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Unit 2 - Matter and Energy

Electrochemical Energy

LEARNING OBJECTIVES

• Determine the standard reduction potentials and use them to
calculate the emf of a cell and hence the spontaneity of a cell
reaction.



1.0 Oxidation-Reduction Reaction

From the different forms of energy, electrical energy has remarkable practical
importance. A day without electricity from either the power company or batteries is
unimaginable in our technological society. The area of chemistry that deals with the
interconversion of electrical energy and chemical energy is electrochemistry.
Electrochemical processes are redox (oxidation-reduction) reactions in which the
energy released by a spontaneous reaction is converted to electricity or in which electricity
is used to drive a nonspontaneous chemical reaction.
In redox reactions, electrons are transferred from one substance to another. The
reaction between magnesium metal and hydrochloric acid is an example of a redox reaction:

Recall that the numbers above the elements are the oxidation numbers of the
elements. The loss of electrons by an element during oxidation is marked by an increase in
the element’s oxidation number. In reduction, there is a decrease in oxidation number
resulting from a gain of electrons by an element. In the preceding reaction, Mg metal is
oxidized and H+ ions are reduced; the Cl- ions are spectator ions.

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LEARNING ENRICHMENT ACTIVITIES

Watch the following videos for review on redox reactions:

• https://www.physicsandmathstutor.com/chemistry-revision/a-level-ocr-
a/module-2/redox-videos/
• https://www.youtube.com/watch?v=YWl4KHsUxuw

2.0 Galvanic and Electrochemical Cells

When a piece of zinc metal is placed in a CuSO4 solution, Zn is oxidized to Zn2+ ions
while Cu2+ ions are reduced to metallic copper.
Zn(s) + Cu2+(aq) à Zn2+(aq) + Cu(s)
The electrons are transferred directly from the reducing agent (Zn) to the oxidizing
agent (Cu2+) in solution. Though, if we physically isolated the oxidizing agent from the
reducing agent, the transfer of electrons can take place via an external conducting medium
(a metal wire). As the reaction progresses, it sets up a constant flow of electrons and hence
generates electricity. The apparatus for producing electricity through the use of a
spontaneous reaction is called a galvanic cell or voltaic cell, after the Italian scientists Luigi
Galvani and Alessandro Volta, who constructed early versions of the device. A zinc bar is
immersed in a ZnSO4 solution, and a copper bar is immersed in a CuSO4 solution. The cell
operates on the principle that the oxidation of Zn to Zn2+ and the reduction of Cu2+ to Cu can
be made to take place simultaneously in separate locations with the transfer of electrons
between them occurring through an external wire. The zinc and copper bars are called
electrodes. This particular arrangement of electrodes (Zn and Cu) and solutions (ZnSO4 and
CuSO4) is called the Daniell cell. By definition, the anode in a galvanic cell is the electrode at
which oxidation occurs and the cathode is the electrode at which reduction occurs.
For the Daniell cell, the half-cell reactions, that is, the oxidation and reduction
reactions at the electrodes, are

To complete the electrical circuit, the solutions must be connected by a conducting
medium through which the cations and anions can move from one electrode compartment
to the other. This requirement is satisfied by a salt bridge, which, in its simplest form, is an
inverted U tube containing an inert electrolyte solution, such as KCl or NH4NO3, whose ions
will not react with other ions in solution or with the electrodes. During the course of the
overall redox reaction, electrons fl ow externally from the anode (Zn electrode) through the
wire to the cathode (Cu electrode). In the solution, the cations (Zn2+, Cu2+, and K+) move

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toward the cathode, while the anions (SO4 -2 and Cl-) move toward the anode. Without the
salt bridge connecting the two solutions, the buildup of positive charge in the anode
compartment (due to the formation of Zn2+ ions) and negative charge in the cathode
compartment (created when some of the Cu2+ ions are reduced to Cu) would quickly prevent
the cell from operating. An electric current flows from the anode to the cathode because
there is a difference in electrical potential energy between the electrodes. This flow of
electric current is analogous to that of water down a waterfall, which occurs because there
is a difference in gravitational potential energy, or the flow of gas from a high-pressure
region to a low-pressure region. Experimentally, the difference in electrical potential
between the anode and the cathode is measured by a voltmeter.

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The voltage across the electrodes of a galvanic cell is called the cell voltage, or cell
potential. Another common term for cell voltage is the electromotive force or emf (E),
which, despite its name, is a measure of voltage, not force. We will see that the voltage of a
cell depends not only on the nature of the electrodes and the ions, but also on the
concentrations of the ions and the temperature at which the cell is operated. The
conventional notation for representing galvanic cells is the cell diagram. The single vertical
line represents a phase boundary.
2+ 2+
Zn (s) | Zn (1 M) || Cu (1 M) | Cu (s)

3.0 Cell Potentials and Spontaneity
When the concentrations of the Cu21 and Zn21 ions are both 1.0 M, we find that the
voltage or emf of the Daniell cell is 1.10 V at 25°C. The overall cell reaction can be thought of
as the sum of two half-cell reactions, the measured emf of the cell can be treated as the sum
of the electrical potentials at the Zn and Cu electrodes. Knowing one of these electrode
potentials, we could obtain the other by subtraction (from 1.10 V). It is impossible to
measure the potential of just a single electrode, but if we arbitrarily set the potential value
of a particular electrode at zero, we can use it to determine the relative potentials of other
electrodes. The hydrogen electrode serves as the reference for this purpose.
The superscript “°” denotes standard-state conditions, and E° is the standard
reduction potential, or the voltage associated with a reduction reaction at an electrode when
all solutes are 1 M and all gases are at 1 atm. Thus, the standard reduction potential of the
hydrogen electrode is defined as zero. The hydrogen electrode is called the standard
hydrogen electrode (SHE).

