1
13. A → B : Isochoric increase in P, T V nR
19. Slope = T = P
B → C : Isothermal expansion as PV is constant

\ as slope increses, P must
C → D : Isochoric decrease in P, T
be decreasing
D → A : Isothermal compression as PV is constant
\ PA < PB
Chemistry
20. C p - C v = nR for non-molar heat-capacity 34. Because two states of a system can not be connected
C p,m - C v,m = R for non-molar heat-capacity by one adiabatic & one isothermal path.
21. Isochoric rocess ⇒ w = 0 35. q = 0 ` 9U = w
\ Du = q
⇒ nC v,m (T2 - T1) =- Pext : P 2 - P 1 D
nRT nRT

22. For Isothermal Process Du = 0 2 1

\ q+w=0⇒q=-w \ C v,m [T2 - T1] = Pext $ R : P - P D

T T
1 2

Now work done by the system = - w 1 2

⇒ 2 R [T2 - 300] = 2×R : 300

\ work done by the system = q 5 T2 D
5 - 2
23. During adiabatic expansion P, T both decrease.
⇒ T2 = 248.5 K .
24. T1 V1c - 1 = T2 V2c - 1 & 300×V1/3 36. |Wrev |>| WIrr |
T2 (8V) 1/3 & T2 = 150 K

Tfinal(rev) < Tfinal(Irr)
W = nC v (T2 - T1) = 1×3R (150 - 300)
3×2 (- 150) =- 900 cal
9Trev > 9TIrr
25. Magnitude of work done
\ 9H \ 9T \ |DHrev| > |DHIrr| but as T decreases
is maximum for largest during adiabatic expansion so DH is < 0 ⇒ DHrev
area under the P.V. curve < DHIrrev
with the V axis.
9H rev > 9H Irr
26. Slope of adiabatic curve is greater than isothermal 37. State 1 $ State 2
curve (1L, 10 atm, 300 K) (4L, 5 atm, 600 K)
27. TV c-1
= constant q
a C = 3 T q = 50 × (600 - 300) = 15000 J
5 2

c= 3 `c-1 = 3 W =- Pext (V2 - V1) =- 1 (4 - 1) =- 3L atm =- 300 J

\ 300×(8) 2/3 = 250× (V2) 2/3
9u = q + W = 15000 - 300 = 14700 J

⇒ (V2) = 4.8 2/3
9H = 9u + P2 V2 - P1 V1

⇒ V2 = (4.8)3/2 @ 10.5 L 14700
= J + (20 - 10) ×100 J = 15.7 KJ
28. At A and D the temperatures of the gas will be equal, 38. 9U = 9W
so 9u = 0, 9H = 0
nCv (T2 - T) =- P×(V2 - V1)
Now W = WAB + WBC + WCD 3
2 R (T2 - T) =- 1
=- P0 V0 - 2P0 V0
2
ln 2 + P0V0
\ T2 = T - 3×0.0821
= 2 + P0V0 ln 2 and q = - W = 2 + P0V0 ln 2. 39. Since work done on the system, is maximum in
29. In isothermal reversible process ideal gas has single stage compression hence all other adiabatic
constant temperature and so DU=0 and DH = DU=0. points will fall between 1 and 2.

30. The product PV is increasing so temperature will 40. Final temperature of gas must be double of the initial
keep or increasing in the process, hence DH = Du + temperature as P remains constant and V doubles.
D (PV) will increase constantly Initially PV = 1 bar L = 100 J

9H = 9u + 9 (PV) = nC v 9T + 9 (PV)
31. D (PV) = 40 L atm = 40 × 100 J = 4000 J

a 9T = Tf - T1 = T1

D u = 200 J

D H = D u + D PV = 4200 J = 4.2 kJ \ = (cnR
3
- 1) T1 + 9 (PV) = 2 ×100 + 100 = 250 J.
32. P2V2 = 20 L atm P1V1 = 3 L atm
41.
⇒ D(PV) = 17 L atm
D u = 40 L atm ⇒ DH = Du + D(PV) = 57 L atm
33. DH = heat given. So process is isobaric.

W =- Pext (9V) =- 1×2 litre atm =- 202.6 J
Hence, q = 202.6 J = 9H and 9U = q + w = 0

42. Vwater < Vice ⇒ for ice to water DV < 0
Now W = - P D V and D V < 0
\ W>0
43. During freezing DHfusion amount of heat is lost by the
system to freeze 1 mole water.
25 0.0821×373
44. W = - PD V. Now Vsteam = 18 × = 42.53 L
1
4250
\ W = - 1 × 42.5 L atm = - 4.18 cal = - 1030 cal
25
q = DH = 9270 × 18 = 13500
a DH = Du - w at constant pressure
\ Du = 13500 - 1030 = 12470 cal
45. Molecules of gas are most free to move about and
hence possess the highest entropy.
46. Dng is + ve
47. Mixing of non-reacting gases increases randomness
and so increase entropy.
48. Dng is most - ve
49. Reaction is endothermic and no. of moles increases
on decomposition.
50. NaNO3 is a solid, which is converted to liquid ions.
51. Greater value of Dng ⇒ more entropy change.
52. Second Law of Thermodynamics can also be
stated as - Entropy of the universe is continuously
increasing as the universe is expanding.
53. S (gas) is always > S (liquid)
T 5 600
54. 9S = nC p,m ln T2 = 2× 2 R ln 300 = 5R ln2
1
Thermodynamics
62. Equilibrium at standard state means DGo = 0⇒K=1.
63. Once curd formation beings in milk, the entire milk
gets converted to curd on its own i.e. spontaneously.
64. At 100oC and 1 atm water and steam are at
equilibrium, Hence DG = 0.
65. It is because of the fact that for spontaneity, the value
of DG (DH - T D S) should be < 0. If DS is – ve, the
value of T D S shall have to be less than DH or the
9H x
value of DS has to be less than T i.e., 298 .
66. DH = - 33 × 103 J and DS = - 58 J/k
For spontaneity : DH - T D S < 0
\- 33000 - T (-58) < 0
or, 58 T < 33000
\ T < 568.96 k
1
67. K = 4
1
DGo = -RT ln KP = -RT ln KP = -RT ln 4 = RT ln 4
68. DG for 3Fe (s) + 2O 2 (g) $ Fe3 O 4 (s) can be
1
obtained by taking [(2) + 4×(1)] × 3
1
Hence, we get 9G f = [- 19 + 4×(- 177) × 3
=- 242.3 K cal for 1 mole Fe3 O 4
69. 9G o = 9H o - T9S o
For spontaneous process 9G o < 0
So, 9H o - T9S o < 0
Hence, T < 339 K or < 66 o C .
70. DG at equilibrium = 0.

55. 9S gas = nC v,m ln T2 = 2× b 2 - 1 l R ln 2 71. 9H o = 9U o + 9n g RT

T 5
1
1×2×500
3R= ln 2.
- 4.6 = 9U o - 1000 & 9U =- 3.6 kCal
o

T 3 573
56. 9S gas = nC v,m ln T2 = 2× 2 R ln 473 = 3 R 72. w =- Pext 9V =- 9n g RT and 9n g is - Ve for I and
1
II also 9V =- ve for IV. Hence, w is + ve.
ln b 473 l .
573
3R=
73. 9n g = 0 & 9H o = 9U o
V For 2 mole 9U o =- 370 kJ .
57. 9S gas = nR ln V2 = R ln 3
1

1× - 401.7 74. Sublimation would involve absorption of heat and

58. 9S(system) = 368 =- 1.09 JK - 1 thus, the temperature of the air inside the balloon wil
The ice-water both absorbs the 401.7 J decrease.
401.7 \ Du < 0.
\ DSsur = 273 = 1.47 J/K
75. Using DH = DE + Dng RT, if Dng ! 0 the DH ! Du
9S(universe) =- 1.09 + 1.47 = 0.38 JK -1
59. 9S reaction = 6 (87) - 4x - 205 =- 266 76. 3C(s) + 3H 2(q) + O 2(q) $ CH3 COOCH3 (,)
& x = 145.75 J moleK
9H fo =- 442.91
60. Gibb’s free energy is expressed in kJ/mol or J/mol
9U = 9H - 9n q RT where Dnh = - 4
and hence is an intensive property.
\ Du = b - 442.91 - (- 4) ×8.314× 1000 l kJ mole -1
298

61. For spontaneity DG < 0, which is possible when DH
< 0, DS > 0.
=- 433 kJ mole -1
Chemistry
77. 2C + O 2 " 2CO; 9H =- 220 KJ 85. S + O2 → SO2 DH = - 298.2 KJ/mole ...(1)
This reaction does not represent complete
1
SO2 + 2 O2 → SO3 DH = - 98.7 KJ/mole ...(2)
combustion of carbon, hence heat of combution of
carbon will not be equal to 110 kJ. The negative SO3 + H2O → H2SO4 DH = - 130.2 KJ/mole ...(3)
sign of DH indicates that this reaction is exothermic.
1
H2 + 2 O2 → H2O DH = - 287.3 KJ/mole ...(4)
Also, despite being spontaneous reaction, it requires ------------------------------------------
initiation. Adding (1), (2), (3) and (4) we get desired equation.
78. C (s) $ C (g) can be obtained as, 5644
86. nC H = 1411 = 4
2 4

1 C2H4 + 3O2 → 2CO2 + 2H2O ⇒ nO needed = 4 × 3

9H = 9H1 - 9H 2 - 2 9H3 + 9H 4 2

79. We have
\ VO = 4 × 3 × 22.4 = 268.8 L
2

H 2 O (l) " H 2 O (g) 9H = 40.63 kJ mol -1 9H
87. Calorific value = mol.wt
o

9U = 9H - (9n g) RT,
o o
3 ng = 1 341
for ethane (C 2 H6) =- 30 =- 11.37

\ Duo = 40.63 kJ mol-1 - (8.314 × 10-3 × 373)
310
= (40.73 - 3.10) kJ mol-1 for ethyne (C 2 H 2) =- 26 =- 11.9
= 37.63 kJ mol-1 So, better calorific value is better fuel hence, C2H2.

80. DH represents heat of reaction. 88. MgCl2 $ H2O → MgCl2(aq) DH1 = ?

81. H2(g) + Br2(g) → 2HBr(g) DH = DHo1
Br2(g) → Br2(l) DH = DH
[eq1 - eq2]
H2(g) + Br2(l) → 2HBr(g) DH = DHo2
1 1
Required equation, 2 H 2 (g) + 2 Br2 (,) $ HBr (g)
MgCl2(aq) → Mg2+(aq) + 2Cl-(aq) DH1= -30 cal/mol
... (i)
MgCl2 $ H2O(s)→Mg2+(aq)+2Cl-(aq)DH3=-25cal/mol
o
... (ii)
2 a R1 = R3 - R2.
\ DH1 = DH3 - DH2 = - 25 + 30 = + 5 cal/mol.
89. Since process is exothermic thus heat is evolved. So,
temperature of water increases.

9H = ; 9H1 - 9H 2 E 90. C 2 H 2 (g) + H 2 (g) $ C 2 H 4 (g)

0 0

2
9H = 9U + 9n g RT = 9U + P9V
82. C (diamond) + O2 → CO2(g); DH = - 94.3 kcal/mol 100
\ - 0.5 = 9U + 1.5 (- 5) × 1000
C (graphite) + O2 → CO2(g); DH = - 97.6 kcal/mol 9U =- 0.5 + 0.75
C (diamond) → C (graphite) DH = 3.3 kcal 9U = 0.25 kJ

Heat required to convert 12 gram diamond to 91. KBr (s) $ K + (g) + Br - (g)
graphite = 3.3
& 9H = Lattice energy (By definition)
\ Heat required to convert 1 g diamond to graphite
3.3 92. 9H 0f (LiCl) =- q = 9Hsub (Li) + 1 2 9H diss
= 12 = 0.275

(Cl 2) + 9H IP (Li) + 9H EA (Cl) + 9H L.E.
83. Combustion reaction of solid boron 244

- 400 = 160 + 2 + 520 - 365 + 9H L.E.
3 1

B (s) + 4 O 2 (g) $ 2 B 2 O3 (s)
9H L.E. =- 400 - 437 =- 837 kJ mole -1

1
9H 0r = 9H 0c = 2 H 0f (B 2 O3, s) - 9H 0f (B, s) 93. Strong acid and strong base neutralization heat is
equal to – 13.7 kcal.
3

- 4 9H 0f (O 2, g)
94. HCOOH is a weak acid so heat of neutralization is

9H 0f of element in standard state is assumed to be less than X.
zero. 95. H + + OH - $ H 2 O (,) 9H = 013.7 kcal ...(i)
1

\ DHoC (B(s)) = 2 DHof (B2O3(s))
CHCl 2 COOH $ CHCl 2 COO - + H +
84. Heat evolved from 1 mole of sucrose (342 g) 9H = 0.7 kcal ...(ii)
= 1350 kcal CHCl2COOH + OH- → CHCl2COO- + H2O(l) DH = ?
Heat evolved from 17.1 g of sucrose Adding equation (i) and (ii) DH = -13 kcal.
1350 The required heat released will be (13.7 - heat
= 342 ×17.1 = 67.5 kcal.
required to dissociate CHCl2COOH = 13.0 kcal.
 Thermodynamics
96. CH 4 $ C + 4H 1 1
2 H 2 (g) + 2 Cl 2 (g) $ H (g) + Cl (g);
9H = 320 = 9H C - H; 9H C - H = 80
9H = 81 kcal .... (4)
C 2 H6 $ 2C + 6H
Subtracting equation (3) from equation (4)
9H = 600 = 9H C - C + 69H C - H
HCl (g) $ H (g) + Cl (g) ; 9H = 103 kcal ...(3)
600 = 9H C - C + 6×80
1 1
9H C - C = 120 cal 2 H 2 (g) + 2 Cl 2 (g) $ HCl (g) ; 9H =- 22.0 kcal
\ Enthalpy of formation of HCl gas =- 22.0 kcal
97. Given
1 1
H 2 (g) $ 2H (g); 9H = 104 kcal ...(1) 98. 2 A - A + 2 B - B " AB 9H =- 100 KJ/mole
Cl 2 (g) $ 2Cl (g); 9H = 58 kcal ...(2) 1 1
2 x + 2 (0.5x) - x =- 100
HCl 2 (g) $ H (g) + Cl (g); 9H = 103 kcal ...(3)
x
Heat of formation of HCl & 2 + 0.25x -+ x =- 100
1 1 &- 0.25 x =- 100
2 H 2 (g) + 2 Cl 2 (g) $ HCl (g) ; 9H = ?
x& = 400 KJ/mole
Divide equation (1) and (2) by 2, and then add
bond enthalpy = 400 kJ/mol.x
EXERCISE - 3
1× 2.44 So, for adiabatic Ti = 2 × 300 = 600
1. There is 2.44 L C2H4 → n = 0.082 × 298 = 0.1 mol
1×1.22 Vi = 40
there is 1.22 L CH4 → n = 0.082 × 298 = 0.05 mol
Tf = ?, Vf = 110

\ DH = 0.1 × 1400 + 0.05 × 900 = 185 kJ. for reversible adiabatic process TVg-1 = constant
2. P4(s) → 4P(g); DH = 53.2 × 6 \ Ti V i5/3 - 1 = Tf V f2/3
H2(g) → 2H(g); DH = 104.2 600 # (40) 2/3 = Tf # (40) 2/3 = Tf # (110) 2/3
Tf = 600× b 11 l = 300K
1 3 4 2/3

4 P4(s) + 2 H2(g) → PH3(g); DH = 5.5
1 3 300
4 × 6 × 53.2 + 2 × 104.2 - 3!P-H = 5.5
Ans. 100 = 3 .

⇒ !P-H = 76.866 i.e. 76.9 kcal mol-1 3

7. w =- # PdV
3. DG = DH - D(TS) 1

DG = DH - TDS (isothermal)
w =- # KV3 dV = :- K V4 D = 4 [81 - 1]
3
4 3
-K

DG = 0 - TDS = - T c # m
dq rev 1
1
T 1
- 5 # 4 # 80 =- 4 L atm ⇒ w by the gas = 4 L atm
DG = - # dq rev =- q rev = Wrev

8. DU = 30.0 L atm
As Wrev = -nRT ln b Vf l DH = DU + D (PV)
V
i
= 30 + (P2V2 + P1V1)
So, DG = -nRT ln b V l
V f
= 30 + ( 4 × 5 - 2 × 3) = 30 + 14 = 44 L atm
i

DG = -RT ln 2 9. DSsys = nR ln3 = 9 J/K

DG = -2 × 8.3 × 300 × 0.7 × 10 KJ mol K V
-3 -1 -1
q = - w = nRT ln V2
1

\ DG = -3.486 KJ mol-1 K-1 \ qrev = 8.314 × 300 × ln3 = 2700 J
4. Extensive properties are - \ qirrev = 2700 - 900 = 1800 J ⇒ DSsurr
1800
= - 300 =- 6

(i) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (x)

\ DStot = 9 - 6 = 3 J/K
5. State function are (i) ; (iii) ; (iv) ; (v) ; (vi) ; (vii)
10. DHdissolution = DH(Lattice energy) + DH(hydration)
(ix) and (x) are constants and not variables
= 780 - 775 = 5 kJ mol-1
6. I procese is isobaric, volume become double so,
st
DGdissolution = DHdissolution - T D Sdissolution

\ T is also doubled = 5000 - 300 × 40 = - 7000 J = - 7 kJ mol-1
Chemistry
11. 9H fo = 2 # (- 10) =- 20 kcal
Ca +2 (aq) + 2Cl - (aq) + 2Na + (aq) + CO3-2 (aq)

9S = 90 - (40 + 90) =- 40 cal K -1 " CaCO3 .+ 2Na + (aq) + 2Cl - (aq)
300x - 40 or Ca +2 (aq) + CO3-2 (aq) " CaCO3 (s)

9G = 9H - T9S =- 20 - 1000 = 8 kcal
\ 9H = / H oProducts - / H oreactants

12. Given : 9H =- 217.77 kJ K -1 mol -1
or 9H = 9H fo CaCO - [9H fo Ca 9H fo CO ] +2 -2

9G =- 213.3 kJ mol -1
3 3

T = 273 + 25 = 298 K \ 9H o of a compound = 9H formation

o

9G = 9H - T9S =- 288.5 - (- 129.80 - 161.7) = 3 kcal

\ - 213.3 # 103 =- 217.77 # 103 - 298 # 9S 40 # (- 1.25) # 100
17. 9H = 9U + 1000
- (217.77 # 103 - 213.3 # 103)
or 9S = 298
9U =- 92 + 5
9S =- 15 J/mol K
9U =- 87 kJ.

13. For the formation reaction above 18. Required equation is :

9S fo = S oNH Cl - b 2 S oN + 2S oH + 2 SCl
1 1 o l C 2 H 2(g) + H 2(g) $ C 2 H 4(g)
4 2 2 2
1

H 2(g) + 2 O 2(g) $ H 2 O (,) 3 H o =- 67.8 ...(1)
94.6
= - [1 2 (191.5) + 2 (130.6) + 1 2 (223.0)]
=- 373.85 J K -1 mol -1
5
C 2 H 2(g) + 2 O 2(g) $ 2CO 2 + H 2 O (,) 3 H o
Now that we have DH and DS we can find DG, =- 310.1 ...(2)
9G fo = 9H fo - T9S ot

C 2 H 4 + 3O 2(g) $ 2CO 2(g) + 2H 2 O (,) 3 H o

= -313×103 J mol-1-(298 K)×(-373.85 J K-1 mol-1)

=- 337.2 ...(3)
=- 201.6 # 103 J mol -1 or - 201.6 kJ mol -1
Reg. Eq. = (1) + (2) - (3)
=- 48 Kcal mol -1 .
C
& 2 H 2(g) + H 2(g) $ C 2 H 4(g)
14. C6 H12 O6 (s) + 6O 2 (g) $ 6CO 2 (g) + 6H 2 O (,)

9H rxn = –67.8–310.1 + 337.2 = –40.7 kcal
0.36
No. of Mole of C6 H12 O6 = 180 = 2 # 10 -3 mole 9H = 9U + 9n^gh RT
q
–40.7 = 9U + (–1) ×2×10 –3 ×350
C = 9T ` q = C # 9T = 600 # 10 J = 6 kJ

9U = –40.7 + .7
6
Heat released per mole = = 3 # 103 kJ
9U = –40 kcal/mole
2 # 10 -3
3= MJ 19. 2C (g) + 3H 2 (g) " C 2 H6 (g)

9U =- 3 MJ 9H reaction = 9H fo (C 2 H6) ...(i)

9H = 9U + 9n g RT here 9n g = 0 2C (s) " 2C (g) 9H1 = 2×170 kcal ...(ii)

9H = 9U =- 3 MJ mole -1 equations (i) + (ii)
2C (s) + 3H 2 (g) " C 2 H6 (g)
15. Fe 2 O3 (s) + 3H 2 (g) $ 2Fe(s) + 3H 2 O (I)
9H reaction = 9H fo (C 2 H6)
o
9H300K =- 35kJ
= 9H1 + 39H H–H –69H C–H –9H C–C
9H =- 26 KJ
o
–20 = 340 + 3×104–6×99–9H C–C
9C P = 2C P (Fe, s) + 3C P (H 2 O, ,) - C P (Fe 2 O3, s)
9H C–C = 78 kcal.
- 3C P (H 2, g) 10 10
9C P = 80 20. 9W = # Pdv =- 20 # dv
V =- 20 [,n (V))] 1
10

\ Using Kirchoff’s Equation: 1 1

- 26 # 103 =- 80 # 26720 + 80 (9T)
=- 20 In (10) =- 4605 J

9T = 9
9q = 9U - 9W
16. On mixing CaCl2(aq) and Na2CO3 400
= - (- 4605) = 5005 J c 5 kJ.
CaCl2 + Na2CO3 → CaCO3 + 2NaCl
Solutions are very dilute and thus. 100 % dissociation
occurs.
 Thermodynamics
21. n = 4
w = dU = c 2 c2 - 11 1 m
P V - P V

V1 = 20 lit. V2 = 80 lit.
9w =- Pext (V2 - V1)
PV = nRT
- 125 10×10
& = n×0.082×273 & n = 4.47 moles
=- 1000 ×(80 - 20) ×100 =- 750 J.
- Pext (V2 - V1) = c 2 c2 - 11 1 m
P V -PV
In case of adiabatic process q = 0
DU = 0 + Dw = - 750 J 1×V2 - 10×10

&- 1× (V2 - 10) = 1.67 -1
nCV = DT
V2 - 100

3
4× 2 ×R9T =- 750 (10
& - V2) = 0.67
6.7
& - 0.67 V2 = V2 - 100
9T =- 15 K 106.7
& = 1.67 V2
7.8
22. moles = 78 = 0.1 V
& 2 = 64.
V T
9H = n×9H vap 26. 9Ssys = nRln V2 + nC V ln T2
1 1
0.1×29.7
= KJ V

9Ssystem = nR ln V2 = 2×8.314 ln 7.5
2.97
= KJ 1

2970
= J 33.6
= J = 8 Cal .
9H V.i.t
= 27. (i) In case of adiabatic reversible expansion,
9H 2970 dq rev = 0 & 9S = 0.
\ t = V.i = 11.4×.5
\ t = 540 second (ii) In case of free expansion (Adiabatically)
⇒ t = 9 minute. w = 0, q = 0,
23. C(graphite) → C(diamond) 9U = 0 & nC V (T2 - T1) = 0 & T2 = T1
1 mole 1 mole
9S = nR ln b V2 l = 2R ln (3) = 18 J/K.
V
t = 2 g/cm3 t = 3 g/cm3
1

12 12 28. Heat generated = C T 9T = 2108×1 cal.

V = 2 ml V = 3 ml
9H = 9U + P9V
2108×1
\ nCH = 210.8×103 = 0.01
9U - 9H =- P9V
4

PV
n total = RT = 0.04
=- 5×105 b 3 - 2 l ×103 L. bar
12 12

0.01
- 12 \ mol% = 0.04 ×100 = 25%
=- 5×105 × 6 ×10 -1 J = 100 KJ/mole
29. 2C(s) $ 5C(g)
9U - 9H 100
20 = 20 = 5 .
9H1 = 5×718 = 3590
n1 C V,m + n 2 C V,m
4H 2(g) $ 8H(g)
24. Avg.C V,m =
1 2

n1 + n 2
9H 2 = 4×435 = 1740
3
1×3R + 2× 2 R
5C(g) + 8H(g) $ C5 H8(g)

= = 2R & c = 3 2
3 9H3 = – (8×913 + 2×348 + 2×615) = –5230
T1 V1c - 1 = T2 V 2c - 1 & 320×1 2 - 1 = T2 × ]4g3/2 - 1
3
(1) + (2) + (3)
T
& 2 = 160 K 5C(s) + 4H 2(g) $ C5 H8(g)

9U = (n1 + n 2) C V.avg 9T
9H r×n = 9H f (C5 H8) = 9H1 + 9H 2 + 9H3 = 100
3×2R×(160
= - 320) =- 960 R So resonance energy = 79 - 100 =- 21 kJ mole -1

|(9U/10R) | = |- 960 R/10R | = 96 Hence resonance energy in Kcalmole-1 = 5
25. This is adiabatic irreversible process so, for this 30. DHion = DHneut of WA + SB - DHneut of SA + SB
process
=- 56.1 - (- 57.3) = 1.2 KJ eq -1
PVg= Constant, is not applicable
Enthalpy of ionization for making 100% ionization
w =- Pext (V2 - V1) when there is no ionization at all = 1.5 KJ eq -1
But for adiabatic process 1.5 - 1.2

\ % of ionization = 1.5 ×100 = 20%
Chemistry
EXERCISE - 4
1. There is a decrease in the magnetic potential energy 10. Volume = 5×10×3 = 150m3 = 150×103 L ;
which will be compensated by an increase in the T = 27 o C = 300 K; P = 1 atm
K.E. of the water molecules. Thus, temperature of PV = nRT ⇒ 1 × 150 × 103 = n × 0.082 × 300
the water will increase.
⇒ n = 6097.6
2. From the graph it can be derived that the PV work Total energy released per second
of the system is zero. Thus, we can say that dw = 0 = 150 × 50 = 7500 J/sec.
only if non - PV work is aso zero.
Amount of energy released by persons = energy
3. Degrees of freedom : O3 > N2 > Ne and we know gained by air ⇒ [7500] tsec = nC [dT]
1
that K.E. = f × 2 RT 7500t
&
7
sec = 6097.6×
2 ×8.312×15
4. The latent heat of vapourization is used to break the 354.87
bonds between the liquid molecules. In other words, t & sec = 354.87sec. = 60 = 5.91 minutes.
it is used to increase the potential energy of the 11. At constant volume 9U = q v = nC vm 9T
system. This is so because when there are forces of 3
attraction between particles P.E. < 0, and if there are = 2 R×300 = 450 R
no interactions then P.E. = 0. At constant pressure 9H = q p = nC p,m 9T
5. a The process is of free expansion thus W = 0, as
5
= 2 R (- 150) =- 375 R
pext = 0.
12. a H = U + PV and 9H = 9U + P9V
6. For polytropic process (n = 2)
P9V = nR9T
PV2 = C

\ 3 H = 9U + nR9T
TV = C’
T1V1 = T2V2
For isothermal and reversible process
300 × 1 = T2 × 3 ⇒ T2 = 100 K DT = 0
DU = nCv, m DT
\ DH = 0

5R
\ DU = 1 × 2 (T2 - T1) 13. In isolated system, the expansion of gas is carried
out adiabatically. Since heat exchange between
5×R
= 1 × 2 × (100 - 300) system and surrounding is not possible i.e. q = 0 and
1×5×R secondary Wrev is always greater than WIrr therefore
= - 2 ×200 =- 500R =- 4.2 kJ for reversible process there must be comparatively
higher decreases in internal energy i.e. DU for
7. Since ice-water ratio is maintained as 1 : 1. So, DT=0
reversible process will be more negative. Hence,
as on supplying q, ice melts, hence C = 3 .
final temperature in reversible process will be
8. w =- nR9T =- 2×8.314×100 =- 1662.8 J smaller than irreversible process.
400 400

\ (Tf)irrev > (Tf)rev

9U = n # C V,m dT = 2× # (20 + 10 -2 T) dT
14. 9S = nC p,m ln T2 = 2.5×18×4.2 ln b 300 l
300 300
T 360

= :20×100 + 102 (400 2 - 300 2)D = 4700 J

-2 1
2 34.02
= J/K

\ 4700 = q - 1662.8 15. Reversible adiabatic processes are called Isoentropic
q = 6362.8 J. as DSsys = 0 for such processes.

9. Latent heat of vaporisation of water = 2.25×106 J/kg. 16. H 2 O (,) $ H 2 O (g) 9H vap = 9S vap TB.P. = x1 T1

DH = 2.25 × 106 J/kg.
9H f (H 2 O, g) = 9H f (H 2 O, ,) + 9H vap = x 2 + x1 T1

work done = - Pext (V2 - V1) = - 105 b 0.6 - 1000 l

1 1
DHreaction = 2DHf(CO2,g)+3DHf(H2O,g)-DHf(C2H6,g)


\ DHreaction= 2x3 + 3 (x2 + x1 T1) - x4

= - 0.166 × 106 J/kg = 2x3 + 3x2 + 3x1 T1 - x4.

\ = DU = DH - V = DH + w 17. Less negative the DGof lesser its stability and more
= 2.08 × 10 J/kg 6
easily it can decompose.
 Thermodynamics
18. The compressor has to run for longer time releasing 26. H3 PO3 $ 2H + + HPO32-; 9 r H = ?
more heat to the surroundings.

2H + + 2OH - $ 2H 2 O; DH = -55.84 × 2
V
19. 9Ssystem = nR ln V2 = 2×R×ln2 = 11.52 J/K 9 r H =+ 55.84×2 - 106.68
1
3.41×1000
9 r H = 5 kJ/mol.

9Ssurrounding =- 310 =- 11 J/K
27. CS 2 (,) + 3O 2 (g) $ CO 2 (g) + 2SO 2 (g)

9S total =+ 11.52 - 11 = 0.52 J/K

9H =- 256 Kcal
T V
20. 9S = nC v,m ln T2 + nR ln V2 Let 9H f (CO 2, g) =- 4 x and 9H f (SO 2, g) =- 3 x
1 1

= v,m ln2 + R ln b 2 l = (C v,m - R) ln 2

DHreaction = DHf(CO2,g)+2DHf(SO2,g)-Hf(CS2,l)
1
C
21. As dew formation is spontaneous process, therefore, \ -256 = - 4x - 6x - 26
entropy or randomness of the universe will increase. x = + 23.9
As randomeness of the system has decreased but
\ 9H f (SO 2, g) = 3 x =- 71.7 Kcal/mol.
randomness of the surrounding will increase larger 28. Required reaction & 6C(graphite) + 3H 2(g) $ C6 H6(g)
so that in DSuiverse is positive.
1. For formation of C6H6(g) from gaseous C and H
22. Sliding of layers in possible in graphite due to atoms
weak Vanderwaal’s forces between layers of carbon
9H1 =- (6×9H C - H + 39H C - C)
atoms. Within a layer each carbon atom is covalently
bondid to 3 other carbon atoms. =- (6×416 + 3×591 + 3×331)
P =- 5262 kJ mole -1
23. 9S (gas) = nR ln P1 = 3×8.314×ln 2
2 2. Formation of gaseous C atoms from graphite
17.29
= J/K (at constant temperature) 6C(graphite) $ 6C(g) 9H 2 = 6×718 = 4308
Since DT = 0, therefore, DU = 0, 3. Formation of atomic H atoms from H2
So, q = - W = + pext DV = +P2(V2-V1)=P2V2 b1 - V1 l 3H 2(g) $ 6H(g) 9H3 = 3×436 = 1308
V
Adding (1) + (2) + (3)
2

nRT
= : P2 D V1
1 - P , as V = P
P2
1 2 1 6C(graphite) + 3H 2(g) $ C6 H6(g)

\ q = T×12.47 J/K 9H = 9H 0f (C6 H6, (g)) = 9H1 + 9H 2 + 9H3
q

9Ssurr =- T =- 12.47 J/K = 354 kJ mole -1
Hence resonance energy

9S tot = 17.29 - 12.47 =+ 4.82 J/K
= 9H f (cal.) - 9H fo (theo) = 354 - 83
24. 0.40 = aT13 + bT1 = 271 kJ mole -1

& 0.40 = a× (1000) + b×10 25
29. C8 H18 (,) + 2 O 2 (g) $ 8CO 2 (g) + 9H 2 O (,)

& 0.4 = 1000a + 10b ...(1)
25 16 - 25 9
0.92 = aT 23 + bT2 9n g = 8 - 2 = 2 =- 2 =- 4.5

& 0.92 = a×8000 + 20b ...(2) 9H - 9U = 9n g RT =-
4.5×8.314×298
1000
from Eqs. (1) and (2)
=- 11.15 kJ
a = 2×10 -5, b = 0.038
30. CH 2 = CH 2 + H 2 " CH3 - CH3 9H = x1
20
aT + bT
3 a [T 23 - T13] 020 So, Hydrogenation energy of benzene should be 3x1
S m = # T $ dT = 3 + b [T2 - T1] 020
0
DH calculated = 3x1
= 0.813 J/K - mol So, Resonance energy = [3x1 - x2]
25. 9G o
200 = 9H o
200 - T9S o
200
31. Au(OH)3+4HCl→HAuCl4+3H2O, DH= -28 kcal

9H o
200 = 20 -= 16 kJ/mol HAuBr4+3H2O→Au(OH3+4HBr, DH= +36.8 kcal
-------------------------------------

9H oT = 9H oT + 9C P [T2 - T1]
2 1
HAuBr4+4HCl→HAuCl4+3H2O, DH= +8.8 kcal

20×200
9H o400 = 9H o200 + 1000 kJ/mol When 100% conversion, heat absorbed = 8.8 Kcal
0.44
16
= + 4 = 20 kJ/mol . % converstion = 8.8 ×100 = 5%
Chemistry
32. Let mixture contain x mole of steam & y mole 38. System surroundings are aways separated by a
oxygen then, since temperature is constant. boundary. This boundary is real in case of closed
So, amount of heat released = amount of heat gain systems and imaginary in case of open systems. A
x 220 1.66 perfectly isolated system is impossible to create.
x×132 = y (220) ⇒ y = 132 = 1 During a reversible process system and surrounding
⇒ x : y = 1:0.6 are always in equilibrium. Hence, it is called quasi
static.
39. PV = constant for isothermal process
33.

PVg = constant for adiabatic process so more value
of g, more decrease in pressure as volume increases.
40. For sublimation, q > 0 and process is always

DH = 4eXe-F + DHIoni[Xe → Xe+] - eF-F - DHeg [F→F-] endothermic ⇒ DH > 0. Also, for sublimation DS>0
4×34
= + 279 - 85 - 38 = 136 + 279 - 123 as solid → gas. Thus TDS > 0.
415
= - 213 = 292 kcal/mole.
Now, DG = DH - TDS and for spontaneity DG < 0.
34. FeO + Fe 2 O3 Also, DH = DH + Dng RT → DG = Du + DngRT-TDS
2x x
\ For DG < 0, Du > 0 at low T and at hight T it is
1 possible to have DG < 0 even if Du < 0.
Fe + 2 O 2 $ FeO 9H fo =- 65 Kcal/mole
41. DT = 0, DE = 0, DH = 0
3
2Fe + 2 O 2 $ Fe 2 O3 9H 0f =- 197 Kcal/mole
42. During ice(s) → water (l) or vapourization of
1 comphour, it is easy to understand that entropy of
2FeO + 2 O 2 $ Fe 2 O3
the system increases as Ssolid < Sliquid < Sgas. However
9H =- 197 + 65×2 & 9H =- 67 Kcal/mole in case of rusting of iron: 4Fe + 3O2 → 2Fe2O3 the
1
2FeO + 2 O 2 $ Fe 2 O3 entropy of the universe is increasing dispite the
2 1 decrease in the entropy of the system.
3 3 43. For isothermal expansion, T is constant so:
2 1
3 - 2x 3 +x DH = 0, DU = 0, DG = -T.DS, Tfinal = TInitial
2
- 2x 1 44. Liquid → solid is generally an exothermic process
1
31 = 2 ⇒ x= 5 and also SLiquid > SSolid.
3 +x 45. q = 0 for reversible adiabatic ⇒ DSsys = 0 ⇒
1
So, energy released = 5 ×67 = 13.4 kcal/mole Isoentropic. For irreversible adiabatic : DSsurr = 0
35. The heat evolved in the second case is half of the \ DStot = DSsys > 0
heat evolved in the first case. However, since the For free expansion also, DSsurr = 0 and DSsys > 0
mass of solution in the second case is also half, For isothermal compression qsys < 0
therefore the increase in temperature is the same. \ qsurr > 0 ⇒ DSsurr > 0

36. 46. Molar entropy depends upon the degrees of freedom

1 Wrev | > | Wirrev | but as the process is expansion so
W is negative.
Hence Wirrev > Wrev. Also as q = - W ⇒ qrev > qirrev.
37. In adiabatic expansion, q = 0. So DU = W = - Pext DV
Irreversible adiabatic So PVg constant not valid.
Since q = 0, so gas does work by utilizing its internal
energy.
So, T decreases and also enthalpy (H) decreases.
of a gas
As atomicity increases Cv, Cp increases ⇒ S
increases
For ideal gases there are no forces of interaction
between molecules.
47. Boiling of a liquid at normal boiling point is a
equilibrium process and on decreasing the pressure
equilibrium will go forward and DG will be negative
and vice versa.
48. At constant pressure heat of reaction = DH and at
constant volume heat of reaction = Du.
since both Du, DH are state functions therefore value
of heat of reaction is independent of method or steps
followed : Hess’ Law.
 Thermodynamics
49. Combustion reaction are exothermic, hydrogenation 60. a) Linear compound will have more entropy than
of alkenes are exothermic and graphite is cyclic compound.
thermodynamically more stable. b) S is same for both
50. Heat of formation is DH of that reaction in which 1 c) S at 300 K < S at 300oC (573 K)
mole of the substance is formed from its constituent d) More H bonding in CH3OH than C2H5OH
elements in their standard elemental states.
61. OH = (n1 C p,m + n 2 C p,m ) OT
51. (a) Correct : BE > 0
1 2

= b0.5 # 2 R + 0.5 # 4R l (- 100) =- 375 R and

7
(b) Correct : Dn > 0 ⇒ DS > 0
(c) Incorrect : It depends on T OU = b0.5 # 2 R + 0.5 # 3R l (- 100) =- 275R.
5

(d) Incorrect : DH = DE + RT > DE
62. From graph, slope = -1
52. DHo.reaction = DHof only for formation reactions. i.e.
\ eq & log10 V + log10 T = constant
are mole of the product should be formed from its
constituent elements and these constituent elements \ VT = constant or PV2 = constant
should be in their standard elemental states.
R
a C = CV + 1 - n
53. Since, DHof (C2H6(g)) = 218 ⇒ DHH-H = 436 5R R 3R
\ C = 2 +1-2 = 2
2C + 3H2 → C2H6
3R
Also DHof (C2H6(g)) = 2 × 718 + 3 × 436 - a - 6b \ q = nCDT = 3 × 2 × (1000 - 100) = 4050 R

(9H C - C = a, 9H C - H = b) 5R
DU = nCVDT = 3 × 2 × (1000 - 100) = 6750 R
a + 6b = 2829

\ W = DU - q = 6750 R - 4050 R = 2700 R
3C + 4H2 → C2H8

DHof (C2H6(g)) = 3 × 718 + 4 × 436 - 2a - 8b 63. DH = 4 KJ
2a + 8b = 4002 DH = DU + D (PV)
DU = 4 - P (V2 - V1)
a = 345 & b = 414 kJ.
105 (18 - 19) # 10 -6
54. Formation reaction of CH4 can be obtained by: 4 = -
103
R1 + 2R2 - R3 ⇒ DHof (CH4) = DHo1 + 2 DHo2 - DHo3 = 4 + 1 × 10-4
= - 394 - 568 + 892 = - 70 kJ = 4.0001 KJ
= - 16.607 kcal. 64. V-T curve for a given mass of the gas is given
55. Refer Q. 50.
PV = nRT; V = b P l T
nR

56. Strong acid with strong base heat of neutralization is
57.32 kJ (b 13.7 kcal) .
57. I – Work done by the system in case of infinite stage
expansion is more than single stage expansion.
III – Single stage process is a irreversible process.

IV – We have 5 points on PV diagram.
a V3 = V1 ⇒ P3 > P1 as T3 > T1
58. All are examples of non PV work. 65. NO, NO2, N2O4 have positive heats of formation
a) electrical work b) Mechanical work
Also, DHof (F2O) = 24.5 kJ/mol.
c) Gravitational work d) Magnetic work

Combustion reactions are always exothermic
59. 1 × Vf = 5 × R × 546 = 224 L
66. a, b, :- Factual
W = - Pext (DV) = - 1atm (224 L) = - 224 L atm
c :- Dissolution of ionic salt is an example where

\ work done by system = 224 L atm DS > 0 although Dng = O
Enthalpy change (DH) = q = 273 × 5 V
d :- For isothermal process DS = nRln V2 &
= 1365 L atm V2 P1 1
=
DU = q + W = 135 - 224 = 1141 L atm V 1P 2
Chemistry
67. (a) Incorrect : For an isothermal change, DE = 0
(b) Correct : Precise and accurate measurement of
state function is impractical.
(c) Correct : E is a state function. In cyclic process,
initial and final states are the same, hence DE=0.
(d) Incorrect : E is a state function.
68. DS = nCV ln b Tf l + nR ln b Vfi l
T V
i
373
= 5 ln 298 + 2 ln 10
DH = nCP DT = n (CV + R) DT = 1 × 7 × 75 = 525 cal
69. Electrical work is done in b and d.
79. 9H Nutralization = 9H Ionization - (H + OH - $ H 2 O)
=- 49.86 - (- 55.84) kJ/mole
5.98
= kJ/mole
80. 9H o = 2 # (- 55.84) kJ/mole =- 111.68 kJ
81. For max. rise in temp.; max. neutralization of H+ and
OH­­- required.
If we take equal volume, all H+ (5 m-mole) will
react with all OH­­- (5 m-mole).
82. Work done in isothermal process will be more than
PV2 = const, process whatever be the value of K1
and K2 as is shown in the diagram.

70. a) Dng > 0, so DV > 0 ⇒ W is negative

b) Dng = 0 ⇒ DV = 0 ⇒ w = 0
c) Redox reaction ⇒ non-PV work as there is flow
of change, electrical work
d) Dissolution of salt ⇒ Wnon PV ! 0
83. Clearly (Vf)Isothermal > (Vf)adiabatic
71. For ACB Du = q + w = 80 - 30 = 50
So for ADB, Du = 50 J as Du is state function

\ 50 = q - 10 ⇒ q = 60 J
72. For B to A

Du = - 50 J as DuB→A = - DuA→B
w = + 20 J 84. Work done “by” the gas in isothermal process
q = - 50 - 20 = - 70 J is more than in adiabatic process as shown in the

\ 70 J heat is liberated. diagram above.

73. In ADB process, DB process is isochoric so WDB = 0 85. For isothermal irreversible process (T = constant)
So, DUAD = qAD + WAD Po
P o V o = P ' 2V o & P = 2

- 40 = qAD + (-10); qAD = - 30 J For P2V = constant
Now, qAB = qAD + qDB; 60 = -30 + qDB P o2 V o = P 2 2V o & P =
Po
qDB = 90 J 2
Final pressure of isothermal process > Final
74. DG = DH - T D S pressure of adiabatic process and Final pressure of

T D S dominates DH at high temperature, thus DG<0. irreversible adiabatic process > Final pressure of
Hence, CaCO3 decomposes at high temperature. reversible adiabatic process.
So, final pressure order II > I > IV > III.
75. DG = DH - T D S = 2.1 × 103 - 20 × 298 < 0.
86. DHr = fC / C + f H - H - ( fC = C + 2 fC - H )
76. For reaction to be spontaneous
or DHr = 812 + 435 - (615 + 2 × 416)

DG < O ⇒ DH - T D S < 0
\ DHr = 200 kJ/mol.
100 # 103

⇒ T> & T > 2000 K. 87. Let moles of C2H8 = x, moles of X2H2 = y & moles
.05 # 103
of CO2 = z.
77. Clearly at 400 K, reaction is in equilibrium
9H 40000 Calculation of 9H fo of C3 H8 (g)
& 9G = 0 & 9S = T =- 400 =- 100 cal K -1 3C (s) + 4H 2 (g) $ C3 H8 (g)
78. Use 9G = 9H - T9S 9H fo of C3 H8 (g)
300 # (- 7.2) =[3(718) + 4(435)] – [2(347) + 8 (416)]
9G =- 15 - 1000 =- 12.84 Kcal mol -1
=3894 - 4022 = -128 kJ / mol.

Calculations of 9H fo of C2H2(g)
2C (s) + H 2 (g) $ C 2 H 2 (g)
9H fo C 2 H 2 (g) = [2(718) + (435)] – [(812) + 2(416)]
= (1436 + 435) – [1644]
= 227 kJ/mol.
Calculations of 9H fo of C2H4(g)
2C (s) + 2H 2 (g) $ C 2 H 4 (g)
9H fo of C2H4(g) = 2 (718) + 2 (435)–[615 + 4(416)]
= 2306 – 2279 = 27 kJ/mol.
Calculations of 9H Comb o
of C2H4(g)
C3 H8 (g) + O 2 (g) $ 3CO 2 (g) + 4H 2 O (,)
9H Comb o
of C3H8(g)
[3
= 9H f (CO 2) + 49H f (H 2 O, ,)] - 9H f (C3 H8, (g)
o o o
= [3 (–394) + 4 (–286)] – (–128)
= –2198 kJ/mol.
Calculations of 9H Comb o
of C2H2(g)
C 2 H 2 (g) + 2.5O 2 (g) $ 2CO 2 (g) + H 2 O (,)
9H Comb
o
of C2H2
[2
= 9H f (CO 2) + 9H f (H 2 O, ,)] - 9H f (C 2 H 2)
o o o
= [2 (–394) + (–286)] – 227
= –1301 kJ/mol.
\ DHcomb (C3H8) + DHcomb (C2H2)
= -2198 + (-1301) = -3499 kJ/mol
88.Now total heat released during combustion
2198 x + 1301 y = 4800 ...(i)
Iron volume of CO2 : 3x + 2y = z = 10 ...(ii)
Total moles of H 2 O (,) formed = 4x + y.
3808
Moles of C2H4(g) to be prepared 22.4 = 170 .
Total heat absorbed during evaporation of water
formation of 170 moles C2H4 = 4800.
[(4x + y) × 0.875 x 40] + (170 x 27) = 4800
4x + y = 6 ...(iii)
on solvent (i), (ii) and (iii)
we get x = 1, y = 2, and z = 3.
89. (a) Reversible isothermal expansion of ideal gas
V
w = -2.303 nRT log V2 and DU=DH=0 (asDT=0)
1
Thermodynamics
(b) Reversible adiabatic compression of an ideal gas
PV c = constant and w =
nR (T2 - T1)
c-1
P2 V2 - P1 V1
= c-1
(c) Irreversible adiabatic expansion of an ideal gas
nR (T2 - T1)
w = c-1
(d) Irreversible isothermal compression of an ideal
gas 9H =- (as 9T = 0)
90. (a) A process carried out infinitesimally slowly is
called reversible process
(b) A process in which no heat enters or leaves the
system is called adiabatic process
(c) A process carried out at constant temperature is
called isothermal process
(d) In a cyclic process, state function have no change
in their value.So, 9U = 0, 9H = 0 .
91. (a) 9Gsys = 0 & equilibrium and free energy is zero.
So, no useful work.
(b) 9S universe > 0 & Spontaneous process and able to
do useful work.
(c) 9S universe < 0 & Nonspontaneous process and
unable to do useful work.
(d) 9Gsys > 0 & Nonspontaneous process and
unable to do useful work.
92. (a) For reversible process 9S universe = 0 and for
adiabatic process 9Ssystem = 0
(b) For reversible process 9S universe = 0 , and in
vaporisation entropy of system increases
(c) Number of gaseous moles decreases. So, entropy
of system decreases and N2 is more stable. So,
process is spontaneous. For spontaneous process
9S universe > 0
(d) Number of gaseous moles increases. So, entropy
of system increases.
93. (a) This is combustion reaction as well as formation
reaction of CO2.
(b) This is sublimation, atomization as well as
formation reaction of C(g).
(c) This is combustion reaction of CO (g).
(d) This is atomization of CH4(g).
Chemistry

1. DG = DH - TDS = 0 at equilibrium 7. H 2 O]s g DS1

H 2 O] l g DS 2
H 2 O] l g

⇒ -165 × 10 - T × (-550) = 0 ⇒ T = 300K
3 273k 273k 373k

The answer is 300K. DS3

H 2 O ^g h DS 4
H 2 O ^g h
2. 3HC / CH (g) $ C 6 H 6 ] , g; TG o =- RT ln K 373k 383k
334

J
TG f - 2.04 # 10 mol - 1.24 # 10 J/mol
o 5 5 S
3 1 = 273

& TG = / ]TG f gP - / ]TG f gR

373
S
3 2 = 1× 4.2 × ln 273
o o o

2491

⇒ -RT ln K = 1 × (-1.24 × 105 ) - (-3 × 2.04 × 105) S
3 3 = 373

⇒ -2.303 × R × T log K = 4.88 × 105 S
383
3 4 = 1× 2 × ln 373
5
4.88×10 488000

& log K = - 2.303×R×T =- 5705.848 =- 85.52
\ DStot = DS1 + DS2 + DS3 + DS4

⇒ - log K = - 855 × 10-1
⇒ DStot = 9.26 kJ kg-1K-1­.

⇒ x = 855
8. DG = DH – TDS
J
3. T = 298 K, R = 8.314 mol K For a spontaneous reaction,
→ Chemical reaction is DG = –ve thus, DH < TDS
Fe + 2HCl → FeCl2 + H2(g) DH 200
< T , 40 < T
50g P = 1 bar DS
50 Thus, T should be greater than 5 K.
moles of Fe = 55.85 = moles of H2
9. C6 H6 ] l g + 2 O 2 ^g h 6CO 2 ^g h + 3H 2 O ] l g
15
→ Work done for a mol gas
= -Pext × DV = -Pext × (V2 - 0) n 3 g =- 3
2
RT
= - 1× n H 1 2 H 3 0C = Heat of combustion at const. press
50 E
3 0C = Heat of combustion at const. vol.
= -8.314 × 298 × 55.85 J
H
3 0C = 3 E0C + 3 n g RT
= - 2218.059 J H
3 0C =- 3263.9 KJ/mol. - 3/2 # 8.314 # 298

- - 2218 J
=- 3267.6 KJ/mol .
4. ΔH = ΔU + ΔngRT 10. From 1st law:
= 2.1 × 10 + 2(2) (300)
3 DU = q + w
= 2100 + 1200 For adiabatic process:
q = 0
= 3300 cal
\ DU = w
ΔG = ΔH – TΔS = 3300 – (300) (20) = 3300 – 6000 \ Work in adiabatic process is at the expense of
= –2700 cals = –2.7 kcal change in internal energy of the system.
5. DH = SDHC(Reactant) - SDHC(Product) 11. C (s) + O 2 (g) " CO 2 (g); 9H =- 393.5 kJ/mol.

