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INTRODUCTION and Reminders:

Ionic redox reactions can be 'split' into two half equations (half cell reactions) to
analyse what is going on redox wise, but spectator ions should not be included (
these are ions which do not take part in the reaction i.e. do not change their c
hemical 'status'.
Electrons are shown in the half cell reactions BUT should not be 'spotted' in the
complete and correctly balanced ionic redox equation for the reaction because elec
trons lost = electrons gained.
Getting the right ratio of the oxidation/reduction half cell reactions should ensu
re the electron transfer is 'hidden'.
In sections 5. and 6. where a reagent is specified as 'acidified', unless otherw
ise stated, this means with dilute sulphuric acid, H2SO4(aq) .
It is used in this context because it cannot be oxidised (unlike hydrochloric ac
id, HCl(aq)), it is a very weak oxidising agent (unlike nitric acid, HNO3(aq)) a
nd shows little tendency to form complexes with metal ions.
If required as part of equation, acidification will be shown as H+(aq).
All the reactions listed below are analysed in detail using the guidelines in se
ctions 3.1 to 3.4.
Section 5 reaction example sub index: 5.1 aluminium + copper(II) salt * 5.2 sulphu
r dioxide/sulphite + halogens * 5.3 ammonia + oxygen * 5.4 iron + steam * 5.5 ti
tanium extraction * 5.6 hydrazine + oxygen * 5.7 manganese(IV) oxide to potassiu
m manganate(VI)/manganate(VII) * 5.8 disproportionation of copper(I) oxide in ac
id * 5.9 conversion of cobalt(II) to cobalt(III) * 5.10 conversion of chromium(I
II) to chromium(VI) * 5.11 hydrogen sulphide + iron(II) * 5.12 copper(II) + iodi
de * 5.13 more examples of disproportionation and vice versa involving O and N i
ons/compounds * 5.14 Some chlorine, chlorates and chloride redox changes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.1 The reaction between aluminium and a copper(II) salt solution
2Al(s) + 3Cu2+(aq) ==> 2Al3+(aq) + 3Cu(s)
(i) half reaction oxidation Al atom: Al ==> Al3+ + 3e (electron loss, Al ox. state
change 0 to +3)
(ii) half reaction reduction Cu ion: Cu2+ + 2e ==> Cu (electron gain, Cu ox. state
change +2 to 0)
two aluminium atoms lose a total of 6 electrons which transfer to three copper(I
I) ions which gain a total of 6 electrons to balance the redox changes.
In other words 2 x (i) + 3 x (ii) equals the balanced equation.
The copper(II) ion is the oxidising agent (gain/accept e s, lowered ox. state),
and aluminium is the reducing agent (loses e s, inc. ox. state).
Section 5. Index of examples of redox equation analysis
For more on copper chemistry see Part 10b 3d block Transition Metals Fe to Zn de
tailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.2 The reaction between sulphur dioxide/sulphite and halogens
If neutral molecules or more complex ions are involved, a bit more care must be
taken e.g. when the sulphur dioxide is oxidised to sulphate by bromine (or the r
eduction of bromine to bromide).
SO2(aq) + Br2(aq) + 2H2O(l) ==> SO42 (aq) + 2Br (aq) + 4H+(aq)
(i) the oxidation half reaction is: SO2(aq) + 2H2O(l) ==> SO42 (aq) + 4H+(aq) + 2e
The sulphur changes from ox. state +4 to +6 (SO2 to SO42 ).
(ii) the reduction half reaction is: Br2(aq) + 2e ==> 2Br (aq)
Two bromine atoms (as molecule) change from ox. state 0 to 1.
The hydrogen (+1) and oxygen ( 2) do not change oxidation state.
(i) + (ii) equals the balanced equation, 2 electrons gained and lost or an ox. s
tate rise and fall of 2 units.
Bromine is the oxidising agent (gain/accept e s, lowered ox. state),
and sulphur dioxide is the reducing agent (loses e s, inc. ox. state of S).
Sulphur dioxide does ionise to a small extent in water to give the sulphite ion,
and adding a strong non oxidising acid like dilute hydrochloric acid to sodium me
tabisulphite produces the ion, which means another equation can also adequately
describe the redox change in terms of sulphur and bromine.
e.g. if the sulphite ion acts as the reducing agent the reaction with chlorine w
ould be written as:
SO32 (aq) + Cl2(aq) + H2O(l) ==> SO42 (aq) + 2Cl (aq) + 2H+(aq)
Section 5. Index of examples of redox equation analysis
Advanced Inorganic Chemistry Page Index and Links
Ex 5.3 The oxidation of ammonia with molecular oxygen
The concept of oxidation state can now be fully applied to reactions which do no
t involve ions e.g.
The oxidation of ammonia via a Pt catalyst at high temperature which is part of
the chemistry of nitric acid manufacture.
4NH3(g) + 5O2(g) ==> 4NO(g) + 6H2O(g)
The oxidation number analysis is:
4N at ( 3) each in NH3 and 10O all at (0) in O2 change to ...
4N at (+2) each in NH3, 4O at ( 2) each and 6 O at ( 2) each in H2O.
H is +1 throughout i.e. does not undergo an ox. state change.
Oxygen is reduced from ox. state (0) to ( 2).
Nitrogen is oxidised from ox. state ( 3) to (+2).
The total increase in ox. state change of 4 x ( 3 to +2) for nitrogen is balanced
by the total decrease in ox. state change of 10 x (0 to 2) for oxygen i.e. 20 e or
ox. state units change in each case.
Oxygen is the oxidising agent (gain/accept e s, lowered ox. state) and ammonia is
the reducing agent (loses e s, inc. ox. state of N).
Section 5. Index of examples of redox equation analysis
Advanced Inorganic Chemistry Page Index and Links
Ex 5.4 The reaction between iron and steam at >400oC
4Fe(s) + 4H2O(g) ==> Fe3O4(s) + 4H2(g)
Oxidation state analysis:
O stays at ox. state 2 (no change) but for the ....
8H's in H2O, the ox. state decreases from +1 to 0 in H2 (reduction, 8e gained),
this oxidation number decrease is balanced by the oxidation number increases fro
m ...
iron, 3Fe ox. state increases from 0 to one at +2 and two at +3
both oxidations, total 8e loss, because the compound consists Fe2+, 2Fe3+ and 4O2
ions.
Water is the oxidising agent (gain/accept e s, lowered ox. state of H),
and iron is the reducing agent (loses e s, inc. ox. state).
