Republic of the Philippines

NUEVA VIZCAYA STATE UNIVERSITY

Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
Module 1.7: ELECTROLYSIS

I. CHAPTER TITLE: Electrolysis – Causing Reactant-Favored Redox Reactions to

Occur

II. LESSON TITLE: Electrochemistry IV

III. LESSON OVERVIEW

Reactant-favored redox systems (positive ΔG°) can be made to produce products

if electrons are forced into the electrochemical system from an external source of
electrical current, such as a battery. This process, called electrolysis, provides a
way to carry out reactant-favored electrochemical reactions that will not take
place by themselves. Electrolytic processes are even more important in our
economy than the product-favored redox reactions that power batteries. Such
electrolytic processes are used in the production and purification of many metals,
including copper and aluminum, and in electroplating processes that produce a
thin coating of metal on many different kinds of items.

IV. DESIRED LEARNING OUTCOMES

1. Analyze electrolytic equations.
2. Understand and apply electroplating.

V. LEARNING ACTIVITIES

SECTION 1. ELECTROLYSIS

Voltaic and electrolytic cells share some characteristics, but they also differ in important ways:

Properties of all electrochemical cells:

• Two electrodes are in contact with a conducting medium and an external circuit.
• Oxidation occurs at the anode.
• Reduction occurs at the cathode.

Properties of voltaic cells:

• The anode is the source of electrons and has a negative charge.
• The cathode is the sink of electrons and has a positive charge.
• Electrons flow through the external circuit from the anode to the cathode.
• The two half-reactions occur in separate cells, which are joined by a salt bridge.

Properties of electrolytic cells:

• The external circuit must contain a source of direct electrical current, for
example, a battery. The battery forces electrons at a sufficiently high voltage
into the anode (which becomes negative) and removes electrons from the
cathode (which becomes positive).
• The two half-reactions often can be carried out in the same cell, in which case
no separation is necessary and no salt bridge is necessary.
• The electrodes are often inert, their function being to provide a path for
electrons to enter and leave the cell.

An example of electrolysis is the decomposition of molten sodium chloride. In this process,

a pair of electrodes dips into molten NaCl as what is shown in Figure 1. In the molten liquid, Na+
and Cl– ions are free to move. The Na ions are attracted to the negative electrode, and the Cl– ions

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
are attracted to the positive electrode. Reduction of Na ions to metallic Na atoms occurs at the
cathode (negative electrode). Oxidation of Cl– ions to Cl2(g) occurs at the anode (positive
electrode).

0
The 𝐸𝑐𝑒𝑙𝑙 for this reaction as written is negative—the reaction is not product-favored. An
external source of direct current at a potential higher than the negative potential of the reaction is
required for the forward reaction to proceed.
The electrolysis of molten salts is an energy-intensive process because energy is needed to
melt the salt as well as to cause the anode and cathode reactions to take place.

Figure 1. Electrolysis of molten sodium chloride. A direct current supplied

by the battery drives the reaction in the product-favored direction. At the
anode, Cl– ions are oxidized to Cl2(g). At the cathode, Na+ ions are reduced
to Na(l) atoms. The electrodes are made of inert materials.

What happens if a direct current is passed through an aqueous solution of a salt, such as
potassium iodide, KI, rather than through the molten salt? To predict the outcome of the
electrolysis we must first decide what in the solution can be oxidized and reduced. For KI(aq), the
solution contains K+ ions, I– ions, and H2O molecules. Potassium is already in its highest common
oxidation state in K+, so it cannot be oxidized. However, both the I– ion and the H2O could be
oxidized. The possible anode half-reaction oxidations and their reduction potentials are:

Whenever two or more electrochemical reactions are possible at the same electrode, use
Table 1 to decide which reaction is more likely to occur under standard-state conditions.

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
Considering the two possible anode reactions, Table 1 indicates that the less positive the reduction
potential, the more likely a half-reaction is to occur as an oxidation. That is, the farther toward the
bottom of Table 1 a half-reaction is, the more likely it is to occur as an oxidation. Oxidation of I–
to I2 has the less positive E°, so this is the more likely anode reaction.

Table 1. Standard Reduction Potential

–
Since I is the lowest common oxidation state of iodine, there are only two species that
can be reduced at the cathode: K+ ions and water molecules. The possible cathode half-reaction

reductions and their reduction potentials are:

Table 1 suggest that the more positive the reduction potential, the more easily a substance
on the left-hand side of a half-reaction can be reduced. Since E° for H2O is more positive (less
negative) than E° for K+, H2O is more likely to be reduced. Therefore, in aqueous KI solution, the
overall reaction and cell potential are:

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
An experiment in which electrical current is passed through aqueous KI (Figure 2) shows
that this prediction is correct. At the anode (on the right in Figure 2a), the I– ions are oxidized to
I2, which produces a yellow-brown color in the solution. At the cathode, water is reduced to

Figure 1. The electrolysis of aqueous potassium iodide. (a) Aqueous KI is found in both
compartments of the cell, and both electrodes are platinum. At the anode (left), the I– ion is oxidized
to iodine, which gives the solution a yellow-brown color.

