Determining the transport number

1. Introduction
1.1. Charge transport in electrolytic solutions
In the solution of electrolytes, the charge is transported by ions. Different ions do not
contribute equally to the charge transport, and the proportion of their participation in the so-called
transport number (t).
|𝑄𝑖 | |𝑄𝑖 |
𝑡𝑖 = = 1.
∑|𝑄𝑖 | 𝑄
where ti is the transport number of the i-th ion, Qi is the charge carried by this ion, Q is the total
charge. (The absolute value is necessary because although the cations move in one direction carrying
a positive charge (current) and the anions move in the opposite direction carrying a negative charge
(current), their contribution to the total current or charge is equivalent.) The carried charge depends
on the charge that can be carried by one ion (this is the charge number of the ion, zi), the number of
ions (its concentration, ci), and the migration velocity of the ion (𝑣⃗⃗⃗𝑖 ). The latter is proportional to the
magnitude of the electric field, the field strength (𝐸⃗ ). The ratio of the two is the so-called electrical
mobility (u).
𝑣𝑖
⃗⃗⃗
𝑢𝑖 = | | 2.
𝐸⃗
So, for each i
|𝑄𝑖 | ∝ |𝑧𝑖 | ∙ 𝑐𝑖 ∙ 𝑢𝑖 3.
If we have a binary electrolyte solution in which the charge number of the cation and the anion is
equal in absolute value ( z+ = |z-|, so c+ = c- ), then
𝑢+
𝑡+ = = 1 − 𝑡− 4.
𝑢+ + 𝑢−
1.2. Hittorf's method
The method is based on the fact that if one (only one) component of a given dissolved
electrolyte can be reversibly oxidized and reduced, its concentration in an electrolysis cell will change
around the electrodes during electrolysis. The change is caused by the dissolution or precipitation of
ions and the migration of the ions in the opposite direction. In this practice, a solution of copper (II)
sulfate will be studied, and accordingly, this will be our example in the further discussion.
Anodic process:
Cu(s) → Cu2+ (aq) + 2 e-
Cathodic process:
Cu2+ (aq) + 2 e- → Cu(s)
That is, the dissolution
(or precipitation) of 1
mole of Cu means the
transfer of 2 moles of
electrons, i.e., the
transfer of 2F charge.
F is the so-called.
Faraday constant
(molar elementary
charge,
96 485 C / mol).
Figure 1 Subprocesses of electrolysis

Thus, for Q charge, Q/ (2F) amount dissolves in the anode space at the anode, and due to charge
transport, t+·Q/(2F) amount of Cu2+ ion passes away, i.e., the net change (increase):
𝑄 𝑡+ ∙ 𝑄 𝑄 5.
∆𝑛𝐶𝑢2+ = − = 𝑡− ∙
2𝐹 2𝐹 2𝐹
During the same time t- ·Q/(2F) mole SO42- ion comes here, i.e.,
𝑄
∆𝑛𝐶𝑢𝑆𝑂4 = 𝑡− ∙ 6.
2𝐹
In the cathode space, the opposite is true, i.e., Q/ 2F) of Cu2+ ion are released for Q charge, and
t+·Q/(2F) of Cu2 + ions come here due to charge transport, i.e., the net change (decrease):
𝑄
∆𝑛𝐶𝑢𝑆𝑂4 = − 𝑡− ∙ 7.
2𝐹
The net process is thus the transfer of Δn amount of CuSO4 from the cathode space to the anode
space. From the total charge and the change of the amount of substance of CuSO4 in the anode and
cathode part, t+ and t- can be determined.

1.3. Concentration cells

During the electrolysis, the concentration of copper (II) sulphate in the anode and cathode
compartments changes, thus a so-called a concentration cell is formed. (The only difference between
the two electrodes / half-cells is that the electrolyte concentrations in the solution are different.)

In the case of concentration cells without ion transport, the cell voltage, if no current flows and if the
two half-cells are in equilibrium separately, is equal to the cell reaction potential, the difference
between the equilibrium electrode potentials of the two half-cells:
𝑅𝑇 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑎𝑛𝑜𝑑𝑒 − 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = (𝐸 0 + 𝑙𝑛𝑎𝐶𝑢2+,𝑎𝑛𝑜𝑑𝑒 ) − (𝐸 0 + 𝑙𝑛𝑎𝐶𝑢2+,𝑐𝑎𝑡ℎ𝑜𝑑𝑒 ) 8.
2𝐹 2𝐹
𝑅𝑇 𝑎𝐶𝑢2+,𝑎𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑛 9.
2𝐹 𝑎𝐶𝑢2+,𝑐𝑎𝑡ℎ𝑜𝑑𝑒
Then the solutions do not mix, the electrical connection of the solutions is a so-called salt bridge
(e.g., in this practice a glass tube filled with an agar agar gel impregnated with 1 mol/dm3
concentration KCl, see later, Fig. 4), where no so-called diffusion potential (Ediff) develops, because
the electrical mobility and the diffusion coefficient of potassium and chloride ions are almost the
same.

