It is the part of Inorganic for Doctors DAY-6

p-B lock E lements

NCERT Based Some Key Point

Lecture-4
Vth Group (Nitrogen Family)
Some important key points.
1. We are having less reactivity of N2 as compare to P4 at
room temp and this is due to triple bond in case of N2 and
single bonds in case of P4 . Triple bond requires more
energy as compare to single bonds for breaking.

2. NCl 5 is not possible but PCl 5 is possible. The reason is

absence of d-orbital in N and due to this it is not having
valency more than 3.
3. PCl 3 is stable while NCl 3 is explosive and this is due to
less electro-negativity difference, between N and Cl.
4. From top to bottom in p-block elements, lower oxidation
state become more stable due to inert pair effect.

49
 eg. Bi +3 more stable than Bi +5 , Pb +2 is more stable
then Pb +4 .
Inert pair effect : It is the tendency, of an S 2 electron pair
to take part in bond formation in p-block elements. This is
called inert pair effect means higher oxidation is not
stable down the group.
5. BiCl 3 is possible while BiCl 5 is not due to inert pair effect.
6. In case of halides, PCl 5 is having equilibrium mixture of
PCl 3 and Cl 2 on heating. This also indicates that in PCl 5
all the Cl bonds are not same. Because on heating Cl 2 is
removed and this is formed from the combination of upper
and lower Cl.
PCl5 PCl 3 + Cl 2
Cl Cl
b P
p
a
Cl Cl Cl Cl
Cl

Cl
Length of bond b is more then a due to repulsive force
developed by cl at the triangular side on upper and lower Cl.
7. In case of solid PCl5 x-ray analysis gives

[ PCl4]+ [Pcl6]-
Tetrahedral Octahedral
structures.

50
8. Ammonia is prepared by Haber's process
N2 + 3H 2 A 2NH 3 + Q (heat )
For better production of amonia.
Pressure should be more and temperature should be less
with Pt (platinum) catalyst and Mo as promoter.
9. NO 2 is paramagnetic and N2 O 4 is diamagnetic.
2NO 2 A N2 O 4
Paramagnetic Diamagnetic

My Secrets
Your Secrets
Not to be Copied by Others
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................

51
10. NH 3 is basic in nature and basic characters decreases
down the group and it is having more B.P. as compare to
PH 3 , and this is due to hydrogen bonding in NH 3 , in
general, B.P. increases with molecular weight.
wt. BiH 3 > SbH 3 > NH 3 > ASH 3 > PH 3 (B.P. order)
11. From top to bottom reducing power increases. If a
compound gives H easily then it is good reducer.
NH3 BiH3
+ +
NH2 H- BiH2 H-
In case NH 3 after the removal of H +Ve charge is on N i.e,
+
N. Which is more electronegative as compare to Bi, Bi + is
stable because +Ve charge is on metal which is stable, So
remove of H is easy While non metal N is not stable as
N+ .
12. Bond angle -
NH 3 > PH 3 > As H 3 > SbH 3 > BiH 3
-d N -d -dI P -dI

q1 q2 Induced d = Charge
H H H H
+d +d +d I +d I
Since d > d So, more repulsion between two hydrogen in
NH 3 as compare to PH 3 due to this angle increases means
q1 > q2 .
Q. Which is more basic in the given option.

(a) CH3 - N - CH3 (b) Si H3- N = Si H3

CH3 Si H3
52
 a is having pyramidal shape while in case of 'b' lone pair
of nitrogen goes into 'd' orbital of Si and form pp - dp
bond and become planer and less basic form in nature.
H PO OH
13. 3 4
HO P OH it is triprotic acid and
O gives 3H+
H3PO3 OH
HO P H it is diprotic acid and
O gives 2H+
H3PO2 H
HO P H it is mono protic and
O gives 1H+
H 3 PO 2 > H 3 PO 3 > H 3 PO 4 (Acidic order)
Because K a of H 3 PO 2 is more than H 3 PO 3 and of H 3 PO 3
is more than H 3 PO 4 .
14. PCl 5 cannot act as reducer because it is having highest
oxidation state of P and oxidation state decreases in any
process and we know that decreasing oxidation number
(reduction) means increasing oxidising power.
15. O
=

N2O5 P4O6 P P4O10 P

O
P O O O
O O O O
N N O P O= P O P =O
O O O O OO O
P P
||
O

53
 My Secrets
Your Secrets
Not to be Copied by Others

................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................

