2- Electrochemistry

Week 3 – Topic 2

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 1

Topic Outline
• Electrochemistry
• Oxidation – Reduction Reaction
• Cell Potentials
• Cell Potentials and Equilibrium
• Batteries
• Electrolysis
• Electrolysis and Stoichiometry

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 2

Learning Outcomes
• Define electrochemistry
• Differentiate oxidation and reduction reaction
• Write and balance half-reaction for simple redox processes
• Describe the different types of batteries

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 3

Key Concepts
• Redox Reactions and Electrochemical Cells
• Equations representing redox reactions can be balanced using the half-reaction method. These reactions involve
the transfer of electrons from a reducing agent to an oxidizing agent. Using separate compartments, such
a reaction can be used to generate electrons in an arrangement called a galvanic cell.
• Thermodynamics of Galvanic Cells
• The voltage measured in a galvanic cell can be broken down into the electrode potentials of the anode (where
oxidation takes place) and cathode (where reduction takes place). This voltage can be related to the Gibbs free
energy change and the equilibrium constant of the redox process. The Nernst equation relates the cell voltage to
the cell voltage under standard-state conditions and the concentrations of reacting species.
• Batteries
• Batteries are electrochemical cells that can supply direct electric current at a constant voltage. There
are many different types of batteries used in automobiles, flashlights, and pacemakers. Fuel cells are a special type of
electrochemical cell that generates electricity by the oxidation of hydrogen or hydrocarbons.
• Corrosion
• Corrosion is a spontaneous redox reaction that results in the formation of rust from iron, silver sulfide
from silver, and patina (copper carbonate) from copper. Corrosion causes enormous damage to buildings,
structures, ships, and cars. Many methods have been devised to prevent or minimize the effect of corrosion.
• Electrolysis
• Electrolysis is the process in which electrical energy is used to cause a nonspontaneous redox reaction
to occur. The quantitative relationship between the current supplied and the products formed is provided by
Faraday. Electrolysis is the major method for producing active metals and non-metals and many essential industrial
chemicals.
Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 4
Electrochemistry
• What is electrochemistry?
• Electrochemistry is the branch of chemistry that deals with the interconversion of
electrical and chemical energy. Electrochemical processes are redox (oxidation-
reduction) reactions wherein the energy released by a spontaneous reaction is converted
to electricity or wherein the electrical energy produced is used to cause a non-
spontaneous reaction.

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What are redox (oxidation-reduction) reactions?
• In redox (oxidation-reduction reactions), electrons are transferred from one
substance to another. They are also called electron-transfer reactions.
• Example: Burning of magnesium in oxygen
2𝑀𝑔 𝑠 + 𝑂2 → 2𝑀𝑔𝑂(𝑠)
• Magnesium oxide (MgO) is an ionic compound made up of 𝑀𝑔2+ and 𝑂2− ions. In this reaction, two Mg
atoms give up or transfer four electrons to two O atoms (in O2). This process can be separated into two
steps:
2𝑀𝑔 → 2𝑀𝑔2+ + 4𝑒 − (Loss of four electrons by 2 Mg atoms)
𝑂2 + 4𝑒 − → 2𝑂2− (Gain of four electrons by an O2 molecule)
• Each of the step or reaction shown above is called half-reaction. Half-reactions explicitly show the
electrons involved in a redox reaction. Adding the two half-reactions gives the overall reaction:
2𝑀𝑔 + 𝑂2 + 4𝑒 − → 2𝑀𝑔2+ + 2𝑂2− + 4𝑒 −
• Cancelling the electrons from both sides, we get:
2𝑀𝑔 + 𝑂2 → 2𝑀𝑔2+ + 2𝑂2−
• Magnesium and oxygen then combine to form MgO:
2𝑀𝑔2+ + 2𝑂2− → 2𝑀𝑔𝑂
Figure 1. Burning of magnesium in oxygen
Image source: (Chang & Overby, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 6

What are redox (oxidation-reduction) reactions?
• Oxidation Reaction
• half-reaction that involves the loss of electrons
• Reduction Reaction
• half-reaction that involves the gain of electrons
*Useful mnemonic in redox reactions: OILRIG- Oxidation Is Loss (of electrons), Reduction is Gain (of
electrons)
• Oxidizing Agent
• accepts electrons
• Reducing agent
• donates electrons
** All Oxidizing agents are always reduced, and reducing agents are always oxidized. This
statement may be somewhat confusing, but it is simply a consequence of the definitions of the
two processes.

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Oxidation Number
• Also known as oxidation state, signifies the number of charges the atom
would have in a molecule (or an ionic compound) if electrons were
transferred completely.
• Examples:

• The numbers above the element are the oxidation numbers.

• Oxidation numbers reflect the number of electrons “transferred”.
• Oxidation numbers help us to identify elements that are oxidized and reduced.
• Increase in oxidation number (hydrogen and sulfur in the preceding examples) denotes that
the element is oxidized. While a decrease in oxidation number (Cl and O) means that the
element is reduced.

