Topic 2.

4
REDOX REACTIONS
Oxidation and Reduction
Oxidising and Reducing Agents
Redox Reactions
OXIDATION AND REDUCTION
1. Simple half-equations
In inorganic chemistry, oxidation and reduction are best defined in terms of electron
transfer.
Oxiation is the loss of ele!t"ons. When a species loses electrons it is said to be
oxidised.
Eg Na Na
+
+ e (each sodium atom loses one electron)
2I

I2 + 2e (each iodide ion loses one electron, so t!o in total)

Reu!tion is the #ain of ele!t"ons. When a species gains electrons it is said to be
reduced.
Eg "l2 + 2e 2"l

(each chlorine atom gains one electron, so t!o in total)

#l
$+
+ $e #l (each aluminium ion gains three electrons)
%rocesses !hich sho! the gain or loss of electrons by a species are &no!n as half-
equations. 'hey sho! simple oxidation or reduction processes.
$. Oxiation num%e"s
The oxiation num%e" of an atom is the !ha"#e that &oul exist on an ini'iual
atom if the %onin# &e"e !ompletel( ioni!.
In simple ions, the oxidation number of the atom is the charge on the ion(
Na
+
, )
+
, *
+
all ha+e an oxidation number of +,.
-g
2+
, "a
2+
, %b
2+
all ha+e an oxidation number of +2.
"l

, .r

, I

all ha+e an oxidation number of ,.

/
2
, 0
2
all ha+e an oxidation number of 2.
In molecules or compounds, the sum of the oxidation numbers on the atoms is 1ero.
0/$2 oxidation number of 0 3 +4, oxidation number of each / 3 2.
+4 + $(2) 3 5
*2/22 oxidation number of * 3 +,, oxidation number of / 3 ,.
2(+,) + 2(,) 3 5
0"l22 oxidation number of 0 3 +2, oxidation number of "l 3 ,.
2 + 2(,) 3 5
In complex ions, the sum of the oxidation numbers on the atoms is e6ual to the o+erall
charge on the ion.
0/7
2
2 oxidation number of 0 3 +4, oxidation number of / 3 2.
+4 + 7(2) 3 2
%/7
$
2 oxidation number of % 3 +8, oxidation number of / 3 2.
(+8) + 7(2) 3 $
"l/

2 oxidation number of "l 3 +,, oxidation number of / 3 2.

+, +(2) 3 ,
In elements in their standard states, the oxidation number of each atom is 1ero.
In "l2, 0, Na and /2 all atoms ha+e an oxidation number of 1ero.
-any atoms, such as 0, N and "l, can exist in a +ariety of oxidation states. 'he oxidation
number of these atoms can be calculated by assuming that the oxidation number of the
other atom is fixed (usually / at 2).
#ll group I atoms al!ays adopt the +, oxidation state in their compounds.
#ll group II atoms adopt the +2 oxidation state in their compounds.
#luminium al!ays adopts the +$ oxidation state in its compounds.
9luorine al!ays adopts the , oxidation state in its compounds.
*ydrogen adopts the +, oxidation state in its compounds unless it is bonded to a metal,
0ilicon or boron in !hich case it adopts the , oxidation state.
/xygen adopts the 2 oxidation state in its compounds unless it is bonded to a group I or
group II metal or hydrogen (!ith !hich it sometimes adopts the , oxidation state), or
!ith fluorine (!ith !hich it adopts the +2 oxidation state).
'he oxidation numbers of all other atoms in their compounds can +ary.
.y follo!ing the abo+e guidelines, the oxidation number of any atom in a compound or
ion can be deduced.
:uring oxidation and reduction, the oxidation numbers of atoms change.
If an atom is oxii)e* its oxiation num%e" in!"eases
+ie it %e!omes mo"e ,'e o" less -'e.
If an atom is "eu!e* its oxiation num%e" e!"eases
+ie it %e!omes less ,'e o" mo"e -'e.
'hese ideas can be summari1ed in the follo!ing table(
/xidation ;oss of
electrons
Increase in
oxidation
number
<eduction =ain of
electrons
:ecrease in
oxidation
number
/. 0o"e !omplex half-equations
-any oxidation and reduction processes in+ol+e complex ions or molecules and the half
e6uations for these processes are more complex. In such cases, oxidation numbers are a
useful tool(
'here are t!o !ays to balance halfe6uations(
-ethod ,( (this sho!s you straight a!ay !hether oxidation or reduction is ta&ing place)
Identify the atom being oxidised or reduced, and ma&e sure there are the same
number of that atom on both sides (by balancing)
insert the number of electrons being gained or lost(
(on the left if reduction, on the right if oxidation)
No of ele!t"ons #aine1lost 2
!han#e in oxiation num%e" x num%e" of atoms !han#in# oxiation num%e"
balance / atoms by adding !ater
balance * atoms by adding *
+
Example( Write a balanced halfe6uation for the process 0/$
2
0/7
2
there is one sulphur on each side, so the 0 is already balanced
the oxidation number of the 0 is increasing from +7 to +4, so t!o electrons are
being lost (inserted on the right)(
0/$
2
0/7
2
+ 2e
there are three / atoms on the left and four on the right, so one !ater is needed on
the left(
0/$
2
+ *2/ 0/7
2
+ 2e
there are t!o * atoms on the left and none on the right, so t!o * ions are needed
on the right(
0/$
2
+ *2/ 0/7
2
+ 2*
+
+ 2e
'he oxidation number of the 0 is increasing and electrons are being lost. It is an oxidation
process.
-ethod 2( (this does not use oxidation numbers and is easier in more complex processes)
Identify the atom being oxidised or reduced, and ma&e sure there are the same
number of that atom on both sides (by balancing)
balance / atoms by adding !ater
balance * atoms by adding *
+
add the necessary number of electrons to ensure the charge on both sides is the
same
Example( Write a balanced halfe6uation for the process *20/7 *20
there is one sulphur on each side, so the 0 is already balanced
there are four / atoms on the left and none on the right, so four !aters are needed
on the right(
*20/7 *20 + 7*2/
there are t!o * atoms on the left and ten on the right, so eight * ions are needed
on the left(
*20/7 + >*
+
*20 + 7*2/
the total charge on the left is +> and on the right is 5. 0o eight electrons must be
added to the left to balance the charge(
*20/7 + >*
+
+ >e *20 + 7*2/
'he oxidation number of the 0 is decreasing and electrons are being gained. It is a
reduction process.
3. Reox "ea!tions
*alfe6uations consider gain and loss of electrons, but in fact electrons cannot be created
or destroyed2 they can only be transferred from species to species. =ain of electrons by
one species necessarily in+ol+es loss of electrons by another. /xidation and reduction
thus al!ays occur simultaneously2 an oxidation is al!ays accompanied by a reduction
and +ice +ersa. #ny reaction consisting of the oxidation of one species and the reduction
of another is &no!n as a "eox reaction.
# redox reaction can be deri+ed by combining an oxidation halfe6uation !ith a
reduction halfe6uation in such a !ay that the total number of electrons gained is e6ual to
the total number of electrons lost.
Eg *20/7 + >*
+
+ >e *20 + 7*2/ reduction
2I

