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 •
> __
*V
-;

6
'llmi 'An Easy Approach

It is at .
ta ch ed wi th fo ur
ChemiSj
^^ r
-
—. --
’

Jb e ox id at io
atoms Hydrogen atomsare
n nu m be r
tta
au au
of
ch
.
su
ed
fp
wi
hu
th
rJ
in
ox
n H
yg
2

en
SO4
ato
is
ms
+
and
, no t wi
:©:
th su
1
tpu
_
r dir ec
Oxyo
tly. - •
1

. .. •• •o
M
©>_ X_ _XSx
,'Hx
XX
0
•
- xH or , H — — © S— 0
•• • ©
—H 11

. • • •
-
[THE HALOGENS AND
X

:0: ar e br ok .
in wa te r, ox yg en hy dr og en bo nd s en Th e 0
H
When 2 SO di ss oc ia te s .
|

negative charges on
4
su lph ate ion s ar e du e to the ele ctr on s of hy dr og
:©
en
:
ato ms
' THE NOBLE GASES

5.1 GROUP Vll-A HALOGENS

Introduction:
®
Hence‘SO is tetrahedral * in str uc tu re. Al l th e fou r bo nd s ar e no t pu rel y sin gle or
-
The elements of group Vll A of the Periodic Table consists of five elements ,
.
i e. ,

purely double. A -
peirfect fetrahedral ge om et ry is de ve lop ed for S 04
(2
^,!
— — — — — — — — — — a
fluorine (F), chlorine (Gl), bromine (Br)r iodine (!) and astatine (At). They are called
halogens . •

EXERCISE Origin of word “ halogen” :

The term “ halogen" is derived from the Greek word ‘Halos'
which means 'salt' and
Fill in the Blanks 'genes' means 'born' . •

Ans
Arsenic, antimony
'

(ii) NO (iii) catenation ' Astatine (At) differs from other halogens:
i)
(Wi
Astatine was discovered (l\ ciUj) in 1940. It is an unstable element
(v) red (non-metallic) (vi) . 1.834
(iv) allotropy
grey, (metallic)
*
radioactive ( jtyr ) in nature. Its half life period is 8.3: hours.
and is

;(x)
. .^
(vii) Fe Mg Z Sn
paramagnetic
•• (viii) +5
(xi) deliquescent
. *
(ix) Vl-A
‘

(xii) solid
Other four elements are stable and they resemble (l/ J
physical andchemical properties.
each other in I
(xiv) variable ;(xv) nitrogenous |
Txiiil aaua regia
Indicate true or false: 5.2 OCCURRENCE OF HALOGENS
Ans1; • * The halogens exist in nature in the form of compounds. Their most
"
(ii) True (iii) False (iv) True common
(i) . True
(v) True
• ' (
_
(vi) False (vii) False
'
(viii) True
oxidation states in naturally occurring compounds is -1'. These compounds are soluble in
H2O and so they are - found in ‘
•
|
I
True XL True
Multiple choibe questions Encircle the correct- answers: . (i) Sea
^ (ii)
(iii)
Salt lakes
Underground beds of salts as Khewera salt mines and Kalabagh salt
.
mines in Pakistan A large deposits
other parts of the world.
of NaGI are found in some
Seellmi Objective.
See llmi Objective. |; ORES AND MINERAL QF HALIDES
(b) See llmi Objective.
(b) See llmi Objective; Following are some important ores and minerals of halides: (Guj. 2005)
(vi) See IlmitObjective. .
r -

(vii) See - llmi Objective.

M See Ilmi- Objective. 127
 r
* JiUU »P . V
128 [ Chapter 5] The Halogens and the Noble Gases
CaF2 129
Fluorspar
Fluorine Na3AIF6 Bond energy, (x - x), (kJ 154.80 242.67 192.46
Cryolite '

[CaF2 mole 1) "

Apatite
j1.51 H88°G) j 1.66 ( 70 °Q )
0 Density (g cm 3)
-
'
" '

3Ca3(P04)2 3.19 (0°C) 3.96 (120°G)

NaCI (xiii) |Oxidation states 1 -1, +1, +3, +5, +7 | -1, +1, +5, +7 -1, +1, +5, +7
Chlorine Halite
‘
( Salt beds , brine wells sea water) Gradual Variation of Physical Properties ofHalogens
(Lahore 2004)
P. arnallite KCI . MgCh 6 H2Q
(i) Physical states: (AJK 2005)
, NaBr , KBr
(iii) Bromine Brine wells , sea water
MgBr2.
Firsttwo members F2 and GI2 are gases, Br2 is liquid and I2 is solid .
. (ii) . Colour:
: (iv) Iodine NalOa, Nal04 deposits in Chile All the halogens are coloured. There is a progressive deeping (t\ iiyffy jM ) of the
„ brine wells. colour from F2 to I2 . *
Electronic Distribution (a) . F2 is yellow (;>;) g,as.
(Faisalabad 2005) (b) CI2 is greenish yellow gas.
Group Vll-A:
1i 1l 1[ 1
1 (c) Br2 is reddish brown (IJAJ\i5y ) liquid.
F9 1s 2 2px 2py 2pz
; s _
(d) I2 is deep violet (tpiJ!) solid or shiny greyish black- (Hisolid,
1[ 11 1
Cli/ 1s22s22p63s113px 3py 3pz (iii) .Odour:

1s22s22p53s23p34 sn 1i
3d10 4p x 4p y 4p z
1 AH the halogens have very pungent and unpleasant odour .
(iv) Atomic Sizes:
I s2 2s2 2p6 3s2 3p6 4s2 3d1 0 4ps 5s2 4d1 0 5p X- . ..
\ Atomic radii, ionic radii and covalent radii increase down the group in halogens .
Is 2s 2
2 2 p 3s 23
^ p64 s23 dl04 p65 s2'4 dr 0 5p6 6s24 f 14 5d10 6px - 6py1 6pz ^ ^ ^ This is due to the increasing number of shells and increasing shielding effect
They all
’
electrons in
have seven'
their outermost; shells. Two are in (v) lonizatiomEnergy:
STorbitals a -
ndRemaining five in;prorbitals. Since they have outermosfsubshell as p, so they They have high ionization energies. Anyhow, ionization energies decrease down
^
'

the group. So the tendency to form the negative ion . goes on decreasing down the
’
are pfblock elements;
group. .
(vi) Electron Affinity:
Table (5.1): The Electronic Configurations and the Electron affinities .
decrease from Cl2 to l2 Anyhow, the electron
. ImportahtJPhysical Propertjes of » theHalbgens;
' - .
affinity offluorine is less than that of GI2 This is its abnormal behaviour.
C ’
Properties Fluorine .Chlorine Bromine Iodine (vii) Density:
I
iliTO .i number 9 17 35 53 Due . to the phase change from gases to solids from F2 to l2, the halogens increase
•

1 (ii) ' Physical form at room Pale.yellow | Greenish yellow Redfbrown Shiny,greyish their densities down the group .
...

• 1 temperature , . gas - . . • gas liquid black- solid . (viii) Melting and Boiling Points:
•

1 (iii) Atomicradij pm) * ? '

f Melting and :boilingipoints gradually (>^T ^rT) increase from F2 to I2 This shows -
^ 79 99 1I4
'

that the attractive forces are increasing.among the molecules of halogens.

,

(iv),; [q,njcradil(pni) _
' n 181 •
4ft
_ t

Covalent radn (pm) Vi] (ix) Dissociation of Diatomic Molecules:

•1140 . ( .
The heats of dissociation J f -
/i L j? ) of diatomic halogen molecules decrease
.
Electron affinity, J
- . downihe group. Anyhow F2 shows
,
very smalltbond length of F2
The
.
exceptional (Ub i) behaviour
^This is due to the

(kJmpr1) "A
— (X) -
Diatomic nature: .
5ni jl iraO
•

iTa " .
Jviiij [Ejectrqnegativ.ty - ° : TTf molecules in gases and liquid and
t

L All the halogens exist as covalent diatomic by weak

miMelting PointfC) : -220 "
1 and l . They are held together
-101 crystalline states. These molecules are F2, Cl2, Br2 2

. (x) |Boiling Point(°G) . . j -188 m Van der Waarsforces.

'
34:
- 'tXl'
 zrr -- .Cf ;k
' *w -
130
Ilmi An Easy Approach Chemistry part
/f v .
fChapter 5] The Halogens and the Noble Gases 131
(xi) Oxidizing properties:
tendency to accept one electron, so they oxidize other species, (ii) Reactivity:
Halogens have a
Since electronegativities go on decreasing down the group ,
_ so tendency to have the The fluorine is the most reactive -
/ f p ) element amongthe halogens. This
electron becomes low and oxidizing capability ( =
< < ru 1 z //> d i f ) /
decreases down the is due to the reason that the bond dissociation energy of F2 is minimum among all the
halogens.
group.
(ii ) Hydrogen Bonding In HF:
(xii) Oxidation states:
- . Other halogens also do the
* The halogen acid of fluorine (HF) has different properties than other halogen acids
Fluorine always shows oxidation state of 1 same,
. due to extensive H-bonding in HF.

