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Ion Mobility: Transference

Number of Ions
Analysis of Electrochemical
Reactions
1. Introduction

“Electrochemistry is the study of the interchange of chemical and electrical energy” (Zumdahl,
2012). This involves redox (reduction-oxidation) reactions that occur in electrochemical cells,
which “consist of two electrodes or metallic conductors, in contact with an electrolyte, an ionic
conductor (which may be a solution, a liquid, or a solid)” (Atkins, 2010). The electrode at which
oxidation occurs is called the anode, while the one where reduction takes place is called the
cathode. An electrode compartment is composed of an electrode and its electrolyte.

Electrochemical cells can be classified into two types—galvanic cells, in which the redox
reactions occur spontaneously to produce electric current, and electrolytic cells, in which input of
electrical energy is required for the redox reaction to proceed.

Whether or not the redox reaction can proceed spontaneously can be determined by
calculating the cell potential and/ or the change in Gibbs free energy, which is “a measure of the
energy available to do work” (http://chemed.chem.purdue.edu/).

When electrons are transported through a connecting wire, work is done by the electrons that
flow through the wire and this work depends on the electromotive force that pushes the electrons,
enabling them to flow. This electromotive force of the cell is called the cell potential. This
relationship between work and the electromotive force (potential difference) is expressed as

−𝑤 (1)
𝜀= ,
𝑞
where 𝑞 = 𝑛𝐹, with 𝑛 being the number of moles of electrons and 𝐹 being Faraday’s constant,
which is 96,480 Coulombs / mole. Thus, work can be expressed as
𝑤 = −𝑛𝐹𝜀 (2)
Since the maximum work possible for a given process at constant temperature and pressure
is equal to the change in Gibbs free energy (Δ𝐺), then Δ𝐺 is equal to
Δ𝐺 = −𝑛𝐹𝜀 (3)
The cell potential is calculated using the Nernst equation, which relates the standard cell
potential (𝜀 𝑜 ), to the reaction quotient (𝑄), the amount of electrons (in moles) taking part in the
reaction (𝑛), and the temperature at which the reaction took place (𝑇). The standard cell potential
is calculated from the standard reduction potentials of the redox reactions involved in the
electrolysis. The reaction quotient takes into account the concentration of the species involved in
the redox reactions and is expressed as
[𝐶]𝑐 ∙ [𝐷]𝑑
𝑄= , (4)
[𝐴]𝑎 ∙ [𝐵]𝑏
which is based from the reaction
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
Thus, the cell potential is given by the Nernst equation as shown below
𝑅𝑇
𝜀 = 𝜀𝑜 − ln 𝑄 , (5)
𝑛𝐹
where 𝐹 is Faraday’s constant, 𝑅 is the universal gas constant with a value 8.314 J/mol·K, and
𝑄 is the reaction quotient expressed as
When the cell potential is positive, the change in Gibbs free energy is negative and thus, the
reaction is said to proceed spontaneously, as in galvanic cells. On the other hand, if the cell
potential is negative, the change in Gibb’s free energy is positive and the reaction does not occur
spontaneously, but instead, needs an input of work in order for it to proceed, as in electrolytic cells.
Such work is provided by supplying electrical energy (direct current) in order to drive the reaction,
and this technique is called “electrolysis.”

In electrolysis, the anode is connected to the positive terminal of the power supply and thus, is
positively charged while the cathode is negative. Thus, the negatively charged anions in the
electrolytic solution will be attracted to the anode, where they will be oxidized, and the positively
charged cations to the cathode, where they will be reduced, in order to maintain the
electroneutrality of the solutions.

Due to this attraction of the ions to the electrodes whose charge is opposite their own, they tend
to migrate towards that specific electrode and consequently, the anions migrate towards the
anode, while the cations to the cathode. However, the rate at which these ions move in an electric
field are different and at a given time, more of the faster moving ions are transported towards the
electrode to which they are attracted to compared to that of the slower moving ions to the opposite
electrode. The factors affecting the rate of their movement include the current supplied to the
electrolytic cell, the temperature at which the electrolysis took place, the concentration of the ions
in the solution, and the nature of the ions involved (i.e size, mass, charge).

As a result of the different mobilities of the ions (𝑢+/− ), the cation and the anion would also
differ in their contribution to the total charge transported and this is described by their transference
numbers, which is the fraction of the total charge (𝑞) or current (𝐼) carried by the ions,
𝐼± 𝑞±
𝑡+/− = = , (6)
𝐼− + 𝐼+ 𝑞− + 𝑞+
where, 𝑞− and 𝐼− are the charge and current carried by the anion respectively, and 𝑞+ and 𝐼+ for
the cations.

Based on the principle of electroneutrality which requires that the net charge carried by pure
substances must be zero, the sum of the transference numbers of the anion and the cation must
then equal to 1 since transference numbers are merely fractions of the total charge carried by the
anions and the cations.
𝑡+ + 𝑡_ = 1 (7)
The transference number of ions can be determined experimentally using Hittorf’s method,
which is based on the principle that changes in the concentration or amounts of the ions in the
vicinity of the electrodes occur due to differences in the mobilities of the ions. The apparatus for
Hittorf’s method consists of a power source, a meter for reading the current, a transference vessel
(U-tube or double U-tube) in which the electrolyte solution of the ions to be investigated is
contained, and a coulometer, consisting of metal electrodes immersed in an electrolyte solution of
the metal.

