,, \' ~.l:r- ,., 1,,f t t.

, ►'' J

'""{i¾roup 16 Elem ents,,

l':~~~1\lti~i~~~"9,XY;{J;~~;tl lf~~~~~·
8.1 ·Int roduction ·
Gro_up 16 elements are: oxygen (0, atomic number= 8), sulphur (S, atomic number= 16), selenium
(Se, atormc number= 34), tellurium (Te, atomic number= 52) and polonium (Po, atomic number= 84).
Group 16 elements are also known as chalcogens.
Occurrence : Oxygen is the most abundant of all the elements on earth. It forms about 46·6% by
mass of earth's crust. :qry
air contains about 21 % oxygen by volume. Oxygen has three stable isotopes :
0-16, 0-17 and 0-18. Abundance of sulphur in earth's crust is only about0·05%. Sulphur is found in
earth's crust mainly as sulphates such as gypsum (CaSO4.2H2O), epsom salt (MgSO 4 .7H2O) and baryte
(BaSO 4) and as sulphides such as galena (PbS), zinc blende (ZnS) and copper pyrite (CuFeS 2). Traces of
sulphur is also found as hydrogen sulphide in air. Organic materials such as eggs; protejns, garlic, onion
and mustard contain small amounts of sulphur. Selenium .and tellurium are found as metal selenides and
tellurides in sulphide ores. Polonium occurs in nature as a decay product of thorium and uranium.
Polonium is radioactive with a half-life of 13·8 days.
General Characteristics of Group 16 Elements
2 4
1. Electronic configuration : General .electronic configuration of group 16 elements is ns , np .
Electronic configuration of group 16 elements are given below :
4
80 ls2 , 2s2 , 2p
16S 1s2, 2s2, 2p6, 3s2; 3p4
3d10, 4s2, 4p4 .
34Se ls2, 2s2 ' 2p6 ' 3s2, 3p6, 6 10 2 4
10 2
ls2 2s2 2p6 3s2, 3p6, 3d , 4s , 4p , 4d , 5s , 5p
i'
s2Te . 1 2 2' 2p6, 3s2 3p6, 3d10, 4s2, 4p6, 4d10, 4f14, 5s2, 5p6, 5d10, 6s2, 6p4
s , s , , , . .. . . .
84Po .
. d. . Like other groups, atomic radn·mcrease on gomg down the group. The increase
.
2 Atomic ra ms ·
·.
m atormc radms om
. fr Os .
· s t p
· d.
t O is much more than mcrease m atomic ra ms from S onwards. This is because
. ld" f intervening d- and f-electrons m . e . o o. . .
of poor sh ie mg o .
. . th· 1 . Like other groups, 10msation enthalpies ·decrease on gomg down the group.
3. lomsat1on en a PY . . fr 1 ft . h I . . .
. . . . thalpies generally mcrease om e to ng t. omsation enthalpies of group 16
In a penod iomsation en l trend and are· lower th an correspon· d.mg group 15 e1ements. This is because of
.' h.
elements violate t is genera_ 15 elements.
·1·ty of half-filled p-orbitals of group .
t b
saii . hl" b
· . thalpy : In a group, electron gam ent a pies · ecome less negative on going
4 Electron gam en · d h .c f ·
· group. Th"is is . b e cause the size mcreases an t e 1orce o attraction between additional electron
down the
412 Che1111stl'J
and the nucleus decreases. Electron gain enthalpy of oxygen is however less negativ~ than that of sulphur.
This is because of smaller size of oxygen atom and 2p subshell of oxygen atom which acc~mmodates the
additional electron. Additional electron faces greater electronic repulsion, less energy ts released on
addition of one electron and electron gain enthalpy is less negative in case of ~xygen. F_rom sulphur
onwards, the general trend is followed and electron gain enthalpy becomes less negative on gomg down the
group.
5. Electronegativity : Next to fluorine, oxygen is the second most electronegative elem~nt among all
elements. Like ·other groups, electronegativities of elements of this group also decrease on gomg down the
group. ,
6. Physical state : Oxygen is a gas whereas other elements of this group · are solids at roorn
temperature. The boiling and melting points increase on going down the group.
7. Metallic character : Oxygen and sulphur are non-metals. Selenium and tellurium are metalloids
and polonium is a metal.
8. Allotropy : All the elements of this group show allotropy.
9. Catenation : The first two elements of this group, oxygen and sulphur, show the property of
catenation. As in case of group 15 (cf p. 368); because of repulsion between non-bonding electrons, the
0 - 0 single bond is weaker than S-S single bond. Becau_se of this reason, catenation tendency of
oxygen is weaker than that of sulphur.
10. Anomalous behaviour of oxygen : Like first member of other groups, oxygen differs from rest
of the members of its group in many ways. This is due to small size, higher electronegativity and higher
ionisation enthalpy of oxygen and due to unavailability of d-orbitals in oxygen. Some of the important
differences between oxygen and the other members of this group are as follows :
(i) Oxygen is a gas whereas other elements of this group are solids at room temperature. This is
explained on the basis of atomicity of elements of this group. Oxygen, because of its small size, is capable
of forming p1t-p1t bonds and hence exists as diatomic (0 2) molecules. Other elements of this group are not
able to form p1t-p1t bonds and exist as polyatomic molecules. Sulphur exists as s . Because of small size
8
of oxygen molecule, van der Waals forces of attraction between oxygen molecules are much weaker.
Hence oxygen is a gas whereas .other elements of this group are solids at room temperature.
_ (ii) Because of the absence of d-orbitals in oxygen, maximum covalency of oxygen is four. In
practice, covalency of oxygen rarely exceeds two. On the other hand, other elements of this group can
expand their octet and covalency may exceed four.
(iii) Oxygen (0 2) is paramagnetic whereas other elements of this group are normally diamagnetic.
11. Oxidation States : ?xi_d~tio~ state of _oxygen in most of its compounds is -2. In peroxides, its
oxidation state is -1. In 0 2F2 its ox1dat1on state 1s + 1. In OF 2 its oxidation state is + 2 . Oxidation states of
s, Se and Te are -2, +2, +4 and +6. Oxidation states of Po are +4 and +6. ·
The stability of -2 oxidation state decreases o~ going down the group. This is because the
electronegativity of these
. . elements also decreases on. . gomg down the group . B ecause o f me . rt parr
• effect'
the stability of +6 oxidation state decreases and stab1hty of +4 oxidation state 1· . down the
ncreases on gomg
group. ·
Bonds formed by elements of this group with +4 and +6 oxidation stat . t
• . . es are mamly cova1en .
12 Nature of hydrides : The important properties of hydrides of .
• · e1ements of this group are
summarised below :
Group 16 Elements (The Oxygen Family)
413
( 1) Ionic character decreases
(2) Bond strength decreases
( 3) Thermal stability decreases
(4) Reducing character increases
(5) Acidic character increases
( 6) Basic character decreases
(7) Bond angle decreases
Bond angles in H20, H2S, H2Se and H 2Te are 104·5°, 92·5°, 90° and 89° respectively.
Ionic ~h~acter of hydrides of group 16 elements decreases on going down the group. This is because
electronegativity of ele~en~s of group 16 decreases on going down the group. Hence the polarity of
E-!f
This ·
bond decreases _and the 10mc characte r decreases. Bond strength decreases on going down the group.
is because the size of the atoms of elements of group 16 increases on going down the group. Bonds formed
group
by smaller atoms are in general stronger bonds. Thermal stability decreases on going down the
the
because the bond strength decreases. Reducing character increases on going down the group because
bond strength decrease s and it is easier to break the E-H bond to get hydrogen which acts as a reducing
it is
agent. Acidic characte r increase s on going down the group because the bond strength decreases and
the
easier to break the E-H bond to get H+. Basic character decreases on going down the group because
group. Bond
stremrth of the bond formed by elements of group 16 with H+ decreases on going down the
and
angl; decrease s on going down the group because the size of atoms of elements of group 16 increases
angle
the electrone gativity decrease s. Hence the repulsion between bond pairs decreases and the bond
decreas.es.
Boiling points of hydrides of group 16 elements are as follows :
H 2O (l00°C) , H 2S (-60°C) , H 2Se (-41 °C), H2Te (-4°C) and H2Po (36°C).
The increasing- order of. boiling points is as follows :
Boiling point : H 2S < H2Se < H2Te < H2Po < H2O
des of elements of group 16 increase on going down· the group. Hence the
Molecul ar masses of h Ydri · d th th

