C epu of H 3PO2 on the basis of its str u ctu r e ?

Solution In H 3PO2, two H atoms are bonded directly to P

atom which imparts reducing character to the acid.

N r 16 group
Intext Q uestions
7.11 What is the basicity of H 3 PO4 ?

© be
7.12 Wh at h appen s wh en H 3 PO3 is h eat ed?

7.10 Group 16 Oxygen, su lphu r , seleniu m , tellu r iu m and poloniu m constitu te Gr ou p

Elements 16 of t h e per iodic t able. Th is is som et im es k n own as gr ou p of
chalcogens. The nam e is der ived fr om the Gr eek wor d for br ass and
points to the association of su lphu r and its congener s with copper.

o
Most copper m iner als contain either oxygen or su lphu r and fr equ ently

t
the other m em ber s of the gr ou p.

7.10.1 Occur r en ce Oxygen is the m ost abu ndant of all the elem ents on ear th. Oxygen

t
forms abou t 46.6% by mass of earth’s cru st. Dry air contains 20.946%
oxygen by volu m e.

o
However, the abu ndance of su lphu r in the ear th’s cr u st is only
0.03-0.1%. Com bined su lphu r exists pr im ar ily as su lphates su ch as
gypsum CaSO4 .2H 2 O, epsom salt MgSO 4 .7H 2 O, baryte BaSO4 an d

n
Ch em i st r y 180
su lphides su ch as galena PbS, zinc blende ZnS, copper pyrites Cu FeS2 .
Tr aces of su lphu r occu r as hydr ogen su lphide in volcanoes. Or gan ic
m ater ials su ch as eggs, pr oteins, gar lic, onion, m u star d, hair and wool
con tain su lph u r.

Seleniu m and tellu r iu m ar e also fou nd as m etal selenides and

tellu r ides in su lphide or es. Poloniu m occu r s in natu r e as a decay
pr odu ct of thor iu m and u r aniu m m iner als.
The im por tant atom ic and physical pr oper ties of Gr ou p16 along
with electronic configu ration are given in Table 7.6. Some of the atomic,
physical and chemical properties and their trends are discu ssed below.

7.10.2 El ect r on i c The elements of Grou p16 have six electrons in the ou termost shell and

d
2 4
Configuration h ave ns np gener al electr onic configu r ation.

7.10.3 At om i c Du e to increase in the nu mber of shells, atomic and ionic radii increase
an d I on i c
Radi i

7.10.4 I on i sat i on
En t h al py

he
fr om top to bottom in the gr ou p. The size of oxygen atom is, however,
exceptionally small.

Ionisation enthalpy decr eases down the gr ou p. It is du e to incr ease in

size. However, the elements of this gr ou p have lower ionisation enthalpy

T lis
valu es com par ed to those of Gr ou p15 in the cor r esponding per iods.
This is du e to the fact that Gr ou p 15 elem ents have extr a stable half-
filled p or bitals electr onic configu r ations.

7.10.5 El ect r on

7.10.6
Gai n
En t h al py R
E u b
Becau se of the com pact natu r e of oxygen atom , it has less negative
electr on gain en th alpy th an su lph u r. However, fr om su lphu r onwar ds
the valu e again becom es less negative u pto poloniu m .

Next to flu orine, oxygen has the highest electronegativity valu e amongst

C ep
El ect r on egat i vi t y the elem ents. Within the gr ou p, electr onegativity decr eases with an
incr ease in atom ic nu m ber. This im plies that the m etallic char acter
incr eases fr om oxygen to poloniu m .

N r
Elem ents of Gr ou p 16 gener ally show lower valu e of fir st ionisation
enthalpy com par ed to the cor r esponding per iods of gr ou p 15. Why?
Example 7.10

© be
Du e to extr a stable half-filled p or bitals electr onic configu r ations of Solution
Gr ou p 15 elem ents, lar ger am ou nt of ener gy is r equ ir ed to r em ove
electr ons com par ed to Gr ou p 16 elem ents.

7.10.7 Ph y si cal Som e of the physical pr oper ties of Gr ou p 16 elem ents ar e given in
Pr oper t i es Table 7.6. Oxygen and su lphu r are non-metals, seleniu m and tellu riu m

o
m etalloids, wher eas poloniu m is a m etal. Poloniu m is r adioactive and
is shor t lived (Half-life 13.8 days). All these elements exhibit allotr opy.

t t The m elting and boiling points incr ease with an incr ease in atom ic
nu mber down the gr ou p. Th e lar ge differ ence between the melting and
boiling points of oxygen and su lphu r m ay be explained on the basis
of their atom icity; oxygen exists as diatom ic m olecu le (O2 ) wher eas

o
su lphu r exists as polyatom ic m olecu le (S8 ).
7.10.8 Ch em i cal Ox i d a t i on st a t es a n d t r en d s i n ch em i ca l r ea ct i vi t y
Pr oper t i es The elem ents of Gr ou p 16 exhibit a nu m ber of oxidation states (Table
7.6). The stability of -2 oxidation state decr eases down the gr ou p.
Poloniu m har dly shows –2 oxidation state. Since electr onegativity of
 At om ic n u m ber 8 16 34 52 84
At om ic m ass/ g m ol –1 16.00 32.06 78.96 127.60 210.00
Elect r on ic con figu r at ion [He]2s22p 4 [Ne]3s23p4 [Ar]3d 10 4s24p4 [Kr]4d 10 5s25p 4 [Xe]4f 14 5d 106s2 6p4
Covalen t r adiu s/ (pm )a 66 104 117 137 146

/ ∆egH k J m ol –1
d
Ion ic r adiu s, E 2–/ pm
Elect r on gain en t h alpy,

e
Ion isat ion en t h alpy (∆i H 1 )
140
–141

1314
Pr op er t y
184
–200
198
–195
221
–190
230b
–174
Tabl e 7 .6 : Som e Ph y si cal Pr oper t i es of Gr ou p 1 6 El em en t s
1000
O
941
S
869
Se
813
Te Po

h
–1
/ k J m ol
Elect r on egat ivit y At om ic n u3.50
m ber 2.58 8 2.5516 342.01 52 1.76 84

T lis d
Den sit y / g cm –3 (298AtK) 1.32gc m ol –1
om ic m ass/ 2.06 d16.00 e
4.1932.06 6.25
78.96 –
127.60 210.00
Melt in g poin t / K con figu r at ion 393f [He]2s 22p490
Elect r on ic 55 4
[Ne]3s23p4 [Ar]3d 10 2
725 4s 4p
4
[Kr]4d 10 2
520 5s 5p
4
[Xe]4f 14 5d 106s26p4
a
Boilin g poin t / K Covalen t r90
adiu s/ (pm ) 718 66 958 104 117
1260 1371235 146

R
Ion ic r adiu s, E 2–/ pm 140 184 198 221 230b
Oxidat ion st at es* –2,–1,1,2 –2,2,4,6 –2,2,4,6 –2,2,4,6 2,4

b
Elect r on gain en t h alpy, –141 –200 –195 –190 –174

e
–1
b
/ ∆egvalue;
Single bond; Approximate H k J cm
Atolthe melting point;
d e f
Rhombic sulphur; Hexagonal grey; Monoclinic form, 673 K.

