LABORATORY ACTIVITY 7

ELECTROCHEMISTRY: MEASURING CELL POTENTIAL

EXPECTED LEARNING OUTCOMES

At the end of this activity, the students shall be able to:

1. define oxidation and reduction;
2. write and balance reduction-oxidation (REDOX) reactions fromhalf-reactions;
3. use standard reduction potentials to calculate cell potentials under both standard and
nonstandard conditions; and
4. use standard reduction potentials to predict the spontaneous direction of a REDOX
reaction.

INTRODUCTION

The basics of electrochemistry begin with the chemical reaction that involves a transfer of
electrons from one atom to another—the oxidation-reduction reaction orREDOX reaction.
Oxidation is the process by which a substance loses electron/s, in effect, the substance being
oxidized (reducing agent). The electron that is lost is accepted/gained by another substance and
undergoes reduction reaction. Most chemistry practitioners use the mnemonic device below to
remember which substance is which:

LEORA: Loss of Electrons is Oxidation–Reducing Agent

GEROA: Gain of Electrons is Reduction–Oxidizing Agent

The substances that can either lose or accept electrons are summarized in the Appendix 1 of
Chemistry for Engineering Students by Holme Brown, 2 nd edition. All reactions showed in the
table are called half-reactions which has individual standard electrode potential, E°.REDOX
reactions from these half-reactions can be carried out in two ways — (1) direct and (2) indirect
contact. In this activity, we will focus more on indirect contact which is carried out in an
electrochemical cell.
 Figure # 1. Galvanic cell.

In electrochemical cells particularly in closed circuits, the wires connect metal rods that are
suspended in the solution. The rods are the anode and the cathode.Oxidation takes place at
the anode, for instance,

Cu(s) ⇌Cu2+ + 2e-E° = - 0.337 volt

The generated electron from this reaction travels through the wire into the cathode where the
electron is use for reduction, for example,

Ag+ + e-⇌ Ag(s)E° = 0.7994 volt

What's noteworthy is that the metals are actually consumed/used up in the anode as they are
oxidized, and it slowly wears away. Meanwhile, the opposite happens at the cathode rod,
where metal ions from the solution gain electrons and adhere on the surface of the cathode as
pure metal and gradually grows larger. The solution in which the electrode is immersed is
composed of salt solution of the metal that composes each electrode. The solution of the
anode serves as the catch basin of the cation, Cu2+, formed during oxidation while the solution
of the cathode serves as the source of cation, Ag+, needed for reduction.A salt bridge that
contains a strong electrolyte is needed to complete the circuit. If the wire allows the flow of
electrons, the salt bridge allows either cations or anions of the strong electrolyte to migrate
into the solution where they are needed to maintain charge neutrality. In the case of our
example above, the potassium (K+) of the strong electrolyte will flow into the beaker of silver
solution to offset the removal of Ag+and chloride (Cl-) will flow into the beaker of copper
solution to offset the production of Cu 2+ (aq) in the copper solution beaker.

Figure # 2. Movement of charges in an electrochemical cell.

The electrochemical cell that is constructed in this manner is called the galvanic cell (Figure # 1)
where a net reaction proceeds to equilibrium spontaneously. When dealing with different
combinations of half-reactions, assign the more positive or less negative potential as the half-
reaction that occur at the cathode. The other half-reaction should be assigned as the anodic
reaction. A cell notation allows us to lists themetals and ions involved in a REDOX reaction. A
vertical line, |, denotes a phase boundary, and a double line,∥, represents the salt bridge. The
anode is always written on the leftand the cathode on the right:

Anode | electrolyte of anode∥electrolyte of cathode | cathode

The previous example of copper and silver would be written as follows:

Cu(s) | Cu2+(aq)(1 M)∥Ag+(aq)(1 M) | Ag(s)

The cell potential, E°cell of this REDOX system can be calculated by

Cu(s) ⇌Cu2+ + 2e-E°left = - 0.337 volt

2 [Ag+ + e-⇌ Ag(s)] + E°right = 0.7994 volt

2 Ag+ + Cu(s)⇌2 Ag(s) + Cu2+E°right = 0.4624 volt

If the cell potential is positive, the ∆G° is negative as indicated by the relationship ∆G° = -
nFE°cell. Whenever this is the case, the net reaction is said to be spontaneous. The more
positive the value of the standard E°cell, the more feasible the REDOX reaction is. Furthermore,
if the cell potential is negative, the ∆G° is positive so the net reaction is not spontaneous.

