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docbthe_halogens updated Mar 3rd 2008

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GCSE-IGCSE-KS4 Science Revision-Chemistry Information Notes on

 Group 7 The Halogens

GCSE Quiz Foundation or HigherEMAIL comment?query

(c) doc b KEYWORDS: astatine * bleach * bromine * chemical characteristics * chlorine * data on the elements * displacement reaction * electrolysis of NaCl * explaining reactivity trend * fluorine * hydrochloric acid * hydrogen halides * iodine * naming halogen compounds * physical characteristicsPVC * reaction of sodium hydroxide and chlorine * reaction with metals * reaction with hydrogen * silver halide photography * uses of chlorine * uses of fluorine, bromine and iodine * uses of hydrogen * uses of sodium chloride * uses of sodium hydroxide * and on separate web pages: GCSE-KS4-IGCSE Group 7 Halogens task/worksheet * Halogen Quizzes * Extra electrochemistry with more on electrolysis


(c) doc b

Note: Using 0 to denote the Group number of Noble Gases is very historic now since compounds of xenon known exhibiting a valency of 8. Because of the horizontal series of elements e.g. like the Sc to Zn block (10 elements), Groups 3 to 8 can also be numbered as Groups 13 to 18 to fit in with the actual number of vertical columns of elements. This can make things confusing, but there it is, classification is still in progress!

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Introduction to the Halogens (see also halogens data table below)

The Halogens are typical non-metals and form the 7th Group in the Periodic Table (the vertical pink column above). 'Halogens' means 'salt formers' and the most common compound is sodium chloride which is found from natural evaporation as huge deposits of 'rock salt' or the even more abundant 'sea salt' in the seas and oceans.

Physical features and important trends down the Group with increasing atomic number (see halogens data table below too) ...

  • typical non-metals with relatively low melting points and boiling points.

  • The melting points and boiling increase steadily down the group (so the change in state at room temperature from gas ==> liquid ==> solid), this is because the weak electrical intermolecular attractive forces increase with increasing size of atom or molecule.

  • They are all coloured non-metallic elements and the colour gets darker down the group.

  • They are all poor conductors of heat and electricity - typical of non-metals.

  • When solid they are brittle and crumbly e.g. iodine.

  • The size of the atom gets bigger as more inner electron shells are filled going down from one period to another.

Chemical features, similarities, and physical property and reactivity trends

  • The atoms all have 7 outer electrons, this outer electron similarity, as with any Group in the Periodic Table, makes them have very similar chemical properties e.g.

    • they form singly charged negative ions e.g. chloride Cl- because they are one electron short of a noble gas electron structure. They gain one negative electron (reduction) to be stable and this gives a surplus electric charge of -1. These ions are called the halide ions, two others you will encounter are called the bromide Br- and iodide I- ions.

    • they form ionic compounds with metals e.g. sodium chloride Na+Cl-. (ionic bonding revision notes page)

    • they form covalent compounds with non-metals and with themselves (see below). The bonding in the molecule involves single covalent bonds e.g. hydrogen chloride HCl or H-Cl. (covalent bonding revision notes page)

  • Note on naming halogen compounds:

    • When combined with other elements in simple compounds the name of the halogen element changes slightly from ...ine to ...ide.

    • Fluorine forms a fluoride (ion F-), chlorine forms a chloride (ion Cl-), bromine a bromide (ion Br-) and iodine an iodide (ion I-).

    • The other element at the start of the compound name e.g. hydrogen, sodium, potassium, magnesium, calcium, etc. remains unchanged.

    • So typical halogen compound names are,  potassium fluoride, hydrogen chloride, sodium chloride, calcium bromide, magnesium iodide etc.

  • The elements all exist as X2 or X-X, diatomic molecules where X represents the halogen atom.

  • A more reactive halogen can displace a less reactive halogen from its salts (halogen displacement description).

  • The reactivity decreases down the group (explanation of halogen reactivity trendn.

  • they are all TOXIC elements (for more detail see uses of Halogens).

  • (c) doc bAstatine is very radioactive, so difficult to study BUT its properties can be predicted using the principles of the Periodic Table and the Halogen Group trends!

  • Details of how to identify halogens and their compounds are on the Chemical Tests page (use the alphabetical list at the top of this other page).

DATA Selected Properties of the Group 7 Halogens (more Group 7 halogens AS-A2 data)

Symbol and Name

Atomic Number Electron arrangement State and colour at room temperature, colour of vapour when heated Melting point Boiling point atom radius pm

F Fluorine

9 2.7 (c) doc bpale yellow gas -219oC, 54K -188oC 85K 64

Cl Chlorine

17 2.8.7 (c) doc bgreen gas -101oC, 172K  -34oC, 239K 99
Br Bromine 35 2.8.18.7 (c) doc bdark red liquid, brown vapour -7oC, 266K 59oC, 332K 114

I Iodine

53 2.8.18.18.7 (c) doc b dark crumbly solid, purple vapour 114oC, 387K 184oC, 457K 133
At Astatine 85

2.8.18.32.18.7

(c) doc b(c) doc bblack solid, dark vapour 302oC 575K 380oC 653K 140
 

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(c) doc b

The Reactivity Order and Displacement Reactions

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 3 don't!).

