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CHAPTER

I Group 15 Elements : The Nitrogen Family


1. In group 15 of the Periodic Table, the elements,
nitrogen (7N), phosphorus (15P), arsenic (33As),
antimony (51Sb) and bismuth (83Bi) are present.
2. (a) The elements of this group can exhibit
various oxidation states ranging between
3 to + 5.
(b) Maximum covalency of Nitrogen is four
because it does not have d- orbitals to expand
its covalency.
3. The atomic (covalent) and ionic radii (in a
particular oxidation state) of the elements of
nitrogen family (group 15) are smaller than the
corresponding elements of carbon family (group
14).
There is a considerable increase in covalent
radius from N to P. However, from As to Bi, only
a small increase is observed.
4. Nitrogen displays a great tendency to form
pp pp multiple bonds with itself as well as with
carbon and oxygen. The tendency to exhibit
pp pp multiple bonding decreases as we move
down the group.
5. Group 15 elements are more electronegative than
group 14 elements. Electronegativity decreases
on moving down the group from N to Bi.
6. All elements of group 15 form gaseous hydrides
of the type MH3.
(a) Th e basic str ength of the hydrides
decreases as we down the group. Thus, NH3
is the strongest base.
NH3 > PH3 > AsH3 > SbH3
(b) The thermal stability of the hydrides
decreases as the atomic size increases,.
7. N cannot form NX5 because of non-availability
of d-orbitals. Bi cannot form a BiX5 because of

reluctance of 6s electrons of Bi to participate in


bond formation.
8. Nitrogen forms a number of oxides. The rest of
the members (P, As, Sb and Bi) of the group form
two types of oxides: E2O3 and E2O5.
II Group 16 Elements
9.
In group 16 of the Periodic Table, elements,
oxygen (8O), sulphur (16S), selenium (34Se),
tellurium (52Te) and polonium (84Po) are present.
10. The elements have the electronic configuration
ns2np4 for their valence shells. The first element
of the group 16 differs in its chemical behaviour
from that of other members of the group due to
its small size and high electronegativity.
11. The metallic character increases with increase in
atomic number. The first four elements are nonmetallic in character. Non-metallic character is
strongest in O and S, weaker in Se and Te while
Po is metallic.
12. Atomic and ionic radii increases from top to
bottom, due to increase in the number of shells.
13. Ionisation enthalpy decreases down the group,
due to increase in size. Elements of group 16 have
lower ionisation enthalpy values as compared to
group 15 in the corresponding periods. This is
due to the fact that group 15 elements have extra
stable half-filled p-orbital electronic
configurations.
14. Oxygen has less negative electron gain enthalpy
than sulphur due to compact nature of oxygen
atom.
15. Next to F, O has highest electronegativity value
among the elements. Within the group,
electronegativity decreases with increase in
atomic number.

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16. The tendency for catenation decreases as we go
down the group.
17. All the elements of the group form volatile
hydrides.
(a) The volatility increases from water to
hydrogen sulphide and then declines.
This is evident in their boiling point.
Increasing order of boiling points of
hydrides is H2S < H2Se < H2Te < H2O. Down
the group boiling point increases because
of increase in molecular weight which
increases the van der Waals forces of
interaction. H2O has abnormally high b.p.
due to hydrogen bonding.
(b) The thermal stability of the hydrides
decreases in the order:
H2O > H2S > H2Se > H2Te > H2Po.
(c) The strength of the hydrides as acids
increases in the order:
H2O < H2S < H2Se < H2Te.
18. All the elements of group 16 form binary halides.
19. (a) S, Se and Te form a number of oxo-acids.
Among the oxo-acids of S, sulphuric acid is
most important.
(b) Sulphurous acid (H2SO3) and thiosulfuric
acid (H2S2O3) are unstable and cannot be
isolated. They exist only in aqueous
solutions or in the form of their salts.
III Group 17 Elements
20. The group 17 of the Periodic Table contain
fluorine (9F), chlorine (17Cl), bromine (35Br), iodine
(53I) and astatine (55At).
21. Electronic configuration is ns2 np5 for valence
shells.
22. Halogens have the smallest atomic radii in their
respective periods due to maximum effective
nuclear charge.

23. The first ionisation energies are relatively high


but decreases down the group. Iodine can lose
an electron and form I+ ion.
24. Electron affinity varies as Cl > F > Br > I
25. F is the most electronegative element known.
Electronegativity decreases down the group.
26. Halogens are good oxidising agents. The
oxidising power decreases down the group.
27. (a) Reactivity varies as F2 > Cl2 > Br2 > I2
(b) Order of ionic character in M X bond is
M F > M Cl > M Br > M I
28. Strength of hydrohalic acids varies as:
HF < HCl < HBr < HI
The order of B.P is HCl < HBr < HI < HF
29. (a) Hypohalous acids are all weak acids and
exist in solution only. Acid strength
decreases down the group.
HOCl > HOBr > HOl
(b) Acid strength increases as the number of
O-atoms increases for a given halogen atom.
HOCl < HClO2 < HClO3 < HClO4
IV Group 18 Elements : The Noble Gases
30. In group 18 of the Periodic table, elements helium
(2He), neon (10Ne), argon (18Ar), krypton (36Kr),
xenon (54Xe) and radon (86Rn) are present. They
are collectively called as noble gases.
31. Noble gases are located at the end of each period.
Their valence shell orbitals are fully occupied.
32. They are monoatomic and are sparingly soluble
in water.
33. Xe forms fluorides XeF2, XeF4 and XeF6.
34. XeO3 is trigonal pyramidal in shape whereas
XeOF4 is square pyramidal.
35. Uses:
(a) He is a non-inflammable gas, lighter than air,
therefore, used in filling balloons for
meteorological observations.
(b) Ar is used to provide an inert atmosphere.

