Experiment 8

Determination of Electrode Potentials

Gerry and Yla

Introduction

 One of the characteristics of oxidation-

reduction reactions is the transfer of
electrons (similar to the exchange of protons
in acid/base reactions). If the electrons can
be directed through a piece of metal during
this transfer, then an electric current is
created. This is generally called a cell. A
group of cells hooked together is a battery.
Introduction

 Galvanic Cells harness the electric energy

available from the electric transfer in a
oxidation-reduction reaction to perform the
electrical useful work. The key to gathering
the electron flow is to separate the flow
through that wire. The electron flow, called a
current, can be sent through a circuit which
could be part of any number of electrical
devices.
Introduction

 The salt bridge or porous disk is necessary to

maintain the charge neutrality of each half cell by
allowing the flow of ions with minimal mixing of the
half cell solutions. As electrons are transferred from
the oxidation half cell to the reduction half cell, a
negative charge builds in the reduction half cell and
a positive charge in the oxidation half cell. The
charge build up would serve to oppose the current
from anode to cathode—effectively stopping the
electron flow – if the cell lacked a path (salt bridge)
for ions to flow between the two solutions.
Introduction

 The electromotive force of the cell is then

given by,
εcell = εcathode - εanode
 Electromotive force (emf) of the cell is the
difference in potential between electrodes
which causes a current to flow from the
electrode of higher potential to the one of
lower. Without potential difference, no
electricity can flow from one point to another.
Methodology
 1. Assemble the following test half-cells:
 a. Zn│Zn2+ electrode: Dip a piece of Zn metal strip (5cm long, 1cm
wide) in a 50mL beaker containing 25mL of 0.1M ZnSO4.

 b. Pb│Pb2+ electrode: Dip a 10cm long Pb wire in a 50mL beaker

containing 0.1M Pb(NO3)2.

 c. C│Fe2+, Fe3+ electrode: Dip a graphite rod in a 50mL beaker which

contains 12.5mL of 0.2M Fe(NH4)2(SO4)2 and 12.5mL of 0.2M
FeNH4(SO4)2.

 d. Pb│PbSO4 (s), SO4-2 electrode: Dip a lead wire coated with PbSO4 in
a 50mL beaker which contains 25mL of 0.1M K2SO4. Prepare the wire
by dipping a Pb wire into a solution of 6M H2SO4 until the wire becomes
coated with PbSO4 , a white powdery substance.
Methodology
 2. Set up a cell by coupling a Cu│Cu2+ electrode with one of the assembled
half-cells.

 (1) If the reference electrode is that prepared by the first procedure, dip
the electrode into the electrolyte of the test electrode.

 (2) If the second type of Cu│Cu2+ electrode is used, connect the two
solutions by dipping one end of the filter paper strip in the CuSO4
solution and the other end in the electrolyte of the test electrode.

 Measure the voltage of the cell by connecting the Cu│Cu2+ electrode to the
positive (red) terminal of a voltmeter and the metal strip or wire or carbon rod
of the test electrode to the negative (black) terminal.


Methodology
 For the Cu│Cu2+ reference electrode (cathode), the reduction half-reaction
and the corresponding potential is:

 Cu2+ + 2e- → Cu(s) ε = 0.34 volt

 The measured potential of the cell is the difference in reduction potentials of

the cathode (reference electrode) and the anode (test electrode).

 εcell = εcathode - εanode

 Record your data on the table.

Data

Test Electrode Reduction Half-Reaction εcell (V) εanode(V)

Zn|Zn2+ Zn2+ + 2e- → Zn(s) 0.572 -0.232
Pb|Pb2+ Pb2+ + 2e- → Pb(s) 0.441 -0.101
2+ 3+
C|Fe ,Fe Fe3+ + e- → Fe2+ -0.3522 0.6922
Pb|PbSO4(s),SO42- PbSO4(s) + 2e- → Pb(s) + SO42- 0.581 -0.241
Data

Sample Computation:

For Zn|Zn2+:

Anode: Zn2+ + 2e-  Zn(s) ε anode = ?

Cathode: Cu2+ + 2e-  Cu(s) ε cathode = +0.34V
Cell: Cu2+ + Zn(s)  Cu(s) + Zn2+ ε cell = 0.572V Measured potential

ε cell = ε cathode - ε anode

ε anode = ε cathode - ε cell = 0.34V – 0.572V = -0.232V