Redox reactions in Inorganic Chemistry sections 5-7

The concepts of oxidation, reduction, oxidation state/number and redox reactions were introduced and explained using a variety of examples in Part 1 sections 1-4. Here in Part 2 sections 5-7, how to redox analyse more complex reactions and combine half-cell equations to write a full ionic-redox equation is explained and how redox chemistry is used in preparative and titration chemistry.Application of redox concepts to cells are described in Equilibria Part 7 "Redox Equilibria". 7.1 Examination of some redox equilibrium situations (i) A metal atom and metal ion o When a piece of metal (M) is dipped into an aqueous solution of its ions (M
n+ (aq))

an equilibrium exists between the two chemical

states of the metal, and importantly, in different oxidation states (0 for the element and +n for the cation). o o o o (i) M
n+ (aq)

+ ne

M(s)

n is the numerical value of the positive charge on the cation and the number of electrons involved in the oxidation state change. This is an example of a half-cell equation which represents the particular oxidation (electron loss) or reduction (electron gain) of an atom/ion related by electron transfer connecting two different oxidation states of the element. The same idea of an equilibrium between two species of the same element in two different oxidation states expressed as a half-cell equationalso applies to many other situations e.g.

(ii) A non-metal atom/molecule and associated anion e.g. o o Cl2(g/aq) + 2e

-

2Cl (aq)

Ox. states: chlorine molecule, 0, and chlorine in chloride ion, -1.

(iii) Two different cations of the same metal e.g. o o Fe

3+ (aq)

+e

Fe

2+ (aq)

Interchange of iron(II) and iron(III) ions, i.e. interchange of the +2 and +3 ox. states of iron.

(iv) An anionic and cationic species of the same metal e.g. o o o MnO4 (aq) + 8H
+ (aq)

+ 5e

Mn

2+ (aq)

+ 4H2O(l)

Interchange of manganate(VII) and manganese(II) ions in acid solution, +7 and +2 ox. states. Note that half-cell equations are often, but not always, presented as a reduction (electron gain). For examples (ii) to (iv), a chemically inert platinum electrode is dipped into the solution when used in electrochemical cell construction (see later). For an example of situation (i) and its consequences consider the diagram Fig.1 below comparing the relative positions

of the metal-metal ion equilibrium for copper and zinc.

Fig.1 In the case of the copper atom/copper(II) ion equilibrium, you get a positive charge on a piece of copper when it is dipped into an aqueous copper(II) ion solution. This is due to an electron deficiency on the copper because the right-hand side of the equilibrium, the solid copper, is favoured, and copper(II) ions remove negative electrons to form copper atoms on the surface (reduction process). The +'s represent the electron deficiency in the copper metal, which in cells would make it the positive pole, and the -'s represent surplus anion charge in the solution.

However, in the case of the zinc atom/zinc(II) ion equilibrium, you get a negative charge on a piece of zinc when it is dipped into an aqueous zinc(II) ion solution. This is due to an electron surplus on the zinc metal because the left-hand side of the equilibrium, the aqueous zinc(II) ion, is favoured, and zinc atoms lose negative electrons to form zinc(II) ions in the solution (oxidation process). For

Zn/Zn : The +'s represent the extra zinc ion charge in solution, the -'s represent the surplus electrons in the zinc metal which in cells would be the negative pole. Quite simply, thermodynamically, zinc atoms have a much greater tendency or potential to lose electrons than copper atoms and copper(II) ions have a much greater tendency or potential to accept electrons than zinc ions. Therefore the two half-cell reactions would be Zn(s) ==> Zn
2+ (aq) 2+ (aq) -

2+

+ 2e and Cu

+ 2e ==> Cu(s)
2+ (aq)

and the overall reaction is Zn(s) + Cu

==> Zn

2+ (aq)

+ Cu(s)