\ DH = 3 × (-1300) - [-3268]
1
CO (g) + 2 O 2 (g) " CO 2 (g); 9H =- 283.5 kJ/mol.
DH = -632 kJ mol-1
1
6. Br () Hatomisation = x kJ/mole C(s) + 2 O2(g)→CO(g);DH =-393.5+283.5 kJ/mol
2 2Br(g)
= -110 kJ/mol.
le
Hvap. kJ/mo
y =y
de nerg
Br2(g) Bon
ΔHatomisation = ΔHvap + Bond energy. Hence x > y
 Thermodynamics
12. CH 4 (g) $ C (g) + 4H (g) 16. The process is isothermal expansion Hence,
4×
& fC - H = 360 KJ/Mol. \ q = -w as Du = 0
q = + 208 J
& fC - H = 90 KJ/Mol.
and C 2 H6 (g) $ 2C (g) + 6H (g) \ w = - 208 J (expansion work)

& fC - C + 6×90 = 620 17. 9G o = 9H o - T9S o

& fC - C = 80 kJ/mol - RTlnK = 9H o - T9S o
9H o - T9S o
hc lnK =-
N
& A× = 80×1000 J RT
m
18. C 2 H5 OH (,) + 3O 2 (g) $ 2CO 2 (g) + 3H 2 O (,)
6.02×10 23 ×6.62×10 -34 ×3×108

m= 80000 9n g = 2 - 3 =- 1
14.9×10
= -7
m = 1.49×10 -6 m = 1.49×103 nm . 9U = 9H - 9n g RT
8.314
13. 29G f(NO
o
) - [29G f(NO) 9G f(O )] = 9G r =- RT,n K p
o o o
=- 1366.5 - (- 1) × ×300
2 2
103

29G o
f(NO 2) - [2×86, 600 + 0] =- RT,n K p =- 1366.5 + 0.8314×3 =- 1364 KJ

9G o
= 0.5 [2×86, 600 - R (298) ,n (1.6×1012)] 3
f(NO 2)
19. N 2 (g) + 2 H 2 (g) $ NH3 (g);
14. C 2 H5 OH (,) + 3O 2 (g) $ 2CO 2 (g) + 3H 2 O (,) 9H fo =- 46.0 kJ mol -1

9U =- 1364.47 KJ/mol.
2H (g) $ H 2 (g); 9H fo =- 436 kJ mol -1

9H = 9U + 9n g RT

2N (g) $ N 2 (g); 9H fo =- 712 kJ mol -1

9n g =- 1 1 3

NH3 (g) $ 2 N 2 (g) + 2 H 2 (g);
9H =- 1364.47 + :
- 1×8.314×298 D
1000
9H =+ 46

=- 1364.47 - 2.4776 =- 1366.94 KJ/mol. 3 3
2 H 2 $ 3H ; 9H =+ 436× 2
15. 4NO2(g) + O2(g) → 2N2O5(g), DH = -111 kg
1 1
. -54 × 2 2 N 2 $ N; 9H =+ 712× 2
2N2O5(s)
NH3 (g) $ N (g) + 3H (g); 9H =+ 1056 kJ mol -1
\ DH1 = -111 - 54 × 2 1056
- 219 kJ
Average bond enthalpy of N - H = 3

=+ 352 kJ mol -1

1. C6H6(l) + 7.5O2(g) → 6CO2(g) + 3H2O (l) qsurr

(
` 9S) system > 0, also (9S) surrounding = T

Dng = -1.5
surr

Heat gained by system = heat lost by surroundings
Given, DU = -3263.9 kJ/mol q
` surr. < 0 ` (9S) surr < 0
\ DH = DU + Dng RT
4. C6 H12 O6 (s) + 6O 2 (g) $ 6CO 2 (g) + 6H 2 O (,)
⇒ DH = -3263.9 -

1.5×8.314×298 9C H = 6×9f H (CO 2) + 69f H (H 2 O)
1000
\ DH = -3267.61 kJ/mol
- 9f H (C6 H12 O6) - 69f (O 2, g)
6×= (- 400 - 300) - (- 1300) - 0
2. As DG = useful work =- 4200 + 1300
\ DG = -PDV ⇒ P = -33GV =- 2900 KJ/mol
From given data, DG = 2.9 kJ and DV = -2 x 10-6 m­3 For one gram of glucose, enthalpy of combustion
3 2900
\ P = 2.9 ×10-6 = 1.45×109Pa=×1.45×104 bar =- 180 =- 16.11 KJ/g.
2 ×10

\ P = 14500 bar 5.
3. For H 2 O (,) " H 2 O (g) at T = 100 o C, 1 atm
equilibrium exists. ` 9G = 0, 9H - T9S = 0
9H = T9S > 0 for system, since evaporation is
endothermic
\ 9H =+ 140 + 330 - (350×2) - EC / C =+ 225

\ EC / C = 1740 - 700 - 225 =+ 815 KJ/mol.
Chemistry
6. I → II → reversible, isothermal expansion, 8. Standard enthalpy of formation of a compound is
T → constant, DV → +ve, DS → +ve DH ⇒ 0 the standard enthalpy when one mole of a compound
is formed from the elements in their stable state of
II → III → Reversible, adiabatic expansion
aggregation.
Q = 0, DV → +ve, DS → 0
9. (c) Internal energy is a state function and if T1 ! T2
I then Du ! 0. Hence c is incorrect.
10. Since the vessel is thermally insulated so
p II
(a) q = 0
pext = 0, so w = 0
III
so DU = 0 (ideal gas)
V Hence DT = 0
-ve slope for isothermal < adiabatic
& 9T = 0
I → II → Isothermal T
& 2 = T1
II → III → Adiabatic P
& 2 V2 = P1 V1
The process is however adiabatic irreversible.
So we cannot apply P2 V 2c = P1 V1c
Hence ans is (A), (B), (C)
(b)
11. DSsys is a state function but

w is a path function.

I → II → T constant, P↓ ⇒ V↑
II → III → adiabatic expansion as P↓

(A) 9S x " z = 9S x - y + 9S y " z (Correct)

(B) Wx " y = Wx - y + Wy " z (Incorrect)

(c) (C) Wx " y " z = Wx - y (Correct)

Because y → z is an iso choric process
(D) 9S x " y " z = 9S x - y (Incorrect)

12.
I → II → DS → +ve, DH = 0
II → III → DS → 0, DH → -ve

I II
T
(d)

III

S
I → II → DS → +ve, DT = 0
(A) T1 = T2 (due to isothermal)
II → III → DS → 0 (B) T3 > T1 (incorrect) cooling will take place in
7. For 1 mole Vanderwaal’s gas adiabatic expansion)

RT
P = V-b - 2
a (C) WIsothermal > Wadiabatic {with sign, this is incorrect}
V
(D) 9U Isothermal = 0 > 9U adiabatic =- ve
If Pext = P, means process is reversible. For Vanderwaal
gas, expression is correct for all reversible process. So, answer is (A,D).
 Thermodynamics
13. Let the heat capacity of insulated beaker be C. 17. Qrxn = CDT
Mass of aqueous content in expt. 1 = 200 g |DU| × 2 = 20 × 14.8
⇒ Total heat capacity = (C + 200×4.2) J/K |DU| = 148 kJ/mol
Moles of acid, base neutralized in expt. 1 = 0.1 DU = -148 kJ/mol

⇒ Heat released in expt. 1 = 0.1×57 = 5.7 KJ 1
Hg(g) + 2 O2(g) → HgO(s): DU = -148 kJ/mol
5.7×1000
& = (C + 200×4.2)×9T.
DH = DU + Dng RT
5.7×1000 = (C + 200 + 4.2) ×5.7
3 8.3
& (C + 200×4.2) = 1000 = -148 - 2 # 1000 × 298 = -151.7101
In second experiment, nCH COOH = 0.2, n NaOH = 0.1 1
3

Hg(l) + 2 O2(g) → HgO(s)
Total mass of aqueous content = 200 g
DH = -151.7101 + 61.32 = -90.39 kJ/mol

⇒ Total heat capacity = (C + 200×4.2) = 1000
⇒ Heat released = 1000×5.6 = 5600 J. Ans. 90.39
Overall, only 0.1 mol of CH3 COOH undergo 18. Process I is adiabatic reversible
neutralization.
Process II is reversible isothermal process
- 5600
& 9H neutralization of CH3 COOH = 0.1 Process I - (Adiabatic Reversible)
=- 56000 J/mol =- 56 KJ/mol. TU
& 9H Ionization of CH3 COOH = 57 - 56 = 1 KJ/mol R = 450 - 2250
DU = -1800R
14. Final solution contain 0.1 mole of CH3 COOH and
CH3 COONa each. WI = DU = -1800R
[CH3 COO ] - Process II - (Reversible Isothermal Process)


pH = pK a + log [CH COOH]
3 T1 = 900 K
0.1
5 = - log 2 + log 0.1 = 4.7 Calculation of T2 after reversible adiabatic process
15. X(s) Y(s) + Z(g) –1800R = nCv(T2 – T1)
d <ln d K nF
pz
5
pz 1 p - TH o –1800R = 1 × 2 R(T2 – 900)
Given K = K vs T is =
db l T2 = 180 K
p 1 R
T v3
WII = -nRT2 ln v = WI
- TH o
From the graph, we have R =- 2×10 4
2
v3
⇒ -1 × R × 180 ln v = -1800R
⇒ DHo = 2 × 104 × 8.314 J v3
2

ln v = 10

DHo = 166.28 kJ mol-1 2

19. SnO2(S) + C(S) → Sn(S) + CO2(g)

16. -RT ln K = DGo = DHo - TDSo
DH°rxn = [–394] – [–581] = 187 kJ/mole
TH o TS o
ln K = - RT + R DS°rxn = [52 + 210] – [56 + 6]
TS o = 200 J/k–mole
R = 17 3 H o 187 ×1000
T= = = 935 K
DSo = 17 R 3 So 200
5B?
= 141.338 J K-1 20. K eq. = 5 ?
A
10 100
K1000 = 1 = 10 and K 2000 = 1 = 100
0
3 G1000 ^- RT,nkeq h1000 1000 # ,n10
Now,
3 G 2000 ^- RT,nkeq h2000 2000 # ,n100
0 = =

= 0.25
Chemistry
1
21. (i) 2Cu(s)+ 2 O2(g)—→Cu2O(s):ΔGº=–78000J/mol 23. (A) H 2 O (,) $ H 2 O (s) at 273 K & 1 atm
1 9H =- ve = q
(ii) H2(g)+ 2 O2(g)—→H2O(g), ΔGº=–178000J/mol
9Ssys < 0, 9G = 0.
(i) – (ii) then

w ! 0 (as water expands on freezing), 9U ! 0
2Cu(s) + H2O (g) —→ Cu2O(s) + H2(g)
(B) Free expansion of ideal gas. q=0
ΔGº = –78000 + 178000 = 100000 J/mol
w=0
Now for the above reaction
9U = 0
ΔG = ΔGº + RTln c P H m
P

2

H O 2
9Ssys > 0
To prevent the above reaction : 9G < 0
ΔG ≥ 0 (C) Mixing of equal volume of ideal gases at constant
ΔGº + RTln c P H m > 0
P 2 pressure & temp in an isolated container
H O 2
q = 0, w = 0, 9U = 0 , 9Ssys > 0, 9G < 0
10 4 ^,nPH - ,nPH Oh > - 105
2 2

(D) H 2 (g) 300K

Reversible

,nPH > - 10 + ,nPH O
2 2
Heating, 1 atm

Re versible
> - 10 + 2.3 log (0.01) 600 K Cooling, 1 atm
300 K.

,nPH > - 10 + 4.6
2
q = 0, w = 0, 9U = 0 , 9G = 0, 9Ssys = 0

,nPH > - 14.6
24. (A) CO 2 (s) $ CO 2 (g)
2

\ Minimum ,nPH =- 14.6

It is phase transition. The process is endothermic
2

22. Process shown by solid line is reversible isothermal (sublimation). Gas is produced, so entropy increases.

So, work Ws =- 4×0.5 ln (5.5/0.5) (B) On heating CaCO3 decomposes. So, process is

=- 2 ln 11 L atm. endothermic. The entropy increases as gaseous
product is formed.

For dotted process (3 step irreversible) work done is
2 (C) 2H : $ H 2 (g)

Wd =- {4×1.5 + 1×1 + 3 ×2.5} L atm.
Entropy decreases as number of gaseous

5 26
=- {6 + 1 + 3 }L atm. =- 3 L atm. particles decreases.
(D) It is phase transition.
W 26

so, Wd = 3×2 ln 11 . 2. White and red P are allotopes.
s

Red P is more stable than white. So 9H is – ve.

 Chemical Equilibrium

Chapter 8 Chemical Equilibrium

INTEXT EXERCISE: 1
1. Reversible reaction always attains equilibrium which
proceeds both sides and never go for completion.
2. In a reversible reaction some amount of the reactants
remains unconverted into products.
3. In lime klin escaping regularly so reaction proceeds
in forward direction.
4. Reactions resulting in precipitation are not reversible
5. When rate of forward reaction is equal to the rate of
backward reaction then equilibrium is supposed to
be established.
INTEXT EXERCISE: 2
64 gm
1. [HI] = 128gm/mole # 2 litre = 0.25 M
⇒ activity = 0.25
6. Equilibrium can be achieved only in closed vessel.
7. When Rf = Rb then the reaction is said to be in
chemical equilibrium.
8. When rate of forward reaction is equal to rate of
backward reaction the reaction is said to be in
equilibrium.
9. At equilibrium rate of forward reaction is equal to
the rate of backward reaction.
10. At equilibrium, the rate of forward & backward
reaction become equal.
6. H2 + I2 2HI; [HI]e = 0.80, [H2]e = 0.10, [I2]e= 0.10
[HI] e2 0.80 # 0.80
K c = [H ] [I ] = 0.10 # 0.10 = 64 .
2 e 2 e

2. As we increase the concentration of substance, then 7. A + 2B ? C + 3D

speed of the reaction increases. [PC] [PD] 3 0.30 # 0.50 # 0.50 # 0.50
KP = = 0.20 # 0.10 # 0.10
3. Chemical reaction quantitatively depend on the [PA] [PB] 2
reactant and product molecule. = 18.75
4. Equilibrium constant for the reaction: 8. For A + B C+D
[C] [C] [D] 0.4 # 1

3A + 2B C is K = . K C = [A] [B] = 0.5 # 0.8 = 1 .
[A] 3 [B] 2
k
9. K c = k f
5. A + B C +D b
kf = K c # k b = 1.5 # 7.5 # 10 -4 = 1.125 # 10 -3

Initial conc. 4 4 0 0
10. A + B C + D

After T time conc.(4-2) (4-2) 2 2 a a 0 0
[C] [D] 2 # 2 a-x a-x 2(a-x) 2(a-x)

Equilibrium constant = [A] [B] = 2 # 2 = 1
[C] [D] 2 ]a - xg × 2 ]a - xg
K c = [A] [B] = ]
a - xg × ]a - xg
= 4.

INTEXT EXERCISE: 3
1. Kp = Kc only if Dng = 0 5. For reaction 2SO3 ? O 2 + 2SO 2
2. K p = K c (RT) 9n
= 26 (0.0821 # 523) -1
= 0.61 .
9n is + ve so Kp is more than Kc.

9n g = 1 - 2 =- 1
By K p = K c (RT) 9n
3. K p = K c (RT) 9n ; When Dng< 0 i.e. negative, Kp< Kc 6. 9n = 2 - 1 = 1
4. Kp = Kc if Dng = 0 K p = K c (RT)
7. K p = K c (RT) 9n

9n = 3 - 2 = 1; K p > K c .
Chemistry
8. [C]eq = 0.5 M and V = 2 L ⇒ neqc= 1 6NH 3@2
9. Kc = & 6NH3@

A + 2B 2C 6N 2@6H 2@3

initial 2 3 2 = K C 6N 2@6H 2@3 & 6NH3@ = 0.358 M

eq lb. 2.5 4 1
]0.5g 5HI?2 ]28g2
2
10. K C = 6 @6 @ = 8 × 3 = 32.66
]2g2 ]1.25g

\ Kc = = 0.05 H2 I2

INTEXT EXERCISE: 4
2
[NO 2] [NO] [O 2] [NO] 2 [O 2] [NO 2]
1. K1 = 1/2 ;K 2 =
K # K' = #
[NO] [O 2] [NO 2] 2 [NO 2] 2
[NO] [O 2] 1/2
2 1/2
[NO 2] 1 [NO 2] 1 [NO] [O 2] 1
& = & =
= [NO ] = '
[NO] 2 [O 2] K 2 [NO] [O 2] 1/2 K2 2 K
1 1 1
K & 1=
1
;K 2 = 2
1
K # K ' = ' ; K = '2 ; K ' = = 7.9 × 105
K2 K1 K K K
[SO 2] 2 [O 2]
8. log b K2 l = 2.303 ×1.897 : 280 - 300 D
[SO3] 1 1.15 ×10 4
2. K1 = 1/2 and K 2 = ; K2 = 2 K 1 1
[SO 2] [O 2] [SO3] 2 K1 1

3. Reaction is reversed. Hence log b K2 l = 0.5983 . 0.6 = log4

K

1
1
K= = 4.2 # 10 2 K2
(2.4 # 10 -3) \ K . 4 & K 2 . 4K1
1
4. K1 for H 2 + I 2 ? 2Hl is 50 9. For the reaction, CaCO3 (g) CaO(s) + CO2 (g)
K2 for 2Hl ? H 2 + I 2
K p = PCO and K c = [CO 2]
2

1 1
K 2 = K = 50 = 0.02
(a [CaCO3] = 1 and [CaO] = 1 for solids)
1

5. There is no change in equilibrium constant by 9H or

Now, log K p = log A - RT (2.303)
change of volume.

This is an equation of straight line. When log K is
1
6. K ' = K n; Hence n = 2 plotted against 1 /T. we get a straight line.
K ` ' = K1/2 = K
7. 2NO 2 ? 2NO + O 2 ...(i)
K = 1.6 # 10 -12
1
NO + 2 O 2 ? NO 2 ...(ii)
Reaction (ii) is half of reaction (i)
[NO] 2 [O 2]
K= ...(i)
The slope =- 9H or /2.303 R
[NO 2] 2
10. Since it is an exothermic reaction, so the value of K
[NO 2]

K' ...(ii) decreases on increasing temperature. Hence, more
[NO] [O 2] 1/2
product is formed at lower temperature.

On multiplying (i) and (ii)
INTEXT EXERCISE: 5
1. DH = + ve for the reaction ⇒ if T increases the K 5. DH is positive so it will shift toward the product
increases & K decreases if T decreases. side by increasing temperature, as the value of K
increases.
2. Kc does not depend upon volume of container.
6. DH is positive so reaction move forward by increase
3. Those reaction which have more value of K proceeds
in temperature as the value of K will increase.
upto close to completion.
7. PCl5 (g) ? PCl3 (g) + Cl 2 (g)
4. DH = - 92.3 kJ ⇒ exothermic reaction.

\ K increases on decreasing temperature. KP

a= KP + P

\ as P is increased, a decreases.
 Chemical Equilibrium
8. Kp is constant and does not change with pressure. 2 # 40 # 2 # 40
# 100 # 2 = 0.266 .
9. PCl5 ? PCl3 + Cl 2 K c = 100 22 # 60
2 0 0
100 # 2
2 # 60 2 # 40 2 # 40
100 100 100 10. N 2 O 4 ? 2NO 2
1 0

Volume of container = 2 litre. (1 - a) 2a

total mole at equilibrium = (1 - a) + 2a = 1 + a
INTEXT EXERCISE: 6
1. Reaction is exothermic and ngases is decreasing from 8. NH2COONH4(s) ) 2NH3(g) + CO2(g)
left to right so for higher production of SO3 there
At equilibrium, if partial pressure of CO2 = P, then
should be low temperature and high pressure. that of NH3 = 2P
2. Both Dn and DH are negative. Hence, low volume K p = P NH
2
# PCO = (2P) 2 # P = 4p3 = 2.9 ×10-5
3 2

and low temperature will forward reaction. or P3 = 0.725 # 10 -5 or

3. Dn = 0, No effect of pressure. P3 = 7.25 # 10 -6 or P = 1.935 # 10 -2 .
4. Contact process is exothermic. High concentration
Hence total pressure 3P = 5.81 # 10 -2 = 0.0581 atm
of reactants always gives better yield.
P
5. The reaction takes place with a reduction in number 9. PNH = PH S = 2 .
3 2

of moles and is endothermic. So high pressure and P P P2

high temperature will favour the reaction in forward
Hence K p = PNH = 2 # 2 = 4 3

direction
10. A very high value of K for the given equilibrium
6. H2X2 + heat 2HX. shows that dissociation of glucose to form HCHO is

Reaction is endothermic and ngases increasing in very very small. Hence at equilibrium, we can take
forward direction so according to Le chatelier’s [C6H12O6] = 1M
principle for formation of HX, Temperature of the [C6 H12 O6] 1
reaction should be high and pressure should be low.
K= i.e. 6 # 10 22 = or
[HCHO] 6 [HCHO] 6
7. In reaction CO + 3H2 CH4 + H2O
[HCHO] = c # 22 m = 3.4 # 10 -4 M.
1/6
1


ngas is decreasing in forward direction so on increasing 6 10
pressure the yield of product will increase.
INTEXT EXERCISE: 7
1. If 9G o = 0 4. Decreases the activation energy of both forward and

9G =- 2.303 RT log K p
o backward reaction.

log K p = 0
(a log 1 = 0) 5. As we know that, 9G o =- 2.303 RT log K p

K p = 1. Therefore, 9G o =- 2.303 # (8.314) # (298)

2. At equilibrium, DG = 0. (log 2.47 # 10 -29)

3. 9G o =- 2.303 # 8.314 # 10 -3 # 298 log K p

9G o = 16, 3000 Jmol -1 = 163 KJ mol -1

1.7 =- 2.303 # 8.314 # 10 -3 # 298 # log K p

K p = 0.5 .
Chemistry
EXERCISE - 1
1. Theoretical
Molar 2 (1 - x)/V (1 - x) / V 2x/V conc.
no. of moles of O (2x/V) 2 x2 V
2. Molar conc. = volume (in litre) 2
K= 3 =
; E ; E (1 x)
2 (1 - x) (1 - x)
2
- 3
96 1 V V
= 32 # 2 = 1.5 M
[Cu 2+] [Ag (s)] 2 [Cu 2+]
3. Cl2 is gaseous and escapes out. 13. K = = as [solid] = 1.
[Cu (s)] [Ag +] 2 [Ag +] 2
4. At eqm. 9G = 0 i.e. G (ice) = G (H2O) ! 0.
14. For 2A + B 3C + D
5. A + B C + D
Since moles of A, B taken are same and A gets
Initial 1 1 0 0 consumed at double the rate of B
At equili. (1-x) (1-x) x x

\ moles of A is always less than moles of B
[C] [D]
\ K c = [A] [B] = 9
\ [A] < [B]

\
x.x
=9 15. K depends upon units of concentrations when
(1 - x) 2 np ! nr
or x2 = 9 + 9x2 - 18 x
PN # P H3 (atm) 4
or 8x - 18x + 9 = 0
2 16. K p = 2
2 = = atm 2
2

P NH (atm) 2
3

3 3
\ x = 2 or 4 56 6
17. 56 g N2 = 28 = 2 moles, 6 g H2 = 2 = 3 moles,
Hence, among the given options, the options (3) i.e., 27.54
0.75 is correct. 27.54 g NH3 = 17 = 1.62 moles

6. N2 + O2 ? 2NO N2 + 3H2 ? 2NH3

Initial 2 moles 4 moles
Initial moles 2 3
1 1 1
At. eqm. 2 - 0.81 3 - 2.43 1.62

At Eq. 2- 2 4- 2 2 # 2 = 1 mol
= 1.19 = 0.57

Molar concentration of NO at equilibrium
2
1 (1.62)
= 2.5 = 0.4.
Kc = = 11.9 . 10
(1.19) (0.57) 3
b 0.2 l # b 0.8 l
2
18. 2 SO3 2SO2 + O2
2 2 0.2 2 # 0.8
7. K c = 1 =
Initial 1 mole 0 0
12
2
At eqm. 1 - 0.6 = 0.4 0.6 0.3
0.04 # 0.04 = 0.016.
8. Units of K P = ]atmg3 n
2
(0.6) (0.3)
g

K= = 0.675
(0.4) 4
9. A 2 (g) + 2B 2 (g) ? 2C 2 (g) 19. A + 2B 2C + D

PA = 0.80 atm,
2 PB = 0.4 atm.
2

Initial moles 1.1 2.2
Total pressure of the system = 2.8 atm.
Moles at eqm. 1.0 2.0 0.2 0.1
P
` C = 2.8 - 0.8 - 0.4 = 1.6
2 2
(0.2/V) (0.1/V)
P C2 (1.6) 2
K= = 0.001

Kp = 3 =
2
= 20 (1/V) (2/V) 2
PA # P B 0.8 # (0.4) 2
20. A + 2B C
2 2

10. Rate = k [A] [B]. 2

Initial moles 1 0.5
11. Basic form of KC
Moles at eqm. 0.9 0.3 0.1
12. 2SO2 + O2 2SO3
Molar concs. 0.3 0.1 0.1/3

Initial 2 moles 1 mole 0
K=
0.1/3
= 11.11
0.3 # (0.1) 2

At eqm. (2 - 2x) (1 - x) 2x

= 2 (1 - x)
 Chemical Equilibrium
[CO 2] [CO 2] [C] 3
(3/3) 3
21. K c = [CO] i.e. 5 = 36. Q = = = 6.75 \ Q < KC
2.5 # 10 -2 [A] 2 [B] (2/3) 2 (1/3)
or [CO2] = 12.5 × 10-2 mol L-1 The reaction will proceed in forward direction to
attain equilibrium.
22. K p = K c (RT) 9n or K c = K p (RT) - 9n
[C] [D]
23. 9n g = 2 - 3 =- 1 37. Q = [A] [B] . As [C] and [D] increase with time. So
K
` p = K c (RT) -1 = K c /RT Q increases, also [A] and [B] decreases.

24. 9n g = 1 - b1 2 l =- 2 38. The reaction proceeds from right to left when Q > Kc
1 1
so that Q tends to decrease to become equal to Kc.
K
` p = K c (RT) -1/2 or K p /K c = (RT) -1/2
39. a = : d D ; a = : d - 1D ; b D l = a + 1.
D-d D
d
25. K p = K c when 9n g = 0 .
a = b d l - 1.
D-d D-d D
26. K = Product of KC of the step added.
a = (n - 1) d ; a= d ;
27. Reaction (b) is double of (a) and reverse of (a). The point at which a = 0 .
1 1
Hence K 2 = 2 or K12 = K .
K1 2

28. As the reaction is reversed and divided by 2, new

1
eqm. Const. = 64 = 8 .
1 : D - 1D = 0 ;
So b d l = 1 .
D
d
k k
29. K = k f = k1 . a2
b 2 40. K p = P . a 2 P.
1 - a2
30. Reaction (2) is inverse of (1) and half of (1).
Kp
Hence K 2 = K or K1 = b K l .
So,
1 1 2 a. P .
1 2

31. The first two are the step reactions of the required 41. PCl5 (g) ? PCl3 (g) + Cl 2 (g)
1 0 0
reaction. 1-0.5 0.5 0.5
32. Reaction (ii) is inverse and double of (i).
At equilibrium total mole = 1 - 0.5 + 0.5 + 0.5 = 1.5
Hence K 2 = 1/K . 2
M

mmix = m0 = 1 + (nInitial
1
- 1) a
33. Required Equation = Eq2 - 2 × Eq 1
208.5 208.5 208.5
K 10 29 1
m0 = 1 + (2 - 1) # 0.5 = 1 + 0.5 = 1.5 = 139 g
K1 ]5×1052g2 25
\ KC = 22 = = ×10 -75

\ KC = 4 × 10-77 Weight Pm 2 # 139

Density = V = RT = 0.0821 # 800
0

1
34. SO 2 (g) + 2 O 2 (g) ? SO3 (g) K p = 4 # 10 -3
4.232
= g/L
1 1
SO3 ? SO 2 (g) + 2 O 2 (g) K 'p = Kp
42. C (s) + CO 2 (g) ? 2CO (g)
K 'p = c # -3 m
1
3P
4 10
P - P/2 P = 2 = 12
2SO3 ? 2SO 2 + O 2 (g)
P2

So, K p = (P/2) = 2P = 2 # 8 = 16 atm.
K = (K ) = ; # -3 E = : 4 D
2
1 1000 2
''
p
' 2
p
4 10
43. Apply law of mass action taking [solid] = 1.
= 6250 = 625 # 10 2
6.25 x 104 atm. 44. Vapours and liquid are at the same temperature, and
KE \ T
35. N 2 + 3H 2 ? 2NH3 , K p = 4.28 # 10 -5 atm -2
2
45. [CaO (s)] = [CaCO3 (s)] = 1. Hence K = PCO . 2
P NH 32 9

Reaction Quotient, Q p = 3 =
3
= 46. 3Fe (s) + 4H 2 O (g) ? Fe3 O 4 (s) + 4H 2 (g) .
PN (PH 2) 2 #
1 (2) 3 8

Q p > K p, \ Reaction will go Backward.
Take [solid] = 1.
Chemistry
47. K p = (PH O) 2 = 4 # 10 -4 atm
2
54. Reaction is exothermic with n p < n r

PH O = 2 # 10 -2 atm = 2 # 10 -2 # 760 torr =15.2torr 55. Conversion of graphite to diamond is an endothermic

reaction. All other reactions are exothermic (Note
2

15.2
RH = 22.4 ×100 = 67.85%
48. Addition of inert gas at constant volume has no
effect on equilibrium concentrations.
49. For constant volume, reaction quotient (Q) will
remain constant.
For constant pressure, reaction quotient (Q) will
remain constant when 9n g = 0 .
50. n p < n r and reaction is endothermic. Hence high
pressure and high temp. will favour forward reaction.
51. Doubling the volume means decrease of pressure. It
will shift to right for reaction in which n p < n r .
52. As np=nr, equilibrium will not be disturbed by pressure.
53. Decrease of K with rise of temp. means that the
forward reaction is exothermic or the backward
reaction (formation of HI) is endothermic. As the
given reaction is exothermic, energy of HI is greater
or stability is less than H2 and I2.
that decomposition of ozone is also exothermic).
56. (d) is not an equilibrium reaction, being irreversible.
57. On adding more PCl5, reaction moves forward.
58. Pressure has no effect when np = nr.
59. Low pressure favours forward reaction when np< nr
60. Forward reaction will be favoured by increase of
temperature as reaction is endothermic.
61. High pressure favours forward reaction if np< nr. High
temp. favours forward reaction if it is endothermic.
62. (d) By Le-chatelier principle.
63. Concentrations of reactants and products at
equilibrium are same even in the presence of catalyst.
64. Reaction is exothermic with n p < n r . Apply Le
Chatelier principle.
65. Endothermic reaction is favoured by increase of temp.

EXERCISE - 2

1. When Rf = Rb then reaction is said to be in 7. N2(g) + 3H2(g) 2NH3(g)

equilibrium. P
At equilibrium 3 P,
2. At equilibrium rates of backward and forward
reactions become equal, relative concentrations of P
3 + P + PNH = 2P 3

reactants and products can be anything. 2P

PNH = 3
3. These will be N 2 NHD 2 _bb
3

bb 2P # 2P
present at equilibrium H NH D bb 3 = 1 $4 & K = 4
K p = 3P
2 2
bb p
D 2 HD b` = 8 P2 3 3P 2
3 #P
3
bb
NH3 bb 8. 2SO 2 (g) + O 2 ? 2SO3 (g)
bb
ND3 b
a
KP = 4.0 atm-2
k1 b+x
4. A k B
k 3
Kc = k = a - x
1
PSO
2 2
KP = 2
3

PSO PO 2 2

k a-k b
Given that at equilibrium the amount of SO2 and SO3

a-x b+x x = 1k + k2
1 2 3
PSO

Therefore, (A) option is correct. is the same so 2 =4 3

PSO PO 2 2

5. A + B C + D 1
& PO = 4 = 0.25 atm .
2

3n n 0 0 t=0
P ' (PCl3) # P ' (Cl 2)

(3n-x) (n-x) x x t = teq. 9. K p = =
P ' (PCl5)
(n-x) = x b c
# #
n = 2 x
n
x = 2 = [D] (a + b + c) P (a + b + c) P
a
[B] 2 (0.4) 2 (a + b + c) P
6. K c = [A] = 0.1 = 1.6
bc.P

K p = a (a + b + c)
 Chemical Equilibrium
10. 2NO 2 ? 2NO (g) + O 2 (g) 17. Using K p = K c (RT) 9ng
K
(PNO) 2 (PO )
So, log K P = 9n g logRT

Kp =
2
C
(PNO ) 2 2

so, 9n g =- 1 .

given, PO = 0.25; PNO = 0.5
18. Since, Kp is temperature dependent only.
2

2

100 =
(0.5) (0.25) 19. A + D ? AD; K1
(PNO ) 2

2

AD + D ? AD 2; K 2
(0.5) 2 (0.25)

(PNO ) 2 = 2
100
AD 2 + D ? AD3; K3

PNO = 0.025
2

A + 3D ? AD3; K

11. N2 + O2 ? 2NO 2x = 1.0 mole/litre

As we know that K = K1 . K2 . K3

a b 0 x = 1.0/2 mole litre
Or, logK = logK1 + logK2 + logK3

= 0.50 mole/litre 1
20. SO 2 (g) + 2 O 2 (g) ? SO3 (g) K p = 4 # 10 -3

(a – x) (b–x) 2x 1 1
SO3 ? SO 2 (g) + 2 O 2 (g) K 'p = Kp

If a – x = 0.25, b – x = 0.05
K 'p = c # -3 m
1

[N2] = a = a – x + x = 0.25 + 0.50 = 0.75 mole/litre
4 10
12. PCl5 ? PCl3 + Cl2 2SO3 ? 2SO 2 + O 2 (g)
1 0 0 Initial mole
K ''p = (K 'p) 2 = ; # -3 E = : 4 D
2
1 1000 2
1 - 0.7 0.7 0.7
5 5 5 Conc. at equilibrium
4 10
Total mole of PCl3 = 0.7, Concentration = 0.14 6250
= = 625 # 10 2

x2 0.7 # 0.7 49 6.25 # 10 4 atm .

K C = (1 - x) V = 0.3 # 5 = 150
21. SO3(g) + CO(g) SO2 (g) + CO2 (g)
13. PCl5 ? PCl3 + Cl 2 2 2 2 2
at t = 0 a 0 0
t =teq. a-x x x
2+x 2+x 2-x 2-x

9 =b2-xl ⇒x=1
PPCl = X PCl # PT = .25 # 2 = .5 atm 2+x 2

3 3

PPCl = PCl = .5 atm ` PPCl = 1 atm
3 2 5

\ neq = 3 + 3 + 1 + 1 = 8
14. 2O3 (g) ? 3O 2 (g) K p = 4 # 1014 PO >> PO
2 3
n (SO 2) 1
P O3
n(SO3) + n(CO2) = 4 n (CO) = 2 < 1

K p = 2 PO + PO = 8
2
& PO b 8 atm

Therefore, (D) option is correct.
2 3 2
PO 3

83

4 # 1014 = 2 P O = 11.3 # 11 -7 3 22. From given information, Q = tan 75º
PO 3

Therefore, (b) option is correct. conc. of isobutane

= conc. of n - butane > K c = 3
15. H2F2(g) H2(g) + F2 (g)

so backward reaction
a 0 0
a - x x x 23. When Q > KC, the reaction will proceed in backward
a-x 1 a direction to attain equilibrium.
\ XH F = a + x = 2 & x = 3
2 2

[C] [D]
a/3 1 24. Q c = [A] [B] , < Kc as [C] = 0
\ X H = 2a/3 = 2 = X F
2 2

\ PH = PF = 2atm and PH F = 2atm Q

` c - with time
2 2 2 2

2.2 25. LaCl3 (s) + H 2 O (g) + $ LaClO (s) + 3HCl (g)

\ K P = 2 = 2
16. Dng = 1 P2 P2

K p = P HCl = 2PHCl PHCl 2 PHCl
H O 2 H O 2

\ KP = KC (RT)1

\ KP = KC (800 R)
Chemistry
26. CuSO 4 $ 5H 2 O (s) ? CuSO 4 $ 3H 2 O (s) + 2H 2 O (g) a
aMSO + 2 $ M O + (1 - a) MSO

=
2 2 3

K P = 2.25 # 10 -4
1+ 2
a

K P = P 2 H O = 2.25 # 10 -4 PH O = 1.5 # 10 -2 a 80 a 20

2 2
1 + 2 = 60 2 = 60
22.8
Vapour Pr = 760 = 3 # 10 -2
a= 3
2

32. D = d b1 - \ + 2 l
PH O \
R.H. = V.P. # 100 = 50%
2

Therefore, (B) option is correct. D \

\ d = 1- 2
27. N2O4 (g) 2NO2(g) 2D
⇒ \= 2 - d

nini : 1 0
D 1

neq : 1- \ 2\ 33. d0 = 1 + (n - 1) a n = 1 + 2 = 1.5
1 -\ 2\ 40

Xeq : 1 + \ 1 +\ 35 = 1 + 0.5a
40
4\2 KP 1 + 0.5a = 35

\ KP = P &\ K P + 4P
1 -\ 2 0.5a = 1.14 - 1
28. 2SO3(g)
2SO2(g) + O2(g)
0.5a = 0.14
t=0 a 0 0
a = 0.28
ab 2 l
a

t = teq. a(1-a) aa 34. K C = [CO 2] = 0.5 mole/litre
Total mole at eq. = a b1 + 2 l
a
So moles of CO 2 = 6.50 # 0.05 = 0.3250 moles


CaCO3 ? CaO + CO 2
PSO = c 1 + (a/2) m P0 = < F # P0 ;
1-a 2 (1 - a)
1 mole of CO2 is obtained from 1 mole of CaCO3
3
1 + (a/2)

\ 0.3250 moles of CO2 needs 0.3250 moles of
PSO = c 1 + (a/2) m P0 = b 2 + a l # P0
a 2a
2 CaCO3

⇒ 0.3250 # 100 g of CaCO3 = 32.5 gm of CaCO3
PO 2 = c 1 + (a/2) m P0
a/2

35. Gas product concentration increases while that of
solid reactant is constant. Also increase in [NH3] is
#b 2 +
a l#
4a 2 (P0) 2 twice the increase in [CO2].
P0
=< F
(2 + a) 2 a a3 P0
KP =
4 (1 - a) (2 + a) (1 - a) 2 36. NH4HS(s) NH3(g) + H2S(g)
2

52 + a?2
# (P0) 2

P P
(1 - a) 92 + 2a # 46 2P = 1.2
29. N2O2 2NO2 M mix = 1+a
P = 0.6
92

1- a 2a M mix = 1 + a KP = P2 = (0.6)2 = 0.36 atm2
D 46
d = 46/(1 + a) = (1 + a) . 37. NH4HS(s) NH3(g) + H2S(g)

Therefore, (A) option is correct.
Since flask already contain NH3(g), the equilibrium
pressure of NH3 and H2S will not be equal.
M mix M
30. (VD) mix = 2 = 2 (1 + a) p NH = 2 + p H S3 2

So, as a increases (VD)mix decreases.
& (p NH ) # p H S 3 2

& (p H S + 2) (p H s) = 3
2 2

0.9 × 0.082 ×1000

31. Mmix = 1.23 = 60
p H S + 2p H S - 3 = 0
2
2 2

1 - 2 ! 4 + 12 -2 ! 4

SO3(g) SO2(g)+ 2 O2(g)
pH S = 2
2 = 2 & 1, - 3
a
p H S = 1 atm

1-a Mmix
2

a 2
p NH = 2 + 1 = 3 atm
3
 Chemical Equilibrium
19.355 mmHg 49. N2(g) + O2(g) 2NO(g)
38. 55.3 # 100 = 35 %

1 mole 2 mole 3 mole
39. K P = 4 # 10 = (PH O)
-4 2

KC = 1 # 2 = b 2 l
2
(3) 9

1 2

PH O = 2 # 10 -2
2

K P = 243 # 10 -10 = (PH O) 5

2 2
Let a mole of O2 is added, Then,

PH O = 3 # 10
2
-2

N2(g) + O2(g) 2NO(g)

K P = 6.4 # 10 -5 = (PH O) 3
3 2
1 mole 2 mole 3 mole

PH O = 4 # 10
2
-2
t = 0 1 (2 + a) 3
Order of V.P. c>b>a
(1 - x) (2 + a)-x (3+2x)
RH order c > b > a [NO] = : 100 D = 0.04;
3 + 2x

(3+2x)=4
40. KP = 0.800 atm = PCO = maximum pressure of
2

2x = 1, x = 0.5.
CO2 in the container to calculate maximum volume
of container the PCO = 0.8 atm and none of CO2 (3 + 2x) 2 9
2

K C = (1 - x) (2 + a - x) = 2 .
should get converted int CaCO3(s).
So, V(0.0800 atm) = (10 L) (0.2 atm) (4) 2 9

K C = 0.5 [(1.5) - a] = 2 .

\ V = 2.5 L
16 9

= 0.5 (1.5 + a) = 2 .
41. On adding any reactant equilibrium shifts in forward
direction, so amount of product increases. 35

= 4.5 = [1.5 + a]
42. On adding inert gas at constant pressure effect
on equilibrium will be similar to as if volume of
7.11 = 1.5 + a.
container has been increased.

101
a = 18 = 5.61
43. High temperature will favour backward reaction as 50. Equilibrium partial pressure of H2O(g)=(64 × 10–18)%
reaction is exothermic. While on increasing pressure
reaction will shift in direction higher density.
= 2 × 10–3 atm = 1.52 torr. a QP < KP ⇒ forward
44. For any physical equilibrium on increasing pressure 51. From thermodynamics.
equilibrium shifts in the direction of higher density. 52. T - KC - ⇒ Endothermic
45. 2A(s) + 3B(g) 3C(g) + D(g) + O2 1 3H
53. Slope of graph ln K vs T is - R

If pressure on system is reduced to half its original Endothermic ⇒ DH > 0
value then equilibrium will shift in forward direction
to increase no.of moles of gas to compensate
\ Slope < 0
reduction of pressure. 54. If KC = 1 \ DGo = - RT ln 1 = 0

\ Amounts of C & D will increase. 55. Refer No. Q. 53.
46. a Dng < 0 1 1
56. If T2 > T1 ⇒ T < T

\ Increasing pressure will result in the reaction 2 1

moveing forward. \
1 1
T2 - T1 < 0
47. Inert gas addition has no effect at constant volume.
57. AB ? A + + B - AB + B - ? AB -2
48. Pinert remains same as number of moles of inert gas &
volume remains same after changes been done. [A +] [B -] [AB -2 ]

K1 = K2 =
[AB] [AB] [B -]

—→ Ptotal increased more than increase in Pinert, so
clearly there has been reduction in volume, by Le [A +] [B -] [AB] [B -] [A +]

K1 /K 2 = $ - = $ [B -] 2
chatelier’s principle pressure will decrease but will [AB] [AB 2 ] [AB -2 ]
remain more than initial. [A +] K 1

& = 1$
[AB -2 ] K 2 [B -] 2

Therefore, (D) option is correct.
Chemistry
58. AB A+ + B- AB + B- AB2- 40 = (x + y)(x)
a-x-y y (y-x) (a-x-y) y-x x 40 = 10x
y (y - x) x x = 4 atm

K1 = (a - x - y) K 2 = (a - x - y) (y - x)
y = 6 atm
< F
y (y - x) X(s) B(g) + E(g)
(a - x - y)
K1 x K1 y
t=0 – 0 0
K 2 = (a - x - y) (y - x) & K 2 = x (y - x)
2

t = eq. – (x + y) y
59. Cl2 (g) will get consumed and PCl5 will furnish Cl2
\ K P = PB $ PE
2

in the first reaction. = (10) (6)

60. A(s) B(g) + C(g) KP = 60 atm

t=0 – 0 0
DG2 = –RT ln K2

at eq. – x+y x = –(2) (300) (2.303) log 60
K P = PB $ PC
1
= –(2) (300) (2.303) (1.78)
= 2.48 kcal/mol
EXERCISE - 3
1. A(s) + 2B(aq.) 2C(s) + D(aq.) 3 So
Also intercept of the line = 2.303R
1
Initial 1 0 0 3 So
4
\ 2.303R = 2 (given)
At eq. 1x
1
2x xx
4 \ DSo = 2.303 × R × 2
1

As K is very high so, [D] = x . 4 and also C is a = 2.303 × 8.314 × 2 c 38.30 JK-1
solid
Now, using equation (ii),
1 1

DGo = DHo - TDSo = 13.5 - 298 × 38.3
\ 10 20 = 4 2 & 10 20 = 42
5B?

a
DGo = -11399.9 J
-20 -10
a
& 2=
1 10 10
= 4 &a= 2 = 5 ×10 -11 M or, DGo = -11.399 kJ
4 ×10 20
or, DGo c -11.40 kJ
5Z?2 9 53/2?2
2. K c = 5 ? & 4 = 5 ? 1
Y Y 4. SO2(g) + 2 O2(g) SO3(g)
⇒ [Y] = 1
No. of mole 2 1 4
3. DGo = -2.303 RT log Keq ... (i) 2 1 4

conc. 4 4 4

DG = DH - TDS
o o o
...(ii) [SO3] 1
KC = =
From equation (i) and (ii), we get
[SO 2] [O 2] 1/2 (1/2) (1/4) 1/2

-2.303 RT log Keq = DHo - TDSo

1
= (1/2) # (1/2) = 4
log K eq = b 2.303R
-3 H o l 1 + 3 S o
T 2.303R ...(iii)
5. A + B C + D

Equation (iii) shows that if log Keq is plotted vs 1/T, t=0 2a a 0 0
a graph of the following type is obtained: t = teq 2a -x a-x x x

Slope of the line = tan(p-q) a
a - x = x & x = 2
3 Ho

From eq. (iii) slope = - 2.303R a#a
2 2 1
3 Ho ⇒ KC = =3
b 2a - l #
1

so, - 2.303R =- (given) a a
2 2 2
1 1 1

\ DHo = 2.303R × = 2.303 × 8.314 × ⇒ KC = 3
2 2

\ DHo = 13.5 J
 Chemical Equilibrium
6. For reaction 11. LiCI. 3NH3(s) LiCI. NH3(s) + 2NH3(g)
1 0.1 a

H2(g) + I2(g) 2HI (g) K ' = 0.25 = 4

Kp= 9 atm2 = P 2 NH

For reaction 3

1 1
& PNH = 3 atm
2 H 2 + 2 I2 HI (g) K '' = 4 3

no. of moles of NH3 at equilibrium
7. CH3COOH(1)+C2H5OH(1) ? CH3COOC2H5(1)+H2O(1) 3#5

= 0.082 # 313 = 0.5844
Initial 1 1 0 1
At eq. 1-x 1-x x 1+x
For 0.1 mol of LiCI NH3 to convent 0.2 mol of NH3
must be needed.
1-0.543
1-0.543 0.543 1+0.543

Total number of mol of NH3 req. = 0.7844
1 # 54.3
(54.3% of 1 mole = 100 = 0.543 mole)
Answer : 0.7844 × 100 = 78.44

Hence given x = 0.543 mole
After rounding of Answer is 78.

Applying law of mass action
12. T = 445oC = 445 + 273 = 718K
[ester] [water] 0.543 # 1.543
K C = [acid] [alcohol] = 0.457 # 0.457 = 4.0

P = 207 atm

n = 1 mole
8. N2O5(g) 2NO2 (g) + 1/2 O2 (g) 1
Initial 600 0 0
Ag2O 2Ag (s) + 2 O2 (g)

eq. 600 (1-a) 1200a 300a
Kp = PO 2 = (207)1/2 = 14.39

600 (1-a) + 1200a + 300a = 960
DG = DG0 + 2.303 RT log Keq.
0

⇒ 900 \ = 360 ⇒ \ = 0.4

But at eq. DG = 0 (DG = 0),

DG0 = – 2.303 RT log Keq.
9. Ni(s) + 4CO(g) Ni(CO)4(g)
P P
But for formation,
1
For backward reaction
2Ag (s) + 2 O2 (g) Ag2O (s)
QP $ KP
1 Mole
1 1

P
$ KP
Kp = =
P4 (PO ) 1/2 (207) 1/2
2

1
\ $ 0.125 atm -3
9G o =- 2.303 # 2 # 718 log
1
P3 (207) 1/2
P3 # 8 atm3

DG0 = 3789.46 Cal
P # 2 atm

DG0 = 3.789 KCal
PTotal = 2 P = 4 atm.

DG0 = 3.8 KCal
10. C (s) + H 2 O (g) ? CO (g) + H 2 (g)
After rounding of Answer is 4.
t=0 - 1 2 3
Carbon solid will start forming when there will be 13. X (s) A (g) + B (s) + C (g)
equilibrium in the container P1 + P 2 P1
PCO $ PH (2P)(3P) Y (s) D (g) + A (g) + E (s)
KP = P = 3 atm =
2
= 6P = 3 atm
H O2 P P2 P 2 + P1

1
So P = 2 atm (P1 + P2) P1 = 500 ...(i)
So Total pressure in the container will be (P1 + P2) P2 = 2000 ...(ii)

PT = P + 2P + 3P = 6P = 3atm Adding the above 2 equations:
(P1 + P2)2 = 2500
\ P1 + P2 = 50
Ptot = 2 (P1 + P2) = 100
P 100
\ 25T = 25 = 4 atm
Chemistry
14. C2H5OH+CH3COOH ? CH3COOC2H5+H2O 19. A2(g) + B2(g) 2AB(g)

Initial moles 1 1 0 0 at t = 0 60 42 0

at eq. moles 1-x 1-x x x at eq. (60-x) (42-x) (2x)
2
(Partial pressures)

Given x = 3

⇒ 2x = 28 ⇒ x = 14
2 2 2 2
Moles at eq. 1 - 3 1- 3 3 3 (PAB) 2 (28) 2 14

K P = (P ) (P ) = (46) (28) = 23
b 2 lb 2 l
A B 2 2

3 3
KC = =4
a Dng = 0
14
\ K P = K C = 23
b lb 1 l
1 1

3 3

Let degree of dissociation for AB is \ , then
C2H5OH+CH3COOH ? CH3COOC2H5+H2O
2AB (g) ? A 2 (g) + B 2 (g) b K C = K = 14 l
Initial moles 3 3 - - 1 23

at eq. moles 3-x 3-x x x
2
C 1

x2
at t = 0 1 0 0
K =4= a a
C (3 - x) 2
at eqlb. (1-a) 2 2
x
3-x = 2 b a lb a l
2 2 23
x = 6 - 2x = 14 $ a = 0.719
(1 - a) 2
3x = 6

Hence percentage of dissociation=0.719×100 = 72%
x = 2
20. NH4HS(s) NH3(g) + H2S(g)
Ans. 2 x 10 = 20.

1-0.5 1
D-d
15. a = (n - 1) d 1 3

NH3(g) 2 N2(g) + 2 H2(g)
92
1-0.5 0.25 0.75
- 40
a = (22- 1) .40 = 0.15

K P = 0.5
1

16. N2O4(g) 2NO2(g) (0.251/2) (0.75) 3/2 3

3
K P = 0.5
2 = 8
922 = (1 + a) × 61.33
c 3m
3 2
92
1 + a = 61.33 KP2
8 27/64

= 6 = 1/64 = 27
2

a = 0.5 K6P b l1 1

2
17. NH2COONH4(s) 2NH3(g) + CO2(g)
21. As VCO produced in Rxn. I = VO used ⇒ DV = 0
2P0 P0
2 2

for Rxn I.
K P = (2P0) # P0 = 4P 0
2 3

\ DV for Rxn II = 5 L ⇒ VCO produced- used=5L.
3P0 P’

\ VCO produced = 10L and VO used in Rxn II=5L

2

K P = (3P0) 2 # P ' = 9P 02 .P
Let, vol of O2 used in Rxn I = xL
4
P ' = 9 P0 \ Vol. of CO2 produced = xL.
⇒ PO = ]15 - xg atm
4 20 - 5 - x
Pf 3P0 + 9 P0 31 a \ X O finally =
l = 3P0 = 27 = b & a + b = 58 2
105 2

P x
X CO = 105 ⇒ PCO = x atm
2 2

18. Let PCO initally = P

2
10
X CO = 105 ⇒ PCO = 10 atm
\ C(s) + CO2 (g) —→ 2CO(g)
P From: 2 C + O2 → 2CO KP = 12.5
P- 2 P 2
P 100

4P
\ Ptotal at equilibrium = 2 = 12 atm 12.5 = PCO & PO = 12.5 = 8 atm = 15 - x
2
O 2

\ P = 8 atm. \ x = 7 atm.

\ PCO at eqlb. = 8 atm and PCO at eqlb. = 4 atm
\ PCO = 7 atm and PCO = 10 atm
2
2

\ PCO + PCO = 17 atm
82
2

\ KP = 4 = 16
 Chemical Equilibrium
22. A (s) ? B (g) + D (g) K P = 625
1 25. A (s) ? B (g) + C (g) K P1 = 300
P1 (P1 + P2)
- P1 (P1+P2) K P1 = P1 (P1 + P2)

C (s) ? E (g) + D (g) K P = 975

2
P2 (P1 + P2) D (s) ? E (g) + C (g) K P2 = 600

K P + K P = (P + P + 2P1 P2)
1 2 1
2 2
2 P2 P1+P2 K P2 = P2 (P1 + P2)
(P
= 1 + P2) = (625 + 975) & (P1 + P2) = 40
2

b K P1 l =
P1 (P1 + P2)
So total pressure = 2[P1 + P2] = 80 atm. K P2 P2 (P1 + P2)
23. H2 + Br2 2HBr 300 b P1 l
600 = P2
t = 0 0.4 0.2 -
t = teq. 0.2 y 0.4
P1 1
P2 = 2 P2 = 2P1
= negligible = y

KP1=P1(P1 + P2)
1 0.4 # 0.4
a 4 # 1010 = 0.2 # y
KP1=P1(P1 + 2P1)
y = 3.2 # 10 -10
300 = P1 (3P1)
Br2 3.2 -10
P12 = 100 (P1 = 10)
HBr # 10 = 0.4 # 10 # 10 = 80
11 11

P2 = 20 atm
24. PCl5 ? PCl3 + Cl 2
Now Total pressure
2 - - K C = 2a = 2 # 0.8 = 1.6
P B + PE + PC
2-1.6
= 0.4 1.6 1.6
(P1+P2) + (P1+P2) = (10+20) + (30) = 60 atm.
1.6 # 1.6
0.4 1.6 1.6
5 5 5 K C = 5 0.4 5
#
4 1.6 64 5
KC =
5 = 50

EXERCISE - 4

1. S (s) + S 2- (aq) ? S 22- (aq)
2S (s) + S 2- (aq) ? S32- (aq) K 2 = 132
K1 = 12 (C) False –Temperature of system will change but
relative humidity remains same.
(D) False – PH O(g) doesnot remain same on changing
2

Now (vc), S 22- (aq) + S (s) ? S32- (aq) temperature.