Do Yourself -7.6

Q.1. When conc. H 2SO 4 was added into an unknown salt present in a test tube,
a brown gas (A) wa evolved. This gas intensified when copper turnings
were also added into this test tube. On cooling, the gas A changed into a
colourless gas B.

(a) Identify the gases A and B.

(b) Write the equations for the reactions involved.

Ans. The given salt is a nitrate salt. On reaction with conc. H 2 SO 4 , vapours
of HNO 3 are produced when then decompose to give a brown gas. A (NO 2 )
D
2NaNO 3 + H 2SO 4 Na 2SO 4 + 2HNO 3
54
 Sad. nitrate (Colourless)

D
4HNO 3 4NO 2 + 2H 2O + O 2
(Brown gas. A)

This gas intensified when copper turnings are added into the test tube due to
the reduction of HNO 3 to give more NO 2 gas
D
Cu + 4HNO 3 Cu(NO 3 )2 + 2NO 2 + 2H 2O

On cooling the gas A (NO 2 ) changes into a colourless gas B (N 2O 4 )

2NO 2 a
colling
N 2O 4
(A ) ( B)

Q.2. NO 2 readily forms a dimer. Explain.

Ans. In NO 2 , the orbital of nitrogen has an unshared electron which tends to pair up
forming a dimer.

Q.3. (i) Why does PCI 3 gives fume in moistrue ?

(ii) Why is Pl 5 unknown ?

Ans. (i) PCl 3 hydrolysis in the presence of moisture giving fumes of HCl.

PCl 3 + 3H 2O H 3PO 3 + 3HCl

(ii) PI bonds being very large are weak. This made Pl 5 unstable.

Q.4. Explain why BiCl 3 is more stable than BiCl 5 .

Ans. The electronic configuration of Bi (Z = 83) is Xe 4 f 14 5d10 6s2 6 p3 , the

s-electrons of the valence shell are reluctant to take part in bond formation
(inert pair effect). only three electrons in the p-orbital take part in the
formation of BiCl 3 . Thus, BiCl 3 is more stable than BiCl 5 .

Q.5. (SiH 3 )3 N is a weaker base than (CH 3 )3 N.

Ans. In (SiH 3 )3 N with planar structure, the lone electron pair on the nitrogen atom
is used up in pp-dp bonding with silicon atom. It is therefore, not so easily
available to the attacking acid. But the lone pair electron is free in case of
(CH 3 )3 N which has a pyramidal structure similar to that of NH3 . Therefore, it
can be easily donated. (CH 3 )3 N is thus a stronger base than (SiH 3 )3 N.

Q.6. Why does the reactivity of nitrogen differ from that of phosphorus ?

55
Ans. Molecular nitrogen exists as a diatomic molecule (N 2 ) in which the two
nitrogen atoms are linked to each other by triple bond (N N). It is a gas at
room temperature. Multiple bonding is not possible in case of phosphorus due
to its large size. It exists as P4 molecule (soild) in which P atoms are linked to
one another by single covalent bond. Because of greater bond dissociation
enthalpy (due to triple bond), molecular nitrogen is very less reactive as
compared to phosphorus.

Q.7. Discuss the trends in chemical reactivity of group 15 elements.

Ans. Trends in chemical reactivity.

(i) Reactivity towards hydrogen (Formation of Hydrides). All elements of

this group forms hydrides of the general formula MH3 . These hydrides are :

NH 3 PH 3 AsH 3 SbH 3 BiH 3

Ammonia Phosphine Arsine Stibine Bismuthine

Characteristics of hydrides,

(a) Bond angles. All hydrides are pyramidal in shape. The bond angle
decreases on moving down the group due to decreases in bond pair repulsion.