Figure 2 Illustration of the formation of diffusion potential (difference)

If it is possible to mix the solutions between the half-cells (diffusion is possible between the
halves of different concentrations), ion transport can occur, then the measurable unloaded cell
voltage (electromotive force, EMF) also includes the diffusion potential at the solution-solution
interface between the half-cells.
A schematic of the formation of the diffusion potential is shown in Fig. 2. Faster ions with
higher electrical mobility overcome slower ions, resulting in a charge separation at the boundary of
solutions of different concentrations. This means the formation of a potential difference (diffusion
potential) that slows down the faster ions, accelerates the slower ions until an average, common
diffusion rate is reached. However, due to the formation of the diffusion potential:

𝑅𝑇 𝑎𝐶𝑢2+,𝑎𝑛𝑜𝑑𝑒
𝐸𝑀𝐹 = 𝐸𝑐𝑒𝑙𝑙 + 𝐸𝑑𝑖𝑓𝑓 = 2 ∙ 𝑡− ∙ 𝑙𝑛 10.
2𝐹 𝑎𝐶𝑢2+,𝑐𝑎𝑡ℎ𝑜𝑑𝑒
Thus, in principle, it is possible to determine the transport number from the measurement of the
electromotive force of the concentration cell with ion transport if the activities are known. It is much
simpler to measure the electromotive force at the same concentration element with and without ion
transport, and then
𝐸𝑀𝐹,𝑤𝑖𝑡ℎ
= 2 ∙ 𝑡− 11.
𝐸𝑀𝐹,𝑤𝑖𝑡ℎ𝑜𝑢𝑡

2. Measurement

2.1.1. Hittorf's method

Hittorf (Johann Wilhelm, 1824-1914) designed a special cell (see Fig. 3) in order to separate the
changes in the cathode and anode spaces as much as possible during electrolysis.
 Figure 3 Schematics of a Hittorf’s cell
The cell has three parts: a cathode space, an anode space, and an indifferent portion connecting the
two. Each of the three parts has a separate tap, so that after electrolysis the solution of the three
parts can be separated.

2.1.2. Carrying out the measurement

- Prepare a solution of 250 cm3 of copper (II) sulphate of a concentration of 0,1 mol/dm3.
- The electrodes of the Hittorf cell have to be polished with a sandpaper, moistened with water,
washed, dried with acetone and weighed on an analytical balance. From the electrodes of the cell,
the lower mass is chosen as the cathode. This way, you can avoid losing only one electrode at a time
during exercises.
- Mount the cell on a Bunsen stand to accommodate the Erlenmeyer flasks used to drain the
solutions. Weigh the dry flasks before draining the solutions.
- Grease the taps (if necessary) before filling the cell.
- Fill the Hittorf cell with the copper (II) sulphate solution so that it also fills the connecting pipes of
the indifferent part (see Fig. 3).
- Insert the electrodes into the electrolysis cell as close as possible to the bottom of the anode and
cathode compartment, but do not touch the glass wall.
- Connect the electrodes to the DC power supply and start electrolysis and data acquisition after
setting the correct voltage. Electrolysis of about two hours is advisable, see Supplement 1 as well.
- After completion of the electrolysis, drain the solutions from the cell parts. First, the cathode and
anode compartment taps (together) must be opened so that the drip rate is approx. be the same
from both parts (it can't flow, it can just drip!). The tap of the indifferent part can only be opened
after the liquid has already flowed out of the pipes connecting the three compartments, i.e., the
compartments already contain independent solution parts. After draining, measure the mass of the
solutions. Electrodes washed with distilled water and dried with acetone must also be weighed.
- The molality of the original/starting/stock solution and the copper (II) sulphate solution from the
three different compartments must then be determined by complexometric titration. See
Supplement 2. (Due to the change in density and temperature, it is advisable to use molality instead
of molar concentration, i.e., to use mass measurements instead of volume measurements.)

