Montil, 2019 CHEM

18.1 41L

Voltaic Cell and Electrolysis

Danna Louisse E. Montil

BS Agricultural Chemistry
College of Agriculture and Food Science- College of Arts and Sciences

Reduction: 2Fe3+(aq) + 2e¯ ⇌ 2Fe2+(aq)

INTRODUCTION Overall Reaction: Sn2+(aq) + 2Fe3+(aq) ⇌ Sn4+(aq) +
Reactions that produce or consume free 2Fe2+(aq)
electrons in a battery is called Electrochemistry.
They are oxidation or redox reactions, the ones Electrodes are classified according to
where electrons are exchanged. When the flow of whether oxidation or reduction takes place there.
electrons in these kinds of reactions are sent If the oxidation takes place, the electrode is
through a conductor like a piece of metal, it can called the anode. If reduction takes place, the
be used to produce all kinds of work depending electrode is called the cathode. (Petrucci 2010)
on how strong the push and pull of electrons are
between two reactants. This reaction occur Galvanic Cell
simultaneously through half reactions, the half Electrochemical cell in which the
that donates the electrons and the half that Oxidation-Reduction reaction proceed
accept them (Green 2013). Two half arrows are spontaneously. An electron’s electrical potential is
used in a half reaction (⇌). simply known as voltage. If the voltage is high,
each electron can do a lot of work than if the
When used in the electrochemical studies, voltage is low. A setup and process was
a strip of metal, M, is called an electrode. An performed of this cell, it will be described later
electrode immersed in a solution containing ions on.
of the same metal, Mn+, is called a half-cell. Two
kinds of interactions are possible between metal
atoms on the electrode and metal ions in the The Standard Reduction Potential Table
solution (Rxn 1). The standard reduction potential is the
tendency for a chemical species to be reduced,
Rxn 1. and is measured in volts (V) at standard
Reduction conditions. The more positive the potential is the
M(s) ⇌ Mn+(aq) + ne¯ more likely it will be reduced.
Oxodation
The standard reduction potential is in a
1. A metal ion Mn+ from solution may collide category known as the standard cell potentials or
with the electrode, gain n electrons from standard electrode potentials. The standard cell
it, and be converted to a metal atom M. potential is the potential difference between the
The ion is reduced. cathode and anode.
2. A metal atom M on the surface may lose n
electrons to the electrode and enter the Eqn 1.
solution as the ion Mn+. The metal atom is E°cell = E°(cathode)- E°(anode)
oxidized.
An equilibrium is quickly established between When solving for the standard cell
the metal and the solution, which can be potential, the species oxidized and the species
represented as in Rxn 1. reduced must be identified. This can be done
using an activity series. The standard reduction
Although oxidation and reduction must take table is simply a table of standard reduction
place simultaneously, it is often convenient to potentials in decreasing order. The species at the
consider them as separate processes. For top have a greater likelihood of being reduced
example, the oxidation of Sn2+ by Fe3+, while the ones at the bottom have a greater
likelihood of being oxidized. Therefore, when a
Rxn 2. species at the top is coupled with a species at the
Oxidation: Sn2+(aq) ⇌ Sn4+(aq) + 2e¯ bottom, the one at the top will become reduced
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 Montil, 2019 CHEM
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while the one at the bottom will become oxidized = E°(cathode)- E°(anode)
(Wang et.al. 2019). The table of standard = E°(reduction half-cell)- E°(oxidation half-cell)
reduction potentials can be found on books or its
appendices, and on online websites like the The relationships between ΔG°, K, and E°cell
Institute of Chemistry, UPLB website under course is given by figure 0.1. Given any one of the three
handouts. quantities, the other two can be calculated, so
any of the quantities could be used to determine
whether a process was spontaneous.
Cell potential, Ecell
A cell potential is a measure of the driving
force of the cell reaction. This reaction occurs in
the cell as separate half-reactions: an oxidation
half-reaction and a reduction half-reaction. The
total work done is the product of three terms: (a)
Ecell; (b)z, the number of electrons transferred
between the electrodes; and (c) the electric Figure 0.1 (Flowers et. al. 2019)
charge per mole of electrons, called the Faraday
constant (F). The Faraday constant is equal to
96,485 coulombs per mole of electrons (96,485
C/mol). (Petrucci 2010)

The cell potential is related to the

composition of the reaction mixture via the
Nernst Equation.

