Chemistry SampleSolvedArihant Chap 1 4
Chemistry SampleSolvedArihant Chap 1 4
Chemistry SampleSolvedArihant Chap 1 4
Mole Concept
l
1
th part by weight of an atom of ( C12 ) isotope
12
Molecular formula
1
g = 1.66 10-24 g
=
NA
C6 H6 (benzene)
CH
C6 H12O6 (glucose)
Empirical formula
CH2O
HO
H2O2
H2S 2 O8 (persulphuric acid)
HSO4
H2 +
2g
1
O H2 O
2 2
16 g
18 g
1000 dx 10dx
=
100 M
M
M
(basicity = 3)
3
Molar mass
(iii) Equivalent weight of bases =
Acidity
Moles of solute ( n )
1000
Weight of solvent in gram
NOTE
Molality is a true concentration unit, independent of temperature
while molarity depends on temperature.
N =
ni
n
ni
Eq
M
=
= n-factor
n
Equivalent weight
M 1 V1 + M 2 V2 + M 3 V3 K
V1 + V2 + V3 K
Normality/Molarity Relationship
N =
M 1 V1 = M 2V2
Weight of compound
w
=
Equivalent weight
Equivalent weight
i=1
M
M
, Al(OH)3 =
2
3
ci =
M
(basicity = 2)
2
H3PO4 =
m=
Eq
n
N Eq MW
and M =
=
= n-factor
=
V
EW
V
M
n
Titration
of a Mixture of NaOH/Na2CO3
The mixture is analysed by titrating against a standard acid in
presence of phenolphthalein and methyl orange indicators.
Phenolphthalein end point occur when the following
neutralisation is complete :
Quick
Equivalent Weight of OA / RA
e.g. KMnO4 + H+ Mn 2+ : E =
5
K 2 Cr2 O7 + H+ 2Cr 3+ : E =
6
2KI I2 + 2K + :
[ E = M ( DON per I- = 1)]
98
2Na 2 S2 O3 Na 2 S4 O6 + 2Na + :
80
(% Strength-100)
18
+2
Eq
V
n
and
M =
V
N Eq
=
M
n
MW
=
= n-factor
EW
(n-factor = Change in oxidation number per formula unit).
+3
+ Cr2 (SO4 )3
In the above redox reaction, chromium is reduced from
(+ 6 to +3) and iron is oxidised from (+ 2 to + 3). Hence,
K 2 Cr2 O7 is known as oxidising agent (itself reduced)
and FeSO4 reducing agent (itself oxidised).
Reaction
18
Redox
DON = 12 - 6 = 6
80
of
DON = 1
Balancing
(2013 Main)
54 Fe, 56 Fe and 57 Fe
are 5%, 90% and 5%, respectively, the atomic mass of Fe is
(a) 55.85
(b) 55.95
(c) 55.75
(d) 56.05 (2009)
(2003, 1M)
(c)
6.023
1054
9.108
(a) 0.1
(c) 0.3
(b) 0.9
(d) 0.6
(1999, 2M)
(1988, 1M)
(d) Molality
(1986, 1M)
(1979, 1M)
(c) 2.32 g
(d) 2.64 g
(1979, 1M)
(a) 36 g of water
(b) 28 g of CO
(c) 46 g of ethyl alcohol
(d) 54 g of nitrogen pentaoxide (N2 O5 )
(1979, 1M)
(b) 44
(c) 66
(d) 88
(2003, 1M)
(b) 56 g of Fe (56)
(d) 108 g of Ag (108)
1
(2002, 3M)
(b)
1031
9.108
1
(d)
108
9.108 6.023
. .
(1991, 1M)
(1983, 1M)
(1980, 1M)
(1980, 1M)
Subjective Questions
25. 20% surface sites have adsorbed N2 . On heating N2 gas
evolved from sites and were collected at 0.001 atm and 298 K
in a container of volume is 2.46 cm 3 . Density of surface sites
is 6.023 1014 /cm 2 and surface area is 1000 cm 2 , find out the
number of surface sites occupied per molecule of N2 .
(2005, 3M)
(2003)
-3
(1990, 1M)
(2001, 1M)
(a)
(b)
(c)
(d)
MnO-4
2
16
5
2
C2 O42 5
5
16
16
H+
16
2
2
5
(b) 8.4
(c) 3.0
(1992)
(1990, 1M)
(d) 8.0
(b) +2
(d) 1
(1988)
(1988, 1M)
(d) MnO24
(2001)
example of
(a) oxidation reaction
(b) reduction reaction
(c) disproportionation reaction
(d) decomposition reaction
(2000)
(d) CrO2 Cl 2
(1999)
(1997)
(2011)
Subjective Questions
20. Calculate the amount of calcium oxide required when it
reacts with 852 g of P4 O10 .
(1992, 4M)
(2005, 2M)
30.
(1999, 3M)
31.
32.
33.
Topic 1
1.
5.
9.
13.
17.
21.
24.
(1983, 4M)
Topic 2
(d)
(c)
(d)
(d)
(a)
(6.02310 24 )
(8)
2.
6.
10.
14.
18.
22.
(d)
3.
(b)
7.
(d)
11.
(a)
15.
(c)
19.
C-12 isotope
(b)
(a)
(d)
(a)
(4.14 g)
4.
8.
12.
16.
20.
23.
(a)
(a)
(a)
(a)
(0.4)
(8)
1.
5.
9.
13.
17.
(a)
(a)
(a)
(b)
(5)
2.
6.
10.
14.
18.
(d)
(d)
(a)
(a, b, d)
(2)
3.
7.
11.
15.
19.
(b)
(a)
(b)
(b)
(3)
4.
8.
12.
16.
(c)
(b)
(c)
7/3
Volume given = 50 mL
= 12 8 + 1 7 + 32 + 16 3 + 23 = 206
we have to find, mole per gram of resin.
412
2 206
= 0.9 60 mg = 54 mg
(mO 2 )
3.
nO 2
nN 2
(M O 2 )
(mN 2 )
(M N 2 )
M 1V1 + M 2V2
V1 + V2
OH
Therefore, normality = molarity basicity = 0.3 2 = 0.60
5. Molarity =
Moles of solute
Volume of solution (L)
120
Moles of urea =
=2
60
Weight of solution = Weight of solvent + Weight of solute
= 1000 + 120 = 1120 g
1120 g
1
Volume =
= 0.973 L
1.15 g / mL 1000 mL / L
2.000
Molarity =
= 2.05M
0.973
54 5 + 56 90 + 57 5
= 55.95
100
Excess
+ AgBr
1.0 mol
Excess
1 mol
24
Number of atoms in 24 g C =
NA = 2NA
12
56
Number of atoms in 56 g of Fe =
NA = NA
56
27
Number of atoms in 27 g of Al =
NA = NA
27
108
Number of atoms in 108 g of Ag =
NA = NA
108
Hence, 24 g of carbon has the maximum number of atoms.
-31
9.108 6.023 1023
9.108 10
1
=
108 mole of electrons
9.108 6.023
\ 1 kg =
14. Unlike other metal carbonates that usually decomposes into metal
oxides liberating carbon dioxide, silver carbonate on heating
decomposes into elemental silver liberating mixture of carbon
dioxide and oxygen gas as :
Heat
1
O (g )
2 2
MW = 276 g
2 108 = 216 g
Hence, 2.76 g of Ag2CO3 on heating will give
216
2.76 = 2.16g Ag as residue.
276
15. The balanced chemical reaction of zinc with sulphuric acid and
NaOH are
Zn + H2SO4 ZnSO4 + H2 (g )
Zn + 2NaOH + 2H2O Na 2[ Zn(OH)4 ] + H2 (g )
Since, one mole of H2 (g ) is produced per mole of zinc with both
sulphuric acid and NaOH respectively, hydrogen gas is produced in
the molar ratio of 1:1 in the above reactions.
36
16. Number of molecules present in 36 g of water =
N A = 2N A
18
28
Number of molecules present in 28 g of CO =
NA = NA
28
46
Number of molecules present in 46 g of C2H5OH =
NA = NA
46
54
Number of molecules present in 54 g of N2O5 =
N A = 0.5 N A
108
Here, NA is Avogadros number. Hence, 36 g of water contain the
largest (2NA ) number of molecules.
=
32
NA
w (N2 ) N (N2 )
And
(ii)
=
28
NA
Dividing Eq. (i) by Eq. (ii) gives
N (O2 ) w (O2 ) 28 1 28 7
=
=
=
N (N2 ) w (N2 ) 32 4 32 32
Molar mass
Volume in mL
3 1000
=
= 0.4 M
30 250
23.
Molarity = 3.2 M
Let volume of solution = 1000 mL = Volume of solvent
Mass of solvent = 1000 0.4 = 400 g
Since, molarity of solution is 3.2 molar
\
n solute = 3.2 mol
3.2
Molality (m) =
=8
400 / 1000
Hence, correct integer is (8).
Molarity =
1000
= 55.56 mol L-1
18
8.83 10-17 cm 3
= 1.1773 10-16 g
0.75 cm 3 g-1
98
91
x = 2, i.e. A is KO2.
MW :
330
222
D
85
1
O
2 2
1
O
2 2
69
28
= 1.4 g
100
Weight of residue left = 5 1.4 = 3.6 g
Now, let the original mixture contain x g of Pb(NO3 )2.
