Grp VII Tutorial Ans Discussion Questions 6.

(N2001/I/4, J90/III/6, N90/III/6)

(a) When sparked, hydrogen reacts explosively and completely with chlorine but with iodine it reacts only slowly and reaches an equilibrium. Write equations for the reactions that occur, and explain the difference in extent of reaction in terms of relevant bond energy values. H2(g) + Cl2(g) 2HCl(g) H2(g) + I2(g)
-1

2HI(g) HCl 431 HI 299

Bond energy/ kJ mol

The bond energy values show that H-I bond is weaker than HCl. Hence HI forms less readily and any HI formed also decomposed readily into H2 and I2. This results in an equilibrium being established for the reaction between H2 and I2. H-Cl bond is stronger and hence is formed more readily. This results in a vigorous reaction between H2 and Cl2. (b) NaCl and NaBr react differently when warmed with concentrated sulfuric acid. Describe what you would observe when these reactions are carried out, write equations for the 2 reactions and suggest an explanation for these different reactions. When NaCl reacts with c.H2SO4, only white fumes of HCl observed. NaCl + H2SO4 HCl + NaHSO4 When NaBr reacts with c.H2SO4, white fumes of HBr is observed together with orange-brown fumes of Br2. NaBr + H2SO4 HBr + NaHSO4 2HBr + H2SO4 Br2 + SO2 + 2H2O The reactions are different as HBr is a stronger reducing agent than HCl and hence can reduce sulfur in H2SO4 from +6 to +4 in SO2. OR Ease of oxidation increases from Cl- to Br- and hence c.H2SO4 can oxidize Br- in HBr to Br2 but not Cl- in HCl to Cl2. (c) Group VII elements can act as oxidising agents, but some are stronger oxidising agents than others. With the aid of relevant equations and E values from the Data Booklet, justify the relative oxidising abilities of chlorine and iodine using their reactions with sodium thiosulfate and iron(II) ions.

4Cl2 + S2O32- + 5H2O 8Cl- + 2SO42- + 10H+ I2 + 2S2O32- 2S4O62- + 2IThe oxidation number of S in S2O32 increases from +2 to +6 when oxidised by Cl2 but only increases from +2 to +2.5 when oxidised by I2. This illustrates that Cl2 is a stronger oxidising agent than I2. Cl2 + 2e 2ClFe2+ Fe3+ + e E0red = +1.36V E0oxid = -0.77V

E0cell = +0.59V Cl2 + 2Fe2+ 2Cl- + 2Fe3+ Since E0cell > 0, reaction is spontaneous. I2 + 2e 2ClFe2+ Fe3+ + e E0red = +0.54V E0oxid = -0.77V

E0cell = -0.23V < 0, reaction is non-spontaneous. This illustrates that Cl2 is a stronger oxidising agent than I2 as Cl2 can oxidise Fe2+ to Fe3+ but I2 cannot do that. (d) Explain the chemistry that is occurring during the following series of reactions that all take place under aqueous conditions. When NaCl is added to silver nitrate, a white precipitate forms which dissolves in excess dilute ammonia. Subsequent addition of sodium bromide to this latter solution causes the precipitation of a cream-coloured solid. Suggest why this latter precipitate dissolves when sodium cyanide is added. Ag+(aq) + Cl-(aq) AgCl(s) White ppt formed is AgCl. Since ionic product [Ag+][Cl-] > KspAgCl, precipitation occurs. Upon addition of aqueous ammonia, formation of complex ion occurs and the following equilibrium is established. Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq) Formation of complex ion decreases [Ag+] and hence ionic product [Ag+][Cl-] decreases. Since KspAgCl is high, the ionic product falls below its Ksp and hence the white ppt AgCl dissolves. AgBr(s) Ag+(aq) + Br-(aq) Precipitation of AgBr occurs to give rise to the cream-coloured solid. In the presence of aq NH3, the complex ion is present resulting in a low [Ag+]. Since the KspAgBr is lower, the ionic product [Ag+][Br-] falls below its Ksp and hence precipitation occurs.

The addition of NaCN gives rise to a more stable complex ion according to the equilibrium as shown as CN- is a stronger ligand. Ag+(aq) + 2CN-(aq) Ag(CN)2-(aq) This further decreases [Ag+] and hence ionic product [Ag+][Br-] will now fall below its Ksp. Hence the ppt dissolves. (e) When chlorine is bubbled through a solution of iodine in hot aqueous sodium hydroxide, the two halogens react in the Cl2 : I2 ratio of 7 : 1, forming a white precipitate A and a solution of sodium chloride. A has the following compositions by mass: Na, 16.9%; H, 1.1%; I, 46.7%; O, 35.3% Calculate the empirical formula of A and thus deduce the balanced equation for the reaction. What is the oxidation number of iodine in A?

