Millennia Institute PU2 H2 Chemistry (2011)

Group VII Elements

Content Group VII elements: Physical and Chemical Properties (i) (ii) (iii) Volatility Reactions with hydrogen Reactions of the halide ions

Learning Outcomes Candidates should be able to: a. Describe the trends in volatility and colour of chlorine, bromine and iodine b. Analyse the volatility of the elements in terms of Van der Waals' forces

c. Describe and deduce from E values the relative reactivity of the elements as
oxidising agents d. Describe and explain the reactions of the elements with hydrogen e. (i) Describe and explain the relative thermal stabilities of the hydrides (ii) Interpret these relative stabilities in terms of bond energies f. Describe and explain the reactions of halide ions with (i) (ii) aqueous silver ions followed by aqueous ammonia concentrated sulphuric acid

g. Describe and analyse in terms of changes of oxidation number the reaction of chlorine with cold, and with hot, aqueous sodium hydroxide

Millennia Institute PU2 H2 Chemistry (2011)

Introduction

Assessment Objective: (a)

The members of Group Vll (fluorine, chlorine, bromine, iodine and astatine) are known as halogens, which is derived from the Greek word, 'salt formers'. The elements of Group Vll are p-block elements, with a characteristic outer-shell configuration ns2 np5. e.g. fluorine chlorine bromine : : : 1s2 2s2 2p5 1s2 2s2 2p6 3s2 3p5 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5

1. 2

Physical Properties
Colour Pale yellow Green Brown Black State at r.t. Gas Gas Liquid Solid b.p./ C -188 -35 58 183 Solubility in water in organic solvent --Very pale yellow moderately yellow solution soluble slightly soluble brown solution insoluble purple solution

Molecule F2 Cl2 Br2 I2

Fluorine is a poisonous pale yellow gas

Chlorine is a poisonous dense green gas Chlorine water, Cl2 (aq) turns moist blue litmus red and then bleaches it. Cl2 (g) + H2O (l) Cl- (aq) + ClO- (aq) + 2H+ (aq) Note: It is ClO- (aq) ion that bleaches the litmus paper

Bromine is a caustic and toxic brown liquid

Iodine, I2 (s) sublimes to form a purple vapour upon gentle heating. I2 (s) dissolves in KI (aq) which lead to the formation of reddish brown I3- (aq) I2 (s) + I- (aq) I3- (aq)

In organic solvents, the halogens, X2 exists as relatively free molecules as in the gas phase.

Volatility of Halogens

Assessment Objectives: (a), (b)

Millennia Institute PU2 H2 Chemistry (2011)

Volatility of Group VII elements decreases down the group. 'Volatile' means 'evaporates easily' or 'having a low boiling point'.

Molecule F2 Cl2 Br2 I2

State of matter at r.t Gas Gas Liquid Solid

Atomic radius / nm 0.071 0.099 0.114 Volatility Strength of TD-ID between down Group VII

0.133

The halogens have simple molecular structures consisting of diatomic covalent molecules (e.g. F - F) held together by temporary dipole-induced dipole forces of attraction. As we go down the Group, Size of molecules molecules , No. of electrons in molecule ,

. (recall: strength of IMF is directly proportional to size of electron cloud).

Hence, the boiling point of Halogens increases down the Group and the Halogens become less volatile. This explains the following order of melting and boiling temperatures of Halogens molecules: F2 (g) < Cl2 (g) < Br2 (l) < I2 (s) In iodine, the Van der Waals' forces are strong enough to sustain a solid structure of iodine molecules (I2). But iodine crystals (Simple molecular structure) sublime to form a violet vapour upon gentle heating. i.e. I2 (s) I2 (g), violet vapour

Millennia Institute PU2 H2 Chemistry (2011)

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3.1

Reactivities of Group VII Elements

As oxidising agents (Linked to Electrochemistry)

Assessment Objectives: (c), (d, (e)

Halogens are all oxidising agents. The oxidising power of Halogens is measured by the value of the standard electrode potential, E. Group. From the Data Booklet, the value of E decreases down the Group. This implies that its the oxidising power decreases down the

Ionic equation F2 + 2e- 2FCl2 + 2e- 2ClBr2 + 2e- 2BrI2 + 2e- 2I-

E / V +2.87 +1.36 +1.07 +0.54

The oxidising power decreases down the Group because i. ii. the elements become less reactive its electron affinity decreases.