The reduction potentials given in the most chemistry books are measured at standard
conditions. Whenever a system deviates from these conditions, a corresponding change in the
value of E° should be accounted. For instance, let's say I decided to use 2.0M instead of 1.0M of
Cu2+ as usually used under standard conditions. To figure out the value of the new E° of copper
electrode, we use will Nernst equations that relates the concentration of ionic species in the
half reaction to its new potential.

RT ions in the product side a

∘
E=E − ln
nF ion in the reactant side b

where E°= the standard electrode potential; R = the gas constant, 8.314 J K¯¹ mol¯¹; T =
temperature in Kelvin; n = number of moles of electrons; F = the faraday constant; and ln =
natural logarithm = 2.303 log; a and b = coefficients of the ions involved in the half-reaction. At
25°C, if we substitute the constants, the equation becomes
0.0592
∘
ions in the product side a
E=E − log
n ion in the reactant side b

0.0592 0.0592
E = E∘ − log Cu2+ = −0.337 − log 2.0 = −0.346 V
2 2

MATERIALS

Lab gown multimeter (voltmeter) sand paper Lab gown

crucible with cover wire leads filter paper forceps
petri dish scissors sponge

CHEMICALS

small pieces of metals: Cu Fe Zn Mg

20 drops of, 1.0 M each Cu(SO4)2 FeCl3 Zn(NO3)2 Mg(NO3)2 KNO3
20 drops of, 2.0 M Cu(SO4)2 FeCl3 Zn(NO3)2 Mg(NO3)2

PROCEDURE

1. Clean the surface of metals using sandpaper or steel wool to remove any oxidation. Hold in
paper sothat your hands stay clean.
2. Place into each well, a small piece of each of the following metals and the associated
nitrate solution.The top of each piece of metal must remain dry.

Cu/Cu2+ Fe/Fe3+ Fe/Fe3+ Cu/Cu2+

Mg/Mg2+ Cu/Cu2+ Zn/Zn2+ Zn/Zn2+

3. Make salt bridges by soaking small strips of filter paper in saturated solutions of
potassium nitrate or potassium chloride.
4. Set the multimeter at 2000mV. Connect the black wire to the negative terminal, and the
rewire to the positive terminal.
5. Place the wire leads in contact with the dry portion of two different metals. Record the
positive voltage on Table 1. If the voltage is negative, switch the wire connectors.
6. Record the cell potential of magnesium ribbon in 1.0 M Magnesium nitrate scupper in
2.0 M Copper sulfate. Record the positive voltage. If the voltage is negative, switch the
wire connectors.
DATA

Zn Cu Fe Mg

Zn

Cu

Fe

Mg

Voltage of Mg/Mg2+(1.0M) vs. Cu/Cu2+ (2.0M): ___________________________

QUESTIONS

1. How well do your data (from Table 1) match the predicted values from the EMF reference
table? Is the difference significant? What do you think is the cause of this difference?
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2. You are asked to report the positive voltage, what type of electrochemical cell did you
expect to build? Explain briefly whether the overall reaction that occurred in the cell is
spontaneous or not.
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3. Using the data in Table 1, indicate which of the combined half-reactions occurred at the
anode and at the cathode.

Combined Half-
Anode Cathode Overall reaction of the Electrochemical Cell
reactions

Cu vs Zn

Fe vs Zn

Mg vs Zn

Fe vs Cu

Mg vs Cu

Mg vs Fe

4. Given the schematic notation: Cu | Cu 2+ (0.0200 M) ∥ Ag+ (0.0200 M) | Ag, calculate the cell
potential of this system. Show all calculation.

REFERENCES

https://l.facebook.com/l.php?u=https%3A%2F%2Fdocfish.com%2Fwp-
content%2Fuploads%2F2017%2F02%2F450L.17_Electrochemistry_Voltaic-Cell_Actvity-
Series_KI-Phenophthalein.pdf&h=AT1lcZK1ah5-
7P1SJam1nFvj11pU7VoAFzoYfXBesJGl0FNzbcBF4ExssCCOVtkyDyfoXQE8x3WtR9CkaLGVkPO_yJ
UoM_owlCIhI7DJAWhThx_kd-LZqGK9wX4hSQ2GOYtwwA

Brown and Holme. Chemistry for Engineering Students. 2011. 2nd ed., Chapter 13.

Skoog, West, Holler and Crouch. (2012) Fundamentals of Analytical Chemistry, 8th ed., Cengage
Asia