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Cl Colourless
Br Reddish brown
I Purple

+!!   ^   ^  ", 


*   
Ô
      
Proton number (Z) 17 35 53
Valence electron configuration 3s2 3p5 4s2 4p5 5s2 5p5

Relative atomic mass 35.5 79.9 127.0


State at room temperature Gas Liquid Solid
Colour Greenish Reddish brown Dark purple
yellow
Boiling point / 0 C -35 59 184
Covalent radius/ nm 0.099 0.114 0.133
Ionic radius/nm 0.181 0.196 0.216
Electronegativity 3.2 3.0 2.7
Electron affinity/ kJ mol-1 -348 -325 -295
Ionisation energy/kJ mol-1 1250 1141 1009
Standard electrode potential/V +1.36 +1.07 +0.54
( X2 + 2e G 2X- )
atomic radius/ionic radius
Ô
      
Covalent radius/ nm 0.099 0.114 0.133
Ionic radius/nm 0.181 0.196 0.216

 Down Group 17, the nuclear


charge and the screening
effect increases.
 However, the increase in
the screening effect is larger
than the increase in the
nuclear charge, causing a
decrease in the effective
nuclear charge.
atomic radius Ionic radius
Electronegativity
Ô
      
Electronegativity 3.2 3.0 2.7

 Is the measure of the


relative strength of atoms
to attract electrons in a
covalent bond to which
they are bonded.
 The smaller the size of
the atom or/and the
higher the nuclear
charge, the stronger is the
attraction for the Proton number
electrons in a covalent
bond
The Colour Intensity Of Group 17
Elements
The Volatility Of Group 17 Elements
 Decreases down the group.
 The higher the melting point or boiling point,
the stronger the intermolecular forces of
attraction.
 The van der Waals forces of attraction
between the halogen molecules increase as
the molecular size of the molecules increases.
The Relative Reactivity Of The Elements as
Oxidising agents
 an    
is an  
 
 X2 (aq) + 2e- G 2X ʹ (aq)
Cl2 (aq) + 2e- 2Cl- (aq) ÔA + 1.36 V
Br2 (aq) + 2e- 2Br -(aq) ÔA + 1.07 V
I2 (aq) + 2e- 2I- (aq) ÔA + 0.54 V
 The more positive the ÔA value, the stronger the
element acts as an oxidising agent.
 The smaller is the atomic radius, the stronger the
element act as an oxidising agent. & '(  ') ' 
 The reactivity of halogens as oxidising agents can be
shown by the following reactions
Cl2 (aq) + 2Br ʹ (aq) 2Clʹ (aq) + Br2 (aq) ÔA + 0.27V
Cl2 (aq) + 2I ʹ (aq) 2Clʹ (aq) + I2 (aq) ÔA + 0.82V

Br2(aq) + 2I ʹ (aq) 2Br ʹ(aq) + I2 (aq) EA + 0.27V

2Fe2+(aq) + I2 (aq) 2Fe3+(aq) + 2I ʹ (aq) EA - 0.23V

2Fe2+(aq) + Cl2 (aq) 2Fe3+(aq) + 2Clʹ (aq) EA + 0.59V


2Fe2+(aq) + Br2 (aq) 2Fe3+(aq) + 2Brʹ (aq) EA + 0.30V
Reactions Of Chlorine, Bromine and
Iodine With Hydrogen
 Hydrogen halides G hydrides of halogens
 H2 (g) + 2 2H (g) , where  F, Cl, Br, and I.
 The order of reactivity decreases down the group.
Eg: a) Fluorine explodes with hydrogen at low
temperature and in the dark to form hydrogen
fluoride.
H2 (g) + F2 (g) 2HF (g)
b) at room temperature, a mixture of chlorine and
hydrogen will explode if exposed to sunlight or
ultraviolet light.
H2 (g) + Cl2 (g) 2HCl(g)
c) Bromine reacts with hydrogen only at a high
temperature of 200 oC and in the presence of
platinum catalyst to form hydrogen bromide.
Pt
H2 (g) + Br2 (g) 200 oC 2HBr(g)

d) at 400 oC and in the prensence of platinum


catalyst, iodine and hydrogen react slowly to
form hydrogen iodide.
Pt
H2 (g) + I 2 (g) o
2HI(g)
400 C
Thermal Stability Of The Hydrogen
Halides
 when heated , 2Hо (g) H2 (g) +  2 (g)
2000 oC
 2HCl (g) H2 (g) + Cl2 (g)
600 oC
 2HBr (g) H2 (g) + Br2 (g)
200 oC
 2Hl (g) H2 (g) + l2 (g)

 +&-+( -+) -+ 


On descending Group 17, the atomic size of the halogens
increases, and hence the H-X bond length increases.
H-F < H-Cl < H-Br < H-I
Bond length increases

