Element Atomic radius (nm) Physical state at room temperature Electronic configuration Melting point (oC) Boiling point

(oC) Bond energy (kJ/mol) Electron affinity (kJ/mol) Electronegativity Solubility in water

Chlorine, Cl2 0.099

Bromine, Br2 0.114

Iodine, I2 0.133

Yellow greenish gas 3s2 3p5

-102 -34.5 242.5 -364 3.0

Red brown liquid 4s2 4p5

-7.1 58.6 191.5 -340 2.8

Black solid 5s2 5p5

-184 150.0 -297 2.5

soluble

soluble

Sparingly soluble

1. Atomic radius When goes down to group 17, atomic radius increase. This is due to, when going down to Group 17, nuclear charge increase, as the proton number increase. As number of proton increase, number of electrons also increased, which caused more shells are required to fill in electrons and gradually increase the screening effect. As a result, the effective nuclear charge decreased and caused the atomic radius increase 2. Melting point, boiling point, physical state at room temperature, colour intensity & density of Group 17 All Group 17 elements exist as diatomic molecules, where fluorine, chlorine, bromine, iodine and astatine exist as F2, Cl2,Br2,I2,and At2 respectively The physical state of chlorine, bromine and iodine are different despite they are from the same classification of elements, nonmetal. Chlorine exist as yellow-greenish gas, bromine exist as brown liquid, while iodine exist as purplish-black solid. These observations were supported by the data of melting point and boiling point of Group 17 elements

All these were due to when going down to Group 17, relative molecular mass increased from Cl2 to Br2 to I2 and caused the weak Van Der Waals' forces increase. As a result, the melting point and boiling point increase down the Group and each elements of Group 17, hence exist as different physical forms. At the same time, as the weak intermolecular forces increased, molecules become more close packed, causing the number of molecules per unit volume increased, hence increase the density of elements, which consequently increased the colour intensity of halogen. This will cause the colour of halogens to become darker. This can also be used to explain the volatility of molecules, where going down Group 17, volatility decreased which were also due to stronger intermolecular forces between particles hence harder to vapourise.

3. Electronegativity, bonding energy and electron affinity Electronegativities measure the ability to pull the bonding pair towards the direction of the atom. Electronegativity of the group 17 decrease when goes down to group due to the increase of covalent radius of the elements. Fluorine has the highest electronegativity among all Group 17 elements. This will influence the bonding length of the Group 17 which directly causing the decrease in bonding energy. Bonding energy measure the heat (energy) required to break the bond formed between 2 atoms. Example : Cl - Cl (g) 2 Cl (g) H = + 242.5 kJ mol-1 Bonding energy decreased, as the bond length increased from chlorine to iodine. As the bond length of the covalent molecules increased, it is getting easier to break the bond, thus lower the bonding energy.

Fluorine has a lower bonding energy compare to chlorine as the fluorine atom is too small, which result the lone pair electrons between F-F repel each other, causing the bond length increased. (since lone pair - lone pair electrons repulsion is stronger than lone pair - bond pair electrons repulsion). Electron affinity is the heat liberated when one mole of gaseous atom accept one mole of electron to form a gaseous anion under standard condition. Equation : F (g) + e- F- (g) HEA = - 364 kJ mol-1 The electron affinity of Group 17 become less negative when goes down to group 17. This is due to, as atomic size increased, nucleus is further away from the outermost shell. As a result, electron received is further away and the electrostatic forces of attraction is weaker, hence less exothermic

4. Solubility of halogens in water Solubility of halogen decrease when goes down to Group 17. Fluorine is the most soluble halogen among the Group 17 because enthalpy change of hydration of fluorine is very exothermic. Furthermore, fluorine can form hydrogen bond with water. Both chlorine and bromine are considerably soluble in water and form an acid and acid halide via disproportionation reaction (oxidation and reduction occur simultaneously on the same substance), while iodine is sparingly soluble in water. Equation : Cl2 (g) + H2O (l) HCl (aq) + HOCl (aq) Br2 (g) + H2O (l) HBr (aq) + HOBr (aq) Iodine aqueous solution can be prepared by dissolving iodine in potassium iodide (KI) aqueous solution and form a brown solution of I3-. Equation : I2 (s) + I- (aq) I3- (aq)