Eqn 2.
RT Electrolytic Cell
Ecell=Eocell- lnQ Electrochemical cell in which the
nF oxidation-reduction reaction does not proceed
Where: spontaneously, needs electricity. The process of
Ecell= cell potential producing a chemical change in an electrolytic
Eocell= standard cell potential cell is called electrolysis. A setup and process was
R= 8.314J/mol K (gas constant) performed of this cell described in the next parts.
T= Temperature in Kelvin
n= Number of electrons transferred between the Electrolysis
electrodes (It is quite common to see the symbol To maintain electrical neutrality if there
n used for the number of electrons; however, are two electrodes in a cell, some process within
IUPAC recommends z to avoid confusion with the the cell must consume electrons at A and liberate
use of n as the amount of substance.) them at B. This process is an oxidation-reduction
F= 96485 C/mol (Farraday’s constant) reaction; when carried out in an electrolytic cell, it
Q= aqueous product over reactant is called electrolysis. (Masterton & Hurley 2009)
 Michael Faraday- Electroplating is a
- If Ecell is positive, a reaction occurs process of coating deposition on a part,
spontaneously in the forward direction for immersed into an electrolyte solution and
the stated conditions. If Ecell is negative, used as a cathode, when the anode is
the reaction occurs spontaneously in the made of the depositing material, which is
reverse direction for the stated conditions. dissolved into the solution in form of the
If Ecell – 0, the reaction is at equilibrium for metal ions, traveling through the solution
the stated conditions. and depositing on the cathode surface.
- If a cell reaction is reversed, Ecell changes  Faraday’s law- The amount of the
sign. deposited material is directly proportional
to the amount of electric charge, passed
Where E°cell from half reaction can have an overall through the circuit. The equation is
difference using modification of Eqn 1. described in Eqn. 3.

E°cell = E°(right)- E°(left)

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 Montil, 2019 CHEM
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Since amount of electric charge Q=I(t) (I – CE-EE EE-CE
electric current, t – time), then the Faraday’s law Energy
may be expressed by the formula: (Kopeliovich conversion CE: current efficiency
2013) EE: energy efficiency
Anode reaction Oxidation
Eqn. 3 Cathode reaction Reduction
MIt Polarity of anode - +
m=
nF Polarity of + -
cathode
Where: Flow of electron Anode to Cathode
m= Mass of the deposited material Flow of ions
M= Molar mass of one mole of the metal (a) cation Cation goes to cathode
It= Amperes x Time of plating in Kelvin (b) anion Anion goes to anode
= Expressed in Columb
For any half-reaction, the amount of To know more about the differences, process,
substance reduced or oxidized in an electrolytic and application of Galvanic and Electrolytic Cell,
cell is directly proportional to the number of the objectives of the following exercise was to:
electrons passed into the cell. The quantity of  Construct a voltaic cell;
charge passing through an electrical circuit, such  Determine the cell potential of the voltaic
as that in an electrolytic cell is generally cell;
measured in coulombs. A coulomb is the quantity  Determine the effect of concentration on
of charge passing a point in a circuit in 1 s when the cell potential using Nernst Equation;
the current is 1 ampere (A). Therefore, the  Set up a cell for the Electrolysis with
number of coulombs passing through a cell can copper;
be obtained by multiplying the current in  Determine the mass of deposited copper
amperes by the elapsed time in seconds. (Brown for the electrolysis of copper using the
et.al. 2012) Faraday’s Law of Electrolysis

Eqn. 3.1 MATERIALS AND METHODS

Coulombs= Amperes x seconds A. Construction of a Galvanic Cell

Where: Figure 1
n= number of electrons transferred by the ion
into solution
F= 96485 C/mol (Faraday’s constant)

