Modules in

CHEM 114
Chemistry for Engineers
Laboratory

Prepared by:
CAS-Chemistry and Environmental Science
Department

This module is a property of NEUST.

UNIT I. ELECTROCHEMISTRY

Learning Objectives

At the end of this activity I am able to:

• Identify and observe the basic set up of a galvanic cell; and

• Solve problems using Nerst equation

Introduction

We may not know it be we are already familiar with some voltaic cells. These cells were named
after Allesandro Volta and Luigi Galvani. The batteries we use in portable radios, cameras and
many toys and household appliances are voltaic cells. Car batteries too, they consist of several
voltaic cells connected in a series.

Voltaic Cells

A half-cell contains the oxidized and reduced forms of an element. A common example of a
half-cell consists of a piece of metal (the electrode) submerged in a solution of its ions. The
electrodes are connected by a wire. The electric current is the result of the spontaneous redox
redox reaction that occurs.

The circuit between the two solutions is completed by a salt bridge. This a medium by which
ions can pass. Salt bridge can be made by bending a piece of glass tubing. A salt bridge allows
electrical contact between two solutions, prevents mixing of the electrode solutions, and
maintains the electrical neutrality in each half-cell as ions flow into and out of the salt bridge.00

We use batteries as portable sources of electrical energy in many ways- I'm sure you can name
a few. A battery is a voltaic cell (or a set of voltaic cells). As any voltaic cell produces current,
chemicals are consumed. Primary voltaic cells cannot be "recharged". The electrolytes or
electrodes (or both) cannot be regenerated by reversing the current flow. Ordinary "dry" cells
are the most common example of primary voltaic cells.

Secondary voltaic cells or reversible cells are those that can be recharged. The original reactants
can be regenerated in secondary voltaic cells. This is done by passing a direct current through
the cell in the direction opposite of the current flow. The most common example for this type
of voltaic cell is the lead storage battery used in automobiles

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i. Using arrows, label the parts of a voltaic cell.

ii. Fill-in the table

Voltaic Cell Anode Cathode Pros Cons

Reaction Reaction
Ex. Dry cell Zn(s) → 2MnO2(s) + Inexpensive; Short shelf-life;
Zn2+(aq) + 2e‒ 2NH4+(aq) + reliable large and heavy;
2e‒ not rechargeable
→ Mn2O3(s) +
2NH3(aq) +
H2O(l )
Alkaline
battery

Nickel-
cadmium
battery

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 Lead-Acid
Battery

Lithium battery

The Nernst Equation

The Nernst equation is used to calculate electrode potentials and cell potentials for
concentrations and partial pressures other than standard-state values. Standard electrode
potentials, designated E0, refer to standard-state conditions. These standard-state conditions
are one molar solutions for ions, one atmosphere pressure for gases, and all solids and liquids
in their standard states at 25°C. The Q expression that is used in the Nernst equation is the
thermodynamic reaction quotient; it can include both concentrations and pressures.
Substituting these values into the Nernst equation at 25°C gives

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The Nernst equation for any cathode half-cell (reduction half-reaction) is

SP 1.1

Calculate the potential, E, for the Fe3+/Fe2+ electrode when the concentration of Fe2+ is exactly
five times that of Fe3+ .

Tips

The Nernst equation lets us calculate potentials for concentrations other than one molar. The
tabulation of standard reduction potentials gives us the value of E0 for the reduction
halfreaction. We use the balanced half-reaction and the given concentration ratio to calculate
the value of Q. Then we substitute this into the Nernst equation with n equal to the number of
moles of electrons involved in the half-reaction.

Solution

The reduction half-reaction is

We are told that the concentration of Fe2+s five times that of Fe 3+. Calculating the value of Q,

The balanced half-reaction shows one mole of electrons, or n 1. Putting values into the Nernst
equation,

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SP 1.2

A cell is constructed at 25°C as follows. One half-cell consists of a chlorine/chloride, Cl2/Cl-,

electrode with the partial pressure of Cl2 = 0.100 atm and [Cl-] = 0.100 M. The other halfcell
involves the MnO4 - /Mn2+ couple in acidic solution with [MnO4-] = 0.100 M, [Mn2+] = 0.100
M, and [H+] = 0.100 M. Apply the Nernst equation to the overall cell reaction to determine the
cell potential for this cell.

Tips First we determine the overall cell reaction and its standard cell potential, E 0 cell. Then
we apply the Nernst equation to the overall cell.

Solution

(a)

The MnO4 - /Mn2 half-reaction has the more positive reduction potential, so we write it first.
Then we write the Cl2/Cl- half-reaction as an oxidation, balance the electron transfer, and add
the two half-reactions and their potentials to obtain the overall cell reaction and its E0cell.

(b)

In the overall reaction, n=10. We then apply the Nernst equation to this overall reaction by
substituting appropriate concentration and partial pressure values. Because Cl 2 is a gaseous
component, its term in the Nernst equation involves its partial pressure, PCl2.

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 References

Bishop, M., & Locket, G. H. (2002). Introduction to chemistry. San Francisco: Benjamin
Cummings.

Chang, R. (2008). General chemistry: the essential concepts. Boston: McGraw-Hill,.

Whitten, K. W., Davis, R. E., Peck, M. L., & Peck, M. L. (2000). General chemistry.
Cengage Learning.

Assessing Learning
Activity 1
Name:_______________________________ Score:_________
Course/Year/Section:___________________ Date:__________
I. Complete the following statements by writing one of these words or phrases in each blank.
chemical energy not rechargeable
electrical conductors oxidation
electrical energy positive
electrolysis positive electrode
flow rechargeable
force reduction
half-reactions voltaic cells

1. A voltaic cell keeps two oxidation-reduction ________________ separated, causing the

electrons released in the oxidation half of the reaction to pass through a wire connecting the
two halves of the apparatus.

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 2. A battery is a series of ________________ joined in such a way that they work together. A
battery can also be described as a device that converts _____________ into _____________
using redox reactions.
3. The electrode at which ________________ occurs in a voltaic cell is called the anode.
Because electrons are lost, forming more positive (or less negative) species at the anode, the
anode surroundings tend to become more _____________.
4. Metal strips in voltaic cells are called electrodes, which is the general name for
_____________ placed in half‑cells of voltaic cells.
5. Batteries that are _____________ are called primary batteries. A(n) _____________ battery
is called a secondary battery or a storage battery.
6. Voltage, a measure of the strength of an electric current, represents the _____________ that
moves electrons from the anode to the cathode in a voltaic cell. When a greater voltage is
applied in the opposite direction, electrons can be pushed from what would normally be the
cathode toward the voltaic cells anode. This process is called _____________.
7. The component of the voltaic cell through which ions are able to _____________ is called
the electrolyte.
8. The cathode is the electrode in a voltaic cell at which _____________ occurs. By
convention, the cathode is designated the _____________. Because electrons flow along the
wire to the cathode, and because substances gain those electrons to become more negative (or
less positive), the cathode surroundings tend to become more negative. Thus cations are
attracted to the cathode.

II. Explain the differences between a primary galvanic cell—one that is not rechargeable—
and a storage cell which is rechargeable.

III. Calculate E°, E, and ∆G for the following cell reactions.

(a) Mg(s) + Sn2+(aq) → Mg2+ (aq) + Sn(s) ; [Mg2+] = 0.045 M, [Sn2+] = 0.035 M

(b) 3Zn(s) + 2Cr3+ (aq) → 3Zn2+ (aq) + 2Cr(s) ; [Cr3+] = 0.010 M, [Zn2+] = 0.0085 M

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