Redox reactions

(a) Redox Candidates should be able to: describe redox in terms of electron transfer, use oxidation states (numbers) to identify redox reactions and decide which species have been oxidised and which reduced; Oxidation may be defined as electron loss and reduction as electron gain. The following equations represent examples of redox reactions and the half equations clearly show the transfer of electrons. 2I (aq) +
!

l2(g)
!

2 l (aq) + I2(aq) I2(aq) 2 l (aq)

2+ !

2I (aq) ! 2e l2(g) + 2e
2+ !

oxidation reduction

"n(s) +

u (aq) ! 2e
! !

"n (aq) + u(s) "n (aq) u(s)

2+

"n(s)
2+

oxidation reduction

u (aq) + 2e

Oxidation state or oxidation number This concept was introduced in Topic 6.1(d) Oxidation is an increase in oxidation number and reduction is a decrease in oxidation number. #xamples
onsider the changes in oxidation state (number) in the following

(i) $nO% (aq) + &'e (aq) + () (aq)

2+ +

$n (aq) + &'e (aq) + %)2O

2+

*+

the element manganese changes from ++ to +2 and so has been reduced.

,ummary

$anganese Iron

++

+2 & - +*

change & change +&

& - +2

% (ii) * l2(g) + ./aO)(aq) &/a l(aq) + /a lO*(aq) + *)2O

Oxidation state 0 !1 +&

,ix chlorine atoms oxidation state 2ero change to fi3e chloride ions oxidation state ! !1 and chlorine in one lO* ion with oxidation state +& hlorine is simultaneously oxidised and reduced. This is called disproportionation. ,ummary hlorine . -0 (& - 1) + (1 - +&) change 2ero

(iii) one copper atom changes from 0 to +2 so has been oxidised

24g (aq) +

u(s)

24g(s) +

u (aq)

2+

two sil3er ions change from +1 to 0 so ha3e been reduced ,ummary ,il3er opper 2 - +1 0 0 +2 change 2 change +2

& (a) Ion-electron half e uations Candidates should be able to: write ion-electron half equations for redox reactions for which stoichiometric information is supplied, and use titration and other data to carry out appropriate calculations; It is sensible that candidates should be familiar with the following reductions of oxidising agents $nO% (aq) + () (aq) + &e olour change r2O+
2 + +

$n (aq) + %)2O(l) purple to almost colourless 2 r (aq) + +)2O(l)

*+

2+

(aq) + 1%) (aq) + .e

olour change I2(aq) + 2e olour change 2I (aq)

orange to green

brown to colourless

These reactions are important in 3olumetric analysis. (The following co3ers Topic 1!." (h) to (#)) Candidates should be able to:
(h)

describe the use of Cr2O

2!

as an oxidisin" a"ent, includin"

2!

(i) (ii) (iii) (i) ()) (,)

the appropriate ion#electron half equation for the Cr2O

2% $%

Cr

$%

conversion

its reaction with &e to produce &e and 2! 2! the interconversion reaction Cr2O CrO' and recall the colours of all the above listed species;
! 2%

describe the redox reaction between acidified (nO' and &e describe the redox reaction between Cu 2! the liberated iodine with +2O$ ;
2%

and *

and the determination of

carry out titration calculations for all reactions specified in 15.2 and for other redox reactions where all necessary data is supplied-

5oth aqueous potassium manganate(6II)7 8$nO%7 and potassium dichromate(6I)7 82 r2O+7 can be used as the titrimetric oxidising agent in the burette. Other oxidising agents can be used to liberate iodine7 I27 from excess aqueous potassium iodide and the released iodine determined by aqueous sodium thiosulfate in the burette.

. 2,2O* (aq)
2 2

,%O. (aq) + 2e
2

)ence the o3erall reaction between iodine and sodium thiosulfate is I2(aq) + 2,2O* (aq) ,%O. (aq) + 2I (aq)

The use of potassium man$anate(%II) in &olumetric anal'sis The aqueous potassium manganate(6II) is placed in the burette and the reducing agent pipetted into the conical flas9 with an excess of aqueous sulfuric acid. These titrations require no external indicator. 4s soon as all the reducing agent has been oxidised7 the next drop of potassium manganate imparts a pin9 colour to the contents of the flas9. The aqueous potassium manganate(6II) must always be standardised by titration with a standard solution of a reducing agent such as ammonium iron(II) sulphate. The ion:electron half equation is; 'e (aq)
2+

'e (aq) + e
!

