CATHOLIC JUNIOR COLLEGE H2 CHEMISTRY (Syllabus 9647) VOLUMETRIC ANALYSIS

REDOX TITRATIONS
CALCULATIONS IN REDOX TITRATIONS
The calculations that are involved in redox titrations are similar to those in acid-base titrations (they all use the underlying concept of mole relationships). However, unlike acid-base titrations whose stoichiometric equations are easy to write, redox titrations tend to have more difficult stoichiometric equations to work with.

Redox titrations using ACIDIFIED POTASSIUM MANGANATE(VII), KMnO4

This will be done in the SPA session where experiment on it will be carried out and the theory of the titration will be discussed.

Redox titrations involving SODIUM THIOSULFATE(VI) Na2S2O3.5H2O, AND IODINE

Titrations involving sodium thiosulfate are known as iodometric titrations and are described below.
Step 1:

Excess potassium iodide is added to an oxidising agent (O.A.) which is the limiting reagent. The oxidising agent then oxidises the iodide ions from the potassium iodide solution to give iodine, which gives a brown coloured solution. The amount of iodine liberated is dependent on the amount of O.A. originally present. (The relationship is shown in the stoichiometric equation). Step 2: The iodine formed is then titrated against sodium thiosulfate(VI) of a known concentration, which is placed in the burette, using starch solution as indicator. From the volumes of titration (volumes of sodium thiosulfate(VI) used), the concentration of the O.A. can be determined.

Sodium thiosulfate(VI) reacts with iodine liberated to give sodium iodide and sodium tetrathionate. This is an important equation and it must be remembered.

I2(aq) + 2 Na2S2O3(aq) Na2S4O6(aq) + 2 NaI(aq) Or ionically as: I2(aq) + 2 S2O32-(aq) S4O62-(aq) + I-(aq)

Experimental considerations In iodometric titrations, the indicator used is starch solution. Starch solution is added only when the titration is approaching the end-point; i.e. when the brown iodine solution turns pale yellow. When starch indicator is added, the solution turns deep-blue due to the formation of the starch-iodine complex. The titration is continued until the end-point is reached when the deep-blue solution is discharged.

Starch solution is not added at the beginning of the titration unlike other titrations. Why is this so? Since iodine is being trapped in the starch molecules, adding starch solution at the beginning may cause lots of iodine to be trapped as the starch-iodine complex. The release of iodine from the starch molecules takes time and as such, it might decrease the accuracy of the volumes of titration.

E.g., if K2Cr2O7 is the oxidising agent, it will oxidise I ions to give I2 according to: Step 1: Cr2O72 + 6 I + 14 H+ 2 Cr3+ + 3 I2 + 7 H2O

The iodine liberated is then titrated with S2O32-. Step 2: so, Cr2O72 I2 + 2 S2O32 S4O62 + 2 I

3 I2 6 S2O32 6 S2O32

Therefore, Cr2O72

We say, 1 mol of K2Cr2O7 oxidises iodide to give 3 mol of iodine which then react with 6 mol of S2O32. Therefore 1 mol of Cr2O72 is stoichiometrically equivalent to 6 mol of S2O32. You must be able to derive this stoichiometric relationship before you can even begin to do any calculation on this iodometric titration! Worked Example 1 In an experiment, 20.0 cm3 of potassium iodate(V), KIO3, solution was added to excess acidified potassium iodide, KI. The iodine produced was then titrated with a solution of sodium thiosulfate(VI). In the titration, 22.45 cm3 of sodium thiosulfate(VI) was used. The concentration of the thiosulfate was 29.8 g of Na 2S2O3.5H2O per dm3. [Mr of Na2S2O3.5H2O = 248, Mr of KIO3 = 214] Calculate the concentration of the potassium iodate(V) in g dm3. Given: Solution: IO3 + 5 I + 6 H+ 3 I2 + 3 H2O 2 S2O32 + I2 S4O62 + 2 I so, therefore, IO3 3 I2 6 S2O32 IO3 6 S2O32
29.8 mol dm3 = 0.120 mol dm3 248 22.45 = 0.00270 mol 1000

IO3 + 5 I + 6 H+ 3 I2 + 3 H2O

Conc of Na2S2O3.5H2O =

Amount of S2O32 = 0.120 Amount of IO3 =

1 0.00269 6 = 0.000450 mol

1000 ) = 0.0225 mol dm3 20.0

Conc of KIO3 = (0.000450

Conc of KIO3 = (0.0225 214) g dm3 = 4.81 g dm3

Worked example 2* To about 2 g of potassium iodide dissolved in dilute sulfuric acid, 25.0 cm 3 of 0.02 mol dm3 KMnO4 were added. The iodine liberated required 24.70 cm 3 of sodium thiosulfate, Na2S2O3.5H2O, solution for titration. What is the concentration of the sodium thiosulfate solution, in grams of hydrated salt per dm3, and how much water must be added per dm3 of the solution to change its concentration to 0.1 mol dm3? [Mr of Na2S2O3.5H2O = 248] Reduction: 2 [MnO4 + 8 H+ + 5 e Mn2+ + 4 H2O] Oxidation: Overall:
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[Ans: 25.1 g dm3; 12 cm3]

5 [2 I I2 + 2 e]

2MnO4 + 10I + 16H+ 2Mn2+ + 5I2 + 8H2O I2 + 2S2O3 S4O6 +2I

2 2

2 MnO4 5 I2 10 S2O32

MnO4- 5 S2O32Amount of MnO4 = 0.02

25.0 1000

= 5.00 104 mol Amount of S2O32 = 5 5.00 104 = 2.50 10-3 mol Conc of S2O32 = 2.50 103

1000 24.70

= 0.1012 mol dm3

Conc. of Na2S2O3.5H2O = 0.1012 248 = 25.1 g dm3 mol of S2O32 after dilution = mol of S2O32 before dilution 0.1 Vafter dil = 0.1012 1000 Vafter dil = 1012 cm3 Vol. of H2O to be added = 1012 1000 = 12 cm3

Points to note: This is an iodometric titration. The first reaction involves the oxidation of iodide ion to iodine. The iodine liberated is then titrated with sodium thiosulfate in the second reaction. The iodine formed from the first reaction is used subsequently in the second reaction. Thus the stoichiometric relationship wrt iodine is important. Do not start off by calculating the number of moles present in 2 g of KI. This is incorrect since KI is added in excess. 4