;:::~/:n
.. 1t 1s expecte at e
f ti also increase on gomg down the group. Hence
va~ _der W:aals forces;~ going down the group. Because of high electronegativity of oxygen,
boding pomts also wi . ted through intermolecular hydrogen bonding. Because of this reason,
water (H20) molecul es are ass~~ia are maximum in water. Thus boiling point of water is maximum .
10
intermol ecular forces of attra~ ~. uid at room temperat ure and H2S, H 2Se and H 2Te, inspite of having
Because of this reason, water is a iq tur
ses at room tempera e. . . . .
higher molecul ar masses, are ga sulphur dioxide (SO 2),
• • Im rtant oxides formed by elements of this group are

~n:u
13. Na~re of o:udes ·1 _po dioxide (TeO 2) sulphur tri-oxide (SO 3),
selenium diox1~e (Se02), tel
selenium tri-oxide (SeO
oxides are acidic. SO2 and SO 3 are gases whereas other oxides listed
tellurium tri-ox1de (Te03), A t : e Reducing property of dioxides decreases from SO 2 to TeO 2 . Sulphur
3) and

above are solids at rooi_n tempera r;-llurium dioxide (TeO 2) is oxidising in nature.
. . (SO ) . reducmg whereas e
dioxide 2 is . es. The elements of group 16 form halides of the type E 2X 2 (monohalides), EX2
14. Nature of hali~ . · . d EX (hexahalides) where E = element . .
of group 16 and X == halogen.
.
1 ) EX4 (tetrahalides) an tr negative
ih rd 6
than chlorine, bromme or 10dme, the compounds of oxygen
(d a es , 'd h .
. . . more e1ectermed o kn
as halides. They are own as ox1 es. T us Cl 2O 7 1s named as
Smee oxygen is b
with these halogens can not. enamed as iodine pentoxide. Such compounds have not been included in the
. d Io 1s
chlorine heptox1de an 2 5
following discussio n.
414
Chemistry
Monohalidcs : 02F2 is highly unstable at room temperature. The well known monohalides ares F
S2CI~, S2Br2, Se2Cl2 and Se2Br2, They are dimeric in nature. They slowly undergo disproportiona:io~
reaction as follows :
2Sc2Cl2 - ~ ScC l4 ~ 3Se
.Dihalidcs : The we.II k'.1own di halides arc OF 2, SF 2, SCl2, TeCl 2, Te8r2, Tel 2, PoCJ 2 and PoBr .
3 2
Selenium does not fonn d1hahdcs . The central atom in these molecules is sp hybridised and the shape of
the molecule is angular.

Tetrahalides : The well known tetrahalides arc SF 4, SCl4, SeF 4 , SeC14 , SeBr4, TeF4, TeCJ 4, TeBr ,
4
Tel4, PoCI.i and PoBr4 . Among tetra fluorides, SF 4 is a gas, SeF 4 is a liquid and TeF4 is a solid. The central
3
atom in these molecules is sp d hybridised, the lone pair occupies one of the equatorial positions and the
shape of the molecule is irregular tetrahedral or see-saw shaped.
The structure of SF 4 is shown in Fig. 8· I . Structures of other tetrahalides are similar.

or

F
Fig. 8· 1. Structure of SF4

.It is obvious from the above structure that all the S-F bonds in SF4 are not equivalent.
Hexahalides : Among hexahalides, only hexafluorides are stable. The well known hexafluorides are
SF 6 ,SeF 6 and TeF 6 . All hexafluorides are gaseous in nature. The central atom in these molecules is sp3d2
hybridised and the shape of the molecule is octahedral.
SF6 is exceptionally stable and chemically inert. SeF6 is slightly more reactive and TeF 6 is still more
reactive. The relative reactivities of hexafluorides .is explained on the basis of steric hindrance. S atom in
SF6 is highly sterically hindered. It is a smaller atom and is surrounded by six fluorine atoms. Hence the
attacking reagent do not get space to reach the sulphur atom and react. Hence SF6 is exceptionally stable
and chemically inert. Se and Te atoms are larger than S. Hence extent of steric hindrance is less in SeF6 and
even lesser in TeF6 . Hence SeF 6 is slightly more reactive and TeF6 is still more reactive and can be
hydrolysed. Hexachlorides, hexabromides and hexa-iodides do not exist because six large atoms can not be
accommodated because of lack of space around one single atom. Tetrachlorides, tetrabromides and
tetra-iodides exist because it is possible to accommodate four large atoms around one single atom.

8.2 Oxygen (0 2 )
Oxygen exists as diatomic molecules (0 2). According to systematic I.U.P.A.C. nomenclature,
molecular oxygen is known as dioxygen. We will be retaining the common name oxygen for molecular
oxygen in the following discussion.
Group 16 Elements (The Oxygen Family)
Methods of preparation : l. In the · 415
of potassium chlorate (KClO ) laboratory, oxygen is
this reaction. 3 and manganese dioxide (MnO )usually prepare~ b~ heating a 5 : 1 mixture
_ 2 · Manganese d1ox1de acts as a catalyst in
2KC1O Mn02, A
3
2 O · 2KCI + 30
• xygen can also be obtained b h . 2
y eating potassium nitrate or potassium permanganate.
. 2KN A
03 - ~ 2KNO 2 + O
2
2KMn04 .
A K2MnO4 + MnO + 0
3. Oxygen can also be obtained b h . . 2 2
Y eating oxides of heavy metals, e.g.,
2Ag2O(s) .- ~ 4Ag(s) ·+ O2(g)
2HgO(s) - - 2Hg(/) + O2(g)
2Pb304Cs) - - 6PbO(s) + O2(g)
2PbO2(s) - - 2PbO(s) + O2(g)
4. Oxygen can also be obtained by decomposition of hydrogen peroxide.
2H~Oi(aq) - - 2H2O(l) + Oi(g)
. The rate of decomposition of .hydrogen :Qeroxide can be increased by using finely divided metals or
manganese dioxide as catalysts. The rate of decomposition of hydrogen peroxide can also be increased by
heating:
5. On a large scale, oxygen is prepared from air. For this purpose carbon dioxide and water vapours
are first removed from air. The remaining gases are liquefied and fractionally distilled to give nitrogen and
oxygen. Liquid nitrogen (b.p. 77·2 K) distils out and liquid oxygen (b.p. 90 K) is left behind in the
distillation flask.
6. On a large scale, oxygen is prepared by _electrolysis of water containing traces of an acid or alkali.
Electrolysis
2H2 (g) + 0 2(g)
(at cathode) (at anode)

