CHM171L Physical Chemistry 2 Laboratory

1
st
Quarter SY 2014-2015

Experiment 03 Group No. 4 September 03, 2014 1 of 4

Transference Number

Marquez, Ariziel Ruth
1
, Goce, Ivan Rei.
2
, Lagamayo, Linear.
2
, Landingin, Junard
2
, Lau, John Victor
2

1
Professor, School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology;
2
Student (s), CHM170L/B41, School of Chemical Engineering,
Chemistry and Biotechnology, Mapua Institute of Technology

ABSTRACT

Transference/transport number is a dimensionless parameter which informs about the contribution of the particular charged
species present in the electrolyte (ions and electrons) to the overall charge transport across the cell by the process of
electrolysis. Applying electric current in the solution of electrolytes can cause movement of the anions and cations with
unique speeds towards the cathode and anode. Such speeds vary with respect to the magnitude of the applied voltage,
temperature, and nature of the individual ions. During the experiment, nitric acid was placed in a W tube and was subjected
for a certain voltage for one hour. Aliquots of this charged solution, 5 mL each from the left and right of the W tube, was
collected and titrated by using sodium hydroxide for the determination of end point. The results show that the transference
numbers of the nitrate and hydrogen ions are 0.8175 and 0.1825, respectively.

Keyword: Transference Number, Electrolysis, Overall Charge Transport

INTRODUCTION
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. V/m in SI
units). The mobility of ions is generally quite small (in the
order of 6x10
-8
m
2
.s
1
.V
-1
). The exceptions are hydrogen and
hydroxyl ions with the abnormally high mobilities of 36.3x10
-
8
and 20.5 x 10
-8
m
2
.s
-1
.V
-1
, 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;

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;

( 1 )
CHM171L Physical Chemistry 2 Laboratory
1
st
Quarter SY 2014-2015

Experiment 03 Group No. 4 September 03, 2014 2 of 4
Total current carried by both ions,

( 2 )
The electroneutrality principle expresses the fact that all
pure substances carry a net charge of zero;

( 3 )
Thus, the total current becomes

( 4 )
The fraction of the total current carried by cations,

( 5 )
The fraction of the total current carried by anions,

( 6 )
Thefore, the fraction of the total current carried by the ions
are directly proportional to their velocities.

( 7 )
In summary, the transference numbers of the ions in a
particular electrolyte are defined as follows:

( 8 )
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.

( 9 )
Although the speed of a particular ion does not dependent
on the nature of the ion, the transference numbers depends
on each other.
METHODOLOGY
The laboratory apparatus used were beaker,
pipette, burette, Erlenmeyer flask, Phywe Transference
Number Apparatus and the W tube.

The reagents used were the nitric acid, NaOH,
acetone and Copper sulfate.

The two electrodes were measured using
analytical balance. Nitric acid was transferred in the W tube.
The heights in each column were equal when the Phywe
Transference Number Apparatus were inserted in the right
and left column of the W tube. The two electrode were dip
in a solution of copper sulfate and the current flowing in the
system were adjusted. The set-up was left for 1 hour and
after that, the two electrodes were washed by acetone and
water and their weights were measured again. Five
milliliters were withdrawn from the right and left column and
were titrated by NaOH solution. Five milliliter of the original
nitric acid was also titrated with the use of NaOH solution.
The indicator used in this titration was the methyl red and
the solution turned pink after dropping a methyl red. The
titration stopped when the solutions turned to light yellow.
The volume of NaOH solution was recorded as well as the
initial and final weights of the electrodes. These data were
used to compute for the transference number of hydrogen
and nitrogen ion.

RESULTS AND DISCUSSION
CHM171L Physical Chemistry 2 Laboratory
1
st
Quarter SY 2014-2015

Experiment 03 Group No. 4 September 03, 2014 3 of 4
Table 3.1 The following table shows the mass of
the copper electrodes before and after electrolysis.
W1 (mg) W2 (mg)
Left 1645 1640
Right 1758 1761

The setup in the experiment is an example of a
galvanic cell. In such a cell, the polarity is determined
based on which node is connected to the positive and
negative terminal of a voltage source. In this case, the right
hand side is the positive (cathode) and the left hand side is
the negative (anode). Theoretically, the anode will
spontaneously undergo oxidation converting Cu(s) to Cu
2+

and, the net electrons would travel from the anode to the
cathode where it would reduce Cu
2+
to Cu(s). From this, it is
expected that the left electrode would decrease in mass
while the right electrode would increase in mass. Looking at
the table 3.1, it can be seen that this is exactly what was
observed. The copper on the left side decreased in mass
from 1645 mg to 1640 mg. On the other hand, the copper
on the right side increased in mass by roughly the same
magnitude from 1758 mg to 1761 mg. This observation is
consistent with the theory discussed, thus confirming the
polarity of the galvanic cell in the experiment.