In the transference vessel, the changes in the amounts (number of moles) of the anions, cations
and the electrolyte solution in the electrode compartments are related to the charge carried by the
ions (i.e 𝑞− for the anion) and Faraday’s constant (𝐹), as shown in the equation below
|𝑞_|
𝛥𝑛_ 𝐴 = 𝛥𝑛+ 𝐴 = 𝛥𝑛 𝐴 = (8)
𝐹
|𝑞_|
𝛥𝑛_𝐶 = 𝛥𝑛+ 𝐶 𝐶
= 𝛥𝑛 = −
𝐹 (9)
From the subtraction of equation 9 from equation 8, the total charge transported by the anion
can then be expressed as:
𝐹(𝛥𝑛 𝐴 − 𝛥𝑛𝐶 )
|𝑞_| = (10)
2
Based on Faraday’s First Law of Electrolysis, which states that “the amount of a substance
consumed or produced at one of the electrodes in an electrolytic cell is directly proportional to the
amount of electricity that passes through the cell (http://chemed.chem.purdue.edu/),” the total
charge (𝑞) supplied to the electrolytic cell during the course of the electrolysis can then be
determined experimentally by measuring the change in the masses of the metal electrodes in the
coulometer before and after the electrolysis (∆𝑚𝑐 for the cathode and ∆𝑚 𝐴 for the anode). This is
expressed in the following equation,
𝑍𝑅 𝐹(∆𝑚𝐶 −∆𝑚𝐴 )
𝑞= 2𝑀 (11)
where 𝑧𝑅 is the charge number of the reaction, and 𝑀 is the molar mass of the metal electrode.
With the calculated values for the 𝑞_ and the 𝑞, the transference number of the ions can then
be determined by using equation 6 and 7, wherein 𝑞 = 𝑞+ + 𝑞_ .

2. Objectives of the Experiment

Ion Mobility: Transference Number of Ions (ION)

 To determine the transference number of nitrate and hydronium ions


 To discuss the effect of mass on the transference number of an ion
Analysis of Electrochemical Reactions (ECR)

 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 the
electrochemical reactions

3. Methodology

3.1 Materials

Table 1. Properties of the substances or chemical species involved in the experiment

Name of Chemical Molar Mass Solubility


Color Density Assay
Substance Formula (pure) in H2O

Clear, colorless 1.41


Concentrated 63.01 Miscible/ 68-70
HNO3 to pale yellow g/mL
nitric acid g/mol Soluble wt%
solution

Concentrated Clear, colorless 98.08 1.84 Miscible/ 95-98


H2SO4
sulfuric acid solution g/mol g/mL Soluble wt%
Clear, colorless 18.02
Distilled water H2O 1 g/mL
liquid g/mol
Copper sulfate 249.68 2.29
CuSO4·5H2O Blue crystals ~317 g/L 99-100%
pentahydrate g/mol g/mL
Potassium
204.22 1.63
Hydrogen C8H5KO4 White crystals 102 g/L 100.2%
g/mol g/mL
Phthalate

Prepared 0.1 M sodium (2) Copper sheets (3 pairs) nitrile gloves


hydroxide solution
3.2 Equipment and Apparatus

Beakers:

(2) 10-mL (3) 250-mL (1) 2-L

Erlenmeyer Flasks:

(3) 250-mL (4) 10-mL

Graduated Cylinders:

(2) 100-mL (2) 10-mL

(1) 10-mL pipette (1) test tube brush (2) carbon electrodes

(2) 250-mL volumetric flasks (1) blow dryer (1) clamp


(for double U-tube)
(2) screw-cap bottles (3) iron stands
Transference vessel
(1) weighing boat (4) connecting wires (double U-tube)

(1) stirring rod (1) multi-range meter Power supply (PHYWE)

(1) wash bottle (1) Burette clamp Analytical balance

(1) alcohol thermometer (1) Electrode holder Pipettor

(4) droppers (2) O-rings


EXPERIMENTAL SET-UP

Transference Number Apparatus Set-Up

3.3 Procedures

The experiment was concerned with determining the transference numbers of hydronium and
nitrate ions during the electrolysis of nitric acid solution by comparing the concentration changes
of hydronium ions in the anode and cathode regions of the transference vessel. In order to do
this, a nitric acid solution and a basic solution (NaOH) were required in the experiment. Copper
plates immersed in an acidic copper sulfate (CuSO4/H2SO4) solution were also needed so that
the actual total charge applied during the electrolysis, which will be used in the calculation for the
transference numbers, can be determined.

Thus, the following solutions were prepared for the experiment: a 250 mL 0.1 M nitric acid
(HNO3) solution; a 250 mL sulfuric acid/ copper sulfate solution (0.5 M with respect to each
species) and a 250 mL 0.1 M sodium hydroxide (NaOH) solution.