The cell diagram is

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The Pt electrode provides the surface on which the reduction takes place. When all
the reactants are in their standard states (that is, H2 at 1 atm, H+ and Zn2+ ions at 1 M), the
emf of the cell is 0.76 V at 25°C, We can write the half-cell reactions as follows:

By convention, the standard emf of the cell, E°cell, which is composed of a
contribution from the anode and a contribution from the cathode, is given by

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It is important to know the following points about the table in calculations:

• The E° values apply to the half-cell reactions as read in the forward (left to
right) direction.
• The more positive E° is, the greater the tendency for the substance to be
reduced.
• The half-cell reactions are reversible. Depending on the conditions, any
electrode can act either as an anode or as a cathode.
• Under standard-state conditions, any species on the left of a given half-cell
reaction will react spontaneously with a species that appears on the right of
any half-cell reaction located below it.
• Changing the stoichiometric coefficients of a half-cell reaction does not affect
the value of E° because electrode potentials are intensive properties. This
means that the value of E° is unaffected by the size of the electrodes or the
amount of solutions present.
• Like ΔH, ΔG, and ΔS, the sign of E° changes but its magnitude remains the
same when we reverse a reaction.

Example 1
Predict what will happen if molecular bromine (Br2) is added to a solution
containing NaCl and NaI at 25°C. Assume all species are in their standard states.
Strategy To predict what redox reaction(s) will take place, we need to
compare the standard reduction potentials of Cl2, Br2, and I2 and
apply the diagonal rule.
Solution we write the standard reduction potentials as follows:
Cl2(1 atm) + 2e- à 2Cl2(1 M) E° = 1.36V
Br2(l) + 2e à 2Br2(1 M)
- E° = 1.07 V
I2(s) + 2e à 2I (1 M)
- - E° = 0.53 V
Applying the diagonal rule we see that Br2 will oxidize I2 but will not
oxidize Cl2. Therefore, the only redox reaction that will occur
appreciably under standard-state conditions is
Oxidation: 2I-(1 M) à I2(s) + 2e-
Reduction: Br2(l) + 2e- à 2Br2(1 M)
Overall: 2I-(1 M) + Br2(l) à I2(s) + 2Br-(1 M)


Practice Exercise 1

Can Sn reduce Zn2+(aq) under standard-state conditions?

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The measured emf (Ecell) is the maximum voltage the cell can achieve. The negative
sign indicates that the electrical work is done by the system (galvanic cell) on the
surroundings. we defined free energy as the energy available to do work. Specifically, the
change in free energy (ΔG) represents the maximum amount of useful work that can be
obtained in a reaction. For a spontaneous reaction, ΔG is negative.

LEARNING ENRICHMENT ACTIVITIES

Study the following links on electrochemistry:

• https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Gener
al_Chemistry_(Petrucci_et_al.)/20%3A_Electrochemistry/20.3%3A_Ecell%2C_
%CE%94G%2C_and_K
• https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemi
stry_(Zumdahl_and_Decoste)/11%3A_Electrochemistry

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ASSESSMENT TASK


1. Define the following terms:

a) Anode
b) Cathode
c) Cell Voltage
d) Electromotive Force
e) Standard Reduction Potential

2. Describe the basic features of a galvanic cell. Why are the two components of the
cell separated from each other?


3. What is the function of a salt bridge? What kind of electrolyte should be used in
a salt bridge?

4. What is a cell diagram? Write the cell diagram for a galvanic cell consisting of an

Al electrode placed in a 1 M Al(NO3)3 solution and a Ag electrode placed in a 1 M
AgNO3 solution.

5. After operating a Daniell cell for a few minutes, a student notices that the cell emf

begins to drop. Why?

6. Discuss the spontaneity of an electrochemical reaction in terms of its standard
emf (E° cell).

References:
Chang, R. and Goldsby, K. A. (2017). Chemistry, (12th International Edition), New York:
McGraw-Hill.

Brown, L., Brown, L. S., & Holme, T. (2011). Chemistry for engineering students. Nelson
Education.

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Fahlman, B. D., Purvis-Roberts, K. L., Kirk, J. S., Bentley, A. K., Daubenmire, P. L., Ellis, J. P., &
Mury, M. T. (2018). Chemistry in Context: Applying Chemistry to Society (No. 540
C517cc). McGraw-Hill.

Silberberg, M. (2012). Principles of general chemistry. McGraw-Hill Education.

https://chem.libretexts.org/

SCI 401 –GENERAL CHEMISTRY