K 132
K eq = K2 = 12 = 11 5. Partial pressure of equilibrium does not changes that
1
is PH O = 3 × 10–2 atm.
2. H 2 O (,) ? H 2 O (g)
2

6. CuSO 4 $ 5H 2 O (s) ? CuSO 4 $ 3H 2 O (s) + 2H 2 O (g)

K P = (PH O)
K P = 2.25 # 10 -4
2

When neon is added at constant pressure, we have to
increase volume of the container. So more water will K P = P H2 O = 2.25 # 10 -4 PH O = 1.5 # 10 -2
2 2

evaporate to mantain equilibrium. 22.8

Vapour Pr = 760 = 3 # 10 -2

2.303R T1 - T2 D
K2 9H o : 1 1 PH O
3. log K1 = R.H. = V.P # 100 = 50%
2

Therefore, (B) option is correct.

= 2.303 # 8.314 :1300 - 1200 D
K2 597.4 # 103 1 1
log 0.0118
7. On increasing temperature though reaction

log K 2 =- 2 + log (0.0118) =- 3.928 equilibrium shifts in the backward direction but for

& K 2 = 1.18 # 10 -4 rate of reaction to be higher, higher temperature is
required and particle 500ºC is found to be optimum

Therefore, (A) option is correct.
temperautre.
4. (A) False – PH O remains same but pressure in
2

container = PH O + Pinert. 2

(B) True –Equilibrium will have PH O = vapour 2

pressure.
Chemistry
8. N 2 O 4 ? 2NO 2(g) x 3

Ptotal = 28.65 - x + 2 + 2 x
9n = 2 - 1 = 1, K P = K C (given)

or 28.65 + x = 40.11 .
We know, K P = K C ^RTh9n

x = 11.46.
1
1 = RT, T = .0821 = 12.19K 11.46
Degree of dissociation of NH3 = 28.65 = 0.4
9. K P = ]RTg3 n . Highest value of Dng will give
K
16. (1)
g

C A (s) ? D (g) + C (g) K P = (20) 2

highest ratio and lowest value will give lowest ratio.
20 atm 20 atm
1
10. K1 = K for same value of T.
(2) B (s) ? E (g) + F (g) K P = (30) 2
2
⇒ similar to yx = const.
30 atm 30 atm
11. An efflorescent salt is one that loss of H2O to (3) container Kp is same so on doubling the volume
atmosphere. partial pressure does not change but moles of
C, D, E, F will change to maintain their partial
CuSO4.5H2O(s) CuSO4.3H2O(s) + 2H2O(g)
pressure. So total pressure = 40 + 60 = 100 atm.
KP = (P '
H2 O) = 4 × 10–4
2
17. K P = (PH O) 5 = 56.25 # 10 -10
'
= 2 × 10–2 atm = 15.2 mm Hg
2
P H2 O

If P H' O at 25ºC < 15.2 mm only then reaction will

(PH O) = (56.25 # 10 -10) 1/5 = (56.25) 1/5 # 10 -2
2
2

proceed in forward direction. 2.23

= # 10 -2 # 760 = 17.01 torr
12. 2AB 4 (g) ? A 2 (g) + 4B 2 (g) / n = 1 + 2 - 1
3a % Relative humidity
a Partial pressure 17.01
1-a 2x 1 - a - 1 = Vapour pressure # 100 = 22.8 # 100
2
b a P lb 2a # P l = 74.60% (less than 74.60%)
4

2 1

KP = = 8P3 a5 18. A (s) X + Y
(P) 2
a a+b
13. Rigid vessel ⇒ constant volume.
B (s) Y + Z
Adding inert gas at constant volume has no
a+a b
effect.
⇒ K P = a (a + b)
1

14. C(S) + CO2 (g) 2CO (g) ⇒ K P = b (a + b)

2

(PCO) 2 Ptotal = (a + b) + a + b = 2 (a + b)

KP = ' = 1.0
P CO 2 ⇒ 2 (a + b) = 50 ⇒ a + b = 25

At equilibrium PCO = K P = 4 # 10 -2
2 remain ⇒ 250 = 25 a ⇒ a = 10, b = 15
constant ⇒ K P = b (a + b) = 15 × 25 = 375
2

2

(PCO )
=1
2 19. X (s) Y (g) + 2Z (g) A (s) Y (g) + B (g)
4 # 10 -1 t = eq. (a+b) 2a t=eq. (a+b) b

PCO = 4 # 10 -2 = 0.2 atm given P Z = PB
2a = b
15. P1 = 15 atm ; T1 = 300 K.
Equilibrium temperature is 300ºC that is 573 K. and PZ + PB = PY + 10
So first of all we have to calculate pressure of NH3 at (2a + b) = (a + b) + 10
573 K. a = 10 atm
P P
T1 = T2 = 300 573
15 P2 \ b = 20 atm
1 2
K P = (a + b) (2a) 2 = (30) (400) = 12000
1

P2 = 28.65 atm at 300 o C. K P = (a + b) (b) = (30) (20) = 600

2

1 3

NH3 (g) ? 2 N 2 (g) + 2 H 2 (g) 9G =- RTInK
t = 0 28.65 atm 0 0 9G1 ,nK1 log12000 3 + log12
9G 2 = ,nK 2 = log600 = 2 + log6
x 3
t = teq. [28.65-x] 2 atm 2x

But according to question.
 Chemical Equilibrium
20. NH4I(s) NH3(g) + HI(g) 26. Statements a, b, c are factual.
at eq. total pressure = 304 mm of Hg a) At equilibrium reaction does not stop, the rates

304
pNH = pHI = 2 = 152 mm of Hg = 0.2 atm of forward and backward reactions become
equal.
3

2HI(g) H2(g) + I2(g) NH4I(s) NH3(g) + HI(g)

27. Equilibrium const. is temp. dependent only.

t=0 0.2 0 0 eq. – 0.2+y 0.2+y–x
x x 28. At equilibrium all properties solution (i.e. chemical

t = eq.0.2+y–x 2 2 composition of eq. mixture) becomes constant.

We assumed that x atm of HI is used for dissociation 1
which results formation of y atm of HI from NH4I(s) 29. 2NH3 N2 + 3H2 K1' = K
1

for NH4I(s) NH3(g) + HI(g)
N2 + O2 2NO K '2 = K 2

KC = 0.2 × 0.2
1
3 × (H2 + 2 O2 H2O) K3' = (K3) 3

in other case KP = (0.2 + y) (0.2 + y – x)
-------------------------------------

(0.2 + y) (0.2 + y – x) = 0.2 × 0.2 ...(i) 5 K 2 # (K3) 3

2NH3 + 2 O2 2NO + 3H2O K 4 = K1

For 2HI(g) ? H2(g) + I2(g)
(x/2) (x - 2) K 1
30. log KC = log (RT)

KC = KP = = 0.010 ...(ii)
(0.2 + y - x) 2 P

on solving the equation : x = 0.036 & y = 0.016
⇒ KP = KC (RT) ⇒ Dn = 1

total pressure at eq. = p NH + pHI + p H + p I
31. For KP = KC
3 2 2

= 0.432 atm

= 328 mm of Hg 32. Relation between KP & KC

K P = K C (RT) 9n
21. 2A 2 B (g) ? 2A 2 (g) + B 2 (g) KP = P
/ n = 4 + 2a \ log b K P l = (9n) log (RT)
K

4 (1 - a) 4a 2a
C

b
4a # l2 b 2a # l
4 + 2a P 4 + 2a P

KP = =P
c m
4 (1 - a) 2

4 + 2a # P

& 2a3 = (1 - a) 2 (4 + 2a)

2a3 = (1 + a 2 - 2a) (4 + 2a)
2a3 = 4 + 2a + 4a 2 + 2a3 - 8a - 4a 2 33. (A) N2O4 2NO2 KC = 4
2
a= 3 at point - A
22. A (s) B (g) + C (g) [Product]
Q = [Reactant] = 0

E (s) B (g) + D (g) So, Q have minimum value at point A.
(P1 + P2) P1 (P1 + P2) P2

(B) at point [N 2 O 4] = [NO 2] = 0.1 M

Total pressure = 2 (P1 + P2) = 2 Ksp + Ksp = 20 atm
1 2
[NO 2] 2 0.1 # 0.1
23. On adding inert gas at content temperature & Q = [N O ] = 0.1 = 0.1
2 4
pressure 2nd reaction will be shifted in backward
A < KC
direction.
So, reaction proceeds left to right
24. On mixing, P(N2) & P(H2) will add up. This will shift (C) KC = Q at point [D & F]
both the equilibrium backwards thereby decreasing
the number of moles. 34. We know that
D
25. K P = K C (RT) 9n 9n =- 1 d = 1 + (n - 1) a

KP 1
where n is number of mole of gases produced from
K C = RT = 0.0301. one mole of a gas.
Chemistry
35. A + B ? C + D (D) Same equilibrium will be attained from either
1-x 1-x x x direction.
5 5 5 5 t=eq
(E) Catalyst does not change equilibrium
KC to question
concentrations.
K 9

KF = 9 Kb KC = KF = 1 PPCl (g) # PCl (g)
b
42. According to K P =
3 2

(K/5) 2 9 PPCl (g) 5

KC = 2 = 1
b 5 l
- (n PCl (g)) eq. # (n Cl (g)) eq.
1 x x =
3 2
and on adding inert gas
1-x = 3 V # (n PCl (g)) eq. 5

x = 3 - 3x at constant pressure effect on equilibrium will

4x = 3 be similar to as if volume of container has been
3 increased.

x = 4 = 0.75
0.25 43. a) Inc. P ⇒ less no. of gaseous moles i.e. forward.
[A] = 5 # 100 = 5 # 10 -2 mole L-1 [B] = [A]
b) Adding inert gas at constant volume increases
0.75
C = 500 = 15 # 10 -2 mol L-1 the total pressure and hence the reaction moles
towards more density substance i.e. forward.
36. For given reaction 9ng = 0 c) Adding inert gas at const. pressure ⇒ more no.
37. For given reactions 9ng =+ ve, 9H =- ve, of gaseous moles i.e. forward.
high temperature & low pressure favours forward d) Reaction is exothermic ⇒ high T favours
reaction which increases number of moles. backward.
38. 10 -10 atm = P H5 O 2 44. Value of K for given reaction changes only on

⇒ PH O = 10 atm.
2
-2 changing temperature.
PV 10 -2 # 2.5 45. Equilibrium gets disturbed on changing volume for
n = RT = 1 = 10 -3
all such reactions in which Dng ! 0.
12 # 300
39. (A) KP = (PH O) 2 46. (A) As reaction is endothermic therefore it will go in
the forward direction hence moles of CaO will
2

= 0.4 × 10–3 = 4 × 10–4 atm2

increase.
(PH O) equi = 2 × 10–2 atm
(B) With the increase or decrease of volume partial
2

= 2 × 10–2 atm pressure of the gases will remain same.

= 2 × 10–2 × 760 = 15.2 torr
(C) Due to the addition of inert gas at constant
15.2
(B) Relative humidity = 15.2 ×100 = 100% pressure reaction will proceed in the direction
in which more number of gaseous moles are
(If V.P. = 15.2 torr) formed.
(C) When PH O > (PH O) equi backward shift so at 24
2 2
47. (A) Backward shifting will take place.
torr pressure reaction shift backward.
(B) Forward shifting will take place.
(D) In dry atmosphere and open container reaction
shift completely in forward. (C) Backward shifting will take place.
(D) Forward shifting will take place.
40. For endothermic reaction, DHo is positive so, if
T2 > T1 then K2 > K1. 48. Upon addition of NH3, 1st equilibrium will shift
backward leading to decrease in amount of CO2.

For exothermic reaction, DHo is negative so, if
As a result , 2nd equilibrium will shift forward
T2 > T1 then K2 > K1.
compensating for the amount of decreased CO2.
41. H2 (g) + I2 (g) 2HI (g)

So, nCaCO (s) will definitely decrease.
3

(A) For changing pressure volume has to be changed,

though number of moles of HI (g) do not get
Now, K P = P 2 NH # PCO & K P = PCO
1 3 2 2 2

changed but its concentration will get changed.

Since no change in temperature would have taken
(B) Temperature change will change KP and hence place, K P & K P will have same values at both
1 2

concentration. equilibrium states. So, amount of NH3 & CO2 at the

two equilibrium states will remain the same.
(C) Volume change will change concentration, not
the number of moles.
 Chemical Equilibrium
49. From given reations 55. Addition of solids have no effect on equilibrium
1 1 and temperature favours endothermic direction
(i) =- (iii) ; 2 (i) =- (iv) ; 2 (iii) =- (ii)
while increasing pressure will shift equilibrium in
50. [A]i = 0.5 [B]i = 0.5 ⇒ Q = 1 and K = 1.5 backward direction as 9n g is + ve .

a Q < K \ reaction goes forward 56. Solubility of gas is favourable at high pressure and

\ [A] decreases and [B] increases this process is exothermic hence solubility will be
more at low temperature.
51. X (s) Y (g) + 2Z (g)
57. Since density of gold decreases after melting
P 2P
therefore it is favourable at low pressure and high

\ KP = 4P3 temperature.
and ptot = 3P 58. Number of moles will remain unchanged but due to
V (s) W (g) + 2Z (g) decreased volume pressure will get increased and
P’ 2P’ also the concentrations.
Ptot = 3P’ = 6P ⇒ P’ = 2P - 9H o 230
59. Slope = 2.3R =- 2.3 # 2 =- 50
KP = 3P’3 = 32 P ⇒ K P = 8K P 2 1

60. a DHo < 0, \ Slope is positive.

X (s) Y (g) + 2Z (g) K P = 4P
1
3

P1 2P1 + 2P2
Also, as DHo < 0 so y-intercept should be negative

V (s) W (g) + 2Z (g) K P = 32P3

⇒ (c)
2

P2 2P1 + 2P2 61. As KC increases on increasing temperature therefore

it is an endothermic reaction.

\ 4P1 (P1 + P2)2 = K P = 4P3 1

4P2 (P1 + P2) = K P = 32P3

2 62. (A) Addition of O2 will cause the equilibrium to shift
is forward direction because that way it is consumed.
2

\ (P1 + P2)3 = 9P3 Reduction in volume i.e., increase in pressure also

\ (P1 + P2) = 9 P causes the equilibrium to shift in forward direction
1
3

\ 4P1 ( 9 P)2 = 4P3

1
3 leading to smaller number of moles of gases.
P 1
P1 = 4/3 ⇒ Py (3rd case) = 3 × Py (1st case) 63. In both reactions, the number of moles of gaseous
3 3 3 species on the left side is smaller than right side.
P 1 1 Hence, increase in pressure (reduction in volume)
Also P1 = 8 ⇒ Py (3rd case) = 8 Pw (3rd case)
2 makes the equilibrium to shift to left.
Pw P2 32P3 64. In open container, CO2 formed in the reaction,
Pz = 2 (P1 + P2) $ Now, P2 = 4 ]P1 + P2g2 CaCO3(s) + Heat CaO(s) + CO2(g) , passes into
atmosphere and equilibrium continues to shift in
P2 32P3 4P3
2 ]P1 + P2g 8 ]P1 + P2g ]P1 + P2g3
` = 3 = forward direction leading the reaction to completion.
65. On increasing pressure, the equilibrium will shift in
Now, (P1 + P2)3 = 9P3 the backward direction, so to get equilibrium again
P 4 temperature must be increased hence melting point
` Pw = 9
z will get increased.
52. Second equilibrium will not be affected by CO2
66. Since the slope of the straight line graph between
addition only first will shift backward. 1
logK and T is positive, 9H reaction would be negative,
53. Since ­- in temperature results in shifting of equilibria i.e., the forward reaction would be exothermic.
in forward direction hence reaction is endothermic
in nature. Endothermic reaction is driven in forward 67. As the no. of particles that each molecule dissociates
D D
direction upon increase in temperature. into increases, the value of d increases as d = 1
+ (n - 1) \ .
54. R.H. > 1 & PH O > V.P.
2

Rxn l :- n = 2 Rxn ll :- n = 3 Rxn lll:- n = 7

& Q>K & left ward shift

R.H. < 1 & PH O < V.P.
2

& Q<K & right ward shift
Chemistry
68. N2O4 2NO2 71. (A) Dng is +ve so as P is increased, backward shifting
1-a 2a will take place. Total pressure even after shifting
D will remain same.
d = 1 + (n - 1) \ (B) Dng is –ve so as V is increased, backward shifting

46
⇒ 69/2 = 1 + a
4
⇒ 3 = 1+a will take place. But Pfinal < Pinitial.
(C) No change but Pfinal < Pinitial as volume has
1

⇒ a= 3 increased.
1
4# 9 (D) Forward shifting will take place and Pfinal < Pinitial.
4a 2 & =
KP =
.P K P
1 #2 = 1
1 - a2 1- 9 72. If reaction is multiplied by a number, the equillibrium
constant is raised to the power the same numbers.
M NH
69. M = 1 + (n - 1) a
3

73. P : Dng = 0 so independent of pressure

mix

17
⇒ 34/3 = 1 + a & a = 0.5 Exothermic so high temperature
Q : Dng = (–)ve High pressure
3a

\ moles of H2 in the mix = 2 # 2 = 1.5 Exothermic so Low Temperature
R : Dng =(+)ve so low pressure
70. (A) 9 ng = 2 – 4 = – 2 and K P = K C ^RTh9n g

Exothermic so Low Temperature

(B) 9 ng = 2– 1 = 1 and K P = K C (RT) 9n g

(C) 9 ng = 2– 1 = 1 and K P = K C (RT) 9n g

(D) KP is not defined.

1. N2O4 2NO2 4.
1 
1  0.5 2 × 0.5
0.5 1 1 At equilibrium:

X N O = 1.5 = 3 ⇒ PN O = 3 atm
2 4 2 4

X A = b 1 + a/2 l ⇒ PA = b 1 + a/2 l P
1-a 1-a

2
X NO = 3 2
2
⇒ PNO = 3 atm 2

]2/3g2 4 X B = b 1 + a/2 l ⇒ PB = b 1 + a/2 l P

a a

\ KP = ] g = 3

1/3
X C = b 1 + a/2 l ⇒ PC = b 1 + a/2 l P
a/2 a/2

DG = -RTlnKp
0
1
= -8.31 × 300 × ln(1.33) = -710.45 J/mol PC 2 ×PB
\ K= PA
= -710 J/mol. 3 1
a 2 ×P 2
2. N2O4(g) @ 2NO2(g) ; D ng = 2 - 1 = 1 K=
]2 + ag2 ]1 - ag
1

Now, KP = KC . (RT)Dng 5. A → 6 moles

or, 600.1 = 20.4 × (0.0831 × T)1 B → 11

\ T = 353.99 K = 354 K 5B? 11
Keq = 5 ? = 6 . 2
A
5B?5C?
3. Cl2 @ 2Cl
Let mol of both of Cl2 and Cl is x 6. A ? B + C K]eq1g = 5A? .....(1)

x 1 ]2g 5P?
B 5C?
PCl = 2x ×1 = 2
B+C?P K eq = 5 ? .....(2)
1
For
5P?
x
PCl = 2x ×1 = 2
K eq = 5 ?
2

A?P
b1 l
2 A
2 1
Multiplying equation (1) & (2)
K P = 1 = 2 = 0.5 & 5×10 -1 5P?
K]eq1g # K]eq2g = 5 ? = K eq

2 A
 Chemical Equilibrium
5AB?2 10. A + B C + D
7. K1 = 6 @6 @ ...(i)
A2 B2
t=0 1 1 1 1
6A2@3 6B2@3

teq 1–x 1–x 1+x 1+x
5AB?6
K2 = ...(ii)
(1 + x) 2
1+x
K2 = 3
1
& = 100 & 1 - x = 10
K1 (1 - x) 2

& 1 + x = 10 - 10x & 11x = 9
K2 = K1-3
9
8. Kp = Kc(RT)Dng
& [D] = 1 + 11
(i) For, N2(g) + O2(g) 2NO(g)
& [D] = 1.818
Dng = 2 – 2 = 0 11.
9G = 9G o + RT In Q
Kp = Kc ∴ Kp/Kc = 1 = 2494.2 + 8.314 # 300 ln 4
(ii) For, N2O4(g) 2NO2(g)
\ DG is Positive
Dng = 2 – 1 = 1
Since, DG is positive so, Q > K, so reaction moves
Kp in backward direction.
K = (RT)1 = 24.62 dm3 atm mol–1
c
12. K P = K C (RT) 9n g

(iii) For N2(g) + 3H2(g) 2NH3(g)

1
Dng = 2 – 4 = –2 9n g =- 2
Kp 1 1 13. CO 2 (g) + C (s) ? 2CO (g)
K c = (RT) = ]RTg2 = ]24.62g2
−2

0.5 atm
= 1.65 × 10–3 dm–6 atm–2 mol2

0.5 - P 2P
9. ln ]Kg = R - R & T 0
3 S° 3 H° 1
Total pressure = 0.5 - P + 2P = 0.8
Exothermic 3 H < 0 P = 0.3
-3 H° 2
PCO (2P) 2 (0.6) 2
slope = R > 0 K P =
PCO = =
(0.5 - P) (0.5 - 0.3)
2

3 S°
y-intercept = R can be (+)ve & (-)ve
K P = 1.8
14. PV = nRT
V = 1 dm3 = 10–3 m3
P = 3170 Pa
R = 8.314 J K–1 mol–1
T = 300 K
3170 × 10–3 = n × 8.314 × 300
3170 # 10 -3
n = 8.314 # 300 = 1.27 # 10 -3

1. DGo is not necessarily zero at equilibrium, it is DG 3. At equilibrium, DG = 0

that is zero. Hence statement 1 is false. From criteria i.e. / Gproducts = / Greactants
of spontaneity statement 2 is true.

\ Option (b) is correct.
2. DGo298 = DHo298 - T D So298
4. For a reaction in which Dng ! 0, changing the pressure

\ DGo298 = - 54070 - 298 × 10 or volume changes the degree of dissociation \ . The
= - 54070 J/ mol. equilibrium constant K depends only on temperature
for a given reaction.
Also, DGo = - 2.303 RT log K
- 57050 5. Same logic as above question. Dng > 0. So on
\ log K = 5705 = - 10
increasing pressure degree of dissociation decreases
\ log K = 10. but KP remains constant.
Chemistry
6. As temperature increases concentration of product 7. We have learnt in Thermodynamics that DH of a
decreases reaction depends on the temperature at which the
so reaction is exothermic ⇒ ΔH° < 0 reaction is taking place.
ln K T Equilibrium constant K is dependent on only T and
ln K > 1 ⇒ lnKT1 > lnKT2
1
so, KT1 > KT2 hence statement (b) is true but statement (c) is not.
T 2

ln K T T
A catalyst does not change the DH of the reaction.
Also, ln K > T2 1

T 1 2

or T1 lnKT1>T2 lnKT2⇒-R T1 lnKT1<-R T2 lnKT2 8. Fe2+(aq) + S2-(aq)  FeS(s) Kc=1.6×1017

or 3 G oT < 3 G oT
1 2
Initial 0.06 M 0.2 M
or DHo - T1DSo < DHo - T2DSo After mixing 0.03 M 0.1M
As 3 G oT < 3 G oT , since as temperature increases
1 2 final ? 0.07M
DG increases this is possible only when DS < 0
o

1
or
6Fe2+@ # 0.07
1.6 # 1017 =

10 -17 10 -15
[Fe2+] = 1.6 # 0.07 = 11.2 = 8.928 # 10 -17
⇒ 8.93 × 10-17 = Y × 10-17
\ Y = 8.93
 Ionic Equilibrium

Chapter 9 Ionic Equilibrium

INTEXT EXERCISE: 1
1. Those substance accept the proton are called
Bronsted base and which is donate the proton are
called Bronsted acid. HCO3- can do both.
2. NH-2 NH2- + H+
Conjugate acid, base pair.
3. CH3COOH+HF CH3COOH+2 +F-. HF gives H+
to the CH3COOH. So it is a conjugate base of HF is F-
4. HF is a stronger acid than HNO3. Thus, when liquid
HNO3 is dissolved in HF acts as the acid and HNO3
acts as the base.
INTEXT EXERCISE: 2
1. Due to common ion effect.
2. 10-3 N KOH will give [OH-] = 10-3 M
pOH = 3
a pH + pOH = 14, pH = 14 - 3 = 11
3. Kw increases with increase in temperature.
4. Common ion effect is noticed only for weak
electrolyte dissociation. H2SO4 is strong electrolyte.
5. H2SO4 H++ HSO-4.
6. HClO 4 > H 2 SO 4 > HCl > HNO3 :- Factual
Acidic character decreases
7. The conjugate base of a substance has one than the
substance.
8. I- donates e- pair, hence it is Lewis base.
9. The conjugate base of weak acid is a strong base.
10. On increasing oxidation number of central atom
Acidic strength increases.
6. [H+] = 10-3 M, pH = - log [10-3], pH = 3
7. NaOH is a base, so that its pH > 7, but since very
dilute so pH . 7.
8. pH = 4 means; [H+] = 10-4 mol
9. NaOH is a strong base and NH3 is a weak base.
1 M NaOH has maximum OH- and minimum H+
and maximum pH.

5. 0.001 M of NH4OH means [OH-] < 0.001 as NH4OH 10. [OH­-] = 10-2 M; pOH = 2
is weak electrolyte.
pH + pOH = 14; pH = 14 - pOH

\ pOH > 3 ⇒ pH < 11
pH = 14 - 2 = 12
INTEXT EXERCISE: 3
1. pH of the solution A = 3 5. On mixing equal volumes concentration are halved.
[H+] A = 10-3 M.
\ c1 = c2 = 0.2 M and K a = 4×10 -7, K a = 5×10 -8
1 2

pH of the solution B = 2 \ [H+]mix =

-7
4×10 ×0.2 + 5×10 ×0.2 -8

[H+] B = 10-2 M. = 1.8×10 -7 = 18 ×10 -4

When equal volumes of both are mixed: 6. [OH-]total = 0.1 + 2 × 0.05 = 0.2
10 -3 V + 10 -2 V 11 \ pOH = 1 - log 2
[H+]mix = 2V = 2 ×10 -3 M
\ pH = 14 - (1 - log 2) = 13.3
= 5.5 × 10-3M = 55 × 10-4 M
7. For mixture of SB + WB, [OH-] from WB is
pH = 4 - log 55 = 4 - 1.74 ⇒ pH = 2.26.
negligible.
2. Less the pH, more acidic is the solution. \ [OH-] = 0.01 ⇒ pOH = 2
3. [H+] = K a c . Thus for same value of c, greater the 8. Since K a >> K a , therefore it can be treated as a
1 2

value of Ka, greater is [H+] and hence lower is the pH. weak monoprotic acid.
0.1 + 2×0.1
4. [H+]mix = = 0.3 M
Also, \ 1 =
Ka -4 -2
c = 10 = 10
1
1

\ pH = 1 - log 3 = 1 - 0.47 \ [H+] = ca1 = 10-4

= 0.53
\ pH = 4
Chemistry
9. CH3COOH CH3COO- + H+ 10. H2S 2H+ + S2-
C(1-a) Ca 0.01 [H +] 2 [S 2-] [0.1 2] [S 2-]
K = 1.1 × 10-21 = =
0.1 6CH3 COO -@ [H 2 S] 0.1
0.05 ]1 - ag

\ Ka = ; if a << 1
\ S2-= 1.1 × 10-20 × 6.02 × 1023 ions


\ [CH3COO-] = 5 Ka = 5 × 2 × 10-5 = 10-4 M = 6.62 × 103 ions.
INTEXT EXERCISE: 4
1. NH4Cl is hydrolyzed and give [H+] as the cation 7. Fe3+ ions are hydrolysed to form an acidic solution.
comes from a weak base. Kw
8. K h = K ×K for salt of WA + WB.
2. Because it is a salt of strong acid and strong base. a b

9. KCN is salt of strong base and weak acid and will

3. pH of 9 means the salt solution should be fairly basic undergo anionic hydrolysis giving a basic solution.
i.e. salt of a weak acid and strong base.
10. For the salt of a WA + WB
4. If we mix any salt into the solution, then the value of h
pH is increased if it is a salt of weak acid and strong 1 - h = K h and here n = 0.25%
base.
\ Kh = c
2.5×10 -3 m2

5. Salt of a weak acid and strong base will undergo 1 - 2.5×10 -3
anionic hydrolysis and produce a basic solution. 6.25×10 -6
]0.9975g2
=
6. For hydrolysis either the cation or the anion should
be coming from a weak component. In CH3COOK,
\ K h . 6.25 ×10 -6
the anion gets hydrolysed.
INTEXT EXERCISE: 5
1. Ka = 10-5; pH = 6 [Salt]
5. pH = pKa + log [Acid]
[Salt]
pH = - log Ka + log [Acid] ; [1]
pH = - log (1.8 × 10-5) + log [2]
[Salt] = 5 - log 1.8 - log 2
6 = - log 10-5 + log [Acid]

\ pH = 5 - 0.26 - 0.3 = 4.44 . 4.5
[Salt] [Salt]
6 = 5 + log [Acid] ; 6 = 5 + log [Acid] 6. The pH of buffer solution remains almost constant.
[Salt] [Salt] 10 1
log [Acid] = 6 - 5 = 1 ; [Acid] = 1 7. pH = - 2 [log Ka + log Kw - log Kb]
2. It is a buffer solution of stronger acid and its
1 1
= - 2 [- 5 - 14 + 5] = - 2 (-14) = 7
conjugate base, as HCOOH is stronger acid than
[salt]
CH3COOH 8. pOH = pKb + log [base]
3. Buffer is formed by a weak acid and its salt with a
0.02 1
= 5 + log 0.2 = 5 + log 10 = 5 + (-1) = 4
strong base. HCl is not a weak acid, hence solution
of HCl and NaCl will be acidic. pH = 14 - pOH = 14 - 4 = 10
[Salt] 9. pH of a buffer solution does not change significantly
4. pH = pKa + log [Acid]
on adding small amount of acid or base.
= 9.30 + log : 0.1 D = 9.30 + 0.3010 = 9.6.
0.2 10. Buffer solutions have constant pH. When we add the
water into this buffer solutions pH is unchanged. So
no effect on it.
INTEXT EXERCISE: 6
1. Solution become acidic and methyl orange act on 3. For the saturated solution of a salt, Ionic Product =
acidic pH. Solubility Product.

2. Ksp = 4 s3, s3 =
4×10 -9
= 10-9 4. Ksp = 4 s3
4 3 Ksp 3 1.0 ×10 -6

\ s = 10-3 M. s= = 6.3 × 10-3.
4 = 4
 Ionic Equilibrium
5. AB is a binary electrolyte. 9. CuS : s= 8×10 -37

s = Ksp = 1.21×10 -6 = 1.1 × 10-3 M MnS : s= 7×10 -16

s = b 10 l
6. CaCO3 ? Ca ++ + CO3- - -70 1
5

s s s Bi2S3 : 108
Solubility product of CaCO3
s = b 6×10 l
-51 1
3

Ksp = s 2; s= Ksp Ag2S : 4

It is a binary electrolyte.
MnS will have the highest value of ‘s’. Thus, it is the
most soluble among the given salts.
s2 = Ksp ; (3.05 × 10-4)2 = Ksp ; Ksp = 9.3 × 10-8
10. For Ag2SO4 → 2Ag + + SO 24-
7. Ca(OH) 2 Ca ++ + 2OH -2 2x x
s (2 s)
Ksp = (2x)2 . x ; Ksp = 4 x3 ; Ksp = 4 × (2.5 × 10-2)3
Ksp = 4 s3 = 4 × 3× 3× 3 = 12 3
Ksp = 62.5 × 10-6
8. Ksp = s2 = 10-8 ⇒ s = 10-4 mol/L
Given, M.W. = 100 g/mol

\ s in g/L = 100 × 10-2 = 10-2 g/L
INTEXT EXERCISE: 7
1. AgCl ? Ag + + Cl -
\ s = 5 × 10-10 M
a a a
6. When ionic product is greater than then precipitation

NaCl ? Na + Cl - +
0.02 0.02 0.02 occur Ksp < 10-2 M Ca­2+ + 10-3 M F-
Ksp (AgCl) = [Ag+][Cl-] = a × [a + 0.2] = a2 + 0.2 a 7. Addition of NH4OH causes reaction with H+ which
a2 is a very small so it is a neglected. drives the reaction H2S 2H+ + S2- forward.
2-
Hence, [S ] increases.
Ksp AgCl = 0.2 a
Ksp AB 1×10 -8
1.20 × 10-10 = 0.2 a 8. [B -] = = = 1 × 10-5 M
[A +] 10 -3
1.20×10 -10 Where ionic product > Ksp, ppt formed
a = 0.20 = 6 × 10-10

\ [B-] should be more then 10-5 M.
2. 0.01 M CaCl2 gives maximum common ion
concentration. In order to keep Ksp of AgCl constant, 9. For Al3+ :- [OH-] = 3
8.5×10 -22
decrease in [Ag+] will be maximum. For Zn2+ :- [OH-] = 18×10 -14
3. Due to the common ion effect. a [OH-] needed for Al3+ precipitation is less,

4. Ksp of BaSO4 = 1.5 × 10-9 ; Ba2+ = 0.015 M
\ It forms ppt.
1.5×10 -9 10. AgCl " Ag + + Cl -
SO 24- = 0.015 = 10-7 x
x

5. CaCl2 —→ Ca2+ + 2Cl- ⇒ [Cl-] = 0.8 M After NaCl is added AgCl will precipitate out.

\ s (0.8) = 4 × 10-10 That is why Ag+ will decrease.

EXERCISE - 1

1. The molecule shows three H atoms are replaceable, 5. Conjugate acid base pair are differ by an proton
i.e., basicity of acid. (H+).
-H +
2. H3O+ can give proton.
H2 F+ HF
3. H3BO3 is weak, Lewis monobasic acid and shows 6. 1 M H2SO4 produces maximum number of ions as it
the given equilibrium. is a strong electrolyte.

H3 BO3 + H 2 O ? B (OH) -4 + H + 7. NH3.H2O is a weak monoacidic base.
4. NH + H ? NH3
-
2
+
8. I- can accept protons and hence is a Bronsted base.
Chemistry
9. In the forward reaction PO3- +
4 accepts H and in the concentration, theoretically pH should further
2- +
backward reaction C2O4 accepts H . decrease and become negative. However, the
maximum value of activity is 1 and for highly
10. N3H N3- + H+
concentrated solutions [H+] ! aH.
11. pKW = - logKW = - log 1 × 10-12 = 12
25. [H +] = ca = 0.1 # 0.013 = 1.3 # 10 -3
KW = [H+][OH-] = 10-12
\ pH =- log (1.3 # 10 -3) = 3 - 0.11 = 2.89
[H+] = [OH-]
⇒ [H+]2 = 10-12 ; [H+] = 10-6; pH = - log[H+]
c Ka m
26. Relative strengths of weak acids = 1

Ka 2

= - log 10-6 = 6 Assume c1 and c2 are same (Although not given).

\ Relative strength = c K a m = c
H2O is neutral because [H+] = [OH-] K 1.8 # 10 -4 m
1

1.8 # 10 -5
at 373 K even when pH = 6
a 2

Relative strength for HCOOH to CH3COOH
(d) is not correct at 373 K, water is acidic
= 10 :1
if pH < 6.
27. HA ? H + + A -, [H +] = 10 -3 M
12. An acidic solution has [H+] > 10-7.
10 -3 # 10 -3

\ [A -] = 10 -3 M. Hence K a = 10 -5
13. [H+] = [OH-] = 10-7 only at 25oC. 0.1
14. On adding H2SO4,[H+] increases. Therefore to keep [H3 O +] [HCO3-] [HCO 3-]
28. K a = or
Kw constant, [OH-] decreases. [CO 2] [CO 2]
-7
15. 2HCOOH HCOO- + HCOOH+2
Ka 3.8 # 10

= = = 3.8 # 10 -1
[H3 O +] 10 -6
\ [HCOO-] = [HCOOH+2]

1

K = [HCOOH +2 ] [HCOO -] = 10 -3 # 10 -3 = 10 -6 29. pH = 2 (pK a - log c) & 9 = pK a + 1

16. pH = - log [H+] pK& a = 8 & K a = 10

-8

17. [OH -] = K W in pure water. 30. [H +] = ca = 0.1 # 0.02 = 2 # 10 -3 M

So as temperature increases KW increases ⇒ [OH-] \ [OH -] = 10 -14 (2 # 10 -3) = 5 # 10 -12 M
increases ⇒ pOH decreases, also pH decreases.
10 -2 + 10 -4 0.01010
31. [H +] = = = 0.00505 M
18. NaCl solution is neutral. Its pH = 7. 2 2
\ pH = 3 - log 5.05 . 2.3
19. On heating H2O, [H+] and [OH-] both increase and
remain equal. As [OH-] increases, pOH decreases. (Taking log 5.05 . log 5 . 0.7)
2
20. When pH = 2 , [H+] = 10-2 M. 32. Initial & [OH -] = 200 = 10 -2 M ` pH = 12
21. As concentration of solution decreases, degree of 0.04
Final & [OH -] = 10 -2 + 40 # 0.1 = 2 # 10 -2
dissociation of weak electrolyte increases.
\ pH = 12.3
22. [H+] = ca = 0.2 × 0.40 = 0.08 M
So, change = 12.3 - 12 = + 0.3
23. H2O H+ + OH- 33. CH3 COOH (aq) ? H + (aq) + CH3 COO - (aq)
x1 x1+ x2

BOH B+ + OH- t = 0 0.01

x2 x1+ x2
t = eq 0.1 - x x x

x1 (x1 + x2) = 10-14 [H ] = x + 0.1 . 0.01 M
+

x 2 (x1 + x 2) [H +] [CH3 COO -]

-2 = 10-12 ⇒ x2 (x1 + x2) = 10-14
\ K a = [CH COOH]
10 3
x1
x 2 = 1 ⇒ x1 = x2
0.01 # [CH3 COO -]

⇒ 1.69 # 10 -5 = 0.01

x1 (x1+x1) = 10-14
\ [CH3 COO -] = 1.69 # 10 -5 M
1 # -7
So, degree of dissociation of CH3COOH

2x12 = 10 -14 & x1 = 10
2
1.69 # 10 -5

[OH -] = 2x1 = 2 # 10 -7
= 0.01 = 1.69 # 10 -3
24. 1 M HCl = 10 M HCl and pH = 0. For greater
 Ionic Equilibrium
34. Initial ⇒ [OH-] = -5
6.4 # 10 # 0.01 = 8 # 10 -4 43. NaOH : strongly basic
CH3COONa : weakly basic due to anionic hydrolysis

\ pH = 10.9
CH3COONH4 : salt of a weak acid weak base
10 -2
Final ⇒ [OH-] = 2 ` pH = 11.7 ; has pH = 7
CH3COOH : weak acid.
So, change = + 0.8
10 -2 44. Degree of hydrolysis of a salt of WA + WB is
+
[OH -] [C6 NH16
+
] 2 [C6 NH16] independent of concentration.
35. K b = &
[C6 NH15] 10 -2 h Kw
2 1 - h = Ka K b
[C +
& 6 NH16 ] = Kb 45. pH of final solution would also depend on the
concentrations of the acid and base mixed.
36. H2SO4 H+ + HSO-4 K a = 10 -2
46. h = 0.03 C = 0.1 M
1

HSO-4 H+ + SO2-
4 K a = 10
-6
2
Kh = Ch2 = 9 × 10–5
Since K a >> K a therefore H+ comes from first
K 10 -14
1 2 Kh = KW = 9 × 10–5 ⇒ Ka =
step only and the anion produced in 2nd step has a 9 # 10 -5
–10
= 1.11 × 10 . 1 × 10 –10
concentration = K a 2

\ 6SO @ = 10 M
2-
4
-6 47. (a) HCl NaOH
1 1
37. H2S 2H+ + S2- No. of mili eq. = 10 × 100 = 10 10 ×100=10
So solution is Neutral
[H +] 2 [S 2-] [0.1 2] [S 2-]

K = 1.1 # 10 -21 = [H 2 S] = 1 1
0.1 (b) 10 × 55 = 5.5 10 × 45 = 4.5

or [S 2-] = 1.1 # 10 -20 1
[H+] = 100 = 10–2 M, pH = 2
1.1
= # 10 -20 # 6.02 # 10 23 ions 1 1

(c) 10 × 10 = 1 10 × 90 = 9 Basic
6.62
= # 10 ions. 3
1 1

(d) 5 × 75 = 15 5 × 25 = 5
38. For all weak polyprotic acid, K a > K a > K a ..........
1 2 3

[H+] = 0.1 M, pH = 1
39. It is factual
48. Ka . Kb = Kw (Valid only for conjugate acid-base
40. H 2 A ? H + + HA -
pair, not for any weak acid and weak base).
As pH = 4, [H+] = 10-4 M

49. pH > 8 at the equivalence point means that the salt
[H +] [HA -] 10 -4 # [HA -] formed on hydrolysis should give basic solution i,e.

K a = [H A] or = 4.45 # 10 -7
1
2 10 -2 when acetic aced reacts with NaOH.

or [HA-] = 4.45 × 10-5
50. Ka = Ka of HF & Kb = Kb of F–.
41. H3 PO 4 ? H 2 PO -
4 + H+ Ka . Kb = Kw (since HF and F– are conjugate acid-


0.1 - x x x base pair)
51. It is definition of Levelling effect.
2
x
K a = 0.1 - x = 10 -3 . Solving quadratic :
1

52. Factual : Property of buffers.

x = 0.01 = [H +] = [H 2 PO -4 ] ⇒ pH = 2
and [HPO 24-] = 10 -7 M 53. Weak base should be in excess.

[H +] [PO34-] (0.01) [PO34-] 54. pKb (X-) = 4 pKa (HX) = 14 - 4 = 10

K a = & 10 -12 = 6X -@
3 2-
[HPO 4 ] 10 -7 0.1
\ pH = pKa + log HX ⇒ pH = 10 + log 0.2
[PO34-] = 10 -17 M \ pH = 10 - log 2.
[H3PO4] = 0.1 - x = 0.09 M
55. HC2 H3O2 + NaOH → C2 H3O2Na + H2O
42. NH4Cl undergoes cationic hydrolysis giving an nl 1 0.5 0 0
acidic solution as it is a sat of strong acid and weak nf 0.5 0 0.5 0.5
base.
This solution contains weak acid & its salt with
strong base and thus acts as buffer.
Chemistry
56. pH of buffer remains almost constant. 67. Ag2SO4 2Ag+ + SO2–
4

57. Blood is a buffer and hence pH will not change

2s s
significantly.
Here [Ag+] =2s=3× 10–4 M ⇒ s = 1.5×10–4 M
[Salt] \ Ksp = 4s3 = 4(1.5 × 10–2)3 = 1.35 × 10–5

58. pOH = – log Kb + log [Base]
68. Pb Cl 2 " Pb 2+ + 2Cl - ,

Let a mol litre–1
be concentration of salt, then s s 2s
concentration of base = (0.29 – a) mol/L Ksp = s . (2s)2
a 69. Solubility of BaSO4 =
4.4 = – log 1.8 × 10–5 + log (0.29 - a)
Ksp = 10 -10 = 1 # 10 -5 M

\ a = 0.09. \ wt. of BaSO4 = 1 × 10–5 × 233 = 233 × 10–5 g/

[Salt] = 0.09 M litre

& [Base] = 0.29 – 0.09 = 0.20 M.
\ Volume of water needed to dissolve 1 g BaSO4
1
is equal to . 430 litres.
59. Ka = 5 × 10–10 pKa = 10 log 5 = 9.3 233 # 10 -5

pH = pKb + log ; HCNCN E -

70. M 2 X " 2M + + X 2
s1 2s1 s1

Ksp = 4s or s1 = (Ksp /4) 1/3
3

9 = 9.3 + log ; 10 # 2ml E ⇒ – 0.3 = log : 4ml D

5#V V 1

MX → M+ + X– , Ksp = s 22
or s2 = (Ksp)1/2
0.3 = log : V D
MX3 " M3+ + 3X - ,
4 4
⇒ V = 2 ⇒Vml = 2 ml s3 3s 3
ml ml

Ksp = 27 s or 4
s3 = (Ksp/27)1/4
60. Find solubility for each separately by s2 = Ksp for
3

MnS and ZnS, 108s5 = Ksp for Bi2S3 and 4s3 = Ksp
Evidently, s3 > s1 > s2 as Ksp < < 1.
for Ag2S. 71. For different salts such as AB, AB2 , AB3, ..........
61. A2X3 2A3+ + 3X2– etc. Ksp = s2, 4s3, 27s4............ respectively. If Ksp is
same for different salts, then s is more for the salt in

2y 3y which produces more number of ions, because the

Ksp = (2y)2 (3y)3 value of Ksp is less than 1.
Ksp = 108y5
72. NaBrO3 gives BrO3- ions. Hence [BrO3-] increases.
62. HgSO4 Hg2+ + SO42– Solubility of AgBrO3 decreases due to common ion
effect.
Ksp = s2
73. Solubility of silver halides decreases down the
⇒ 6.4 × 10–5 =s2
group. Thus AgI is precipitated first and AgCl last.
⇒ s = 8 × 10–3 mole/L

74. Ksp = 1.8 × 10–10
s=8× 10–3 × 103 mole/m3 Precipitation of AgCl will occur only where :
⇒ s = 8 mole/m3
IP (AgCl) > Ksp
63. (a) Li3Na3[AlF6]2 3Li+ + 3Na+ + 2[AlF6]3–
Note that on mixing equal volumes, conc. will be
halved.

3s 3s 2s
10 -4 10 -4
Ksp = (3s)3 (3s)3 (2s)2 = 2916 s8.
IP = 2 × 2 = 2.5 × 10–9

64. s = 2.33 × 10–3g L–1 = 2.33 × 10–3 / 233 = 10–5M,
IP > Ksp ⇒ precipitate is formed.

Ksp = 10–10.
75. [Ag+] required to precipitate Cl- ions
Ksp 10 -10
65. Ksp = 4 × 10–12 = [M+] [OH–]x = [10–4] [x.10–4]x = + = 0.05 = 2.0 # 10
-9
[Ag ]

= xx. (10–4)1+x [Ag+] required to precipitate I- ions

\ x = 2. 4 # 10 -16
= 0.05 = 8.0 # 10 -15
66. Total [I–] = 10–4 + 10–16 = 10–4 M

\ When AgCl starts to precipitate the solution is
[Ag+] [I–] = Ksp
\ [Ag+] [10–4] = 1.0 × 10–16 saturated wrt both AgI and AgCl
or [Ag+] = 10–12.

For AgI : 2×10-9 [I-] = 4×10-16 ⇒ [I­-] = 2×10-7 M
 Ionic Equilibrium
76. Ksp (BaCrO4) = 2.4 × 10–10 M2 79. Mg(OH)2 Mg2+ + 2OH-, Ksp = [Mg2+][OH-]2
[CrO4–2]
= 6 × 10–4 M or 1.2 × 10-11 = 0.1 × [OH-]2 or [OH-]2 = 1.2 ×10-10

Ksp (BaCrO4) or [OH-] = 1.1 ×10-5 or [H+] = 10-14 / (1.1 × 10-5)
= [Ba+2] [CrO4–2] = 2.4 × 10–10 = 9.09 × 10-10 M
⇒ [Ba+] × 6 × 10–4 = 2.4 × 10–10

or pH = -log (9.09 × 10-10) = 10 - 0.9586 = 9.04.
[Ba+2] = 4 × 10–7 M
80. (a) NaF ——→ Na+ + F–
0.1 0.1 0.1
77. In (b), after mixing, [Ca2+] [F-]2 > Ksp,
CaF2 ——→ Ca2+ + 2F–
78. Let Ksp of AgCl = x
x (2x+0.1) . 0.1

(a) solubility of AgCl in pure water = s1 = x Ksp = x (0.1)2 = 5.3 × 10–9
x

(b) solubility of AgCl in 0.01 M CaCl2 = s2 = 0.02 So, x = 5.3 × 10–7 M.
x

(c) solubility of AgCl in 0.01 M NaCl = s3 = 0.01 81. Let S is the solubility of BaF2 in a solution of
x Ba(NO3)2 (x M).

(d) solubility of AgCl in 0.05 M AgNO3 = s4 = 0.05

s1 will be maximum as common ion effect will BaF2 Ba2+ + 2F–
decrease solubility in remaining cases. S + x 2S

So, s1 > s3 > s2 > s4 1
Then, S = 2 [F–].

