Department of Chemical Engineering

University of San Carlos- Technological Center

Nasipit, Talamban, Cebu City

ChE 412L
Physical Chemistry Laboratory 2

Ion Mobility: Transference Number of Ions (ION) and

Analysis of Electrochemical Reactions (ECR)
Date Performed: September 14, 2015
Date Submitted: September 28, 2015

Submitted by:

Banaag, Kristian Gregg C.

Cauagdan, Diane S.

Duterte, Jan Rommel T.

A laboratory report submitted to

Dr. Alchris W. Go
Instructor, ChE412L
1. Introduction

If an electric current is passed through a solution of an electrolyte, anions

and cations move at characteristic speeds toward the anode and cathode, whereby
both contribute to the charge transport in an electrolytic process. Transport
number or transference number is the fraction of the total current carried by an
ion1. Thus, the sum of the transport numbers of cation (t +) and anion (t-) in the
solution will be equal to one.
=1
++t
t

(Equation 1)

Transport numbers can be determined in many ways. In this experiment,

Hittorfs method is used. The fact that in electrolysis, ions move with different
speeds that cause different concentrations around the electrodes 2; the nature of
these changes can be understood of what had happened in the transference
number apparatus wherein in the compartments of the double U-tube, oxidationreduction reactions occur at the anode and cathode regions correspondingly and
this leads to the determination of transport numbers of the cation and anion that
also paves way in measuring ionic mobilities.
The following are the reactions that occur in the electrolysis of nitric acid
in the transference vessel:
2 H 2( g )

++ 4 e
Cathode region
:

4 H (aq)

++ 4 e
Anode region:

2 H 2 O l O 2(g )+ 4 H (aq)

The non-spontaneous reactions above would have not been possible if

electrical energy is not used.
The changes in concentration in the cathode and anode can be related to
the charge quantities and Faradays constant (96485.3399 Coulomb/mole) of
which the charge transported by the anions can be calculated using,

F ( n A nC )
=
2
q
(Equation 2)
The total amount of electricity that is used can be determined by analyzing
the mass changes of the copper sheets in the copper coulometer according to
Faradays law. That is,
q=

z R F ( mC m A )
2 M Cu

(Equation 3)
where n and n are the changes in the amounts (mol) of electrolyte in the
A

anode and cathode respectively, mA and mC are the changes in the mass of
copper on the anode and cathode correspondingly, MCu is the molar mass of
copper (63.54g/mol), and ZR is the charge number of the reaction which is in this
case is 2. Another way of determining the total charge quantity is through
q=It
(Equation 4)
where I is the current reading in the multi-range meter and t is the corresponding
time of the amount of current delivered.
The transference number of anion can be calculated by
q
q
=
t

(Equation 5)

or simply,
A

( n n )M Cu

( m C m A ) z R
t

(Equation 6)
and simultaneously, t+ can be calculated using Equation 1.

With the occurring electrolytic process, a thermodynamic property can be

obtained which is the Gibbs free energy, G. The latter can be calculated using
the equation:
G=q

(Equation 7)

RT
lnQ
nF

(Equation 8).

and where
=

2. Objectives of the Experiment

2.1 ION

To determine the transference numbers of nitrate and hydronium

ions
To discuss the effect of mass on the transference number of an ion

To describe the reactions that occur in the cathode and anode

regions of the transference vessel and copper coulometer

To analyze the thermodynamic properties and material balance of

2.2 ECR

the electrochemical reactions

3. Methodology
3.1 Materials
The materials used in the experiment were 0.1 M nitric acid solution
g
(HNO3 with a percent purity of 69% g

and a density of 1.42 g/mL, 0.1 M

g
,
sodium hydroxide stock solution (NaOH) with a percent purity of 97% g 0.5

g
M sulphuric acid solution (H2SO4) with a percent purity of 96.5% g

and a

density of 1.84 g/mL, 0.5 M copper (II) sulphate solution (CuSO45H2O) with a
g
,
percent purity of 99.5% g dried potassium hydrogen phthalate (C8H5KO4 or
KHP), methyl red solution, phenolphthalein solution and distilled water (H2O).
3.2 Equipment and Apparatus
(4) 250 mL Erlenmeyer flask