• l roperties : Oxygen is a·colourless. and odourless gas. It is soluble in water to the extent of_
Phys1ca p . 1 . . f . d . . al
3 3 of water which is sufficient for norma resprration o manne an aquatic anim s. It
3·08 cm per 100 cm . .
. K d fr ezes at 55 K. Inspite 'of havmg even number of electrons, oxygen (0 2) molecule
liquefies at 90 an e
rty that it is paramagnetic. This is explame on e b asis
. . . . d th . f 1 ul .
. o mo ec ar orbital theory
has the umque prope · .
(see Chapter of Chemical Bondmg, Class XI Book). . .
• ti . Oxygen directly reacts with nearly all metals and non-metals except some
Chemical propPe)r esd · ome noble gases to form binary compounds known as oxides. For example,
met a1s (e.g., Au and t an · s co·
C+O2 --➔ 2
P 4 + 502 --➔ P4O10
2Ca + 02 --➔ 2CaO
4Al + 302 --'---➔ 2Al2O3
. e uire some initiation. Some external heat is required to star! the reaction as
All thes~ reactions r q f O=O bond is high (493·4 kJ mol- 1) . All these reactions are generally
bond dissociation enthalpy
O
·f th' s reason once the reaction starts, it goes on and on till the reaction is
· Because o i ' .
strongly exoth .ermic. . known as combustion reactions.
completed. Such reactions are
 416
Ohe1111stry
Oxyge n brings about oxidat ion of many organi c and inorga nic
. h . compo unds also. The reaction ma
requrr e eatmg or presen ce of cataly st or both . y
Comb ustion of gaseou s hydro carbon s takes place as follow s :

C,H,, +(x+: ) 02- - xC0 2 + ~ HzO

For examp le,
CH 4 + 20 2 CO 2 1- 2H 20
C2H4 + 30 2 2C0 2 + 2H20
Reactions of oxyge n with some other compo unds are given below
:
2ZnS + 302 - - 2Zn0 + 2S02
Pt or Vz0 5
2S0 3
4so c
0

CuCl2
4HCI + 0 2
450 °c
Uses : 1. The chief importance of oxyge n lies in its supporting vital proces
ses such as respiration and
combu stion. The compl ex forme d betwe en oxyge n and haemo globin
transp orts oxyge n round the body to
the cells which actual ly use it. Energ y is produ ced in the body by
combu stion of glucos e as follows :
C 6 H 120 6 + 60 2 --➔ 6C0 + 6H 0 + energy
2 2
It is also used for artificial respiration. Oxyge n cylinders are widely
used in hospitals.
2. It is used in oxy-h ydrog en and oxy-acetylene flames used in weldin
g and cutting metals .
3. It is used as an oxidis ing agent in many metallurgical processes, ·e.g.,
it is used in manufacture of
steel.
4. Mixtu res of liquid oxyge n and liquid fuels such as hydrazines
are used as propellants in rockets.
8.3 Oxides
Binary compo unds of oxyge n with other elements (except fluorin
e) are known as oxides. In many
cases, one eleme nt forms two or more oxides. Oxides can be simple
(e.g., MgO and Al2 0 3 ) or mixed (e.g..
Pb 3o4 and F~04 ). Mixed oxides are stoichiometric mixtures of
two simple oxides of the same element.
For examp le, Fe30 4 is a I : I stoichiometric mixture of FeO and
Fe20 3.
Simpl e oxides are classified according to their properties as follow
s :
L Acidic oxides : Most of the oxides of non-metals are acidic. Oxide
s of some metals in higher
oxidation state are acidic . S0 2, Cl207, N205, Mn207, Cr03 and V
20 5 are examples of acidic oxides. They
react with bases to form salts and dissolve in water to form acids.
For examp le,
S0 2 + 2NaO H - - - + Na2S0 + H 0
3 2
S02 + H2 0 . H2S03
2. Basic oxides : Most of the oxides ·of metals are basic. Na 0 , CaO and
2 BaO are examples of basic
oxides. They react with acids to form salts and dissolve in water to
fom1 bases. For example,
CaO + 2HC1 - - CaC1 2 + H20
CaO + H20 _ __, Ca(OH )i
3. Amphoteric oxides : Some metallic oxides show dual behaviour.
Al20 3, ZnO and Sn02 are
examples of amphoteric oxides. They react with both acids and bases
to form salts. For example,
 16 Elements (The Oxygen Family)
GrOU P 417
Al2O3(s) + 6HCl(aq) + 9H 2O(l)
2 [Al(H2O)6] 3 ~(aq) + 6C l- (aq)
Al 2O)(s) + 6NaOH(aq) + 3H 2O(/)
➔ 2Na3 (Al(OH) 6 ](a q)
Simplified version of the above reactions is :
Al2O3(s) + 6HCl(aq)
Al2O3(s) + 2NaOH(a )
. q 2NaAJO 2 (aq) + H20 (/)
4. Neutral oxides : There are some oxides h. .
tral oxides. Examples of neutral 'd w ich neither react with acids nor bases. T hey are kn o wn
as neu oxi es are CO, NO and N2O.
s.4 Ozone 103 1
Ozone is an allotropic fonn of. oxyge n. It exists · ·
. m very small amounts in atmosph ere at sea level.
(
Lower stratosphere atmospheric .
region 20 t 0 30 k 'lometers above earth) contains much high
. h . i er concen -
tration .of ozone t an other regions of atmo sp h ere. Th is • of atmosphere 1.s known as ozone layer.
' region
.
Ozone m stratosphere 1s a product of W radiations acting upon oxygen.
, t et hod 0 ~ p r epara_tion : Ozo_ne i~ prepared by pa~sing silent ele~tric discharge through pure and
dry oxygen °~ arr. The silent electric discharge is performed by packing insulating materials between
electrodes. This prevents any local rise in temperature which would lead to the decompositio n of ozone.
302 ~ 203; Mi=+ 142 kJ mol- 1
The above reaction is an endothermic reaction and energy is to be supplied to carry out this reaction.
The apparatus used for this purpose is known as ozonizer. There is only about 10% conversion of oxygen
to ozone and the product is known as ozonised oxygen. If concentration s of ozone greater than I 0% are
required, a bat!ery of ozonizers can be used. Fractional liquefaction of ozonised oxygen can also be
employed for this purpose. On cooling ozonised oxygen, ozone separates as a liquid much earlier than
oxygen. This is because boiling point of liquid ozone (-112°C) is higher than the boiling point of liquid
oxygen (-183°C).
Physical properties : Ozone is a pale blue gas. It has a 'characteristic smell. In small- concentration s
it is harmless but at higher concentration s in air, it is harmful as breathing becomes uncomfortabl e resulting
in headache and nausea. It is heavier than oxygen. It is sparingly soluble in water but readily soluble in
turpentine oil. In liquid state it is dark blue and in solid state it is violet-black in colour.
Chemical properties :
· l. Sta hilitv : Ozone is thermodynam ically unstable with respect to oxygen. This is because AH for
decompositio n of ozone to oxygen is - ve and /:1S is +_ve. Both these factors reinforce each other an? /:lG is
-ve . H'gh ·
1 concen trat'ions o f ozone , e·g··, liquid or sohd ozone can therefore be dangerously explosive.
e gas ·decomposes spontaneously at a slow rate, which increases rapidly
At room t emperature, Ozon
with temperature.
203 --➔ 302
.. . b catalysed by substances such as plati~um, palladium, silver and MnO?. _
The decompos1tio n can e .
. . . _ • _, • • Ozone is an endothermic compound and 1s thennodynam ically unstable. It
2. Ox1d1smg ch.aractcr.. en and nascent oxygen as follows :
slowly decomposes to give molecular oxyg _
03 ---? 0 2 +0
. . hi reactive and powerful oxidising agent. Hence ozone is a powerful
_ . ~ascent oxygen is ~ig Y f of O and p 2 are +2·7 V and +2·87 V respectively and hence 0 ~--- is
ox1dismg agent. The reduction poten ia1 3
the most powerful oxidising agent after F 2 · . _. .
- • of ozone as ox1d1smg agent are given below :
Some of the important reactions
 418 Cbenitat.-,
(I) Oxldntlon of sulphur :
S + H20 + 30 3
(ii) Oxidation of phos1>horus :
2P + 3H 2O + 50 1
(Iii) Oxidation of orscnlc :
2As + 3H 20 + 503
(Iv) O:ddntion of Iodine :
12 + H 20 + 503 2HI0 3 + 502
(v) Oxidation of HCI :
2HCI + 03 --➔