EXERCISE - 2

1. Factual. 6. Ka = 10-6 for HA + H2O H3O+ + A-

10 -6
Thus K for reverse reaction is
1
2. New concentration of HCl = 100 = 10-8 M 10 -6
= 106
[H+] = 10-7 + 10-8 (approximately) 7. As concentration of solution decreases, degree of

(Little less than 10-7 from water). dissociation of weak electrolyte increases: Ostwalds
dilution law.
3. Given density of formic acid = 1.15 g/cm3
8. BOH B+ + OH-

\ Weight of formic acid in 1 litre solution

t=0 10-4 0 0
= 1.15 × 103 g

t = eq 10-4 (1-a) 10-4a 10-4a
1.15 # 103
Thus, [HCOOH] = = 25 M
46 [B +] [OH -] 10 -4 a $ 10 -4 a

Kb = [BOH] = 10 -4 (1 - a) .....(1)
Since in case of auto ionisation
[HCOOH2+] = [HCOO–] and Expecting a < < 1, 10-4 = 10-4 a2

[HCOO–] [HCOOH2+] = 10–6
\ a = 1 (not negligible)
⇒ [HCOO–] = 10–3 So, solve quadratic (1) :
Now % dissociation of HCOOH 10 -4 a10 -4 a
10 -4 = -4 & a2 + a - 1 = 0
[HCOO -] # 100 10 -3 10 (1 - a)
= [HCOOH] = 25 # 100 = 0.004%.
-1 ! 1 + 4 5 -1

a= &a= . 0.62
10 -2 # 10 + 10 -4 # 990 2 2
4. [H+] after mixing = 1000
\ [OH -] = Ca = 10 -4 # 0.62 = 6.2 # 10 -5 M
0.1 + 0.0990 0.1990
= 1000 = 1000 = 1.99 # 10 -4
\ pOH = 4.21
\ pH = 4 - 0.3 = 3.7
\ pH = 9.79
5. (A) At 25ºC, [H+] in a solution of 10–8 M HCl > 2.4 # 10 -2 a 2
9. 2 # 10 -3 = 1-a & 12a 2 + a - 1 = 0
10–7M
(B) [H+] = 10–8 M
⇒ a = 0.25

(C) [OH–] = 4 × 10–6 M⇒ [H+] = 2.5 × 10–9 M 10. As V → ∞, solution becomes almost neutral so pH
become 7.
(D) [OH-] = 10–8 + 10–7 (from water)
Chemistry
0.25 pK a + pK a 7.2 + 12
11. [OH-]= Kb c + Kb c × 6.4 × 10-5 + 19. For Na2HPO4 , pH = =
2 3
1 1 2
5 2
2 2
4b 1 l = 9.6.
5 18 ×1.8 × 10
-5

= 2 × 10-3 M 20. Lesser the pH of solution of sodium salts, less is the

hydrolysis of anion, stronger is the acid.
2 # 10 -3 [C6 NH16
+
]
Now, 6.4 # 10 -5 = 0.25 21. CH3COOH + OH– —→ CH3COO– + H2O
5
t = 0 20 20
[C +
& 6 NH16] = 1.6 # 10 M -3

t = eq – – 20
2 # 10 -3 [NH +4 ]
and 1.8 # 10 -5 =
4b 1 l So,
20
[CH3COO–] = 200 = 0.1 M
5 18
[NH 1 1 1
& +
4 ] = 4 # 10
-4
M pH = 7 + 2 pKa + 2 log C = 7 + 2.37 + 2 log 10–1
12. HA H+ + A– = 7 + 2.37 – 0.5 = 8.87
1–x x x
x = 1% = 0.01 22. CrO42– + H2O HCrO4– + OH–
⇒ [H+] K
Kh = KW = 2 × 10–8 and Kh = Ch2 = 2 × 10–8
⇒ pH = 2 a

2 # 10 -8
[H +] [OCN -] ⇒ h2 =
0.005 \ h = 2 × 10–3
13. For HOCN-, Ka = [HOCN] ;
Here [H+] = total H+ concentration of solution. \ [OH–] = Ch = 0.005 × 2 × 10–3 = 10–5 M

0.02
\ pOH = 5 & pH = 9
14. [OH -] = 2 = 0.01 M ` pH = 12
23. Solution of HCl & NH4Cl will be acidic, solution
0.01 [BH +]

10 -7 = & [BH +] = 10 -6 M of NaCl neutral whereas solution of NaCN will be
0.1
basic.
(0.01) [BH 22+]

10 -14 = 24. CH3COOH is a weak acid 20 pH < 7 and CH3COONa
10 -6
[BH
& 2+
2 ] = 10
-18
M is a basic salt so pH > 7

15. [H +] = K a # C = 3 # 10 -4 # 3 # 10 -2 25. Salt of weak acid & weak base

1
1
pH = 7 + 2 (pKa - pKb)
3
= # 10 -3 M = [A-]
3×10 -3 6B -@
1
= 7 + 2 (4.8 – 4.78)

For HB : 10-10 = 0.1

1
\ [B ] = 3 × 10 = 3.33 × 10-9 M
- -8
\ pH = 7.01

26. (A) K h << K h

16. [OH -] = b0.1 # 6.4 + 4 # 1.8 l # 10 -5
2 1

45 K
(B) K h = KW
0.002
1
= M ` pH = 11.3 b 2

KW
17. CH3COOH (aq) H+ (aq) + CH3COO– (aq) (D) K h = K2
b 1

t = 0 0.01
27. Factual.
t = eq 0.01 – x x x
Kw
[H+] = x + 0.01 . 0.01 M 28. h = K b c for salt of SA + WB
0.01 6CH3 COO -@
\ h increases as c decreases.
\ Ka = 1.69 × 10–5 =
0.01
\ [CH3COO–] = 1.69 × 10–5 M
29. All salts given are examples of salt of WA +
So, degree of dissociation of CH3COOH = 0.01 a WB. Therefore, pH of solution is independent of
concentration.
= 1.69 × 10–5 ⇒ a = 1.69 × 10-3
30. All solutions have equal number of mmoles of
18. Initial pH = (pKb–log C) = (5–log 2–log 0.1)= 2.85
NH4Cl and Nh4OH remaining after the reaction.
After adding NaOH, pOH of solution = 1
Therefore, pH of all solutions are equal.
Change in pOH = 1.85, final [OH-] = 0.1 M
 Ionic Equilibrium
31. For the buffer solution of NH3 & NH4+ 38. pKHIn = 5
pH = pKa + log
[NH3] (a) CH3COOH + NaOH, end point pH > 7
[NH +4 ]
(b) Aniline hydrochloride + NaOH, end point pH > 7
(500 # 0.01)
⇒ 8.26 = 9.26 + log (c) NaHCO3 + HCl, end point pH < 7
mmoles of NH +4
⇒ m. moles of NH4+ = 50 (d) Ba(OH)2 + H2C2O4 , end point pH > 7

\ moles of (NH4)2 SO4 required = 0.025. 19.6 11.2
39. [H2SO4]= 98 = 0.2 M and KOH = 56 = 0.2 M
32. pH = pKa + log HCO-3 ⇒7=7 – log 4 + log H2CO3⇒= 4
0.2 # 50 # 2

HCO - 4 4
\ H CO3 = 1 ⇒% of C in HCO3– = 5 ×100=80% So, for equivalence point, 0.2 = 100 mL
2 3 of KOH solution should added.
33. m. moles of HA taken = 27 × 0.1 = 2.7 0.2 # 2 - 0.2
[H+] = = 0.1 M
HA + OH- —→ A- + H2O 2

t=0 2.7 1.2 So, pH = 1

teq 1.5 - 1.2 40. C6H5COOH + OH- —→ C6H5COO- + H2O

t=0 2 1
pH = pKa + log [HA] ⇒ 5 = pKa + log b 1.5 l
[A -] 1.2


teq 1 - 1
= pKa + log 5
4 pH = pKa = 4.2
\ pKa = 5.1 ⇒ Ka = 8 × 10-6. C6H5COOH + OH- —→C6H5COO- + H2O
34. CH3 COONa + HCl —→ CH3COOH + NaCl
t=0 2 2

t=0 10 1.25 7.5 –
teq - - 2
2

t = eq 8.75 0 8.75 – [C6H5COOH-] = 200 = 0.01 M

pH = pKa = 4.74 1

\ pH = 7 + pKa + 2 log C
6A -@
35. pH = pKa + log 5 ? 4.2 1
HA
\ pH = 7 + 2 + 2 log (0.01) = 8.1
6A -@
⇒ 5.5 = 5 + log 5 ?
41. WA Vs SB end point > 7Phenolphthalein
HA
6A -@ 42. pH = pKa + log[In-] 6 = 5 + [HIn] 1 = [HIn] = 10
⇒ 5 ? = 3.16
HA 43. C6H5COOH + NaOH C6H5COO N + H2O
Suppose x m. mole NaOH was added 2 1.5
HA + NaOH —→ Na A + H2O 0.5 - 1.5
mmol. 10 x 10 1.5
It is a buffer with pH = pKa + log 0.5
10-x - 10 + x
10 + x \ pH = 4.2 + log 3
\ 10 - x = 3.16 ⇒ x = 5.19 mmol.
44. With phenolphthalein indicator :
5.19×40
\ mass of NaOH added = 1000 = 0.208g NaOH + HCl —→ NaCl + H2O
pK a + pK a 5+7 Na2 CO3 + HCl —→ NaHCO3 + NaCl
36. pH of NaHA = = 2 =6
1 2

2
With methyl orange indicator :
\ [H+] = 10-6 M.

NaHCO3 + HCl —→ NaCl + H2O + CO2
37. NaX + HCl —→ NaCl + HX

If moles of NaOH = Na2CO3 = NaHCO3 = a

HX H+ + X-
then moes of HCl used in both cases = 2a

0.05-x x x pK a + pK a

pH = at phenolphthalein end point
1 2

\ [H+] = K a c = 5×10 ×0.05 = 5 ×
-8
10-5 2
as solution contains only NaHCO3 which is on

\ pH = 5 - 0.7 = 4.3 ampliprotic ion.

\ pH range of indicator = 3 - 5
Chemistry
45. pKa = 5.45 pH = pKa + log 3
6In @ -

1
so difference in pH D (pH) = log 3-log 3 =2 log 3
pH = pKHIn + log 5
HIn?
⇒ pH = pKHIn = 5.45

For a Buffer solution 53. CH3COONa + HCl —→ NaCl + CH3COOH
5salt? 5salt?
t=0 20 m eq. 20 meq.

pH = pKa + log
5acid? ⇒ 5.45 = 4.75 + log 5acid?

teq. - - 20 meq.
5salt? salt

0.7 = log
5acid? ⇒ acid = 5
20
[CH3COOH]= 200 = 0.1 M
46. H3PO4 + NaOH —→ NaH2PO4
1 1
pH = 2 [pKa - log C] = 2 [5 - log 2+1]
9 5 0
4 0 5
1
= 2 [6 - log 2] = 3 - log 2
6H 2 PO -4 @
pH = pKa + log 6 = 3 + 0.1 = 3.1
H3 PO 4@ 54. Order of solubility of a sparingly soluble salt in the
given four options will be of the order
47. Salt of WA-WB formed at equivalence point has pH
independent of concentration and depends on pKa (d) > (a) > (b) > (c)
and pKb of WA and WB respectively. 55. KSP of Ca (OH)2 = 4s3 = 5.5 × 10-6
48. mmoles of H2A = 2 3 5.5 # 10 -6

\ s= 4 = 1.11 # 10 -2
mmoles of NaOH = 2

\ After reaction solution contains 2 mmol of
\ [OH-] = 2s = 2 × 1.11 × 10-2
NaHA
\ pOH = 1.65\ pH = 12.35
a It is an amphiprotic salt, 56. Ksp = 4s3 = 4 (1.26 × 10-4)3
pK a + pK a 6+9
Na2CO3 2Na+ + CO32-
pH = = 2 = 7.5
1 2

2

2 × 0.01 0.01
49. NaH2PO4 + H3PO4; NaH2PO4 + Na2HPO4 ;

Ag2CO3 2Ag+ + CO32-
Na2HPO4 + Na3PO4.

2x (x + 0.01) . 0.01
50. HA + NAOH Na A + H2O
Ksp = 4 x2 (0.01) = 8 × 10-12

20 9 9
\ x2 = 2 × 10-10

11 - 9

\ x= 2 × 10-5 M
For pH = 5 as pKa is given as 5
57. Ion produced from one salt will exert common ion
[HA] sould be = [Na A] effect on the solubility of other salt. As a result,

\ 1 mmol of NaOH is needed solubility of both salts will decrease.

\ 1 = 0.1 × V ⇒ V = 10 mL 58. AgCl Ag+ + Cl- ; AgBr Ag+ + Br-
51. An amphiprotic will be formed (C2N2H9+Cl–). x’ + y’ x’ x’ + y’ y’
52. (i) At equivalence point solution will contain HCN
(both equilibria are established simultaneously in a
and NaCl. So, the pH of solution will be less solution saturated with AgCl and AgBr)
than 7. [Ag+] = [Br-] + [Cl-]

(ii) From ostwalds dilution Law x > y ⇒ x2 > y2 ⇒ Ksp (AgCl) > Ksp (AgBr)

a = Ca & a 2 = b moles
K Ka l Now, for simultaneous equilibrium,
×Volume
Ksp (AgCl) [Cl -]
\ It is a parabola Ksp (AgBr) = [Br -] ( > 1).
(iii) At 1/4th neutralisation
Also Ag+ produced from each salt will exert common

CH3COOH + NaOH CH3COONa + H2O ion effect on the equilibrium of other.
6CH3 COO -@ 1
\ x > [Cl-] & y > [Br-].
pH = pKa + log 6 = pKa + 3
CH3 COOH@
Also, [Ag+] < x + y.
At 3/4th neutralisation
 Ionic Equilibrium
59. Ag+ + 2CN– [Ag(CN)2]– ; KC = 1018 62. The salt with least Ksp is precipitated first (in this

t=0 0.01 0.08 0 case).

t= eq x . 0.06 . 0.01 Ag+ a KC 63. Calculation of concentration of M+ required for
0.01 precipitation
60. 1018 = & x = 2.78 × 10-18­ M.
(0.06) 2 (x) (Ksp(salt) = [Anion] [M+]min. req. for salt’s pptn.)

61. AgCl —→ Ag+ + Cl- AgCNS —→ Ag+ + CNS- 10

MX : [M+]MX = 100 = 0.1 M

(x + y) x (x + y) y 0.1
Ksp (AgCl) [Cl -] MY : [M+]MY = 10 = 0.01 M

x
= =
Ksp (AgCNS) y [CNS -] 1
MZ : [M+]MZ = 1 = 1 M

[Cl -] x 1.8 # 10 -10

So, = = = 1.125×10 = 11.25
Order for precipitation is increasing order of
[CNS -] y 1.6 # 10 -11
x [M+]salt, so, first MY, then MX and then MZ.


⇒ y = 11.25 or x = 11.25 y.
64. For precipitation of Ag2CO3.
Ksp (AgCl) = [Ag+] [Cl-] = (x + y) x = 1.8 × 10-10
Ksp 6.9 # 10 -12
[CO32-] = + 2 = = 6.9 × 10-2

12.25 y × 11.25 y = 1.8 × 10-10 [Ag ] [10 -5] 2

1.8 # 10 -10
and for precipitation of BaCO3.
y2 = 12.25 # 11.25

Ksp 8.1 # 10 -9

So, y = 1.14 × 10-6
[CO32-] = 2+ = = 8.1 × 10-5
[Ba ] 10 -4

& x = 11.25 × 1.14 × 10-6 = 12.83 × 10-6
[Ag +] (0.04) 2

So, [Ag+] = [x + y] = 12.83 × 10-6 + 1.14 × 10-6 65. 4 × 10-19 = 0.03 ⇒ [Ag+] = 7.5×10-18 M

= 13.97 × 10-6 = 1.4 × 10-5 M

EXERCISE - 3

pH = - log (3 × 10-5) + log b 75 l

1. HA + NaOH + NaA + H 2 O at the end point, their 25
]weakg
equivalent amounts reacts together, pH = 4.04 ⇒ [H+] = 9.12 × 105 M

\ In the final solution:
For 75% blue we have
pH = -log 3 × 10-5 + log b 25 l = 5
0.1
[NaA] = 2 = 0.05 M
75
As NaA is a salt of weak acid and strong base, it ⇒ [H+] = 10-5 M

hydrolyses as,
So change in [H+] = 9.12 × 10-5 - 1 × 10-5

A- + H2O HA + OH-
= 8.2 × 10-5 M
1
pH = 7 + 2 [pKa + log c] So, n = 8.12
1
\ pH = 7 + 2 [- log (5 × 10-6) + log 0.05] = 9 4. At isoelectric point amino acid will not migrate
2. NH4OH NH
+
4 + OH

towards any electrode during electrolysis.
pK a + pK a
Isoelectric pH of a aminoacid =
1 2
1 0 0 2
(1)   7 + 9.4
\ pH = = 8.2
pH = 11, [H+] = 10-11 2
[OH-] = 10-3 = Ca 5. TCl + NaOT → NaCl + T2O
Since C = 0.05 m.Moles 2 3
Excess NaOT = 1
10 -3 10 -3

a = C = 0.05 = 2 × 10-2 or 2% 1
\ [OT-] = 25 = 0.04 = 4 × 10-2
3. For 75% red we have pOT = 2 - log 4 = 1.4
pH = pKa + log : Acid D
Salt

pT = 15.2 - 1.4 ⇒ 13.80
Chemistry
6. The reaction taking place on adding NaOH is : 2 # 10 -12
8. [OH–] = = 2 × 10–10 M

HA + NaOH → NaA + H2O 10 -2

m.moles of NaOH added to reach end point = 0.1x pOH = 10 – log 2 = 9.7.

\ m.moles of NaA formed = 0.1x 9. HA (aq) + B– (aq) ? HB(aq) + A– (aq)
Reaction taking place on adding HCl is: Keq. = 10–4

NaA + HCl NaCl + HA Keq. is very small, So reaction shift in backward
0.1x 0.1x direction.
2
0.1x 0.1x 0.1x (1) HB is more stronger acid than HA.
2 2 2
(2) A– is more stronger base than B–.

The final solution contains a weak acid HA and its
salt with a strong base (NaA) (3) B– and HB are conjugate acid-base pair.

\ Final solution is an acidic buffer with [salt] = (4) A– is conjugate base of HA
[acid]
- log b 2 l
1

\ pH = pKa + log 1 = 5.3 pH50% log 2
10. pH = = log 10 = 0.3
- log b 10 l
10% 1

\ pKa = 5.3
Given [HA] taken = 0.1 M 11. For H2O, pKa = pKb & H2O is the conjugate base of
We know that for neutralization, H3O+. So for the conjugate acid base pair, pKa + pKb
= 14. (at 25ºC)
m.moles HA = m.moles of NaOH.

\ [HA] × VHA = 0.1x h Kw
12. For salt of WA - WB : 1 - h K K & h = 1 181
a b

⇒ VHA = x mL [CH3COOH] = Ch

\ Volume of solution at end point = VHA + VNaOH 1
\ [CH3COOH] = 181 × 10-2
= 2x
Also, mmoles of NaA formed = 0.1x 9 # 105 # 10 -4
So, answer = 1.81 . 50.
0.1x
\ [NaA] = 2x = 0.05 M
13. HA ? A– + H+
At end point, NaA undergoes hydrolysis with
1 t = 0 0.2 0.1
pH = 7 + 2 (pKa + log c)
t = eq0.2(1 – a) 0.2 a 0.1 + 0.2a
1
\ pH = 7 + 2 (5.3 + log 0.05)
[H +] [A -] 0.2a (0.1 + 0.2a)

1
7 + 2 (5.3 - 2 + 0.7) Ka = [HA] = 0.2 (1 - a) ....(1)

\ pH = 9. 0.1a (1 + 2a)
\ 5 × 10–2 = ]1 - ag ⇒ 2a + a = 0.5 (1-a)
2

7. Mg(OH)2 Mg2+ + 2OH­-

x 2x+3y or, (2a - 0.5) (a + 1) = 0 ⇒ a = 0.25
Al(OH)3 Al3+ + 3OH- \ [H+] = 0.1 + 0.2 a × 0.15 M

y 2x+3y
\ Ans. 0.15 × 400 = 60
Now x > > y because
14. [H+] is the same for equilibria of both acids.
Ksp of Mg(OH)2 > > Ksp of Al(OH)3
Now, let [HCOO–] = a M and [OCN–] = b M

\ (2x + 3y) c 2x
[H +] # a +
-4 & [H ]
#b
⇒ x × (2x)2 = 4 × 10-12 ⇒ x = 10-4
...(1)
\ 0.1 = 1.8 × 10 0.1 = 4 × 10
-4

and y × (2x)3 = 1 × 10-33 a 9

1 ⇒ b = 20
⇒ y = 8 × 10-21
So, (a + b) = 29
x
So, y = 8 × 1017 ...(2)
15. pH of solutions of amphiprotic species is independent
So answer = 8 of concentration of solution.
 Ionic Equilibrium
16. No. of milieq. of Base = No. of milieq. of HCl = 8 × 10–5 × 6 × 10–5

0.252×1000 = 48 × 10–10
Molar mass = 0.14 × 40 KSP (CaCO3) = 4.8 × 10–9

\ Molar mass of base = 45 \ Ans = 109 Ksp = 4.8 . 5
On adding 20 mL of 0.14 M HCl : 20. H3PO4 = 3, H3BO3 = 1, H3PO2 = 1, rest diprotic
mmoles of BOH taken = 5.6
21. x = 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14
mmoles of HCl added = 2.8 There are 13 possible values.

\ BOH + HCl —→ BCl + H2O 0.98
22. H3PO4 = 98 = 10–2 Mole
5.6 2.8
10 -2
2.8 - 2.8 ⇒ [H3PO4] = 100 × 103 = 0.1 M

\ It is a basic buffer with pH = 14 - pKb pH = 5 \ [H+] = 10–5
H3PO4 & H2PO4–

\ 10.7 = 14 - pKb
[H 2 PO -4 ]

\ pKb = 3.3 ⇒ Kb = 5 × 10-4 pH = pKa1 + log [H PO ]
3 4

\ a = 45 and b = 5 × 10-4 [H 2 PO -4 ] [H 2 PO -4 ]
⇒ 5 = 3 + log [H PO ] ⇒ 102 = [H PO ]
a 45 3 4 3 4

\ 1000 b = 0.5 = 90
[H2PO4–] = 102 [H3PO4]
17. NH4OH + HCl —→ NH4Cl + H2O ⇒ But [H3PO4] + [H2PO4–] = 0.1

Milimole 2.25 2.25 0 H3PO4 + 102 [H3PO4] = 0.1
at end point 0 0 2.25 ⇒ [1 + 102] [H3PO4] = 0.1

Milimole = N1 × VHCl = 2.25 [H3PO4] = 10–3 M ⇒ [H2PO4–] = 0.1 M
2.25 For H2PO4– & H PO42–
VHCl = 0.1 = 22.5
[HPO 2-
4 ]
⇒ pH = pKa2 + log
[NH4Cl] = : 37.5 D = 0.6 M and
2.25 [H 2 PO14]
[HPO 24-] [HPO 2-
4 ]
pKb = 5 - log 1.8 = 4.74 5 = 8 + log -1 ⇒ – 3 = log
[H 2 PO 4 ] [H 2 PO14]
1 1 [HPO 2-

\ pH = 7 - 2 pKb - 2 log C
4 ]
= 10–3
[H 2 PO14]

4.74 1
= 7 - 2 - 2 log 0.06 ⇒ [H PO42–] = 10–3 [H2 PO2–]

⇒ pH = 5.24 [H2PO4–] + [HPO42––] = 0.1
⇒ [H2PO4–] + 10–3 [H2PO4–] = 0.1

18. [Cl-] taken = 10-4 M. If volume of AgNO3 added=VL
10 -4 ×1 8×10 -6 V [1 + 10–3] [H2PO4–] = 0.1
then, [Cl-]final = ]
V + 1g ]V + 1g
& [Ag +] =
final ⇒ [H2PO4–] = 0.1 M ⇒ [HPO42–] = 10–4 M

For no ppt. to occur : [Ag+] [Cl-] < Ksp Again
-4
10 ×8×10 V -6
V 1 [PO -4 3]
pH = pKa3 + log
]V + 1g2 ]V + 1g2 4

\ = 2×10 -10 & =
[HPO -4 2]

\ V=1L [PO -4 3]

⇒ 5 = 12 + log
[HPO -4 2]
19. CaCO3 Ca+2 + CO3-2 CaC2O4 Ca+2 + C2O4-2
x x y y [PO -4 3]
10–7 = ⇒ [PO4–3] = 10–7 [H PO4–2]
(x+y) x (x+y) y [HPO -4 2]
KSP (CaCO3) x [H PO4–2] + [PO4–3] = 10–4
KSP (CaC 2 O 4) = y = 3 & x = 3y ⇒ [1 + 10–7] [H PO4–2] = 10–4

(x + y) = 8 × 10–5 [ PO4–3] = 10–7 ⇒ [H PO4–2] = 10–11 M
(3y + y) = 8 × 10–5 ⇒ y = 2 × 10–5 x = 6 × 10–5
pC1 + pC2 + pC3 + pC4 = 11 + 4 + 1 + 3 = 19
KSP (CaCO3) = [Ca+2] [CO3–2]
Chemistry
23. DpH = 8.50 – 5.5 = 3 s2
25. KSP = +
[H +] 2
⇒ d pK In + log n
[Basic form] [H ]
1+ K + K $K
[Acidic form] a a 2 a 1 2

5Acidic form? m s2
- c pKln + log -14
7.5 # 10 =
5Basic form? = 3
-3
10 10 -6
1+ -11 +
5.5 # 10 25 # 10 -18
[Basic form]

⇒ 2 log [Acidic form] = 10 × log 2
7.5 # 10 -14 =
s2
8
10 1012
1 + 5.5 + 25
[Basic form]
⇒ log [Acidic form] = log 25

25 # s 2

7.5 # 10 -14 =
⇒ [Basic form] = 32 [Acidic form].
1012
s2 = 0.3 × 10­-14 × 1012
24. mmoles of H2CO3 = 50 × 0.2 = 10
s2 = 0.003

\ mmoles of KOH needed for above reaction = 10
s = 0.055 M ⇒ moles in 1000 L = 55.

\ VKOH × 0.1 = 10 ⇒ VKOH = 100 mL.
KHCO3 + KOH —→ K2CO3 + H2O
VKOH = 50 mL needed for mid point
pH = 10.25 is mid titration point of IInd reaction as
pH = pK a so it is possible at VKOH = 150 mL.
2

Ans = (150 + 10.25) × 0.4

= 64.1
EXERCISE - 4
1. Ni2+ accepts a pair of electron and H2O donates it. OH
This an acid-base reaction. 6. H3BO3= HO B
-5
5 # 10 Ca 2
OH
2. a = > 0.1 So, 1 - a =Kb ⇒ 5 × 10-5
10 -4 electron deficient species
10 -4 a 2
= 1 - a ⇒ 2a2 + a - 1 = 0 ⇒ a = 0.5

So it will behave as Lewis acid.

Hence [OH-] = Ca = 5 × 10-5 & pH = 9.7 7. 2 # 10 -4 =
4 # 10 -3 a 2
& 20a 2 + a - 1 = 0
1-a
[H +] [A -] [H +] 2
⇒ a = 0.2
3. K a = [HA] = [HA] (\ [H ] = [A ])
+ -

\ [OH -] = Ca = 8 # 10 -4 M & pOH = 3.1
+ - + 2
[H ] [B ] [H ]

Kb = [HB] = [HB] (\ [H ] = [B ])
+ -
8. NH4OH NH +4 + OH-

K [HB] 4 [HA] 1
t = eq 0.4 (1-a) 2 × 10-5

Also H+ are same ` K a = [HA] = 1 [HB] = 4
b
( = 0.4a)
4. Factual.
So, a = 5 × 10-5 (< < 1) \ 0.4 (1-a) . 0.4
K 2 # 10 -5 # [OH -]
5. A3- + H 2 O ? HA 2- + OH - K h = KW
1
a
3
Kb = 0.4 = 1.8 # 10 -5

t = eq; c(1-h) ch ch
KW 2
KW
[OH -] = 0.36 M
ch
K a = 1 - h . ch ` h =
2
cK a
3 3

cK W

\ [OH -] = [HA 2-] = ch = Ka 3

KW K W Ka
\ [H +] = = 3

[OH -] c
1
& pH = 2 (pK W + pK a + log c) 3
 Ionic Equilibrium
9. AlCI3 C = 0.15 M (AlCI3 is SAWB salt) 16. CO32- + H+ —→ HCO3-
[Al(H2O)6]3++H2O(l)
Initial milli-moles 50×0.05 40×0.1 –
[Al(H2O)5OH]2+(aq) + H3 O+ (aq)
Final milli-moles – 1.5 2.5
Ka = 1.5 × 10–5
HCO +
-
3 H+ —→ H 2 CO3

Initial milli-moles 2.5 1.5 –

At t = 0 0.15 – 0 0

Final milli-moles 1 – 1.5

At t = teq 0.15 (1– a) 0.15 a 0.15 a [HCO3-]
0.15a # 0.15a
pH = pK a + log [H CO ] = 6.173
Ka = 0.15 [1 - a] = 1.5 × 10–5

1
2 3

17. (A) As both salts are sparingly soluble, due to

⇒ 1.5 × 10–1 a2 = 1.5 × 10–5
common ion effect, both will be precipitated in
⇒ a2 = 10–4⇒ a = 10–2
some amount.

[H3O+] = 0.15 × 10–2 = 1.5 × 10–3 M

(B) MX M+ + X– ; Ksp(MX)

⇒ pH = 3 – log 1.5 = 3 – 0.18 = 2.82
x x+y

10. C2O2- NX N+ + X– ; Ksp(NX)

4 + H2O HC2O-4 + OH-;
K 10 -9
y y+x
K h = KW = 5.4
1

Ksp(MX) + Ksp(NX) = (x + y)2

a 2

t = eq 0.005 (1-h) 0.005h 0.005h

⇒ Ksp (MX) . x + y = [X–] ...(1)

( . 0.005)

( a Ksp(MX) >> Ksp(NX))
(0.005h) (0.005h) 10 -9
(0.005) = 5.4 \ h = 1.92 × 10–4 Ksp (NX)
(C) (y + x)y=Ksp(NX) ⇒y=[N+] .
...(2)
Ksp (MX)
[OH-] = 0.005h = 9.6 × 10–7 M.

Ksp (NX)

HC 2 O -4 + H 2 O ? H 2 C 2 O 4 + OH - ; Similarly , [M+] = x . ...(3)
Ksp (MX)
K 10 -12
K h = KW = 5.6
2 From (2) & (3) : [M ] >> [N+]
+
a 1

t = eq; . 9.6 # 10 -7
. 9.6 # 10 -7 18. pKa = 5.45
5 [Base form]

\ [H 2 C 2 O 4] = K h = 28 # 10 -12 M
2
pH=pKHIn+log [Acid form] ⇒ pH = pKHIn=5.45
11. When rain is accompanied by a thunderstorm, For a Buffer solution
H2 O [CH3 COONa]
N2 + O2 —→ NO —→ NO2 HNO2 + HNO3 pH = pKa + log [CH COOH]
3
12. HSO -4 - can accept and donate a proton. [CH3 COONa]
⇒ 5.45 = 4.75 + log [CH COOH]

HSO -4 + H + " H 2 SO 4;HSO -4 " H + + SO 24- 3

Note: Answer could also be NH3 or OH-

[CH3 COONa] 5 [CH3 COONa]
0.7 = log [CH COOH] ⇒ 1 = [CH COOH]
3 3
13. pKHIn = 5
19. (A) As long an a solid-aqueous equilibrium exists, a
(a) CH3COOH + NaOH, end point pH > 7 salt solution is saturated.
(b) Auillne hydrochloride + NaOH, end point pH > 7
(B) MX(s) + Y-(aq.) MY(s) + X-(aq.)
Ksp (MX)
(c) NaHCO3 + HCI, end point pH < 7 K = K (MY)
sp
nx
d) Ba(OH)2 + H2C2O4 , end point pH > 7
t=0 n 100 0 0
14. WA Vs SB end point > 7 Phenolphthalein nx nx nx

t = eq n - 100 y 100
-
100 = [X ]
15. End points of both titration will lie in acidic range. Ksp (MX) [X -] [M +]

(C) K (MY) = - ⇒ [Y-]
sp [Y ] [M +]
Ksp (MY) Ksp (MY) nx
= K (MX) # [X -] = K (MX) # 100
sp sp
Chemistry
10 -38 (0.1) 2 [S 2-]
20. (A) SpH=2 = = 10-2 M 25. 9.6 × 10–21 = & [S2–] = 9.6 × 10–20 M
(10 -12) 3 (0.1)
10 -38 9.6 × 10–20[Cu2+]min = 6.4 × 10–36

(B) SpH=11 = = 10-29 M
(10 -3) 3 2
⇒ [Cu2+]min = 3 × 10–16
21. [H+] = 0.1 M & pH = 1
0.1 [H 2 PO -4 ] 26. Suppose V mL of solution contains 0.1 M Mg2+ and

Ka = 1
0.1 & [H 2 PO -4 ] = K a 1 0.8 M NH4Cl

C
Ka
& a = K a & a = 0.1 = 10K a
1
1
1

Now, V mL of ‘a’ M NH3 is added, which just gives
precipitate of Mg(OH)2. Then :
0.1 [HPO 24-]
Ka = 2
Ka & [HPO 24-] = K a # K a # 10 1 2
[Mg2+] [OH–]2 = Ksp Mg(OH)2

1

22. The concerned chemical reaction is :

: 0.1V D [OH–]2 = 1.62 × 10–11

2 AgCl + Na2CO3 —→ Ag2CO3 + 2 NaCl 2V
Millimole
Calculation of [Ag+] left in the solution : [Mg 2+] = Total volume in mL
Ksp(Ag2CO3) = [Ag+] [CO32–] \ [OH–] = 1.8 × 10–5 M

8.1 # 10 -12 Now, if the [OH–] = 1.8 × 10–5 M, on addition of

[Ag+] = 1.6 = 2.25 × 10–6 M
0.00284 NH3 in NH4Cl, then Mg(OH)2 will precipitate. For
Concentration of Cl– left = 0.00284 g/L = 35.5
buffer solution of NH3 and NH4Cl :
mol/L = 8 × 10–5 M
\ Ksp(AgCl) = [Ag+] [Cl–] = (2.25 × 10–6) (8 ×
[NH3]
[OH–] = Kb ×

[NH +4 ]
10–5) = 1.8 × 10–10. (0.8 # V) /2V
1.8 × 10–5 = 1.8 × 10–5 × (a # V) /2V

# 10 -3 D
23. Solubility of CaCO3 = ; 7 100 mole/L = 7 × 10–5
\ a = 0.8 M.
mole/L = s
27. Dissolved Al(OH)3 present in solution as Al3+(aq) as
Ksp of CaCO3 = s2 = 49 × 10–10.

well as Al (OH) -4 (aq)
When [Ba+2] is 90% precipitated, then only CaCO3

Ksp
starts precipitation. If original solution contain ‘a’
S= + KC[OH–]
[OH -] 3
mole/L Ca+2 & Ba+2, then for CaCO3 precipitation,
dS
[Ca +2] [CO3-2] = 49 # 10 -10, for minimum solubility : =0
d (OH -)
[CO3-2] = : 49 a10 DM
-10
# Ksp # 3
or ;- + KC = 0
[OH -] 4
Now for BaCO3, Ksp = [Ba+2] [CO3-2]

[OH–] = c m
1
4
3Ksp
a # 10 49 # 10 -10
= 100 # = 4.9 × 10–10 KC
a 28. For FeS and MnS to be precipitated from a solution
a # 10
(\90%Ba2+has precipitated, so [Ba+2] = 100 M) of Fe2+ and Mn2+, IPMnS > Ksp(MnS)
24. For FeS and MnS not to be precipitated from a [Mn2+][S2–] > Ksp of MnS

solution of Fe2+ and Mn2+, IPFeS < Ksp(FeS)
[10–2][S2–] > 2.5 × 10–13
\ [S2–] > 2.5 × 10–11 M
[Fe2+][S2–] < Ksp of FeS
[10–2][S2–] < 6.4 × 10–18 \ [S2–] < 6.4 × 10–16 M So, at [S2–] = 2.5 × 10–11 M or more, precipitation of

So, at [S2–] = 6.4 × 10–16 M or less, no precipitation FeS and MnS will occur.
of FeS and MnS will occur. H2S ? 2H+ + S2–
H2S ? 2H+ + S2– \ [H+]2 [S2–] = Ka(H S) × [H2S] = 9.6 × 10–22
2

\ [H+]2 [S2–] = K a(H S) × [H2S] = 9.6 ×
2 10–22
\ [H ] + 2
max [2.5 × 10–11] = 9.6 × 10–22
\ [H ]
+ 2
[6.4 × 10–16] = 9.6 × 10–22
[H +] 2max = 3.84 × 10–11 \ [H+]max = 8

3 –6
5 × 10 M
min

3
[H +] 2min = 3/2 × 10–6
\ [H+]min = –3
2 × 10 M 3
Thus, if [H+] = 8
–6
5 × 10 M or less, the
3
Thus, if [H+] = –3
2 × 10 M or more, the precipitation of FeS and MnS will take place.
precipitation of FeS and MnS will not take place.
192
3 Therefore, pH(min.) = 6 – ½ log 5 = 5.21 Ans.
Therefore, pH(max.) = 3 – ½ log 2 = 2.91 Ans.
 Ionic Equilibrium
29. Order of solubility : Complex formation > Pure 10 -9
water > Common ion effect. a = 1000/18 = 1.8 × 10–11 M

AgBr form complex [Ag(NH3)2]+ in NH3, so

% ionisation = 1.8 × 10–9 %
solubility is maximum in NH3(aq). 37. No. of OH- per mL of solution = 10-9 × 10-3 × Na
30. In acidic medium, it behaves as a base & in basic = 6.02 x1011
medium, it behaves as an acid (accepting OH),
6H +@from H O = 6OH -@from H O = 10 -9

driving the equilibrium forward in both cases. 2 2

On the basis of ostwald dilution law, number of H+

31. Bronsted bases are proton acceptor and each Lewis
base contains one or more electron pair and thus
accept proton. On the other hand Bronsted acids
are proton donor and may or may not be capable
of accepting lone pair of electron, e.g., H2SO4 is
ions will increase but increase in volume will be
more. Therefore, [H+] decreases, pH increases.
38. H2SO4 is a strong acid and it gets completely
dissociated in H2O. Hence its K a and K a are
1 2

Bronsted acid but not Lewis acid BF3 is Lewis acid determined in CH3COOH.
but not Bronsted acid. Most cations are acids and Also H2SO4 is neutral while HSO4– because the –

most anions are bases. ve charge has more affinity towards H+ ion. Hence
32. On heating pure water the value of ionic product of choices (A) and (B) are correct while (C) is incorrect.
water increases i.e., Kw = 10–14 at 25oC and at 100oC
From given Ka values H2SO4 is not completely
Kw = 10–12. Thus pH and pOH both becomes 6 at ionized. Hence [H+] < 0.02.
100oC (pH and pOH = 7 at 25oC).
39. (A) In 0.6 m M HCOOH solution
33. (A) It is weak acid.
[H +] 2 [H +] 2
K a = ⇒ 8 × 10–4 =

(C) It is a strong base. C - [H ] +
6 # 10 -4 - [H +]
\ [H+] = 4 × 10–4 M.
34. Sr(OH)2 + 2HCl —→ SrCl2 + 2H2O
initial m mol 0.2 V 0.2 V 0
So solution in (A), (C) & (D) are ISOHYDRIC.
final m mol 0.1 V 0 0.1 V
40. (A) H2CO3 + OH– —→ HCO3– + H2O
0.1V moles 1.5 1

[Sr(OH)2] = 2V = 0.05
0.1V 0.5 – 1

[SrCl2] = 2V = 0.05 so it is a buffer solution.
Sr(OH)2 —→ Sr2+ + 2OH– ; SrCl2 —→ Sr2+ + 2Cl–
(B) H2CO3 + OH– —→ HCO3– + H2O


0.05 0.1 0.05 0.1
moles 1.5 2
2+
[Sr ]total = 0.1 M – 0.5 1.5
[Cl–] = 0.1 M
HCO3– + OH– —→ CO32– + H2O
[OH–] = 0.1 M, pH = 13.

moles 1.5 0.5
– – 0.5
35. Let BA be this salt BA → B+ + A–
so it is a buffer solution.
A– does not undergo hydrolysis because HA is
strong acid. B+ undergoes hydroysis
(C) NH4OH + H+ —→ NH4+ + H2O

moles 5 4
Kh 1 – 4

h= c h = degree of hydrolysis where Kh =
K
Hydrolysis constant = KW .
so it is a buffer solution.
b
h \ K h greater the hydrolysis constant greater the 41. Higher the Ka of acid lower is the pH of acid for
h (degree of hydrolysis). same concentration.

h \
1
greater the Kb lesser the h. 42. C6H5NH2 + H+ —→ C6H5NH3+
Kb t=0 5 2.5
Hydrolysis is endothermic, Kh increases with teq 2.5 – 2.5
temperature and h also increase with temperature. pOH = pKb = 14 – 8 = 6
h \ V V = volume of salt solution hence h \ pKb = 6
K
increases with dilution. Kh = KW
b Now for the solution of [C6H5NH3+] = 0.01 M

36. In this solution, source of OH– is water 1 1 6 1

pH=7– 2 pKa– 2 log c = 7– 2 – 2 log (0.01) = 5
\ Ca = [OH–]

Chemistry
43. CH3COOH is a WA compared to H2O and NH3 is a 50. Given graph is plotted for the titration of weak
base. So, in a solution of NH3, CH3 COOH behaves diprotic acid with base.
as a SA.
51. HIn —→ H+ + In-
HNO3 is a weaker acid than HF in water.
[H +] [In -]
1.6 # 10 -3 a 2 1
K In = [HIn]
44. Initial : 8 × 10–5 = 1-a ⇒a= 5
[In -] K 10 -9
\ [OH–] = 3.2 × 10–4 ⇒ pH = 10.5
⇒ [HIn] = In+ = -9.6 = 100.6 = 4
[H ] 10
(3.2 # 10 -4) 2 [C 2 N 2 H10
2+
]i \ % of [In ] in solution = 54 # 100 = 80%
-
8 × 10–5 × 2.7 × 10–8 =
-3
1.28 # 10
So, pink colour will be visible.
⇒ 2.7 × 10–8 = [C2N2H102+]i

52. The concerned chemical reaction is :
Final : pH = 11 ; 8 × 10–5 = 10–3 × a ⇒ a = 0.08

2 AgCl + Na2CO3 —→ Ag2CO3
+ 2 NaCl
+]
[C2N2H9 = 1.28 × 10–4.

Calculation of [Ag+] left in the solution :
(10 -6) [C 2 N 2 H10
2+
]f Ksp(Ag2CO3) = [Ag+] [CO32–]

2.7 × 8 × 10–13 =
-3
#
1.6 10
⇒ [C2N2H102+]f = 1.28 × 2.7 × 10–9 M
8.2 # 10 -12
[Ag+] =
1.5 = 2.34 × 10–6 M

So, (A), (B) and (D) are correct but 0.0026
Concentration of Cl– left = 0.0026 g/L = 35.5

2+
[C 2 N 2 H10 ]i 1 mol/L = 7.33 × 10–5 M
= 0.128
2+
[C 2 N 2 H10 ] f \ Ksp(AgCl) = [Ag+] [Cl–] = (2.34 × 10–6) (7.33 ×

45. [H+] = Ca = 1.5 × 10-3 M 10–5) = 1.17 × 10–10
-3
Ka = 2.5 × 10-3 = ]
Ca 2 -3 = 1.5×10 a 1.4 # 10 -5
1 - ag
2.5 × 10 100 3
⇒ 1 - a 53. [Ag+] concentration = 350 × 2 × 4
a 5 = 8.68 × 10–3.
\ 1 - a = 3 ⇒ a = 8 a = 5 ⇒ a = 0.625
100 3 1.4 # 10 -5
1.5×10 -3 [SO42–] concentration = 350 ×


\ c = .625 = 2.4 × 10-3 M 4
= 4.34 × 10–3.

[FCH2COOH] = c (1 - a) = 9 × 10-4 M
250
[Pb2+] = 350 × 2.8 # 10 -13 = 3.78 × 10–7.

7.2 # 10 -2 a 2
46. 1.2 × 10–7 = 1-a [CrO42–] = 3.78 × 10–7.

1
⇒ 6a2 + a – 1 = 0
⇒ a = 3 [Ag+]2 [CrO42–] = 2.85 × 10–11 > Ksp of Ag2CrO4.

0.072

So, pH = – log 3 = 1.62 [Pb2+] [SO42–] = 1.64 × 10–9 < Ksp of PbSO4.

47. Facutal.
Only Ag2CrO4 will precipitate.
54. AgCl(s) + 2NH3(aq) ? Ag(NH3)2+ (aq) + Cl–(aq)
K1 = 1.6 × 10–10 × 107 = 1.6 × 10–3

[Ag (NH3) +2 ] [Cl -]
=
48. [NH3] 2
AgCN(s) + 2NH3(aq) ? Ag (NH3)2+(aq) + CN–(aq)

K2 = 2.5 × 10–16 × 107 = 2.5 × 10–9

[Cl -] 1.6 # 10 -3

When conc. of weak base or acid increases buffer - = = 6.4 × 105
[CN ] 2.5 # 10 -9
capacity increases. s12 s1

K1 = ⇒ 1 - 2s1 = 0.04 50
-2
49. Initial decrement is due to consumption of free (1 - 2s1) 2
OH– ions, then slow decrement in pH is due to basic
⇒ s1 = 27
1
buffer solution and minimum slope will be there
when there is best buffer action ([salt] / [base] = 1) 0.037
\ [CN–] =
= 5.78 × 10–8 M
6.4 # 105
 Ionic Equilibrium
55. Factual. 61. As the value of Ksp is very low so we can assume that
precipitation of Mg (OH)2 will reach completion.
56. In AgNO3 solution, the solubility of AgCN will
decrease as compared to pure water because of
Mg+2 + 2OH– —→ Mg(OH)2
common ion effect of Ag+ ion.

t=0 0.2 0.2 0

In NH3 solution and buffer of pH = 5, the solubility
of AgCN will increase due to complex formation in
0.1 x 0.1
case of NH3 solution and hydrolysis of CN– ions in At the end of reaction [Mg+2] = 0.1 (OH- is the L.R.)

case of buffer of pH = 5.
Ksp [Mg (OH)2 ] = [Mg+2] [OH–]2 = 1.6 × 10–12

57. (A) Ag2CO3 —→ 2Ag+ + CO 2-
3
1.6 # 10 -12
(2x + 2y) x ⇒ [OH–]2 =
0.1 ⇒ [OH–] = 4 × 10–6 M
Ag2CrO4 —→ 2Ag+ + CrO 2-
4

⇒ pOH = 6 – log 4 ⇒ pH = 14 – 6 + 0.6 = 8.6
(2y + 2x) y
62. Mg+2 + 2OH– —→ Mg (OH)2 (s)
4(x + y)2(x + y) = (4 + 2.4) × 10–12 ⇒ (x + y)3

83 # 10 -12
0.1 0.04
= 1.6 × 10–12 =
0.04
43 # 5 At the end of reaction [Mg+2]=0.1– 2 = 0.08

⇒ (x + y) = 1.168 M
Ksp (Mg(OH)2) = [Mg+2] [OH–]2 = 1.6 × 10–12

\ [Ag+] = 2(x + y) = 2.336 × 10–4 M

1.6 # 10 -12
4 # 10 -12 [OH–]2 =
⇒ [OH–] = 4.47 × 10–6

(B) [CO32-] = = 7.3 × 10–5 M 0.08
(2.336) 2 # 10 -8
\ pOH = 6 – log 4.47 = 5.35
2.4 # 10 -12 pH = 14 – 5.35 = 8.65

(C) [CrO 24-] = = 4.35 × 10–5 M
(2.336) 2 # 10 -8
63. Mg(OH)2 + 2HCI —→ Mg+2 + 2CI– + 2 H2O

(D) [Ag+] = 2([ CO32- ] + [ CrO 2-
4 ])
0.1 0.04 0.1 - -
58. (A) pH of 10–8 m sol. of HCl is 6.97
(consider the H+ from H2O also) 0.1 – 0.02 0 0.1 + 0.02

(B) H2PO4–
-H +

H+ HPO42– [Mg+2] = 0.12 M

(C) Kw = [H+] [OH–] Ksp [Mg (OH)2] = [Mg+2] [OH–]2 = 1.6 × 10–12

Kw increases on increasing temperature. 1.6 # 10 -12 4
[OH–]2 =
0.12 = 3 × 10–11 M2

D) HA + NaOH → NaA + H2O

C/2 C/2 C/2 ⇒ [OH–] =
4
3 # 10 M
-11

salt
pH = pKa + log acid ⇒ pH = pKa ⇒ pOH = 5.44 ⇒ pH = 14 – 5.44 = 8.56
60. At eq. point pH = 4.5 [HPO 24-]
64. pH = pKa2 + log =7
pOH = 9.5 [H 2 PO -4 ]
pOH = 1/2 [PKb + pKw + log C ] [HPO 24-] [HPO 24-]

⇒ log - = - 0.22 ⇒ = 0.6
9.5 = 1/2 [5.6 + 14 + log C] [H 2 PO 4 ] [H 2 PO -4 ]
Total volume be (100 + V) 65. In 50 ml buffer solution
0.25 × (100 + V) = 0.5 × C ⇒ V = 100 ml [H2PO4–] = 0.1 M = 5 milimole,
100 M = 0.5 V [HPO42–] = 0.06 = 3 milimole
100 × M = 0.5 × 100 milimole of NaOH added = 20 × 0.01 = 2
M = 0.5
H2PO4–
+ OH– —→ HPO42– + H 2O
100 ml _________ 0.5 mole
5 2 3 0
100 ml _________ 0.055 mole of base
3 0 5 0
wt.
0.05 = 45 ⇒ wt. = 2.25 gm
+ log b 3 l = 7.44.
5

pH = pKa2
2.25
% of base = 2.5 ×100 = 90%
Chemistry
66. For SrF2 in pure water 69. Since CHCl2COOH is relatively strong acid having
more Ka.
4s13 = Ksp

CHCl2.COONa —→ CHCl2COO– + Na+


For SrF2 in 0.1 M NaF solution

0.1 0.1
s2 (0.1)2 = Ksp


CHCl2.COOH CHCl2 COO– + H+
3
⇒ 4s1 = s2 (0.01)
0.2 0 0
⇒ 4s13 = s1 ×

256
(0.01)
(0.2–x) (x+0.1) x
106 -
[CHCl 2 COO ] [H +]

⇒ s1 = 8 × 10 M
-4

\ Ka = [CHCl COOH]
2

\ Ksp = 4s1 = 2.048 ×3 10-9
[0.1 + x] [x]
67. [Sr2+]i = 0.0011 = 11 × 10-4 M
or 5 × 10–2 = [0.2 - x]
[Sr2+]f = 2 × 10-4 M

\ x = 0.05.

\ [Sr2+] precipitated = (11 - 2) × 10-4 M

70. Let V mL of NaOH be needed to give CH3COONa.

= 9 × 10-4 M
NaOH + CH3COOH —→ CH3COONa + H2O

[F-] needed for this precipitation = 2 × 9 × 10-4

0.2×V 50×0.2 0 0

= 18 × 10-4 M
— [10–0.2V] 0.2V 0.2V
[Salt] [Salt]
Also, [Sr2+]f = [F-]2f = Ksp = 2.048 × 10-9
\ pH = pKa + log [Acid] = pKw – pKb + log [Acid]
But, [Sr2+]f = 2 × 10-4 M [Salt]
= 14 – 9.26 + log [Acid]

\ [F-] f = 3.2 × 10-3 M

\ Total [F-] needed = 3.2 × 10-3 + 18 × 10-4 : 50
0.2V D
+V
= 14 – 9.26 + log
= 5 × 10-3 M :1050-+0.2V
V
D

\ NaF needed for 100 ml solution
4.74 = 4.74 + log :10 - 0.2 V D
0.2 V
5 # 10 -3 # 42
= 10 = 0.021 g.
10
\ V = 0.4 = 25 mL.
68. SrF2 —→ Sr2+ + 2 F-
71. CH3COONa + HCl —→ CH3COOH + NaCl

s 2s
1 1 0 0
F- will react with H+ to produce HF

0 0 1 1
F- + H+
HF 1

\ [CH3COOH] = 1 = 1.
1 [HF] 7

K = K = + - = -5
a [H ] [F ] 10 Ka

\ [H+] = Ca = C C = K a .C = K a
\ [HF] = 7 × 105 [F-] [H+] ( a [H+] = 10-5; pH = 5)

1 1
= 7 × 105 [F-] × 10-5 = 7 [F-]
or pH1 = – 2 logKa 2 pKa.

Here [F-] + [HF] = 2s (Material balance)
CH3COOH + CH3COONa

\ [F-] = 4
s
1 1 ⇒ Acidic Buffer
1
\ pH = pKa + log 1
Ksp = s b 4 l = 2.048 × 10-9
s 2


pH2 = pKa

\ s = 3.2 × 10-3 mol/L 1
\
pH1 2 pK a 1
pH 2 = pK a = 2
 Ionic Equilibrium
11.85 5 # 0.08 - 10 # 0.015 # 2
72. Moles of Potash Alum = 474 = 0.025 79. (A) [H+] = 500
Molees of Al3+ = 0.025 = 2 × 10–4 M \ pH = 3.7
Moles of K+ = 0.025
(B) For salt CH3COONa : pH
If none of the Ion Hydrolyze then [H+] = 10-7 M

= 2 b14 + 4.74 + log b 150 ll = 8.87
1 15

73. Al3+ + H2O Al(OH)2+ + H+ Kkh = 1.4 × 10-4

C-x x x 1
(C) For RNH2 : pOH = 2 (pKb – log 0.25)
0.025

C = 100 # 1000 = 0.25 M K
& Kh = KW \ Kb = 10–5
b
x2 pOH = 2.8 \ pH = 11.2

& 0.25 - x = 1.4 # 10 -5

x
& 2 = 1.4 # 0.25 # 10 -5 ( a x < < 0.25) pK a + pK a 4+7
(D) For NaH2A : pH = = 2 = 5.5
2 1

2
x
& = 1.87 # 10 -3
80. (A) H2C2O4 + OH– —→ HC2O4– + H2O
Kw
74. SO2-4 + H2O HSO-4 + OH-
K a ^HSO -4 h
Kh = m.moles 50 25

0.5-x x x 25 – 25
x2 10 -14 Buffer solution pH = pK a

1
=
0.5 - x 1.25 # 10 -2 (B) H2C2O4 + OH– —→ HC2O4– + H 2O

a x < < 0.5 m.moles 50 50

\ [OH-] = x = 6.32 x 10-7 – – 50
10 -14 pK a + pK a 13
[H
& +] = = 1.58 # 10 -8 Amphiprotic, pH =
1
= 2 = 6.5
2

6.25 # 10 -7 2
(C) H2C2O4 + OH– —→ HC2O4– + H2O
75. Al3+ + SO 24- + H 2 O Al(OH) 2+ + HSO -4
KW
K a .K b
m.moles 50 75

0.25-x 0.5-x x x – 25 50
HC2O4 +– OH– —→ C2O4 2– + H2O
1.4 # 10 -5

Kh = = 1.12 # 10 -3
1.25 # 10 -2 m.moles 50 25
25 – 25
2
x

& (0.25 - x) (0.5 - x) = 1.12 # 10 -3
Buffer solution pH = pK a 2

x
& = [HSO -4 ] = 0.0114
(D) H2C2O4 + OH– —→ HC2O4– + H2O

Considering only the ioniztion of HSO-4 m.moles 50 100
+

&
[H ] [0.5 - 0.0114]
= 1.25 # 10 -2 – 50 50
[0.0114]
HC2O4– + OH– —→ C2O42– + H2O
[H
& +] = 2.92 # 10 -4 M m.moles 50 50
76. From the Graph 19 ml – – 50
77. From the Graph pH . 8.5 Salt hydrolysis, pH > 7.
1.2
78. Mol. mass =
0.222 # 19 81. a) pH at eq. pt. = 7
1000
1

⇒ Mol. mass = 284.5 b) pH at eq. pt. = 7 + 2 ( 3.74 + log 0.1) = 8.37
1
c) pH at eq. pt. = 7 - 2 (4.74 + log 0.1) = 5.13
d) At Eq. pt. solution contains 0.1 M H2CO3
⇒ pH = 3.7
Chemistry

1. 0.001 M NaOH
[OH-] = 10-3
3

[Y]/mM
pOH = 3
pH = 11 6. 2
1
2. Since (NH4)3PO4 is salt of weak acid (H3PO4) &
weak base (NH4OH).
1 2 3
1
pH = 7 + 2 {pKa – pKb} [X]/mM
1
= 7 + 2 (5.23 – 4.75) XY2 $ X + (aq) + 2Y - (aq)
10 -3 2 # 10 - 3

= 7.24 c 7. Ksp = [X+] [Y–]2

3. Given : 6Ksp@PbI = 8 × 10-9
2
or, Ksp = 10–3 ×(2 × 10–3)2 or Ksp = 4 × 10–9 M3

To calculate : solubility of PbI2 in 0.1 M sol of 7. 20 mL 0.1 M H2SO4 ⇒ nH+ = 4
Pb(NO3)2
30mL 0.2M NH 4 OH & n NH OH = 6 4

(I) Pb(NO3)2 Pb
+2
(aq) +

2NO (aq)
3 NH 4 OH + H + ? NH 4+ + H2 O
0.1 M 6 4 0 0
0.2 M 0.2 M
2 0 4 4

(II) Pbl2(s) Pb (aq) + 2I(aq)
+2

s 2s Solution is basic buffer.

