CHE 001 (Chemistry for Engineers) – Lecture Series

Electrochemical Energy: Fundamentals

and Applications
Carlos Miguel Dacaimat, Ch. E.
September 2023
 Topic Outline
1. Introduction: Electrochemistry
2. Redox Reactions
3. Voltaic Cells
4. Standard Reduction Potentials
5. Thermodynamics of Redox Reactions
6. The Effect of Concentration of Cell EMF
7. Batteries and Fuel Cells
8. Corrosion
9. Electrolysis
 Introduction: Electrochemistry

• Electrochemistry is the branch of chemistry that deals with the

interconversion of electrical energy and chemical energy.

• Electrochemical processes are redox (oxidation-reduction)

reactions in which the energy released by a spontaneous reaction
is converted to electricity or in which electrical energy is used to
cause a nonspontaneous reaction to occur.
 Redox Reactions

• Acid-base reactions can be characterized as proton-transfer

processes.
• Redox (Reduction-Oxidation) reactions can be characterized as
electron-transfer processes.

One atom LOSING e- (OXIDATION)

REDOX
REACTIONS
One atom GAINING e- (REDUCTION)
 Redox Reactions
One atom LOSING e- (OXIDATION)

REDOX
REACTIONS
One atom GAINING e- (REDUCTION)

OIL RIG
OXIDATION is REDUCTION is GAIN
LOSS (of electrons) (of electrons)
 Half-Reactions

• Half-reactions are reactions which explicitly shows the electrons

involved in a redox reaction.

HALF- REACTIONS

OXIDATION REDUCTION
REACTION REACTION
 Half-Reactions

Example: Synthesis of Magnesium Oxide by Burning Elemental

Magnesium in Pure Oxygen

2 Mg(s) + O2(g) → 2 MgO(s)

 Half-Reactions

2 Mg(s) + O2(g) → 2 MgO(s)

2 Mg → 2 Mg2+ + 4e- O2 + 4e- → 2 O2-

Each of the reaction steps is called the half-reaction.
 Half-Reactions
2 Mg → 2 Mg2+ + 4e-

O2 + 4e- → 2 O2-
The sum of the half-reactions gives the overall reaction.
2 Mg + O2 + 4e- → 2 Mg2+ + 4e- + 2 O2-
2 Mg + O2 → 2 Mg2+ + 2 O2-
Then the Mg2+ and O2- ions combine to form MgO.

2 Mg(s) + O2(g) → 2 MgO(s)

Half-Reactions: Oxidation & Reduction Reactions

• Oxidation Reaction refers to the half-reaction that involves loss

of electrons.
• Reduction Reaction refers to the half-reaction that involves gain
of electrons.
2 Mg(s) + O2(g) → 2 MgO(s)

2 Mg → 2 Mg2+ + 4e- O2 + 4e- → 2 O2-

OXIDATION REDUCTION
REACTION REACTION
Half-Reactions: Oxidizing & Reducing Agents

• Oxidizing Agents refer to the atoms that accepts e-

• Reducing Agents refer to the atoms that donates e-

2 Mg → 2 Mg2+ + 4e-

REDUCING
AGENT
O2 + 4e- → 2 O2-

OXIDIZING
AGENT
Half-Reactions: Oxidizing & Reducing Agents

Example. Given the reaction:

Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu (s)

1. Write the half-reactions.

2. Identify the oxidation and reduction reactions.
3. Identify the oxidizing and reducing agents.
 Oxidation Number

• To keep track of electrons in redox reactions, it is useful to assign

oxidation numbers to the reactants and products.
• An atom’s oxidation number (oxidation state) signifies the
number of charges the atom would have in a molecule (or an
ionic compound) if electrons were transferred completely.
• The oxidation numbers reflect the number of electrons
“transferred.”
• Oxidation numbers enable us to identify elements that are
oxidized and reduced at a glance.
2 Mg → 2 Mg2+ + 4e- O2 + 4e- → 2 O2-
Rules in Assigning Oxidation Number

1. In free elements (that is, in the uncombined state),

each atom has an oxidation number of zero.

H2, Br2, Na, Be, K, O2

Rules in Assigning Oxidation Number

2. For ions composed of only one atom (that is,

monatomic ions), the oxidation number is equal to
the charge on the ion.