About 3-5 mL of 68-70 wt% HNO3 stock solution was poured into a 10-mL beaker.
Approximately 1.60 mL of the HNO3 solution in the beaker was measured using a graduated
cylinder and was transferred into a 250-mL volumetric flask containing a small amount of distilled
water (about 50-100 mL). The HNO3 solution in the volumetric flask was then diluted to the mark
and mixed.

Similarly, about 8-10 mL of H2SO4 was poured into a 250-mL beaker containing a small amount
of distilled water (about 50-100 mL). 31.3610 grams of CuSO4·5H2O, weighed using an analytical
balance, was dissolved in the H2SO4 solution in the beaker. After the CuSO4·5H2O was fully
dissolved in the sulfuric acid solution, the mixture was transferred to a 250-mL volumetric flask,
was diluted to the mark and was mixed.

The prepared NaOH solution was standardized by two trials of titration using potassium
hydrogen phthalate (KHP) as primary standard and phenolphthalein as indictor. Two samples of
approximately 0.4 grams of KHP were weighed in 250-mL Erlenmeyer flasks using an analytical
balance. The KHP solids were then dissolved with distilled water in the flasks and were diluted to
about 100 mL. For the titrations, 100 mL of distilled water was titrated with the prepared NaOH in
order to serve as the blank, followed by the (titration of the) two 100 mL KHP solutions. Using the
volume of the NaOH consumed, the masses of the KHP samples and the stoichiometric
relationship between NaOH and KHP, the concentration of the prepared NaOH solution was
determined.

Afterwards, the concentrations of two 5-mL samples of the prepared HNO3 solution were
determined by titration using the standardized NaOH solution as titrant and methyl red as indicator
(color change from red to yellow).

The three compartments of the transference vessel (double U-tube) were marked about an
inch below the lateral connecting tubes and was filled to the mark with the prepared HNO 3
solutions. The carbon electrodes were then immersed into the anode and cathode compartments
of the transference vessel. The levels of the HNO3 solutions in the three compartments were
adjusted so that they were all the same and the compartments were once again marked at these
new levels.

Afterwards, the transference vessel was lowered into the 2-liter beaker and was held firmly in
place using a clamp and an iron stand. The filled beaker was then with water until the (new level)
marks in the compartments of the transference vessel were submerged in the water. An alcohol
thermometer was placed in the water bath in order to monitor the temperature of the nitric acid
solutions in the transference vessel during the electrolysis because the temperature must be
maintained throughout the electrolysis.
The transference vessel set-up was connected to a coulometer which consists of two copper
sheet electrodes immersed in acidified copper sulfate solution. Prior to electrolysis, the copper
sheets were weighed and their masses were recorded. One of the copper sheets would be the
anode and the other would be the cathode. The copper sheets were fixed onto the electrode
holders and were immersed in a 250-mL beaker containing the prepared CuSO4/H2SO4 solution.

The transference vessel, the coulometer, the multi-range meter and the power supply were
connected in series as shown in the transference number apparatus set-up in page 7.

After setting-up the apparatus, the power supply was switched on and its settings (voltage and
current) were adjusted such that the current supplied for the electrolysis (as read by the multi-
range meter) was 50 mA. However, during the experiment, the possible maximum current
supplied was only 44 mA. The current supplied was maintained throughout the experiment.

The electrolysis of the nitric acid solution was timed using a stopwatch and was carried out for
approximately an hour (60 minutes). Towards the end of the electrolysis, approximately 5 mL
HNO3 samples were taken from the anode and the cathode compartments using a pipette.
Immediately after, the electrolysis was brought to a stop by switching off the power supply.

The HNO3 samples taken from the anode and the cathode compartments were titrated using
the standardized NaOH solution in a similar manner as the prepared HNO3 solution at the
beginning of the experiment.

The copper electrodes were carefully washed, dried and weighed in order to determine the
change in the masses of the copper electrodes.

After the electrolysis, the transference vessel was once again filled to the (new/final) marks
made on the compartments prior to the electrolysis—taking into account the volume of the
immersed electrodes. The electrodes in the anode and cathode regions were removed while the
middle compartment was still covered by its cap. Then, two graduated cylinders were positioned
beside each other such that the distance between the two would correspond to the distance
between the openings of the anode and the cathode compartments of the transference vessel.
The transference vessel was then slowly removed from the 2-liter beaker and the solutions at the
anode and cathode regions were simultaneously poured into the two graduated cylinders in order
to measure the volume of the solution in the two compartments. (It was recommended that a
pipette be used to accurately determine the volumes of the solutions at the marked levels of the
compartments. However, since the solutions from the different compartments were not solely
contained in a specific compartment but were able move to the other compartments, measuring
the volume of the anode and cathode regions using a pipette would have been difficult and might
result to more errors.)