7.1. Why are pentahalides more covalent than


trihalides ?
Ans. The group 15 elements have 5e1s in their valence
shell. It is difficult to lose 3e1s to form E3+ and
even more difficult to lose 5e1s to form E5+.
Thus, they have very little tendency to form ionic
compounds. Further, since the elements in +5
state have less tendency to lose e1s than in the

+3 state, elements in +5 state have more tendency


to share e1s and hence pentahalides are more
covalent than trihalides.
7.2. Why is BiH3 the strongest reducing agent
amongst all the hydrides of Group 15 elements?
Ans. This is because as we move down the group, the
size increases, as a result, length of EH bond
increases and its strength decreases, so that the

7.3.
Ans.

7.4.
Ans.

bond can be broken easily to release H2 gas.


Hence, BiH3 is the strongest reducing agent.
Why is N2 less reactive at room temperature?
Due to presence of triple bond between two
N-atoms (N N), the bond dissociation energy
of N2 is very high. As a result, N2 becomes less
reactive at room temperature.
Mention the conditions required to maximise
the yield of ammonia.
Ammonia is prepared by Haber's process as given
below :
5

N2(g) + 3H2(g)

700 K, 200 10 Pa
Fe2O3 + K2 O + Al2O3
Mo (promoter)

2NH3(g)

tetrammine copper
(II) ion (deep blue)

+ 4H2O
7.6. What is the covalence of nitrogen in N2O5 ?
Ans. In N2O5, each N-atom has four shared pairs of e1s
as shown:
O

O
N

PH 3
Phosphine

3NaHPO2
sod. hypo-phosphite
7.9. What happens when PCl5 is heated?
D
Ans. PCl5
PCl3 + Cl2
On heating, the less stable axial bonds break to
form PCl3.
7.10. Write a balanced equation for the hydrolytic
reaction of PCl5 in heavy water

POCl3 + 3D2 O
D3PO4 + 3DCl
PCl5 + 4D 2O
D3PO 4 + 5DCl
7.11. What is the basicity of H3PO4?
Ans. H3PO4 is tribasic as shown below :

O
Due to three ionizable POH

Ans. Cu2+(aq) + 4NH4OH(aq) [Cu(NH3 ) 4 ]2+

N O N

CO2atm

Ans. PCl5 + D 2O
POCl3 + 2DCl

DfH = 92.4 kJ mol1


According to Le Chatelier's principle, to maximise
the yield of ammonia, high P and
T ~ 700 K should be used. The catalyst increases
the rate of reaction and Mo promoter increases
the efficiency of Fe catalyst.
7.5. How does ammonia react with a solution of
Cu2+?

Ans. P4 + 3NaOH + 3H2O

O
O
O
O
Thus, the covalency of N is 4.
7.7. Bond angle in PH4+ is higher than that in PH3 .
Why?
Ans. P in PH3 is sp3hybridized with 3 bond pairs and
one lone pair around P. Due to stronger lpbp
repulsions than bpbp repulsions, tetrahedral
angle decreases from 10928' to 93.6. As a result,
PH3 is pyramidal.
In PH4+, there are 4 bp's and no lone pair. As a
result, there are only identical bpbp repulsions
so that PH4+ assumes tetrahedral geometry and
the bond angle is 10928'.
Hence, bond angle of PH4+ > bond angle of PH3
7.8. What happens when white phosphorus is heated
with concentrated NaOH solution in an inert
atmosphere of CO2 ?

HO

OH
OH

bonds, H3PO4 is tribasic.


H3PO4 + H 2 O H3O+ + H 2PO 4H 2 PO-4 + H 2 O H3O+ + HPO42 HPO 24- + H 2 O H3O+ + PO347.12. What happens when H3PO3 is heated?
Ans. On heating, H3PO3 disproportionates to form
PH3 and H3PO4 with O.S. of 3 and + 5.
+3

H3 PO3
Orthophosphorous
acid

PH3
Phosphine

+5

H3 PO4
Orthophosphoric
acid

7.13. List the important sources of sulphur.


Ans. Sulphur mainly occurs in the combined states in
earth's crust in the form of sulphates and
sulphides.
Sulphates : gypsum (CaSO4 .2H2 O); epsom
(MgSO4.7H2O); baryte (BaSO4), etc.
Sulphides : Galena (PbS); zinc blende (ZnS);
copper pyrites (CuFeS2); iron pyrites (FeS2), etc.
Traces of sulphur occur as H2S and in organic
materials such as eggs, proteins, garlic, onion,
mustard, hair and wool.

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7.14. Write the order of thermal stability of the
hydrides of Group 16 elements.
Ans. The thermal stability of hydrides of group 16
elements decreases down the group. This is
because down the group, size of the element (M)
increases, M-H bond length increases and thus,
stability of M-H bond decreases so that it can
be broken down easily. Hence, we have order of
thermal stability as
H2O > H2S > H2Se > H2Te > H2Po
7.15. Why is H2O a liquid and H2S a gas ?
Ans. Due to high electronegativity of O than S, H2O
undergoes extensive intermolecular H-bonding.
As a result, H2O exists as an associated molecule
in which each O is tetrahedrally surrounded by
four H2O molecules. Therefore, H2O is a liquid at
room temperature.
On the other hand, H2S does not undergo Hbonding. It exists as discrete molecules which
are held together by weak van der waals forces
of attraction. A small amount of energy is
required to break these forces of attraction.
Therefore, H2S is a gas at room temperature.
7.16. Which of the following does not react with
oxygen directly?
Zn, Ti, Pt, Fe
Ans. Pt being a noble metal does not react with oxygen
directly. In contrast, Zn, Ti and Fe are active
metals and hence they react with oxygen directly
to form their oxides.
7.17. Complete the following reactions:
(i) C2H4 + O2
(ii) 4Al + 3 O2
Heat
Ans. (i) C2 H 4 + 3O 2
2CO 2 + 2H 2O
Heat