Section 5. Index of examples of redox equation analysis
For more on iron chemistry see Part 10b 3d block Transition Metals Fe to Zn deta
iled revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.5 The formation of titanium(IV) chloride from titanium(IV) oxide in the ext
raction of titanium metal
TiO2(s) + C(s) + 2Cl2(g) ==> TiCl4(l) + CO2(g)
Oxidation number changes:
The carbon, C is oxidised (0 to +4 in CO2) and the chlorine is reduced (0) in Cl
2 to ( 1) in TiCl4.
The oxidation of 1 x C from (0) to (+4) is balanced by the reduction of 4 x Cl f
rom (0) to ( 1).
Titanium (+4) and oxygen ( 2) do not change.
Chlorine is the oxidising agent (gains e s, lowered ox. state) and carbon is the r
educing agent (loses e s, inc. ox. state of C), but not in sense carbon reduces an
iron oxide to iron in a blast furnace because titanium does not change oxidatio
n state and another step is required to obtain the metal.
The titanium itself is extracted via another redox reaction by displacement with
a more reactive metal.
TiCl4(l) + 4Na(s) ==> Ti(s) + 4NaCl(s)
Ox. state changes :
The titanium is reduced from (+4) in TiO2 to (0) as Ti, and the displacing metal
is oxidised (from 0 to >+1).
The reduction of 1 x Ti (+4) to (0) is balanced by the oxidation of 4 x Na (0) t
o (+1)
or TiCl4(l) + 2Mg(s) ==> Ti(s) + 2MgCl2(s)
Ox. state changes : The 1 x Ti (+4) to (0) reduction is balanced by the 2 x Mg (
0) to (+2) oxidation.
In both cases titanium(IV) chloride is the oxidising agent (gain/accept e s, lower
ed ox. state of Ti) and sodium/magnesium are the reducing agent (lose/donate e s,
inc. their ox. state).
Section 5. Index of examples of redox equation analysis
For more on titanium chemistry see Periodic Table Advanced Inorganic Chemistry
Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.6 The combustion of liquid hydrazine and oxygen
This has been used as a liquid rocket fuel mixture.
N2H4(l) + O2(l) ==> N2(g) + 2H2O(g)
Oxidation state changes:
The nitrogen in hydrazine oxidised (N from 2 to 0) and the oxygen molecules are r
educed (O from 0 to 2).
The oxidation of 2 x N from ( 2) to (0) is balanced by the reduction of 2 x O from
(0) to ( 2).
H at (+1) does not change in oxidation state and nitrogen is initially ( 2) here,
NOT ( 3) as in ammonia, NH3.
Oxygen is the oxidising agent (gains/accepts e s, lowered ox. state) and hydrazine
is the reducing agent (loses/donates e s, inc. ox. state of N).
Section 5. Index of examples of redox equation analysis
Advanced Inorganic Chemistry Page Index and Links
Ex 5.7 Converting manganese(IV) oxide into potassium manganate(VI)/manganate(VII
)
5.7.1: If a mixture of manganese(IV) oxide, potassium hydroxide and potassium ch
lorate(V) is heated strongly and fuse in a crucible, the following redox reactio
n takes place:
3MnO2 + 6OH + ClO3 ==> 3MnO42 + 3H2O + Cl
The manganate(VI) ion is formed and the ox. number changes are ...
the oxidation of 3 x Mn from (+4) to (+6), MnO2 ==> MnO4 , total 6 e's lost
Is balanced by the reduction of 1 x Cl from (+5) to ( 1), ClO3 ==> Cl , total 6 e's g
ained
and hydrogen (+1) and oxygen ( 2) do not change oxidation state.
The chlorate(V) ion is the oxidising agent (gains/accepts e s, lowered ox. state o
f Cl) and manganese(IV) oxide is the reducing agent (loses/donates e s, inc. ox. s
tate of Mn).
5.7.2: When the fused mixture is dissolved in water, the initially green solutio
n of the manganate(VI) ion, slowly changes to the purple colour of the manganate
(VII) ion and a black precipitate of manganese(IV) oxide.
3MnO42 (aq) + 2H2O(l) ==> 2MnO4 (aq) + MnO2(s) + 4OH (aq)
Oxidation number changes:
Initially there are three Mn at (+6).
Two Mn at (+6) are oxidised to two Mn(+7), an ox. state total increase of 2 unit
s or 2e lost,
and one Mn at (+6) is reduced to Mn(+4), an ox. state total decrease of 2 units
or 2e gained.
This is an example of disproportionation where an element in one oxidation stat
e simultaneously changes into a higher and lower oxidation state species.
It also means that the manganate(VI) ions simultaneously acts as a reducing agen
t and oxidising agent!
As in 5.7.1, hydrogen (+1) and oxygen ( 2) do not change in oxidation state.
Section 5. Index of examples of redox equation analysis
For more on manganese chemistry see Periodic Table Advanced Inorganic Chemistr
y Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.8 The disproportionation of copper(I) oxide in acid
When brown copper(I) oxide is dissolved in dilute sulphuric acid, a deposit of c
opper is formed and a blue solution of copper(II) sulphate.
Cu2O(s) + H2SO4(aq) ==> Cu(s) + CuSO4(aq) + H2O(l)
Cu2O(s) + 2H+(aq) ==> Cu(s) + Cu2+(aq) + H2O(l)
The hydrated copper(I) ion, Cu+(aq) is unstable and changes into two oxidation s
tates simultaneously,
elemental Cu(0) and the blue copper(II) ion (+2), and is another example disprop
ortionation (see also 5.7.2).
i.e. 2 x Cu (+1) changes to 1 Cu at (0) by reduction and 1 Cu at (+2) by oxidati
on.
Oxygen in its ( 2) ox. state and hydrogen in its (+1) ox. state do not change.
It also means that the copper(I) ions simultaneously acts as a reducing agent an
d oxidising agent and are simultaneously oxidised and reduced.
You also observe the same disproportionation if copper(I) sulphate is dissolved
in water
Cu2SO4(s) + aq ==> Cu(s) + Cu2+(aq) + SO42 (aq)
Section 5. Index of examples of redox equation analysis
For more on copper chemistry see Part 10b 3d block Transition Metals Fe to Zn de
tailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.9 The conversion of cobalt(II) to cobalt(III) via molecular oxygen (air) or
hydrogen peroxide
When aqueous ammonia is added to cobalt(II) salt solutions the hexaamminecobalt(
II) complex is formed which is readily oxidised to the cobalt(II) complex by (i)
oxygen dissolving from air or (ii) adding hydrogen peroxide solution.
[Co(H2O)6]2+(aq) + 6NH3(aq) ==> [Co(NH3)6]2+(aq) + 6H2O(l)
NOT a redox reaction, just a ligand exchange or ligand substitution reaction.
(i) 4[Co(NH3)6]2+(aq) + O2(aq) + 4H+(aq) ==> 4[Co(NH3)6]3+(aq) + 2H2O(l)
Oxidation: In the complexes 4 Co at (+2) change to 4 Co at (+3), total increase
of 4 ox. state units.
