Modules in

CHEM 114
Chemistry for Engineers

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 unit I am able to:

• define electrochemistry concepts;

• determine applications of electrochemistry;
• write half-reactions and balance redox reactions; and
• identify and explain the different electrochemical reactions in electrolytic cells.

Introduction

Before you proceed, you must first be familiar with the following concepts:

• determining the charge on a monoatomic ion in an ionic formula;

• be familiar with the formula, including the charges (common polyatomic ions) ; and
• determine if the chemical formula is a binary ionic compound, an ionic compound with
one or two polyatomic ions, or a molecular compound.

This is a good time to read on and test your readiness before you proceed.

OXIDATION-REDUCTUCTION REACTIONS

Chemical reactions can be classified as oxidation-reduction, or redox reactions. Some

chemical reactions can be characterized as proton-transfer processes, oxidation-reduction
reactions on the other hand are considered electron transfer reactions. This reaction can be
found everywhere, from the burning of fossil fuels, to the release of energy in our bodies, even
the action of common household bleach. These all involved redox reactions.

Zinc oxide is a substance commonly found in sun-block lotions, paints, plastics and is also used
as a dietary supplement. Zinc oxide can be made from the reaction of pure zinc and oxygen.

When an element (zinc) combines with oxygen, it is said to be oxidized (or undergoes
oxidation).

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Zinc oxide is an ionic compound made up of zinc cations, Zn2+, and oxide anions, O2‒. When
uncharged zinc and oxygen atoms react to form zinc oxide, electrons are transferred from the
zinc atoms to the oxygen atoms to form these ions. Each zinc atom loses two electrons, and
each oxygen atom gains two electrons.

The transfer of electrons from metal to nonmetal atoms is how binary ionic compounds are
formed.

Magnesium oxide (MgO) is an ionic compound made up of Mg 2+ and O2- ions. Two Mg atoms
give up or transfer four electrons to two O atoms (in O2).

Chemists often describe oxidation-reduction reactions separately. The separate oxidation and
reduction equations are called half-reactions. For example;

The first step involves the loss of four electrons by the two Mg atoms (oxidation half-reaction)
and the other being the gain of four electrons by an O 2 molecule (reduction half-reaction).

Another example, when sodium chloride is formed from the reaction of metallic sodium with
gaseous chlorine, each sodium atom loses an electron, and each chlorine atom gains one.

From the examples given we can deduce that:

• Zinc atoms that lose electrons in the reaction with oxygen are said to be oxidized;
therefore,

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 • when sodium atoms undergo a similar change in their reaction with chlorine, chemists
say they too are oxidized, even though no oxygen is present; and
• any chemical change in which an element loses electrons is called an oxidation.

Figure 1.1 Magnesium reaction with oxygen to form magnesium oxide.

Figure 1.2 Oxidation and formation of binary ionic compounds.

At high temperature, zinc oxide, ZnO, reacts with carbon, C, to form molten zinc and carbon
monoxide gas. Bonds between zinc atoms and oxygen atoms are lost in this reaction, so
chemists say the zinc has been reduced. The zinc ions in zinc oxide have a +2 charge, and the
atoms in metallic zinc are uncharged. Thus, in the conversion of zinc oxide to metallic zinc,
each zinc ion must gain two electrons.

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When there is a chemical change in which an element gains electrons is called a reduction.
(Yup, reduction = gain of electrons.)

Oxidation corresponds to the loss, or apparent loss of electrons. Reduction corresponds

to a gain or apparent gain of elections.

Because this is confusing, you may use a memory aid what oxidation and reduction mean in
terms of electron transfer. The phrase commonly used is oil rig (oxidation is loss and reduction
is gain of electrons)

When an electric current passes through molten sodium chloride, the sodium ions, Na +, are
converted to uncharged sodium atoms, and the chloride ions, Cl ‒, are converted to uncharged
chlorine molecules, Cl2. Because sodium ions gain one electron each, we say they are reduced.
Chloride ions lose one electron each, so they are oxidized.

We have to remember that electrons are neither created nor destroyed in chemical reactions.
Thus, for one element or compound to lose electrons and be oxidized, another element or
compound must be there to gain the electrons and be reduced. So, oxidation and reduction
always occur simultaneously, that is why we call them redox reactions.

Based on our examples, in the reaction that forms ZnO from Zn and O 2, the uncharged zinc
atoms cannot easily lose electrons and be oxidized unless something such as oxygen is there to
gain the electrons and be reduced. In the reaction that converts NaCl to Na and Cl 2, the chloride
ions can lose electrons and be oxidized because the sodium ions are available to gain the
electrons and be reduced. We can say that reduction requires oxidation. Because electrons are
not likely to be found separated from an element or compound, a substance cannot gain

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electrons and be reduced unless there is another substance that is able to transfer the electrons
and be oxidized.

