INTRODUCTION
It is also formally
An electrochemical cell is composed of two
electronic conductors/electrodes and an
ionic conductor (electrolyte). Charge
transport in the cell through the motion of
both electrons and ions happens when
electric current is applied through a solution
of an electrolyte [1]. Transference number
(or transport number) is the fraction of the
total current carried by an ion during
electrolysis. It is associated with the ionic
mobility defined as the speed in which the ion
moves under the same potential gradient [2].
In general, an anion and a cation can carry
different amount of current during
electrolysis.
Transference number is a quantity that can be
used in calculations involving electrochemical
processes. It is the quotient of the current
carried by the ion through a cross section of an
electrolytic solution to the total current passing
through the specific cross section. It is also the
ratio of the velocity/mobility, of a given ion to
the sum of the velocities/motilities of the cation
and anion. Temperature, concentration and
velocity/mobility of the ions in the electrolytic
solution are factors that affect the transport
number.
𝐼+ 𝐼−
𝑡+ = 𝑜𝑟 𝑡− =
𝐼 𝐼
If one mole of current passed through a cell, the
amount of ions elated in the electrolyte is
equivalent to 1 mole [3]. Therefore, the
electrochemical change at each electrode is
proportional to the amount of current applied.
𝑡+ + 𝑡− = 1
Ion transport yields to either an
accumulation of negative or positive
charges, thus causing movement from the
anode to the cathode. Ionic mobility is
defined as the speed through which ions
are shifted in a solution.
defined as the limiting velocity of anion with
respect to the direction of an electric field
of unit strength. Molar conductivity is
proportional to the ionic mobility and also
to the concentration and charge of the ion.
Conductivity (λ) is a quantity that is
acquired by experimentation while the ionic
mobility (u) is a theoretical quantity, both of
which can be utilized to show transference
numbers [4].
For ionic mobility:
𝑢+ 𝑢−
𝑡+ = 𝑜𝑟 𝑡− =
𝑢+ + 𝑢− 𝑢+ + 𝑢−
For molar conductivity:
λ+ λ−
𝑡+ = 𝑜𝑟 𝑡− =
λ+ + λ− λ+ + λ−
Transport number can be determined using
different method like Hittorf’s method,
moving boundary method, EMF method, and
from ionic mobility. In the experiment,
Hittorf’s method is used wherein the mobility
of ions during electrolysis can be observed
by getting the measurement of change in the
amount of electrolyte in both electrodes.
Cations and anions contribute in transporting
the charge in electrolytic processes, in
accordance with the distinction in the mobility
of ions. The principle behind this method is
that the concentration changes occur around
the electrodes due to the
Figure 1. Hittorf transference setup for the
determination of transference number. Retrieved
November 09, 2017 from
http://users.metu.edu.tr/chem355/assets/4-355-
Hittorf.pdf
The concentration loss in an electrode is
proportional to the mobility of the ion moving
away from the electrode while the electrolysis is
occurring. That is, even if only cations are
moving, the same number of positive and
negative charges will be discharged to their
electrodes [6]. The transference numbers
through Hittorf Method is done by means of
titration of solutions within the anode and
cathode compartments v.s. the central
compartment which serves as the reference (no
change in concentration must be observed). This
experiment aims to relate the ionic mobility and
size of the hydrogen and nitrate ions to their
transport numbers through Hittorf method.
DISCUSSION
The property that the experiment primarily aims
to quantify is the ion-transport number or the
transference number of the nitrate ion and
hydrogen ion: that is, the fraction of the total
current carried by each of the ions. For the
treatment of the data, the initial number of
moles of the hydrogen ion from the stock
solution of nitric acid was determined by
titrating 5.00-mL of the nitric acid solution with
0.1-M NaOH secondary standard. The same
procedure was applied to determine the initial
number of moles of the hydrogen ion at the
anode compartment and the final number of
moles of the same species in the anode
compartment. This applies basic acid-base
stoichiometry, where the reaction occurring
between NaOH and HNO3 is
𝑁𝑎𝑂𝐻 + 𝐻𝑁𝑂3 → 𝑁𝑎𝑁𝑂3 + 𝐻2𝑂
and it can clearly be seen that the balanced
equation suggests that the reactants react in a
one is to one ratio. Therefore, given the molarity
and volume of titrant NaOH used, the moles of
hydrogen ion, which is equal to the moles of
HNO3 since the acid is a strong acid (it
dissociates completely) and is monoprotic, can
be directly calculated using the following
relationship.