NH 3 (107 ) > PH 3 (94 ) > AsH 3 (92 ) SbH 3 (91 ) > BiH 3 (90 )

(b) basic strength. The decreasing order of basic strength of hydrides is as

follows : NH 3 > PH 3 > AsH 3 > SbH 3 > BiH 3

(c) Boiling points of hydrides. The increasing order of boiling points is as

follows:

PH 3 < AsH 3 < NH 3 < SbH 3 < BiH 3

(d) Reducing character of hydrides. The increasing order of reducing

character is as follows :

NH 3 < PH 3 < AsH 3 < SbH 3 < BiH 3

(ii) Reactivity towards halogens (Formation of Halides). The elements of

group 15 combine with halogens to form trihalides as well as pentahalides. The
structure of trihalides are pyramidal in nature. All possible trihalides of N, P,
As, Sb and Bi are known except NBr3 and NI3 . These trihalides, act as Lewis
bases (Except NF3 ), since they have a lone pair of electrons. All trihalides are
covalent in nature. The halides are volatile liquids and readily hydrolysed by
water (Except NF3 and PF3 ).

56
 (iii) Reactivity towards metals. All the members of the family have a tendency
to form binary compounds with metals in which they exhibit-3 oxidation state.
For example,

(i) Calcium nitride (Ca 3N 2 ) (ii) Calcium phosphide (Ca 3P2 ) (iii) Sodium
arsenide (Na 3 As) (iv) Zinc antimonide (Zn 3Sb 2 ).

In addition to these, bismuth also forms a similar compund called magnesium

bismuthide (Mg 3Bi 2 ).

(iv) Reactivity towards oxygen (Formation of oxides). The members of the

nitrogen family generally form two types of oxides i.e. trioxides and pentoxides
except for nitrogen which forms a few more oxides.

Q.8. Why does NH3 form hydrogen bond while PH 3 does not ?

Ans. The NH bond in ammonia is quite polar due to electronegativity difference of

N (3 0) and H (21). Due to polarity, intermolecular hydrogen bonding is
present in the molecules of amonia.

H H H
d d+ d d+ d
HNHNHN
H H H

On the contrary, PH bond in phosphine is almost non-polar because both P

and H atoms have almost same electronegativity (2 1). Thus PH3 does not
show hydrogen bonding.

Q.9. Give reason : CN - ion is known but CP - is not known.

Ans. Nitrogen due to small size and higher electronegativity than phosphorus, can
form multiple bonds so CN - is formed by p-bond formation between 2p orbitals
of C and N. On the other hand, CP - is not known since no p-bond formation is
possible between 2p orbital of C and 3p-orbital of P (due to larger size of P).

Q.10. Account for the following :

(a) Chlorine water has both oxidizing and bleaching properties.

(b) H 3PO 2 and H 3PO 3 act as good reducing agents while H 3PO 4 does not.

Ans. (a) Chlorine water is formed when Cl 2 is dissolved in water. Its oxidising and
bleaching action is due to nascent oxygen.

57
 Cl 2 + H 2O [HCl + HOCl] 2HCl + [O]

(b) H 3PO 2 and H 3PO 3 act as good reducing agents due to the presence of PH
bonds. H 3PO 4 does not act as reducing agent due to the absence of PH bond.

Q.11. Illustrate how copper metal gives different products on reaction with
HNO 3 .

Ans. With concentrated nitric acid.

Cu + 2HNO 3 CuO + 2NO 2 + H 2 O

Cu + 2HNO 3 Cu(NO 3 )2 + H 2 O

Cu (NO 3 )2 + 2NO 2 + 2H 2 O l
Cu + 4HNO 3 (conc. )
Copper nitrate

With dilute nitric acid

3Cu + 2HNO 3 3CuO + 2NO + H 2 Ol

CuO + 2HNO 3 Cu(NO 3 )2 + H 2 O] 3

3Cu + 8HNO 3 (dilute)

3Cu(NO 3 )2 + 2NO + 4 H 2 O

Q.12. Can PCl 5 act as oxidising as well-as reducing agent ? Justify.

