The Group 17 (Halogen) Elements: Fluorine, Chlorine, Bromine, Iodine and Astatine

Most electronegative elements in the periodic table. table. -1 oxidation state occurs in the halide anions (e.g. Cl-). (e. This oxidation state becomes increasingly reducing on going down the group. group. I-1, is a moderate reducing agent, while chloride shows few reducing characteristics, except with very strong oxidizing agents. agents. For example PbI4 is a non-existent compound, owing noncompound, to the combination of an oxidising metal centre, PbIV, and a reducing iodide anion. anion. In contrast, PbCl4 and PbF4 are stable. stable.

+1, +3, +5 and +7 occur for chlorine, bromine and iodine, mainly in oxyanions and interhalogen compounds. compounds. Compounds in the highest oxidation states generally contain the electronegative elements oxygen and fluorine, e.g IF7 and IO4- . Fluorine with its small size and high electronegativity, coupled with electronegativity, the weakness of the F-F bond, means it is able to stabilize the very highest oxidation states of elements, e.g AuF5, NiF4, PtF6. Iodine (and to a lesser extent bromine) forms solvated cations (with iodine in the +1 oxidation state) such as [I(pyridine)2]+, by reaction of I2, pyridine and AgNO3 in a non-aqueous solvent. nonsolvent. I2 + AgNO3 + 2 Pyridine I(pyridine)2]+NO3- + AgI

I+

Elements Fluorine

Source CaF2, Fluorspar; CaF2.3Ca3(PO4)2, fluorapatite Elemental fluorine by electrolysis of KF dissolved in anhydrous HF 2HF + 2KF 2KF + H2 + F2

Chlorine

from large underground NaCl deposits (formed by the evaporation of ancient sea) Elemental chlorine by electrolysis of aqueous salt solutions, which produces NaOH as a by-product. Chlorine compounds byhave numerous industrial and house-hold houseapplications. Cl2 + 2Br 2Cl- + Br2

Bromine

Bromide ions occur in seawater (concentration 30 ppm), ppm), from which Br2 is obtained by reaction with chlorine Sodium iodate (NaIO3), from which elemental iodine is obtained by reduction. I- are found in some brines, from which the element is obtained by oxidation with chlorine.

Iodine

Iodine shows metallic luster and high electrical conductivity under pressure Astatine All isotopes are radioactive, trace amounts occur in uranium ores. Astatine isotopes are obtained by the ores. irradiation of a bismuth target with -particles, from which elemental At is obtained in the form of isotopes 209At, 210At and 211At. At.

Hydrogen Halides, HX, and halide salts, XAll hydrogen halides are known, and stability decreases down the group, owing to the increasing mismatch in atomic sizes. sizes. HI is rather unstable (the fHo is positive, +26.5 kJ mol-1), and HI exists 26. in equilibrium with H2 and I2. The m.p. and b.p. increase down the group with the exception of HF which has very high b.p. due to hydrogen bonding. bonding. The hydrogen bonding also occurs in the gas phase. phase. The F---HF unit is always linear about the hydrogen, and also occurs ---H in the so-called hydrogenfluoride salts such as K+HF2-. soThe hydrogen halides dissolve in water to give highly acidic solutions. solutions. HX + H2O H3O+(aq) + X-(aq) aq) aq)
F H H F H F

H F H F

HCl, HCl, HBr and HI are all strong acids and are essentially fully dissociated H in dilute solution; however, HF is a much weaker acid. solution; acid. The structure of HF
in the solid state

Aqueous

HF

solutions contain

undissociated

HF,

together with

fragments of the (HF)n polymeric chain such as H2F3- and H3F4-, held together by the strong H----F hydrogen bonding that is so important in ----F this system. system. A number of monoanions are known which behave in a manner similar to halides, and form similar compounds: these anions are called compounds: pseudohalides. pseudohalides. N3-, CN-, NCO-, NCS-. Inter-pseudohalogen iodine azide IInterN3 is explosive

Halogen Oxides All of the halogen form oxides; those of iodine are the most stable, while those of bromine tend to be the least stable All are oxidizing agents.

