7.

18 Group 17 Fl u or i n e, ch l or i n e, br om i n e, i odi n e an d ast at i n e ar e m em ber s of

Gr ou p 17. Th ese ar e col l ect i vel y k n own as t h e h al ogen s (Gr eek
Elements halo m ean s sal t an d genes m ean s bor n i .e., sal t p r odu cer s). Th e
h al ogen s ar e h i gh l y r eact i ve n on -m et al l i c el em en t s. Li k e Gr ou ps 1
an d 2, t h e el em en t s of Gr ou p 17 sh ow gr eat si m i l ar i t y am on gst
t h em sel ves. Th at m u ch si m i l ar i t y i s n ot fou n d i n t h e el em en t s
of ot h er gr ou ps of t h e per i odi c t abl e. Al so, t h er e i s a r egu l ar
gr adat i on i n t h ei r ph ysi cal an d ch em i cal pr oper t i es. Ast at i n e i s a
r adioact ive elem en t .

7.18.1 Occur r en ce
ed
Flu or in e an d ch lor in e ar e fair ly abu n dan t wh ile br om in e an d iodin e
less so. Flu or in e is pr esen t m ain ly as in solu ble flu or ides (flu or spar
CaF 2 , cr yolit e Na 3 AlF 6 an d fl u or oapat i t e 3Ca3 (PO 4 )2 .CaF 2 ) an d sm all
qu an t it ies ar e pr esen t in soil, r iver wat er plan t s an d bon es an d t eet h
of an im als. Sea wat er con t ain s ch lor ides, br om ides an d iodides of

h
sodiu m , pot assiu m , m agn esiu m an d calciu m , bu t is m ain ly sodiu m
ch lor ide solu t ion (2.5% by m ass). Th e deposit s of dr ied u p seas

pu T
is
con t ain t h ese com pou n ds, e.g., sodiu m ch lor ide an d car n allit e,
KCl.M gCl 2 .6H 2 O. Cer t ain for m s of m ar in e life con t ain iodin e in t h eir
re R syst em s; var iou s seaweeds, for exam ple, con t ain u pt o 0.5% of iodin e
an d Ch ile salt pet r e con t ain s u pt o 0.2% of sodiu m iodat e.

bl
Th e i m por t an t at om i c an d ph ysi cal pr oper t i es of Gr ou p 17
el em en t s al on g wi t h t h ei r el ect r on i c con fi gu r at i on s ar e gi ven i n
E
Tabl e 7.8.
be C

Tabl e 7 .8 : At om i c an d Ph y si cal Pr oper t i es of H al ogen s

Pr op er t y F Cl Br I At a
o N

At om ic n u m ber 9 17 35 53 85
At om ic m ass/ g m ol –1 1 9 .0 0 3 5 .4 5 7 9 .9 0 126.90 210
Electronic configu ration [He]2 s 2 2p 5 [Ne]3s 2 3p 5 [Ar ]3d 10 4s 2 4p 5 [Kr ]4d 10 5s 2 5p 5 [Xe]4f 14 5d 10 6s 2 6p 5
Covalen t r adiu s/ pm 64 99 114 133 –
tt ©

Ion ic r adiu s X –/ pm 133 184 196 220 –

Ion isat ion en t h alpy/ k J m ol –1 1680 1256 1142 1008 –
Electron gain enthalpy/ k J mol –1 –3 3 3 –3 4 9 –3 2 5 –2 9 6 –
Elect r on egat ivit y b 4 3 .2 3 .0 2 .7 2 .2
∆Hyd H (X –)/ k J m ol –1 515 381 347 305 –

F2 Cl 2 Br 2 I2 –

M elt in g poin t / K 5 4 .4 1 7 2 .0 2 6 5 .8 3 8 6 .6 –
Boilin g poin t / K 8 4 .9 2 3 9 .0 3 3 2 .5 4 5 8 .2 –
Den sit y/ g cm –3 1.5 (85)c 1.66 (203)c 3.19(273) c 4 .9 4 (2 9 3 )d –
Dist an ce X – X/ pm 143 199 228 266 –
Bon d dissociat ion en t h alpy 1 5 8 .8 2 4 2 .6 1 9 2 .8 1 5 1 .1 –
no

/ (k J m ol –1 )
E V / Ve 2 .8 7 1 .3 6 1 .0 9 0 .5 4 –

a
Ra d i oa ct ive; b Pa u li n g sca le; c For t h e liqu id a t temper a tu r es (K) given in t h e pa r en th eses; d
solid ; e
The
half-cell reaction is X 2 (g) + 2e– → 2X –(aq).

Ch em i st r y 192
 ar e discu ssed below.

7.18.2 El ect r on i c All these elem ents have seven electr ons in their ou ter m ost shell
Con fi gur at i on (ns 2 np 5 ) which is one electr on shor t of the next noble gas.

7.18.3 At om i c The halogens have the smallest atomic r adii in their r espective per iods
an d I on i c du e to maximu m effective nu clear charge. The atomic radiu s of flu orine
Radi i lik e the other elements of second period is extremely small. Atomic and
ionic r adii incr ease fr om flu or ine to iodine du e to incr easing nu m ber
The tr ends of som e of the atom ic, physical and chem ical pr oper ties

ed
of qu antu m shells.
ar e discu ssed below.
7.18.4 I on i sat i on They have little tendency to lose electr on. Thu s they have ver y high
7.18.2 El ect r on i c All these elem ents have seven electr ons in their ou ter m ost shell
En t h al py ionisation enthalpy. Du e to increase in atomic size, ionisation enthalpy
Con fi gur at i on (ns 2np 5 ) which is one electr on shor t of the next noble gas.
decr eases down the gr ou p.

h
7.18.3 At om i c Th e halogens have the sm allest atom ic r adii in their r espective per iods
7.18.5 El ect I on i c Halogen
an dr on du e tosmaximu h ave m m axim u m nu
effective n egat
clearivechar elect r on atomic
ge. The gain en t h alpy
radiu inorine
s of flu the
GaiRadi
n i corlik r esponding per iods. This is du e to the fact that the atom s of these

pu T
d
e the other elements of second period is extremely small. Atomic and

is
En t h al py elements
ionic r adii haveincr onlyeaseonefrelectron
om flu orless ine than stabledunoble
to iodine gas easing
e to incr configurations.
nu m ber
Electron
of qu antu gainmenthalpy
shells. of the elements of the group becomes less negative

e
re R
down the gr oup. However, the negative electr on gain enthalpy of fluorine

bl
7.18.4 I on i sat i on is They less than havethat littleoftendency
chlor ine. to It islose
du eelectr on. Thu
to small sizes ofthey have
flu or ver y high
ine atom. As
En t h al py a rionisation enthalpy.
e ar e strDu e tointer
increase
electrin atomicr epusize, ionisation
in the renthalpy

h
esu lt, ther ong onic lsions elatively
smalldecr2p eases down ofthe
or bitals flugr
orouin p.
e and t h u s, t h e in com ing elect r on does n ot

E
exper ience mu ch attr action.

T lis
7.18.5 El ect r on Halogen s h ave m axim u m n egat ive elect r on gain en t h alpy in t h e
7.18.6 Gai n They cor rhave
esponding
ver y highper iods.
electrThis is du e to The
onegativity. the fact
electr that the atomdecr
onegativity s of eases
these
be C
En ti h
El ect r on egat vialt ypy down elements the gr have
ou p.onlyFluone electron
or ine is theless thanelectr
m ost stable noble gaselem
onegative configurations.
ent in the

R
perElectron
iodic table. gain enthalpy of the elements of the group becomes less negative

b
down the gr oup. However, the negative electr on gain enthalpy of fluorine
to N
is less than that of chlor ine. It is du e to sm all size of flu or ine atom . As
e Exam ple 7.14

E u
Halogen s h ave m axim a ur m esu nlt,egat
therive
e arelect
e strr on
ong gain en t h alpy
inter electr onic rineput hlsions in the r elatively
r espective per iods of the per iodic table. Why?
sm all 2p or bit als of flu or in e an d t h u s, t h e in com in g elect r on does n ot
Halogens have the smallest expersize ience in m attr action.periods and therefore Solution
u ch respective
their

C ep
high effective nu clear char ge. As a consequ ence, they r eadily accept
©

7.18.6 They have ver y high electr onegativity. The electr onegativity decr eases
one electr on to acqu ir e noble gas electr onic configu r ation.
El ect r on egat i vi t y down the gr ou p. Flu or ine is the m ost electr onegative elem ent in the
per iodic table.
7.18.7 Ph y si cal
Halogen

N r
Pr opers t ihes
r espective per iodsmof
Halogens display smooth variations in their physical properties. Fluorine
ave mandaxim chlor
u m ine
the per
elting and
ar eive
n egat
iodic
gases,
table.
boiling
electbr omine
r on gainis ena liqu id and
t h alpy t h e Exam
in iodine
Why?steadily incr ease with atom ic nu m ber. All
points
is aple 7.14 Their
solid.