E uT sh
Ion isat
* Oxy gen show s oxidation ion en
states oft h+2
alpyand
(∆i H+1
1 ) in 1314 1000 OF2 and
oxy gen fluorides 941 O2 F2 respectively
869 . 813
/ k J m ol –1
Electin
r onthe
egatcase
ivit y of OF 2 where
3.50 its oxidation
2.58 state
2.55 is + 2. Other
2.01 elements1.76 of the
–3

C epR bli
Den gr
sit you/ g
p cm
exhibit + 2, +1.32
(298 K) 4, + 6 oxidation
c
2.06 d
states
4.19 bu t + 46.25
e
and + 6 ar –e m or e
Meltcommon.
in g poin t / K Su lphu r , seleniu
55 m and393f tellu r iu m u su ally show
490 725 + 4 oxidation
520
state
Boilin g poin int /their
K compounds
90 with oxygen
718 and 958+ 6 with fluorine.
1260 The stability
1235
of ion
Oxidat + 6stoxidation
at es* –2,–1,1,2
state decr eases –2,2,4,6
down –2,2,4,6
the gr ou p and–2,2,4,6
stability 2,4of + 4

N rE u a oxidation b state incr eases c (iner

Single bond; Approximate value; At the melting point;
oxidation states is pr im ar ily
t pair
covalent.
effect). Bonding
d in
* Oxy gen show s oxidation states of +2 and +1 in oxy gen fluorides OF and O F respectively .
+4
e and +6
Rhombic sulphur; Hexagonal grey; Monoclinic form,
2 2 2
f
673 K.

© beNC ep
An om a l ou s beh a vi ou r of ox y gen
in the case of OF 2 where its oxidation state is + 2. Other elements of the
The anom alou sgrbehaviou r of
ou p exhibit oxygen,
+ 2, + 4, + 6lik e other states
oxidation m em berbu t s+ of p-block
4 and + 6 ar e m or e
pr esen t i n seconcom m d on.
per
Sui od
lphuirs, seleniu
du e m t oand
i t stellu
sm alml usi
r iu suze
allyan d h+i 4ghoxidation
show
electr onegativity.state
One in typical
their compounds
exam plewith oxygen and
of effects of sm +6 allwith
size fluorine. The stability
and high
electr onegativityof is+ 6the
oxidation
pr esencestate of decr easeshydr
str ong down ogenthe bonding
gr ou p andinstability
H 2 O of + 4

r
which is not fouoxidation
nd in H 2state
S. incr eases (iner t pair effect). Bonding in +4 and +6
oxidation states is pr im ar ily covalent.
The absence of d orbitals in oxygen limits its covalency to fou r and

o © be
An om a l ou s beh a vi ou r of ox y gen
in pr actice, r ar ely exceeds two. On the other hand, in case of other
The anom thealou s behaviou
shellsr can
of oxygen, lik e other
andmcovalence
em ber s of p-block

t
elements of the group, valence be expanded
pr esen t i n secon d per i od i s du e t o i t s sm al l si ze an d h i gh
exceeds fou r.
electr onegativity. One typical exam ple of effects of sm all size and high
(i) Reactivity electr
w ith onegativity
hydrogen:is All the the elem ents of Gr ouogen
p 16bonding
for m in H 2 O

t
pr esence of str ong hydr
hydr ides ofwhich
the type H E (E = O,
is not 2fou nd in H 2S.S, Se, Te, Po). Some pr oper ties of
hydr ides ar e given in Table 7.7. Their acidic char acter incr eases
Th e absence of d or bitals in oxygen lim its its covalency to fou r and

o o
from H 2 O toinHpr
2 Te. The rincrease
actice, in acidic
ar ely exceeds two. character
On the other can hand,
be explained
in case of other
H–Ecovalence

t
in ter m s ofelements
decr ease of the group,enthalpy
in bond the valence shells
for the can be expanded
dissociation of and
exceeds fou r.

n ot
bond down the gr ou p. Owing to the decr ease in enthalpy for the
dissociation (i)
of Reactivity
H–E bondwdown the gr ouAll
ith hydrogen: p, the
the ther
elemmal
entsstability of 16 for m
of Gr ou p
hydr ides also decrhydreases
ides offrthe
om type
H 2 OHto2E H(E Po.
= O,All
S, Se,
the Te, Po).
hydr Som
ides e pr oper ties of
except
2
hydr ides ar e given in Table 7.7. Their acidic char acter incr eases
water possess redu cing property and this character increases from
from H O to H 2Te. The increase in acidic character can be explained
H 2 S to H 2Te. in ter m2s of decr ease in bond enthalpy for the dissociation of H–E

n
Ch em i st r y 182 bond down the gr ou p. Owing to the decr ease in enthalpy for the
dissociation of H–E bond down the gr ou p, the ther m al stability of
hydr ides also decr eases fr om H 2 O to H 2 Po. All the hydr ides except
water possess redu cing property and this character increases from
H 2 S to H 2Te.
Ch em i st r y 182
 3. Because it turns star ch iodate paper blue (due to star ch and I 2).
3. Because it turns star ch iodate paper blue (due to star ch and I 2).
2K I O 3 + 5SO 2 + 4H 2O I + 2K H SO + 3H 2SO 4
2K I O 3 + 5SO 2 + 4H 2O I 22 + 2K H SO 4 4+ 3H 2SO 4

Other methods for its detection based on its r educing property are already covered in Chapter 7.
Other methods for its detection based on its r educing property are already covered in Chapter 7.

Uses
Uses

1. 1.
SOSO
2 is used to make other products such as sulphites, bisulphites and thiosulphates.
2 is used to make other products such as sulphites, bisulphites and thiosulphates.