_*
,
Anyhow, GI2 Br2 and l2 can also show positive oxidation states
(iv) Physical State of Halogen Acids:
(xiii) Solubility in H2O:
Halogens are slightly ( # ) soluble in H20. Their solubilities decrease from Gl210 HF is a liquid at room temperature while the acids of other halogens as HGI, HBr,
l2. F2 cannot ' be dissolved -in H20, because it decomposes H20 liberating (fc/u i) 02 and HI are gases.
' Reaction of HF:
03. (v)
®
Halogens can dissolve in organic solvents like carbon disulphides (GS2), HF gives a number of compound containing HF2 . Most important compound is
chloroform CHCb and ether HjC Hs). I2 is not soluble in H20. It becomes soluble in the KHF2. No such compound is available for other halogens.
^ ^
presence of Kl. In this way it produces l (tri-iodide). Ij ion is water soluble.
1

(xiv) Electronegativity:
^ (vi) Strength of HF:
HF is exceptionally ( Jl L ,fc\) weak acid as compared to the other halogen
-
Halogens have large values of electronegativities. However, electronegativities acids.
decrease down the group. F2 is most electronegative element of the Periodic Table. (vii) Solubilities of Salts:
f The silver salt of fluorine l.e., AgF is soluble in H20 but AgGI, AgBr and Agl are
I
.
1 insoluble in H2 O.
[Uir 2d04fMultan 2bb.4;B.Pur 2005,Rwp.:2005,'Lhr 2005;Lhr 20b7, Lhr 2008,Sarg 2009, Lhr 2009, M.Pur 2009)
- '
CaF2 is insoluble in H2Q but CaGI2, GaBr2 and Cal2 are water soluble.
Introduction (viii) Nature of bonds:
Halogens form homologous series, but fluorine differs from other halogens in The metal fluorides are purely ionic compounds. The percentage of ionic character
'

many respects . in metal bromides and metal iodides is less.

Reasons: (ix) Complex formation:
(i) The size of the fluorine atom (F) is very small as compared to other
°
F ion has the greatest tendency to give complex .
ion For example, [AIF6] 3 and
"

halogens;(OI, Br, I). [FeFeP are important complex ions. Other halides have least tendency to do so.
®
Size ofF ion is also very- small as compared to Cl ® , BrQ, l .
Fluorine has veryhigh ionization energy and electronegativity. , ° (x) Reactiomwith sulphur:
Since fluorine is the most electronegative element so it combines with ‘S’ to give
The bond dissociation energy of the fluorine molecule is very low as SFB. Other halogens do not give such compounds.
compared to Gl2 and Br2.
the valence electrons of the fluorine are restricted (UAt) to the octet
• (xi) - ®
Formation of- X} :
( yt) fule.: d,flu6rihefis.Gofnpelledito shpvvipniy one'oxidation state of 1 —. ® combine .
with F to give Fy . This is due to absence of d-orbital
^ ^
Other halogensican expand the valence shells due to availability (it/ *)
of dwrbitals. *
F ions does not 2

in fluorine. Anyhow, other members of this family give such ions as CI3 , Eta and b .
® ®, ’

1 (xii) Lattice energy:

(vi)
ExceptipnaltBehaviour
1
Fluorine has a capability ( t ) to join with inert gases.
^^ The lattice energy (J J o
,
f the fluorides
bromides and
of m-etal
iodides .
are
very high as compared to the lattice energies ofmetal chlorides
(Multan 2008)
(0 Oxidation!State: (xiii) Xe only combines with fluorine but not with other halogens .
It shows only negative oxidation state of
negative (-1) as well as positive - 1, but other halogens can show
oxidation states +1 +3, +5, +7:
 IImi An Easy Approach Chemistryp J; [Chapter 5] The Halogens and the Noble Gases
^^ 2NaCI + F2
133 3

Definition
-—
oxidatio
of n
miDlZim
electro
PROPERTIES
and reduction: (
ns is
OF
Gujranw
oxidation
called
HALO
ala
GENS
==
2006
and
, —
T
Rwp.
gain
2007
of
,
5
Sarg. 2009, sarg 201
electro ns ic
“
- ^\ 1?
a3E s
*

° cmtf I
1
(ii)
2NaBr + Cl2
2N a l + Br2
> 2NaF + Glz
Chlori ne can displa ce ( li Jf ) B r2 a n d Br2 can displa ce
2NaCI + Br2
2NaBr + 12
l2 from their salts '

_ Loss of y
reduction. .gain ELECTRODE POTENTIALS i

Halogens are electron egative elemen ts . They have tendenc y to the electro E
. The metals and nomm etals react with halogen s Th Definition:
They oxidize the others substan ces 6 7

/ u positive oxidati on state in the halides forma tion It is relative tendency of the electrode to oxidize or reduce the standard
reacting element acquires.
^^ ) the
'

hydrogen electrode. -c
•- 1

Examples: When we look at the electrochemical series, then it is observed that F2 has the
V

acceptt he electron s and develop the negative charges

F2, GI2 Br2
I and l2 maximum standard reduction potential (/ c/V j\ j j ) and 12 has the least reduction
0 7
. . F 2 + 2 e
°
®
2
2
F
CI ®
potential among the halogens. Following table shows the values of ’the standard reduction
potential. :
:
; : '
Gl 2
^ 2 e ;;
% Br2 + 2eG . 2Br ®
Property . | Fluorine
rChlorine Bromine1 Iodine
;
f1
The metals of ' the group
I2 + 2eG
l -A and
—
ll -A
i
react with
2I0

the halogen s to form the salts In

’ ,
Standard reduction potential (E°)
X2 + 2e 0
-> 2XS
+ 2.87 + 1.36 + 1.07 I + 0.54
_
I
"

thisiway metals
/ are oxidize d and halogen s /are . reduce d Greater reduction potential of F2 means the F2 has greater tendency to be reduced
yStJjji F . When it is connected with Gl2 electrode, then reaction
L

O
.
.
Trenas' of the oxidizing power:
xidizing power - of
_2Na_ + Gl2

halogen s decreas e with

.
2NaGI

the increase of atomic number down

will happen in such a way
. displace Cl2 from the substance
0
^
that Cl ion is converted to Cl2 gas. In other words, F2 can
'
5

lowest 0 0
the group. Fluorine has highest oxidizing power and :| 2 has the ' . F2 + 2e 2F E° = 2.87 V
0
F2 > Gl2 > Br2 > b 2GI
°
Gl2 + 2e E° = -1.36 V
Factors affectingtheoxidizingpower:
Following factors are responsible for the oxidizing ,powers ofihalogens: F + 2CI°
2 GI + 2e
°
2 E° = 1.51 V n

(i) Heat of dissociation.

' By looking at the reduction potential of other halogens we reach the conclusion
E Electron affinities ofithe atoms . -
( £ ), that:
(Pi) Hydration energy- of theions. (i)' F2 can oxidize Cl2, Br2 and l2.
(iv) Heat of > vaporization. (ii) Gl2 can oxidize Br2 and l2.
Heatofdissociation: (iii) Br2 can oxidize only l2.
If a halogen ' has low heat of dissociation ( iJ.-siMfajA.* II<M) a n d a high electron
' TtecolourizingiReagents
affinity, then there is greater hydration energy of the ion. For these reasons
; it has higher i
_ _ Due to great oxidizing capabilities of F2 and Cl2, they can act as a decolourizing
oxidizing.power.- (2 iji iJiJT^) agents. H

0xidizingipowerdf‘F2 is maximum among > the halogens. There are two

'
' reaso ns for (i) They can oxidize dyes to colourless substances. 1
that: (ii) Litmus and univers al indicato r can be decolou rized, when exposed . to F2
• (i) .
Low heatof dissociationofiF2. * f
!
i and '
GI2.
. ^ _
.

1
;
, , 0 Cl2 is used in bleaching powder and bleaches [c. HiJrJ)
t the substan ces
L (ii)
^
Relative strength: of( oxidizing 1 powepampng > the;halogens:;
( (
^
High‘hydration:energy (£;i ili yiyi.y j tZli :of the F 'ioni

Since allithe halogens do,notlhavelhe equal oxidizingipowers, so they.can 0x1

30
.
(iii)
due to the oxidizing capabil ities of Cl2.
n
1
-
each other*in •their salts. For example, . .
(i) F2 can oxidize- chlorine from its - compound and liberate (W ' W ) \
ctjjorinjL ^ -

. »

A
 Appr oach istr
J « // -.
^ ^
l!mi An Easy Chem r -:
L
• i
{Chapter 5] The Halogens and the Noble GaSGS
HALOGENS J
135
GOiVIPQUiMDS QF Pt;/Asbestos
H2(S) + Br2 (i) 2HBrw
g
.