2.1.3. Evaluation of experimental data

- First determine the total charge (Q) through the solution. For this, the measured/registered
current-time function is numerically integrated. Since the current changes are not very large, the
sampling is quite dense, so the simplest numerical integration formula, the trapezoidal rule, is
sufficient.
- The mass change of the anode is used to determine, based on Faraday's laws, how much charge
was actually applied to the dissolution of copper. Its approx. must match the total charge, otherwise
it was too large e.g., the contribution of the Cu (s) → Cu+ (aq) + e- process to the current, and thus
the result obtained for the transport number will not be reliable.
- The charge is also calculated from the mass change of the cathode, but this is less reliable, because
the copper precipitates in a loose, spongy state, it does not adhere well to the surface, it falls off e.g.,
as a result of washing, thus falsifying the measurement of weight gain.
- The changes in the amount of substance must be determined from the changes in the composition
of the anode, indifferent and cathode compartments.
To do this, prepare the following (recommended) table.
Sum up the total mass of the samples, the molalities of the samples determined by titration, the
amount of copper (II) sulphate in each compartment, the masses of water in each compartment (this
did not change during the electrolysis because no decomposition took place under the given
conditions), and the masses of water and the molality of the stock solution of the original/starting
copper (II) sulphate (n0).

Sample msolution/ molality nCuSO4 / mwater/ n0/ Δn/

g (mol/g) mol g mol mol
Stock ------------------- m0
̅̅̅̅ ------------------- ------------------- ------------------- -------------------

Anodic
Cathodic
Indifferent

(The amount of dissolved electrolyte in the indifferent part should not change. Measuring this is
useful because it indicates how successful the electrolysis was. However, a small change always
occurs. If the amount of substance increases in the indifferent part, it should be added to the change
in the anodic part, if the amount of material decreases in the indifferent part, it should be assigned
to the cathode compartment (the copper has leaked from there).)
- Calculate the transport numbers knowing Q and Δn.
- The ratio of the transport number of copper (II) to sulphate ions must be justified. The result
obtained should be compared with the literature data. (In many cases, it is not the transport number
that is found directly, but the ion mobility or ionic molar specific conduction in an infinitely dilute
solution.)
2.2. Concentration cells
At these measurements do not use the concentration element produced by electrolysis because the
concentration difference is too small to make a reliable measurement. Instead:
- Prepare 100 cm3 of a 0.5 mol/dm3 copper (II) sulphate solution (solution 0)
- Dilute 30 cm3 of solution 0 to 100 cm3 (solution 1)
- Dilute 30 cm3 of solution 1 to 100 cm3 (solution 2)
- Dilute 30 cm3 of solution 2 to 100 cm3 (solution 3)
etc. to solution 6.

Select two copper electrodes. Since these electrodes are not 100% copper (they always contain some
zinc as an alloying material), they require pretreatment before potentiometric measurements.
- Clean the copper electrodes used for the measurements with a wet sandpaper (lightly, gently),
wash thoroughly with water and dry with acetone.
- Put both electrodes in solution 0 and wait until in the surface zinc is replaced by copper (see also
Supplement 1).
𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)
The simplest way to check this is to measure the difference in electrode potential (voltage, ΔE)
between the two copper electrodes occasionally stirring the solution. If the potential difference,
|ΔE|<1 mV and no longer changes, you have the same (pure copper surface) electrodes with a good
approximation. (Experience has shown that surface atom exchange takes place in 5 to 10 minutes.)
The electrodes should no longer be wiped, only washed with water and dried with acetone between
solution exchanges.
- With solutions 1 and 2 and the two copper electrodes, assemble a concentration cell (without the
KCl salt bridge yet!) as shown in Fig. 4.

Figure 4 Concentration cells

- Use two narrow 50 ml beakers as a cell. It is advisable to mount the two half-cells (beaker with
solution + electrode) separately on a Bunsen stand (movably) because the salt bridge and the
electrolyte key do not require the same distance between the two half-cells.

- After the charge transfer equilibrium have been established (approx. 5 minutes), the two half-cells
are connected to a washed and externally wiped KCl salt bridge (Fig. 4). Measure the potential
difference between the two electrodes (EMF, without ion transport).
Coupling with a salt bridge only takes 2-3 seconds for the voltmeter to stabilize, then remove the salt
bridge immediately because dissolved KCl (especially significantly in dilute copper (II) sulfate
solutions) changes the ionic strength, so the activity of the copper (II) sulfate) ions, and it will be
different for each measurement. After washing the salt bridge, return it to the original 1 M KCl
beakers.
- For the same system, use an electrolyte key instead of a salt bridge to connect the half-cells and use
the syringe to contact the solutions (see Fig. 4). If the voltage stabilizes (2-3 seconds), read from the
voltmeter (EMF, with ion transport).
- Do not return the (partially) mixed solutions from the electrolyte key to the half-cells but empty it
into a separate container and wash it with water. It does not need to be dried, but the outer part in
contact with the half-cells must be wiped off before the next experiment.
- Solution 1 half-cell remains. Replace solution 2 with solution 3 and repeat the previous
measurements with this solution, salt bridge and electrolyte key. Then do the same with solutions 4,
5, 6.
- If you have enough time, repeat the experiments with solution pairs 2-3, 2-4, 2-5, 2-6 or also with
solution pairs 3-4, 3-5, 3-6, 4-5, 4-6, 5-6.

