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Characteristic Properties of the Halogens

Learning Outcome
describe the trends in volatility and colour of chlorine, bromine and iodine interpret the volatility of the elements in terms of van der Waals forces

Describe the relative reactivity of the elements as oxidising agents


describe and explain the reactions of the elements with hydrogen (i) describe and explain the relative thermal stabilities of the hydrides
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(ii) interpret these relative stabilities in terms of bond energies

Learning Outcome

describe and explain the reactions of halide ions with (i) aqueous silver ions followed by aqueous ammonia (ii) concentrated sulfuric acid outline a method for the manufacture of chlorine from brine by a diaphragm cell describe and interpret in terms of changes of oxidation number the reaction of chlorine with cold, and with hot, aqueous sodium hydroxide

explain the use of chlorine in water purification


recognise the industrial importance and environmental significance of the halogens and their compounds (e.g. for bleaches, PVC, halogenated hydrocarbons as solvents, refrigerants and in aerosols) 3

Introduction
Group VIIA elements include
fluorine chlorine bromine iodine

halogens (Salt producer)

astatine
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Introduction
Astatine
chemistry not much known radioactive the total amount present in the Earth's crust is probably less than 30 g at any one time.

High Electronegativity / Electron Affinity


highest among the elements in the same period have high tendency to attract electrons

strong oxidizing agents

High Electronegativity / Electron Affinity


-1 is the most common oxidation state of halogens in their compounds Ionic : NaF, NaCl, NaBr, NaI

Covalent :

HF, HCl, HBr, HI

Variable Oxidation State


All halogens (except fluorine) can expand their octet of electrons by utilizing the
vacant,

energetically low-lying
d-orbitals.

Fluorine (1) the most electronegative element only one unpaired p electron available for bonding

oxidation state is limited to 1

Fluorine (1) cannot expand its octet

no low-lying empty d orbitals available the energy required to promote electrons into the third quantum shell is very high
Absence of HFO, HFO2, HFO3, HFO4
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2. Colour becomes darker down the group

Halogen

F2

Cl2

Br2

I2

Colour

Pale yellow

Greenish Reddish yellow brown

Violet black

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chlorine

Appearances of halogens at room temperature and pressure: chlorine


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bromine Appearances of halogens at room temperature and pressure: bromine


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iodine Appearances of halogens at room temperature and pressure: iodine


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Colour
Fluorine atom
has the smallest size appears yellow (the unabsorbed radiation)

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Colour
Atoms of other halogens
larger sizes absorb radiation of lower frequency

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Colour
Iodine
absorbs the radiation of relatively low frequency

appears violet

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Colour
Halogens
different colours when dissolved in different solvents

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Colours of halogens in pure form and in solutions


Colour Halogen in pure form F2 Pale yellow in water Pale yellow

Cl2
Br2

Greenish yellow
Reddish brown

Pale yellow
Yellow Yellow (only slightly soluble) Brown in KI(aq)

I2

Violet black

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Colour
Halogens
non-polar molecules

not very soluble in polar solvents (such as water)


but very soluble in organic solvents

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(a)

(b)

(c)

Colours of halogens in water: (a) chlorine; (b) bromine; (c) iodine


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2) Variation in Chemical Properties


Reactivity : F2 > Cl2 > Br2 > I2 React by gaining electrons Oxidizing power : F2 > Cl2 > Br2 > I2

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1. Reactions with Sodium


All halogens combine directly with sodium to form sodium halides

the reactivity decreases down the group from fluorine to iodine

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1. Reactions with Sodium


Fluorine
react explosively to form sodium fluoride 2Na(s) + F2(g) 2NaF(s)

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1. Reactions with Sodium


Chlorine
react violently to form sodium chloride 2Na(s) + Cl2(g) 2NaCl(s)

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1. Reactions with Sodium


Bromine
burns steadily in bromine vapour to form sodium bromide

2Na(s) + Br2(g) 2NaBr(s)