Order of oxidising ability: F2 (Most oxidising) > Cl2 > Br2 > I2 (Least oxidising) Each halide ion can be oxidised by the halogen above it. A more reactive halogen will displace a less reactive one from its compounds. Hence, F2 is the strongest oxidising agent while I2 is the least oxidising. F2 will oxidise all other halide ions. However, F 2 is too reactive to be a useful oxidising agent and Cl2 (aq), 'Chlorine water' is often used as an oxidising agent. Cl2 (aq) + 2Br- (aq) Br2 (aq) + 2Cl- (aq) E cell = +0.29V

When chlorine water is passed through a solution of a bromide (Br - (aq)), bromine solution (Br2 (aq)) and chloride ions are formed. Chlorine has oxidised bromide ions to bromine.

Millennia Institute PU2 H2 Chemistry (2011)

Observation: Brown bromine solution formed. Example Molecule Chlorine, Cl2 Bromine, Br2 Iodine, I2 No reaction No reaction * Use overall E cell to prove that the reaction is feasible. On the other hand, I2 is the strongest reducing agent. standard Na2S2O3 solution using starch indicator). The decrease in oxidising power of Halogens can be illustrated by its reaction with Na 2S2O3 solution and Fe2+ (aq). Examples of some oxidising reactions of the Halogens: Oxidant All Halogens All Halogens Cl2, Br2 e.g. Reaction Sulfite, SO32- Sulfate, SO42Hydrogen sulfide, H2S Sulfur, S Thiosulfate, S2O32- Sulfate, SO424Cl2 + S2O32- + 5H2O 2SO42- + 10H+ + 8Cl(Oxidation no. of S changes from +2 to +6) Thiosulfate, S2O32- Tetrathionate, S4O62I2 (This reaction is used for titrimetric analysis of iodine) e.g. I2 + 2S2O32- S4O62- + 2IReaction with ClNo reaction No reaction Reaction with BrCl2 + 2NaBr Br2 + 2 NaCl (displaces bromine) No reaction Reaction with ICl2 + 2NaI I2 + 2 NaCl (displaces iodine) Br2 + 2NaI I2 + 2 NaBr (displaces iodine) No reaction

It is widely used in tests for

oxidising agents by measuring the amount of iodine liberated. (Recall: By titrating with

Cl2, Br2 F2 I2

(Oxidation no. of S changes from +2 to +2.5, thus I2 is less oxidising) Organic compounds are oxidised, e.g. CH4 Reacts explosively with organic compounds Does not oxidise organic compounds

Cl2 and Br2 would oxidise Fe2+ to Fe3+, but I2 would not (Ecell < 0) e.g. Cl2 + 2Fe2+ 2Cl- + 2Fe3+ Br2 + 2Fe2+ 2Br- + 2Fe3+ I2 + 2Fe2+ No reaction (Ecell = +1.36V - 0.77V = +0.59V, > 0V) (Ecell = +1.07V - 0.77V = +0.30V, > 0V) (Ecell = +0.54V - 0.77V = -0.23V, < 0V)

Millennia Institute PU2 H2 Chemistry (2011)

Extra Information:
H formtion a X2 (standard state) X-(aq)

H atom ation is

H hydration

Electron affinity X(g) X-(g)

Element H atomization / kJ mol-1

-1 Electron affinity / kJ mol -1 hydration / kJ mol -1 formation / kJ mol

F 79 -328 -473 -722 +2.80

Cl 121 -349 -339 -567 +1.36

Br 112 -325 -306 -519 +1.07

I 106 -295 -262 -451 +0.54

H H E/V

The oxidizing power of the halogen is measured by the value of the standard reduction potential for the process. H X2(g) + 2e 2X-(aq)

Millennia Institute PU2 H2 Chemistry (2011)

3.2

Reaction with Hydrogen

All Halogens react with Hydrogen to form the Hydride, HX (g). H2 + X2 2HX (g) e.g. H2 + F2 2HF

Reactivity decreases down the Group as the H - X bond becomes longer and weaker. The relative reactivity of the Halogens in Covalent bond formation is shown in their reactions with hydrogen.

Reaction H2 + F2 2HF (g) H2 + Cl2 2HCl (g) H2 + Br2 2HBr (g) H2 + I2 2HI (g)

Description of reaction Reacts explosively under all conditions Reacts explosively in the presence of light; slowly in the dark below 200C Reacts slowly above 200C and at lower temperature with Pt catalyst No reaction unless strongly heated; reaction is incomplete and an equilibrium mixture is obtained

The lessening vigour of the reaction of the Halogens with hydrogen to form hydrides also illustrates the decreasing oxidising power of the Halogens down the Group (section 3.1).

3.2.1

Thermal Stability of hydrides

As the size of the Halogen increases down the Group, the H - X bond becomes longer and weaker and so it is easily broken. Thus, the thermal stability of the hydrides decreases down the Group, due to the decrease in strength of the H - X bond. Order of Thermal Stability: HF (g) > HCl (g) > HBr (g) > HI (g)

The thermal stability of Hydrides, HX is illustrated by the bond dissociation energy of the H - X bond (Linked to Chemical Energetics).

