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CHEM 355

EXPERIMENT 4
Determination of Transference Number by Hittorfs Method
If an electric current is passed through a solution of an electrolyte, the anions and cations move with
characteristic speeds toward the anode and cathode. These speeds vary with magnitude of the
applied voltage, temperature and nature of individual ions. Among the factors associated with the
nature of the ions are its charge and size. One type of ion does not affect the velocity of another type
under a given set of conditions unless the concentration is sufficiently great to result in appreciable
interionic attraction effects.
The mobility of an ion is defined as its velocity in the direction of an electric field of unit strength (i.e.
-8
2 1 -1
V/m in SI units). The mobility of ions is generally quite small (in the order of 6x10 m .s .V ). The
-8
exceptions are hydrogen and hydroxyl ions with the abnormally high mobilities of 36.3x10 and 20.5 x
-8
2 -1 -1
10 m .s .V , respectively.
Ionic mobilities are important factors in many electrochemical phenomena. However, it is more
convenient to use a quantity called the transference number of an ion rather than the ionic mobilities in
the formulas applicable to such phenomena. The transference numbers of the cation and anion are
simply the numbers which gives the fraction of the current carried by each of the ions. Hittorfs Method
has been generally employed for the experimental determination of transference numbers and
involves measurement of changes of concentration in the vicinity of the electrodes .

Current carried by the cations;


(1)

where;
= number of cations
= velocity of the cation in the solution [cm/s] or mobilities of the cation
= charge of the cation
= quantity of electricity associated with a unit charge [volts]
= separation distance of the two plates
Following a similar definition, current carried by the anions;
(2)

Total current carried by both ions,

(3)

The electroneutrality principle expresses the fact that all pure substances carry a net charge of zero;
(4)

Thus, the total current becomes


(5)

The fraction of the total current carried by cations,

(6)

The fraction of the total current carried by anions,

(7)

Thefore, the fraction of the total current carried by the ions are directly proportional to their velocities.
(8)

In summary, the transference numbers of the ions in a particular electrolyte are defined as follows:

(9)

It is clear that the sum of the transference numbers of the ions of a particular electrolyte equals to unity
since each is a fraction of a unity.

( 10 )

Although the speed of a particular ion does not dependent on the nature of the ion, the transference
numbers depends on each other.

Apparatus and Chemicals


Apparatus: The apparatus consists of two separated compartments joined by a substantial middle
compartment, a coulometer, and an AC-DC converter as shown in Figure 1.

Ag(s)

Ag (aq) + e (aq)

Ag (aq) + e (aq)

Ag(s)

Figure 1. The experimental set-up for the determination of transference number by Hittorfs Method
In the anode compartment of Hittorf Cell, during electrolysis Ag electrode dissolves and increases the
+
+
+
Ag ion amount ( ) in its compartment from an initial amount of Ag ions ( ), but some Ag ions
migrate (
) towards cathode using the middle compartment as a bridge according to principle of
+
electroneutrality. At the same time Ag ions are removed by deposition in the cathode compartment
3and NO ions in this compartment migrate to allow electroneutrality to be maintained. It must move
+
out at the same rate as Ag disappears. Measurement of the changes in concentration in the anode
compartment after a passage of current in predetermined time yields the transport numbers of the
anion and cation.
+

At the anode compartment the amount of Ag ions at any given instant is, therefore;
( 11 )

Meantime, at cathode compartment the amount of Ag ions is;


( 12 )

the number of moles of Ag introduced into the anode compartment ( ) can be determined
+
theoretically and also experimentally. The dissolved amount of Ag ions can be calculated from the
current applied, I, and time passed, t, for the electrolysis process through equation (13);

( 13 )

where F is Faradays constant.

From the experiment, one may also determine ne by measuring weight change of the copper plate
after a certain time(s) since the number of moles of electron introduced into the cathode compartment
+
in coulometer is directly equal to the amount of Ag dissolved.

( 14 )

In Figure 2, the motion of ions during the electrolysis of HCl solution in Hittorf Cell is shown. As it is
seen from the figure the cell is divided into three compartments; anode, middle and cathode
compartment. In electrolysis, the concentration of the electrolyte in the middle compartment does not
change, while it changes in the anode and the cathode compartment. Before the electrolysis the
concentration of the electrolyte in all compartments is the same, each compartment contains six pairs
of ions which is shown part I of Figure 2.

