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This lab was largely adapted from an experiment from the United States Naval Academy, Annapolis, MD
Special Thanks for this lab revision goes to Zach Houston, CHEM 1330 TA Winter Semester 2009
In a past week’s lab you studied the properties of a Galvanic Cell, whereby a
spontaneous, thermodynamically favored process produced an electrical current with various
metals. This process occurred within the cell, or battery, without outside influence. The
process known as Electrolysis occurs when voltage from an outside power source is applied to a
cell causing a different kind of electrochemical process. Michael Faraday, an early pioneer in
electrochemistry and other disciplines, set two laws that govern the process of Electrolysis, and
today you will verify the first of those two laws.
Faraday’s First Law of Electrolysis:
In a two electrode cell; the moles of a substance produced at both electrodes are directly
proportional to the moles of electrons in the cell.
With an understanding in voltaic cells, a good way to understand electrolytic cells is by
comparison. The constituents remain the same, but their roles are reversed (Table 13.1).
Table 13.1 ‐ Comparison of Voltaic and Electrolytic Cells
Anode Cathode ECathode – EAnode = Eo Go Spontaneous?
Oxidation Reduction
Voltaic (electrons (electrons (+) (‐) Positive Negative YES
lost) consumed)
(Same as above but
Electrolytic (‐) (+) Negative Positive NO
with reversed signs)
In a voltaic cell, electrons are generated at the anode and consumed at the cathode; whereas in
an electrolytic cell, electrons are provided by an outside source to the cathode and are lost
from the system at the anode. Wherever the source of the electrons is, the charge will be
negative and where they are lost, the charge will be positive, thus reversing the charges in the
electrolytic cell. If you can rationalize this in your head and understand this reversal, you
understand the core concept of electrolysis.
The Down’s Electrolytic Cell
So that above is what is happening with respect to the electronics of the electrolytic cell,
what happens chemically is of more interest to us, and there are several different types of
electrochemical reactions that occur in an electrolytic cell. One of the most used cells, is that
for the production of chlorine gas (Cl2), and by electrolysis it comes from a possibly
unsuspecting source…salt. In the Downs Cell, sodium chloride (NaCl) and calcium chloride
(CaCl2) are mixed and heated to 580oC. This molten mix undergoes electrolysis and forms
sodium metal (Nao) and chlorine gas (Cl2). Sodium is produced as a liquid and is siphoned off
and the gas is collected. Other considerations are made to prevent the dangerous and highly
energetic reconstitution of NaCl. This type of cell is commonly used to produce chlorine gas in
the United States. See your textbook for a more thorough explanation.
Electrolytic Cells of Aqueous Salts
Another type of cell, the one you will use today, is that of aqueous solutions. Here things are
more tricky, because you have more than one species able to be reduced or oxidized, as water
with salt present can undergo both processes.
2 H2O (l) + O2 (g) + 4 H+ + 4e‐(aq) E = ‐1.23 V
(O2‐ O0; oxidation @ anode) Equation 13.1
2 H2O (l) + 2e‐ H2 (g) + 2 OH‐ (aq) E = ‐0.83 V
(H+1 H0; reduction @ cathode) Equation 13.2
Today you will be looking at the electrolysis of an aqueous solution of potassium iodide (KI).
The redox potentials possible (excluding water) are shown below
K+ (aq) + e‐ K0(s) E = ‐2.93 V Equation 13.3
I2(s) + 2e‐ 2I‐ (aq) E= 0.53 V Equation 13.4
Thus there are now 4 possible redox reactions, two for reduction and two for oxidation. In
electrochemical reactions where more than one reduction or oxidation is possible the path of
least resistance is taken, For reduction, the less negative (or more positive) reduction potential
is the one that occurs; whereas, for oxidation the less positive (or more negative) reduction
potential will go.
Figure 1 ‐ Setup of the KI
Electrolytic Cell
The Lab in Short
As we are now ready to do, we will verify Faraday’s First Law of Electrolysis by setting up an
electrolytic cell for KI and measure the volume of gas produced at one potential and titrate the
solution after electrolysis to determine the amount of the other substance produced. The
techniques for determining both of these values have been assessed in previous experiments
(Lab 3 & Lab 11), review these methods and the equations needed if necessary.