© be
Halogens have thehalogens smallest size are incolou
theirred. This is du
respective e to absorption
periods and therefore of radiations
Solution in visible
region which resu lts in the excitation
high effective nu clear char ge. As a consequ ence, they r eadily accept of ou ter electrons to higher energy
level. By absor bing differ
one electr on to acqu ir e noble gas electr onic configu r ation. ent qu anta of r adiation, they display differ ent
colou r s. For example, F 2 , has yellow, Cl 2 , gr eenish yellow, Br 2 , red and
I 2 , violet colou r. Flu or ine and chlor ine r eact with water. Br om ine and
7.18.7 Ph y si cal Halogens display smooth
ingly variations
solu ble ininwater their physical
bu t ar e properties.
solu ble in Fluorine
t

iodine ar e only spar var iou s

and chlor
Pr oper t i es or ganic ine ar esu gases, br om ineofor
is amliqu id bon
and iodine is a ide,
solid.car
Their

o
solvents ch as chlor , car tetr achlor bon
no

disu m elting
lphideand andboiling
hydr ocar points
bonssteadily
to giveincrcolouease r edwith
soluatom
tions. ic nu m ber. All

t
halogens are colou red. This is du e to absorption of radiations in visible
One cu r iou s anom aly we notice fr om Table 7.8 is the sm aller
region which resu lts in the excitation of ou ter electrons to higher energy
enthalpy of dissociation of F 2 com par ed t o th at of Cl 2 wh er eas X-X

t
level. By absor bing differ ent qu anta of r adiation, they display differ ent
bond dissociation enthalpies from chlorine onw ards show the expected
colou r s. For exam ple, F 2 , has yellow, Cl 2 , gr eenish yellow, Br 2 , red and
I 2 , violet colou r. Flu or ine and chlor ine r eact with water. Br om ine and

o
trend: Cl – Cl > Br – Br > I – I. A reason for this anomalybuist the
iodine ar e only spar ingly solu ble in water 193 Th e relatively
ar p-Block Elem en t s
e solu ble in var iou s
large electr on-electr or ganic on rsolvents
epu lsionsuamong ch as chlor the ofor
lone m ,pair
car bons in tetrF2 achlor
molecu le car bon
ide,

n
wher e they ar e mu disuch closer
lphide andtohydr eachocarother
bons to than
give in coloucase r ed of Cltions.
solu 2.
One cu r iou s anom aly we notice fr om Table 7.8 is the sm aller
enthalpy of dissociation of F 2 com par ed t o t h at of Cl 2 wh er eas X-X
Example 7.15 Although electronbond gaindissociation
enthalpy ofenthalpies fluorine from is less negative
chlorine onwas ardscompared
show the expected
to chlorine, flu orine is a stronger oxidising agent than chlorine. Why?
193 Th e p-Block Elem en t s
Solution It is du e to

d
(i) low enthalpy of dissociation of F-F bond (Table 7.8).
(ii) high hydr ation enthalpy of F– (Table 7.8).

7.18.8 Ch em i cal
Pr oper t i es

he
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
All the halogens exhibit –1 oxidation state. However , chlorine, br omine
and iodine exhibit + 1, + 3, + 5 and + 7 oxidation states also as

T lis
explained below:

Halogen atom ns np nd
in gr ou nd state 1 u npair ed electr on accou nts
(ot her than flu or ine) for –1 or +1 oxidation states
3 u npair ed electr on s accou nt
 _
@unacademyplusdiscounts
514 Chapt er 10 The p-Block Elements and their Compounds

10.56 | EXTRACTION AND USES OF THE ELEM ENTS

Fluorine
Fluorine is extremely reactive, and this causes great dif culties in the preparation and handling of the
element. The rst preparation of uorine was by M oissan in 1886. H e was subsequently awarded the Nobel
Prize for Chemistry in 1906 for this work. Fluorine is obtained by treating CaF2 with concentrated H 2SO 4
to give an aqueous mixture of H F. This is distilled, yielding anhydrous liquid H F. Then a cooled solution of
K H F2 in anhydrous H F is electrolyzed, giving F2 and H 2 (Figure 10.52).

CaF2 + H 2SO 4 CaSO 4 + 2H F

KF + HF K [H F2]

H F + K [H F2 ] H 2 + F2
electrolyt e

HF F2 H2
(in) (out) (out)

Cooling impact

Carbon anode

Steel cathode

Electrolyte

Figure 10.52 Fluorine cell.

There are many dif culties in obtaining uorine.

1. H F is corrosive, and etches glass and also causes very painful skin wounds. These arise partly by
dehydrating the tissue, and partly from the acidic nature of H F. The wounds are slow to heal because
F− ions remove Ca2+ ions from the tissues.
2. Gaseous H F is also very toxic (3 ppm) compar ed with H CN (10 ppm).
3. A nhydrous H F is only slightly ionized and is therefore a poor conductor of electricity. Thus a mixture
of K F and H F is electrolysed to increase the conductivity. M oissan used a solution of K F in H F with
a mole ratio of 1:13. This has the disadvantage that the vapour pressure of H F is high, and this gives
problems with toxicity and corrosion, even when the reaction mixture is cooled to −24 °C. M odern
methods use medium temperature uorine generators. These use a mole ratio of 1:2 of K F: H F so that
the vapour pressure of H F is much lower. This mixture melts at about 72 °C which is a much easier
temperature to maintain. Note that K F and H F r eact to form the acid salt K +[F—H —F] −.
4. Water must be rigorously excluded or the uorine produced will oxidize it to dioxygen.
5. The hydrogen liberated at the cathode must be separated from the uorine liberated at the anode by
a diaphragm, otherwise they will r eact explosively.
6. Fluorine is extremely reactive. I t catches re, for example with traces of grease or with crystalline
silicon. Glass and most metals are attacked. I t is dif cult to nd suitable materials from which to
make the reaction vessels. M oissan used a platinum U -tube, since platinum is very unreactive (but
it is very expensive). Copper or M onel metal (Cu/Ni alloy) are now used instead, because they cost
less. A protective uoride lm forms on the surface of the metal and slows down further at tack.

Chapter 10.indd 514 3/21/2017 11:31:07 AM

 1,2–dichloroethane
vinyl chloride monomer
Both are used in the plastics industry.
_
@unacademyplusdiscounts
Large amounts of chlorine are used for bleaching textiles, wood, pulp and paper. Chlorine is widely used

wide variety of inorganic chemicals including:

bleaching powder
_
throughout the developed world to purify drinking water, because it kills bacteria. It is also used to make a
10.56 Extraction and Uses of the Elements 515

@unacademyplusdiscounts
7. Thesodium hypochlorite
cathodes are made NaOCl
of steel, the anodes are carbon, and te on is used for electrical insulation
chlorine dioxide ClO
(Figure 10.61). Graphite 2 anodes must not be used, since graphite reacts with uorine, forming graphite
10.57 General Properties 517
sodium chlorate
compounds CF. I n NaClO
these, 3uorine atoms progressively invade the space between the sheets of graphite,
manythem
forcing metalapart,
and non-metal
and bucklingchlorides
them. This gradually stops the graphite from conducting, the current
the pH to about 3.5. Then Cl 2CCl
gas4is passed through
DT andthe solution to oxidize the Br − to Br 2. This is an example
needed increases, more heat ,isCH
organic compounds like Cl 3, D
produced, eventually an explosion may occur. U ngraphitized
of is
It displacement
also used toofprepare
one element by another
poisonous gases higher in the electr
like phosgene (COClochemical series.
2), tear gas (Cl 3CNO 2) and mustard gas
carbon is used to avoid this. I t is made from powdered coke compacted and impr egnated with copper .
(ClCH 2 CH 2S CH 2 CH 2Cl). Cl + 2Br − 2Cl − + Br 2 2

(b.p. 12 °C), which though very reactive is less unpleasant and easier to tr ansport.
Bromine _
Cylinders of F2 are now commercially available. H owever, for many purposes F2 is converted to ClF3
The Br 2 is removed by a stream of air, because Br 2 is quite volatile. The gas is passed through a solution of
Na2CO 3, when the Br 2 is absorbed, forming a mixture of NaBr and NaBrO 3. Finally the solution is acidi ed
@unacademyplusdiscounts
and distilled
Bromine to give pur
is obtained frome bromine.
sea water and 3F2brine
200 300 C
+Cl 2 lakes. Sea water 2ClFcontains about 65 ppm Br −. Thus 15 tonnes
3
of sea water contain about 1 kg of bromine. Bromine is extracted from sea water, but it is more economic to
3Br + 3Na CO 5NaBr + NaBrO 3 +inorganic
3CO 10.57 General Properties 517
Production
use more of uorine rst
concentrated became
brine sourcesimportant
2 2 for the2000–5000
3
which contain manufacture ppm of of Br −2. First uorides
H 2SO 4 issuch
addedas to
A lF 3 and
adjust
synthetic Na3[A lF6]. Both are 5NaBrused+ in the extraction
NaBrO 3 + 3H 2 SO of
4
aluminium.
5H Br + H BrO 3 + 3Na 2SO 4
the pH to about
The uorocarbons are3.5. Then interesting
a very Cl 2 gas is passed
and through the solution
useful group to oxidize the
of compounds, Br − to Br
derived 2. This
from is an example by
hydrocarbons
of displacement of one element by 5H Br + higher
another H BrOin the3Br
electr+ 3H O
ochemical series.
substituting F for H . Tetra uoromethane CF4 is the 3 uorocarbon 2
corresponding
2
to methane. Completely
− −
uorinated compounds
1,2-dibromoethane isCadded
nF2n+2 are calledtoper
to petrol Cl 2uoro
act as2Br
+ a compounds.
lead + BrThus
scavenger.
2Cl 2 CF4 is perlead
Tetraethyl uoromethane.
is added to Per petroluoro
to
compounds
improve its have very
octane low
rating,boiling
but whenpoints for
it burns their molecular
it forms weight:
lead deposits. this is associated
1,2-dibromoethane
The Br 2 is removed by a stream of air, because Br 2 is quite volatile. The gas is passed through a solution of
with very
is added weak inter-
to prevent
the build-up
molecular
Na2COforces.of Fluorocarbons
lead deposits onare theextremely
sparking plug inert.and U in the methane,
nlike engine. The CFlead passes out with the exhaust
4 can be heated in air without
3, when the Br 2 is absorbed, forming a mixture of NaBr and NaBrO 3. Finally the solution is acidi ed
gases,
Chapter 10.indd 516burning. mainly
and as PbClBr.
Fluorocarbons
distilled to giveareThe
pure useto
inert of PbEt
bromine. 4 as an anti-knock
concentrated H NO 3 and additive
H 2SOto petrol has already declined, and will 3/21/2017
4, to strong oxidizing agents such as
11:31:13 AM