SO22++Na
22SO CO33 +
Na22CO +HH 22O
O 22NaH
NaHSOSO33++COCO2 2
sodiumhydrogen
sodium hydrogen
sulphite
sulphite
((sodium
sodiumbibissulphite)
ulphite)
22NaH SO33++Na
NaHSO Na22CO
CO 3 2 Na SO33++ HH2O
Na22SO + CO 2 2
2 O + CO
sodium
sodium
sulphite
sulphite

Na SO 3 ++ S
Na2SO S heat
heat Na
Na22SS22OO33
2 3
sodium
sodium
thiosulphate
thiosulphate

2. 2.
SOSO 2 has also been used as a non-aqueous solvent. A wide range of covalent compounds, both inorganic
2 has also been used as a non-aqueous solvent. A wide range of covalent compounds, both inorganic
and organic, are soluble in liquid SO , and it is a useful reaction medium.
and organic, are soluble in liquid SO 22, and it is a useful reaction medium.
3. I t is used bleaching wool and silk, as antichlor, disinfectant and preservative of food.
3. I t is used bleaching wool and silk, as antichlor, disinfectant and preservative of food.
Trioxide SO
Trioxide SO 3 3
SO 3 is the only important trioxide. I t is manufactured on a huge scale by the Contact process in which SO 2
SOreacts
3 is the only
with O 2important trioxide.
in the presence of a Icatalyst
t is manufactured
(Pt or V 2O 5).on Maosthuge scale
of the SO 2by the Contact
produced process
is oxidized to in
SOwhich SO 2
3 by the
reacts with O in the presence of a catalyst
Contact process, and used to manufacture H 2SO 4.
2 (Pt or V 2O 5). M ost of the SO 2 produced is oxidized to SO 3 by the
Contact process, and used to manufacture H 2SO 4. -1
2SO 2(g) + O 2(g) 2SO 3(g) H = −98 kJ mol
-1
The forward reaction is exothermic, 2SO 2(g) + O 2(g)
and is favoured = −98 kJ molSince
2SO 3(g)by a lowHtemperature. there is a decrease in the
The forward
number reaction
of moles is exothermic,
of gas, the process and is favoured
is favoured by apressure.
by a high low temperature.
I n practiceSince there isisacarried
the reaction decrease outinatthe
number of moles
atmospheric of gas,The
pressure. the formation
process isof favoured by a highbypressure.
SO 3 is favoured an excessI nofpractice the reaction
O 2, and removing theis SOcarried
3 from out the at
atmospheric pressure.
reaction mixture. The formation
A catalyst is used toofobtain
SO 3 isafavoured
reasonable byconversion
an excess of in O , and removing
a 2reasonable time. the SOContact
I n the 3 from the
processmixture.
reaction a platinum gauze and
A catalyst platinized
is used to obtain asbestos were both
a reasonable used at one
conversion in atime. Pt is an time.
reasonable excellent
I n thecatalyst,
Contact
and it aworks
process at moderately
platinum gauze andlow temperatures.
platinized asbestosH owever,
were bothit is very
usedexpensive
at one time. and Pt is susceptible to poison-
is an excellent catalyst,
anding,
it particularly by metals such
works at moderately as A s. Nowadays
low temperatures. a V 2O 5 catalyst
H owever, it is veryactivated
expensive withand K 2Oisissusceptible
used instead, toand is
poison-
supported on kieselguhr or silica. This is much cheaper, and is resistant to poisoning.
ing, particularly by metals such as A s. Nowadays a V 2O 5 catalyst activated with K 2O is used instead, and is The catalyst is inactive
below 400
supported on°C and breaks
kieselguhr ordown
silica.between
This is much600 °C and 650and
cheaper, °C. D isust may clog
resistant the catalystThe
to poisoning. surface, andisimpair
catalyst inactive
its ef400
below ciency.
°C andTo breaks
preventdown this the gases are
between 600passed
°C andthrough
650 °C.an electrostatic
D ust may clog precipitator. The catalyst
the catalyst surface, and may impair
itslast
ef for overTo
ciency. 20prevent
years. this the gases are passed through an electrostatic precipitator. The catalyst may
last forThe
overSO203 is not usually isolated, and practically all of it is converted to H 2SO 4. SO 3 reacts vigorously
years.
with water, evolving a large amount of heat and forming H 2SO 4. Commercially it is not possible just to
The SO 3 is not usually isolated, and practically all of it is converted to H 2SO 4. SO 3 reacts vigorously
react SO with water. The SO 3 reacts with water vapour and causes the formation of a dense mist of H 2SO 4
with water,3 evolving a large amount of heat and forming H 2SO 4. Commercially it is not possible just to
droplets, which are dif cult to condense and pass out of the absorber into the atmosphere. To avoid this, it
react SO 3 with water. The SO 3 reacts with water vapour and causes the formation of a dense mist of H 2SO 4
has been found best to dissolve SO 3 in 98–99% H 2SO 4 in ceramic packed towers, to give oleum or fuming
droplets,
sulphuricwhich
acid.are difis mainly
This cult to condense
pyrosulphuric and acid
passHout of the absorber into the atmosphere. To avoid this, it
2S2O 7. Water is continuously added to keep the concen-
has been found best to
tration of H 2SO 4 constant.dissolve SO 3 in 98–99% H 2SO 4 in ceramic packed towers, to give oleum or fuming
sulphuric acid. This is mainly pyrosulphuric acid H 2S2O 7. Water is continuously added to keep the concen-
tration of H SO constant. H 2S2O 7 + H 2O 2H 2SO 4
2 4

I n the gas phase SO 3 has a plane triangular

H 2S2structure
O 7 + H 2O(Figure
2H 210.46).
SO 4 The bonding is best described as sul-
phur forming three s -bonds, giving rise to a plane triangle, and three delocalized bonds.
I n the gas phase SO 3 has a plane triangular structure (Figure 10.46). The bonding is best described as sul-
phur forming three s -bonds, giving rise to a plane triangle, and three delocalized bonds.

Chapter 10.indd 493 3/21/2017 11:29:42 AM

Chapter 10.indd 493 3/21/2017 11:29:42 AM

 _
@unacademyplusdiscounts
494 Chapt er 10 The p-Block Elements and their Compounds

O
S
O O

Tabl e 7 .6 : Som e Ph y si cal Pr oper t i es Figure

of Gr10.46
ou p Structure
1 6 El emofen
SOt s3 gas.
A t room temperature SO 3 is solid and exists in three distinct forms. g-SO 3 is ice-like and is a cyclic trimer
Pr op er t y (SO 3O
) 3, m.p. 16.8 °C. ISf SO 3 is kept for
Sea long time, or ifTaetrace of water is present,
Po either b-SO 3 or a-SO 3 is
formed. Both look like asbestos, and comprise bundles of white silky needles. b-SO 3 (m.p. 32.5 °C) is made
n u m ber up of in nite helical
8 16 chains of34 tetrahedral [SO 4] units
52 each sharing 84 two corners. This structure is similar to
that of chain phosphates. a-SO 3 (m.p. 62.2 °C) is the most stable form, and is made of chains cross-linked
m ass/ g m ol –1 16.00 32.06
into sheets (Figure 10.47). 78.96 127.60 210.00
2 4 2 4 10 2 4 10 2 4
on ic con figu r at ion [He]2s 2p [Ne]3s 3p [Ar]3d 4s 4p O [Kr]4d O O5s 5p [Xe]4f 14 5d 106s26p4
n t r adiu s/ (pm ) a 66 104 117 137
S O S O S O 146
adiu s, E 2–/ pm 140 184 198 O 221
O O 230b
–141 –200 –195 b-SO
–190 (solid) –174

d
on gain en t h alpy, 3

–1
k J m ol
O O
ion en t h alpy (∆i H 1 ) 1314 1000 941 869S 813

he
O O
ol –1 O
S S
O

on egat ivit y 3.50 2.58 2.55 O 2.01O O 1.76

g-SO 3 (solid)
y / g cm –3 (298 K) 1.32 c 2.06 d 4.19 e 6.25 –
g poin t / K 55 393f Figure 490
10.47 Structure of725
SO 3 chains and SO
5203 cyclic trimer.
pu T
is
poin t / K
ion st at es*
90
–2,–1,1,2
3
718
SO 3 is a powerful
SO is important in the
–2,2,4,6
958 especially when
oxidizing agent,
manufactur e of H SO .
1260
hot. I t oxidizes H1235
–2,2,4,6 2 4 –2,2,4,6
Br to Br 2 and P to P4O 10. Commercially
2,4
re R

