12ChF321 Group 7 Group 7 The Halogens

Candidates should be able to: (a) explain, in terms of van der Waals forces, the trend in the boiling points of Cl2, Br2 and I2; (b) describe the redox reactions, including ionic equations, of the Group 7 elements Cl2, Br2 and I2 with other halide ions, in the presence of an organic solvent, to illustrate the relative reactivity of Group 7 elements; (c) explain the trend in reactivity of Group 7 elements down the group from the decreasing ease of forming negative ions, in terms of atomic size, shielding and nuclear attraction; (d) describe the term disproportionation as a reaction in which an element is simultaneously oxidised and reduced, illustrated by: (i) the reaction of chlorine with water as used in water purification, (ii) the reaction of chlorine with cold, dilute aqueous sodium hydroxide, as used to form bleach, (iii) reactions analogous to those specified in (i) and (ii); (e) interpret and make predictions from the chemical and physical properties of the Group 7 elements and their compounds; (f) contrast the benefits of chlorine use in water treatment (killing bacteria) with associated risks (hazards of toxic chlorine gas and possible risks from formation of chlorinated hydrocarbons); (g) describe the precipitation reactions, including ionic equations, of the aqueous anions Cl,Br and I with aqueous silver ions, followed by aqueous ammonia; (h) describe the use of the precipitation reactions in (g) as a test for different halide ions.

The elements in Group 7 (the halogens) all exist as DIATOMIC MOLECULES, containing a single covalent bond. They are all NON METALS. As a chemical family they show related reactions.

Physical properties

F2 Cl2 Br2 I2 Going down the group we see a number of trends in physical properties. Most notably: - the melting and boiling points increase (gas liquid solid at room temp.) - the colour becomes more intense
The trend in boiling points (-188C, -34.6C, 58.8C, 184C) is explained in terms of the intermolecular forces which hold the halogen molecules to one another. There are no polar bonds (same atom so same electronegativity at each end of the bond) and no prospect of hydrogen bonding, so Van der Waals is the only intermolecular force present. Van der Waals forces increase with the number of electrons present so these forces increase as we go down Group 7, as do the boiling points. Iodine has a simple molecular lattice. I2 molecules are positioned in regular spatial arrangement in a lattice, held in symmetrically by a network of intermolecular forces.
Note: Iodine is unusual because it SUBLIMES when it is heated (goes straight from solid to vapour without going through a liquid state).

Page 1

12ChF321 Group 7 On the basis of the observed properties we can PREDICT what the properties of fluorine and astatine would be: Fluorine is a very pale coloured gas at room temperature (and is too dangerous to investigate in school labs) Astatine is a black solid at room temperature (and is very rare, so not investigated)

Chemical properties The halogens all form HALIDE ions (F-, Cl-, Br- and I-) by gaining an electron to become isoelectronic with noble gases. Halide ions are colourless, dissolving in water to produce colourless solutions (unless a coloured ion such as a transition metal ion is present too). Reactivity Trend The ease with which the halogens can attract an electron to become a halide determines their reactivity: The reactivity DECREASES down the group with fluorine being the most and iodine the least reactive halogen. The reasons for this are based on the same factors as for ionization to form positive ions (e.g. in Group 2), but in this case it is about how effectively the halogen's nucleus can attract the electron it needs. Down the group reactivity decreases because: 1: the atomic size increases as more shells are filled the smaller the halogen atom is, the closer it's (positively charged) nucleus can get to other atoms to attract an electron from them. Fluorine will be able to get closer than any other halogen. 2) shielding increases the more filled shells there are between a halogen atom's nucleus and the "outside world", the less its nucleus will be able to attract an electron from nearby atoms. Fluorine has fewer filled shells surrounding the nucleus. 3) nuclear charge increases BUT the two factors above OUTWEIGH the fact that going down the group the nucleus becomes more positively charged (bigger atomic number), so the electron to be attracted experience LESS attraction. Oxidising power Group 7 are oxidising agents they cause other atoms/ions to lose electrons, becoming oxidised. The more reactive the halogens, the better oxidising agents they are. Oxidising power therefore increases as we go up the group. Reactions of Group 7 DISPLACEMENTS We can illustrate the relative reactivity of the halogens compared to one another since a more reactive halogen can remove an electron from the halide ion of a less reactive halogen, completing its own outer shell and turning the halide ion back into a halogen atom. This is a displacement reaction, and also a redox reaction. If a less reactive halogen is mixed with the halide ion of a more reactive halgen, NO REACTION takes place.