4. Results and Discussion

Results From Electrolysis of Nitric Acid at Transference Vessel


In this experiment, the transference number of hydronium ions and nitrate ions from the
electrolysis of nitric acid electrolyte solution in the transference vessel were determined by
comparing the changes in the amounts of ions (i.e. H+) in the anode and cathode compartments
of the transference vessel in order to determine the charge transported by the ion (i.e. anion,
NO3-)

Inasmuch as possible, the temperature and the current supplied during the electrolysis were
kept constant so that the only factors that would affect the mobilities of the ions and thus their
transference numbers, were the concentration of the ions and their size, mass and charge.

In the transference vessel, the electrolytic cell is represented by the following cell notation

𝐶(𝑠) |𝐻𝑁𝑂3(𝑎𝑞) ⋮⋮ 𝐻𝑁𝑂3(𝑎𝑞) |𝐶(𝑠)

The hydronium ions (of the HNO3) from the anode compartment migrate to the cathode
compartment, where they are to be reduced to hydrogen gas.

+
2𝐻(𝑎𝑞) + 2𝑒 − → 𝐻2(𝑔)

Meanwhile, the nitrate ions (of the HNO3) are to be oxidized at the anode compartment, but
since the anode has a higher deposition potential, the nitrate ions are not oxidized. Since the
nitrate ions cannot be oxidized, in order to ensure electroneutrality of the solution, the water
molecules were the ones that were oxidized instead, forming hydronium ions and oxygen gas.

+
2𝐻2 𝑂𝑙 → 4𝐻(𝑎𝑞) + 𝑂2 (𝑔) + 6𝑒 −

The formation of hydrogen and oxygen gas at the anode and the cathode was observed by
the evolution of bubbles at both the carbon electrodes. However, the there was a more rapid
evolution of bubbles at the anode compartment where hydrogen gas was produced. This is due
to the fact that the migration of hydronium ions to the anode is expected to be faster than that of
the nitrate ions to the cathode.
During electrolysis, the positively charged cations (H+) migrate to the cathode, which has
a negative charge, while the negatively charged anions (NO3-) migrate to the anode, which has a
positive charge. In the cathode, the H+ ions that have migrated become reduced to H2 gas, thereby
decreasing the concentration of the H+ ions (from the HNO3) in the cathode. Meanwhile, to
maintain electroneutrality, the NO3- ions at the cathode which were not oxidized, were paired with
the H+ ions produced from the oxidation of water. Thus, the H+ ions from the anode which have
migrated to the cathode just end up being “replaced” by the H+ from water, and so the
concentration of H+ in the anode only undergoes minimal changes throughout the duration of the
electrolysis.

Table 2. Changes in the Amount of NItric Acid in the Transference Vessel

Concentration of HNO3
When sample Number of Moles HNO3 (𝑛)
samples
was taken (mmol)
(mol/L)
Trials
Before Electrolysis Average
1 2
Anode 2.9472
0.1185 0.1271 0.1228
Cathode 3.0086
After Electrolysis
Anode 0.1222 2.9328
Cathode 0.07819 1.9157

Sample calculation for the concentration of HNO3


Trial 1 (before electrolysis)
0.1297 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 1 𝑚𝑜𝑙 𝐻𝑁𝑂3
4.57 𝑚𝐿 𝑁𝑎𝑂𝐻 × ×
𝐿 𝑠𝑜𝑙 ′ 𝑛 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 = 0.1185 𝑚𝑜𝑙 𝐻𝑁𝑂3
5.00 𝑚𝐿 𝐻𝑁𝑂3 𝐿 𝑠𝑜𝑙 ′ 𝑛

Average Concentration of HNO3 (before electrolysis)


𝑚𝑜𝑙 𝐻𝑁𝑂3 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
0.1185 + 0.1271
𝐿 𝑠𝑜𝑙 ′ 𝑛 𝐿 𝑠𝑜𝑙 ′ 𝑛 = 0.1228 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
2 𝐿 𝑠𝑜𝑙 ′ 𝑛
The average concentration of HNO3 calculated is used for calculating the number of moles of
HNO3 in the anode and cathode compartments of the transference vessel.

By titrating the HNO3 samples with NaOH before and after electrolysis at the anode and
cathode regions, the concentrations of the H+ ions (and thereby of the NO3- ions and the HNO3
compound) in the anode and cathode compartments can be determined.
With the known volumes of the solution in the anode and cathode compartments and with the
calculated concentrations of the HNO3 samples, the change in the number of moles of HNO3 in
the anode and the cathode can be determined.

 Solving for 𝛥𝑛 𝐴/𝐶


- Number of moles of HNO3 before electrolysis
𝑚𝑜𝑙 𝐻𝑁𝑂3 1𝐿
𝑛 𝐴 = 0.1228 × 24.00 𝑚𝐿 × = 2.9472 × 10−3 𝑚𝑜𝑙 𝐻𝑁𝑂3
𝐿 𝑠𝑜𝑙 ′ 𝑛 1000 𝑚𝐿
- Number of moles of HNO3 after electrolysis

𝑚𝑜𝑙 𝐻𝑁𝑂3 1𝐿
𝑛 𝐴 = 0.1222 ′
× 24.00 𝑚𝐿 × = 2.9328 × 10−3 𝑚𝑜𝑙 𝐻𝑁𝑂3
𝐿 𝑠𝑜𝑙 𝑛 1000 𝑚𝐿

𝛥𝑛 𝐴 = (2.9472 − 3.0086) × 10−3 𝑚𝑜𝑙 = 0.0144 𝑚𝑚𝑜𝑙


Using the changes in the number of moles of HNO3 in the anode and cathode regions, the
charge transported by the anion can then be calculated using equation 10.