. high temperature
ACIPS
5.5.1 HALOGEN
Introduction:
^ (ii) iWhen elemental Br2 is reacted with phosphorus or sulphur in aqueous
'solution, then HBr is produced
1
S(S) + 3Br2 + 4H_2Qn
-
S 04
\
'
I
All the:halogens react with hydr ogen to give halog en acid s of gene ral form ula ' Hx 1 .. . , u on
Note: H2SO4 prod
r A J- , > 2 (aq ) + 6
^
HBr
~ uced in above reaction does not oxidize HBr because H2SO4 is dilute
M M

H2 + X2 2HX [ Gommercial preparation of HI:

+ F -> 2HF Hydroiodic acid (HI) is produced directly by the reduction of elemental iodine
H2 2
H2 2+ GI -> 2HGI '
suspension by H2S or hydrazine (N2H4) i
H2 + Br2 2 HBr - . H20
2I2 + N2H4 4HI + N2
H2 + 12 2HI

Salient features about the preparations

ofiha logen acid s: PROPERTIES QF HALOGEN AGIOS j
and fluor ine is very fast and explo sive 1
(i) The reaction of mole cule of hydr ogen 1 Table (5.2) Some Physical Properties of Hydrogen Halides.
'(&
j ilMistfez / . .
Lfo ) '
com bina tion of H with Gl and Br
.
S No Property HF HBr HI
HGI and HBrcan be prep ared by the direc t 2 2 2 at
(ii) 1 1 .

7
.

. , M.P. (°G) ,-83-FI -144.2 | -86.9 | -50.8

highitemperatufer '
Reaction ofil2 with H2 is very slow and it is reve rsibl e. B;P. (°G) 19.5 - 85.0 -66.7 -35.3
(iii)
. (iv) HF andlHGl.can also be obta ined by the reac tions of conc entr ated ,
H 2S 04 on meta l ' (iii). Heat of fusion at M.P. (kJ mol 1) ~
4.58 1.99 2.41 2.87
. fluorides and metal chlorides. .
(iv) Heat of vapo rizati on at B .P, (kJ mol )'1
16.2 17.6
When metal brom ides and meta li iodid es are reac ted with cone . H 2S 04 i then HBr .
(v) ' Heat of formation (kJ moH)
unde rgo parti al (ri ) oxid ation ; to give free Br2 and l2. -270.0 -36.0
t andf llpro
Gommercialpreparation
duce d(
ofHF : ^ ^
^ .
— • | (vi) I Bond energy (kJ moP) 566 431 366 m

prep ared by reac tion of conc entr ated H SO on fluor spar i.e, (vii) H-X Bond length (pm) 128 141 160
|. •
HF is com merc ially 2 4

GaF2. Theirreaction is violent ( fc J even at room temperature

'
(viii) Dissociation into elements at 1000°C (%) | 0 0.014
^ ^
GaF2(s) +:H2S04(Conc.)
- GaS04(S) + 2HF(g) ,
(ix) Dipole moment (Debye) .8 1.1 I 0.8
\
Commercial preparation ofHGI: Physical property of HF:
_
There are two methods:
• ()
i On commercial scale, HGI is prepared by the direct combination of Hi
and Cl2 .
(i)
(ii)
(iii)
Anhydrou sHF is a colourles
HF is a strongly fuming liquid.
s (uf / z

Its boiling point is 19.5°G and freezing point is -83.8°G.

^ ^
- ) volatile liquid ( WUo cX^iXScijJ?).

H2(S) .+.GI2(g) - - 2HGI g) . - (iv) HF is extremely poisonous.

'
(0) - .
When NaGI'istreactediwth' concentratediHiSOi
two steps Atilow 4emperature:NaHS04 is.produced albng with HCI gas
, then iHG IJis
.
} prod
,
uce d in (v) It is highly soluble in water and forms azeotropic mixture containing 36 % of the
acid and boils at 120°G.
' (vi) It is a bad conductor ytfij?) of electricity.
NaGI(s) + H2S04 — > HG!(g) + NaH S 04(s) ‘

cone. (vii) It is strongly - H-bonded and exists (fcCwti) in the form of polymeric structure
, NaHS© in.the secondstep is heated.-WithlNsiGMoiget more HCl - *
4 \ 6HF .= (HF)6
NaHS04(s) + NaGI(aq)
(viii) HF attacks on glass and has found. applications as a non-aqueous solvent.
HGJ[g) + Na2S04(s)
• V'

. Thes e plast ics are mad e up of

' (ix) It is handled (tt- uC) in fluorine cont ainin g plas tics
GommercialpreparationofHBr:
of a polytetrafloroethylene.
(i) H2 andiBr2 reSctiwith each,other afhigh temperature in .the presence
'

catalyst. The catalysfwhich is.used is;platinum asbestos

(x) If HF is absolutely ( > 1 ) ;
* / dry then it is stor ed in copp er or stain less stee l
vessels kept into a vacuum.
,
 llmrAn Easy Approac h Ghohiis in V
'

. " — - - n

C3

,
• •
fChapter 5] The Halogens and the Noble Gases
:
.
Pure liquid HF
viscosity is less
is strongly
than that
H
of
-bonded
H20 due
and
to
is a
absenc
viscous
e of
(Mty
three
liquid
dimens
Anyho
ional not
'
lewor
l
i
S
|(! ^ |
(V) . Boiling points of halogen acids:

,
137

(Jl? j inwater
~
.
_ consist of a equilib rium mixture ol monom ers HF aJ hr *rT
There is no
o rs'
bssssi.:stris
hydrofl tc
uoricj acid s
Gaseous
its hexamer
6HF =^
i (HF ) 6 •
-! due to
* ;
Structure of - HF:
[(Multan 2004 , Faisala bad 2008 , Multan 2009)
-
' Reason for abnormal behaviour of HF in melting and boiling point
The extensive H-bonding present in HF is the main reason . for high melting point
5-
5- 5
,F
.
and bo ng pomt of HF Hr exists in the . '
^ sojd
V "
state The solid HF shows that it is consisted !
y :F 54- '
V
/ 120 H
lC£2 J , CTr HF contains long
I each hydrogen atom is covalently .bonded to one fluorine atom and at the same
chain in which !
time it is H-l
bondedas_well.
(vi) Dipole moment:

pig. (5:2) Hydrogen bonding in HF . -

Dipole moment values of halogen acids decrease from HGI to HI Actually dipole- .
— —
^
induced dipole (* > / i / \Ji Jd <! / » J> JijJCI > ) forces play an important role in the
bonding in HF molecu le. Chain polymer s also exist under , ^
intermolecular binding of heavier HX. ^
There is strong
^ (vii) Heat offormation:
.
pointi;than many,H-bonded.compounds Fig. (5.2)
Standard heat of formation of halogen acids decrease from upper to the downward
direction. The reason is that electronegativity differences between the halogen and I
,
Gradual 'Variation of properties ofhaloge n acids (HF , HGI , HBr , HI) hydrogen go on decreasing.
Thermodynamic properti es ( $ aw ® pur' •
)
(viii) Stabilities ofhalogen acids:
(0 Melting points, boiling points, heat of fusion and heat of vaporiza tion increase! • •
The stability of halogen acid depends upon the difference of electronegativity
regularly from HGI to HI. These above mentioned thermodynamic properties of HF
. between the bonded atoms. HF is considerably stable. It does not dissociate atl
are greater than other- halogen acids.due to H-bonding high temperature. The degree of dissociation increases down the groups. |
(ii) Bond dissociation energies:
Bond dissociation energies decrease down the group. 5.5.2
OXIDES 0F HALOGENS
_ HF < HGI < HBr < HI _ Halogens do not react with oxygen directly. There are some indirect methods to
~

(iii) Reducing.properties: prepare the following oxides. It depends upon the oxidation state of the halogens that which
Halogen acids are reducing agents and the sequence (h ?:/) of the reducing
properties is as follows:
- oxide is to be formed. Table (5.3)
Table (5.3) Oxides of Halogens.
HF < HGI < HBr < HI Fluorine Chlorine Bromine Iodine
It means that HI is best reducing agent, it can reduce sulphur to H2S The . Oxygen difluoride ( OF: |oichlorine monoxide CI2O Bromine monoxide BrjO llodine tetraoxide1:04
[ oxidation numberof SdecreasesTrom zero \o - jf •
,Dioxygen difluoride O2F2 Chlorine dioxide CIO2 Bromine dioxide BrO
* |lodino iodate UO» i

(iv) Acid strength:

2HI + S - l2 + H2S .
[ irioxygen difluoride O3F2 Chlorine hexaoxide Cl20i |Bromine trioxide

Trioxygen Difluoride (O3F2):

Chlorine heptaoxide CI2O7
BrOj jodine pentoxide bOs|

r ' Acid strength goes on increasing down,the group. HF is exceptionally

Weak acid due to extensive ( j? j^);hydrogen:bo'nding. The sequence (
strength is as - follows:
' ^ ^ )
Preparation:
< .t
It is prepared by passing electrical.charge (<= L
_ through a mixture of
F2 and O2
HF < HGI < HBr < HI.
E.C.
2F2 + 302 -> 203F2
 »
Ilmi An Easy Approach Chemistry p rt
138 * :li tChapters] The Halogens and the Nnh!» nasos
139
Properties: liquid but turnslo rerM*!' (i) As an antiseptic.
II
(i) At 363 °
brown (
G
osfj
it
’
is a
ljs
dark
)
red
solid at
viscous
350 °G.
.
(ii)
(iii)
-
For purification (Jti ) of water.
To bleach (tiJiJT,) the cellulose material.
(ii) 0n decompositions (C y).it -
gives oxygen
20
gas
F + 0 Chlorine Heptaoxide (Cl207):
203 2F 2 2 2