- Plot the EMF,with values as a function of the EMF,without values, and determine the transport number
from the slope (see Equation 11).
- Table your data, interpret the results compared to the results of practice 2.1 or with literature data.

Control questions:
1. What is the transport number? Define it with charges and electrical mobility.
2. What is the relationship between the average migration rate of ions and the electric field strength.
What is electric mobility?
3. What does the transport number of a given ion depend on?
4. Outline the structure of the Hittorf cell. What is the role of each part?
5. If the amount of dissolved copper (II) sulphate in a sample of 2.052 g is 2.11 · 10-4 mol, what is the
molality of copper (II) sulphate? Mr (CuSO4) = 159.62
6. If the weight of the anode part solution is 87.90 g, the molality of copper (II) sulfate iss 1.11·10-4
mol/g, the molality of the initial solution was 1.02·10-4 mol/g, what was the change in the amount of
substance of copper (II) sulfate due to electrolysis? Mr (CuSO4) = 159.62
7. How do you calculate the transport number if you have determined the total charge through the
Hittorf cell and the change in the amount of substance of CuSO4 in the anode part?
8. How do you calculate the transport number if you have determined the total charge through the
Hittorf cell and the change in the amount of substance of CuSO4 in the cathode part?
9. Why can the change in the amount of substance calculated from the total charge and from the
amount actually measured differ from the anode of the Hittorf cell?
10. Why can the change in the amount of substance calculated from the total charge and the amount
actually measured differ for the cathode of the Hittorf cell?
11. How much heat is generated in the cell if a charge of 300 C passes through the cell during
electrolysis at 50 V? How much would this raise the temperature of 200 g of solution if there were no
heat exchange with the environment? The specific heat capacity of the solution should be 4 J/(g K).
12. What are concentration cells? What kind of cell reaction takes place in them?
13. What is the diffusion potential and how does it affect the electromotive force of the
concentration cells? When can we expect no diffusion potential?
Supplement 1
The electrolysis voltage (current) must be chosen optimally.
At low currents, electrolysis takes such a long time that convection due to the difference in density
and diffusion due to the difference in concentration will play a significant role in the concentration
change of the anode and cathode part. At high currents, overheating of some components leads to
unwanted mixing. The rate of heat production during electrolysis (electrical power)
𝑑𝑞
=𝑈∙𝐼 12.
𝑑𝑡
where U is the cell voltage, I is the current flowing. Total heat at constant cell voltage (so-called Joule
heat):
𝑡

∫ 𝑈 ∙ 𝐼 ∙ 𝑑𝜏 = 𝑈 ∙ 𝑄 13.
0
During the measurement, this must be given to the environment so that approx. let our system be
isothermal. (With current electrodes, this means 30-40 mA currents and 40-45 V cell voltage.)
If the cell voltage or current is too high, the anode process is not pure Cu(s) → Cu2+(aq) + 2e-
process, but the Cu(s) → Cu+(aq) + e- process can also be started. In this medium, however, Cu (I) is
not stable but disproportionates: 2 Cu+ → Cu (s) + Cu2+. This means greater dissolution of the anode,
but some of the dissolved copper precipitates on the wall of the cell as metallic copper, causing
errors in measurements and calculations. Therefore, it is necessary to measure the mass change of
the anode and cathode (change of the amount of substancel), how true it was in the measurement
that Cu dissolved as Cu2+, and the dissolved copper is indeed precipitated at the cathode.
Also, a source of error is that the available electrodes are not made of 100% pure copper but copper-
zinc alloys. Zinc dissolves in the same way as copper during electrolysis (even faster):
𝑍𝑛(𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 −
which reduces power consumption for copper. However, surface zinc atoms are dissolved in the
copper (II) sulphate solution without electrolysis in a heterogeneous redox process:
𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)
(There is a characteristic "redness" of the electrode. Contrary to popular belief, pure copper is not
yellow but deep red.)
This means, on the one hand, that the surface of the electrodes will be pure copper, which is good,
on the other hand, dissolved zinc will contaminate the solution, and zinc ions will also be involved in
current conduction, which is bad, causing an error in evaluation. At current electrodes, the zinc
content is small enough that this error is negligible compared to other measurement errors.