At the cathode (right), water is reduced, and the presence of OH– ion is indicated by the pink color
of the acid-base indicator, phenolphthalein.

(b) A close-up of the cathode shows bubbles of H2 and evidence of generation of OH.
gaseous hydrogen and aqueous hydroxide ions. The formation of excess OH– ions is shown by the
pink color of the phenolphthalein indicator added to the solution.

When electrolysis is carried out by passing a direct electrical current through an aqueous
solution, the electrode reactions most likely to take place are those that require the least voltage,
that is, the half-reactions that combine to give the least negative overall cell voltage. This means
that in aqueous solution these conditions apply.

1. A metal ion or other species can be reduced if it has a reduction potential more positive
than 0.8 V, the potential for reduction of water. Table 1 shows that many metal ions are in
this category. If a species has a reduction potential more negative than 0.8 V, then water
will preferentially be reduced to H2(g) and OH– ions. Metal ions in this latter category
include Na+, K+, Mg2+, and Al3+. Consequently, producing these metals from their ions
requires electrolysis of a molten salt with no water present.
2. A species can be oxidized in aqueous solution if it has a reduction potential less positive
than 1.2 V, the potential for reduction of O2(g) to water. If the reduction potential is less
positive than for reduction of O2(g), then oxidation of the species on the right-hand side of
a half-reaction is more likely than oxidation of water. Most of the half-equations in Table
1 are in this category. If a species has a reduction potential more positive than 1.2 V (that
is, if its half-reaction is above the water-oxygen half-reaction in Table 1), water will be
oxidized preferentially. For example, F(aq) cannot be oxidized electrolytically to F2(g)
because water will be oxidized to O2(g) instead.

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
The voltage that must be applied to an electrolysis cell is always somewhat greater than
the voltage calculated from standard reduction potentials. An overvoltage is required, which is an
additional voltage needed to overcome limitations in the electron transfer rate at the interface
between electrode and solution. Another factor affecting the necessary voltage is that
concentrations and pressures are usually not at standard-state conditions. Redox reactions that
involve the formation of O2 or H2 are especially prone to have large overvoltage. Since overvoltage
cannot be predicted accurately, the only way to determine with certainty which half-reaction will
occur in an electrolysis cell when two possible reactions have similar standard reduction potentials
is to perform the experiment.

EXAMPLE 1. Electrolysis of Aqueous NaOH

Predict the results of passing a direct electrical current through an aqueous solution of NaOH.
Calculate the cell potential.

Answer. The net cell reaction is 2H2O(l) → 2H2(g) + O2(g). Hydrogen is produced at the cathode
and oxygen is produced at the anode. The cell potential is – 1.23V.

Strategy and Explanation. First, list all the species in the solution: Na+, OH–, and H2O. Next,
use Table 1 to decide which species can be oxidized and which can be reduced, and note the
reduction potential of each possible half-reaction.

Reductions:

Oxidations:

Water will be reduced to H2 at the cathode because the potential for this half-reaction is more
positive. At the anode, OH– will be oxidized because the potential is smaller than that for water.
The net cell reaction is:

and the cell potential under standard conditions is

SECTION 2. COUNTING ELECTRONS

When a direct electric current is passed through an aqueous solution of the soluble salt AgNO3,
metallic silver is produced at the cathode. One mole of electrons is required for every mole of Ag+
reduced.

If a copper (II) salt in aqueous solution were reduced, 2 mol electrons would be required to
produce 1 mol metallic copper from 1 mol copper (II) ions.

Each of these balanced half-reactions is like any other balanced chemical equation. That is, each
illustrates the fact that both matter and charge are conserved in chemical reactions. Thus, if you

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
could measure the number of moles of electrons flowing through an electrolysis cell, you would
know the number of moles of silver or copper produced. Conversely, if you knew the amount of
silver or copper produced, you could calculate the number of moles of electrons that had passed
through the circuit.
The number of moles of electrons transferred during a redox reaction is usually determined
experimentally by measuring the current flowing in the external electrical circuit during a given
time. The product of the current (measured in amperes, A) and the time interval (in seconds, s)
equals the electric charge (in coulombs, C) that flowed through the circuit.

The Faraday constant (96,500 C/mol of electrons) can then be used to find the number of moles of
electrons from a known number of coulombs. This information is of practical significance in
chemical analysis and synthesis.
EXAMPLE 2. Using the Faraday Constant
How many grams of copper will be deposited at the cathode of an electrolysis cell if an electric
current of 15 mA is applied for 1.0 h through an aqueous solution containing excess Cu2+ ions?
Assume the process is 100% efficient.

Answer. 0.018 g C

Strategy and Explanation. First, write and balance the relevant half-reaction that occurs at the
cathode.

Then, calculate the quantity of charge transferred.

Finally, determine the mass of copper deposited.