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Rules in Assigning Oxidation Numbers
• We use the following rules to assign oxidation numbers:
1. In free elements (that is, in the uncombined state), each atom has an oxidation number of zero.
Thus, each atom in H2, Br2, Na, Be, K, O2, and P4 has the same oxidation number: zero.
2. For ions composed of only one+ atom (that is, monatomic ions), the oxidation
2+
number3+is equal to
the
−
charge on
2−
the ion. Thus, 𝐿𝑖 ion has an oxidation number of +1; 𝐵𝑎 ion, +2; 𝐹𝑒 ion, +3;
𝐼 ion, -1; 𝑂 ion, -2; and so on.
3. The oxidation number of oxygen in most compounds (for example, MgO and H2O) is -2, but in
hydrogen peroxide (H2O2) and peroxide ion (O22-) it is -1.
4. The oxidation number of hydrogen is +1, except when it is bonded to metals in binary
compounds. In these cases (for example, LiH, NaH, CaH2), its oxidation number is -1.
5. Fluorine has an oxidation number of -1 in all its compounds. Other halogens (Cl, Br, and I) have
negative oxidation numbers when they occur as halide ions in their compounds. When combined
with oxygen—for example in oxoacids and oxoanions- they have positive oxidation numbers.
6. In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero. In a
polyatomic ion, the sum of oxidation numbers of all the elements in the ion must be equal to the
net charge of the ion. For example, in the ammonium ion, NH4+, the oxidation number of N is -3
and that of H is +1. Thus, the sum of the oxidation numbers is -3 + 4(+1) = +1, which is equal to
the net charge of the ion.
7. Oxidation numbers do 1not have to be integers. For example, the oxidation number of O in the
superoxide ion, O2- is -2.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 9

Example 2-1
• Assigning Oxidation Numbers
• Assign oxidation numbers to all the elements in the following compounds and
ion:
• 𝑁𝑎2 𝑂
• 𝐻𝑁𝑂2
• 𝐶𝑟2 𝑂72−
• Strategy
• In general, we follow the rules just listed for assigning oxidation numbers. Remember that
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.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 10

Example 2-1
• Solution
• By rule 2, we see that sodium has an oxidation number of +1 (Na+) and oxygen’s oxidation
number is -2 (O2-).
• This is the formula for nitrous acid, which yields a H+ ion and a NO2- ion in solution. From
rule 4, we see that H has an oxidation number of 11. Thus, the other group (the nitrite 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 nitrite ion can be written as:
𝑥 2− −
𝑁 𝑂2
• So that
𝑥 + 2 −2 = −1
• Or
𝑥 = +3

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 11

Example 2-1
• From rule 6, we see that the sum of the oxidation numbers in the dichromate ion 𝐶𝑟2 𝑂72−
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:
y 2−
Cr2 O72−
• So that
2 𝑦 + 7 −2 = −2
• Or
𝑦 = +6

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 12

Assigning Oxidation Numbers
Figure 2. The oxidation number of elements in their compounds. Colored
oxidation numbers are more common.
Image source: (Chang & Overby, 2011)

Figure 2 can be summarized as follows:

• Metallic elements have only positive oxidation
numbers, whereas non-metallic elements may
have either positive or negative oxidation
numbers.
• The highest oxidation number an element in
Groups 1A–7A can have is its group number.
For example, the halogens are in Group 7A, so
their highest possible oxidation number is 17.
The transition metals (Groups 1B, 3B–8B)
usually have several possible oxidation
numbers.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 13

Balancing Redox Reactions
• Balancing Redox Equations using Half-reaction method
• Redox reactions can be balanced using the half-reaction method. In this method, the overall
reaction is divided into two half-reactions, one for reduction and another one for oxidation.
The equations are then balanced separately and then added to give the overall balanced
equation.

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Example 2-2
• Example:
• Balance the equation showing the oxidation of 𝐹𝑒 2+ ions to 𝐹𝑒 3+ ions by dichromate ions 𝐶𝑟2 𝑂72−
in an acidic medium.
• Step 1: Write the unbalanced equation for the reaction in ionic form.
𝐹𝑒 2+ + 𝐶𝑟2 𝑂72− → 𝐹𝑒 3+ + 𝐶𝑟 3+
• Step 2: Separate the equation into two half-reactions.
• Oxidation:
• Reduction:
• Step 3: Balance each half-reaction for number and type of atoms and charges. For reactions in an acidic
medium, add H2O to balance the O atoms and H+ to balance the H atoms.
• Oxidation half-reaction:The atoms are already balanced. To balance the charge, we add an electron to the right-hand
side of the arrow:
𝐹𝑒 2+ → 𝐹𝑒 3+ + 𝑒 −
• Reduction half-reaction: Because the reaction takes place in an acidic medium, we add seven H2O molecules to the
right-hand side of the arrow to balance the O atoms:
𝐶𝑟2 𝑂72− → 2𝐶𝑟 3+ + 7𝐻2 𝑂
• To balance the H atoms, we add 14 H1 ions on the left-hand side:
14𝐻 + + 𝐶𝑟2 𝑂72− → 2𝐶𝑟 3+ + 7𝐻2 𝑂
• There are now 12 positive charges on the left-hand side and only six positive charges on the right-hand side. Therefore,
we add six electrons on the left:
14𝐻 + + 𝐶𝑟2 𝑂72− + 6𝑒 − → 2𝐶𝑟 3+ + 7𝐻2 𝑂
Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 15
Example 2-2
• Step 4: Add the two half-reactions together and balance the final equation by inspection. The electrons
on both sides must cancel. If the oxidation and reduction half-reactions contain different numbers of
electrons, we need to multiply one or both half-reactions to equalize the number of electrons. Here we
have only one electron for the oxidation half-reaction and six electrons for the reduction half-reaction, so
we need to multiply the oxidation half-reaction by and write

• The electrons on both sides cancel, and we are left with the balanced net ionic equation:
𝟔𝑭𝒆𝟐+ + 𝟏𝟒𝑯+ + 𝑪𝒓𝟐 𝑶𝟐− 𝟕 → 𝟔𝑭𝒆
𝟑+ + 𝟐𝑪𝒓𝟑+ + 𝟕𝑯 𝑶
𝟐
• Step 5: Verify that the equation contains the same type and numbers of atoms and the same charges on
both sides of the equation.
• A final check shows that the resulting equation is “atomically” and “electrically” balanced.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 16

