Experiment-1

Determination of Distribution Coefficient [i.e., Partition Coefficient] of Iodine

Between Two Immiscible Solvent [ H2O -Benzene]
Theory: The distribution coefficient, often referred to as the partition coefficient,
describes the equilibrium distribution of a solute between two immiscible liquid phases.
In this experiment, iodine is distributed between two immiscible solvents, typically water
and an organic solvent like carbon tetrachloride or chloroform. At equilibrium, the ratio
of the concentration of iodine in the organic phase to its concentration in the aqueous
phase remains constant at a specific temperature. This constant ratio is the distribution
coefficient. The principle underlying this phenomenon is that the solute, in this case,
iodine, tends to preferentially dissolve in the solvent in which it exhibits greater solubility.
By accurately measuring the equilibrium concentrations of iodine in both phases, the
distribution coefficient can be determined. This experiment provides valuable insights
into the relative solubilities of iodine in different solvents and can be applied in various
fields such as solvent extraction, chromatography, and drug delivery.
The distribution of a solute between two immiscible solvents can be understood through
the Nernst distribution law and the concept of chemical potential. The Nernst distribution
law states that at equilibrium, the ratio of the concentrations of a solute in two immiscible
solvents is constant at a given temperature, provided the solute exists in the same
molecular form in both phases. Mathematically, this can be expressed as:
C1/C2 = K ---------------[1]
Where C1 is the concentration of the solute in the First solvent (generally organic solvent)
C2 is the concentration of the solute in the second solvent (generally organic solvent).
If Organic solvent is benzene and aqueous solvent is water and solute molecule is iodine
then equation 1 can be written as
K = [I2]benzene / [I2]water -----------[2]
where: K = Distribution coefficient (or partition coefficient)
[I2]benzene = Concentration of iodine in the benzene phase
[I2]water = Concentration of iodine in the water phase
The distribution coefficient of iodine between two immiscible solvents can coefficient is
a thermodynamic property that is related to the difference in standard chemical potentials
of the solute in the two phases.
The distribution of iodine between two immiscible solvents can be also understood the
concept of chemical potential. he chemical potential (μ) of a substance is a
thermodynamic property that represents the change in Gibbs free energy of a system when
one mole of the substance is added to the system at constant temperature and pressure. At
equilibrium, the system is in a state of minimum free energy. For a solute distributed
between two immiscible solvents, equilibrium is reached when the chemical potential of
the solute is equal in both phases.
Relating Chemical Potential to Distribution Coefficient:
The chemical potential of a solute in a solution is related to its concentration by the
following equation:
μ = μ° + RT ln C -------------(3)
Where:
μ° is the standard chemical potential of the solute.
R is the ideal gas constant.
T is the absolute temperature.
C is the concentration of the solute.
At equilibrium, the chemical potentials of the solute in both phases are equal:
μ₁ = μ₂
Where:
μ₁ is the chemical potential of the solute in the first phase.
μ₂ is the chemical potential of the solute in the second phase.
This leads to:
μ°₁ + RT ln C₁ = μ°₂ + RT ln C₂ -------------------(4)
Rearranging:
ln (C₁/C₂) = (μ°₂ - μ°₁)/RT --------------------(5)
This equation shows that the distribution coefficient (K = C₁/C₂) is directly related to the
difference in standard chemical potentials of the solute in the two phases.
The Nernst distribution law and the principle of equilibrium, where the chemical potential
of the solute is equal in both phases, provide a thermodynamic framework for
understanding the distribution coefficient. The distribution coefficient is a constant at a
given temperature, reflecting the relative tendencies of the solute to dissolve in each of
the two immiscible solvents.
If organic solvent is benzene and aqueous solvent is water and solute molecule is iodine
then equation can be written as
RT ln [I2]benzene - RT ln [I2] water = µ°(I2, water) - µ°(I2, benzene) ------------(6)
Simplifying:
RT ln ([I2]benzene / [I2]water) = Δµ°
where: Δµ° = Difference in standard chemical potentials between the two phases
Taking the exponential of both sides:
[I2]benzene / [I2]water = exp(Δµ°/RT)
Defining the Distribution Coefficient:
K = [I2]benzene / [I2]water = exp(Δµ°/RT) ----------------------(7)