The longer the bond length, the weaker the H-X bond and
hence the more easily the bond can be broken.
BOND LENGTH(nm)
÷ ÷ ÷
0.127 0.141 0.161
BOND ENERGY( kJ mol-1 )
÷ ÷ ÷
432 366 298
Reactions Of Chlorine, Bromine and Iodine
With Metal
 Halogens react with every metal in the
Periodic Table forming halides.
 examples:
2Na (s) + Cl 2 G 2NaCl (s)
Mg (s) + Cl 2 G MgCl2 (s)
Fe (s) + Cl 2 G FeCl2 (s)
 In the above reaction, reactivity of the
halogen decreases down the group.
Reactions Of The Halides Ions With
aqueous Silver Ions
 Chloride ions react with aqueous silver
nitrate to produce a white precipitate of
silver chloride.
ag+ (aq) + Cl ʹ (aq) G agCl (s)
 Silver chloride turns violet in sunlight.
 The white precipitate of silver chloride
dissolves readily in dilute ammonia solution
to form a colourless solution of silver
complex.
agCl (s) + 2NH3 (aq) G ´ag(NH3)2]+ (aq) + Cl- (aq)
silver complex
 Bromide ions react with aqueous silver
nitrate to form a cream precipitate of silver
bromide.
ag+ (aq) + Br ʹ (aq) G agBr (s)

 The cream coloured silver bromide is


insoluble in dilute ammonia solution but
dissolves in concentrated ammonia solution
agBr (s) + 2NH3 (aq) G ´ag(NH3)2]+ (aq) + Br-(aq)
 Iodide ions react with aqueous silver nitrate
to form a yellow precipitate of silver iodide.
ag+ (aq) + I ʹ (aq) G agI (s)

 The yellow precipitate of silver iodide is


insoluble in both dilute ammonia solution
ammonia solution and concentrated
ammonia solution.
Reaction Of Halogens With alkali
 Chlorine reacts with cold dilute sodium hydroxide to
give a mixture of sodium chloride and sodium
chlorate(I).

Cl2 (g) + 2NaOH (aq) 15oC NaCl (aq) + NaClO(aq) + H2O(l)

0 -1 +1

 In the above reaction, chlorine undergoes


disproportionation to -1 in Cl- and +1 in ClO- .
 Heat ClO- from NaClO, it will undergoes
disproportionation to ClO3- and Cl- .

3ClO- (aq) ѐ 2Cl- (aq) + ClO3- (aq)


3 NaClO (aq) ѐ 2NaCl(aq) + NaClO3 (aq)

+1 -1 +5
 Reaction of chlorine with hot concentrated sodium
hydroxide.
o
70 C
3Cl2(aq) + 6NaOH(aq) ѐ 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
Reactions Of Halides Ions With
Concentrated Sulphuric acid
ʹ (aq) + H2SO4 (l) G HX (g) + HSO4 ʹ(aq)
 In these reactions, concentrated sulphuric acid acts as a
strong acid to displace the acid, HX, from its salt.
 When solid halides are heated with concentrated
sulphuric acid, white fumes of hydrogen halides are
liberated.
 NaCl (s) + H2SO4 (aq)G NaHSO4(aq) + HCl(g)
 NaBr(s) + H2SO4 (aq)G NaHSO4(aq) + HBr(g)
 dI (s) + H3PO4 (aq)G dHSO4 (aq) + HI(g)
 Concentrated sulphuric acid is also an oxidising agent.
 Thus, it will further oxidise
~ HBr G Bromine ( reddish brown vapour)
~ HI G Iodine (a violet vapour)
~ HCl G Because concentrated sulphuric acid is not
strong enough to oxidise HCl.
To oxidise HCl to chlorine, a stronger oxidising agent such as
manganese (IV) oxide is used in the presence of concentrated
sulphuric acid.

4NaCl(s)+4H2SO4(aq)+MnO2(s) ѐ
Cl2(g)+MnCl2(aq)+4NaHSO4(aq)+2H2O(l)
 Concentrated sulphuric acid is also an oxidising agent
and will further oxidise HBr and HI to Br2 (g) and I2(g)
respectively.
 NaBr(s)+ H2SO4(aq) GNaHSO4(aq)+ HBr(g)
 2HBr(g) + H2SO4(aq)GBr2(g)+2H2O(l)+SO2(g)
 2Br-(s) + 3H2SO4(aq)G2HSO4-(s)+Br2 (g)+SO2(g)+2H2O(l)

 NaI(s) + H2SO4(aq)G NaHSO4(aq) + HI(g)


 2HI(g) +H2SO4(aq) GI2(g)+ 2H2O(l)+ SO2(g) FURTHER
 8HI(g) +H2SO4(aq) G4I2(g)+ 4H2O(l)+ H2S(g) OXIDaTION
Overall reaction:
 2I-(s)+ 3H2SO4(aq)G2HSO4-(aq)+I2(g)+SO2(g) +2H2O(l)
Or, 8I-(s)+ 9H2SO4(aq)G8HSO4-(aq)+H2S(g) +4I2(g) +4H2O(l)
Cl - < Br - < I -
 Ease of oxidation of halide ions.
 Reducing power of halide ions.