SECTION 3. ELECTROLYTIC PRODUCTION OF HYDROGEN

Hydrogen can be produced by the electrolysis of water to which a drop or two of sulfuric acid has
been added to make the solution electrically conductive. The overall electrochemical reaction is.

Oxygen is produced at the anode and hydrogen at the cathode. The minimum voltage required for
this reaction is 1.24 V (J/C), but in practice overvoltage requires a higher voltage of about 2 V.
Let’s consider how much electrical energy would be required to produce 1.00 kg of gaseous H2
(about 11,200 L at STP) and at what cost. First calculate the required charge in coulombs by using
the Faraday constant; then use the fact that 1 joule = 1 volt × 1 coulomb.
The reduction half-reaction shows that 2 mol electrons produces 1 mol (2.02 g) H2 (g).

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
The amount (number of moles) of electrons required to produce 1.00 kg H2 is calculated as follows:
Now we calculate the charge using the Faraday constant.

The energy (in joules) is calculated from the charge and the cell voltage.

We convert joules to kilowatt-hours (kWh), which is the unit we see when we pay the electric bill.

At a rate of 10 cents per kilowatt-hour, the production of 1.00 kg hydrogen would cost $3.31.
Hydrogen holds great promise as a fuel in our economy because it is a gas and can be transported
through pipelines, it burns without producing pollutants, and it could be used in fuel cells to
generate electricity on demand. Both water and sulfuric acid are in plentiful supply. The major
problem with producing hydrogen in quantities large enough to meet the nation’s energy demands
is finding a cheap enough source of electricity to decompose water to its elements. Another
challenging problem is the development of economical, reliable, and safe methods for hydrogen
transfer and storage.

SECTION 4. ELECTROPLATING
If a metal or other electrical conductor serves as the cathode in an electrolysis cell, the conductor
can be plated with another metal to decorate it or protect it against corrosion. To plate an object
with copper, for example, we have only to make the object’s surface conducting and use the object
as the cathode in an electrolysis cell containing a solution of a soluble copper salt as a source of
Cu2+ ions. The object will become coated with metallic copper, and the coating will thicken as the
electrolysis continues and electrons reduce more Cu2+ ions to Cu atoms. If the plated object is a
metal, it will conduct electricity by itself. If the object is a nonmetal, its surface can be lightly
dusted with graphite powder to make it conducting.
Precious metals such as gold are often plated onto cheaper metals such as copper to make jewelry.
If the current and duration of the plating reaction are known, it is possible to calculate the mass of
gold that will be reduced onto the cathode surface. For example, suppose the object to be plated is
immersed in an aqueous solution of AuCl3 and is made a cathode by connecting it to the negative
pole of a battery. The circuit is completed by immersing an inert electrode connected to the positive
battery pole in the solution, and gold is reduced at the cathode for 60. min at a current of 0.25 A.
The reduction half-reaction is

The mass of gold that is reduced is calculated by

Assuming that gold is selling for $900 per ounce, that’s about $19.25 worth of gold.

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 Republic of the Philippines
NUEVA VIZCAYA STATE UNIVERSITY
Bayombong, Nueva Vizcaya
INSTRUCTIONAL MODULE
IM No.:IM-CHEM ENG-1ST SEM-2020-2021
VI. ASSIGNMENT
1. In 1886, Moissan was the first to prepare F2 by the electrolysis of F– ions. He
electrolyzed KF dissolved in pure HF. No water was present, so only F– ions were
available at the anode. What was produced at the cathode? Write the half-equations
for the oxidation and reduction reactions, and then write the net cell reaction
(REFER TO EXAMPLE 1).
2. In the commercial production of sodium metal by electrolysis, the cell operates at
7.0V and a current of 25×103 A. Calculate what mass of metallic sodium can be
produced in 1h (REFER TO EXAMPLE 2).
3. In the production of aluminum metal, Al3+ is reduced to Al metal using currents of
about 50,000 A and a low voltage of about 4.0V. Calculate how much energy (in
kilo-watt-hours) is required to produce 2000, metric tons of aluminum metal
(REFER TO SECTION 3).

VII. EVALUATION
1. Predict the result of passing a direct electrical current through (a) molten NaBr, (b)
aqueous NaBr, and (c) aqueous SnCl2 (REFER TO EXAMPLE 1).
2. Which would require more moles of electrons? (REFER TO EXAMPLE 2)
(a) Making 1 mol Al from Al3+
(b) Making 2 mol Na from Na+
(c) Making 2 mol Cu from Cu2+
3. Think of a battery you just purchased at the store as energy source that can deliver
some number of joules. Name the two pieces of information you need to calculate
how many joules this battery can deliver. Which one is obviously available as you
read the label on the battery? Devise a means of determining the other information
needed (REFER TO SECTION 3).
4. Calculate the mass of silver that could be plated from solution with a current of
0.50A for 20 mins. The cathode reaction is Ag+(aq) + e– → Ag(s) (REFER TO
SECTION 4)

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