1 of 3 Student

Practical 4.6 Measurement of an equilibrium constant, Kc

[There is a microscale alternative to this experiment – Practical MS4.6]

Purpose Safety

To calculate a value for the equilibrium constant for a reaction Wear eye protection. Silver nitrate
based on data from experiment, e.g. the reaction of ethanol and solution stains skin and clothing.
ethanoic acid (this can be used as an example of the use of ICT
to present and analyse data), the equilibrium
Fe21(aq) 1 Ag1(aq) ⇋ Fe31(aq) 1 Ag(s)
or the distribution of ammonia or iodine between two
immiscible solvents [4.5d]

Background
Silver ions and iron(II) ions react in a slow redox reaction. This reaches an equilibrium in
which both ions are present in measurable concentrations:
Ag1(aq) 1 Fe21(aq) ⇋ Ag(s) 1 Fe31(aq)
The concentration of silver ions can be measured by titration with potassium thiocyanate.
The equilibrium constant can then be calculated from the relationship:
[Fe31(aq)]
Kc 5 ___________________
[Ag (aq)] [Fe21(aq)]
1
​ 
  
  
[Ag(s)] does not appear in the Kc expression because the mass of solid silver present does
not alter the concentration of solid silver, which therefore remains constant.
When titrating the reaction mixture with potassium thiocyanate, KCNS, the first reaction is
the precipitation of silver thiocyanate:
KCNS(aq) 1 AgNO3(aq) → AgCNS(s) 1 KNO3(aq)
When all the silver ions have been removed from solution, thiocyanate ions react with the
iron(III) ions in the equilibrium mixture to give a deep red colour:
CNS2(aq) 1 Fe31(aq) → Fe(CNS)21(aq)
This acts as an indication of the end-point of the titration. The procedure that follows should
be successful because the equilibrium changes quite slowly.

Each group of students will need: Access to:

Eye protection 0.10 M iron(II) sulfate (freshly made from Analar grade),
Burette 25 cm3 solid har ful
m
Small funnel 0.10 M silver nitrate, 25 cm3 solid corrosive;
Pipette filler solution low hazard but stains skin and clothing
Pipettes – 25.0 cm3 3 2, 10.0 cm3 31 0.020 M potassium thiocyanate, 50 cm3 solid har ful
m
Conical flask, 100 cm3, stoppered and dry
Conical flask for titrations
White tile

Edexcel practical materials adapted from Nuffield Advanced Chemistry materials

94
 Student 2 of 3

Practical 4.6 (cont.) Measurement of an equilibrium constant, Kc

Method
1 Using separate clean pipettes and a safety filler, put 25.0 cm3 each of 0.10 M silver nitrate
solution and 0.10 M iron(II) sulfate solution in a dry 100 cm3 conical flask. Stopper it so
that it is airtight and allow to stand undisturbed overnight.
During this time the equilibrium is established. There should be a precipitate of silver,
which settles to the bottom of the flask.

2 Using a pipette and a safety filler, transfer 10.0 cm3 of the solution into another conical
flask, disturbing the silver precipitate as little as possible. Titrate the sample with 0.020 M
potassium thiocyanate. The end-point is marked by the first permanent brown-red colour.
Take care: it is easy to ‘overshoot’ the end-point.

3 Repeat step 2 (twice if possible) and calculate the average of your ‘good’ titres.

Results
Rough 1 2
End titre /cm3
20.20 24.20 21.20
Start titre /cm 3
25.85 29.80 26.80
Actual titre /cm3 5.65 5.60 5.60
5.60
Average titre 5 ________________

Questions
1 Why is it necessary to keep the mixture in an airtight flask and leave it overnight before
doing the titration?
To prevent oxidation and reach equilibrium

2 When you mix equal volumes of two solutions, you are effectively diluting both of them
by half so the initial concentrations are:
[Fe21]initial 1 0.05 mol dm23 and [Ag1]initial 5 0.05 mol dm23
The equation for the titration reaction is:
KCNS(aq) 1 AgNO3(aq) → AgCNS(s) 1 KNO3(aq)
Use this is to calculate the concentration of [Ag1]eq from your titration results.
Amount of silver ion in 10 cm3 = amount of thiocyanate =
5.6/1000 x 0.0200 = 0.000112/1.12 x 10-4 (mol)

So concentration of silver ion = 0.000112 x 1000/10 = 0.0112/1.12 x 10-2(mol dm-3)

Edexcel practical materials adapted from Nuffield Advanced Chemistry materials

95
 3 of 3 Student

Practical 4.6 (cont.) Measurement of an equilibrium constant, Kc

3 Since [Fe21]initial 5 [Ag1]initial it follows that [Fe21]eq 5 [Ag1]eq

So, [Fe21]eq 5 your answer to question 2
and [Fe31]eq 5 [Fe21]initial 2 [Fe21]eq
[Fe31(aq)]eq
Using Kc 5 _____________________
[Ag1(aq)]eq [Fe21(aq)]eq
​ 
  
   
calculate Kc and give its correct units.
0.0500 – 0.0112 = 0.0388/3.88 x10-2(mol dm-3)
See below also

4 Explain why [Fe31]eq 5 [Fe21]initial 2 [Fe21]eq.

Try this . It works!

If you are unsure, imagine starting with five ions of each reagent and letting two react.
Work it out with labelled pieces of paper.
Kc = [Fe3+(aq)]
------------------------ =0.0388
[Fe2+(aq)] [Ag+(aq) ---------
0.01122

= 309.311 = 309 dm3 mol-1

Edexcel practical materials adapted from Nuffield Advanced Chemistry materials

96