LEC

06.04

Transport numbers

Related concepts
Electrolysis, Faradays laws of electrolysis, charge transport,
ionic mobility, Hittorf numbers.
Principle
Cations and anions contribute to charge transport in electrolytic
processes in accordance with their different mobilities in an electric field. Hittorf transport numbers characterise the fraction of
the total charge transported by a particular ion during electrolysis. They enable the calculation of ionic conductivities, the values of which are important in electrochemical practice.
Transport numbers are to be experimentally determined from the
characteristic concentration changes which take place at the
cathode and the anode during electrolysis.
Tasks
Determine the Hittorf transport numbers for hydronium and
nitrate ions from measurements resulting from the electrolysis of
an 0.1 molar nitric acid solution.
Equipment
Power supply, universal
Multirange meter
Connecting cord, l = 750 mm, red
Connecting cord, l = 750 m, blue
Connecting cord, l = 500 mm, blue
Double U-tube with frits and stopcock, GL25
Contact socket for bar electrodes
Carbon electrodes, d = 7 mm
Plate electrodes, copper
Holder for 2 electrodes
Retort stand, h = 750 mm

13500.93
07021.01
07362.01
07362.04
07361.04
44451.00
45283.00
44512.00
07854.00
45284.01
37694.00

1
1
1
1
2
1
2
1
2
1
3

Right angle clamp

Universal clamp
Burette clamp, roller mounting
Precision balance, 620 g
Digital thermometer, NiCr-Ni
Thermocouple, NiCr-Ni, sheathed
Stopwatch, digital, 1/100 s
Microburette, 10 ml
Burette, 50 ml, with Schellbach line
Erlenmeyer flask, 250 ml, wide neck
Beaker, 100 ml, tall
Beaker, 250 ml, short
Beaker, 5000 ml, short
Volumetric flask, 1000 ml
Volumetric pipette, 5 ml
Volumetric pipette, 50 ml
Pipettor
Pipette dish
Pasteur pipettes
Rubber bulbs
Funnel, glass, do = 55 mm
Funnel, glass, do = 80 mm
Spoon
Laboratory pencil, waterproof
Washbottle, 500 ml
Nitric acid, 1.0 M, 1000 ml
Sulphuric acid, 0.05 M, 1000 ml
Sodium hydroxide, 0.1 M, 1000 ml
Copper (II) sulphate, 250 g
Methyl red solution, 50 ml
Acetone, 250 ml
Water, distilled, 5 l

37697.00
37715.00
37720.00
48852.93
07050.00
13615.03
03071.01
36527.01
36513.01
36134.00
36002.00
36013.00
36272.00
36552.00
36577.00
36581.00
36592.00
36589.00
36590.00
39275.03
34457.00
34459.00
33398.00
38711.00
33931.00
48448.70
31831.70
48328.70
30126.25
30145.05
30004.25
31246.81

2
1
1
1
1
1
1
1
1
4
1
2
1
2
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1
1
1
1
1
1
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1
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1

Fig. 1. Experimental set-up.

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen

P3060401

LEC
06.04

Transport numbers

Set-up and procedure

Set up the experiment as shown in Fig. 1.
Prepare the solutions required for the experiment as follows:
0.1 molar nitric acid solution: Pipette 100 ml of 1.0 molar
nitric acid solution into a 1000 ml volumetric flask and fill up
to the calibration mark with distilled water.
0.05 molar sulphuric acid / CuSO4 solution: Weigh 124.08 g
of CuSO4 5 H2O in a 1000 ml volumetric flask, dissolve it in
approximately 100 ml of 0.05 molar sulphuric acid, and fill up
to the calibration mark with 0.05 molar sulphuric acid.
Fix the transport vessel (double U-tube with frits and cock) with
the support rod so that the lateral connecting tubes are approximately 2 cm above the surface of the water in the beaker which
serves as a temperature controlling bath. Fill the transport vessel with 0.1 molar nitric acid solution up to the external water
level. Immerse the carbon electrodes, adjust the electrolyte solution in the three legs of the U-tube to the same level and mark
this level with a waterproof laboratory pencil. Subsequently,
lower the transport vessel until the markings are submerged in
the bathwater to ensure sufficient temperature control. Weigh
the cathode and the anode of the coulometer which consists of
two pieces of copper sheet, and record their weights. Fix the
pieces of copper with the help of the electrode holder and
immerse them into a 250 ml beaker filled with the sulphuric acid
/ CuSO4 solution. Connect this coulometer, the transport vessel
and the multirange meter in series and to the power supply
according to Fig. 1. Now perform the electrolysis for 60 to 90
minutes at 50 mA. Ensure that the current and the temperature
are nearly constant during the reaction. Measure the exact duration of the electrolysis procedure with the stopwatch.