While doing the electrolysis we will also measure the current and determine the number of
moles of electrons produced over a period of time. We will then use the information from the
equations above, and the following equations
ng(moles of gas) ∝ ns(moles of other substance) ∝ ne(moles of electrons)
where ng, ns, and ne are the respective stoichiometric coefficients.
After we’ve determined the number of moles of the substances produced at the anode and
cathode, we will verify the relationship of the electrons in and out in the above by measuring
the current and recording the total time of the experiment. From the calculated charge we can
then use to determine the number of moles of electrons produced.
Procedure:
1. Clean the carbon electrode by washing it thoroughly in KI solution. If you see a yellow
color form in your solution, repeat the procedure with fresh KI. Do this until no more
yellow color appears.
2. Set up the electrolytic cell by using the carbon rod as the anode and the J‐electrode as
the cathode as in
3. Figure 1 . Include the digital multimeter and power supply as part of the circuit so that
the current can be measured during the electrolysis. (See
4. Figure 1 .) Test to make sure that the electrodes have been properly identified by
electrolyzing a small amount (a few mLs) of the 0.20 M KI solution, and verifying that the
anode and cathode reaction products are, in fact, produced where expected.
5. Fill a 600 mL beaker about 2/3 full of 0.20 M KI solution. Add the electrodes to the
solution. Fill the gas collection tube with 0.20 M KI solution and introduce the inverted
tube into the solution without allowing any bubbles to enter the tube. Your instructor
will provide some guidance on how to accomplish this. Place the tube over the end of
the J‐electrode so that the gas produced there will be trapped in the collection tube.
Verify with your instructor that your setup is correct.
6. Record the time and turn on the power supply (at a voltage setting of 9 V) and record
the amperage every 30 seconds until the gas collection tube is filled to about the 8 mL
mark. Periodically stir with the carbon rod. Turn the power supply off when sufficient
gas has been collected. Record the time when the power supply was turned off. For
your calculations take the average amperage value for each trial.
7. Carefully equalize the pressure of the gas with the barometric pressure by adjusting the
height of the gas collection tube until the liquid levels inside and outside the tube are
equal. Record the volume of gas collected under these conditions. Also record the
barometric pressure and the temperature.
8. Acidify the solution by adding about 10 mL of 1.0 M H2SO4. Determine the number of
moles of I2 produced in the electrolysis by titrating the solution with 0.0200 M Na2S2O3
solution, using starch near the endpoint, as you have done in Lab 11
Repeat the electrolysis procedure of steps 3 through 6 2 more times, using fresh solutions each
time.
References:
Silberberg, Martin S. Principles of General Chemistry. 1st ed. New York; McGraw Hill, 2007
For an interactive video of this electrolytic cell and how it works go to:
http://www.infoplease.com/chemistry/simlab/electrolpt2.html
Electrolysis of KI solution
All of your calculations should be carried out in your lab notebook.
Electrolysis.
Potentially useful Equations:
C = A × t
C = n × F
Average Electrolysis
Trial Amperage (A) Time (s) mole‐
Potentially useful Equations:
Ptot = PH2O + PH2
PV = nRT
VH2 collected Barometric T (K) Water Vapor PH2(mmHg) molH2
Trial (mL) Pressure Pressure at T
[Ptot] (mmHg) [PH2O] (mmHg)
Titration.
[Na2S2O3] = M
2I2 (aq) + 4Na2S2O3 (aq) → 2Na2S4O6 (aq) + 4NaI (aq)
VH2SO4 added
VNa2S2O3 used (mL) molNa2S2O3 molI2
Trial (mL)
Analysis.
Knowing:
2I‐ (aq) → I2 (aq) + 2e‐
2H2O (ℓ) + 2e‐ → H2 (g) + 2OH‐ (aq)
1. Are the calculated moles of hydrogen gas, iodine, and electrons consistent with the anode and
cathode half‐reactions for each trial? Explain.