Na Mass per 100g/g Amount/ mol Simplest ratio 16.9 0.735 2

H 1.1 1.1 3

I 46.7 0.368 1

O 35.3 2.21 6

Empirical formula: Na2H3IO6 Balanced equation: 7Cl2 + I2 + 18NaOH 2Na2H3IO6 + 14NaCl + 6H2O Let the oxidation no. of I in H3IO62- by x. 3(+1) + x + 6(-2) = -2 x = +7 (a) Iodine and chlorine react together to form a compound X (ICln). When 0.0010 mol of X was reacted with an excess with KI(aq), all of its iodine was converted into I2. The iodine liberated requited 40.0cm3 of 0.10 mol dm3 sodium thiosulfate, Na2S2O3, for complete reaction. (i) Calculate the amount (in moles) of iodine produced. Amount of I2 = (ii)

1 40 0.10 0.002 mol 1000 2

Hence calculate the value of n in ICln

0.001 mol of X produces 0.002 mol of I2

 1 mol of X produces 2 mol of I2.

ICln + nKI (

n 1 ) I2 + nKCl 2
n=3

n 1 =2 2

(iii) Write a balanced equation for the reaction between Cl2 and I2. I2 + 3Cl2 2ICl3 (b) Describe what you would see if chlorine water is added to aqueous sodium bromide. Write an equation for the reaction. Cl2 + 2NaBr 2NaCl + Br2 Solution changed from yellowish green to yellowish brown due to formation of Br2. (c)

When chlorine is bubbled through an aqueous solution containing sodium hydroxide and sodium bromide, bromide ions are oxidized to a bromine containing oxyanion. Careful addition of aqueous silver nitrate to the resulting solution precipitates 4.31g of AgCl. When this precipitate is filtered off, and more silver nitrate solution added, 1.18g of a cream solid is produced. The solid had the following composition by mass: Ag: 45.8% ; Br: 33.9%; O: 20.3%
(i)

Calculate the formula of the cream solid.

Ag Mass per 100g/ g Amount/ mol Simplest ratio 45.8 0.42 1 Br 33.9 0.42 1 O 20.3 1.27 3

(ii)

Formula of the cream solid = AgBrO3. Calculate the number of moles of cream solid and silver chloride formed. Mr of AgBrO3 = 108 + 79.9 + 3(16.0) = 236 1.18 = 5 x 10-3 mol Amount of cream solid = 236 Amount of AgCl =

4.31 = 0.03 mol 108 35.5

(iii) Construct a balanced equation for the reaction between chlorine, sodium bromide and sodium hydroxide. Mol ratio Cl- : BrO3= 0.03 : 5 x 10-3 =6 : 1 3Cl2 + NaBr + 6NaOH 6NaCl + NaBrO3 + 3H2O 8 (a) Acidified aqueous potassium bromate(V), KBrO3, reacts with hydrogen sulfide H2S, to give a precipitate of sulfur and an orange-red solution. On shaking the solution with trichloroethane, the colour is transferred to the organic layer.

Describe the type of reaction taking place and suggest an identity for the orange-red product. Construct a balanced equation for the reaction.
Since the colour of the orange-red solution is transferred to the organic solvent, trichloroethane, the product of the reaction between KBrO3 and H2S must be Br2. Redox reaction has occurred. Balancing the 2 half-equations, 2BrO3- + 12H+ + 10e Br2 + 6H2O H2S 2H+ + S + 2e Overall : 2BrO3- + 2H+ + 5H2S Br2 + 6H2O + 5S (b) Bromine has been obtained from sea salt for a number of years. For simplification, sea salt can be considered to be sodium chloride containing some sodium bromide.

One early method of obtaining bromine is outlined below.

(a) (i)

What causes the yellow colour produced in A?

Br2 liberated from displacement reaction with Cl2.

(ii)

Write an equation for the reaction in A.

2NaBr + Cl2 Br2 + 2NaCl (b) Ether is an organic solvent immiscible with water. Explain why the yellow substance dissolves in the ether in B but the salt does not dissolve in ether. The yellow substance is Br2 which is non-polar. Hence it will dissolve better in the organic solvent (with low polarity) by forming van der Waals forces with ether. The salt, however, is ionic and hence will form strong ion-dipole forces with a polar solvent like water. Therefore it does not dissolve well in the organic solvent due to weak solute-solvent interactions. (c)

Suggest an equation for reaction C.