SO 3 is used to make sulphamic acid NH 2SO 3H

b c d e

_ f
bl
ond; Approximate value; At the melting point; Rhombic sulphur; Hexagonal grey; Monoclinic form, 673 K.
NH 2 à CO àNH 2 + SO 3 + H 2SO 4 2NH 2SO 3H + CO 2
n show s oxidation states of +2 and +1 in oxy gen fluorides
urea OF2 and O2 F2 respectively
sulphamic . acid
@unacademyplusdiscounts
E

in theSulphamic
case of acid OF is 2 where
the onlyits strong oxidation
acid that existsstateasisa solid
+ 2. atOther elements Iof
room temperature. t isthe
used for cleaning the
gr ou pplant at sugar+re2,neries
exhibit + 4,and + 6breweries.
oxidation states bu t + 4 and + 6 ar e m or e 10.54 Hydrides 501
common. Su lphu r, seleniu m and tellu riu m u su ally show + 4 oxidation
be C

state 10.52
in their| compounds
OXOACIDS with OFoxygen SULPHUR and + 6 with fluorine. The stability
10.54 | HYDRIDES
of + 6 oxidation state decr eases down the gr ou p and stability of + 4
oxidation
The oxoacidsstate
Tablofeincr 7 .7eases
sulphur: Pr areoper (iner
more t pair
of H yeffect).
t inumerous
es and moreof
dr i des Bonding
important 1in6 those
pthan +4emandofenSe +6 Te. M any of the
t sand
waterGr Hou El
o N

Theoxoacids
oxidation elements of all
states form
sulphur
is pr docovalent ily hydrides.
notarexist
im as free acids,
covalent. These
but areareknown as 2O, hydrogen
anions and salts.sulphide
A cids ending H 2S,inhydrogen
ous have selenide
H 2Se,
S inhydrogen
the
Pr op er t y telluride
oxidation state H
(+I2Te
V ), and
and hydrogen
form
H 2O salts polonide
ending in
H 2S 2 H
-ite. Po.
A Water
cids ending
H 2 Se is liquid
in -ic at
have room
H 2T eS in temperature,
the oxidation but the
Anothers
omstate
a l ou (+V
are sall
Ibeh a vi ou rsalts
) colourless,
and form of ox
ending
foul ygen
smellingin -ate. toxic gases.
mA.p/
s discussed previously pby–d
TheOuranompoint ofKinterest
alou s behaviou runder
is H 2S which bond
can
of oxygen, 273 belengthslikand
prepared 188
e other thebonding,
maction
em ber208theminer
of s oxoanions 222
al acids
of p-block haveonstrong bonds
metal sulphides or
and so they have little tendency to polymerize compared with the phosphates and silicates. To emphasize
prhydrolysis.
esen t
b.p/ i nK secon d per i od i s 373du e t o i t s
213 sm al l si
232ze an d h i
269 gh
tt ©

structural similarities the acids ar e listed in four series:

electr onegativity.
H–E dist anOne typical exam 96 ple
+ H 2of SOeffects 134 of sm all146 size and high
4 ® H 2S ¹ + FeSO 4
ce/ pm FeS 169
1. sulphurous acid series
electr onegativity is the pr esence of str ong hydr ogen bonding in H
902 O
2.HEHsulphurican gleacid(°) series A104
l 2S3 + 6H 2O ® 922A l(OH) + 913H S
which is not fou nd –1 in H 2 S.
3 2

d
3.∆thionic
f H/ k Jacid m ol –286 –20 73
( OH) 3 + 3H to
100
2S3 + 6H 2O ® its
series Cr 2Crcovalency
The absence of d orbitals –1 in oxygen limits 2 S fou r and
4.∆peroxoacid
diss H (H–E)/ series.
k J m ol 463 347 276 238
inThis
pr actice,
gas can be r ardried
ely exceeds two. On the –16 other hand, –7 in sulphuric
case –4of acidother –3 a very good drying
ion by conanhydr
st an t aous CaCl or P O . Concentrated is also

e
D issociat 1.8×10 2 2 5 1.3×10 1.3×10 2.3×10
elements of the group, the valence shells
agent but cannot be used for this purpose because it oxidizes H 2S to S. can be expanded and covalence
exceeds a
fou r. solution, 298 K
Aqueous
4 +H2 S® S ¯ +SO of2 ¹Gr+2H

h
(i) Reactivity w ith hydrogen: HAll 2SOthe elem ents ou2pO 16 for m
(ii) Reactivity w ith oxygen: All these elem ents for m oxides of the EO2
H 2S,hydrides
is soluble of the type
in water and H burns E (E in = airO,with S, aSe,
blue Te,ame.Po). Some properties of
and EO t ypes wh2 er e E = S, Se, Te or Po. Ozon e (O ) an d su lph u r

T lis
hydr ides ar e3 given in Table 7.7. Their acidic char acter 3incr eases
dioxide (SO ) ar e gases while seleniu 2Hm2Odioxide 2SO 2be(SeO 2 ) is solid.
from H 2O to H 2Te.2 The increase2H in 2S + 3O
acidic 2character + can explained
Redu cing pr oper ty of dioxide decr eases fr om SO2 t o TeO2 ; SO2 is
H 2Sinis about
ter m stwice of decrsolubleease in bond as enthalpy
CO 2, and for the dissociation of H–E 4.6 volumes of H 2S at 0 °C
r edu cingas while in water
TeO 1 volume of water can absorb
2 is an oxidisin g agen t . Besides EO2 t ype,
no