(iii) When O 3F2 istrealed with F2, then O2F2 is produced . Method of preparation: \
F It is prepared by the dehydration of anhydrous
F
203 2 2 + F > 3Q 2 2 HCIO4 with P2O5 at~io°e.
2HGIO4 + P2O5 — io °e
_

> ei2O7 + 2HP03

OXIDES OF CHLORINE Properties:
Ghlorine gives fourdifferent types of oxides: (i) .
It is a colourless oily liquid with B P. 82°C. 1
L
— Oxidation number of (ii) 1 It is extremely explosive (i)u nature.i
r

Name Formula i n
chlorine (iii)
1
It slowly reacts with'H © giving HCIO4
(i) :
Dichlorine monoxides Ci20 +1 I *
Cl207_+J 20
1

(ii) I Ghlorine dioxides CI02 +4 ^ > 2HGIO4

•

.
• •••
/

. 111 Ghlorine hexaoxide

«
__ CbOa (CIQa)
'

+6 OXIDES QF BROMINE
(iv Ghlorine heptaoxide GI2O7 +7 Introduction:
Introduction: Bromine is a coloured substance, so the oxides of
bromine are dark volatile
Oxides of chlorine are generally unstable. They are not prepared by the direct ! .
liquids They have low thermal stabilities
combination of chlorine and oxygen! These oxides are extensively (^- ^/) used on Bromine Monoxide (Br20)
.
industrial scale as bleaching agents (<Lu<Liji X) for wood, paper- and.pulp (i>/) etc. Preparation: '
J _
.
_

_ Oxides are also used for water treatment (cit^ Jijl) Let us discuss these oxides (0 pr20 can be prepared by the action of bromine vapours on mercuric oxide,
one’by one. 50°C J
HgO + 2Br2 > HgBr2 + Br20
Ghlorine dioxide (CI02) ( ). It can also be produced by treating the suspension (oWL
Methods of.preparation: " GGh with bromine
'
/
1
ut JP) of HgO in
(i) CI02 can be preparedhy reducing NaCIOs (Na-chlorate) with NaCI, HGI, S02 or CCL
HgO + 2Br2 HgBr2 + Br20
^
GHsOH in strongly (w b).acidic solution
Properties:
. 2CI0J + 2GI + 4H* 2GI02 + Cl2 + 2H20
”

• (i) It is stable substance in the dark in GGU at - 20°G.

(ii) When a concenbaled H2S04 is reacted with KGIO3, 0102 can be produced..ThiSi it has oxidizing properties.
1
•

,
(ii) ' :
' reaction is violent (£c ). In ordertb control it, some oxalic acid is used
*
1 2KCI0i+ H2G204-+ H2SO4 K2SO4 + 2H20:+ 2GOi+ 20102 r
_ _
OXIDES OF IODINE
Properties of GI02: Introduction:
(i) it is dark-yellow. ;!//] pungent (
^ s m e l l i n g gas. ; .
Iodine has three oxides as I2O4 I4O9 and l205. Out of these three oxides only I2O5
is important. I2O4 andI4O9 are salt like compounds. They are considered (tLbf) as iodine-,
(ii) II can be condensed toadark-liquidwith -BiP. 11°C..
iodates. .
,
(iii)

(iv)
By electric spark (w/.
Cl2 and 02. ^
or by warming the gaseous CI02l is decomposed into

Itdissolves in.HiG giving a mixture of HCI andHGIOa. (Fd Abad.2009)

Iodine Pentoxide l2Os
Preparation:
(Rawalpindi 2008, FaiSalabad 2011)

^
(v) . It slowly (i -t Tj decomposes into HGi and HGIO . I2O5 can be prepared by heating iodic acid, HIO3 at 240°C
'
^ 3
(vi) It is paramagnetic in nature. 240°C
2HI03 I2O5 + H20
1/ses bfGlO
^
CI02 is used:
-

iodic acid iodine pentoxide

 llmi An Easy Approach Chemistry n
• .
- 1
. - -‘•H' -
IT
140
Properties: [ Chapter 5] The Halogens and ( ho
(i) It is a while crystalline solidT Noble
(ii) It is stable up to 300°C.
It has a polymeric (#J>rJ.fc
f 5.5 4 . OXYACIDS QF HALOGENS
141
(iii)
It is insoluble in organic solvents.
Introduction:
(iv) All the halogens except fluorine give
(V) When it reacts with H2 O, it gives HIO 3-
2HI03 , (i) HCIO
- the following: oxyacids:
(Sargodha 2007)
- r H 2O + I2 CD5
I Hypochlorous acid
(vi ) It
• is an oxidizing agent and can oxidize HGI, H 2S and GO (ii) HCI02 Chlorous acid
+
5CO 2 5 I O > I2 + 5 G © 2 I (iii) HCIOj
5 to zero
Chloric acid :
1 The oxidation number of iodine decreases from + and that of carhn (iv) HGI04
0001 Perchloric arid :
increases from +2* to +4.
(i) HBrO
1 I 5.5.3 REACTION OF CHLORINE WITH | ,
(ii) HBrGj
Hypobromous acid; 1

GOLD AND HOT MaOH | (iii) HBr04

Bromic acid
Perbrcmic acid
Disproportionation Reaction (i) HIO . Hypoiodous acid
Definition: (Bahawalpur 20C5, Saryuuiid 20GS, Fdisaiafc sd 2008, Multan -2009)1
(ii) HI03 '
A reaction in which an atom, ion or molecule is oxidized and reduced Iodic acid
(iii) HIO4
simultaneously is called disproportionation reaction. Periodic acid
It is a self oxidation-reduction reaction. Certain part of the molecule is ,oxidized and
the other part of same molecule is reduced.
'
• •
. Actually halogens change their
positive oxidation states in all the
oxyacids.
oxidation ,
"number in these oxyacids. They have]
Example:. General Features:
Chlorine reacts with NaOH at 15°C to give us NaCI and' NaCIO. The Cl? is iin zero () The oxyacids of fluorine do not
. . V
r
- • ' * ' '
unstable. :
exist. [HOF has been prepared but
— is highly
^
it
©0 * - L - - -

oxidation states.
*1 -2
give NaCIO .
®
It is reduced to Cl , andgives NaCI.
.
If is oxidizedto +1 oxidation state lo
. : ^ (ii)
(iii)
Above oxyacids are unstable compounds
They cannot be isolated in the pure
form .
.
(iv) They are stable only in aqueous
0 15°C +1 —1 -— 2
+1 +1 .solution or in the form oftheir salts.
2NaOH + Cl2 NaCI + NaCIO + H20 (a) Nomenclature of Oxyacids:
Na-hypochlorite 1
'

Following rules are adopted to name the oxyacids (Bahawalpur 2005)

Sd Gl2 has undergone a disproportionation [ <- & /? ) reaction. When the above I (i)
:
* The oxyacids with one oxygen
atom having the formula HXO is called
reaction is heated up to 7O°C, then NaCI0 is converted to NaCI and NaCI03 ihypoholous acid. The name of the ;
' —
,
salt of acid is a hypo ite salt.
1
* *1 -2 70°C • - *15 (-2)3 - .
I NaCIO = Sodium hypochlorite
3NaCI0 0 2NaGI + NaCI03 - ...... (b) NaBrO = Sodium hypobromite
“

Na-chlorate NalO = Sodium hypoiodite

In this reaction.the chlorine atom:on the left bond side is in +1 oxidation state. It is i

(») The oxyacids with two oxygen atoms

converted info -1 and +5 in NaCI and NaCI03, respectively This is again a
disporportionation reaction. These reactions can be written as
. lare named as halous acids. The
name
having the general formula HX02
of the salt of the acid ends in
follows:
'• 2Na0H + CI2 — —
> NaCl.+ NaCIO + H20
'

x3 ... (a)
1
ite. '
NaQIOa = Sodium chlorite
tr
3NaCIO
-
2NaGI + NaCIOj (b) , . (iii) [ The oxyacids with three oxygen atoms having the formula HX are
03 !
palled haloic acids. The name of the salt of
Overall Reaction: this acid ends in ate.
NaCIGs = Sodium chlorate
6NaOH + 3CI2 si _ (iv) The oxyacids having four oxygen atoms having the
V
5NaGI + NaCI03 + 3H20 formula HXO4 are
palled perhaloic acids. Jhe name of the salt of
Na-chlorate this acid end in _
per _ ate salt.
NaCI04 = Sodium perchlorate
 Approach Cfte /nfetruo ,
llmi An Easy ^ '
{ Chapter 5] The Halogens and tho WnM^rr.
;
i , the
^
'
fornu
X
3 . 142
',following Table (5.4) shows the oxidation
. with
stale
the
,
of the
names
halogens
of the salt of oxyacids i ° Number of oxygen atoms and thermal stability!
,°
^^
The oxyacids along f oxyacids of ha 3en grater
oxyacids and the names of
OxyacidsofHalogens . is the thermal stability. Actually hen . ° '
he y9 aoms lncrease then the oxidation
oxvqen
various
Table (5:4) 0
Name of
Name of number of halogens increase . '
Formulas of oxyacjdg Oxyacids
Salts of
Increase of oxidation number of halogen and oxidizing strength:
Oxidation
,
'
j . Iodine . oxyacids i
states of | Bromine When the oxidation numbers of halogen atoms increases and the number of
Chlorine
IjHalogens . ~
v HBr HIO Hypo^us Hypo-ite oxygen atoms increase, then oxidizing properties of_ acids_decrease . . i
'