(ii) 4Al + 3O2


2Al2 O3
7.18. Why does O3 act as a powerful oxidising agent?
Ans. On heating, O3 readily decomposes to give O2
and nascent oxygen.
Heat

O3
O2 + O(nascent oxygen)
Since nascent oxygen is very reactive, therefore,
O3 acts as a powerful oxidising agent.
7.19. How is O3 estimated quantitatively?
Ans. When O3 is treated with excess of KI solution
buffered with borate buffer (pH = 9.2), I2 is
liberated quantitatively.
2I(aq) + H2O(l) + O3(g) 2OH(aq) + I2(s)
+ O2(g)
The I2 thus liberated is titrated against a standard
solution of sodium thiosulphate using starch as
an indicator.
2Na 2S2O3 + I2
Na 2S4O6 + 2NaI

7.20. What happens when sulphur dioxide is passed


through an aqueous solution of Fe(III) salt?
Ans. SO2 acts as a reducing agent and reduces
aqueous solution of Fe (III)salt to Fe (II) salt.
SO 2 + 2H 2 O
SO24 - + 4H + + 2e 2Fe3+ + 2e -
2Fe 2 +

2Fe3+ + SO2 + 2H2O


2Fe2+ + SO24- + 4H+
7.21. Comment on the nature of two SO bonds formed
in SO2 molecule. Are the two SO bonds in this
molecule equal ?
Ans. SO2 exists as an angular molecule with OSO bond
angle of 119.5. It a resonance hybrid of two
canonical forms :

S
O

S
O

Due to resonance, the two p-bonds are equal.


7.22. How is the presence of SO2 detected ?
Ans. SO2 is a pungent smelling gas. It can be detected
by two test :
(i) SO2 turns pink colour of KMnO4 to colourless
due to reduction of MnO4 to Mn2+
2MnO 4 + 5SO2 + 2H2O 2Mn 2+
(Pink)

(colourless)

5SO42 + 4H+
(ii) It turns orange colour of acidified K2Cr2O7 to
green due to reduction of Cr2O72 to Cr3+
Cr2 O27- +3SO2 +2H + 2Cr 3+ + 3SO42 +
(orange)

(green)

H2O
7.23. Mention three areas in which H2SO4 plays an
important role.
Ans. (i) It is used in the manufacture of fertilizers such
as (NH4)2SO4, calcium superphosphate.
(ii) It is used as an electrolyte in storage
batteries.
(iii) It is used in petroleum refining, detergent
industry and in the manufacture of paints,
pigments and dyes.
7.24. Write the conditions to maximise the yield of
H2SO4 by Contact process.
Ans. The main step in the production of H2SO4 is :
SO2 ( g ) + O2 ( g ) 2SO3 ( g );
D f H = -196.6kJmol-1
The reaction is exothermic, reversible and
forward reaction proceeds with decrease in

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volume. According to Le-Chateliers' principle, to
maximise the yield of SO3 and hence H2SO4, a
low T, a high pressure and V2O5 is used as a
catalyst.
7.25. Why is Ka << Ka for H2SO4 in water ?
1
2
Ans. Being a dibasic acid, H2SO4 ionized in two stages
as follows:
H 2SO 4 (aq ) + H 2 O(l ) H3 O+ (aq ) + HSO4- (aq)
Ka > 10
1

H3O + ( aq) + SO 42- ( aq)


HSO -4 (aq) + H 2 O(l )
Ka = 1.2 102
2
Ka << Ka because negatively charged HSO4
1
2
has much less tendency to donate a proton to
H2O as compared to neutral H2SO4.
7.26. Considering the parameters such as bond
dissociation enthalpy, electron gain enthalpy
and hydration enthalpy, compare the oxidising
power of F2 and Cl2.
Ans. F2 is a much stronger oxidising agent than Cl2.
The oxidising power of a species depends upon
the electrode potential. Higher is the electrode
potential value, greater is the oxidising power.
Electrode potential, in turn, depends upon 3
factors :
(i) bond dissociation energy (BDE)
(ii) electron gain enthalpy (EGE)
(iii) hydration energy (HE)
Although the EGE of fluorine is less negative
than that of chlorine, the BDE of F2 is much lower
than that of Cl2 but HE of F ion is much higher
than that of Cl ion. It compensates the effect of
other two (BDE and EGE). As a result, the
electrode potential of F2 is higher than that of
Cl2 and hence F2 is a much stronger oxidising
agent than Cl2.
7.27. Give two examples to show the anomalous
behaviour of fluorine.
Ans. Two examples to show the anomalous behaviour
of fluorine are :
(i) Due to non-availability of d-orbitals in its
valence shell, fluorine cannot expand its
octet and thus it shows only 1 O.S. On the
other hand, other halogens due to presence
of d-orbitals show positive O.S. of +1, +3,
+5 and +7 besides O.S. of 1.
(ii) Due to its small size, the three lone pair of
e1s on each F-atom in FF molecule, repel
the bond pair. As a result, FF BDE is lower
than that of ClCl bond.