Balancing Redox Reactions in Basic Medium
• For reactions in a basic medium, we proceed through step 4 as if the reaction
were carried out in an acidic medium.Then, for every H1 ion we add an equal
number of OH- ions to both sides of the equation.Where H+ and OH- ions
appear on the same side of the equation, we combine the ions to give H2O. The
example below shows a reaction in a basic medium:

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 17

Example 2-3
• 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 (MnO2).
• Strategy
• We follow the preceding procedure for balancing redox equations. Note that the reaction takes place in a basic medium.
• Solution
• Step 1: The unbalanced equation is:
𝑀𝑛𝑂4− + 𝐼− → 𝑀𝑛𝑂2 + 𝐼2
• Step 2
• Oxidation:

• Reduction:

• Step 3: We balance each half-reaction for number and type of atoms and charges.
• Oxidation half-reaction:We first balance I atoms:
2𝐼 − → 𝐼2
• To balance charges, we add two electrons to the right-hand side of the equation:
2𝐼 − → 𝐼2 + 2𝑒 −
• Reduction half-reaction:To balance the O atoms, we add two H2O molecules on the right:
𝑀𝑛𝑂4− → 𝑀𝑛𝑂2 + 2𝐻2 𝑂
• To balance the H atoms, we add four H+ ions on the left:
𝑀𝑛𝑂4− + 4𝐻 + → 𝑀𝑛𝑂2 + 2𝐻2 𝑂
• There are three net positive charges on the left, so we add three electrons to the same side to balance the charges:
𝑀𝑛𝑂4− + 4𝐻+ + 3𝑒 − → 𝑀𝑛𝑂2 + 2𝐻2 𝑂

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 18

Balancing Redox Reactions
• Step 4: We now add the oxidation and reduction half reactions to give the overall reaction. 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:
6𝐼 − + 2𝑀𝑛𝑂4− + 8𝐻 + → 3𝐼2 + 2𝑀𝑛𝑂2 + 4𝐻2 𝑂
• 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 an equal number of OH- ions to both sides of the equation:
6𝐼 − + 2𝑀𝑛𝑂4− + 8𝐻 + + 8𝑂𝐻 − → 3𝐼2 + 2𝑀𝑛𝑂2 + 4𝐻2 𝑂 + 8𝑂𝐻 −
• Finally, combining the H+ and OH- ions to form water, we obtain:
𝟔𝑰− + 𝟐𝑴𝒏𝑶− 𝟒 + 𝟒𝑯𝟐 𝑶 → 𝟑𝑰𝟐 + 𝟐𝑴𝒏𝑶𝟐 + 𝟖𝑶𝑯
−

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

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 19

Cell Potentials
• Galvanic Cells
• Or voltaic cell, after the Italian scientists Luigi Galvani and Alessandro Volta, who made
early versions of the device.
• Any electrochemical cell in which a spontaneous chemical reaction can be used to
generate an electric current.
• Salt Bridge
• Contains a strong electrolyte that allows either cations or anions to migrate into the solution where they
are needed to maintain charge neutrality.
• Electrodes
• Electrically conducting sites where either oxidation or reduction occurs.
• Anode
• Electrode where oxidation occurs
• Cathode
• Electrode where reduction occurs

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 20

Galvanic Cells

Figure 3. A galvanic cell set-up. The salt bridge is an essential

component of a galvanic cell. It allows ion flow into each of the
half-cell, therefore, closing the circuit and allowing current to
flow. A wire can carry a current of electrons but cannot
transport ions that are needed to complete the circuit.
Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 21

Cell notation or Cell Diagram
• Cell notation or Cell Diagram
• A shorthand notation for representing the specific chemistry of an electrochemical cell.
• How to write a cell diagram:
• Lists the metals and ions involved in the reaction
• A vertical line, |, denotes a phase boundary, while a double line, ∥, represents a salt bridge.
• The anode is always written on the left and the cathode on the right.
Anode | electrolyte of anode ∥ electrolyte of cathode | cathode
• Example: 𝐶𝑢 𝑠 𝐶𝑢2+ 1𝑀 ∥ 𝐴𝑔+ 𝑎𝑞 1𝑀 𝐴𝑔 𝑠
• Spectator ions are not included in the notation.
• In the example above, we include concentrations of 1 M. They are the assigned concentrations
for the standard state of an electrochemical cell.
• If the electrochemical half-reaction includes the production or consumption of a gas,
the standard state is a pressure of 1 atm.
• A standard state also implies that the electrode material is in its thermodynamic standard state,
which is commonly the case because most electrode materials are solids at room temperature
Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 22
Cell Potentials and Equilibrium

Figure 4. Without a salt bridge to close the circuit, local charges will build up
around both electrodes. Neither electrode reaction can proceed to any
significant extent, so no cell voltage can be measured.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 23

Cell Potentials and Equilibrium
• A system that does not yet have a complete circuit undergoes partial reaction.
• At the anode, some oxidation occurs and cations dissolve into solution, leaving
behind a negative charge on the anode.
• At the cathode, reduction brings positively charged ions to the electrode, and the
result is a build-up of positive charge on that electrode.
• Thus before the circuit is complete, a form of equilibrium is quickly achieved where charge
builds up on the individual electrodes, and it is locally offset by the ions in the solution, as
shown in Figure 4. This equilibrium state at each electrode is considered the half-reaction
equilibrium—but it is not redox equilibrium.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 24

Cell Potential
• Also known as electromotive force (EMF)
• Voltage across the electrodes of a galvanic cell.
• Related to the work that can be done by the electrochemical cell through the equation:
𝑤𝑚𝑎𝑥 = 𝑞𝐸 (1)
• Where:
𝑞 = 𝑐ℎ𝑎𝑟𝑔𝑒 𝑡ℎ𝑎𝑡 ℎ𝑎𝑠 𝑚𝑜𝑣𝑒𝑑 (through 𝑡ℎ𝑒 𝑓𝑙𝑜𝑤 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛);
𝐸 = cell 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 25

Measuring Cell Potential
• Figure 5 shows the following:
• A behavior of cell potentials that is akin to that of a state function.
• It suggests that if we choose a specific standard electrode to which we compare all other
electrodes, we can devise a practical system for determining cell potential.