In explanation of the Faraday’s constant--

a charge carried by a single electron is 1.6023 x
10 -19 C. If 1 mole of electron is represented by
6.022 x 1023 electrons. Therefore, 6.022 x 1023
electrons carries a charge of 6.022 x 1023 x
1.6023 x 10-19 C/mol = 96,485 C/mol. 96,485
C/mol, or one Faraday, denoted by the symbol F,
is the amount of electricity that is carried by one
mole of electrons and is known as the Faraday
constant. (Seeboo n.d.)
In this experiment, two sets of trials were
tested that differed in concentrations of solutions.
Table 0.9
The materials and reagents needed were 1.0 M
and 0.5 M concentrations of both Fe(NO 3)3 and
Galvanic vs. Electrolytic Cell Cu(NO3)2 solutions, two 100-mL beakers, a
Voltmeter and its positive and negative terminals,
Galvanic Electrolytic a salt bridge, saturated KCl solution, cotton plugs,
Spontaneity of Spontaneo Nonspontaneo electrodes of Cu and Fe; you may also need
the reaction us us tissue paper and water bottles for waste
Overall emf (Ecell) + - management.
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 Montil, 2019
18.1 41L
The measurements of reagents used for
trial 1 were 1.0 M Fe(NO3)3 and 0.5 M Cu(NO3)2
solutions. They were put in two separate 100-mL
beakers; then, an Fe electrode was dipped into
the beaker containing Fe(NO3)3 solution while the
Cu electrode was for the Cu(NO3)2 solution. The
two electrodes were joined by wires to an electric
meter which was the voltmeter. There were two
different colors of the wires, the positive terminal
(red) was connected to the Cu electrode and the
negative terminal (black) was connected to the Fe
electrode. That was just for the external circuit, to
complete the electrochemical cell, the two
solutions have also been connected electrically
which was through the salt bridge containing
saturated KCl. Because the charge was carried
through solutions by the migration of ions, a wire
could not have been used for this connection. The
solutions needed to be in direct contact through a
porous barrier or joined by a third solution in a U-
tube—the salt bridge. (Petrucci 2010)
The salt bridge was prepared by using a Pasteur
pipette to obtain the KCl from its container to the
salt bridge, invert the bridge in a U-shape first
and put in the KCl to the end that does not have a
cotton plug. The end with the cotton plug can be
used as an indicator of when to stop putting KCl.
Then cover up the ends with cotton plug once the
salt bridge is completely filled and has no
bubbles. The cotton’s use is also to create a semi-
permeable membrane that that the three
solutions can pass through for equilibrium.
When the cotton plugs were dipped and
the wires were connected to the electrodes, that
created a circuit. As it stood for five minutes, the
cell potential was obtained from the voltmeter;
temperature was given later on during the
calculations but a part of the procedure was to
measure the temperature of the solutions. Then it
was made sure that the electrodes and its
deposits were observed.
Disposing of the solutions were put in a
D499 waste bottle while the same KCl and
electrodes were still used for trial 2 with 0.5 M
Fe(NO3)3 and 1.0 M Cu(NO3)2 solutions. To prepare
for the second trial, the electrodes were wiped
dry by tissue paper, the same procedures were
done like trial 1 but a solution of 0.5 M Fe(NO 3)3
and 1.0 M Cu(NO3)2 were prepared.
B. Electrolysis
Figure 2
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CHEM
These procedures of the experiment only
needed one 100-mL beaker, a power supply,
positive and negative wires with alligator clips,
CuSO4 electrolyte solution, brass and copper
electrodes, a weight measure, and a waste bottle
for disposal. Before completing the setup of the
experiment, the mass of the brass electrode was
measured. The masses of the copper electrodes
were not measure throughout the experiment, for
through the mass of the brass electrode, the
theoretical and experimental mass of Cu
produced was calculable. Once the brass
electrodes were initially measured, the positive
lead (red) was connected to the copper electrode
while the negative lead (black) was to the brass