In the reaction of zinc and oxygen:

oxidation half-reaction is

and the reduction half-reaction is

Because the zinc atoms lose the electrons that make it possible for the oxygen atoms to gain
electrons and be reduced, the zinc is called the reducing agent. A reducing agent is a substance
that loses electrons, making it possible for another substance to gain electrons and be reduced.
The oxidized substance is always the reducing agent. Because the oxygen atoms gain electrons
and make it possible for the zinc atoms to lose electrons and be oxidized, the oxygen is called
the oxidizing agent. An oxidizing agent is a substance that gains electrons, making it possible
for another substance to lose electrons and be oxidized. The reduced substance is always the
oxidizing agent.

An oxidizing agent is reduced, while the reducing agent is oxidized.

Oxidizing agents (1) oxidize other substances (2) contain atoms that are reduced, and (3)
gain electrons.

Reducing agents (1) reduce other substance, (2) contain atoms that are oxidized, and (3)
lose electrons.

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A chemical equation does not readily tell us whether a redox reaction have occurred, thus a
numerical system to identify one has been developed. The system allows chemist to tell which
element is oxidized or reduced as well as the reducing and oxidizing agents. To do this,
oxidation numbers are assigned to the reactants and products. Oxidation numbers will tell us if
the elements are oxidized or reduced.

An oxidation number is the number of charges the atom would have in a molecule if electrons
were transferred completely.

Simply said, if any element undergoes a change of oxidation number, the reaction is a redox
reaction.

How to recognize a redox reaction? Determine the oxidation number of each element. If
no elements change in oxidation number, the reaction is not a redox reaction. If changes
occur, the reaction is redox. Remember that both oxidation and reduction occurs; if there
will be an increase in oxidation number, then others must decrease.

By examining the difference/changes in the oxidation numbers in the reaction, we can answer
the following questions:

Q: Which element is oxidized?

A: The element that had an increase in oxidation number.
Q: Which element is reduced?
A: The element which decreases its oxidation number.
Q: What is the reducing agent?
A: The reactant that has the oxidized element.
Q: What is the oxidizing agent?
A: The reactant that contains the reduced element.

Now that we know what information we can get from oxidation numbers, it is a must that we
know how to assign oxidation numbers to individual atoms.

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We apply the following rules to assign oxidation numbers

• The oxidation number for each atom in a pure element is zero.

• The oxidation number of a monatomic ion is equal to its charge.
• When fluorine atoms are combined with atoms of other elements, their oxidation
number is ‒1.
• When oxygen atoms are combined with atoms of other elements, their oxidation
number is ‒2, except in peroxides, such as hydrogen peroxide, H 2O2, where their
oxidation number is ‒1.
• The oxidation number for each hydrogen atom in a molecular compound or a
polyatomic ion is +1.

If a compound’s formula contains one element for which you cannot assign an oxidation
number using the guidelines listed above, calculate the oxidation number according to the
following rules.

• The sum of the oxidation numbers for the atoms in an uncharged formula is equal to
zero.
• The sum of the oxidation numbers for the atoms in a polyatomic ion is equal to the
overall charge on the ion.

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 Figure 1.3 Oxidation numbers of elements in their compounds

Sample Problem 1

Assign oxidation numbers to all the elements in the following compounds and ion: (a) Li 2O, (b)
HNO3, (c) Cr2O72-.

Tip: All alkali metals have an oxidation number of +1, and in most cases hydrogen has an
oxidation number of +1 and oxygen has an oxidation number of -2 in their compounds.

Solution:

(a) Lithium has an oxidation number of +1 (Li+) and oxygen’s oxidation number is -2 (O2-).

Why?

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For ions composed of only one atom (that is, monatomic ions), the oxidation number is equal
to the charge on the ion. Thus, Li+ ion has an oxidation number of +1; Ba2+ ion, +2; Fe3+ ion,
+3; I- ion, -1; O2- ion, -2; and so on.

(b) The formula for nitric acid, which yields a H + ion and a NO3- ion in solution. H has an
oxidation number of +1. Thus the other group (the nitrate ion) must have a net oxidation
number of -1.

Oxygen has an oxidation number of -2, and if we use x to represent the oxidation number of
nitrogen, then the nitrate ion can be written as

[N(x)O3(2-)]-

so that

x+3(-2) = -1

or

x= +5

(c) We see that the sum of the oxidation numbers in the dichromate ion Cr2O72- must be -2. We
know that the oxidation number of O is -2, so all that remains is to determine the oxidation
number of Cr, which we call y. The dichromate ion can be written as

[Cr2(y)O7 (2-) ]2-

so that

2(y) + 7(-2)=-2

or

y=+6

Sample Problem 2

Determine the oxidation number of each atom in the equation. Is the reaction a redox reaction?
How so? Identify the element that is oxidized, reduced, the oxidizing and reducing agent.