bleaching agent. The hypohalous acid formed can be used as When hypohalous is exposed to sunlight, it will decomposed and oxygen is evolved. Hypochlorous acid and hypobromous acid both give different reaction. 2 HOCl 2 HCl (aq) + O2 (g) Overall : 2 Cl2 + 2 H2O 4 HCl (aq) + O2 (g) As extra notes, halogens also dissolve in organic solvent such as tetrachloromethane, CCl4, or benzene solution.

Halogen Colour in aqueous solution Colour in organic solvent (CCl4)

Chlorine, Cl2 Bromine, Br2 Pale yellow Colourless Brown Brown

Iodine, I2 Brown Purple

6.2 Chemical properties of Group 17 elements Halogens are strong oxidising agent. This is supported with the value of standard reduction potential where F (aq) Eo = + 2.87 V F2 (aq) + e Cl2 (aq) + eCl (aq) Eo = + 1.36 V Stronger oxidising Br2 (aq) + eBr (aq) Eo = + 1.07 V agent o I2 (aq) + eI (aq) E = + 0.54 V A displacement reaction can take place between halogens. Using this method, the reactivity of halogen can also be deduced. The following mixture of halide and halogen are added and observation is made

Observation

Equation Reactants : Cl2 + BrSo the half equation for reaction: Cl2 + 2e2 Cl- E0 = + 1.36 V 2 BrBr2 + 2e- E0 = - 1.07 V -------------------------------------------Cl2 + 2 Br2 Cl- + Br2 Ecell = + 0.29 V Since the Ecell is positive, the reaction is spontaneous. Reactants : Br2 + ISo the half equation for reaction: Br2 + 2e2 Br- E0 = +1.07 V 2 II2 + 2eE0 = - 0.54 V -------------------------------------------Br2 + 2 I2 Br- + I2 Ecell = + 0.53 V Since the Ecell is positive, the reaction is spontaneous.

Chlorine in Tetrachloromethane Colourless solution is added to aqueous in CCl4 turned potassium bromide brown (KBr).

Bromine in tetrachloromethane is added to aqueous potassium iodide (KI)

Brown colour in CCl4 turn purple colour.

Iodine is tetrachloromethane Purple colour in is added to aqueous CCl4 remain potassium chloride unchanged (KCl)

Reactants : I2 + ClSo the half equation for reaction: I2 + 2e2 IE0 = + 0.54 V 2 ClCl2 + 2e- E0 = - 1.36 V -------------------------------------------I2 + 2 Cl2 I- + Cl2 Ecell = 0.82 V Since the Ecell is negative, the reaction is non-spontaneous.

5.2.1 Changing of iron (II) ion to iron (III) ion and vice versa Given the half equation of iron (II) ion and iron (III) ion and its standard reduction potential. Fe3+ (aq) + eFe2+ (aq) E = + 0.77 V If the halogen aqueous solution is added to iron (II) ion, Fe2+, solution respectively Chlorine in iron (II) ion aqueous solution. Reactants : Cl2 + Fe2+ ; So the half equation for reaction: Cl2 + 2e2 ClE0 = + 1.36 V Fe2+ Fe3+ + eE0 = 0.77 V Cl2 + 2 Fe2+ 2 Cl- + 2 Fe3+ Ecell = + 0.59 V Since the Ecell is positive, the reaction is spontaneous. Obs : pale yellow solution dissolve in green solution to form yellow solution Bromine in iron (II) ion aqueous solution. Reactants : Br2 + Fe2+ ; So the half equation for reaction: Br2 + 2e2 BrE0 = + 1.07 V Fe2+ Fe3+ + eE0 = 0.77 V Br2 + 2 Fe2+ 2 Br- + 2 Fe3+ Ecell = + 0.30 V Since the Ecell is positive, the reaction is spontaneous. Obs : brown solution first dissolve in green solution and form yellow solution

Iodine in iron (II) ion aqueous solution.