Ans. Phosphorus can show a maximum oxidation state of +5 in its compounds. In

PCl 5 , the oxidation state of phosphorus is +5. Since it cannot increase the same
beyond +5, it cannot act as reducing agent. However, it can act as oxidising
agent by undergoing a decrease in oxidation state. For example, it oxidises Ag to
AgCl.
0 +5 +1 +3
2 A g + P Cl 5 2 Ag Cl + P Cl 3

Q.13. BH 4 and NH +4 are isolobal. Why ?

(C.B.S.E. All India 1998)
Ans. This is because both have sp3 -hybridisation (or tetrahedral shape).

Q.14. Mention an important property of hydrazine.

(C.B.S.E. All India 2000)

Ans. Hydrazine is a strong reducing agent.

Q.15. Why is bond angle in PH 3 molecule lesser than that in NH 3 molecule ?

(C.B.S.E. Outside Delhi 2008)

58
Ans. Due to more electronegativity of N than P the bond pair of NH bond is more
closer to N as compared to that of PH bond. So bond pair-bond pair
repulsions in PH 3 are lesser than in NH 3 which leads to lesser bond angle in PH 3
than in NH 3 .

Q.16. In which one of the two structures, NO+ -

2 and NO 2 , the bond angle has a
higher value ?
(C.B.S.E. Delhi 2008)

Ans. NO+
2 (Because less electron pair repulsion)

Q.17. Why is red phosphorus less reactive than white phosphorus ?

(C.B.S.E. All India 2009)

Ans. It is because red phosphorus has a polymeric structure whereas yellow

phosphorus has discrete P4 molecules and is understrain.

Q.18. Nitrogen is less reactive than phosphorus. Why ?

(C.B.S.E All India 2010; C.B.S.E. Delhi 2012)

Or

Phosphorus is much more reactive than nitrogen. Why ?

(C.B.S.E. Delhi 2009)

Ans. It is due to the presence of N N triple bond in N 2 . As such bond enthalpy of

N 2 is very high. On the other hand, phosphorus exists as P4 molecule with PP
simple bonds having lesser bond enthalpy, so it is more reactive.

Q.19. The bond angles (ONO) are not of the same value in NO -2 and NO+
2.
Explain.
(C.B.S.E. Delhi 2012)

Ans. N in NO+ -
2 is sp-hybridized, therefore, its bond angle is 180. In NO 2 , N has one
pair of electrons, so lp-bp repulsions are stronger and the bond angle decreases
from 120 to 115.

Q.20. Give appropriate reason for each of the following observations :

(i) Only higher members of group 18 of the periodic table are expected to
form compounds.

(ii) NO 2 readily forms a dimer, whereas ClO 2 does not.

(C.B.S.E. All India 2003)

Ans. (i) Higher members of group 18 i.e., Krypton and Xenon form compounds on
account of their low ionisation energies. Xenon form compounds with fluorine
59
 and oxygen because these elements are highly electronegative and can create
unpaired electrons in xenon by excitation of electrons from fully filled 5p
orbitals to empty 5d orbitals.

(ii) In NO 2 the orbital of nitrogen has an unshared electron which tends to pair
up, forming a dimer. Such a situation does not exist in ClO 2 .

Q.21. Why does H 3PO 2 act as monobasic acid ?

(C.B.S.E. All India 2006)

Ans. H 3PO 2 (hypophosphorus acid) acts as monobasic acid because it has only one
replaceable hydrogen atom present as OH group which it can easily release.

P
H H
OH
Q.22. Bismuth is a strong oxidising agent in the pentavalent state.

(C.B.S.E. Delhi 2005 S)

or
Pentavalent bismuth is a strong oxidising agent.
(C.B.S.E. Delhi 2006 S)

Ans. Since that inert pair effect is very prominent in Bi, therefore, its +5 oxidation
state is much less stable than its +3 oxidation state. In other words, bismuth in
the pentavalent stable can easily accept two electrons and thus gets reduced to
trivalent bismuth.

