Halogen

Fahad Islam 

Ali Haidar
Group-v
Baber Ali 

M. Muneeb Munir
Introduction of
Halogens 
v Elements of group VII A are known
as Halogens.
v Halogens include Fluorine,
chlorine, bromine , iodine and
astatine.
v Valence electronic configuration of
these elements is ns2 p5.
v Halogens (except astatine) are
non-metals.
Gradation of characteristics properties within
a group 
Atomicity and  physical state:

Halogens exist as They contain

Flourine is pale
diatomic single covalent
yellow gas.
molecule. bond.

Chlorine is Iodine is a shiny

Bromine is a dark
greenish yellow black solid at
brown liquid.
gas. room temperature.
Electronegativity 
 Halogens have high electronegative values.
 High electronegativities of halogens show that they attract electrons
strongly.

Dissociation Energy ​
 The dissociation energies of halogens decrease from chlorine to iodine.​
           Cl2 > Br2 > I2​
 Fluorine have exceptionally low value of dissociation energy.​
Melting and boiling points
 Melting and boiling points of halogens increase from fluorine to
iodine.

Reactivity 
vAll the halogens are very reactive.
vFluorine is the most reactive.
vHalogens react with both metals and non metals.
vReactivity decrease from flourine to iodine.
 Oxidation states

 Halogens mostly show negative

oxidation states.
 Fluorine always show -1 oxidation
state.
 Halogens exhibit higher Oxidation
states of +3 , +5 and +7.
 Maximum oxidation state of halogens
is +7.
  Fluorine forms no oxyacids.
 Other forms oxyacids which are of four types.
Formation of  Hypohalous acid

oxyacids 


Halos acid
Halic acid
 Perhalic acid 
Characteristics
reactions of
halogens
 With Hydrogen

 All the halogens combine with hydrogen. 

 General reaction of the halogens with hydrogen is
            X2 + H2                     2HX

          Cl2 + H2                      2HCl

          Br2+ H2                        2HBr

        
  With water

 F2 has strong affinity for water and decompose water to give HF.
          F2 +2H2O                      4HF +O2
  Cl2 and to lesser extent Br2 , reacts with water to give mixture of
acids.
        Cl2 + H2O                       HCl + HCLO
        2HClO                             2HCl +O2
        2Br2 + 2H2O                    4HBr + O2
     I2 doesn’t react with water under ordinary conditions.
  Disproportionation reaction

 Reaction in which same compound is both oxidised and reduced

are called disproportionation reaction.
  Halogen disproportionates to form hydrohalic acid and
hypohalous acid in water.
              X2+ H2O                     HX-  + HOX+
 When Cl2 dissolved in water , disproportionaction reaction occurs.
            Cl2 + H2O                     HCl + HOCl
 With Alkalies
 When gaseous flourine is passed through dilute NaOH solution ,
oxygen difluoride is obtained.
               2F2 + 2NaOH                     2NaF + OF2 + H2O
   with more concentrated NaOH , oxygen is formed.
              2F2  + 4NaOH                     4NaF + 2H2O + O2
  Reaction of other halogens with alkalis is :
               X2 + 2NaOH                      NaX + NaXO +  H2O ; in cold state
               X2 + 6NaOH                      5NaX + NaXO3 + 3H2O; in hot state
 With Hydrogen Sulphide

 All the halogens react with hydrogen sulphide.

     X2 + H2S                     2HX + S

    Cl2 + H2S                     2HCl + S

Displacement reaction
F2 ,CL2,BR2 have ability to displace hydrogen from hydrocarbon.

              CH3CH3 + 7F2                    2CF4 +6HF

  Each halogen able to displace other elements which are
less electronegative then it self.

F2 can displace all other halogens.

             2NaCl   + F2                       2NaF  +   Cl2
           2CH3Cl   +  F2                      2CH3F  +  Cl2
Displacement reaction

 Cl2 will displace bromine and iodine 

                  Cl2 +2NaBr                       2NaCl Br2
                  Cl2+2NaI                       2NaCl I2
  Bromine will displace iodine 
                  Br2 +2NaI                    2NaBr I2
Oxidation reaction
 Oxidation reaction 
 F2 is strong oxidizing agent 
 It convert chlorate into perchlorate and  hydrogen sulphate ion to
peroxy disulphate.

             KClO3+H2O+F2                     KClO4 + 2HF

ALI HAIDAR 
Oxides of Halogens

 Halogens are form number of oxides like:

OF2               Cl2O          Br2O          I2O4
O2F2              ClO2          BrO2           I2O5  
Cl2O6           Br3O8          I4O9
 In this chapter wo only discuss oxides
of chlorine.
 Chlorine monoxide  Cl2O

 Cl2O is a brownish yellow gas.