Q 330 g Pb(NO3 )2 gives 222 g PbO
222 x
g PbO
\ x g Pb(NO3 )2 will give
330
Similarly, 85 g NaNO3 gives 69 g NaNO2
69 (5 - x )
g NaNO2
(5 x) g NaNO3 will give
85
222 x 69 (5 - x )
= 3.6 g
Residue :
+
330
85
Solving for x gives,
x = 3.3 g Pb(NO3 )2
NaNO3 =1.7 g.
Weight loss = 5
Weight %
69.77
11.63
18.60
Mole %
5.81
11.63
1.1625 (obtained by
dividing from M )
10
Simple ratio
C3H7 C CH3
Based on the above information, the compound may be one of
the following :
O
CH3 O
3-methyl -2-butanone
37. (a) Let us consider 1.0 L solution for all the calculation.
(i) Weight of 1 L solution = 1250 g
Weight of Na 2S2O3 = 3 158 = 474 g
474
Weight percentage of Na 2S2O3=
100 = 37.92
1250
(ii) Weight of H2O in 1 L solution = 1250 - 474 = 776 g
3
Mole fraction of Na 2S2O3 =
= 0.065
776
3+
18
3 2
+
(iii) Molality of Na =
100 = 7.73 m
776
x = 0.6
Hence, original 1.0 L mixture has 0.4 L CO and 0.6 L of CO2 ,
i.e. 40% CO and 60% CO2 by volume.
(b) According to the given information, molecular formula of
the compound is M 3N2. Also, 1.0 mole of compound has 28 g
of nitrogen. If X is the molar mass of compound, then :
28
X
= 28
100
39. In the present case, V n (Qall the volumes are measured under
identical conditions of temperature and pressure) Hence, the
reaction stoichiometry can be solved using volumes as :
y
y
x=2
y
(remaining unreacted)
y = 4, hence hydrocarbon is C2H4.
+
=
58.5
74.5
143.5
Solving for x gives x = 0.0338 g (mass of NaCl)
100 = 3.58 %
0.5
0.053
Mass % of K2O =
100 = 10.6 %
0.5
46 x + 92 (1 - x ) = 76.6
x = 0.3348
100
76.6
100
0.3348 = 0.437
76.6
2. n-factor of dichromate is 6.
Also, n-factor of Mohrs salt is 1 as :
O. A
Molecular weight
6
63 250
N 1V1 = N 2V2
Hence,
0.1 V1 = 0.4 10
V1 = 40 mL
x = 20%
Molar mass
n-factor
(ii)
Stoichiometric coefficient of
HSO-4
is 6.
15. Both assertion and reason are factually true but the reason does
not exactly explain the assertion. The correct explanation is,
methyl orange and phenolphthalein changes their colour at
different pH.
7
3
(v)
OH
O = O- , O2 - , O2 + ;
Cl = - 1to + 7
14.
x=+1
E=
HO
O
(0)
N = - 3 to + 5
P = - 3 to + 5
Sn = + 2, + 4
Tl = + 1, + 3 (rare but does exist)
Ti = + 2, + 3, + 4
0.20
Molarity of H2O2 =
= 0.10 M
2
The balanced reactions are
2KMnO4 + 5H2O2 + 3H2SO4 2MnSO4 + 5O2
+ K2SO4 + 8H2O
MnO2 + Na 2C2O4 + 2H2SO4 MnSO4 + Na 2SO4
+ 2CO2 + 2H2O
0.50
100 = 50%
20
4
Vol % of CH4 =
100= 20%
20
Vol % of He = 30%
+ 5I + 6H
3I2 + 3H2O
2I- + S4O620.1
millimol of KIO3 used =
1000 = 0.467
214
millimol of I2 formed = 3 0.467 = 1.4
millimol of Na 2S2O3 consumed = 2 1.4 = 2.8
2.8
Molarity of Na 2S2O3 =
= 0.062 M
45
I2 +
2S2O32-
2+
Fe2O3 + I 2Fe
+ I2 (n-factor of Fe2O3 = 2)
2x + 2 y = 11 0.5 5 = 27.5
Now, total millimol of Fe2+ formed = 3x + 2 y. In the reaction
Fe2+ + MnO-4 + H+ Fe3+ + Mn 2+
n-factor of Fe2+ = 1
Meq of
MnO-4
2+
= Meq of Fe
3x + 2 y = 12.8 0.25 5 2 = 32
Solving Eqs. (i) and (ii), we get
x = 4.5
and
y = 9.25
4.5
Mass of Fe3O4 =
232 = 1.044 g
1000
1.044
% mass of Fe3O4 =
100 = 34.80%
3
9.25
Mass of Fe2O3 =
160 = 1.48 g
1000
1.48
% mass of Fe2O3 =
100 = 49.33%
3
(ii)
1
O (g ) CO2 (g )
2 x2
2
mL
x mL
2 y mL
y mL
x + + y + 2 y - (x + y) = 13
2
(i)
x + 4 y = 26
The second volume contraction is due to absorption of CO2.
Hence,
(ii)
x + y = 14
M = 0.4
Also, n-factor of H2O2 is 2, therefore normality of H2O2 solution
is 0.8 N.
Volume strength = Normality 5.6 = 0.8 5.6 = 4.48 V
x = 3.75
7.5 84
= 0.63 g
Mass of NaHCO3 =
1000
3.75 106
Mass of Na 2CO3 =
= 0.3975 g
1000
0.63
% mass of NaHCO3 =
100 = 42 %
1.50
0.3975
% mass of Na 2CO3 =
100 = 26.5%
1.5
0.552
1000 = 3.45
160
During treatment with Zn-dust, all Fe3+ is reduced to Fe2 + ,
hence
millimol of Fe2 + (in 100 mL) = 3.45 2 = 6.90
6.90
= 1.725 millimol Fe2+ ion.
In 25 mL aliquot,
4
Finally Fe2+ is oxidised to Fe3+ , liberating one electron per Fe2+
ion. Therefore, total electrons taken up by oxidant.
= 1.725 10-3 6.023 1023
millimol of Fe2O3 =
= 1.04 1021
+
2MnO-4
+ 16H 2Mn
2+
+ 10CO2 + 8H2O
2x = 0.02 5 22.6
x = 1.13
-
2+
is reduced as :
2Cu 2+ + 4I - 2CuI + I2
2S2O32-
and
I2 +
2I +
Let there be x millimol of Cu 2+ .
S4O62-
Moles of Cu 2+ :
H
4.04
4
2
Cl
71.72
2
1
35.5
2.9 = 0.717 g
143.5
2x + y = 3 0.1 = 0.3
When titrated against acidic KMnO4, n-factors of both oxalic
acid and NaHC2O4 would be 2.
(ii)
2x + 2 y = 4 0.1 = 0.4
Solving equations (i) and (ii) gives
y = 0.1, x = 0.1
0.1
100 = 0.01
In 1.0 L solution, mole of H2C2O4 =
1000
0.1
Mole of NaHC2O4 =
100 = 0.01
1000
Mass of H2C2O4 = 90 0.01 = 0.9 g
Mass of NaHC2O4 = 112 0.01= 1.12 g
Cl CH2 CH2 Cl
and
CH3 CHCl 2
II
OH
OH
(Y )
H2 O
(Z )
34. Let the n-factor of KMnO4 in acid, neutral and alkaline media
are N 1, N 2 and N 3 respectively. Also, same volumes of reducing
agent is used everytime, same number of equivalents of KMnO4
would be required every time.
5
100
N 2 = 100N 3 N 1 = N 2 = 5N 3
20N 1 =
3
3
Also, n-factors are all integer and greater than or equal to one but
less than six, N 3 must be 1.
N 1 = 5, N 2 = 3
\ In acid medium
MnO-4 Mn 2+
In neutral medium
MnO-4 Mn 4+
In alkaline medium MnO-4 Mn6+
meq of K2Cr2O7 required = 100
100 = 1 6 V (n-factor = 6)
V = 100/ 6 = 16.67 mL
1
35. Meq of MnO-4 required = 20 5 = 2
50
Meq of Fe2+ present in solution = 2
millimol of Fe2+ present in solution = 2 (n-factor = 1)
Also,
Q 4 millimol of Fe2+ are formed from 1 millimol N2H4
1
1
\ 2 millimol Fe2+ from 2 = millimol N2H4
4
2
286 100
Normality of carbonate solution = 2 0.035 = 0.07 N
85
= 0.02
In acid solution : Normality of HNO3 =
2000
5 4.8
Normality of HCl =
= 0.012
2000
Let normality of H2SO4 in final solution be N.
(N + 0.02 + 0.012) 30 = 0.07 42.9
N = 0.0681
Gram equivalent of SO24 in 2 L solution = 2 0.0681
Molarity of carbonate solution =
Mass of
SO24
= 0.1362
96
= 6.5376 g
in solution = 0.1362
2
n=+2
20 millimol
MCl 2 + H2O
BaO
+
2HCl
BaCl 2 + H2O
60 20 = 40 millimol
Therefore, the residue contain 20 millimol of BaO.