+1. — ous — rite

lOxidation number of - halogen and acid strength . 1

— . ;
^
HGIOz . ic — ale
r
r* .
- : rt
7 \
+3
+5 HGI03 HBrOa HI03
HlQi, HlQs Per > ~~ c per— ate ; «“ S
The£ j
Generally,
numb
*
HXO4 > HX03 > HX02 > HXG
HG1Q 4
i
'- TO
A vs-
;-.
+7 .

structure of the oxyacids are as follows:

L
So
'
HGIO > HCIGj > HCIG2 > HGIO
*
HBr04 > HBr03 > HBrO
,
••
.
-
:0‘
A ' ^
HI04 HI03 > HIO
_ _ _ J
Reason:
»

s
F'
/ (i) H o
••
•
Cl
•
.
*
V

*
( in) H — 0
Chloric acid
ei
;
» O
[
Greater the number of oxygen atoms, greater the electron withdrawing effect.
Greater the polarity of -OH bond and greater its ionizing power
'
m •
HypocHlorous acid :0: ®
i • Hr '
I
t••
H^ - Os - GI — > 0
"

H* + 0 — Gl 0

I r ‘
— Glv o Hs* - Gs - Cl -> G
"
H* + 0° —
— Gl -> • 0

I
M

-
r

M
••
© Cl (iv) H 0 ••
-0
4 4
‘ 7,
r
(ii)
Chlorous . acid *
Perchloric
O:
acid
Comparison of acid strengths of oxyacids of different halogens
0

All acids of chlorine are more acidic than the corresponding (J.>£) acids of
' \\ 1 a ’i
of Oxyacids : bromine, which are stronger than the corresponding acids of iodine
1
"
Salient Features
is the central atom in all the oxyacids . So HCIG4 > HBrG4 > HIG4
r ! . (i) It is -
cleantiiat halogen
, connected with oxygen atoms . HCIG3 > HBrG3 > HIG3 I
: directly
1

(ii) Halogens are 3n is attached with the

dissociation HCIG > HBrO > JM
'

*i
which is to be removed during its
The hydrogen‘
' > It oxygen,
: Reason:
4: -. 11 i
31'

(iv ) Some
.. .
of the bonds areco -ordinate
' covalent ;
bond .
others are covalent, 1

The electronegativity of halogens decrease from CI2 to I2. Their sizes increase
. .-
This decreases the polarity of 0 - H bond So HClO is stronger than. HBrO than HIO.,
.
_l» u
as acids by ionizing the oxygen hydrogen :
(V ) Theyall
'
act •
Similarly HGIO3 is stronger than HBrQ3 thanH103. |
1u ' l Nature:dfith
'
ebohds : .
•

; ;
(i) The halogen oxygembonds are polar .
polarity of the bond PERCHLORIC ACIDS (HCIO4)
electronegativity of the halogen lesser the
Vi (ii), .Greater the ,
between halogen and oxygen. '

and
Introduction:
1 \
electronegativity of halogen
’
greater the polarity of 0H group It is moststable oxyacid of chlorine.
L V (iii
) Greater the Preparation:
4 . greaterthe .strength of:the acids . . mm
the mixture of KCIO41
. Effect of,increase of oxidation number on the properties of oxyacids:,
Pure anhydrous HGI04 can be prepared by distilling
.

change o f # |3nd concentrated H2SQ4 under r e d u c e d p r e s s u r e

Oxidation number ohhalogen increasesTrom + 1 to +7. Due to the
I
> KHSO4 + HGI04
•

are observed : • KGIO4 + H2SO4 •

oxidation numberthe following changes cone. perchloric acid

the thermal stability . *

It is prepared at a pressure of 1 0 - 2 0 torr. G under a

in
.^ 40 - 60
i
1 (i) Increase ’ '
( • But it is distilled at °
J V
(ii) Decrease in oxidizing : power (djU J '
T );
Pressureof 60 torr.
, ( )
iii Increase in acid strength ;

rp L
iv
.
 /.

* UmiAn &syA pP2? Cjiem str

ch .^ nd jhc }o jQ Q
MS
r 144
Physica l pr op er tie s:
ic ac id is a co lou rle ss mo bil e ( Ub J-^if ) liq uid . '
' hapterjjf-

^ ^:
GKemical reaction ^^^ ^ ^
9 f ' ~~ ^
^ ===l
SQs 145

(i) Anhy dro us pe rch lor an oily loo k. Ca(OH)2 + 0I2 CaGI(QGI) + H2Q
A /J ) in .nature an d ha s '
(. «) IFis - h yd ros co pic (Ub i - ^ at 1i12°G
jf :
. Slaked lime Bleaching powder
(iii) AtnormaT pr es su re; [ Ffr ee zes - Description of the process:
de co mp os itio n at 90 ° G .
-^^
i It boils with
(iv)
mo ist air an d dis so lve s in wa ter wit h his sin g The plant is consisted of four horizontal cylinders. These are made up of cast iron
It gives fum es str on gly in the
(v) r tat in sh afl ( /) . which is - fitted with blades. Slaked
, ° 9 '
53
sound. .
(Vi ) Itfo rm s hy dra tes .
.
lime Ca (0 H )2 s ed int o the se cyl ind ers thr ou
.
gh ho op er It is pus
•
hed fro m on e - end of the
' i

^
wo un ds . ; ) on the sk in the oth er wit h the he lp of the bla de s I
dan ger ous ac id an d ca us es se ve re • cylinder to
(vii) It is highly
Chemical properties: ! . ? !° . t
h rin® ,9as, is
.°
dUCed from near the bollom - Chlorine travels in opposite
, . to the slaked lime During this travelling, chlorine is completely absorbed.
direction
‘ ' •

(i) HC 4 IO is an oxi diz ing ag en t:

. .
The chlonn® rea e® t0 l P of cylinder The bleaching powder is collected in al

(ii)
(a)
(b)
Th e dis
In the co ld
When it is hot an
sol vin g po we
-s

r
tat

of
e the

HC
d co
I04
dilu
nc
is
te
en
hig
HC
tra
he
IO
ted
st
4
,
is
the
du e
ve
n
to
wit
ry
it

h
'
its
we
is po

ex
ox
ak
we
ox

idiz
plo
idiz
rfu
ing
sio n
l
ing
ox
pro
(kV
idi

’
age

pe
zin

) .
g
rty
Fo
nt

.
age

r
nt

thi s
.
i
(ii)
. ..
Beckmann's method:
^ °
barrel through an outlet in the lowest cylinder.
,

(Gujranwala 2004, Gujranwala 2005, Fed. 2013)

This is the modern method for the preparation of bleaching powder.
When pure HG 4 IO is he ate d it dec om pos es j
rea son
(iii) .
co nc en tra tio n les s tha n 67 % - inH 20 Raw material:
HGIO4 is stored and used in
IfreactsA vit h org an ic sub sta nce s vio len tly (i) Slaked lime
.i ftv) ^ (ii)
Uses: Chlorine
Due to its oxidizing effect , its ac id str en gth an d so lub ility of its sa lts, it is Chemical reaction:
I. considered (tbitf) as av alu ab le an aly tica l rea ge nt ( '
< / /6 -6 ) - ^ ^ Ca(QH) 2 + Cl2 CaCI(OCI) + H20

| 5.5.5 BLEACHING POWDER ] | Description ofthe process:

iron tower. This tower is fitted

^
Beckmann's plant is consisted of a vertical (1
[GaGI(QGI)] 1 _/
with 8-shelves at different - heights. Each shelf is equipped (< j i ) with rotating rakes ( L) as
-
(Gu jra nw ala ' 20 04, Fa isa lab ad 20 05, La ho re -2 00 9) •
showminthe following diagram. ^
Introduction: Slaked lime with
, xtu re of ca lciu m - sa lts of compressed air
Bleaching powder is not a single co mp ou nd bu t - it is a mi
|yt Hopper
HGI and:HGIO. ' Chlorinating
T lower
Formula ofibleachingipowder: Waste
Itdsiwrittennn two ways: '
gases
(i) GaG.I(0GI) - . V . •

Rake
(ii) Ga0CI2
^
:

(Manufacture ofibleachingipowder: •
.
This shows that bleaehing powder is calcium chloride hypochlorite.
Chlorine
Bleaching powder can be manufactured by the action of chlorine on dry sl a ke d t Hot air
.
lime:(t£uuf) There are two well-known methods in this respect:
Bleaching
(i) Hasenclever's method (old method) '

powder
(ii) Beckmann's method (modern method)
LeFus disGuss these two methods one by one. Fig. (5.3) Beckmann’s method.
'

(i) Hasencjever’smethod: 20 05 ) . It is int rod uc ed thr ou gh . the ho op er at

(ShprtiquestioniL ah ore Slaked lime is taken in the form of powder
(D-G- Khan - 20.0'4, - Faisalabad 2005, Multan 2006, Fd Abad 2009, Guj 2014 . an d ch lor ine is int rod uc ed !
the top with compressed air ( ix \ SA mix tur e of ho t air
the rot ati ng rak es . In the
Rawmaterial: m -
fro the bottom of the - tow er. Th e sla ke lim e is pu sh ed do wn by .
IT
(i) Slaked lime (ii) Chlorine
 146
Ilmi An Easy Approach Chemist* „ .
. Slaked lime and chlorine react together and 5] The Halogens and the Noble Gases
meantime , chlorine rises up frhnoter
bleaching powder. This is collected in a barrel placed at the base . Explanation:
This apparatus also - w orks on the countercur rent principle . A little loss of chlo
'
Actually the activity [ Syfjtf ) of bleaching powder is measured ' in term of available
happens and there happens maximum reaction in slaked lime and chlorine . fine
chlorine. The average percentage of chlorine in the bleaching powder is 35 - 40 %. The
Packing.of bleaching powder: bleaching action of the bleaching powder is due to this available chlorine. The reason is
Bleaching powder should!be always;packedurn air tight container in order to a
void that chlorine is an oxidizing agent.
.... of. chlorine.
. . . loss
the The theoretical percentage of available chlorine is = 49.
Anyhow, the actual percentage of available chlorine in the commercial sample of
-

Physical properties:
bleaching powder is lower than this. The reason for the low percentage is as follows:
(i) It is a yellowish white powder: (i) Chlorine is lost, when the bleaching powder is exposed to air.
(ii) . Ithas a strong smell of chlorine. (ii) The reaction between the slaked lime and chlorine is incomplete.
Ghemical.properties: (Rawalpindi 2007) (iii) Impurities are present in slaked lime.
(i) Oxidizing agents: (iv) Oxidation of halogen acids:
Bleaching powder is a very good oxidizing agent. This is due to the presence of
- Bleaching powder can oxidize HCI, HBr and HI giving us the corresponding
V ) OCI ion. This ion is generated when bleaching powder is dissolved in water
0 halogen:
Caei(OCI) + 2HCI - CaCI2 + H20 + Cl2
H2O
GaGI(OGI) Ca + Cf + oer
+ 2 ’
(v) Reaction with ammonia:
QCI gives oxygen which is a strong oxidizing agent.
° . . .
(Guj 2005, Guj 2008, B:P. 2008, D.G K 2009, Sarg 2011, F. Abad 2014)
-
(ii) Solubility imH20: When bleaching powder is heated with NH3, then N2 gas is liberated
3GaGI(OCI) + 2NH 4QH
yi
-
Bleaching :powder is soluble in H20. But a clear solution is never obtained. This is
• 3CaCI(OGI) + 2NH3
3CaCI2 + 5H20 + N2
3CaCI2 + 3H20 + N2
due to the presence of impurities (u? fr) ,of lime in it.
' Uses of bleaching powder: (Short question AJK 2005) (Gujranwala 2004)
(iii) Reaction with acid: (Gujranwala 2005) Bleaching powder is used:
The reactions of bleaching powder with acids is of two types;
(i) For the laboratory preparation of Cl2 and 02.
(a)
^ eavdilu te - acid 1in!smalltquan
tity: When ibleaching i powder is;reacted (ii) For the manufacture of GHGI3 on industrial scale (yi £Tj). _
\ with diluta acid in small’(quantity; then , nascent oxygen iis- produced which is very strong
1

oxidizing agent.
1

(Guj. 2008, Fd. Abad 2009, D;G:K 2009, F. Abad 2014)

(iii) Used as disinfectant
" "
^
\7. ) and the sterilization (£-/
’
.
is ) of
HiO. . . - •
2CaGI(GCI) + dil. H2SG4 . GaSG4 + 0aGI2 + 2HGIO . (iv) For - making unshrinkable wool.
'

2HGIG — , > - 2HGI + 20 I (v) For bleaching cotton, linen, paper, pulp and wool pulp. Anyhow, delicate
v (b) With excess of dilute acids: (Bahawalpur 2008, f

' Fd. Abad 2009, Sargodha 2011) (Jjt ) articles like wool and silk cannot be bleached with it because these
:? When bleaching powder reacts with, excess of
dilute , gas is are damaged (t U* ) with chlorine.
evolved acids then chlorine ^ ’
(vi) As an oxidizing agent in industry.
GaCI(GGI) + 2HGI CaGI2 + H20 + GI2 (vii) For the removal of poisonous gases from the atmosphere during,war time.
CaGI(QCI) + H2SG4 - GaS04 + H20 + Gl12
(excess) 5.6 GOWliViERGIAL USES OF HALOGENS
Available Chlorine AND THEIR GOIVIPOUNDS
Definition: (FEDERAL 2008)
Bleaches, refrigerants and aerosols:
(Guj Boad 2004, Faisalabad 2004 , D.G. Khan 2004, Multan -2005, B.Pur 2009)
^ reaCti0n of bleaChin9
dreori]
One of the important uses of fluorine is the preparation of chiorofiuoro carbons.
Ghlorofluorocarbons obtained from *GGh are called freons. This is a mixture of GGI 2 2 and
^
GGIF3. '
 i> . 4
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llmi An Easy Approach .Chemist I —
7^ ^

148^ r£ rt:tl
,

^
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Properties offreon:
hyd roca rbo ns bec aus e they are - che mic ally
fr.hapter 5] The Halogens and the Noble Gases
149
(i) Freo n diffe rs from very \inert (v) H2F2 is used for etching glass (tlS l
n from iron causting.
- ^ ^^
P) and for the removal of Si02,

m (ii) They, are nomtoxic

(. iii) ’ They are non-inflammable . Uses of chlorine:
Chlorine is used:
Uses of freons: (i) ^ In the manufacture of bleaching powder which is a bleaching agent
(i) Freons are used: * • (Uu^LtfisX) and e x t e n s i v e l y u s e d in paper and textile industry.
(a) as solvents ’
• (ii) As disinfectant in swimming pools and water- treatment plants.
(b) as lubricants . . (iii) For the manufacture of:
(c) as insulators. (a) antiseptics
(ii) In refregeration and air-conditions in place of NH3 and SO2 . •
(b) insecticides
(iii) -
As a solvent forDDT and some other insecticides. (c)
(d)
'
weedkillers
herbicides *.
' I
I Teflon I
(D.G. Khan 2004, B. Pur 2009)
(iv)
(v)
-
For preparation of HGI, which is cheapest industrial acid
For the preparation of PVG.
.
(vi) For the preparation of chemicals like GHCI3 and GGI4.
.
^
1 Tetrafluoroethene G2F4, can be polymerized to give poiytetrafiuoroethene
(C2F4),,. This poiymenis called Teflon
(vii).
(viii)
In the extraction of gold and platinum. .
In the manufacture of poisons, like mustard gas and.phosgene .
V Properties of teflon: 1
Uses of bromine:
• *
iri
(Federal 2008)
(i) It is plastic-like inert material. Bromine is used:
•

(ii). IMs not soluble in any solvent. (i) For the preparation of ethylenedibromide (G2H4Br2). The chemical is
(iii) It is not attacked by strong acids, alkalies and oxidizing agents. .
added to leaded gasoline Leaded gasoline is dangerous for the engines
Uses of teflon: because PbQ andPbS04 is deposited in the engine.
(i) Itiisrused1|n> the •construction ofchemical plants because it is not affected by add, As germicide (t/ f 17.) and fungicide fj ®).
"
(ii)
alkali and oxidizing agent.
(iii) As AgBr in photography .
(ii) It has high:electrical resistance [ 1/
. material in cables . ^ , .
J $$ ) and is used as an!insulating (iv) As an oxidizing agent.
(v) In the manufacture of dyes, tear-gas r ?T), photographic films,
Halotfiarie plastics and paper.
Its formula is (vi) As an important laboratory reagent.
.
Uses of iodine :
Cl -
Iodine is used:
CF3 - GH -Br (i) in pharmaceutical (<Lfcsijl?i«) industries.
Halothane (ii) As a disinfectant and germicide.
lt:is;used:as;an anaesthetic (iii) For the preparation of tincture of iodine, it is a solution ofriodine in ethyl
Uses ofifluofine: alcohol and H2O containing Kl.
(iv) " As an analgesics (WJ IJ). .
(0;
(ii) -
Inithe preparation ofifreoh.
In the.preparation of teflon.
'

