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Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

Hwa Chong Institution (College) 2011 H2 Chemistry – Group VII GROUP VII – THE HALOGENS Problem-Solving

GROUP VII THE HALOGENS

Problem-Solving Questions

Question 1 (N08/III/1 modified)

Section 3.1
Section 3.1
  • (a) Describe and explain the variation in volatility of the elements in Group VII.

The halogens exist as simple, non-polar diatomic molecules. Dispersion forces exist between molecules. Going down Group
The halogens exist as simple, non-polar diatomic molecules. Dispersion forces exist
between molecules. Going down Group VII from fluorine to iodine, the size of the electron
cloud of X 2 increases. Thus, polarisability of the molecule increases. Dispersion forces
between molecules become stronger and more energy is required to overcome the
intermolecular forces of attraction. Hence, volatility decreases down Group VII.
  • (b) Under certain conditions the hydrogen halides decompose into their elements.

Section 5.2
Section 5.2

2HX

H 2

+

X 2

(X = Cl, Br or I)

  • (i) How can this reaction be carried out? By inserting a hot wire or glass rod into a test-tube of hydrogen halides.

(ii) State and describe the trend of this reaction when X = Cl, X = Br
(ii)
State and describe the trend of this reaction when X = Cl, X = Br and X = I.
The extent of reaction increases down Group VII.
HCl does not decompose even on strong heating, HBr yields brown fumes of Br 2
under strong heating while violet fumes of I 2 obtained when red-hot rod is plunged
into jar of HI.
(iii) Use bond energy values from the Data Booklet to calculate ΔH for this reaction when
(iii) Use bond energy values from the Data Booklet to calculate ΔH for this reaction when X
= Cl and when X = I.
2HX (g) ⇌ H 2 (g)
+
Bond energy
HX
HH
X 2 (g)
XX
For X
= Cl:
2 (431)
(436)
(244)
For
X = I:
2 (299)
(436)
(151)
H for HCl = 2 × 431 – 436 – 244 = +182 kJ mol –1
H for HI = 2 × 299 – 436 – 151 = +11 kJ mol –1

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

(iv) Use your results from (iii) to explain the trend you stated in (ii).

Results from (iii) shows that the reaction becomes less endothermic from HCl to HI, i.e. it
Results from (iii) shows that the reaction becomes less endothermic from HCl to HI, i.e.
it required less energy for the thermal decomposition of HX, therefore reaction occurs
to a greater extent down the group (the trend stated in (ii)).

Question 2 (N06/II/1c)

Section 5.1
Section 5.1

Fluorspar reacts with concentrated sulfuric acid to form hydrogen fluoride gas.

 

CaF 2

+

H 2 SO 4

CaSO 4

+

2HF

Data about HF, HCl, HBr and HI are given below.

 
       

HF

 

HCl

HBr

HI

boiling point / ˚C

   

+20

 

-85

-67

-35

bond energy / kJ molˉ 1

   

562

 

431

366

299

H o f / kJ molˉ 1

   

-269

 

-92

-36

+26

  • (a) State and explain the trend in boiling points of HCl, HBr and HI.

  • (b) Suggest why the boiling point of HF is much higher than those of the others.

(a) From HCl to HI, boiling point increases. This is due to increasing size of electron
(a)
From HCl to HI, boiling point increases. This is due to increasing size of electron cloud, thus
increasing the strength of van der Waals’ forces.
(b)
HF has much higher boiling points due to hydrogen bonding which is stronger than van der
Waals’ forces.

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

Question 3 (N93/I/7 modified)

  • (a) How do the chloride, bromide and iodide ions differ in their reactions with

    • (i) silver nitrate followed by dilute aqueous ammonia,

Section 6.1
Section 6.1

(ii)

concentrated sulfuric acid?

Section 6.3
Section 6.3

In each case, suggest the products of the reaction and write equations, where appropriate.