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1. Reactions with Sodium


Iodine
burns steadily in iodine vapour to form sodium iodide

2Na(s) + I2(g) 2NaI(s)

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Q.2(a) Variation: bond enthalpy decreases from Cl2 to I2 Reason : The size of atoms and thus the bond length between atoms increases down the group. The shared electron pair is getting further away from the bonding nuclei. weaker bond and lower B.E. F2 has an exceptionally small B.E. because the F atoms are so small that the repulsive forces between lone pairs on adjacent bonding atoms become significant.
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2.1 Reactions with hydrogen X2 + H2(g) 2HX(g)


F2 reacts explosively even in the dark at 200C Cl2 reacts explosively in sunlight Br2 reacts moderately on heating with a catalyst I2 reacts slowly and reversibly even on heating

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Q.3

Explain the extreme reactivity of fluorine in terms of the bond enthalpies of FF and HF bonds.

F2 + H2(g) 2HF(g)
Fluorine has an exceptionally small F-F bond enthalpy.
Thus, the activation energy of its reaction with hydrogen is also exceptionally small. Hydrogen fluoride has the highest bond enthalpy among the hydrogen halides. Thus, the formation of HF from H2 and F2 is the most exothermic. The energy released from the reaction further speeds up the reaction.
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Chlorine removes hydrogen completely from turpentine(C10H16)


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

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Displacement reactions
Cl2(aq) + 2Br(aq) 2Cl(aq) + Br2(aq) Cl2(aq) + 2I(aq) 2Cl(aq) + I2(aq) Br2(aq) + 2I(aq) 2Br(aq) + I2(aq)
More reactive Less reactive

I2(aq) + I(aq) I3(aq)


(yellow)
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(brown)

Reactions of halide ions with halogens


Aqueous solution F Halogen added F2 No reaction A pale yellow solution is formed (Cl2 is formed) Cl2 No reaction No reaction Br2 No reaction No reaction I2 No reaction No reaction

Cl

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Reactions of halide ions with halogens


Aqueous solution Halogen added F2 A yellow solution is formed (Br2 is formed) A yellowish brown solution is formed (I3 is formed) Cl2 A yellow solution is formed (Br2 is formed) A yellowish brown solution is formed (I3 is formed) Br2 No reaction I2 No reaction

Br

A yellowish No brown reaction solution is formed (I3 is formed)

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5.

Disproportionation

Disproportionation is a chemical change in which oxidation and reduction of the same species (which may be a molecule, atom or ion) take place at the same time.

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A. Reactions with Water

HOCl : chloric(I) acid or hypochlorous acid

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B. Reactions with Alkalis


All halogens react with aqueous alkalis

All halogens (except F2) undergoes disproportionation with alkalis In general,


their reactivities decrease down the group

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B. Reactions with Alkalis


The products formed depend on

1. Temperature
2. The type of halogen reacted 3. The concentration of alkali used

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B. Reactions with Alkalis


In general, Halogens react with cold, dilute alkali to give halate(I) ions, halide ions and water X2(aq) + 2OH XO(aq) + X(aq) + H2O(l) Halogens react with hot, concentrated alkali to give halate(V) ions, halide ions and water. 3X2(aq) + 6OH XO3(aq) + 5X(aq) + 3H2O(l)
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B. Reactions with Alkalis


2F2 + 2OH(aq)
very dilute
0 2

20C

+2 1

OF2(aq) + 2F(aq) + H2O(l)

2F2 + 4OH(aq)
concentrated

70C

O2(aq) + 4F(aq) + 2H2O(l)

Being the strongest oxidizing agent, F2 undergoes reduction rather than disproportionation with alkalis.

