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group 7, the HALOGENS Non-metallic elements, VERY reactive.

ve. Diatomic covalent molecules OXIDISING agents (they are reduced themselves), and become less oxidising, or reactive down the group. Halogen Fluorine Chlorine Bromine Iodine Physical state and colour Pale yellow gas Green gas Red-brown liquid Grey solid Appearance in water N/A Pale yellow/green solution Red/brown/orang e Brown Appearance in hydrocarbon solvent N/A Pale yellow/green solution Red/brown/orang e Pink/violet

Reactions of halogens: 1. Disproportionation with alkalis NaOH or KOH COLD alkali to give halide and halate (I) ions: halide and halate (V) ions: X2 + 2NaOH NaXO3 + 5NaX +3H2O X2(g) + 2OH-(aq) XO3- (aq) + 5X- + 3H2O O.S: +5 0 -1 NaI + H 2O 3Br2 + 6NaOH
Sodium Sodium bromate (V) bromate

HOT alkali to give 3X2 + 6NaOH 3X2 (g) + 6OH-(aq) 0

NaXO + NaX + H2O XO-(aq) + X-(aq) +H2O +1 -1

e.g: I2 + 2NaOH NaIO + NaBrO3 + 5NaBr + 3H2O Sodium Sodium


iodate (I) iodide

2. Oxidise metals, non-metals and ions

Metals: e.g. fluorine and chlorine react with iron to form iron (III) halides Iron is oxidised: 2Fe 2Fe 3+ + 6e-

Chlorine is reduced: 3Cl2 + 6eOverall equation: 3Cl2(g) + 2Fe(s)

6Cl2FeCl3(s)

Non metals: e.g. chlorine reacts with sulphur to form sulphur (I) chloride. Sulphur is oxidised to +1 and chlorine is reduced to -1) S8(s) + 4Cl2(g) 4S2Cl2(l)

Ions: e.g. all halogens except iodine (weak oxidising agent) will oxidise iron (II) ions to iron (III) ions in solution. The solution will change colour from green to orange. 2Fe2+(aq) 2Fe3+ (aq) + 2e-

Reactions of Halides: 1. Potassium halides with concentrated sulphuric acid: React to give a hydrogen halide. The trend in strength of the halide ions as reducing agents is: I- > Br- > Cl-

KCl and H2SO4: KCl(s) + H2SO4(l) KHSO4(s) + HCl(g)

But hydrogen chloride is not a strong enough reducing agent to reduce the sulphuric acid, so reaction stops there. Misty fumes of hydrogen chloride gas will be seen when it comes into contact with moisture in air. This is NOT a redox reaction O.S of halide and sulphur stay the same (-1 and +6) KBr and H2SO4: KBr(s) + H2SO4(l) KHSO4 (s) + HBr(g)

This reaction gives misty fumes of hydrogen bromide gas, and the HBr is strong enough to reduce the H2SO4 in a redox reaction. Then this reaction: 2HBr + H2SO4 (l) O.S of Br: -1 0 Br2(g) + SO2(g) + 2H2O(l) OXIDATION

O.S of S: REDUCTION KI with H2SO4: O.S of I: OXIDATION O.S of S: REDUCTION KI(s) + H2SO4(l) 2HI + H2SO4(l)

+6

+4

KHSO4(S) + HI(g) I2(s) + SO2(g) + 2H2O(l)

Same first two reactions, but because iodine is a very strong reducing agent, it goes further, and reduces SO 2 to H2S : 6HI(g) + SO2(g) -1 +4 -2 H2S(g) + 3I2(s) + 2H2O(l) 0

H2S is a toxic gas, and gives a bad egg smell.

2. Hydrogen Halides with ammonia and water Hydrogen halides are colourless gases. They are very soluble, and dissolve in water to make STRONG acids: HCl (dissociation)
(g)

H+(aq) + Cl- (aq)

Hydrogen chloride forms hydrochloric acid; hydrogen bromide forms hydrobromic acid and so on.

With ammonia: react to form white fumes of the corresponding ammonium halide: NH3 (g) + HCl(g) NH4Cl(s)

3. Displacement by more reactive halogens

The oxididising strengths of the halogens can be seen in their displacement reaction with halides. E.g. Br 2(aq) + 2KI(aq) 2 KBr(aq) + I2(aq)

The bromine displaces the iodine ions (it oxidises them) giving iodine I2(aq) and potassium bromide A halogen will displace a halide from solution if the halide is below it in the periodic table

4. Silver nitrate solution, and silver halides solubility in ammonia and reactions with sunlight:

To test for halides in solution:

1. Add dilute nitric acid this removes ions that could interfere with test and ppt. 2. Add silver nitrate solution (AgNO3(aq) ) A precipitate of the silver halide will form, the reaction is:

Ag+ (aq) + X-(aq)

AgX(s)

The colour of precipitate identifies the halide, and they have different solubilitys in ammonia solution: Chloride Cl- : White ppt which dissolves in dilute NH3 (aq) and darkens in sunlight Bromide Br- : Cream ppt, dissolves in concentrated NH3 (aq) and darkens in sunlight Iodide I- : Yellow ppt, insoluble in concentrated NH3 (aq) and does NOT darken in sunlight.

The reaction of silver halides with sunlight (decomposition) is:

2AgBr

2Ag + Br2

Making predictions about fluorine and astatine from trends in group 7: Number of electrons increases down group, so London forces will increase. Astatine will be a solid and have the highest boiling temperature. Electronegativity decreases down group, so astatine will have lowest EN value. Fluorine will be most oxidising