To Obtain Just HBr and HI


a non-oxidising acid such as excess concentrated phoshoric(v)
acid is used together with heat.

 dBr(s)+H3PO4(aq) ѐ dH2PO4(aq)+HBr(g)
 dI(s)+ H3PO4(aq) ѐ dH2PO4(aq)+HI(g)
OXOaCIDS OF CHLORINE

The important oxidations states of chlorine are


-1,+1,+3,+5, and +7
The oxo-acids are:
a. HOCI : chloric(I) acid
b. HCIO2 : chloric(III) acid
c. HCIO3 : chloric(V) acid
d. HCIO4 : chloric(VII) acid
 all the oxo-acids dissociate in water:
a. HOCI (aq) H+ (aq) + CIO - (aq)
b. HOCI2 (aq) H+ (aq) + CIO2- (aq)
c. HOCI3 (aq) H+ (aq) + CIO3- (aq)
d. HOCI4 (aq) H+ (aq) + CIO4- (aq)
 The acid dissociation constant, da

a 



HCIO 1.0×10Ё6
HCIO2 1.0×10Ё2
HCIO3 1.0×10
HCIO4 1.0×1010
as oxygen is more electronegative than chlorine, the O-H
bond in the oxo-acids are weakened by the U  

(electron-withdrawing effect) of the oxygen atoms


which are bonded to the chlorine atoms as shown below.
a. HCIO : H-O-CI
b. HCIO2 : H-O-CI O
O
c. HCIO3 : H-O-CI O
O
d. HCIO4 : H-O-CI O
O
HCIO < HCIO2 < HCIO3 < HCIO4
INDUCTIVE EFFECT INCREaSES
aS THE NUMBER OF OXYGEN aTOMS BONDED TO THE CHLORINE
INCREaSES,THUS CaUSING THE STRENGHT OF THE OXO-aCIDS TO INCREaSE
IN THE SaME ORDER
PREPaRaTION OF HaLOGENS
THE MERCURY CaTHODE CELL
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CHLORINE
used in the extraction of bromine from seaweed
used in the sterilising water supplies for home and industrial
use, for swimming pools.
CI2 (g) + H2O (l) G HCI (aq) + HOCI(aq)
The OCI- ion which is formed kills bacteria by oxidising life-
sustaining compounds within them.
 used as bleaching agent in the paper and fabric industry.
 used as antiseptics and disinfectants
eg: TCP( trichlorophenol)
Dettol (4-chloro-3,5-dimethylphenol)
Compounds of chlorine include:
Trichloromethane and tetrachloromethane are used as
organic solvents.
Chloroethene is the monomer for PVC.
Sodium chloride is used as table salt.
D.D.T (dichlorodiphenyltrichloroethane) is used as
insecticide.
Sodium chlorate(V), NaClO3 is a weed killer.
Sodium chlorate(I) ,NaCIO ,and calcium chlorate(I), Ca(OCI)2,
is used as household bleach.
Freons (e.g. CCI2F2 , CFCI3 ) are used as refrigerants or as
propellants in aerosol cans.
BROMINE
 1,2- dibromoethane, BrCH2CH2Br, is added to leaded petrol
to remove the lead oxide sticking to the piston surface.
Silver bromide is used in the manufacturing of photographic
film and photochromic lenses.
Used in the manufacture of dyes and drugs.

IODINE
a 50%( by mass) solution of iodine in ethanol (known as
tincture) is used as an antiseptic.
Silver iodide is used in photographic film and in ͚cloud
seeding͛
BLaCd-aND-WHITE PHOTOGRaPHY
Silver chloride and silver bromide slowly turn purple and
finally dark grey when exposed to sunlight because of the
following photochemical decomposition.
agCl (s) sunlight ag(s) + ½ Cl2 (g)
agBr (s) sunlight ag(s) + ½ Br2(g)
 the use of silver halides in black-and-white photography
depends on this photosensitive nature of silver salts.
 Black-and-white photographic film is a clear, cellulose strip
coated with grains of silver bromide.
 When the film is exposed, the light coming from the
subject passes through the lens of the camera and strikes
the film. The silver bromide that was exposed gets
activated: agBr (s) sunlight agBr *(s)
The exposed film is then treated with aqueous hydroquinone
(a reducing agent), where the activated silver bromide is
preferentially reduces to metallic silver.

2agBr(s)*+C6H6O2(aq)G2ag(s)+2HBr(aq)+C6H4O2(aq)

The film is then immersed in an aqueous solution of


thiosulphate (͚hypo͛) where the unreactive silver bromide is
removed:
agBr(s)+2S2O32-(aq)G´ag(S2O3) 2 ]3- (aq)+Br- (aq)
The resulting film is now a ͚negative͛.

Where light shines through the ͚negative͛ onto a piece of


photographic paper, the dark areas containing precipitate or
metallic silver that are opaque to light on the negative appear
white on the photography paper while the white areas- the
unactivated areas on the negative will appear dark.

a print of the photograph is obtained.


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