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Variation in chemical properties of halides


A Comparative study 1. Reactions with conc. sulphuric acid 2. Reactions with conc. phosphoric acid 3. Reactions with silver ion

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Reactions with Concentrated Sulphuric(VI) Acid


Concentrated sulphuric acid non-volatile (b.p. ~330C)

oxidizing

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Fluoride and chloride : KF(s) + H2SO4(l) KHSO4(s) + HF(g) KCl(s) + H2SO4(l) KHSO4(s) + HCl(g)
non-volatile volatile warm warm

Warming is required to speed up the reaction and to drive out the volatile acids

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KF(s) + H2SO4(l) KHSO4(s) + HF(g) KCl(s) + H2SO4(l) KHSO4(s) + HCl(g)


acid salt Acid salt rather than normal salt is formed because HSO4 is a relatively weak acid A convenient way to prepare HCl in the laboratory warm

warm

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KF(s) + H2SO4(l) KHSO4(s) + HF(g) KCl(s) + H2SO4(l) KHSO4(s) + HCl(g)


Observation : White fumes are produced Confirmatory test : Dense white fumes with NH3(aq)
warm

warm

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Bromide: KBr(s) + H2SO4(l) KHSO4(s) + HBr(g)


reduction
warm

2HBr(g) + H2SO4(l) SO2(g) + Br2(g) + 2H2O(l)


oxidation

-1

+6

warm

+4

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Bromide: (1) KBr(s) + H2SO4(l) KHSO4(s) + HBr(g) (2) 2HBr(g) + H2SO4(l) SO2(g) + Br2(g) + 2H2O(l)
warm
warm

Overall reaction : 2(1) + (2) 2KBr(s) + 3H2SO4(l)


warm

2KHSO4(s) + SO2(g) + Br2(g) + 2H2O(l)

Not suitable for preparing HBr


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2KBr(s) + 3H2SO4(l) 2KHSO4(s) + SO2(g) + Br2(g) + 2H2O(l)


Halide Observation Product Confirmatory Test

White fumes are formed A pungent smell is detected A brown gas is evolved on warming
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HBr

Dense white fumes are formed with aqueous ammonia It turns orange dichromate solution green A brown colour is observed when adding hexane

Br

SO2

Br2

iodide: KI(s) + H2SO4(l) KHSO4(s) + HI(g) 2HI(g) + H2SO4(l) SO2(g) + I2(g) + 2H2O(l) 8HI(g) + H2SO4(l) H2S(g) + 4I2(g) + 2H2O(l) HI is strong enough to reduce sulphur to its lowest possible oxidation state
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warm

-1

+6

warm

+4

-1

+6

warm

-2

KI(s) + H2SO4(l) KHSO4(s) + HI(g) 2HI(g) + H2SO4(l) SO2(g) + I2(s) + 2H2O(l) 8HI(g) + H2SO4(l) H2S(g) + 4I2(s) + 2H2O(l)
warm warm

warm

Overall reaction : 10KI(s) + 12H2SO4(l) 10KHSO4(s) + SO2(g) + H2S(g) + 5I2(s) + 4H2O(l) No suitable for preparing HI
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10KI(s) + 12H2SO4(l)
10KHSO4(s) + SO2(g) + H2S(s) + 5I2(s) + 4H2O(l) Observation : A bad egg smell is detected

Confirmatory test : It turns lead(II) ethanoate paper black (CH3COO)2Pb + H2S PbS(s) + 2CH3COOH

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10KI(s) + 12H2SO4(l)
10KHSO4(s) + SO2(g) + H2S(s) + 5I2(s) + 4H2O(l) Observation : Violet fumes are formed and condense when cooled to give a black solid Confirmatory test : A violet colour is observed when adding hexane
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Conclusion : -

Increases down the group

Reducing power : HI > HBr > HCl > HF

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Interpretation:Consider the reaction,

2HX + H2SO4 XX + SO2 + 2H2O


The feasibility of the reaction depends on 1. the strength of HX bond to be broken

the stronger the bond, the less feasible is the rx


2. the strength of XX bond to be formed the stronger the bond, the more feasible is the rx