Bi 5+ + 2e - Bi 3+

Therefore, it acts as a strong oxidising agent.

Q.23. Account for the following :

NH 3 is a stronger base than PH 3 .

(C.B.S.E. Delhi 2008, 2009)

Ans. Due to smaller size of N than P, electron density is more on N-atom in NH 3

than in PH 3 . Thus, ammonia is a stronger base than phosphine.

Q.24. Write chemical equations for the following processes :

Orthophoshorus acid is heated.

Ans. 4H 3PO 3 3H 3PO 4 + PH 3

60
25. Arrange the following in order of the property mentioned :

PH3 , NH3 , SbH3 , AsH3 (increasing basic strength)

Ans. Increasing basic strength : SbH 3 < AsH 3 < PH 3 < NH 3

Q.26. How would you account for the following ?

NCl 3 is an endothermic compound while NF3 is an exothermic one.

Ans. NCl 3 is an endothermic compound (i. e., energy is absorbed when NCl 3 is
prepared this is because of following two reasons.

Q.27. How would you account for the following :

The oxidising power of oxoacids of chlorine follows the order :

HClO 4 < HClO 3 < HClO 2 < HClO

(C.B.S.E. Foreign 2011, C.B.S.E. Delhi 2012)

Ans. Oxidising power of oxoacids of chlorine is due to the presence of oxonion in

them. As the stability of oxoanion increases, As the stability of oxoanion
increases, the oxidising power of anion decreases. The stability order of these
oxoanions is as follows.

ClO -4 > ClO -3 > ClO -2 > ClO -

As such, oxidising power of these anions is in the order

ClO -4 < ClO -3 < ClO -2 < ClO -

Q.28. How would you account for the following :

H 2S is more acidic than H 2O.

(C.B.S.E. Delhi, All India 2011)

Ans. Higher acidic character of H 2S than H 2O can be explained on the basis of the
fact that bond enthalpy of HS bond is less than the bond enthalpy of HO
bond due to greater size of sulphur.

Q.29. Complete the following chemical equations :

(i) HgCl 2 + PH 3 (ii) SO 3 + H 2SO 4

(iii) XeF4 + H 2O

(C.B.S.E. All India 2011)

61
Ans. (i) 3HgCl 2 + 2PH 3 Hg 3P2 + 6HCl

(ii) SO 3 + H 2SO 4 H 2S 2O7

(iii) 6XeF4 + 12H 2O 4Xe + 2XeO 3 + 24HF + 3O 2

Q.30. What is the shape of P4 ?

Ans. Tetrahedral.

Q.31. Which allotropic form of phosphorus is poisonous and is used to kill rats

Ans. White phosphorus.

Q.32. Which phosphorus causes the disease Phossy Jaw ?

Ans. White phosphorus.

My Secrets
Your Secrets
Not to be Copied by Others

................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................

62
 Lecture-5
VIth Group (Oxygen Family)
1. Oxygen and ozone are allotropes.
2. Oxygen is most electronegative while sulphur is most
electron affinitive, less electron affinity of O is due to
high electron density which repules coming electron
3. Oxygen doesn't form oxyacid with fluorine, because in
oxyacid, halogen is having +ve oxidation state, but
fluorine is not having +ve oxidation state. In any
compound, because it is most electronegative in the
periodic table and having oxidation number 1.
Ex- HClO 4 , O.N. of Cl=+7,
HFO 4 O.N. of F=+7 which is not possible.
4. Ozone form a blue color liquid on condensation.
5. OF6 is not possible while SF6 is possible and this is due to
absence of d-orbital in case of oxygen. While in case of S
d orbitals is there. So, SF 6 is possible.
F
F F
S
F F
F
Note: In SF6 all the S - F bonds are having equal bonds length
while in case of SF4 all the S - F bonds are not equal.
S a
b
F F F F
bonds length a > b this is due to lone pair repulsion.