4 or O 3, and to strong reducing agents such as Li[A lH 4] or C at 1000 °C. They are attacked by molten
decline
K MnO further because of legislation against its use, and environmental concern over the toxic effects of
3Br 2 + 3Na2CO 5NaBr + NaBrO 3 + 3CO 2
lead. Therefore
Na. When pyrolysed theatuse
veryof 1,2-dibromoethane
high temper atures thehas C—Cdeclined.
3 also
bonds break rather than the C—F bonds.
Tetra uoroethene F2C = CF2 (b.p. 5NaBr −76.6 °C) can
+ NaBrO 3 + 3H SO 4 5H Br + H BrO 3 + 3Na2SO 4
be2made:
Iodine 5H Br + H BrO 3Br + 3H O
2CH ClF2 500 1000 °C 3 CF2 =2 CF2 +2 2H Cl
There 1,2-dibromoethane
are two different is added to petrol
commercial methods to act as a lead iodine.
of obtaining scavenger.TheTetraethyl
method used leaddepends
is addedon towhether
petrol tothe
Fluoroalkenes
improve of
itsthis
octane type can be
rating, butpolymerized
when it burnseitherit forms thermally,
lead deposits. or using a free radical initiator.
1,2-dibromoethane is added toDprevent epending
source is Chile saltpetre or natural brines.
on the degree
the of polymerization,
build-up of lead deposits that
on is on
the the molecular
sparking plug and weight
in the produced,
engine. The the products
lead passes outmay
with be theoils, greases
exhaust
Chile saltpetre is mainly NaNO 3, but it contains traces of sodium iodate NaI O 3 and sodium periodate
or aNaIsolid of
gases, high
mainly molecular
as PbClBr. weight
The usecalled
of polytetra
PbEt as an uoroethylene.
anti-knock additive
O 4. Pure NaNO 3 is obtained by dissolving saltpetre in water and crystallizing NaNO 3. The iodate
4
Thisto is similar
petrol has to ethene
already (formerly
declined, and called
will
ethylene) polymerizing
decline further to
because giveof polyethylene
legislation (polythene).
against its use, and Polytetra
residues thus accumulate and concentrate in the mother liquor. Eventually, this concentrate is dividedenvironmental uoroethylene
concern is
over known
the commercially
toxic effects of
as PTFE lead.
or Therefore
Te on. I t theause
is very ofinert
1,2-dibromoethane
solid plastic has also declined.
material, and − is useful because it is completely resistant to
into two parts. One part is reduced with NaH SO 3 to give I . This is mixed with the untreated part, giving
chemical
I 2, which attack and isoff
is ltered anas electrical
a solid and insulator.
then puri Thoughed byexpensive,
sublimation. it is used in laboratories. I t is also used as
a coating for non-stick pans.
Iodine -
Freons are mixed chloro uorocarbons. 2I O -3 + 6H Compounds
SO 3 2I −such
+ 6SO as2-CClF
+ 6H3+, CCl 2F2 and CCl 3F are important
There are two different commercial methods of obtaining iodine.4 The method used depends on whether the
as non-toxic refrigerating uids and aerosol propellants.
- They too are very inert, and are discussed later.
source is Chile saltpetre or natural brines. 5I − + I O 3 + 6H + 3I 2 + 3H 2O
CF3CH BrClChile is used as an anaesthetic called Fluothane.
saltpetre is mainly NaNO 3, but it contains traces of sodium iodate NaI O 3 and sodium periodate
A nother
There use
is no
NaI O 4. Pure NaNOof F
one2 isdominant
to ismake SF
obtained 6, which
use. H alf
by is athe
of
dissolving very inert produced
iodine
saltpetre gas
in used
wateras is aused
and dielectric
to make
crystallizing (insulating)
a variety
NaNO medium
of organic for
3 3. The iodate
highcompounds
voltage including
equipment.
residues thus accumulate iodoform
F 2 is also CH
used I to
and concentrate
3 (used
make asotheran antiseptic),
uorinating and methyl
agents ClF
in the mother liquor. Eventually,3 this concentrateiodide
, BrF 3 CH
and 3II.F A
5 gl
and is used
SbF
is divided
5. for
The
photographic
earlier use of
into twoliquid lms,
parts. FOneandan
2 as part
foroxidizing
seeding
is reducedclouds
agent
with NaH to rocket
in produce
SO 3 tomotors rain.
give I −.Small
has isamounts
Thisnow beenwith
mixed of the
iodine
discontinued. are A
untreated required
nhydrous in the
part, giving HF
hashuman
many diet, so
uses.
I 2, which is traces
ltered off (10as ppm)
a solidofandNaIthenarepuri added ed toby table salt. K I is added to animal and poultry feeds.
sublimation.
TheTracesthyroidof gland ions F - in
uorideproduces a growth
drinking regulating
-
water (about -
hormone 1 ppm)
−
called
2-
thyroxine
greatly +
reduce whichthecontains
incidence iodine. The
of dental
de ciency of iodine causes - disease goitre. 2I O +
I 6H
odine SO has
caries (tooth decay). The F ions make the enamel on teeth much harder, by converting hydroxyapatite
3 3 2I
limited+ 6SOuse4 +
as 6H
an antiseptic; tincture of iodine is an
-
aqueous
[3(Ca 3(PO solution
)
4 2 Ca(OH of I
) 2
2]in K
(theI , and French
enamel iodine
on −
the is a solution
surface
5I + I O 3 + 6H +
of in alcohol.
teeth)
3I 2 + 3H 2O I
into n the
the laboratory
much iodides
harder and iodates
uoroapatite
are (PO
[3(Ca used )in volumetric analysis,Fand - Nessler’s reagent K 2[H gI 4] iscause
used to detect ammonia.
3 2 CaF
4There ]. H owever, concentrations above 2 ppm
is 2no one dominant use. H alf of the iodine produced is used to make a variety of organic
discoloration, the brown mottling
of teeth, and higher concentrations are harmful. I
compounds including iodoform CH I 3 (used as an antiseptic), and methyl iodiden some places NaF and H [SiF ] are
6 CH Iadded to drinking
3 . A gl- is used for
2
water, where the natural water is very soft and contains insuf
photographic lms, and for seeding clouds to produce rain. Small amounts of iodine are required inNaF cient naturally occurring F ions. the is
now 10.57
usedhuman in | GENERAL
uoride
diet, so toothpaste.
traces (10 ppm)
PROPERTIES
(Theoforiginal
NaI are added uoridetotoothpaste
table salt. Kcontained
I is added SnF 2 and Sn
to animal and2Ppoultry
2O 7.) feeds.
The thyroid gland produces a growth regulating hormone called thyroxine which contains iodine. The
Sizedeofciency
at oms and causes
of iodine ions disease goitre. I odine has limited use as an antiseptic; tincture of iodine is an
Chlorine
aqueous solution of I 2 in K I , and French iodine is a solution in alcohol. I n the laboratory iodides and iodates
The ionic and covalent radii of Group 17 elements are listed in Table 10.26.
are used in volumetric analysis, and Nessler’s reagent K 2[H gI 4] is used to detect ammonia.
Chlorine was rst prepared by Scheele by oxidizing H Cl with MnO 2. This method was used as a laboratory
preparation, but chlorine is now 10.26
Table readilyIonic
available in cylinders.
and covalent radii
10.57 | GENERAL PROPERTIES
H SO Covalent
+ NaCl radius
H Cl + NaH SOIonic radius X
−

2 4
(Å) 4
(Å)
Size of at oms and
F ions 4H Cl + MnO 2 0.72MnCl 2 + 2H 2O + Cl 2 1.33
Cl radii of Group 17 elements
The ionic and covalent 0.99 are listed in Table 10.26.
1.84
Br 1.14 1.96
Table 10.26 Ionic and covalent radii
I 1.33 2.20
Covalent radius Ionic radius X−
(Å) (Å)
F 0.72 1.33
Chapter 10.indd 515 3/21/2017 11:31:10 AM
Cl 0.99 1.84
Chapter 10.indd 517 Br 1.14 1.96 3/21/2017 11:31:15 AM
I 1.33 2.20
7.19 Chlorine Chlorine was discovered in 1774 by Scheele by the action of HCl on
MnO2. In 1810 Davy established its elementary natu re and su ggested the
name chlorine on accou nt of its colou r (Greek, chloros = greenish yellow).
Pr ep a r a t i on
It can be pr epar ed by an y on e of th e followin g m eth ods:
(i) By heating manganese dioxide with concentrated hydrochloric acid.
Mn O2 + 4HCl → Mn Cl 2 + Cl 2 + 2H 2O

d
However, a m ixtu r e of com m on salt an d con cen tr ated H 2 SO 4 is
u sed in place of HCl.
4NaCl + Mn O 2 + 4H 2 SO 4 → Mn Cl 2 + 4NaHSO 4 + 2H 2 O + Cl 2
(ii) By th e action of HCl on pot assiu m per m an gan ate.
2KMn O 4 + 16HCl → 2KCl + 2Mn Cl 2 + 8H 2 O + 5Cl 2

h
Ma n u f a ct u r e of ch l or i n e e
T lis
(i) Deacon’s process: By oxidat ion of h ydr ogen ch lor ide gas by
atm osph er ic oxygen in th e pr esen ce of Cu Cl 2 (cat alyst ) at 723 K.
Cu Cl 2
4HCl + O2 → 2Cl 2 + 2H 2 O

R
(ii) Electrolytic process: Ch lor in e is obtain ed by th e electr olysis of

E u b
br ine (concentr ated NaCl solu tion). Chlor ine is liber ated at anode.
It is also obtain ed as a by–pr odu ct in m an y ch em ical in du str ies.
Pr op er t i es
It is a gr een ish yellow gas with pu n gen t an d su ffocatin g odou r. It is

C ep
abou t 2-5 times heavier than air . It can be liqu efied easily into gr eenish
yellow liqu id wh ich boils at 239 K. It is solu ble in water.
Chlorine reacts with a number of metals and non-metals to form chlorides.