 Very reactive and unstable.
 Strong, unpleasant odour.
 It has 2.2°C boiling point and –
120.6°C melting point.
Ø Chlorine monoxide  Cl2O

v It dissolves in water and

give golden yellow solution.

  Cl2O +  H2O               2HClO

v It is strong oxidizing agent.

  Cl2O +  2HCl               2Cl2 +H2O

v In liquid form readily to explode.
   Cl2O                   2Cl2 + O2
 Uses
 Chlorine • Used as a wood bleach.
monoxide  Cl2 •  Used as biocide
O • Its use in the preparation
of chlorinated solvents.
• Used to treatment of water
in swimming pool.
  Chlorine dioxide 

 It is heavy dark yellow gas.

 It has irritating odor.
 It is liquid at 11°C and frozen at -79°C.
 Chlorine dioxide is very different
from elementary chlorine.
  Chlorine dioxide 

 Chlorine dioxide is an unstable gas

that dissociates into chlorine gas (Cl2),
oxygen gas (O2) on heat.
 It is highly soluble specially in cold water

    2ClO2 + H2O                    HCLO2 + HClO3

 chlorine dioxide is a powerful
oxidizing agent.           
  Chlorine dioxide 

 It react with alkalies to give chlorate and

chlorite.
  2ClO2+ 2KOH                 KClO2+KClO3+H2O
 Uses

 Chlorine dioxide gas is used to

sterilize medical and laboratory
equipment, surfaces, rooms
and tools. 
 Chlorine dioxide can be used as
oxidizer or disinfectant. 
 Dichlorine Hexaoxide 

 It is dark red liquid.
 it explodes violently on contact with
organic compounds.
 It react with alkali and gives perchlorate
and chlorate.
 It react with HF and gives HClO4 and chloryl fluoride.

      Cl2O6  +    HF                      HClO4   +   ClO2F

 In the vapour state it exists principally as ClO3.
 In the  liquid state it gets dimerised and Cl2O6.
 Chlorine heptaoxide 

 Colourless oily liquid

 Extremely explosive in nature.
 It react slowly with water to form HClO4
     ClO   +   H2O                        2HClO4
 It is anyhydride of perchloric acid.
Formation of oxyacids

 Fluorine forms no oxyacids.

 Other forms oxyacids which are of four types.
1. Hypohalous acid
2. Halos acid
3. Halic acid
4. Perhalic acid 
 Hypochlorous acid 

 It exists in pale yellow and decompose into HCl and O 2 in light.
            2HClO                      2HCl  +  O2     
 On distillation, it decompose into the H2O and Cl2O
            2HClO                     Cl2O  +  H2O
Action with metals
 HClO dissolved in metals with evolution of H2, Cl2 and O2

       Mg + 2HClO                    Mg(ClO)2 + H2

       2Fe + 6HClO                      2Fe(ClO)3 + 3H2

       2HClO + Ni(OH)2                    2H2O + Ni(ClO)2        

      Cu + 4HClO                     Cu(ClO)2 + 2H2O + Cl2        

Oxidizing properties

 HClO act as  a powerful oxidizing and bleaching agent.

           2HClO                    2HCl  +  O2

Action of H2O2
 HClO react with H2O2 to give O2
           HClO   +   H2O2                     HCl  +   H2O  +  O2
 With metallic mercury

 When it react with metallic mercury it gives a light brown precipitate.

      HClO +  H2O2                    2HgCl(OH)2

With Alkalies

 It react with alkalies and give salts called hypochlorite sodium,

hypochlorite calcium and bleaching poweder
    
Uses
 Hypochlorous Acid is used to convert alkenes to chlorohydrins.
 Used in cosmetics such as baby products.
 Used in swimming pools.
 Used to generate sufficient quantities of safe disinfectant.
 Used in marine sanitation devices to convert seawater into
HOCl.
 Used as a wound care agent.
BABER ALI
MUHAMMAD
MUNEEB MUNIR
Interhalogen Compounds
 
 When two different react with each
other,interhalogen compounds are
formed.
 In general,XY2 n=1,3,5,7
 X is halogen atom which is less
electronegative and large in size.
 Y is halogen atom which is more
electronegative then X and smaller in
size.
 Interhalogen Compounds
 