(v)
(vi)
^
* Forthe preparation ofiodoform .
"

In the form of Nal it is added to the table salt for supplying the body
(iii), As an insecticide
’

(iv) .
needs of I2 Diet insufficient of iodide ion (f) leads to an enlargement
(fc*£) of the thyroid (« ) (Goiter) .
(vii) *
Ih'the manufacture of dyes. ,
(viii) For the preparation of photosensitive ( t / i^ paper films and
plates.
 Ilmi An Easy Approach Chemtety
150
"

| 5,7 GROUP VHI, NOBLE GASES

~^
| ^ rChapter 5] The Halogens and the Noble Gases

Neoo.(Ne):
Neon is also obtained from the liquefaction of the ail It is 1/65000th
5.-7.1 INTRODUCTION I atmosphere.
Argon (Ar):
part of the

(Rawalpindi 2005, Faisalabad 2006, Multar Argon was discovered by Ramsay. It was oblainedas a by-product
> 2007) from the
The elements like helium (He ), neon (Ne ) , argon (Ar ), krypton ( Kr), xeon (Xe) and liquefaction of the air.
which are placed in zero group of the Periodic Table are called noble gase. Krypton (Kr):
radon (Rn)
They are also known as rare gases or inert gases . Actually, they are - chemically inert and Kr is also present in air to the extent of one ppm.
are present in a very small quantities in our atmosphere . Xenon (Xe):
Electronic configuration of the noble gases: (Lahore 2004 It is obtained as by-produc! rrom the liquefactionand separation of air
)
. components. It is present in atmosphere to a very small extent /.e.).08 ppm.
Table (5.5) Electronic Configuration of Noble Gases
Radon (Rn):
Atomic Rn is present to a very small extent in the air and it c; be obtained as a by
. .
S No Elements
number
Electronic configuration
product from the liquefaction of air.
-
Rn is a a-decay product of Ra. Small quantities of this g an be collected from
L .(0 J l He 2 1s
radioactive decay of radium isotopes ^
(ii) Ne 10 :1s2 2s 2px 2py 2pz 'pxn pyu pzn
•

-7 Ra226 —> Rn 222 + He4

(i i) Ar ii Is 2s3 2p 3s 3
2 6 1t 3 3 ,
'
|i i:. ( jv). .. Kr Physical properties of noble gases:
' ^ ^
Is 2s2 2ps 3s2 3ps 4s23d104px 14py 4pz
' '
' 36 2
Table (5.6): Some Physical Properties of Noble G;s.
Xe I. 54 Its22s22p63s23ps 4s23dt 04ps 5s 4d bpx Lspy 1’ 5pz:; :
^ '
'
(v) 2
|;
(vi)'
Rn 86
, ’°
1s2 2s2 2p6 3s2 3p6 4s2 3d 04p6:5s24d10 5p6 6s24fH 5d13
S. No.
i,
Property
. ..
. At Wt .(a m u)
'
|
He
4 I
Ne
29.18 39.95
Ar | Krf-
83.f
"

Xe
131.3 :1 222
Rn

! 11 11
Spx Gpy 6pz 1[
M (ii). ; Atomic radii (pm) :3i m : : 98 : 112 131
,
140
-
Except!He, allithe noble gases have eight.electrons in) the outermost - shells. Their
octet is complete. That is why, they have little tendency to do the chemical reactions
(iii) J.lonization.ehergy.kJ mor1
; (iv)
,

: mm
! 2 3 7 2- ; ! 2081 1521 ! ,
,

: ~272 ; : -r249 : : ^189 : ;

t 1351 117Q : 1037
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. ; (v) ; B P: (°cy : j ; -269 ; -246 ; -m:

^15? -n? £751
Occurrence oLNobleGases ^153 -m . ^61
Air as one of the sources ofthe noble gases:
'
'
7 .(vi). . Density (gdrrT?),
'
. t 0;i?8 ; ; 0.90 : u s ; :
, 3:75 5:90 9:73
'
Water solubility (ml/dni ) af
'

Noble ga$es> occur as minor constituents ’

of - our atmosphere. They' are ‘
.
(vii)
, 2Q°£
, J .
^ '
13:8 14.7 37-9 73.00
•
approximatelyi
^ jione percent.
NobIe;gases )are isolated
(i) Fractional distillation 6
* .
from the air by using:
> Z ).
(viii) Heat of vaporization
. ..(kJ.moH).
Physical Properties of Noble Gases:
0.08 1.77

(Multan 2004, Rolpindi 2005)

6.5 9.7 i3}7 i 18.0

. Oi)
'
Chemical methods (i) Golourand odour:
Helium (He): All the.gases are colourless and odourless.

- _
In 1868, Helium was detected in chromosphere of sun
-&bdb>vj£ 2 (Zl r- / £- b>
* (ii) Reactivity:
^. ^ ^ ^
^itil># UiPkV ), During;:thetotalsolareclipse (oA/ )dt
was namedihelium, whichw/as derived:- from' Greek word ,Heilosf .which
'

hydrogen it is fhe.second most abundantelement in the

^
means sun. After (iii)
They are chemically inert.
Application of high voltage:
universe. When these gases are subjected to high voltage, they give different cpurs in the
The helium ,
> whichiis presentiin:the
.
- earthiis due to > emission (t
^ of the .
•
„ spectra
. radioactivesubstances.lii/ v ) they/are .
isolation of’He: ^^ doubleionizedheliumions
~ (a) Ne glows reddish
voltage and current.
(JW/ ' ) and its discharge is most intense t ordinary

4
by liquefaction (# l);method.- ” ' ' -
Itlisisimplejanct feponorhical f(.*A ' ) to isolate the He.gas from some neutral gase£
(iv)
(b) Kr has brilliant
Availability;
green ( iy;& r ) and orange (J A) spectral lines.

Xe is available commercially in cylinders at high pressures .

 , '
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*
f

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. .-
•
/> llmi An Easy Approach Chemistr ».
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Sr
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££
* 152
(v) Melting points and boiling points :
T'
[ Chapter 5] Tho Halogens and the Nobln
Gases
153
Ud ;
-
Aif
-

Their M .P . and B.P . go on increas ing from upper to the down ward directi0
1 r . 5.7.3 -. _
Jj ) and increas ing Lond on f - FLUORIDES OF XENON I

increas ing polariz abilitie s ( U < 2 k disn

is is
* ^
^.
ireason ~ '
tees. J .
v

(vi) Ionization energies: Xenon Difluoride (XeF2):

(Lahore 2004, Rwp 2014)
ft. - .

Their ionization energie s decrea se down the

' group . This is due to jncr
as fl9 J preparation:
i number of shells and increasing shielding effect. ' Ther|e are three different ways to prepare XeF :
2
fcy, f
(vii) Solubility in water: (1) A mixture of Xe and F2 gas is exposed t
«
A .
They are least soluble in water Xe is slightly soluble in water, to the extract
( /fettuiUS) to light. The light is IPT
•v-

/
A >\ mL dm-3 at 20 C. Anyhow, the solubilities increase down the group. This is due i
°
reason that big sized atoms are more readily polarized by the water molecule.
0110
0
, i
obtained from high pressure Hg arc:
Xe + F2
-
Light from a Hg-arc
I
:
wr
“

-> XeF2
(viii ) Heat of vaporization: Xenon difluoride
i
(2) Mixtur i
They are all gases at ordinary temperature and pressure and so their ho i . e of Xe and F2 is taken in the ratio of 1
: 3 in a Ni tube at 400°GJ
vaporization increase ' down the,group. This is due to the increasing sizes and inrteasing
"
f
!° '
XeF2 is produced in the form of vapours. It is
obtain ed as colour less solid1
. i

y
polarizabilities. * (
'
on cooling •

•
'
»
— 5.7.2 COMPOUNDS OF XENON
J
Xe + F2 -
Ni tubes
400°C ‘> XeF2
•
ip
Introduction: r ~
1:3 Xenon difluoride
T.
'
>
t
(Sargodha'2009)
•

IF Noble gases are sufficiently (Jr ^ cA) inert. Anyhow, the first compound Xe| Caution:
* i >
was discovered by Berthlot in 1962. That was XePtFe. ^ The product so obtained should be removed
immediately from reaction vessel .
This is done to stop the reaction of F2 with XeF2, so that it may.not
v
u Anyhow/ some fluorides of Xe are very popular Jy ) Xe shows different] . be converted to XeF4.
1 oxidation states These oxidation states vary from +2 to +8. These^compounds - are stable
. Actually XeF2 is condensed
.
J& ) at -50°G The reaction completes in ,
eight hours.
T
-
and ean be obtained by large quantities Some important compounds of Xe are given .
in thel I
i following Table {5.7), along with the physical states and melting ,points. Physical properties of XeF2;
i (i)
1
It is a white crystalline solid at room temperature.
'
1
Table (5.1) Compounds,1 ofrXenon ViX . (ii) Its melting point is 140°G.
1
m
Physical States .. 1
. Melting Pointi(°C) (iii)
(iv)
It can be sublimed (tu &W ) .. 1

in XeF2
~x It is sufficiently stable and can be stored for indefinite period in Ni ,
m containers. * *