= s + 0.1 6NH +4 @
So, pOH = pK b + log 6
NH 4 OH@
- 0.1 4
= 4 7 + log 2 = 4.7 + log 2 = 5
Now : Ksp = 8 × 10-9 = [Pb+2][I-]2
⇒ 8 × 10-9 = 0.1 × (2s)2
pH = 14 – pOH = 14 – 5 = 9

⇒ 8 × 10-9 = 4s2 ⇒ s =
2 × 10-4 8. Ba 2+ + SO 24- BaSO 4

⇒ s = 141 × 10-6 M #
C 450 #
50 1
1000 mol 1000 mol

⇒ x = 141 For precipitation
4. M H SO &
9.8
= 10 -3 6Br 2+@6SO 24-@ $ Ksp ]BaSO 4g

98 # 100
& C # 450 0& 50 0 # 4 $ 1 # 10 -10
2 4

4 1000 1000
M NaOH & = 10 -3
40 # 100 1 # 10 -10 # 1000
40 # 10 -3 - 10 # 10 -3 # 2 20
C$ 90 = 1.1 # 10 -9 M
= = # 10 -3
50 50 9. Methyl orange works better
2 For range 4 to 6 therefore weak alkali to strong acid
[OH -] = # 10 -3
5 - + -7
pOH = 3.397 10. H 2 S ? HS + H k1 = 1 # 10
HS - ? S 2 + H - k 2 = 1.2 # 10 -13
pH = 10.603
H 2 S ? S 2- + 2H + keq = k1 # k 2 = 1.2 # 10 -20
5. Bi2S3  2Bi3+ + 3S2-

= ^S 2h]H +g2
Ksp = (2s)2(3s)3 = 108s5

6H 2 S@
1.08 # 10 -73

\ (s)5 = = 10 -75
6S 2-@ = 1.2 # 10 -20 # 0.1
108


⇒s= 10-15 0.04
6S 2-@ = 3 # 10 -20

 Ionic Equilibrium
11. Only anionic hydrosis is in CH3COOK 16. In IInd equation H2PO4– gives one H+ ion to H2O
Ans. CH3COOK therefore in the IInd equation it act as an acid.
1
12. pH = 7 + 2 (pKa - pKb) 17. KSP = 1.0 × 10–11 = [Mg+2] [OH–]2
1 1.0 × 10–11 = (0.001) [OH–]2
= 7 + 2 (3.2 - 3.4)

\ pH = 6.9 [OH–] = 10–4
pOH = 4
13. pH = 1 ⇒ [H+] = 10–1 = 0.1 M
pH = 14 – 4 = 10.

pH = 2 ⇒ [H+] = 10–2 = 0.01 M
18. For precipitation to start, Ksp = IP

for dilution of HCl M1V1 = M2V2
Ksp = [Ag+] [Br–]


0.1 × 1 = 0.01 × V2

But, [Ag+] = 0.05 M

V2 = 10 L

\ [0.05] [Br–] = 5.0 × 10–13

Volume of water added = 10 – 1 = 9 litre
5.0 # 10 -13
14. HQ H+ + Q– [Br–] =
0.05 = 1 × 10–11 M
0.1

moles of KBr required
0.1 – x x x
= M × V = 1 × 10–11 × 1 = 1 × 10–11
pH = 3, [H+] = 10–3, x = 10–3

weight of KBr required
(x) # (x) (10 -3) 2 10 -6
Ka = (0.1 - x) = -3 - 0.1 = 10
-5
= 1 × 10–11 × 120 = 1.2 × 10–9 g
0.1 - 10
15. (1) and (4) are incorrect since H2CO3 is not a strong 19. Na 2 CO3 $ 2Na + + CO32-
acid.
1 × 10-4 M 1 × 10-4 M 1 × 10-4 M

H2CO3 H+ + HCO3– K1 = 4.2 × 10–7 KSP [BaCO3] = [Ba+2] [CO32-]

HCO3–
H+ + CO32– K2 = 4.8 × 10–11 5.1 × 10-9 = [Ba+2] × 1 × 10-4

a K1 >> K2, so H+ produced from IInd ionisation

[Ba+2] = 5. 1 × 10-5 M

can be neglected as compared to those produced in
Ist ionisaiton.
\ [H+] = [HCO3–] (from Ist ionisation)

Also, [CO32–] << [HCO3–] ( a IInd ionisation will

occur upto negligible extent).

1. BOH + HCl BCl + H2O (in titration) 0.1h 2

or Kh = (1 - h) = 10–2 (solve quadratic equation to

B+ + H2O —→ BOH + H+


For titration : get ‘h’, as we can’t write 1 – h . 1, since h > 0.1)

Macid Vacid = Mbase Vbase (since both are monoacidic
\ h = 0.27
and monobasic) & [H+] = 0.1 × 0.27 = 2.7 × 10–2 M

2
15 # V = 2.5 # 5
2 2.

V = 3 × 2.5 = 7.5 mL MX MX2 M3X
s12=4×10–8 4s2 = 3.2×10–14
3 27s3 =2.7×10–15
4

In resulting solution,
2# s1 = 2×10–4 s23 = 8×10–15 s34 = 10–16
5 2.5 2
+
[B ] = = 20 = 0.1 M
10 s2 = 2 x 10–5 s3 = 10–4
K 10 -14
Kh = KW = -12 = 10–2 ⇒ s1 > s3 > s2
b 10
⇒ MX > M3X > MX2

Chemistry
3. CH3NH2 + HCI —→ CH3+ + CI– 8. H2SO4 HSO -4 + H+

Initial moles 0.1 0.08 1M – –
– 1M 1M

moles after reaction 0.02 0 0.08 mole (in
1 L solution) ⇒ buffer
Na2SO4 —→ 2Na+ + SO2-
4
–2
1.8 × 10 M – –
[OH -] [CH3 NH3+]

Kb = [CH3 NH 2] 3.6 × 10–2 M 1.8 × 10–2 M
[OH -] # 0.08 5 HSO -4 H+ + SO2- 4 ; K a = 1.2 × 10–2 M

or, 5 × 10–4 = or, [OH–] = 4 ×10–4
2

0.02 1M 1.8 × 10–2 M

1 + x 1 – x 1.8 × 10–2 – x
]1 - xg^1.8 # 10 -2 - xh
KW 10 -14 # 4
a [H+] =
- or, [H+] =
]1 + xg
[OH ] 5 # 10 -4 K a = 1.2 × 10–2 =
2

= 8 × 10– 11 M. Since x is very small (1 + x) - 1 and (1 – x) - 1
4. NaX is a salt of weak acid and strong base.
SO2-
4 = (1.8 × 10–2 – 0.6 × 10–2)M

\ Hydrolysis constant of NaX is Kh = = 1.2 × 10–2 M
K
KW =
1 # 10 -14
= 1 × 10–9 PbSO4 —→ Pb2+ + SO2- 4
a 10 -5 – 1.2 × 10–2 M
For this type of salt, Kh = Ch2
s (s + 1.2 × 10–2)
Ksp = s(s + 1.2 × 10–2) = 1.6 × 10–8)
C = molar concentration (PbSO4)
h = degree of hydrolysis Here, (s + 1.2 ×10–2) ≈1.2 × 10–2 (since ‘s’ is very small)
s(1.2 × 10–2) = 1.6 × 10–8
\ 1 × 10–9 = 0.1 × h2
1.6
⇒ s = 1.2 × 10–6M = X × 10–Y M

1 # 10 -9
or h2
= 0.1 = 1 × 10–8 h = 1 × 10–4 ⇒Y=6


\ percentage hydrolysis of NaX salt 9. at V = 6 ml rxn is complete
= 1 × 10–4 × 100 = 1 × 10–2 = 0.01 % So V = 3 ml is half of eq. pt
5. Lesser the Ksp, earlier is the precipitation (if the at which pH = 11
formula type of precipitation & concentrations of pOH = (14 – 11) = pKb + log1
various precipitating ions is same). pKb = 3
6. (c) HNO3 + CH3COONa mixture can act as buffer 10. For ppt, [Zn+2] [S–2] = Ksp
solution if volume of HNO3 solution taken is lesser
6S -2@ = 1.25 ×10
-22

than volume of CH3COONa solution because of 0.05

following reaction : = 2.5 × 10-21 M

CH3COONa + HNO3 —→ CH3COOH + NaNO3 H2S 2H+ + S-2
6H +@2 × 2.5 ×10 -21

(d) CH3COOH + CH3COONa - mixture will act as
K Net = 10 -21 = 0.1
buffer.
6H @ =
+ 2 1
25
7. H2CO3 + NaOH → NaHCO3 + H2O
6
+
@ 1
H = 5 M = 0.2 M
Milli moles 10 10 -
At end 0 0 10 + 10 = 20 11. AB] s g A+ + B- K = 2 # 10 -10
Final mixture has 20 milli moles NaHCO3 and 10 milli
B- + H+ HB K = 108
moles Na2CO3

Adding the above equation we get
Salt
pH = pKa2 + log Acid

AB] s g + H + A + + HB K = 2 # 10 -2
pH = pKa2 + log b 20 l [Buffer : Na2CO3 + NaHCO3]
10 s s
2
s
= 10.32 - log 2 = 10.02
` = 2 # 10 -2
10 -3
s
` 2 = 2 # 10 -5

or, s = 20 # 10 -3 = 4.47 # 10 -3

` Y = 4.47.
 Ionic Equilibrium
12. AgCl (s) Ag+ + Cl– Ksp(AgCl)=1.6×10–10 13. Basic solutions will convert red litmus blue.
Z Z+Y KCN b_b
bb
CuCl (s) Cu+ + Cl– Ksp(CuCl) = 10–6 K 2 CO3 b` their aqueous solution will be basic due
b
Y Z+Y LiCN bb to anionic hydrolysis.
a
Z (Z + Y) = 1.6 × 10–10
14. Given Ka = 10–4
and Y (Z + Y) = 10–6


pKa = 4
⇒ (Z + Y)2 = 1.6 × 10–10 + 10–6


C = 0.01 M
⇒ (Z + Y)2 . 10–6

1 1 1 1
⇒ Z + Y = 10–3

pH=7+ 2 pKa + 2 log C=7 + 2 (4) + 2 (–2) = 8

We know,
⇒ Z (Z + Y) = 1.6 × 10–10

⇒ Z × 10–3 = 1.6 × 10–10

⇒ Z = 1.6 × 10–7

⇒ 1.6 × 10–x = 1.6 × 10–7

⇒x=7

 IUPAC Nomenclature

Chapter 10 IUPAC Nomenclature

INTEXT EXERCISE: 1
14 - 10 6. Answer self explainatory
1. Degree of unsaturation = 2 =2
7. Answer self explainatory
2. 5 p bond and 2 ring hence 7
12 - 12 + 0 8. Answer self explainatory
3. degree of unsaturation = =0
2 9. Answer self explainatory
4. Do self
10. Answer self explainatory
5. 2 pi and 2 sigma hence sp hybridization
INTEXT EXERCISE: 2
1. Fact
2. All atom of cycle are carbon
7.
3. At least one atom of cycle is non-carbon
8. In homologous series functional group must be same
4. Answer self explainatory
9. homocyclic - all atom carbon
5. Homolog have same functional group
→ alicyclic - non aromatic cycle
6. Fact
10. N-connected to 3-carbon atom
INTEXT EXERCISE: 3
1. OH - connected to 2o­ carbon.
2. Answer self explainatory four methyl group at
7. 2, 3, 4, 7 positions.
3. Do self
4. Do self
8. If substituent positions are same then give smaller
5. position to substituent which comes Alphabatically
first.
9. Do self

CH3 10. Do self

6. H3C CH2 CH2 CH2 CH2 CH C CH2 CH3

10 9 8 7 6 5 4

3 2 1
CH3 CH2 CH2 CH3
INTEXT EXERCISE: 4
1. Do self
2. Do self 6.

3.
7.
double bond has priority over triple bond.
4.
8. Do self
Br
9. Put cis before alkene name
5. Fact
10. Do self
Chemistry
INTEXT EXERCISE: 5
1. Answer self explainatory
2. (a) If linear chain and cyclic chain has same No. of 6. (c) 3,3-Dimethylcyclohexene
carbon atom then cyclic chain is main chain
(c) linear chain is main chain because it has double 7.
bond.
(d) If linear chain and cyclic chain both chain has
double bond hence cyclic chain is main chain. 8. Substituents which comes alphabetically first should
be given smaller number.
3. Answer self explainatory
9. Do self
4. Answer self explainatory
10. lowest locant rule should be followed for substituents
5. Answer self explainatory
INTEXT EXERCISE: 6
1. Follow Locant’s Rule.
6.
2. acid, alcohol, aldehyde, ketone
3. Answer self explainatory 7. Carboxylic Acid is principal functional group and
4. No degree of unsaturation hence alcohol. the C atom of the -COOH group is a part of the
parent chain.
5. Formula does not have degree of unsaturation where
as cyclohexanol has 1 degree of unsaturation 8. Answer is self explainatory
9. —OR is Alkoxy substituent
10. Answer self explainatory
INTEXT EXERCISE: 7
1. Answer self explainatory 8. —CHO formyl
2. - one for one ketone group
—COOH carboxylic acid as
3. Open chain is main chain as it has functional group carbon is not included in main
4. Bromine should get smaller no. as it comes chain
alphabatically first.
9. , ,
5. Acyl chloride group
6. Numbering starts from carbon of aldehyde group
7. Cyanide is principle functional group
10. 2-methyl pent-3-ynoic acid

INTEXT EXERCISE: 8
1. Answer self explainatory
2. Butyl at 3rd position 5.
3. Acid is main funcational group
6. 3-(Cyclohexylcarbonylamino)-2-hydroxy-6-
sulphobenzoicacid

7.
4.
 IUPAC Nomenclature

8.
9.

10. Ester is main functional group and is

substituent

EXERCISE - 1

1.
24.

2. No. of 2o hydrogen = 3 × 2 = 6 25. First lowest locant rule then double bond should get
smaller number as compare to triple bond.
4. (c) I → alkyne II → diene 27. long chain containing double bond, numbering start
from double bond.
5. degree of unsaturation
4-ring → 4 28. double bond has more priority over triple bond.
double bond → 10 ( 9 C==C, 1 C==O) 29. (c) chain containing double bond has priority.
6. Formula: C6H6 hence double bond equivalent 30. Answer correction (a) and (c) are correct
6×2+2-6
2 =4
(b) (d)

7.

9. Non aromatic and has hetro atom in ring 31.

10. d is aromatic hence not alicyclic
32. Linear chain has double bond hence it is parent
13. (d) as it contain C, H and double bond.
chain
15. homologue should have same functional group
34. —OH is functional group, lowest locant rule is same
for OH hence apply it for substituents

18. 35. is principal functional group, and

C==C should be included in main chain
19.
36.

21.
37. —COOH is principal functional group and —NH2 is
substituent
23. 38. —CHO, functional group, longest chain including
—CHO and C==C is parent chain
Chemistry

39. is principal functional group

54.
40. Longest chain containing CHO at both end
41. anhydride is principal functional group
42. ester is the functional group

43. 56. acid is prinicipal functional group and —NH2 is

substituent
oxy 57. Methoxy ethane.
60. Numbering start from carbon of OH and goes
44. is principle functional group clockwise so that double bond get minimum number
61. Priority: functional group > double bond >
45. substituent
62. aldehyde is principal functional group and its carbon
is not included in parent chain.
63. acid chloride is principal functional group and its
47. ,
carbon is not included in cyclic chain.
48. homologue should have 2o amine 64. —CHO is principal functional group
65. ester is principal functional group
49. , 3-carbon chain
66. ester is principal functional group and is
substituent.
51. OH is principal functional
group and -NH2 is substituent. 67. lowest locant and methyl comes
before nitro hence it should get
minimum number
52.
70. Numbering should start from carbon of acid
53. acid is principal
functional group
71. (a) numbering should be done so that
Cl gets smaller number

EXERCISE - 2
4. Longest chain has seven carbon

1. 5.

2.
6.
3. Cyclic but not aromatic

1oC has 3H, 2oC has 2H and 3oC has 1H.
o o
1H 2H
o
3H
7. Longest chain containing double bond.
8.
9. Longest chain containing both double bond
numbering follow lowest locant rule for substituents.
10. Chlorine should get lowest number as compare to
ethyl as it comes alphabatically first
11. Lowest locant rule then ethyl, methyl, propyl gets
lowest numbers according the alphabatic sequence.
12. Double bond should get minimum number then
lowest locant rule for substituents
13. H3C–CH= is called ehtylidene
15. Double bond should get minimum number then
lowest locant rule for substituents.
16. —SO3H is principal functional group and
—OH are substituents.
17. Ketone is principal functional group and —OCH3,
—OC2H5 are substituents.
18. In case of cyclic anhydride -dioic anhydride should
be used.
19. , amide is principal functional group
—NH2, are substituents.
20. As all three —COOH groups are connected to parent
chain hence their carbon are not included in parent
chain.
21. Amide is functional group.
22. Main chain include carbon of —OH and double
bond.
23.
24.
26. COOH is principal functional group, , —OH,
NO2 are substituents.
IUPAC Nomenclature
27. Epoxy group
28.
29. methyl
31. —NH2 and —CHO are
substituent
32. Chain containing both —COOH group should be
main chain
34. , epoxy at 2, 3 position
36. ester is main functional group and its carbonyl
, carbon is not included in parent chain.
37. Aldehyde is principal functional group and it carbon
is not included in parent chain.
38. Carboxylic acid is principal functional group and its
carbon is not included in parent chain.
39. Linear chain is parent chain as it has 4-carbon
40. Cyclic chain has more carbon hence parent chain
41. Acid is principal functional group
42. Ester is principal functional group
43. Aldehyde is principal functional group
45. —NH2 is principal functional group
46. —COOH is principal functional group
47. Ester is principal functional group
48. amine is principal functional group
49. is functional group and linear chain is parent
chain
50. —OH is functional group
51. —COOH is principal functional group
52. —OH is functional group
53. Chloromethyl is substituent
54. —CN is principal functional group
55. Spiro compound, first number in smaller ring then
bigger ring such that double bonded carbon get
minimum number.
Chemistry
56. Bicyclo compound, first number in bigger ring then 58. Acid is principal functional group

smaller ring such that get minimum number. 59. (amide) is principal functional group
60. Acid is principal functional group

EXERCISE - 3
9.

1. Ans : 4.

10.
2. N
H

3. Total —CH3 groups = 2

11.
4.

5. Answer correction → 4
12.

6.
13.

8
16 ⇒ 1 + 6 = 7

7. 14. hence 4 + 5 = 9
H 2o 4×2 6×2
+ +
H 3o 1×1 + 3 × 1 = 24
⇒2+4=6 15.
8. (i) × (ii) : (iii) : (iv) : (v) : (vi) : (vii) :

hence 5
 IUPAC Nomenclature
EXERCISE - 4

21.
1. common name -Isobutyl; as —CH3
substituent on second last carbon
(2-methyl propyl)
2. One degree of unsaturation and one oxygen hence 22. Amide is principal functional group
acyclic Aldehyde
24.
3. II I IV III
v 11 12 9 10
r 3 3 2 2
5. Acid is principal functional group
25. (I) -6 (II) -3 Total = 15

Numbering start from carbon connected to —COOH
(III) -1 (IV) -5
and C==C should get least locant
26. All are different in position of —OH or substituents
6. Amide the principal functional group, carbon of both
or length of parent chain
amide should include in parent chain numbering
should be such that —C—C—C—C get minimum
locant.
7. Acid is principal functional group 27.

8. Bromine should get smaller

number as it comes 28. a ⇒ Cn H2n-6
alphabatically first b = Cn H2n-2
11. —OH is principal function group and numbering d - Cn H2n-6
should be like that —Br get smaller number
12. double bonds should get minimum numbers 29.
13. Cyclic anhydride hence -dioic anhydride
14. —CHO is principal functional group hence
numbering start from it.
15. E-2-Chloro-3-iodo-2-pentene
30.
16. Amide is principal functional group, parent chain
should include double bond.
Answer (a) and (d)
17. Lowest locant rule: (1,2,3,5) and chlorine should get
smaller number as compare to Iodine 31. (a) acyclic part is main chain

18. Parent chain include carbons of both —COOH (b) acyclic part has C=C
group
\ main chain.
32. (a) cyclic part is main chain
19. —COOH is principal functional (b) acyclic part is main chain
group (c) acyclic chain has more carbon atoms
(d) cyclic chain has double bond
20.
33. (a) 3-methylbutan-2-one
(b) 3-ethyl pent-4-en-2-one
(d) 2-hydroxy-4-methylpentan-3-one
34. (d) cyclohexane carbaldehyde
Chemistry
35. (b) benzene carbonyl chloride
38. —COOH is principal functional group 53.
39. One is common name other is IUPAC
41. If carbon of —C≡≡N is included in parent chain then
nitrile otherwise cyanide Molecular formula → C18 H38
Mol. wt = 18 × 12 + 38 × 1 = 254
43. 44. 45.
57. Three in ring, one in —COOH
59. Acid is principal functional group
60. Answer is self explainatory
61. p bonds - 3 p bond in ring, 1 p bond in —COOH,

1 p bond in
50.
63.
64. 65. 66.

51.

52. follow alphabetical order

(c) cyclopenta-1, 3-diene is correct name
(d) follow alphabetical order of substituents

Cl 1
CH3
1. 5. 2 3
: 4-Bromo-2-methylpent-2-ene
4

Cl 5
Br
“1, 1 - Dichloroethane is Ethylidene chloride” CH3
7
2 6.
2. O2N 6 5
4
3 1 H

O O
4Methyl6nitro3oxohept4enal 7. Self explainatory answer
O
3. 2
4
8. : 2, 2-dimethyl propane
1 3 5
Mesityloxide
IUPAC [4-Methylpent-3-en-2-one] 9. Fact
6 10. Do self
CHO
3
4. 2 CH3
5
H3 C 4

COOH
1

IUPAC name 2, 5-dimethyl-6-oxo-hex-3-enoic
acid
 IUPAC Nomenclature

1. —SO3H is principal functional group

2. —COOH is principal functional group
OH

3. HC C 3
2
1
COOH
4
HC C
6 5

3-ethynyl-2-hydroxy-4-methyl-hex-3-en-5-
6. —C≡≡N is principal functional group
ynoic acid.
7. Answer self explanatory
4.

5.
 Isomerism

Chapter 11 Isomerism

Intext Exercise 1
1. Option (b) has all same 1 hydrogen
o
7.
2. No. of C-atom different in (a)
3. (b) option has same functional group but different
arrangement around them.
4. (i) and (iv) are 1o and 2o amine respectively hence 8.
functional isomers.
9.
5.
10.
6. Cl
Cl
Cl Cl
C
C
C C C C

Intext Exercise 2
3. Phenol is aromatic hence max enol % in d. 8. (b) active methelene group and no +m group.
4. (a) has no a-hydrogen on sp3 in keto form 9. (c) has 3-intramolecular hydrogen bonding and
once aromaticity is over then keto form is more
5. (b) has a-hydrogen on sp3 carbon.
stable then enol form.
6. (d) has a-hydrogen on sp3 carbon.
10. B, C, D, F, G will show tautomerism.
7. (a) has active methelene group and its enol form is
resonance stabilized.
Intext Exercise 3
3. All have different groups on two atoms.
7.

4.

8.

5. (a) (b) (c)

Ans. 4
9. (i) cis (ii) trans (iii) trans
No GI No GI No GI
6. Cumulenes with even No. of double bond do not
10.
show GI.
Chemistry
Intext Exercise 4
0 × 20 + 80 (- 12)
5. a mix = 100
amix = - 9.6 8.

6. (d) is mirror image of structure given in Q.

9. I and II are G.I. and II has intramolecular hydrogen

7. bonding between
10. If you make even No. of changes about a chiral
atoms then its configuration remains same. If odd
No. of changes then its configuration changes.
Intext Exercise 5
1. Odd No. of changes about both the chiral carbon 4. (d) two chiral atoms without symmetry.
produces enantiomers
5. Odd No. of changes about chiral atom produces
2. ⇒ 24 = 16. enantiomers.

6. Put lowest priority group on dash line by making

even no. of changes. Move 1 → 2 → 3 If clockwise
then R otherwise S.
3.
7. Three chiral atom hence 23 = 8.

Intext Exercise 6
1. Gauche form has intramolecular hydrogen bonding. 6. in (b) dihedral angle is 60o hence minimum torsional
o o strain, CH3—CH3 group are at maximum distance
2. CH3, CH3 has 180 angle after 120­ rotation angle
o hence minimum VW strain.
between then is 60 hence gauche form.
7. Energy : Eclipse > partial Eclipse > gauche > anti
4. In most stable conformational isomers bulky group
should be on equatorial position as it is trans both 8. (a) Intramolecular hydrogen bonding and minimum
group at (e, e). tarsional strain.
5. Stability : III > II > IV > I 10. Energy level of propane is above ethene
Me3C → e e a a eclipsed ethane → high energy
CH3 → e a e a staggered propane → low energy

EXERCISE - 1
1. length of parent chain changes

3.

2.

4.
 Isomerism

27.
6.

7.
29. (a) Shows about 6 member ring

(b) (c)
8. H3C CH3
30. (a) compound has Z-conf. about C=C and Z should
be written first while writing name.
9. C—C—C—C—C—C
31. It has single chiral carbon hence it is optically active.

32. (a) no chiral carbon atom.

33. 2-chiral carbon with symmetricity hence
2n-1 + 2n/2-1 = 21 + 2o = 3

34.

11. C – C – C – O – C C – C – O – C – C C - C - O - C
|
C
12. (b) has 2 degree of unsaturation while other has 1. 35.
15. III pair is functional isomers.
rd

16. (d) as it form aromatic enol form. 36. (b) —→ (d), 2 changes hence identical
37. (b) —→ (c), 2 changes hence identical
17. (d) has no-a-hydrogen.
38. 3 No. of chiral atom with symmetricity hence meso
18. compounds are

19. Alcohols do not exhibit Tautomerism.

20. H - C / N diad
C! = N-H
2 1
21. (d) active methylene group has more enol content.
22. (c) both double bonded carbon has different groups. 39. cis — cis, trans — trans, cis S trans
cis R turn hence 4
23. both vectors cancel out. 25 × (- 158) + 75 ×158
C 40. a = 100 =+ 79 o
|
24. C—C—C==C C—C==C—C C - C = C
cis/trans 41.

25. (a) Ph - C - C = C - C different groups on double

| | bonded carbon
H H
42. Same physical property but different optical
property.
43. (d) because it is always unsymmetric
Chemistry
44. (c) has center of symmetry.
53.
45.

—→ 2 changes hence same (lowest priority group

should be on | | | | | line) 54. two chiral atom with symmitricity
two optically active, one optically
inactive
46. 55. Restricted rotation : C ≡≡ C > C == C > C — C
56. (d) as it is aromatic.
47. Identical substituent on the same side. 57. Fact
48. Mirror image 58. Intramolecular hydrogen bonding make stable
C confermers.
51. (c) C C C COOH
C 61. Flagpole-flagpols repulsion
(a) C C C C 62. Baeyer’s angle strain :
C cyclopropane>cyclobutane>cyclohexane>cyclopentane
(b) C C C C
63.
H
(d) C C C* COOH
64.
C
EXERCISE - 2

1. Ans. 4 6.

2.
7. Relative position changes hence position isomers
3. C—C—C—N—C, C—C—N—C—C,
C 9. \ metamers groups around changes
;
C-C-N-C
C C
10. \ metamers groups around changes
4. ; ;C C C C
12. Acidic hydrogen replaced with D
OH 

5. ; Ph C

C C CH2
C C C 13. Enol content :
NH2
1o
 Isomerism
14. Enol content :
30. In case of MP : trans > cis

DM : cis > trans

BP : cis > trans

15.

16.
31. (a) 2 (b) 2 (c) 4 (a) 2

32.
17.

18.

33.
19.

20. Both the double bonded c-atoms have same groups

21. (c) 34. hence I and II same

22.
35.

23. numbering from bottom to top hence D configuration

36. (b) Same group on opposite side at equal distance
24. This show GI and it has E-configuration
from center.

25. 37. (d) has plane of symmetry and center of symmetry.

Other has no symmetry

38. hence enantiomers

26.

27. 39.

40.
28.

41. Energy :
29.
 Chemistry
42. Stability : 46. Minimum v w strain, minimum torsional strain.

47.

45. Minimum torsional strain condition

49. bulky group should be on equatorial position for
stability
EXERCISE - 3
CH3 CH3

2. CH3 CH CH2CH3 on monochlorination
ClCH2 CH CH2CH3
CH3 CH3
10.
 

onochlorination
ClCH2 CH CH2CH3 and CH3 CH CH CH3
Cl
11. acetic acid is optically inactive hence zero.
I Cl F Cl Cl I
3. C C + G.I. ; C C + G.I. ; C 12.
C 1, 2+ →G.I.cis → (a, e) → (iii), (viii)
Br F Br I F Br1, 3 → cis → (e, e), (a, a) → (v), (vi), (vii)
Cl F Cl I Cl
1, 4 → cis → (a, e)
C C + G.I. ; C C + G.I. ; C C + G.I.
F Br I F Br
4. (iii) is incorrect. 13. a →

With one or more chiral center a molecule may or
may not be optically active.
(p) Same
5. In (ii), (iii) and (iv) they are metamers. (Q) enantionmer

In (i), they are positional isomers. (r) enantiomers (s) enantiomer
6. CH3CH2CH2COOH, CH3 CH CH2COOH , (t) enantiomer
CH3 8
14. x % = 32 × 100 = 25 %

CH3CH2COOCH3, CH3COOCH2CH3,
CH3 15. [a]mix = 60×150 + 40× - 150 = 20×150 = 30 o
100 100

HCOOCH2CH2CH3, HCOOCH
CH3

16. 23 = 8
7.

17. cis - cis

tran - trans
8. cis - R - trans
cis - S - trans
hence 4.

9. (i) E (ii) Z (iii) E (iv) E 18. two chiral carbon with symmetricity hence 3 optical
isomers and geometrical isomers about double bond
hence 3 × 2 = 6 (four optically active, two meso).
 Isomerism
20. Z = 2 R=3

Y = 2 W=2
19. 25 - 1 = 31

EXERCISE - 4
1. Specific rotation fixed for a compound at given
temperature and light
10.

2.

11. Intramolecular hydrogen bonding

6 ×13.5 - 4 ×13.5 2
3. a mix = 10 = 10 ×13.5 =+ 2.7 units

2
excess % = 10 ×100 = 20% 13.

4. Optically pure compound can separate enontioners

5.

6.
hence 4 fraction

7.

14. at 1, 2 position —→ (a, a) or (e, e) —→ trans

(a, e) —→ cis

C 15.

C C C C C C C C C Total 7
16. (a) plane of symmetry
C O C O

(b) plane of symmetry
8. ⇒ 2 = 16
4

(c) plane of symmetry

(d) No. element of symmetry
all are unsymmetrical hence optically active
17.

9.
19. (a) has center of symmetry,

(b) does not have any plane of symmetry
20. Both structure are diasteromer
21. No element of symmetry due to methyl group.
Chemistry
22. Product should no show geometrical isomerism 34. (a), (b) and (c) show GI about double bond and (d)
otherwise there will be more than two product hence will show around single bond.
products are Ph—NH—N==CH2,
35. (d) does not show GI.
36. Threo-functional group opposite side, erythro-
functional group same side
37. (c) has same group on double bonded carbon atom
23.
25 = 32.
(b)

24. 27 = 128

25. 2 =8
3
38. (a) planar, not chiral
(b) Chiral, resolvable
(c) Chiral, non resolvable
(d) planar, not chiral
26. (d) does not have a-hydrogen to show tautomerism Ans (b)

40.
,

(A) has 4 carbon (B) has 3 carbon hence they are not
27. , , related

, 41.
28. For cis-trans Nomenclature at least one group
should be common on double bonded carbon atoms.
29. (c) two geometrical isomers about partial double 42. I is 2s, 3s and II is 2s, 3R hence configuration changes
bond about only one carbon hence they are diastereomers.
43. (a) chain isomers (b) position isomers
(c) position isomers (d) functional isomers
s-cis s-trans 44. (a) and (b) are optically active and mirror image
(d) No. of geometrical isomers = 2 = 35 5 to each other in horizontal mirror. (b) and (c) are
diastereomers as there is configuration change on
30. (a) resonating structure one chiral carbon only.
(d) Functional isomers 45. (a), (b) and (d) does not have H for tautomerism
31. (a) function isomers
(c) position isomers
(c)
32. (II) is optically inactive
46. enantiomers have same physical and chemical
properties but different reactivity with chiral reagent
33.
and different optical rotation of plane polarized
light.
 Isomerism

47.
54.

55. (a) chain isomers (d) functional isomers

56. (a) I → syn II → anti

57. (c)
48.

58. (d) functional isomers

49. (d) no H for tautomerism 59. II → dihedral angle 60o hence minimum torsional
strain and CH3 groups are at maximum distance
hence minimum VW strain.

(a) (b) (c)

60. (b)

(a) and (d) has plane of symmetry

50.
(c)

61.
51. enol context :

1 2 62. (a) does not have any chiral atom.

63.

3 4

2>3>4>5>1

5
52. (b) no H for tautomerism

(a)

(c) (d)

64. Asymmetric - optically active and free from all
symmetry elements.
53. (b) has repulsion betuaen groups hence enol
form more stable.
Dissymmetric - optically active compound with Cn
symmetry elements.
(d) becomes aromatic in enol form.
Chemistry
75. (a) Structure isomers, GI = 2 for both
65. (b) Structure isomers, GI = 3 for both
(c) GI, GI = 2 for both
GI
76. * 2+2

66. (a) minimum VW strain and tortional strain

*
2 + 2
67. (c) Intramolecular HB and minimum VW strain *

69. (c) maximum VW strain and maximum torsional

strain 23 = 8
70. (d) small groups hence less torsional strain
71. (b) has plane of symmetry
72. p form is racemic mixture hence optically inactive
due to external compensation. 77. (a) Position isomers hence structural isomers first E
74. I II → conformers and second Z.
(a) DM : > (b) GI, first Z and second E.
Stability : > : hydrogen bonding (c) GI, first E and second Z.
(b) Same as (a) (d) Position isomers, structual isomers, first E and
(c) I II → Not confermers but diasteromers second Z.
DM : >
Stability < : Less VW strain
(d) I II → confermers
DM : >
Stability > : hydrogen bonding

1. Dimethyl cyclopentane CH3

H3C CH3
1,3-dimethylcyclopentane
1,1-dimethylcyclopentane no stereoisomer
CH3 CH3
CH3 will show stereo isomerism, Its stereo isomers are
1,2-dimethylcyclopentane CH3 CH3
will show stereo isomerism, Its stereo isomers are =
CH3 CH3 (identical)
CH3 CH3 CH3 CH3
=
(identical)
CH3 CH3
CH3 CH3
CH3 CH3
(enantiomers)
(enantiomers) CH3 CH3
 Isomerism
O 7. (a) Ph—C—C==C—C
Cl
NH C CH cis + trans
Cl
2. O2N CH CH CH2 OH
8.
OH
chloramphenicol
9.
O H
H S CH3 
3. R C HN   CH3 
mol wt = 12 × 5 + 4 × 3 = 72
N  COOH


O H
Star marked atoms are chiral centers. 10. (a)
O
11. 2×2=4
4. is tautomer of
O O
O O

12.
O

O O is aromatic
O in nature.

13. (a) is chiral. \ rotates plane of polarised light.

5. C3H6O ⇒ CH3–CH2–CH=O (aldehyde)
& CH3 C CH3 (ketone) 14. Fact.
C C C C
O
15. C C C C ; C C C C
Therefore they are functional isomers.
Cl Cl
CH3
6. (2S, 3R)
S

H Cl
16. H
R

Cl POS is present
CH3
17. I, II have chiral carbon atom.

1. Meso compounds have plane of symmetry. In case OH 1

of butan-2, 3-diol, gauche form is the most stable CH3 2 CH3

due to intra-molecular H-bonding. H H

H Q. 3ethyl2methyl pentan2ol
Hbonding 3 4 5
O
H O H H C2H5
CH3
CH3
H Me C2H5 H
Me R. 3ethyl2methyl pentan2ol
2 1
2. HO 3 CH3
CH3 C2H5
4 5
HO CH3
CH3 CH3
P.
3 2, 3, 3trimethyl pentan2ol 5
4 5 C 2H 5 CH
2
CH3 2 C2H5 S. 4 3
CH3
1 3ethyl2methyl
1
CH3 H H pentan3ol
OH
Q and R is same.
Chemistry
CHO 7. (a) can rotate about partial double bond
H OH (b) planar (c) planar
3. H OH (d)
CH2 OH
DErythrose 8. Total 6 optical isomers, 4 OA, 2 OIA
CHO
RER RES
H OH
RZR RZS
Compound P It is Identical P-2
H OH
SES
CH2 OH SZS
CHO CH3 CH2Br
9. + Br2 UV
HO H
Compound Q It is Diastereomer
Q-1 H OH Br (A)
CH2 OH CH2 + CH3
CHO + +
+
Br
H OH
Compound R It is Diastereomer (B)(+) (C)(+)
R-1 HO H
CH3 CH3
CH2 OH + + Br
+
CHO
Br E(+)
HO H
Compound S It is Enantiomer S-3 (D)(+)
HO H
Br CH3
CH2 OH + + +
Ans. P-2, Q-1, R-1, S-3 Br
F(+) G(+)
4. Chiral atom is not necessary for chiral molecule

Monobromination of 1-methylcyclohexene in
presence of UV light proceeds by free radical
5. (a) (b) mechanism. The allyl radicals are formed which
are stabilised by resonance. The secondary alkyl
radicals are also formed which are stabilised by
hyperconjugation. Out of the seven products formed,
(c) (d) six of them are optically active. So, 13 possible
isomers are formed.
O
6. M, Q are diastereomers. 10. O O O O O
* *
about one chiral atom hence diastereomers * *
(1) (2) (1) (2) (1) (3)
 Isomerism
HO H OH HO H OH HO H OH

11. HH
Pe
HH
Pe
HH
Pe
Pe Pe Pe
HO H OH HO H OH HO H OH
Optically Inactive Optically Active Optically Active
OH OH
HO H OH HO H HO H
Pe Pe
H OH H OH
Pe
HH
Pe
Pe Pe
HO H HO H H HO H H
OH
Optically Inactive Optically Active Optically Active
OH OH
HO H Pe HO H Pe
H OH H OH

Pe Pe
HO H H HO H H
Optically Active Optically Active
12. Two chiral atom but bridge head does not allow other diastereomers to form hence only given structure and its
mirror image. Ans 2

13.

 General Organic Chemistry

Chapter 12 General Organic Chemistry

INTEXT EXERCISE: 1
1. In (c) structure II has more number of bonds, so 6. There are 10e! on carbonation which is impossible.
more stable. 7. IV > II > III > I
2. Theoretical HOH = 5 × 28.8 = 144.0 kJ/mol -ve on O atom -ve on O atom -I of two
Exp. Ho = 99 kJ/mol RE = 45 kJ/mol
Resonance energy = (DHydrogenation) double bond conjugation
(Theoretical-Exp) 5 6
8. CH 2 = C = C = CH 2 * CH 2 - C / C - CH 2
3. 1st structure is aromatic in all these examples and 6 5
2nd structure is not aromatic and resonance energy
* CH 2 - C / C - CH 2
of aromatic compound is higher than non-aromatic
compound. 9. pentavalent nitrogen is impossible
4. For resonance conjugation should be present as that
conjugate site does not have p bond. 10. (a) and (b) are proper resonating structures while (c)
+ and (d) violate octet rule. However, the N atom of
5. H 2 N = CH - CH = CH - O CH3
(a) should not have the lone pair.

Octet is complete and +ve charge is on less
electronegative nitrogen.
INTEXT EXERCISE: 2
1. CH3 - CH 2 # MgBr 5. More is the number, of aH, more is hyperconjugative
structures.
6. -ve charge species has more + I
3.
7. C≡≡C has more EN then benzene
9. C==C—C—C—C—C
2aH +

C—C==C—C—C—C C—C—C==C—C—C
4. In (d) no H.C. is
possible (Bredt’s rule) 5aH + 4aH == 11aH

INTEXT EXERCISE: 3
1. Aromatic compound → Cyclic delocalization 9. B has empty orbital and it has 4 p e-
→ (4n + 2) p e-
→ sp2 hybrid only

8. due to resonance strain is released for three

p bond hence more resonance energy.
10.

INTEXT EXERCISE: 4
1. CH3 - CH = CH - CH = CH - CH3 In ‘b’ there is only resonance. In ‘c’ there is
(a) reso + H.C. hyperconjugation.

bond order↓, bond length↑ In ‘d’ pure double bond.

Chemistry
2. ‘C’ has less number of a - H so it is less stable and
high value of heat of hydrogenation.
5.
3.

1 1
6. BE \ Resonance of free radical form \ a - H
BE: Hb > Hc > Ha > Hd
sp2C 1 a H 2 a H 5 a H + Resonance
+ Resonance
7. BE: Hd > Hb > Hc > Ha
1 a H 3 a H 8 a H Resonance
+2aH
8. H of H : ii > iv > iii > i
3 a H 8 a H Resonance Resonance
4. Bond dissociation energy of C - H is inversely +5aH +8aH
proportional to stabily of the free radical.
9. Bond strength ∝ Bond order
10. Heat of combustion ∝ No. of carbon atoms
INTEXT EXERCISE: 5
1. Mesomeric effect is applicable at ortho and para 7. : CF2 >: CCl 2 >:CBr2 >: Cl 2 $ Stability
position
If no back bonding is possible, singlet carbene is less
2. Vacant d-orbital resonanace stable than triplet carbene.
3. Fact
6
CH3 .- CH 2 PP CH 2 8. aromatic \ more stable
Carbanion Carbene Singlet Triplet carbene
+ +
4. + M, + I stabilize carbocation 9. C - O - C - C < C - O - C
-I of O +M of O
5. R - Cl $ R + + Cl 6 9H 0
Bond Energy of carbon halogen bond
1
\ Stability of carbocation 10.
6. More stable carbocation due to delocalisation and
hyperconjugation.
INTEXT EXERCISE: 6

1.
II.

III.

1

pK a \ K
a
2. EWG increases acidic strength (- I, - m)
EDG decreases acidic strength
Ka ∝ Stability of carboxylate ion.

Stability of ion is III > II > I

I. ⇒ Ka III > II > I
⇒ pKa III < II < I
 General Organic Chemistry

7. - m increases acidic strength

1
3. Acidic strength \ pK
a

8. Acidic strength ∝ stability of its conjugate base or

anion stability order

EWG increases acidic strength.
4. Acidic strength a number of EWG. >
5. As more stable is carboxylate ion, more in acidic
strength.

∵ III > II > I

HC / C - COO - CH 2 = C H - COO -
- - 9. Acidic strongest ∝ E. N. of atom containing
sp sp2 Hydrogen

CH3 - CH 2 - COO - CH3 OH > CH / CH > NH3 > CH 2 = CH 2
-
sp3 *
sp hybrid carbon is more electronegative than
nitrogen.

% s character ∝ E.N. of carbon ∝ stability of anion.
10. CH3 C O O H CH3 C O O+H
6.
O O
Peroxyacetic acid No resonance
CH3 C O H CH3 C O+H
O O
ve charge stabilized
by resonance
INTEXT EXERCISE: 7
1. EWG decreases basic strength EDG inceases basic + M of 2 NH2 group
strength

6.

2. N-1 gets protonated because charge on this nitrogen
atom is stabilized by resonance.
7. lone pair of N is part of aromaticity
hence least basic

8. + I of 2 CH3 group and due to
3. N (II) is the most basic. SIR effect, N-lp doesn’t involve
in resonance.

4. localized lone pair NH

<
9. NH 2 - C - NH 2 + M of 2 NH2
NH2 r
:

NH 10. Ph - NH 2 lone pair of nitrogen is delocalized

5. NH2 C H+
NH2 C NH2
NH2
Chemistry
EXERCISE - 1

1. Resonance structures are separated by a double 20. Information

headed arrow ())
21. Information
2. Contributing structures contribute to the resonance
energy inversely in proportion of their relative 22. -COO- -ve charge group show + 1
energies, i.e. structures with high energy contribute r
23. - O - N = 0 lone pair on o atoms hence it will show
less while those with low energy contribute more, r
+M
Therefore, option (a) is wrong.
3. In structure (c), N contains ten electrons in the
valence shell which is not possible. 24. It will show -M as -ve charge is
stable on 0-atom
4.
25. Information
+

These structures involve only movement of electrons 26. (CH3) 3 C - CH 2 it does not have a-H
but not of atoms and hence are resonating structures.
5. The heat of hydrogenation of cyclohexene is 29 27.
kcal mol-1. Since cyclohexadiene has two double
bonds while cyclohexene has one, therefore, heat of
hydrogenation of cyclohexadiene is double(58 kcal
mol-1) the heat of hydrogenation of cyclohexene (29
kcal mol-1).
6. III-N is most basic as its lone pair in localized and
sp3 hybridised.
7. Resonance is delocalization of p electrons

8. Information
9. More stable resonating structure has less energy. 28. II and III have delocalized six p-electrons and hence
10. More stable RS contribute more in RH are aromatic.
-O
;
29. Only is not aromatic; rest all are aromatic.
11. NH 2 - C - O CH3
+

Octet of carbon is incomplete hence less stable 30. I has cyclic conjugation, planarity and 8 + 2 = 10 p
electrons and hence is aromatic.
31. Aromatic character increases as the resonance
energy increases, Now resonance energies decrease
12. S I R effect due to substitution
in the order : pyridine (125.5 kJ mol-1) > thiophene
at ortho
(117 kJ mol-1) > pyrrole (88 kJ mol-1) > furan (71 kJ
13. Hyperconjugation. mol-1). Thus, option (c) is correct.
14. Greater the electronegativity, higher is the I-effect, 32. Only (b) has two completely delocalized p-electrons
i.e. - NR 2 < - OR < - F . and hence is aromatic.
15. + I of 30 R > + I of 20 R > + I of 10 R 33. Delocalization of p-electrons always leads
16. Option (a) is incorrect since the - I -effect of to stabilization is an incorrect statement since
halogens follows the order : I < Br < Cl < F. cyclobutadiene is destabilized by resonance (Anti
aromatic).
17. - I of - C / CH is more than -Ph
18. Self explainatory
34. 2 p e- hence aromatic
19. 1
35. Bond length ∝ Bond order
BO of Acetylene is 3

36. BL : HC≡≡CH < H2C==CH2 <
BO : 3 2 1.5
< H3 C - CH3
1
37. Bond length \ Bond order
38. Bond length ∝ No. of a H
CH3 - C = CH 2 has 6 a H
; 51. Both structures (I and IV) are stabilized by
CH3
39. 1, 3-Butadiene has two double bonds while all other
alkenes have one double bond. Therefore, its heat
of hydrogenation is the maximum (226 kJ mol-1)
Further, the heat of hydrogenation of any alkene
depends upon its stability. Since trans-2-butene
is the most stable alkene (due to hyperconjugation
and least steric hindrance) amongst the alkenes:
1-butene (126 kJ mol-1), trans-2-butene (115
kJmol-1) and cis-2-butene (119kJ mol-1) therefore,
its heat of hydrogenation is the least(115 kJ mol-1).
General Organic Chemistry
benzene ring. I & II are destabilised by -I effect of
benzene ring. In I cation, -I effect is maximum \ I
is least stable. Thus the overall order of stability is :
II < I < III < IV i.e., option (a) is correct.
49. being the 3o carbocation is the most stable.
+
50. C6 H5 CHC6 H5 (IV) > CH 2 = CH -
+ + +
CH 2 (III) > CH3 - CH 2 (II) > CH 2 CH (I)
resonance.
52. Carbocation (a) is antiaromatic and hence is least
stable. Carbocation (b), (c) and (d) are all secondary
but (b) and (c) are aromatic. Further since (c) is
more strained than (b), therefore, (b) is the most
stable carbocation.
53. Carbocation (II) is most stable due to resonance,
+ r +
CH3 - C - O - CH3 ) CH3 - CH = O - CH3
r r
II

Carbocation (III) is least stable due to electron

40. trans-2-butene (III) > cis-2-butene (II) > I-butene
withdrawing effect of the adjacent carbonyl group
(I)
while carbocation (I) is less stable than (II) because
41. Stability: it is only stabilized by the + I-effect of the two CH3
I < III < IV < II groups. Thus,the overall order of stability is : II > I
6\H 6\H 9\H 12 \ H > III.
on same +
carbon are more stable 54. (i) First carbocation (CH 2 = CHCH 2) is stabilized by
42. Stability : I < III < II resonance but the second (CH 2 = CHCH 2 CH +2 )
4aH 6aH 10aH is not. Therefore, first carbocation is more stable
than the second.
43. Carbocations have three pairs (6) electrons in the
valence shell. (ii) CH3 N CH2 CH3 NH CH2

44. Homocyclic fission of C-C bond gives free radicals CH2 OH CH2 OH
in which carbon is sp2-hybridized. In both the cases, +ve charge is dispersed due
+ to resonance but in the second carbocation +ve
45. (CH3) 3 C is the most stable carbocation. The actual charge is located on a more electronegative O-
order is: atom. Therefore, first carbocation is more stable
+ + + + than second.

(CH3) 3 C > C6 H5 CH 2 > (CH3) 2 CH > CH3 CH 2 .
(iii) Second carbocation (CH3 O CH2) is stabilized
+

46. C6 H5 CH -2 (IV) > CH3 CH -2 (III) > +

by resonance but first (CH3 - O - CH 2 - CH 2)

(CH3) 2 CH - (II) > (CH3) 3 C - (I) . is not. Therefore, carbocation second is more
stable than the first.
+
(iv) First carbocation (CH3 CHCH 2 CH 2 CH3) has
47. -M of NO2 hence -ve charge is more five a-hydrogen atoms and hence has five hyper
stable conjugation structures are possible while the
+
second carbocation (CH3 CH 2 CHCH 2 CH3) has
48. IV is stabilized by +I-effect of two CH3 group and only four a-hydrogen atoms and hence has four
by dispersal of +ve charge on the benzene ring by hyper conjugative structures. Therefore, first
resonance. III is stabilized by + I-effect of one carbocation is little more stable than the second,
CH3 group and by dispersal of +ve charge on the Thus the correct answer is option (b).
Chemistry
+ 73. Acidic strength:
55. CH3 B F3 -
CH3 0
CH3
sp2 sp2 sp3 sp2
COOH > > COOH > COOH
; ; ;
COOH C C
; ;
C C
; ;
COOH C
;
56. + M of -O CH3 hence most stable C
;
COOH
I III II IV

----------->-------------------------
57. HC ≡ C- is most stable due to SP hybridisation of C
-I of other COOH decreases
atom
74. Acidic strength:
58. Stability:

59. Ph3C+ is most stable due to + M of 3 Ph.

75. acidic strength:
60. (CH3)3C- is least stable due to +I of 3 CH3 group I > III > II
-M of NO2 No effect +M of - OCH3
61. -ve charge is more stable on s-atom due to large
size. 76. acidic strength
62. Information
o o o o
63. Stability: 3 - C > 2 - C > 1 - C > CH3
+
64. CH 2 - CHO is least stable due to -I of CHO 77. Acidic Strength :
V > IV > III > I > II
ortho -m of -I of -I of No-effect
65. aromatic carbocation is very stable
effect NO2 NO2 OCH3

66. 78. Basic strength :

CH3NH2 > NH3 > NH2Cl

F is close to OH group so strongest -I
+I of CH3 No effect -I of Cl

67.