This overall reaction can be accomplished in two very different ways. (a) by adding zinc metal to blue copper(II) sulphate solution when the blue colour fades and a red-brown deposit of copper forms. The reaction is exothermic which can be observed as a significant temperature rise if zinc powder is added to 1M copper(II) sulphate solution. (b) By setting up a simple chemical cell ('battery') in which the two half-cell reactions are kept physically separated. To complete the electrical circuit, the zinc and copper(II) ion solutions are connected by a salt bridge (a supported ion solution). Wires connect strips of zinc and copper metal to a voltmeter or other device. The energy release from the exothermic reaction is not in the form of heat energy as in (a) but in the form of electrical energy because the electrons from the two electron transfers of the two half-cell reactions are 'forced' around the circuit due to the potential difference between the two half-cells. This, so-called Daniel cell is described in detail in the next section 7.2 Simple cells notation and constructio

5. Using oxidation states to describe redox changes in a given reaction equation

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 chemical '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 becauseelectrons lost = electrons gained. Getting the right ratio of the oxidation/reduction half-cell reactions should ensure the electron transfer is 'hidden'.

In sections 5. and 6. where a reagent is specified as 'acidified', unless otherwise stated, this means with dilute sulphuric acid, H2SO4(aq) . o o It is used in this context because it cannot be oxidised (unlike hydrochloric acid, HCl (aq)), it is a very weak oxidising agent (unlike nitric acid, HNO3(aq)) and shows little tendency to form complexes with metal ions. If required as part of equation, acidification will be shown as H
+ (aq).

x 5.1 The reaction between aluminium and a copper(II) salt solution 2Al(s) + 3Cu
2+ (aq)

==> 2Al

3+ (aq)

+ 3Cu(s)
3+ -

(i) half-reaction oxidation Al atom: Al ==> Al (ii) half-reaction reduction Cu ion: Cu o o o o

2+

+ 3e (electron loss, Al ox. state change 0 to +3)

+ 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(II) 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).
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Section 5. Index of examples of redox equation analysis For more on copper chemistry see Part 10b 3d-block Transition Metals Fe to Zn - detailed revision notes

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 reduction of bromine to bromide). SO2(aq) + Br2(aq) + 2H2O(l) ==> SO4 o
2(aq) + (aq) 2(aq)

+ 2Br (aq) + 4H

(i) the oxidation half reaction is: SO2(aq) + 2H2O(l) ==> SO4
-

+ 4H

+ (aq)

+ 2e

The sulphur changes from ox. state +4 to +6 (SO2 to SO4 ).

2-

(ii) the reduction half-reaction is: Br2(aq) + 2e ==> 2Br (aq) o Two bromine atoms (as molecule) change from ox. state 0 to -1.

The hydrogen (+1) and oxygen (-2) do not change oxidation state. o o o (i) + (ii) equals the balanced equation, 2 electrons gained and lost or an ox. state 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 metabisulphite produces the ion, which means another equation can also adequately describe the redox change in terms of sulphur and bromine. o o e.g. if the sulphite ion acts as the reducing agent the reaction with chlorine would be written as: SO3
2(aq) 2(aq) + (aq)

+ Cl2(aq) + H2O(l) ==> SO4

+ 2Cl (aq) + 2H

Section 5. Index of examples of redox equation analysis

Ex 5.3 The oxidation of ammonia with molecular oxygen The concept of oxidation state can now be fully applied to reactions which do not 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: o o o o o o o 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).
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Section 5. Index of examples of redox equation analysis

Ex 5.4 The reaction between iron and steam at >400 C 4Fe(s) + 4H2O(g) ==> Fe3O4(s) + 4H2(g) Oxidation state analysis: o o o 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 from ...
-

o o o o

iron, 3Fe ox. state increases from 0 to one at +2 and two at +3 both oxidations, total 8e loss, because the compound consists Fe , 2Fe 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).
2+ 3+

and 4O ions.

2-

Section 5. Index of examples of redox equation analysis Ex 5.5 The formation of titanium(IV) chloride from titanium(IV) oxide in the extraction of titanium metal

TiO2(s) + C(s) + 2Cl2(g) ==> TiCl4(l) + CO2(g) Oxidation number changes: o o o The carbon, C is oxidised (0 to +4 in CO2) and the chlorine is reduced (0) in Cl2 to (-1) in TiCl4. The oxidation of 1 x C from (0) to (+4) is balanced by the reduction of 4 x Cl from (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 reducing 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 oxidation 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) o o o o o 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) to (+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, lowered ox. state of Ti) and sodium/magnesium are the reducing agent (lose/donate e s, inc. their ox. state).