 Solving for |𝑞_|

1 𝑚𝑜𝑙
96,480 𝐶/𝑚𝑜𝑙 [(0.0144 𝑚𝑚𝑜𝑙 − 1.0929 𝑚𝑚𝑜𝑙) ×
|𝑞_| = 1000 𝑚𝑚𝑜𝑙 ]
2

|𝑞_| = 52.0268 𝐶

Results from the electrolysis reaction in the coulometer


As mentioned earlier, by virtue of Faraday’s First Law of Electrolysis, the actual amount of the
total charge that was supplied for the electrolysis can be determined from the change in the
masses of the copper sheets at the anode and the cathode of the coulometer.

In the coulometer, the cathode (copper sheet) receives the electrons that have been
transported from the oxidation at the anode of the transference vessel. Thus, the copper ions in
the electrolyte solution are attracted to the negatively charged cathode where they are reduced
and deposited as copper metal, increasing the mass of the copper sheet cathode.

On the other hand, the copper sheet at the anode oxidizes into copper ions which are dissolved
in the electrolyte solution in order to “pair” with the SO42- ions so as to maintain electroneutrality.
As a result, the concentration of the copper sulfate solution remains constant while the copper
metal at the anode is “eaten away” by oxidation and therefore undergoes a decrease in its mass.
The following redox reactions occur at the coulometer.
2+
𝐶𝑢(𝑎𝑞) + 2𝑒 − → 2𝐶𝑢(𝑠)
2+
𝐶𝑢(𝑠) → 𝐶𝑢(𝑎𝑞) + 2𝑒 −

 Solving for the change in masses of the copper sheets at the anode and the cathode
𝐴 𝐴
∆𝑚 𝐴 = 𝑚𝑎𝑓𝑡𝑒𝑟 − 𝑚𝑏𝑒𝑓𝑜𝑟𝑒

∆𝑚 𝐴 = 3.7288 𝑔 − 3.7893 𝑔 = −0.0605 𝑔


Table 3. Change in Masses of the Copper Sheet Electrodes

Copper Sheet Mass ∆𝑚


Electrode
Before (g) After (g) (g)
at Anode 3.7893 3.7288 -0.0605
at Cathode 7.2855 7.3331 0.0476

 Solving for q using the change in the masses of the copper sheets in the coulometer using
equation 11, where 𝑍𝑅 = 2

𝐶
2(96,480 )(0.0476 𝑔 + 0.0605 𝑔)
𝑞= 𝑚𝑜𝑙
𝑔
2(63.54 𝑐𝑜𝑝𝑝𝑒𝑟)
𝑚𝑜𝑙
𝑞 = 164.1405 𝐶
The calculated charge presented above is the actual total charge supplied during electrolysis.
However, the theoretical total charge can also be calculated by multiplying the amount of current
supplied, based on the multi-range meter reading, and the period of time that the electrolysis was
allowed to take place.

𝑞=𝐼 × 𝑡
𝐶
𝑞 = 0.044 × 3862.062 𝑠
𝑠
𝑞 = 169.9307 𝐶
 Comparing the actual and theoretical total charges (𝑞)

|𝑎𝑐𝑡𝑢𝑎𝑙 𝑞 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑞|
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑒𝑟𝑟𝑜𝑟 (%) = × 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑞

|164.1405 𝐶 − 169.9307 𝐶|
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑒𝑟𝑟𝑜𝑟 (%) = × 100%
169.9307 𝐶

𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑒𝑟𝑟𝑜𝑟 (%) = 3.41%


The actual total charge can vary from the theoretical total charge due to uncontrollable factors
such as minor fluctuations in the current (that can no longer be adjusted due to the limitations of
the settings of the power supply) and the resistances present in the wires, power supply and multi-
range meter.

Also, the amount of charge that will be supplied to the cathode in the coulometer is dependent
on the amount of charge that can be transported from the oxidation at the anode of the
transference vessel. As mentioned previously, the rate of electrolysis is dependent on the
temperature, current supplied and the concentration of the electrolyte solution. Increasing the
concentration of the nitric acid solution in the transference vessel (i.e. at the anode) decreases
the transference number of the ions, which means that the ions carry a lesser amount of charge
compared to more dilute solutions. This is due to the fact that there are interionic reactions that
might take place, which would then decrease the mobility of the ions.

As a result, the amount of charge supplied to the cathode in the coulometer would lessen and
accordingly, the rate of reduction of copper ions at the cathode would decrease, thereby reducing
the amount of deposited copper at the cathode over a given time.

