GROUP 17- Cl, Br, I

By: Tea-bun Sam Thongss Huan Yih

Known as the p-block elements or halogens(salt formers) exits as simple covalent molecule, X2 non-metallic elements. High reactivity, found in combine state in nature. Astatine do not occur naturally. Unstable and radioactive. - synthetically made in laboratory. Commercially, - Chlorine is manufactured by the electrolysis of brine. - Bromine is manufactured by oxidation of Br- ions in seawater by chlorine. - Iodine is obtained by reducing sodium iodate(V) by sodium hydrogen sulphate(IV) Laboratory, Cl2, Br2, I2 are prepare by oxidising the appropriate halide ions using manganese(IV) oxide and concentrated sulphuric(VI) acid.

F Cl Br I At

        

Atomic radius increase Electronegativity decrease Electron affinity decrease M.P & B.P increase Enthalpy of vaporisation increase Volatility decrease Metallic property of elements increase Colour intensity increase Bond energy decrease

 the nuclear charge and screening effect increase down the group Elements Atomic radius Ionic radius Cl 0.099 0.181 Br 0.114 0.196 I 0.183 0.216

Element Electronegativity

Cl 3.0

Br 2.8

I 2.5

Column1
3.2 3 2.8 2.6 2.4 2.2 Cl Br I

Smaller size=higher nuclear charge=stronger the attraction of the covalent bond Hence going down the group, the electronegativity decrease.

Element Melting point Boiling point H vaporisation/kJ mol-1

Cl -101.0 -34.7 +10.2

Br -7.2 58.8 +15.0

I 114.0 184.0 +30.0

Physical state (298k)

Pale yellow gas

Reddish brown liquid

Black solid

the intermolecular increase as the total number of electron increase down the group. hence increasing the m.p, b.p and enthalpy of vaporisation ( volatility decrease ) In I2 the van der Waals force are strong enough to sustain as solid, hence the metallic property increase as well as the colour intensity.

Chemical properties
of the halogen

Recap !
The colour intensity increases! Volatility decreases ! E0 becomes less positive, more negative Oxidising power
Going down The group from Cl2 Br2 I2

REACTION OF GROUP 17

Reaction of Elements with hydrogen and the relative stability of the halides

Reactions of chlorine with NaOH

Reaction of halide ions

Reaction of Cl2 , Br2 , I2 with hydrogen

General equation : H2 + X2 2HX(g)
F

The order of reactivity between halogens and hydrogen descending the group

Cl Br

Reaction become less vigorous Reaction rates become slower

I At

Reaction of Cl2 , Br2 , I2 with hydrogen

H2(g) +F2(g) 2HF(g) Rapid reaction Fluorine explodes with in low temperature and in the dark to form Hydrogen Fluoride H2(g)+ Cl2(g) 2HCl(g) Explode when reaction exposed to sunlight /ultraviolet light H2(g)+ Br2(g)

pt 200c

2HBr(g)

React only at high temp(200oc) and in presence of Pt catalyst

Thermal stability of hydrogen halide

Reaction 2HCl 2HBr 2HI H2 + Cl2 H2 + Br2 H2 + I2 Condition 20000c 6000c 2000c

The stability of HX towards decomposition decreases in the order The result shows the thermal stability of hydrogen halides decreases with increasing relative molecular mass. HCL > HBR > HI

Thermal stability of hydrogen halide

Atomic size of halogens Bond length of H-X Bond strength Thermal stability

Going down The group

The decomposition of hydrogen halides involve bond breaking of the H-X bonds. The longer the bond length the weaker the bond the more easily the bond can be broken .

REACTIONS of hydrogen halide

Aqueous Ag+ ions Conc Sulphuric Acid

1. Reaction with Aqueous Ag+ ions

Cl- (aq)
AgNO3(aq)

AgCl(s) dilute NH3(aq) [Ag(NH3)2]+(aq)

White ppt dilute NH3(aq)

Insoluble [Ag(NH3)2]+(aq)

Br- (aq)

AgNo3(aq)

AgBr(s)
Pale yellow ppt

Conc NH3(aq)

dilute NH3(aq)

Insoluble

I- (aq)

AgNo3(aq)

AgI(s)
yellow ppt

Conc NH3(aq)

Insoluble

REACTIONS of hydrogen halide

1. Reaction with Concentration Sulphuric acid.

HCl(g)

Hot, concentrated H2SO4

HBr(g) + Br2(g)
Reddish brown

HI(g) + I2(g)
Purple fumes

H2 SO4 reduced to SO2

Concentrated H2SO4 act as an oxdising agent.