Reduction: 2 O in O2 at (0) change to 2 O at ( 2) in 2H2O, total decrease of 4 ox.
state units.
No redox change involving the NH3 ligand or the H+ ions, N stays at 3 and H at +1
.
(ii) 2[Co(NH3)6]2+(aq) + H2O2(aq) + 2H+(aq) ==> 2[Co(NH3)6]3+(aq) + 2H2O(l)
Oxidation: 2 Co at (+2) change to 2 Co at (+3), total increase of 2 ox. state un
its.
Reduction: 2 O at ( 1) in H2O2 change to 2 O at ( 2) in 2H2O, total decrease of 4 ox
. state units.
No redox change involving the NH3 ligand or the H's of the hydrogen peroxide mol
ecule or hydrogen ions.
Oxygen/hydrogen peroxide act as the oxidising agent (gains/accepts e s, lowered ox
. state of O) and the cobalt(II) complex is the reducing agent (loses/donates e s,
inc. ox. state of Co).
Section 5. Index of examples of redox equation analysis
For more on cobalt chemistry see Part 10b 3d block Transition Metals Fe to Zn de
tailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.10 The conversion of chromium(III) to chromium(VI) compounds
When sodium hydroxide is added to a green aqueous solution of a chromium(II) sal
t, followed by hydrogen peroxide solution, the yellow chromate(VI) ion is formed
. The overall reaction can be expressed as ....
2Cr3+(aq) + 3H2O2(aq) + 10OH (aq) ==> 2CrO42 (aq) + 8H2O(l)
Oxidation: 2 Cr at (+3) change to 2 Cr (+6) in the chromate(VI) ion, a total inc
. of 6 ox. state units or 6e's lost.
Reduction: 6 O at ( 1) in 3H2O2 change to 6 O at ( 2) in 3 of the 8H2O's, total decr
ease of 6 ox. state units, 6e's gained.
No change at in any of the 6H's (+1) involved or oxygen ( 2) ox. state in the hydr
oxide ions.
Hydrogen peroxide act as the oxidising agent (gains/accepts e s, lowered ox. state
of O) and the chromium(III) ion acts as the reducing agent (loses/donates e s, in
c. ox. state of Cr).
Section 5. Index of examples of redox equation analysis
For more on chromium chemistry see Periodic Table Advanced Inorganic Chemistry
Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.11 The oxidation of hydrogen sulphide with iron(III) ions
If an iron(III) salt (old name, ferric salt) is added to hydrogen sulphide solut
ion a precipitate of sulphur forms and the orange brown solution turns pale green.
H2S(aq) + 2Fe3+(aq) ==> 2Fe2+(aq) + 2H+(aq) + S(s)
Oxidation: 1 S at ( 2) change to 1 S at (0), H2S ==> S, a loss of 2 electrons, inc
. 2 ox. state units.
Reduction: 2 Fe at (+3) change to 2 Fe at (+2), gain in total of 2 electrons, de
crease in 2 ox. state units.
No change in the oxidation state of the 2H's (+1) involved.
The iron(III) ion acts as the oxidising agent (gains/accepts e s, lowered ox. stat
e of Fe) and the hydrogen sulphide is the reducing agent (loses/donates e s, inc.
ox. state of S).
Section 5. Index of examples of redox equation analysis
For more on iron chemistry see Part 10b 3d block Transition Metals Fe to Zn deta
iled revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.12 The reaction of copper(II) ions with iodide ion
When potassium iodide solution is added to a copper salt solution, a white preci
pitate of copper(I) iodide is formed which is masked by a brown solution/black p
pt. of iodine. If sodium thiosulphate solution is added dropwise carefully, it r
eacts to remove the iodine giving the colourless iodide ion (see Ex 5.12), hence
the CuI precipitate is better scene.
2Cu2+(aq) + 4I (aq) ==> 2CuI(s) + I2(aq/s)
Oxidation: 2 I at ( 1) of the 4I change to 2 at (0) in I2, total 2e loss, inc. 2 ox.
state units.
Reduction: 2 Cu at (+2) change to 2 Cu (+1) in the CuI, total 2e gain, decrease 2
ox. state units.
Two of the I iodide ions do not change oxidation state, but they do change their
physical chemical situation.
The copper(II) ion acts as the oxidising agent (gains/accepts e s, lowered ox. sta
te of O) and the iodide ion is the reducing agent (loses/donates e s, inc. ox. sta
te of I).
Section 5. Index of examples of redox equation analysis
For more on copper chemistry see Part 10b 3d block Transition Metals Fe to Zn de
tailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 5.13 More examples of disproportionation and vice versa (involving O and N io
ns/compounds)
5.13.1 Hydrogen peroxide decomposition, catalysed by the black solid manganese(I
V) oxide, MnO2.
2H2O2(aq) ==> O2(g) + 2H2O(l)
Ox. state changes: 4O at ( 1) change to 2O at (0) in O2 and 2O at ( 2) in H2O
and H is unchanged at (+1).
A case of disproportionation where an element in a species simultaneously change
s into a higher and lower oxidation state i.e. here two oxygen atoms increase th
eir oxidation state and two oxygen atoms decrease their oxidation state.
It also means that hydrogen peroxide simultaneously acts as a reducing agent and
oxidising agent.
5.13.2 The reaction between ammonium and nitrate(III) (nitrite) ions
NH4+(aq) + NO2 (aq) ==> 2H2O(l) + N2(g)
Here its the opposite of disproportionation where two species of an element in d
ifferent oxidation states react to produce one species of a single intermediate
oxidation state.
Ox. state changes: Nitrogen in a ( 3) and a (+3) state both end up in the (0) stat
e.
Oxygen at ( 2) and hydrogen (+1) remain unchanged in oxidation state.
The nitrite ion acts as the oxidising agent and gets reduced (N +3 to 0, 3e's ga
ined, decrease of 3 ox. state units)
and the ammonium ion acts as the reducing agent and gets oxidised (N 3 to 0, 3 e'
s lost, inc. ox. state 3 units).
The nitrite ion acts as the oxidising agent (gains/accepts e s, lowered ox. state
of N) and the ammonium ion acts as the reducing agent (loses/donates e s, inc. ox.
state of N).
See other disproportionation reactions 5.7.2 MnO42 , 5.8 Cu2O, 5.14 chlorine and a
n organic example.
and the opposite of disproportionation! reactions 6.6 iodate(V) + iodide.
Section 5. Index of examples of redox equation analysis
Advanced Inorganic Chemistry Page Index and Links
5.14 Some chlorine, chlorates and chloride redox changes
In all the reactions quoted in section 5.14, (i) the oxidation states of hydroge
n (+1) and oxygen ( 2) remain unchanged and (ii) the process descriptions are over
simplified but the main reactions described provide good examples of the redox
chemistry of chlorine.