N r
2Al + 3Cl 2 → 2AlCl 3 ; P4 + 6Cl 2 → 4PCl 3
2Na + Cl 2 → 2NaCl ; S8 + 4Cl 2 → 4S2 Cl 2
2Fe + 3Cl 2 → 2FeCl 3 ;

© be
It h as gr eat affin it y for h ydr ogen . It r eact s wit h com pou n ds
con tain in g h ydr ogen to for m HCl.
H 2 + Cl 2 → 2HCl
H 2 S + Cl 2 → 2HCl + S
C10 H 16 + 8Cl 2 → 16HCl + 10C
With excess ammonia, chlorine gives nitrogen and ammonium chloride

o
whereas with excess chlorine, nitrogen trichloride (explosive) is formed.

t
8NH 3 + 3Cl 2 → 6NH 4 Cl + N 2 ; NH 3 + 3Cl 2 → NCl 3 + 3HCl
(excess) (excess)

t
With cold and dilu te alkalies chlorine produ ces a mixtu re of chloride
and hypochlorite bu t with hot and concentrated alkalies it gives chloride
an d ch lor ate.

o
2NaOH + Cl 2 → NaCl + NaOCl + H 2 O
(cold an d dilu t e)

n
6 NaOH + 3Cl 2 → 5NaCl + NaClO3 + 3H 2 O
(h ot an d con c.)
With dr y slak ed lim e it gives bleach in g powder.
2Ca(OH)2 + 2Cl 2 → Ca(OCl)2 + CaCl 2 + 2H 2 O

197 Th e p-Block Elem en t s

 Cl 210 1.99
Br 158 2.28
I 118 _ 2.66

@unacademyplusdiscounts
The bond energy in F2 is abnormally low (126 kJ mol −1), and this is largely responsible for its very high
520 reactivity.
Chapter (Other
10 Theelements
p-Block Elements
in the rst androwtheir
of Compounds
the periodic table also have weaker bonds than the elements
The com position of bleaching
which follow in their respective groups. For example powder is Ca(OCl)
in Group N—N2 .Ca(OH)
15 the2 .CaCl 2 .2H 2 O.
bond in hydrazine is weaker
than P—P , and in Chlor
Group ine
16 ther O—O
eacts with
bond hydr
in ocar bons
peroxides isand gives
weaker su
than S—S.)
bstitu tion
Two pr odu ctsexplanations
different
orbitals. Cl 2, Br 2 and I 2 show the expected trend (Table 10.29), but the bond energy for F2 does not t the
have been suggested withfor
satuther ated hydr ener
low bond ocar bons and addition pr odu cts with u nsatu r ated
expected trend. Hence the order is Cl 2 > Brgy:
2 > F2 > 2.
hydr ocar bons. For exam ple,
1. Mulliken postulated that in Cl 2, Br UV2
and I some pd hybridization occurred, allowing some multiple
CH 4 + Cl 2 → CH2 3 Cl + HCl
bonding. This would make Table the bondsBond
10.29 stronger thanand
energy in Fbond
2 in which there
lengths ofare
X2 no d orbitals available.
Met h an e Met h yl ch lor ide
2. Coulson suggested that since uorine tatoms are small, the F—F distance is also small (1.48 Å ), and
C2 H 4 + Cl 2 Bond Roomenergy
em p.
→(free
C 2 H 4 Cl 2 Bond length X2
hence internuclear repulsion isenergy
appreciable. The
of dissociation)large electron –(Å)
electron repulsions between the lone
pairs of electrons onEtthe

d
h en e 1,2-Dich
−1 lor oet h an e
two uorine(kJ atoms
mol ) weaken the bond.
Chlor ine water on standing loses its yellow colou r du e to the

e
It seems unnecessary to invoke
formation F multiple
of HCl and bonding to explain these
126 Hypochlorou
HOCl. s acidfacts,
1.43and the
(HOCl) sosimpler
formed, Coulson
gives explanation
is widely accepted. n ascen t oxygen Cl wh ich 210 is r espon sible for oxidisin 1.99 g an d bleach in g
pr oper ties of chlor ine.

h
Br 158 2.28
Oxidizing power (i) It oxidises fer r ou s to fer r ic and su lphite to su lphate. Chlor ine
oxidises I su lphu r dioxide 118 to su lphu r tr ioxide 2.66 and iodine to iodate.

T lis
Electron af nity is the tendency of the atoms to
In the pr esence of water they for m su lphu gain electrons. This
r ic reaches
acid anda iodic
maximum acid at chlorine.
(See Table 10.27) Oxidation may
respectively. be regarded as the removal −1
of electrons, so that an oxidizing agent gains
The bond
electrons. Thusenergy in 2FeSO
the halogens F2 isact
abnormally
as oxidizinglow (126
agents. kJ
Themol ),
strength and this
of an is largely
oxidizing responsible
agent (that for
is, itsoxidation
its very high
4 + H 2 SO 4 + Cl 2 → Fe2 (SO 4 )3 + 2HCl

R
reactivity. depends
potential) (Other elements
on several in energy
the rstterms row ofand theisperiodic
best table alsoby
represented have
a weaker bonds
Born–Haber typethan
of the elements
energy cycle
Na2 SO 3 + Cl 2 + H 2 O → Na2 SO 4 + 2HCl

b
which follow
(Figure 10.54). in their respective groups. For example in Group 15 the N—N bond in hydrazine is weaker
SO 2 + 2H 2 O + Cl 2 → H 2 SO 4 + 2HCl
thanTheP—P , and in Group
oxidation potential 16 the O—O
is the bondchange
energy in peroxides
between is weaker
the elementthan S—S.)
in its Two different
standard state,explanations
and in its

E u
I 2 + 6H 2O + 5Cl 2 → 2HIO 1 3 + 10HCl -
have beenions.
hydrated suggested
Thus for foriodine
the low the bond enerisgy:
change from 2 I 2(solid) to I (hydrated) . Thus the oxidation potential is equal
(ii) It is a powerful bleaching agent; bleaching action is due to oxidation.
to the sum of the energy put in as the enthalpies of fusion, vaporization and dissociation, less the energy
1. Mulliken
evolved as the postulated
electron af Clthat+ Hin
2nity 2O
and Cl→2, Br 2 and
2HCl
enthalpy + I hydration.
of 2 some pd hybridization occurred, allowing some multiple
O

C ep
bonding. This would make
Colou r the
ed bonds
su stronger
bstance
In a similar cycle the oxidation potential for bromine + Othan incan
→ Colou F2 inrbewhich
less su there are
bst anfor
calculated no change
ce the d orbitals available.
from 1 Br
-
2 2(liquid)
to2.Br Coulson
Use is suggested
ss: It. (Note
hydrated u sed thatbleaching
that(i)since
for insince uorine
its standard atoms
state
woodpu lp are
bromine small,
(r equ ised
ir forF—F
the
liquid, the distance
theenthalpy
m anu factuofisfusion
also
r e ofsmall
must(1.48 Å ), and
be omitted.
hence
Similarly ininternuclear
calculating repulsion
the oxidationis appreciable.
potential The
for large
chlorine electron
and – electron
uorine, sincerepulsions
they arebetween
gases, the
both lone
the

N r
paper and r ayon), bleaching cotton and textiles, (ii) in the extr action of gold
enthalpies
pairs
and ofelectrons
of
platinu fusion and
m (iii) invaporization
on the
thetwom anu mustratoms
uorine
factu be
e ofomitted.)
weaken
dyes, dr uthe
gs bond.
and or ganic com pou nds
Chlorine
su ch has as CClthe highest electron af nity, so gaseous Cl atoms accept electrons most readily. However, Cl is
4 , CHCl 3 , DDT, r efr iger ants, etc. (iv) in ster ilising dr ink ing water
It seems
not and
unnecessary
the strongest
(v) pr epar
to invoke
oxidizing
ation of agent. multiple
poisonou
bonding
Table 10.30 shows
s gases
to that,
su ch
explain these facts,
assumming
phosgene
and
all the the),simpler
energy
(COCl termsgas
tear
Coulson
in explanation
the cycle, uorine

© be
2
is widely
has(CCl
the most accepted.
NO negative
), mu star d H°
gasvalue.
(ClCH SinceCH the
SCHdifference
CH Cl). between G° and H ° is not signi cant, it follows
3 2 2 2 2 2
that uorine accepts electrons more readily than chlorine, so uorine is the strongest oxidizing agent. There
Exam
are plemain
two
Oxidizing 7.17power
reasons
Writefor thethis change of
balanced or der: equ ation for the r eaction of Cl 2 with hot
chemical
an d con cen t r at ed NaOH. Is t h is r eact ion a dispr opor t ion at ion
1. F2 hasafa low
Electron nityrenthalpy of dissociation
is the tendency (arising fr om the weakness of the F—F bond).
eaction? Ju stify.of the atoms to gain electrons. This reaches a maximum at chlorine.
−
(See
2. FTable 10.27) Oxidation may be regarded as the removal of electrons, so that
2 has a high free energy of hydration (arising from the smaller size of the F ion).
an oxidizing agent gains
Solution 3Cl 2 + 6NaOH → 5NaCl + NaClO3 + 3H 2 O
electrons. Thus the halogens act as oxidizing agents. The strength of an oxidizing agent (that is, its oxidation

o
Yes, chlor ine fr om zer o oxidation state is changed to –1 and +5
potential) depends on several energy terms and is best represented by a Born–Haber type of energy cycle

t
oxidation states.
(Figure 10.54).
The Inte oxidation
xt Q ue potential
stions is the energy change between the element in its standard state, and in its

t
-
hydrated ions. Thus for iodine the change is from 21 I 2(solid) to I (hydrated) . Thus the oxidation potential is equal
to the sum 7.29 of the Give the rput
energy easonin asforthebleaching
enthalpiesactionof fusion,of Cl 2.
vaporization and dissociation, less the energy

o
evolved as 7.30the electron
Name two af nity and enthalpy
poisonou s gases of hydration.
which can be pr epar ed fr om chlor ine gas.
In a similar cycle the oxidation potential for bromine can be calculated for the change from 21 Br 2(liquid)
-
7.20520 Hydrogen
to Brhydrated . (Note that since in itsvegetable
It bleaches standard or state bromine
organic is liquid,
matter thepresence
in the enthalpy of of moistu
fusion must
re. be omitted.