Figure 5. Measurement of standard cell voltages for different combinations of the

same half-reactions. The results suggest that a characteristic potential can be
associated with a particular half-reaction.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 26

Standard Hydrogen Potential (SHE)
• Choice for the standard component in cell potential measurements
• Composed of a platinum foil or wire as the conducting source of electrons. Hydrogen gas is
bubbled over the electrode at standard pressure, and the electrolyte solution is 1M
HCl(aq). The half-reaction is shown below:
2𝐻 + 𝑎𝑞 + 2𝑒 − → 𝐻2 𝑔
• The half-cell notation is:
𝑃𝑡 𝑠 𝐻2 𝑔, 1𝑎𝑡𝑚 𝐻 + (1𝑀)
• SHE has an assigned cell potential of 0.00 V
• SHE is always connected on the positive terminal of a voltmeter. Therefore, the
sign of the measured potential tells the direction of the redox reaction. When the
measured cell potential is positive, the SHE is the anode, H2 is oxidized to
H+(aq):
𝐻2 𝑔 → 2𝐻 + 𝑎𝑞 + 2𝑒 −
• When the cell potential is negative, the SHE is the cathode, H+ is reduced to H2.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 27

Standard Reduction Potential
• Potential of any half-reaction connected to a
SHE
• Voltage associated with a reduction reaction at an
electrode where all solutes are 1 M and all gases
are at 1 atm.
• Figure 6 shows the standard reduction potentials
at 25oC.

Figure 6. Standard Reduction Potential at 25oC

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 28

Standard Cell Potential
• Also called the standard emf.
• Composed of a contribution from the anode and a contribution from the cathode,
represented by the equation:
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 − 𝐸𝑜𝑥 (2)
or
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 (3)
• In any galvanic cell, the half-reaction with the more positive reduction potential will be the cathode.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 29

Example 2-4
• Copper and iron (generally in the form of steel) are two of the many metals used
in designing machines. (a) Using standard reduction potentials identify the anode
and the cathode and determine the cell potential for a galvanic cell composed of
copper and iron. Assume standard conditions. ( b) We can also construct a
galvanic cell using copper and silver. Confirm that the potential of the following
galvanic cell is 0.462 V:
𝐶𝑢 𝑠 𝐶𝑢2+ 1𝑀 ∥ 𝐴𝑔+ 1𝑀 𝐴𝑔(𝑠)
• Strategy
• We must interpret the nature of an electrochemical system based on the information
available in a table of standard reduction potentials. With two half- reactions there are only
two possible outcomes—and one outcome yields a negative value for the cell potential.
Because we know that a galvanic cell cannot have a negative E° value, we must determine
the combination of half-reactions that provides a positive value for E°.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 30

Example 2-4
• Solution
• Using the data from Figure 6, we find the following half-reactions:
𝐶𝑢2+ 𝑎𝑞 + 𝑒 − → 𝐶𝑢(𝑠) Eo=0.34 V
𝐹𝑒 2+ 𝑎𝑞 + 2𝑒 − → 𝐹𝑒(𝑠) Eo=-0.44 V
• Iron must be oxidized for a combination of these two half-reactions to yield a positive cell
potential:
𝐹𝑒 𝑠 + 𝐶𝑢2+ 𝑎𝑞 → 𝐹𝑒 2+ 𝑎𝑞 + 𝐶𝑢(𝑠) Eocel;=?
• Using the equation:
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜
𝐸𝑐𝑒𝑙𝑙 = 0.34𝑉 − −0.44𝑉 = 0.78 𝑉
• Copper is the cathode in this cell because copper is reduced; iron is the anode because it is
oxidized.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 31

Example 2-4
• For part (b). Find the two half-reactions Figure 6:
𝐴𝑔+ 𝑎𝑞 + 𝑒 − → 𝐴𝑔(𝑠) Eo= 0.80 V
𝐶𝑢2+ 𝑎𝑞 + 2 𝑒 − → 𝐶𝑢(𝑠) Eo= 0.34 V
• From the values of the standard reduction potentials, we can see that copper is oxidized,
and silver is reduced. Using the equation for cell potential, we get:
𝐶𝑢 𝑠 + 2𝐴𝑔+ 𝑎𝑞 → 𝐶𝑢2+ 𝑎𝑞 + 2 𝐴𝑔(𝑠) Eo=0.46 V

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 32

Nonstandard conditions
• When nonstandard conditions are present, the Nernst equation is used to find
the cell potential.
𝑅𝑇 𝑜
𝐸=𝐸 − 𝑙𝑛𝑄 (4)
𝑛𝐹
• Where:
𝑄= reaction quotient
• For a generic reaction:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
𝐶 𝑐 𝐷𝑑
𝑄= 𝑎 𝑏
(5)
𝐴 𝐵
• Where:
𝐽 𝐶
𝐹 = 𝐹𝑎𝑟𝑎𝑑𝑎𝑦 ′ 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 96485 𝑜𝑟 96485
𝑉∙𝑚𝑜𝑙 𝑚𝑜𝑙
8.314𝐽
𝑅 = 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡(
𝑚𝑜𝑙∙𝐾
𝑛 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑟𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑟𝑒𝑑𝑜𝑥 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝑇 = 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 (𝐾)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 33