63
6. First Ionisation energy of 6th group element is less than
5th group and this is due to half filled subshell of 5th
group.
N O
1s2 2s2 2p3 1s2 2s2 2p4
last subshell
2P3 2P4
N is having more IE then O due to more stable half filled
subshell of 'N'.
N+ O+

In case of N+ and O + more stable is O + it is due to half

filled subshell of O +
If N and O + then.

In both the cases number of electrons are 7 but in case of

O + is number of protons are 8. So more attraction on
electrons In O + there due to which remove of electons will
not be easy and more ionisation energy.
7. H 2 O is having Hydrogen bonding while H 2 S is not
having hydrogen bonding and due to hydrogen bonding
H 2 O is liquid while H 2 S is a gas and boiling point of
H 2 O is more than H 2 S.
8. Isonisation energy (I.E.) of 7th group is more as compare
to 6th group and this is due to more number of protons in

64
 7th group as compare to 6th and having more attraction
on electrons.
9. Due to hydrogen bonding, thermal stability is as -

H 2 O > H 2 S > H 2 Se
10. In case of melting and boiling point we are having order
as -
It depends upon molecular weight mainly but in case of
H 2 O B.P. is more than H 2 S due to Hydrogen bonding

H 2 O > H 2 Te > H 2 Se > H 2 S

11. Bond angle and dipole moment is as -
H 2 O > H 2 S > H 2 Se > H 2 Te
-d O -d d' S d'

q1 q2
H H H H
+d +d +d' +d'
In case of OH bond more polorisation is there and due to
this charge develop on OH in H 2 O is d while in case of
SH it is d' and d is more than d' due to which more
repulsion between two H atoms in H 2 O as compare to in
H 2S
12. Sulphur is having allotropic forms.
Ex- Plastic sulphur, orthorohmbic, monoclinic etc.
13. ClO 2 is strong oxidising agent and used as bleaching
agent for paper industry and as a germicide.
14. 6th group elements are not colored but 7th group elements
are having color, In case of 7th it is due to absorbtion of
65
 energy from visible light by the molecules for the
excitation of outer electron to higher energy levels and
when this electron or electrons return to lower energy level
then it radiates the light which is in visible region.
15. SO 2 is air pollutant and this is the cause of acid rain
because the combination of SO 2 with water in presence of
oxygen gives H 2 SO 4 an acid.
1
H 2 O + SO 2 + O 2 H 2 SO 4
2
16. SO is good oxidiser and trimerise. as 3 So
3 3 S 3O 9
and the structure of trimer is as.
O O
S
O O

O O
S S
O O O
17. In case of contact process for the preparation of H 2 SO 4 low
temperature, high pressure and presence of V2 O 5 (as a
catalyst).
18. Ozone is good oxidiser and a bleaching agent and having
resonating structure with bond order 3/2.
19. Sulphur is having catenation property better than Se
because in case of Se, bond is weak due to large size of Se
and less weak overlapping of orbitals.
20. SF6 is not hydrolysed because S is surrounded by 6F and
it is not easy to approach S by H 2 O .
66
21. SF6 is colorless, odovrless and non toxic gas at room temp
and due to its complete octet, it is inert towards the
reaction.
22. H 2 S is good reducer and can reduce SO 2 to S

So 2 + H 2 S
H 2 O + S

23. All the acids are stored in glass bottle, but HF is the only
acid which is stored in steel vessel or in wax bottle because
HF reacts with silicate of glass to give a waxy compound
and due to this impression on glass is there. This is
known as etcing of glass.

Na2 SiO 3 + HF
Na2 SiF6 + H 2 O
Waxy compound

24. Oxygen is paramagnetic in nature due to two unpaired

electron in antibonding site and also attracted by the
magnet.

Anti bonding electrons

P4 P4
Bonding electrons

25. SF6 is there but not SH 6 . It is due to low polarisation

between S and H or high promotion of electron by
fluorine.