7.28. Sea is the greatest source of some halogens.


Comment.
Ans. Sea water contains Cl, Br and I of Na, K, Mg
and Ca, but mainly NaCl. Dried up sea beds
contain NaCl and carnallite, KCl. MgCl2.6H2O.
Certain seaweeds contain upto 0.5% of iodine
as NaI and chile saltpetre (NaNO3) contains upto
0.2% of NaIO3. Thus, sea is a great source of
halogens.
7.29. Give the reason for bleaching action of Cl2.
Ans. In presence of moisture or in aqueous solution,
Cl2 liberates nascent oxygen.
Cl 2 + H 2O
2HCl + [O]
nascent oxygen

This nascent oxygen brings about the oxidation


of coloured substance to colourless substances.
Coloured Substances + O Colourless
substance
Thus, the bleaching action of Cl 2 is due to
oxidation.
7.30. Name two poisonous gases which can be prepared
from chlorine gas.
Ans. Phosgene and mustard gas are two poisonous
gases which can be prepared from Cl2.
(i)
(ii)

hv
charcoal

CO + Cl 2
COCl 2
S8
(boiling)

Phosgene

+ 4Cl2

CH2

4S2 Cl 2
sulphur monochloride

CH2Cl

CH2Cl

+ S2Cl2
CH2

+ S
CH2 S CH2
Mustard gas

7.31. Why is ICl more reactive than I2?


Ans. ICl is more reactive than I2 because ICl bond is
weaker than II bond. Consequently, ICl breaks
easily to form halogen atoms which readily bring
about the reactions.
7.32. Why is helium used in diving apparatus?
Ans. Because of its low solubility (as compared to
N2) in blood, a mixture of oxygen and helium is
used in diving apparatus used by deep sea divers.
7.33. Balance the following equation:
XeF6 + H2O XeO2F2 + HF.
Ans. XeF6 + 2H 2 O
XeO 2 F2 + 4HF
7.34. Why has it been difficult to study the chemistry
of radon?
Ans. Because radon is a radioactive element with a
short half life of 3.82 days. This makes the study
of chemistry of radon difficult.

E X E R C I S E S
7.1 Discuss the general characteristics of Group
15 elements with reference to their electronic
configuration, oxidation state, atomic size,
ionisation enthalpy and electronegativity.
Sol. In group 15 of the Periodic Table, the elements,
nitrogen (7N), phosphorus (15P), arsenic (33As),
antimony (51Sb) and bismuth (83Bi) are present.
The elements of this group can exhibit various
oxidation states ranging between 3 to + 5.
Negative oxidation state will be exhibited when
they combine with less electronegative element
and positive oxidation state will be exhibited with
more electronegative element. Positive oxidation
state becomes more favourable as we more down
the group due to increasing metallic character &
electropositivity. Although due to inert pair effect
the stability of +5 state will also decrease. The
only stable compound of Bi (V) is BiF5.
The atomic (covalent) and ionic radii (in a
particular oxidation state) of the elements of
nitrogen family (group 15) are smaller than the
corresponding elements of carbon family (group
14). On moving down the group, the covalent
and ionic radii (in a particular oxidation state)
increase with increase in atomic number. There
is a considerable increase in covalent radius from
N to P. However, from As to Bi, only a small
increase is observed.
As the size increases on moving down the group,
the ionisation enthalpy increases. The ionisation
enthalpy of nitrogen group elements is more than
the corresponding elements of oxygen group.
This is because of more stable half filled
outermost p- subshell of nitrogen group
elements. Electronegativity decreases down the
group with increase in atomic size.
7.2 Why does the reactivity of nitrogen differ from
phosphorus?
Sol. N2 exist as a diatomic molecule containing triple
bond between two N-atoms. Due to the presence
of triple bond between the two N-atoms, the bond
dissociation energy is large (9414 kJ mol1). As
a result of this, N2 is inert and unreactive whereas,
phosphorus exists as a tetratomic molecule,
containg P P single bond. Due to the presence

of single bond, the bond dissociation energy is


weaker (213 kJmol1) than N N triple bond
(941 4 kJ mol1) and moreover due to presence
of angular strain in P4 tetrahedra. As a result of
this, phosphorus is much more reactive than
nitrogen.
7.3 Discuss the trends in chemical reactivity of
group 15 elements.
Sol. Hydrides : All elements of group 15 form gaseous
hydrides of the type MH3.
In all the hydrides the central atom is sp 3
hybridized and their shape is pyramidal due to
presence of lone pair of electrons.
(a) Th e basic str ength of the hydrides
decreases as we move down the group.
Thus, NH3 is the strongest base.
NH3 > PH3 > AsH3 > SbH3
(b) The thermal stability of the hydrides
decreases as the atomic size increases, i.e.,
the M H bond strength decreases which
means reducing character increases.
(c) In the liquid state, the molecules of NH3 are
associated due to hydrogen bonding. The
molecules of other hydrides ar e not
associated.
(d) NH3 is soluble in water whereas other
hydrides are insoluble.
(e) All the hydrides, except NH3, are strong
reducing agents and react with metal ions
(Ag +, Cu 2+ , etc.) to form phosphides,
arsenides or antimonides.
Halides : The elements of group 15 form two
series of halides MX3 and MX5.
(a) All the elements of the group form trihalides.
The ionic character of trihalides increases
as we move down the group. Except NCl3
all the trihalides are hydrolysed by water.
This is due to the absence of d-orbitals in
nitrogen.
(b) PF3 is not hydrolysed because fluorine
being more electronegative than oxygen
forms more stable bonds with phosphorus
than P O bonds.
(c) N cannot form NX 5 because of nonavailability of d-orbitals. Bi cannot form BiX5
because of reluctance of 6s electrons of Bi
to participate in bond formation.

N2 (g) + 3H2 (g)


2NH3 (g)
D

D f H = -46.1kJ mol-1

* iron oxide, K2O, Al2O3


The optimum conditions for the production of
NH3 are pressure of 200 atm and temperature of
100 K.
7.7 Illustrate how copper metal can give different
products on reaction with HNO3.
Sol. On heating with dil HNO3, copper gives copper
nitrate and nitric oxide.
Heat
3Cu + 8HNO3 (dil)

3Cu (NO3)2 + 4H2O + 2NO


With concentrated HNO3, copper gives NO2
instead of NO.
Heat
Cu + 4HNO3(conc.)