Also,
molar mass of BaO = 138 + 16
= 154
154 20
= 3.08 g
Mass of BaO =
1000
Mass of MCO3 = 4.08 3.08 = 1.0 g
Q 0.01 mole of MCO3 weight 1.0 g
\ 1 mole of MCO3 = 100 g
100 = (Atomic weight of metal) + (12 + 3 16)
Atomic weight of metal = 40, i.e. Ca
CHAPTER TEST
(a)
5 M 75 mL 2
60 mL
60 mL 75 mL 2
(d)
5.0 M
(b)
(b) 24.60 mL
(d) 0.30 mL
(b) 1.2
(c) 1.50
(d) 1.8
B + C + NR
B + D + B + + D
C + D + C + + D
A+ + C C + + A
D + A+ D + + A
Assertion-Reason Type
Following two questions have assertion followed by
the reason. Answer them according to the following
options.
(a) Both assertion and reason are correct and reason is
the correct explanation of the assertion,
(b) Both assertion and reason are correct but reason is
not the correct explanation of assertion.
(c) Assertion is correct but reason is incorrect.
(d) Assertion is incorrect but reason is correct.
(b) 1.45
(d) 1.88
(b) 8.15 kg
(d) 24.4 kg
-5
(b) 2.4 10 20
(d) 6.02 10 23
(a) 20
19. Assertion A 8.0 g N2H4 (M = 32) has more atoms than 6.0
g H2O.
Column I
7
6
5
3
2
1
5
10 15 20 25 30 35 40 45 50
Volume of AgNO3
Different number of
atoms
p.
B.
Same number of
molecules
q.
C.
r.
D.
Different numbers of
atoms as well as
molecules
s.
4.80 g O2 and
2.80 g CO
22. If equal volumes of 3.5 M CaCl2 and 3.0 M NaCl are mixed,
Column II
A.
(a) 25
(c) 60
(d) 60
(c) 56
Assertion-Reason Type
(b) 40
(b) 0.5
(d) 1.5
Answers
1. (a)
2. (c)
3. (b)
11. (b)
12. (a)
13. (b, c)
20. A s; B p; C q; D r
4. (c)
14. (a, b, d )
21. (8)
5. (a, b, c, d)
15. (d)
22. (5)
6. (a, c, d)
16. (c)
7.
17.
(d)
(b)
8. (b)
18. (a)
9.
19.
(a)
(b)
10.
(a)
2
Atomic Structure
Preliminary Developments and Bohrs Model
l
Isotopes
Atoms of same element having different mass number, e.g. 6C12, 6C14.
Isobars
Atoms of different elements having same mass number, e.g. 6C14, 7 N14.
Isotones
Isoelectronic
Isodiaphers
Isosters
Species having same number of atoms and electrons are isosters, e.g. N 2, CO.
The Details About Some of the Important Subatomic Particles are given in the Table Below:
Particles and
symbol
Absolute
charge (C)
Relative
Mass
(gram)
Mass
(MeV/C 2)
Discoverer
charge
Electron (e)
-1.602 10-19
-1
9.1 10-28
0.511
JJ Thomson
Proton (p)
+1.602 10-19
+1
1.6726 10-24
938.5
Rutherford
940
Chadwick
Positron (B + / e+ )
(anti-electron)
+1.602 10-19
+1
9.1 10-28
0.511
D Anderson
Anti-proton ( p)
-1.602 10-19
-1
1.6726 10-24
938.5
Neutron (n)
-24
1.6749 10
Rutherfords Nuclear Model of Atom Rutherford performed an alpha particle ( He2+ ) scattering experiment on a thin gold foil and
presented that :
(i) most part of atom is empty.
(ii) every atom possesses a highly dense, positively charged centre called nucleus.
(iii) entire mass of atom is concentrated inside the nucleus.
(iv) later Rutherford model was abandoned due to its failure to comply with classical theory of electromagnetic radiation. This theory
also failed to explain the line spectrum of H-atom.
Atomic Structure 21
l
Plancks Equation
Potential Energy
hc
E = hn =
l
Ep =
(where, h = 6.625 10-34 Js)
Advanced Concept
(Quantum Mechanical Theory)
Electronic Configuration and
Quantum Number
l
n 0 = Threshold frequency
-34
Js
1 1
1
men 2 = hc -
2
l l0
...(ii)
l
(iii)
(iv)
(v)
l
1
1
1
= n = RH Z 2 2 - 2 ; RH = 1.09678 107 m - 1
l
n1 n2
For Lyman series : n1 = 1, n2 = 2, 3
(occur in UV region)
For Balmer series : n1 = 2, n2 = 3, 4
(occur in visible region)
For Paschen series : n1 = 3, n2 = 4 , 5
(occur in IR region)
For Brackett series : n1 = 4, n2 = 5, 6
(occur in IR region)
For Pfund series : n1 = 5, n2 = 6, 7
(occur in IR region)
En =
- kZ 2
n2
( p = momentum ( mv ))
h
;
p
(ii)
(ii)
mv
Ze
=
r
4 pe 0 r2
l
(i)
(orbit number)
(ii) Centrifugal force of orbiting electron is exactly balanced
by the electrostatic attraction between nucleus and
electron.
- Ze2
2kZ 2
=- 2
4 pe 0 r
n
l=
l
h
2meV
Dx Dp
h
4p
22 Atomic Structure
l
2s
2p
3s
3p
3d
4s
4p
4d
4f
5s
5p
5d
5f
6s
6p
6d
7s
7p
2y
y
2y
z
8 p2 m
h2
(E - V ) y = 0
1 1
p a0
y1 s =
y 2s
3/ 2
e- r / a 0
1
=
4 2p a0
for px -orbital y 2 px =
3/ 2
r - r / 2a 0
2 - a e
1
r sin q cos f e- r / 2 a 0
4 2p a0
1
Atomic Structure 23
2s
2.
3.
r
3p
3s
4.
y
r
|Rnl| 2r 2
1s
|Rnl| 2r 2
1. y
|Rnl| 2r 2
2. Rutherfords
experiment
(1986, 1M)
(b) 10-13 cm
(d) 10-8 cm
(1985, 1M)
(1985, 1M)
(c) n, p, a , e
(1983, 1M)
(b) atom
(c) electron
(d) neutron
(1981, 1M)
(b) protons
(d) neutrons
Objective Questions II
(One or more than one correct option)
8. The energy of an electron in the first Bohr orbit of H-atom is
13.6 eV. The possible energy value(s) of the excited state(s)
for electrons in Bohr orbits of hydrogen is (are)
(1988)
(a) - 3.4 eV
(c) - 6.8 eV
(b) - 4.2 eV
(d) + 6.8 eV
(1988, 1M)
(b) neutrons
(d) photons
10. The sum of the number of neutrons and proton in the isotope of
hydrogen is
(a) 6
(c) 4
(1986, 1M)
(b) 5
(d) 3
11. When alpha particles are sent through a thin metal foil, most of
them go straight through the foil, because
(1984, 1M)
24 Atomic Structure
Match the Columns
K n = Kinetic energy
rn = Radius of nth orbit
called ................ .
Column I
A. Vn / K n = ?
If radius of nth orbit
B.
E nx , x = ?
r.
s.
Angular momentum in
lowest orbital
1
y
D. n Z , y = ?
r
C.
(1982, 1M)
Column II
p.
0
q.
(1993, 1M)
(1982, 1M)
(1983, 1M)
Subjective Questions
18. With what velocity should an a-particle travel towards the
nucleus of a copper atom so as to arrive at a distance 10-13 m
from the nucleus of the copper atom ?
(1997 (C), 3M)
(2015 Main)
(b) 6.8 eV
(d) + 6.8 eV
(2013 Main)
1
2
1
2
(2013 Main)
-7
h2
(a)
4p 2ma02
h2
(b)
16p 2ma02
h2
(c)
32p 2 ma02
h2
(d)
64p 2ma02
(2012)
(b) 0 and 2
(d) 2 and 1
(b) n = 2, Be
(c) n = 2, He+
(d) n = 3, Li 2+
(2002, 3M)
1
1
and - for the electron spin
2
2
represent
(2001, 1M)
(2004, 1M)
3+
(a) n = 2, Li
2+
(2005, 1M)
(b) 10-20 m
(c) 10-30 m
(b) two
(d) zero
(2001, 1M)
(d) 10-40 m
(2001, 1M)
Atomic Structure 25
11. The
(c) 6.8 eV
(d) + 6.8 eV
h
(d) 2
2p
h
(c)
2p
(1997, 1M)
(b) Bohr
(d) Einstein
unpaired electrons ?
(b) Ti 3+
(1996, 1M)
(d) Fe2+
(c) V3+
1 h
(a) +
2 2p
(b) zero
h
(c)
2p
(d) 2
h
2p
(1992, 1M)
(b) E = mc2
(d) E = hn
(1992, 1M)
of chlorine atom is
(a)
(c)
m
0
1
l
1
0
m
1
0
chromium atom is
(1989, 1M)
(a) [ Ar ] 3d 5 4 s1
(b) [ Ar ] 3d 4 4 s2
(c) [ Ar ] 3d 6 4 s0
(d) [ Ar ] 4 d 5 4 s1
(b) 4
(1986, 1M)
1
(c)
2
(d) 2
(1986, 1M)
(1985, 1M)
(b) 2p
(c) 2s
1
(a) 5, 0, 0, +
2
1
(c) 5, 1, 1, +
2
(1984, 1M)
(d) 1s
(1984, 1M)
1
(b) 5, 1, 0 , +
2
1
(d) 6, 0, 0, +
2
(1988, 1M)
(1989, 1M)
n
(b) 2
(d) 3
is inversely related to
20. The correct set of quantum numbers for the unpaired electron
l
1
1
(d)
n
2
3
(c)
(b)
(a) 3.4 eV
(1988, 1M)
(a)
(1983, 1M)
(1983, 1M)
26 Atomic Structure
38. The orbital angular momentum quantum number of the
Objective Questions II
(One or more than one correct option)
state S 2 is
(a) 0
(2010)
(b) 1
(c) 2
(d) 3
(1999, 3M)
(a)
(b)
Column I
(c)
p.