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 2Ca3(PO4)2 + 6SiO2 + 10C → P4 + 10CO + 6CaSiO3

Solution

The first thing you have to do is determine the oxidation number for each atom.

• Because the sum of the oxidation numbers for the atoms in an uncharged molecule is
zero, the oxidation number of the carbon atom in CO is +2:

(ox # C) + (ox # O) = 0

(ox # C) + −2 = 0

(ox # C) = +2

• Using a similar process, we can assign a +4 oxidation number to the silicon atom in
SiO2: (ox # Si) + 2(ox # O) = 0

(ox # Si) + 2(−2) = 0

(ox # Si) = +4

• Calcium phosphate, Ca3(PO4)2, is an ionic compound that contains monatomic calcium

ions, Ca2+, and polyatomic phosphate ions, PO43‒. The oxidation number of each
phosphorus atom can be determined in two ways. The following shows how it can be
done considering the whole formula.

3(ox # Ca) + 2(ox # P) + 8(ox # O) = 0

3(+2) + 2(ox # P) + 8(−2) = 0

(ox # P) = +5

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 • The oxidation number for the phosphorus atom in PO43‒ is always the same, no matter
what the cation is that balances its charge. Thus we could also have determined the
oxidation number of each phosphorus atom by considering the phosphate ion
separately from the calcium ion.

(ox # P) + 4(ox # O) = −3

(ox # P) + 4(−2) = −3

(ox # P) = +5

The silicon atoms in CaSiO3 must have an oxidation number of +4.

(ox # Ca) + (ox # Si) + 3(ox # O) = 0

(+2) + (ox # Si) + 3(−2) = 0 (ox # Si) = +4

• The oxidation numbers for the individual atoms in the first reaction are below.

Answer

Therefore, phosphorus atoms and carbon atoms change their oxidation numbers, so the reaction
is redox. Each phosphorus atom changes its oxidation number from +5 to zero, so the
phosphorus atoms in Ca3(PO4)2 are reduced, and Ca3(PO4)2 is the oxidizing agent. Each
carbon atom changes its oxidation number from zero to +2, so the carbon atoms are oxidized,
and carbon is the reducing agent.

Balancing Redox Equations

The ion-electron method is a technique for handling redox reactions. Using this approach, the
overall reaction will be divided into two half-reactions, then the equations for the two half-
reactions are balanced separately and then put back together to give the overall balanced
equation.

The following steps will be used to balance the equation.

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Step 1: Write the unbalanced equation for the reaction in ionic form.

Step 2: Separate the equations into two half-reactions.

Step 3: Balance each half-reaction for number and types of atoms and charges. Add H2O to
balance O atoms and H+ to balance H atoms.

Step 4: Add the two half-reactions together and balance final equation. The electrons on both
sides must cancel. If the oxidation and reduction half-reactions contain different numbers of
elections, multiply one or both half-reactions to equalize the number of electrons.

Step 5: Check if the equation has the same type and numbers of atoms and same charges on
both sides of the overall equation.

Sample Problem 3

Write a balanced ionic equation to represent the oxidation of iodide ion (I-) by permanganate
ion (MnO4- ) in basic solution to yield molecular iodine (I2 ) and manganese(IV) oxide (MnO 2).

Tip: Follow the steps for balancing redox reaction.

Solution

Step 1: The unbalanced equation is

Step 2: The two half-reactions:

Step 3: Balance each half-reaction for number and type of atoms and charges.

(a) Oxidation half-reaction: We first balance the I atoms. To balance charges, we add two
electrons to the right-hand side of the equation:

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(b) Reduction half-reaction: To balance the O atoms, we add two H2O molecules on the right:

To balance the H atoms, we add four H + ions on the left:

There are three net positive charges on the left, so we add three electrons to the same side to
balance the charges:

Step 4: We now add the oxidation and reduction half reactions to give the overall reaction. In
order to equalize the number of electrons, we need to multiply the oxidation half-reaction by 3
and the reduction half-reaction by 2 as follows:

The electrons on both sides cancel, and we are left with the balanced net ionic equation:

This is the balanced equation in an acidic medium. However, because the reaction is carried
out in a basic medium, for every H+ ion we need to add equal number of OH2 ions to both sides
of the equation:

Finally, combining the H1 and OH2 ions to form water, we obtain

Step 5: A final check shows that the equation is balanced in terms of both atoms and charges.