electrode. The 250 mL beakers were still empty
when an approximate of 100mL CuSO4 electrolyte
solution were added. After the settings or
preparations had been done, a timer was set
when the electrodes have been placed in the
electrolyte solution and the power supply switch
has been flipped. A duration of 10 minutes for the
submersion had to be awaited while making sure
that the electrodes did not touch each other and
the alligator clips did not immerse in the solution.
When the 10 minutes was up, the current was
read then the power supply was turned off.
Finally, the mass of the final brass electrode was
weighed and the CuSO4 solution was disposed in
a D499 waste bottle.
RESULTS AND DISCUSSION
A. Voltaic Cell
Rxn. 3
RHR: 3Cu2++6e¯⇌3Cu+
E°cell= 0.34 V
OHR: 2Fe ⇌2 Fe3++ 6e¯
E°cell= 0.04 V
Overall reaction: 3Cu2++2Fe⇌2Fe3++3Cu 𝚫E°cell=
0.38 V
 Montil, 2019 CHEM
18.1 41L
crusting that decreases flow between solution
E°cell was based on the Standard and electrodes.
reduction potential table (SRT) and solved using There were two trials, that tested how
equation 1, you have to analyze the half reactions concentration of solutions affected cell potential.
first before finding it in the SRT. The ones that It was observed that the concentration with
were higher at the table has the higher tendency higher Cu(NO3)2 but lower Fe(NO3)3 affected the
to be reduced and have more oxidation at the voltage to go higher too.
bottom. Iron was higher than Copper in the table B. Electrolysis
so it had lesser E°cell at a certain temperature. Table 2.0
The topmost part of the SRT was observed to Current (A) 0.45 A
have a more negative voltage. Time (sec) 600 s
Copper was on the RHR which is located at Initial mass of brass 1.32 g
the cathode of the galvanic cell. After five electrode (g)
minutes of submersion, the electrodes were Final mass of brass 1.44 g
placed in a plain background and as observed, electrode (g)
the Copper contained deposits in terms of Exp. Mass of Cu 0.12 g
discoloration of the electrodes. On the other produced (g)
hand, Iron as the one being the reducing agent, Theoretical Mass of Cu 0.089g
after five minutes in the experiment, the liquid produced (g)
that it was surrounded with had a yellowish color, Rxn. 4 Anode: 6H2O⇌O2+4H3O++4e-
which showed that it was dissolving because of Cathode: Cu2++ 2e-⇌Cu
the reactions in the galvanic cell.
Copper Nitrate was the catholyte-- is the In the experimental outcome after 10
part of an electrolyte which is on the cathode side minutes of submersion, there were copper
of an electrochemical cell that is effectively particles surrounding the part of the brass
divided into two compartments, and Ferrous electrode that was dipped. And during the
nitrate was the anolyte-- that portion of the submersion, small air bubbles were forming.
electrolyte in the immediate vicinity of the anode According to Strallen and co-writers, due to the
in an electrolytic cell. presence of hydrogen and oxygen bubbles in the
Table 1.0 Trial 1 Trial 2 electrolyte during water electrolysis, the potential
1.0 M Fe(NO3)3 0.5 M Fe(NO3)3 drop between the cathode and the anode in the
and 0.5 M and 1.0 M two phase mixture electrolyte-gas bubbles will be
Cu(NO3)2 Cu(NO3)2 increased.
Experimental 0.44 V 0.50 V The data in table 2.0 were the
cell potential, experimental data, to get the theoretical mass of
V Cu produced we refer to Eqn. 3. which told that
Theoretical 0.37 V 0. 39 V the experimental mass of Cu was greater than
cell potential, expected at 35%. It may have been temperature,
V procedure, or too much of something like
Percent error, 19 % 28 % overtime in plating and submersion perhaps.
% The reaction occurring on the anode is a
reactant of water as it partially dissociates to
Using eqn. 2 and the last computation, the oxygen and H3O+ while the cathode lost electrons
theoretical cell potential was solved. To calculate of copper. Something that is important to
for percent error the formula is: remember in these experiments is neutral atoms
Eqn. 4 make up a solid metal, metal ions usually dissolve
% error= in water.
Experimental potentian cell−Theoretical potential cell
Additional:
Theoretical potential cell Using the data; calculate the value of F,
x 100 the Faraday’s constant.
The possible sources of may be due to the MIt
m=
temperature, the possible contact of unexpected nF
conductors or insulators between the electrolytes,
alligator clips or the equipment. Also, electrode
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 Montil, 2019 CHEM
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MIt (63.55 g/mol Cu)(270 C)
F= = = LITERATURE CITED
nm 2 mol e/1 mol Cu(0.089 g)
9.6E4 C/mol e- BROWN TL, LEMAY JR. HE, BURSTEN BE, MURPHY
CJ, WOODWARD PM. 2012. Electrochemistry.
Calculate the mass of copper (in g) Chemistry: The Central Science, Twelfth Edition.
produced by a current of 1.5 A in 1.00 hours in USA: Pearson Prentice Hall. p. 827- 873
the electrolysis of CuSO4 solution.
MIt
m= C=(1.5A)(3600s)=5400C
nF
CHANG R. 2010. Electrochemistry. Chemistry, 10 th
(63.55 g /mol Cu)(5400 C) Edition. Williamstown, Massachusetts: Williams
m= = 1.8 g Cu College. p. 836-883
2 mol e/1 mol Cu(96485 c /mol e)
EBBING DD, GAMMON SD. 2009. Electrochemistry.
SUMMARY AND CONCLUSION General Chemistry, Ninth Edition. Boston, New
The voltaic cells had two sets of trials that York: Houghton Mifflin Company. p. 770–809.
differed in concentrations of solutions. The
electrodes were set-up into wires and a voltmeter KOPELIOVICH D. Electroplating. [Internet].
and was dipped in the two solutions for five SubsTech [2013 December 14]. Available from:
minutes together with a salt bridge. The https://www.substech.com/dokuwiki/doku.php?
electrodes were then observed, data for volts id=electroplating#electroplating_methods
were recorded, and waste was disposed. The
electrolytic cell needed ten minutes of MASTERTON WL, HURLEY CN. 2009.
submersion into the CuSO4 solution with the two Electrochemistry. Chemistry: Principles and
electrodes connected in a power supply that Reactions, Sixth Edition. South Carolina:
showed an example of electroplating. The mass University of South Carolina. p. 480-505.
of the brass copper has increased due to the
attraction of electronegative charge from the PETRUCCI RH, HERRING FG, MADURA JD,
copper electrodes. The experimental value was BISSONNETTE C. 2010. Electrochemistry. General
greater with 0.12 g while the theoretical was Chemistry: Principles and Modern Applications,
0.089g, the brass electrode data was also used to Tenth Edition. Toronto: Pearson Canada. p. 863-
get the faraday’s constant and there was also 916.
solving of another situation.
With the guidelines of the objectives, the SEEBOO H. Faraday's Laws of Electrolysis:
participants of the experiments were able to: Definition & Equation Video. [Internet]. Study.com
observe first and then construct or drew a [2018 April 1]. Available from:
galvanic cell; cell potential was determined using https://study.com/academy/lesson/faradays-laws-
half reactions, SRT, and Nernst equation; learn of-electrolysis-definition-equation.html
the do’s and don’ts during setting up a cell for
electrolysis with copper and even the expected WANG J, WOOD J, LEE E, BRAR L. Standard
outcomes; and used Faraday’s law to determine Reduction Potential. [Internet]. LibreText:
mass deposited which was only a matter of Chemistry [2019 June 6]. Available from:
measuring, calculating, and substitution. One can https://chem.libretexts.org/Bookshelves/Analytical
even apply that galvanic cells are the batteries _Chemistry/Supplemental_Modules_(Analytical_Ch
that are very useful and that the half reactions emistry)/Electrochemistry/Redox_Chemistry/Stan
that we have practiced happens in our everyday dard_Reduction_Potential
life. Electrolytic cell showed that sometimes
things just need a little push to change others’ or Retrieved from https://www.youtube.com/watch?
their own being. v=IV4IUsholjg
on 25 October 2019
RECOMMENDATIONS
It is recommended that everyone involved Retrieved from https://www.youtube.com/watch?
could perform this experiment or even in setting v=7b34XYgADlM on 25 October 2019
up a galvanic or electrolytic cell. Given the limited
resources and time, it is somehow understood.
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