Reactants : I2 + Fe2+ ; So the half equation for reaction: 2 IE0 = + 0.54 V I2 + 2eFe3+ + eE0 = 0.77 V Fe2+ I2 + 2 Fe2+ 2 I- + 2 Fe3+ Ecell = 0.23 V Since the Ecell is negative, the reaction is non-spontaneous. Obs : no changes occur *Conversely when iron (III) ion is added to iodide ion, 2 I- + 2 Fe3+ I2 + 2 Fe2+ Ecell = + 0.23 V iodide ion (which act as reducing agent) are able to reduce iron (III) ion to form iron (II) ion and iodine is formed.

It can be conclude that Chlorine and bromine can act as oxidising agent while iodine is not .. a good oxidising agent. Conversely, iodide ion can act as a good reducing agent.

The oxidation of thiosulphate ions, S2O32-, by halogen is quantitative. Using volumetric analysis, the exact concentration of the reagent (S2O32-) used can be found. Since chlorine and bromine are strong oxidising agent, when chlorine and bromine react with thiosulphate solution, thiosulphate ion is sulphate ion, SO42oxidise to its highest oxidation state, which is S2O32- + 5 H2O 2 SO42- + 8 e + 10 H+ Cl2 + 2 e 2 Cl -------------------------------------------------------------------S2O32- + 5 H2O + 4 Cl2 2 SO42- + 8 Cl + 10 H+ But when it react with a weaker oxidising halogen like iodine, it only slightly oxidised. Thiosulphate ion will be oxidised to become tetrathionate ion, S4O62-, which can be used in the volumetric analysis 2 S2O32S4O62- + 2 e I2 + 2 e 2 I --------------------------------------2 S2O32- + l2 S4O62- + 2 l

Example : The carbon monoxide in a sample of polluted air can readily be determined by passing it over solid iodine(V) oxide, I2O5, to give carbon dioxide and iodine. (a) Write a balanced equation reaction between carbon monoxide and iodine(V) oxide. I2O5 + 5 CO 5 CO2 + I2 ............................................................................................................................................ (b) The iodine produced is removed and titrated with aqueous sodium thiosulphate: 2 Na2S2O3 (aq) + I2 (s) Na2S4O6 (aq) + 2 NaI (aq) A 1.0 dm3 sample of air produced iodine that required 20.0 cm3 of 0.10 mol dm-3 sodium thiosulphate to discharge the iodine colour. Calculate the mass of carbon monoxide in this sample of polluted air. [4] Mol of Na2S2O3 = MV / 1000 ; mol = (0.10)(20.0) / 1000 Mol of Na2S2O3 = 0.002 mol From eq (b) since 2 mol of Na2S2O3 = 1 mol of I2 Mol of I2 = 0.001 mol In (a) since 1 mol of I2 = 5 mol of CO Mol of CO = 0.005 mol Mass of CO = mol x RMM @ mass = 0.005 x (12.0 + 16.0) Mass of CO = 0.14 g

6.3

Hydrogen halide and hydrides. HF 23 +560 HCl - 85 +433 HBr - 66 +366 HI - 35 +298

Halides Boiling point (oC) Bonding enthalpy (kJ/mol)

When chlorine is mixed with hydrogen gas under the presence of sunlight, an explosive reaction occur and yellow-greenish (chlorine) gas turned to white fumes (hydrogen chloride). Equation : Cl2 (g) + H2 (g) 2 HCl (g) The reactivity decreased when going down to Group 17 (as suggested by their respective E0 value) where bromine react with hydrogen upon heating to 2000C to form hydrogen bromide While iodine react partially with hydrogen until reaction established an equilibrium between hydrogen, iodine and hydrogen iodide, at 450oC under the presence of platinum as catalyst

