Halogens

Chlorine
Chlorine was first discovered by skill in 1774 when he heated some concentrating hydrochloric acid with
manganese (IV) oxide. In 1810, Devy named the gas chlorine, a derivative of the Greek word chloride
meaning greenish-yellow

Chlorine does not occur free in nature because it is too reactive. it is usually found in the combined state
as chlorides. The most abundant of these is sodium chloride or common salt which is found both in the
sea and as salt deposits.

Laboratory preparation
 Using Manganese (IV) oxide: heat a mixture of manganese (IV) oxide and concentrated
hydrochloric acid the acid is oxidized to liberate chlorine.
MnO²(s) + 4HCl(aq)----heat----->MnCl²(aq) + 2H²O(l) + Cl²(g)
Ionically,
Mn⁴+(O²-)2(s) + 4H+(aq) + 2Cl-(aq)---->Mn²+(aq) + 2H²O(l) + Cl²(g)
Alternatively,add concentrated H²SO⁴ to a mixture of NaCl and MnO². On heating, the acid
reacts with NaCl to give HCl which is then oxidized by the MnO⁴ to liberate chlorine..
2NaCl(s) + MnO²(s) + 2H²SO⁴(aq)---->Na²SO⁴(aq) + MnSO⁴(aq) + 2H²O + Cl²(g)
Ionically,
2Cl-(s) + Mn⁴+(O²-)2(s)+4H+(aq)--->Mn²+(aq) + 2H²O +Cl²(g)
 Using Tetraoxomanganate(VII): KMnO4 oxidizes concentrated HCl to liberate Chlorine
2KMnO⁴(aq) + 16HCl(aq)--->2MnCl²(aq) + 2KCl(aq) + 8H²O(l) + 5Cl²
Ionically,
2MnO4-(aq) +16H+(aq) + 10Cl-(aq)--->2Mn²+(aq) + 8H²O(l) + 5Cl²(g)

Industrial Preparation
 Electrolysis of brine
 Electrolysis of the chlorides of molten sodium, magnesium or calcium

The Chlorine is then liquefied and stored,under pressure,in steel cylinders.

Physical properties
 Chlorine is a greenish yellow gas with an unpleasant choking smell
 It is moderately soluble in water.About 2.3 cm³ of it will dissolve in 1.0cm³ cube of water at
S.T.P.
 It is about 2.5 times denser than air
  It can easily be liquefied under a pressure of about 6 atmospheres
 It is poisonous.As little as 20 parts per million of it in the air can damage the mucus lining of our
lungs.

Chemical properties
 By gaining an electron, usually from the metals of group 1 and 2 ,to form a negative ion, Cl-, as
in electrovalent compounds like NaCl and CaCl2.
 By sharing a pair of electrons in a single covalent bond with another atom, having a fairly similar
electronegative value as in gaseous chlorine,Cl-Cl and Hydrogen chloride,H-Cl.

Displacement of other halogens: With the exception of fluorine, chlorine can displace any of the other
halogens from solutions of their respective acids and salts .This is because it is more reactive than the
halogen it replaces as indicated by its electrode potential value.

Displacement occurs when chlorine gas is bubbled into the appropriate solutions e.g

Cl²(g) +NaBr(aq)--->2NaCl(aq) + Br²(l)

Direct combination with other elements

 With metals: Metals reacts readily with chlorine especially when heated to form the
corresponding chlorides.
2Na(s)+ Cl²(g)---->2NaCl(s)
Anhydrous metallic chlorides such as iron(III), aluminium and tin (IV) chloride are prepared by
direct combination.

Note: when a metal forms more than one chloride the higher chloride is usually formed e.g in the case
of Iron,Iron(III) chloride is formed and not Iron (II) Chloride.This is due to the oxidizing nature of
Chlorine.