(i)

 

Halide

 

Expected observations

 

Equations

   
 

Cl -

 

white AgCl precipitates; ppt soluble in

Ag + (aq)

+

Cl (aq) AgCl(s)

 
 

excess aq ammonia

Ag + (aq)

+ 2NH 3 (aq)

[Ag(NH 3 ) 2 ] + (aq)

 
 

Br -

 

pale yellow AgBr precipitates; ppt insoluble in excess NH 3

 

Ag + (aq)

+ Br (aq)

AgBr(s)

 
 

I

-

yellow AgI precipitates; ppt insoluble in excess NH 3

Ag + (aq)

+ I (aq)

AgI(s)

 
 

(ii)

 

Halide

   

Expected observations

 

Equations

 
 

Cl -

 

white fumes of HCl evolve

 

Cl (s)

+

H 2 SO 4 (l)

HCl(g) + HSO 4 (s)

 
 

Br -

 

white fumes of HBr & a little reddish brown fumes of Br 2

 

Br (s) +

H 2 SO 4 (l)

HBr(g) + HSO 4 (s)

 
 

evolve (may also have SO 2 )

2HBr(g)

+

H 2 SO 4 (l)

Br 2 (g)

+

SO 2 (g)

+

2H 2 O(l)

 
 

I

-

A little bit of white fumes of

 

I (s)

+

H 2 SO 4 (l)

HI(g) + HSO 4 (s)

 
 

HI & purple fumes of I 2 evolve

2HI(g)

+

H 2 SO 4 (l)

I 2 (g)

+

SO 2 (g)

+

2H 2 O(l)

 

(may

also have pungent SO 2 or

H 2 S).

Yellow solid of S is

 

6HI(g)

+

H 2 SO 4 (l)

3I 2 (g)

+

S(s)

+

4H 2 O(l)

observed.

8HI(g)

+

H 2 SO 4 (l)

4I 2 (g)

+

H 2 S(g)

+

4H 2

O(l)

  • (b) What explanations can you offer for the differences in their reactions in (a)?

    • (i) The difference in the reactions is due to decreasing K sp from AgCl to AgI. For AgCl, its ionic product is lower than the K sp value when aqueous NH 3 is added. Addition of ammonia results in the formation of the diamminesilver(I) complex, [Ag(NH 3 ) 2 ] + .

Ag + (aq) + 2NH 3 (aq) [Ag(NH 3 ) 2 ] + (aq)

This causes [Ag + ] to decrease and causes position of

equilibrium Ag + (aq) + X (aq)

AgX(s) to shift to the left, increasing the solubility of AgX.

For AgBr and AgI, due to their lower K sp , the ionic product is greater than K sp when aqueous ammonia is used as [Ag + ] is not sufficiently lowered.

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

(ii)

Reducing power of halides: I - > Br - > Cl -

HI can reduce H 2 SO 4 to H 2 S and SO 2 and itself oxidized to I 2 .

HBr

can reduce H 2 SO 4 to SO 2 and itself oxidized to Br 2 .

HCl

cannot reduce H 2 SO 4 .

Question 4 (N90/III/6)

(a)

Describe the reactions that occur when chlorine is bubbled through cold aqueous sodium

hydroxide and the mixture is then heated.

Section 4.4.2
Section 4.4.2

Write equations and explain how the oxidation number of chlorine changes during these reactions. What observation would make it clear that the chlorine had reacted?

(b)

When chlorine is bubbled through a solution of iodine in hot aqueous sodium hydroxide, the two halogens react in the Cl 2 :I 2 ratio of 7:1, forming a white precipitate A and a solution of sodium chloride. A has the following composition 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?

