EMA4303/5305

Electrochemical Engineering
Lecture 01 Basic Concepts

Prof. Zhe Cheng

Mechanical & Materials Engineering
Florida International University
 Electrochemistry - Definition

❑Definition
“Electrochemistry is the branch of physical chemistry that studies the relationship
between electricity, as a measurable and quantitative phenomenon, and identifiable
chemical change, with either electricity considered an outcome of a particular
chemical change or vice versa. These reactions involve electric charges moving
between electrodes and an electrolyte (or ionic species in a solution). Thus
electrochemistry deals with the interaction between electrical energy and chemical
change.” https://en.wikipedia.org/wiki/Electrochemistry

“Electrochemistry is the branch of chemistry concerned with the interrelation of

electrical and chemical effects. A large part of this field deals with the study of
chemical changes caused by the passage of an electric current and the production of
electrical energy by chemical reaction” Bard & Faukner (2001).

“Electrochemistry is a branch of chemistry that studies the chemical changes that

occur due to the flow of electrical current or, conversely, the production of electricity
from chemical changes” Fuller & Harb (2018)

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 2

 Electrochemistry - Applications

❑History aspect
▪ Early Cu-Zn battery, by Volta in late 1790s

❑Major applications
▪ Energy storage/conversion via batteries,
fuel cells, and more

▪ Electrolytic production of chemicals or

materials
− Chlorine & sodium hydroxide
2NaCl (aq) + 2H2O = 2NaOH (aq) + Cl2(g) + H2(g)
− Aluminum
https://www.researchgate.net/figure/262148554_fig3_Flow-sheet-of-the-
▪ Electroplating/electro-deposition aluminum-production-process

https://en.wikipedi
Benefits from a.org/wiki/Blood_gl
▪ Sensors accurate ucose_monitoring

− Glucose sensor for blood sugar monitoring measurement

of electrical
▪ Obtaining basic thermodynamic properties signal (current)

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 3

 Solution

❑Solution HCl aqueous solution Water-Oil mixture

A uniform, homogeneous mixture of 2 substances 2 substances
Homogeneous NOT homogenous
two or more substances (or components)
▪ Example: HCl solution

❑Solvent
The continuous (often majority) substance
(or component) that forms the medium in
a solution
▪ Example:
− H2O in the HCl aqueous solution

❑Solute
The dissolved substance (or component) in
a solution http://www.carolina.com/specialty-chemicals-d-l/hydrochloric-acid-in-
plastic-coated-safety-bottle-121-m-reagent-acs-grade-25-l/867793.pr
▪ Example: http://carpinteriavalleyassociation.org/2013/07/oil-and-water-do-not-
− HCl in the HCl aqueous solution mix/

https://en.wikipedia.org/wiki/Solution
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 4
 Electrolyte

❑A substance or phase that primarily conducts electrically charged ions

(not so much electrons or holes) or that, upon dissolution in a solvent,
form charged ions.

❑Categories
▪ Molten/Liquid electrolyte – no solvent
− Molten NaCl

▪ Electrolyte solution in a (liquid) solvent/solvents

− KCl in water (hydrated K+ and Cl-)

▪ Solid electrolyte
− AgI – Ag+ & I-
− Y2O3-stabilized ZrO2 (YSZ) – oxide ion O’’ (or oxygen vacancy VO••)
− Nafion® polymer – proton H+

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 5

 Electrolyte Solution vs. Nonelectrolyte Solution

Electrolyte solution – Nonelectrolyte solution –

solute, polar or ionic, upon dissolution in the solute remains as molecules (electrically
liquid solvent (or solvents), dissociate neutral) in solvent
(completely or partially) into positively and
negatively charged ions surrounded by Example:
solute molecules

Example:
NaCl in water:

Both + and - ions

surrounded
by (polar) solvent
molecules

Weak electrolyte
solutions have https://jmbeach.github.
io/CH101-
both ions and 008/2016/10/26/week-
molecules 11-day-2.html

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 6

 Strong & Weak Electrolyte Solutions

❑Strong electrolyte solutions

Complete dissociation of cations and anions
▪ NaCl = Na+ + Cl-
▪ HCl = H+ + Cl-

❑Weak electrolyte solution

Incomplete dissociation of molecules into cations and anions
▪ Acidic acid solution
CH3COOH = CH3COO- + H+
Solution contains H+, CH3COO- ions as well as significant CH3COOH
molecules

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 7

 Different Forms of Solution Concentration (1)

❑Mass fraction
Ratio (or fraction) of mass for substance of interest to total mass of substances in the
system, unitless 𝑤𝑁𝑎𝐶𝑙 10𝑔
10 g NaCl + 90 g H2O, 𝑚 𝑁𝑎𝐶𝑙 = = = 10.0%
𝑤𝑁𝑎𝐶𝑙 + 𝑤𝐻2𝑂 10𝑔 + 90𝑔

❑Mole fraction
Ratio (or fraction) of moles for substance of interest to total moles of substances in
the system, unitless 𝑛𝑁𝑎𝐶𝑙 0.171𝑚𝑜𝑙
0.171 mol NaCl + 5.00 mol H2O, 𝑋𝑁𝑎𝐶𝑙 = = ≈ 3.31%
𝑛𝑁𝑎𝐶𝑙 + 𝑛𝐻2𝑂 0.171𝑚𝑜𝑙 + 5.00𝑚𝑜𝑙