 The interhalogen compounds are grouped into four
categories:
 1.XY:ClF,BrF,BrCl,lBr
 2.XY3:CIF3,BrF3,IF3,ICl3
 3.XY5:ClF5,BrF5,IF5
 4.XY7:IF7
Various types of interhalogen
compounds
 Halogen molecules react directly to form interhalogen
compounds.
 Cl2 + F 2           200C               2ClF   
 A halogen molecule reacts with other interhalogen
compounds to fermed other low  interhalogen compounds
 Examples:
 Cl2 + 3F2(excess)         300C                  2ClF3
     IF5 +   F2                              IF7
SOME PROPERTIES OF
INTERHALOGEN COMPOUNDS
 •PHYSICAL STATE: They are covlant in nature.
 •COLOUR:These compounds are colourless.
 •BOILING POINT:Boiling point increases with
increase in electronegative differences.
 •THERMAL STABILITY:Thermal stability decreases
with decrease in electronegative difference.
 •REACTIVITY:AB type compounds are more reactive
than A2 and B2 molecules.
 XY
TYPE
 PREPRATION: Is is obtained by the direct combination of elements.
 
    Ex: ClF, BrF etc.
     Cl2 + F2                   2ClF                 ;         Br2 + F2                   2BrF
 PROPERTIES:
 ClF is colourless which liquefies to a yellow and solidifies to
colourless solid.
 BrF is ple brown and liquefies to red brown and solidifies to a yellow
solid.
 BrF is decomposes to BrF3 and BrF5 along with free bromine.
 XY3 TYPE
 
 PREPRATION:ClF3 is prepared by the action of CL2 and F2 at 200 -300C
in a cu vessel. Ex:ClF3,BrF3,ICl3 etc
 PROPERTIES :
 2ClF3 reacts with glass and attacks many compounds and most of the
elements.
 BrF3 is a good ionizing solvent.
         2BrF3                       [BrF2- ] + [BrF4+]
 ClF3  combines with metal chlorides  to form compounds ,MICl4.It reacts
with CS2 to give CCL4
          4CCl+3CS2                        CCl4+2CSCl2+2S2Cl+2I2
 XY5
TYPE
 •PREPRATION:It (IF5) is prepared by the direct combination of I 2
 and F (excess).  Ex:IF ,BrF ect
2 5 5

 2I2O5 + 10F2                      4IF5 + 5O2 

 HYDROLYSIS: 2IF5 + 5H2O                    I2O5 + 10HF
 PROPERTIES:
 It is colourless liquid whose melting point is 9.6C.
 It is hydrrolysed by water to give halogen and oxy-acid of larger
halogen.
 It is good conducter of electericity.
 XY7 TYPE 
 PREPRATION: It is prepared by the action of F2 on IF5 at 250-
300C. Ex:IF5
                                 IF5 + F2                  IF7
  PROPERTIES:
 It is colourless gas. It reacts vigorously with non-metals but less so
with metals. It is slowly decomposed by water.
                          IF7 + 6H2O                    7HF + H5IO6 
 It act as a fluorinating agent, and fluorinates CCL 2F2 to CClF3.
USES OF INTERHALOEN
COMPOUNDS
 Used ass non-water solvents.
 Used as a catalyst.
 Used as fluorinating compounds.
PSEUDOHALOGENS
 
 DEFINATION:Pseudohalogens are groups formed by the combbination of
the two or more p-block elements with a unit negative charge.
  Ex:Cyanogen (CN)2,Thiocyanogen (SCN)2 etc.
 1.CYANOGEN(CN)2 is an inflammable gass (b.p.-25C),is prepared in the
laboratory by heating Hg(CN)2,or by the reaction of the Cu2+ ion with
cyanide in aqueous solution.
         Hg(CN)2                        Hg + (CN)2
         2Cu2+ 4CN_                        2CuCN + (CN)2
 It is also mformed by the action of Hg(CN)2 with HgCl2.
        Hg(CN)2 + HgCl2                       HgCl2 + (CN)2
 •THIOCYANOGEN(SCN)2 is prepared bybbthe reaction of iodine ,or
better,bromine with an etheral solution of silver of lead
thiocyanogen.Evaporation of the solvant after filtrating the silver halides
gives free ,which polymrizes irreversibly at room temperature at a brick
red amorphus solid .
 2AgSCN + Br2                     2AgBr + (SCN)2
 n(SCN)2                     2(SCN)n
 It can also be prepared by the electrolyzing an alcholic solution of
ammonium or potassium thiocyonate.
PROPERTIES OF PSEUDOHALOGENS

 These are volatile.

 Pseudohalogens, like the halogen ,react with
alkalies.
 Pseudohalogens,like the halogens,add at ethylenic
double bond linkage.
 Pseudohalogens form covlent pseudohalogens.
USES OF PSEUDOHALOGENS 
 
 Used as an oxidizing agent.
 Used for the determination of the inorganic compounds.
Thank You