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) o o o o o Oxidation state changes: The nitrogen in hydrazine oxidised (N from -2 to 0) and the oxygen molecules are reduced (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
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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 chlorate(V) is heated strongly and fuse in a crucible, the following redox reaction takes place: o o o o o 3MnO2 + 6OH + ClO3 ==> 3MnO4 + 3H2O + Cl
2-

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 gained 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 of Cl) and manganese(IV) oxide is the reducing agent (loses/donates e s, inc. ox. state of Mn).
-

5.7.2: When the fused mixture is dissolved in water, the initially green solution of the manganate(VI) ion, slowly changes to the purple colour of the manganate(VII) ion and a black precipitate of manganese(IV) oxide. o o o o o o o o 3MnO4
2(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 units 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 state simultaneously changes into a higher and lower oxidation state species. It also means that the manganate(VI) ions simultaneously acts as a reducing agent and oxidising agent! As in 5.7.1, hydrogen (+1) and oxygen (-2) do not change in oxidation state.
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Section 5. Index of examples of redox equation analysis 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 copper is formed and a blue solution of copper(II) sulphate. o o o o o o Cu2O(s) + H2SO4(aq) ==> Cu(s) + CuSO4(aq) + H2O(l) Cu2O(s) + 2H
+ (aq) 2+ (aq) (aq)

==> Cu(s) + Cu

+ H2O(l)

The hydrated copper(I) ion, Cu

is unstable and changes into two oxidation states simultaneously,

elemental Cu(0) and the blue copper(II) ion (+2), and is another example disproportionation (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 oxidation. Oxygen in its (-2) ox. state and hydrogen in its (+1) ox. state do not change.

o o o

It also means that the copper(I) ions simultaneously acts as a reducing agent and 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) + Cu
2+ (aq) 2(aq)

+ SO4

Section 5. Index of examples of redox equation analysis For more on copper chemistry see Part 10b 3d-block Transition Metals Fe to Zn - detailed revision notes

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. o o [Co(H2O)6] o
2+ (aq) 2+ (aq)

+ 6NH3(aq) ==> [Co(NH3)6] + O2(aq) + 4H

+ (aq)

+ 6H2O(l)
3+ (aq)

NOT a redox reaction, just a ligand exchange or ligand substitution reaction.

2+ (aq)

(i) 4[Co(NH3)6]

==> 4[Co(NH3)6]

+ 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.
2+ (aq) +

(ii) 2[Co(NH3)6]

+ 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 units. 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 molecule 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 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) salt, followed by hydrogen peroxide solution, the yellow chromate(VI) ion is formed. The overall reaction can be expressed as .... o o o o o 2Cr
3+ (aq) 2(aq)

+ 3H2O2(aq) + 10OH (aq) ==> 2CrO4

+ 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 decrease 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 hydroxide 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, inc. ox. state of Cr).
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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

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 solution a precipitate of sulphur forms and the orange-brown solution turns pale green. o o o o o H2S(aq) + 2Fe
3+ (aq) 2+ (aq) + (aq)

==> 2Fe

+ 2H

+ 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, decrease 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. state of Fe) and the hydrogen sulphide is the reducing agent(loses/donates e s, inc. ox. state of S).
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Section 5. Index of examples of redox equation analysis For more on iron chemistry see Part 10b 3d-block Transition Metals Fe to Zn - detailed revision notes

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 precipitate of copper(I) iodide is formed which is masked by a brown solution/black ppt. of iodine. If sodium thiosulphate solution is added dropwise carefully, it reacts to remove the iodine giving the colourless iodide ion (see Ex 5.12), hence the CuI precipitate is better scene. o o o o 2Cu
2+ (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. state of O) and the iodide ion is the reducing agent (loses/donates e s, inc. ox. state 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 - detailed revision notes

Ex 5.13 More examples of disproportionation and vice versa (involving O and N ions/compounds) 5.13.1 Hydrogen peroxide decomposition, catalysed by the black solid manganese(IV) oxide, MnO 2. o o o o o o o o o 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 changes into a higher and lower oxidation state i.e. here two oxygen atoms increase their 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.
+ (aq) -