(vi) Oxidation of lead sulphide :

PbS + 4~3 PbS04 + 402
(vii) Oxidation of FeS04 :
2FeS04 + H2S04 + 03
(viii) Oxidation of Hg :
2Hg + 0 3 - - Hg20 + 02
Hg o is soluble in Hg. The solution of Hg 0 in Hg sticks with glass and due to this reason mercury
2
loses its :roperty of free flowing. Droplets of mercury sticking with glass therefore consist of a solution of
Hg 0 in Hg. These are known as tailings of mercury. Mercury in eontact I . f 1 .
2 o ozone oses its meniscus
because of the above reaction.
(ix) Oxidation of KI :
2KI(aq) + H20(/) + O)(g)
The abQve reaction is used for testing the presence of ozone as follows :
A paper soaked in KI and starch solution, when brought in contact of ozone, turns blue because of
the above reaction. Iodine, which is blue in colour, forms deep blue coloured starch-iodi de complex with
starch solution.
The above reaction is used for quantitativ e estimation of ozone as follows :
The above reaction is normally accompani ed by side reactions leading to the formation of iodates
and other compound s of iodine. When this reaction is carried out with potassium iodide solution buffered
with a borate buffer (pH 9·2), iodine is liberated quantitativ ely. Amount of iodine liberated is determined
by titrating it against a standard ~olution of sodium thiosulpha te. Amount of ozone reacted can then easily
known from the amount of liberated iodine and equation of the reaction.
(x) In addition to the above reactions, ozone oxidises NO to N0 , N0 to N o , stannous chloride to
2 2 2 5
stannic chloride, K2Mn04 •to KMn04, K4Fe(CN) 6 to K Fe(CN) , nitrites to nitrates and arsenites to
3 6
arsenates.
(xi) It does not react with KMn0 4 or K 2Cr 0 .
2 7
'3. Reaction with sUvtr :
2Ag + 0 3 Ag20 +02
Ag2 0 + 0 3 2Ag + 20 2

302
Group 16 Elements (The Oxygen Family) 419
The_ ab_ove reaction explains the catalytic action of silver in decomposing ozone. It can also be used
for quantitative estimation of ozone. For this purpose, a sample of ozonized oxygen is catalytically
decomposed and change in volume is noted. It also explains why silver jewellery is tarnished in air. Small
amo~ts of ozon~ present in air are decomposed into oxygen in presence of silver. During this reaction
iliere is no chemical change in silver but its particle size is reduced and hence there is change in colour.
Ano ther reason why silver jewellery is tarnished in air is that Ag 20 formed above reacts with H2S to form
black coloured Ag 2S.
4 · Reaction with peroxides : It reacts with peroxides and converts them into normal oxides. For
example,
Ba0 2 + 0 3 - - - - 4 BaO + 20 2
H202 + 0 3 - - - 4 H 20 + 20 2
Oxidation n~ber of O in 0 3 is zero which is maximum for oxygen (only in F 20, the oxidation
number of oxygen .is more than zero). Ozone itself therefore can not be oxidised and hence can not act as
reducing a~ent. In a _few reactions, (for example, the above two reactions and reaction of Ag20 with 0 3), it
appe~s as if ozone 1s acting as a reducing agent and because .o f this reason, many authors consider it as a
reducmg agent also which obviously is not correct.
5. Bleaching action : Being a strong oxidising agent, ozone is ·u sed as a bleaching agent.
03 - - - » 02 + 0
Coloured substance + 0 _ __,. Colourless substance
Structure of ozone : Ozone is a resonance hybrid of the following two structures :

0 0
~'---... /~
0 0 0 0
It has a bent structure with 0-0-0bond angle equal to 116·8°. The two 0-0bond lengths are
equal to 1·278 A.
Importance and depletion of ozone layer : The ozone layer is important because it absorbs
ultraviolet rays of sun that are harmful for human beings and can even cause skin cancer. Recently,
ecologists have become concerned by thinning of the ozone layer by freons and oxides of nitrogen.
The main reason of ozone layer depletion is believed to· be the. release of N0 2 and chloro-
fluorocarbons into the atmosphere. Nitric oxide (NO) is formed by combination of nitrogen and oxygen
gases under the influence of high temperature of automobile and supersonic jet aeroplane engines and
emitted from their exhaust systems. It immediately reacts with oxygen to .form nitrogen dioxide (N0 2) gas.
Chlorofluorocarbons also known as freons are man-made industrial chemicals mainly used in air-
conditioning and ·in aerosol sprays used for cleaning computer parts. Once these chemicals (N0 2 and
freons) are released into the atmosphere, they mix with normal atmospheric gases and eventually reach the
stratosphere.
Depletion of ozone by N0 2 takes place as follows :
N0 (g) hv NO(g) + O(g) X 2
2
O(g) + 03(g) - - 202(g) x2
2NO(g) + 0 2(g) - - 2N02(g)
 420
(for examp· Ie CCI 2F2j takes place as follows :
· of ozone by freons
Depletion

CClzFz(g)
hv Cl• + • CCIF2

Chlorine free radicals catalyse the decompos1'fon

1 of ozone as follows :
Cl. + O}(g) _ _ , ClO• + Oz(g) ·
ClO• + O3(g) _ _ , Cl• + 2Oz(g)

2O 3(g) - ~ 3Oz(g)
· · 1 use 1s
l lses of ozone : 1. Its prmc1pa · ten·1·s
· ms 1 1·ng water and air.
. . As it is a strong oxidis·ing agent ·
. .
unmediately . germs and bactena
kills . present
· · wat er or air and stenhse them.
m ' 11
2. it is used as a bleaching agent for oils, ivory,. flour, starch and many 0ther substances.
3. It is used as an oxidising agent in many reactions.
4. It is used in the manufacture of potassium permanganate.
5. It is used in ozonolysis of alkenes and location of double bonds.

8.5 Allotropes of Sulphur .·. ·:..•; / .

Sulphur forms a large number of allotropes. Rhombic sulphur (yellow sulphur, a-sulphur) and
monoclinic sulphur (~-sulphur) are the most important allotropes of sulphur. Rhombic sulphur on heating
above 96-5°C is slowly converted to monoclinic sulphur. Monoclinic sulphur on cooling below 96-5°C is
slowly converted to rhombic sulphur. At 96-5°C, there is an equilibrium between rhombic sulphur and
monoclinic sulphur. This temperature is called transition temperature.
96-5 ° C
Rhombic sulphur. ~ Monoclinic sulphur
' .
_ All other forms of sulphur on long standing at room temperature are converted to rhombic sulphur.
Rhombic sulphur (a-sulphur) : It is lemon-yellow in colour. Its specific gravity is 2·06. When
heated quickly -beyond 96·5°C, which prevents its transformation to monoclinic sulphur, it melts at
112·8°C. It has rhombic crystals. Crystals of rhombic sulphur can be obtained by di;solving roll sulphur
(rolls of sulphur made by c~sting molten sulphur) in carbon disulphide (CS ) and evaporating the solution.
2
It is insoluble in water, slightly soluble in alcohol and ether arid readily soluble in cs .
2
. Monoclinic s_ulphur : ~t is amber?ello~ in colour. Its m.p. is 120°c. Its ·specific gravity is 1·98. It
is prepared by melting rhombic sulphur m a dish and cooling. When a crust is formed on the surface, two
holes are ~ie~ced in it and the rem~ining l~quid ~s poured out. On removing the crust,' needle shaped crysta!s
of monochmc sulphur are found m the dish. Like rhombic sulphur, it is insoluble in water and soluble lil
·cs 2 .
Both rhombic and monoclinic sulphur have s8 molecules Th S • . b h h .:: · puckered
· . - · e 8 rmg m ot t e 1orms 1s
and has a crown shape (Fig. 8·2). Th~ two forms differ in the overall packing of Sg rings in the crystals.
s s '

Fig. 8·2. The structure of S .

grmg

I
Group 16 Eleme~ts (The Oxygen Family) 421
Other forms of , I h . . . . . .
are know su ~ Ul • Several other allotropic forms of sulphur contammg 6 to 20 sulphur atoms
O 0
adopts ch:ir fon~ ~:he_se is cyclo-S6 which contains s6 molecules. T~e ring in S6 molecule in cyclo-S 6
. · higher temperatures, chains break and other chains or rings are formed. At 200°C, the
vapours consist mostly O f S . . . . .
R nngs . At 600°C the gas mainly consists of S2 molecules which, hke 0 2
l l
mo ecu es, are paramagnetic. '

8.6 Sulphur Dioxide

d. _dlt ~cc~s ii~ ~olcanic gases . lt also occurs in small amounts in air of towns. The presence of sulphur
ioxi e m a~r on gmates from burning of coal which contains small amounts of sulphide ores such as
copper and iron pyrites · It al so ongmates
· · from burning of other fossil· fu els. Sup
I hur d'10x 1·de Is
· an aJT
·
pollutant. Even low concentrations of sulphur dioxide in air cause respiratory di seases, irritation to eyes
a nd some other complications (cf Chapter ·of Environmental Chemistry, Class XI Book).
}\,lc~ho~s of preparation : 1. Sulphur dioxide (SO ) is formed together wi th a little (6 to 8%)
2
sulphur tnoxide when sulphur is burnt in air or oxygen.
S(s) + Oi(g) - - - SOi(g)
2. In the laboratory, it is prepared by treating a sulphite salt with dilute sulphuric acid. For example,
Na2SO3(s) + H 2SO 4(aq) - - Na2SOiaq) + H2O(1) + SO2(g)
3. Industrially, it is produced as a by-product of roasting of sulphide ores. For example,
4FeS2(s) + 11O2(g) - - 2Fe2O3(s) + 8SOi(g)
The gas after drying is liquefied at room temperature under a pressure of about 2 atmospheres and
stored in steel cylinders. ·
Physical p r operties : It is a colourless gas with a pungent and suffocating odour. The boiling point
of liquid sulphur dioxide is -10°C. It is freely soluble in water.
C hemical prope-r tie§ : ·
1. Reaction with water : When sulphur dioxide is passed through water, sulphurous acid is formed
as follows :
SOi(g) + H 2 O(l) ~ H 2 SOiaq)
Sulphurous acid is an unstable acid and has never been isolated. It is stable only in aqueous solution
and in the form of its salts.
2. Reaction with NaOH : Sodium sulphite (Na2SO3) is formed on passing SO 2 gas in NaOH
solution . Sodium hydrogen sulphite (sodium bisulphite, NaHSO 3) is formed on passing SO 2 gas in excess.
2NaOH + SO 2 - - - Na2SO3 + H 2O
NaiSO 3 + H 2O + SO2 - - 2NaHSO3
Note : Reactions ofSO 2 with water and NaOH solution are similarto reactions of CO 2 ,,vith water and
NaOH solution. . .
3. Reaction with chlorine : Sulphur dioxide reacts with chlorine in presence of charcoal (which acts
as a catalyst) to give sulphuryl chloride (S02Cl2)-
SO2(g) + Cl2(g) - - - + SO2Cl2(l)
.
4 Reactio n wi th PCJ5 : It reacts with PC1 5 to give thionyl chloride (SOC1 2) .
so2(g) + PC1 5(s) - - SOC12(l) + POC13(l)
. Reaction with oxyge·n : It reacts with oxygen as follows :
5
Pt or VzOs ( catalyst)
2SOz(g) + Oz(g) 45O 0c 2SO3(g)
 . Ohenilstl'y
4 22
. 1 hur dioxide acts as a redu cmg agent. For exalllple,
tion s, su P
6. Red ucin g prop ertie s : In many reac. . ferrous ions as follows+ :
2- + 48
(i) In aqueous solution , it redu ces ferric ions to 2+
2Fe3~ + S0 2 + 2H20 . 2Fe + S04
ride as follows :
Thu s feJTic chloride is reduced to ferrou s chlo
2F eCl 2 + 2HC1 + H2S
04
2FcC I + 2H O + SO _ __,, , to chro mic ions as folJows :·
3 2 . 2 .
d1ch roma te ions J + + SO 2-
(ii) In acidic solution , it reduces 3 4
Cr2o / - + 2H~ + 3S0 2 _ __,, Cr + HzO
2
. h. omtc · sulphate as foJlows :
t
Thu s potassium dichromate ,s reduced to c
K2C r20 7 + H2S 04 + 3S0 2 _ _..., K2S04
+ Cri( S04 )} + H20_
. of potassmm · d · hromate '. whe n brou ght m contact of so2 gas,
. . . . solution IC . h
A paper dipped m ac1d1c used m dete ctmg t e pres ence of S02 gas.
reaction is thus
turn s green because of the abov e reaction . This
· · · na · ns to man gane se ions as follows :
te 10
···
(m) In acidic solut1on ' 1t redu ces perm anga 2+ + 5SO4z-
2Mn 04 - + 2H 20 + 5S0 2 _ __,, 2Mn
+ 4H · +
manganese sulp hate as follo ws :
Thus potassium permanganate is reduced to
2K.Mn0 4 + 5S0 2 + 2H20 _ __,, K 2S04
+ 2Mn S04 + 2Hz S04
ting the
urless. This reac tion can also be used for detec
KM. no is pink in colour and MnS 0 4 is colo
4
pres ence of S02 gas.
(iv) It reduces Cl 2 to HCl as follows :
Cl2 + 2H2 0 + S02 - - 2HC1 + H 2S04
7. Oxi disin g ~prop ertie s : Sulphur dioxide
acts as an oxid ising agen t also. For example,
2H2 S + S02 - - 2H2 0 + 3S-i
4Mg + S02 - - - 2Mg 0 + Mg2 S
0 + sj,
2SnCI2 + S02 + 4HC1 --➔ 2SnC14 + 2H2
like flowers,
as a blea chin g agen t for man y substances
8. Blea ching acti on : Sulphur dioxide acts property.
n of sulphur dioxide is due to its redu cing
leaves and dyed fibres. The bleaching actio
Coloured substance Colo urle ss subs tanc e
(redu ced state)
(oxidised state)
on long
lly temporary. The colo ur is usua lly restored
The bleaching action of sulphur dioxide is usua
stan ding because of atmospheric oxidation.
the following
dioxide (S.0 2) is a reso nanc e hyb rid of
Structur e of sulp hur diox ide : Sulphur -
structures :
•• ••
Of- --S= O ~<---+> O=S ➔ O
Because of
2
d and the mol ecul e is angu lar in shape.
The sulphur atom in SOz is sp hybridiseare equal.
S02
reso nanc e, the two sulphur-oxygen bonds in
Use s of sulp hur diox ide : 1. It is used in
refining petr oleu m and sugar.
silk.
2. It is used as a bleaching agent for wool and
preservative.
3. It is used as an antichlor, disinfectant and
h •dr . d. sulphite,
is used in the man ufac ture of sulp h~ic acid sod• m
4. It · o) and' mm h Y oge~ sulphi!e, so _m
ate (hyp
c~lcium hydr ogen sulphite, sodium thiosulph man y ot er cherrucals of mdu stna1 use.
for m . . . d
5. Liqu id SOz is _used as non-aqueous solvent any orga mc and mor gam c com poun s.

- ◄
Group 16 Elements (The Oxygen Family) 423
8. 7 Oxo-acids of sulphur
Structures of import ant oxo-ac1ds .
· of sulphur are given below :
0
i
1. Sulphurous acid (H 2so 3) : H-0-S-O-H
0
2. Sulphuric acid (H 2so4) :
i
H-0-S-O-H
J,
0
0
i
3. Thiosulphuric acid (H 2s2o 3) : H-O-S-0-H
J,
s
4. Permonosulphuric acid or Caro's acid (H 2S0 5) :
0
i
H-O-S-0-0-H
J,
0
0 0
i i
5. Hydrosulphurous acid (H2S20 4) : · H-0-S-S-O-H
0 0
i i
H-O-S-S-0-H
J, J, .
0 0
7. Pyrosulphuric acid, fuming sulphuric acid or oleum CH2S207) :
0 0
i i
H-0-S-O-S-O- H
-!, -!,
0 0
8. Perdisulphuric acid or Marshalls acid (H2S20s) :
0 0
i i
H-O-S-0-0-S -0-H
-!, -!,
0 0
0 S 0
i i . i
9. Tetrathionic acid (H2S406) : H-O-S-S-S-0- H
-!, -!,
0 0
Some of these acids are unstable and can not be isolated. They are known in aqueous solution or in
the form of their salts.
 Chemistry
424

a.a Sulp huric ,acid .

· · I (FeSO 4· 7H 20) and JS also known as oil of
It can be prepared by the distillation of green vitno
vitriol.
FeSO 4 + 7HzO] X 2
[FeSO 4 .7HzO
2FeSO 4 Fe 2O 3 + SO2 + SO3
SO + H O2
H2SO4
3

2FeSO 4.7H2O Fe2O3 + SO2 + H2SO4 + 13H2 0

Sulphuric acid is manufactured by Conta ct process which
'1anu factur(' of sulphuric acid
involves the following three steps :
(i) Burnjng of sulphur or sulphide ore : Burning of sulphu
r or sulphide ore in air leads to the
formation of sulphur dioxide gas.
S+O 2 - - S02
4FeS 2 + 1102 - - 2Fe2O3 + 8SO2
(ii ) Oxida tion of sulphur dioxid e : Oxidation of sulphur dioxid
e by atmospheric oxygen takes place
as follows : 1
M-I = -196- 6 kJ mol-
is accompanied by a decrease
The above reaction is an exotheniric reaction and the forward reaction
high pressu re are the favourable
in volume. According to Le-Chatelier's principle, low temperature and
n is howev er very slow at low
conditions for the maximum yield of sulphur tri-oxide. The reactio
reaction. Platin um (Pt) or Vanadium
temperatures. Therefore a catalyst is used to increase the rate of the
n rate is not reasonable even after
pentoxide (V2O5) can be used as a catalyst in this reaction. The reactio
used. The most favourable conditions
using the catalyst at low temperatures. Hence a higher temperature is
of sulphuric acid are a pressure of 2
for production of sulphur: tri-oxide by this reaction for the manufacture
bar and a temperature of 450°C and presence of V 20 5 as catalyst.
(iii) Absorption of S03 by concentrated H2S0 4 : SO3 dissolves
in H 20 and produces H 2SO 4 as
follow s:

lt to condense. Therefore,
The reaction is violent and produces a dense chemical mist which is difficu
acid. Fumin g sulphuric acid or oleum
instead of passing SO 3 in water, it is passed in concentrated sulphuric
is obtained as follows :

to give H?SO of desired

Fuming sulphuric acid or oleum is sold as such or is diluted with water - 4
.
concentrat10n .
ntrated sulphuric acid is
Note : 1. ~ilutio n of all ~cids is ~xo!hermic. ?ilutio n of oleum or conce
be poured into acid
highly_ exothermic. For dilution o~ acids, therefore, water should never
but acid should be added slowly mto water with constant stirring.
now been replaced
2. Contact proc~ss ~ormerly used platinize_d asbestos as catalyst. This has
by V20 5 which is cheaper and less easily poisoned.
now obs~lete. It used
3. The older lead chamber process for manufacture of sulphuric acid is
of the procedure was
oxides of nitrogen as catalysts for conversion of SO 2 to SO 3. The rest
the same. The dis~dvantages were that it only produ ced 78% H 2so4
, not concentrated