 With non-metals: with the exception of noble gases oxygen nitrogen and carbon all other non
metals burn in chlorine to produce the corresponding chlorides. Hydrogen and chlorine combine
exclusively in bright sunlight, although the reaction is slower in diffused light. The combination
reaction between these gases can be shown by introducing a jet or of burning hydrogen into a
gas jar of chlorine.As the reaction proceeds ,the greenish yellow colour of chlorine diminishes in
intensity as misty fumes of HCL appear.
H²(g) + Cl²(g)---->2HCl(g)

Reactions with hydrogen

 With hydrocarbons: a piece of filter paper saturated with warm turpentine (C¹⁰H¹⁶) will rapidly
catch fire in a jar of chlorine for misty and Misty fumes of HCL.

C¹⁰H¹⁶(l) + 8Cl²(g)---->10C(s) + 16HCl(g)

Chlorine also removes hydrogen from burning hydrocarbons like wax candle petrol or maintain to form
hydrogen chloride fumes and soots. Under controlled conditions, substitution reactions occur. In such
reactions,chlorine reacts with saturated hydrocarbons to produce chlorinated hydrocarbons and HCL

CH⁴(g) + Cl²(g)--->CH³Cl(g) + HCl(g)

Methane. Chloromethane

 With Ammonia: Chlorine will remove hydrogen from ammonia with the formation of nitrogen
and hydrogen chloride, the latter then combines with excess ammonia to form ammonium
chloride.

2NH³(g) + 3Cl²(g)--->N²(g) + 6HCl(g)

HCl(g) + NH³(g)---->NH⁴Cl(s)

 With Hydrogen Sulphide: when Chlorine and Hydrogen sulfide are mixed, yellow deposit of
sulphur is formed as a result of the oxidation of the sulphide by chlorine.
H²S(g) + Cl²(g)---->2HCl(g) +S(s)
 With water: Chlorine water, made by bubbling chlorine through water, gives off oxygen when
exposed to sunlight. This is due to the formation of oxochlorate(I) acid which decomposes slowly
to give hydrogen chloride and oxygen
Cl²(g) + H²O(l)--->HCl(aq) + HOCl(aq)
2HOCl(aq)--sunlight--->2HCl(aq) + O²(g)

As an oxidizing agent

 With iron (II) salts:Chlorine oxidizes a solution of green iron (II)chloride to yellow iron (III)
chloride.
2FeCl²(aq) + Cl²(g)--->2FeCl³(aq)
Ionically,
2Fe²+(aq) + Cl²(g)---->2Fe³+(aq) + 2Cl-(aq)
 With tetraoxosulphate (IV) ion: When bubbled through a freshly prepared solution of
trioxosulphate (IV) acid,chlorine oxidizes the trioxosulphate (IV) ion to tetraoxosulphate (VI)
acid.
H²SO³(aq) + H²O(l) + Cl²(g)--->H²SO⁴(aq) + 2HCl(aq)
Ionically,
SO3²-(aq) + H²O(l) + Cl²(g)--->SO4²-(aq) + 2H+(aq) + 2Cl-(aq)

As a bleaching agent

Chlorine is a common bleaching agent in the presence of water. It bleaches most dyes and inks except
those containing carbon .For example, printers ink. The bleaching action of chlorine is due to its ability
to react with water to form of oxochlorate(I)acid. The latter decomposes to release oxygen which
oxidizes the dye to form a colourless compound.

