Experiment Number : 05

Name of The Experiment:

DETERMINATION OF EQUILIBRIUM
CONSTANT BY DISTRIBUTION METHOD.

Date of Performance: 10.05.16

Temperature: 34°C

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Objective:
The equilibrium constant of a reaction maybe defined as the rate of forward reaction with
backward reaction in terms of concentration.This is a experimentally determined quantity. Many
chemical reactions are not completed and a dynamic equilibrium is established between the
reactants and the products. From these equilibrium constants, we are able to know how far the
reaction has gone and at what rates the product is produced. So it is important for us to know

 How to determine equilibrium constant.

 What kinds of reactions occur spontaneously and which reactions do not occur.
 Observing the distribution of a solute in two immiscible solvents
overally, shows the economic viability of a chemical about the rate of a reaction, it is a must to
study about equilibrium constant. But sometimes it becomes difficult to get the concentration of
reactants and products all at a time so,In this experiment we determine equilibrium constant by
distribution method.

Theory:
When a second solvent is introduced into a solution (solute + solvent 1) which is immiscible with
the solvent 1 but in which the solute is soluble, then the solute distributes itself into two layers.
This is known as the ‘Distribution Method’. In most practical cases one layer is aqueous &
another is organic.

In this experiment, equilibrium constant of a chemical equilibrium is to be determined using this

method. A reaction is said to be in equilibrium when the rate of the forward & reverse reaction is
equal; and it’s expressed as the ratio of concentrations of products & reactants. Considering the
following reaction:

KI + I2 KI3; equilibrium constant of this equilibrium is

Kc = [KI3]/[KI][I2]

At first aqueous solution of KI is introduced into a solution of I2 in CCl4. As CCl4 is an organic

layer it won’t be miscible with the aqueous layer, but I2 is soluble in aqueous layer. So it’ll
distribute itself between two immiscible layers when the mixture is shaken vigorously. Now, I2
present in the aqueous layer makes equilibrium with KI to form KI3.

KI + I2 KI3

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 Equilibrium constant of this reaction is to be determined.

H2O

KI + I2 KI3

I2

CCl4

Figure :Equilibrium between I2in H2O& I2InCCl4

The concentration of I2 in CCl4 layer is determined by titrating with Na2S2O3 solution which is
[I2]CCl4.
Concentration of free I2 in aqueous layer is [I2]CCl4/KD = x mole L-1
Concentration of total I2 in aqueous layer is obtained by titrating with Na2S2O3 = y mole L-1
= free iodine(x) + I2 combined with KI giving KI3 (z)
z = (y-x) mole L-1 = [KI3] ……………………………..
(I)

Initial concentration of KI = [KI]o mole L-1

Amount of KI combined with I2 to form KI3 is equal to z (1:1 = 1; reaction stoichiometry)
So, equilibrium concentration of KI = [KI]e = ([KI]o – z) mole L-1 …………………………….
(II)

So, Kc = z ÷ {x ([KI]0 - z)}

………………………………………………………………… (III)

Apparatus:
 5 mL & 10 mL pipette
 Glass stoppered separating funnels
 Burette
 Pipette fillers
 Conical flask
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  0.1 M KI solution
 I2 in CCl4 solution
 0.045 M sodium thiosulfate solution
 Starch Solution

Figure: Separating Funnel Figure: Shaker

Experimental Data:
Distribution co-efficient of I2 into CCl4& aqueous layer, KD = 82
Now, the concentration of I2 in two layers can be determined by following this manner:
2 Na2S2O3 + I2 = Na2S4O6 + 2NaI
So, 2V2S2 = V1S1; where V1, S1 refers to Na2S2O3& V2, S2 refers to I2

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 S2 = (V1× S1)/ (2×V2), where S2 = Concentration of I2
S2 = (V1× 0.045)/ ( 2×V2)
…………………………………………………….. (IV)

Table 02:

Data for determination of the concentrations I2 at different layers by titrating against standard
Na2S2O3solution :

Burette Readings for Average

Volume of Na2S2O3
Solution Volume of Conc. Of I2
System Layers taken soln (mL)
type Na2S2O3 (M)
(mL)
Initial Final (mL)

01 Organic I2 (CCl4) 10 0.1 7.7 7.6 0.019

01 Aqueous KI(H2O) 50 0.0 17.8 17.8 .0089

02 Organic I2 (CCl4) 20 18 39.9 21.9 0.0274

0.0
02 Aqueous KI(H2O) 50 7.7 35.5 .0139

Calculations:

Calculations:
System 1:
Given, KD = 82
Concentration of free I2 aqueous layer, x = [I2]CCl4/KD

= 0.019÷82
= 2.32×10-4 N

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 Concentration of total I2 in aqueous layer, y = 8.9×10-3 N
Now, y = x + z
Where, z = Concentration of KI3
z = y-x
= 8.9×10-3 - 2.32 ×10-4N
= 8.67×10-3 N

Concentration of KI in equilibrium = [KI]0 – z

= 0.1 – 8.67×10-3
= 0.09133 N

Kc = z ÷ {x ([KI]0 - z)} = ( 8.67×10-3 )÷ (2.32×10-4 × 0.09133)

= 409.2

System 2:
Concentration of free I2 aqueous layer, x = [I2]CCl4/KD

= 0.027 ÷ 82
= 3.3 × 10-4 N

Concentration of total I2 in aqueous layer, y = 0.0139 N

z = y-x
= 0.0139 – 3.3 × 10-4
= 0.01357 N
Concentration of KI in equilibrium = [KI]0 – z
= 0.1 – 0.01357
= 0.0997 N

Kc = z ÷ {x ([KI]0 - z)} = 0.01357 ÷ (3.3 × 10-4 × 0.0997)

= 412.6

Result:
For System 1, Equilibrium constant, Kc = 409.2L/mol

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For System 2, Equilibrium constant, Kc = 412.6 L/mol

Discussion:
As seen from the experimental results, the value of Kc for two different layers is found to be
dissimilar. But Kc should be fixed for certain equilibrium if there is no change in temperature.
So, there might be some reasons & wrong assumption behind this error:

 The value of KD was assumed to be 82, but depending on temperature it can vary over a
range of 80-82. We were not sure that at the temperature of the performance day value of
KD would be 82. If the value would be taken 82, then value of Kc would be found to be
602 & 618 for system 1 & system 2 respectively.

 After shaking, an appreciable amount of mixture remained attached to the sides of the
conical flasks which led us to erroneous estimation of I2.

 The separation couldn’t be done 100% accurately. It was very tough not to allow one or
two drops of CCl4 solution into the aqueous layer which means error in determination of
[I2] in CCl4.
 Error might happen because of air bubble formed inside the pipette while taking out
organic solution and aqueous solution from bottle.

Though the value of Kc for this equilibrium should have been almost 700, due to the reasons
stated above the value wasn’t found experimentally.

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