I
.
I (iii),
WE Chemical Proportions of XeF2:
(i)
*

l r
r--r
. Colourless crystalline 1 90 It has fluorinating properties, when it is reacted with G2H6, C H NO,
3 8/ N 02 andi
(>y)
1
m
U. Colourless crystallinem SB
• •
(ii)
S03 then substances are fluorinated and Xe gas is set free.
l

It remains unchanged in H20 or in acidic solution. Anyhow, if it is allowed to

1
i

A WE wnr* standi
fora long time then hydrolysis occurs slowly. 1
(vi) ;
.Colourless crystallineI 25 (explodes) •;
(vii] XENON TETRAFLUORIDE (XeF4) k

Xe©4 +8 - 39.9 (explodes Preparation:

Let us discuss them one by. one;
i Colourless gas
on warming) (Rwp 2014) .
It' is prepared by heating a mixture of Xe and F2. The ratio of the gases maintained!
.
is 1:5 Container is underthe pressure of six- atmospheres fora few hours.
The temperature1
is maintained at 400 G Finally, the reaction is quenched ( bji ?) by cooling the
.
° / nickel
» *
vessel rapidly * in cold water .
* •
 ' IImi An Easy Approach Chemistry p
154 mi 5] Tho Halogons and tho Noblo
[Chapter Gaso
Ni vessel s
Xe + 2F2 XeF4 XeF4 + 2Hg
400°e, 6-alm. > Xe + 2HgF2
•

(iii) Reaction with liquid NH3:

The excess 2 :F is rem ove d by pum ping at 78°C.I
XeF4 and XeFe react with NH3 very violently
Physical properties of XeF4:
(i) XeF 4 is a whit e crys tallin e solid at room tem pera ture. 3 XeF4 + 4 NH: > 3Xe + 12HF + 2N2
(ii) Its m.p. is 114°e. J XeFo + 8NH3 > Xe + 6NH4F + N2
•

(iii) It can be sublimed very easily. (iv) Hydrolysis:

(iv) It is less volatile than XeF6. All the xenon fluorides reacts with H2O as follows:!
Hydrolysis reaction:
It reacts with H2O to give XeOj, which is highly explosive solid compound.1
2XeF2 + 2H20
2XeF4 + 3H20
- > 2 Xe + 4 HF + 02 1

> Xe + Xe03 + 6HF + F2

•

XeF6 + 3H2O > XeOj + 6HF

XENON HEXAFLUORIDE ( XeFG)
Method of preparation: 5.7.4 XENON OXYFLUORIDE J
This compound is not prepared so easily as compared to XeF2 and XeF4 . Preparation:
It can be prepared by heating the mixture of Xe and F2 in the ratio of 3 : 20 in a When X 0F5 is heated with silica at S0°C, the yellow colour of
nickel vessel. The temperature is maintained (tu ljjf ) below 300°C and pressure is 50 XeFs disappears
and XeOF4 is produced
atmospheres . 2XeFG + Si02 > 2XeOF4 + SiF4
Nickel container Physical properties:

Xe + 3F2
200°C
XeF6
(i) .
It is a colourless substance
_
50-atm |(ii) It is a mobile (iJbi u <) liquid.
3 : 20 , (iii) ^
It can be stored in nickel container.
(95 %)
The yield of this reaction is 95 %. Chemical properties:
Physical properties of XeFe: |(i) When reacted with H20 it undergoes hydrolysis and gives the explosive
XeCb.
(i) XeFs is white solid. iii) It reacts with H2 at 300°C to formXe gas
(ii) Its melting point is 48°C. 300°C
XeOF4 + 3H2 > Xe + H20 + 4HF
(iii) .
After melting it gives yellow liquid Preparation of XeOF2:
•

(iv) It can be sublimed at room temperature. XeOF2 is obtained when Xe reacts v/ith oxygen difluoride in an electric discharge:
(v) It can be stored in nickel container for indefinite period. It should Xe + F20 •> XeOF2
not be stored in glass container because it reads with silica.
Chemical properties of xenon fluorides: 5.7.5 OXIDES OF XENON
(i) Reaction with H2: There are tv/o oxides of Xe:
All the xenon fluorides are oxidizing substances, and so they can react v/ith (i) Xenon trioxide XeOa
give HF.and Xe is.set free. (ii) Xenon tetraoxide XeOj
'
XeF2 + H2' Xenon trioxide (XeOj):
-> Xe + 2HF Preparation:
\
XeF< 2Hz
XeFg + 3H2
Xe + 4HF XeOa is obtained when XeFs is hydrolyzed slowly
Xe + 6HF XeFs + 3H20 > XeOa + 6HF
•

| ln all three reactions xenon fluorides are reduced to 'Xe' gas. Physical properties:
Reaction with Hg: (i) It is a crystalline solid.
Xenon fluoride resets v/ith Hg to give the mercury fluoride and gas is set fre5
Xe (i>) iltjs a non-volatile substance.1

-n
 v;
v - — - -r-
.

— - -
— -
^
'
-a -tf-

156
It is soluble in H2O.
Ilmi An Easy Approach Chemistr\rpart.n
[Chapter 5] The Halogens and tho Noble
Gasos
^ 5? l
(iii)
(iv) It is weakly
electricity.
acidic and its aqueous solution is almost non -conductor of
(iii)
metals
0
' pr0duC
^^^ Phere in welding and metallurgy of certain '

(v)
(Vi)
It explodes violently
It also explodes violently by
\t nwhen
heating , rubbing ( W
dry
J )
.
or .
pressing
.
(iv)
M
For the filling of fluorcent tubes and
^
obtained ^9
°
radio valves,
'
,
ne n signs the i9ht - of varying colour can be I*

Xenon tetraoxide (Xe © 4): (Lahore 2005) Uses of krypton

Krypton is used:
Methods ofipreparations: .
(i) To fill fluorscent (dua ) tubes.
The compounds
with concentrated H2SQ4 .
can

Ba2XeGe + 2H2SO4
be prepared by the addition of barium

Xe04 + 2BaS04 + 2H20

or sodium perxenate
(ii)
(iii)
^
In flash lamps for high speed photography.
Kr85 is used for me measurement of the thickness
(0 tv) of the sheets of .
the metal and plants, n
Barium perxenate
Na4 Xe06 + 2H2SO4 > Xe ©4 + 2Na2S©4 + 2H2© Uses of xenon .
Sodiumperxenate Xenon is used:
(i) In bactericidal ( tffw
) lamp, e
5.7.6 APPLICATIONS OF NOBLE GASES (ii) I ^mic energy field in bubble chamber. In bubble chamber
liquid Xe is
Uses of' Helium ‘ > ed for the detection of gamma photons and
,
- neutral mesons.
. . . Khan 2004, Rwp. 2005, Multan 2005, AJK 2005, Rwp. 2006, F. Abad 2007)
(F 'Abad 2004, D G Uses of radon ii
Helium is used: Radon is used:
(i) In the treatment of asthma (I// ^J) by mixing with oxygen.
LT (i) In radiotherapy 0f cancer.
(ii) _
For filling weather balloons (<^ ^L> c/ r ) and airships.
' (ii) For earthquake predications i
*
For- producing low. temperalure in research work . (iii) For the preparation of ointment ' [ / ) for the treatment of cancer and r
(iii) f
'
:
Of! j In the preservation (t/iv ) of food.
* other diseases. tl
T I F (iv) * (i») For photographing the interior of opaque materials.
(v) For producing inert atmosphere in welding and certain metallurgical
L
operations (u iifsskl0u£l? jj;
•
:_ , EXERCISE :
•* (
I
(vi) As a shielding gas for arc welding
1 r

1 (vii) In measuring low temperature in gas thermometry. Q.1 Fill in the blanks:
I (viiij Used in signal light. Arisv
(ix) Used in atomic reactors. This is due to the reason That helium has high
j (i) fluorine (ii) reducing (iii) HF .

. ^ -
thermal conductivity r'l/^ my’), low viscosity. and inert nature. (iv) iodine (v) F2
'
(vi) Ga(QH)2, Cl2
'

. Uses ofeneon (vii) F2 (viii) CaCI(OCI) (ix) He, © 2

Neon is used: (Rwp. 2010) M Kr
(i) In making neon advertising signs. Actually neon lights are visible from Q.2 Indicate true or false:
long distances and even- visible in fog { / ) and mist ( i). Ans:
(ii) ^
In high voltage indicator and T.V. tubes, in voltage stabilizers and current (i) True (ii) False (iii) True (iv) False
rectifiers. £ (v) True (vii) True (viii) True
(vi) False
\
N
(iii) In making glass lasers . (ix) True - (x) False
m *4
j, Uses of argon
.

Argonis used:.
Q.3
Ans
Multiple choice questions. Encircle the correct answer:
(i) For filling the electrical bulbs to increase the life of
filament It is mixed
with 15 % Ni- . I
(H) Used in Geiger counters, which are employedio
detect the radioactivity .