Fig. 2:

During electrolysis, titrate a 5 ml sample taken from the volumetric flask against 0.1 molar NaOH using methyl red as an indicator (colour change: red-yellow). At the end of the electrolysis
period, take 5 ml samples from the anode and cathode regions
of the vessel and titrate them later to determine their concentrations. Interrupt the electric circuit and record the exact duration
of electrolysis.
Wash the copper electrodes of the coulometer carefully with
water and acetone, dry them in air, and weigh them again to
determine the change in weight. Determine the marked volume
of the cathode and anode regions by filling them with water from
the burette (take the fluid displacement by the immersed electrodes into consideration).
Theory and evaluation
In an electrolytic solution, cations and anions both contribute to
charge transport in an electric field. In electrolytic processes, the
transport numbers t+ and t- characterise the share of the cations
and anions respectively in carrying current (I+, |I-| ) and transporting charge (q+, |q-|).
t


q

I

u



(1.1)



I

0I 0
q

0q 0
u

0u  0


0  0

t 

q
I
u

(1.2)



I

0I 0
q

0q 0
u

0u  0


0  0

From equations 1.1 and 1.2, the sum of the transport numbers
of the cations and anions is found to be:
t

t  1

(2)

Transport and electrode processes in the electrolysis of diluted nitric acid

cathode area

middle area

anode area

before electrolysis

during electrolysis

after electrolysis

P3060401

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen

LEC
06.04

Transport numbers

According to the definition equations (1.1) and (1.2), the transport numbers are related to the ionic mobilities (u+, u-) and ionic
conductivities (+, -) and are thus a function of the migration
velocity of the respective counter-ions.
If the mobilities of the cations and anions differ (u+ u-, t+ t-
0.5), quantities of the two types of ions which are proportional to
these values are transported in the given unit of time. As the
same charge is transported in each case, characteristic alterations in concentration occur at the cathode and the anode,
from which the Hittorf transport numbers can be experimentally
determined.
Fig. 2 illustrates the transport and electrode processes that
occur during the electrolysis of nitric acid. Due to the higher ionic
mobility of the cation (u+ = 5 u-), five hydronium ions are transported from the anode region into the central region, and from
there into the cathode region, within the same time period as just
one nitrate ion is transported in the reverse direction. To ensure
electroneutrality in all the compartments, five hydronium ions
must be simultaneously reduced to hydrogen at the cathode.
Due to the higher deposition potential at the anode, no discharge of nitrate ions occurs, but instead of this, there is an
equivalent formation of hydronium ions from water.
Due to the migration of n- mol of nitrate ions with a charge of
|q-| = n- F (F = 96480 As mol-1, Faradays constant) towards
and away from the electrodes, the quantities of anions (n-K/A),
cations (n+K/A) and electrolyte (nK/A) in the regions of the cathode and anode change during electrolysis according to:
n  K  n
K  nK 

0q 0

(3.1)

n  A  n
A  nA 

0q 0

(3.2)

From this, the charge |q-| transported by the anions can be

established. However, in order to check any error, it is advantageous to determine the changes in the amount of substance at
both electrodes and to calculate |q-| via the relationship obtained
from (3.1) and (3.2):
0q 0 

F 1nA  nK 2
2

(4)

The total amount of electricity used q = q+ + |q-|can be determined from the mass changes at the electrodes in the copper
coulometer according to Faradays law:
q

zR F 1mK  mA 2
2M

where
mK, mA
M
zR

Changes in the mass of copper at the anode

and cathode, respectively
Molar mass of copper (63.54 g mol-1)
Charge number of the reaction (= 2)

Substituting the relationships (4) and (5) in the defining equation

(1.2) for the transport number of the anions provides a practical
approach for the calculation of t-.
t 

M 1nA  nK 2

zR 1mK  mA 2

(6)

The changes in the quantity of electrolyte nA and nK which are

required to perform this calculation, can be calculated using stoichimetric considerations.
nK>A 

where
VK/A
V10, V1K/A

 V01 2
c1 VK>A 1VK>A
1
V2

(7)

Volumes of the cathode and anode regions, respectively

Consumption of NaOH (c1 = 0.1 mol l-1) in the neutralisation of V2 = 5 ml before (V10) and after electrolysis from the cathode (V1K) and anode (V1A)
regions of the transport vessel, respectively.

Data and results

As a result of electrolysis performed at a temperature of T =
293 K over a period of t = 60 min where I = 48 mA, the cathode
region lost nK = - 0.284 mmol of electrolyte, whereas the quantity of electrolyte in the anode region increased by nA =
0.247 mmol. Concurrently, the electrode masses of the copper
coulometer changed by mK = 56.29 mg and mA = - 57.80 mg.
Substituting these values in equation (6), the transport number
for the nitrate ion is calculated to be t- = 0.148. From equation
(2), the transport number of the hydronium ion is calculated to be
t+ = 0.852. The literature values at infinite dilution and a temperature of T = 298 K are t- = 0.170 and t+ = 0.830.

(5)

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen

P3060401

LEC
06.04

P3060401

Transport numbers

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen