Chemguide – questions

GROUP 7: OXIDISING ABILITY

1. Chlorine gas is bubbled through potassium bromide solution.

a) Describe what you would see.

b) Write the ionic equation for the reaction.

c) Explain why this is a redox reaction, stating clearly what is being oxidised and what is being
reduced.

d) Explain why the equivalent reaction with fluorine would be more complicated than this.

e) What happens to the oxidising ability of the halogens as you go down the group.

2. The following table is taken from the Chemguide page, and shows the various enthalpy changes
involved in the reaction:
½X2(s, l or g)) + e- X-(aq)

a) Define:

(i) atomisation energy;

(ii) electron affinity;

(iii) hydration enthalpy.

b) Ignoring fluorine for the moment, why do the electron affinities of the other three elements
decrease as you go down the group?

c) Why is the fluorine value lower (less negative) than you might expect?

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d) Why is the fluorine value also out of line with the general trend in atomisation energy?

e) Why do the hydration enthalpies of the halogens fall as you go down the group?

f) Explain how the final column (in red) relates to the oxidising ability of the halogens.

g) What are the two most important factors in producing the changes in the last column as you go
down the group from chlorine to iodine?

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GROUP 7: TESTING FOR HALIDE IONS

1. You can test for the presence of the halide ions chloride, bromide and iodide by adding dilute nitric
acid to a solution of the suspected halide followed by silver nitrate solution, and looking for a
precipitate.

a) Why can't you test for fluoride ions by this method?

b) What is the point of adding the dilute nitric acid?

c) Name the precipitate if you had iodide ions present.

d) Write the ionic equation for the reaction involving iodide ions.

e) Complete the following table to show the results of doing this:

ion observation
Cl-
Br-
I-

f) Two of the precipitates are easy to confuse, and to distinguish between them, you can add
ammonia solution, both dilute and concentrated. Complete the following table to show the results
of adding the two different concentrations of ammonia solution to the precipitates.

precipitate from effect of adding dilute ammonia effect of adding concentrated

solution ammonia solution
chloride ions
bromide ions
iodide ions

2. There are two equilibria involved in the reactions in question 1(f):

AgHal(s) Ag+(aq) + Hal-(aq)

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

In the first equation, equilibrium can only occur if you have some solid silver halide present – in
other words, you have to have enough silver and halide ions present to form a saturated solution in
the presence of some solid.

Use these equilibria to explain the results of adding ammonia solution to the silver halide
precipitates.

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GROUP 7: HALIDE IONS AS REDUCING AGENTS

1. Sodium bromide reacts with concentrated sulphuric acid in two different ways:

Reaction 1: NaBr + H2SO4 NaHSO4 + HBr

Reaction 2: H2SO4 + 2H+ + 2Br- Br2 + SO2 + 2H2O

In the second equation, the hydrogen ions come from more sulphuric acid, and the bromide ions
from the sodium bromide.

a) What is the function of the sulphuric acid in the first equation? Explain your answer.

b) What is the function of the sulphuric acid in the second equation? Explain your answer.

c) What is the function of the bromide ions in the second equation? Explain your answer.

d) If you did this reaction by adding concentrated sulphuric acid to solid sodium bromide, what
would you see?

e) Suppose you repeated this reaction using sodium fluoride, sodium chloride and sodium iodide
instead of sodium bromide. How would this differ in each case?

f) The title of this page of questions is “Halide ions as reducing agents”. How does the reducing
ability of the halide ions change as you go down the group?

g) How does the ease with which the halide ions are oxidised to halogen molecules change as you
go down the group?

I am not going to ask questions about the explanations for these changes as you go down the group,
because it is too dependent on what your examiners might want. Use your syllabus, past papers and
mark schemes if they are available to find out exactly what sort of questions (if any) your examiners
ask, and what they expect you to say. There is no point in learning a complex explanation if your
examiners only want a simple one (however faulty!). And, equally, there is no point in learning an
over-simplified explanation if your examiners want you to do it properly – and no point in worrying
about an explanation at all if your syllabus doesn't mention it.

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