HOCl(aq)--->HCl(aq) +[O]

Dye(coloured) + [O]--->(Dye +O)( colourless)

Reaction with alkalis

 With dilute alkali solutions: when chlorine is bubbled through a cold dilute solution of sodium
hydroxide a pale yellowish mixture of the oxochlorate(I) and chloride of the metal is formed.
Cl²(g) + 2NaOH(aq)--->NaOCl(aq) + NaCl(aq) + H²O(l)
Sodium oxochlorate(I)
Ionically,
Cl²(g) + 2OH-(aq)--->OCl-(aq) + Cl-(aq) + H²O(l)
Bleaching powder is produced by bubbling chlorine through a freshly prepared solution of
slaked lime
Cl²(g) + Ca(OH)2(s)--->CaOCl².H²O(s)
Slaked lime. Bleaching powder
 With concentrated alkali solutions: If chlorine is bubbled through a hot concentrated solution
of sodium hydroxide a mixture of the trioxochlorate(V) and chloride of the metal is formed
3Cl²(g) + 6NaOH(aq)--->NaClO3(aq) + 5NaCl + 3H²O(l)
Sodium trioxochlorate(V)
Ionically,
3Cl²(g) + 6OH-(aq)--->ClO3-(aq) + 5Cl-(aq) + 3H²O(l)

Test for Chlorine

 Damp blue litmus paper test: Drop a piece of damp blue litmus paper into a gas jar of the
unknown gas. If the litmus paper turns pink and then becomes bleached the gas is chlorine.
 Starch-iodide paper test: Drop a piece of damp starch iodide paper into the unknown gas if the
paper turns that dark blue then the gas is chlorine. Chlorine turns starch iodide paper blue
because it displaces iodine from the iodide.The iodine liberated then turns the starch blue.
2KI(aq) + Cl²(g)--->2KCl(aq) + I²(s)

Uses

 Chlorine is a powerful germicide because of its oxidising nature .it is used in the sterilization of
water for domestic and industrial use and in the treatment of sewage.
 It is used as a bleaching agent for cotton, linen and wood pulp. it is too strong for bleaching
animal fibres like silk and wool.
 It is used in the manufacture of important organic solvents ,plastic, hydrochloric acid Potassium
trioxochlorate(V) bleaching agents and domestic antiseptics.

Chlorides
The chloride are normal salts formed when metallic ions replace the hydrogen ions in hydrochloric acid
fluorite stone by water except

 Copper(I) chloride,CuCl
 Mercury(I) Chloride,Hg²Cl²
 Silver Chloride,AgCl
 Lead (II) Chloride,PbCl², is in soluble in cold water but dissolves gradually when warmed

Laboratory preparation

 Action of hydrochloric acid or hydrogen chloride on metals: The chlorides of magnesium and
zinc are prepared by the action of dilute hydrochloric acid on the corresponding metals.
Mg(s) + 2HCl--->MgCl²(aq) + H²(g)
Zn(s) + 2HCl--->Zncl² +H²(g)
Anhydrous aluminium chloride and iron (III) chloride are formed by passing dry HCL gas over the
heated metals
2Al(s) + 6HCl(g)---->2AlCl³+ H²(g)
Fe(s) + 2HCl(g)---->FeCl²(s) + H²(g)
 Action of the acid on the oxides,hydroxides or trioxocarbonates(IV) of metals:The chlorides of
potassium, sodium and calcium are prepared by neutralizing their hydroxides with dilute
hydrochloric acid or by adding the acid to their oxides or trioxocarbonate (IV).
2HCl(aq) + K²CO³(aq)--->2KCl(aq) + H²O(l)
HCl(aq) + NaOH(aq)--->NaCl(aq) + H²O(l)
2HCl(aq) + CaO(s)--->CaCl²(aq) + H²O(l)
Copper is too inactive to react with dilute hydrochloric acid. Instead copper (II) chloride is
prepared by the action of the acid on copper (II) oxide or trioxocarbonate (IV).
2HCl(aq) + CuO(s)--->CuCl²(aq) + H²O(l)
2HCl(aq) + CuCO³---->CuCl²(aq) + H²O(l) + CO²(g)
 Double Decomposition: Metallic lead ,silver and Mercury are also too inactive to react with
dilute hydrochloric acid .Since their chlorides are insoluble, they are usually prepared by double
decomposition .Mercury (II) chloride, however, cannot be prepared by this method.
Pb(NO³)2(aq) + 2KCl(aq)--->PbCl²(s) + 2KNO³(aq)
AgNO³(aq) + NaCl(aq)--->AgCl(s) + NaNO³(aq)
Hg(NO³)2(aq) + 2NaCl(aq)--->Hg²Cl²(s) + 2NaNO³(aq)
 Direct combination of the metal with chlorine: Under appropriate conditions, chlorine can react
with any metal to produce the respective chlorides. For example, iron (III) chloride and Mercury
(II) chloride can be prepared by passing a steam of dry chlorine over heated iron wire and
Mercury respectively.
2Fe(s) + 3Cl²(g)---->2FeCl³(s)
Hg(l) + Cl²(g)---->HgCl²(s)
Methods of preparing chlorides
Metal Method Property of the metal
K, Na, Ca Action of dilute hydrochloric Attacked by dilute hydrochloric acid and
acid on their oxides, hydroxides chlorine
and trioxocarbonate (IV)