5.13.2 The reaction between ammonium and nitrate(III) (nitrite) ions NH4 + NO2 (aq) ==> 2H2O(l) + N2(g)

Here its the opposite of disproportionation where two species of an element in different 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) state. Oxygen at (-2) and hydrogen (+1) remain unchanged in oxidation state.

o o o

The nitrite ion acts as the oxidising agent and gets reduced (N +3 to 0, 3e's gained, 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).
2-

See other disproportionation reactions 5.7.2 MnO4 , 5.8 Cu2O, 5.14 chlorine and an organic example. and the opposite of disproportionation! reactions 6.6 iodate(V) + iodide. Section 5. Index of examples of redox equation analysis

5.14 Some chlorine, chlorates and chloride redox changes In all the reactions quoted in section 5.14, (i) the oxidation states of hydrogen (+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. o When chlorine reacts with aqueous sodium hydroxide at least two different reaction can occur depending on the temperature and concentration of the strong base-alkali. 5.14.1 With cold dilute sodium hydroxide solution alkali sodium chlorate(I) (NaClO, the bleach sodium hypochlorite) is formed as well as sodium chloride. o o o o 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 lost (1 ox. state unit increase).
-

5.14.2 However, with hot concentrated sodium hydroxide solution, above 75 C, the formation of sodium chlorate(V) predominates as well as sodium chloride. o o o o 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, chlorate(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 instability of the chlorate(I) ion, which at higher temperatures disproportionates into the chloride ion and the chlorate(V) ion. o o o o 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, chloride 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).
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5.14.4 A concentrated solution of sodium chlorate(I) is a useful source of chlorine in the laboratory because it readily reacts with conc. hydrochloric acid to give off the gas. o o o o 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 1 Cl(+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 gained (1 ox. state unit decrease). Section 5. Index of examples of redox equation analysis

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 question source and this is how they are initially presented in section 6. BUT, to produce 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 Equilibria 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) (titration) * 6.5 Fe(II) salt + dichromate(VI) * 6.6 iodate(V) + iodide ions * 6.7hydrogen peroxide + potassium manganate(VII) (titration) * 6.8 ethanedioate + potassium manganate(VII) (titration) * 6.9 vanadium(IV) salt + tin(II) salt * 6.10 iodine and sodium thiosulphate (titration) * 6.11 oxidation of chloride by manganate(VII) * 6.12 reduction of dichromate(VI) with iodide * 6.13Oxidation of hydrogen sulphide by acidified potassium manganate(VII) *

REDOX EQUATION CHECKS Use of the correct 'species' of the half-cell equations to be put together, the right way round AND in the correct ratio based on the number of electrons transferred or oxidation state changes. Getting the right ratio of the oxidation/reduction half-cell reactions should ensure 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 reduced? from E data supplied (half-cell potentials) and the most +ve (least -ve) half-cell 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 oxidation states of elements , or, total electrons gained by species = total electrons lost by the species involved. Add up the ion charges, the totals should be the same on both sides of the equation. 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 redox equations!
+

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 must be reversed! See also Equilibria Part 7 Redox Reactions for Half cell equilibria, electrode potential, standard hydrogen electrode, Simple cells and notation,Electrochemical Series, E Half-cell reaction data: o o o (i) Zn
2+ (aq) + (aq) cell

for reaction feasibility, 'batteries' and fuel cell systems etc.

+ 2e ==> Zn(s) (E = -0.76V*, Zn will act as reducing agent, E less positive) + e ==> Ag(s) (E = +0.80V*, reduction of the oxidising agent with the more positive E )

(ii) Ag

* It doesn't matter here if you haven't yet studied E , half-cell potentials in detail, but the more +ve half-cell species acts as the oxidising agent and so is the reduction half of the reaction.

The more reactive metal Zn, displaces the less reactive metal (Ag) from one of its compounds, which is the reaction feasibility rule at lower academic levels for such a redox reaction (see also halogen displacement reaction 6.2 below). With redox analysis of the reaction we can now say:

o o

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 ) than silver, or to put it another way, the Ag ion is a stronger oxidising agent (more powerful e acceptor, more +ve E ) than the Zn
+ 2+

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 2 x reduction half cell, (ii) added gives full redox equation

Zn(s) ==> Zn 2Ag

+ (aq) + (aq) -

2+ (aq)

+ 2e

+ 2e ==> 2Ag(s) ==> Zn

2+ (aq)

Zn(s) + 2Ag

+ 2Ag(s)

This sort of displacement reaction can be used to plate more reactive metals with a less reactive metal without the need for electrolysiselectroplating e.g. dipping 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 equation 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

Ex 6.2 The reaction between aqueous chlorine and potassium iodide solution Half-cell reaction data: o o (i) /2Cl2(aq) + e ==> Cl (aq) (E = +1.36, can be Cl2(aq) + 2e ==> 2Cl (aq) but E still +1.36) (ii) /2I2(aq) + e ==> I (aq) (E = +0.54V, can be I2(aq) + 2e ==> 2I (aq) but E still +0.54V)
1 1

Chlorine molecules are reduced from ox. state (0) to (-1) of the chloride ion, 1 electron gain. Iodide ions are oxidised from ox. state (-1) to (0) of the iodine molecule, 1 electron 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 2 x reduction half-cell, (i) added gives full redox equation

2I (aq) ==> I2(aq) + 2e

-

Cl2(aq) + 2e ==> 2Cl (aq) 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 thiosulphate, which itself is another redox reaction (see Ex 6.10) Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data

Ex 6.3 The reaction between hydrogen peroxide and iron(II) ions

Half-cell reaction data: o o (i) H2O2(aq) + 2H (ii) Fe

3+ (aq) + + (aq)

+ 2e ==> 2H2O(l) (E = +1.36, reduction of oxidising agent with the more positive E )
2+ (aq)

e ==> Fe

(E = +0.77, less positive, so Fe

3+

can't oxidise hydrogen peroxide)

Both the iron(III) ion and hydrogen peroxide molecule can act as oxidising agents, but hydrogen peroxide is stronger and so oxidises the iron(II) ion to the iron(III) ion. Oxidation: Two iron(II) ions at (+2) lose an electron each to give iron(III) ions 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 1 x reduction half-cell, (i) added gives full redox equation 2Fe
2+ (aq)

2Fe

2+ (aq)

- 2e ==> 2Fe
+ (aq) + (aq) -

3+ (aq)

H2O2(aq) + 2H

+ 2e ==> 2H2O(l) ==> 2Fe

3+ (aq)

+ H2O2(aq) + 2H

+ 2H2O(l)

This reaction is used to convert e.g. iron(II) sulphate, FeSO 4, into iron(III) sulphate, 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 equation from half-cell/E data For more on iron chemistry see Part 10b 3d-block Transition Metals Fe to Zn - detailed revision notes

Ex 6.4 The reaction between acidified manganate(VII) ions and iron(II) ions Half-cell reaction data: o o (i) MnO4 (aq) + 8H (ii) Fe
3+ (aq) + + (aq)

+ 5e ==> Mn
2+ (aq)

2+ (aq)

+ 4H2O(l) (E = +1.52, reduction of oxidising agent)

2+

e ==> Fe
2+

(E = +0.77, Fe
-

acts as reducing agent, Fe

2+

gets oxidised, E less positive)

3+ 2+ 2+

Oxidation: Iron(II) ions, Fe , (+2) lose an electron, so oxidised to the iron(III) ion, Fe , (+3), Fe +2 to +3 ox. state. Reduction: Manganate(VII) ions, MnO4 , (+7) are reduced to manganese(II) ions, Mn , (+2), 5e gain, so five Fe oxidised, Mn +7 to +2 ox. state. Hydrogen (+1) and oxygen (-2) do not change oxidation state. ions can be

5 x ox. half-cell, (ii) reversed 1 x reduction half-cell, (i) added full redox equation
-

5Fe

2+ (aq) + (aq) 2+

==> 5Fe
-

3+ (aq)

+ 5e
2+

MnO4 (aq) + 8H MnO4 (aq) + 8H

+ (aq) +

+ 5e ==> Mn
(aq)

(aq)

+ 4H2O(l)
3+ (aq)

5Fe

==> Mn

2+ (aq)

+ 5Fe

+ 4H2O(l)

This reaction is used to quantitatively estimate iron(II) ions and is self-indicating. On the addition of standardised potassium manganate(VII) to the iron solution,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 the end-point is the first permanent pale pink with =< 1 drop excess of the oxidising agent.