Principal
quantum
number
B.
A hydrogen-like one-electron
wave function obeying Paulis
principle.
q.
Azimuthal
quantum
number
C.
r.
Magnetic
quantum
number
D.
s.
Electron spin
quantum
number
34. An isotone of
(c)
76
32 Ge
is
77
32 Ge
77
34 Se
(1984, 1M)
(b)
(d)
77
33 As
78
34 Se
(2000)
(1989, 1M)
(1993, 1M)
(1993, 1M)
45. When there are two electrons in the same orbital, they have
spins.
(1983, 1M)
True/False
(2010)
(b) 2s
(d) 3s
state energy is
(2010)
(b) 1.50
(d) 4.50
y2
orbital is
(1986, 1M)
48. The energy of the electron in the 3d-orbital is less than that
in the 4s-orbital in the hydrogen atom.
(1994, 1M)
41. 8 g each of oxygen and hydrogen at 27C will have the total
(a) 1s
(c) 2p
Column II
A.
(d)
(a)
(2008, 6M)
(1983, 1M)
(1983, 1M)
(1982, 1M)
Atomic Structure 27
61. Calculate the wave number for the shortest wavelength
(2014 Adv.)
1
and ms = - is
2
52. The atomic masses of He and Ne are 4 and 20 amu,
respectively. The value of the de-Broglie wavelength of He gas
at -73C is M times that of the de-Broglie wavelength of Ne
at 727C. M is
(2013 Adv.)
n = 4, | ml | = 1
53. The work function (f) of some metals is listed below. The
number of metals which will show photoelectric effect when
light of 300 nm wavelength falls on the metal is
(2011)
Metal Li Na K Mg Cu Ag Fe Pt
F (eV) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3
W
4.75
Subjective Questions
55. (a) Calculate velocity of electron in first Bohr orbit of hydrogen
atom (Given, r = a0 ).
(b) Find de-Broglie wavelength of the electron in first Bohr orbit.
(c) Find the orbital angular momentum of 2p-orbital in terms of
(2005, 2M)
h / 2p units.
1
4 (2p )1/ 2
1
a0
3/ 2
r
2 - e-r / 2a 0
a0
(1994, 3M)
(2004, 2M)
(1985, 2M)
3p
3s
3p
and not
21.7 10-12
(2000)
71. The energy of the electron in the second and third Bohrs
orbits of the hydrogen atom is - 5.42 10-12 erg and
- 2.41 10-12 erg respectively. Calculate the wavelength
of the emitted light when the electron drops from the third
to the second orbit.
(1981, 3M)
28 Atomic Structure
Topic 1
1. (d)
5. (d)
9. (a,b)
2. (b)
3. (b)
21. (a)
22. (c)
23. (b)
24. (c)
4. (b)
25. (d)
26. (c)
27. (b)
28. (d)
29. (a)
30. (a)
31. (d)
32. (a,d)
33. (a,b,c)
34. (b,d)
35. (c)
36. (b)
6. (a)
7. (c)
8. (a)
10. (d)
11. (a,c)
12. (a,c)
37. (c)
15. (1 . 66 10 27 kg)
39. A q;
Topic 2
1. (c)
2. (a)
3. (a)
4. (c)
5. (a)
6. (b)
7. (c)
8. (d)
9. (c)
10. (a)
11. (b)
12. (a)
13. (a)
14. (a)
15. (b)
16. (d)
17. (b)
18. (d)
19. (c)
20. (c)
13.6
eV
where,
n2
13.6
In excited states, E2 = = - 3.4 eV
4
13.6
E3 = = - 1.51eVetc.
9
n =1, 2, 3, ....
38. (b)
B ,p q, r, s
C p, q, r
D p, q, r
40. Cr = [Ar] 3d 5 , 4s 1
41. 1 : 16
43. orbital
45. opposite
46. True
47. False
48. True
49. False
50. False
52. (5)
53. (4)
54. (9)
51. (6)
13. A. Vn = Kn =
B.
1
4 pe 0
1
8pe 0
Ze2
Ze2
En = -
Vn
= - 2 (r )
Kn
Ze2
r- 1
8pe 0 r
C. Angular momentum = l ( l + 1)
D.
rn =
a0 n 2
Z
x =-1 (q )
h
= 0 in 1s-orbital
2p
( p ).
1
Z (s )
rn
10-3
6.023 1023
kg = 1.66 10-27 kg
Atomic Structure 29
Potential energy of this a-particle can be determined as
PE = -
Z1 Z2 e
( 4 pe 0 ) r
(Z1 = + 2, Z2 = + 29,
e 0 = 8.85 10-12 J-1 C2 m-1 , r =10-13 m)
| PE | =
2 29 (1.6 10-19 )2
-12
4 3.14 8.85 10
-13
= 1.33 10
10
2 1.33 10-13
when n = 2, Z = 4.
= 6.3 106 ms -1
4 1.66 10-27
En = -
13.6
where, n = 1, 2, 3 ...
eV
n2
-13.6
In excited states, E2 =
= -3.4 eV
4
6.625 10-34
h
=
= 2.3 10-30 m
5
mv 0.2
60 60
DE = 2.178 10
KE =
nh
2p
( mv )2 =
n2h2
4 p2 r 2
2 2
1 2
n h
mv = 2 2
2
8p r m
state
electronic
where, k = Constant,
Z = Atomic number,
n
n = Orbit number
= - 13.6 eV for H ( n = 1)
- 13.6
when n = 2 , E2 =
eV = - 3.40 eV
22
(n can have only integral value 1, 2, 3, )
h
14. The orbital angular momentum ( L ) = l ( l + 1)
2p
h
= 6
( l = 2 for d -orbital )
2p
En = -
l 1.21 10-7 m
mvr =
ground
1 hc
1
2 - 2=
2 l
1
is
Now, E1 - E2
i.e.
(ii) n = 4 , l = 0 4s-orbital
(iii) n = 3, l = 2 3d-orbital
(iv) n = 3, l = 1 3d-orbital
1
E1 = - 2.178 10-18 J 2
1
1
E2 = - 2.178 10-18 J 2
2
-18
Z = 1,
So,
px
configuration of Cr.
Z2
2
n
a0 n 2
= a0
Z
-13
(i)
kZ 2
2
30 Atomic Structure
15. Bohr first made use of quantum theory to explain the
3+
h
= 0 for 2s-electrons
2p
[ Kr ] 5s1
n = 5, l = 0, m = 0, s= +
32. Both (a) and (d) are correct. The three electrons in the
2 p-orbitals must have same spin, no matter up spin or down
spin.
76
n - 0 -1=1
n = 2 i.e. S 1 = 2s-orbital.
1
i.e.
DE
l
E
hc
l
25.
1 = 2 =2
E=
E2 l1
l
l
1
2
144
42444
3
Ar
26.
1
or
2
n12
1 hc
=
n22 l
s
1
2
3
-3
2
This is the wrong set of quantum number because | m | cannot
be greater than l.
EH =
kZ 2
n2
= k ( Z = 1, n = 1)
For S 1 state of Li 2+ ,
E=
k ( 3 )2
22
9
k = 2.25 k
4
qk
n2
n=3
Since, S 2 has one radial node.
3 - l -1 = 1
l =1
h
2p
Atomic Structure 31
C. For shape, size and orientation, only n, l and m are needed.
known.
40. Cr = [Ar] 3d 5 4 s1
41. 1 : 16
42. Heisenberg proposed uncertainty principle and de-Broglie
43. orbital
44. 2 px ,2 p y and 2 p z have different orientation in space.
45. Two electrons in same orbital must have opposite spin.
46. Very large mass of alpha particles than beta particles is
responsible for less deflection in former case.
4p
1 0 +1
4d
2 1 0 +1 +2
4f
3 2 1 0 +1 +2 +3
52.