Li+, Ba2+, O2-

Rules in Assigning Oxidation Number

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.
LiH, NaH, CaH2
Rules in Assigning Oxidation Number

5. Halogens (F, Cl, Br, I) have negative oxidation

numbers when they occur as halide ions in their
compounds. When combined with oxygen (in
oxoacids and oxoanions), they have oxidation
numbers

ClO4-, OCl-, OClO2-

Rules in Assigning Oxidation Number

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.

Example: NH4+, MnO4- , Cr2O72-

 Oxidation Number: Summary

Metallic elements have only positive oxidation numbers, whereas

nonmetallic 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.
The transition metals (Groups 1B, 3B–8B) usually have several
possible oxidation numbers.
Half-Reactions: Oxidizing & Reducing Agents

Example. Determine the oxidation numbers of the atom specified:

1. Al in AlBr3
2. P in H3PO4
3. Cr in K2CrO4
4. N in NH52+
5. Pt in PtCl62-
6. Sb in SbF6-
Balancing Redox Reactions: Ion-Electron Method

• In principle, we can balance any redox equation using the

procedure based on law of conservation of mass.
• Balancing redox reactions can be done using special techniques
that gives insight into electron transfer processes.
• Ion-Electron Method is a technique in which the overall reaction
is divided into two half-reactions, one for oxidation and one for
reduction. The equations for the two half-reactions are balanced
separately and then added together to give the overall balanced
equation.
Steps in Balancing Redox Equations using
Ion-Electron Method

Step 1: Write the unbalanced equation for the reaction in ionic form.
Step 2: Separate the equation into two half-reactions.
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.
Step 4: Add the two half-equations 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.
Step 5: Verify that the equation contains the same type and numbers of
atoms and the same charges on both sides of the equation.
Steps in Balancing Redox Equations using
Ion-Electron Method

Additional Notes:
1. For reactions in a basic medium, proceed through step 4 as if
the reaction were carried out in a acidic medium. Then, for every
H+ 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 H 2O.
Steps in Balancing Redox Equations using
Ion-Electron Method

Example. Balance the equation showing the oxidation of Fe 2+ ions

to Fe3+ ions by dichromate ions (Cr2O72-) in an acidic medium.
Steps in Balancing Redox Equations using
Ion-Electron Method

Example. Br2 → BrO3- + Br - (in basic solution)

Example. S2O32- + I2 → I- + S4O62- (in acidic solution)

S2O32- + I2 → I- + S4O62-

2 S2O32- → S4O62- + 2 e-
2 e-+ I2 → 2 I-

2 S2O32- + I2 → S4O62- + 2 I-
Voltaic Cells: Introduction
Voltaic Cells: Introduction
 Voltaic Cells: Introduction
The electrons are transferred directly from the reducing agent (Zn)
to the oxidizing agent (Cu2+) in solution.
If we physically separate 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.
 Voltaic Cells: Introduction
The experimental apparatus for generating 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.
Voltaic Cells: Components
 Voltaic Cells: Components
ELECTRODE

ANODE CATHODE

SALT
BRIDGE
 Voltaic Cells: Components
Electrodes – metal bars where oxidation and reduction takes
place separately and simultaneously with the transfer of electrons
between them occurring through an external wire.
ELECTRODES

ANODE CATHODE
(OXIDATION) (REDUCTION)
Salt Bridge – a tube containing an inert electrolyte solution whose
ions will not react with other ions
 Voltaic Cells: Principle of Operation

• The cell operates on the principle that the oxidation and the
reduction can be made to take place simultaneously in separate
locations with the transfer.
• 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,
• During the course of the overall redox reaction, electrons flow
externally from the anode through the wire to the cathode.
• In the solution, the cations move toward the cathode, while the
anions move toward the anode.
 Voltaic Cells: Principle of Operation

• An electric current flows from the anode to the cathode because

there is a difference in electrical potential energy between the
electrodes.
• The difference in electrical potential between the anode and the
cathode is measured as a cell voltage or cell potential.
 Voltaic Cells: Principle of Operation

• 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.
 Voltaic Cells: Cell Diagram

Cell Diagram is the conventional notation for representing voltaic

cells

Representation:
Anode | Cation || Anion | Cathode
 Voltaic Cells: Cell Diagram

Example:
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)
ANODE

CATHODE
 Standard Electrode Potential
The driving force behind the spontaneous reaction in a voltaic cell is measured
by the cell potential (or voltage).
Cell Voltage which is an intensive property, independent of the number of
electrons passing through the cell.
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.
 Standard Electrode Potential