3Br2 + 6KOH 5KBr + KBrO3 + 3H2O

(d) Suggest an equation for reaction D, the reaction of acid on the products of reaction C. 5KBr + KBrO3 + 6H+ 3Br2 + 6K+ + 3H2O Assignment Question 9 (a) The halogens can act as oxidisng agents. Arrange Cl2, I2 and Br2 in decreasing order of oxidizing strength and explain your answer using relevant data from the data booklet. [3] Decreasing order of oxidizing strength: Cl2 > Br2 > I2 Half-equations Cl2 + eCl Br2 + eBr I 2 + eI E/V +1.36 +1.07 +0.54

Oxidizing strength depends on the tendency for the halogen to undergo reduction. Tendency for halogen to undergo reduction decreases in the order: Cl2 > Br2 > I2 as shown by the decreasing E values. Hence oxidizing strength also decreases in the order Cl2 > Br2 > I2 . (b) In the laboratory, there are three bottles labeled A, B and C. Each bottle contains one of the following reagents:

Cl2(aq), NaI(aq) and KBr(aq) The tests were carried out using the reagents in the bottles. The results were summarized in the table below:

Tests Mixing reagent in bottle A with reagent in Bottle B Mixing reagent in bottle A with reagent in Bottle C Mixing reagent in bottle B with reagent in Bottle C
(i)

Observations No observable change Mixture turned brown Mixture turned brown

Deduce which bottle contains Cl2(aq). Write relevant chemical equations to account for those reactions that occurred.
Bottle C contains Cl2 as it oxidizes Br- to Br2 and I- to I2 giving rise to the brown colour mixture upon mixing. Cl2 + 2KBr 2KCl + Br2 Cl2 + 2NaI 2NaCl + I2

(ii)

If hexane is also provided, suggest how you would carry out a simple experiment to identify the contents of the other two bottles. [4]
Add hexane to bottle A and B separately after the addition of Cl2 to each of them. Shake and allow to stand. The bottle with reddish-brown organic layer is KBr and the bottle with purple organic layer is NaI.

(c)

(i)

Aqueous bromine is added to a solution containing an excess of sodium iodide. The resulting mixture is shaken with an equal volume of an organic solvent. The aqueous layer is then separated out and aqueous silver nitrate is added to it. The mixture is filtered. Concentrated ammonia is then added to the residue and the resulting mixture is then filtered. State what you would observe in the steps above and explain the reactions involved. [6]
Bromine oxidizes iodide ions to iodine and is reduced to bromide ions as Br2 is a stronger oxidizing agent than I2. The solution becomes brown colour due to the formation of I3- complex. Br2 + 2NaI 2NaBr + I2 I2 + II3 Upon shaking with the organic layer, iodine is non-polar and dissolves well in the organic layer to give a purple organic layer. The brown colour of the aqueous layer becomes yellow due to a decrease in [I2] and [I3-]. The aqueous layer contains excess I- and Br- ions formed from the earlier displacement reaction between Br2 and NaI. When silver nitrate is added, a mixture of cream and yellow ppt is observed. The halide ions form yellow AgI ppt and cream colour AgBr ppt. When filtered, both Ag halides are collected as residues. Addition of c.NH3

to the residues caused AgBr ppt to dissolve due to the formation of Ag(NH3)2+ ions. AgX (s) + aq Ag+(aq) + 2NH3(aq) Ag+ (aq) + X (aq) [Ag(NH3)2 ]+ (aq) ----(1) ----(2)

The formation of soluble Ag(NH3)2+ complex ion in equilibrium (2) reduces [Ag+] to a large extent and hence reduces the ionic product for both halides.. AgBr has a greater Ksp value than AgI. Hence its ionic product, [Ag+][Br-] falls below its Ksp and AgBr ppt dissolves. AgI has a small Ksp value and hence its ionic product [Ag+][I-] is unable to fall below it. Hence ppt does not dissolve. In the last filtration step, yellow AgI is collected as the residue and the colourless filtrate contains Ag(NH3)2+ and bromide ions. (ii)

Aqueous bromine is decolourised when aqueous sodium thiosulfate is added to it. When aqueous barium chloride is then added, a white precipitate is observed. Explain the observations and give equations for the reactions involved. [3]
Br2 oxidises thiosulfate ions to sulfate ions and it itself is reduced to bromide ions. Hence yellow bromine solution decolourised. 4Br2(aq) + S2O32-(aq) + 5H2O(l) 8Br-(aq) + 2SO42-(aq) + 10H+(aq) On addition of barium chloride, barium sulfate is obtained giving rise to the white ppt. Ba2+(aq) + 2SO42-(aq) BaSO4(s)

(d) Iodine and chlorine react together to give compound A, IxCly.

When a sample of A was dissolved in an excess aqueous potassium iodide, a brown solution was obtained. The brown solution required 34.0 cm3 of 0.50 mol dm-3 sodium thiosulfate for reaction. When the experiment was repeated with another sample of A of the same mass with excess potassium iodide, it was found that a yellow precipitate was first obtained with aqueous silver nitrate. When the yellow precipitate was filtered off and more aqueous silver nitrate solution was added, a white precipitate of mass 1.83 g was obtained. Construct a balanced equation for the reaction between compound A and potassium iodide. [4]
amount of I2 =

34 1 0.50 = 0.0085 mol 1000 2

amount of Cl- = ratio I2 : Cl= 2: 3

1.83 = 0.01275 mol 108 35.5

ICl3 + 3I- 2I2 + 3Cl-