Mg. Al. Zn. Fe Action of dilute hydrochloric Attacked by dilute hydrochloric acid and
acid on the metals,their oxides chlorine
and trioxocarbonates
(IV).Action of chlorine on the
metal for iron (III) chloride.

Pb By double decomposition

Cu Action of dilute hydrochloric

acid on the oxide,
trioxocarbonate(IV)

Hg By double decomposition for Attacked by chlorine but not by dilute

Mercury (II) chloride and by the hydrochloric acid
action of chlorine on metal for
Mercury (II)

Ag By double decomposition

Au By the action of chlorine on the

metal

Recovery of chlorides from their solutions

Chlorides are not decomposed by heat. Hence,they can be recovered by evaporating their solutions to
dryness.Sometimes,they are also prepared from their solutions by crystallization.

Properties

 Action of heat: chlorides are not decomposed by heat. They are used in flame tests where the
metals are identified by the colours of their flames.
 With tetraoxosulphate(VI)acid: all chloride react with hot concentrated H²SO⁴ to produce HCl.
2Cl-(s) + (H+)2SO4²-(aq)--->SO4²-(aq) + 2HCl(g)
When a metallic chloride is heated with concentrated H²SO⁴ and a strong oxidizing agent chlorine is
produced.

2Cl-(s) + Mn⁴+(O²-)2(s) + 4H+(aq)--->Mn²+(aq) + 2H²O(l) + Cl²(g)

Test for soluble chlorides

 Acidify the test solution with excess dilute trioxonitrate (V) to prevent the precipitation of other
salts and then add a few drops of silver trioxonitrate(V). A white precipitate of silver chloride
which readily dissolves in aqueous ammonia indicates the presence of a chloride.
Ag+NO3-(aq) + Cl-(aq)--->AgCl(s) + NO3-(aq)
This test can also be carried out with lead (II) trioxonitrate (V), a white precipitate of lead (II)
chloride which dissolves when heated and reappears when cooled indicates the presence of a
chloride.
Pb²+(NO3-)2(aq) +2Cl-(aq)--->PbCl2(s) + 2NO3-(aq)

The Halogen Family

Besides chlorine,the halogen family includes fluorine ,bromine ,iodine and astatine.Fluorine is
the most reactive element among the halogens and is in many ways unique .Astatine is
radioactive and it is made artificially. Bromine and iodine are chemically very similar to chlorine

Fluorine

Fluorine does not occur in free state in nature because of its high reactivity instead it is found mainly in
minerals like cryolite,3NaF.AIF³ and flourspar,CaF².

Preparation

By electrolysis: the electrolyte used in the solution of potassium fluoride in anhydrous hydrogen
fluoride.In order to resist attack by the Fluorine produced, carbon is used as the anode and a steel vessel
as cathode. Water must not be present because it will react with chlorine formed.