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.
 Standard Electrode Potential

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.
 Standard Electrode Potential

The hydrogen electrode, shown below, serves as the

reference for this purpose. Hydrogen gas is bubbled into a
hydrochloric acid solution at 25°C. The platinum electrode
has two functions.
1. It provides a surface on which the
dissociation of hydrogen molecules can
take place.
2. It serves as an electrical conductor to
the external circuit.
 Standard Electrode Potential

• The superscript “°” denotes standard-state conditions,

and E° is the standard reduction potential,
• Standard Reduction Potential is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.
 Standard Electrode Potential

Under standard-state conditions (when the pressure of H2

is 1 atm and the concentration of the HCl solution is 1 M;),
the potential for the reduction of H+ at 25°C is taken to be
exactly zero:
Standard Electrode Potential: Standard Hydrogen
Electrode
The standard reduction potential of the hydrogen electrode
is defined as zero.
The hydrogen electrode is called the standard hydrogen
electrode (SHE).
 Standard Electrode Potential: How other
electrodes is measured?
We can use the SHE to measure the potentials of other
kinds of electrodes.
 Standard Electrode Potential: How other
electrodes is measured?
Zn = Anode
SHE (or H) = Cathode

Cell Diagram:
 Standard Electrode Potential: How other
electrodes is measured?

Standard EMF of the Cell (EcellO)

 Standard Electrode Potential: How other
electrodes is measured?

Standard EMF of the Zn-H2

𝐸𝑍 ¿
𝑛 =− 0.76 𝑉 ¿
 Standard Electrode Potential: How other
electrodes is measured?
Cu = Electrode
SHE (or H) = Anode

Cell Diagram:
 Standard Electrode Potential: How other
electrodes is measured?

Standard EMF of the Cell (EcellO)

 Standard Electrode Potential: How other
electrodes is measured?

Standard EMF of the Zn-H2

𝐸𝑍 ¿
𝑛 =+ 0.34 𝑉 ¿
Standard Electrode Potential: How Standard EMF
of a Cell is Measured?

Standard EMF of the Zn-Cu Cell:

𝑂
𝐸 𝑐𝑒𝑙𝑙 =+1.10 𝑉
Standard Electrode Potential: How Standard EMF
of a Cell is Measured?
Standard Electrode Potential for Half-Cell
Reactions
The table below shows the list of standard reduction
potentials for a number of half-cell reactions.
SHE has an EO value of 0.00 V
Standard Electrode Potential for Half-Cell
Reactions
Standard Electrode Potential for Half-Cell
Reactions
Standard Electrode Potential for Half-Cell
Reactions
Standard Electrode Potential for Half-Cell
Reactions
Standard Electrode Potential for Half-Cell
Reactions
 Standard Electrode Potential: Key Points

1. The E° values apply to the half-cell reactions as read in

the forward (left to right) direction.
2. The more positive E° is, the greater the tendency for
the substance to be reduced.
STRONGEST
OXIDIZING AGENT
WEAKEST OXIDIZING
AGENT
 Standard Electrode Potential: Key Points

3. The half-cell reactions are reversible. Depending on the

conditions, any electrode can act either as an anode or as
a cathode.
 Standard Electrode Potential: Key Points

4. 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. (Diagonal Rule)
 Standard Electrode Potential: Key Points

5. Changing the stoichiometric coefficients of a half-cell

reaction does not affect the value of E° because electrode
potentials are intensive properties.
 Standard Electrode Potential

Example. A galvanic cell consists of a Mg electrode in a 1.0 M

Mg(NO3)2 solution and a silver (Ag) electrode in a 1.0 M AgNO 3
solution. Calculate the standard EMF of the cell.
 Standard Electrode Potential

Example. Calculate the standard emf of a cell that uses the

Mg/Mg2+ and Cu/Cu2+ half-cell reactions at 25°C. Write the equation
for the cell reaction that occurs under standard-state conditions.
 Standard Electrode Potential

Example. What is the standard EMF of a galvanic cell made of a

Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr electrode in a
1.0 M Cr(NO3)3 solution at 25OC?
Thermodynamics of Redox Reactions: Introduction

Ecello is related to thermodynamic quantities such as ΔGo and K.