Dihalogen monoxides; E2O

2F2 + 2OH-

OF2 + 2F- + H2O

OF2 is the most stable and is a powerful oxidizing agent, oxidize water to oxygen Explodes when mixed with halogens but a spark is required to ignite mixtures of OF2 and hydrogen or CO.

OF2 + H2O 2Cl2 + 2HgO

O2 + 2HF Cl2O + HgCl2.HgO

Cl2O, Br2O, OF2

Br2O3

Cl 2O4, Br2O4 ,

Br2O 5

Cl2O6

Cl2O7

Br2O 7

ClO2 is a yellow gas

Cl O O D

Cl OH O
G# =+121 kJmol-1

Cl O

explosive in high concentration Prepared by the reduction of KClO3 in acidic solution KClO3 +2H2C2O4 K2C2O4 + 2ClO2 + 2CO2 +2H2O NaClO3 +SO2 + H2SO4 2NaHSO4 + 2ClO2 Despite being a radical, show no tendency to dimerize but is slowly hydrolysed to HCl + HClO3 Paramagnetic molecule Because of delocalization of the unpaired electrons over the entire molecule, shows little tendency to dimerization However, in the solid state it forms loose dimers, with a dimers, Cl O distance of 270.8 pm, whereas the ClO bond 270. Cl distance is 147 pm
ClO2 is commercially important as a bleaching and sterilizing agent

Iodine oxides
Among all the halogen oxides, those of iodine, particularly in higher oxidation states, are the most stable. stable. Iodine(V) oxide, I2O5, which decomposes only at temperatures greater than 300 oC, is made by heating HIO3. Iodine oxides, unlike the chlorine and bromine ones, have polymeric structures. structures.

2HIO3

I2O5 + H2O

Oxyacids and oxyanions of the halogens

HOCl, HOCl, HOF, HClO2, HClO3, HClO4 For a given element, the strength of the acid increases with oxidation state.

Acid HOCl HClO2 HClO3 HClO4

Acid dissociation constant, Ka 2.8 x 10-8 1.0 x 10-2 103 107

Halic(VII) Halic(VII) acids (HXO4) and halate(VII) salts (XO4-) halate(VII)

Known for chlorine, bromine and iodine Chloric acid is a strong oxidizing agent but least strongly oxidizing of all chlorine acids. The chlorate(VII) anion can be used to crystallize large cations. cations. Chlorate salts are explosive and shock sensitive

Chlorate(VII) salts are often referred to as perchlorates

Interhalogen compounds Neutral, Direct combination of elements provides a general method of synthesis IF, BrF, ClF, ICl, IBr, BrCl EF3, EF5 (E = Cl, Br, I) IF7 Interhalogen cations and anions Many are known Fluoride compounds are generally formed by addition or removal of F- from a parent neutral compound Fluoride addition: ClF3 + CsF Fluoride removal: ClF3 + AsF5 CsClF4 ClF2+AsF6-

Oxidation and fluoride ion removal is equivalent to the addition of F+, which is not stable on its own. Vigorous oxidation (using KrF2) of a lower oxidation state compound can also be employed. ClF5 + KrF2 + AsF5 ClF6 + AsF6- + Kr

Selected interhaolgen cations and anions Oxidation state Cations +1 ClF2+ ICl2+ Anions BrCl2ICl2IBr2I3 +3 ClF4+ BrF4+ IF4+ ClF4BrF4ICl4+5 ClF6+ BrF6+ IF6+ BrF6IF6IF8+7

Summary on Halogen Series The dominence features of the chemistry of the halogens are the formation of X- anions, or covalent compounds with strong M-X bonds. bonds. Many interhalogen species are known, as neutral, cationic and anionic species, and are most stable when the central atom is iodine, in combination with fluorine. fluorine. Fluorine is an extremely reactive element, able to stabilize the highest oxidation states in compounds with other elements. elements. A wide range of oxyacids and oxyanions are formed, except for fluorine; fluorine; the compounds are all strong oxidizing agents. agents.