AS Information Sheet 2.

5(2)

OXIDISING AND REDUCING ABILITYIN GROUP 7

This information sheet is intended to try to prevent misunderstandings in questions on redox
and to help you answer exam questions in the right way. Oxidation and reduction will be
discussed in terms of electrons in the following paragraphs.
SOME DEFINITIONS
Oxidation

Loss of electrons (oxidation number increases)

Reduction

Gain of electrons (oxidation number decreases)

Oxidising Agent
A substance which can oxidise another
substance. In doing this, the oxidising agent takes away
electrons from the other substance. This means that it gains
electrons and is itself reduced. Oxidising agents are, therefore,
easily reduced.
Oxidising Power
The oxidising power (or ability)
describes how easily one substance can take away electrons
from another. A powerful oxidising agent is keen to gain
electrons it must be highly electronegative. Fluorine is the
best example.
Reducing Agent
A substance which can reduce another
substance. In doing this, the reducing agent gives electrons to
the other substance. This means that it loses electrons and is
itself oxidised. Reducing agents are, therefore, easily oxidised.
Reducing Power
The reducing power (or ability) describes
how easily one substance can give electrons to another. A
powerful reducing agent is keen to donate electrons. Alkali
metals are good examples (caesium is the best).
TYPICAL EXAM QUESTIONS
Questions which ask you to compare oxidising ability/power or reducing ability/power are
often in the context of trends in Group 7 (the Halogens).
It is important to be very clear about the difference
between Halogens and Halide ions.
Halogens
These are the elements, fluorine, chlorine,
bromine and iodine. They consist of diatomic molecules (F2,
Cl2, Br2 and I2). Notice that the names end in INE.
Halide Ions These are the negative ions (-1 oxidation state)
fluoride (F-), chloride (Cl-), bromide (Br-) and iodide (I-)

AS Information Sheet 2.5(2)

formed when the halogen atoms gain an electron each. The
ions have noble gas electron configurations. Notice that their
names end in IDE.

AS Information Sheet 2.5(2)

TRENDS WITHIN GROUP 7

Atomic & Ionic Radii

The radii of both the atoms and the ions increase down the Group from F to I. This is
because there is an additional electron shell added from one period to the next. Each
successive shell has a larger average radius than the previous one. Remember that the
ionic radius for a negative ion (like the halide ions) is larger than the corresponding atom
because the nucleus has to hold in an extra electron.
Electronegativity
Electronegativity is a measure of how much an atom attracts electrons to itself in a
(covalent) bond. The electronegativity of the elements decreases down the Group.
Fluorine has the highest value and iodine has the lowest. Although the atomic number
increases (and therefore the actual positive charge on the nucleus) down the Group, the
valence electrons are further away from the nucleus. There are also more inner shells to
shield the nucleus from the valence electrons. This means that the outer electrons
experience a smaller force of attraction to the nucleus as we go down the Group. Fluorine
atoms are small with a high effective nuclear charge and can, therefore, attract bonding
electrons easily. Iodine has large atoms with a much smaller effective nuclear charge,
making it less good at attracting other electrons.

Oxidising Power of the Elements

The ability of the elements to oxidise other substances decreases down the Group. This is
due to a combination of the increasing atomic radius and decreasing electronegativity
described above. Fluorines small size and high electronegativity make it a powerful
oxidising agent. Iodine has large atoms and a low electronegativity, so is a much less
powerful oxidising agent.

Reducing Ability of the Halide Ions

This is concerned with the ability of the negative ions to give away their extra electron
and act as reducing agents, as shown in the equations below:2F- F2 + 2e-

2I- I2 + 2e-

very difficult

quite easy

This increases down the Group (it is the opposite of the oxidising power of the element).

Exam questions relating to redox reactions in Group 7 are typically of two types:
1) Halogen displacement reactions.
2) The reaction of concentrated sulfuric acid with solid sodium or potassium halides (e.g.,
sodium chloride or potassium iodide).
These are discussed in more detail on the next two pages.