Anode
Compartment

Middle
compartment

Cathode
compartment

II
-

4Cl (aq) 2Cl2(g)+ 4e(aq)


3 mol H

4H (aq) + 4e (aq)H2(g)
+

1 mol Cl
3 mol H

1 mol Cl
-

III

Figure 2. The illustration of the motion of ions in a solution of HCl in electrolysis


Distribution of ions after passage of 4 Faraday through the electrolytic cell is shown in part II; the
+
+
velocity of H is three times greater than that of Cl , the H ions will migrate from anode to cathode
during a definite time over a distance that is three times greater than that covered by Cl from cathode
+
to anode. So three times more ions H will migrate through sections from anode to middle
+
compartment and after a short period of time the same amount of H ions in the middle compartment
will migrate from middle compartment to cathode. Six surplus ions of hydrogen appear in the cathode
compartment and there must be the same number of surplus ions of chlorine in the anode
compartment. These ions discharge at the electrodes and leave the solution in the form of chlorine
and hydrogen gas.
In part III three pairs of ions remains in the anode compartment and five pairs in the cathode one. The
decrease in the amount of electrolyte at the anode is three times greater than that at the cathode.
In this example, the transference number of the cation is 0.75 and that of the anion is 0.25 then when
4 Faraday pass through the solution, the cation in this experiment moves three times faster than
anions and carries three-fourths of the current. In other words, for each anion passing a given plane in
the solution there will be three cations passing in the opposite direction.
Chemicals: 0.1 M AgNO3 stock solution, 0.1 M KSCN solution, 6 M HNO3 solution, CuSO4 solution
and ferric ammonium sulfate (indicator).

Procedure
1.

Polish the copper plates and silver electrodes with sand paper. Wash them with distilled water
and then with alcohol. Dry all of them. Weight both of copper plates ( ).

2.

Fill the Hittorf Cell with 0.1 M AgNO3 slowly; be careful to make sure no air bubbles present in the
cell.

3.
4.

Fill the coulometer with CuSO4 solution.

5.
6.
7.

Adjust the current to 5 mA.

8.

After the electrolysis, measure the total volume of anode compartment. Take 25 mL from anode
compartment, add 5 mL 6 M HNO3, 50 mL distilled water and 1 mL ferric ammonium sulfate, and
titrate this solution with KSCN up to a first permanent red tint color.

9.

After the electrolysis, measure the total volume of middle compartment. Take 25 mL from middle
compartment, add 5 mL 6 M HNO3, 50 mL distilled water and 1 mL ferric ammonium sulfate, and
titrate this solution with KSCN up to a first permanent red tint color.

Construct the cell in a serial connection. The experiment involves passage of a direct electric
current from a power source through the cell.
Note the time at the beginning of the electrolysis and continue the electrolysis for 90 minutes.
While the electrolysis is going on determine the concentration of AgNO3 stock solution. To do this
take 25 mL AgNO3 stock solution, 5 mL 6 M HNO3, 50 mL distilled water and 1 mL ferric
ammonium sulfate, and titrate this solution with KSCN up to a first permanent red tint color.

10. Remove the electrodes from coulometer, rinse with distilled water then alcohol, dry them and
weight them at the end of the electrolysis (

).

(Waste container of experiment: silver waste container for


AgNO3and Coulometer bottle for CuSO4)

Treatment of Data
+

1. Calculate initial number of moles of Ag ions ( ) from 25 mL stock solution.

( 15 )

2.
3.
4.
5.
6.

Calculate initial number of moles of Ag ions ( ) for total volume of anode compartment.
+
Calculate final number of moles of Ag ions ( ) for 25 mL volume of anode compartment.
+
Calculate final number of moles of Ag ions ( ) for total volume of anode compartment.
+
Calculate number of moles of Ag ions in middle compartment.
Calculate
theoretically.

( 16 )

( 17 )

7. Calculate
experimentally. Use the equation ( 14 ).
8. Calculate
theoretically by using , which was calculated theoretically. Use the equation ( 11 )(
14 ).
9. Calculate
experimentally.
+
310. Calculate transference numbers of Ag ( ) and NO ions ( ) experimentally and theoretically. For
calculation of transference number of anion use equation 10.

( 18 )

Questions
1. Discuss other two methods to determine transference number.
2. What will be the change in the mass of the copper plates (increase/decrease)? Explain
3. What will be the change in the mass of the silver plates in the Hittorf cell (increase/decrease)?
Explain.
4. How would the concentration of middle compartment change? Explain briefly.
5. Discuss factors influencing the transport number.
6. Discuss the function of the coulometer in this experiment.
7. Explain the function of middle compartment in this experiment.
8. Associate electrophoretic effect and relaxation effect with this experiment.

DATA SHEET
Hittorfs Method

Experiment 4. Determination of Transference Number by

Group Number:
Student name:
Assistant name and Signature:

Date:

Before electrolysis;

After electrolysis;