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2HX + H2SO4 XX + SO2 + 2H2O


The feasibility of the reaction depends on 1. the strength of HX bond

the stronger the bond, the less feasible is the rx


2. the strength of XX bond the stronger the bond, the more feasible is the rx The reaction with HF is least feasible because 1. H-F bond is the strongest

2. F-F bond is exceptionally weak due to repulsion between lone pairs of bonding atoms.
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H-X H-Cl H-Br H-I

B.E.(kJ mol1) 432 366 298

X-X Cl-Cl Br-Br I-I

B.E. (kJ mol1 244 192 152

On moving down the group, both HX bonds and XX bonds become weaker

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2HX + H2SO4 XX + SO2 + 2H2O


The strength of H-X bond is more important Since two H-X bonds have to be broken for each X-X bond formed.

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Reactions with Silver Ions


Aqueous solutions of chlorides, bromides and iodides give precipitates when reacting with acidified silver nitrate solution

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Reactions with Silver Ions


Ag+(aq) + Cl(aq) AgCl(s)
white ppt

Ag+(aq) + Br(aq) AgBr(s) Ag+(aq) + I(aq) AgI(s)

pale yellow ppt


yellow ppt

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AgCl(s)

AgBr(s)

AgI(s)

Colour intensity down the group


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On moving down the group, the size of the halide anions The electron cloud of the anions becomes more easily polarized by Ag+

The halides become more covalent and less ionic


The halides become less soluble in polar solvents like water

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Reactions with Silver Ions


The reaction can be used as a test to show the presence of halide ions.
Different halides give ppt with different colours. Sometimes ambiguous. Confirmatory tests are needed.

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Two confirmatory tests for halides


1.Adding NH3(aq) to the AgX ppt

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AgX(s) dissolve in NH3(aq) due to the formation of soluble complex ions. AgCl(s) + 2NH3(aq) [Ag(NH3)2]+(aq) + Cl(aq) AgBr(s) + 2NH3(aq) [Ag(NH3)2]+(aq) + Br(aq) AgI(s) + 2NH3(aq) No reaction Solubility in NH3(aq) down the group

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Anomalous Behaviour of Hydrogen Fluoride


1. Hydrogen fluoride has abnormally high boiling point and melting point among the hydrogen halides
HX b.p./C
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HF 19.5

HCl 85

HBr 66.4

HI 35

Molecules of all other hydrogen halides held together by weak van der Waals forces only

Formation of the extensive intermolecular hydrogen bonds among hydrogen fluoride molecules
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2.

Acidic Properties of Hydrogen Halides


The acid strength of hydrogen halides decreases in the order:
HI > HBr > HCl >> HF

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Uses of fluorine and its compounds


The glass object to be etched

coated with wax or a similar acidproof material


cutting through the wax layer to expose the glass apply hydrofluoric acid

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Uses of fluorine and its compounds

A glass is etched by hydrofluoric acid


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Uses of Chlorine and its compounds


Polyvinyl chloride, PVC

making electrical insulation, bottles, floor tiles, table cloth, shower curtain, etc.

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Making chlorine bleach


Cl2(g) + 2NaOH(aq) NaCl(aq) + NaOCl + H2O(l)

Disinfectant in sterilizing water and sewage treatment. Extraction of bromine from sea water Cl2(g) + 2Br(aq) 2Cl(aq) + Br2(aq)

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Uses of Bromine and its compounds Manufacture of 1,2-dibromoethane

Air pollutant CH2Br-CH2Br + Pb(C2H5)4 PbBr2 volatile and emitted to air easily
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Uses of Iodine and its compounds Making iodine tincture (antiseptic) I2 in alcohol or KI(aq) Radioactive iodine-131 as tracer in medical diagnosis Iodide is used to make iodized table salt for preventing development of goitre.

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The END

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