67
26. Ozone remove fluidity of mercury and this is known as
tailing of mercury. When O 3 reacts with Hg then solid
Hg2 O is formed.

Hg + O 3
Hg2 O + O 2
Solid

27. Sulphur in vapour state having paramagnetic nature.

28. SF6 is more stable than SF4 and this is due to complete
orbital filling of SF6 while in case of SF4 , 2 orbitals are
incomplete and due to these two incomplete orbitals SF4 is
more reactive than SF6 .
29. If Excess of So 2 reacts with NaOH then product formed is
NaHSO 3 .

NaOH + SO 2
NaHSO 3
excess

30. SO 3 is oxidiser, H 2 S is reducer and SO 2 is having both

oxidising and reducing nature.
31. H 2 SO 4 is dehydrating agent
2H SO
4
HCOOH H 2 O + CO
COOH H SO
2 4
| H 2 O + CO + CO 2
COOH
32. H 2 SO 4 burns sugar
H SO2 4
C 12 H 22 O 11 C + H 2O

H 2 S2 O 7 is known as oleum.
33. H 2 So 4 + So 3

68
 Do Yourself -7.7

Q.1. Of PH 3 and H 2S which is more acidic and why ?

Ans. In H 2S, SH bond is weaker due to larger size of sulphur. So this bond breaks
easily to give H+. Thus H 2S is more acidic.

Q.2. SF6 is well know compound but SCl 6 is not known. Explain.

(C.B.S.E. Delhi 2005 C)

Ans. Six floride ions can be accomadated around sulphur because of smaller size of
florine. On the other hand, Cl ion is large in size so six Cl ions cannot be
accomadated around sulphur as there will be interelectronic repulsions.

Q.3. Bleaching of flowers by chlorine is permanent while by sulphur dioxide is

temporary. Explain.
(C.B.S.E. Delhi 2004 S)

Ans. Bleaching action of chlorine is due to oxidation and hence bleaching is

permanent.

Cl 2 + H 2O 2HCl + [O]

Coloured material + [O] Colourless

On the other hand, SO 2 bleaches coloured material by reduction and hence

bleaching is temporary because when the bleached colourless material is
exposed to air, it gets oxidised and the colour is restored.

SO 2 + 2H 2O 2H 2SO 4 + 2[H]
Aerial
Coloured material + [H] colourless material
Coloured material
oxidation

Q.4. Why does sulphur in the vapour state exhibit paramagnetic behaviour
(C.B.S.E. All India 2006, 2008)

Ans. In the vapour state sulphur exists as diatomic (S 2 ). Due to the presence of
unpaired electrons in the antibonding p-orbitals, it exhibits paramagnetic
character.

69
Q.5. Account for the following :

NH 3 is a stronger base than PH 3 . (C.B.S.E. Delhi 2008, 2009)

Ans. Due to smaller size of N than P, electron density is more on N-atom in NH 3
than in PH 3 . Thus, ammonia is a stronger base than phosphine.

Q.6. Explain the following facts giving appropriate reason in each case :

(i) NF3 is an exothermic compound whereas NCl 3 is not.

(ii) All the bonds in SF4 are not equivalent.

(C.B.S.E. All India 2012)

Ans. (i) Since NF3 is very unstable compound. Due to very high repulsive fore
between F F atom & NF atom, it is an exothermic compound where as this
all thing happen in NCl 3 but with less repulsive fore thats why NCl 3 is not

(ii) SF4 has trigonal bipyramidal structure with lone pair in the equatorial
position. This lone pair in the equatorial position. This lone pair repels the axial
bond pair greater than the equtorial bond pair. So the bonds in SF4 are not
equivalent.
F
m
5p

F
16

m
S 155p
F
F

Q.7. How would you account for the following :

(i) Sulphur vapour exhibits paramagnetic behaviour.

(ii) Red phosphorus is less reactive than white phosphorus.

(C.B.S.E. Foreign)

Ans. (i) Sulphur in vapour state contains S2 molecules. Due to the presence of two
unpaired electrons, S2 molecules are paramagnetic in nature.