NaCl(s) +H2 SO4 (l)

NaHSO4 (s)+ HCl(g)

When sodium chloride is heated with concentrated sulphuric acid, HCl gas is produced.

NaBr(s) +H2SO4 (l) HBr(s) +H2SO4 (l) 2Br-(s) +3H2SO4(l)

NaHSO4 (s)+ HBr(g) Br2(g) + H2O(l) + SO2(g)

. .

HSO4(s)+ Br2(g) + SO2(g) + H2O(l)

In this reaction, Br- is oxidised to Br2 to H2SO4 is reduced SO2

NaI(s) +H2SO4 (l) 2HI(g) +H2SO4 (l) 2HI(g) +H2SO4 (l) 2I-(s) +3H2SO4(l) 2I-(s) +9H2SO4(l)

NaHSO4 (s)+ HI(g)

I2(g) + 2H2O(l) + SO2(g) 4I2(g) + 4H2O(l) + H2S(g) HSO4(s)+ I2(g) + SO2(g) + H2O(l)
or

Further oxidation

8HSO4(s)+H2S + 4I2(g) + SO2(g) + 4H2O(l)

In this reaction I- is oxidised to I2 andH2SO4 is reduced to H2S and SO2.

ClBrI-

Ionic size increases Reducing power increases

REACTIONS of hydrogen Reaction of Chlorine with

aqueous sodium Hydroxide.

Cold dilute NAOH

Cl2
Hot, concentrated NAOH

NaCl + NaClO+ H2O NaCl + NaClO3 + H2O

This reaction is a Disproportionation reaction. A Disproportionation reaction is a reaction in which a particular molecule is simultaneously oxidised and reduced . Example : Cl2 Cl2 (g)+ 2OH (Aq) Cl (aq)+ ClO (aq) + H2O(aq)

Cl2 (g)+ NaOH (Aq)

NaCl + NaClO3 + H2O

The halogen atoms with valence shell configuration of ns2np3, short of one electron to achieve octet configuration. The atoms can achieve octect configuration by:

The halogens are slightly soluble in water. But iodine is very soluble in aqueous potassium iodide due to the formation of the soluble I3ion. In aqueous solution, Chlorine is almost colourless Bromine and iodine are yellowish/ orange In CCl4, Bromine is reddish brown Iodine is violet.

Halogen as Oxidising Agents

Element Standard electrode potential/ V Cl +1.36 Br +1.09 I +0.54

The S.E.P become less positive showing that the oxidising power of the halogens decrease down the Group. This is because the size of the element increases and the electron affinity as well as the hydration energy decreases.

Reaction of the halogen with hydrogen

The halogens react with hydrogen to produce the hydrogen halides, which are colourless gas but form white fumes in moist air. H2(g)+X2(g) 2HX(g) In the reaction, hydrogen is oxidised from an oxidation state of zero to +1. Going down the Group, the oxidising power of the element decreases hence the reactivity with hydrogen also decreases.

Reactions of Chlorine with Alkali

Reactions of aqueous halide ions with silver nitrate solution

Reactions of solid halides with concentrated sulphuric (VI) Acid

All halogens (expect flourine) can exhibit variable oxidation states in their compounds. Oxidation state Example
-1 0 +1 +3 +5 +7 NaCl , HCl Cl2 Cl2O , NaOCl HClO2 , NaClO2 HClO3 , KClO3 KClO4 , Cl2O7

The oxo-acids of chlorine are : HOCl , HClO2 , HClO3 , HClO4 All the oxo-acids dissociate in water. The strength of acids depends on the strength of the O --- H bond in molecule. oxygen is more electronegative than chlorine, the O --- H bond is weaken by the I inductive effect of the oxygen atoms bonded to the chlorine atoms. The inductive effect increase in the order HOCl < HClO2 < HClO3 < HClO4 because the number of oxygen atoms bounded to the chlorine increase causing the strength of the oxo-acids to increase in the same order.