n
Chapter 10.indd 3/21/2017 1
Bleaching effect of chlor ine is per m anent.
Similarly in calculating the oxidation potential for chlorine and uorine, since they are gases, both the
Chloride Glauand bervaporization
pr epar ed this
enthalpies of fusion must acid in 1648 by heating com m on salt with
be omitted.)
concentrated sulphuric
Chlorine has the highest electron af nity, so gaseous Cl acid. Davy in atoms
1810 showed that it ismost
accept electrons a compound
readily. However, Cl is
of hydr ogen and chlor ine.
not the strongest oxidizing agent. Table 10.30 shows that, summing all the energy terms in the cycle, uorine
Ch em i sthas
r y the
198most negative H° value. Since the difference between G° and H° is not signi cant, it follows
that uorine accepts electrons more readily than chlorine, so uorine is the strongest oxidizing agent. There
are two main reasons for this change of or der:
1. F2 has a low enthalpy of dissociation (arising fr om the weakness of the F—F bond).
−
2. F2 has a high free energy of hydration (arising from the smaller size of the F ion).
 1
2 Enthalpy of vaporization

1
2 X 2(liquid)
_
@unacademyplusdiscounts
1
Enthalpy Oxidation
Enthalpy
2 of
of potential hydration
fusion for 10.58 Reaction with Water 521
1 Oxidation chlorine
X (solid)
2 2 potential
for
bromine X ( gas)
Oxidation
potential
for
Electron
iodine
1 affinity
2 Enthalpy of
Energy dissociation X -( hydrated)
X -( gas)
1
Figure 10.54 2Energy
X 2(gas) cycle showing the oxidation potentials of the halogens. (Oxidation potential is
used here in preference
1 to reduction potential to stress that the halogens are strong oxidizing agents.
Enthalpy of vaporization
Note G° = −nFE°).2
1
2 X 2(liquid)
1 Enthalpy
1 ( H°) values for
Table 10.30 Enthalpy
2
Enthalpy 2 X2 X(hydrated) (all values in kJ mol −1)
Oxidation of
of potential hydration
1 1 1 Enthalpy of
2
Enthalpy of fusion
2 Enthalpy of 2 Enthalpy of foraffinity
Electron Sum of H°
fusion
1 vaporization Oxidation
dissociation chlorine hydration
X (solid)
2
2 potential
F2 − − for + 159/2 −333 −513 −836
Cl 2 − − bromine
+ 243/2 −349 −370 −597.5
Oxidation
Br 2 −potential + 30/2 + 193/2 −325 −339 −552.5
for
I2 + 15/2 iodine + 42/2 + 151/2 −296 −274 −466
X -( hydrated)
Fluorine is a very strong oxidizing agent, and it will replace Cl − both in solution and also when dry.
Similarly, chlorine gas will displace Br − from solution. (This is the basis of the commercial extraction of
Figure 10.54 Energy cycle showing the oxidation potentials of the halogens. (Oxidation potential is
bromine from sea water.) I n general any halogen of low atomic number will oxidize halide ions of higher
used here in preference to reduction potential to stress that the halogens are strong oxidizing agents.
atomic number.
Note G° = −nFE°).

10.58 | REACTION WITH WATER 1

Table 10.30 Enthalpy ( H°) values for X X 2 2 (hydrated) (all values in kJ mol −1)
The halogens1 are all soluble 1in water, but the1extent to which they react with theEnthalpy
water, and
of the reaction
2
Enthalpy of 2 Enthalpy of 2 Enthalpy of Electron affinity Sum of H°
mechanism thatfusion
is followed, vary. Fluorine is sodissociation
vaporization hydration
strong an oxidizing agent that it oxidizes water to dioxygen.
The
F2 reaction is spontaneous
− and −strongly exothermic.
+ 159/2 (The free energy
−333 change is−513
large and negative.)
−836
Oxidation may be regarded as the removal of electrons, so that an oxidizing agent gains electrons. Thus the
Cl 2 − − + 243/2 −349 −370 −597.5
uorine atoms are reduced to uoride ions.
Br 2 − + 30/2 + 193/2
1
−325 −339 −552.5
F2 + 3H 2O 2H 3O + + 2F− + 2 O 2 G° = −795 kJ mol −1
I2 + 15/2 + 42/2 + 151/2 −296 −274 −466

Fluorine is a very strong oxidizing agent, and it will replace Cl − both in solution and also when dry.
Similarly, chlorine gas will displace Br − from solution. (This is the basis of the commercial extraction of
bromine from sea water.) I n general any halogen of low atomic number will oxidize halide ions of higher
atomic number.
Chapter 10.indd 521 3/21/2017 11:31:23 AM

10.58 | REACTION WITH WATER

The halogens are all soluble in water, but the extent to which they react with the water, and the reaction
mechanism that is followed, vary. Fluorine is so strong an oxidizing agent that it oxidizes water to dioxygen.
The reaction is spontaneous and strongly exothermic. (The free energy change is large and negative.)
Oxidation may be regarded as the removal of electrons, so that an oxidizing agent gains electrons. Thus the
uorine atoms are reduced to uoride ions.
1
F2 + 3H 2O 2H 3O + + 2F− + 2 O 2 G° = −795 kJ mol −1

Chapter 10.indd 521 3/21/2017 11:31:23 AM

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

A similar reaction between chlorine and water is thermodynamically possible, but the reaction is very
slow because the energy of activation is high.
Cl 2 + 3H 2O 2H 3O + + 2Cl −+ 21 O 2
With chlorine an alternative dispr oportionation reaction occurs rapidly:
Cl 2 + H 2O H Cl + H OCl
Oxidation state of chlorine (0) ( I) (+I )
A similar disproportionation reaction occurs to a very limited extent with Br 2 and I 2. Thus a saturated

_
aqueous solution of Cl 2 at 25 °C contains about two thirds hydrated X 2 and one third OCl −. Solutions of Br 2
and I 2 contain only a very small amount of OBr −, and a negligible amount of OI −, respectively (Table 10.31).

academyplusdiscounts Table 10.31 Concentrations in saturated aqueous solutions at 25 °C

Solubility Concentration X 2 (hydrated) Concentration HOX
(mol l−1) (mol l −1) l −1)
10.60
(mol Hydrogen Halides HX 523
Cl 2 0.091 0.061 0.030
−3
Both of these propertiesBrarise 2 from0.21 the small size 0.21 of uorine. The weak 1.1 ×F—F
10 bond arises because of
I 0.0013 0.0013
repulsion between the lone pairs of electron on the two atoms. Strong bonds
2 6.4 × 10−6arise because of the high
coordination number
I odine and high
is an even lattice
weaker energy.
oxidizing agent. The free energy change is positive, which shows that energy
Some bond
must beenergies
suppliedare shown
to make in Table
it oxidize 10.32. These explain why the halogens form very strong bonds.
water.
M any are stronger than the C—CI 2bond, + H 2O which
2H + +is2Iitself
−
+ 21O 2regarded
G° = + as mol −1strong bond. (The C—C bond
105akJvery
−1
energy is 347 kJ mol .) −1
I t follows that for the reverse reaction G° would be − 105 kJ mol , so the reverse reaction should occur
−1
spontaneously.
Table 10.32 ThisSome
is the case.
bond A tmospheric
energies dioxygen oxidizes
of halogen iodide ions(all
compounds to iodine.
valuesAint the
kJend
molpoint ) of
an iodine titration with sodium thiosulphate, the iodine originally present is all converted to iodide ions.
HX producedBX
Thus the bluish colour AlX3
by3 the starch indicator CX4 disappears, NX
with iodine and3 the solutionXbecomes
2
colourless.
F 566 645 582 439 272 126
I 2 + 2S2O 2- 2I − + S4O 62-
Cl 431 444 427
3
347 201 210
I f the
Br titration ask
366is allowed to
368stand for two360
or three minutes,
276 the indicator243
turns blue again.
158This is
because some atmospheric oxidation has taken place, forming I 2, which reacts with the starch to give the
blueI colour again.299 272 285 238 * 118
1
* U nstable and explosive. 2I − + 2 O 2 + 2H + I 2 + H 2O
The end point of the titration is usually taken as being when the colour disappears and the solution remains
Some important reactions
colourless for half aofminute.
halogens ar e given in Table 10.33.

Table 10.33 Some reactions of the halogens

10.59 | REACTIVITY OF THE ELEM ENTS
Reaction Comment
Fluorine
2F2 +is 2HtheOmost4H reactive
+
+ 4F−of+all
O 2the elements in Vigorous
the periodic table. Iwith
reaction t reacts
F with all the other elements
2
except the lighter
2I 2 + 2H 2O noble
+ gases − H e, Ne and A r. I t reacts with xenon under mild conditions to form xenon
4H + 4X + O 2 I reaction in r everse direction
uorides. Reactions+ with− many elements are vigorous, and often explosive. I n the massive form a few
X 2 + H 2O H + X + H OX Cl >Br >I (F not at all)
metals such as Cu, Ni, Fe and A l acquire a protective uoride coating. H owever, if these metals are
in powdered
X 2 + H 2 2H Xform (with a large surface area), or Aif llthe
thereaction
halogens mixture is heated, then the reaction is
vigorous. The reactivity of the other halogens decreases in the order Cl > Br > I . Chlorine and bromine
nXwith
react 2 + 2M
most of2M theXelements,
n M ostthan
though less vigorously metals
doesform halides
uorine. I odine is less reactive and does
not combine with some elements such as S and Se.FFluorine the mostand vigor ous often oxidize elements further
chlorine
than do bromine and iodine, by this means bringing out higher valencies, for example in PBr 3 and PCl 5,
X + CO COX Cl and Br form carbonyl halides
and in2 S2Br 2, SCl 2 and 2SF 6.
The3Xgreat + reactivity
2P PX of uorine is attributable to two A factors:
ll the halogens form trihalides
2 3