(3) iron clamp

(3) 250 mL beaker

(3) iron stand

(3) 5 mL pipette

(2) copper electrodes

(3) pipettors

(2) carbon electrodes

(2) 250 mL volumetric flask

(1) 3000 mL beaker

(1) 50 mL base burette

thermometer

nitrile gloves

dropper

waterproof marker

transference vessel

wash bottle

stirring rod

copper coulometer

digital stopwatch

connecting cords

power supply

multi-range meter

analytical balance

(b
)

(a)

(c)
(d)

Figure 1. Transference Number Apparatus. (a) Power supply, (b)

transference vessel,(c) Copper coulometer, (d) multi-range meter
3.3 Procedure
Two hundred fifty milliliters each of 0.1 M HNO 3 solution and 0.5 M
H2SO4/CuSO4 solution were prepared. Nitric acid solution was prepared by
pipetting 1.61 mL HNO3 from the reagent bottle with the use of nitrile gloves in
the fume hood and transferring it into the 250-mL volumetric flask with distilled
water in it. The solution was then diluted to the mark. In preparing H 2SO4/CuSO4
solution, 31.3660 g of CuSO45H2O was weighed in the analytical balance and
was then dissolved in 50 mL water in the beaker. The solution was then
transferred into the 250-mL volumetric flask. After, 6.7 mL of H 2SO4 was pipetted
from the reagent bottle in the fume hood and was transferred in the volumetric
flask with the CuSO45H2O solution in it. The solution was then diluted to the
mark. The 0.1 M NaOH stock solution was standardized to know its actual
concentration by using KHP as a primary standard and phenolphthalein as an
indicator. The color change was noted to be from colorless to pink. The prepared
0.1 M HNO3 solution was also standardized by getting 5 mL of the solution and
titrate it with the standardized NaOH solution having methyl red as an indicator.
The color change was noted to be from red to yellow.
In setting up the transference number apparatus as shown in figure 1, the
following were done. The transference tube was immersed in the 3000-mL beaker
filled with water that serves as the temperature-controlling bath. The U-tube was
fixed to the support rod and it was then filled with HNO 3 solution. The carbon
electrodes were hung into the double U-tube and the level of the solution in the
three compartments of the tube was made sure to be the same. The level of the
solution was then marked with a waterproof pen. The transference vessel was
lowered until the markings are submerged in the water bath. In the part of copper
coulometer, the masses of two copper sheets labeled with anode and cathode were
measured and recorded. The two copper sheets were then fixed into the electrode
holder and immersed into the 250-mL beaker filled with 0.5 M H 2SO4/CuSO4
solution. The coulometer, together with the transference vessel, multi-range meter
and power supply are connected in series using the connecting cords.
6

Afterwards, electrolysis was done for 80 minutes at about 50 mA, and

since the current intensity was changing, for every 5 minutes, the current reading
was recorded. The temperature of the bath was maintained at 28C. Few minutes
before electrolysis was finished, two 5-mL samples were taken in the anode and
cathode regions of the transference vessel very quickly. Right away, the
electrolysis was stopped. The obtained samples were then titrated using the 0.1 M
NaOH standardized stock solution to determine the concentration.
The copper electrodes of the coulometer were carefully washed with
water, dried, and weighed. The transference vessel was also emptied and dried.
The marked volume of the cathode and anode regions was determined by filling it
with water and the fluid displaced by the immersed electrodes was considered. A
pipette was used for accurate measuring of volume.