You can get the observations from the diagrams! A darkening effect compared to a water blank confirms a displacement reaction has happened. Chlorine displaces bromine from potassium bromide and iodine from potassium iodide.  Bromine only displaces iodine from potassium iodide but iodine displaces non of the other two.

On the basis that the most reactive element displaces a least reactive element the reactivity order must be chlorine > bromine > iodine.

Word and symbol equations: e.g. (i)

chlorine + potassium bromide ==> potassium chloride + bromine

Cl2(aq) + 2KBr(aq) ==> 2KCl(aq) + Br2(aq)

Higher GCSE level Oxidation-Reduction Theory

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 ...

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.

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Explaining the Reactivity Trend of the Group 7 Halogen

(c) doc b  F [2.7] + e- ==> (c) doc bF- [2.8]-

(c) doc b Cl [2.8.7] + e- ==> (c) doc bCl- [2.8.8]-

Br [2.8.18.7] + e- ==> Br- [2.8.18.8]-

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 ...

    • the atomic radius gets bigger due to an extra filled electron shell,

    • the outer electrons are further and further from the nucleus and are also shielded by the extra full electron shell of negative electron charge,

    • 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.

(c) doc b


Other Reactions of the Halogens

note: fluorine forms fluorides, chlorine forms chlorides and iodine forms iodides

Reaction with hydrogen H2

  • (c) doc bHalogens readily combine with hydrogen to form the hydrogen halides which are colourless gaseous covalent molecules. Complete covalent bonding details revision notes on another page.

  • 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 the group formula pattern.

Reaction with Group 1 Alkali Metals Li Na K etc.

  • (c) doc bAlkali 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.

  • Complete ionic bonding details revision notes on another page.

Reaction with other metals
  • If aluminium or iron is heated strongly in a stream of chlorine (or plunge the hot metal into a gas jar of chlorine carefully in a fume cupboard) the solid chloride is formed.

  • aluminium + chlorine ==> aluminium chloride(white solid)

    • 2Al(s) + 3Cl2(g) ==> 2AlCl3(s)

  • iron + chlorine ==> iron(III) chloride(brown solid)

    • 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 also illustrate the halogen reactivity series.

(c) doc bThe Industrial Electrolysis of Sodium Chloride Solution or brine

made from concentrated 'rock salt' solution (sodium chloride (brine) electrolysis product uses further on)

(c) doc b

THE ELECTROLYSIS CELL

Summary of the ions involved and what happens to them at the two electrodes.

negative electrode (cathode) product

ions from water ions from salt

positive electrode (anode) product 

hydrogen gas formed H2(g) <==

hydrogen ion H+(aq) changes to <==

chloride ion Cl-(aq) changes to ==>

==> chlorine gas formed Cl2(g)

ion left ==>

OH- Na+

<== ion left in solution

When electricity is passed through the sodium chloride solution (brine) there are three products(1) hydrogen is formed at the negative electrode (-ve cathode), (2) chlorine at the positive electrode (+ve anode) and (3) sodium hydroxide is left in solution (Na+ plus OH-).

Summary equation

  • sodium chloride + water ==> sodium hydroxide + hydrogen + chlorine
  • 2NaCl (aq) + 2H2O (l) + elec. energy ==> 2NaOH (aq) + H2 (g) + Cl2 (g) 
  • (c) doc bThe industrial electrodes must be made of an inert material like titanium which is not attacked by chlorine or alkali.
  • However a simple cell using carbon electrodes can be used to demonstrate the industrial process in the laboratory.
  • The (-) cathode gas gives a squeaky pop with a lit splint - hydrogen. The (+) anode gas turns damp blue litmus red and then bleaches it white - chlorine.
The electrode equation theory and details
  • The (-) cathode attracts the Na+ and H+ ions. The hydrogen ions are reduced by electron (e-) gain to form hydrogen molecules:

  • 2H+(aq) + 2e- ==> H2(g)

  • The (+) anode attracts the OH- and Cl- ions. The chloride ions are oxidised by electron loss to give chlorine molecules:

  • 2Cl-(aq) ==> Cl2(g) + 2e-

  • See Electrochemistry page for more on electrolysis

 

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The Uses of Chlorine, the brine electrolysis products and other halogens and their compounds
Sodium Chloride

NaCl

(c) doc b(c) doc b

CHLORINE

Cl2

(c) doc b(c) doc b

  • All the Halogens are potentially harmful substances and chlorine in particular is highly toxic. It is dangerous to ingest halogens or breathe in any halogen gas or vapour.
  • Chlorine is used to kill bacteria and so sterilise water for domestic supply or in in swimming pools.
  • The sodium hydroxide and chlorine can be chemically combined at room temperature to make the bleach, sodium chlorate(I) NaClO. This is used in some domestic cleaning agents, it chemically 'scours' and chemically 'kills' germs!

    • sodium hydroxide + chlorine ==> sodium chloride + sodium chlorate(I) + water

    • 2NaOH(aq) + Cl2(aq) ==> NaCl(aq) + NaClO(aq) + H2O(l)

  • Organic phenolic chlorine compounds are used antiseptics and  disinfectants like 'dettol' or 'TCP'
  • Organic chlorine compounds are used as pesticides, including the now mainly banned DDT.
  • Chlorine is used in making CFC refrigerant gases/liquids but their production and use are being reduced. They break down in the upper atmosphere and the chlorine atoms catalyse the destruction of ozone O3 which absorbs harmful uv radiation.
  • PVC: Chlorine (from electrolysis of NaCl) and ethene (from cracking oil fractions) are used to make a chemical called chloro(ethene), which used to be called vinyl chloride, this is then converted into the plastic-polymer poly(chloroethene) or PVC, because it is shorthand for the old name polyvinylchloride! (equation below)
    • (c) doc b
    • Poly(chloroethene), old names PVC, from chloroethene (vinyl chloride) is much tougher than poly(ethene) and very hard wearing with good heat stability. so it is used for covering electrical wiring and plugs. It is also replacing metals for use as gas and water drain pipes and has found a use as artificial leather and readily dyed to bright colours! (old names : polyvinyl chloride, shortened to PVC)
  • Liquid organic chlorine compounds are used as dry cleaning or de-greasing solvents.
  • PVC is very tough hard wearing useful plastic and a good electrical insulator and is used for water piping, window frames, part of electrical fittings e.g. plug covers etc.
  • Chlorine is used in the manufacture of potassium chlorate weed killer, KClO3.
(c) doc b(c) doc b

(c) doc b

  • HCl(g => aq) As described above, some of the hydrogen and chlorine from the electrolysis of sodium chloride solution are combined to form hydrogen chloride gas.
    • H2(g) + Cl2(g) ==> 2HCl(g) 
  • This gas is dissolved in water to manufacture hydrochloric acid.
    • HCl(g) + aq ==> HCl(aq) or ==> H+(aq) + Cl-(aq) 
  • This is a very important acid used in the chemical industry to make chloride salts.
(c) doc b

silver salts Ag+X-

  • Silver chloride (AgCl), silver bromide (AgBr) and silver iodide (AgI) are all sensitive to light ('photosensitive'), and all three are used in the production of various types of photographic film used to detect visible light and beta and gamma radiation from radioactive materials.

  • Each silver halide salt has a different sensitivity to light. When radiation hits the film the silver ions in the salt are reduced by electron gain to silver (Ag+ + e- ==> Ag, the halide ion is oxidised to the halogen molecule 2X- ==> X2 + 2e- ).

  • AgI is the most sensitive and used in X-ray radiography, AgCl is the most sensitive and used in 'fast' film for cameras, AgBr is used in most standard photographic films.

The other halogens

FLUORINE F2

BROMINE Br2

IODINE I2

  • Fluorine is used as fluoride salts in toothpaste or added to domestic water supplies to strengthen teeth enamel helping to minimise tooth decay. (e.g. potassium fluoride).

  • Fluorine is used in the manufacture of the tough non-stick plastic PTFE coating of cooking pans.

  • Fluorine is used in manufacture of aerosol propellants and refrigerant gases.

  • Apart from its silver salt use in photography, bromine is used to manufacture organic pesticides and fungicides because of their poisonous nature

  • Organic bromine compounds are used as flame inhibitor chemicals (flame retardants) for plastic products to reduce their flammability and as petrol additives to reduce the buildup of lead in car engines (a use decreasing as 'green' unleaded fuels are becoming more popular).

  • Bromine and iodine are both used in 'halogen' car headlamps.

  • Iodine is used in hospitals in the mild antiseptic solution 'tincture of iodine'.

HYDROGEN H2
  • Hydrogen is used in the manufacture of ammonia (for fertilisers), margarine (by adding hydrogen to unsaturated fats) and hydrochloric acid.

  • It isn't a halogen, but it is made from the electrolysis of salt solution.

SODIUM HYDROXIDE

NaOH

  • Sodium hydroxide is used in the manufacture of soaps, detergents, paper, ceramics and to make soluble salts of organic acids with low solubility in water (e.g. soluble Aspirin).
  • It isn't a halogen compound, but it is made from the electrolysis of salt solution.
  • The sodium hydroxide and chlorine can be chemically combined at room temperature to make the bleach, sodium chlorate(I) NaClO. This is used in some domestic cleaning agents, it chemically 'scours' and chemically 'kills' germs!

    • sodium hydroxide + chlorine ==> sodium chloride + sodium chlorate(I) + water

    • 2NaOH(aq) + Cl2(aq) ==> NaCl(aq) + NaClO(aq) + H2O(l)top index

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docbthe_halogens updated Mar 3rd 2008

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