𝑀𝑁𝑎𝑂𝐻𝑉𝑁𝑎𝑂𝐻
𝑛𝐻+ = V(HNO3) (Vanode )]
The same calculations may apply in solving for
the moles of hydrogen ion in the other
compartments. Another essential quantity to
determine the transport number of the ions is
the amount of the cation that was electrolyzed
and deposited on the copper plates. This was
calculated by obtaining the difference in the
initial and final masses of the two copper plates
multiplied by two and dividing it with the atomic
mass of copper. Mathematically, it may be
expressed as
𝑛𝑓 + 𝑛𝑚𝑖𝑔 = 𝑛𝑖 + 𝑛𝑒
The transference number was then obtained by
getting the ratio of the moles that migrated to
the moles electrolyzed.
𝑛𝑚𝑖𝑔
𝑡=
ne
Substituting the values obtained experimentally,
a transference number of 0.8240 for the
hydrogen ion was obtained. Utilizing the
definition that the sum of the transference
numbers of the cation and anion equals unity,
the transference number of the nitrate ion may
be experimentally obtained as well to be 0.1760.
At standard temperature of 25°C, the literature
values for the transport numbers of the ions
involved are 0.170 and 0.830 for the nitrate and
hydrogen ions, respectively, incurring errors of
3.5294% for the nitrate ion and 0.7229% for that
of the hydrogen ion. From the experimental
results, one may deduce that the hydrogen ion
moves faster than the nitrate ion by a factor of
approximately 4.68, and it also implies that the
hydrogen ion carries approximately 80% of the
total current applied to the system, whereas the
nitrate ion carries around 20%. The results of the
experiment actually conform to the theoretical
concept of ion transport phenomena. This can be
explained by taking into consideration the ionic
size of the species involved. It is known that the
nitrate ion is significantly larger than the
hydrogen ion, and it is also a common notion
that heavier objects move slower, since they
need to overcome a larger amount of force for improvement can come from the researchers
them to be set in motion. Theory suggests that themselves and the methods used in performing
larger ionic size means lower mobility, which the experiment. For example, using the balance
explains why the hydrogen ion has a higher properly and properly performing the titration of
transport number than that of the nitrate ion. the nitric acid. The recommendations above
Moreover, lower mobility implies lesser might result in much lower percentage of error
capability to carry current, which also explains the next time this experiment is performed.
why the hydrogen ion carried much more As an over-all conclusion, this experiment was a
current than that of the nitrate ion. success due to the fact the researchers were able
to fulfill the objectives and the researchers were
CONCLUSIONS AND RECOMMENDATIONS able produce results that were acceptable with
The researchers were given a set of objectives low percentage of error.
that must be achieved by the time that the
experiment was finished. These objectives were REFERENCES
1: to determine the transport numbers of Atkins, P., & de Paula, J. (2006). Physical
Hydrogen and Nitrate ions and 2: to relate the Chemistry, Eighth Edition. New York City:
transport number with ionic size and mobility. W. H. Freeman and Company.
Through the results of the experiment, the Chang, R., & Goldsby, K. (2011). General
researchers were able to determine Chemistry: The Essential Concepts. New
experimental values for the transport numbers York City, United States of America:
of hydrogen and nitrate ions at 301K, which was McGraw-Hill.
0.8240 and 0.1760 respectively. These values Levine, I. N. (2009). Physical Chemistry, Sixth
were not that far from the actual values, which Edition. New York City: McGraw-Hill.
were 0.83 and 0.17 respectively.
The relationship between the transport number
with the ionic size and the mobility was also
obtained from the results of the experiment. The
hydrogen ion has a higher transport number
compared to nitrate ion. This is due to hydrogen
having a smaller ionic size. The smaller the ionic
size, the lesser the chance for ions to bump or
interfering with one another that will slow down
the transport. The relationship between
transport number and ionic size is inversely
proportional. The hydrogen ion has a higher
transport number compared to nitrate ion. This
is due to hydrogen having a higher value for
mobility than the nitrate ion. The higher the
mobility, the faster it is for an ion to travel
between two points, thus resulting in a higher
transport number. The relationship between the
transport number and the mobility is directly
proportional.
Though the results of the experiment were
acceptable with low percentage of error, there is
still room for improvement. There is not much to
say about the equipment and glassware used as
well as the reagents that were consumed. The