68. Information
69. -NO2 has -M effect hence acidity ↑ 79. localized lone pair hence more basic

70. Cl-C-C-COOH weak -I effect of Cl atom hence

less acidic 80. + I alkyl group and
+
localized lone pair
71. - NH3 group has very strong -I effect
81. Information
72. acidic strength: Sulphonic acid > Carboxyclic acid >
82. Information
Phenol > Alcohol
 General Organic Chemistry
83. basicity: 92. Basic strength:
- - - - - -
I3 > III > II > IV CH3—C H2 > CH2==CH > N H2 > CH≡≡C > HO > F
sp N sp3 N sp2 N sp2 N
localized localized localized delocalized remember this order
-I of O
84. pKa:
III > I > II 93. it does not have lone pair hence can not be
+ I of -I of -I of 2 a basic.
alkyl C 6 H5 C 6 H5
94. Information
85. Basic strength:
II > I > IV > III 95. Ka : CH 4 < NH3 < H 2 O < HF
+M of NH2 No effect -I of Cl -M of NO2 In a period from left to right acidity increases.
86. Basic strength: 96. - SO3 H is more acidic then - COOH
IV > III > I > II
HC of CH3 +I of CH3 No effect SIP effect 97. Phenol weaker acid than H2CO3.
87. Salt of WB + SB —→ Salt of SB + WB 98. C 2 H5 - NH 2 is more basic then NH3 due to +I of
basic strength: NH3 < Ph3 CH < HC / CH < H 2 O C2H5.
88. Down the group size increases so, basic strength 99. DM:
decreases C - C - CN > C - C - F > C - C - NO 2 > C - C - NH 2
EN . hence DM .
89. Acidic strength : HCl > HF > CH3 COOH > H 2 O
100. electron density ∝ Electron donating tendency
basic strength of anion: Cl - < F - < CH3 COO - < OH -
IV > II > III > I
90. HC / C Na + H 2 O " NaOH + HC / CH + M of + M of HC of -M of
Salt of WA SA Salt of SA WA O O
< <
91. C 2 H5 O - + H 2 O " C 2 H5 OH + OH - - NH - C - CH3 - O - C Et CH3 - COO Et
SA WA
EXERCISE - 2
9. CH2=C=CH2 both p bonds are ^ to each other
1. does not have conjugation hence no
\ Resonance is not possible.
resonance.

CH2 C CH CH2 C CH
+
2. does not have conjugation hence no empty orbital of CH is parallel to p bond.
resonance. O
<
3. CH2==CH—CH3 → This carbon does not have 10. - I of - C - destabilizing + ve charge.
empty orbital or lone pairs.
11. Stability :
4. CH2==CH—CH2—Cl chlorine is not in conjugation (I) neutral > (III) - ve charge on more electronegative
with double bond. atom > (II) - ve charge on less electronegative atom
5. nitrogen can not form five bonds. 12. Stability :
I > IV > II > III

6. Isolated double bond system neutral No. of bond

resonance is not possible
13.

7. Max. No. of double bond and -ve charge on oxygen

14. NO2 group at C1 and C5 are not in resonance with
8. benzene ring due to SIR effect hence No partial
double bond.
Chemistry
15. a - hydrogen to double bond show hyperconjugation.
16. Order of Inductive effect (+ I) 32. equal contributing resonating
structure. C - C bond order is
17. Order of Inductive effect (- I) 1.5.
18. N(CH3)3 is stronger - I because of + ve charge 33. C==C bond length ∝ No. of resonating structure
N atom is more electronegative than + ve charge ∝ No. of a - hydrogen
S-atom
19. OH lone pairs so + M and O - atom hence -I

O

20. O C R O R F COOH
+M>I O I>M  M,  I 34.
 M,  I
Bond order of C1—C2 > bond order of C2—C3 B L of
21. NO2 NH2 OH F
C1—C2 < C2—C3
M, I M, I M, I M, I V
35. x " partial / bondWW
22. O lone pair hence +M, -ve charge atom hence +I W
y " partial = bondWWW Resonance
23. In Iodine lone pair is present in 5p-orbital. W
z " partial = bond W
X
24. Number of hyperconjugation form ∝ a-hydrogen w " pure single bond hence longest
has 3 a -hydrogen
36.

25.

3 a-hydrogen hence hyperconjugation 1

37. Heat of hydrogenation \ Resonating Structure
26. CH3 - has max Number of a -hydrogen.
1
\ a - hydrogen
27. This has 4n p e- but it is non-planar hence Heat of hydrogenation:
it is non-aromatic. IV > III > II > I
2\H 4\H 9\H (Resonance, 7 \ H
2
28. Second p bond between C1 and C2 is not 38. Stability : II > IV > III > I
12 \ H 9\H 6\H 6\H
1 in conjugation hence 6 p e- and it is CH3
benzyne
planar hence aromatic. C CH2 is more stable than
HC
29. 3 H3C—HC==CH—CH3
anti aromatic O N
aromatic 39.
aromatic but hydrocarbon
not hydrocarbon
as they contain O Ph Ph
and N atoms C C
Ph o
30. o
CH2 CH

all carbon of cyclic ring are in conjugation and total No Resonance No Resonance
p e- are 10 hence (4n + 2) Free radial stability ∝ Resonance

\ aromatic. 40. - M of NO2 stabilizes - ve charge.
31. Sooty flame due to incomplete combustion hence
high % of carbon in compound.
 General Organic Chemistry
41. Triplet nirene has 2 unpaired e- 53. Stability:

\ Multiplicity = 2 b 2 # unpaired e - l + 1 = 3
1

42. + ve charge stabilized by

resonance as well as

2 a- hydrogen
43. Stability of C+ ∝ No. of a hydrogen
- M of NO2 > - M of CN

has zero a - hydrogen 54. Stability :

44. The compound which form more stable carbocation

will react faster o o
> C = C - Co > C - C - C > C - C
Resonance 6\H 3 \-H
Most stable carbocation due to resonance
and 3 - a - hydrogen
1
45. Energy of activation \
Stability of C + 55. Resonance, 7 a - hydrogen
+

R3 C is most stable due to 3 carbocation o

46. -CCl3 is most stable because -M and -I both are 56. Stability : IV > III > II > I
more for Cl as compare to Br and I. More Resonance 3∝H 0∝H
Resonance
47. aromatic carbocation are max stable.

57. Least stable because least resonance in case

48. from bridge head position resonance and of stability of free radicals resonance has
hyper conjugation is not possible, because priority over hyperconjugation.
at bride head position planar geometry is not +
58. Stability : + m of - OCH3 > HC of CH3 in CH3 - CH 2
possible.
> No effect but resonance > No resonance
49. Information from benzyne. C C C
50. Stability : - CF3 < - CCl3 59. C C C C
Me-shift
C C C C
-I - I, - M
o
- C 3 , more stable

HC / C - > H 2 C = CH 2 2o
sp sp

- -
(CH3) 3 C < H3 C - CH 2
60.

3o 1o

51. Stability :

61.

electron withdrawing group increases stability of
carbanion.

52. aromatic carbanion are extremly stable.

Chemistry
62. As stability of O- ion increases dissociation constant 1
71. bond rotation \ Bond order
increases
E W G ↑ stability of O- ion \
Ka order : III > I > II > IV
- M of - M of - M of - I of
3 NO2 2 NO2 NO2 NO2
63. Acidity : Phenol > Phenol with EDG
> Alcohol > Alkyne
1
64. pK a \ acidic strength
acidic strength : Sulphonic acid > Carboxyclic acid
> alcohol
NH
65. z
72. - C - NH - NH 2 , + M qf - NH2
- M group

highest acidic as Cl is close to COOH hence its -I is
O
very effective. z
> + M of NH - C - NH 2
66. F-C-COOH is more acidic then Br-C-COOH Cl Cl Cl
because of -I of F is more then Br.
CH3
67. basicity : II > III > IV > I Oo
sp3N sp2N delocalized delocalized 73.
localized localized lone pair lone pair CH3 CH3
lone pair lone pair part of r q p
aromaticity

as angle ↑ DM ↓
68. acidity : Phenonl > alcohol > terminal alkyne
74. Salt of WB + SB —→ Salt of SB + WB
69. acidity: III > II > I
O O
Basicity : CH3 - C - NH 2 >
z z z
- M of - M of C - M of - C - NH

and
O O
z z
2-C- - I of - C - > CH3 - NH 2 >

70. is more stable then HC≡≡C - due to 75. CH3NH2 + NH4Br —→ CH3 NH3 Br + NH3
aromaticity

CH3 SO3 H + NaHCO3 —→ CH3 SO3 Na + H2O+CO2

CH3—C≡≡CH + NaH —→ CH3—C≡≡CNa + H2
EXERCISE - 3
+
1. H O C N H O C N
 CH2 :Cl :
+
O

CH2 CH NH2 CH2 CH NH2
4.

i, iii, iv, vii are not resonance structures N

∵ change in position of atom. H

2. C=C-Cl
O 5.

3. + M group: -NH2, -SH, -F, --O, - O CH3 O

C C C N
O
 General Organic Chemistry
o
6. Ph - CH3, C 2 H5 - CH - CH3, CH3 - CH 2
+

7.
N O
O

8.
O OH

star 16. , HCl, , , HCOOH, CH3COOH

9. O OH

17. Cl - CH 2 - COOH , NC - CH 2 - COOH ,

18. HCOOH,

10.

11. 6-carbon atoms

12. 19.

CH2

O
<-
20. + I group: - NH, - C - O -
CH3

-I group: - Cl, - COOH, - NH 2, CN
CH3
+

- CCl3, - NPh3, - OH
y - x ⇒ 7 - 2 = 5
21. -ve charge in conjugation hence C-atom is sp2
- r -
O O
hybridized, hence answer : CH3, CH3 - CH 2

13. resonance stabilized

o
22.
aromatic as singlet
14. Basicity order:
: CF2
: C (O CH3) 2 : C (NHCH3) 2
S1 : Correct S2: Correct
+ M of F + M of O CH3 + M of NHCH3
S4 : Correct S5 : Correct
:
CCl 2
+ M of Cl

CH3 CH NH
15. , ,
 CH3 H3C CH3
Chemistry C O CH3 C N
HC H3C CH3
3
CH3
23. 4 electrons O
CH3 CH3
C
CH3
CH3
24.

CH3 H3C CH3
25. C O CH3 C N
H3C H3C CH3
CH3

O
CH3 EXERCISE - 4
CH3 C
CH3 10. - CHO is - M and - I hence s bond pair and p bond
CH3 pair are attracted towards - CHO
1. here + charge indicate empty orbital 11. II = III > I = IV
hence delocalization take place more aromatic less aromatic ring (1)
1
2. Potential energy \ stability rings (2)

Stability: III > I > II

PE : < <
12.
3. Stability of -ve charge atom : -S > -O > -N
r - +
4. C = C - NH 2 is more stable then C - C = NH 2
because neutral structure is more stable then charged.
-O -O
| |
5. C - C - C = C is less stable then C - C = C - C 13. empty orbital of boron is in conjugation
because delocalized -ve charge is more stable. with double bond.
O 14. Stability: -C-NO2 > -C-CN > -C-Cl > -C-CH3
6. C C N -ve charge on c-atom is less stable
O
 -I, -M ↑↑ -I, -M ↑ -I, -M + I
as compare to -ve charge on 0-atom. 15. Stability:

→ like charges are close hence repulsion. IV 2 III 2 II 2 I
O O O O O O O O
- m of 3CHO - m of 2CHO - m of 2 - m of CHO

7. O <
O O O O O O O O
- C - CH3

16. Hyperconjugation is deciding factor

not inductive effect.
8. localized lone pair is more basic then
delocalized lone pair

+ r +
O 17. CH3 - C = NH * CH3 - C / NH
<
r
9. + M order: - NH 2 2 - NMe 2 2 - N - C - CH3 + m of nitrogen atom
18. (a) both rings are in conjugation with +ve charge

(b) left ring in conjugation

(c) right ring in conjugation

(d) No ring in conjugation
 General Organic Chemistry
32. All have 6p e- in conjugation hence aromatic
pyridine has localized lone pairs
19.
Basic strength : II > III > I
33. Stability:
C
<
- -
C = C-C = C-C > C-C-C-C
more resonance
Resonance hence more stable 34. acidic hydrogen:
20. Basic strength:
r > p > q > s
+I of Et SIP -M of NO 2

21. Basic strength:

III > II > I > IV
sp N + I
35. (a) Acetic acid is stronger acid than H2CO3
3 3 3
sp N sp N delocalized
-I of N -I of N lone pair with
less + I -C = 0
(b) Acid has stronger hydrogen bonding
22. Basic strength: (c) Cl-C-COOH is more acidic then C-COOH due
2 > 1 > 3 to -I of Cl
Isolated delocalized delocalized with
lone pairs with C = N 2-C=0
(d) Phenol ion is resonance stabilized
36. Stability of anion a extent of delocalization of
23. Nitrogen and localized lone pair
charge.
24. Basic strength order:
\ Stability order 4 > 3 > 2 > 1
III > II > I 37. → NH2-OH has -I of o atom
-I of -M of -M of

O O O
< < <
- C - CH3 - C - Ph - C - CH3 and - Ph has delocalized lone pair hence less basic

- M of Ph
38. (a) + I of - CH3

(b) No resonance
25. crowding due to 2-CH3 group (c) + M of - NH2
at ortho position.
(d) No resonance
39. Information
26. anion form after loosing H+ is aromatic in
nature. 40. Information
27. (a) bridge head a-hydrogen does not take part in 41. Structure having complete octet is more stable
tautomerism.
42. (b) resonating structure with aromatic ring is more
stable.
28. -OH has stronger +M effect than (c) +ve charge is more stable to N atom as compare
29. Information to o atom.
43. - OH - NO 2 - NH 2
30. one ring as + M, - I - M, - I - I, + M
aromatic but other
44. Information
becomes antiaromatic hence it is not contributing
structure hence no polarity
31. - M group increases acidity of phenol hence - NO 2
- CN , - CHO
Chemistry
45. (a) non planar

(b) 54.

(c) One ring is aromatic and other is anti aromatic

(d)

O
<
46. (a) - CH - O - C - CH3 - O -
3
HC +M + M more 55. Q → S transfer of atom not allowed in resonating
- OCH3 - OH - CN structure.
(b) + M strong + M very strong - M

(c) not aromatic

56. (a) (b)
1
(d) DM \ angle between groups

47. (a) a has partial double bond due to HC.

r +
(b) C - C - NH 2 ) C - C = NH 2
< ;
+NH2 NH2
(c) (d)
(c) CH3 - C - O - ) CH3 - C = O
< ;
O O-
(d) d has partial double bond character due to 57.
resonance
48. Information
49. (a) Information 58. (a) Heat of combustion ∝ No of carbon
(b) Information 1
(b) heat of hydrogenation \ stability
(c) more delocalization means less basic
(d) > > 1
(c) Bond energy \ stability of free radical
N N N

H H H x has 2 a H, z has 4 a H, y has 5 ∝ H

-I of sp2 delocalized
carbon (d) basicity: sp3 N > sp2 N > sp N
50. Imidazole —→ N-3 lone pair in localized, purine 59. c, d does not have a hydrogen
—→ N-9 lone pair is delocalized
51. Acidic strength ∝ Electron with drawing effect 60.
EWE: -I of NO2 > -I of F > -I of Ph > +I of CH3

O O
52. Carbolic acid: C6H5 - OH

(a) CH3COO- has resonance 61. CH2 C H CH2 C H

(b) + I of CH3 O
62. CH3 N Octet of nitrogen is incomplete hence
(c) -M of NO2 is more dominating O


(d) -M of 2NO2 less stable structure.

63. Nitrogen can not expand its octet hence structure II

is not possible.
53.
64. is most stable 4∝H and more + I
 General Organic Chemistry
+ + 71. Resonance energy ∝ No. of p bond in conjugation
65. C = C is less stable then CH3 - CH 2
H O H ∝ No. of p bond
-I of sp2 C-atom 3∝H H O C ∝ No. of carbon
66. I —→ aromatic IV —→ does not have resonance 1
72. H O H \ stability of compound
67. Basicity:
II > I > IV > III
SIR No - effect -I of -M of
effect NO2 NO2 73. aromatic, No. of carbon is more hence more
HOC No. of p bond is more hence more
HOH

68. SIR effect \ most acidic 74. Carbanion stability: 10 C - > 20 C - > 30 C -
75. Stability: I > II > III
SIR effect - as well as a - H .
76. - NO 2 $ - I, - M - O - CH3 " - I, + M
69. I —→ Resonance between NO2 and benzene hence
partial double bond between C and N
- O - $ + I, + M - C / N " - I, - M
II —→ SIR effect hence no resonance so no partial
double bond. 77.
70. Stability:
I > III > II
+ I of CH3 - I of NO 2 - M of NO 2
and HC SIR effect

(c) – Aromatic
1. is the most stable carbocation due to
hyperconjugation and lone pair
stabilization. (d) – Aromatic
Carbocation (III) is least stable due to -I effect of
oxygen atoms 5. Option “B” represent Guanadine, the conjugate acid
 of which is resonance stabilised. The option ‘C’ is
2. is most stable as it is aromatic. aliphatic amine, here the ‘N’ is sp3 whereas in option
CH3 ‘A’ the ‘N’ is sp2, hence C is more basic than A.
O


O
CH2 NH2 N CH3 NH CH3 NH2
+
H3O
6. (Aromatic)
3.
CH3 CH3
(A) (B) (C) (D) 7. Order of electron withdrawing effect exerting group

B.S. order (A) > (B) > (C) > (D) is —NO2 > —CN > —F > —Cl.
4. For the following ion/compounds Hence, the acid strength order is
O2NCH2COOH > NCCH2COOH >
(a) – Non aromatic FCH2COOH > ClCH2COOH.

(b) – Aromatic
O
Chemistry
14. b is non aromatic while others are aromatic
8. Kb of :1.3 × 10–3 Kb of : = 2.3 × 10–9;
15. Acidic strength:
N N
H

Kb of = 2.5 × 10–14
N

H
Hence, decreasing order of basicity is III > I > II.
10. pKb + +
16. H 2 C = CH - CH 2 H3 C - CH 2 - CH 2
CH3CH2NH2 3.29
CH3CH2—NHCH2CH3 3.00 Resonance HC More resonance
CH3 Stability: III > I > II

H3C N CH3 4.22
CH3
17. localized lone pair while other have

Ph N H 9.30 delocalized lone pair benzyl amine
1 Cl

pK b \ Basicity
Hence, the correct order is S < R < P < Q. 18. C
Cl zero dipole due to symmetricity
11. Due to greater stability of allyl radical formed after Cl
Cl
replacement of g-hydrogen in compound (E), allylic Cl H
bromination can easily be taken place. 19. C C C-Cl dipoles are cancel and
12. –I effect group increase acidity whereas +I effect H3C Cl C-C, C-H bond is very
group decreases acidity. The more acidic the lesspolar
compound, lesser will be its pKa value. Therefore,
the correct increasing order of pKa value is
C Cl
B < C < A < D. 20. C C
Cl C
13.
Zero Zero

H NO2
C C
O2N H

Zero Non Zero

 General Organic Chemistry

1. acidic strength NH2 H3C CH3

N
7.

I
II
H3C CH3
is more acidic NH2 N
2. Information O2N NO2 O2N NO2
3. Information
4. Stability:
NO2 NO2
I > III > II > IV
+M of O + M of O 5\H 2\H III IV
6\H 3\H
pKb different between I and II is 0.53 and that of III
⊕ ⊕
5. H3C—O—CH=CH—CH—CH2 Incomplete octet. and IV is 4.6.
H
So option (B) is incorrect

Correct Statement (C), (D)
6. (I) Ph CH Ph (II)

The most basic compound in the given option is (II)
Ph and least basic compound is (III)
pKa = 43
pKa = 33.3 H
In 2,4,6-trinitro aniline (III) due to strong –R effect
of –NO2 groups, the l.p. of –NH2 is more involved
(III) H CH3 (IV) with benzene ring hence it has least basic strength.
pKa = 50
Whereas (IV) N,N-Dimethyl 2,4,6-trinitro aniline,
pKa = 16 due to steric inhibition to resonance (SIR) effect; the
lone pair of -e is not in the plane of benzene, hence
(V) CH CH make it (l.p.) more free to protonate
pKa = 25


NH2
(a) Ph CH Ph


+
Ph C Ph + H O2N NO2
Ph Ph
(Resonance stabilised)
H H NO2
L.P. is not in conjugation


(b) + H
+

Me Me


Aromatic N steric repulsion

(c) –NO2 is –I group (electron withdrawing group). O2N NO2
It increases acid strength.
(d) Acid strength order : IV > V > I > II > III
NO2
more effective resonance
Chemistry

8.

NH2

9. melamine N N
H2N N NH2
 Hydrocarbons

Chapter 13 Hydrocarbons

INTEXT EXERCISE: 1

6. ZnHg + HCl reducer to CH2

1. then Wurtz reaction
7.
2. Kolbe electrolysis
3. RMgBr + Acidic hydrogen → RH
8.

Acidic D → RD
4. Only symmetrical alkanes can form in high yield. 9. Fact
5. Intramolecular wurtz reaction 10. Corey - House synthesis
INTEXT EXERCISE: 2
1. Monohalogination substitution is major. 5. Cubane → total hydrogen = 8

total carbon = 8

less No. of hydrogen = 8 × 2 + 2 = 18 – 8
2. = 10
10
bond cleavage = 2 = 5
6. Syn addition of D, D
cis
7. 1, 2 → (a, e) means gauche in chair form
hence answer is (c) correction
o
o
8. quantity of Cl and CH3 are less and their life span
3. is also very less.

9. (d) major
4.
10. reactivity vs selectivity for 1o product = 9 × 1 = 9
for 3o product = 5 × 1 = 5
hence 1o is major

INTEXT EXERCISE: 3
3. antimarkonikov addition of -OH and H+ and syn
1. addition.

2. 4.

Chemistry
5. Li / NH3 —→ Brich reduction, anti addition of 2H 8. Pyrolysis of ester → elimination of RCOOH via
Br2 —→ anti addition cyclic transition state, Hoffman alkene.

6.

Correction Q. figure

9. Bulky bare give hofmann alkene as major

10.

7. Lindlar’s catalyst → syn addition of 2H

Na + NH3 → anti addition of 2H

INTEXT EXERCISE: 4
5. rate a stability of carbocation hence least reactive is
1. (a) ans correction.
6. allylic bromination
7. anti markonikov addtion of HBr
8. all double bond converted into single bond by
catalyic hydrogenation
2. 9. addition of D+ and OD-
3. 1,2 product, less stable, formed fastest, formed at
low temperature, least substituted alkene.
10.
4. trans meso.
anti
addition
of Br2

INTEXT EXERCISE: 5
8. 1,2-addition and 1,4-addition of Br2 product.
R H
1. reductive ozonolysis of H C C
R⇒ 9.
R H

2.

3. reductive ozonolysis of C C ⇒
4. conjugated alkene is more stable due to resonance
5. reductive ozonolysis
6. both form but major will be the product of more
stable carbocation
10. RMg Br + D2O —→ RD + Mg Br (OD)
7. reductive ozonolysis
 Hydrocarbons
INTEXT EXERCISE: 6
1. 6. Syn diol

7.

2. four break in ring hence. 4 product will form.

3.

8. H H H H

9. Fact
4.
10.

5. Solvent act as
nucleophile in last
step as it present in excess
INTEXT EXERCISE: 7
1. addition on all p bonds 7. addition of H2O, markonikov with out rearrangement
2. Markonikov addition, both Br at same carbon.
3. reductive ozonolysis
4. C—C≡≡C—C—C—C≡≡C—C—C≡≡C—C—C 8. Fact
C—COOH, HOOC—C—C—COOH,
9. Birch reduction
HOOC—C—COOH, HOOC—C—C NaNH2
5O?
10. C—C—C≡≡CH
5. alkyne acid
C—C—C≡≡C—C → C—C—COOH + C—COOH

H 2 + Pd
6. C—C≡≡C—C—C +CaCO 3
Chemistry
EXERCISE - 1
1. Fact.
2. CH4 → sp3, H2C==CH2 → sp2 HC≡≡CH → sp 24.

3. 
25. C H + O2 CO2 + H2O

4. (a) 0 degree of unsaturation 26. Fact.

(b) 1 degree of unsaturation hence alkene or
cycloalkane 27. C—C—C—Br,
(c) 2 degree of unsaturation 1
28. BP \ Branching
(d) 3 degree of unsaturation
5. 29. Fact.

6. Fact.
30. (c) will form 3o free radial hence most stable
7.
8. Fact. and rate of reaction a stability of free radial.
9. Methane can not be prepared as R—R or R—R’ 31. alc KOH gives Satzeff alkene
must have atleast two carbon 32. base take H+ in the second step and alkene will form.
10. R MgX + D2O —→ R—D + MgX(OD) 33. Fact.

11. (c) 34.

12. Fact.
13. Fact. 35.
14. Fact.
Na
15. CH3I ether
CH3—CH3 36. C—C—C—OH
PCl3
C—C—C—Cl
LiAlH 4
CH3I
CH4
Alc KOH
C—C==C
16. C - COONa + C - C - COONa
Kolls
electrolysis
37. H2 + Ni2B convert C≡≡C to C==C, cis addition
A B

C - C +C - C - C - C+C - C - C 38. Stability of alkene a number of a hydrogen

A-A B-B A-B

→ trans alkene is more stable then cis alkene
17. (a) give R—R
Red P 39. <
18. R—OH HI
RH + PI3 + +
40. (b) CH2==CH— C ==CH2 ) C H2—CH==C==CH2
19.
stable +ve charge due to resonance
20. BP a Vanderwaal force a Number of C-atoms in rate of
chain. 41. Electrophilic a 1 nucleophilicity of alkene
5
21. Fact. Addition a 2 stability of C
22. Fact. 42. → Markonikov addition of Br+ and OH-

→ anti addition due to bridge carbocation
23.
Major Minor
 Hydrocarbons
43. reactivity a partially charged carbocation stability
by number of a hydrogens 58.
44. rate a stability of carbocation a number of a - Br
hydrogen
(2)
45. Stability of carbocation : Br

59. single carbene hence single step addition hence syn

addition
46. rate a stability of carbocation.
47. Markonikov addition of Br+ and OH-
60.

48. 61. antimarkonikov addition of D and OH, syn addition

62. (a) hydrolysis
49. (b) alc KOH
(c) alc KOH
50. → 1-step oxymercuration

→ 2-step demercuratiion 63. Bulky base gives Hoffman alkyne as major product.

→ Markonikov addition of H2O without 64.
rearrangement
51. anti addition of Br2
52.
65. Weaker acid (C2H2) is displaced by stronger acid
(H2O) from it’s salt.
66. triple bond can not form in 6 member ring hence two
molecule combine
1
67. Bond length a Bond order
53. antimarkonikov addition of D and OH
Bond order a %s in hybridisation
54. Answer self explanatory
68. 64 kg CaC2 has 24 gm of carbon, 24 gm of carbon
55. Markonikov addition of Cl+ and OH- give 28 gm of C2H4 hence polythene is 28 gm
69. self explanatory
70. self explanatory

stable due to resoanance 71. Fact
56. Stable carbocation : as other carbon
72.
has strong - I of CCl3
+
57. Ph—CH2— CH—CH==CH—PH

Chemistry
EXERCISE - 2

1. 17.

R12 CuLi
2. R X R—R1 + Li X + R’Cu

3.

18.
4. All reagent convert

5. Beta keto acid

6. Fact.
7. Rate of free radial halogenation a stability of free
radial.
8. rate a free radial stability
Stability of free radial a number of a-hydrogen
9. Ho can not exist. 19. Stability of carbocation increases rate
10. H of C : C—C—C—C—C—C—C


> C—C—C—C—C
H of C a number of carbon 20.
1
If number of carbon same then H of C a branching
21. Three step, every step has more stable product hence
11. Fact. energy decreases.
12. It is syn elimination via cyclic transition state 22. Addition of carbene on double bond.
hence that H is eliminated which is same side of —
NMe—O- and NMe2—OH is eliminated. 23. Ans correction answer is (c)
Stability :
13. anti elimination hence H anti to OTs eliminated.

14. Most stable carbocation:

24.
H3C H2C O HC CH3
15. alc. KOH gives anti elimination. Since no H-atom is
OH
present at anti position to the Br atom at the adjacent H
C-atoms therefore no E2 reaction occurs. C CH3 + H3C CH2 OH
16. -NR3+ give Hoffman alkene as major product. O
OH
Hint C C O + ROH
OR
 Hydrocarbons

25.
42.
26. addition of (+CHO and H-) oxoprocess
27. diels alder reaction
28. Markonikov addition of H+ and OH-, +ve charge is
more stable at benzylic position.
29. Markonikov addition of H+
and -OH
on double
bond, Intramolecular -OH attack on more substituted
double bonded carbon. 43.
30. (1) → 1, 2-addition → Kinetic (more stable
intermediate) 44.
(2) → 1, 4-addition → Thermodynamic (more
stable product)
31. Stability : C = C = C - C - C C = C - C = C - C
commulated Conjugated diene
diene (3) (1) 45.

C = C-C-C = C
isolated diene
(2)
1
H of C a stability

32. 1, 4-addition of Br2

46. Self explainatory
33. At room temperature 1, 4-addition is major.
34. do self 47. reactivity :
H Br
35.
Br
36. At room temperature 1,4-addition is major
37. Free radical polymerisation. 48.
38. Free radical addition of oCCl then Bro and
3
1,4-addition 49. Ph—CH≡≡CNa + C—C—OTS

39. SN2
Ph—C≡≡C—C—C

40. Ans (a) Alkyne is less reactive then alkene for

electrophilic addition because intrermediate of 50.
Alkyne is less stable. Addition of HBr in presence
of peroxide is via antimarkonikov’s rule.

41.

Chemistry
EXERCISE - 3

2.
5H 6H
3H
4. C—C, C—C—C—C, C—C—C—C—C—C
C 10.
;
C—C—C, C—C—C— C , These five product
exist in
s-trans form
5.

6. C—C—C—C—C—C—C, insertion of :CH2 in

C—H bond 11. benzene, cyclobutatdiene, cyclooctateraence.
C—C—C—C—C—C—C—C, 12. a, b, e-oxidizing agent
C c, d, f-reduction
;
C—C—C—C—C— C —C
C
;
C—C—C—C— C —C—C 2 13. ;
*
C
;
C—C—C— C —C—C—C

7. CH2N2 and CH2=C=O can be used for :CH2 insertion

8. 14.

15. CH3CH2MgBr give ethane gas
9. (b) Na give H2 gas
NaNH2 give NH3 gas
CH3CH2Li give ethane gas
CH3
NaH give H2 gas
H D
(d) 2 (two pairs) diastereomers H H 2 [(CH3)2CH]2NLi give [(CH3)2CH]2 NH liquid
2 H Cl C6H5Li give C6H6 liquid
Ph

(e)

(f)
 Hydrocarbons
EXERCISE - 4

1.
11.

12. Self explainatory

2. Electrophilic Addition of Cl+ and I-. 13. Markonikov addition of H2O
14. rate a stability of carbocation
3. 15. For meso reagent should give syn addition
Br2 + H2O → anti addition
HCO3H → anti diol
4. Cold + alkaline KMnO4 → Syn diol
16.

5. Self explainatory

6.
17.

18. reaction on less crowded double bond.

19. do self

20.

7. 21. A → Markovnikoff’s product.

B → Anti Markovnikoff’s product.
22. self explainatory

23. methyl acrylate 2

8. C—C==C—C— symmetric
9. E2 → elimination

10. B → anti Markonikov addition of H2O

24.
A → Markonikov addition of H2O

25. (a) elimination

(b) 1o R—I does not give product with NaBH4
Chemistry
26. (d) C2H5MgBr(CH3)2NH—→C2H6+(CH3)2NMgBr 39.
27. (a) dipole moment of CF4 is zero hence lower
boiling point.
(b) BP a No. of carbon
(c) correct
40. Bulky base and LG: NMe3 gives Hoffman alkene.
1
(d) Octane a No. of carbon Ans: (a, c)
28. Insertion of :CH2 between C—H bond. 41. (a) product
29. Has only one type of H.
30. 42. HI give Markonikov addition with peroxide as well
hence product of (b) in

31. Fact
43. (a)
32. (a) is C4H6
H2, Pt O3
C—C≡≡C—C 1 eq
C—C==C—C H2 O

or C—COOH
(c) fact
C==C—C==C
(d) Only two CH3-CH3 and CH2D-CH2D
33. Water has hydrogen bonding
44.

MP, BP and density of alkane is slightly greater than
cyclo alkane due to larger london forces because of
large contact area.
34. (a) They are inert
(b) cyclopropane give addition with HBr

45. Answer self explainatory

(c) 46. Symmetric alkene give same product from
Markonikov and anti markonikov addition.
+
35. bulky base and -N Me3 leaving group give hoffmann 47. → Cycloalkene upto 11-carbon, cis is more stable
alkene as major → In case of alkene trans is more stable than cis
36. Answer self explainatory → Double bond is not stable at bridge head carbon
48. Answer self explainatory
49. (a) insertion of :CH2
37.
(b) insertion of :CCl2

50.

51. (a) (b)

38. (a) porolysis of ester

(b) (c)
(c), (d) L.G : NMe3, SMe2
52. Answer self explainatory
 Hydrocarbons
61. P, S Hydrogen will give two products.
53.

X
H3C C CH2 CH3
CH3

H3C
HC CH2 CH2

→ HBr peroxide, antimarkonikov addition H3C X
Total products = 6
54.

62.

55.

63.

1, 2 dimethyl cycloheptene
56. Ans (b) carbocation option 1,2-dimethylcycloheptene
64. (b) Self explainatory

Br
65. (c) Br

57. 66. strong-I group hence carbocation is stable at more
+
distance G - C - C (stable)
but CH4 can not form. -I
67. reactivity of electrophilic addition ∝ stability of C+
58. 3o RX give mainly disproportion reaction

68. Answer self explainatory

69. Answer self explainatory
59. reactivity a stability of free radial intermediate
60. free radical at S position has 6 ∝-H and resonance
hence most stable.
Chemistry

70. (a) , allylic hydrogen = 5 (d) allylic hydrogen = 6

71. Answer self explainatory

72. Answer self explainatory
(b) allylic hydrogen = 7 73. (a) antimarkonikov addition of H2O
(b) Markonikov addition of H2O
(c) elimination by Satzeff rule
(d) elimination by Hoffman rule as bulky base.
(c) allylic
hydrogen = 8

Br Cl

1. (C5H10) + Br2 (C5H10Br2) “A”

Br UV light
moles of Br2 = moles of C5H10
Cl
w 5
⇒ 160 = 70
5.
#
⇒ W = 5 70160 g = 11.428 g ≈ 1143 × 10-2 g

Reaction of HgSO4/dil.H2SO4 with alkyne gives
2. Ni/H2 Cl2
addition of water as per markonikoff’s rule.
hv
CH3 CH3 O
HgSO

Simplest O.A. Alkene (1) HC CH H2SO4
4
CH2 CH CH3 CH
Cl
 1 chiral centre 2 products OH
(2) C CH
HgSO4
C CH2
H2SO4
Cl
 OH
2 chiral centre 4 products

O
No chiral centre 1 products C CH3
Cl
HgSO
No chiral centre 1 products (3) CH3 C CH H2SO44 CH3 C C2H
Cl OH
Cl

O
4. “A”
CH3 C CH3
Cl Hence CH3–CH2–CHO cannot be form.
HgSO4

For substitution at allylic position in the given (4) CH3 C C CH3 H2SO4 CH3 C CH CH3
compound, the reagent used is Cl2/uv light. OH

The reaction is free radical halogenation.
CH3 C CH2 CH3
O
 Hydrocarbons
me me
H2/Ni
6.

Optically Optically 13.

active inactive
CH3 H
8. CH3 C C CH3
Na/Liq.NH3
C C
H CH3
9. (c) will not produce alkene hence it will not
decolourize bromine water.
14.
10. Ph—CH==CH—Ph
cis + trans 15. Ph—CH2—CH==CH—CH3
cis/trans

11.
16.

22 = 4

12. 17.

H R
18. R C C R
Li
NH3 C C
R H
O
19.
N2H4
C OH
CH2
O3
20. ==CH2 HCHO

1. It is a case of Birch reduction. Alkynes on reaction Q > P > R > S

with alkali metal in liq. NH3 gives trans-alkene. But 1
Stability of free radical \ Bond energy
terminal alkynes do not get reduced.
NaNH2
\ Order of bond energy :
Na S>R>P>Q
liq. NH3

1 5. (1) Cl2 → 2Cl• (Initiation step) DH = 58 kcal/mol

2. Boiling Point a Branching (2) CH4 + Cl• → •CH3 + HCl
Propagation step
3. C - C - C - C - Br + C - C - C / C (3) •CH3 + Cl2 → CH3Cl + Cl•

NaNH2
S N2
C-C-C / C-C-C-C-C Propagation step
Step (1) → Endothermic (bond breaking)
4. H CH(CH3)2 HC CH3 Step (2) → DH = 105 – 103
CH3 = 2 kcal/mol (Endothermic)
Step (3) → DH = 58 – 85
H CH2Ph CH2 Ph = –27 kcal/mol (Exothermic)
Benzyl radical For complete reaction
light
H CH CH2 CH CH2 CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)
H C CH C CH DH = 58 + 105 – 85 – 103
Order of stability of free radical = –25 kcal/mol
Chemistry
6. & 7. 10.

1.Na, liquid NH3

2.Br2
(excess)

Br

Br
Br
Br

3. alc. KOH
Cl Zn, dil. HCl
8. H3C
NaOH, CaO, 
H3C COONa cis/trans
2 isomers
9. (i) (M, N)

 
O
11. 1. O3, Zn/H2O C
H
KMnO4
(ii) (O, P)
O
C
OH
Cr2O3 NaOH
770 K Electrolysis
20 atm
 Hydrocarbons
12.
OH OH
(P)

HO HO OH
O3/Zn/H2O

OH
OH O O OH
O O O
O O
HO HO
Achiral
Achiral Chiral Achiral
Chiral

O
O O
HO Achiral
Achiral
O O
1. O3 (excess)
then Zn/H2O
13.
O O
2. NH2OH (excess)

+ +
OH OH OH OH
N N N N
( ) ( )
( ) ( )

N N N N
+ +
OH OH OH OH
The total number of atoms having sp2 hybridisation in the major product (P) = 12
This includes 4 C-atoms, 4 N-atoms and 4 O-atoms.

14. H2/Pd-H2SO4

H H
dil. KMnO4

HO OH

HO HO OH OH
Chemistry
I Position-1-chiral
15. II Position-1-chiral 16. Cl
III Position-2-chiral
V Position-1-chiral
(2) (4)

(1) (1)
 Aromatic Compounds

Chapter 14 Aromatic Compounds

INTEXT EXERCISE: 1

6.
1.

2. -CH3 group is ring activating towards electrophilic
aromatic substitution reaction.
Middle Benzene ring is activated by two terminal
benzene rings towards electrophilic substitution
reaction.

3. 7. : Electron withdrawing groups increase rate

of nucleophilic substitution on benzene ring
(-NO2) and -CHO)

: Electron donating groups decrease rate of
nucleophilic substitution on benzene ring.

4.

8.

Cl- at 1st position is at ortho and para position to

9. Electron donating groups (-CH3) increases
2nd and 3rd position Cl- atoms. \ It can participate stability of carbocation.
in nucleophilic substitution easily.
10. Sulphonation on benzene has Kinetic isotopic
5. -CH==CH2 is o/p-directing group for electrophilic effect.
aromatic substitution reaction.
INTEXT EXERCISE: 2
1. Cyclic conjugated planar molecules with
(4n+2) p bonded electrons are aromatic.
• Cyclo octatetraene is non planar 3.

\ non-Aromatic.

• It has tub-shape.

4. : When strongly activating groups (like -NH2);
2. deactivating groups (like -NO2) are present
Friedel-craft’s reactions are not possible.

: -CH3 group activates benzene ring more than
group.

\ is more reactive.
Chemistry

5. 8. As C—F bond is more polar will show

faster ArSN2 reaction.
9.

6. Pyridine is less reactive towards electrophilic

substitution, because nitrogen destabilises
carbocation inermediate.

7.

10. In nitration of benzene elimination of H 5 is fast
step

\ C6H6; C6D6, C6T6 are equally reactive towards
nitration.
INTEXT EXERCISE: 3
5.

1.

Alcohol is more reactive than phenol towards
nucleophilic substitution reaction.

2. 6. Electron withdrawing groups increase rate of

nucleophilic substitution reaction on benzene.
Therefore

7.

3.

Electron donating groups increase stability of
carbocation, and thus increase rate of reaction.

4.
 Aromatic Compounds
8.
9.

10.

INTEXT EXERCISE: 4
5. Halogens (F, Cl, Br, I) weakly deactivating groups
for electrophilic substitution reactions, but ortho/
para directing groups.
1.

6. In , as nitrogen lone pair involved in

resonance it is least basic in nature.

7.

2.

8.

3. 9. Coupling reaction produces Azodyes.

4. 10.
Chemistry
EXERCISE - 1
sp3-sp3 > sp3-sp2 > sp2-sp2 > sp2-sp > sp-sp

1.

2. -Cl, -NO2; -CHO groups are deactivating groups 11. , due to presence moderately activating
for electrophilic substitution reaction. group it is more reactive towards
electrophilic substitution reaction.

3. 12. Electron withdrawing groups at ortho/para w.r.t.

4. -NH2 is ring activating group1 -CHO is ring
deactivating group for electrophilic substitution
reaction.
5. -CH3 is weakly activating group for electrophilic
substitution reaction. -Cl and -NO2 are weakly
and strongly deactivating groups for electrophilic
aromatic substitution reaction.
leaving groups increases rate of nucleophilic
substitution on benzene.
13. With increasing number of electron withdrawing
groups and C—X bond polarity rate of electrophilic
substitution reaction increases.
14.

6. In , as there is no cyclic conjugation non-

Aromatic.

7. tert-butyl benzene

8. -NH2 is strongly activating group for electrophilic

substitution reaction.

9.
15.
10. bond length order is directly by proportional to %
of p-orbital

16.

17.
 Aromatic Compounds
18. Cyclic conjugated, planar molecules with 4n+2
cyclic delocalised p electrons are aromatic. These
are more stable molecules.
25.
19. -NO2 is strongly deactivated group towards
electrophilic aromatic substitution reaction.
Therefore nitro benzene is inert towards Friedel-
Craft’s reactions.
20. 4n + 2 = 18
18 - 2
n= 4
\ n=4
26.

21.

27.

28.
22.

29.

30.

23.

24.
31.

32.
Chemistry

33.
34.

35.

36. 38.

37.
39.

40.

EXERCISE - 2
1. halogens are deactivating groups for
Electrophilic Aromatic Substitution (due to more
Electronegativity of halogens). But these are
ortho/para directing groups (due to stability of
carbocation intermediate).
2. —OH is strongly activating group for electrophilic
aromatic substitution reactions.
3. —OH group strongly activating and ortho/
para directing group for electrophilic aromatic
substitution reaction.
4. Alkoxy group (-OCH3) is moderately activating
group; -CH3 group is weakly activting group for
electrophilic substitution reaction -CF3 is strongly
deactivating group.
5. Due ot more number of hyperconjugating protons
-CH3 group more activating group than -CH2-CH3;
and groups.
6. Negative charged oxygen atom activates benzene
ring more than -OCH3; -NH2; and -OH groups
for electrophilic substitution reaction.
7. With decreasing C—X bond polarity, rate
of nucleophilic substitution on benzene ring
decreases.
8. Benzene is aromatic compound. Remaining
molecules are non aromatic because no cyclic
canjugation is present.
 Aromatic Compounds
9. Nitronium ion ` NO2 j is attacking electrophile in
5 23. C7H8O is insoluble in NaHCO3 \ it has no -CO2H
but soluble in NaOH. \ It is a phenolic compound.
nitration reaction.

10.

11. 24.

12.

13.
25.

a-position is more reactive than b-position

14. 26.

15. Due to presence of cyclic delocalized 4n + 2 re 6

^6re 6h is aromatic.

16. ; As 3rd nitrogen atom lone pair is not

involved in resonance, act as basic.

17. As benzene is non polar it is least soluble in water.

27.
18. As is non planar molecule it is non-
aromatic

19.
28.

20. As group is ring activating group

it is ortho/para directing for electrophilic aromatic
substitution reaction.
21. As cyclooctatetraene is non-planar molecule it is
non aromatic compound.

22. 29.
Chemistry

30.

37.
31.
(Hofmann rearrangement).

38.

32. 39.

33. 1o-amides show Hoffman

bromamide degradation reaction.
40. Strongly activated benzene undergoes coupling
reaction. Nitro benzene is strongly deactivated
34. molecule \ doesn’t undergo coupling reaction.

41.

In acidic medium coupling takes place on ortho/
KCN 45H? para position w.r.to -NH2 group.
35. R - X R - CN R - CH2 - NH2
1o amine.
36. Gabried phthalimide synthesis is best method for 42.
preparation for 1o-amines. Using R—X without
change in number of carbons.

In basic pH coupling takes place on ortho/para
w.r.t. -OH group.
EXERCISE - 3
1. Highly deactivated benzene does not undergo 3. Note that it forms optically active compound in
Friedel-Crafts reaction. one case.
N


2.
N

 Aromatic Compounds

4.

10.

5.

11.
6.

12.

7.

8.
13. Electron withdrawing groups (-m groups) are
meta directing groups.

En: ; —C≡≡N ;

14. ⇒ deactivating but o/p-directing for

9. electrophilic substitution
Chemistry

15. due to Planar cyclic conjugated (4n + 2) p delocalised electrons aromatic

EXERCISE - 4
1. Due to resonance benzen is more stable and all
carbon-carbon bond lengths are equal.

2. Benzal is divalent. 8. Due to presence of lone pair electrons -Br; -OCH3

-OH; -NH-CH3 donate electrons by resonance,
attract electrons by inductive effect (due to more

Benzyl is monovalent. electronegative than carbon).
9. In nitration of benzene removal of H 5 is fast step.
3. \ rate of nitration: C6H6 . C6D6 . C6H6 . C6D6

10.

11.

4.

As two structures are with double bond between
C1 and C2; C1-C2 bond has maximum double bond
character \ C1-C2 bond is shorter than C2-C3

5. Due to non-planar form, is non- 12.

Aromatic.
6. Reactivity towards electrophilic substitution
reaction:

-CH3 is activating group

-Cl is weakly deactivating group
5
13.

- NH3 is strongly deactivating group.

7.

 Aromatic Compounds
14. Sulphonation is a reversible reaction it has kinetic
isotopic effect i.e., rate: C6H6 > C6D6 > C6T6

18.

Electron donating groups increases rate of
electrophilic substitution.
H2
19. R - NO2 Ni
R - NH2
LiAlH 4

R - NO2 R - NH2
15. Sn/HCl

R - NO2 R - NH2
Zn

R - NO2 NH 4 Cl
R - NH - OH

due to Intramolecular H-bonding 20.
has low B.P.

16.

21.

(x) is more acidic due to ortho effect

(y) is more soluble due to intermolecular
H-bonding
(x) is more volatile due to intramolecular
H-bonding

(y) has more melting point due to efficient packing
in crystal lattice. 22. 1st position is ortho w.r.t. -OH. \ more reactive
position than 3rd. In napthalene derivatives
a-positions (1, 3) are more reactive than
b-positions (2nd).
17.

23.

Chemistry

24.

25.

29.
26.

27.

30. Acylation and alkylatiion on benzene are Friedel-
craft’s reactions.

31.
28.

• Free Radical substitution reaction.

• It is substitution on side chain
32. Directing influence for Electrophilic aromatic
substitution follows: strongly activating group >
moderately activating group > weakly activating
group > deactivating group.
 Aromatic Compounds

33.

6
( - Cl is better leaving group)

34. 37.

35.

• Due to intramolecular H-bonding; (P) has more

B.P. than (Q);
• (P) is less stable than (Q); P is less acidic.
38.
• (Q) has more m.p. than (P) due to close packing
in lattice.

36.
Chemistry

39.

40.

43.

41. Strongly activated molecules participate in

:
coupling reaction with benzene diazonium salt.

: due to extended conjugation exhibit colour

: Diazonium ion is weak electrophile, participate

\ a-naphthol ; in electrophilic substitution with phenol.

: coupling takes place at para position due to
steric factor (Large size).

44.

N, N-dimethylaniline Phenol

participate in coupling reactions.

42.
 Aromatic Compounds

50.
45.

46. ⇒ -CH3 is weakly activating and ortho/

para directing group.
⇒ -CH3 activates benzene ring by 51. : Benzene; (Aromatic compound) burns with
hyperconjugation. sooty flame due to high carbon content.

: It, is a nucleophile, participate in nucleophilic
substitution reaction.

: Resonance energy 36 K.cal/mol

52.

47.

48. -OH and groups are ring

activating groups towards Electrophilic aromatic
substitution reaction. 53.

49.

Chemistry

54. ⇒ due to planar cyclic, planar, (4n+2)

p-bonded electrons Aromatic in nature.
62.

55.

56. If o/p-directing and meta-directing groups are 63.
present on benzene electrophile attack on benzene
w.r.to o/p-directing group.

57. ⇒ As cyclic conjugatiion is not present

non-Aromatic.

58. due to repulsions between the two

hydrogens, molecule changes to 64, 65, 66.
non-planar.

59. 3 p-bonded electrons ]6e 6g participate in

delocalisation.

60. due to quasi aromatic, has

maximum dipole moment

61.

In anthracene d-position is more reactive due to
stability of intermediate.

 Aromatic Compounds
69.

67.

(Hoffman Bromamide reaction)

70.
68.
(Friedel-crafts Alkylation)
isopropyl benzene (Electrophilic substitution)

(Schotten-Baumann reaction)

(Friedel-crafts’ reaction)
(Electrophilic substitution)

(coupling reaction)

(Reimer-Tiemann Reaction)
(electrophilic substitution)
Chemistry

NO2 O
3. C O O C
HNO3
1. H2SO4 O
hv
1 mole 1 mole O

: :
78 gm 123 gm C O
3.9 gm 123 3.9 = 6.15 gm [X]
×
78

But actual amount of nitrobenzene formed is 4.92 + CO2
gm and hence.
4.92 NO2 Br

Percentage yield = 6.15 ×100 = 80%

4.
Br
NO2 NO2 NH2
CrO3/Acetic anhydride
2.
Br2/Fe Sn
 +HCl
Br Br
NaNO2/HCl

Br N2Cl

CuBr
HBr
Br Br

N2Cl 
+
NH2 Br

(1) NaNO2 + HCl (2) Cu2Br2

5.
Br Br Br
Br

HNO3
H2SO4
Br
NO2

6. Aniline and phenol form complex with Lewis acid O O

so most reactive among the given compounds for
AlCl3
Friedel Craft reaction is chlrobenzene. 8. O O AlCl3

7. OH
CH2Cl CH2NC CH3
HCHO AgCN 
HCl

Benzyl chloride Benzyl isocyanide OH

(A) (B) CH3
O
 Aromatic Compounds
9. Compounds which
r
due to acid-base reaction - NH2 (activating group)
– do not follow (4n + 2) p electron rule, 5
changes to - NH3 (deactivating and m-directing

– do not have cyclic, planar and conjugated system group)
are not aromatic. Hence, is not aromatic,
12.
infact it is antiaromatic as it contains 4np
electrons. change in M.wt
number of -OH groups = 42
10. 390 - 180
= 42 =5

Aromatic compounds more resonance stabilised. 13.

⇒ : Non-aromatic
: least resonance stabilised.

11. 14. due to intramolecular H-bonding

less soluble in water

1.
3.

2.

Chemistry

Alkaline solution converts -OH group to - O 6
which activates ring towards coupling reaction
4. more than -OH group.

⇒ 1st is ortho to -OH group. 7.

⇒ a-position is more
reactive than b-position
towards electrophilic aromatic
substitution.
8.

5.

6.

Aromatic diazonium salts on treatment with
strongly activated aromatic compounds produce
brilliant colored dye.
O
O
O C
O O C OH C
O OH

9.
AlCl3 Zn/Hg,
HCl
(P) (Q)
Carboxylic Acid Carboxylic Acid
SOCl2
O
C
Cl
(R)

AlCl3

(S)
Zn/Hg,
HCl
O
O O
C C
Cl R

(R)
R2Cd
 Aromatic Compounds

10.

11. (B)
NaOEt

13.
H3C
(i) alc. KOH
(D) Br (ii) NaNH2 H3C C CH Red hot iron tube
873 K
Br

KOH
NH2 H3C
C CH Red hot iron tube
873 K

12.

⇒ Q is steam volatile due to Intramolecular
H-bonding

⇒ Q is positive towards FeCl3 Test. (due to

group).

⇒ Due to presence of -CHO compound
(S) is positive towards 2,4-DNP (2,
4-dinitrophenylhydrazine).

⇒ As phenolic group is not present (S) is negative
towards FeCl3 Test.
Chemistry
15.

14.

⇒ (due to steric factor of -C(CH3)3 and -I di, tri
Iodo product is not possible.)

⇒ (due to steric factor of -C(CH3)3 tri bromo
product is not possible).

: -OH group is o/p-directing group. (strongly
activated group).

16.

17. & 18.

 Aromatic Compounds
19. & 20.

21.

22. ⇒ free radical

substitution reaction.

23.