Determining the Transference Numbers of the Cation (H+) and the Anion (NO3-)
Since the actual total charge transported by the anion, 𝑞_ , and the total charge, 𝑞+ , supplied
during the electrolysis have already been determined, the transference numbers of the H+ cation
and the NO3- anion can then be calculated using equation 6

 Solving for the transference number of NO3-


𝑞_ 52.0268 𝐶
𝑡− = 𝑡− =
𝑞_ + 𝑞+ 164.1405 𝐶
𝑞_ 𝑡− = 0.3170
𝑡− =
𝑞
Since the sum of the transference numbers of the anion and the cation is equal to 1 as given
by equation 7, the transference number of H+ is then,

𝑡+ = 1 − 𝑡_

𝑡+ = 1 − 0.3170
𝑡+ = 0.6830
As expected, the transference number of the hydronium ion (cation) is greater than that of
the nitrate ion (anion). This is due to the fact that that the hydronium ion is smaller, lighter
(based on molar mass) and less bulky compared to the nitrate ion.

Gibb’s Free Energy of the Electrolytic Cell

As mentioned previously, electrochemical reactions can either proceed spontaneously or


otherwise as indicated by the sign of the cell potential and the change in the Gibbs free energy
of the process or reaction. In an electrolytic cell, the cell potential is expected to be negative
and the Δ𝐺, positive.

The half reactions (with their corresponding standard reduction potentials) of the
electrolysis of the nitric acid solution at the anode and the cathode of the transference vessel
are presented below,

Half Cell reactions:

Cathode: 3[2𝐻 + + 2𝑒 − → 𝐻2 ] 0.00 V


Anode: 2𝐻2 𝑂 → 4𝐻 + + 𝑂2 + 6𝑒 − -1.23 V .
6𝐻 + + 2𝐻2 𝑂 → 3𝐻2 + 4𝐻 + 𝜀 𝑜 = −1.23 𝑉

 Solving for the cell potential (𝜀) and change in Gibbs free energy (∆𝐺):
𝑅𝑇
𝜀 = 𝜀 𝑜 − 𝑛𝐹 ln 𝑄 ,

wherein,
[𝐻 + ]4 (𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑎𝑡 𝑡ℎ𝑒 𝑎𝑛𝑜𝑑𝑒)
𝑄=
[𝐻 + ]6 (𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛)

Thus,
8.314 𝐽/𝑚𝑜𝑙 ∙ 𝐾(27 + 273.15𝐾) 0.1224
𝜀 = −1.23 𝑉 − 𝑙𝑛
6 ∙ (96,480 𝐶/𝑚𝑜𝑙) 0.12286
𝜀 = −1.25 𝑉
The change in Gibbs free energy is therefore,
∆𝐺 = −(−1.25 𝑉)(164.1405 𝐶)

∆𝐺 = 204.84 𝐽

As expected of an electrolytic cell, ∆𝐺 is positive and therefore, the electrolysis of nitric


acid is a non-spontaneous reaction. This is because a positive Δ𝐺 implies a decrease in
Δ𝐺
the entropy of the system (Δ𝑆) as given in the relationship Δ𝑆 = − 𝑇
.

Based on the second law of thermodynamics, natural (and therefore spontaneous)


processes proceed in the direction that increases the entropy of the system. Thus,
processes that tend to decrease the entropy of the system would not occur unless work is
done on the system such as in electrolysis, wherein the work is in the form of electrical
energy.

5. Conclusions
During electrolysis, the ions taking part in the reactions have different mobilities which
are influenced by the current supplied, temperature, concentration of the solution, and the
size, mass and charge of the ions. These ion mobilities are best described or represented
by transference numbers, which are the fractions of the total charge carried by the ions
(cations and anions).

In order to determine the transference numbers of the ions of HNO3 during electrolysis,
the redox reactions that occur simultaneously in the transference vessel (double U-tube)
and in the copper coulometer, as presented below, must be taken into account. It is
important to note that since these reactions are electrolytic reactions, they require the
input of work in the form of electrical energy in order to enable the reactions to proceed.
The experimentally determined change in Gibbs free energy of the electrolysis of nitric
acid is 204.84 𝐽, which is positive, and therefore indicates the non-spontaneity of the
reaction.

Half Cell reactions at the transference vessel:

Cathode: 3[2𝐻 + + 2𝑒 − → 𝐻2 ]

Anode: 2𝐻2 𝑂 → 4𝐻 + + 𝑂2 + 6𝑒 − .

6𝐻 + + 2𝐻2 𝑂 → 3𝐻2 + 4𝐻 +
Half Cell reactions at the copper coulometer:

2+
Cathode: 𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)

2+
Anode: 𝐶𝑢(𝑠) → 𝐶𝑢(𝑎𝑞) + 2𝑒 −

2+ 2+
𝐶𝑢(𝑎𝑞) + 𝐶𝑢(𝑠) → 𝐶𝑢(𝑠) 𝐶𝑢(𝑎𝑞)

Both reactions in the transference vessel and the coulometer must be taken into
account despite the fact that only the transference numbers of the ions in HNO3 are to be
determined because the method used to experimentally determine these transference
numbers is the Hittorf’s method, which requires measuring the changes in the
concentration of the ions in the HNO3 solution inside the transference vessel in order to
determine the total charge or current carried by an ion, and the changes in the masses of
the copper sheet electrodes in the coulometer, to determine the total charge or current
supplied during electrolysis.

