ESTIMATION OF HALIDES USING POTENTIOMETER.

AIM: To estimate the amount of halide (chloride/iodide) ions individually using potentiometer.

PRINCIPLE: During the course of the titration of halide mixture with AgNO3 solution ,
silver halide having lower solubility gets precipitated first, followed by a more soluble halide
in order of solubility is AgI ‹ AgBr ‹ AgCl. Due to the precipitation of a halide, Ag+¿¿ ion
activity changes in the solution, thus potential of the indicator electrode changes. E.m.f. of
the cell depends on the potential of the indicator electrode. Thus e.m.f. measurements can
be used to find the end point for precipitation reaction.
The end points for the two halides can be determined by plotting a graph of e.m.f. against
volume of AgNO3 added. The graph shows two distinct inflection points. If ΔE/ΔV against
volume of AgNO3 added is plotted, it will show two maxima. The plot of Δ 2 E / ΔV 2 against
volume of AgNO3 gives the end points for the two halides. Thus, from the titration and
differential titration curves, it is possible to determine the individual concentration of the
two halide ions in the mixture.

REQUIREMENTS: A solution containing mixture of halides, 0.1 M silver nitrate solution,

silver and calomel electrodes, potassium nitrate-agar salt bridge, saturated potassium
nitrate solution , potentiometer, 100 cm3 beaker, burette, 25 cm 3 pipette, 100 cm3 and 250
cm 3 standard measuring flasks.
PROCEDURE:
1. Pipette 25 mL of the given mixture solution in a 100 cm 3 beaker .Insert a clean silver
electrode in this beaker along with magnetic stirrer and connect to the positive terminal of
the potentiometer.
2. Take saturated KNO3 solution in a 100 cm3 beaker ,place a calomel electrode in this
solution and connect it to the negative terminal of the potentiometer.
3. Insert the salt bridge connecting the two beakers.
4. Standardise the potentiometer and measure the e.m.f. of the cell.
5. Add 1cm3of 0.1 M AgNO3 solution at a time from the burette. Stir the solution vigorously
and determine e.m.f. of the solution.
6. Continue the experiment by adding 1cm3 of AgNO3 solution initially, add 0.1cm 3 of AgNO3
solution at the time towards first end point and again 1cm 3beyond the endpoint . Continue
the addition ¿ a similar manner ¿ arrive at the second end point .
7. Plot the graphs of :
i. E.m.f against volume of AgNO3 added.
ii. ΔE/ΔV against volume of AgNO3 added.
Δ E / ΔV against volume of AgNO3 added.
2 2
iii.
Determine the exact end point from the latter. Determine individual concentrations of
halides in the mixture.

OBSERVATIONS:

1. Volume of halifde mixture pipetted out for titration= 25 cm 3 .

2. Normality of AgNO3solution = 0.1 M.
 Volume of E.m.f of ΔE ΔV ΔE/ΔV Δ 2 E / ΔV 2
3
AgNO3 the cell (Mv) (cm ) (Mv/cm3)
solution (cm3) (mV)

0
1
2
3
4

GRAPHS:

CALCULATIONS:
N AgNO × V AgNO 0.1× V 2
1. Normality of the mixture= 3 3
=
V mixture V mixture

N mixture ×V 1
2. Normality of KI =
V2

N mixture ×(V 2−V 1)

3. Normality of KCl =
V2
Since, Normality × equivalent weight = ----------- g/dm 3
∴ Amount of iodide ions present in the mixture = -------- g/dm 3
N KI × eq wt of iodine × total volume of mixture
= -------------g
1000
Similarly, amount of chloride can be calculated.