Example 2-5
• Suppose that you work for a company that designs the drive mechanisms for large ships.
The materials in this mechanism will obviously come into contact with environments
that enhance corrosion. To estimate the difficulties that corrosion might cause, you
decide to build a model electrochemical cell using electrolyte concentrations that might
be present in your system when it is in service. Assume that you have a cell that has an
iron(II) concentration of 0.015 M and an H+ concentration of 1.0 x 10-3 M. The cell
temperature is 38°C, and the pressure of hydrogen gas is maintained at 0.04 atm. What
would the cell potential be under these conditions?
• Strategy
• This problem defines nonstandard conditions that must be addressed using the Nernst equation.
Virtually anytime you are given concentrations of electrolytes present in a cell (other than 1 M), you
need this equation. This problem also presents the challenge of identifying the reactions involved.
Iron will be the anode, but we will need to scan the table of standard reduction potentials to
identify a possible cathode reaction. The most likely suspect is the reduction of H+ to H2. Once we
know both half-reactions, we can calculate the standard cell potential and fill in the appropriate
values in the Nernst equation.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 34

Example 2-5
• Solution
• Anode reaction: 𝐹𝑒 2+ 𝑎𝑞 + 2𝑒 − → 𝐹𝑒 𝑠 Eo=-0.44 V
• Cathode reaction: 2𝐻 + 𝑎𝑞 + 2𝑒 − → 𝐻2 (𝑔) Eo=0.00 V
• The Eo is equal to:
𝐸 𝑜 = 0.00 𝑉 − −0.44𝑉 = 0.44 𝑉
• No. of electrons transferred= 2 e-
• Using the Nernst equation, we get:
𝐽
8.314 311 𝐾 0.015 0.04
𝑚𝑜𝑙 ⋅ 𝐾
𝐸 = 0.44𝑉 − 𝑙𝑛 = 𝟎. 𝟑𝟓 𝑽
𝐽 0.0010 2
2 96485
𝑉 ⋅ 𝑚𝑜𝑙

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 35

Cell Potentials and Free Energy
• In a galvanic cell, work done is electrical work. The relationship between free
energy and the cell potential is expressed as:
∆𝐺 𝑜 = −𝑛𝐹𝐸 𝑜 (6)
• For spontaneous processes:
∆𝐺 𝑜 = − , therefore 𝐸 𝑜 = (+)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 36

Example 2-6
• Suppose that we wish to study the possible galvanic corrosion between zinc and
chromium, so we set up the following cell:
𝐶𝑟 𝑠 |𝐶𝑟 2+ 𝑎𝑞 ∥ 𝑍𝑛2+ 𝑎𝑞 |𝑍𝑛(𝑠)
What is the chemical reaction that takes place, and what is the standard free energy change
for that reaction?
• Strategy
• To calculate the free energy change, we must know two things: the cell potential and the
number of electrons transferred in the reaction. Then we can simply use these values in
Equation 6 to obtain the free energy change.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 37

Example 2-6
• Solution
• First we need the balanced chemical equation, which in this case can be written
immediately because two electrons are transferred in each half-reaction (n=2):
𝑍𝑛2+ 𝑎𝑞 + 𝐶𝑟 𝑠 → 𝐶𝑟 2+ 𝑎𝑞 + 𝑍𝑛(𝑠)
• Now if we look up the standard reduction potentials, we find:
𝑍𝑛2+ 𝑎𝑞 + 2 𝑒 − → 𝑍𝑛 𝑠 𝐸° = −0.76 𝑉
𝐶𝑟 2+ 𝑎𝑞 + 2 𝑒 − → 𝐶𝑟(𝑠) 𝐸° = −0.91 𝑉
• According to Equation 3, the cell potential is:
𝐸°𝑐𝑒𝑙𝑙 = −0.76 𝑉 − −0.910 𝑉 = 0.15 𝑉
• Inserting this in Equation 6,
𝐽
∆𝐺° = −𝑛𝐹𝐸° = − 2 𝑚𝑜𝑙 96,485 0.15 𝑉
𝑉 ⋅ 𝑚𝑜𝑙
𝟒
= −𝟐. 𝟖𝟒 𝒙 𝟏𝟎 𝑱 = −𝟐𝟖. 𝟒 𝒌𝑱

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 38

Equilibrium Constants
• ∆𝑮 is related to the equilibrium constant, K by:
∆𝐺 = −𝑅𝑇𝑙𝑛𝐾 (7)
• The relationship between cell potential and equilibrium constant is given by:
𝑅𝑇
𝐸𝑜 = 𝑙𝑛𝐾 (8)
𝑛𝐹
• Replacing the natural logarithm with common (base 10) logarithm we obtain:
𝑜
2.303𝑅𝑇
𝐸 = 𝑙𝑛𝐾
og (9)
𝑛𝐹
• The factor 2.303 is from ln (10)= 2.303. Because R and F are constants we can further simplify equation 9. Most
experiments are carried out at 25OC (298 K). Simplifying leads to:
𝑜
0.0592 𝑉
𝐸 = log 𝐾 (10)
𝑛
• Rearranging the equation we get: 𝑜𝐸 𝑛
(11)
𝐾= 10 0.0592 𝑉
• Figure 7 shows the variation of equilibrium with cell potential.

Figure 7. The variation of equilibrium constant with cell potential.

Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 39

Batteries
• A battery is a galvanic cell, or a series of combined galvanic cells, that can be used
as a source of direct electric current at a constant voltage.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 40

Primary Cells
• Primary Cells
• Single use batteries that cannot be recharged
• Most prevalent type is alkaline batteries

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 41

Alkaline Batteries
• Alkaline Batteries
• Anode: Zinc electrode, 𝑍𝑛 𝑠 + 2𝑂𝐻 − 𝑎𝑞 → 𝑍𝑛 𝑂𝐻 2 𝑠 + 2𝑒 −
• Cathode: manganese (IV) oxide, 2𝑀𝑛𝑂2 𝑠 + 𝐻2 𝑂 𝑙 + 2𝑒 − → 𝑀𝑛2 𝑂3 𝑠 + 2𝑂𝐻 −
• Combining the two half-reaction yield to a net equation that represents the chemistry of an
alkaline cell battery:
𝑍𝑛 𝑠 + 2𝑀𝑛𝑂2 𝑠 + 𝐻2 𝑂 𝑙 → 𝑀𝑛2 𝑂3 𝑠 + 𝑍𝑛 𝑂𝐻 2 (𝑠)
• The essential design features of an alkaline battery are shown in Figure 8. The electrolyte
used is KOH, but rather than dissolving the electrolyte in liquid water, it is in the form of a
paste or a gel—hence the term dry cell. The MnO2 for the cathode is mixed with graphite
to increase conductivity. The anode is a paste containing powdered zinc. (Powdering the
zinc increases the surface area and improves performance.) The battery case is also
important in the design. Electrons generated by oxidation are collected by a piece of tin-
coated brass connected to the bottom of the battery case. The remainder of the battery
case is in contact with the cathode, but a protrusion on top makes it easier for a consumer
to identify the positive terminal. All of these design elements are used to facilitate the
underlying chemistry that powers the battery.
• Dry cell voltage is about 1.5 V
Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 42
Alkaline Batteries

Figure 8. Construction of a typical alkaline battery

Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 43

Mercury Batteries
• Mercury Batteries
• Used in pacemakers
• Anode: Zinc electrode, 𝑍𝑛 𝑠 + 2𝑂𝐻 − 𝑎𝑞 → 𝑍𝑛 𝑂𝐻 2 𝑠 + 2𝑒 −
• Cathode: mercury(II) oxide, 𝐻𝑔𝑂 𝑠 + 𝐻2 𝑂 𝑙 + 2𝑒 − → 𝐻𝑔 𝑙 + 2𝑂𝐻 − (𝑎𝑞)
• Voltage: ~1.35 V

Figure 9. Mercury Battery (aka zinc-mercuric oxide cell). This cell has a stable voltage output over long periods of time.
Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 44

Zinc-air Batteries
• Zinc-Air batteries
• Single-use, long lasting products for emergency use in cellular phones.
• Anode: Zinc electrode, 𝑍𝑛 𝑠 + 2𝑂𝐻 − 𝑎𝑞 → 𝑍𝑛 𝑂𝐻 2 𝑠 + 2𝑒 −
1
• Cathode: air, 2 𝑂2 𝑔 + 𝐻2 𝑂 𝑙 + 2𝑒 − → 2𝑂𝐻 −
• The oxygen used is obtained from air.
• A challenge in the widespread application of this technology involves environmental factors,
such as humidity, can affect its performance.

Figure 10. Schematic diagram of a zinc-air battery

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 45

Secondary Cells
• Secondary Cells
• Rechargeable batteries

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 46

Nickel-Cadmium Batteries
• Nickel-cadmium Batteries
• Aka ni-cad batteries
• Anode: Cadmium, 𝐶𝑑 𝑠 + 2𝑂𝐻 − 𝑎𝑞 → 𝐶𝑑 𝑂𝐻 2 𝑠 + 2𝑒 −
• Cathode: Complex but can be represented by 𝑁𝑖𝑂 𝑂𝐻 𝑠 + 𝐻2 𝑂 + 𝑒 − → 𝑁𝑖 𝑂𝐻 2 𝑠 + 𝑂𝐻 − (𝑎𝑞)
• Can be recharged many times but is susceptible to performance-decreasing memory effect. Memory effect
involves an inability to use all of the possible chemical energy of the battery unless it is completely discharged.
So successive recharging ultimately results in shorter times before the battery appears to die. The chemistry
that gives rise to this effect involves the formation of a thin layer of material on the electrodes inside the
battery, limiting the oxidation–reduction reaction needed to generate electrical work.

Figure 11. Design features of a nickel-cadmium battery.

Image Source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 47

Nickel-metal-hydride batteries
• Nickel-metal-hydride batteries
• Less prone to memory effect during the life of the battery
• Cathode: Same as nickel-cadmium batteries, 𝑁𝑖𝑂 𝑂𝐻 𝑠 + 𝐻2 𝑂 + 𝑒 − → 𝑁𝑖 𝑂𝐻 2 +
𝑂𝐻 − (𝑎𝑞)
• Anode: 𝑀𝐻 𝑠 + 𝑂𝐻 − 𝑎𝑞 → 𝑀 + 𝐻2 𝑂 + 𝑒 − , wher M stands for some metal or metal
alloy