PLAN KE = 1 mv 2 = 3 RT
2
2
= 2.18 106 ms - 1
(b) l =
l (wavelength) =
(b)
h
h
h
=
mv
2mKE
2m(T )
T = Temperature in Kelvin
h
l(He at -73 C = 200 K ) =
2 4 200
2 20 1000
2 20 1000
l( He )
=5
=M =
2 4 200
l( Ne )
M =5
r0
1
r0 - a 0
y 22 s = 0 =
2 - e
a0
4 2p
r0
2= 0 r0 = 2a0
a0
l=
h
6.625 10-34
= 6.625 10-35 m
=
mv 100 10-3 100
= 6.625 10-25 (negligibly small)
where,
h
6.625 10-34
=
= 0.33 10-9 m
mv 9.1 10-31 2.18 106
m2 v2 = 2mKE \ mv = 2mKE
nh
6.625 10-34
=
2pmr 2 3.14 9.1 10-31 0.529 10-10
n=
1
1
1
= R ( Z )2 2 - 2
l
n1 n2
1
Z2
l
l ( He+ )
1
Z ( H )2
=
=
+ 2
l (H)
4
Z ( He )
l ( He+ ) =
l ( H ) 91.2
nm = 22.8 nm
=
4
4
32 Atomic Structure
pV
1 1
= 0.0409
=
RT 0.082 298
58. Moles of H2 =
1 - J
4
3
2.18 10-18 J
4
Total transition energy
3
= 2.18 10-18 4.93 1022 J
4
= eV , here p = momentum ( mv )
2m
h
h
Using de-Broglie equation, l = =
p
2meV
1.54 10-10 =
( 2 9.1 10
+ 2 Ek
=
4500 10-10
6.023 1023
Ek = 2.16 1020 J/atom
-19
1.6 10
1
1
1
= RH Z 2 2 - 2
l
n1 n2
1/ 2
V)
a0
RH 1.09 107
=
= 2.725 106 m-1
4
4
6.625 10-34
-31
F dr
e2
and
F =
e 2 1
e2
W =
=
= Total energy ( E )
4 pe 0 r a 0
4 pe 0 r
4pe 0 r2
2pe 0 r
1
2
Equating termwise on left to right of the above equation
gives
n1 = 1 and n2 = 2
k
n2
1 3
DE ( n = 2 to n = 1) = k 1 - = k
4 4
= 1.635 10-18 J
Atomic Structure 33
For a H-like species, energy of stationary orbit is determined
as
En = -
kZ 2
n2
where, Z = atomic number
1
1
DE = kZ 2 2 - 2
n1 n2
1 DE k 2 1 1
3
Z - = RH Z 2
=
=
1
l hc hc
4
4
4
4
2
Z =
=
= 4.05
3RH l 3 1.097 107 3 10-8
Z = 2 (He )
E ( X ) = Z2 E (H )
For He+ ( Z = 2 )
E =-
4 21.7 10-19
J
n2
For longest wavelength transition from 3rd orbit, electron
must jump to 4th orbit and the transition energy can be
determined as
1 1
DE = + 4 21.7 10-19 - J = 4.22 10-19 J
9 16
hc
Also, Q
DE =
l
hc 6.625 10-34 3 108
l=
=
m
\
DE
4.22 10-19
= 471 10-9 m = 471 nm
hc
-18
= 1.6275 10 J l =
DE
6.625 10-34 3 108
=
m
1.6275 10-18
= 122 10-9 m = 1220
DE =
l=
[Q 1erg = 10-7 J ]
hc
l
6.625 10-34 3 108
3.01 10-19
eV unit ?
(a) 13.6
(b) 54.4
(a) 6 5
(c)122.4
(d) 217.6
(b) 6 4
(c) 5 4
(d) 4 3
Assertion-Reason Type
Following two questions have assertion followed by the
reason. Answer them according to the following
options.
(d) 6 4
(d) 5
(a) n = 5, l = 3, ml = 2, m s = 1/2
(b) n = 3, l = 2 , ml = 3, m s = - 1/2
(c) n = 1, l = 1, ml = 0, m s = - 1/2
(d) n = 6, l = 3, ml = - 3, m s = 1/2
(b) 7 4
(c) 4
(a) 6 3
(b) 3
III
CHAPTER TEST
Column I
Column II
A.
n=6
p.
B.
n=5
q.
C.
n=4
r.
D.
n=3
s.
Answers
1. (c)
2. (b)
3.
(d)
4.
11. A q,r,s; B q,r,s; C p,q,s; D p
(c)
5. (a, c, d)
12. (6)
6.
(b)
7.
(c)
8.
(c)
9.
(d)
10.
(b)
3
Periodic Classification and
Periodic Properties
History and Periodic Classification
l
Periodic Properties
l
d
Covalent rad =
d
2
d
d = rA + rB
Remember
For a group of isoelectronic species involving cation,
anion and neutral atom, radius is inversely proportional
to Z (atomic number).
e.g. N3 + > O2 - > F- > Na + > Mg 2 +
(Order of radius)
l
d
van der Waals radius = d
2
Ionic Radius
(a) When a cation is formed, effective nuclear charge
number of protons
increases resulting a decrease in
number of electrons
radius than the radius of normal atom.
(b) When an anion is formed, effective nuclear charge
decreases, resulting an increase in radius than the radius
of normal atom.
2s2
Be =1s2
B = 1s2
e.g. Na > Mg
2+
> Al
3+
3-
2-
e.g. N > O
>F
2p
2s2
N =1s2
2s2
O =1s2
2s2
Removal of electron is
easier from 2p-orbitals
than from completely
filled, stable 2s-orbital.
Removal of electron is
difficult from completely
half-filled orbitals of
N than from oxygen.
Anionic radius
c A - c B - 0.208 D
where, c A and c B are electronegativities of A and B
D = E A - B - A A - A EB - B
2p3
, has less affinity for electron.
N=
2p2
C=
(1992, 1M)
Objective Questions II
(One or more than one correct option)
2. The statements that is/are true for the long form of the periodic
table is/are
(1988, 1M)
2-
(a) CaSO4
(c) BaSO4
(2015 Main)
(b) Br2
(d) ICl
(b) Ne
(c) Kr
(2015 Main)
(d) Xe
(2013 Main)
(b) - 5.1 eV
(d) + 2.55 eV
(a) Li +
(c) B-
(2002, 3M)
potential is
(2001, 1M)
(1997(C), 1M)
(c) V 3+
(d) Fe2+
(b) Pb
(c) Fe
(b) O2(d) Na
(1989, 1M)
order
(1988, 1M)
(1987, 1M)
(b) N, Si, C, P
(d) P, Si, N, C
respectively given by
(a) 0.72, 1.60
(c) 0.72, 0.72
(1987, 1M)
(1987, 1M)
(a) Al 3+
(c) Be2+
(b) Na +
(d) Mg3+
(1984, 1M)
(b) carbon
(d) oxygen
(1982, 1M)
(b) Ti 3+
(a) N3-
(a) boron
(c) nitrogen
unpaired electrons ?
(a) Mg2+
15. The first ionisation potential of Na, Mg, Al and Si are in the
(c) F
(1995, 1M)
(d) Ag
(1981, 1M)
Objective Questions II
(One or more than one correct option)
22. Ionic radii of
(1999, 3M)
35
Cl - <
(a) Ti 4+ < Mn 7 +
(b)
37
(c) K + > Cl -
(d) P 3+ > P 5+
Cl -
(1989, 1M)
(1989, 1M)
(1985, 1M)
Topic 1
1. (d)
2. (b,c,d)
Topic 2
1. (c)
5. (b)
9. (b)
2. (b)
6. (c)
10. (b)
3. (d)
7. (b)
11. (d)
4. (d)
8. (b)
12. (b)
13. (b)
14. (d)
15. (a)
16. (c)
(1982, 1M)
True/False
34. The basic nature of the hydroxides of group 13 (III B) decreases
progressively down the group.
(1993, 1M)
35. The decreasing order of electron affinity of F, Cl, Br is F > Cl > Br.
(1993, 1M)
37. The softness of group IA metals increases down the group with
increasing atomic number.
(1986, 1M)
Subjective Questions
38. Arrange the following ions in order of their increasing radii
Li + , Mg 2+ , K + , Al 3+ .
(1997, 1M)
39. Compare qualitatively the first and second ionisation potentials of
copper and zinc. Explain the observation.
(1996, 2M
(1986, 1M)
17. (a)
21. (c)
18. (a)
22. (d)
19. (b)
23. (a,b,c)
25. (a)
29. (c)
26. (c)
27. (c)
30. (inert pair effect)
20. (c)
24. (a,b)
28. (c)
34. F
36. F
35. F
37. T
(1985, 3M)
On the other hand, rest of the metals, i.e Ca, Ba, Sr have
bigger size and thats why lattice energy is greater than
hydration energy.
Number of electrons in F = 9 + 1 = 10
Since, all the three species have each 10 electrons, hence they
are isoelectronic species.
It is considered that, in case of isoelectronic species as the
negative charge increases, ionic radii increases and therefore
the value of ionic radii are
N3- = 1.71
2-
= 1.40
.
F = 136
5.
Na Na + + e- First IE
Na + + e- Na
Electron gain enthalpy of Na + is reverse of (IE)
Because reaction is reverse so
DH ( eq ) = - 5.1 eV
16
Ca
Ba
Se
18
Ar
7. Be- is the least stable ion, Be (1s2 2s2 ) has stable electronic
configuration, addition of electron decreases stability.
2s2
N+ (6e-) = 1s2
2s2
2p
3+
3+
Fe
2+
2p
2s2
12. Pb has most stable +2 oxidation state due to inert pair effect.
2
> Group 13 =
Group 2 =
ns2
ns2
np1
2p
F+
(8e-)
= 1s2
2s2
2p
23. (a) and (b) are infact the same statements and both are
correct. N has slightly greater ionisation energy than
oxygen which is against periodic trend. This exception is
due to completely half-filled ( 2 p 3 ) orbital in nitrogen that
makes ionisation slightly difficult than oxygen.
(c) Also correct : Although N has greater first ionisation
potential than oxygen, two values of ionisation potentials
are comparable since they are adjacent in a period, i.e.
electrons are removed from same orbit during ionisation.