4. Results and Discussion

4.1 Ion Mobility: Determination of Transference Numbers of Ions
The change of concentration of nitric acid solution and the change of mass
of two copper sheets in both anode and cathode regions are used to obtain the
transference numbers of nitrate and hydronium ions.
Table 1 shows the average concentration of HNO3 in the anode and
cathode regions before and after electrolysis. (See Appendices for sample
calculations.)
Table 1. Average molarity of HNO3 in the anode and cathode regions in electrolysis

Anode
Before
After
electrolysis electrolysis
Average molarity of
HNO3 (mol/L)

0.0956

0.101685

Cathode
Before
After
electrolysis electrolysi
s
0.0956
0.0753

As seen in Table 1, the concentration of nitric acid solution in the anode

region increases whereas in the cathode region, it decreases. The increased
7

concentration of HNO3 solution in the anode region is due to the formation of H +

ions during electrolysis. In the cathode region, concentration of HNO3 solution
has lowered due to the consumption of H + to produce hydrogen gas and which is
why formation of bubbles was evident in the electrode during electrolysis. Also,
bubbles were evident in the electrode of the anode region since oxygen gas is also
produced with the formation of H+ ions.
Table 2 shows the masses of copper electrodes in the anode and cathode
regions before and after electrolysis.
Table 2. Masses of copper electrodes in the anode and cathode regions in electrolysis

Anode

Mass of Cu electrode (g)

Before
electrolysis

After
electrolysis

6.8793

6.7995

Cathode
Before
After
electrolysis electrolysi
s
4.0545
4.1351

It can be observed in the table above that the mass of the copper electrode
in the anode region has decreased while in the cathode region, the mass of the
copper electrode has increased. This result is reasonable because the ions migrate
towards the electrode in the cathode region to stabilize themselves thereby
increasing the mass of the Cu electrode in the cathode region and decreasing the
mass of Cu electrode in the anode region.
Aforementioned the information needed to obtain the transference
numbers of cations,

+
t

(hydronium ions) and anions,

(nitrate ions),

equations 6 and 1 can be used. In addition to that, transference numbers using the
total charge quantity based from equation 4 simultaneously applying equations 5
and 1 were also obtained. The experimental results are summarized in Table 3
with corresponding percent differences as with reference to the theoretical values
of the transference numbers. (See Appendices for calculations.)
Table 3. Transference numbers of cation and anion
8

Using concentration and mass changes

(Eqs.6, 1)

Using total charge quantity (Eqs. 4,5,1)

Experimenta
l Values at
28C

Literature
Values at
25C

Percent
Difference
(%)

Experimental
Values at 28C

Literature
Values at
25C

Percent
Difference
(%)

+
t

0.87007

0.8304

4.78

0.8177

0.8304

1.53

0.12993

0.1696

23.39

0.1823

0.1696

7.49

As seen in the table above, the transference number of hydronium ions is

greater than that of nitrate ions. The values obtained are justifiable because
hydronium ions have lighter mass making them more mobile compared with
nitrate ions which have heavier mass that make them less mobile. Having said
that, more of the hydronium ions are transported from the anode to the cathode
and at the same time, less nitrate ions are transported from the cathode to the
anode area. Also, the faster the ions move, the higher is the transference number
because transference number can be expressed as the ratio of the ionic mobility of
the specie to that of the summation of all the ionic mobilities of the ions.
The difference between the experimental and literature values is due to the
dissimilarity in temperature and the extent of dilution of electrolyte with reference
to how the experiment is conducted the literature values are obtained at 298K
and the nitric acid solution is at infinite dilution.
It can also be observed that the values of the transference numbers
obtained from different methods are quite far. This difference arise due to the
fluctuating current being displayed by the multi-meter over time as the
electrolysis is ongoing.
4.2 Analysis of Electrochemical Reactions
During electrolysis, the anode carries a positive charge while the cathode
carries a negative charge and this is because of the influence of an external source.
9