Figure 12. Design features of a nickel-metal-hydride battery

Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 48

Lead-Acid Storage Batteries
• Lead-acid storage batteries
• The lead storage battery commonly used in automobiles consists of six identical cells
joined together in series. Each cell has a lead anode and a cathode made of lead dioxide
(PbO2) packed on a metal plate. Both the anode and the cathode are immersed in an
aqueous solution of sulphuric acid.
• Anode reaction: 𝑃𝑏 𝑠 + 𝐻𝑆𝑂4− 𝑎𝑞 → 𝑃𝑏𝑆𝑂4 𝑠 + 𝐻 + 𝑎𝑞 + 2𝑒 −
• Cathode reaction: 𝑃𝑏𝑂2 𝑠 + 3𝐻 + 𝑎𝑞 + 𝐻𝑆𝑂4− 𝑎𝑞 + 2𝑒 − → 𝑃𝑏𝑆𝑂4 𝑠 + 2𝐻2 𝑂(𝑙)
• Electrolyte: sulphuric acid
• Under normal operating conditions, each cell produces 2 V; a total of 12 V from the six cells
is used to power the ignition circuit of the automobile and its other electrical systems. The
lead storage battery can deliver large amounts of current for a short time, such as the time
it takes to start up the engine.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 49

Lead-Acid Storage Batteries

Figure 13. Interior of lead storage battery. Under normal operating conditions, the
concentration of the sulfuric acid solution is about 38 percent by mass.
Image source: (Chang & Overby, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 50

Lithium-ion Batteries
• Lithium-Ion batteries
• Used in handheld devices such as cellular phones and tablets
• The advantage of the battery is that lithium has the most negative standard reduction
potential
• Lithium is the lightest metal so that only 6.941 g of Li (its molar mass) are needed to
produce 1 mole of electrons.
• Anode: carbonaceous material (usually graphite) which has tiny spaces in its structure that can hold Li +
ions; 𝐿𝑖 𝑠 → 𝐿𝑖 + + 𝑒 −
• Cathode: made of a transition metal oxide such as CoO2, which can also hold Li+ ions; 𝐿𝑖 + + 𝐶𝑜𝑂2 +
𝑒 − → 𝐿𝑖𝐶𝑜𝑂2 𝑠
• Overall Reaction: 𝐿𝑖 𝑠 + 𝐶𝑜𝑂2 → 𝐿𝑖𝐶𝑜𝑂2 𝑠
• Cell voltage: 3.4 V

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 51

Fuel Cells
• Fuel Cells
• A galvanic cell that requires a continuous supply of reactants to keep functioning.
• Unlike batteries, fuel cells do not store chemical energy. Reactants must be constantly
resupplied, and products must be constantly removed from a fuel cell. In this respect, a fuel
cell resembles an engine more than it does a battery.

Figure 14. A car powered by hydrogen fuel cells manufactured by General Motors
Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 52

Hydrogen-oxygen Fuel Cell
• Hydrogen-oxygen Fuel Cell
• Most common type of fuel cells are based on the reaction of hydrogen and oxygen to
produce water.
• Anodic reaction: 2𝐻2 𝑔 + 4𝑂𝐻 − 𝑎𝑞 → 4𝐻2 𝑂 𝑙 + 4𝑒 −
• Cathodic Reaction: 𝑂2 𝑔 + 2𝐻2 𝑂 𝑙 + 4𝑒 − → 4𝑂𝐻 − 𝑎𝑞
• Overall Reaction: 2𝐻2 𝑔 + 𝑂2 𝑔 → 2𝐻2 𝑂 𝑙
• Standard emf of the cell: 1.23 V

Figure 15. A hydrogen-oxygen fuel cell

Image Source: (Chang & Overby, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 53

Propane-oxygen Fuel Cell
• Propane-oxygen fuel cell
• Anodic reaction: 𝐶3 𝐻8 𝑔 + 6𝐻2 𝑂 𝑙 → 3𝐶𝑂2 𝑔 + 2𝑂𝐻 − 𝑎𝑞 + 20𝑒 −
• Cathodic Reaction: 5O2 g + 2OH − aq + 20e− → 10H2 O(l)
• Overall Reaction: 𝐶3 𝐻8 𝑔 + 5𝑂2 𝑔 → 3𝐶𝑂2 𝑔 + 4𝐻2 𝑂(𝑙)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 54

Electrolysis
• Electrolysis
• is the process of passing an electric current through an ionic solution or molten salt to
produce a chemical reaction
• Cathode: Negatively charged, reduction site
• Anode: Positively charged, oxidation site
• Passive electrolysis
• electrodes are chemically inert materials that simply provide a path for electrons
• Application: Production of aluminium [Read more from (Brown & Holme, 2011)]
• Active electrolysis
• electrodes are part of the electrolytic reaction
• Application: electroplating or the process of depositing a thin coat of metal by using
electricity.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 55

Electrolysis

Figure 16. Electrolysis set-up

Image source: (Brown & Holme, 2011)

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 56

Electrolysis and Stoichiometry
• Current and Charge
• Current
• Flow of charge per unit time
• Charge
• If a known current is flowing through a circuit for a known time, charge can be calculated using:
𝐶ℎ𝑎𝑟𝑔𝑒 = 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑥 𝑡𝑖𝑚𝑒
𝑄 = 𝐼𝑡 (12)
• Where: Q is in coulombs, I is in amperes.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 57

Example 2-7
• In a process called flash electroplating, a current of 2.50 x 10 3 A passes through
an electrolytic cell for 5.00 minutes. How many moles of electrons are driven
through the cell?
• Strategy
• Because we know both the current and the time for which it was applied, we can use the
relationship between charge and current in Equation 12 to obtain the charge. Then
Faraday’s constant will let us convert that charge into moles of electrons. We must be
careful with units, however, because the ampere is charge per second and time is given here
in minutes.
• Solution:
𝑄 = 2500𝐴 300𝑠 = 7.5𝑥105 𝐶
• Now use Faraday’s Constant:
−
1𝑚𝑜𝑙 𝑒
7.5𝑥105 𝐶 = 𝟕. 𝟕𝟕 𝒎𝒐𝒍 𝒆−
96485 𝐶
Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 58
Electrolysis and Stoichiometry
• Rate of Power
• Electrical power is the rate of electricity consumption. Utility charges are based on
consumption. SI unit for power is watts:
𝐽
1 𝑤𝑎𝑡𝑡 = 1
𝑠
• To determine the amount of energy used, we multiply the rate of power by the time during
which it occurs. Electrical utilities usually use kilowatt-hours (kWh) to determine energy
consumption. One kilowatt-hour is equal to 3.6x106 J. One J is equal to 1 C-V.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 59