R
andbond down at
2.6 volumes the 20gr °C.ouA p.saturated
Owing to the decr
solution is used easeas ainlaboratory
enthalpyreagent,for thebut it does not keep well
su lphu r, seleniu m and tellu r iu m also for m EO 3 t ype oxides (SO3 ,
Chapter 10.indd 494
dissociation
since air slowly oxidizes of H–E bond
it and downisthe
sulphur grou p,Hthe
deposited. S isthermal
a very weak stability
dibasic of 3/21/2017 11:29:44 AM
acid. Most metal sulphides

b
SeO3 , TeO3 ). Both types of oxides ar e 2acidic in natu r e.
canhydrides
be regarded also decreases
as salts of H 2S, and from sinceH 2itOisto H 2 Po.
dibasic two Allseries
the of hydrides
salts can except
be derived from it, the hydrogen
(iii) Reactivity tow
and ards the halogens and: this
Elements of Grou p 16 form a large

E u
water
sulphides, possess
e.g. NaHS,redu cing
the property
normal sulphides, e.g. Na character
2S. increases from
nu
H 2 S to H 2 Te. mber of halides of the type, EX 6 , EX 4 and EX 2 wher e E is an
element of the grou p and HX2Sis+aNaOH halogen.NaHS The stability
+ H 2O of the halides
t r y 182 decreases in the order F – > Cl – > Br – > I –. Amongst hexahalides,

C p
H S + NaHS Na2S + H 2O
hexaflu orides are the only2 stable halides. All hexaflu orides are
The alkaligaseou s in n atare
metal sulphides u r e. all Th ey hin
soluble ave wateroctand ah edr al st r ustrongly
hydrolyse ct u r e. (a Su1M lphsolution
ur is about 90%
hydrolysed), hexafluso they oride, SF6 is basic.
are strongly exceptionally stable for ster ic reasons.
Amongst tetr aflu or ides, SF Na4 S is+aHgas, O SeF NaHS 4 a+ liqu
NaOH id and TeF 4 a solid.
3 2 2
 1. Sulphurous acid series
HO
H 2SO 3 sulphurous acid S O S(+IV)
HO
O O
H 2S2O 5 di- or pyrosulphurous HO S S OH S(+V)
acid S(+III)
O
O O
H 2S2O 4 dithionous acid HO S S OH S(+III)
2. Sulphuric acid series
O
H 2SO 4 sulphuric acid HO S OH S(+VI)
O
S
H 2S2O 3 thiosulphuric acid HO S OH S(+VI)
S( -II)
O
O O
H 2S2O 7 di- or pyrosulphuric HO S O S OH S(+VI)
acid
O O
3. Thionic acid series
O O
H 2S2O 6 dithionic acid HO S S OH S(+V)
O O
O O
H 2SnO 6 polythionic acid S (S) n S OH S(+V)
HO
( n =1 - 12) S(0)
O O
4. Peroxoacid series
O
H 2SO 5 peroxomonosulphuric HO S O OH S(+VI)
acid
O
O O
H 2S2O 8 peroxodisulphuric acid HO S O O S OH S(+VI)
O O

Sulphurous acid
Though SO 2 is very soluble in water, most is present as hydrated SO 2 (SO 2 · H 2O). Sulphurous acid H 2SO 3
may exist in the solution in minute amounts, or not at all, though the solution is acidic. Its salts, the sulphites
SO 2-
3
, form stable crystalline solids. Many sulphites are insoluble or are sparingly soluble in water, e.g. CaSO 3,
BaSO 3 or A g2SO 3. However, those of the Group 1 metals and ammonium are soluble in water, and in dilute
solutions the hydrogen sulphite (bisulphite) ion H SO 3- is the predominant species. Crystals of hydrogen
sulphites have only been formed with a few large metal ions, e.g. RbHSO 3 and CsHSO 3. Most attempts to isolate
hydrogen sulphites lead to internal dehydr ation with the formation of d isulphites S2O 52-:
2NaH SO 3(aq) Na2S2O 5 + H 2O
Na2SO 3 is an important industrial chemical. I t is made by passing SO 2 into an aqueous solution of Na2CO 3
to give aqueous NaH SO 3, then treating the solution with mor e Na2CO 3.
Na2CO 3 + 2SO 2 + H 2O 2NaH SO 3 + CO 2
2NaH SO 3 + Na2CO 3 2Na2SO 3 + H 2O + CO 2

Chapter 10.indd 495 3/21/2017 11:29:48 AM

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496 Chapt er 10 The p-Block Elements and their Compounds

The main use of Na2SO 3 is as a bleach for wood pulp in the paper making industry. Some is used to treat
boiler feed water (it removes O 2 and thus reduces corrosion of pipes and boilers). Small amounts are used
in photographic developer.
Sulphites and hydrogen sulphites liberate SO 2 on treatment with dilute acids:
Na2SO 3 + 2H Cl 2NaCl + SO 2 + H 2O
Sulphites and hydrogen sulphites both contain S in the oxidation state (+I V ) and are moderately strong
reducing agents. Sulphites are determined by reaction with I 2, and determination of the excess I 2 with
sodium thiosulphate.
NaH SO 3 + I 2 + H 2O NaH SO 4 + 2H I
2Na2S2O 3 + I 2 Na2S4O 6 + 2Na+ + 2I -
The sulphite ion exists in crystals and has a pyramidal structure (Figure 10.48), that is tetrahedral with one
position occupied by a lone pair. The bond angles O—S—O are slightly distorted (106°) due to the lone
pair, and the bond lengths are 1.51 Å . The bond is delocalized, and hence the S—O bonds have a bond
order of 1.33.

S
O O-

O-

Figure 10.48 Structure of sulphite ion SO 23−.

3s 3p 3d
Electronic structure of sulphur
atom – excited state
three unpaired electron form s bonds forms
p bond with three oxygen atoms
four electron pairs, hence tetrahedral
. with one position occupied by a lone pair

Sulphuric acid series

H 2SO 4 is the most important acid used in the chemical industry. By far the most important commercial
process for its manufacture is the Contact process, in which SO 2 is oxidized by air to SO 3, using a catalytic
surface. Formerly a platinum gauze or platinized asbestos was used as catalyst. This has now been replaced
by vanadium pentoxide, which is slightly less ef cient but is cheaper and less easily poisoned. The SO 3 could
be mixed with water to give H 2SO 4, but the reaction is violent and produces a dense chemical mist which
is dif cult to condense. I nstead, the SO 3 is passed into 98% H 2SO 4, forming pyrosulphuric acid H 2S2O 7,
sometimes called oleum or fuming sulphuric acid. (Some trisulphuric acid H 2S3O 10 is also formed.) This
solution may be sold as oleum, or diluted with water to give concentrated sulphuric acid which is a 98%
mixture with water (an 18 M solution).
H 2S2O 7 + H 2O 2H 2SO 4
H 2S3O 10 + 2H 2O 3H 2SO 4

Physical pr opert ies

Pure sulphuric acid melts at 10.5 °C, forming a viscous liquid. I t is strongly hydrogen bonded, and in the
absence of water it does not react with metals to produce H 2. M any metals reduce H 2SO 4 (S + V I ) to SO 2
(S + I V ), especially if heated. I f pure H 2SO 4 is heated, a little SO 3 is evolved, and an azeotropic mixture of
98.3% H 2SO 4 and 1.7% water is produced. This boils at 338 °C. Pure H 2SO 4 is used as a non-aqueous solvent
and as a sulphonating agent.