The presence of dilute sulfuric ('supplier' of the proto, H ion), ensures the desired sole reduction of the manganate(VII) ion to the Mn(II) ion, thereby preventing the formation of a manganese(IV) oxide precipitate. Formation of MnO 2 which would not give a good end point and cause a duality in the redox reactions occurring, 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 reactions under the conditions of this titration.

Dilute hydrochloric acid cannot be used because the manganate(VII) ion will oxidise the chloride ion ( see 6.11) and dil. nitric acid, via the nitrate(V) ion, will oxidise the iron(II) ion, i.e. both acids will lead to false titration results. Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data For more on manganese 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

Ex 6.5 The reaction between acidified potassium dichromate(VI) and iron(II) ions Half-cell reaction data: o o (i) Cr2O7 (ii) Fe
3+ 2(aq)

+ 14H
-

+ (aq)

+ 6e ==> 2Cr
(aq)

3+ (aq)

+ 7H2O(l) (E = +1.33, reduction of the oxidising agent)

2+

(aq) +

e ==> Fe

2+

(E = +0.77, Fe

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 Cr2O7 ion is the oxidising agent and each can oxidise 6 Fe Hydrogen (+1) and oxygen (-2) do not change oxidation state.
22+ -

ions.

6 x ox. half-cell, (ii) rev. 1 x red'n half-cell, (i) Cr2O7

2(aq)

6Fe

2+ (aq) +

==> 6Fe
-

3+ (aq)

+ 6e
3+

+ 14H

(aq)

+ 6e ==> 2Cr

(aq)

+ 7H2O(l)

added full equation

Cr2O7

2(aq)

+ 14H

(aq) +

6Fe

2+ (aq)

==> 2Cr

3+ (aq)

+ 6Fe

3+ (aq)

+ 7H2O(l)

Like with potassium manganate(VII), standardised potassium dichromate(VI) solution can be used to estimate quantitatively iron(II) ions in solution, though a special 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 Fe , i.e. the dye's E is more +ve than Fe
2+ 2+

but lees than for the manganate(VII) ion, hence it is capable of being oxidized by the

dichromate(VI) ion to show the end-point. Section 6. Index of examples of constructing balanced ionic redox reaction equation 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

Ex 6.6 The reaction between iodate(V) and iodide ions in acidified aqueous solution Half-cell reaction data: o o (i) /2I2(aq) + e ==> I (aq) (E = +0.54V, iodide gets oxidised, acts as reducing agent, less positive E ) (ii) IO3 (aq) + 6H
+ (aq) 1 1

+ 5e ==> /2I2(aq) + 3H2O(l) (E = +1.19V, reduction of oxidising agent, more positive E )

The iodide ions (I at -1) are oxidised to iodine molecules (I at 0) by electron loss 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 electron 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 1 x reduction half-cell, (ii) added gives full equation
-

5I (aq) ==> /2I2(aq) + 5e IO3 (aq) + 6H IO3 (aq) + 6H

+ (aq) (aq) 1

+ 5e ==> /2I2(aq) + 3H2O(l) + 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 using the liberated iodine from a known quantity of potassium iodate(V) salt with excess KI (aq) salt solution to standardise the sodium thiosulphate. Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data

Ex 6.7 The reaction between acidified potassium manganate(VII) and hydrogen peroxide solutions aqueous Half-cell reaction data: o o (i) MnO4 (aq) + 8H (ii) O2(g) + 2H
+ (aq) + (aq)

+ 5e ==> Mn
-

2+ (aq)

+ 4H2O(l) (E = +1.52, reduction of the oxidising agent)

+ 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 oxidation state.
+ -

5 x ox'n half-cell, (ii) rev'd 2 x reduction half-cell, (i) added full equation
+ +

5H2O2(aq) ==> 5O2(g) + 10H 2MnO4 (aq) + 16H 2MnO4 (aq) + 6H

+ + (aq) + + (aq) -

+ (aq)

+ 10e
(aq)

+ 10e ==> 2Mn

2+

2+

+ 8H2O(l)