Cu(NO3)2 + 2H2O + 2NO2


7.8 Give the resonating structures of NO2 and N2O5.
Sol. Resonating structures of NO2 are:

..

..

..

..

..

..

..

..

..

..

..
..

..
..

..

..
..

..

..
..

..

..
..

..

O..

..

..
..

..

O
O N
N
+
+
O
O..
..

..

O
ON
N
+ O
+
O
.

O.

..
..

O
ON
N
O.. +
+ O
O

---H

Phosphorus have an electronegativity value 21.


Thus, P H bond is not polar and hence PH3
does not undergo H bonding.
7.5 How is nitrogen prepared in the laboratory?
Write the chemical equations of the reactions
involved.
Sol. In laboratory, nitrogen is prepared by heating an
equimolar aqueous solution of ammonium
chloride and sodium nitrite. As a result of double
decomposition reaction, ammonium nitrite is
formed. Ammonium nitrite is unstable and
decompose to form nitrogen gas.

NH4Cl (aq) + NaNO2 (aq)


NH4NO2 (aq) + NaCl (aq)
Heat
NH4NO2 (aq)
N2 (g) + 2H2O (l)

..

..

Resonating structures of N2O5 are:

H
H
d
d
d
- - - H N- - - H N - - - H N- - - ---H

.
N
+
O
O
..

..

..
..

.
.O
O
..

PCl3 + Cl2
PCl5
Oxides :
(a) Nitrogen forms a number of oxides. The rest
of the members (P, As, Sb and Bi) of the
group form two types of oxides: E2O3 and
E2O5.
(b) The reluctance of P, As, Sb and Bi to enter
into pp pp multiple bonding leads to cage
structures of their oxides and they exist as
dimers, E4O6 and E5O10.
(c) The basic nature of the oxides increases
with increase in atomic number of the
element. Thus, the oxides of nitrogen (except
N2O and NO), P (III) and As (III) are acidic,
Sb (III) oxide is amphoteric and Bi (III) oxide
is basic.
7.4 Why does NH3 form hydrogen bond but PH3 does
not?
Sol. Nitrogen has an electronegativity value 30,
which is much higher than that of H (21). As a
result, N H bond is quite polar and hence NH3
undergoes intermolecular H bonding.

7.6 How is ammonia manufactured industrially?


Sol. Commercially, by Habers process.

(d) The hybridisation of M in MX3 is


and
shape is pyramidal. M in MX5 is sp3d as
hybridised and shape is trigonal pyramidal.
The axial bonds in MX5 are weaker and
longer, So MX 5 are less stable and
decompose on heating eg:

..
..

sp3

7.9 The HNH angle value is higher than HPH, HAsH


and HSbH angles. Why?
[Hint : Can be explained on the basis of sp3
hybridisation in NH3 and only s-p bonding
between hydrogen and other elements of the
group].
Sol. In all these cases, the central atom is sp 3
hybridized. Three of the four sp3 orbitals form
three s-bonds, while the fourth contains the
lone pair of electrons. On moving down from N
to Sb, the electronegativity of the central atom
goes on decreasing. As a result of this, bond
pairs of electrons lie away and away from the
central atom. This is because of the force of
repulsion between the adjacent bond pairs goes

8
on decreasing and the bond angles keep on
decreasing from NH3 to SbH3. Thus, bond
angles are in the order:
HNH
>
(107 8)

HPH
(93 6)

>

HAsH
(91 8)

>

HSbH
(91 3)

7.10 Why does R3P = O exist but R3N = O does not


(R = alkyl group)?
Sol. Nitrogen does not contains d-orbitals. As a result,
it cannot expand its covalency beyond four and
cannot form pp dp multiple bonds. In
constrast, P contains the d-orbitals, and can
expand its covalency beyond 4 and can form
pp dp multiple bonds.
Hence R3P = O exist but R3N = O does not.
7.11 Explain why NH3 is basic while BiH3 is only
feebly basic.
Sol. In both NH3 and BiH3, N and Bi have a lone pair
of electrons on the central atom and hence

should behave as Lewis bases. But NH3 is much


more basic than BiH3. Since the atomic size of N
is much smaller than that of Bi, therefore, electron
density on N-atom is much higher than that on
Bi-atom. Thus, the tendency of N in NH3 to
donate its lone pair of electrons is much more in
comparison to tendency of Bi in BiH3. Hence,
NH3 is more basic than BiH3.
7.12 Nitrogen exists as diatomic molecule and
phosphorus as P4. Why?
Sol. Nitrogen exists as a diatomic molecule having a
triple bond between the two N-atoms. This is
due its small size that it forms pp pp multiple
bonds with itself and with carbon /oxygen as
well. On the other hand, phosphorus due to its
larger size does not form multiple pp pp bonds
with itself. It prefers to form P P single bonds
and hence it exists as tetrahedral P4 molecule.

7.13 Write main differences between the properties of white phosphorus and red phosphorus.
Sol.
Property

White Phosphorus

Red Phosphorus

(i)

State

Translucent

Brittle, substance

(ii)

Colour

White gets yellowish on


exposure to light

Red

(iii)

Odour

Garlic like odour

Odourless

(iv)

Hardness

Soft like wax and can be


cut by knife

Hard

(v)

Poisonous nature

Poisonous

Non- poisonous

(vi)

Solubility

Soluble in CS2

Insoluble in CS2

(vii)

Chemiluminescence

Glows in dark

Dose not glow in dark.