The experimental transference number obtained for nitrate ions is 0.3170, while that of
the hydronium ions is 0.6830.

This is to be expected since hydronium ions are smaller, less bulky, and lighter in terms
of molar mass compared to the nitrate ions, and therefore, are able to move faster towards
the electrode (cathode) which is charged opposite the charge they are carrying, their
transference number is expected to be larger than that of the nitrate ions.
6. References

Book/ Manual:

Atkins, P., de Paula, J (2014). Atkins’ Physical Chemistry 10th edition. Oxford University
Press, United Kingdom.

Zumdahl S.A, Zumdahl, S.A (2012). Chemistry An Atoms First Approach. Cengage
Learning, USA.

Operating Manual. PHYWE Transference Number Apparatus

Websites:

Electrochemistry: Voltaic Cells and Voltage. Chempages Netorials. Retrieved July 19,
2015, from
https://www.chem.wisc.edu/deptfiles/genchem/netorial/rottosen/tutorial/modules/electroc
hemistry/04voltage/18_41.htm

Electrolysis of copper sulfate solution. DocBrown. Retrieved July 19, 2015, from
http://www.docbrown.info/page01/ExIndChem/electrochemistry04.htm

Electrolytic Cells. Bodner Research Web. Retrieved July 19, 2015, from
http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch20/faraday.php#law

Gibbs Free Energy. Bodner Research Web. Retrieved July 19, 2015, from
http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch21/gibbs.php

How is the rate of electrolysis affected by temperature? MadSci Network. Retrieved July
19, 2015, from http://madsci.org/posts/archives/1998-08/904105918.Ch.r.html

Principles of electrolysis of copper sulfate electrolyte. electrical4u.com Online Electrical


Engineering. Retrieved July 19, 2015, from http://www.electrical4u.com/principle-of-
electrolysis-of-copper-sulfate-electrolyte/

The extraction of copper from copper ores & purification by electrolysis. DocBrown.
Retrieved July 19, 2015, from http://www.docbrown.info/page04/Mextractc.htm
7. Appendices

Preparation of Solutions

Table 4. Data on Solution Preparation


Required Percent Required
Actual Mass/
Name of Substance Mass or Purity Concentration
Volume
Volume (mass %) (mol/L)

CuSO4·5H2O 31.3568 g 99-100 0.5 31.3610 g


Nitric Acid (HNO3) 1.62 mL 68-70 0.1 1.60 mL
Sulfuric Acid (H2SO4) 6.90 mL 95.98 0.5 6.90 mL

Calculations for the preparation of solutions (required mass and volumes):


1. CuSO4·5H2O
 % 𝑝𝑢𝑟𝑖𝑡𝑦
99 + 100
% 𝑝𝑢𝑟𝑖𝑡𝑦 =
2
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 99.5%

 Required mass:

0.5 𝑚𝑜𝑙 𝐶𝑢𝑆𝑂4 ∙5𝐻2 𝑂 249.6 𝑔 𝐶𝑢𝑆𝑂4 ∙5𝐻2 𝑂 100 𝑔 𝐶𝑢𝑆𝑂4 ∙5𝐻2 𝑂
0.250 𝐿 𝑠𝑜𝑙 ′ 𝑛 × × ×
𝐿 𝑠𝑜𝑙′ 𝑛 1 𝑚𝑜𝑙 𝐶𝑢𝑆𝑂4 ∙5𝐻2 𝑂 99.5 𝑔 𝑝𝑢𝑟𝑒 𝐶𝑢𝑆𝑂4 ∙5𝐻2 𝑂

= 31.3568 𝑔 𝐶𝑢𝑆𝑂4 ∙ 5𝐻2 𝑂 𝑠𝑎𝑚𝑝𝑙𝑒

2. H2SO4 / CuSO4 solution


𝑤
 % 𝐻2 𝑆𝑂4 𝑜𝑓 𝑠𝑡𝑜𝑐𝑘 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑤)

99 + 98
% 𝐻2 𝑆𝑂4 =
2
% 𝐻2 𝑆𝑂4 = 96.5%

 Required Volume of 𝐻2 𝑆𝑂4 𝑠𝑡𝑜𝑐𝑘 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 :