Chapter 15
EXERCISE - 1
1.
2. Classical smog is mixture of sulphur dioxide and
coal smoke with fog. The causes for classical
smog are the heavy usage of fuel in industry and
household purposes. Winter season is predominated
by this smog. Photo chemical smog is precipitate in
the reaction of the nitrogen oxide and other chemical
compounds in sunlight.
3. Asbestos cause lung cancer.
Answer correction (A)
5. Great smoke of London was a severe air pollution
event in London during cold weather of 1952
December during morning mainly.
6. Troposphere → Stratosphere → Mesosphere
→ Thermosphere → Exosphere
7. The nitrogen dioxide and sulphur dioxide combined
with fog rather than humidity; larger droplets of
water diluted the acid products; allowing more
sulfate production as sulfuric acid. Sunrise burned
off the fog, leaving concentrated acid droplet that
killed citizens.
8. Secondary pollutants are pollutants which form in
the atmosphere.
PAN (Peroxyacyl nitrates) produced in the
atomsphere when oxidized volatile organic
compounds combine with nitrogen oxide.
9. Chlorofluorocarbons cause ozone depletion.
10. Methylisocyanate was leaked.
11. Due to depletion of ozone, UV light is particularly
effective at damaging DNA. It is a cause of
melanoma and other types of skin cancer.
Environmental Chemistry
Environmental Chemistry
12.
13. Ozone layer is present in stratosphere.
15. Mesosphere is coldest
17. Green house gases are water vapours, CO2, CH4
nitrous oxide, ozone and chlorofluorocarbons.
19. Methane is used in fuel hence it is main hydrocarbon
pollutant.
20. CO2 is not pollutant as it does not harm nature, plant,
animals and humans. In fact plants need CO2 and it
is part of atmosphere.
21. SO3 + H2O → H2SO4 (main)
NOx + H2O → HNO3
22. BOD5, The 5 day biochemical oxygen demand.
23. Pollution is release of toxic / undesirable materials
in environment.
24. Automobile exhausts.
25. When we burn a fossil fuel, the sulfur reacts with
oxygen and forms sulfur dioxide gas (SO2).
26. SO2 + H2O → H2SO3, SO2 + O2 → SO3
SO3 + H2O → H2SO4, NO2 + H2O → HNO3
27. , N2O, NO, O3 are main photochemical oxidant
28. Carbon monooxide form complex with haemoglobin
and supply of oxygen stops.
32.
33. Pathogens and PCB (polychlorinated biphenyl) both
present in water.
PCB cause cancer in animals and are probable
human carcinogens.
34. If BOD conc. is less than 5 PPM then water polution
is less.
Chemistry
36. BOD is a measure of the amount of oxygen needed
by bacteria and other micro organism to oxidize
the organic matter present in a water sample over
a period of 5 days. The BOD of drinking water
should be less than 1. That of raw sewage may run
to reversal hundred.
37. Eutrophication, induce excessive growth of plants
and algae. This process may result in oxygen
depletion of the water body.
EXERCISE - 2
2. Noise is not a chemical pollutant.
3. H2 is not an air pollutant.
4. Domestic wastes are biodegradable pollutants.
5. Acid rain is a secondary pollutant.
6. Automobile exhaust is not a water pollutant.
EXERCISE - 3
1. Particulates acquire negative charge and are attracted
by the positive electrode.
2. PSCs react with chlorine nitrate and HCl to give
HOCl and Cl2.
3. Ozone does not absorb infrared radiation at all. It
absorbs UV radiations coming from the sun in the
upper atmosphere and acts as an umbrella, thus
protecting human being living on earth.
4. Biomagnification is a process of increasing the
amount of persistent pesticides per unit weight of
organisms due to their accumulation in fat.
5. Coagulation can be carried out by adding alum and
ferric chloride in waste water.
6. Reaction of methylamine and phosgene to produce
MIC (Methyl isocyanate) is not an example of green
chemistry.
7. Aerosols use CFCl and flying jets release NO. Both
cause depletion of ozone layer.
8. Ozone absorbs U.V. radiations that are harmful to
human beings.
9. Oil slick in sea water decreases D.O. value.
10. Presence of CO in the exhaust shows incomplete
combustion.
11. In presence U.V. rays O2 is converted into O3.
39. Microbes decompose the organic compound in
sewage water.
41. Biosphere is the global ecological system integrating
all living beings.
44. Biosphere includes lithosphere, geosphere
hydrosphere and atomsphere.
8. PAN, NO2, O3, CO, SO2 and VOC
10. CO2 is not harmful.
11. CO2, N2O, CH4, O3, N2, CFC
12. O3 is a molecule of three atoms of oxygen, which is
triangular shaped.
12. The thermosphere is the fourth layer of the
earth’s atmosphere and is located above the
mesosphere. The air is thin in the thermosphere.
The earth’s thermosphere also includes the region
of the atmosphere, called the ionosphere. The
ionosphere is the region of the atmosphere that is
filled with charged particles such as O+, NO+. The
high temperature in the thermosphere can cause
molecules to ionize.
13. Classical smog contains smoke, fog, sulphur
dioxide (SO2) and compounds of reducing nature.
It is produced in cold and humid climate. But its
main components are not produced by the action of
sunlight on emissions of automobiles and factories.
14. Biochemical oxygen demand (BOD) is a measure
of organic material present in water. BOD value less
than 5 ppm indicates a water sample to be rich in
dissolved oxygen. For fresh water, value of BOD is
less than 5 ppm while for polluted water the value of
BOD is 17 ppm or more than 17 ppm.
15. Sewage containing organic waste should not be
disposed in water bodies because it causes major
water polluttion. So, fishes in such a polluted water
die because of decrease in the amount of dissolved
oxygen in water.
16. Tetraethyl lead used in fuel to reduce engine
knocking, boost octane ratings and help with wear
and tear on valve within the motors.
17. It occurs in cool humid climate.

19. Components of photochemical smog are NO, NO2,
O3, Aldehyde and peroxyacyl nitrates.
21. Nuclear chemistry is related to nuclear reactions.
22.
UV radiation also splits CFCs in the upper
atmosphere to produce chlorine atoms.
23. UV radiations cause skin burn and skin cancer.
25. Photosynthesis absorbs CO2 and release O2.
26. → A viable particle is a particle that contains one or
more living microorganism
→ O2 is not green house gas.
27. Ozone cuts off the ultra violet radiation of the sun.
28. Incomplete combustion produces CO.
29. Sodium chlorate and sodium arsenate are weedicides
while DDT and BHC are pesticides.
30. Lead, Mercury and Cadmium are toxic and
pollutants.
31. Ozone, Methane, Carbon dioxide and water vapours,
nitrous oxide, CFCs are green house gases.
47. (a) The dark blue colour of ozone is due to intense
32. Non-degradable solid pollutants are those which do
not degrade, e.g., DDT, plastic etc.
33. The acids present in acid rain are H2CO3, HNO3 and
H2SO4 as the CO2, SO2 and NO2 gases are present in
the atmosphere which dissolve in water to give these
acids.
34. The consequences of global warming may be
increase in average temperature of the earth and
melting of glaciers. BOD and eutrophication are the
result of water pollution.
35. 10 ppm value of biochemical oxygen demand (BOD)
and eutrophication show that the environment is
polluted.
1. CH4, O3 and H2O causes global warming in
Tropospheric level.
H2 does not cause global warming.
2. Eutrophication of water body results in loss of
Biodiversity
3. The green house gases are CO2, H2O(vapour) & CH4.
4. Reducing or classical smog is the combination of
smoke, fog and SO2.
5. The amount of oxygen required by bacteria to break
down the organic matter present in a certain volume
Environmental Chemistry
36. Phosphate containing fertilizers cause water
pollution. Addition of such compounds in water
bodies causes enhanced growth of algae and hence,
results in decreased amount of dissolved oxygen
in water. Due to lack of dissolved oxygen, fish
population greatly reduces.
38.
Hence NO2 is more harmful.
→ Acid rain mainly contains H2SO4
40. Weedicides are the chemicals which are sprayed
over field to get rid of weeds
43. Cadmium, lead and mercury are toxic if exceed
limit.
44. Greenhouse gases are water vapours, CO2, CH4,
nitrous oxide, ozone and CFCs.
45. All reactions are responsible for the depletion of
ozone layer.
46. Its (i.e., ozone) advantage over chlorine is that it
avoids the unpleasant smell and taste of chlorine.
2500 o C
True, O2 2O; O + O2
quenching
O 3.
absorption of red light.
(b) Oxides of nitrogen and the halogen can damage
the O3 layer.
(c) 2I2 + 9[O3] —→ I4O9 + 9O2
(d) 2KOH + 5O3 —→ 2KO3 + 5O2 + H2O
48. Parathion, aldrin, chlordane, DDT, Dieldrin and
endrin are non biodegradable pesticides.
49. Herbicide is a chemical substance that farmers use
to kill plants that are growing where they are not
wanted.
50. BHC - Benzene hexachloride - insecticide.
Malathion is an organophosphate insecticide.
of a sample of water, is called Biochemical Oxygen
Demand (BOD).
6. The highest allowable amount of Mn is 0.05 ppm.
All other elements are present as per their maximum
permissible values.
7. Higher the value of BOD, more the oxygen
requirement which implies more polluted in the
water sample.
10. Green chemistry is related to minimize the use and
generation of hazardous substances.
 Hydrogen & Its Compounds

Chapter
16 Hydrogen & Its Compounds
Intext Exercise 1
1. Protium :- 1p + 0n 5. Fact. Ca and Mg bicarbonates cause temporary

Deuterium :- 1p + 1n hardness while their chlorides and sulphates cause
permanent hardness.

Tritium :- 1p + 2n
6. Acetanilide is used to arrest the decomposition of
2. p-hydrogen is more stable and at 0K, hydrogen exists H 2O 2.
as 100% p-hydrogen. At room temperature it is
found to be 75% o-hydrogen and 25% p-hydrogen. light 1
7. H2O2 H2O + 2 O2.
3. Zn + H2SO4 —→ ZnSO4 + H2 8. Black colour is due to reaction of Pb in the paint
Zn + 2NaOH —→ Na2ZnO2 + H2 used to PbS on exposure to H2S, H2O2 oxidizes black
PbS to white PbSO4 thus removing the back colour.

1 mole H2 is produced per mole of Zn for both the
above reactions. 9. Hydrogenation is done by H2.
4. This is the washing soda method. 10. D2O is added primarily because it can act as a
moderator for the fast moving neutrons in a nuclear
reactor.

EXERCISE - 1
1. H(g) —→ H(g)
+
+ e- DHIE = +1310 kJ/mole 12. Mg2+ has highest polarizing power among the
given options. Thus, by Fajan’s rule MgH2 is most

H(g) + e- —→ H(g)
+
DHEGE = -77 kJ/mole
covalent.
2. The reaction CO + H2O → CO2 + H2 is called water
13. H2O is liquid at room temperature due to H-bonding.
gas shift reaction.
14. Group 1 and Group 2 hydrides are ionic.
3. On the basis of nuclear spin two types of H2 is
present. These are called spin isomers. 15. Solid NH4F has a structure similar to ice and is the
boil only solid which can form mixed crystals with ice.
4. Mg (HCO3)2(aq.) MgCO3 . + H2O + CO2 -
16. CaSO4 = produces Ca+2 ions in water (responsible
5. Possible O.N. of H = - 1 in hydride
for hardness).

H = 0 in H2
17. H2O H+ + OH- Kw = 1 × 10-14

H = + 1 in HCl, H2SO4,

H2O etc. D2O D+ + OD- Kw ≈ 3 × 10-15

\ a H O . 1.8a D O
6.
2 2

18. Cation exchange reaction takes place.

7.
8. 1 s orbital of Be3+ is more stabilize and has lower
energy as compared to H.
9. H is most abundant in universe.
10. Hydrogen and deuterium are stable.
11. Zn is amphoteric and reacts with a base like NaOH
to liberate H2.
19. Zeolites remove hardness causing Mg2+ and Ca2+
from water.
20. Fact.
21. Water undergoes expansion on freezing
22. Due to the polarity of bonds H2O can form H-bonding.
Thus, H2O has higher critical temperature than O2.
23. Refer structure on Pg 13 of the chapter.
Chemistry
24. Vol. strength=N×5.6 ⇒ Vol. strength = 1.5×5.6=8.4. 35. H2O2 acts as a reducing agent with strong oxidizing
agents like KMnO4 and K2Cr2O7.
25. NH O = 10/5.6
2 2
36. Acetanilide prevents decomposition of H2O2.
10
\ 5.6 × VH O = 200 × 2 ⇒ VH O = 224 mL.
2 2 2 2 37. Fact.
26. Na2O2 is the only peroxide among the given options.
38. MnO speeds up the decomposition of H2O2.
27. Factual. Used in identification of peroxides.
39. Loss of e- is oxidation and gain of e- is reduction
28. CO2 has strongest acidic character while H2O is
neutral. 40. Water contains traces of D2O. On prolonged
electrolysis H2O is decomposed and D2O is obta
3
29. (NH4)2S2O8 2NH3 - + 2SO3 + H2O2
41. Facts.
30. Each 0 atom has 2 bond pair and 2 lone pair of
42. Greater rate of reaction is due to lower activation
electrons. Thus, hybridization is sp3.
energy.
31. Proton can exist as H(H2O)n+ in solution.
43. Ionic substances will be more soluble in solvents
32. S is oxidized from -2 to 0 oxidation state. having higher dielectric constants.
33. The O—H bond is polar and O—O bond is non- 44. SO3 + D2O —→ D2SO4
polar. Be2C + 2D2SO4 —→ 2BeSO4 + CD4
34. H2O2 can act as both oxidizing and reducing agent.

EXERCISE - 2
1. Electrolysis of water produces pure H2. 10. At 0 K, 100% para H2.
11. (a) 2KOH + CO2 —→ K2CO3
(b) K2CO3 + CO2 + H2O —→ 2KHCO3
2. (c)

1

So removing electron from H is easier. 12. At anode : H2O → 2 O2 + 2H+ + 2e-

3. Zeff = Z - s ⇒ Zeff = 1 - 0 At cathode : 2H2O + 2e- —→ 2OH- + H2

1
4. B.P. = T2 > D2 > H2 Overall H2O —→ H2 + 2 O2
M.P. = T2 > D2 > H2 13. LiH + H2O —→ LiOH + H2
DHvap. = T2 > D2 > H2
CaO + H2O —→ Ca(OH)2
5. H2 has 2e- and 2 proton in each molecule. Zn + dil.H2SO4 —→ ZnSO4 + H2
3 1

H2 gas has no colour, odour, or taste and burns with H 2O 2 H2O + 2 O2 -
a pop sound. 14. Thermal stability increases with increasing Lattice
6. CaO + H2O —→ Ca(OH)2 (No gas) energy. Smaller size of ions, more the lattice energy
if charge on ions is same.
7. It existas as H- in ionic hydrides and forms covalent
bonds with Cl, C etc. Many compounds have H as 15. Covalent or molecular hydride are discrete molecule
H+. i.e., B2H6, SiH4, PH3 etc.
8. (a) CH4 + H2O
Ni
CO + 3H2 16. Ionic hydrides are called saline hydride e.g., NaH,
3
3 CaH2, BaH2 etc.
(b) C + H2O CO + H2
(c) C + Air —→ CO2 + N2 17. Saline hydrides are ionic compound so that they
3 have same features as ionic solid.
(d) CO + H2O Catalyst
CO2 + H2
18. NaH / CsH etc. are called saline hydride.
9. Para H2 = proton spin in opposite direction.

Ortho H2 = proton spin in same direction.
 Hydrogen & Its Compounds
19. Electron precise hydrides like CH4, SiH4 have all
bonds as 2c-2e and no lone pair of electrons on
central atom.
25.
20. For H2 to be produced at anode during electrolysis,
hydrogen must be present as H- in the molten salt as
anions are discharged at anode during electrolysis.

H2O2 cannot reduce dichromate. It oxidizes SO32-
21. H3BO3(s) = 2-D sheet like structure
and I- as shown above.

Diamond = 3-D network like structure (covalent
bonded)

H2O(s) = 3-D network like structure (hydrogen 26.
bonded)
r r r r
22. XH n & PH3, NH3, AsH3 , one lone pair on central 27. BaO2 is peroxide, others are oxide.
atom. 28. Glass containers also contain trace of alkali.
23. N is in -1 O.S. in NH2OH it cannot be further reduced 29. All are true.
by H2O2. Hence it is oxidized. The product varies on
the reaction conditions and is not necessarily N2. 30. N2H4 + 2H2O2 —→ N2 + 4H2O

24. Na2O2 = peroxide of sodium

EXERCISE - 3
1. MnO4- is a strong oxidizing agent in both acidic and bonds.
basic media. In the acidic medium its O.S. changes
5. II, IV, VI are correct order.
from +7 to +2 and in basic medium its O.S. changes
from +7 to +4.
+
H2O2/H
 +2
6.
+
MnO4/H Mn (OS = +2)
 
MnO4/OH MnO2 (OS = +4)
O2

Thus, sum of O.S. of Mn in the products formed in 7. Boiling and Ca(OH)2 can remove only temporary
the two reactions = 2 + 4 = 6 hardness.
Note : It is only in highly alkaline solutions that O.S. 8. I, IV and V are correct.
of Mn changes from +7 to +6 when it acts as an
oxidizing agent.
2. Hybridization of B in BH3 is sp2. 9.
Hence x = 2.

In B2H6, the 2-B atoms and 4 of the 6H atoms are 10. Group 13 hydrides are electron deficient, group 14
in the same plane and the two H atoms involved in hydrides are electron precise and hydrides of Group
banana bonds are out of plane. So, y = 6. 15 to 17 are all electron rich hydrides.

\ (x × y) = 12. Thus, only B2H6 is electron deficient.
3. BaCl2.2H2O. Fact.
4. P2H4 is electron rich hydride . The

normal covalent or coordinate bonds are 2c-2e

Chemistry
EXERCISE - 4
1. Due to intermolecular hydrogen bonding bond
parameters change in solid phase.
2. When sodium reacts with ethyl alcohol some
hydrocarbon gas is also formed along with H2.
3. Polyphosphates form soluble complexes with Mg2+
and Ca2+ present in hard water.
20 × 0.1
4. Normality of H2O2 = 50 = 0.04 N
wt. of H2O2 = V × N × E = 1 × 0.04 × 17 = 0.68 g/L
5. H2O2 is oxidized in the following manner with
KMnO4. H2O2—→ 2H+ + O2 + 2e-. So, all 18O is
liberated as O2.
6. Salts are less soluble in heavy water than in water
due to lower dielectric constant of D2O.
7. According to Le Chatelier’s principle when pressure
is increased equilibrium shifts in the direction of
lesser volume. Thus, formation of water is favoured.
Hence, ice melts.
8. 2KMnO4 + 3H2SO4 + 5H2O2 —→ K2SO4 + 2MnSO4
+ 8H2O + 5O2
K2Cr2O7 + 4H2SO4 + 3H2O2 —→ K2SO4 + Cr2(SO4)3
+ 7H2O + 3O2
9. Ca3P2 + 3H2O —→ 3Ca(OH)2 + 2PH3 -
10. If water molecule was linear it would be non-polar
and its dielectric constant will be zero. So, b.p. and
m.p. will decreases.
11. While KMnO4 acts as oxidizing agent, in acid
medium 5e- and in alkaline medium 3e- are involved.
So, V2 × 0.01 × 3 = 0.05 × 100
500
\ V2 = 3 mL
12. Mg3N2 + 6D2O → 3Mg(OD)2 + 2ND3
13. O—D bond is stronger than O—H bond.
14. 2KMnO4 + 8H2SO4 + 5Na2O2 → K2SO4 + 5Na2SO4
+ 2MnSO4 + 8H2O + 5O2
15. 2Na2O2 + 2H2O → 4NaOH + O2
1
nO = 2 n Na O & n O = 0.25
2 2 2 2
16. 106g or 1000 L of water would require 56 g CaO
\ moles of CaO needed = 1
Now, Ca(HCO3)2 + CaO → 2CaCO3 + H2O
\ moles of CaCO3 produced = 2.
From these 2 moles of CaCO3, 1 mole is formed
from the added CaO.
Thus, moles of CaCO3 from the Ca2+ already present
in the water = 1
\ Mass of CaCO3 = 100g
\ Hardness of water = 100 ppm.
17. Zn with conc. H2SO4 liberates SO2 and with dil.
HNO3 liberates NO. Pure Zn does not liberate H2
with dil. H2SO4 due to hydrogen over voltage.
18. Only cations are removed by Res. COOH.
19. PbO2 is a dioxide. It does not give H2O2.
20. Hardness is only due to Ca2+ or Mg2+ and not due to
Na+ or K+.
21. With increase in mass, heat of fusion increases.
22. With increasing ionic character exchange of H with
D takes place easily.
23. Meq of H2O2 = Meq of MnO-4 (H+)
W 0.316
17 ×1000 = M/5 ×1000
WH O = 0.17g
2 2
\ 0.2 g of H2O2 contains 0.17 g of pure H2O2
\ percent purity is 85%.
24. When water containing salt and sugar is passed
through cation exchange resin Na+ ions are
exchanged with H+ ion and the water get acidic
character. In acid medium inversion of sugar gives
glucose and fructose.
25. Metallic hydrides have more electrical conductivity
due to metallic property.
26. Ca2+ + 2RH → R2Ca + 2H+
77.5
106 mL of H2O has 77.5 g Ca2+ = 40 mole Ca2+
77.5
⇒ 2 × 40 mole H+ in 1000 L water
\ 103 mL of H2O has H+ = 3.875 × 10-3 M
pH = -log [H+] = 2.41
27. (a) O—D bond is stronger than O—H. So, ordinary
water decompose rapidly on electrolysis,
(b) the activation energy of D2 and Cl2 is more than
H2 and Cl2 and
(c) Freezing point of D2O is higher than H2O
(d) D—D bond energy is greater than H—H.
28. Increase in the reactivity of H2 in the presence of
catalyst is not a reason for the more reactivity of
atomic hydrogen.

29. In BeH2 due to sp3 hydridization, in Be all atoms are
not in the same plane.
30. Both H2 and D2 show spin isomerism.
r r
31. Group 15 = PH3, AsH3, etc
r r r \ g/L = 10 × 13.6 = 136
Group 16 = H2 S:, H2 Se: etc form electron rich
hydrides.
32. 10 volume solution of H2O2 means that 1L of this
H2O2 solution will give 10L of oxygen at STP.
2H2O2(l) —→ O2(g) + H2O (l)
2 × 34 g 22.4 L at STP
68 g
On the basis of above equation 22.4 L of O2 is
produced from 68 g H2O2 at STP
68 × 10
10 L of O2 at STP is produced from 22.4 g
= 30.35g - 30g H2O2
Therefore, strength of H2O2 in 10 volume H2O2
solution = 30 g/L = 3% H2O2 solution.
33. Ice has open type structure with wide holes, which
are called interstitial holes.
34. H2 = no colour, no odour, no taste, non polar and
combustible gas.
35. Ca2+/Mg2+ + Na2CO3 —→ CaCO3 . /MgCO3 . + 2Na+
White ppt.
Ca2+/Mg2+ + Na6P6O18 —→ [Na2MgP6O18]2- + 4Na+
Solution
2NaAlSiO4 + Ca2+ —→ Ca(AlSiO4)2 . + 2Na+
ppt.
36. Demineralised water is free from all soluble mineral
salts. It is obtained by exchanging all cations by H+
and all anions by OH-.
37. 25 × 30 = 750 mL
38. 68 g of H2O2 liberates 22.4 lit of O2 at STP
6.8 g of H2O2 liberates 2.24 lit of O2 at STP.
Hydrogen & Its Compounds
g/L of H 2 O 2 Volume strength
39. Normality = 17 = 5.6
5.6
\ Volume strength = 17 × (g/L of H2O2)
Also, (g/L) = 10 × %(w/V)
5.6
\ Volume strength = 17 ×136 = 44.8
40. Temporary hardness is due to bicarbonates of Mg
and Ca.
41. Calgon is sodium hexametaphosphate.
42. 120 g MgSO4 = 100 g of CaCO3
\ 6 mg/kg = 5 mg/kg or 5 ppm
43. (a) NaH + H2O —→ NaOH + H2 -
H- and H+ both get converted to H2.
(b) Na2O + H2O —→ 2NaOH
1
(c) Na + H2O —→ NaOH + 2 H2
(d) 2NaOH + Zn + 2H2O —→Na2 [Zn(OH)4]+ H2 -
44. (a) 11H, 12D are atomic isomers.
(b)
(c) H2O, D2O are oxides of 11H and 12H respectively
(d) Hard water contains soluble salts of Ca+2, Mg2+
which precipitate as respective carbonates on
adding Na2CO3.
45. (p) H2 has H-H s bond.
(q) H2O contains 2s bonds and 2 L.P.
(r) H—O—O—H has peroxy linkage
(s) CaH2 is hydrolith. It contains H as H-.
Chemistry

1. Nitrogen. Around 55% of hydrogen around would 8. Hydrogen have 3 isotopes protium, deuterium and
goes to ammonia production tritium, out of which tritium is radioactive.
2. Sodium hydroxide is generally prepared 10. & [Fe ]CNg6] 4- + H 2 O 2 6Fe ]CNg6@3- + H 2 O
H+

commercially by electrolysis of sodium chloride in

In the oxidation by H2O2, liberated oxygen by
castner Kellner cell. decomposition of H2O2 pull electrons from
at cathode: Na + e- Na - amalgum
Hg
[Fe(CN)6]4– & get converted into H2O
1
Anode: Cl- → 2 Cl2 + e-
The Na–amalgam is treated with water to give
sodium hydroxide and hydrogen gas :
& 6Fe ]CN6g@3 + H 2 O 2
6Fe ]CNg6@4- + H 2 O + O 2
- OH

2Na (amalgam) + H2O → 2NaOH + H2 + 2Hg

Here H2O2 acts as a reducing agent thus it
3. 10–3 molar MgSO4 ≡ 10–3 moles of MgSO4 present in disproportionate in basic medium
1 L solutions.
nCaCO / n MgSO
H2 O2 H 2 O -2 + O 02
3 4

10 -3 # 100 11. Only temporary hardness can be removed by boiling.

ppm(in term of CaCO ) = # 106
3
1000 12. H2O2 can act both as oxidizing as well as reducing
ppm(in term of CaCO ) = 100
3
agent.
4. Most abundant gas in the troposphere is nitrogen. 13. There is intermolecular H-bonding in water, not
intramolecular.
5. Hydrogen has 3 isotopes called Protium, Deuterium
and Tritium. 14. 2LiH + B2H6 —→ 2LiBH4
6. Temporary hardness is due to bicarbonates of Ca2+ 15. D2O is used as a moderator in nuclear reactors, to
and Mg2+. control the speed of the reaction and not as a coolant.
7. H2O2 can get both as a reductant and oxidant in both
acidic and basic medium.
 s-Block Elements

Chapter 17 s-Block Elements

Intext Exercise 1
1. Sodium has higher I.E. because of smaller atomic
size.
2. After removal of an electron the effective nuclear
charge per electron increases hence the size
decreases.
3. Reaction of Na with water is exothermic and the
heat released in the process melts sodium. Thus, the
surface area increases, increasing rate of reaction.
4. Element – Li Na K Rb
Atomic radius (pm) – 152 186 227 248
5. All alkali metals readily react with air and hence are
stored under kerosene.
Intext Exercise 2
1. Group 2 elements have 2 electrons in the valence
shell.
2. Because of small ionic size and high polarizing
power, Be forms covalent chloride (Fajan’s rule).
3. Factual.
4. Factual.
5. All group 2 carbonates and Li2CO3 decompose on
heating to liberate CO2 and form respective oxides.
6. All A.E.M. chlorides are soluble. Hence, by
elimination PbCl2 is insoluble.
7. The tendency to form cations or get oxidized in
aqueous solution follows the order Be<Ca<Sr<Ba.
LiOH < NaOH < KOH < RbOH
6. Down the group basic character increases
7. The losely attached outermost electron gets excited
by the oxidizing flame. It emits rays in the visible
region during de-excitation.
8. In aqueous solution, reducing power of alkali metals
or oxidation potential follows the order:
Li > Cs > Rb > K > Na
9. Cs > Rb > K > Na > Li
Metallic character decreasing order
10. By definition.
So, Ba is the strongest reducing agent.
8. Be shows anomalous behaviour due to its small size,
high charge density and absence of d-orbitals.
9. On moving down the group lattice energy remains
almost constant as the sulphate is so big that small
increase in the size of the cations from Be to Ba does
not make any difference. However the hydration
energy decreases from Be to Ba. This causes
decrease in the solubility of the sulphates as the
ionic size increases.
10. Larger the atomic size, more loosely is the ouer most
electron bonded and easier it is to remove it. Hence
larger size lead to lower Ionization energy.

Intext Exercise 3
1. Lithium shows digonal relationships with Mg. 7. BeSO4 is most soluble because hydration energy is
3 more than lattice energy.
2. 2NaHCO3 Na2CO3 + H2O + CO2
BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO
3. NH3 + CO2 + H2O —→ NH4HCO3 Hydration energy decreases hence, solubility decreases
NH4HCO3 + NaCl —→ NaHCO3 + NH4Cl
8. 2 ]CaSO 4 $ 2H 2 Og
120 o C
3
2CaSO 4 $ H 2 O + 3H 2 O
NaHCO3 Na2CO3 + H2O + CO2
Dehydration
Gypsum Plaster of paris

4. Solvay’s process or Le Blane process is used to 9. Lithopone (ZnS + BaSO4) is used as a white pigment.
produce Na2CO3 commercially.
10. Lime stone - CaCO3
5. 2NaCl + 2H 2 O " 2NaOH + Cl 2 + H 2
Anode Cathode
Clay - silica and alumina
6. Factual.

Gypsum - CaSO4 . 2H2O
Chemistry
EXERCISE - 1
1. Oscillation of loose electrons, gives metals their
Lusture.
2. With the same anion, smaller the size of the cation,
higher is the lattice energy, if same charge on all
cations.
3. Factual. With cryptand-222, Na forms an unusual
compound of the formula, [Na (cryptand-222)]+ Na-.
The large cryptand ligand (C18N2H36O6) completely
shields the Na+ ion and prevents it combining with
Na-.
4. Mg2+ is the smallest cation and Cl- is the largest
anion among the given salts. Hence, MgCl2 has the
minimum cation/anion ratio.
5. On dissolving moderate amount of Na metal in
liquid NH3, the solution becomes blue in colour
and paramagnetic due th presence of unpaired
ammoniated electrons. [e(NH3)x]-
6. Alkali metals are highly electropositive and thus
highly reducing. There is no stronger reducing agent
than alkali metals. Therefore, reduction, double
decomposition and displacement methods for
their extraction are not suitable. Only electrolytic
methods are suitable for their extraction.
7. Factual.
8. LiCl being covalent has the lowest melting point.
The melting points of other halides decrease form
NaCl to CsCl as the lattice energies decrease.
9. All Alkali metals impart colour to the Bunsen flame.
10. As the IE decreases, the frequency of light emitted
goes on increasing.
11. When the electronegativity difference between the
cation and the anion is the maximum, the compound
formed has the highest ionic character.
Therefore, CsF is most ionic and hence has the
strongest bond.
12. Alkali metals always show monovalency in their
compounds.
13. Rb being most electropositive has the highest
reactivity towards water.
14. As the size of the anion increases from F to I , the
- -
covalent character increases and hence the solubility
in non-polar solvent increases:
LiI > LiBr > LiCl > LiF.
15. Within a group, ionic radius increases with increase
in atomic number.
16. Higher the solubility, higher is the solubility product.
Thus, CsOH being more soluble has the highest
solubility product.
17. All alkali metals are strong bases and hence Na
cannot be amphoteric in nature.
18. Only Li reacts with nitrogen directly to form Li3N.
19. Li due to highest hydration energy among the alkali
metals is a strongest reducing agent despite having
the highest I.E. among the alkali metals.
20. For anion to cation ratio to be low, the anion must be
small and cation must be large, i.e. Cs+ F-.
21. Be < Mg and Li < Na as size increases down a group.
Also Be < Li as size increases across a period.
22. Be2+ has the highest hydration energy among alkaline
earth metals. However, it is not able to compensate
for the high sublimatiion energy and high I.E. of Be.
thus, Be has the lowest oxidation potential among
A.E.M. and hence is the weakest reducing agent.
23. (I.E.1 + I.E.2) of Mg > I.E.1 of Ba also, I.E. of Mg >
I.E. of Ca as I.E. decreases down the group.
24. A.M. have lower I.E.1 than A.E.M. as size decreases
across a period and I.E.1 increases.
25. Mobility of hydrated ions follows the order Li+ <
Na+ < K+ < Rb+ < Cs+. As greater charge density on
smaller ion leads to greater extent of hydration and
bulkier hydrated ions.
26. Be does not react with air at room temperature due t
o the formation of a possive oxide layer.
27. Mg belongs to group 2. Therefore, its size is less
than that of Na.
28. K+ is the largest among Na+, K+, Mg2+ and Ca2+.
Thus, K+/Cl- ratio is the largest.
29. While LiCl is the most covalent alkali metal chloride,
for A.E.M. chlorides, BeCl2 is the msot covalent due
to high polarizing power of Be2+.
30. The ratio of their charge to size i.e. polarizing power
is nearly the same.
31. Be and Mg do not react with water at room
temperature.
32. Na + (x + y) NH3 → Na (NH3)+x + e (NH3)-y. Thus
due to solvated (ammoniated) electrons, solution of
Na metal in liquid ammonia is highly reducing in
nature, and also paramagnetic.

33. Be is the only amphoteric element in s-block.
Thus Be(OH)2 and Al(OH)3 are amphoteric due
to diagonal relationship. Remember, B(OH)3 is a
Bronsted acid.It is called Boric Acid.
34. Mg has the highest value of reduction potential
2+
hence it is the strongest oxidising agent.
35. Not necessarily true as Na2 CO3 . 10H2O exists
while alkaline earth metal compounds seldon have
10 water of crystallizaiton.
36. Washing soda is Na2CO5 . 10H2O.
37. Le Blanc’s Process uses limestone and NaCl.
38. Because KO2 not only provides oxygen but also
removes CO2 both of which are important life
supporting processes.
4KO2 + 2CO2 → 2K2CO3 + 3O2
4KO2 + 4CO2 + 2H2O → KHCO3 + 3O2
39. Sodium in excess of oxygen forms Na2O2.
40. Ca(OH)2 is used to remove temporary hardness.
Ca(OH)2 + Na2CO3 → CaCO3 . + 2NaOH
Ca(OH)2 + CO2 → CaCO3 (milky) + H2O
41. Presence of chlorides of Ca and Mg as impurities
leads to the hygroscopic nature of common salt.
42. Cs+ and Br-3 ions. Larger cations form stable
compounds with large anions.
43. Factual. KHSO5 is called oxone.
200 o C
44. NaOH + CO HCOONa
Solid Sod. formate
45. Na2CO3 + H2O + 2SO2 → 2NaHSO3 + CO2
46. The hydroxides of Ist group are strong bases and HCl
is a strong acid, therefore, the chlorides of Ist group
elements are salts of strong acids and strong bases.
As such they do not undergo hydrolysis thereby
yielding neutral solutions
47. 4KO2 + 2CO2 → 2K2CO3 + 3O2
EXERCISE - 2
1. Thermal stability of Alkali Metal hydroxides
increases down the group.
2. CO3- is a large anion. It is most stable with a large
cation.
s-Block Elements
48. NaOH + AgNO3 → AgOH + NaNO3
Deliq.white cryst unstable
(X) (Y)
2AgOH → Ag2O + H2O
Brown
(X) is a powerful cautery and breaks down the
proteins of skin flesh to a pasty mass. i.e. X is caustic
soda.
49. NO2 contains three electron bond and in NO+2 odd
(unpaired) electron is removed. Peroxides (O2- 2
) do
not possess unpaired electrons as the antibonding p
M.O.’s acquire one more electron each for pairing.
AlO­-2 is obtained by the interaction of Al3+ ( 2s2p6
configuration ) and 2 oxide (O2-) ions each of which
does not contain unpaired electron. Superoxide O-2
has one unpaired electron in p antibonding M.O. and
is therefore paramagnetic.
50. The raw materials used in Solvay’s Process (NaCl,
NH3, CO2) are partially recovered in the recovery
tower. Thus, NH3 CO2 and by product CaCl2 are
obtained in the recovery tower.
51. O2- ion is not possible and K2O4 is unknown.
4
52. H+ ions are discharged at a higher potential when Hg
cathode is used than that using Pt cathode.
53. 2LiOH + H2O2 → Li – O – O – Li + 2H2O
54. KF + HF → K+[HF2]–. In HF–2 , there exists a
hydrogen bonding such as F– ……H—F.
1
55. Plaster of paris (CaSO4. 2 H2O) undergoes hydration
to form gypsum (CaSO4.2H2O) during setting.
56. Since NaHCO3 is an acid salt of H2CO3, it reacts
with NaOH to form Na2CO3 and H2O.
NaHCO3 + NaOH → Na2CO3 + H2O
57. K2CS3 is called potassium thiocarbonate.
58. KO2 (potassium superoxide) contains superoxide
ion O-2 which contains one unpaired electron and
hence is paramagnetic.
59. K2O + H2O → 2KOH
60. Mixture of K2CO3 and Na2CO3 is called fusion
mixture. Its melting point is 712oC while that of
K2CO3 is 900oC.
3. Alkali metals have strong tendency to get
oxidized and hence are good reducing agents or
reductants.
4. Fact: All alkali metals are silvery white metals.
Chemistry
5. (a) Down the group, the atomic size increases with
increasing atomic number and so attraction
for shared pair of electrons decreases. Hence
electronegativity decreases.
(b) Down the group, the atomic size increases with
increasing atomic number and so attraction
between valence electron and nuclear decreases.
Hence ionization energy decreases.
(c) Down the group atomic size increases with
increase in number of atomic shells while
effective nuclear charge remains constant.
(d) Down the group atomic size increases with
increase in number of atomic shells and therefore,
the strength of metallic bond decreases. So
melting point decreases.
6. Alkali metals have low ionisation energy and hence
can show photo electric effect.
7. All are wrong. The solution has strong reducing
nature and coloured due to ammoniated electron.
Dilute solution is paramagnetic where as
concentrated solution is diamagnetic.
8. S1 : Li+ being smaller have high polarising power
and I- being larger have high polarisability. So
it is most covelent among alkali metal halides
according to Fajan’s rule.
S2 : The IE1 of potassium atom is less then sodium
atom. Hence, its work function is lesser.
S3 : The presence of transition metals like iron and
other impurities catalyses the decomposition
of deep blue solution forming amide and
liberating H2.
S4 : Two opposing tendencies exists. With greater
charge and smaller size of cation, lattice energy
increases which tends to increase the melting
point ; while increase in covalent character
causes a decrease in melting point. Hence, no
unique generalised trend may be stated for
melting points. (You need not worry about or
memorise such experimental data).
9. The reaction of alkali metals with water becomes
increasingly violent on descending the group. So,
the order of reactivity is :
Li < Na < K < Rb.
10. They have weak metallic bond because of one
valence electron per atom. So they have low melting
points.
11. They easily lose valence shell electron because of
their low ionisation energies, on account of their
bigger atomic sizes. So they behave as strong
reducing agents.
12. 2Na + O2
Heat
Na2O2;
2Na2O2 + 2CO2 → 2Na2CO3 + O2.
13. True statement. The CsI, because of bigger cation
(Cs+) and bigger anion (I–), has smaller hydration
enthalpy. As a result, it does not exceed its lattice
energy ; so CsI is insoluble in water.
14. The element is K (s-block element), which forms
basic oxide.
15. (a) Down the group due to increase in size the
strength of metallic bond decreases and so,
melting point decreases.
(b) Atomic volume of K is larger as compared to
Na. Increase in atomic mass does not over come
the effect of increase atomic volume in case of
potassium.
(c) They have low ionisation energies because
of their larger atomic size. The heat from the
flame excites the outer most orbital electron to a
higher energy level. When the excited electrons
come back to the ground state, there is emission
of radiation in the visible region. Hence, salts
of Li to Cs impart characteristic colour to an
oxidising flame (of Bunsen burner).
16. MgCl2, BaCl2 and CaCl2 appreciably dissolve in
cold water because their hydration energies exceed
the lattice energies. Ba2+ and Ca2+ impart apple green
and brick red colour to the flame respectively.
The electrons in magnesium are too strongly bound
to get excited by flame. Hence this element does not
impart any colour to the flame.
17. (a) Ca salt imparts brick red colour to the flame.
(b) Sr salt imparts bright crimson colour to the
flame.
(c) Ba salt imparts apple green colour to the flame.
(d) Mg salt does not impart any colour to the flame
because of high ionization energy.
18. Be is smaller than Mg in size. The valence shell
electron is tightly bound with nucleus and therefore,
more energy is required to eject out the electron. So
Be has higher ionisation energy than that of Mg.
19. Along the period from left to right, atomic number
increases and, therefore, nuclear charge also
increases. So first ionization energy of alkaline earth
metals are higher than those of the alkali metals of
the same period because of higher nuclear charge.
20. According to Fajan’s rule Large size (Rb+) cation
will have low polarisation power so have less
covalent character and high ionic character.
 s-Block Elements
21. Basic nature of hydroxides increases down the 36. 2NaOH + ZnO $ Na 2 ZnO 2 + H 2 O
^ampoterich ]Sodium Zincateg
group. The strength of a base depends on ionisation
of the hydroxide which depends on polarity of bond 37. 3Mg + N2 —→ Mg3N2 ; 2Mg + O2 —→ MgO
and internuclear distance between the oxygen of the 38. BaO2 exists as Ba2+ and O22–, therefore, O22– is
hydroxide and metal atom. peroxide ion.
22. Be + 2NaOH + 2H2O —→ Na2[Be(OH)4] + H2 39. 6NaOH + 4S —→ 2Na2S + Na2S2O3 + 3H2O
or Sulphur undergoes disproportionation.
Na2BeO2.2H2O + H2
40. Alkali metal carbonates except Li2CO3 are stable
(Sodium beryllate)
towards heat because they are most basic in nature
23. 2M + H2SO4 —→ M2SO4 + H2 (M = alkali metal) and basic character increases down the group and

M + H2SO4 —→ MSO4+ H2 (M = Alkaline earth thermal stability increases down the group.
metal)
Bigger CO32– anion is polarised by smaller Li+ and
24. Among the s-Block elements, Be is the least reactive thus readily decomposes to give CO2 gas.
towards water.
Li2CO3
3
Li2O + CO2
25. (a) Factual 41. KHCO3 is soluble in water so it can not be separated
1
(b) Hydration energy \ size of cation as a precipitate in the intermediate process.
(c) Both are diagonally related ; because of more 42. Acidic oxide + Base —→ salt + water.
positive charge on Mg, Mg2+ is smaller than Li+. heat
43. 2(Na2CO3.NaHCO3.2H2O) 3Na2CO3 + CO2
Li = 76 pm, Mg = 72 pm.
+ 2+
(trona) + 5H2O
(d) Salt of weak base and strong acid, thus easily
hydrolysed in water giving acidic solution. 44. CaCO3 + 2HNO3 —→ Ca(NO3)2 + H2O + CO2

26. Be + Air
o
T > 1000 C
BeO + Be3N2 (white powder) 45. Na2CO3 + SO2 (excess) + H2O —→ NaHSO3 + CO2

Be3N2 + 6H2O → 3Be (OH)2 (white precipitate) + 46. Ca2+ (from soluble Ca salt) + soluble SO42- gives
CaSO4.
2NH3 (Colourless gas)
47. Be2C + 4H2O —→ 2Be(OH)2 + CH4

Since the metal also reacts with NaOH, it must be an
amphoteric metal 48. It is a salt of Be(OH)2 (weak base) and HCl (strong
3 acid), hence a solution of BeCl2 is acidic.
27. NaHCO3 Na2CO3 + H2O + CO2
49. (i) CaOCl2 + H2O —→ Ca(OH)2 + Cl2
Na2CO3 + dil. HCl —→ NaCl + H2O + CO2
(ii) Cl2 + H2O —→ HOCl + HCl
28. Mg2+ has 10 electrons and so does F-.
HOCl —→ HCl + [O]
__________________________
Ca2+ has 18 electrons and so does S2-.
Cl2 + H2O —→ 2HCl + [O]
__________________________
29. Mg3N2 + 6H2O —→ 3 Mg(OH)2 + 2NH3
Cl2 + H2O —→ 2HCl + [O]
30. Stability of hydrides decreases from Be to Ba.
This nascent oxygen bleaches the litmus paper.
31. Basic character increases down the group and
decreases across a period. Thus, BeO is least basic 50. MgCO3 + H2SO4 —→ MgSO4 + H2O + CO2
BeO is amphoteric. 51. Along the period, atomic size decreases and nuclear
32. KOH(dry powder)+O3(ozonized oxygen) charge increases and thus lattice energy increases,
-10 o C to - 15 o C Ch arg e on cation
KO3(organge solid)
lattice energy ∝ Size of cation . More the
33. Na2O2 + H2SO4 —→ Na2SO4 + H2O2 lattice energy less likely it is to be soluble.
other options given are not peroxides. 52. Neither cation nor anion get hydrolyzed as they
34. MgCl2.6H2O
3
MgO + 2 HCl + 5H2O come from strong base and strong acid respectively.
hydrolysis

35. NaOH + I2 —→ NaIO3 + NaI, with dilute NaOH, 53. X = CaH2 , Y = Ca(OH)2, Z = H2
NaI and NaOI are formed.
Chemistry
54. SO42- is a large anion and forms a more stable 59. Slaked lime :- Ca(OH)2
compound with a large cation. Thus, Cs2SO4 is most Milk of lime :- Ca(OH)2
stable.
Quick lime :- CaO
55. CaC2 + N2 —→ CaCN2 + C. Lime stone :- CaCO3
56. Both BeO and Be(OH)2 are amphoteric and dissolve 60. NaCl —→ Na+ + Cl–; 2 Cl– —→ Cl2 ­- + 2e–
in NaOH forming soluble [Be(OH)4]2–.
2H2O + 2e —→ H2 - + 2OH-
57. CaCN2 + 3 H2O —→ CaCO3 + 2 NH3. Na+ + OH– —→ NaOH
58. CaO + CO2 —→ CaCO3 ; CaO + H2O → Ca(OH)2 .

CaCl2 is not a suitable drying agent for ammonia as
CaCl2 + NH3 → CaCl2 . 6NH3

EXERCISE - 3
1. Except Be and Sr all are correctly matched. 7. x = MOH; y = H2O2 ; z = O2
2. x = Na2PbO2 y = Na2SnO3 z = NaAlO2 8. 4 (KO3, RbO2, Cs2O2, BaO2). It should be basic as
well as a bleaching agent.
3. By product is CaCl2, x = CaCO3, y = CO2.
CaCl2 + Na2CO3 —→ CaCO3 + 2NaCl 9. A = NH3 = 4 atoms ; B = CO2 = 3 atoms ;
3
C = NaHCO3 = 6 atoms ; D = Ca(OH)2 = 5 atoms.
CaCO3 CaO + CO2
10 x = 2 . Compound formed b CaSO 4 $ 2 H2 O l is
4KO2 + 2CO2 —→ 2K2CO3 + 3O2 1 1

4. Except Li2CO3, Na2CO3 all form polymeric chains. plaster of paris.

AlCl3 dimeric chain.
5. Glauber’s salt is Na2SO4.10H2O.
6. (e), (f), (g) are false.
(e) On hydrolysis of Na2CO3. We get an basic
solution due to the formation of NaOH.
(f) K2CO3, does not form precipitate like NaHCO3
and hence can not be prepared by Solvay
process.
(g) Excess of carbondioxide should be avoided
since this leads to the formation of water soluble
calcium hydrogen carbonate.
11. LiH, Mg3Bi2, Al4C3, Ca3P2
12. [Be4O(NO3)6] is called basic beryllium nitrate.
13. x —→ Mg, Pb, N ⇒ 3
y —→ N ⇒ 5
z —→ Pb, Al ⇒ 2
14. Mg does not dissolve in liquid ammonia.
15. Be and Mg have very high I.E. Hence, do not impart
colour to the flame. Ca2+, Sr2+, Ba2+ are less volatile
and do not impart colour to the flame in lower
oxidation flame.

EXERCISE - 4
1. Na + (x + y) NH3 (moderate amount) 3. Reducing Nature in gas phase = Li < Na < K < Rb <
—→ [Na(NH3)x]+ + [e(NH3)y]-. Cs.

The blue colour solution is attributed to the solvated
Reducing Nature in aqueous condition = Li > Cs >
electrons. Rb > K > Na.

The blue colour solution is highly conducting due Heat 1
4. KNO3 KNO2 + 2 O2 ; C + O2 —→ CO2
to the presence of mainly solvated electrons and
5. Sodium hydroxide is manufactured by the
solvated Na+ ions.
electrolysis of brine using Castner-Kellner cell.

The blue colour solution is not diamagnetic but
6. Sulphur is in + 6 and – 2 and in acidic medium they
paramagnetic due to the presence of solvated
undergo disproportionation
unpaired electrons. 0
+4
Na2S2O3 + 2 HCl —→ 2 NaCl + SO2 + S + 3 H2O
2. 6Na + Al2O3 —→ 2Al + 3Na2O
Na2O + CO2 —→ Na2CO3 7. Na2O, Na2O2 and KO2 reacts with water being more
basic than water.