(viii)

Density

1.8

2.1

(ix)

Reactivity

Very reactive

Less reactive

(x)

Action of oxygen

Burns with greenish


glow to form P4O10

Combines with O2 only


on heating to form
P4O10

9
Structure of white and red phosphorus are given
below:
P
60
P

P
P

(i) Structure of white phosphorus


P

(ii) Structure of red phosphorus

7.14 Why does nitrogen show catenation properties


less than phosphorus?
Sol. The extent of catenation depends upon the
strength of the element element bond. The
N N bond strength (159 kJ mol1) is weaker
than P P bond strength (213 kJ mol1). Thus,
nitrogen shows less catenation properties than
phosphorus.
7.15 Give the disproportionation reaction of H3PO3.
Sol. On heating, H3PO4 undergoes self - oxidation
reduction, i.e., disproportionation to form PH3.
+3

+5

4H3 PO3 PH3 + 3H3 PO4


Phosphorus acid

Phosphine

Orthophosphoric
acid

7.16 Can PCl5 act as an oxidising as well as a


reducing agent. Justify.
Sol. The oxidation state of P in PCl5 is + 5. Since P has
five electrons in its valence shell, therefore, it
cannot donate electron and cannot increase its
oxidation state beyond + 5, Thus, PCl5 cannot
act as a reducing agent. It can act as oxidizing
agent by itself undergoing reduction.
+5

+3

+1

P Cl5 + H2
PCl3 + 2HCl
0

+5

+1

+3

2Ag + PCl5
2 AgCl + PCl3
7.17 Justify the placement of O, S, Se, Te and Po in
the same group of the periodic table in terms of
electronic configuration, oxidation state and
hydride formation.

Sol. (1) Electronic configuration:


O (At. no. = 8) = [He] 2s2 2p4
S (At. no. = 16) = [Ne] 3s2 3p4
Se (At. no. = 34) = [Ar] 3d10 4s2 4p4
Te (At. no. = 52) = [Kr] 4d10 5s2 5p4
Po (At. no. = 84) = [Xe] 4f14 5d10 6s2 6p4
Thus, all these elements have the same ns2
np4 (n = 2 to 6) valence shell electronic
configuration, hence are justified to be
placed in group 16 of the Periodic Table.
(2) Oxidation state : Two more electrons are
needed to acquire the nearest noble gas
configuration. Thus, the minimum oxidation
state of these elements should be 2.
O and to some extent S show 2 oxidation
state. Other element being more
electropositive than O and S, do not show
negative oxidation state. As these contain
six electrons, thus, maximum oxidation state
shown by them is + 6. Other oxidation state
shown by them are + 2 and + 4. O do not
show + 4 and + 6 oxidation state, due to the
absence of d-orbitals.
Thus, on the basis of maximum and
minimum oxidation states, these elements
are justified to be placed in the same group
16 of the periodic table.
(3) Hydride formation: All these elements
share two of their valence electrons with
1s orbital of hydrogen to form hydrides of
the general formula EH2, i.e., H2O, H2S,
H2Se, H2Te and H2Po. Thus, on the basis
of hydride formation, these elements are
justified to be placed in the same group 16
of the Periodic Table.
7.18 Why is dioxygen a gas but sulphur a solid?
Sol. Due to the small size and high electronegativity,
oxygen forms pp pp multiple bonds. As a
result, oxygen exists as diatomic (O2) molecules.
These molecules are held together by weak van
der Waals forces of attraction which can be
overcome by collisions of the molecules at room
temperature. Therefore, O2 is a gas at room
temperature. Due to its bigger size and lower
electronegativity, sulphur does not form
pp pp multiple bonds. It prefers to form S S
single bonds. S S single bond is stronger then
O O single bond. Thus, sulphur has higher
tendency for catenation than oxygen. Due to
higher tendency for catenation and lower

10
tendency for pp pp multiple bonds sulphur
exits as octa-atomic (S8) molecule. Due to bigger
size, the force of attraction holding the S8
molecules together are much stronger which
cannot be overcome by collisions of molecules
at room temperature. Therefore, sulphur is solid
at room temperature.
7.19 Knowing the electron gain enthalpy values of
OO and OO2 as 141 and 702 kJ mol1
respectively, how can you account for the
formation of a large number of oxides having
O2 species and not O?
Sol. Let us consider the reaction of oxygen with
monopositve metal, we can have two compounds
MO(O in -1 state) and M2O (O in -2 state). The
energy requir ed for formation of O 2 is
compensated by increased coulombic attraction
between M+ and O2. Coulombic force of
attraction, FA is proportional to product of
charges on ions i.e.

FA

7.22
Sol.

q1q2

where q1 and q2 are charges on ions


r2
and r is distance between ions. Same logic can
be applied if metal is dispositive.
7.20 Which aerosols deplete ozone?
Sol. Aerosols like chlorofluorocarbons (CFCs), i.e.,
freon (CCl 2F2), depletes the ozone layer by
supplying Cl free radicals which convert O3 to
O2.

7.23
Sol.

7.24
Sol.

hn

gCl( g ) + gCClF2 ( g )
CCl2 F2 ( g )
Freon

ClO(g) + O2 (g)
Cl (g) + O3 (g)
Cl (g) + O2 (g)
ClO(g) + O (g)
7.21 Describe the manufacture of H2SO4 by contact
process?
Sol. Preparation of sulphuric acid:
By Contact Process: Burning of sulphur or
sulphide ores in presence of oxygen to produce
SO2. Catalytic oxidation of SO2 with O2 to give
SO3 in the presence of V2O5.
V2O5
2SO2 (g) + O2 (g)
2SO3 (g)
Then SO3 made to react with sulphuric acid of
suitable normality to obtain a thick oily liquid
called oleum.
H2S2O7( l )
SO3(g) + H2SO4( l )
Then oleum is diluted to obtain sulphuric acid of
desired concentration.