*+

The ion:electron half equation for $nO% is; $nO% (aq) + () (aq) + &e
! + !

$n (aq) + %)2O(l)

2+

,ince the total number of electrons lost must be equal to the number gained7 the o3erall equation is; $nO% (aq) + () (aq) + &'e (aq)
+ 2+

$n (aq) + %)2O(l) + &'e (aq)

",

2+

*+

1 mol (nO) (a ) reacts *ith ! mol +e (a ) Other reducing agents whose concentration may be determined by potassium manganate(6II) titrations are (i) ethanedioate ions and ethanedioic acid ( OO )2(aq) The o3erall equation is; 2$nO% (aq) + 1.) (aq) + &( OO )2(aq)
+

2 O2(g) + 2e
2+

2$n (aq) + ()2O(l) + 10 O2(g)

" mol (nO) (a ) reacts *ith ! mol (COO )"(a ) (.his reaction proceeds very slowly at room temperature and must be heated to about / C to proceed at a reasonable rate but once started, it is catalysed by the (n more heat is required)
2% o

ions produced and no

+ (ii) aqueous hydrogen peroxide )2O2(aq) The o3erall equation is; 2$nO% (aq) + .) (aq) + &)2O2(aq)
+ +

O2(g) + 2) (aq) + 2e

(0ote hydro"en peroxide is reactin" as a reducin" a"ent rather than as an oxidisin" a"ent)
2+

2$n (aq) + ()2O(l) + &O2(g)

" mol (nO) (a ) reacts *ith ! mol -"O"(a ) The use of potassium dichromate(%I) in &olumetric anal'sis )ere the orange aqueous potassium dichromate(6I) is placed in the burette but this time an indicator is required e.g. during the oxidation of aqueous iron(II) ions. 'e (aq)
2+

'e (aq) + e
2!

*+

,ince the ion:electron half equation for r2O+ r2O+ (aq) + 1%) (aq) + .e The o3erall equation is; r2O+ (aq) + 1%) (aq) + .'e (aq)
" 2 + 2+ 2! +

is; 2 r (aq) + +)2O(l)

*+

2 r (aq) + +)2O(l) + .'e (aq)

",

*+

*+

1 mol Cr"O. (a ) reacts *ith 6 mol +e (a ) /ote that the intercon3ersion of dichromate(6I)7 r2O+ (aq)7 and chromate(6I)7 rO% (aq)7 is /OT redox as the chromium does not change its oxidation number.
2 2 + 2: 2

r2O+ (aq) + O) (aq) 2 rO% (aq) + ) (aq)

orange yellow

or 2 rO% (aq) + 2) (aq)

yellow
2 +

r2O+ (aq) + )2O(l)

orange

The oxidation number of the chromium is +. in both of these ions. This is an acid<base equilibrium and shows that dichromate(6I) ions are stable in acidic solution and chromate(6I) is stable in al9aline solution.

( The use of sodium thiosulfate(%I) in &olumetric anal'sis 4queous sodium thiosulfate(6I) is oxidised by aqueous iodine. The concentration of oxidising agents can be determined by reaction with excess aqueous iodide ions7 and then titrating the iodine released with aqueous sodium thiosulfate. The aqueous sodium thiosulfate is placed in the burette= the oxidising agent is pipetted into the conical flas9 which contains excess aqueous potassium iodide. The sodium thiosulfate solution is run into the flas9 until the colour due to iodine fades to a pale straw colour. 4t this point starch solution is added as indicator7 turning the mixture dar9 blue. The end point is reached when the blue colour is completely discharged.

2!

(aq)

The ion:electron half equation is; I2(aq) + 2,2O*

,%O. (aq) + 2I (aq)
2!