All hydrogen halide exist as gas under room temperature and pressure, except hydrogen fluoride, which exist as a volatile liquid at room temperature. Hydrogen fluoride exist as volatile liquid because H-F has strong hydrogen bond between them, which are stronger than the weak Van Der Waals forces that exist between HCl, HBr and HI. The boiling points eventually increased from HCl < HBr < HI, since the relative molecular mass increased, which increase the weak intermolecular forces. The thermal stability of hydrogen halide decreased down Group 17. This can be explained by the fact of the increasing bond length of H X. When going down Group 17, the atomic radius increased. As a result, the bond length between hydrogen atom and halogen atom increased, which eventually caused lesser heats were required to break the covalent bond between H - X. When heated at high temperature, all hydrogen halide will decomposed to form back their respective elements. Some hydrogen iodide can even decomposed to form hydrogen and iodine under room temperature pressure until equilibrium is established. Equation : 2 HX (g) H2 (g) + X2 (g)

The factor of bond length can also be used to explain the acidity of hydrogen halide. When dissolved in water, acidity increase from HF <<HCl<HBr< HI. Hydrofluoric acid is a weak acid, which dissociate partially in water, where HF (g) + H2O (l) F- (aq) + H3O+ (aq) while hydrochloric acid, bromic acid, iodic acid dissociate completely in water. [where X may be Cl, Br, I] HX (g) + H2O (l) X- (aq) + H3O+ (aq) The acidity increase down Group 17 since the bond length of H-X increase. As a result, H-X is easier to dissociate in water, hence causing the acidity increased. Even though hydrogen halide can be prepared using direct reaction between hydrogen and halogen, but in laboratory / industrial process, they are prepared in different way. Hydrogen fluoride and chloride can be prepared using fluoride / chloride salt with concentrated sulphuric acid (H2SO4), while hydrogen bromide and iodide is prepared via hydrolysis of phosphorous (III) halide

5.3.1 Displacement from salt When react with concentrated sulphuric acid is added to halides salt and heated, hydrogen halide fumes will be released MX (s) + H2SO4 (aq) HX (g) + MHSO4 (aq) Using this method, hydrofluoric acid can be produced, when fluorspar (calcium fluoride) react with hot concentrated sulphuric acid to form hydrogen fluoride, which is a super acid.

2 H2SO4 (aq) + CaF2 (s)

Ca(HSO4)2 (s) + 2HF (aq)

Hydrogen chloride is produced when sodium chloride is heated and concentrated acid is added slowly to the salt solution. Equation :

NaCl (s) + H2SO4 (aq)

HCl (g) + NaHSO4 (aq)

Hydrogen bromide and hydrogen iodide cannot be prepared using this method as concentrated sulphuric acid is a strong oxidising agent, and this will result the hydrogen halide produced to further oxidise to become the individual halogen involved. For bromide salt ;

NaBr (s) + H2SO4 (aq) 2 HBr (g) + H2SO4 (aq)

HBr (g) + NaHSO4 (aq) Br2 (l) + SO2 (g) + 2 H2O (l)

Observation : brown liquid is formed around the test tube, and a colourless pungent gas evolved which turn blue litmus to red. For iodide salt ;

NaI (s) + H2SO4 (aq) 8 HI (g) + H2SO4 (aq)

HI (g) + NaHSO4 (aq) 4 I2 (l) + H2S (g) + 4 H2O (l)

Observation : black spot is formed on the wall of the tube. A bad egg smell gas evolved from the mixture.

6.3.2 Hydrolysis of covalent halides In order for hydrolysis of phosphorous halide to take place, phophorous (III) tribromide and phosphorous triiodide must be first prepared by direct reaction between phosphorous and halogen, where Equation : P4 (s) + 6 X2 (l) 4 PX3 (l) [X may be Br ot I] [However, when excess chlorine is reacted directly with phosphorous, it formed an expand octet of phosphorouspentachloride, PCl5. As for phosphorous pentabromide, PBr5 and phosphorous pentaiodide, PI5, cannot be formed due to steric hindrance effect] Bromine and iodine react with phosphorus to form phosphorus(III) tribromide and phosphorus(III) iodide respective. PBr3 (l) + 3 H2O (l) 3 HBr (aq) + H3PO3 PI3 (l) + 3 H2O (l) 3 HI (aq) + H3PO3 This method is suitable for preparing hydrogen bromide and hydrogen iodide since the phosphorous acid, H3PO3, produced is not an oxidising agent

5.4 Oxoacid of chlorine. All halogens (except fluorine) can exhibit various oxidation states in their compound In chlorine, it can exhibit 6 oxidation states
Chemical Formula Oxidation state
Hydrochloric acid

Chlorine

Hypochlorous acid

Chlorous acid

Chlorite acid

Perchlorite acid

HCl

Cl2

HClO

HClO2

HClO3

HClO4

+1

+3

+5

+7

The hydrogen chloride which contain oxygen atom in it, is called as oxoacid All oxoacids are soluble in water. When dissolve in water .