Properties

 Fluorine is a poisonous yellow gas with an irritating smell

 It is the most reactive elements found on Earth
 Most metals catch fire in fluorine and even inactive metals like gold and platinum are attacked,
if heated in the stream of the gas.
 It combines directly with all other non metals except nitrogen oxygen helium neon and argon to
form fluorides like PF⁵ and SF⁶.
 Fluorine reacts vigorously with any compound containing hydrogen because of its great affinity
for hydrogen.Hydrogen and fluorine combine explosively to form hydrogen fluoride.
 Fluorine dissolves readily in water to form hydrofluoric acid which unlike the other hydrohalic
acids is only mildly acidic.
2H²O(l) + 2F²(g)--->4HF(l) + O²(g)
 Fluorine is the most electronegative element and so it is the strongest oxidizing agent
  It can display all of the halogens form aqueous solutions of their compound
 It can also react with most reducing agents and elements even noble gases like Krypton and
xenon.
Xe(g) + 2F²(g)--->XeF⁴(s)

Uses

 Fluorine and hydrogen fluoride are used to make uranium hexafluoride which is used in
separating the isotopes of uranium.
 In minute quantities ,sodium fluoride is used for the fluoridation of drinking water while tin (II)
fluoride is used in many toothpaste to prevent tooth decay.
 Hydrofluoric acid is used in etching glass and in cleaning steel.
 Some fluorides and other fluorine compounds also have a wide variety of uses example as a
refrigerant, anaesthetic, non-stick agent, insulator and so on.

Bromine, Iodine and their Salts

Bromine and iodine were found by Courtois(1812) and Ballard(1826) respectively.Like chlorine, they
usually occur naturally in the combined state. Bromides such as those of potassium,sodium and
magnesium occur in seawater and in salt deposits but they are not as abundant as the chloride. Iodides
occur in minute concentration in seawater.They are also found as organic compounds in some seaweeds
and as deposits of sodium and calcium trioxonitrate (V) in association with sodium trioxonitrate (V).

Preparation

Some bromine is obtained from saltwells but most of the world's supply is obtained from seawater. The
water is first acidified and the chlorides which are less soluble are crystallized out. Chlorine is then used
to displace bromine from the bromide solution.

Cl²(g) + 2Br-(aq)--->2Cl-(aq) + Br²(l)

Some iodine is extracted from seaweeds but most of it is obtained from sodium or calcium
trioxoiodate(V) by treatment with sodium hydrogen trioxosulphate (IV).

In the laboratory bromine and iodine are prepared by the oxidation of the appropriate halides. The
gases are evolved when the halides are heated with manganese (IV) oxide and concentrated
tetraoxosulphate (VI) acid.

2KBr(s) + 3H²SO⁴(aq) + MnO²(s)--->2KHSO⁴(aq) + MnSO⁴(aq) + 2H²O(l) + Br²(g)

2KI(s) + 3H²SO⁴(aq) + Mno²(s)--->2KHSO⁴(aq) + MnSO⁴(aq) + 2H²O(l) + I²(g)

Properties of bromine and iodine

 They are all non metals

  They form poisonous vapours which exist as diatomic molecules
 The combine with hydrogen to form very soluble gases which dissolve in water to yield acidic
solutions
 They form constant boiling mixtures when distilled

Test for bromide and iodide ions

 With tetraoxosulphate (VI)acid: hit some of you will own solid with a little concentrated
tetraoxosulphate VI acid.

If bromine is present,white fumes of hydrogen bromide and brown fumes of bromine will be evolved.If
iodine is present,purple fumes of iodine will be evolved.

 With silver trioxonitrate (V): add some dilute trioxonitrate (V) acid and silver trioxonitrate (V)
solution to the unknown solution.

If a bromide is present a pale yellow precipitate of silver bromide will be formed. if an Iodine is present a
yellow precipitate of silver iodide will be formed.