Chapter 10.indd 496 3/21/2017 11:29:51 AM

 Intext Q uestions
7.20 Wh at h appen s wh en su lph u r dioxide is passed th r ou gh an aqu eou s
solu tion of Fe(III) salt?
7.21 Com m en t on th e n atu r e of two S–O bon ds for m ed in SO 2 m olecu le. Ar e
th e two S–O bon ds in th is m olecu le equ al ?
7.22 How is th e pr esen ce of SO 2 det ect ed ?

16 O xoacids of

ed
Su lph u r for m s a n u m ber of oxoacids su ch as H 2 SO 3 , H 2 S2 O 3, H 2 S2 O4 ,
Sulphur H 2 S2 O5 , H 2 Sx O6 (x = 2 t o 5), H 2 SO 4 , H 2 S2 O 7 , H 2 SO 5 , H 2 S2 O8 . Som e of
th ese acids ar e u n stable an d can n ot be isolated. Th ey ar e k n own in
aqu eou s solu tion or in th e for m of th eir salts. Str u ctu r es of som e
im por tan t oxoacids ar e sh own in Fig. 7.6.

h
pu T
is
re R
bl
E

Fi g. 7 .6 : Structures of some important oxoacids of sulphur

be C

17 Sulphuric Ma n u f a ct u r e
A cid Su lph u r ic acid is on e of th e m ost im por tan t in du str ial ch em icals
o N

wor ldwide.
Su lphu ric acid is manu factu red by the Con t act Pr ocess which involves
th r ee steps:
tt ©

(i) bu r n in g of su lph u r or su lph ide or es in air to gen er ate SO2 .

(ii) conversion of SO 2 to SO3 by the reaction with oxygen in the presence
of a catalyst (V 2 O5 ), an d
(iii) absor ption of SO3 in H 2 SO 4 t o give Oleum (H 2 S2 O7 ).
A flow diagr am for th e m an u factu r e of su lph u r ic acid is sh own in
(Fig. 7.7). Th e SO2 pr odu ced is pu r ified by r em ovin g du st an d oth er
im pu r ities su ch as ar sen ic com pou n ds.
Th e k ey step in th e m an u factu r e of H 2 SO4 is th e catalytic oxidation
of SO2 with O2 t o give SO3 in t h e pr esen ce of V 2 O5 (catalyst ).
2SO 2 ( g ) + O 2 ( g ) V2 O 5
→ 2SO 3 ( g ) ∆ r H 0 = −196.6 k Jmol −1
The reaction is exothermic, reversible and the forward reaction leads
no

to a decrease in volu me. Therefore, low temperatu re and high pressu re

ar e th e favou r able con dition s for m axim u m yield. Bu t th e tem per atu r e
sh ou ld n ot be ver y low oth er wise r ate of r eaction will becom e slow.
In pr actice, th e plan t is oper ated at a pr essu r e of 2 bar an d a
tem per atu r e of 720 K. Th e SO 3 gas fr om t h e catalyt ic con ver t er is

189 Th e p-Block Elem en t s

 _
@unacademyplusdiscounts
498 Chapt er 10 The p-Block Elements and their Compounds

Thiosulphuric acid and t hiosulphat es

Thiosulphuric acid H 2S2O 3 cannot be formed by adding acid to a thiosulphate because the free acid
decomposes in water into a mixture of S, H 2S, H 2Sx, SO 2 and H 2SO 4. I t can be made in the absence of water
(e.g. in ether) at low temper atures (–78 °C).

H 2S + SO 3 ether H 2S2O 3 (Et 2O) n

I n contrast, the salts which are called thiosulphates are stable and numerous. Thiosulphates are made
by boiling alkaline or neutral sulphite solutions with S.

Na2SO 3 + S ¾boiling
¾¾¾¾ water
® Na2S2O 3 ¾evaporation
¾¾¾® Na2S2O 3 × 5H 2O
monoclinic crystals
H ere, Na2SO 3 is prepared by passing SO 2 through a solution containing Na2CO 3 in excess.
I t is also prepared by oxidizing polysulphides with air .

2Na2S3 + 3O 2 heat in ai r 2Na2S2O 3 + 2S

2Na2S + 2O 2 + H 2O ® Na2S2O 3 + 2NaOH

Other methods of pr eparation of sodium thiosulphate include the following.

1. Na2SO 4 + 4C ¾roasting
¾¾® Na2S + 4CO
2Na2S + 3SO 2 ® 2Na2S2O 3 + S
2. 2Na2S + Na2CO 3 + 4SO 2 ® 3Na2S2O 3 + CO 2

3. 6NaOH + 4S ® 3Na2S2O 3 + 2Na2S + 3H 2O

4. 3Ca(OH ) 2 + 12S ® CaS2O 3 + 2CaS5 + 3H 2O
5. Na2SO 3 + Na2S + I 2 ® Na2S2O 3 + 2NaI

The thiosulphate ion is structur ally similar to the sulphate ion (Figure 10.49).
2Na2S2O 3 + I 2 Na2S4O 6 + 2NaI
sodium
tetrathionate
O

S
O O-

O-

S
S O-

O-

Figure 10.49 Structure of sulphate and thiosulphate ions.

Chapter 10.indd 498 3/21/2017 11:30:03 AM

 _
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10.52 Oxoacids of Sulphur 499

H ydrated sodium thiosulphate Na2S2O 3 5H 2O is called ‘hypo’. I t forms very large colourless hexagonal
crystals, m.p. 48 °C. I t is readily soluble in water and solutions are used for iodine titrations in volumetric
analysis. I odine very rapidly oxidizes thiosulphate ions S2O 32- to tetrathionate ions S4O 62-, and the I 2 is
reduced to I - ions.
Na2S2O 3 is used in the bleaching industry to destroy any excess Cl 2 on fabrics after they have been
through a bleach bath. Similarly Na2S2O 3 is sometimes used to remove the taste from heavily chlorinated
drinking water. Since Cl 2 is a stronger oxidizing agent than I 2, hydrogensulphate ions are formed rather
than tetrathionate ions.
Na2S2O 3 + 4Cl 2 + 5H 2O 2NaH SO 4 + 8H Cl
H ypo is used in photography for ‘ xing’ lms and prints. Photographic emulsions are made of A gNO 3,
A gCl and A gBr. Parts of the lm exposed to light begin to decompose to A g, thus forming a negative image.
The process is enhanced by the developer solution. A fter developing, the lm or print is put in a solution
of hypo (Na2S2O 3). This forms a soluble complex with silver salts, thus dissolving any unchanged silver salts
in the photographic emulsion. When there is no photographic emulsion left, the lm or print can safely be
exposed to light.
+ 2Na2S2O 3
Na2S2O 3 + A gBr A g2S2O 3 Na3[A g(S2O 3) 2]
Note: Other properties of S2O 32- are already covered in Chapter 7.