This external source which made current passed through the electrochemical cells
produces non-spontaneous chemical reactions that take place at the electrodes of
the electrolytic cells. The electrolytic cells involved are the transference vessel
with HNO3 solution and the copper coulometer with the H2SO4/CuSO4 solution.
In the transference vessel, reduction occurs at the cathode region where
hydrogen ions have been consumed to produce hydrogen gas which causes the
formation of bubbles in the carbon electrode of that vicinity and oxidation occurs
at the anode region where electrons are released and that water is oxidized to form
oxygen gas of which also causes the formation of bubbles in the carbon electrode
within that vicinity.
In the copper coulometer, reduction and oxidation happen in the cathode
and anode regions respectively. The following are the reactions involved:
Cu(s )
2 +

Cathode: Cu(aq) +2 e

2+

Cu(aq) +2
Anode: Cu(s )

In the cathode region, Cu2+ ions are reduced to solid copper of which are
deposited on the copper electrode and this justifies why there is an increase in
mass of the copper sheet in the cathode region. In the anode region, the solid
copper dissolves from the electrode and gives rise to Cu2+ ions that mix with the
solution, and this result to the decreased mass of the copper sheet in this region.
The standard cell potential,

of the reactions that occur in the anode

and cathode regions in the transference vessel resulted to be negative which is

equal to -1.23 V. This value is equal to the cell potential, , that is used to
calculate for the Gibbs free energy by applying equation 7. The total charge

10

quantities used are the values obtained from equations 3 and 4. (See Appendices
for the calculations.)
Table 4 summarizes the results of Gibbs free energy with varying total
charge quantity.
Table 4. Gibbs free energy of the electrochemical reaction
Total charge quantity, q (C)
qequation3= 243.57
qequation4= 173.59
Gibbs free energy,G (J)
299.59
213.52
It can be observed in the table above that the values of the Gibbs free
energy being obtained are positive and so the electrochemical reaction is
nonspontaneous and therefore requires electrical for it to occur.
The values of the Gibbs free energy obtained as with reference to the total
charge quantity being used are not that precise having a percent difference of
28.73%. This difference is due to the drastic decrease of current for every five
minutes being delivered as displayed in the multi-range meter reading. Therefore,
its better to determine the total charge quantity through the mass changes of
copper electrodes in the copper coulometer.
5. Conclusion
Transport number is a way of determining ion mobilities of cations and
anions dispersed throughout the solution. This can be done through the use of
Hittorfs method that deals with the changes in concentration that occurs around
the electrodes due to the migration of ions.
The mass of an ion affects its transference number. The lighter the mass of
an ion, the faster it can move, the higher is its transference number. Furthermore,
the more mobile the ion is, the faster the rate of transfer, the higher the
transference number.
In an electrolytic cell, oxidation-reduction reaction is not spontaneous and
electrical energy must be supplied for this to occur. Here, the anode is positive and
the cathode is the negative electrode. Oxidation takes place at the anode region
while reduction takes place at the cathode region.

For a non-spontaneous

reaction, the resulting Gibbs free energy is positive.

11

6. Answers to Questions
Ion Mobility: Determination of Transference Numbers
1.

Carefully observe the cathode and anode regions during electrolysis. What
gas is produced in the cathode/anode areas during the electrolysis of nitric
acid?
During electrolysis, there were bubbles formed at the anode and the

cathode regions of the transference vessel. For the electrolysis of nitric acid,
hydrogen gas was produced in the cathode region where reduction occurs and
oxygen gas was produced in the anode region where oxidation occurs.
2.

Write down the species involved in the electrolysis of nitric acid by

determining the reaction that occur in the cathode and anode regions of the Utube.

Anode:

Cathode:

3.

++ 4 e
Oxidation

2 H 2 O l O 2(g )+ 4 H (aq)

2 H 2( g )

++ 4 e

4 H (aq)

Reduction

Determine the transference numbers of the hydronium and nitrate ions.

+=0.87007
H + =t
t
=0.12993
NO 3 =t
t
4.