H2SO4, and the acid was less pure than that from Contact proces s.
liroup 16 El ements (The Oxygen Family) 42 5
"ai d c: • of I h . . . s is shown in Fig . 8·3.
A flo w diaITT
o n use ior the manufacture su p un c acid by Contact proces
Water Cone. H2 so4
spray spray

+ +

Su lph ur -
, '

·~
_,

.' u' 'l.,'

,"'I

,-
'
- V205
..I..LL!L Quartz
c (' I) l l
, ) ... - ,) .Lll ...l.
" ·
V CJ 0 0
0 0 (),.,:
" Coke fI
Preheater
~
.LU ...L
- t
() Ol' 0
o o ao .LL U.

-
0 Oc o
D V 0 0
0 n '0
Air 0 o ,oo
C' (,.I \ 0
lJ ( j ,__; 0
\) C, O0
Catalytic
Sul phu r converter
bur ner Arsenic purifier
containing
Drying gelatinous hydrated
Du st tower ferric oxide
pre cip itat or
s
phuric acid by Contact proces
Fig. 8·3. Manufacture of sul
larity
: Co ne. H SO use d in lab oratories is 98% w/w. Its mo
ph ur ic aci d 2 4 H O in pure
P hy sic al pr op ert ies of sul g po int is 33 8°C . The mole ratio of SO3 and 2
y is l ·84. Its bo ilin in a greater proportion
is 18 M. Its spe cif ic gra vit Fu mi ng sul ph uri c acid or oleum contains SO3
) is 1 : 1. tage of
su lph uri c ac id (10 0% H 2SO4 lly rep res ent ed as H 2 SO 4..xSO3 or H 2S2O7 . The percen
d. It is chemica
tha n in pu re sul ph uri c aci ight percentages unless oth
erwise stated.
alw ay s ex pre sse d as we
su lph uri c ac id is
lph ur ic acid :
ChemicaJ pr op ert ies of su dibasic acid. In aqueous sol
ution, it dissociates as
lph uri c aci d is a str on g
1. Ac idi c ch ara ct er : Su
follow$ : - K 1 > 10
H 2SO4 ~ H+ + HSO4 2
X 10 -
HS O4 - ~ H+ + so /- K2 == 1·2
and CuSO4
for ms tw o typ es of sal ts : normal salts such as Na2SO4
ure, it ative
Be ca us e of its dib asi c nat t is act ual ly for me d in a reaction depends upon rel
Na HS O4. Wh ich sal
an d aci dic sal ts suc h as
oth er reaction conditions . omposition reactions with
various
am ou nts of rea cta nts an d : It un der go es do ub le dec
n rea cti on s
. 2. Do ub le de co mp os itio
salts. Fo r ex am ple , 2H Xi +M 2S O4
2M X + H 2SO4
(M =Metal, X =F, Cl or
NO3)
Na2SO4 + H2O + SO2i-
Na2SO3 + H2 SO 4
FeSO4 + H 2Si
FeS + H2SO4 ent. In
ted sul ph uri c aci d is a mo derately strong oxidising ag
_ Ox idi sin g pro pe rti es z
Ho t concentra ox ida tio n
3 ho ric an d nit ric aci ds . It supplies na sce nt ox yg en for
iat e between phosp
thi s res pe ct, it is int erm ed
as fol low s : H 20 + SO 2 + 0
426
~om(" i,f 1h(' nnrmil\n t fC'M 1Hll1 CI nf n,uh ttlllj!
t
AC HHI 0
CbemJstry

f hot , nru cntratcd cwlphuric acid are gi ven

r
• 2u'l ,n.t -\ < o, , 2\ 0 ) • 7H7' )
( 11

(111
(

\ I "H. \ O•
-\ ,,o,, n 1~0
( 111 I "r ,u. ,o. ~ ~,o , Jtt ,o • 211 ,Po,.
<" l l\llr ◄ H.,n, • K ll \01 IIB,
1HR, ~ H.~o. - - + \0 , • lh 1 • 211 10
l' I J.: I ◄ u.,n.
,. "-11"0 4 • Ill
~HI ~ H: ~O., ~ \{) , • I: 1 211 _:i O

( \ 11 H ~ • H .. ~n. --. 211 20 • 'iO 2 .. ~

l , 111 I , a~k, l,1 (" lllat,on nl metal-. , 1tuatcd hcl ow hydrogen in clcctrochcm1cal sen~ are gi,cr.

l u 1H : S0 4 _ CuS0 4 + 21-1 20 ~ S02

___,

: '\~ 1H:S0 4 _ __, Ag 2S0,1 + 211 20 ~- S0 2

Hf • ! H: S0 4 - ----i ll gS0 4 ➔ 211 20 + S02

, . R ~ • 'th mctah 'litu a ted above hydroge n in elcctroc hcmicaJ series :
Metals s1cm~
a!,..-,, e h~drog-cn 1n electroc hemical series evolve hydrogen with di!. H2S04. For example.
Zn + H'.) S0 4 - - - , ZnSO-t + H2
Mg + H2S0 4 --➔ MgSO-t + H2
5. Ructio a "itb gold and platinum : Gold and platinum do not react with sulphuric ac1d.
gases.
, . Dclndn ting action : Concentrated su lphuric acid is a strong dehydrating agent. Wet
'll hich do not ·react \\-1th sulphuric acid. can be dried by passing
them through concentrated sulphuric ac1d.
formation. For
lt i.ho remo, o ·~at.er molecules from various organic compounds and brings chemical trans
CA.ample .
cone. H2SO 4 • 160 °C

12C + llH --.O

Tne ~ nd of th e above reaction s is known a.s charring (black~ning) of sugar.
7. S.lphaa tic,n : Fummg .)ul phun c ac id is used as a sulphonating agent in orguni1.·
chemistr: .
' solution .
T~ for , ulpb ale ion : Pn::>ence of sulphate ion is 1es1ed by using barinm 1.·h.loridc
m of white'
Add.tuon of bmum chlonde :>-Oluuon 10 u solu11on con1aining sulphai~ ions results in tht' fommtit
prcc,p1tB t.e ol ba.num :>ulphate which I:> insoluble in cone. nitric nnd hydrochloric ttc ids.
Na 2S0 4 , BaCl2 - -~ 2NaCI 1-- 8aS0 4 t
in the'
l ~ of ~ulpburfc utid : Sulphuric acid is II very imponant industrial l.'hc•mirnl. lt is us-.'\:i
is mainly ust'd in ti)
mEU1ufiicture ot large number of other compounds and in many industrinl pl'\)Cessc-s. lt
, (ii) rt·fining of
manufac ture of frmh1xfo bUCh a~ ammonium sulphaw and culcium super•phosphntt>
(, ) metallurgical
pe!foleum. ( 111) manufac ture of p1 gmc111 ~. pn1111s und dyes, (iv) nrnnufoc nirt> uf cktt-rgents.
as a laboratory
optrauon!), (vi) k 1:1 d :> tornge ball trn::-., (v 11) manufac tu re uf 11itr0i:ellulose pmdu~ts. nnd (viii)
rc:ligen t.
Group 16 Elements (The Oxygen Family)
427