When chlorine reacts with aqueous sodium hydroxide at least two different react
ion can occur depending on the temperature and concentration of the strong base al
kali.
5.14.1 With cold dilute sodium hydroxide solution alkali sodium chlorate(I) (NaC
lO, the bleach sodium hypochlorite) is formed as well as sodium chloride.
2NaOH(aq) + Cl2(aq) ==> NaCl(aq) + NaClO(aq) + H2O(l)
2OH (aq) + Cl2(aq) ==> Cl (aq) + ClO (aq) + H2O(l)
The chlorine disproportionates from 2Cl(0) to 1Cl ( 1, chloride ion) plus 1Cl(+1,
chlorate(I) ion).
Overall 1 electron gained, (1 ox. state unit decrease) balanced by 1 electron lo
st (1 ox. state unit increase).
5.14.2 However, with hot concentrated sodium hydroxide solution, above 75oC, the
formation of sodium chlorate(V) predominates as well as sodium chloride.
6NaOH(aq) + 3Cl2(aq) ==> 5NaCl(aq) + NaClO3(aq) + 3H2O(l)
6OH (aq) + 3Cl2(aq) ==> 5Cl (aq) + ClO3 (aq) + 3H2O(l)
The chlorine disproportionates from 6Cl(0) to 5Cl( 1, chloride ion) plus 1Cl(+5, c
hlorate(V)ion).
Overall 5 electrons gained, (5 ox. state unit decrease) balanced by 5 electrons
lost (5 ox. state unit increase).
5.14.3 The change in reaction mode from 5.14.1 to 5.14.2 is due to the instabili
ty of the chlorate(I) ion, which at higher temperatures disproportionates into t
he chloride ion and the chlorate(V) ion.
3NaClO(aq) ==> 2NaCl(aq) + NaClO3(aq)
3ClO (aq) ==> 2Cl (aq) + ClO3 (aq)
The 'chlorine' in the chlorate ion disproportionates from 3Cl(+1) to 2Cl( 1, chlor
ide ion) plus 1Cl(+5, chlorate(V) ion).
Overall 4 electrons gained, (4 ox. state unit decrease) balanced by 4 electrons
lost (4 ox. state unit increase).
5.14.4 A concentrated solution of sodium chlorate(I) is a useful source of chlor
ine in the laboratory because it readily reacts with conc. hydrochloric acid to
give off the gas.
NaClO(aq) + 2HCl(aq) ==> NaCl(aq) + H2O(l) + Cl2(aq/g)
ClO (aq) + Cl (aq) + 2H+(aq) ==> H2O(l) + Cl2(aq/g)
The 'chlorine' here does the opposite of disproportionation and changes from 1Cl
(+1, chlorate(I) ion) plus 1Cl( 1, chloride ion) to give 2Cl(0, chlorine molecule)
.
Overall 1 electron lost, (1 ox. state unit increase) balanced by electron gaine
d (1 ox. state unit decrease).
Section 5. Index of examples of redox equation analysis
Advanced Inorganic Chemistry Page Index and Links
6. Constructing full ionic redox equations from half cell equations
Half cell reactions or half equations are often quoted as an electron gain reduction
e.g. when given as half cell potential data from a databook/textbook or exam ques
tion source and this is how they are initially presented in section 6. BUT, to p
roduce the full equation, you have to juggle and balance things around to derive
the correct full equation.
The direction of chemical change in redox reactions is fully explained in the Eq
uilibria Part 7 but many examples of equation construction, full redox analysis
of the reaction and use of half cell potential (E) data are also described.
Section 6 reaction example sub index: 6.1 zinc + silver salt (metal displacement)
* 6.2 chlorine + potassium iodide (halogen displacement) * 6.3 hydrogen peroxide
+ iron(II) ==> iron(III) * 6.4 iron(II) salt + potassium manganate(VII) (titrat
ion) * 6.5 Fe(II) salt + dichromate(VI) * 6.6 iodate(V) + iodide ions * 6.7 hydr
ogen peroxide + potassium manganate(VII) (titration) * 6.8 ethanedioate + potass
ium manganate(VII) (titration) * 6.9 vanadium(IV) salt + tin(II) salt * 6.10 iod
ine and sodium thiosulphate (titration) * 6.11 oxidation of chloride by manganat
e(VII) * 6.12 reduction of dichromate(VI) with iodide * 6.13 Oxidation of hydrog
en sulphide by acidified potassium manganate(VII) *
REDOX EQUATION CHECKS
Use of the correct 'species' of the half cell equations to be put together, the ri
ght way round AND in the correct ratio based on the number of electrons transfer
red or oxidation state changes.
Getting the right ratio of the oxidation/reduction half cell reactions should ensu
re the electrons are 'hidden' and you can add them up in a simple algebraic way
see the tabular expression of the way of thinking.
If not told, you must decide on the direction of change which is oxidised or red
uced? from E data supplied (half cell potentials) and the most +ve (least ve) half cel
l potential indicates the reduction half equation. Much more on this in Equilibria
Part 7.
The total increase in oxidation states of elements = the total decrease in oxida
tion states of elements,
or, total electrons gained by species = total electrons lost by the species invo
lved.
Add up the ion charges, the totals should be the same on both sides of the equat
ion. I find this a handy extra check especially with stray H+'s and H2O's.
The 'traditional' atom count do last because its not completely reliable with re
dox equations!
Advanced Inorganic Chemistry Page Index and Links
Ex 6.1 The reaction between zinc metal and a silver salt solution
All the half cell equations are presented as a reduction electron gain, so one mus
t be reversed!
See also Equilibria Part 7 Redox Reactions for Half cell equilibria, electrode
potential, standard hydrogen electrode, Simple cells and notation, Electrochemic
al Series, Ecell for reaction feasibility, 'batteries' and fuel cell systems etc.
Half cell reaction data:
(i) Zn2+(aq) + 2e ==> Zn(s) (E = 0.76V*, Zn will act as reducing agent, E less posit
ive)
(ii) Ag+(aq) + e ==> Ag(s) (E = +0.80V*, reduction of the oxidising agent with the
more positive E)
* It doesn't matter here if you haven't yet studied E, half cell potentials in deta
il, but the more +ve half cell species acts as the oxidising agent and so is the r
eduction half of the reaction.
The more reactive metal Zn, displaces the less reactive metal (Ag) from one of i
ts compounds, which is the reaction feasibility rule at lower academic levels fo
r such a redox reaction (see also halogen displacement reaction 6.2 below).
With redox analysis of the reaction we can now say:
The zinc is oxidised from 0 to +2 in ox. state, 2e loss,
and the two silver ions are reduced from 1 to 0 ox. state, 2 x 1e gain.
The zinc metal is a stronger reducing agent (more powerful e donor, less +ve E) th
an silver,
or to put it another way,
the Ag+ ion is a stronger oxidising agent (more powerful e acceptor, more +ve E) t
han the Zn2+ ion.
So one of the Zn half cell equations will be balanced by two of the silver half cell
equations giving the complete ionic redox equation, showing NO electrons.
1 x oxidation half cell, (i) reversed Zn(s) ==> Zn2+(aq) + 2e
2 x reduction half cell, (ii) 2Ag+(aq) + 2e ==> 2Ag(s)
added gives full redox equation Zn(s) + 2Ag+(aq) ==> Zn2+(aq) + 2Ag(s)
This sort of displacement reaction can be used to plate more reactive metals wit
h a less reactive metal without the need for electrolysis electroplating e.g. dipp
ing iron/steel into copper(II) sulphate to give a pink brown coating of copper.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
See also Periodic Table Advanced Inorganic Chemistry Notes Part 10a "3d block
Transition Metals Series Introduction and Elements Sc to Mn on Period 4 detailed
revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.2 The reaction between aqueous chlorine and potassium iodide solution
Half cell reaction data:
(i) 1/2Cl2(aq) + e ==> Cl (aq) (E = +1.36, can be Cl2(aq) + 2e ==> 2Cl (aq) but E still
+1.36)
(ii) 1/2I2(aq) + e ==> I (aq) (E = +0.54V, can be I2(aq) + 2e ==> 2I (aq) but E still +
0.54V)
Chlorine molecules are reduced from ox. state (0) to ( 1) of the chloride ion, 1 e
lectron gain.
Iodide ions are oxidised from ox. state ( 1) to (0) of the iodine molecule, 1 elec
tron loss.
So chlorine molecules are the oxidising agent (more powerful e acceptor, more +ve
E) and iodide ions are the reducing agent (e donor, less +ve E).
2 x oxidation half cell, (ii) reversed 2I (aq) ==> I2(aq) + 2e
2 x reduction half cell, (i) Cl2(aq) + 2e ==> 2Cl (aq)
added gives full redox equation Cl2(aq) + 2I (aq) ==> Cl2(aq) + I2(aq)
One method of estimating chlorine in water e.g. from bleaches, is to add excess
potassium iodide and titrating the liberated iodine with standardised sodium thi
osulphate, which itself is another redox reaction (see Ex 6.10)
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
Advanced Inorganic Chemistry Page Index and Links
Ex 6.3 The reaction between hydrogen peroxide and iron(II) ions
Half cell reaction data:
(i) H2O2(aq) + 2H+(aq) + 2e ==> 2H2O(l) (E = +1.36, reduction of oxidising agent w
ith the more positive E)
(ii) Fe3+(aq) + e ==> Fe2+(aq) (E = +0.77, less positive, so Fe3+ can't oxidise h
ydrogen peroxide)
Both the iron(III) ion and hydrogen peroxide molecule can act as oxidising agent
s, but hydrogen peroxide is stronger and so oxidises the iron(II) ion to the iro
n(III) ion.
Oxidation: Two iron(II) ions at (+2) lose an electron each to give iron(III) ion
s at (+3) ox. state.
Reduction: 2 O at ( 1) in each H2O2 are reduced to the ( 2) state in the 2H2O.
The hydrogens (+1) do not change oxidation state.
2 x oxidation half cell, (ii) reversed 2Fe2+(aq) 2e ==> 2Fe3+(aq)
1 x reduction half cell, (i) H2O2(aq) + 2H+(aq) + 2e ==> 2H2O(l)
added gives full redox equation 2Fe2+(aq) + H2O2(aq) + 2H+(aq) ==> 2Fe3+(aq) + 2
H2O(l)
This reaction is used to convert e.g. iron(II) sulphate, FeSO4, into iron(III) s
ulphate, Fe2(SO4)3, because dissolving iron in dil. sulphuric acid gives the Fe(
II) salt.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on iron chemistry see Part 10b 3d block Transition Metals Fe to Zn deta
iled revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.4 The reaction between acidified manganate(VII) ions and iron(II) ions
Half cell reaction data:
(i) MnO4 (aq) + 8H+(aq) + 5e ==> Mn2+(aq) + 4H2O(l) (E = +1.52, reduction of oxidis
ing agent)
(ii) Fe3+(aq) + e ==> Fe2+(aq) (E = +0.77, Fe2+ acts as reducing agent, Fe2+ gets
oxidised, E less positive)
Oxidation: Iron(II) ions, Fe2+, (+2) lose an electron, so oxidised to the iron(I
II) ion, Fe3+, (+3), Fe +2 to +3 ox. state.
Reduction: Manganate(VII) ions, MnO4 , (+7) are reduced to manganese(II) ions, Mn2
+, (+2), 5e gain, so five Fe2+ ions can be oxidised, Mn +7 to +2 ox. state.
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
5 x ox. half cell, (ii) reversed 5Fe2+(aq) ==> 5Fe3+(aq) + 5e
1 x reduction half cell, (i) MnO4 (aq) + 8H+(aq) + 5e ==> Mn2+(aq) + 4H2O(l)
added full redox equation MnO4 (aq) + 8H+(aq) + 5Fe2+(aq) ==> Mn2+(aq) + 5Fe
3+(aq) + 4H2O(l)
This reaction is used to quantitatively estimate iron(II) ions and is self indicat
ing. On the addition of standardised potassium manganate(VII) to the iron soluti
on, decolourisation occurs as the almost colourless Mn(II) ion (a VERY pale pink
) is formed from the reduction of the intensely purple manganate(VII) ion, and t
he end point is the first permanent pale pink with =< 1 drop excess of the oxidisi
ng agent.
The presence of dilute sulfuric ('supplier' of the proto, H+ ion), ensures the d
esired sole reduction of the manganate(VII) ion to the Mn(II) ion, thereby preve
nting the formation of a manganese(IV) oxide precipitate. Formation of MnO2 whic
h would not give a good end point and cause a duality in the redox reactions occ
urring, so introducing errors and quantitative complications.
There is a 2nd good reason for using dilute sulphuric acid, as opposed to using
other common mineral acids. Dil. sulphuric acid does not undergo any redox react
ions under the conditions of this titration.
Dilute hydrochloric acid cannot be used because the manganate(VII) ion will oxid
ise the chloride ion (see 6.11) and dil. nitric acid, via the nitrate(V) ion, wi
ll oxidise the iron(II) ion, i.e. both acids will lead to false titration result
s.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on manganese chemistry see Periodic Table Advanced Inorganic Chemistr
y Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.5 The reaction between acidified potassium dichromate(VI) and iron(II) ions
Half cell reaction data:
(i) Cr2O72 (aq) + 14H+(aq) + 6e ==> 2Cr3+(aq) + 7H2O(l) (E = +1.33, reduction of the
oxidising agent)
(ii) Fe3+(aq) + e ==> Fe2+(aq) (E = +0.77, Fe2+ will act as reducing agent, E less
positive)
Oxidation: Iron(II) ions at (+2) lose an electron each to give an iron(III) ion
at (+3), Fe +2 to +3 ox. state.
Reduction: Each Cr at (+6) is reduced by gaining 3e to give Cr at (+3) ox state,
Cr +6 to +3 ox. state.
the Cr2O72 ion is the oxidising agent and each can oxidise 6 Fe2+ ions.
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
6 x ox. half cell, (ii) rev. 6Fe2+(aq) ==> 6Fe3+(aq) + 6e
1 x red'n half cell, (i) Cr2O72 (aq) + 14H+(aq) + 6e ==> 2Cr3+(aq) + 7H2O(l)
added full equation Cr2O72 (aq) + 14H+(aq) + 6Fe2+(aq) ==> 2Cr3+(aq) + 6Fe3+(a
q) + 7H2O(l)
Like with potassium manganate(VII), standardised potassium dichromate(VI) soluti
on can be used to estimate quantitatively iron(II) ions in solution, though a sp
ecial redox organic dye* indicator which must be used to detect the end point.
The organic dye changes colour when oxidised to another form, but only after the
iron is oxidised i.e. it is not as easily oxidised as Fe2+, i.e. the dye's E is
more +ve than Fe2+ but lees than for the manganate(VII) ion, hence it is capabl
e of being oxidized by the dichromate(VI) ion to show the end point.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on chromium chemistry see Periodic Table Advanced Inorganic Chemistry
Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.6 The reaction between iodate(V) and iodide ions in acidified aqueous solut
ion
Half cell reaction data:
(i) 1/2I2(aq) + e ==> I (aq) (E = +0.54V, iodide gets oxidised, acts as reducing age
nt, less positive E)
(ii) IO3 (aq) + 6H+(aq) + 5e ==> 1/2I2(aq) + 3H2O(l) (E = +1.19V, reduction of oxid
ising agent, more positive E)
The iodide ions (I at 1) are oxidised to iodine molecules (I at 0) by electron lo
ss to the iodate(V) ion, I 1 to 0 ox. state.
The iodate(V) ions (I at +5) are reduced to iodine molecules (I at 0) by electro
n gain from the iodide ions (the reducing agent), I +5 to 0 ox. state.
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
5 x ox'n half cell, (i) reversed 5I (aq) ==> 5/2I2(aq) + 5e
1 x reduction half cell, (ii) IO3 (aq) + 6H+(aq) + 5e ==> 1/2I2(aq) + 3H2O(l)
added gives full equation IO3 (aq) + 6H+(aq) + 5I (aq) ==> 3I2(aq) + 3H2O(l)
The reaction can be used to estimate iodate(V) by adding excess potassium iodide
and titrating the liberated iodine with standardised sodium thiosulphate or usi
ng the liberated iodine from a known quantity of potassium iodate(V) salt with e
xcess KI(aq) salt solution to standardise the sodium thiosulphate.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
Advanced Inorganic Chemistry Page Index and Links
Ex 6.7 The reaction between acidified potassium manganate(VII) and hydrogen pero
xide solutions aqueous
Half cell reaction data:
(i) MnO4 (aq) + 8H+(aq) + 5e ==> Mn2+(aq) + 4H2O(l) (E = +1.52, reduction of the ox
idising agent)
(ii) O2(g) + 2H+(aq) + 2e ==> H2O2(aq) (E = +0.68, H2O2 will act as reducing agent
, E less positive)
Both are well known oxidising agents but in this situation hydrogen peroxide is
the one to get oxidised (less +ve E).
Reduction: Mn (+7) is reduced to Mn (+2), 5e gain, Mn +7 to +2 ox. state.
Oxidation: The O at ( 1) in H2O2 is reduced to ( 2) in H2O, O 1 to 2 ox. state.
Hydrogen (+1) of the H+ ions and the oxygen's ( 2) of the MnO4 ion do not change ox
idation state.
5 x ox'n half cell, (ii) rev'd 5H2O2(aq) ==> 5O2(g) + 10H+(aq) + 10e
2 x reduction half cell, (i) 2MnO4 (aq) + 16H+(aq) + 10e ==> 2Mn2+(aq) + 8H2O(l
)
added full equation 2MnO4 (aq) + 6H+(aq) + 5H2O2(aq) ==> 2Mn2+(aq) + 5O2(g) +
8H2O(l)
Note the 16H+ on left and 10H+ on right result in just 6H+ on left after additio
n of the half equations, so watch it!
The reaction can be used to quantitatively measure hydrogen peroxide concentrati
ons. The end point is the 1st permanent faint pink from a tiny excess of the potas
sium manganate(VII) solution from the burette.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on manganese chemistry see Periodic Table Advanced Inorganic Chemistr
y Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.8 The titration of ethanedioate with acidified potassium manganate(VII) sol
ution
Half cell reaction data:
(i) MnO4 (aq) + 8H+(aq) + 5e ==> Mn2+(aq) + 4H2O(l) (E = +1.52, reduction of the ox
idising agent)
(ii) 2CO2(aq/g) + 2e ==> C2O42 (aq) (E = 0.49V based on (COOH)2)
Reduction: Mn (+7) is reduced to Mn (+2), 5e gain, acts as the oxidising agent, e
lectron acceptor.
Oxidation: Each ethanedioate ion loses two electrons to form carbon dioxide, act
s as reducing agent.
(carbon's ox. state increases from +3 to +4, 1e loss per C to get CO2 where C is
+4)
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
5 x ox'n half cell, (ii) rev. 5C2O42 (aq) ==> 10CO2(aq/g) + 10e
2 x red'n half cell, (i) 2MnO4 (aq) + 16H+(aq) + 10e ==> 2Mn2+(aq) + 8H2O(l)
added full equation 2MnO4 (aq) + 16H+(aq) + 5C2O42 (aq) ==> 2Mn2+(aq) + 8H2O(l)
+ 10CO2(g/aq)
This reaction can be used to analyse samples of ethanedioc acid (oxalic acid) an
d ethanedioate salts (oxalates) or by starting with a very pure weighed samples
of the acid or salt, you can standardise the potassium manganate(VII) solution.