Discuss the relationship between transport number and mass of ions.

12

Nitric acid consists of hydronium and nitrate ions. Hydronium ions have
lighter mass compared to that of the nitrate ions which makes them more mobile
that resulted to a higher transference number compared to that of nitrate ion.
Nitrate ions have heavier mass that made them less mobile and resulted to a
lower transference number.
Analysis of Electrochemical Reactions
1.

Describe what are the reactions in cell (b) and (c) and which ones occur at the
cathode or anode.
Cell (b) reactions:
2 H 2( g )
++ 4 e
Cathode:
4 H (aq)

++ 4 e
Anode:
2 H 2 Ol O2(g )+ 4 H (aq)
Cell (c) reactions:
Cu(s )
2 +

Cathode: Cu (aq) +2 e

2+
Cu(aq)
+2
Anode: Cu(s )

2.

What is the importance of cells (b) and (c) in the electrolytic determination of
transference numbers?
In the electrolytic determination of transference numbers, cells (b) and (c)
give significant importance. Cell (b) is where the nitric acid was placed and is
where movement of ionic species is allowed to occur. The movement of ions was
13

observed by calculating the concentration of the nitric acid in the anode and
cathode regions after electrolysis. Cell (c), copper coulometer, is where the copper
sheets or electrodes are placed and this relies on the change in the mass of an
electrode when a metal is dissolved or deposited at it and coulometer can measure
the amount of electric charge that passed through it which can be used in the
determination of transference numbers as well.
3.

Predict the mass changes in the copper electrodes if the nitric acid concentration
in cell (b) is greater than 0.1 molar. Explain your answer.
If the concentration of nitric acid would be greater than 0.1 molar, the
change of mass that occurs in the copper electrode would be much greater than
the results acquired in the experiment. Increasing the concentration of the
electrolyte will increase its conductivity which furthermore increases its rate of
charge transport thereby causing the reaction in cell (b) as well as in the copper
coulometer to speed up. More copper will be dissolved in the anode region and
more will be deposited in the cathode region.

4.

Compare the calculated value of the total charge quantity from Eq. 3 with the
value obtained from q=It.
The calculated value of the total charge quantity from Equation 3 is equal
to 243.57 C.
In the experiment, we expected that the current delivered is 50mA but the
actual current delivered has changed which we have recorded for every 5 minutes.
That is,
Time,
min
5
10
15
20
25
30
35

Current, A
42
42
41
41
41
40
39

q(q=5*current), C
210
210
205
205
205
200
195
14

40
45
50
55
60
65
70
75
80

38
36
35
33
31
29
25.5
22
20

190
180
175
165
155
145
127.5
110
100

To get the total charge quantity, the mean of q is obtained which is equal to
173.59 C.
The calculated value of q based from Equation 3 has a greater value than
obtaining it from q=It and this is due to the fluctuating current reading in the
multi-range meter over time as the electrolysis is ongoing.
5.

Determine the Gibbs free energy of the electrolysis of nitric acid.

The calculated Gibbs free energy of the electrolysis of nitric acid using
the total charge quantity obtained from equation 3 is 299.59 J and the Gibbs free
energy calculated based from the total charge quantity obtained from equation 4 is
213.52 J.

7. References
1

Wilson, J.M., et.al. (1968). Experiments in Physical Chemistry Second revised

and enlarged Edition. Pergamon Press: New York.

Negi, A.S., et.al. (1985). A Textbook of Physical Chemistry. New Age

International: New Delhi

Lide, David R., et.al. (N.D.). CRC Handbook of Chemistry and Physics. pp 940941. Retrieved from http://www.fptl.ru/biblioteka/spravo4niki/handbook-ofChemistry-and-Physics.pdf

Zumdahl, Steven S. and Zumdahl, Susan A.(2012). Chemistry: An Atoms First

Approach, International Edition. United States of America: Brooks/ Cole
Cengage Learning
15

8. Appendices
See initial report.

16