(a) When chlorine is bubbled through cold aqueous sodium hydroxide, chlorine will undergo disproportionation according to
(a)
When chlorine is bubbled through cold aqueous sodium hydroxide, chlorine will undergo
disproportionation according to the equation below:
Cl 2 (aq) +
2NaOH(aq)  NaCl(aq) + NaClO(aq) + H 2 O(l) ------ (1)
When heated, a further disproportionation reaction occurs:
3NaClO(aq)  2NaCl(aq) + NaClO 3 (aq) ------ (2)
The oxidation number of Cl changes from 0 in Cl 2 to -1 in NaCl and +1 in NaClO.
The oxidation number of Cl changes from +1 in NaClO to -1 in NaCl and +5 in NaClO 3 .
The
characteristic smell
of
Cl 2
disappears.
The
yellowish-green
gas
dissolves
into
a
colourless solution.
(b)
Na
H
I O
Mass in 100g / g
No. of moles
16.9
1.1 46.7
35.3
16.9
1.1
46.7
35.3
 0.7348
 1.1
 0.3677
 2.2063
23.0
1.0
127
16.0
0.7348
1.1
0.3677
2.2063
 2
 3
 1
 6
Ratio
0.3677
0.3677
0.3677
0.3677
Empirical
formula of A: Na 2 H 3 IO 6
Balanced equation:
7Cl 2 (g) + I 2 (aq) + 18NaOH(aq) → 14NaCl(aq)
+ 2Na 2 H 3 IO 6 (s)
+ 6H 2 O(l)
Let
the oxidation number of I in H 3 IO 6 2 ֿ be y,
3 × (+1) + y + 6 × (-2) = -2
The oxidation number of I is +7.

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

Question 5 (J89/I/5 modified)

State what you would observe in each of the following experiments. Explain these observations with the aid of the Data Booklet where appropriate.

(a) Solid iodine is shaken with aqueous potassium iodide; aqueous sodium thiosulfate is then added. 
(a)
Solid iodine is shaken with aqueous potassium iodide; aqueous sodium thiosulfate is then
added.
Shiny black solid iodine dissolves in aqueous potassium iodide to give a brown solution.
This is due to the formation of I 3
.
Upon addition of aqueous sodium thiosulfate,
I 2 (s) + 2e
S 4 O 6 2 (aq)
⇌ 2I ֿ (aq)
E  = +0.54
E  = +0.09
V
+
2e  ⇌
2S 2 O 3 2 (aq)
V
= +0.45 V > 0 (feasible)
 E o cell
Overall:
I 2 (s) + 2S 2 O 3 2 (aq)
2I − (aq)
+ S 4 O 6 2 (aq)
Thus solution turns from brown to colourless.
(b) Aqueous chlorine is added to aqueous iron(II) sulfate and aqueous sodium hydroxide is then added.
(b)
Aqueous chlorine is added to aqueous iron(II) sulfate and aqueous sodium hydroxide is
then added.
Upon addition of aqueous chlorine to aqueous iron(II) sulfate,
Cl 2 (aq) + 2e ⇌ 2Cl ֿ (aq)
Fe 3+ (aq)
+
e  ⇌
Fe 2+ (aq)
E  = +1.36 V
E  = +0.77 V
= +0.59 V > 0 (feasible)
 E o cell
Overall: Cl 2 (aq) + 2Fe 2+ (aq)  2Cl − (aq)
Thus solution turns from green to yellow.
+ 2Fe 3+ (aq)
When aqueous sodium hydroxide is added, reddish-brown precipitate of Fe(OH) 3 formed.
(c) Aqueous iron(III) sulfate is added to aqueous potassium iodide and a few drops of starch
(c)
Aqueous iron(III) sulfate is added to aqueous potassium iodide and a few drops of starch
indicator are then added.
Upon addition of aqueous iron(III) sulfate to aqueous potassium iodide,
I 2 (s) + 2e
Fe 3+ (aq)
⇌ 2I ֿ (aq)
E  = +0.54
V
+
e  ⇌
Fe 2+ (aq)
E  = +0.77 V
= +0.23 V > 0 (feasible)
 E o cell
Overall:
2Iֿ (aq)
+ 2Fe 3+ (aq)
I 2 (s)
+
2Fe 2+ (aq)
Thus solution turns from yellow to brown.
Upon addition of starch indicator, a blue-black complex will be formed.

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

Question 6 (N98/II/2)

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.

Hwa Chong Institution (College) 2011 H2 Chemistry – Group VII Question 6 (N98/II/2) Bromine has been

(a)(i)

What causes the yellow colour produced in A?

Section 4.4.1

(ii)

Write an equation for the reaction in A.

 

(i)

Aqueous bromine

(ii)

2Br (aq) + Cl 2 (aq)

Br

2 (aq) + 2Cl (aq)

  • (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.

Br 2 is non-polar and so it dissolves in a non-polar solvent like ether. The salt
Br 2 is non-polar and so it dissolves in a non-polar solvent like ether. The salt is ionic and will
not dissolve in a non-polar solvent like ether as there is no favourable solute-solvent
interaction.
  • (c) Suggest an equation for reaction C.

Section 4.4.2
Section 4.4.2

Br 2 (aq) + 2KOH(aq) KBr(aq)

+

KBrO (aq)

+

H 2 O(l)

  • (d) Suggest an equation for reaction D, the reaction of acid on the products of reaction C. Br - (aq) + BrO - (aq) + 2H + (aq) Br 2 (g) + H 2 O(l) [reverse of disproportionation]

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

Question 7 (N06/III/5)

When sodium thiosulfate is reacted separately with chlorine and iodine, different products are formed.

4Cl 2 + Na 2 S 2 O 3 + 5H 2 O 2NaHSO 4 + 8HCl

I 2 +

2Na 2 S 2 O 3 Na 2 S 4 O 6 + 2NaI

Use the following data and data from the Data Booklet, to suggest an explanation for this difference.

S 4 O 6 2− + 2e − 2S 2 O 3 2− E  =
S 4 O 6 2− + 2e −
2S 2 O 3 2−
E  = +0.09 V
4SO 2 +
4H + + 6e −
S 4 O 6 2− + 2H 2 O
E
= +0.51 V
SO 4 2− + 4H + + 2e −
SO 2 + 2H 2 O
E  = +0.17 V
Cl 2 + 2e
⇌ 2Cl ֿ
3 2-
Cl 2 + 2S 2 O
2Cl - +
S 4 O 6 2-
6 2-
3Cl 2 + S 4 O
6Cl - + 4SO 2 + 4H +
Cl 2 + SO 2 + 2H 2 O  2Cl - + SO 4 2- + 4H +
E  = +1.36 V
E  = +1.27V > 0 (feasible)
E  = +0.85V > 0 (feasible)
E  = +1.09V > 0 (feasible)
I 2 + 2e
⇌ 2I ֿ
 I 2 + 2S 2 O 3 2- 
S 4 O 6 2- + 2Iˉ
E  = +0.54 V
E  = +0.45V > 0 (feasible)
For the reaction between I 2 and S 4 O 6 2- , E  = +0.03V, is very small so reaction does not go to
completion.

Question 8 (N02/II/3)

In 1819, the element fluorine was known to exist but had not been isolated. The mineral fluorspar, which contained calcium fluoride, CaF 2 , had many properties similar to those of other calcium halides.

  • (a) What type of bonding is present in calcium fluoride?

Ionic bond

  • (b) When calcium fluoride reacts with concentrated sulfuric acid, gaseous hydrogen fluoride is produced. A similar reaction occurs with calcium chloride but with calcium bromide, bromine is formed.

(i)

Write an equation for the reaction of calcium fluoride with concentrated sulfuric

(ii)

acid. Why, when reacted with concentrated sulfuric acid, does calcium bromide form

(iii)

bromine whereas calcium chloride forms hydrogen chloride? Suggest a possible reaction product of the concentrated sulfuric acid in the reaction (ii) above.

Tay SA/Grace Chua/Jacqueline Tano/Tham YH
Tay SA/Grace Chua/Jacqueline Tano/Tham YH

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

(i)

CaF 2 (s) + 2H 2 SO 4 (l) 2HF(g) + Ca(HSO 4 ) 2 (s)

 

(ii)

Conc. H 2 SO 4 oxidises HBr to Br 2, but not HCl because the reducing power of HCl is lower than HBr.

(iii)

Sulfur

dioxide;

2HBr(g) +

H 2 SO 4 (l)

Br 2 (g)

+ 2H 2 O(l)

+

SO 2 (g)

Question 9 (N03/III/5 modified)

 
  • (a) Describe what you would see if chlorine water is added to aqueous sodium bromide. Write an equation for the reaction.

Colourless solution turns yellow-orange. Cl 2 (aq) + 2NaBr (aq) 2NaCl (aq) + Br 2 (aq)

 
  • (b) 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 4.31 g of AgCl. When the precipitate is filtered off and more silver nitrate solution added, 1.18g of 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 Br O Mass in 100g / g No. of moles 45.8 33.9 20.3 45.8 33.9
Ag
Br
O
Mass in 100g / g
No. of moles
45.8
33.9
20.3
45.8
33.9
20.3
 0.4241
 0.4243
 1.269
108
79.9
16.0
0.4241
0.4243
1.269
 1
1
 3
Ratio
0.4241
0.4241
0.4241
Formula of cream solid is
AgBrO 3 .
(ii) Calculate the number of moles of cream solid and of silver chloride formed. 1 18
(ii)
Calculate the number of moles of cream solid and of silver chloride formed.
1 18
.
5 00
.
10
 3
Number of mol of cream solid =
108
79 9
.
(
3
16 0
.
)
mol
4 31
.
 0 0300
.
Number of mol of AgCl =
108
35 5
.
mol

(iii)

Construct a balanced equation for the reaction between chlorine, sodium bromide and sodium hydroxide.

3Cl 2 (g) + 6NaOH(aq) + NaBr(aq) → 6NaCl(aq) + NaBrO 3 (aq) + 3H 2 O(l)

Question 10 (N97/II/3)

Hwa Chong Institution (College)

2011 H2 Chemistry Group VII

Potassium chlorate(V), KClO 3 , is widely used in fireworks and match heads. It decomposes when heated with a catalyst to form potassium chloride and oxygen.

  • (a) Construct an equation for this decomposition of potassium chlorate(V).

2KClO 3 (s)

2KCl(s)

+

3O 2 (g)

  • (b) Suggest why potassium chlorate(V) is used in fireworks and match heads.

(i)

(ii)

Suggest one substance which could be used as the combustible material in fireworks or match heads.

(i)

Potassium ion gives a lilac flame, OR KClO 3 produces O 2 which supports combustion.

(ii)

Carbon, or any other combustible materials, e.g. P, S, sugar.

  • (c) How can potassium chlorate(V) be obtained from chlorine? Illustrate your answer with an equation.

Pass chlorine through potassium hydroxide at 70°C:

3Cl 2 (aq) + 6KOH(aq)

5KCl(aq) + KClO 3 (aq) + 3H 2 O(l)

  • (d) The standard redox potential of chlorate(V) ions is given below.

ClO 3 + 6H + + 6e Cl + 3H 2 O E = +1.45 V Use the Data Booklet to predict what you would expect to observe when acidified potassium chlorate(V) is added separately to each of the following reagents.

Write a balanced equation for any reaction that occurs.

(i)

aqueous iron(II) sulfate

 
⇌ ClO 3  + 6H + + 6e  ⇌ Cl  + 3H 2
ClO 3  + 6H + + 6e  ⇌ Cl  + 3H 2 O E  = +1.45 V
6Fe 3+ + 6e
6Fe 2+
E  = +0.77 V
= +0.68 V > 0 (feasible)
E o cell
6Fe 2+ + ClO 3  + 6H +  6Fe 3+ + Cl  + 3H 2 O
Thus solution turns from green to yellow.
(ii)
acidified potassium manganate(VII)
E  (MnO 4  , Mn 2+ ) = +1.52 V No reaction will occur,
E  (MnO 4  , Mn 2+ ) = +1.52 V
No reaction will occur, since
both KMnO 4 and KClO 3 are oxidising agents.
The purple colour of KMnO 4 remains.