)ere are some oxidising agents which can be determined by sodium thiosulfate titrations. (i) 4queous copper(II) salts 4queous copper(II) ions oxidise aqueous iodide ions 2 u (aq) + %I blue solution I2(aq) + 2,2O*
", 2! 2+

(aq)

2 uI(s) +
2! "

I2(aq)

buff coloured ppt (aq) ,%O. (aq) + 2I (aq) (a )

1 mol Cu (a ) re uires 1 mol 0"O1 (ii) 4queous hydrogen peroxide )2O2(aq) + 2) (aq) + 2e
+ +

2)2O(l)

The potassium iodide must be acidified with dilute sulfuric acid. 2I (aq) + )2O2(aq) + 2) (aq) I2(aq) + 2,2O*
2

2)2O(l) + I2(aq)
2

(aq)

,%O. (aq) + 2I (aq)

"

1 mol -"O"(a ) re uires " mol of 0"O1

(a )

> (iii) 4queous potassium iodate(6) 4s potassium iodate(6) can be obtained in a 3ery pure state7 it can be used to standardise aqueous sodium thiosulfate. In the presence of excess acid7 potassium iodate(6) will oxidise aqueous iodide ions. IO* (aq) + &I (aq) + .) (aq) I2(aq) + 2,2O*
2 +

*I2(aq) + *)2O(l) ,%O. (aq) + 2I (aq)

" 2

(aq)

1 mol IO1 (a ) re uires 6 mol 0"O1

(a )

The specification requires7 ?use titration and other data to carry out appropriate calculations@. #xamples of wor9ed calculations (i) 2&.0 cm* of aqueous iron(II) sulfate of concentration 2&.00 g 'e,O%.+)2O per dm and containing excess aqueous sulfuric acid7 were pipetted into a conical flas9. On titrating with aqueous potassium manganate(6II)7 2&.&& cm* of the potassium manganate(6II) solution were required for :* complete oxidation. alculate the concentration of aqueous potassium manganate(6II) in mol dm . $olar mass of 'e,O%.+)2O A 2+(.0 g oncentration of 'e (aq) ions A 2&.00<2+(.0 mol dm $nO% (aq) + () (aq) + &'e (aq)
2+ + 2+ 2+ 2+ * *

A 0.0(>>* mol dm
*+

$n (aq) + %)2O(l) + &'e (aq)

*

/umber of mol of 'e (aq) ions used A 3olume (dm ) - concentration A (2&.0 - 0.0(>>*)<1000 A 2.2%( - 10 mol Therefore 2&.&& cm* of potassium manganate(6II) solution contains (2.2%( - 10 )<& mol $nO% oncentration of potassium manganate(6II) A (1000<2&.&&) - (2.2%( - 10 )<& A 0.01+. mol dm
* * * *

/ote that the 3olume of iron(II) sulfate solution was only gi3en to three significant figures which was the least accurate figure quoted7 so final concentration is gi3en to three significant figures. 4ny correct manipulation of data will gain credit in the examination. ,ome candidates may substitute in a rote equation. e.g. 31 - c 1 n1 A 32 - c2 n2 If such a method is employed7 mar9s may be lost if errors are made7 as no credit can be gi3en for explanations or method.

10 (ii) 10.200 g of the contents of a bottle labelled ?copper(II) ethanoate7 u( )* OO)2.)2O@7 were dissol3ed in water and the solution made up to &00 cm* in a 3olumetric flas9. 2&.0 cm* of this solution were pipetted into a conical flas9 containing excess aqueous potassium iodide. The liberated iodine was titrated against aqueous sodium thiosulfate of concentration 0.1000 mol dm 7 using starch as indicator near the end:point. The 3olume of aqueous sodium thiosulfate required was 2%.>& cm*. alculate the percentage purity of the copper(II) ethanoate. Bele3ant equations are 2 u (aq) + %I (aq) I2(aq) + 2,2O*
2 2+ *

2 uI(s) + I2(aq) ,%O. (aq) + 2I (aq)

2

(aq)

2 mol of sodium thiosulfate reacts with the iodine formed by 2 mol of copper(II) ions. /umber of mol of sodium thiosulfate in the titre A (2%.>& - 0.1000)<1000 A 2.%>& - 10 mol therefore the number of mol of u (aq) in 2&.0 cm* of the copper(II) ethanoate solution
* 2+

is 2.%>& - 10 mol. /umber of mol of u (aq) in &00 cm* of solution A (2.%>& - 10 - 20) mol A %.>> - 10 mol $olar mass of u( )* OO)2.)2O A 1>>..* g mol
2 2 1 2+ *

Thus mass of copper(II) ethanoate7 u( )* OO)2.)2O in &00 cm* A 1>>..* %.>> -10 g A >.>.2 g Curity of copper(II) ethanoate7 u( )* OO)2.)2O A (>.>.2<10.200) - 100 A >+.+D