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Electrochemistry

Electrochemistry deals with the production of electricity from energy released during.
chemical reactions. All electrochemical reactions are redox reactions. The site where redox
happens are separated. It requires some method of introducing a stream of electrons into a
reacting chemical system and some means of withdrawing electrons. In most applications, the
reacting system is contained in a cell, and an electric current enters of exits by electrodes.

Classification of electrochemical cells:

• Electrolytic cells are those in which electrical energy from an external source causes
nonspontaneous chemical reactions to occur.
• Voltaic cells are those in which spontaneous chemical reactions produce electricity
and supply it to an external circuit.

Electric current represents transfer of charge. Charge can be conducted through metals and
electrolytes. this is called metallic conduction. It involves the flow of electrons with no similar
movement of the atoms of the metal and no changes in the metal. While ionic, or electrolytic
conduction is the conduction of electric current by the motion of ions through a solution of
pure liquid. Positively charged ions migrate toward the negative electrode, while negatively
charged ions move toward the positive electrode. Both types of conduction occur in
electrochemical cells.

Figure 1.4 The

motion of ions
through a solution
is an electric
current. This
accounts for ionic
(electrolytic)
conduction.
Positively charged
ions migrate
toward the negative
electrode, and
negatively charged
ions migrate toward the positive electrode.

Electrodes are surfaces on which redox half-reactions happen. Regardless of the type of cell,
the electrodes can be identified as follows.

The cathode is defined as the electrode at which reduction occurs as electrons are gained
by some species. The anode is the electrode at which oxidation occurs as electrons are lost
by some species.

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A simple way to remember the name of the electrode is to imagine a "red cat"-
REDuctions always occurs at the CAThode

In some electrochemical cells, nonspontaneous chemical reactions are forced to occur due to
the input of electrical energy, a process called electrolysis. An electrolytic cell has a container
for the reaction material with electrodes immersed in the reaction material and connected to a
source of direct current.

Figure 1.5 Electrolysis of aqueous NaCl solution.

Several elements are produced commercially by electrolysis. some of them produce sodium
(Downs cell), chlorine, hydrogen, and oxygen. Many common metal-plated items like jewelry
and table ware can be produced through electrolysis.

Figure 1.6 A memento that has been electroplated with copper.

Voltaic or galvanic cells are electrochemical cells in which spontaneous redox-reactions

produce electrical energy. The two halves of the redox reaction are separated, by which electron
transfer occur through an external circuit. Batteries commonly used in flashlights are voltaic
cells.

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 Figure 1.7 The zinc-copper voltaic cell.

Figure 1.8 The copper-silver voltaic cell.

Whether a particular electrode acts as an anode or a cathode in a voltaic cell depends on

what the other electrode of the cell is.

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Figure 1.9 A spiral of copper wire was placed in a colorless solution of silver nitrate, AgNO3.
The silver has been displaced from solution and adheres to the wire. The resulting copper nitrate
solution is blue. The same reaction occurs when the two half-reactions are separated in the
copper–silver cell. No reaction occurs when silver wire is placed in a blue copper sulfate
solution. The reaction is the reverse of the spontaneous reaction; it has a negative E0 cell and
is nonspontaneous.

Corrosion is a redox process where metals are oxidized by oxygen

in the presence of moisture. The oxidation of metals occur most
readily at points of strain. A point of strain in steel objects such a a
nail acts as an anode where the iron is oxidized and pits are formed.
Rust is a complex hydrated form of iron (III) oxides and hydroxides
with different water composition.

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 Here are some widely used methods for protecting metals
against corrosion.

• Plating the metal with a thin layer of less easily

oxidized metal.
• Use of a sacrificial anode (a piece of another metal
that is more active and preferentially oxidized).
• Using a protective film, such a metal oxide to form on
the surface.
• Galvanizing, or coating steel with zinc.
• Applying paint.

Figure 1.10 Galavanized steel.

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.

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Assessing Learning
Activity 1
Name:_______________________________ Score:_________
Course/Year/Section:___________________ Date:__________

I. Complete the crossword puzzle.

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II. Determine the oxidation number for the atoms of each element in the following formulas.
(a) S8 (c) Na2S

(b) S2‒ (d) FeS

III.
1. Balance the following redox reactions. Show your solution.
(a) Mn2+ + H2O2→MnO2 + H2O

(b) Cr2O72- + C2O42- → Cr3+ + CO2

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2. What are the advantages and disadvantages of fuel cells over conventional power plants in
producing electricity?

3. Explain why does the tendency of iron to rust depend on the pH of solution?

4. Differentiate between a galvanic cell (such as a Daniell cell) and an electrolytic cell?

5. Describe the electrolysis of an aqueous solution of KNO3.

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