(d) Incorrect opposite to (c). of the bonded atoms which in
turn has periodic trend in long form of periodic table.
39. Zn = 3d 10 4 s2 ,
Cu = 3d 10 4 s1
explanation of statement I.
explanation of statement I.
which is against periodic trend.
Statement II is false 2s-orbital is lower in energy than 2 p,
Aufbaus principle.
(Mulliken formula)
36. Ionisation potential decreases down the group but this is not the
only criteria of reducing power.
2p1
32. Electronegativity =
B+ = 1s2
27. Both statements I and II are true and Statement II is the correct
43.
CHAPTER TEST
(a)
(b)
2 E1 2 E 2
,
N0 N0
(a) VCl2
(b) VCl3
(c) VCl4
(d) VCl5
2p
(c)
2p
(d)
1s2 2s2
1s2 2s2
2p
(a) 18
(d) Ne
(b) 24
(c) 27
(d) 36
(b) 26
(c) 29
(d) 31
Assertion-Reason Type
Following two questions have Assertion followed by the
Reason. Answer them according to the following options.
(a) Both Assertion and Reason are correct and Reason is
the correct explanation of the Assertion.
(b) Both Assertion and Reason are correct but Reason is
not the correct explanation of Assertion.
(c) Assertion is correct but Reason is incorrect.
(d) Assertion is incorrect but Reason is correct.
2p
(c) Li
(b) H
Column I
Column II
A.
Be (Z = 4)
p.
Paramagnetic
B.
C (Z = 6)
q.
Diamagnetic
C.
Mg2+ (Z = 12)
r.
D.
N (Z =7)
s.
Answers
1.
11.
(b)
(a)
2.
12.
(d)
3.
(a)
4.
(c)
5. (a,b,d)
13.
(6)
6. (a,c)
7.
(c)
8.
(c)
9.
(d)
10.
(c)
4
Chemical Bonding
Preliminary Concepts of Electrovalent and
Covalent Bonding Including Bonding
l
s
+
Coordinate
covalent bond
Highlights of MOT
(i) Bond order
No. of bonding electrons - No. of antibonding electrons
=
2
s-bond
Chemical Bonding 45
Valence Shell Electron Pair Repulsion Theory (VSEPR Theory) This theory is based on the concepts of hybridisation
of atomic orbitals. According to this theory, pure atomic orbitals do not take part in bonding, rather the valence shell orbitals
first hybridises and the resulting hybrid orbitals are involved in bond formation. Based on the geometries of hybrid orbitals
at the central atom, molecular structure is proposed and physiochemical properties are interpreted.
Summary of molecular geometries and hybridisation
Total Number of Number of
independent
indepen-dent
electron pairs
bonding
electron
pairs
Number of
nonbonding
electron
pairs
Orbital
geometry
Molecular
geometry
Distortion*
Hybridisation
Bond
angle
Examples
Linear
Linear
No
sp
180
CO2 , BeCl 2
Trigonal
planar
Trigonal
planar
Possible
sp 2
120
BF3 , NO-3 ,
GaI3
Trigonal
planar
Bent
(non-linear)
Always
sp 2
120
NO-2 , SO2 ,
SnCl 2
Tetrahedral
Tetrahedral
Possible
sp 3
109
CH4 , SO24 ,
CF4
Tetrahedral
Trigonal
pyramidal
Always
sp 3
109
SO23 , NH3
Tetrahedral
Bent or
V-shaped
Always
sp 3
109
H2 O, OF2 , NH-2
Trigonal
Bipyramidal
Trigonal
bipyramidal
Possible
sp 3 d
90 and PF , PCl
5
5
120
Trigonal
bipyramidal
See-saw
Always
sp 3 d
Trigonal
bipyramidal
T-shaped
Always
sp 3 d
90
IF3
Trigonal
bipyramidal
Linear
Never
sp 3 d
180
I-3 , IF2-
Octahedral
(square
Octahedral
bipyramidal)
Possible
sp 3 d 2
90
SF6 , PF6-
Octahedral
Square
pyramidal
Always
sp 3 d 2
90
IF5 , BrF5
Octahedral
sp 3 d 2
90
XeF4 , ICl -4 ,
BrF4-
NOTE
Under distortion possible means that the bond angle will be distorted when the outer atoms are not identical, e.g. CH4 is tetrahedral with all other
atoms identical, no distortion, but in CH2F2 , tetrahedral geometry but outer atoms are different, bond angles will be distorted, i.e. some will be slightly
greater than 109 and some smaller than 109.
l
46 Chemical Bonding
AB2 -linear, AB3 -trigonal planar, AB4 -tetrahedral, AB5 -trigonal bipyramidal, AB6 -octahedral, AB4 -square planar, AB2C 2 -symmetric
and square planar. Some examples of these categories:
Type
Shape
Examples
AB 2
Linear
AB 3
Trigonal planar
AB 4
Tetrahedral
AB 5
Pentagonal bipyramidal
PCl 5 , AsF5
AB 6
SF6 , SeF6
AB 4
Square planar
XeF4
Any other molecule having a single central atom will be polar as long as the electronegativities of elements that make it up are not
same. This includes molecules that have the above mentioned geometries but dissimilar outer atoms, e.g. CH3 F, OCS, BeFCl, etc.
*
p 2 py p
2 py *
s 2 px
p 2 pz *
p2 pz
*
p 2 py
p
2 py
*
s 2 px s
2 px
p 2 pz
*
p
2 pz
Li2
Be2
B2
N2
O2
*
s2p
x
*
s2p
x
*
s2p
x
p*2py, p* 2pz
s2px
s2px
p2py, p2pz
p2py, p2pz
p2py, p2pz
p2py, p2pz
s2px
s2s
s2s
s2s
*
s2s
*
s2s
s2s
s2s
s2s
s2s
s2s
*
s1s
s1s
s1s
s1s
s1s
s1s
s1s
s1s
s1s
s1s
(2015 Main)
(2000, 1M)
CaC2 are
(1996, 1M)
(d) ClO2
(1997, 1M)
(1997, 3M)
I-3 ,
19. Explain the difference in the nature of bonding in LiF and LiI.
(1996, 2M)
(1980, 1M)
(d) 10
(1979, 1M)
(c) KCN
Li + , Mg 2+ , K + , Al 3+ .
(1997, 1M)
(1980, 1M)
1
M)
2
(1983, 1M)
bonds in N2 is
bonds is
(a) CH4
True/False
(b) CaO
(d) Na 2S
(c) 6
(1982, 1M)
(1989, 1M)
(b) X -Y +
(d) X Y
(b) 4
Subjective Questions
(a) 2
bond.
(a) H2
(c) KCl
(1985,
(1986, 1M)
(a) 1, 4-dichlorobenzene
(b) cis-1, 2-dichloroethene
(c) trans-1, 2-dichloroethene (d) trans-1, 2-dichloro-2- pentene
(b) BF3
(a) CH2Cl 2
Objective Questions II
(One or more than one correct option)
(d) KCl
-29
C-m which
indicates that it is a highly polar molecule. The interatomic
distance between K + and Cl - in this molecule is
2.6 10-10 m. Calculate the dipole moment of KCl molecule
if there were opposite charges of one fundamental unit
located at each nucleus. Calculate the percentage ionic
character of KCl.
(1993, 2M)
48 Chemical Bonding
21. Give reasons in two or three sentences only for the
following :
Hydrogen peroxide acts as an oxidising as well as a
reducing agent.
(1992, 1M)
(2014 Main)
it is a covalent molecule
it contains Cs+ and I-3 ions
it contains Cs3+ and I- ions
it contains Cs+ , I- and lattice I2 molecule
(2010)
(b) BrF3
(d) OSF2
(2010)
(d) N2
(a) Na 2O2
(c) N2O
(2007, 3M)
(2005, 1M)
(b) XeF 4
(d) I -3
(b) 1
(2004, 1M)
(c) 2
(d) 3
CO2
3 ,
NO3 , CO23
ClO3 , CO2
3
ClO3 ,
SO3
(b)
(d)
(2003, 1M)
moment is
(2003, 1M)
(b) CH 2Cl 2
(d) CCl 4
electron (s)?
(2002, 3M)
(2000, 1M)
C2 C3 bonds is of
(a) sp - sp2
(c) sp - sp3
(1999, 2M)
(1999, 2M)
17. The geometry and the type of hybrid orbital present about the
central atom in BF3 is
(1998, 2M)
sp 2 - hybridisation?
(a) CO2
(b) SO2
(1997, 1M)
(c) N2 O
(d) CO
(d) O2
2
(c) O2
(b) F2
(a) linear, sp
(c) tetrahedral, sp3
SO3 , NO3
CO2
3 , SO 3
(2001, 1M)
(2001, 1M)
are
(2002, 3M)
present in
(1997 C, 1M)
(1997 C, 1M)
Chemical Bonding 49
21. Among the following species, identify the isostructural pairs.
NF3 , NO3- ,
BF3 , H3 O , N3 H
(1996, 1M)
(1996, 1M)
(d) BF3
(c) PH3
24.