Bond H - F (Most thermally stable)

Bond energy/ kJ mol-1 568

Millennia Institute PU2 H2 Chemistry (2011)

Ease of decomposition

H - Cl H - Br H - I (Least thermally stable)

432 366 298

HI has the lowest bond energy (weakest bond) and is most easily decomposed. Thick purple fumes of I2 (g) are observed upon heating. 2HI (g) H2 (g) + I2 (g) In fact, HI is readily oxidised by atmospheric oxygen to give I2 4HI (g) + O2 (g) 2H2O (g) + 2I2 (g) Hence, HI is a very strong reducing agent. HBr decomposes slightly. Slight browning is observed upon heating. HCl and HF do not decompose. They are thermally stable.

3.3

Acid strength of the hydrides

HX (X= Cl, Br and I) dissociates completely in water to give a strong acid. HX(aq) + H2O(l) H3O+(aq) + X-(aq) Acid strength increases down the group in the order of HCl < HBr < HI. This trend is attributed to the decreasing strength of the H-X bond as it becomes longer. Anomaly: HF is a weak acid. It dissociates partially in water. Reason: High bond strength of H-F bond.

Millennia Institute PU2 H2 Chemistry (2011)

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4.1

Reactions of Halide ions

Reaction between Halide Ions and Ag+ ions
Ag+ (aq) + X- (aq) AgX (s) The silver halides formed can be differentiated from one another by The colour of the precipitate formed, and The reaction of the precipitate with NH3 (aq) Ksp/ mol2dm6

Assessment Objective: (f)

Silver halide, AgX, is precipitated when halide ions reacts with AgNO3 (aq).

Ppt

Colour

Reaction with NH3 (aq) AgCl (s) + 2NH3 (aq) [Ag (NH3)2]+ (aq) + Cl- (aq) diamine silver (I) ion

AgCl

1.6 x 10-10

White Precipitate readily dissolves in NH3 (aq) to give a colourless solution, diamine silver (I) ion. AgBr (s) + 2NH3 (aq) [Ag (NH3)2]+ (aq) + Br- (aq)

AgBr

7.7 x 10-3

Pale yellow/ Cream

diamine silver (I) ion

AgI

8.3 x 10

-17

Deep yellow

Precipitate ONLY dissolves in Conc. NH3 solution. Precipitate insoluble in NH3 (aq)

4.1.1

Using Ksp to explain solubility of AgX in aqueous ammonia

Ag+(aq) + X-(aq) AgX(s) -------- (a)

Silver halides AgX are precipitated when aqueous solutions of halides are treated with Ag+.

The subsequent addition of ammonia results in the formation of the diammine silver (I) complex, [Ag (NH3)2]+. AgX (s) + 2NH3 (aq) [Ag(NH3)2]+ (aq) + X- (aq) -------- (b)

By Le Chateliers Principle, the addition of NH3 shifts equilibrium (b) to the right so that [Ag +] decreases. (Ag+ is used in the formation of [Ag(NH3)2]+.) This in turns causes equilibrium (a) to shift to the left, increasing the [Ag+], therefore increasing the solubility of AgX.

Millennia Institute PU2 H2 Chemistry (2011)

4.2

Laboratory preparation of Cl2, Br2 and I2

Chlorine, bromine and iodine can be prepared by oxidation of halides in the laboratory. 2X- X2 + 2e-

4.2.1.
Halide Cl-

Reaction between Halide Ions and concentrated Sulphuric acid

Reaction with conc. H2SO4 NaCl + H2SO4 HCl + NaHSO4 NaBr + H2SO4 HBr + NaHSO4 2HBr + H2SO4 Br2 + SO2 + 2H2O NaI + H2SO4 HI + NaHSO4 6HI + H2SO4 3I2 + S + 4H2O Observations White fumes of HCl (g) produced

When Halides are heated with conc. H2SO4, the following is observed:

Br-

Orange-brown fumes (mixture

of Br2 and HBr) obtained

Some of HBr produced is Purple vapour of I2 obtained HI produced is oxidised by

oxidised by conc. H2SO4 to Br2 I

-

8HI + H2SO4 4I2 + H2S + 4H2O conc. H2SO4 to I2 The ease of oxidation of halide ions, X- X2, increases from Cl- to I- (as the reducing power of the halides increases from Cl- to I-). Hence, I- is readily oxidised by conc. sulphuric acid to I2, Br- is oxidised to Br2 to a lesser extent and Cl- is not oxidised at all. HI cannot be prepared by heating NaI (s) with conc. sulphuric acid because HI produced is readily oxidised by conc. sulphuric acid (strong oxidising agent) to I2. Phosphoric acid, H3PO4 (a non-oxidising agent) is used instead, 2NaI + H3PO4 2HI (white fumes) + Na2HPO4 With stronger oxidising agents (e.g. conc. H2SO4, MnO2), the halogen (X2) is produced instead in each case. NaCl + H2SO4 HCl + NaHSO4 4HCl + MnO2 Cl2 + MnCl2 + 2H2O Cl2 can also be prepared from the reaction of conc. HCl and KMnO4. 16HCl + 2KMnO4 5Cl2 + 2MnCl2 + 2KCl + 8H2O