Page 2

12ChF321 Group 7 The presence of the newly formed halogen can be seen by its colour - bromine in aqueous solution is a yellow-orange - iodine in aqueous solution is an red-brown We can distinguish more clearly by adding an organic solvent layer such as cyclohexane, and shaking to dissolve the newly-formed halogen - bromine gives an orange layer - iodine gives a purple layer We need to be able to write equations for these REDOX reactions, including IONIC equations: 1) CHLORINE displaces bromine from bromides and iodine from iodides

2 KBr(aq) + Cl2(aq) 2 KCl(aq) + Br2(aq) 2 Br-(aq) + Cl2(aq) 2 Cl-(aq) + Br2(aq) -1 0 -1 0 reduction oxidation
2 KI(aq) + Cl2(aq) 2 KI + Br2(aq) 2I-(aq) + Cl2(aq) 2 Cl-(aq) + I2(aq)

after removing K+ spectator ion oxidation numbers

2) BROMINE displaces iodine from iodides, but CAN'T displace chlorine from chlorides 2 NaI(aq) + Br2(aq) 2 NaBr(aq) + I2(aq) 2 I-(aq) + Br2(aq) 2 Br-(aq) + I2(aq) 2 NaCl(aq) + Br2(aq) NO REACTION 3) IODINE can't displace bromine from bromides or iodine from iodides 2 NaCl(aq) + I2(aq) NO REACTION 2 NaBr(aq) + I2(aq) NO REACTION On the basis of these reactions we would PREDICT that fluorine will displace chlorine from chloride ion solutions, bromine from bromide ions, and iodine from iodide ions. None of the other halogens will be able to displace fluorine from a solution containing fluoride ions. Reactions of Group 7 PRECIPITATES (TEST FOR HALIDES) Halide ions in solution are colourless, so it is not possible to tell them apart visually. The best chemical test for halides is their reaction with silver ions in solution, forming a precipitate. Any solution containing halide ions will react this way, and any solution containing silver ions can be used as the REAGENT.

after removing spectator ions

Page 3

12ChF321 Group 7 Typically silver nitrate solution is used. It is acidified using a few drops of nitric acid before the test is done to prevent other ions such as carbonate or hydroxide interfering and producing a precipitate. e.g. AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq) Note: In this example the sodium ions and the nitrate ions are spectators. The IONIC equations for the reactions taking place are: Ag+(aq) + Cl-(aq) AgCl(s) Ag+(aq) + Br-(aq) AgBr(s) Ag+(aq) + I-(aq) AgI(s) white precipitate cream precipitate yellow precipitate A

precipitate is a positive test that a halide ion is present. The colour of the precipitate may be enough to identify the halide, especially if precipitates of all three are available to compare. A further test is commonly used to decide which halide formed the precipitate, using ammonia solution A precipitate of silver chloride will RE-DISSOLVE in dilute ammonia solution A precipitate of silver bromide will not re-dissolve in dilute ammonia but will redissolve in CONCENTRATED ammonia solution A precipitate of silver iodide won't redissolve even in concentrated ammonia solution.

Reactions of Group 7 DISPROPORTIONATION An interesting effect is seen when halogens reacts with water, or with cold dilute sodium hydroxide, known as disproportionation. Definition: Disproportionation is a reaction in which an element is simultaneously oxidised and reduced.

Reaction of chlorine with water Chlorine is added to drinking water and swimming pool water in order to purify it by killing harmful micro-organisms. The right amount of chlorine must be added since too much chlorine would be toxic to larger organisms (i.e. us) not just to the bugs !

Page 4

12ChF321 Group 7 Chlorine reacts with the water according to the following equation:

hydrochloric acid Cl2(g) + H2O(l) HCl(aq) reduction +1 -1 0 oxidation +

chloric acid HClO(aq) +1 +1 -2 oxidation numbers

The resulting solution is acidic because both HCl and HClO are acids, splitting up in solution to produce H+ ions. The ClO-(aq) ion is a powerful oxidizing agent and it is this which kills the micro-organisms. Disadvantages of chlorinating drinking water chlorine gas is toxic, an escape of the gas could be hazardous to people organic material in the water, e.g. hydrocarbons, could react and become chlorinated hydrocarbons. These may be damaging to health e.g. carcinogens. Reaction of chlorine with cold dilute sodium hydroxide This is the reaction used commercially to produce bleach. Bleach is an aqueous solution of sodium chloride and sodium chlorate(I). The reaction is: Cl2(g) + 2 NaOH(aq) NaCl(aq) + NaClO(aq) + H2O(l) 0 -1 +1 The bleaching action occurs because the ClO- ion is a powerful oxidizing agent, reacting with dyes to oxidize them, and itself becoming reduced to Cl- ions. N.B. Similar disproportionation reactions happen with the other halogens. Reaction of chlorine with hot concentrated sodium hydroxide Under these conditions, chlorine reacts differently, forming sodium chlorate(V), NaClO3. This is used as a weedkiller. 3 Cl2 + 6 NaOH NaClO3 + 5 NaCl + 3 H2O As before, disproportionation occurs in this reaction, with chlorine changing oxidation number from 0 to +5 and -1.

Page 5