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Transference Number
Transference Number
Transference Number
Transference Number
Marquez, Ariziel Ruth1, Goce, Ivan Rei.2, Lagamayo, Linear.2, Landingin, Junard2, Lau, John Victor2
1Professor,School of Chemical Engineering, Chemistry and Biotechnology, Mapua Institute of Technology; 2Student (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.
(2)
It is clear that the sum of the transference numbers of the
ions of a particular electrolyte equals to unity since each is a
The electroneutrality principle expresses the fact that all fraction of a unity.
pure substances carry a net charge of zero;
(3) (9)
(4) METHODOLOGY
Table 3.1 The following table shows the mass of and right solutions, respectively. From the data in table 3.2,
the copper electrodes before and after electrolysis. it can be seen that the amount of NaOH needed to
W1 (mg) W2 (mg) neutralize the solution is higher in the right as compared to
Left 1645 1640 the original solution and, it is lower in the left as compared
Right 1758 1761 to the original solution.
The setup in the experiment is an example of a Table 3.3 The following table shows the
galvanic cell. In such a cell, the polarity is determined experimentally determined transference numbers.
based on which node is connected to the positive and Nitrate Ion 0.8175
negative terminal of a voltage source. In this case, the right Hydrogen Ion 0.1825
hand side is the positive (cathode) and the left hand side is
the negative (anode). Theoretically, the anode will The transference number of a particular species
spontaneously undergo oxidation converting Cu(s) to Cu2+ depends on multiple parameters one of which is the ionic
and, the net electrons would travel from the anode to the mobility. The ionic mobility of an ion varies inversely with
cathode where it would reduce Cu2+ to Cu(s). From this, it is the size of the ion. Larger ions tend to be less mobile while
expected that the left electrode would decrease in mass smaller ions tend to be more. The relationship to be
while the right electrode would increase in mass. Looking at considered is shown below:
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 From this relationship, it can be deduced that the
magnitude from 1758 mg to 1761 mg. This observation is transference number is directly proportional to the ionic
consistent with the theory discussed, thus confirming the mobility and inversely proportional to the size of the ion.
polarity of the galvanic cell in the experiment. Since hydrogen ions is much smaller than nitrate ions, it is
expected that hydrogen ions would have higher mobilities
Table 3.2 The following table shows the amount of titrant and, therefore, higher transference number. On the other
needed to neutralize the corresponding nitric acid solutions. hand, it is expected that nitrate ion would have the lower
Volume NaOH Volume W-tube transference number among the two. However, as seen in
(mL) (mL) table 3.3, the transference numbers obtained from the
Left 22.35 23.5 experiment are quite the opposite of what is anticipated.
Right 22.75 24 From the reference materials used, it was found that the
Original 22.68 transference number data might have been switched as it
would have otherwise been quite accurate if they were.
The process described in the previous paragraph
would logically produce an excess of positive ions in the left The trends observed from the data in table 3.1 and 3.2
hand column and an excess of negative ions in the right were accurate and consistent with the theory. The minor
hand column. The W-tube used in the experiment inconsistencies observed in the amount of NaOH used to
possesses semi-permeable membranes in between all neutralize the three nitric acid solutions may have been
three glass columns. These membranes inhibit the passage caused by the inaccurate concentrations of the solutions
of certain ions, thus preventing the three separate columns used. It was undetermined how long the acid and base
from reaching electric equilibrium with one another by were put in storage and, the presumed 0.1 molar might
means of diffusion. The end result is that the three columns have change somewhat throughout the storage duration.
would possess varying acidities as confirmed by the data in Other sources of error possibly include human error,
table 3.2. particularly in the titration process. The titration endpoint
Due to the chemical reaction made spontaneous by the was determined to as high a degree as possible but, due to
electrolysis process, the solution in the right hand column the limitation of the apparatus, the obtained data may still
would become more concentrated in nitric acid whereas the deviate about ±1 mL from the true value. Lastly, for table
solution in the left hand column would become less 3.3, the error committed is mostly likely to be a gross error.
concentrated in nitric acid. The reason behind this is the The transference number for the nitrate and hydrogen ions
presence of excess positive and negative ions in the left
may have possibly been switched but, otherwise, they were [1] Castellan, G.W., Physical Chemistry 3rd edition, 1983.
quite precise.
[2] Atkins, Peter., de Paula, Julio., Physical Chemistry 9th
CONCLUSIONS AND RECOMMENDATIONS editions, 2010
The experiment was quite a success because the [3] Levine, I.N., Physical Chemistry 6th edition, 2009
percent error computed by the group was below 10% which
means the group performed the experiment well with only [4] Perry, Robert., Perry’s Chemical Engineer’s Handbook
few errors. 8th edition, 2008
After the electrolysis, the final weights of one
[5] Alberty, R., Physical Chemistry 4th edition, Wiley
electrode decreases while the other one increase. The left Publishing Co.
electrode was expected to decrease because it is the
anode part and the right side is the cathode so it was
[6] Klein, David., Organic Chemistry 2nd edition, 2010.
expected to increase. This proves the theory when the
group final weights were consistent in the theory.
[7] C.W. Garland, J.W. Nibler and D.P. Shoemaker,
Another theory proven was the decreasing Experiments in Physical Chemistry, 4th edition, 2004.
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.
REFERENCES