Pyrosulphat es
Pyrosulphates can be made by heating hydrogen sulphates strongly, or by dissolving SO 3 in H 2SO 4. Some
trisulphuric acid H 2S3O 10 is also formed, but polysulphuric acids higher than this ar e not known.
2NaH SO 4 Na2S2O 7 + H 2O
H 2SO 4 + SO 3 H 2S2O 7
H 2SO 4 + 2SO 3 H 2S3O 10

Thionic acid series

D ithionic acid H 2S2O 6 is known only in solution. The acid is dibasic, and salts called dithionates are known,
e.g. Na2S2O 6. No acid salts exist. The acid and its salts contain S in the oxidation state ( +V ).
O O
HO S S OH
O O
dithionic acid

The dithionate ion has a structure similar to that of ethane, but the two SO 3 groups adopt an almost eclipsed
conformation. The S—S length is 2.15 Å and the S—O bonds are 1.43 Å – again rather short. The bond
angles S—S—O are close to tetrahedral (103°).
A range of polythionates have been known as salts since the early work of Wackenroder on the effect
of H 2S on aqueous solutions of SO 2. I ons such as trithionate S3O 62- , tetrathionate S4O 62-, pentathìonate
S5O 62- and hexathionate S6O 62- are named according to the total number of S atoms present. I t is only in
recent times that the par ent acids have been made.
O O
HO S (S) n S OH
O O
polythionic acid

Peroxoacid series
The name peroxo indicates that the compound contains an —O—O— linkage. Two peroxoacids of
sulphur are known: peroxomonosulphuric acid H 2SO 5 and peroxodisulphuric acid H 2S2O 8. No peroxoacids

Chapter 10.indd 499 3/21/2017 11:30:09 AM

@unacademyplusdiscounts
500 Chapt er 10 The p-Block Elements and their Compounds
_
@unacademyplusdiscounts
of Se and
500 Teerare
Chapt 10known. H 2S2OElements
The p-Block 8 is a colourless
and theirsolid, m.p. 65 °C. I t is obtained by electrolysis of sulphates at
Compounds
high current density. I t is soluble in water, and is a powerful and useful oxidizing agent. I t will convert M n2+
to permanganate Cr 3+ toHchromate.
andknown. The most important salts ar e (NH 4) 2S2O 8 and K 2S2O 8.
of Se and Te are 2S2O 8 is a colourless solid, m.p. 65 °C. I t is obtained by electrolysis of sulphates at
H ydrolysis of peroxodisulphuric acid
high current density. I t is soluble in water,gives
andperoxomonosulphuric
is a powerful and usefulacid, H 2SOagent.
oxidizing 5, which is often
I t will called
convert M n2+
Caro’s acid. 3+
to permanganate and Cr to chromate. The most important salts ar e (NH ) S O and K S O . 4 2 2 8 2 2 8
H ydrolysis of peroxodisulphuric
O acid
O gives peroxomonosulphuric
O O acid, H 2SO 5, which is often called
Caro’s acid. HO S O O S OH HO S O OH + HO S OH
O O O O O O O O
HO S O O S OH HO S O OH + HO S OH
H 2SO 5 can also be made from chlorosulphuric
O Oacid: O O
(H O)(Cl)SO 2 + H 2O 2 (H O)(H OO)SO 2 + H Cl
H 2SO 5 can also be made from chlorosulphuric acid:
I t forms colourless crystals, m.p. 45 °C, but must be handled with car e since it may explode.
(H O)(Cl)SO 2 + H 2O 2 (H O)(H OO)SO 2 + H Cl
I t forms colourless crystals, m.p. 45 °C, but must be handled with care since it may explode.
10.53 | OXOHALIDES
10.53
Thionyl | OXOHALIDES
compounds
The following thionyl compounds ar e known
Thionyl compounds
SOF2 SOCl 2
The following thionyl compounds are known SOBr 2

SOF2 SOCl 2 SOBr 2

Thionyl chloride SOCl 2 is a colourless fuming liquid, b.p. 78 °C, and is usually prepared as follows:
PClfuming
Thionyl chloride SOCl 2 is a colourless 5 + SO 2 liquid,
SOCl 2+
b.p. POCl
78 °C, and
3 is usually prepared as follows:
M ost thionyl compounds are readily hydrolysed by water,
PCl 5 + SO 2 SOClthough SOF only reacts slowly.
2 + POCl 3 2

M ost thionyl compounds are readilySOCl 2 + H 2Oby water,

hydrolysed SO 2 +though
2H Cl SOF2 only reacts slowly.
The structure of these oxohalides is tetr ahedral
SOCl 2with
+ H 2one
O position occupied
SO 2 + 2H Cl by a lone pair .

The structure of these oxohalides is tetr ahedral with one position occupied by a lone pair .
:
:

S X

O XS X

O X

Sulphuryl compounds
The Sulphuryl compounds
following sulphuryl halides ar e known
The following sulphuryl
SO 2F2 halides arSO
e known
2Cl 2 SO 2FCl SO 2FBr
SO 2F2 SO 2Cl 2 SO 2FCl SO 2FBr
Sulphuryl chloride SO 2Cl 2 is a colourless fuming liquid, b.p. 69 °C, and is made by direct reaction of SO 2
and Sulphuryl
Cl 2 in the chloride
presenceSO of Cl
a catalyst. I t is used as a chlorinating agent. Sulphuryl uoride is a gas and is
2 2 is a colourless fuming liquid, b.p. 69 °C, and is made by direct reaction of SO 2
not hydrolysed by water, but the chloride
and Cl 2 in the presence of a catalyst. I t fumes
is usedinasmoist air and isagent.
a chlorinating hydrolysed by water.
Sulphuryl uorideThe is asulphuryl
gas and is
halides have a distorted tetrahedral structure. They may be regarded as derivatives
not hydrolysed by water, but the chloride fumes in moist air and is hydrolysed by water. Theof H 2SO 4, where both
sulphuryl
OH halides
groups have
have been replaced
a distorted by halogens.
tetrahedral I f onlyThey
structure. one may
groupbeisregarded
replaced,as
halosulphuric
derivatives ofacids
H SOare, where
obtained.
both
2 4
OH groups have been replaced by halogens.
FSO H I f onlyHone group
ClSO BrSOis replaced,
H halosulphuric acids are obtained.
3 3 3

FSO
Fluorosulphuric acid forms many salts, 3H chlorosulphuric
but ClSO 3H acid BrSO 3H none and is used as a chlorinating
forms
agentFluorosulphuric
in organic chemistry.
acid forms many salts, but chlorosulphuric acid forms none and is used as a chlorinating
agent in organic chemistry.

Chapter 10.indd 500 3/21/2017 11:30:11 AM

Chapter 10.indd 500 3/21/2017 11:30:11 AM
 pressure, and sold as a 30% (by weight)2 solution 2 2
which has 2a pH of about 4.0 (85% solutions are also
The H 2O 2 isHextracted
produced). O
2 2
with
solutions water
are as
stored a 1%
in solution.
plastic or Thiscoated
wax is concentrated by distillation
glass vessels, often with under reduced
negative catalysts
pressure, and or
such as urea sold as a 30%
sodium (by weight)
stannate added as solution which
stabilizers. has a pHkeep
Solutions of about 4.0 (85%
quite well, solutions
but must are alsowith
be handled
produced). H 2O 2may
care since they solutions arewith
explode stored in plastic
traces or wax
of organic coatedorglass
material vessels,
specs often with negative catalysts
of dust.
such as urea or sodium stannate added as stabilizers. Solutions keep quite well, but must be handled with
care since they may explode with traces of organic material or specs of dust.
10.55 | HALIDES
10.55 | HALIDES
Compounds with the halogens are listed in Table 10.24. Since F is more electronegative than O, binary
compounds are oxygen uorides, whereas similar chlorine compounds are chlorine oxides. Some of
Compounds with the halogens are listed in Table 10.24. Since F is more electronegative than O, binary
these compounds including the oxides of iodine, are therefore described in under ‘H alogen oxides’.
compounds are oxygen uorides, whereas similar chlorine compounds are chlorine oxides. Some of
these compounds including
Table 10.24 the oxides
Compounds of the
with iodine, are therefore described in under ‘H alogen oxides’.
halogens
Table 10.24MXCompounds
6 MX4with the halogens
MX2 M 2X2 M 2X Others
O MX6 MX4 MXOF
2 M 2O
X2 F M 2X Others
O 3F2, O 4F2
2 2 2

O Cl
OF2 2O O 2F2 ClO 2 O 3FCl 2O 6, Cl 2O 7
2, O 4F2
ClBr
O 2O
2 ClOBrO
2
2 Cl 2OBrO,
6 Cl 2O 7
3

Br 2O BrO 2 BrOI 2O 4, I 4O 9, I 2O 5
3
S SF6 SF4 SF2 S2F2 I 2O 4SSF
, I 4O2,9,SI22FO4,5 S2F10
S SF6 SFSCl
4 4 SFSCl
2 2 S2FS22Cl 2 SSF2, S2F4, S2F10
SCl 4 SCl 2 S22Br 2
S2Cl
Se SeF6 SeF4 S2Br 2
Se SeF6 SeCl
SeF 4 4 Se2Cl 2
SeCl
SeBr 4 4 Se2Se
Cl22Br 2
SeBr 4 Se2Br 2
Te TeF6 TeF4
Te TeF6 TeF
TeCl 4 4 TeCl 2
TeCl
TeBr 4 4 TeCl
TeBr2 2
TeBr
Tel 44 TeBr
TeI22
Tel 4 TeI 2
Po PoCl 4 PoCl 2
Po PoCl
PoBr 4 PoCl
PoBr2
4 2
PoBr
PoI 44 PoBr
(PoI 2 )
2
PoI 4 (PoI 2)
Compounds shown in parentheses are unstable.
Compounds shown in par entheses are unstable.

Fluorinebrings
Fluorine bringsout
outthe
themaximum
maximumvalency
valency
of of
sixsix with
with S, Se
S, Se and
and Te;Te;
andand
SF6SF 6, SeF
, SeF 6 and TeF6 are all formed
6 and TeF6 are all formed
by direct combination. They are all colourless gases and have an octahedral structure
by direct combination. They are all colourless gases and have an octahedral structure as predictedas predicted by the
by the
VSEPR theory. The low boiling point indicates a high degr ee of covalency.
V SEPR theory. The low boiling point indicates a high degr ee of covalency.

Chapter 10.indd
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508 Chapt er 10 The p-Block Elements and their Compounds

3s 3p 3d
Electronic structure
of sulphur – excited
state
six unpaired electrons form bonds with six fluorine atoms,
hence octahedral shape

SF6 is a colourless, odourless, non- ammable gas, which is insoluble in water and extremely inert. SeF6 is
slightly more reactive and TeF6 is hydrolzed by water. This is possibly due to the larger size of Te which
permits the larger coordination number necessary in the rst stage of hydr olysis.
TeF6 + 6H 2O 6H F + H 6TeO 6
SF4 is highly reactive, but is more stable than the lower uorides. I n contrast to the relatively stable
hexa uorides, the tetrahalides are very sensitive to water .

SF4 + 2H 2O SO 2 + 4H F
SF4 is a powerful uorinating agent.
3SF4 + 4BCl 3 4BF3 + 3Cl 2 + 3SCl 2
5SF4 + I 2O 5 2I F5 + 5OSF2
SCl 2 is commercially important since it readily adds across double bonds in alkenes. I t has been used to
produce the notorious ‘mustard gas’, rst used in World War I , and more recently in 1988 in the I ran–I raq war.

SCl 2 + 2CH 2 =CH 2 ® S(CH 2CH 2C l) 2

di(2-chloroethyl) sulphide
or must ard gas

M ustard gas is not a gas but a volatile liquid (m.p. 13 °C, b.p. 215 °C). I t was sprayed as a mist that stayed
close to the ground, and was blown by gentle winds onto the enemy. I t causes severe blistering of the skin
and death. I n living cells it is converted into the divinyl compound (CH 2CH ) 2S which reacts with and
disrupts proteins in the cell.
The dihalides form angular molecules, based on a tetrahedron with two positions occupied by lone
pairs. The lone pairs distort the tetrahedral angle of 109°28 to 103° in SCl 2, 101.5° in F2O and 98° in TeBr 2.

3s 3p
Electronic structure of
sulphuric atom – ground
state
two unpaired electrons can form bonds with two chlorine atom s
four electron pairs, hence structure is tetrahedral with two lone pairs

D imeric monohalides such as S2F2 and S2Cl 2 are formed by direct action between S and the halogens. S2Cl 2
is a toxic yellow liquid (m.p. −76 °C, b.p. 138 °C), with a revolting smell. The structure of S2Cl 2 and the other
monohalides is similar to that of H 2O 2, with a bond angle of 104° which is due to distortion by two lone
pairs.
S2F2 is an unstable compound. It exists in two different isomeric forms, F—S—S—F (like Cl—S—S—Cl
and H—O—O—H), and thiothionyl uoride S = SF2.
The compound S2F10 has an unusual structur e, of two octahedra joined together.

F F F F

F S S F

F F F F

Chapter 10.indd 508 3/21/2017 11:30:47 AM