7.25

Sol.

2H2SO4( l )
H2S2O7( l ) + H2O( l )
The sulphuric acid obtained by contact process
is 96-98 % pure.
How is SO2 an air pollutant?
(1) SO2 dissolves in moisture present in air to
form H2SO 4 which damages building
materials especially marble (acid rain).
CaSO3 + H2O + CO2
CaCO3 + H2SO3
(2) It corrodes metals like Fe and steel. It also
brings about fading and deterioration of
fabrics, leather, paper, etc., and affecting the
colour of paints.
(3) Even in low concentration (; 003 ppm) , it
has damaging effect on the plants. If exposed
for a long time, i.e., a few days or weeks, it
slows down the formation of chlorophyll i.e.,
loss of green colour. This is called chlorosis.
(4) It is strongly irritating to the respiratory track.
It cause throat and eye irritation, resulting
into cough, tears and redness in eyes. It also
cause breathlessness and effects larynx i.e.,
voice box.
Why are halogens strong oxidising agents?
The halogens are strong oxidising agents due to
low bond dissociation enthalpy, high
electronegativity and large negative electron gain
enthalpy.
Explain why fluorine forms only one oxoacid,
HOF.
Cl, Br and I form four series of oxo acids of general
formula HOX, HOXO, HOXO2 and HOXO3. In
these oxo-acids, the oxidation states of halogens
are + 1, + 3, + 5, and + 7 respectively. However,
due to high electronegativity, small size and
absence of d-orbitals, F does not form oxo-acids
with + 3, + 5 and + 7, oxidation states. It just
forms one oxo-acid (HOF).
Explain why inspite of nearly the same
electronegativity, nitrogen forms hydrogen
bonding while chlorine does not.
Both nitrogen (N) and chlorine (Cl) have
electronegativity of 3.0. However, only nitrogen
is involved in the hydrogen bonds (e.g., NH3)
and not chlorine. This is due to smaller atomic
size of nitrogen (atomic radius =70 pm) as
compared to chlorine (atomic radius = 99) pm).
therefore, N can cause greater polarisation of
NH bond than Cl in case of ClH bond.
Consequently, N atom is involved in hydrogen
bonding and not chlorine.

11
7.26 Write two uses of ClO2.
Sol. (1) ClO2 is an excellent bleaching agent. It is 30
times stronger bleaching agent then the Cl2.
It is used as a bleaching agent for paper
pulp in paper industry and in textile industry.
(2) ClO2 is also a powerful oxidising agent and
chlorinating agent. It acts as a germicide for
disinfecting water. It is used for purifying
drinking water.
7.27 Why are halogens coloured?
Sol. The halogens are coloured because their
molecules absorb light in the visible region. As a
result of which their electrons get excited to
higher energy levels while the remaining light is
transmitted. The color of halogens is the color of
this transmitted light.
7.28 Write the reactions of F2 and Cl2 with water.
4H+ (aq) + 4F (aq) + O2 (g)
Sol. 2F2 (g) + 2H2O (l)
6H+ (aq) + 6F (aq) + O3 (g)
3F2 (g) + 3H2O (l)
HCl (aq) + HOCl (aq)
Cl2 (g) + H2O (l)
F2 oxidises water, whereas Cl 2 undergoes
disproportion in water.
7.29 How can you prepare Cl2 from HCl and HCl from
Cl2? Write reactions only.
MnCl2 + Cl2 + 2H2O
Sol. MnO 2 + 4HCl
Oxidising
agent

We can also used KMnO4, K2Cr2O7, etc., in place


of MnO2.
H2 + Cl2 2HCl
7.30 What inspired N. Bartlett for carrying out
reaction between Xe and PtF6?
Sol. N. Bartlett observed that PtF6 reacts with O2 to
give an compound O2+ [PtF6].
O2+ [PtF6]
PtF6 (g) + O2 (g)
Since the first ionization enthalpy of Xe
(1170 kJ mol1) is fairly close to that of O2 molecule
(1175 kJ mol1), he thought that PtF6 should also
oxidise Xe to Xe+. This inspired Bartlett to
carryout the reaction between Xe and PtF 6.
When PtF6 and Xe were made to react, a rapid
reaction took place and a red solid, Xe+[PtF6]
was obtained.
278 K
Xe + PtF6
Xe+ [PtF6]
7.31 What are the oxidation states of phosphorus in
the following:
(i) H3PO3
(ii) PCl3
(iii) Ca3P2
(iv)Na3PO4
(v) POF3
Diffused sunlight

Sol.

(i) H3PO3
3 (+1) + x + 3 ( 2) = 0
\x= +3
(ii) PCl3
x + 3 ( 1) = 0
x=+3
(iii) Ca3P2
3 (+ 2) + 2x = 0
x=3
(iv) Na3PO4
3 (+ 1) + x + 4 ( 2) = 0
x= +5
(v) POF3
x + 1 ( 2) + 3 ( 1) = 0
x = + 5.
7.32 Write balanced equations for the following:
(i) NaCl is heated with sulphuric acid in the
presence of MnO2.
(ii) Chlorine gas is passed into a solution of
NaI in water.
Sol. (i)
NaCl + H2SO4
NaHSO4 + HCl] 4
4HCl + MnO2
MnCl2 + Cl2 + 2H2O
MnCl2 + 4NaHSO4 + Cl2 + 2H2 O
4NaCl + MnO2 + 4H2SO4

i.e Cl is oxidized by MnO2


2NaCl (aq) + I2 (s)
(ii) Cl2 (g) + 2NaI (aq)

i.e. I is oxidized by Cl2.