8. K + O2
burning
KO2.
excess air
Crystallisation
9. CaCl2 + H2SO4 -HCl
CaSO4.2H2O
393 K > 393 K
2 CaSO4.H2O CaSO4.
10. (a) Na2O + H2O —→ 2 NaOH
(b) 2 Na/Hg + 2 H2O —→ 2NaOH + 2 Hg + H2
(c) Na2O2 + 2H2O —→ 2 NaOH + H2O2
(d) Na2CO3 + 2H2O 2NaOH + H2CO3
11. S1 : As they readily lose electron to give monovalent
M+ ions because of low ionisation energies.
S2 : Have low melting and boiling points, as they
have weak metallic bonds due to the presence of
only a single valence electron/atom.
S3 : Because of low ionisation energies, these
elements when irradiated with light, the light
energy absorbed is sufficient to make an atom
lose electron.
S4 : Because of their high reactivity towards air and
water.
12. All alkali metal hydrides are ionic in nature and
react with water according to the reaction ;
NaH + H2O —→ NaOH + H2.
13. MgC2 forms C2H2 on hydrolysis while carbides of
Be and Ac form CH4.
14. (a) Lithium show exceptional behavior in reaction
directly with nitrogen of air to form the nitride,
Li3N.
(b) Smaller cation (Li ) polarises bigger anion (CO )
+ 2-
3
liberating CO2 gas. So it has the lowest thermal
stability.
(c) The solubility of the alkali metal hydroxides
increases down the group from Li to Cs. This
is because of the fact that down the group with
increasing size of cation, the lattice energy as
well as hydration energy also decreases but the
change in lattice energy is more as compare to
that of hydration energy.
15. Li+(aq) has lesser mobility than Na+(aq) due to higer
extent of hydration. H+(aq) has the highest mobility
among all the ions - fact.
s-Block Elements
16. NaNO3 is not used as gun powder because it is
hygroscopic in nature and becomes wet by absorbing
water molecules from the atmosphere.
18. Na2SO4 leads to precipitation of Barium as BaSO4.
19. Basic character increases down the group.
20. The function of Ca(H2PO4)2 is being acidic in nature
and gives CO2 when moistened with NaHCO3. This
released CO2 gives a fluffy nature to the food. e.g.
cake.
21. Loss of water of crystallization in air is called
effloroscene.
22. Ba(NO3)2 results a neutral solution as it is the salt of
strong acid, HNO3 and strong base, Ba(OH)2.
23. is bleaching powder.
24. Methanides give CH4 on reaction with H2O.
Al4C3 + 12H2O —→ 4Al (OH)3 + 3CH4 ;
Be2C + 4H2O —→ 2Be (OH)2 + CH4
25. Milk of magnesia is Mg(OH)2 and it neutralizes
excess acid.
26. Mg2+ ion has higher hydration energy than that of
Na+ and Ca2+ ions because Na+ ion has small charge
and bigger size of atom than that of Mg2+.
Ca2+ ion has bigger size then that of Mg2+.
27. All statements are factual.
28. (a) The solubility of the alkali metal carbonates
increases down the group from Li to Cs. This
is because of the fact that down the group with
increasing size of cation the lattice energy as
well as hydration energy also decrease but the
change in lattice energy is more as compared
to that of hydration energy. Lithium hydrogen
carbonate is not obtained in the solid form
while all other elements of group 1 form solid
hydrogencarbonates.
(b) K2CO3 can not be prepared by Sovay’s process
because intermediate formed, KHCO3 is
appreciably soluble in water.
(c) Li2CO3 and MgCO3 both are not thermally
stable.
(d) KCl.MgCl2.6H2O is a mineral called carnallite.
Chemistry
29. (a) Along the period, the nuclear charge increases
and, therefore, atomic size decreases. So, Na has
larger atomic radius than Mg.
(b) Mg is smaller than Na and Mg has two valence
electrons per atom while Na has only one valence
electron per atom. So Mg has stronger metallic
bond than that of Na (Na is a soft metal).
(c) Since K is larger in size than Na, therefore the
strength of the metallic bond in K is weaker than
that in Na. thus, M.P. and B.P. of K is lower than
that of Na.
(d) Mg does not impart characteristic colour to
the flame because the electrons in Mg are too
strongly bound to get excited by flame. Ca
imparts brick red colour to the flame because of
its low ionisation enthalpy.
30. Polarisation power of Na+ and Ba2+ is almost same.
31. (a) 4LiNO3 —→ 2Li2O + 5O2 + 2N2.
1 through lattice energy effects.
(b) NaNO3 —→ NaNO2 + 2 O2.
1 (c) The low solubility of LiF is due to its high lattice
(c) Mg(NO3)2 —→ MgO + 2NO2 + 2 O2.
32. NaH (s) + NaHCO3 (s) —→ Na2CO3 + H2
NaHCO3 + NaOH —→ Na2CO3 + H2O
NaHCO3 + HCl —→ NaCl + H2O + CO2
33. Down the group size increases and, therefore,
attraction between valence shell electron and nucleus
decreases and thus ionisation energy decrease.
Along the period the atomic size decreases and
nuclear charge increases. So generally the ionization
energy increases. However, half-filled and
completely filled valence shell electron also affect
the ionization energy along the period.
34. In alkaline earth metals solubility of sulphates
decreases down the group of sulphates.
35. Gas is O2.
36. The hydration enthalpies of alkaline earth metal ions
decrease with increase in ionic size down the group.
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+
The hydration enthalpies of alkaline earth metal
ions are larger than those of alkali metal ions,
because of their much larger charge to radius ratio,
exert a much stronger electrostatic attraction on
the oxygen of water molecule surrounding them.
Thus, compounds of alkaline earth metals are more
extensively hydrated than those of alkali metals,
e.g., MgCl2 and CaCl2 exist as MgCl2.6H2O and
CaCl2.6H2O while NaCl and KCl do not form such
hydrates. So all statements are correct.
37. Q is C2H2 or C3H4. Bromine water is decolourized
due to addition of Br2 across the double bond present
in their compounds. Al4C3 produces CH4 which
doesn’t have any double bond.
38. Basic strength Cs2O>Rb2O>K2O>Na2O>Li2O
Large anions like HCO3- and O22- are more stable
with large cations and small anions like H- are more
stable with smaller cations.
39. Factual.
40. Configurations given in options (a) and (b) are
of d-block elements as last electron enters in
d-subshell.
41. (a) The increasing stability of the peroxide or
superoxide, as the size of the metal ion increases,
is due to the stabilisation of large anions by
larger cation through lattice energy effects.
(b) Bigger cation stabilises bigger anion and
similarly smaller cation stabilises smaller anion
energy whereas low solubility of CsI is due to
smaller hydration energy .
(d) NaOH is deliquescent in nature. So, NaOH
absorbs moisture.
42. (a) In alkali metals, the metallic bonds are weaker
on account of large size and one valence electron
per atom. So they are soft and can be cut with
knife.
(b) The alkali metals are highly reactive due to their
large size and low ionisation enthalpy. So alkali
metals do not occur in free state in nature.
(c) The alkali metals are highly electropositive due
to their large size and low ionisation enthalpy.
(d) All alkali metal hydrides are ionic solids with
high melting points.
43. MgCl2 + Na2CO3 → MgCO3 + NaCl
Ca(HCO3)2 + Na2CO3 → CaCO3 + 2NaHCO3
H2SO4 + Na2CO3 → Na2SO4 + H2O + CO2
Na2CO3 + H2O + CO2 → 2NaHCO3
44. If the cathode taken is iner e.g., Pt then H2 is
produced while if Hg is taken at the anode Na-Hg
will be produced. Cl2 is produced at the anode and
NaOH is formed as a by product of electrosis of
Brine solution.

45. (a) The sulphates of the alkaline earth metals
are all white solid and stable to heat. BeSO4
and MgSO4 are readily soluble in water; the
solubility decreases from CaSO4 to BaSO4. The
greater hydration enthalpies of Be2+ and Mg2+
ions overcome the lattice enthalpy factor and
therefore their sulphates are soluble in water.
(b) Hydration energy of alkaline earth metal ions
decrease with increase in ionic size down the
group and the order is,
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+.
(c) The thermal stability of oxy-acid salts of
alkaline earth metals generally increases down
the group with increasing metallic character, i.e.
electropositive character.
(d) Hydration energy of alkaline earth metal ions
decreases with increase in ionic size down the
group so the order of their ionic radius in water
is, Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+.
46. Above 3M concentration, the solutions are no longer
blue but are bronze/copper-bronze coloured with a
metallic luster. Greater concentration of electrons
per unit volume increases the reducing power.
47. (a) The dilute solutions conduct electricity better
than any salt in any liquid and the conductivity is
similar to that of the pure metals. Conduction is
mainly due to the presence of solvated electrons.
(b) The dilute solutions are paramagnetic but
this paramagnetism decreases at higher
concentration. As the concentration of metal
increases, metal ion clusters are formed and
above 3M concentration the solutions are
diamagnetic.
(c) Ammoniated electrons are responsible for the
blue colour of the solution.
48. The dilute solutions have strong reducing properties
on account of the presence of solvated unpaired
electrons.
s-Block Elements
49. NO3- is a large anion and hence most unstable with
the smallest cation. So, LiNO3 is the easiest the
decompose.
50. CO32- is also a large anion and hence most stable
with the largest cation i.e., Cs+.
51. Li does not form alum because of small size of Li+.
52. Only alkali metal bicarbonates exist in solid state,
with the exception of LiHCO3. Also, NH4HCO3.
3
53. (a) Na2O2 Na2O + O2
Na2O is a basic oxide and diamagnetic. O2 is a
paramagnetic gaseous oxidizing agent.
3 3
(b) 2KO2 + S evacuated and sealed tube K2SO4 4 C
K2S + 4 CO.
CO is isoelectronic with N2 and thus diamagentic.
CO acts as reducing agent and is a neutral oxide.
(c) 4 NaNO3
800 o C
2 Na2O + 5 O2 + 2 N2.
N2 is diamagnetic. O2 acts as oxidising agent and
Na2O is basic oxide, Na2O + H2O → 2NaOH.
3
(d) 2 Ba(NO3)2 2 Ba(NO2)2 + O2
NO acts as oxidising as well as reducing agent
-
2
and O2 acts as oxidising agent.
54. Factual.
55. (a) BeO is amphoteric in nature becuase it reacts
with acid as well as base. It is a crystalline solid.
(b) Hydrogen bonding ; HCO3- ions are linked into
an infinite chain through H-bonding.
(c)
(d) 2CsO2 + 2H2O —→ 2Cs+ + 2OH- + H2O2 + O2
56. (a) Na2SO4 is stable to heat
(b) Na2CrO4 and MgCrO4 are soluble in water
(c) Mg does not dissolve in NH3 solution.
(d) Na2SO4 and MgSO4 are soluble in water.

1. BeO + HF + NH3 (NH4)4 [BeF4] (c) Chlorine is prepared by Deacon process

Oxidation state of 
[A] (d) Sodium hydroxide is prepared by Castner-
Be in A is (+2) Kellner process
NHF + BeF2 4.
[B]
Colour l /nm
2. Sodium hydrogen carbonate (Baking soda), NaHCO3
Li Crimson red 670.8
is used in the fire extinguishers.
Na Yellow 589.2
3. (a) Sodium carbonate is prepared by Solvay process Red violet
Rb 780.0
(b) Titanium is refined by Van-Arkel process Blue
Cs 455.5
Chemistry
1 9. Mg can form basic carbonate like
5. CaSO4 . 2H2O CaSO4 . HO
393 K

2 2 5Mg+2 + 6CO2- 3
+ 7H2O
6. Smaller the size of alkaline earth metals, greater is —→ 4MgCO3.Mg(OH)2.5H2O . + 2HCO-3
the tendency of their nitrate to crystallise with water While Li can form only carbonate (Li2CO3) not basic
molecule. Since Ba is the biggest among alkaline carbonate.
earth metal so its nitrate does not crystallise with
10. It is fact.
water molecule.
11. Down the group, solubility of sulphates of group 2
7. Among the alkali metals Li directly reacts with N2 of
metals in water decreases. BeSO4 is soluble in water
air, to give lithium nitride.
(a known fact). Hence, hydration energy of BeSO4
6Li + N2 → 2Li3N should be more in magnitude than its lattice energy.
8. Be is used ofr making X-Ray tube window. 12. CaCO3
3
CaO + CO 2 -
Basic oxide Acidic oxide

1. (a) Pb3O4 is insoluble in water or do not react with 3. Down the group the effective nuclear charge
water. remains almost constant. But down the group with
(b) 2KO2 + 2H2O → 2KOH + H2O2 + O2(g) ↑ increasing atomic number the number of atomic
orbits increases and there by atomic size increases.
(c) Na2O2 + 2H2O → 2NaOH + H2O2 As a result, the distance of valence shell electron
(d) Li2O2 + 2H2O → 2LiOH + H2O2 from nucleus increases and attraction between them
2. Alkali metals dissolve in liquid ammonia to give decreases and therefore ionization energy decreases.
ammoniated cations and ammoniated electrons, the 4. 4NaNO3
800 o C
2Na2O + 5O2 + 2N2
blue colour of the solution is due to ammoniated
electrons. 5. (P) Mg(HCO3)2 + 2Ca(OH)2 → Mg(OH)2 + 2CaCO3 +
2H2O

M + (m + n)NH3 —→ [M(NH3)n]+ + [e(NH3)m]-
(Q) BaO2 + H2SO4 → H2O2 + BaSO4


The conductivity of solution is due to both the ions.
(R) Ca(OH)2 + MgCl2 → Mg(OH)2 + CaCl2

(S) BaO2 + 2HCl → BaCl2 + H2O2

(T) Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O


Chapter 18
Intext Exercise 1
1. Ga has a M.P. of 303 K and B.P. of 2676 K and hence
is used in high temperature thermometry.
2. 4Al + 3O2 → 2Al2O3 is a highly exothermic process
and is used in welding metals.
3. High I.E. makes it difficult to form cations while
small size facilitates better overlap of orbitals
thereby forming stronger bonds.
4. Boron is a nonmetal. Fact.
5. Liquefied Ga expand on solidification. Ga is less
electropositive in nature, it has the weak metallic
bond, so it expands on solidification.
Intext Exercise 2
1. H3BO3 or B(OH)3 is a weak monobasic Lewis acid.
As it produces one H+ ion per molecule by forming
[B(OH)4]- with water.
2. Hybridization of Boron in B2H6 is sp3.
3. Al2O3 + 3Cl2 + 3C → 2AlCl3 + 3CO
4. Al(OH)3 dissolves in excess NaOH forming sodium
metaluminate - NaAlO2.
5.
All atoms marked with * are in the same plane.
3
6. 2H3BO3 B2O3 + 3H2O
7. Al2Cl6, In2Cl6, Ga2Cl6. MgCl2 is not dimeric.
Intext Exercise 3
1. Due the absence of d orbitals in C as it is a 2nd period
element, it can only show a maximum covalency of 4
2. Dioxide and monoxide of both Pb and Sn are
amphoteric.
3. Lab preparation of Si :
SiO2 + 2 Mg → 2MgO + Si
p-Block (Part-I)
p-Block (Part-I)
6. Except B(OH)3 all other hydroxide are of metallic
hydroxide having the basic nature B(OH)3 are the
hydroxide of nonmetal showing the acidic nature. It
can be written has H3BO3 and is called boric acid.
7. Al is the most abundant metal in the earth crust.
8. Due to the formation of the oxide further reaction of
Al is prevented and Al is preserved.
9. Amphoteric substance can react with both acid and
base.
10. None of the Group 13 elements are gas at 25oC.
They can show oxidation states of +1 or +3 and form
halides of type RX3 and oxide of type R2O3.
8. Al2Cl6 + 12 H2O 2[Al(H2O)6]3+ + 6 Cl-
9. Borazine B3N3H6, is isoelectronic to benzene and
hence, is called inorganic benzene some physical
properties of benzene and borazine are also similar.

 
10. Boron form different hydride of general formula
BnHn+4 and BnHn+6 but BH3 is unknown. Bx3 is
known to exist due to the presence of pp-pp back
bonding between the lone pair of halogen atoms and
the vacant p-orbital of B.
4. C and Si are non-metal and Sn and Pb are metals.
Ge is a metalloid.
5. The common pencil available in the market contains
graphite while leaves a mark on the paper.
6. Generally IV group element shows catenation
tendency and carbon has more catenation power.
Chemistry
7. The inert pair effect is most prominent in Pb because
inert pair effect is significant in 6th period elements
only.
8. Factual.
Intext Exercise 4
1. SiCl4 + 4H2O → Si(OH)4 + 4HCl
Si(OH)4
3
SiO2 + 2H2O
2. Red lead is Pb3O4 and on heating it decompose into
PbO and O2.
3. Glass contains SiO2 and SiO2 + 4HF → SiF4 + 2H2O
4. CO + NaOH
200 o C
HCOONa
Sod. formate
5. Sodium oxalate react with conc. H2SO4 to form CO
and CO2 gas.
6. PbO2 is not a peroxide and does not contain O—O
bonding.
EXERCISE - 1
1. In case of Al, the electron is to be removed from
less penetrating p-orbital as compared to Mg where
the electron is to be removed from more penetrating
and completely filled s- orbital. Hence IE1 of Al is
smaller than that of Mg.
2. Boron atom is smaller in size and therefore, the sum
of IE1 + IE2 + IE3 (3659 kJ mol-1) for B is much
higher than that of Al (2744 kJ mol-1) Hence B does
not form B3+ ions.
3. With 3 electrons in the valence shell, the oxidation
state of the element will be +3. The element is Al.
4. Due to the poor shielding (screening) effect of
d-electrons in case of Ga, the valence electrons are
attracted more strongly and hence its size is almost
the same as Al.
5. B(OH)3 or H3BO3 (orthoboric acid) is an acid
because it can take OH- ion from water to form a
stable tetrahedral B(OH)-4 species with the release of
a proton in solution.
6. As there are three electrons in the valence shell of
group 13 elements they show +3 oxidation state.
Also in case of heavier members, due to inert pair
effect, +1 oxidation state is most stable.
7. Boron does not react with cold or hot water.
9. In carbon family stability +2 oxidation state
increases on moving down the group in the periodic
table with an increase in atomic number due to inert
pair effect.
10. The primary use of lead today is in making lead-
acid batteries.
7. Solid CO2 is knows as dry ice because it evaporates
at –78°C without changing in the liquid state.
8. Zeolite have SiO4 and AlO4 tetrahedrons linked
together in a three dimensional open structure in
which four or six membered ring predominate. Due
to open chain structure they have cavities and can
take up water and other small molecules.
9. Pb3O4 is a mixed oxide. It can be represented as
2PbO - PbO2.
10. Sheet structures are formed when three oxygen
atoms of each [SiO4]4- tetrahedral are shared.
8. Al(OH)3 is amphoteric as it reacts with acids as
well as bases to form salts. B(OH)3 is acid whereas
In(OH)3 and TlOH are basic in character.
9. At cathode, reduction takes place i.e, Al3+ + 3e-→ Al
10. Serpeck’s process is used for the purification of
white bauxite which does not contain Fe2O3 as an
impurify.
11. Al liberates H2 from both acids and alkalies. For
example, 2Al + 6HCl → 2AlCl3 + 3H2;
2Al + 2NaOH + 2H2O → 2NaAlO2 + 3H2.
12. Hoope’s electrolytic process is used for refining of
Al.
13. In Serpeck’s process bauxite (white ) is mixed with
coke and heated to 2000 K in an atmosphere of N2 to
give AlN.
Al2O3.2H2O + N2 + 3C → 2AlN + 3CO + 2H2O
14. Al is more electropositive than Fe and therefore,
it reduces Fe2O3 to Fe . The heat produced in this
reaction is so large that the metal is produced in
the molten state which can be used for welding
purposes.
15. Al2O3 is most amphoteric in nature. It reacts with
acids as well as alkalies.
Al2O3 + 6HCl → 2AlCl3 + 3H2O
Al2O3 + 2NaOH → 2NaAlO2 + H2O

16. Boron does not react with HCl but Al does.
17. Boron, the first member of group 13 elements is a
non-metal.
18. All the mentioned acids are strongly oxidising in
character. Hence these will form a thin protective
film of oxide at the surface of Al and render it
passive.
19. Due to non toxicity of Al, it is used for food
packaging.
20. As Ga remains liquid over a wide range of
temperature (303 k to 2510 K), it is used in high
temperature thermometry.
21. As we move from F to Br down the group, the size
of p-orbital of halogen increases and the extent of
overlap between 2-p-orbital of B and p-orbital
of the halogen and tendency of back donation of
electrons from filled p-orbital of halogen to empty
p-orbital of B atom decreases. Consequently, the
electron deficiency of the boron atom increases
from BF3 through BCl3 to BBr3 and hence acidity
increases in the same order.
22. Atomic Number of M is less than 21.
Therefore, M belongs to representative elements.
As MX3 has zero dipole moment, it has a regular
geometry i.e. trigonal planar which is obtained by
sp2-hybridization.
23. In BeCl2. 2 H2O, Be completes its octet by accepting
two lone pairs of electrons from two H2O molecules
and therefore, BeCl2.2H2O is not electron deficient
and hence not a Lewis acid.
24. B4C and SiC are covalent compounds which do not
react with water. Salt like carbides such as CaC2 and
Al4C3 react with water, the former giving acetylene
and methane, respectively.
Al4Cl3 + 12 H2O → 4Al(OH)3 + 3CH4
25. In potash alum,K+ and Al3+ are present as hexaaquo
complex ions such as [K(H2O)6]+ and [Al (H2O)6]3+
ions
26. Size of Li+ ion is too small to form hexaaquo
complex ion which is present in alums.
27. TlCl3 decomposes above 40o to TlCl and Cl2 and in
this way acts as an oxidising agent. This happens
become the +1 oxidation state of Tl is more stable
due to the inert pair effect.
28. FeSO4.Al2(SO4)3.24 H2O is not a true alum because
in place of Fe2+ ion here should be monovalent ion
in true alum
p-Block (Part-I)
29. BF3 is a colourless gas whereas BCl3 and BBr3 are
colourless fuming liquids at room temperature.
30. Because of the large electronegativity difference
between Al and F in AlF3 and Al and oxygen in
Al2O3, Al and sulphate group in Al2 (SO4)3 all these
are ionic compounds. AlCl3 in anhydrous state is
covalent.
31. 4LiH + AlCl3 → LiAlH4 + 3 LiCl.
32. Al2O3 is not used as a constitutent of baking powder.
33. On heating AlCl3.6H2O, hydrolysis takes places
giving Al(OH)3 and hydrogen chloride. Al(OH)3
then loses H2O to form Al2O3.
34. Al2O3 has high lattice energy and low heat of
hydration.It is therefore, insoluble in water.
35. Anhydrous AlCl3 is a covalent compound which
sublimes on heating.
36. AlCl3 (anhydrous ) sublimes at 100oC under vaccum
or at 183oC as such.
37. In BCl3, the pp-pp overlap between the 2p-orbital
of B and 3 p-orbital of Cl is less effective because
of dissimilar sizes but in AlCl3, overlap between
the 3p-orbital of Al and 3p-orbital of Cl is more
effective because of similar sizes. As a result, back
donation is more and electrondeficiency of Al is
reduced relative to B and hence BCl3 is a stronger
Lewis acid than AlCl3.
38. 2Al + 6HCl (dil.) → 2 AlCl3 + 3H2↑
2 Al + 2 NaOH + 6 H2O → 2 Na [Al (OH)4] + 3H2↑
39. Pseudo alum has the general formula MIISO4. MIII2
(SO4)3.24H2O. Therefore FeSO4. Al2(SO4)3. 24 H2O
is a pseudo alum.
40. T1I3 → Tl+ + I3-. Since Tl+ is a large cation, it can
accomodate I3- around it which is a large anion.
41. AlCl3 is a Lewis acid because it is electron deficient.
All other trichlorides given are of Group 15
elements where the central atom contains a lone pair
of electrons.
42. Al(OH)3 dissolves in NaOH solution to give Al(OH)-4
ion which is supposed to have the octahedral complex
species [Al(OH)4(H2O)2]- in aqueous solution.
Al(OH)3+NaOH(aq)→[Al(OH)4(H2O)2]-(aq)+Na+(aq)
43. AlCl3 + 3H2O → Al(OH)3 + 3HCl
44. The phenomenon of occurrence of a substance in two
or more crystalline structure is called polymorphism.
45. SiO2 is acidic, whereas Al2O3, SnO2 and PbO2 are
amphoteric oxides
Chemistry
46. The higher the bond energies of element-element 63. Wood metal is an alloy of Bi (50%) + Pb (25%) + Sn
bond, more is the catenation tendency. (12.5%) + Cd (12.5%). It has m.p. 71oC (344 K) .
47. In isoelectronic species as the charge on cations 64. SiCl4 gets hydrolysed in moist air and gives white
increases, their sizes decrease in that order. Thus fumes which are used as a smoke screen in war fare.
the ionic sizes of the given cation (isoelctronic)
65. Since carbon cannot expand its coordination number
dercrease in the order. Na+ > Mg2+ > Al3+ > Si4+
beyond four due to the absence of d-orbitals, it
48. In Si (CH3)4. Si and each C undergo sp3-hybridization cannot form [CCl6]2- ion.
giving a tetrahedral structure.
66. CCl4 is not hydrolysed as carbon does not have
49. SiO2 + 2Mg
Heat
2MgO + Si vacant d- orbitals to accommodate lone pairs of
electrons from water molecules.
50. Pb will oxidize I to I2 and itself with be reduced to
4+ -

Pb2+. Thus PbI2 will be formed PbI4 → PbI2 + I2. This 67. Silicones contain – Si – O – Si – bonds.
is so because the +2 oxidation state of Pb is more
68. Cu, Sn (Zn and Pb in small amounts) constitute gun
stable due to the iner pair effect.
metal.
51. Quartz is a crystalline variety of SiO2.
69. PbO2 is an oxidising agent; it is used in lead storage
52. Pb2+ reacts with HCl as well as H2S to give batteries and in safety matches
precipitates of PbCl2 and PbS respectively
70. During charging process, PbSO4 is oxidized to PbO2

Pb + 2HCl → PbCl2 + 2H
2+ + in a lead storage battery.

White ppt.
71. Melting point of tin is lower than glass.

Pb2+ + H2S → PbS + 2H+

Black ppt. 72. Quartz watches contain a crystal of quartz as an
essential component. Quartz converts electrical
53. Insert pair effect is more pronounced in heavier
energy to mechanical energy. This property is called
members like Pb. Thus Pb(IV) compounds act as
piezoelectricity.
strong oxidising agents and are reduced to more
stable Pb (II) compounds. 73. Si obtained by reduction of SiCl4 with H2 is further
purified by zone refining method to get Si of very
54. PbSO4 is insoluble in water.
high purity.
55. Volatility decreases as the atomic weight of
74. Si due to its semi conducting nature is used in solar
the hydrides increases down the group, as the
cells.
intermolecular Vanderwaal’s forces increase.
75. PbO2 is not used as a pigment in paints.
56. Inert pair effect is exhibited by Pb (heavier member
of the family) 76. The composition of common glass is
Na2O.CaO.6SiO2. Factual
57. Due to inert pair effect, +2 oxidation state of Pb is
most stable. 77. Common glass is a mixture of Na2SiO3 and CaSiO3.
Both these components react with hydrofluoric acid
58. CCl4 is not acidic, all other compounds give acidic
to give soluble products
solution on hydrolysis. CCl4 does not hydrolyze
appreciably due to highly non polar molecule.
Na 2 SiO3 + 8HF $ 2NaF + H 2 SiF6 + 3H 2 O
Hydrofluorosilicic acid

59. Extent of hydrolysis increases in the order:

CaSiO3 + 8HF → CaF2 + H2SiF6 + 3H2O

CCl4 < MgCl2 < AlCl3 < SiCl4 < PCl5 78. Glass is a super cooled liquid. Factual.
60. Greater electronegativity difference gives rise to 79. Water glass is another name for sodium silicate,
greater ionic character in the bond. And greater the Na2SiO3. Factual.
ionic character, stronger is the bond and more is the
bond strength. 80. SnI4 is a coloured compound. Sn4+ has high
polarizing power and I- is highly polarizible. There
61. SiO 2 + 3C
High temp.
2300 K
SiC + 2CO is significant covalent character and hence by Fajan’s
(Carborundum)
Rules, SnI4 is coloured.
62. Thomas slag or phosphatic slag is a mixture of Ca3
(PO4)2 and CaSiO3.
 p-Block (Part-I)
EXERCISE - 2
1. It is fact.
2.

3.
4. There is no pp-pp back bonding in Me3N → BF3.
thus, the B-F bond length in it is greater than the
B-F bond length in BF3 in which there is partial
double bond character.
5. B(OH)3 is mono basic lewis acid but it cannot act as
an Arrhenius acid.
6. Alumina is mixed with cryolite, in molten state
which makes alumina good conductor and lowers
the fusion temperature also. this is electolyzed to
obtain Al.
7. 2 Al + 3H2O —→ Al2O3 + 3H2O (slow reaction)
Al2O3 forms protecting oxide layer on Al surface
8. If E = Tl and X = I then in TlI3, Tl is in +1 oxidation
state and the anion in I3­-.
14. Ca2B6O11+Na2CO3→2CaCO3 . +Na2B4O7+2NaBO2
15. B(OH)3 is accepting a lone pair of electrons from
OH- to form [B(OH)4]-. Hence, it is a Lewis acid.
16. Factual.
17. (a), (c) and (d) are acidic oxides whereas (b) is
amphoteric in nature.
18. CoO + B2O3 —→ Co(BO2)2 (blue bead)
19. B(OH)3 + 2HOH [B(OH)4]- + H3O+.
In aqueous solution the boron completes its octet by
accepting OH– from water molecules. It therefore
function as a weak monobasic lewis acid.
20. All given reactions are correct.
21. BF3 + 3LiBH4 —→ 3LiF + 2B2H6
LiH
22. B (s) BF3 B2H6 + LiBF4
F2 (Z)

(X) (Y)
9. Down the group the inert pair effect is more
pronounced on account of enhanced increase in 23. 2Al + 2KOH + 2H2O → 2KAlO2 + 3H2↑
effective nuclear charge.
24. Bulky bases give symmetric clevage in B2H6 while
10. [B4O5(OH)4]2– + 5H2O 2B(OH)3 + 2[B(OH)4]– small bases give as symetric cleavage.
or [B4O7]2– + 7H2O —→ 2B(OH)3 + 2[B(OH)4]– 25. B2H6 + 6H2O —→ 2H3BO3 + 6H2↑
11. 4B + 3O2 2B2O3
1173 K
26. There is least Vanderwaal’s force of attraction in BF3
2B(s) + N2(g)
1173 K
2BN(s) on account of less number of polarisable electrons
among the boron halides. So BF3 is gas at 0ºC.
12. General formulae of boranes are BnHn+4 and BnHn+6
27. It is acidic because of the hydrolysis of Al2(SO4)3
13. In the solid state, the B(OH)3 units are hydrogen according to the following reaction.
bonded together in to two dimensional sheet with
Al2(SO4)3 + 6H2O —→2Al(OH)3 + 3H2SO4.
almost hexagonal symmetry.
28. B2H6 + NH3 B2H6.2NH3 or
Excess NH 3
low temperature

[H2B(NH3)2]+ [BH4]– (ionic compound).

29. Na2B4O7 + H2SO4 + 5H2O —→ Na2SO4 + 4H3BO3
Chemistry
30.
44. SiO2 + 2Mg → 2MgO + Si ;
cis 1-2 diol removes [B(OH)4]- from the solution
thus facilitating the neutralization reaction to
proceed forward.
31. Diamond is not oxidised by K2Cr2O7/H2SO4 at
200ºC.
32. It is chemically inert towards concentrated acids as
well as bases.
33. As C belongs to the 2nd period and does not have
any vacant d-orbitals so C can form at the most 4
covalent bonds. Elements in the 3rd and subsequent
periods have d-orbitals and can form 6 covalent
bonds.
34.
35. Order of the bond enthalpies :
C – C > Si – Si > Ge – Ge > Sn – Sn
As C has greatest catenation tendency, its bond
energy must be highest.
36. The EN values of Carbon family are:
Element C Si Ge Sn Pb
EN 2.5 1.8 1.8 1.8 1.9
37. Stability of lower oxidation state increase down the
group (inert pair effect).
38. DHoƒ (Cgraphite) = 0. Heat of formations of others are
positive.
39. Graphite changes to Mellitic acid also called benzene
hexa-carboxylic acid with hot concentrated HNO3.
(Mellitic acid)
40. All given statements are correct.
41. Si + NaOH (hot) —→ Na4[SiO4] (silicate)
42. Heavier the isotope stronger the bond.
43. Factual.
(X)
MgO + 2HCl → MgCl2 + H2O
(Y)
45. Al2O3 + 3Cl2 + 3C
3
2AlCl3 + 3CO.
46. All given statements are true.
47. It is a fact.
48. Fact.
49. Silicones are used as lubricants both as solids and
liquids and this is similar to use of graphite.
50. (a) When a mixture of PhSiCl3 and (Ph)2SiCl2 is
dissolved in toluene and then hydrolysed with
water, silicon resins are obtained.
(b) Silicones from the hydrolysis of a mixture of
(CH3)3 SiCl & (CH3)2 SiCl2
The dichloro derivative will form a long chain
polymer as usual. But the growth of this polymer can
be blocked at any stage by the hydrolysis product of
mono-chloro derivative.
(c)
In this manner several molecules may combine
to form a long chain polymer whose both the
ends will be occupied by –OH groups.
51. Formation of silicones
In this Manner several molecules may combines to
form a long chain polymer whose both the ends will
be occupied by – OH groups.
52. Si3O108-. One O atom is shared between two adjacent
tetrahedron in chain silicates.
 p-Block (Part-I)
53. CH2(COOH)2
P4 O10
C3O2 + 2H2O 57. When a compound like CH3SiCl3 undergoes
hydrolysis, a complex cross-linked polymer is

C3O2 is called carbon suboxide and has a linear obtained as chain can grow in three places as
structure. O = C = C = C = O.
54. (a) SiO44– in ortho silicate
(b) Si2O76– in pyrosilicate
(c) (Si2O52–)n in double chain silicate
(d) (SiO32–)n in simple single chain silicate

58. CCl4 is not readily hydrolysed due to non-

availability of d-orbital in carbon.
55. , Si2O76-
59. Due to inert pair effect stability of +2 oxidation state
increases down the group. Hence Sn and Pb can
form dihalides.
56. Si atoms in silicones are surrounded by non-polar
PbI4 is unstable as I- is readily oxidized by Pb4+ to
alkyl or aryl groups, which repel water molecules. form PbI2 and I2.
60. (1) Pb + H2SO4 —→ PbSO4 (layer) + H2 -

(2) Pb + Conc. HCl —→ PbCl2(Coating) + H2 -

(3) 2Al + 3/2 O2 —→ Al2O3(s) (layer)

EXERCISE - 3
1. [x] is (CH3)2SiCl2. 7. B12H122–
Hence atomicity - (1 + 3) × 2 + 1 + 2 = 11. x + y + z = 12 + 12 + 2 = 26
HCl
2. Acidic nature H3PO4, H3BO3, H3P3O9 8. 3Mg + 2B —→ Mg3B2 diborane + MgCl2

Basic nature Na2B4O7.10H2O, Ba(OH)2, Ca(OH)2
\ x=3& y=2

Amphoteric PbO 9. x = 4

Neutral oxide CO
B, Al, In & Tl are solid at 40ºC. Melting point for
Gallium is 30ºC.
3. Borax Na2[B4O5(OH)4].8H2O
y=4
I.E. : B > Al < Ga > In < Tl
z = 3
The atoms marked with *
do not form pp-pp back
Al is third most abundant element after oxygen and
bond. silicon. So it has to be most abundant element in the
family.
⇒ x + 2y + 3z = 4 + (2 × 4) + (3 × 3) = 21.
10. Al4Cl3 + H2O —→ CH4↑ + Al(OH)3
4.
BaC2 + H2O —→ C2H2 ↑ + Ba(OH)2
Mg2C3 + H2O —→ C3H4↑ + Mg(OH)2
SiC + H2O —→ X (No reaction)
5. (c) is wrong as anthracite is the purest form of coal,
B2H6 + H2O —→ 2 B(OH)3 + H2 -
not carbon. Rest all statements are true.
Fe3C + H2O —→ X (No reaction)
6. It is cyclic silicate anion.
Chemistry
11. 2B + 6 HNO3 (conc) —→ 2H3BO3 + 6NO2

(A) (B) (g) Silicones → sp3

Statements (7) and (9) are incorrect.

NO2 forms a dimer N2O4 (diamagnetic white solid)
12. [Si6O18]–12. So answer is 12. (h) Chlorosilane or
13. a = 12, b = 20, c = 30 all are sp3

3 × 12 – 2 × 20 + 30 = 26 (i) Borax 2-Borons are sp3 and 2 Borons are sp2
14. B2O3 —→ Acidic oxide
(k) (sp3)

Tl2O3, NaAlO2, Sr(OH)2 Basic

Cr2O3, Al(OH)3, Al2O3, Ga(OH)3, Ga2O3 Amphoteric (l) B2H6 (3-centre-2- electron bond) B → sp3
15. (1) K2SO4 Al2 (SO4)3 is a white crystalline solid. (m) SiO2 (3-D silicate)Si → sp3
(2) upon heating it swells up due to the evolution of
water molecules.
(n) c = sp2
3
K2SO4·Al2(SO4)3·24 H2O K2SO4·Al2
(SO4)3 + 24H2O. (o) COCl2 C = sp2

(3) because of presence of potassium it imparts. (p) CH4 sp3

Volilet color to Bunsen flame. (q) CCl4 sp3
(4) Ba + SO → BaSO4 .
2+ 2–
4 17. p = 4, q = 4, r = 0
whiteppt. 18. 2NaBH4 + I2 —→ B2H6↑ + NaI + H2↑
BaSO4 + H2SO4 → Ba (HSO4)2 Soluble
4 moles 2 moles 2 moles

NaOH
(5) Al3+ + 3OH– → Al(OH)3 . NaAlO2 Total moles of gases produced = 4
white soluble
Volume at STP = 4 × 22.4 litres = 89.6 L

NH 4 Cl
Al(OH)3 . 89.6
Answer = 4.48 = 20
(6) 4K+ + [CO(NO2)6]4+ → K4 [CO (NO2)6] 19.
yellow ppt
H2 O
(7) 2Al3+ + 3S–2 → Al2S3 Hydrolysis
Al(OH)3 .
whiteppt.
Except statement (3) all are correct.
16. (a) CO2 → C → sp (b) Graphite → sp2
(c) Diamond → sp3 (d) CO → sp
(e) H3BO3 → B → sp2 20. B2O3 acidic. Rest all are amphoteric.
(f) Zeolite → Si → sp3
 p-Block (Part-I)
EXERCISE - 4

1. All the points mentioned are hindrance to obtaining 15. Potash alum is K2SO4.Al2(SO4)3.24H2O and so,
high purity Boron.

Al2(SO4)3 + 6NaOH —→ 2Al(OH)3 . (white) +
2. I & II is qualified by all four 3Na2SO4; Al(OH)3 + OH– —→ [Al(OH)4]– (soluble
complex)

III corresponds to water gas formation.
3
3. H3BO3(s) + NaOH(aq.) Na[B(OH)4]
16.
3

H3BO3(s) + NaOH (molten) Na3BO3 + 3H2O
4. Bauxite forms by weathering of Aluminosilicates,
which is supported by tropical ecosystem.
5. K4[Fe(CN)6] + 6H2SO4 (conc) + 6H2O
3 17. For reaction II – SiO2 must be taken in excess to
avoid formation of SiC.
2K2SO4 + FeSO4 + 3(NH4)2SO4 + 6CO
18. Al(OH)3 is precipitated by both NaOH and NH4OH
6. Due to greater e– density on N-atoms, there are but on taking the base (NaOH or NH4OH) in excess
acidic & basic centers in the molecule. Al(OH)3 forms a soluble complex with NaOH but
7. not with NH4OH.

19.
8. Diamond – sp3, no p-bond character and C–C
bond length = 154 pm graphite – sp2, aromatic and
p-electrons are delocalised and C–C bond length =
Chain terminating —→ R3SiCl —→ x = 3
141.5 pm fullerene – sp2, not so good delocalisation
Chain multiplication —→ R2SiCl —→ x = 2
and there are two types of bond length. C – C bond 20. At high temperature and oxygen in limited supply,
length decreases as compared with diamond but is formation of CO and SiO2 is favourable as SiO is
more than that of graphite. Bond lengths are 143.5 unstable.
pm and 138.3 pm.
21. Z = F2, X = BF3, Y = B2H6, w = heating.
9. Na2CO3 + H2O → 2NaOH + CO2;
F2 is highly reactive.

4OH– + Al → [Al(OH)4]– (soluble complex) B2H6 is electron deficient.
10. X = Z = Al2O3 and Y = AlCl3 22. Reference : NCERT. Fact.
11. cis-diols form very stable complex with [B(OH)4] , –
23. [B4O5(OH)4]2– + 5H2O 2B(OH)3 (weak acid) +

Thus removing it from solution 2[B(OH4)]– (salt)
24. 2B + N2 —→ 2BN
BN + 3H2O —→ H3BO3 + NH3 (pungent smelling
gas)

The reaction is supressed by C2H5OH as it is not a 25. A = HCl ; B = H2SnCl6
diol and hinders the reaction.
26. (b) 2BCl3 + 3H2 2B + 6HCl
1270 K

12. High purity Si is obtained from this process. In

(c) 2BCl3 2B + 3Cl2
1173 K
case of requirement of ultrapure Si, it can be further
purified by zone refining. (d) K+ [BF4]–
1073 K
K+ + [BF4]–
13. Al does not dissolve in HNO3 due to the formation [BF4]– —→ B + 2F2+ e- (At anode)
of a passive oxide layer which prevents further
reaction reaction. K+ + e– —→ K (At cathode)

14. BF3 + 3H2O —→ B(OH)3 + 3HF (Partial hydrolysis)

BF3 + HF —→ HBF4.
Chemistry
27. HCOOH
3
H2O + CO ; 39. BF3 is gas at room temperature. It is sp2 hybridized
and hence planar. It is electron deficient and can

K4[Fe(CN)6] + 6H2SO4 + 6H2O —→ accept lone pair from lewis base e.g. NH3.
2K2SO4 + FeSO4 + 3(NH4)2SO4 + 6CO
40. Sn(OH)2 + 4OH– + H2O —→ [Sn(OH)6]4– (soluble

Malonic acid gives C3O2 and Mg2C3 gives complex)
1-propyne.
Cr(OH)3 + 3OH– —→ [Cr(OH)6]3–
28. Only hydrated salts of aluminum are generally

Amphoteric metal hydroxides dissolve in excess
ionic but anhydrous salts are covalent in nature e.g.
NaOH.
anhydrous AlCl3 is covalent whereas hydrated AlCl3
is ionic. 41. (a) Both hardness can be removed by it.
29. Boron does not increase its covalency beyond four (b) Zeolite : Na2Al2Si2O8.xH2O
as it does not have d-orbital.
Statements in option (c) and (d) are correct.
3
30. SiO2 + 2 C Si + 2 CO ­-
3
SiO2 + SiC Si + 2 CO ­ -
3
42. As can be seen in the adjoining
SiH4 Si + 2 H2 ­- figure, all statements are true.
SiC is stable to heat.
43. Borax bead test generally given by coloured salt of
31. (a) B2H6 + 2NH3 —→ [H2B (NH3)2]+ + [BH4]–
transition metals.
(b) All boron hydrides catch fire in presence of
44. (a) On burning in sufficient air , both produce CO2.
oxygen to liberate a lot of heat energy. Hence,
they can be used as high energy fuels. (b) On reaction with hot conc. HNO3, diamond is
unaffected while graphite changes to mellitic
B2H6+3O2—→B2O3+3H2O; DCHº= –1976kJ mol –1
acid [C6(COOH)6].
(c) B2H6 + 6H2O —→ 2B(OH)3 + 6H2↑
(c) On reaction with F2, diamond is unaffected but
(d) B3N3H6 hydrolyses slowly. graphite froms (CF)n.
B3N3H6 + 9H2O → 3NH3 + 3H3BO3 + 3H2O (d) Both diamond & graphite do not react with aq.
32. Both are diamagnetic as all electrons are paired. NaOH.
Remaining statements are correct. 45. All statements are correct.
33. Exists as dimer, Al2Cl6 and gets easily hydrolysed. 46. Ca2B6O11+2Na2CO3—→CaCO3+Na2B4O7+NaBO2
AlCl3 is electron deficient, thus acts as Lewis acid.
47. Ammonia, primary amine and secondary amine give
34. Pb forms a passive layer with conc. HNO3. unsymmetrical cleavage of diborane according to
35. All true statements are facts. the following reaction.
36. As chain can grow in three places as B2H6 + 2NH3 —→ [BH2(NH3)2]+ [BH4]–
48. All statements are correct.
SiO2 + 2NaOH —→ Na2SiO3 + H2O
SiO2 + 4HF —→ SiF4 + 2H2O
SiF4 + 2HF —→ H2 [SiF6]

49. Al3+ cannot be reduced by Zn2+. Also, Al2O3 is
37. LiBH4, NaBH4 ; H will reduce Ag .
– + thermally quite stable hence cannot be heated and
Hydrolysis decomposed to give Al.
38. (b) BCl3 + 3H2O H3BO3 + 3HCl ;
Hydrolysis
SiCl4 + 3H2O H2SiO3 + 4HCl
3
(c) B + Mg —→ Mg3B2 + H3PO4 B2H6
(d) 2B + 6NaOH —→ 2Na3BO3 + 3H2 ;
Si + 4NaOH —→ Na4SiO4 + 2H2
 p-Block (Part-I)
50. (a) It is a acidic oxide and is anhydride of boric Reactions involved (55 - 57)
acid and it reacts with alkalies or bases to form in diglyme
(a) 2Na[BH4](A)+I2 B2H6(B)+H2+2NaI
borates. solution

3Na2O + B2O3 → 2Na3BO3 (sodium orthoborate) B2H6 + 6H2O —→ 2H3BO3 (C) + 3H2

It is a weak monobasic acid soluble in water and B(OH)3 + 2H2O H3O+ + [B(OH)4]– ;
in aqueous solution the boron atom completes its pK = 9.25
octet by accepting OH– from water molecules:
B(OH)3(aq) + 2H2O(l) [B(OH)4]– (aq) +
H3O (aq). pK = 9.25.
+

(b) BX3 (except BF3) get hydrolysed due to presence

of vacant p-orbital and SiX4 get hydrolysed due
to presence of vacant d-orbital.
(c) Controlled pyrolysis of diborane leads to most
of the higher boranes.
It catches fire spontaneously in air and explodes B2H6 (B) + 3O2 —→ B2O3 + 3H2O
with O2. Reaction with oxygen is extremely
CoO + B2O3 —→ Co(BO2)2
exothermic.
(cobalt metaborate - blue colour bead).
B2H6 + 3O2 —→ B2O3 + 3H2O
55. Orthoboric acid acts as lewis-acid in water not as
DH = – 2160 kJ mol–1
proton donor (as it does not liberater H+ ion) because
Si2H6 + (4 + n) H2O
trace of alkali
2SiO2 + it completes its octet by accepting the OH– from
nH2O + 7H2 water.
(d) Aluminium hydride is a polymer due to
B(OH)3 + H2O —→ [B(OH)4]– + H+.
formation of electron defecient bond (Al ——
In the solid state, the B(OH)3 units are hydrogen
H – – – Al). bonded together in to two dimensional sheets with
51. Due to effective pp – pp delocalised bonding almost hexagonal symmetry. The layers are quite
between ‘B’ and ‘F’, BF3 is weakest lewis acid in a large distance apart (3.18 Å) and thus the crystal
the series. breaks quite easily into very fine particles.
52. Due to effective pp – pp delocalised bonding
between ‘B’ and ‘F’ there is partial double bond
character between B and F. As a result there is
decrease in bond length as compared to single B–F
bond length.
53. 4BF3 + 3H2O —→ H3BO3 + 3H+ + 3[BF4]–

Some of the total BF3 combine with HF formed
during hydrolysis to form HBF4.
54. Since BCl3 can accept only one lone pair hence Cl3
B (C5H5N)2 is not possible.
Chemistry
56. If certain organic polyhydroxy compounds such as 60. (a) It is a covalent compound.
glycerol, manitol or sugars are added to the titration
(b) It is easily hydrolysed
mixture, then B(OH)3 behaves as a strong monobasic
acid and it can be now titrated with NaOH and the (c) It has lower melting point because it is a covalent
end point is detected using phenolphthalein as compound.
indicator (pH = 8.3 - 10.0). (d) It is a lewis acid.

The added compound must be a cis-diol, to enhance 61. First figure contians 1Si and 4 O atoms while second
the acidic properties. The cis-diol forms very stable figure contains 3 Si and 10 O atoms.
complex with the [B(OH)4]–, thus removing it from
solution. The reaction is reversible and thus removal Hence, SiO42- and Si3O108-
of one of the products shifts the equilibrium in the 62. (a) 3Si and 10 O
forward direction and thus all the B(OH)3 reacts
with NaOH; in effect it acts as a strong acid in the (b) 3Si and 9 O
presence of the cis-diol. 63. It contains Si3O108- units
B(OH)3 + NaOH—→Na[B(OH)4] + NaBO2 + 2H2O 64. (a) 3H2 + 2 BBr3
heated
2 B + 6HBr
titanium metal filament
3
(b) Na2B4O7.10H2O -10H2 O
2NaBO2 + B2O3
2CuSO4 → 2CuO + 2SO2 + O3

CuO + B2O3 → Cu(BO2)2 (blue bead)
(c) AlCl3 + 3H2O → Al(OH)3 + 3HCl (white fumes)
3
(d) Cr2O3 + 2Al Al2O3 + 2Cr
3 3
65. Na2B4O7.10H2O Na2B4O7 2NaBO2+B2O3
57. (a) B2H6 + HCl → B2H5Cl + H2
excess NH 3
B2H6 + 3H2O → 2H3BO3 + 3H2
(b) B2H6 + NH3 low temperature
B2H6.2NH3 3
3B2H6 + 6NH3 (excess) 2B3N3H6 + 12H2
B2H6.2NH3 is ionic compound and comprises +4H2 O 3
[H3N → BH2 ! NH3]+ and [BH4]– ions. SiCl4 -4HCl
Si(OH)4 SiO2 + 2H2O
(c) B2H6 + 2(Me)3N → 2[Me3N.BH3] 66. (a) Al2(C2)3 + 6H2O —→ 2 Al(OH)3 + 3C2H2;
(d) B2H6 + 6H2O → 2B(OMe)3 + 6H2 (b) 3CH2(COOH)2 + P4O10 → 3C3O2 + 4H3PO4;
58. (a) due to high heat of hydration in water it converts (O=C=C=C=O)
in to [Al(H2O)6]Cl3
(c) CH3SiCl3 + 3H2O →
(b) due to formation of complexes of type
R3N → AlCl3 complex cross linked
59. (a) BF3 forms HBF4 polymer (Silicones)
(b) Anhydrous AlCl3 is covalent
(d) SnCl2 + 2H2O —→ Sn(OH)2↓ (white) + 2HCl

 p-Block (Part-I)

1. Moving down the group stability of lower oxidation
state increases
2. (CH3)4 Si is a silance
(CH3)Si(OH)3 polymerise to form 2D silicone
(CH3)2Si(OH)2 polymerise to form chain silicone
(CH3)3Si(OH) form dimer (CH3)3Si-O-Si(CH3)3
3. Structure of C60
6. P4 + NaOH + H2O → PH3 + NaH2PO2
HCl
H3PO2
Basicity = 1
7. The lower O.S. (+1) of Thallium is more stable due
to the inert pair effect.
8. Both AlCl3 and BCl3 have electron deficient central
atoms and are therefore Lewis Acids.
9. Due to non-availability of d-orbitals, boron is
unable to expand its octet. Therefore, the maximum
covalence of boron cannot exceed 4.

10. ;

It contain 20 hexagons 20 and 12 pentagons

12 so option (d) is incorrect. 11. When a compound like CH3SiCl3 undergoes

hydrolysis, a complex cross-linked polymer is
obtained as chain can grow in three places.
4. 12. CO + H2O (g) CO2 + H2 ;

CO2 + 2KOH —→ K2CO3 + H2O
13. Due to the inert pair effect (the reluctance of
 q2 > q1, \ B–H (terminal) having less p character ns2 electrons of outermost shell to participate in
as compared to bridge bond. bonding), the stability of M2+ ions (of group IV
 Both B–H–B bridge bonds have same bond elements) increases as we go down the group.
length.
14. 2AlCl3 + 6H2O Al2O3 + 6HCl + 3H2O
 B–H–B bond angle is c 90°
 BH3 is e– deficient species and therefore acts as 15. Silicon dioxide exhibits polymorphism. It is a
lewis acid network solid in which each Si atom is surrounded
5. B3N3H3Cl3 + LiBH4 → B3N3H6 + LiCl + BCl3 tetrahedrally by four oxygen atoms.
(A) (B)
B3N3H3Cl3 + 3MeMgBr → B3N3H3(CH3)3 + 3MgBrCl
(A) (C)
Chemistry

1. For linear polymer, we need R2SiCl2 and for 6. SnCl2 + Cl-—→SnCl3-

termination, we need R3SiCl. (Q) (X)
2. In p-block elements (14 group here), the lower
th
SnCl2 + Me3N—→SnCl2 [N (CH3)2]
oxidation state becomes more stable on going down (Q) (Y)
the group due to inert pair effect. Thus Pb+4 is less
stable than Sn+4. This makes Pb+4 a stronger oxidising SnCl2 + 2CuCl2 —→SnCl4 + CuCl
agent. Therefore, the statement-2 is incorrect. (Q) (Z)

3. Orthoboric acid acts as lewis-acid in water, not as 7. Since the bridging atom, Cl, in Al2Cl6 has lone pair
proton donor (as it does not liberate H+ ion) because of electrons therefore it forms co-ordinate bonds.
it completes its octet by accepting the OH– from
3c-2e bonds are formed only when the bridging
water. atom does not contain any lone pairs.
B(OH)3 + H2O —→ [B(OH)4]– + H+.
8. H3BO3 does not undergo self ionization.
4. (a) 2B + 2NH3 → 2BN + 3H2
Although Boron produces BN with ammonia but
On adding cis-diols, they form complexing species
Boron is element not compound. So that this option with orthoboric acid.
not involve in answer.
Hence the acidity increases on adding ethylene
(b) 3B 2 H6 + 6NH3 " 3 [BH 2 (NH3) 2] + [BH -4 ] glycol.
T = 200°C
2B3 N3 H6 + 12H 2

H3BO3 + H2O —→ B(OH)-4 + H+
T > 200°C
B3 N3 H6 (BN) x
1200°C
(c) B 2 O3 (,) + 2NH3 2BN(s) + 3H 2 O(g)
(d) HBF4 + NH3 → NH4[BF4]

5. (a) SnCl2.2H2O is a reducing agent since Sn2+ tends

to convert into Sn4+.
(b) SnO + 2KOH(aq.) + 2H 2 O " K 2 [Sn (OH) 6]
2
^Amphoterich ]Baseg

It arranges into planar sheets due to H-bonding.
(c) First group cations (Pb2+) form insoluble
chloride with HCl that is PbCl2 however it is
Hence, it has 2- dimensional structure due to
slightly soluble in water and therefore lead +2 H-bonding.
ion is never completely precipitated on adding
It acts as a weak acid in water, so it is a weak
hydrochloric acid in test sample of Pb2+, rest of electrolyte in water
the Pb2+ ions are quantitatively precipitated with
H2S in acidic medium. 9. B2H6 + 6CH3OH —→ 2B (OCH3)3 + 6H2
So that we can say that filtrate of first group contain
For 3 moles of B2H6 mole of B containing product
solution of PbCl2 in HCl which contains Pb2+ and Cl– formed = 6
However in the presence of conc. HCl or excess HCl 10. BenAl2Si6O18. The value of n comes 3 by charge
it can produce H2[PbCl4] balancing.
So, we can conclude A, B or A,B,C should be
(Be2+)n (Al3+)2 (Si6O18)12– [2 × n + 2 (+3) + (–12) = 0
answers.

\ n = 3].
(d) Pb3 O 4 + 4HNO3 → PbO2 (↓)
]2PbO.PbO 2g
]mixture of oxidesg + 2Pb(NO3)2 + 2H2O 11. In crystalline state, AlCl3 exists as AlCl3.6H2O or
[Al(H2O)6]Cl3.
It is not a redox reaction.