Reaction of Chlorine with NaOH

Assessment Objective: (g)

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Millennia Institute PU2 H2 Chemistry (2011)

With cold, NaOH (aq) at 15C: Cl2 (g) + 2NaOH (aq) NaCl (aq) + NaClO (aq) + H2O (l) Oxidation state of Cl: 0 -1 +1

Cl2 undergoes disproportionation. It is simultaneously oxidised to sodium chlorate (I), NaClO, and reduced to NaCl. The oxidation number of Cl changes from zero in Cl2 to -1 in Cl- (reduction) and from zero in Cl2 to +1 in ClO- (oxidation)

With hot, NaOH (aq) at 70C: 3Cl2 (g) + 6NaOH (aq) 5NaCl (aq) + NaClO3 (aq) + 3H2O (l) Oxidation state of Cl: 0 -1 +5

Cl2 undergoes disproportionation. It is simultaneously oxidised to sodium chlorate (V), NaClO3, and reduced to NaCl. The oxidation number of Cl changes from zero in Cl2 to -1 in Cl- (Reduction) and from zero in Cl2 to +5 in ClO3- (Oxidation) *Recall: Disproportionation is a reaction where a substance which undergoes simultaneous oxidation and reduction reaction.

Application: (Extra Reading)

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Millennia Institute PU2 H2 Chemistry (2011)

Environmental significance of Halogen and its compounds Bleaches are chemical substances which remove unwanted colours by either oxidation (e.g. NaOCl, Ca(OCl)2, H2O2) or reduction (e.g. SO2, Na2SO3)

Chlorine-based bleach is harmful to both environment and health. This is because dioxin, a by-product formed, is highly toxic. Being insoluble in water, dioxin clings to soil where it can remain for decades. Minute quantities of dioxin can cause cancer and birth defects

SO32- ions would reduce oxygen concentration in water. 2SO32- (aq) + O2 (aq) 2SO42- (aq) Water would be depleted of dissolved oxygen and hence, causing harm to the marine or aquatic life!

The use of bleaches should be minimised so as to reduce water pollution and possible health risks.

Uses of CFCs, its properties and its impact on the environment

Properties of CFCs Chemically inert Non-flammable Low toxicity Odourless, tasteless volatile

Uses of CFCs refrigerants (in fridges & air-conditioners) aerosol propellants (in perfume & insecticides) foam-blowing packaging) cleaning agent (solvent) in electronic industries flame retardant in fire extinguisher agents (expanded polystyrene

Consequences of increasing use of CFCs Depletion of stratospheric ozone which shields the earth from the sun's harmful UV radiation. Exposure to excessive UV radiation would result in:

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Millennia Institute PU2 H2 Chemistry (2011)

(i) (ii) (iii) (iv)

Skin cancer, Cataracts Malfunctioning of immune system in human Damage to vegetation, including food crop

Ozone, O3 is constantly being manufactured and destroyed in the atmosphere in natural process (i.e. dynamic equilibrium exists in stratosphere)

CFC molecules are chemically inert. They do not react with air or water and are not biodegradable. CFC molecules persist in the atmosphere and diffuse upwards unchanged until they reached the stratosphere where they are decomposed by UV light to produce chlorine free radicals, Cl, which then initiate the chain reaction breaking down O3 to O2. O3 (g) + Cl (g) ClO (g) + O2 (g) --- step 1 ClO (g) + O (g) Cl (g) + O2 (g) --- step 2 Net result: free radical. Since a chlorine free radical is re-formed in step 2, many ozone molecules may be decomposed per atom of chlorine. This eventually causes a "hole" in the ozone layer. O3 (g) + O (g) 2O2 (g) A molecule of ozone is destroyed each time one molecule of O3 reacts with a chlorine

Possible solutions to protect the ozone layer Reduce the use of CFCs, replace aerosol spray with manual pump spray Find substitutes for CFCs Collect and recycle CFCs for future use, e.g. install machinery for proper recovery and disposal of CFCs.

END

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Millennia Institute PU2 H2 Chemistry (2011)

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