In addition, the time of electrolysis should be chosen so that there are measurable changes in
concentration in the anode and cathode space, but no significant change in the indifferent space.

For current cells and electrodes, these requirements mean an electrolysis voltage of 43 V and an
electrolysis time of two hours.
On the computer-controlled DC power supply, these values (as well as the safety limit voltage and
safety limit current values) are set, only the data collection needs to be started, the current-time
data must be recorded. The instructions for use are included with the exercise.
Supplement 2

For titration, prepare a solution of 0.015 mol/dm3 Na2H2EDTA of a volume of 250 cm3. This can be
done by direct weighing of the chemical. EDTA (ethylene diamine tetraacetate) forms a very stable
1: 1 complex with the Cu2+ ion.
Procedure for titration:
Weigh an exactly known mass, approx. 2 cm3 of CuSO4 solution into a 250 cm3 titration flask and
dilute to ∼100 cm3 with distilled water. Add drop by drop cc. NH3 solution (under a hood switched
on!) until the initial precipitate is completely dissolved (10 to 20 drops).
To the sample thus obtained add a knife-tip solid dilution (1:50 or 1: 100) of murexide as indicator
and titrate with Na2H2EDTA solution. The murexide has its own color violet, the complex with copper
(II) is yellow. Their intensity is much higher than that of other (usually blue) copper (II) compounds in
solution, so the equivalence point can be determined very well when the murexide is displaced by
EDTA, i.e., the murexide has its own violet color. At least two parallel titrations must be performed in
each case! The measurements are summarized in a table. E.g.,

cEDTA, exact = … mol/dm3

M(CuSO4) = 159,62 g/mol
Sample msample/ VEDTA solution/ nCuSO4 / mwater/ m
̅ CuSO4 /
g cm3 mol g (mol/g)
Stock
…
Anodic part
…
Operating Instructions for the AX-6003P DC Power Supply
The device contains the values programmed with the parameters used for the exercise and stored in
its built-in memory. If someone deleted or it would be necessary to change:
Parameter settings
Output voltage setting
Press the [V-Set / I-Set] key until “Voltage” appears on the LCD monitor.
Setting Mode 1: Press the keys corresponding to [numeric keypad (voltage value)] and then press
[Enter] to set the output voltage. To be set: 43 V
Output current setting
Press the [V-Set / I-Set] key so that “Current” appears on the display.
Setting Mode 1: Press the [Numeric Keypad (Current Value)] [Enter] keys to set the output current. To
be set: 0.04 A
Setting overvoltage protection
Press the [OVP] key to set the maximum output voltage. Press the [OVP / OCP] button until “OVP Set”
appears on the LCD monitor.
Setting Mode 1: Press the [Numeric Keypad (Voltage Value)] [Enter] keys to finalize the OVP settings.
To be set: 50 V
Setting overcurrent protection
Press the [OCP] key to set the maximum output current. Press the [OVP / OCP] key until “OCP Set”
appears on the LCD monitor.
Setting Mode 1: Press the [Numeric Keypad (Current Value)] [Enter] keys to finalize the OCP settings.
To be set: 0.04 A
Setting the voltage / current delay time
Press the [Delay] key so that “Delay” appears on the LCD.
Setting Mode 1: Press the [Numeric Keypad (Delay Time)] [Enter] keys to set the voltage and current
delay time. To be set: 1 s

Save the current settings to memory.

Press the [Recall / Store] key until “Utility Store” appears on the LCD, Set the panel operation to the
save setting, enter the desired memory address using the numeric keypad (preferably 0), and then
press [Enter] to finalize the save.

The next time the device is switched on, they will be loaded automatically (from zero memory).

The power supply is turned on with the POWER button on the front.
Start the “Ax-6003P-Logging” program on the computer desktop.
Press the "Settings" button at the bottom left, then:
o By default, the hardware COM port menu is set to COM4 for the USB connection on the back of the
computer. If you use another USB port to connect the device, you must refresh the list with the
“refresh” button in the drop-down menu and then select the appropriate COM port (do not select
COM3, this is not a real connection option).
o The value of "Baud rate" is 9600
o Click on the folder symbol to select the data recording location and the file name, then click on the
"OK" button to accept the changes.
Press the "Connect" button to connect the computer and the power supply.
The basic settings of the power supply are read by the computer. If you want to change these:
The voltage you want to use (e.g., 43 V) can be set under the left-hand screwdriver icon. Set the
maximum (e.g., 0.040 A) below the rotary knob icon on the right.

Press the "Start" button to start the measurement and data recording.

You can stop the measurement and data recording by pressing the "Stop" button.