(ii) The less reactivity of red phosphorus in comparison to white phosphorus is

due to the polymeric nature of red phosphorus.

Q.8. How would you account for the following :

(i) SF6 is kinetically inert. (C.B.S.E. Delhi, All India )

Ans. (i) SF6 is kinetically stable because :

(a) In SF6 , S is sterically protected by the six F-atoms, and

70
 (b) Due to the presence of six SF bonds in SF6 it is co-ordinatively saturated.

Q.9. Complete the following reaction equations :

P4 + NaOH + H 2 O (C.B.S.E. Foreign )

Ans. P4 + 3NaOH + 3H 2 O PH 3 + 3NaH 2 PO 2

Q.10. Explain H 2S is less acidic than H 2 Te.

Ans. Due to decrease in bond (E-M) dissociation enthalpy down the group, acidic
character increases.

Q.11. What happens when sulphur dioxide gas is passed through an aqueous
solutions of a Fe (III) salt ?

Ans. 2Fe 3+ + SO 2 + 2H 2O 2Fe 2+ + SO 24 - + 4H+

Q.12. How would you account for the following :

(i) H 2S is more acidic than H 2O.

(C.B.S.E. All India 2010)

(ii) Both O 2 and F2 stabilize high oxidation states but the ability of
oxygen to stabilize the higher state exceeds that of fluorine.
(C.B.S.E. All India 2011, C.B.S.E. Delhi 2012)

Ans. (i) Higher acidic character of H 2S than H 2O can be explained on the basis of the
fact that bond enthalpy of HS bond is less than the bond enthalpy of HO
bond due to greater size of sulphur.

(ii) Oxygen stabilizes higher oxidation state better than fluorine due to its
ability to form multiple bond.

Q.13. Name the element of group 16 which has maximum tendency for
catenation. (P.S.B. 1999)

Ans. Sulphur.

Q.14. Why the elements of oxygen family are called as chalcogens ?

Ans. Chalcogens means ore-forming element and most of the ores of metals are
available as their oxides or sulphides.

Q.15. Covalency of oxygen never exceeds 2. Why ?

Ans. This is because of the absence of d-orbitals in oxygen.

71
Q.16. What is oleum ?

Ans. Concentrated H 2SO 4 saturated with SO 3 is called oleum.

H 2SO 4 + SO 3 H 2S 2O7

Q.17. What is the shape of SO 3 molecule ?

Ans. Triangular.

Q.18. What happens when SO 3 is passed through water ?

Ans. It dissolves SO 3 to give H 2SO 4 .

SO 3 + H 2O H 2SO 4

Q.19. Why conc. H 2SO 4 is not used for drying of H 2S gas ?

Ans. Conc. H 2SO 4 is an oxidising agent and oxidises H 2S to sulphur.

H 2S + H 2SO 4 2H 2O + SO 2 + S

Q.20. What happens when sulphuric acid is added to sugar ?

Ans. Sugar gets charred.
H SO
C 12H 22O11 2
4
12C + 11H 2O

Q.21. What is Marshalls acid ?

Ans. It is H 2S 2O 8 (peroxodisulphuric acid).

Q.22. H2 S acts only as reducing agent while SO2 can act both as a reducing
agent and an oxidising agent.
Ans. In H2 S, the oxidation state of sulphur is -2. It can only increase its oxidation
state but cannot decrease it. Therefore, it can act as a reducing agent. In SO2 ,
the oxidiation state of sulphur is +4. It is in a position to undergo a decrease as
well as an increase in the oxidation state. Thus, SO2 can act both as an
oxidising agent and a reducing agent.

Q.23. Arrange the following is directed :

H2 O, H2 S, H2 Se, H2 Te (decreasing order of boiling point).

Ans. H2 O > H2 Te > H2 Se > H2 S

72
 This content is the part of book
Inorganic for Doctors
with video lectures and solutions
by Er. Dushyant Kumar(B.Tech., IIT-Roorkee)