Experiment:
Apparatus required:
1. Stopper glass bottle
2. Separating funnel
3. Beakers: 4 no.
4. Conical flask: 2 no.
5. Measuring cylinder: 1 no.
6. Burette
7. Stand
Chemicals required:
1. Saturated solution of I2 in Benzene (50 mL) (8.3 g iodine in 50 mL)
2. Na2S2O3 solution (N/10 and N/100)
3. Starch solution
4. Potassium Iodide (KI)

Procedure (A):
1. Take four glass stopper bottles of about 100 mL or 250 capacity
2. Wash these bottles with water and allow drying. Name the bottles as No. 1, 2, 3 and 4
3. Add 20 mL of distilled water in each of these bottles and add the saturated solution of
Iodine in benzene and benzene as per Table 1
Bottle no. Volume of saturate solution of Volume of only Volume of water
Iodine in benzene in mL Benzene in mL
1 2 8 20
2 4 6 20
3 6 4 20

Procedure (B):

1. Shake each bottle (closed) vigorously for 20 minutes (shaking of each bottle is
necessary for getting accurate results)
2. Keep these bottles undistributed for some time and allow to separate the two layers
3. Pour the contents of these bottles separately into a separating funnel and collect
benzene and water layers of each bottle in separately numbered beaker
4. Pipette out exactly 2mL of benzene layer from the separated layers of bottle no. 1
into a conical flask
5. Add 0.2 g of potassium iodide and 3 drops of the starch solution
6. Do titration for the solution against (N/10) Na2S2O3 from the burette
7. Continue the titration, till the blue color get disappear
8. Repeat three times to get concordant readings
9. Repeat this process with benzene layers of other bottles also in the same manner
10. Pipette out 10 mL of aqueous layer of bottle no. 1 into a conical flask
11. Add 1 g of potassium iodide and 5 drops of the starch solution
12. Titrate this solution against (N/100) Na2S2O3 from the burette
13. Continue the titration till the blue color get disappear
14. Repeat 2 times until get concordant readings
15. Repeat this process with aqueous layers of other bottles in the same way
16. Note the room temperature using thermometer
Observation Table:
Bottle Aqueous layers (C1) Benzene layers (C2)
number
Burette Reading in mL Burette Reading in mL
I.B.R F.B.R Volume Mean I.B.R F.B.R Volume Mean
used value used value
1. 1. 10 mL V1 2mL V5
2. 10 mL 2mL

2 1. 10 mL V2 2mL V6
2. 10 mL 2mL

3. 1. 10 mL V3 2mL V7
2. 10 mL 2mL

Calculations:
For aqueous layer:

Volume of aqueous layer taken for titration = 10

mL Mean value of (N/100) Na2S2O3 solution =
V1
10 mL of N1 iodine = V1 mL of (N/10)
Na2S2O3 or N1 = V1 × (1/100) × (1/10) =
(V1/1000)
Thus, the concentration of I2 in water layer = 127 × (V1/1000) gram equivalent
/ liter (Since equivalent of I2 = 127) = Caqueous

For Organic layer (benzene)

Volume of benzene layer taken for titration = 2

mL Mean value of (N/10) Na2S2O3 solution =
V5 mL

2mL of N2 iodine = V5 mL of (N/10)

Na2S2O3
or N2 = V5 × (1/10) × (1/2) = (V5/20)
 Thus the concentration of I2 in benzene layer = 127× (V5/20) gram
equivalent/liter= COrganic
Partition co-efficient
K = [I2]benzene / [I2]water -----------[2]

Partition coefficient:
= [127 × (V1/1000)]/ (127× V5/50)
= 127 × (V1/1000) × (50/127 × V5)
The value of the partition coefficient (K) is calculated in the same way for other
bottles by using the simplified formulae as given under.

For bottle no. 2, K= C1/ C2= (V2)/ (V6×20)

For bottle no. 3, K= C1/ C2= (V3)/ (V7×20)

The mean value of K obtained after using the relationships (I), (II) and (III) as given
above gives the value of the partition coefficient (K) of iodine between water and
benzene.
Conclusion:

The partition co-efficient of iodine between benzene and water was found to be at
o
C.

***************
Additional Information:
Preparation of N/10 and N/100 Sodium Thiosulfate Solutions
(i) Calculation: N/10 thiosulfate
Molar mass of Na₂S₂O₃·5H₂O = 248.18 g/mol
Normality (N) = Molarity (M) for Na₂S₂O₃
For 100 mL solution:
Mass of Na₂S₂O₃·5H₂O required:
(N/10) * (248.18 g/mol) * (100 mL / 1000 mL) = 2.4818 g

(ii) N/100 Sodium Thiosulfate

Calculate the mass of Na₂S₂O₃·5H₂O required for 100 mL of N/100 solution:
(N/100) * (248.18 g/mol) * (100 mL / 1000 mL) = 0.24818 g
Weigh accurately 0.24818 g of Na₂S₂O₃·5H₂O and dissolve in distilled water in a 100 mL
volumetric flask.
Add distilled water to the mark and mix well.
Or
Pipette 10 mL of the prepared N/10 sodium thiosulfate solution into a 100 mL volumetric
flask.
Add distilled water to the mark and mix thoroughly.
This diluted solution will be N/100.

(iii) Iodine-Thiosulfate Reaction:

The reaction between iodine (I₂) and sodium thiosulfate (Na₂S₂O₃) is a redox reaction:
2Na₂S₂O₃ + I₂ → 2NaI + Na₂S₄O₆
(iv): Role of Starch Indicator:
Starch forms a deep blue-black complex with iodine.
In the titration, as thiosulfate is added, it reacts with iodine, reducing it to iodide ions.
When all the iodine has reacted, the blue-black color of the starch-iodine complex
disappears, indicating the endpoint of the titration.
Starch is added near the endpoint to avoid interference with the titration due to the intense
color of the starch-iodine complex.
Why is starch indicator added near the endpoint?
To prevent interference with the titration and ensure accurate endpoint detection.
The interference arises from the strong adsorption of iodine onto the starch molecules.
Early addition of starch: If starch is added at the beginning of the titration when the
iodine concentration is high, a significant amount of iodine gets adsorbed onto the starch.
Difficulty in endpoint detection: This adsorbed iodine is not readily available for reaction
with the thiosulfate, leading to:
Slow and irreversible color change: The blue-black starch-iodine complex forms
slowly, making it difficult to observe the endpoint accurately.
Over-titration: The titration may proceed beyond the true endpoint before the blue-black
color completely disappears, leading to inaccurate results.
Adding starch near the endpoint:
Minimizes adsorption: When added near the endpoint, the iodine concentration is low,
minimizing the amount of iodine adsorbed onto the starch.
Sharp color change: This allows for a more rapid and distinct color change at the
endpoint, improving the accuracy and precision of the titration.
By adding starch only near the endpoint, you can avoid these interferences and obtain
more reliable results in the iodine-thiosulfate titration. Sources and related content.

Some model Viva questions:

Q: What is the principle behind the distribution of iodine between water and
benzene?
A: Nernst's Distribution Law states that at equilibrium, the ratio of the concentrations of
a solute (like iodine) in two immiscible solvents remains constant, provided the solute
exists in the same molecular form in both phases.
Q: Why is it important to ensure complete mixing of the two phases?
A: Proper mixing ensures that the iodine has sufficient time to distribute itself between
the water and benzene phases, reaching equilibrium. Incomplete mixing can lead to
inaccurate concentration measurements and incorrect distribution coefficients.
Q: How does temperature affect the distribution coefficient?
A: The distribution coefficient is generally temperature-dependent. Changes in
temperature can alter the solubility of iodine in both solvents, affecting the equilibrium
distribution.
Q: What are the limitations of Nernst's Distribution Law?
A: The law assumes ideal behavior of the solute in both phases, that the solute exists in
the same molecular form in both phases, and that there are no interactions between the
solute and the solvents beyond simple dissolution.
Q: What are some practical applications of the distribution coefficient?
A: Solvent extraction, drug delivery, environmental remediation, and chemical analysis.
On Estimation of Iodine using Sodium Thiosulfate
Q: What is the balanced chemical equation for the reaction between iodine and
sodium thiosulfate?

A: 2Na₂S₂O₃ + I₂ → 2NaI + Na₂S₄O₆

Q: Why is starch indicator added near the endpoint of the titration?
A: To avoid interference from the strong adsorption of iodine onto starch, which can lead
to inaccurate endpoint detection.
Q: What precautions should be taken while preparing and storing sodium
thiosulfate solutions?
A: Use freshly boiled and cooled distilled water, store in amber-colored bottles to protect
from light, and standardize solutions frequently due to their susceptibility to
decomposition.
Q: How would you standardize a sodium thiosulfate solution?
A: By titrating it against a known standard solution of potassium iodate/dichromate.
Q: What are the sources of error in the iodine-thiosulfate titration?
A: Improper standardization of thiosulfate solution, inaccurate pipetting or burette
readings, premature or delayed addition of starch, and impurities in reagents.