Titrations

part 3 (Edexcel)

Iodine/thiosulfate

The aim is to generate iodine so it can then be titrated against thiosulfate, which can be done in two
ways:

1. Carry out a reaction where iodine is the product (usually by adding KI as a reactant). We can then
titrate the iodine produced against the thiosulfate.
2. Use iodine as a reactant in excess, so to have any iodine left to titrate.
They always use starch as the indicator with this titration. It forms a blue/black colour with iodine. When
the iodine has all reacted (the end point), it turns colourless as there is no iodine left.
These reactions are all redox and involve two or possibly even three equations.
Type 1
Reaction of the unknown (Cl2) with potassium iodide to generate iodine:
Cl2 + 2KI 2KCl + I2
The aim of the titration is to find the concentration of the Cl2.
As was mentioned above in point 1, they deliberately try to generate I2, so it can then be titrated against
the thiosulfate. This means there has to be a second equation involving iodine and thiosulfate:
I2 + 2S2O32- S4O62- + 2I-
Tip: learn this equation. It is going to be there in every single iodine/thiosulfate question. Sometimes they
give you it, sometimes they dont.
The question is to work out the concentration of 10cm3 of Cl2. 9.05 cm3 of 0.01 moldm-3 thiosulfate was
added during the titration:
Step 1: n = c x v

As with the other ones we have already seen:

n = 0.01 x 9.05/1000 = 9.05 x 10-5 moles of thiosulfate (S2O32-).

Step 2: use the equations

We want to know the Cl2 concentration but we still dont know enough yet to get that concentration.

As we have reacted thiosulfate with iodine we need to start with this equation:

I2 + 2S2O32- S4O62- + 2I-
We can use this to work out the moles of I2. We can see that the thiosulfate:iodine ratio is 2:1 therefore
we need to divide the thiosulfate moles by 2:

Moles of I2 = 9.05 x 10-5/2 = 4.525 x 10-5 moles

Now, we know about I2, which is also in the equation with Cl2, we can use this equation to get the ratio of
I2:Cl2:

Cl2 + 2KI 2KCl + I2
It is clearly a 1:1 ratio, so the moles of Cl2 is also 4.525 x 10-5 moles.

Tip: this might seem long at first but if you are using thiosulfate, the equation with iodine is always the
same, so you always divide by 2. Also, you are looking for a link between the two equations i.e.
something that is common in both, which is the I2.


Step 4: look for portions

No portions were taken in this question so ignore this part. But it is a good idea to remember to check
every single time.


Step 5: Answer the question

In this question, they are looking for a concentration, so you just use n = c x v again. The volume in the
question was 10cm3 of Cl2:


c = n/v c = 4.525 x 10-5/0.01 (10/1000)

= 4.525 x 10-3 moldm-3

Type 2

This is very similar to the acid/base excess type of question. Ideally we would react the unknown with
KI as above and titrate the I2 generated. But I- and Sn2+ in the example below do no react as they are both
reducing agents.

So, we add I2 as a reactant, which will oxidise the Sn2+. The important point again is that we need I2 for
the thiosulphate titration. As I2 is a reactant, we need to add an excess to ensure that there is some left.

They wanted to know the percentage of Sn (tin) existing as SnO2, in a rock sample.

The rock, 10.25 g, was dissolved in sulphuric acid. A reducing agent was added to convert Sn4+ ions to Sn2+
ions.

50cm3 of 0.25 moldm-3 I2 solution was then added to the Sn2+ ions:

Sn2+ + I2 Sn4+ + 2I-

-3

The excess I2 was titrated against 0.1 moldm thiosulfate. 11.6 cm3 of thiosulfate was added during the
titration.

Tip: all that stuff at the start about dissolving in sulphuric acid then reducing the ions etc. Just ignore it. It
doesnt matter, its just done to get the thing into solution ready for the titration. Just focus on the
numbers, equations and steps that you know.

Step 1: use n =c x v

thiosulfate moles = 11.6/1000 x 0.1 = 1.16 x 10-3 moles
Step 2: use the equation

They gave the thiosulfate equation in the question:

I2 + 2S2O32- S4O62- + 2I-
Again divide by 2 I2 moles = 5.8 x 10-4 moles (this is the unreacted I2)

Step 3: moles of I2 reacted

We need to know the original moles of I2 using 50cm3 of 0.25 moldm-3 I2.

Original moles = 50/1000 x 0.25 = 0.0125 moles

Reacted moles = 0.0125 5.8 x 10-4 = 0.0119 moles

Step 4: check for portions

Can ignore again here, none in the question.

Step 5: answer the question.

They want to know the mass of tin, so we do:

0.0119 x 119 = 1.42 g

Finally the want it as a percentage of the original 10.25 g rock sample:

1.42/10.25 x 100 = 13.8%