Table 3.2 The following table shows the amount of titrant
needed to neutralize the corresponding nitric acid solutions.
Volume NaOH
(mL)
Volume W-tube
(mL)
Left 22.35 23.5
Right 22.75 24
Original 22.68

The process described in the previous paragraph
would logically produce an excess of positive ions in the left
hand column and an excess of negative ions in the right
hand column. The W-tube used in the experiment
possesses semi-permeable membranes in between all
three glass columns. These membranes inhibit the passage
of certain ions, thus preventing the three separate columns
from reaching electric equilibrium with one another by
means of diffusion. The end result is that the three columns
would possess varying acidities as confirmed by the data in
table 3.2.
Due to the chemical reaction made spontaneous by the
electrolysis process, the solution in the right hand column
would become more concentrated in nitric acid whereas the
solution in the left hand column would become less
concentrated in nitric acid. The reason behind this is the
presence of excess positive and negative ions in the left
and right solutions, respectively. From the data in table 3.2,
it can be seen that the amount of NaOH needed to
neutralize the solution is higher in the right as compared to
the original solution and, it is lower in the left as compared
to the original solution.

Table 3.3 The following table shows the
experimentally determined transference numbers.
Nitrate Ion 0.8175
Hydrogen Ion 0.1825
The transference number of a particular species
depends on multiple parameters one of which is the ionic
mobility. The ionic mobility of an ion varies inversely with
the size of the ion. Larger ions tend to be less mobile while
smaller ions tend to be more. The relationship to be
considered is shown below:

From this relationship, it can be deduced that the
transference number is directly proportional to the ionic
mobility and inversely proportional to the size of the ion.
Since hydrogen ions is much smaller than nitrate ions, it is
expected that hydrogen ions would have higher mobilities
and, therefore, higher transference number. On the other
hand, it is expected that nitrate ion would have the lower
transference number among the two. However, as seen in
table 3.3, the transference numbers obtained from the
experiment are quite the opposite of what is anticipated.
From the reference materials used, it was found that the
transference number data might have been switched as it
would have otherwise been quite accurate if they were.
The trends observed from the data in table 3.1 and 3.2
were accurate and consistent with the theory. The minor
inconsistencies observed in the amount of NaOH used to
neutralize the three nitric acid solutions may have been
caused by the inaccurate concentrations of the solutions
used. It was undetermined how long the acid and base
were put in storage and, the presumed 0.1 molar might
have change somewhat throughout the storage duration.
Other sources of error possibly include human error,
particularly in the titration process. The titration endpoint
was determined to as high a degree as possible but, due to
the limitation of the apparatus, the obtained data may still
deviate about 1 mL from the true value. Lastly, for table
3.3, the error committed is mostly likely to be a gross error.
The transference number for the nitrate and hydrogen ions
CHM171L Physical Chemistry 2 Laboratory
1
st
Quarter SY 2014-2015

Experiment 03 Group No. 4 September 03, 2014 4 of 4
may have possibly been switched but, otherwise, they were
quite precise.
CONCLUSIONS AND RECOMMENDATIONS
The experiment was quite a success because the
percent error computed by the group was below 10% which
means the group performed the experiment well with only
few errors.

After the electrolysis, the final weights of one
electrode decreases while the other one increase. The left
electrode was expected to decrease because it is the
anode part and the right side is the cathode so it was
expected to increase. This proves the theory when the
group final weights were consistent in the theory.

Another theory proven was the decreasing
concentration of the left column of the W tube and the
increasing concentration of the right column. After titration it
was observed that the concentration in the right side of the
W tube increases because the NAOH required for its
titration is greater than the NaOH required in the titration of
the original nitric acid solution. The left side was decreasing
because of the observed NaOH solution required solution
was less than the original nitric acid solution.

Performing the experiment, the group understands
the effect of the electrolysis in each electrode, the cathode
and anode. Anode part will undergo oxidation while the
cathode part undergoes reduction.

The transference number was determined and the
relationship of it to the ionic mobility and ion size was also
deduced. The group deduced that the transference number
is directly proportional to the ionic mobility and inversely
proportional to the size of the ion. Because of these, the
objectives of the experiment were met thus the experiment
was a success.

The flaw or error that the group committed maybe
in the titration part were NaOH was used the solution to
titrate the three solutions. The volume of the NaOH used
maybe not exact because the color of the solution was not
that light thus the NaOH used was excess. Drop of NaOH
make a big difference in color because every drop counts in
every titration so it was very hard to get an exact volume of
NaOH.

REFERENCES
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[4] Perry, Robert., Perrys Chemical Engineers Handbook
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th
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[5] Alberty, R., Physical Chemistry 4
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edition, Wiley
Publishing Co.
[6] Klein, David., Organic Chemistry 2
nd
edition, 2010.
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th
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