AS Information Sheet 2.5(2)

HALOGEN DISPLACEMENT REACTIONS
This is where a more reactive halogen element displaces a less reactive one from its
compound in solution. The halogen in the compound is in oxidation state 1 (halide ion).
This is oxidised to the element (oxidation state 0). At the same time, the incoming halogen
element is reduced from oxidation state 0 to 1. The example shown below is for chlorine
displacing bromine from a solution of potassium bromide:Cl2 (aq)

2 KBr (aq)

2 KCl (aq)

Br2 (aq)

Cl2 (aq)
0

2 Br- (aq)
-1

2 Cl- (aq)
-1

Br2 (aq)
0

It is important to read the way the question is phrased. It often says explain the reactions
in terms of the oxidising ability of the halogens. In this case, the chlorine oxidises the
bromide because it is a better oxidising agent than bromine. Explain in terms of atomic
radius and electronegativity discussed on the previous page.
Remember that the halide ions (which have a noble gas electron configuration) are colourless,
but the elements (diatomic molecules) have characteristic colours.
Halogen

Colour of Vapour or in
Inert Solvent (e.g. hexane)

Colour of Aqueous Solution

chlorine

green-yellow

very pale yellow-green

bromine

red-brown

iodine

purple

yellow to orange (depending on

concentration)
brown
(blue-black on adding starch)

REACTIONS OF SOLID HALIDES WITH CONC. SULPHURIC ACID

Concentrated sulfuric acid behaves differently to the dilute acid. As well as behaving like a
normal acid (donating H+ ions) and it can act as an oxidising agent. (It can also act as a
dehydrating agent, but this feature is not involved in these reactions.) You must learn the
following observations:HALIDE
NaCl
or
KCl
NaBr
or
KBr

NaI
or
KI

OBSERVATIONS
Misty fumes of strongly acidic HCl gas
are formed.
Misty fumes of strongly acidic HBr gas
are formed. Red-brown bromine vapour
and colourless SO2 gas (pungent and
acidic fumes) are also formed, but SO2 is
disguised by the presence of HBr.
A little HI gas and dark brown solid
iodine are formed (gives purple vapour if
warmed). There is a strong smell of bad
eggs from H2S gas. Pale yellow solid
sulphur is also formed and some SO2 gas.

EXPLANATIONS
This is an acid-base reaction.
Cl is still in oxidation state 1,
so no redox reactions are
involved.
Br ions have been oxidised
to Br2. They have reduced the
S in H2SO4 from oxidation
state +6 to +4 in SO2 gas.
I ions have been oxidised to
I2. They have reduced the S in
H2SO4 from oxidation state +6
to +4 in SO2 gas, 0 in solid
sulphur and 2 in H2S.

AS Information Sheet 2.5(2)

The equations for the reactions are as follows:1

NaCl(s) + H2SO4(l)

NaHSO4(aq) + HCl(g)

(H2SO4 acts as an acid and donates an H+ ion to the Cl ion to form HCl gas)
3) NaBr(s) + H2SO4(l)

2Br - + 2H+ + H2SO4

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

NaHSO4(aq) + HI(g)

2I - + 2H+ + H2SO4

I2(s)

SO2(g) +

2H2O(l)

6I - + 6H+ + H2SO4

3I2(s)

S(s)

4H2O(l)

8I - + 8H+ + H2SO4

4I2(s)

H2S(g) +

4H2O(l)

4) NaI(s) + H2SO4(l)

It is important to read the phrasing of questions on this. They are often of the form
explain the observations in terms of the reducing ability of the halide ions.
Concentrated H2SO4 can act as an oxidising agent and is sufficiently powerful to be able to
oxidise iodide to iodine easily and bromide to bromine partially, but not chloride or fluoride
(for these HCl or HF gas is formed, which is not oxidation, but an acid-base reaction, as
explained above).
Another way of looking at this is to think in terms of the halide ions being able to reduce the
sulfuric acid. F - is least willing to give away its extra electron, so its reducing ability is very
poor. Cl similarly does not readily part with its extra electron. Br can give its extra
electron away relatively easily and the S in the acid is reduced from oxidation state +6 to +4
in SO2. I very readily gives away its extra electron to something else, so its reducing ability
is good. In these reactions, the S in the acid is reduced from oxidation state +6 to a variety of
lower states, e.g., +4 in SO2, 0 in solid S and 2 in H2S. The reducing ability of the halide
ions increases down the group.
The explanation is that the larger ions with the valence electrons far from the nucleus and
shielded by the inner shells can lose the extra electron more easily. So, the halogen element
which is the most powerful oxidising agent (fluorine) has an ion (fluoride) which is the least
powerful reducing agent.