ΔG = Standard Gibbs Energy
K = equilibrium constant

Recall for ΔG :
1. Standard Gibbs Energy is known to be the “free energy” or the energy available to do work.
2. Gibbs Energy is a thermodynamic quantity used to express the spontaneity of a reaction

ΔG = 0 (at equilibrium)
ΔG < 0 (spontaneous in the forward direction) A+B↔C+D
ΔG > 0 (nonspontaneous in the forward direction,
spontaneous in the backward direction)
Thermodynamics of Redox Reactions: Introduction
the rate of the
chemical reaction is directly
Ecello is related to thermodynamic quantities such as ΔGo and
proportional K.product of
to the
the activities or concentrations
of the reactants.
ΔGo = Standard Gibbs Energy
K = equilibrium constant

Recall for K:
1. K is the mathematical expression for the law of mass action.
2. K denotes that for a reversible reaction at equilibrium and constant temperature, a certain ratio of
reactant and product concentrations has constant value.

K > 1 (the equilibrium will favor the product)

A+B↔C+D
K < 1 (the equilibrium will favor the reactant)
Thermodynamics of Redox Reactions: Introduction
Thermodynamics of Redox Reactions: Introduction

Electrical Energy from Chemical Energy

In a voltaic cell, chemical energy is converted into electrical energy

to do electrical work such as running an electric motor, circuits.
Electrical Energy can be quantified as the product of the EMF of
the cell and the total electrical charge (in coulombs) that passes
through the cell.
Electrical Energy = Coulombs x Volts
= Joules
Thermodynamics of Redox Reactions: Introduction

Electrical Energy from Chemical Energy

The total charge is determined by the number of electrons through

the cell.
Total Charge = no. of e- × charge of one e-
= Joules
 Thermodynamics of Redox Reactions: Faraday’s
Constant
Total Charge as a Molar Quantity

The charge of one mole of electrons is called Faraday’s constant.

Recall:
1 mol e- = 6.022 x 1023 e-
charge of e- = 1.602 x 10-19 C

1 F = no. of e- × charge of one e-

1 F = 6.022 x 1023 e- / mol e- × 1.602 x 10-19 C/e-
1 F = 96,500 C/mol e-
Thermodynamics of Redox Reactions: Faraday’s
Constant
Total Charge as a Molar Quantity

The total charge can now be expressed as nF, where n is the

number of moles of electrons exchanged between the oxidizing
agent and reducing agent in the overall redox equation for the
electrochemical process.
 Thermodynamics of Redox Reactions

Maximum Work Done by the Cell

The measured emf (E ) is the maximum voltage the cell can
cell

achieve. Therefore, the electrical work done, w , which is the

ele

maximum work that can be done (w ), is given by the product of

max

the total charge and the emf of the cell:

Note:
1. The negative sign indicates that the electrical work is done by the
system (cell) on the surroundings.
 Thermodynamics of Redox Reactions

Gibbs Energy and Electrical Work

Since ΔG represents the maximum amount of useful work that
can be obtained in a reaction, then:

Therefore, we can write:

𝚫 𝐆=− 𝐧𝐅𝐄𝐜𝐞𝐥𝐥
 Thermodynamics of Redox Reactions

Gibbs Energy and Standard Gibbs Energy

Standard Gibbs Energy represents the reactions for which reactant
and products are in their standard states (1 M or 1 atm):
𝚫 𝐆𝐨 =− 𝐧𝐅𝐄𝐨𝐜𝐞𝐥𝐥 (Standard Gibbs Energy)
 Thermodynamics of Redox Reactions

Relationship between Standard EMF and K

The relationship of and K can be written as:
o
Δ G =− 𝑅𝑇 𝑙𝑛 𝐾 R = 8.314 J/mol-K
Since , it follows that:
𝑜
−𝑛𝐹 𝐸𝑐𝑒𝑙𝑙 =− 𝑅𝑇 𝑙𝑛 𝐾

Solving for , the obtained equation is:

𝑜 𝑅𝑇
𝐸 𝑐𝑒𝑙𝑙 = 𝑙𝑛 𝐾
𝑛𝐹
 Thermodynamics of Redox Reactions

Relationship between Standard EMF and K

When T = 298 K, R = 8.314 J/mol-K, F = 96,500 C/mol or J/V-mol:

𝐸
𝑜
=
( 8.314
𝐽
𝑚𝑜𝑙 − 𝐾 )
( 298 𝐾 )
𝑙𝑛 𝐾
𝑐𝑒𝑙𝑙
𝐽
𝑛 (96,500 )
𝑉 − 𝑚𝑜𝑙
𝒐 ( 𝟎 . 𝟎𝟐𝟓𝟕 𝑽 )
𝑬 𝒄𝒆𝒍𝒍 = 𝒍𝒏 𝑲
𝒏
 Thermodynamics of Redox Reactions

Relationship between Standard EMF and K

𝒐 ( 𝟎 . 𝟎𝟐𝟓𝟕 𝑽 )
𝑬 𝒄𝒆𝒍𝒍 = 𝒍𝒏 𝑲
𝒏

E = non-standard condition cell EMF

E0 = standard condition cell EMF
R = ideal gas constant = 8.314 J/mol-K
F = 96,500 C/mol = Faraday’s Constant
n = no. of moles of electrons exchanged between oxidizing and
reducing agent in the overall redox equation
K = Equilibrium Constant
 Thermodynamics of Redox Reactions

Example. Calculate the equilibrium constant for the following

reaction at 25oC:
+¿ (𝑎𝑞 ) ¿
2 +¿ + 2 𝐶 𝑢 ¿
2+¿ ⇌ 𝑆 𝑛 ¿
𝑆𝑛 ( 𝑠 ) + 2 𝐶 𝑢

Also calculate the standard Gibbs Energy Change for the given reaction.
 Thermodynamics of Redox Reactions

Example. Calculate the standard free-energy change and K c for

the following reactions at 25oC:
2+ ¿ + 𝑃𝑏 ( 𝑠) ¿
2+ ¿ ( 𝑎𝑞) ⇌ 𝑀𝑔 ¿
𝑀 𝑔 (𝑠 )+ 𝑃 𝑏
 Thermodynamics of Redox Reactions

Example. Calculate the standard free-energy change for the

following reaction at 25oC:
3 +¿ + 3 𝐶𝑎( 𝑠) ¿
2 +¿ ( 1.0 𝑀 ) ⇌ 2 𝐴 𝑢 ¿
2 𝐴𝑢 ( 𝑠 ) + 3 𝐶 𝑎
 Thermodynamics of Redox Reactions

Example. What is the equilibrium constant for the following

reaction at 25°C?
 Thermodynamics of Redox Reactions

Example. The equilibrium constant for the reaction

is 2.69 x 1012 at 25°C. Calculate E° for a cell made is up of Sr/Sr2+ and

Mg/Mg2+ half-cells.
The Effect of Concentration on Cell EMF: Introduction

• Standard-State conditions are often difficult, and sometimes

impossible, to maintain.
• Hence, most reactions occur in a non-standard state conditions.
• The relationship presented previous are not applicable.
The Effect of Concentration on Cell EMF: Introduction

The Nernst Equation

For a non-standard state Gibbs Energy it can be written as:
𝑂
Δ 𝐺=Δ 𝐺 + 𝑅𝑇 ln 𝑄
Because and , it follows that:
𝑜
−𝑛𝐹𝐸=−𝑛𝐹 𝐸 +𝑅𝑇 ln𝑄
Solving for E, we get:

𝑹𝑻
𝒐
𝑬 =𝑬 − 𝐥𝐧 𝑸
𝒏𝑭
 The Effect of Concentration on Cell EMF

The Nernst Equation

𝑹𝑻
𝒐
𝑬 =𝑬 − 𝐥𝐧 𝑸
𝒏𝑭
E = non-standard condition cell EMF
E0 = standard condition cell EMF
R = ideal gas constant = 8.314 J/mol-K
F = 96,500 C/mol = Faraday’s Constant
n = no. of moles of electrons exchanged between oxidizing and
reducing agent in the overall redox equation
Q = reaction quotient
 The Effect of Concentration on Cell EMF

Recall: Reaction Quotient

𝒄 𝒅
[𝑪] [𝑫]
𝑸= 𝒂 𝒃
[ 𝑨] [ 𝑩]
Given a chemical reaction: aA + bB cC + dD
[A], [B], [C], [D] = concentration
a, b, c, d = stoichiometric coefficients
 The Effect of Concentration on Cell EMF

Example. Predict whether the following reaction would proceed

spontaneously as written at 298 K:
2+ ¿ ( 𝑎𝑞)+ 𝐹𝑒 ( 𝑠) ¿
2+ ¿ ⇌ 𝐶𝑜 ¿
𝐶𝑜 ( 𝑠 ) + 𝐹𝑒