HClO (Hypochlorous acid)

HClO2 (Chlorous acid)

HClO3 (chloric acid)

HClO4 (Perchloric acid)

HClO + H2O ClO + H3O+

HClO2 + H2O ClO2 + H3O+

HClO3 + H2O ClO3 + H3O+

HClO4 + H2O ClO4 + H3O+

Acidity increase as the number of O increase

As oxygen is more electronegative . than chlorine, O H bond in the oxoacid are weakened by the inductive effect (electron withdrawing effect) of the oxygen atoms which are bonded to chlorine atom. As a increase with the increase of number of oxygen result, the acidity . atom. Explain this : HI is a stronger acid than HBr but HIO3 is a much weaker acid than HBrO3. HI is stronger acid than HBr since the bond length is longer in HI . compare to HBr. However, HBrO3 is a stronger acid than HIO3 since . Br is more electronegative than I, causing the inductive effect of HBrO3 . is stronger, hence the dissociation is stronger.

5.5 Preparation of Chlorine In laboratory, chlorine gas is produced by using manganese base compound When hot concentrated HCl react with potassium permanganate:

16 HCl + 2 KMnO4 4 HCl + MnO2

2 KCl + 2 MnCl2 + 8 H2O + 5 Cl2 MnCl2 + 2 H2O + Cl2

When hot concentrated HCl react with manganese oxide : In industrial process, chlorine gas, together with sodium metal, is prepared using molten sodium chloride (brine) using mercurycathode cell.

In industrial process, chlorine gas, together with sodium metal, is prepared using molten sodium chloride (brine) using mercurycathode cell

2 e + Cl2 Half equation occur at anode : 2 Cl Half equation occur at cathode : Na+ + e Na Mercury is specially used to attract the sodium formed in cathode and form an alloy named amalgam This method is not environment friendly as the mercury used is poisonous.

Despite on the disadvantage given by the mercury, a diaphragm cell is used. Similar to the mercury-cathode cell, the electrolytes used in diaphragm brine cell is also .. The process inside the diaphragm cell is known as the chlor-alkali process

When sodium chloride dissociates under the effect of an electric current, the chloride ions are discharged. At anode : 2 Cl- (aq) Cl2 (g) + 2e-. Titanium is chosen as the anode because it resists corrosion by the very reactive chlorine At cathode, since the sodium ion (Na+) is attracted to cathode through the diaphragm, the selectivity to discharge is between sodium ion and water molecule. Standard reduction potential of sodium : Na+ + eNa E0 = 2.71 V Standard reduction potential of water : 2 H2O (l) + 2 eH2 (g) + 2 OH- (aq) E0 = 0.83 V Since water has a higher SRP value, water is discharge and hydrogen and hydroxide ... ion is produced. The level of brine (left or anode position) is always placed higher than the water (right or cathode position) to prevent a back pressure of the cell and form back flow. If back flow occurs, water will dilute the concentrated brine and chlorine will not be selected.