0.5 𝑚𝑜𝑙 𝐻2 𝑆𝑂4 98.08 𝑔 𝐻2 𝑆𝑂4 100 𝑔 𝐻2 𝑆𝑂4 1 𝑚𝐿 𝐻2 𝑆𝑂4


0.250 𝐿 𝑠𝑜𝑙 ′ 𝑛 × × × ×
𝐿 𝑠𝑜𝑙′ 𝑛 1 𝑚𝑜𝑙 𝐻2 𝑆𝑂4 96.5 𝑔 𝑝𝑢𝑟𝑒 𝐻2 𝑆𝑂4 1.84 𝑔 𝐻2 𝑆𝑂4

= 6.90 𝑚𝐿 𝐻2 𝑆𝑂4 𝑠𝑡𝑜𝑐𝑘 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛


3. 0.1 M HNO3
𝑤
 % 𝐻𝑁𝑂3 𝑜𝑓 𝑠𝑡𝑜𝑐𝑘 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑤)

68 + 70
% 𝐻𝑁𝑂3 =
2
% 𝐻𝑁𝑂3 = 69%

 Required Volume of 𝐻2 𝑆𝑂4 𝑠𝑡𝑜𝑐𝑘 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 :

0.1 𝑚𝑜𝑙 𝐻𝑁𝑂3 63.01 𝑔 𝐻𝑁𝑂3 100 𝑔 𝐻𝑁𝑂3 1 𝑚𝐿 𝐻𝑁𝑂3


0.250 𝐿 𝑠𝑜𝑙 ′ 𝑛 × × × ×
𝐿 𝑠𝑜𝑙′ 𝑛 1 𝑚𝑜𝑙 𝐻𝑁𝑂3 69 𝑔 𝑝𝑢𝑟𝑒 𝐻𝑁𝑂3 1.41 𝑔 𝐻𝑁𝑂3

= 1.62 𝑚𝐿 𝐻𝑁𝑂3 𝑠𝑡𝑜𝑐𝑘 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Standardization of NaOH
Based on the chemical reaction between KHP and NaOH and assuming that 20 mL
of NaOH will be consumed, the amount of KHP to be weighed can be determined.
𝐾𝐻𝐶8 𝐻4 𝑂4 (𝑎𝑞) + 𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑁𝑎𝐾𝐶8 𝐻4 𝑂4 (𝑎𝑞) + 𝐻2 𝑂(𝑙)

0.10 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 1 𝑚𝑜𝑙 𝐾𝐻𝑃 204.22 𝑔 𝐾𝐻𝑃


0.020 𝐿 𝑁𝑎𝑂𝐻 𝑠𝑜𝑙 × × × = 0.4084 𝑔 𝐾𝐻𝑃
𝐿 𝑠𝑜𝑙′𝑛 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 1 𝑚𝑜𝑙 𝐾𝐻𝑃
 Calculating the concentration of NaOH:
1 𝑚𝑜𝑙 𝐾𝐻𝑃 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
0.3554 𝑔 𝐾𝐻𝑃 × × 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
204.22 𝑔 𝐾𝐻𝑃 1 𝑚𝑜𝑙 𝐾𝐻𝑃
= 0.1316
1𝐿 𝐿 𝑠𝑜𝑙′𝑛
13.32 𝑚𝐿 𝑁𝑎𝑂𝐻 𝑢𝑠𝑒𝑑 ×
1000 𝑚𝐿

1 𝑚𝑜𝑙 𝐾𝐻𝑃 1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻


0.3893 𝑔 𝐾𝐻𝑃 × × 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻
204.22 𝑔 𝐾𝐻𝑃 1 𝑚𝑜𝑙 𝐾𝐻𝑃
= 0.1278
1𝐿 𝐿 𝑠𝑜𝑙′𝑛
14.92 𝑚𝐿 𝑁𝑎𝑂𝐻 𝑢𝑠𝑒𝑑 × 1000 𝑚𝐿
Table 5. Standardization of NaOH
Blank Trial 1 Trial 2
Mass of Erlenmeyer flask (g) 124.2213 119.9379
Mass of KHP and flask (g) 124.5767 120.3272
Mass of KHP (g) 0.3554 0.3893
Moles of KHP (moles) 0.0017 0.0019
Volume of solution (mL) 100 100 100
Final NaOH Buret Readings (mL) 5.00 18.31 20.20
Initial NaOH Buret Readings (mL) 0.01 0.30 0.29
Volume of NaOH used (mL) 4.99 18.01 19.91
Molarity of NaOH (mol/L) 0.1316 0.1278
Average Molarity of NaOH (mol/L) 0.1297
% Difference 2.07

Conditions during electrolysis:

 Current used:
Before: 44 mA .
After: . 42 mA .

 Duration: . 1 hr. 4 min. 22 s 62 ms = 3862.062 𝑠


 Temperature: 27 oC .
 Marked volume of HNO3 in transference vessel (with electrodes immersed):
Anode: . 24.00 mL .
Cathode 24.50 mL .

Titration of HNO3 samples


Table 6. Titration of HNO3
Buret Readings
Volume of Volume of (Titration with NaOH)
When sample
HNO3 sample NaOH used
was taken Initial Reading Final Reading
(mL) (mL)
(mL) (mL)
Before
Electrolysis
Trial 1 5.00 4.57 0.10 4.67
Trial 2 5.00 4.90 0.13 5.03
After Electrolysis
Anode 4.00 3.77 5.03 8.80
Cathode 3.50 2.11 8.80 10.91