I2 + 2e ? oxidation
(the oxidation halfe6uation must be multiplied by 7 to e6uate the electrons)
>I

7I2 + >e
o+erall( *20/7 + >*
+
+ >I

*20 + 7*2/ + 7I2 redox

Eg #l
$+
+ $e #l reduction
2/
2
/2 + 7e oxidation
(the reduction halfe6uation must be multiplied by 7 and the oxidation half
e6uation by $ to e6uate the electrons)
7#l
$+
+ ,2e 7#l
4/
2
$/2 + ,2e
o+erall( 7#l
$+
+ 4/
2
7#l + $/2 redox
4. Oxiisin# a#ents an "eu!in# a#ents
'he species !hich is reduced is accepting electrons from the other species and thus
causing it to be oxidised. It is thus an oxiisin# a#ent.
*20/7, #l
$+
and "l2 are all oxidising agents.
'he species !hich is oxidised is donating electrons to another species and thus causing it
to be reduced. It is thus a "eu!in# a#ent.
Na, /
2
, I

and 02/$
2
are all reducing agents.
# redox reaction can thus be described as a transfer of electrons from a reducing agent to
an oxidising agent.
Eg I2 + 202/$
2
2I

+ 07/4
2
*alfe6uations( I2 + 2e 2I

(reduction)
202/$
2
07/4
2
+ 2e (oxidation)
I2 is the oxidising agent2 07/4
2
is the reducing agent.
Eg *20/7 + >*
+
+ >I

*20 + 7*2/ + 7I2

*alfe6uations( *20/7 + >*
+
+ >e *20 + 7*2/ (reduction)
2I

I2 + 2e (oxidation)
*20/7 is the oxidising agent, I

is the reducing agent

5. Disp"opo"tionation
'here are many substances !hich readily undergo both oxidation and reduction, and
!hich can therefore beha+e as both oxidising agents and reducing agents. *2/2 and "l/

are t!o examples(
Eg *2/2 + 2*
+
+ 2e 2*2/ reduction
*2/2 /2 + 2*
+
+ 2e oxidation
Eg "l/

+ 2*
+
+ 2e "l

reduction
"l/

"l/$

+ 7*
+
+ 7e oxidation
0pecies such as these are capable of undergoing oxidation and reduction simultaneously.
The simultaneous oxiation an "eu!tion of the same spe!ies is 6no&n as
isp"opo"tionation.
:isproportionation reactions are special examples of redox reactions.
Eg *2/2 + 2*
+
+ 2e 2*2/ reduction
*2/2 /2 + 2*
+
+ 2e oxidation
2*2/2 2*2/ + /2 disproportionation
oxidation numbers( +, 2 5
Eg ("l/

+ 2*
+
+ 2e "l

) x 2 reduction
"l/

"l/$

+ 7*
+
+ 7e oxidation
$"l/

2"l

+ "l/$

disproportionation
oxidation numbers +, , +8