5H2O2(aq) ==> 2Mn

(aq)

+ 5O2(g) + 8H2O(l)

Note the 16H on left and 10H on right result in just 6H on left after addition of the half-equations, so watch it! The reaction can be used to quantitatively measure hydrogen peroxide concentrations. The end-point is the 1st permanent faint pink from a tiny excess of the potassium manganate(VII) solution from the burette. Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data For more on manganese 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

Ex 6.8 The titration of ethanedioate with acidified potassium manganate(VII) solution Half-cell reaction data: o o (i) MnO4 (aq) + 8H
+ (aq) -

+ 5e ==> Mn
2(aq)

2+ (aq)

+ 4H2O(l) (E = +1.52, reduction of the oxidising agent)

(ii) 2CO2(aq/g) + 2e ==> C2O4

(E = -0.49V based on (COOH)2)

-

Reduction: Mn (+7) is reduced to Mn (+2), 5e gain, acts as the oxidising agent, electron acceptor.

Oxidation: Each ethanedioate ion loses two electrons to form carbon dioxide, acts as reducing agent. o (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. 2 x red'n half-cell, (i) added - full equation
-

5C2O4

2(aq) +

==> 10CO2(aq/g) + 10e + 10e ==> 2Mn

(aq) 2+

2MnO4 (aq) + 16H 2MnO4 (aq) + 16H

+ (aq) +

(aq) 2-

(aq)

+ 8H2O(l)

5C2O4

==> 2Mn

2+ (aq)

+ 8H2O(l) + 10CO2(g/aq)

This reaction can be used to analyse samples of ethanedioc acid (oxalic acid) and 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 equation from half-cell/E data For more on manganese 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

Ex 6.9 Reduction of the vanadium(IV) oxo-cation by tin(II) salts Half-cell reaction data:

o o

(i) VO

2+ (aq) 4+ (aq) 2+

+ 2H

+ (aq)

+ e ==> V
2+ (aq)

3+ (aq)

+ H2O(l) (E = +0.34, reduction of the oxidising agent)

2+

(ii) Sn

+ 2e ==> Sn

(E = +0.15, Sn
-

will act as a reducing agent, E less positive)

-

V at (+4) in VO

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. 2 x reduction half-cell, (i) added - full equation 2VO
2+ (aq)

Sn 2VO
2+ (aq) +

2+ (aq) +

==> Sn
-

4+ (aq)

+ 2e
3+

+ 4H

(aq) 2+

+ 2e ==> 2V ==> 2V
3+

(aq)

+ 2H2O(l)
4+ (aq)

+ 4H

(aq) +

Sn

(aq)

(aq)

+ 2H2O(l) + Sn

Tin(II) salts are used as reducing agents. Section 6. Index of examples of constructing balanced ionic redox reaction equation 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

Ex 6.10 Titrating iodine with standardised sodium thiosulphate solution Half-cell reaction data:

o o

(i) /2I2(aq) + e ==> I (aq) (E = +0.54V, reduction of the oxidising agent, iodide gets oxidised) (ii) /2S4O6
1 2(aq)

+ e ==> 2S2O3

2(aq)

(E = +0.09V, S4O6 will act as reducing agent, E less positive)

2-

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 sulphur atom changes ox. state from an average of four at ( +2) in the two S2O3 ions to an average of four at (+2.5) in the single S4O6 ion. o A bit of an awkward one in analysing sulphur and it is best to reason in terms of an average oxidation state of sulphur.
22-

2 x reduction half-cell, (i) 2 x oxidation half-cell, (ii) rev. added gives full equation

I2(aq) + 2e ==> 2I (aq) 2S2O3 2S2O3

2(aq) 2(aq)

==> S4O6

2(aq) 2-

+ 2e

+ I2(aq) ==> S4O6

(aq)

+ 2I (aq)

This is used to quantitatively estimate iodine in aqueous solution. The indicator 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 iodine to form the coloured complex. The iodine may arise from a variety of reactions, see 6.2, 6.6 and 6.12. Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data

Ex 6.11 The oxidation of chloride by acidified potassium manganate(VII) Half-cell reaction data:

o o

(i) MnO4 (aq) + 8H

1 -

+ (aq)

+ 5e ==> Mn

2+ (aq)