5.6 Reaction with silver nitrate When aqueous halide ions (such as,sodium chloride solution) are added to silver nitrate solution,coloured precipitates are formed. NaCl (aq) + AgNO3 (aq) AgCl (s) + NaNO3 Ag+ (aq) + Cl- (aq) AgCl (s) (white precipitate) Silver chloride is a white precipitate which dissolves in excess aqueous ammonia to form a soluble complex of silver AgCl (s) + 2 NH3 (aq) [Ag(NH3)2]+Cl- (aq) (soluble complex) If chloride ion is replaced by bromide ion, the precipitate formed is cream colour (AgBr) Ag+ (aq) + Br- (aq) AgBr (s) (cream precipitate) Unlike silver chloride, silver bromide dissolve only in concentrated ammonia aqueous solution according to the equation : AgBr (s) + 2 NH3 (aq) [Ag(NH3)2]+Br- (aq) (soluble complex) If iodide ion is replaced, silver iodide (AgI) produced is yellow colour Ag+ (aq) + I- (aq) AgI (s) (yellow precipitate)

5.7

Reaction with aqueous sodium hydroxide

Chlorine reacts with dilute sodium hydroxide solution to form sodium hypochlorite and NaCl.(low temp) NaCl (aq) + NaClO (aq) + H2O (l) Cl2 (g) + 2 NaOH (aq) 1 +1 0 * When NaClO is exposed to uv (sunlight) it will undergoes decomposition to form sodium chloride and oxygen gas. 2 NaClO (aq) 2 NaCl (aq) + O2 (g) The reaction above can also be describe as a futher decomposition upon heating hypochlorite ion 3 NaClO (aq) NaClO3 (aq) + 2 NaCl (aq) +1 +5 1 When concentrated sodium hydroxide is heated to a high temperature of 70oC, sodium chlorate(v) is formed. 3 Cl2 (g) + 6 NaOH (conc) 5NaCl (aq) + NaClO3 (aq) + 3 H2O (l) 1 +5 0

For bromine, it behave the same way as chlorine. When bromine is added to aqueous sodium hydroxide NaBrO3 (aq) + 5 NaBr + 3 H2O 3 Br2 (l) + 6 NaOH (aq) 0 +5 1 Iodine reacts with NaOH in the same ways Cl2 and Br2. Disproportionation occurs even at 0oC. 3 I2 (l) + 6 NaOH (aq) NaIO3 (aq) + 5 NaI + 3 H2O 1 0 +5 It is therefore impossible to prepare the IO- ions without the presence of IO3-

5.8 Uses of Halogen and Their Compounds Fluorine As oxidising agents. Hydrogen fluoride is used to etch glass. Sodium fluoride is added to the water and toothpaste to prevent dental caries. Fluorine in industry is the production of polymer plastic-teflon.Teflon is an insulator of electricity and as linings in non- stick pans .Medically,teflon is an important material in surgical transplants as it can be used to replace broken cartilages. NaF or SnF2 are important constituents in toothpaste and fluoride ion,F-, forms a protective layer

Chlorine Used as bleaching agents. Bleach contains sodium hypochlorite or sodium chlorate(I) and prepared by passing chlorine gas into a cold sodium hydroxide solution. Cl2(g) + 2NaOH(aq) NaCl (aq) + NaClO (aq) + H2O (l) Add to water and swimming pool to kill germs and bacteria. In water forms hydrochloric and hypochlorus acids and ClO- has the disinfecting effect. Cl2(g) + H2O (l) HCl (aq) + HClO (aq) Dichlorodiphenyltrichloroethane (DDT) is used as insecticide. Chloroethene is the monomer for PVC. Chlorine dioxide,ClO2 is used to bleach wood pulp for paper making. Potassium chlorate(V) is used as an oxidant in fireworks and matches

Bromine Bromine occurs naturally in some marine organisms. 1,2-dibromoethene,BrCH=CHBr is used in insecticides. 1,2-dibromoethane,BrCH2CH2Br is added to leaded petrol to remove the lead oxide sticking to the piston surface. Silver bromide is used in photography. The surface of the paper is spread with a layer of silver bromide. When exposed to sunlight, the bromide ion will be oxidised to bromine gas, leaving a grey layer of silver on the surface of the paper This is a redox reaction Ag+ + e- Ag [reduction] 2BrBr2 + 2 e- [oxidation] Overall Reaction 2AgBr 2 Ag + Br2

Iodine Iodine in alcohol is a popular antiseptic used medicinally to treat wounds. The iodine vapour is used in electric bulbs. Silver iodide, AgI is used in cloud-seeding