1. 5X 2+
The 2Pdissociation
low PX 5 A s, Sbresults
energy of the F—F bond (which and Bi in also
a lowform trihalides
activation energy for the reaction).
F, Cl and Br form pentahalides
2. The very strong bonds which are formed.
A sF5, SbF5, BiF5, SbCl 5
X 2 + 2S S2X 2 Cl and Br
2Cl 2 + S SCl 4 Cl only
3F2 + S SF6 F only
Chapter 10.indd 522 3/21/2017 11:31:26 AM
X 2 + H 2S 2H X + S A ll the halogens oxidize S 2− to S
X 2 + SO 2 SO 2 X 2 F and Cl
3X 2 + 8NH 3 N 2 + 6NH 4X F, Cl and Br
X2 + X 2X X I nterhalogen compounds formed higher
X2 + X X X X3 interhalogen compounds

10.60 | HYDROGEN HALIDES HX

I t is usual to refer to pure anhydrous H X compounds as hydrogen halides, and their aqueous solutions as
hydrohalic acids or simply halogen acids.
 p
Usess: It is u sed (i) for bleaching woodpu lp (r equ ir ed for the manu factu r e of

N re
paper and r ayon), bleaching cotton and textiles, (ii) in the extr action of gold
and platinu m (iii) in the manu factu r e of dyes, dr u gs and or ganic compou nds
su ch as CCl 4, CHCl 3 , DDT, r efr iger ants, etc. (iv) in ster ilising dr ink ing water
and (v) pr epar ation of poisonou s gases su ch as phosgene (COCl 2 ), tear gas

© be
(CCl 3 NO2 ), mu stard gas (ClCH 2CH 2SCH 2 CH 2 Cl).

Example 7.17 Write the balanced chemical equ ation for the r eaction of Cl 2 with hot
an d con cen t r at ed NaOH. Is t h is r eact ion a dispr opor t ion at ion
reaction? Ju stify.
Solution 3Cl 2 + 6NaOH → 5NaCl + NaClO3 + 3H 2 O

o
Yes, chlor ine fr om zer o oxidation state is changed to –1 and +5

t
oxidation states.

Intext Q uestions

ot
7.20 Hydrogen
7.29 Give the r eason for bleaching action of Cl 2 .
7.30 Name two poisonou s gases which can be prepared from chlorine gas.

It bleaches vegetable or organic matter in the presence of moistu re.

n
Chloride

Ch em i st r y 198
Pr ep a r a t i on
Bleaching effect of chlor ine is per manent.
Glau ber pr epar ed this acid in 1648 by heating common salt with
concentrated sulphuric acid. Davy in 1810 showed that it is a compound
of hydr ogen and chlor ine.

In l abor at or y, i t i s pr epar ed by h eat i n g sodi u m ch l or i de wi t h

concentr ated su lphu r ic acid.
420 K
NaCl + H 2 SO 4 → NaHSO4 + HCl
823 K
NaHSO 4 + NaCl → Na2 SO4 + HCl
HCl gas can be dried by passing through concentrated sulphuric acid.
Pr op er t i es
It is a colou r less and pu ngent sm elling gas. It is easily liqu efied to a

d
colou r less liqu id (b.p.189 K) and fr eezes to a white cr ystalline solid
(f.p. 159 K). It is extr em ely solu ble in water and ionises as follows:

he HCl ( g ) + H 2 O ( l ) → H 3 O + ( aq ) + Cl − ( aq ) K a = 10 7
Its aqu eou s solu tion is called hydr ochlor ic acid. High valu e of
dissociation constant (K a) indicates that it is a str ong acid in water.
It r eacts with NH 3 an d gives wh it e fu m es of NH 4 Cl.
pu T
is
NH 3 + HCl → NH 4 Cl
When three parts of concentrated HCl and one part of concentrated
re R

HNO 3 ar e m ixed, aqu a r egia is for m ed wh ich is u sed for dissolvin g

bl

noble m etals, e.g., gold, platinu m .

_
Au + 4H + + NO3− + 4Cl − → Au Cl −4 + NO + 2H 2 O
E

@unacademyplusdiscounts 3Pt + 16H + + 4NO3− + 18Cl − → 3Pt Cl 26 − + 4 NO + 8H 2 O

H ydr och l or i c aci d decom poses sal t s of weak er aci ds, e.g.,
be C

528 Chapter 10 The p-Block Elements and their Compounds

car bonates, hydr ogencar bonates, su lphites, etc.
Na2 CO3 + 2HCl → 2NaCl + H 2 O + CO 2
Bridging halides NaHCO + HCl → NaCl + H O + CO
to N

3 2 2
Halide bridges are sometimes
Na2 SO 3formed
+ 2HCl → 2NaCl
between two atoms.
+ H 2O(Less commonly
+ SO 2
they are formed between three
atoms.) Thus A lCl 3 forms a dimeric structure whereas BeF2 and BeCl 2 form in nite chains. The bridges are
depicted as the halogen forming one normal covalent bond, and donating a lone pair of electrons to form
Use ss: It is(coordinate)
a second u sed (i) inbond.
the Both
m anu factuare
bonds r e identical.
of chlorTheine,bridge
NH 4 Clmayand glu cose (fr
be described in om
molecular orbital
©

cor n star
terms as a ch), (ii) for extr
three-centre acting glu
four-electron e frwhich
bond, om bones anddiscussed
is already pu r ifying bone black
in Chapter 3. , (iii)
in m edicine and as a labor ator y r eagent.

10.62 | HALOGEN OXIDES

When HCl reacts with finely powdered iron, it forms ferrou s chloride Example 7.18
and not Thefer rcompounds
ic chlor ide. Why?
with oxygen probably show greater differences between the different halogens than any
other class of compound.
Its r eaction with ir on pr odu ces Differences
H 2. between F and the others arise for the usual reasons (small size,
Solution
lack of d orbitals and high electronegativity). In addition oxygen is less electronegative than F, but more
Fe + 2HCl → FeCl
electronegative + HBr
than2 Cl, 2 and I. Thus binary compounds of F and O are uorides of oxygen rather than
Liber ation of hydr ogen pr events the for mare
oxides of uorine. The other halogens ation
lessof fer r ic chlor ide.
electronegative than oxygen and thus form oxides. There
 O 2Froom
mine oxides all decompose below 2(−I ) temperature. The higher oxidation states are more stable than the

lower states.Oxides
Of the compoundsClshown
2O(+I )in Table
ClO10.36,
2 ClO 2, Cl 2O, ICl2O
2O5 6and OF are
Cl22O 7 the most important.
ClClO 4
ClO 3
Table 10.36 Compounds
Br O(+I )
of the halogensI with
BrO O oxygen (and their oxidation states)
I O I O
2 2 2 5 4 9 2 4
Oxidation state (−I ) (+I ) (+I V ) (+V ) (+V I ) (+V I I I ) Others
Fluorides OF2(−I ) O 4F2
O 2F2(−I )
Oxygen diflOxides
uoride OF 2 Cl 2O(+I ) ClO 2 Cl 2O 6 Cl 2O 7 ClClO 4
ClO 3
OF2 is a pale yellow gas, formed by passing F 2 into dilute (2%) NaOH .
Br 2O(+I ) BrO 2 I 2O 5 I 4O 9 I 2O 4
2F2 + 2NaOH 2NaF + H 2O + OF2
OF2 is a strong oxidizing agent, and has been used as a rocket fuel. I t dissolves in water and gives a neutral
solution, so it is not an acid anhydride. With NaOH it gives uoride ions and dioxygen.
Oxygen difl uoride OF 2
Dioxygen
OF2 is a paledifl uoride
yellow O 2F2 by passing F 2 into dilute (2%) NaOH .
gas, formed

O 2F2 is an unstable orange–yellow solid, 2F2 + 2NaOH 2NaFoxidizing

and is a violent + H 2O + OF and2 uorinating agent. I t is formed by
passing an electric discharge through a mixture
OF2 is a strong oxidizing agent, and has been used asof F and O
2 a rocket
2 at fuel. Itlow
very pressure
dissolves in and at and
water liquid air atempera-
gives neutral
ture. I t decomposes at −95 °C. I ts structure is similar to that of H O , except
solution, so it is not an acid anhydride. With NaOH it gives uoride ions and dioxygen.
2 2 that the O—O bond length of
1.22 Å is much shorter than the O—O distance of 1.48 Å in H 2O 2. The O—F bond lengths are 1.58 Å , which
is much longer than in OF 2. Other oxy uorides reported are: O 4F2, O 5F2 and O 6F2.
Dioxygen difl uoride O 2F2
O 2F2 is an unstable
Dichlorine orange–yellow
monoxide Cl 2O solid, and is a violent oxidizing and uorinating agent. It is formed by
passing an electric discharge through a mixture of F2 and O 2 at very low pressure and at liquid air tempera-
Clture.
2O is yellow–brown
It adecomposes gas.°C.
at −95 I t Its
is commercially important.
structure is similar to thatBoth
of H 2laboratory and the
O 2, except that commercial
O—O bond preparations
length of
are byÅheating
1.22 is muchfreshly
shorterprecipitated
than the O—O (yellow) mercuric
distance of 1.48oxide with
Å in H O
2 2
the
. The halogen
O—F gas
bond diluted
lengthswith
are dry
1.58 Åair, which
.
is much longer than in OF 2. Other oxy uorides 300 °C
reported are: O F , O F and O F .
2Cl + 2H gO
2 H gCl · H gO + Cl O
4 2 5 2
2
6 2
2

Dichlorine monoxide Cl 2O
_
Cl 2O is a yellow–brown gas. It is commercially important. Both laboratory and commercial preparations
are by heating freshly precipitated (yellow) mercuric oxide with the halogen gas diluted with dry air .
@unacademyplusdiscounts 300 °C
Chapter 10.indd 528 2Cl 2 + 2H gO H gCl 2 · H gO + Cl 2O 3/21/2017 11:31:36 AM
10.62 Halogen Oxides 529

Cl 2O explodes in the presence of reducing agents, or NH 3, or on heating.

