Group 17 elements Members of the group : Fluorine , Chlorine , Bromine , Iodine Occurrence : Highly reactive elements and hence

do not occur in free or native state . They mainly occur in combined state in the form of halide and iodine also occurs as iodate ( IO3)- . Fluorine : Occurs as insoluble fluorides such as Fluorspar ( CaF2) , Cryolite : Na3AlF6 . Chlorine : Sodium chloride ( Rock salt ) NaCl , Carnalite KCl . MgCl2 . 6H2O , Calcium chloride ( CaCl2). Bromine is found in sea water and lakes in the form of NaBr , KBr and MgBr2 . Electronic configuration : General electronic configuration is ns2np5 Atomic and ionic radii : Halogens have smallest atomic radii in the respective period. This is due to the increase in nuclear charge across a period . The radius of a halide ion is always greater than the halogen atom as addition of extra electron decreases the net effective nuclear charge and hence electron cloud expands . Ionisation enthalpy : I.E of halogens are very high but less than that of inert gases . However I.E values decreases on moving from F to I . Common oxidation state : When halogen atom combines with element with lesser electronegativity , it shows -1 oxidation state . On the other hand when it combines with element with higher electronegativity , it exhibits +1 oxidation state. Chlorine , bromine and iodine shows positive oxidation state of +3 , +5 and +7 oxidation state due to presence of vacant d-orbitals . Due to absence of vacant d orbitals fluorine does not exhibit positive oxidation state . Electronegativity : Halogens have high value of electronegativity . Electronegativity decreases from fluorine to iodine . Oxidising power : Since all the halogens have strong tendency to accept electrons they act as strong oxidizing agent . However oxidizing power decreases from F to I.

F2 + 2X-

2F- + X2

Nature of oxides : The compounds of oxygen and fluorine are not called as oxides but oxygen fluorides as fluorine is more electronegative than oxygen . The compounds of rest of the halogens and oxygen are termed as oxides . The stability of the oxides of iodine is greater than that of chlorine while bromine oxides are least stable . Iodine oxygen bond is stable due to greater polarity of the bond while chlorine oxygen bond is stable due to the formation of multiple bonds while bromine oxides lacks both of these. Preparation of fluorine: In modern methods, fluorine is prepared by electrolysis of a fused fluoride (usually potassium hydrogen fluoride, KHF2). The electrolytic cells are made of copper, nickel or monel metal. The anode is generally of graphite and the fluorine set free contains some carbon tetrafluoride. Reactions in the electrolytic cell

Dennis method: The electrolytic cell used in this method consists of a V-shaped copper tube (5 cm in diameter) fitted with copper caps. Graphite electrodes through these caps are sealed and insulated in the tube by bakelite cement which is not. affected by fluorine. The cen is covered with an insulating layer of asbestos cement over which is wound a resistance

wire for electrical heating. The tube is thickly lagged to prevent the loss of heat.

Reactions of fluorine ; With hydrogen : Hydrogen explodes violently in fluorine in dark . H2 + With water : Fluorine reacts violently with water to give O2 and O3 2H2O + 2F2 4HF + 3H2O + 3F2 6HF + With hydrogen sulphide : H2S + With alkalis : 4F2 SF6 + 2HF 2NaOH OF2 + 2NaF + H2O O2 O3 F2
2HF

The electrolyte consists of fused potassium hydrogen fluoride which has already been dried for 48 hours at 130C. The electrolyte is kept in fused state by electrical heating externally. For electrolysis, a current of 5 amperes and 12 volts is used. On electrolysis fluorine is liberated at anode. To make the liberated fluorine free from HF vapours, it is passed through copper U-tubes containing sodium fluoride. NaF + HF ---> NaHF2 The following difficulty is experienced in this method: The liberated fluorine at anode does not escape fast enough due to narrow exit. The escape is further hindered due to frothing in the electrolyte. There are, thus, chances of mixing of H2 and F2 which may result in explosion. To avoid this, a modified apparatus has been devised by Whytlaw-Gray. Whytlaw-Gray method: It consists of a copper cell wound with resistance wire for electrical heating. The pure graphite anode is enclosed in a copper cylinder which is perforated at the bottom (Fig. 12.25). The electrolysis of fused KHF2 is carried out in this cell. The escape of fluorine is fast enough and thus no frothing in the electrolyte occurs. There are no chances of mixing of H2 and F2 in this cell.

2F2 + 2F2 +

4NaOH 4NaF + 2H2O + O2

Preparation of chlorine :

MnO2 With H2S : Cl2 +

4HCl

MnCl2

2H2O

Cl2

Reaction of chlorine : H2S 2HCl + S

With ammonia : 2NH3 8NH3 NH3 + + + 3Cl2 3Cl2 3Cl2 + +

N2

6HCl 6NH4Cl

With excess ammonia N2 + NCl3 NaCl + With excess chlorine : 3HCl + NaClO + H2O 3H2 (c) AB5 types i.e. BrF5, IF5 have distorted octahedral (d2sp3hybridization) shapes or square pyramidal due to a lone pair one of the axial positions. With alkalis : 2NaOH 6NaOH 3Cl2 3Cl2 (cold dilute ) 5NaCl + NaClO3 + ( hot , conc ) Interhalogen compounds : The compounds of one halogen with the other are called inter halogens or inter halogen compounds. The main reason for their formation is the large electronegativity and the size differences between the different halogens. Taking A as the less electronegative and B as the more electronegative halogen, they are divided into the following four types the less electronegative halogen (A) is always written first. AB AB3 AB5 AB7 ClF CLF3, BrF3, BrF5IF5 IF7 BrF, BrCl, IF3, ICI3 ICI, IBr, IF Structure: Interhalogen compounds are, (a) AB type i.e. ICl, IBr, IF etc, are linear (b) AB3 type i.e. IF3, ClF3, BrF3 have distorted trigonal bipyramidal (dsp3hybridization) structures of T-shape due to two lone pairs in equatorial positions ICl3 is dimeric, I2Cl6 and has a planar structure.

(d) AB7 type i.e. IF7, have pentagonal bipyramidal (d3sp3-hybridization) structures.