Given that [Co2+] = 0.15 M and [Fe2+] = 0.68 M. Also calculate the
Gibbs Energy Change for the given reaction.
 The Effect of Concentration on Cell EMF

Example. What is the potential of a cell made up of Zn/Zn 2+ and

Cu/Cu2+ half-cells at 25°C if [Zn2+] = 0.25 M and [Cu2+] = 0.15 M?
 Batteries and Fuel Cells: Introduction

• 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.
• A battery has the advantage of being completely self-contained
and requiring no auxiliary components such as salt bridges..
 Batteries and Fuel Cells

1. Dry Cell (Leclanche) Battery

2. The Mercury Battery
3. The Lead Storage Battery
4. Lithium Ion Battery
 Batteries and Fuel Cells: Dry Cells

• A dry cell battery is a cell that has no fluid component.

• The most common dry cell is the Leclanche Battery which is
commercially used powering lights, radios, and circuits.
 Batteries and Fuel Cells: Dry Cells

• The anode of the cell consists of a zinc can or container that is in contact
with manganese dioxide (MnO2) and an electrolyte.
• The electrolyte consists of ammonium chloride and zinc chloride in water, to
which starch is added to thicken the solution to a paste-like consistency so
that it is less likely to leak.
• A carbon rod serves as the cathode, which is immersed in the electrolyte in
the center of the cell.
• The voltage produced by a dry cell is about 1.5 V
Batteries and Fuel Cells: Dry Cells
Batteries and Fuel Cells: Dry Cells
 Batteries and Fuel Cells: Mercury Battery

• The mercury battery is used extensively in medicine and electronic industries

and is more expensive than the common dry cell.
• It is contained in a stainless steel cylinder, the mercury battery consists of a
zinc anode (amalgamated with mercury) in contact with a strongly alkaline
electrolyte containing zinc oxide and mercury(II) oxide.
• There is no change in electrolyte composition during operation.
• The overall cell reaction involves only solid substances—the mercury battery
provides a more constant voltage (1.35 V) than the Leclanché cell.
• It also has a considerably higher capacity and longer life. These qualities
make the mercury battery ideal for use in pacemakers, hearing aids, electric
watches, and light meters.
Batteries and Fuel Cells: Mercury Battery
 Batteries and Fuel Cells: Lead Storage Battery

• 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 cathode and the anode are
immersed in an aqueous solution of
sulfuric acid, which acts as the
electrolyte.
Batteries and Fuel Cells: Lead Storage Battery
 Batteries and Fuel Cells: Lead Storage Battery

• 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.
• The lead storage battery is rechargeable.
• Recharging the battery means reversing the
normal electrochemical reaction by applying an
external voltage at the cathode and the anode.
(electrolysis)
 Batteries and Fuel Cells: Lead Storage Battery

Operations
• The electrochemical reaction consumes
sulfuric acid, the degree to which the battery
has been discharged can be checked by
measuring the density of the electrolyte with a
hydrometer, as is usually done at gas stations.
• The density of the fluid in a “healthy,” fully
charged battery should be equal to or greater
than 1.2 g/mL.
• For a lead storage battery, the temperature
coefficient is about 1.5 x 10-4 V/°C; that is,
there is a decrease in voltage of 1.5 x 10-4 V for
every degree drop in temperature.
Batteries and Fuel Cells: Lead Storage Battery
 Batteries and Fuel Cells: Lithium Ion Battery

• The anode is made of a

conducting carbonaceous
material, usually graphite,
which has tiny spaces in its
structure that can hold both Li
atoms and Li+ ions.
• The cathode is made of a
transition metal oxide such as
CoO2, which can also hold Li+
ions.
Batteries and Fuel Cells: Lithium Ion Battery
 Batteries and Fuel Cells: Lithium Ion Battery

• The advantage of the battery is that

lithium has the most negative standard
reduction potential and hence the
greatest reducing strength.
• Lithium is the lightest metal so that only
6.941 g of Li (its molar mass) are
needed to produce 1 mole of electrons.
• A lithium-ion battery can be recharged
literally hundreds of times without
deterioration.
• These desirable characteristics make it
suitable for use in cellular telephones,
digital cameras, and laptop computers.
 Batteries and Fuel Cells: Fuel Cells

• Fuel Cell is a galvanic cell that requires a continuous supply of

reactants to keep functioning.
Batteries and Fuel Cells: Fuel Cells
 Batteries and Fuel Cells: Fuel Cells

