Task 1: The properties of the Group 7 Halogen elements Atomic number 9 17 35 53 85 Astatine state, colour at room Melting o temperature

point C pale yellow gas -220 Boiling o point C -188 ends in .7 ends in .7 black solid 302 337 ends in .7 Electron arrangement

Element Symbol Fluorine F Cl Br I At

9.2 The halogen displacement reaction and Group 7 reactivity trend

A few drops of chlorine water, bromine water and iodine water are added in turn to aqueous solutions of the salts potassium chloride (KCl), potassium bromide (KBr) and potassium iodide (KI). Three combinations produce a reaction (and three don't!). You can get 'simple' observations from the diagrams! A darkening effect compared to a water blank confirms a displacement reaction has happened. Chlorinedisplaces bromine from potassium bromide and iodine from potassium iodide. Bromine only displaces iodine from potassium iodide and the least reactive iodine cannot displace chlorine or bromine from their salts. Halogen added chlorine Cl2 bromine Br2 iodine I2 KCl solution VERY pale green solution orange-reddish brown solution KBr solution 1. orange-reddish brown solution orange-reddish brown solution KI solution 2. brown solutionblack precipitate 3. brown solutionblack precipitate BLANK of water VERY pale green solution orange-reddish brown solution

dark brown solution dark brown solution dark brown solution dark brown solution

On the basis that the most reactive element displaces a least reactive element the reactivity order must be: chlorine > bromine > iodine The word and symbol equations for the 1 - 3 DISPLACEMENT REACTIONS on the diagram are given below. 1. chlorine + potassium bromide ==> potassium chloride + bromine Cl2(aq) + 2KBr(aq) ==> 2KCl(aq) + Br2(aq) 2. chlorine + potassium iodide ==> potassium chloride + iodine Cl2(aq) + 2KI(aq) ==> 2KCl(aq) + I2(aq) 3. bromine + potassium iodide ==> potassium bromide + iodine Br2(aq) + 2KI(aq) ==> 2KBr(aq) + I2(aq)

The halogen molecule is the electron acceptor (the oxidising agent) and is reduced by electron gain to form a halide ion The halide ion is the electron donor (the reducing agent) and is oxidised by electron loss to form a halogen molecule chlorine molecule + bromide ion ==> chloride ion + bromine molecule ionically the redox equations are written ... 1. Cl2(aq) + 2Br (aq) ==> 2Cl (aq) + Br2(aq) because the potassium ion, K+, is a spectator ion, that is, it does not take part in the reaction. The other two possible reaction equations involving (ii) chlorine + iodide and (iii) bromine + iodide, are similar to the example above. 2. Cl2(aq) + 2I (aq) ==> 2Cl (aq) + I2(aq) 3. Br2(aq) + 2I (aq) ==> 2Br (aq) + I2(aq)
-

Explaining the Reactivity Trend of the Group 7 Halogen

Period 2 halogen:

F [2.7] + e ==>

F [2.8]

Period 3 halogen:

Cl [2.8.7] + e ==>
-

Cl [2.8.8]

Period 4 halogen: Br [2.8.18.7] + e ==> Br [2.8.18.8]

-

Period 5 halogen: I [2.8.18.18.7] + e ==> I [2.8.18.18.8]

When a halogen atom reacts, it gains an electron to form a singly negative charged ion e.g. Cl + e ==> Cl which has a stable noble gas electron structure like argon. (2.8.7 ==> 2.8.8) As you go down the group from one Group 7 halogen element down to the next .. F => Cl => Br => I ... o the atomic radius gets bigger due to an extra filled electron shell, o the outer electrons are further and further from the nucleus and are also shielded by the extra full electron shell of negative electron charge, o therefore the outer electrons are less and less strongly attracted by the positive nucleus as would be any 'incoming' electrons to form a halide ion (or shared to form a covalent bond).

SO, this combination of factors means to attract an 8th outer electron is more and more difficult as you go down the group, so the element is less reactive as you go down the group, i.e. less 'energetically' able to form the X halide ion with increase in atomic number.

9.3 Reactions of halogens with other elements

Reaction with hydrogen H2 Halogens readily combine with hydrogen to form the hydrogen halides which are colourless gaseous covalent molecules. (Halogen compounds - covalent bonding details revision notes) e.g. hydrogen + chlorine ==> hydrogen chloride H2(g) + Cl2(g) ==> 2HCl(g) The hydrogen halides dissolve in water to form very strong acids with solutions of pH1 e.g. + hydrogen chloride forms hydrochloric acid in water HCl(aq) or H Cl (aq) because they are fully ionised in aqueous solution even though the original hydrogen halides were covalent! An acid is a + substance that forms H ions in water. Bromine forms hydrogen bromide gas HBr(g), which dissolved in water forms hydrobromic acid HBr(aq). Iodine forms hydrogen iodide gas HI(g), which dissolved in water forms hydriodic acid HI(aq). Note thegroup formula pattern. The mechanism of the direct combination of chlorine and bromine with hydrogen is a classic case of a free radical chain reaction. . o initiation: X2 ==> 2X Homolytic bond fission by heat or light to give two halogen free radicals. . . . . o propagation: X + H2 ==> HX + H and H + X2 ==> HX + X Two steps of product + radical to continue chain . . . . o termination: H + X ==> HX or 2H ==> H2 or 2X ==> X2 o Three possible ways of ending a chain sequence.

Reaction with Group 1 Alkali Metals Li Na K etc. Alkali metals burn very exothermically and vigorously when heated in chlorine to form colourless crystalline ionic salts e.g. NaCl or + Na Cl . This is a very expensive way to make salt! Its much cheaper to produce it by evaporating sea water! e.g. sodium + chlorine ==> sodium chloride 2Na(s) + Cl2(g) ==> 2NaCl(s) The sodium chloride is soluble in water to give a neutral solution pH 7, universal indicator is green. The salt is a typical ionic compound i.e. a brittle solid with a high melting point. Similarly potassium and bromine form potassium bromide KBr, or lithium and iodine form lithium iodide LiI. Again note the group formula pattern.

(Halogen compounds - ionic bonding details revision notes)

Reaction with other metals Reaction of element with chlorine:

o o

Burns when heated strongly in chlorine gas to form the white solid aluminium chloride on heating in chlorine gas. aluminium + chlorine ==> aluminium chloride 2Al(s) + 3Cl2(g) ==> 2AlCl3(s) * It is often a faint yellow in colour, due to traces of iron forming iron(III) chloride.

Aluminium chloride is a curious substance in its behaviour. The solid, AlCl3, 3+ consists of an ionic lattice of Al ions, each surrounded by six Cl ions, BUT on o heating, at about 180 C, the thermal kinetic energy of vibration of the ions in the lattice is sufficient to cause it break down and sublimation takes place (s ==> g). In doing so the co-ordination number of the aluminium changes from six to four to form the readily vapourised covalent dimer molecule, Al2Cl6, shown above. You can also prepare iron(III) chloride in the same way. o iron + chlorine ==> iron(III) chloride(brown solid) o 2Fe(s) + 3Cl2(g) ==> 2FeCl3(s) If the iron is repeated with bromine the reaction is less vigorous, with iodine there is little reaction, these reactions also illustrate the halogen reactivity series.