+ 4H2O(l) (E = +1.52, reduction of the oxidising agent)

(ii) /2Cl2(aq) + e ==> Cl (aq) (E = +1.36, lower E , so cannot act as an oxidising agent)

Both chlorine and potassium manganate(VII) are strong oxidising agents, but chlorine is the weaker, so chloride ions are oxidised to chlorine. Oxidation: Chlorine as the chloride ions at (-1) lose electrons to give chlorine molecules 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. 2 x red'n half-cell, (i) added - full redox equation
-

10Cl (aq) ==> 5Cl2(aq/g) + 10e 2MnO4 (aq) + 16H 2MnO4 (aq) + 16H
+ (aq) + + (aq) -

+ 10e ==> 2Mn

2+

2+ (aq)

+ 8H2O(l)

10Cl (aq) ==> 2Mn

(aq)

+ 8H2O(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 namepotassium permanganate). Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data For more on manganese 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

Ex 6.12 The reduction of acidified dichromate(VI) with iodide ions Half-cell reaction data: o o (i) Cr2O7
1 2(aq)

+ 14H
-

+ (aq) -

+ 6e ==> 2Cr

3+ (aq)

+ 7H2O(l) (E = +1.33, the reduction of the oxidising agent)

(ii) /2I2(aq) + e ==> I (aq) (E = +0.54V, lower E , so cannot act as oxidising agent)
2-

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 Cr2O7 ion is the oxidising agent. Hydrogen (+1) and oxygen (-2) do not change oxidation state.

6 x oxidation half-cell, (ii) rev. 1 x reduction half-cell, (i) added full redox equation Cr2O7 Cr2O7
2(aq) 2(aq)

3I2(aq) + 6e ==> 6I (aq) + 14H

+ + (aq) -

+ 6e ==> 2Cr
3+

3+ (aq)

+ 7H2O(l)

+ 14H

(aq) +

6I (aq) ==> 2Cr

2-

(aq)

+ 3I2(aq) + 7H2O(l)
2-

This reaction can be used to quantitatively measure chromium(VI) in dichromates, Cr 2O7 , or chromates, CrO4 (which change to dichromate(VI) on acidification, yellow ==> orange). Excess potassium iodide is added and the liberated iodine is titrated with standardised sodium thiosulphate solution (starch indicator, blue ==> colourless), see Ex 6.10.

Section 6. Index of examples of constructing balanced ionic redox reaction equation 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

Ex 6.13 The oxidation of hydrogen sulphide by acidified potassium manganate(VII) Half-cell reaction data: o o o (i) MnO4 (aq) + 8H (ii) SO4
2(aq) + (aq) + (aq)

+ 5e ==> Mn
-

2+ (aq)

+ 4H2O(l) (E = +1.52, reduction of the oxidising agent)

+ 10H

+ 8e ==> H2S(aq) + 4H2O(l) (E = ?, oxidation of the reducing 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 maximum 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. units half-cell

5 x oxi'n half-cell, (ii) rev. 8 x red'n half-cell, (i) added - full redox equation
-

5H2S(aq) + 20H2O(l) ==> 5SO4 8MnO4 (aq) + 64H 8MnO4 (aq) + 14H
+ (aq) + + (aq) -

2(aq)

+ 50H
2+

+ (aq)

+ 40e

+ 40e ==> 8Mn

2+

(aq)

+ 32H2O(l)
2(aq)

5H2S(aq) ==> 8Mn

(aq)

+ 5SO4

+ 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, therefore in addition to the above 'construction' if the hydrogen sulphide is just oxidised to a sulphur precipitate, the equation would be ... o o o 2MnO4 (aq) + 6H (iii) S(s) + 2H
+ (aq) + (aq) + 2+ (aq)

5H2S(aq) ==> 2Mn

+ 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). + 2e ==> H2S(aq) (E = +0.14V, less positive, so hydrogen sulphide gets oxidised)

Section 6. Index of examples of constructing balanced ionic redox reaction equation from half-cell/E data

For more on manganese 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

7. Redox titration questions

Using the correct redox equation is obviously important when problem solving and performing calculations from redox titrations. A set of problems involving some of these redox reactions, complete with worked out answers is available.