8.9 Sodium .thiosulphate or H 0

The molecular formula of sodium th' · 1~p . ·
was thought to be Na2S204 and hence it w1osknup ate is Na~S203.5H20, Formerly its molecular formula
.h as own as sodmm hyp I h
now an establ1s ed common name for thi' osu P ate or hypo. The name hypo is
· s compound because of
. :Methods of preparation : 1. By heatin 1h . . common usage for a long time.
g su P ur with sodmm hydroxide solution ·
[S + 2NaOH _ _,. Na2S + H20 + O] x 3 .
Na2S + 30 _ _____,. Na2S03
Na2SO3 + S _ _____,. Na2S203

.. . 4S + 6Na0H - ~ ~Na2S + Na2S203 + 3H20

2. By heatmg sodium sulphite solution with.sulphur :
Na2S03 + s.. . . ::.~a2S2Q3
3. By adding iodine to a solutionc~n.tairling .so~i~ ~~tpwte and sodium suiphide :
Na2S + Na2S03'· 1:"· 12:· . _. ;,':2Na,L;:t 'N~S20 3 .
4. By passing sulphur dioxide l~_sodium:);'arboh~(e\~(uti~h:aontaining, sulphur:
Na2 C0 3 + SOi +'. S. ', ·,: . . . ;)~8;2S2Q3 :>, ,. . :-+,:.~o~:·
5. By t4e reaction of sodium hydro·g~h: sufp9i4e1itid''s,6 diu~>bi~tiiphlte :
2NaHS + 4NaH_ SQ 3, -·, : ,, :·, ;>, ·. 03,:~3II2d' ,3'.Na~~2 ··
Physical properties : It exists·as :a bdlow:-lys~,'dry~~~ili~~J~lid<
. W4iclfis ~oluble in water.
. . ' ~

Chemical properties : -•,,·., ,;,,,' · •. ·",'<, • , .\ . •

i. Reaction with iodine : Sodium.!pdtd~;:~ ,~I)/ ~d_' s,d'diuin'J,etra:th1~nate (Na2S40 6) are formed.
Both of these compounds are colowless and:,s·oluble 1ff ,water> . - · · · , ·
1 + 2N~4_$29~, -'' .· · :~'. -,? ;4Na1+N32$40_6, · ._ _ .
2
The above reaction is -very import~~t:r~acti~,n.,:a~;it i~.~s"ed jn volumetric estimations of a number of
substances. When a solution of iodine is used as· srn;;h~a:rtd ·titrated against hypo, this type of volumetric
analysis is known as iodimetry. When' i6di,ge is 'fi;St
lib~;ated ih a chemical reaction and then titrated
against hypo, this type of volumetriq ' ~na:lysif is kncnyn· as iodometry. An example .of iodometry is the
estimation of copper sulphate. Starch· is used as an indicator in this titration. The following reactions take
place in this titration : ·
Cv2I2 + 2K2S04 + lz
2CuS04 + 41(1 cuprous iodide
· (white ppt.) .

12 + Kl ~ Kl3
(dark yellow
solution)
~ Starch-iodide complex
12 + starch (deep blue)
2Nal + Na2S406
sodium tetra-thionate

. "th . er nitrate : If silver nitrate is taken in excess, a white precipitate of silver

. 2 •hR eac
• t 10n
b WI
• d fiSl1Vt whi"ch fmally turns black because of the fiormation
. of s1·1ver sulphide.
thlOSU1p ate 1S O tame lfS
 428 Chemistry
Ag 2 S 2 0 3 -l- + 2NaN03
silver thiosulphate
(white ppt.)

Ag 2 S-l- + S0 3
silver sulphide
(black ppt.)
If sodium thiosulphate is taken in excess the white precipitate of silver thiosulphate dissolves in
sodium thiosulphate to form sodium argento-thiosulphate which is a soluble complex salt. .
2AgN0 3 + Na 2 S2 0 3 - - Ag2 S2 0 3 -l- + 2NaN0 3
Ag 2 S 20 3 + 3Na2 S 20 3 - - 2Na3.[Ag(S 2 0 3)z]
sodium argento-thiosulphate
(soluble complex salt)
3. Rraction wit h silver bromide : Silver bromide is insoluble in water. It is soluble_ in sodium
thiosulphate solution. The dissolution takes place as follows :
AgBr + 2Na2 S20 3 ~ - NaBr + Na3[Ag(S203)z] .
sodium argento-thiosulp~,ate
. (soluble complex salt) ·
Chemistry o_f black and white photography : 1)e aboye reaction was formerly used in black and
PllIPP,Se.us~d to be·a thin plastic film coated with
white photography. The photographic film us~d. for'. t~is <
silver bromide. The following reacti,;m take~ p!ac~:af tho~_e .pfa¢es· of th~. film which are exposed to light :
: . ': kv· . :· . . -- · - .
2AgBr :<' . _.,~ -2:A:g +..Br2 , _ _ , _ .
The exposed portion of the film tum~ ,bl~ck :Bec~u~e-~6 f,thi f omiation of minute particles of silver at
these places. Hydroguinone is used'. to portverf e:xpl;sed<bµ~ nn~e(;ompo~ed AgBr to Ag as follows :
2AgBr + .C6H4(0H)z \ ·'<• ;'_ ·)A'.g :+- 4ffBrt C(jpl40z
hydroquinoiJ.e · < ·>.. , . .- quinone ,
(dev:eloper) · ·.• , .
Silver bromide remaining at unexpo~ed ;p'6ftion o:{ihefi~· is theri washed away by hypo. This leads
to the formation of the negative. Anegative:ht#us ·iiegati~eis then made and this leads to the formation of
tµe photograph. · · ·· · · ·
I I!
4. Reaction with ferric chloride · ~~ A .pink c9lour_, is obtained because of the formation of ferric
thiosulphate which disappears after sometim~•- ·. . , . . · . ,
2FeCI3 + 3Na2S203 . - ~ - 6NaCl + Fei(S 2 0 3) 3
ferric thiosulphate
(pink colour)
2Fe3+ + 2S 2 o/- --➔ 2Fe2+ + S4 o/-
5. Reaction with chlorine : It reacts with chlorine to form hydrochloric acid and hence acts as an
antichlor. ,
Na2 S20 3 + 4Cl2 + 5H2 0 2NaHS04 + 8HCI
6. Reaction with cup ric chloride ;
2CuC12 + 3NaiS 2 03 Cu2 S2 0 3 + 4NaCI + Na2 S4 0 6
cuprous thiosulphate ·
·(white ppt.)
2Na[Cu(S 2 0 3)]
(soluble complex salt)
2Na[Cu(S 2 0 3 )] + H2 0 Cu2 St + H2 S04 + Na2 S2 0 3