Self indicating, first permanent pale pink.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on manganese chemistry see Periodic Table Advanced Inorganic Chemistr
y Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.9 Reduction of the vanadium(IV) oxo cation by tin(II) salts
Half cell reaction data:
(i) VO2+(aq) + 2H+(aq) + e ==> V3+(aq) + H2O(l) (E = +0.34, reduction of the oxidi
sing agent)
(ii) Sn4+(aq) + 2e ==> Sn2+(aq) (E = +0.15, Sn2+ will act as a reducing agent, E le
ss positive)
V at (+4) in VO2+ is reduced to V at (+3), 1e gain per V,
Sn at (+2, tin(II) ion) is oxidised to Sn at (+4, tin(IV) ion), 2e loss per Sn.
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
1 x oxi'n half cell, (ii) rev. Sn2+(aq) ==> Sn4+(aq) + 2e
2 x reduction half cell, (i) 2VO2+(aq) + 4H+(aq) + 2e ==> 2V3+(aq) + 2H2O(l)
added full equation 2VO2+(aq) + 4H+(aq) + Sn2+(aq) ==> 2V3+(aq) + 2H2O(l) +
Sn4+(aq)
Tin(II) salts are used as reducing agents.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on vanadium chemistry see Periodic Table Advanced Inorganic Chemistry
Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.10 Titrating iodine with standardised sodium thiosulphate solution
Half cell reaction data:
(i) 1/2I2(aq) + e ==> I (aq)
E = +0.54V, the most positive, so iodine (I2) acts as the oxidising agent, which
gets reduced in the process.
(ii) 1/2S4O62 (aq) + e ==> S2O32 (aq)
E = +0.09V, this E is less positive, so the thiosulfate ion (S2O32 ) will be oxidis
ed.
The iodine is reduced by the thiosulphate ion to form iodide, ox. state of I (0)
to ( 1).
The thiosulphate ion is oxidised to the tetrathionate ion. In doing so the sulph
ur atom changes ox. state from an average of four at (+2) in the two S2O32 ions t
o an average of four at (+2.5) in the single S4O62 ion.
A bit of an awkward one in analysing sulphur and it is best to reason in terms o
f an average oxidation state of sulphur.
2 x reduction half cell, (i) I2(aq) + 2e ==> 2I (aq)
2 x oxidation half cell, (ii) rev. 2S2O32 (aq) ==> S4O62 (aq) + 2e
added gives full equation 2S2O32 (aq) + I2(aq) ==> S4O62 (aq) + 2I (aq)
This is used to quantitatively estimate iodine in aqueous solution. The indicato
r is a few drops of starch solution which forms a blue black complex with iodine.
The end point is when the solution first becomes colourless with no remaining iodi
ne to form the coloured complex. The iodine to be titrated may arise from a vari
ety of reactions for analysis purposes, see 6.2, 6.6 and 6.12.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
Advanced Inorganic Chemistry Page Index and Links
Ex 6.11 The oxidation of chloride by acidified potassium manganate(VII)
Half cell reaction data:
(i) MnO4 (aq) + 8H+(aq) + 5e ==> Mn2+(aq) + 4H2O(l) (E = +1.52, reduction of the ox
idising agent)
(ii) 1/2Cl2(aq) + e ==> Cl (aq) (E = +1.36, lower E, so cannot act as the oxidising a
gent here)
Both chlorine and potassium manganate(VII) are strong oxidising agents, but chlo
rine is the weaker, so chloride ions are oxidised to chlorine.
Oxidation: Chlorine as the chloride ions at ( 1) lose electrons to give chlorine m
olecules at ox. state (0).
Reduction: Mn (+7) is reduced to Mn (+2), 5e gain, acts as the oxidising agent.
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
10 x oxi'n half cell, (ii) rev. 10Cl (aq) ==> 5Cl2(aq/g) + 10e
2 x red'n half cell, (i) 2MnO4 (aq) + 16H+(aq) + 10e ==> 2Mn2+(aq) + 8H2O(l)
added full redox equation 2MnO4 (aq) + 16H+(aq) + 10Cl (aq) ==> 2Mn2+(aq) + 8H
2O(l) + 5Cl2(g/aq)
This reaction is used to prepare chlorine gas (green and toxic) by running conc.
hydrochloric acid on to moistened potassium manganate(VII) crystals (old name p
otassium permanganate).
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on manganese chemistry see Periodic Table Advanced Inorganic Chemistr
y Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.12 The reduction of acidified dichromate(VI) with iodide ions
Half cell reaction data:
(i) Cr2O72 (aq) + 14H+(aq) + 6e ==> 2Cr3+(aq) + 7H2O(l) (E = +1.33, the reduction of
the oxidising agent)
(ii) 1/2I2(aq) + e ==> I (aq) (E = +0.54V, lower E, so cannot act as oxidising agent)
Oxidation: Iodide ions at ( 1) lose electron to give iodine molecules at I(0).
Reduction: Each Cr at (+6) is reduced by gaining 3e to give Cr at (+3), so the Cr
2O72 ion is the oxidising agent.
Hydrogen (+1) and oxygen ( 2) do not change oxidation state.
6 x oxidation half cell, (ii) rev. 3I2(aq) + 6e ==> 6I (aq)
1 x reduction half cell, (i) Cr2O72 (aq) + 14H+(aq) + 6e ==> 2Cr3+(aq) + 7H2O(l)
added full redox equation Cr2O72 (aq) + 14H+(aq) + 6I (aq) ==> 2Cr3+(aq) + 3I2
(aq) + 7H2O(l)
This reaction can be used to quantitatively measure chromium(VI) in dichromates,
Cr2O72 , or chromates, CrO42 (which change to dichromate(VI) on acidification, yel
low ==> orange). Excess potassium iodide is added and the liberated iodine is ti
trated with standardised sodium thiosulphate solution (starch indicator, blue ==
> colourless), see Ex 6.10.
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on chromium chemistry see Periodic Table Advanced Inorganic Chemistry
Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes
Advanced Inorganic Chemistry Page Index and Links
Ex 6.13 The oxidation of hydrogen sulphide by acidified potassium manganate(VII)
Half cell reaction data:
(i) MnO4 (aq) + 8H+(aq) + 5e ==> Mn2+(aq) + 4H2O(l) (E = +1.52, reduction of the ox
idising agent)
(ii) SO42 (aq) + 10H+(aq) + 8e ==> H2S(aq) + 4H2O(l) (E = ?, oxidation of the redu
cing agent )
(ii) assumes that the sulphur is initially in a covalent molecular state and NOT
sulphide ions, which would be readily protonated by the dilute sulphuric acid.
It further assumes the sulphur is completely oxidised from 2 in H2S, to its maxim
um oxidation state of +6 as the sulphate(VI) ion.