• Unlike batteries, fuel cells do not store

chemical energy.
• Reactants must be constantly
resupplied, and products must be
constantly removed from a fuel cell.
• A fuel cell resembles an engine more
than it does a battery.
• However, the fuel cell does not operate
like a heat engine and therefore is not
subject to the same kind of
thermodynamic limitations in energy
conversion
 Corrosion

• Corrosion is the term usually applied to the deterioration of metals by an

electrochemical process.
 Corrosion: Mechanism

Formation of Rust
 Corrosion: Mechanism

Formation of Rust
A region of the metal’s surface serves as the anode, where oxidation
occurs:
 Corrosion: Mechanism

Formation of Rust
The electrons given up by iron reduce atmospheric oxygen to water at
the cathode, which is another region of the same metal’s surface:

The overall redox reaction is:

This reaction occurs in an acidic medium; the H + ions are supplied in

part by the reaction of atmospheric carbon dioxide with water to form
H2CO3.
 Corrosion: Mechanism

Formation of Rust
The Fe2+ ions formed at the anode are further oxidized by oxygen:

The product Fe2O3 . x H2O is known as the rust.

 Electrolysis: Introduction

• Electrolysis is the process in which electrical energy is used to

cause a nonspontaneous chemical reaction to occur.
• Electrolytic cell is an apparatus for carrying out electrolysis.
 Electrolysis: Illustration

Electrolysis of Water
• Water in a beaker under atmospheric
conditions (1 atm and 25°C) will not
spontaneously decompose to form
hydrogen and oxygen gas because the
standard free-energy change for the
reaction is a large positive quantity.
 Electrolysis: Illustration

Electrolysis of Water
• This electrolytic cell consists of a pair of
electrodes made of a nonreactive metal,
such as platinum, immersed in water.
When the electrodes are connected to
the battery, nothing happens because
there are not enough ions in pure water
to carry much of an electric current.
• (Recall: at 25°C, pure water has only 1 x
10-7 M H+ ions and 1 x 10-7 M OH- ions.)
 Electrolysis: Illustration
The reaction occurs readily in a 0.1 M H2SO4 solution
because there are a sufficient number of ions to
conduct electricity. Immediately, gas bubbles begin to
appear at both electrodes.
 Electrolysis: Illustration
Overall Reaction:
 Electrolysis: Quantitative Aspects

Electrolysis of Water
• Water in a beaker under atmospheric
conditions (1 atm and 25°C) will not
spontaneously decompose to form
hydrogen and oxygen gas because the
standard free-energy change for the
reaction is a large positive quantity.
 Electrolysis: Quantitative Aspects

Faraday’s Law
• The amount of substance produced at each electrode is directly proportional to the
quantity of charge flowing through the electrolytic cell.
Applying Faraday’s Law
1. Balance the half-reaction to find the amount (mol) of electrons needed per mole
of product.
2. Use the Faraday constant (F = 9.65×104 C/mol e−) to find the quantity of charge.
3. Depending on the question, do one of the following:
a. Use the molar mass to find the charge needed for a given mass of product,
or vice versa.
b. Use the mass of product and the given current to find the time needed,
or vice versa.
Electrolysis: Quantitative Aspects
Electrolysis: Quantitative Aspects
 Electrolysis: Quantitative Aspects

Example. A technician plates a faucet with 0.86 g of Cr

metal by electrolysis of aqueous Cr2(SO4)3. If 12.5 min is
allowed for the plating, what current is needed?
 Electrolysis: Quantitative Aspects

Example. The MnO2 used in alkaline batteries can be

produced by an electrochemical process of which one-half
reaction is:
Mn2+ (aq) + 2 H2O (l) → MnO2 (s) + 4 H+ (aq) + 2e-
If a current of 25.0 A is used, how many hours are needed
to produce 1.00 kg of MnO2? At which electrode is the
MnO2 formed?
 Electrolysis: Quantitative Aspects

Example. How many seconds does it take to deposit 65.5

g of Zn on a steel gate when 21.0 A is passed through a
ZnSO4 solution?
 Electrolysis: Quantitative Aspects

Example. How many minutes does it take to form 10.0 L of

O2 measured at 99.8 kPa and 28°C from water if a current
of 1.3 A passes through the electrolytic cell? What mass of
H2 forms?
End of Presentation