Example 2-8
• Suppose that a batch of parts is plated with copper in an electrolytic bath running at 0.15 V and
15.0 A for exactly 2 hours. What is the energy cost of this process if the electric utility charges
the company $0.0500 per kWh?
• Strategy
• We can determine the energy expended because we know the current, time, and voltage. The current
multiplied by the time gives us the charge, which when multiplied by the voltage yields the energy. Once we
know the energy expenditure we can convert the value we calculate (in J) to kWh to obtain the cost of the
electricity.
• Solution
𝐶
𝑄 = 𝐼𝑡 = 15.0 7200 𝑠 = 1.08𝑥105 𝐶
𝑠
𝐸𝑛𝑒𝑟𝑔𝑦 = 𝑐ℎ𝑎𝑟𝑔𝑒 𝑥 𝑣𝑜𝑙𝑡𝑎𝑔𝑒 = 1.08 𝑥 105 𝐶 𝑥 0.15 𝑉 = 1.6 3 104 𝐽
• Now convert to kWh and determine the cost
4
1𝑘𝑊ℎ $0.05
1.6𝑥10 𝐽 = $𝟎. 𝟎𝟎𝟎𝟐𝟑
3.6𝑥106 𝐽 1𝑘𝑊ℎ
• Analyze Your Answer
• This value seems small—but does it make sense? Two factors contribute to the small result: a kilowatt-hour is
a rather large energy unit, and the cost per kWh is low. Thus a very small cost is not problematic. This low
cost point to the importance of running electroplating at low voltage: increasing voltage would lead directly to
higher cost.
Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 60
Example 2-9
• Calculations Using Masses of Substances in Electrolysis
• An electrolysis cell that deposits gold (from Au (aq)) operates for 15.0 minutes at a current
1

of 2.30 A. What mass of gold is deposited?

• Strategy
• As in any stoichiometry problem we need a balanced chemical equation, so we will start by
writing the half-reaction for gold reduction. To determine the mass of gold deposited, we
must calculate the number of moles of electrons used from the current and the time. We
can use the half-reaction to obtain a mole ratio and convert moles of electrons into moles
of gold. Once we have moles of gold, we convert to mass using the molar mass, as we have
done many times in stoichiometry problems.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 61

Example 2-9
• Solution
• First write the balanced half-reactions:
𝐴𝑢+ 𝑎𝑞 + 𝑒 − → 𝐴𝑢 𝑠
• Next calculate moles of electrons based on current and time:
𝐶
𝑄 = 𝐼𝑡 = 2.30 900𝑠 = 2.07𝑥103 𝐶
𝑠
1𝑚𝑜𝑙𝑒 −
2.07𝑥103 𝐶 = 2.15𝑥10−2 𝑚𝑜𝑙 𝑒 −
96485 𝐶
• Now we note that the mole ratio of electrons to gold is 1:1, which means that we also have
2.15x10-2 mol of Au.
𝑔
2.15𝑥10−2 𝑚𝑜𝑙 𝐴𝑢 197 = 𝟒. 𝟐𝟑𝒈 𝑨𝒖
𝑚𝑜𝑙

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 62

Example 2-10
• Suppose that you have a part that requires a tin coating. You’ve calculated that you need
to deposit 3.60 g of tin to achieve an adequate coating. If your electrolysis cell (using
𝑆𝑛2+ ) runs at 2.00 A, how long must you operate the cell to obtain the desired coating?
• Strategy
• This problem is different from the last one because it requires that we use the balanced half-
reaction to relate moles of electrons and moles of a desired substance, in this case tin. Because we
are given a mass of tin required, we can obtain the moles of tin, and that will tell us the moles of
electrons required. We then determine the charge of those electrons with the Faraday constant, and
we can use our understanding of electricity to get the time needed at the given current.
• Solution
𝑆𝑛2+ 𝑎𝑞 + 2 𝑒 − → 𝑆𝑛(𝑠)
1𝑚𝑜𝑙 𝑆𝑛 2 𝑚𝑜𝑙𝑒 − 96485 𝐶 3
3.60 𝑔 𝑆𝑛 = 5.85𝑥10 𝐶
118.7 𝑔 𝑆𝑛 1 𝑚𝑜𝑙 𝑆𝑛 1 𝑚𝑜𝑙 𝑒 −
• Now recall that Q=It, so t=Q/I
5.85𝑥103 𝐶
𝑡= = 2930 𝑠 = 𝟒𝟖. 𝟖 𝒎𝒊𝒏
𝐶
2.00 𝑠

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 63

Further Readings
• Further readings on corrosion prevention: (Brown & Holme, 2011) pages
465-466

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 64

References
• Brown, L. S., & Holme, T. A. (2011). Chemistry for Engineering Students, 2nd Edition.
California: Brooks/Cole, Cengage Learning.
• Chang, R., & Overby, J. (2011). General Chemistry The Essential Concepts 6th edition.
New York City: McGraw-Hill.

Chemistry for Engineers 2 - Electrochemistry - Week 3 - Topic 2 65