So you have to balance up an 8 e /8 ox. no. units reduction with a 5 e /5 ox. no. un
its half cell
5 x oxi'n half cell, (ii) rev. 5H2S(aq) + 20H2O(l) ==> 5SO42 (aq) + 50H+(aq) + 40
e
8 x red'n half cell, (i) 8MnO4 (aq) + 64H+(aq) + 40e ==> 8Mn2+(aq) + 32H2O(l)
added full redox equation 8MnO4 (aq) + 14H+(aq) + 5H2S(aq) ==> 8Mn2+(aq) + 5
SO42 (aq) + 12H2O(l)
This is quite a tricky one to do with awkward numbers!
I'm not sure exactly what happens in practice, so above is theoretical, therefor
e in addition to the above 'construction' if the hydrogen sulphide is just oxidi
sed to a sulphur precipitate, the equation would be ...
2MnO4 (aq) + 6H+(aq) + 5H2S(aq) ==> 2Mn2+(aq) + 5S(s) + 8H2O(l)
2 x Mn(VII) ==> 2 x Mn(II) of equation (i) (10 e change), balanced by 5 x S( 2) to
5 x S(0) of equation (iii) reversed (below).
(iii) S(s) + 2H+(aq) + 2e ==> H2S(aq) (E = +0.14V, less positive, so hydrogen sulp
hide gets oxidised)
Ex 6.14 The conversion of chromium(III) to chromium(VI)
When hydrogen peroxide is added to an alkaline chromium(III) solution, oxidation
occurs to give the yellow chromate(VI) ion CrO42 .
2Cr3+(aq) + 3H2O2(aq) + 10OH (aq) ==> 2CrO42 (aq) + 8H2O(l)
Redox changes: oxidation 2Cr(+3) ==> 2Cr(+6), and for the corresponding ....
reduction 6 O( 1) in 3H2O2 ==> 6( 2) in 6 of the 8H2O
a total of 6 'units' oxidation state change, which I sometimes unofficially call
6 'electrons worth' of change!
Both Cr(VI) compounds and hydrogen peroxide and are oxidising agents e.g.
E = +1.33V for the half cell reaction: Cr2O72 (aq) + 14H+(aq) + 6e rev 2Cr3+(aq) + 7H
2O(l)
Hydrogen peroxide is a stronger oxidising agent, and for the half cell reaction:
E = +1.77 V for H2O2(aq) + 2H+(aq) + 2e rev 2H2O(l)
BUT, both of the above half-cell potentials are for acid neutral conditions, so al
ternative half cell potential data must be used for this Cr(III) to Cr(VI) convers
ion.
What we are looking at here is a case of a pH change producing different half cell
potentials and different species involved in a redox reaction.
For strongly alkaline conditions for the conversion of chromium(III) ion to the
chromate(VI) ion the following half cell potential data should be used involving t
he perhydroxyl ion (HO2 or HOO ):
(a) E = +0.88 V for the half cell reaction: HO2 (aq) + H2O(aq) + 2e rev 3OH (aq)
So alkaline hydrogen peroxide solution is still quite a strong oxidising agent.
Note the oxidant species is considered to be the perhydroxyl ion.
However, unlike the orange dichromate(VI) ion (Cr2O72 ) in acid solution, the yell
ow chromate(VI) ion is a very weak oxidising agent in alkaline solution (in acid
solution it reverts to the dichromate(VI) ion).
E = 0.11 V for the half cell reaction (b): CrO42 (aq) + 4H2O(l) + 3e rev Cr(OH)3(s) +
5OH (aq)
From the standard electrode potentials (+0.88 V > 0.12 V) you can clearly see tha
t the hydrogen peroxide can oxidise the chromium(III) ion/hydroxide to the chrom
ate (VI) ion.
Ereaction = Ered Eox = EHOO /OH ECrO42 /Cr(OH)3 = +0.88 0.12 = + 1.00 V, a very
reaction!
Note that the chromium species E used in the argument involves chromium(III) hydr
oxide.
It is quite legitimate to do so, because when you add sodium hydroxide to a chro
mium(III) salt solution you get a green precipitate of chromium(III) hydroxide.
simple equation: Cr3+(aq) + 3OH (aq) ===> Cr(OH)3(s)
When the hydrogen peroxide is added, this green precipitate is oxidised and diss
olves to give a yellow solution of sodium chromate(III). The overall redox equat
ion is:
2Cr(OH)3(s) + 3HO2 (aq) + OH (aq) ===> 2CrO42 (aq) + 5H2O(l)
The oxidation state change numbers and balancing are analysed below.
Some of these redox equations are quite tricky to work out do a triple check ...
.... especially when combining two half cell equations, which I've illustrated for
this reaction ...
(i) balance the number of species in the equation with the oxidation state chang
es
2Cr(+3) ==> 2Cr(+6) and 6 O( 1) in 3HO2 ==> 6 O( 2) in the oxygen's of the H2O's/CrO4
2- ion, overall a 6 'electron' change
(ii) check the ionic charge balance
on the left 3- + 1- = 4 is balanced by 2 x 2 = 4
Note: if it involves both + and ions, just obey the usual mathematical rules
(iii) double check the atom count
2Cr + 13O + 13H on both sides of the equation finally!
Do all three and you shouldn't go wrong!
However on reflection, you do not get equation (c) by combing half cell equations
(a) and (b), BUT, using the perhydroxyl half cell equation I've worked it through
in one of my more 'nerdy' moments on my website to obtain equation (d). I've kin
dly left out the state symbols until the end for logic clarity! Check out the 't
riple check' at each stage in deriving equation (d) for practice, that is well w
orth doing! Equation (d) is the most accurate depiction of the redox reaction th
at actually happens.
You may have to know how to carry out the reaction for your examination, but not
all the details, BUT, you should understand all the principles used in this exp
lanation and appreciate that changing the pH of an oxidant can change both its o
xidising power and species involved.
3 x (a) for 6e change
3HO2 + 3H2O + 6e
===>
9OH
2 x (b) reversed for 6e change
2Cr(OH)3 + 10OH
===>
2CrO42 + 8H2O + 6e
= initial total, 6e cancel out
3HO2 + 3H2O + 2Cr(OH)3 + 10OH
===> 2CrO42 + 8H2O + 9OH
3H2O and 9OH cancel out to give
3HO2 + 2Cr(OH)3 + OH
===> 2CrO42 + 5H2O
leaving the final equation (d)!
2Cr(OH)3(s) + 3HO2 (aq) + OH (aq) ===> 2CrO42 (aq) + 5H2O(l)
Section 6. Index of examples of constructing balanced ionic redox reaction equat
ion from half cell/E data
For more on manganese chemistry see Periodic Table Advanced Inorganic Chemistr
y Notes Part 10a "3d block Transition Metals Series Introduction and Elements Sc
to Mn on Period 4 detailed revision notes