3Cl 2O + 10NH 3 6NH 4Cl + 2N 2 + 3H 2O
Chapter 10.indd 528 Cl 2O gas is very soluble in water (144 g Cl 2O dissolves in 100 g H 2O at −9 °C), forming hypochlorous acid, 3/21/2017 11:31:36 AM
and the two are in equilibrium.
Cl 2O + H 2O 2H OCl
Cl 2O dissolves in NaOH solution, forming sodium hypochlorite.
Cl 2O + 2NaOH 2NaOCl + H 2O
The structures of OF2, Cl 2O and Br 2O are all related to a tetrahedron with two positions occupied by
lone pairs of electrons.
1s 2s 2p
Electronic structure of
oxygen atom in its
ground state

Electronic structure of 1s 2s 2p
oxygen atom having gained
two electrons by forming
bonds to two halogen atoms
four electron pairs – tetrahedral
with two positions occupied b y lone pairs

Repulsion between the lone pairs reduces the bond angle in F2O from the tetrahedral angle of 109°28 to
103° (Figure 10.57). I n Cl 2O (and presumably Br 2O) the bond angle is increased because of steric crowding
of the larger halogen atoms.
O O O
1.41 Å 1.71 Å

F F Cl Cl Br Br
103° 111° 112°

Figure 10.57 Bond angles in F2O, Cl2O and Br 2O.

Bleaching pow der

M ost of the Cl 2O produced is used to make hypochlorites. NaOCl is sold in aqueous solution. Ca(OCl) 2 is a
solid. A n impure form mixed with Ca(OH ) 2 and CaCl 2 is sold as ‘bleaching powder’. The latter is also made
by passing Cl 2 into Ca(OH ) 2. These are used to bleach wood pulp and fabrics, and as disinfectants.
When allowed to stand for long, bleaching powder undergoes the following reactions.
6Ca(OCl)Cl ® Ca(ClO ) + 5CaCl (auto-oxidation)
 O O O
1.41 Å 1.71 Å

F F Cl Cl Br Br
103° 111° 112°

Figure 10.57 Bond angles in F2O, Cl 2O and Br 2O.

Bleaching pow der

M ost of the Cl 2O produced is used to make hypochlorites. NaOCl is sold in aqueous solution. Ca(OCl) 2 is a
solid. A n impure form mixed with Ca(OH ) 2 and CaCl 2 is sold as ‘bleaching powder’. The latter is also made
by passing Cl 2 into Ca(OH ) 2. These are used to bleach wood pulp and fabrics, and as disinfectants.
When allowed to stand for long, bleaching powder undergoes the following reactions.
6Ca(OCl)Cl ® Ca(ClO 3 ) 2 + 5CaCl 2 (auto-oxidation)

2Ca(OCl)Cl ¾Catalyst
¾¾
CoCl 2
® 2CaCl 2 + O 2

Ca(OCl)Cl + H 2O ® Ca(OH ) 2 + Cl 2 ¯
Some important reactions depicting oxidizing pr operty of bleaching powder ar e as follows.

1. Ca(OCl)Cl + H 2S ® S + CaCl 2 + H 2O
2. Ca(OCl)Cl + 2FeSO 4 + H 2SO 4 ® Fe2 (SO 4 ) 3 + CaCl 2 + H 2O
3. Ca(OCl)Cl + K NO 2 ® CaCl 2 + K NO 3 _
4. 3Ca(OCl)Cl + 2N H ® CaCl 2 + 3H 2O + N 2
@unacademyplusdiscounts 3

5. Ca(OCl)Cl+ 2K I + 2H Cl ® CaCl 2 + K Cl + H 2O + I 2
530 Chapt er 10 The p-Block Elements and their Compounds

6. Ca(OCl)Cl + 2K I + 2CH 3COOH ® CaCl 2 + 2K COOCH 3 + H 2O + I 2

7. Ca(OCl)Cl + Na 3A sO 3 ® CaCl 2 + Na3 A sO 4
CaOCl 2 also reacts with acids to liber ate chlorine.
Chapter 10.indd 529 3/21/2017 11:31:43 AM

Ca(OCl)Cl + 2H Cl ® CaCl 2 + H 2O + Cl 2

Ca(OCl)Cl + H 2SO 4 ® CaSO 4 + H 2O + Cl 2

Ca(OCl)Cl + CO 2 ® CaCO 3 + Cl 2

Chlorine dioxide ClO 2

ClO 2 is a yellow gas which condenses to a deep red liquid, b.p. 11 °C. I n spite of its high reactivity (or
perhaps because of this) ClO 2 is of commercial importance, and is the most important of the oxides. ClO 2
is a powerful oxidizing and chlorinating agent. Large quantities are used for bleaching wood pulp and
cellulose, and for purifying drinking water. I t is 30 times as effective as chlorine in bleaching our (to make
white bread).
ClO 2 liquid explodes above – 40 °C. The gas detonates readily when concentrated above 50 mm H g
partial pressure. I t explodes when mixed with reducing agents. Because of this, it is made in situ, and is used
diluted with air or CO 2. The safest laboratory preparation is from sodium chlorate and oxalic acid, as this
automatically dilutes the gas with CO 2.
H 2O 90 C
2NaClO 3 + 2(COOH ) 2 2ClO 2 + 2CO 2 + (COONa) 2 + 2H 2O

The gas is made commercially from NaClO 3. A pure product is formed using SO 2. U sing H Cl causes con-
tamination with Cl 2, but this may be unimportant or even useful for bleaching and sterilization.
trace of NaCl
2NaClO 3 + SO 2 + H 2SO 4 2ClO 2 + 2NaH SO 4
2H ClO 3 + 2H Cl 2ClO 2 + Cl 2 + 2H 2O
ClO 2 dissolves in water, evolving heat, and giving a dark green solution. This decomposes very slowly in the
dark, but rapidly if illuminated.
ClO 2 ClO + O
2ClO + H 2O H Cl + H ClO 3
I t is also used to manufacture sodium chlorite NaClO 2, which is also used for bleaching textiles and paper.
2ClO 2 + 2NaOH + H 2O 2 2NaClO 2 + O 2 + 2H 2O
Some other reactions are:
2ClO 2 + 2NaOH NaClO 2 + NaClO 3 + H 2O

2ClO 2 + 2O 3 Cl 2O 6 + 2O 2
The ClO 2 molecule is paramagnetic and contains an odd number of electrons. Odd electron molecules are
 CaOCl 2 also reacts with acids to liber ate chlorine.
Ca(OCl)Cl + H 2SO 4 ® CaSO 4 + H 2O + Cl 2
Ca(OCl)Cl +
Ca(OCl)Cl + 2H ® CaCO
COCl2 ® CaCl 2 + H 2 O + Cl 2
3 + Cl 2

Ca(OCl)Cl + H 2SO 4 ® CaSO 4 + H 2O + Cl 2

Chlorine dioxide ClO 2
Ca(OCl)Cl + CO 2 ® CaCO 3 + Cl 2
ClO 2 is a yellow gas which condenses to a deep red liquid, b.p. 11 °C. In spite of its high reactivity (or
perhaps because dioxide
Chlorine of this) ClO 2 is
ClO 2
of commercial importance, and is the most important of the oxides. ClO 2
is a powerful oxidizing and chlorinating agent. Large quantities are used for bleaching wood pulp and
ClO 2 is a yellow gas which condenses to a deep red liquid, b.p. 11 °C. I n spite of its high reactivity (or
cellulose, and for purifying drinking water. It is 30 times as effective as chlorine in bleaching our (to make
perhaps because of this) ClO 2 is of commercial importance, and is the most important of the oxides. ClO 2
white bread).
is a powerful oxidizing and chlorinating agent. Large quantities are used for bleaching wood pulp and
ClO 2 liquidand
cellulose, explodes
for purifying – 40 °C.water.
abovedrinking The gas
I t is detonates
30 times as readily
effectivewhen concentrated
as chlorine above
in bleaching our50(tomm
make Hg
partialwhite
pressure. It
bread). explodes when mixed with reducing agents. Because of this, it is made in situ, and is used
diluted withClO air or CO 2. The safest
2 liquid explodes – 40 °C. The
abovelaboratory preparation is from
gas detonates sodium
readily whenchlorate
concentrated and oxalic
above acid,
50 mm asHthis
g
automatically dilutes the
partial pressure. gas withwhen
I t explodes CO mixed
2. with reducing agents. Because of this, it is made in situ, and is used
diluted with air or CO 2. The safest laboratory preparation is from sodium chlorate and oxalic acid, as this
2NaClO
automatically + 2(COOH
dilutes3 the ) 2 2.H 2O 90 C 2ClO 2 + 2CO 2 + (COONa) 2 + 2H 2O
gas with CO
H 2O 90 C
The gas is made commercially
2NaClO 3 +from NaClO
2(COOH ) 2 3. A pure product
2ClO 2 is formed
+ 2CO using SO22.+U2H
2 + (COONa) sing
2O H Cl causes con-
tamination with Cl 2, but this may be unimportant or even useful for bleaching and sterilization.
The gas is made commercially from NaClO 3. A pure product is formed using SO 2. U sing H Cl causes con-
tamination with Cl 2, but this may be unimportanttrace
or even
of NaCluseful for bleaching and sterilization.
2NaClO 3 + SO 2 + H 2SO 4 2ClO 2 + 2NaH SO 4
trace of NaCl
2NaClO 3 + SO 2 + H 2SO 4
2H ClO 3 + 2H Cl 2ClO 2 + Cl 2 +2ClO 2 + 2NaH SO 4
2H 2O
2H ClO + 2H Cl 2ClO + Cl + 2H O
ClO 2 dissolves in water, evolving heat, and giving3
a dark green2
solution.
2
This
2
decomposes very slowly in the
ClOrapidly
dark, but 2 dissolves
if in water, evolving
illuminated. heat, and giving a dark green solution. This decomposes very slowly in the
dark, but rapidly if illuminated.
ClO 2 ClO + O
ClO 2 ClO + O
2ClO + H 2O H Cl + H ClO 3
2ClO + H 2O H Cl + H ClO 3
It is also used to manufacture sodium chlorite NaClO 2, which is also used for bleaching textiles and paper.
I t is also used to manufacture sodium chlorite NaClO 2, which is also used for bleaching textiles and paper.
2ClO2ClO
2 + 2NaOH + H+2O
+ 2NaOH H 2O 2NaClO 2 ++
2NaClO OO2 ++2H
2H2O
O
2 2 2 2 2 2