7.33 How are xenon fluorides XeF2, XeF4 and XeF6
obtained?
Sol. XeF2 , XeF4 and XeF6 are obtained by direct
reaction between Xe and F2 as follows:
Xe(g ) + F2 ( g )
XeF2 ( s )
Ni tube
673 K, 1bar

excess

Xe ( g ) + 2 F2 ( g ) XeF4 ( s)
873 K, 7 bar

(1n 1:5 ratio)

Xe ( g ) + 3F2 ( g ) XeF6 ( s)
573 K, 60 70bar

(1n 1:20 ratio)

7.34 With what neutral molecule is ClO


isoelectronic? Is that molecule a Lewis base?
Sol. ClO has 17 + 8 + 1 = 26 electrons.
Also, OF2 has (8 + 2 9) = 26 electrons.
and ClF has (17 + 9) = 26 electrons.
Out of these, ClF can act as Lewis base. The
chlorine atom has three lone pair of electrons
which it donates to form compounds like ClF3,
ClF5 and ClF7

12

(i) 6XeF4 + 12H2O


4Xe + 2XeO3 + 24HF + 3O2
Hydrolysis

Hydrolysis

XeO3 + 6HF
XeF6 + 3H2O

Cl

..

Cl

I
Cl .. Cl

(ii) IBr2: In IBr2, central atom I has eight


electrons. Two of these are utilized in
forming two single bonds with two Br atom.
Six remaining electrons constitutes three
lone pairs. It is arranged in linear structure.
Br
I

..

Hydrolysis

XeOF4 + 2HF
(ii) XeF6 + H2O
7.36 Arrange the following in the order of property
indicated for each set:
(i) F 2 , Cl 2 , Br 2 , I 2 increasing bond
dissociation enthalpy.
(ii) HF, HCl, HBr, HI increasing acid
strength.
(iii) NH3 , PH3, AsH3, SbH3, BiH3 increasing
base strength.
Sol. (i) Bond dissociation enthalpy decreases as the
bond distance increases from F2 to I2 due to
increase in the size of the atom, on moving
from F to I.
F F bond dissociation enthalpy is smaller
then the Cl Cl and even smaller than Br
Br. This is because F atom is very small and
have large electron-electron repulsion among
the lone pairs of electrons in F2 molecule
where they are much closer to each other
than in case of Cl2. The increasing order of
bond dissociation enthalphy is
I2 < F2 < Br2 < Cl2
(ii) Acid strength of HF, HCl, HBr and HI
depends upon their bond dissociation
enthalpies. Since the bond dissociation
enthalpy of H X bond decreases from
H F to H I as the size of atom increases
from F to I.
Thus, the acid strength order is
HF < HCl < HBr < HI
The weak acidic strength of HF is also due
to H-bonding due to which release of H+
becomes difficult.
(iii) NH3, PH3, AsH3, SbH3 and BiH3 behaves as
Lewis bases due to the presence of lone pair
of electrons on the central atom. As we move
from N to Bi, size of atom increases. Electron
density on central atom decreases and hence
the basic strength decreases from NH3 to
BiH3. Thus basic strength order is
BiH3 < SbH3 < AsH3 < PH3 < NH3

..

Sol.

7.37 Which one of the following does not exist ?


(i) XeOF4
(ii) NeF2
(iii) XeF4
(iv) XeF6
Sol. NeF2 does not exist. This is because the sum of
first and second ionization enthalpies of Ne are
much higher than those of Xe. Consequently, F2
can oxidise Xe to Xe2+ but cannot oxidise Ne to
Ne2+.
7.38 Give the formula and describe the structure of a
noble gas species which is isostructural with:
(i) ICl4
(ii) IBr2
(iii) BrO3
Sol. (i) ICl4: In ICl4, central atom I has seven
valence electrons and one due to negative
charge. Four out of these 8 electrons are
utilized in forming four single bonds with
four Cl atoms. Four remaining electrons
constitutes the two lone pairs. It is arranged
in square planar structure. ICl4 has 36
valence electrons. A noble gas species
having 36 valence electrons is XeF4 (8 + 4
7 = 36). XeF4 is also square planar.

..

7.35 How are XeO3 and XeOF4 prepared?

Br

IBr2

has 22 valence electrons. A noble gas


species having 22 valence electrons is XeF2
(8 + 2 7 = 22).
XeF2 is also linear.
(iii) In BrO3 ion the central Br atom has 8 valence
electrons (7 +1). Out of these, it shares 4
with two atoms of O forming Br = O bonds.
Out of the remaining four electrons, 2 are
donated to the third O atom which accounts
for its negative charge. The remaining 2
electrons constitute one lone pair. In order

13
to minimise the force of repulsion, the
structure of BrO3 ion must be pyramidal.
BrO3 ion has (7 + 3 6 + 1) = 26 valence
electrons and is isoelectronic as well as
iso-structural with noble gas species XeO3
which has also 26(8 + 3 6) electrons.

Br

Xe

7.40 List the uses of neon and argon gases.


Sol. Uses of Neon
Neon is used in discharge tubes and fluorescent
bulbs for advertisement display purposes.
Glow of different colours neon signs can be
produced by mixing neon with other gases.
Neon bulbs and used in botanical gardens and
in green houses.
Uses of Argon

7.39 Why do noble gases have comparatively large


atomic sizes?
Sol. This is because noble gases have only van der
Waals radii while others have covalent radii.
van der Waals radii are larger than covalent radii.

Argon is used mainly to provide an inert


atmosphere in high temperature metallurgical
processes such as arc welding of metals and
alloys. In the laboratory, it is used for handling
substance which are air sensitive.
It is used in filling incandescent and fluorescent
lamps where its presence retards the sublimation
of the filament and thus increases the life of the
lamp.
It is also used in neon signs for obtaining lights
of different colours.

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