The Mercury Cathode Cell 1. Chlorine is produced by the electrolysis of brine (conc. sodium chloride) using mercury as cathode and graphite as anode.

Cathode (mercury) 2 Na(l) 2 Na+(aq) + 2e Na(l) + Hg(l) Na/Hg(l) 3. The sodium produced at the cathode combines with mercury to form unreactive Na/Hg. The Na/Hg is directed into another steel tank where it reacts with water to produce sodium hydroxide and hydrogen gas. The mercury is recycle. 2 Na/Hg(l) + 2 H2O(l) 2 NaOH(aq) + H2(g) + 2 Hg(l) 4. Disadvantage Indiscriminate disposal will lead to mercury poisoning of living things.

2. The electrolysis process are : Anode (graphite) Cl2(g) + 2 e 2 Cl-(aq)

The Diaphragm Cell

1. The brine solution enters the cell through the anode compartment. 2. The chlorine ion is discharged as chlorine gas at the titanium anode and leaves Cl2(g) + 2 e an excess of sodium ions in the anode compartment. 2 Cl-(aq) 3. Hydrogen gas is produced at the steel cathode and leaves an excess of H2(g) hydroxide ions in the cathode compartment. 2 H+(aq) + 2e 4. The level of brine in the anode compartment is deliberately higher so that brine floes through the asbestos diaphragm, carrying with it the sodium ions, into the cathode compartment where it combines with hydroxide ions to form sodium hydroxide. 5. Sodium hydroxide together with excess brine is drained out from the cell. 6. The anode and cathode compartment has to be separated by a porous partition to prevent the chlorine formed at the anode from reacting with sodium hydroxide formed at the cathode. Cl2(g) + 2 NaOH(aq) NaCl(aq) + NaOCl(aq) + H2O(l)

Chlorine Physical State/ 298 K Yellowish green gas

Bromine Reddish brown liquid

Iodine Shiny black solid

Colour of vapour

Yellowish green

Reddish brown

Violet

Reaction with hydrogen Oxidising power Displacement reaction Reaction with S2O32Silver salt Action with concentrated sulphuric acid

Explosive in sunlight Strong Displaces bromine and iodine Oxidised to SO42White. Soluble in ammonia HCl formed

Combines on heating Mild Displaces iodine Oxidised to SO42Pale yellow. Soluble only in conc. ammonia HBr and Br2 formed

Reversibly at 450 C and Pt as catalyst Weak Does not displace the other halogens Oxidised to S4O62Yellow. Insoluble in ammonia HI and I2 formed

Chlorine. -Extraction of bromine from seawater. -Purification of water -As bleaching agent in paper and fabric industry. Bromine -Manufacture of dyes and drugs. - 1,2-dibromoethane is added to leaded petrol to remove the lead oxide in the piston surface. -Silver bromide used to manufacture photograph film and photochromic lenses. Iodine -Silver iodide is used photographic film - used in antiseptic.

AgCl(s) sunlight Ag(s) + Cl2(g) AgBr(s) sunlight Ag(s) + Br2(g) - slowly turn purple and finally dark grey -The silver bromide that exposed to light get activated. AgBr(s) sunlight AgBr*(s) -Then, the exposed film get treated with aqueous hydroquinone, activated silver is reduce to metallic silver. 2 Ag(s) + 2 HBr(aq) + C6H4O2(aq) 2 AgBr*(s) + C6H6O2(aq) Amount of metallic silver formed is directly proportional to the amount of light fell on the film. Then the film is immersed in sodium thiosulphate (aq), where the unactive silver bromide is removed (negative) AgBr(s) + 2 S2O32-(aq) Ag(S2O3)23-(aq) + Br-(aq)

- Photochromic are sunglasses that darken when exposed to the sunlight, silver chloride and copper chloride crystal are added in the lens while its in the molten state. -When exposed to sunlight ClCl + e Ag+ + e Ag -Chloride and silver atoms are produce, silver atom block the transmission of light causing the lens to darken. degree of darkening proportional to the intensity of light. -When remove from sunlight Cl + Cu+ Cl- + Cu2+ Cu2+ + Ag Cu+ + Ag+ - Net result, lens become transparent again.