 Displacement reaction: add chlorine water followed by a small quantity of tetrachloromethane

an unknown solution

If a bromide is present,it will be oxidised to free bromine which will dissolve in the organic layer to give
it a brown colour. If an iodide is present, a similar reaction produces a purple colour due to the presence
of free iodine in the organic layer.

Test for Iodine

Add a drop of the unknown solution to some starch solution, if iodine is present a dark blue coloration
appears due to the formation of an iodine starch complex. This test is sensitive even when only a few
parts per million of iodine is present.

Uses of Iodine and bromine

 Bromine is used in the manufacture of 1,2-dibromoethane, a petrol additive. it is added to

convert the lead in petrol to lead (II) bromide which is then removed through the exhaust. This
prevents lead from being deposited in the engines of motor vehicles.
 Bromine is also used in making dyestuffs ,silver bromide which is used on photographic film and
fire retardants.
 Iodine is used in making dyes for colour photography and pharmaceutical chemicals.
 A dilute solution of iodine in ethanol which is known as tincture of iodine is widely used as an
antiseptic.
 Iodine is used in the treatment of simple goitre, a condition which is caused by a deficiency of
iodine in our diet.

Properties of the halogens

  Electronegative nature
 Oxidising ability
 Tendency to enter into chemical combinations and attain stable octets by gaining an electron to
form a univalence ion eg F- or forming single covalent bonds as in F².

Comparing the properties of chlorine, bromine and iodine

Chlorine(Cl²) Bromine(Br²) Chlorine(Cl²)

Physical Greenish yellow Dark red poisonous Black crystalline solid

state,colour,smell and poisonous gas irritating liquid volatile with On heating sublimes,to
nature smell irritating smell form purple
fumes,poisonous.

Relative density(of 1.9 3.2 4.9

solid)/gcm-³

Melting point/⁰c -102 -7 114

Boiling point/⁰c -34 59 184

Solubility Moderately soluble in Slightly soluble in water Sparingly soluble in

water to yield acidic to yield acidic solution water but soluble in
solution of HCl and of HBr and HBrO Ether, ethanol and
HClO potassium iodide

Electronegativity and Very electronegative Moderately Less electronegative

reactivity and reactive electronegative and and reactive
reactive

Affinity for hydrogen Combines explosively in Combines on heating or Combines reversibly at

sunlight in the presence of a 400⁰c in the presence of
platinum catalyst a platinum catalyst

Reactions with metals Vigorous Moderately vigorous Less vigorous

and non metals

Reactions with dilute Yields chlorides and Yields bromides and Yields iodides and
acids oxochlorates(I) oxobromates(I) oxoiodates(I)

Reactions with Yields chlorides and Yields bromides and Yields iodides and
concentrated alkalis trioxochlorates(V) trioxobromates(V) trioxoiodates(V)
Bleaching action Strong Weak -----------------

Oxidising action Strong Moderate Weak

Displacement reaction Displaces bromine and Displaces iodine from -----------

iodine from bromides iodides
and iodidesrespectively

Hydrogen Halide Colourless gas,denser Colourless gas denser Colourless gas denser
than air, dissolves to than air dissolves to than air dissolves to
give an acidic constant give an acidic constant give an acidic constant
boiling mixture boiling mixture boiling mixture

Silver Halide White solid,soluble in Pale yellow solid, Yellow solid, insoluble
aqueous ammonia, sparingly soluble in in aqueous ammonia,
reduced to silver by aqueous ammonia, reduced to silver by
light reduced to silver by light
light

Thermal stability Very stable to heat Moderately stable to Less stable to heat
heat

Reducing power Low reducing power Moderate reducing High reducing power
power

Note: Silver halides have different degrees of solubility in ammonia.Silver chloride is soluble in
aqueous ammonia while silver bromide and silver iodide are not.In order to differentiate the latter
two, some chlorine water is added to both the halides followed by a little tetrachloromethane.Free
bromine and iodine will go into the organic layer to give a brown and a purple colour respectively.