(b) 4
(1992, 1M)
(c) 3
is
(1992, 1M)
2
(a) sp
(c) sp
(b) sp
(d) None of these
(b) SO3
(c) CO2
3
(1989, 1M)
(d) NO3
(b) CN
(c) CO
(d) NO+
(1989, 1M)
(1988, 1M)
(1988, 1M)
(1988, 1M)
(c) CH+3
(d) SbH3
(1987, 1M)
(a) 1, 1-dichloroethylene
(b) cis-1, 2-dichloroethylene
(c) trans-1, 2-dichloroethylene
(d) None of the above
(b) sp3
(c) sp2
(b) sp-hybridised
(d) sp3-hybridised
(1981, 1M)
Objective Questions II
(One or more than one correct option)
38. The molecules that will have dipole moment are
(a) 2, 2-dimethyl propane
(c) cis-3-hexene
(1992, 1M)
(b) trans-2-pentene
(d) 2, 2, 3, 3-tetramethyl butane
(a) CN
(c) NO+
(b) O2
(d) CN+
(1992, 1M)
(1991, 1M)
(d) NCO
(c) NO+2
(b) CS2
(e) SO2
(a) HgCl 2
(1986, 1M)
(c) SnCl 2
(b) C2H2
(d) NO2
A.
1.
p-d p antibonding
B.
2.
d-d s bonding
C.
3.
p-dp bonding
D.
4.
d-d s antibonding
(1986, 1M)
(1986, 1M)
(d) ClO2
(d) dsp2
32. The bond between two identical non-metal atoms has a pair
of electrons
(1982, 1M)
(c) SO2
Column I
(b) NO2
(a) CO2
(a) SnCl 2
(a) PH3
(b) NO2
(d) SiO2
(a) CO2
(c) SO2
(1982, 1M)
(d) N+2
(c) O-2
(b) O+2
(a) CN-
(d) 1
(1984, 1M)
Codes
50 Chemical Bonding
(a)
(c)
4
2
3
3
2
1
1
4
(b)
(d)
1
4
2
1
3
2
4
3
1
(1985, M)
2
(2009)
ColumnII
(2014 Adv.)
A.
B2
p.
Paramagnetic
B.
N2
q.
Undergoes oxidation
C.
O-2
r.
Undergoes reduction
D.
O2
s.
Bond order 2
t.
Codes
(2013 Adv.)
A
(a) q, r, s
(b) p, q, r, t
(c) q, r, s, t
(d) p, q, s, t
B
C
p, r, t, s q, r, t
q, r, s, t p, q, r, t
p, q, r
r, s, t
p, q, s
p, t
D
p, q, t
p, r, s, t
p, q, r, t
q, r, t
Subjective Questions
62. Predict whether the following molecules are isostructural
(1997 C, 1M)
N+2 ,
O+2
(2010)
(1996, 1M)
(2005, 2M)
65. Using VSEPR theory, draw the shape of PCl 5 and BrF5 .
(1994, 1M)
(1990, 1M)
(1982, 1M)
(2000, 3M)
(1990, 1M)
(2003, 2M)
(1981, 1M)
True/False
53. The dipole moment of CH3 F is greater than that of CH3 Cl.
and NH3 .
H
H O H
(1993, 1M)
(1993, 1M)
(1990, 1M)
.
Lewis
dot
structure
(1987, 1M)
(1987, 1M)
H
H N H
.
Neutral molecule
(1983, 4M)
(i) O22
(ii) CO23
(iii) CN-
(iv) NCS-
(a) Be2
(b) B2
(c) C2
(d) N2
(2013 Main)
H+2 , He22
H22+ , He2
(b)
(d)
(2013 Main)
H -2 , He22H-2 , He2+
2
following orbitals?
(b) s - p
(2008, 3M)
(c) p - p
5. According to MO theory,
(a) O+2
(b) O+2
(c) O+2
(d) O+2
(d) p - p
(2004, 1M)
(2014 Adv.)
Objective Question II
(One or more than one correct option)
(2000, 1M)
(a) C 2
(c) O 2
(2013 Main)
(b) N 2
(d) S 2
. Statement II
O structure is
(1999, 2M)
(a) B > P = As = Bi
(b) B > P > As > Bi
(c) B < P = As = Bi
(d) B < P < As < Bi
(a)
< CO2 < CO
(b) CO2 < CO2
3 < CO
(c) CO < CO2
3 < CO 2
(d) CO < CO2 < CO32
O-2 O2 + O22 -
1.
Redox reaction
B.
CrO24 - + H+
2.
3.
Dimeric bridged
tetrahedral metal ion
4.
Disproportionation
C.
hydrogen bond?
(1983, 1M)
(a) Phenol
(c) Water
(d) HCl
D.
(1997, 1M)
10. Which one among the following does not have the
Column II
A.
(1999, 2M)
CO23-
(a) NH4Cl
(c) H2O2
MnO-4 + NO-2
+ H+
NO-3 + H2 SO4
+ Fe2+
Codes
A
(a) 2
(c) 2
B
1, 4
3
C
3
1
D
4
4
A
(b) 1, 4
(d) 3
B
3
4
C
1, 2
2, 3
D
1
1
52 Chemical Bonding
Subjective Questions
15. Write the MO electron distribution of O2 . Specify its bond order and magnetic property.
(2000, 3M)
(1991, 1M)
17. What effect should the following resonance of vinyl chloride have on its dipole moment?
(1987, 1M)
Topic 1
1. (b)
2. (a)
3. (a)
4. (b)
5. (b)
6. (b)
7. (a)
8. (a)
9. (c)
10. (c)
11. (b, d)
13. (2)
14. F
15. T
12. (c)
41. (a, b)
42. A 2; B 3; C 1; D 4
43. A p, q, r, t; B q, r, s, t; C p, q, r, t; D p, r, s, t
44. N 2O, I 3-
Topic 2
1. (b)
2. (d)
3. (a)
4. (a)
47. hyperconjugation
5. (d)
6. (d)
7. (b)
8. (a)
48. sp
9. (a)
10. (c)
11. (a)
12. (b)
52. CO2
53. F
13. (a)
14. (b)
15. (d)
16. (a)
54. F
55. F
56. F
57. F
17. (b)
18. (b)
19. (c)
20. (b)
58. T
59. (4)
60. (6)
61. (0)
21. (c)
22. (d)
23. (b)
24. (a)
25. (a)
26. (a)
27. (a)
28. (a)
29. (c)
30. (c)
31. (c)
32. (d)
33. (b)
34. (b)
35. (a)
36. (a)
37. (c)
38. (b, c)
39. (a, c)
40. (b, c, d)
50. sp 3
Topic 3
1. (c)
2. (b)
3. (c)
4. (b)
5. (a)
6. (d)
7. (b)
8. (a)
9. (c)
10. (d)
13. (a)
11. (a, b, d)
12. (a, b)
14. A 1, 4; B 3; C 1, 2; D 1
r2
1
r
2q r 4 q a
r6
r3
Superficially it seems as both ion-dipole interaction and
hydrogen bonding vary with the inverse cube of distance
between the molecules but when we look at the exact
expressions of field (force) created in two situations, it comes
as
2| P |
(In case of ion-dipole interaction)
| E | or | F | =
4 p r3
2
120
10. In KCN, the bonding between potassium ion and cyanide ion
and F =
4 p 0 r3
2.
[K] [ C N]
CC
H
Ionic bond
Cl H
Cl
C==C
H
Polar
m=0
Non-polar
H
C==C
C==C
H Cl
4. p-dichlorobenzene is non-polar.
Cl ClCH2
H
Cl
C2 H 5
Polar
Cl
p-dichlorobenzene
Cl
m1
Cl
(o-dichlorobenzene)
dipole vectors are at 60 angle
m2
Cl
(m-dichlorobenzene)
dipole vectors are at 120 angle
54 Chemical Bonding
18. I2 is Lewis acid because I - coordinate its one lone pair to I2 .
No unpaired electron-diamagnetic.
bonding electrons - antibonding electrons
Bond order =
2
6-4
=
=1
2
m = qd
q = 1.6 10-19 C and d = 2.6 10-10 m
Here,
-19
m Theo = 1.6 10
-10
2.6 10
-29
= 4.16 10
3.336 10-29
m obs
100 =
100
m Theo
4.16 10-29
= 80.2%
21. In hydrogen peroxide (H2 O2 ), oxygen is in 1 oxidation
state, can be oxidised to O2 (zero oxidation state) or can be
reduced to H2 O (2 oxidation state of oxygen). Hence, H2 O2
can act as both oxidising agent and reducing agent. With
strong oxidising agent like KMnO4 , H2 O2 acts as a reducing
agent while with strong reducing agent like H2 C2 O4 , it acts
as an oxidising agent.
22. (i) Melting points Ionic compounds have higher melting
points than covalent compounds.
(ii) Boiling points Ionic compounds have higher boiling
points than covalent compounds.
(iii) Solubility Ionic compounds have greater solubility in
water than a covalent compound.
(iv) Conductivity in aqueous solution Ionic compounds
have greater electrical conductivity in aqueous solution
while covalent compounds are usually non-conducting.
% ionic character =
I -3
always paramagnetic.
cm
XeF4 : F
FS==O
F
S is
sp3
hybridised
Pyramidal
S
F
F
I I
I3 :
F
7.
F
Xe
F
At central atom (Xe), there is one lone pair.
11. F B-
*
p2 p z
p 2 p z
SF4 : F
2.
Xe
of three.
+
14.