Some Some
other other
reactions are: are:
reactions
2ClO 2 + 2NaOH
2ClO 2 + 2NaOH NaClO 2 +2 NaClO
NaClO 3+
+ NaClO 3+HH2O
2O

The ClOThe molecule

2
ClO 2 molecule is paramagnetic
is paramagnetic andand contains
contains an an odd
odd
2ClO
2ClO + 2O Cl O 6 +
2 + 22O 3 3 Cl 2O26 +

numberofofelectrons.
number electrons.Odd
2O
2O
_
2 2

Odd electron
electron molecules
moleculesare
are
generally
@unacademyplusdiscounts highly reactive and ClO 2 is typical. Odd electron molecules often dimerize in order
generally highly reactive and ClO 2 is typical. Odd electron molecules often dimerize in order topair to pairthe
theelec-
elec-
trons, but ClO does not. This is thought to be because the odd electron is delocalized. The molecule is angular
trons, but ClO 2 does2 not. This is thought to be because the odd electron is delocalized. The molecule is angular
with an O—Cl—O angle of 118°. The bond lengths are both 1.47 Å and are shorter than for single 10.63bonds. 531
with an O—Cl—O angle of 118°. The bond lengths are both 1.47 Å and are shorter than for single Oxoacids
bonds.

Chlorine per
Dichlorine chlorat e
hexoxide ClO· ClO 4
Chlorine per chlorat e ClCl· 2ClO
6
4
This can be made by the following r eaction at − 45°C.
Cl 2O 6 is a dark red liquid, which freezes to give a yellow solid at –180 °C. Cl 2O 6 is in equilibrium with the
This can be made by the following r eaction at − 45°C.
monomer ClO 3, and is made from ClO4 2+and
CsClO O 3. 2The
ClOSO F structure
Cs(SO 3)F of neither 3the liquid nor the solid is known.
+ ClOClO
Both are diamagnetic, and so have4no
CsClO + unpaired
ClOSO F electrons.
Cs(SO Possible
)F + structures
ClOClO are shown in Figure 10.58.
I t is less stable than ClO , and decomposes to O , Cl and Cl O at room temperature.
2
2
2
3
2
3
2 6

It is less stable than ClO 2, and decomposes

O toOO 2, Cl 2 and
O Cl 2OO 6 at O
room temperature.
O Cl Cl O Cl Cl ClO +2 ClO -4

O O O O O

Chapter 10.indd 530

Figure 10.58 Possible structures of Cl 2O 6. 3/21/2017 11:31:47 AM

Chapter 10.indd 530 Cl 2O 6 is a strong oxidizing agent and explodes on contact with grease. H ydrolysis of Cl 2O 6 with water or3/21/2017 11:31:47 AM
alkali gives chlorate and perchlorate. Reaction with anhydrous H F is reversible.

Cl 2O 6 + 2NaOH NaClO 3 + NaClO 4 + H 2O

chlorate perchlorate
Cl 2O 6 + H 2O H ClO 3 + H ClO 4
H OClO 2 H OClO 3

Cl 2O 6 + H F FClO 2 + H ClO 4
Cl 2O 6 + N 2O 4 ClO 2 + [NO 2] +[ClO 4] −

Dichlorine hept oxide Cl 2O 7

Cl 2O 7 is a colourless oily liquid. I t is moderately stable and is the only exothermic oxide of chlorine, but it
is shock sensitive. I t is made by carefully dehydrating perchloric acid with phosphorus pentoxide, or H 3PO 4
at −10 °C, followed by distillation at –35 °C and a pressure of 1 mm H g. I ts structure is O 3Cl—O—ClO 3, with
a bond angle of 118°36’ at the central oxygen. I t is less reactive than the lower oxides, and does not ignite
organic materials. I t reacts with water, forming perchloric acid.

P4 O 10
2H ClO 4 Cl 2O 7
H O
 Cl 2O 6 + H 2O H ClO 3 + H ClO 4
H OClO 2 H OClO 3

Cl 2O 6 + H F FClO 2 + H ClO 4
Cl 2O 6 + N 2O 4 ClO 2 + [NO 2] +[ClO 4] −

Dichlorine hept oxide Cl 2O 7

Cl 2O 7 is a colourless oily liquid. I t is moderately stable and is the only exothermic oxide of chlorine, but it
is shock sensitive. I t is made by carefully dehydrating perchloric acid with phosphorus pentoxide, or H 3PO 4
at −10 °C, followed by distillation at –35 °C and a pressure of 1 mm H g. I ts structure is O 3Cl—O—ClO 3, with
a bond angle of 118°36’ at the central oxygen. I t is less reactive than the lower oxides, and does not ignite
organic materials. I t reacts with water, forming perchloric acid.

P4 O 10
2H ClO 4 Cl 2O 7
H 2O

10.63 | OXOACIDS
Table 10.37 The oxoacids of halogens
HOX HXO 2 HXO 3 HXO 4
Oxidation states (+I) (+III) (+V) (+VII)
of the halogens
*HOF
HOCl HClO 2 HClO 3 HClO 4
HOBr HBrO 3 HBrO 4
HOl HI O 3 HI O 4
*F is in (–I ) oxidation state.

Four series of oxoacids are known (Table 10.37). The structures of the ions formed are shown in Figure 10.59.
A ll these structures are based on a tetrahedron. The sp3 hybrid orbitals used for bonding form only weak
bonds, because the s and p levels differ appreciably in energy. The ions are stabilized by strong p – d
bonding between full 2p orbitals on oxygen with empty d orbitals on the halogen atoms. Even so, many of
the oxoacids are known only in solution, or as their salts.

Chapter 10.indd 531 3/21/2017 11:31:51 AM

 I Cl 3 + K Cl K + [I Cl 4] −
I F5 + CsF Cs+ [I F6] −
I Cl + K Br K + [BrI Cl] −

Polyhalides are typical ionic compounds (crystalline, stable and soluble in water, conduct electricity when
in solution), though they tend to decompose on heating. The products of the decomposition (that is which
halogen remains attached to the metal) are governed by the lattice energy of the products. The lattice
energy of the alkali metal halides is highest for the smaller halide ions, so the smaller halogen remains
bonded to the metal.
heat
Cs[I 3 ] CsI + I 2
heat
Rb[I Cl 2 ] RbCl + I Cl

The structures of the polyhalides are known. The trihalides K [I 3], K[ICl 2] and Cs[IBrF] all contain a linear
trihalide ion. Structure of I -5 , I -7 , I 9- , I 2-
8 are given as follows.

- I -
I
I I

I I I I
I I
I I
I 5-

I 7-

2-
I - I
I
I

: :
: :
:I : I I :I :
: :

I I :I : I I
I
I
I
I
I 82-
I 9-

10.66 | PSEUDOHALOGENS AND PSEUDOHALIDES

_
A few ions are known, consisting of two or more atoms of which at least one is N, that have properties
@unacademyplusdiscounts
similar to those of the halide ions. They are therefore called pseudohalide ions (Table 10.39). Pseudohalide
ions are univalent, and these form salts resembling the halide salts. For example, the sodium salts are soluble
538in water,
Chapt er 10 The p-Block Elements and their Compounds
but the silver salts ar e insoluble. The hydrogen compounds are acids like the halogen acids H X .

Table 10.39 The important pseudohalogens

Anion Acid Dimer
CN − Cyanide ion H CN H ydr ogen cyanide (CN) 2 Cyanogen
−
Chapter 10.indd 537 SCN Thiocyanate ion H SCN Thiocyanic acid (SCN) 2 Thiocyanogen 3/21/2017 11:32:17 AM

SeCN − Selenocyanate ion (SeCN) 2 Selenocyanogen

OCN − Cyanate ion H OCN Cyanic acid
NCN 2− Cyanamide ion H 2NCN Cyanamide
−
ONC Fulminate ion H ONC Fulminic acid
- H N3 H ydr ogen azide
N 3 A zide ion

Some of the pseudohalide ions combine to form dimers comparable with the halogen molecules X 2. These
include cyanogen (CN) 2, thiocyanogen (SCN) 2 and selenocyanogen (SeCN) 2.
The best known pseudohalide is CN −. This resembles Cl −, Br − and I − in the following respects:
1. I t forms an acid H CN.
2. I t can be oxidized to form a molecule cyanogen (CN) 2.
3. I t forms insoluble salts with A g+, Pb2+ and H g+.
4. I nterpseudohalogen compounds ClCN, BrCN and I CN can be formed.
5. A gCN is insoluble in water but soluble in ammonia, as is A gCl.
6. I t forms a large number of complexes similar to halide complexes, e.g. [Cu(CN) 4] 2− and [CuCl 4] 2−, and
[Co(CN) 6] 3− and [CoCl 6] 3−

| SINGLE CORRECT CHOICE TYPE QUESTIONS

1. The state of hybridization in anionic part of solid 5. Etching action of H F does not in volve
Cl 2O 6 is (A ) formation of SiF 4.
(A ) sp3d2 (B) sp3d (C) sp3 (D ) sp2 (B) corrosion of vessel wall.
(C) formation of H 2SiF6.
2. The structure of Cl 2O 4 is
(D ) white marking on labor atory ware.
(A ) O O- O
6. I n the following statements, which combination of true
(A) Cl Cl (B) O Cl Cl O (C) Cl +ClO -4 (D) None of these
(T) and false (F) options is corr ect?
O O O