O==N==O,
ON==O,
sp2
sp
1
sp3 H
6
Chemical Bonding 55
16. H2 S has sp 3 hybridised sulphur, therefore, angular in shape
H
S
sp2-hybridised
H
(Non-linear, polar molecule)
F
17.
FB
F
sp2
(Trigonal planar)
S
O
O
Electron pair = 2 (s-bonds) + 1 (lone pair) = 3
Hybridisation = sp 2
Carbon in CO2 is sp-hybridised, N in N2 O is sp-hybridised,
carbon in CO is sp-hybridised.
O Cl == O
27.
*
Has one unpaired electron in p
2 p orbital.
24.
p 2 p 2y *
*
Cl
109
Cl
120
Cl
Cl
Cl
Cl
sp2-hybridised
sp3-hybridised
s 2 px0
*
2 p 2z
p
HC
H
sp2-hybridised
21. NF3 :
BF3 :
Triangular planar
(B-sp2)
Pyramidal
(N-sp3)
NO3
O
:
O==N
O
H 3O :
Triangular planar
(N-sp2)
N3 H
FB
dipole moment = 0
H
H
H
Pyramidal
(O-sp3)
N == N == N H
O == S == O
Electron pairs at S = 2 (s-bonds) + 1 (lone-pair) = 3
sp 2 hybridised.
NOTE
p-bonded electrons are not present in hybrid orbitals, therefore not
counted in electron pairs. Rather p bonds are formed by lateral
overlapping of pure p-orbitals.
56 Chemical Bonding
32. Bonds between identical non-metal is purely covalent due to
same electronegativities of the bonded atoms. Hence, the
bonded atoms have equal holds on the shared pair of
electrons.
Any orbital has two phase +ve and ve. In the following
diagram, +ve phase is shown by darkening the lobes and ve by
without darkening the lobes.
Bonding MO
Antibonding MO
Cl
s-bond
Cl
Cl
Net dipole = 0
Cl
p-bond
C (6e ) + N (7e ) + e
CN (14 e )
38. H3 C C CH3
C== C
CH2 CH3
H
CH3
Polar
A.
d-d s bonding
B.
p-d p bonding
C.
p-d p antibonding
D.
d-d s antibonding
Symmetric, non-polar
CH2 CH3
CH3 H2 C
C== C
H
Polar
-
CH3 CH3
H3 C C C CH3
CH3 CH3
Symmetric, non-polar
Linear
Sn
S
Cl
Bent
O C N
Linear
Cl
O== N==O
O
Bent
\ A 2, B 3, C 1, D 4
Hence, (c) is the correct option.
+ ve phase
p2 p1y
p 2 p1z
6-4
=1
2
Bond is formed by mixing of s and p orbitals.
B2 undergoes both oxidation and reduction as
Bond order =
Heat
ve phase
paramagnetic.
B2 + O2 B2 O3
(Oxidation)
B2 + H2 B2 H6
(Reduction)
Chemical Bonding 57
*
*
(B) N2 : s1s2 s
1s2 s2 s2 s
2 s2 s2 px2
p2 p 2y
p 2 p 2z
diamagnetic.
10 - 4
=3>2
2
N2 undergoes both oxidation and reduction as
p-orbitals in hybridisation.
Bond order =
D
N2 + O2
NO
Catalyst
N2 + 3H2 NH3
In N2 , bonds are formed by mixing of s and p orbitals.
-
*
*
(C) O2 : s1s2 s
1s2 s2 s2 s
2 s2 s2 px2
*
p2 p 2y p
2 p 2y
*
2 px0
s
*
p 2 p 2z p
2 p1z
Xe
F
Br
O2
2 *
s2 px2
*
2 p1y
p2 p 2y p
p 2 p 2z
F
2
2+
H3N
NH3
Cl
NH3
Cl
Cu
s 2 px0
*
Cl
Pt
H3N
Cl
*
2 p1z
p
F
F
N+2
60.
F
F
61.
Br
O
H
V-shaped
NH2
NH2
55. Explained in 2.
H 2N
58 Chemical Bonding
62. No, (i) NMe3 is pyramidal while (ii) N(SiMe3 )3 is planar. In
1.
64.
65. Cl
*
*
s1s, s1s, s2s, s 2s, s2 p z , p2 px p2 p y ,
Trigonal bipyramidal
Square planar
Cl
*
*
*
p 2 px p 2 p y , s 2 p z
Cl
*
*
(a) Be2 s1s2 , s1s2 , s2s2 , s 2s2 (diamagnetic)
Br
Trigonal bipyramidal
(P is sp3d-hybridised)
*
*
p2 px0
(b) B2 s1s2 , s1s2 , s2s2 , s 2s2 , s2 p 2z ,
p2 p 0y
Cl
Cl
Xe
Square pyramidal
(Br is sp3d 2 -hybridised)
F
Xe
Xe
Xe
66.
F
F
F
Square planar
Linear
(diamagnetic)
1
p
p
2
*
*
x,
(c) C2 s1s2 , s1s2 , s2s2 , s 2s2 , s2 p 2z ,
p2 p1y
* 0
p 2 px * 0
, s 2 p z (paramagnetic)
* 0
*
* p2 p
p2 px2
(d) N2 s1s2 , s1s2 , s2s2 , s 2s2 , sy 2 p 2z ,
,
p2 p 2y
* 0
p 2 px
See-saw shaped
68.
F O F
-1
O
V-shaped
3-2 1
= = 0.5
2
2
Li 2 (3 + 3 + 1 = 7 ) = s1s2 , s* 1s2 , s2s2 s* 2s1
Bond order =
Electron pair = P = 2 + 2 = 4
Hybridisation = sp 3
2-
and
2(ii) CO3 :
C
O O
(iii) CN - : C N
(iv) NCS- : S
Cl Cl
F B F (BF3 )
C O
and
-
Bond order =
4-3 1
= = 0.5
2
2
(Cl 2 )
2-
and
F-1
, s * 2 p 0z (diamagnetic)
Nb - Na 4 - 2
=
=1
2
2
Li +2 ( 3 + 3 - 1 = 5 ) = s1s2 , s* 1s2 , s2s1
+2
* 0
p2 py
(CO)
N and Cl C N (ClCN)
0
H2+
2 (1 + 1 - 2 = 0 ) = s1s
Bond order = 0
* 1s2
He2 ( 2 + 2 = 4 ) = s1s2 , s
N - Na 2 - 2
Bond order = b
=
=0
2
2
So, both H2+
2 and He 2 do not exist.
Chemical Bonding 59
4. C2 ( 6 + 6 = 12 ) = s1s2 , s* 1s2 , s2s2 , s* 2s2 , p2 px2 p2 p 2y
10. H2 O2
5.
H C CH == CH2 H C == CH CH2
+
H
H
(II)
(I)
*
2 p1y
p2 p 2y p
p 2 p 2z
*
2 px0
s
*
2 p 0z
p
10 - 5
= 2.5; paramagnetic.
2
* 2
*
O2 (16e- ) : s1s2 s
1s s2s2 s
2s2 s2 px2
*
2 p1y
p2 p 2y p
p 2 p 2z
10 - 6
=2
2
Hence, (a) is the correct answer.
7.
F
F
See-saw shape
molecule
12.
O
-O
O-
p 2 p1z
*
Cr
O
O
O
F
Xe
C
F
polar bond
Non-polar bond
OO
H
*
2 px
s
Bond order =
F
F
Tetrahedral
Square planar
Bond order =
*
2 p1y
p2 p 2y p
p 2 p 2z
*
2 p1z
p
10 - 6
= 2, paramagnetic.
2
CHAPTER TEST
2. XeF4
4. ICl -4
(a) 1, 2 and 4
(c) 3 and 4
(b) 2 and 3
(d) 2 and 4
NO+2 ,
NO -3
(b) NO -3 ,
NO -2 ,
NO +2
(c) NO +2 ,
NO 2, NO -2
(d) NO -2 ,
NO -3 ,
NO +2
same plane?
(a) SO 23
(b) SO 3
(c) SO 24
(b) SO 3
(c) SO 24
(d) SO 23 and SO 3
Assertion-Reason Type
(b) 4
(d) 6
(a) Both Assertion and Reason are correct and Reason is the
correct explanation of Assertion
(b) Both Assertion and Reason are correct but Reason is not
the correct explanation of Assertion
(c) Assertion is correct but Reason is incorrect
(d) Assertion is incorrect but Reason is correct
(c) NO
(b) SrCO 3
(d) CuCO 3
(b) O -2
10. Which of the following will have the atoms lying in the
(a) O +2
(a) Na 2CO 3
(c) BaCO 3
(b) SO 3
(c) SO 24
(b) C
(d) O
(a) 3
(c) 5
(a) SO 23
(a) SO 23
(a) F
(c) N
Column II
A.
XeO2F2
p.
Polar
B.
XeF4
q.
Non-polar
C.
AsF5
r.
Planar
D.
SOCl2
s.
Non-planar
15. In the molecule SOF4, how many two fold axis of symmetry
is(are) present?
Answers
1.
11.
(a)
(a)
2.
12.
(d)
(b)
3.
13.
(d)
(a)
4.
14.
(d)
5. (d)
6. (a,b,c,d)
A p,s; B q,r; C q,s; D p,s
7. (a,c,d)
15. (1)
8. (b,c,d)
16. (4)
9.
(b)
10.
(b)