❑Molarity
Moles of substance of interest per unit total system volume, mol/L
93.56 ml (or cc) NaCl solution (at 25oC) containing 0.171 mol NaCl,
𝑛𝑁𝑎𝐶𝑙 0.171 𝑚𝑜𝑙
𝐶𝑁𝑎𝐶𝑙 = = ≈ 1.83𝑚𝑜𝑙 ∙ 𝐿−1
𝑉𝑁𝑎𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 0.09356𝐿
❑Molality
Moles of substance of interest per 1 kg of solvent, mol/kg (of solvent)
0.171 mol NaCl + 90 g H2O, 𝑛 0.171 𝑚𝑜𝑙
𝑏𝑁𝑎𝐶𝑙 = 𝑁𝑎𝐶𝑙 = ≈ 1.90 𝑚𝑜𝑙/𝑘𝑔 (𝑜𝑓 𝑤𝑎𝑡𝑒𝑟)
𝑤𝐻2𝑂 90𝑔
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 8
 Different Forms of Solution Concentration (2)

❑10 wt.% NaCl solution in water

- from mass fraction wNaCl to mole fraction
0.1
𝑛𝑁𝑎𝐶𝑙 58.44𝑔/𝑚𝑜𝑙
𝑋𝑁𝑎𝐶𝑙 = = ≈ 0.0331 𝑜𝑟 3.31%
𝑛𝑁𝑎𝐶𝑙 + 𝑛𝐻2𝑂 1 − 0.1 0.1
+
18.02𝑔/𝑚𝑜𝑙 58.44𝑔/𝑚𝑜𝑙

❑NaCl solution in water with NaCl mole fraction of 3.31%

- from mole fraction XNaCl to mass fraction
𝑤𝑁𝑎𝐶𝑙 0.0331 × 58.44𝑔/𝑚𝑜𝑙
𝑚𝑁𝑎𝐶𝑙 = =
𝑤𝑁𝑎𝐶𝑙 + 𝑤𝐻2𝑂 0.0331 × 58.44𝑔/𝑚𝑜𝑙 + 1 − 0.0331 × 18.02𝑔/𝑚𝑜𝑙

≈ 0.0999 𝑜𝑟 10.0 𝑤𝑡. %

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 9

 Different Forms of Solution Concentration (3)

❑10 wt.% NaCl solution in water,

- from mass fraction to molarity (knowing density 1.06879 g/ml at 25oC)
http://butane.chem.uiuc.edu/pshapley/genchem1/l21/1.html
0.1
𝑛𝑁𝑎𝐶𝑙 58.44𝑔/𝑚𝑜𝑙
𝐶𝑁𝑎𝐶𝑙 = = ≈ 1.83𝑚𝑜𝑙 ∙ 𝐿−1 = 1.83 M
𝑉𝑁𝑎𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1
1068.79𝑔/𝐿

❑10 wt.% NaCl solution in water,

- from mass fraction to molality
0.1
𝑛𝑁𝑎𝐶𝑙 58.44𝑔/𝑚𝑜𝑙
𝑏𝑁𝑎𝐶𝑙 = =
𝑤𝐻2𝑂 1 − 0.1
≈ 0.00190 𝑚𝑜𝑙 𝑝𝑒𝑟 𝑔 (𝑜𝑓 𝑤𝑡𝑒𝑟)

= 1.90 𝑚𝑜𝑙 𝑝𝑒𝑟 𝑘𝑔 (𝑜𝑓 𝑤𝑎𝑡𝑒𝑟)

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 10

 Different Forms of Solution Concentration (4)

❑1.90 mol/kg NaCl solution in water,

- from molality to molarity (knowing density 1.06879 g/ml at 25oC)
http://butane.chem.uiuc.edu/pshapley/genchem1/l21/1.html

𝑛𝑁𝑎𝐶𝑙 1.90𝑚𝑜𝑙
𝐶𝑁𝑎𝐶𝑙 = =
𝑉𝑁𝑎𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1.90𝑚𝑜𝑙 × 58.44𝑔/𝑚𝑜𝑙 + 1000𝑔
1068.79𝑔/𝐿

≈ 1.83𝑚𝑜𝑙 ∙ 𝐿−1 = 1.83 M

❑1.90 mol/kg (of water volent) NaCl solution,

- from molality to mass fraction
𝑤𝑁𝑎𝐶𝑙 1.90𝑚𝑜𝑙 × 58.44𝑔/𝑚𝑜𝑙
𝑚𝑁𝑎𝐶𝑙 = =
𝑤𝑁𝑎𝐶𝑙 + 𝑤𝐻2𝑂 58.44𝑔
1.90𝑚𝑜𝑙 × + 1000𝑔
𝑚𝑜𝑙
≈ 0.0999 𝑜𝑟 10.0 𝑤𝑡. %

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 11

 Molten Electrolyte (Salt)

❑The electrolyte, upon heating to above the melting point, dissociates

(completely or partially) into positively and negatively charged ions without
the need for a liquid solvent

❑Examples:
▪ Salts in the molten state
example:
ZnCl2 = Zn+ + 2Cl-
Tm = 290oC
https://youtu.be/LwwmRP8Zpaw

▪ Ionic liquid - (electrolyte with melting point below ~100 oC)

example:
1-butyl-3-methylimidazolium
hexafluorophosphate ([BMIM]PF6)

https://en.wikipedia.org/wiki/Ionic_liquid
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 12
 Solid Electrolyte

❑A solid phase containing charged ions and/or vacancies.

❑Examples:
Yttria-stabilized zirconia (YSZ or Y2O3
doped in ZrO2)
▪ Y2O3 uniformly & randomly “dissolved”
in ZrO2
▪ Charged species (ions) of VO•• and YZr’
⎯2 → 2YZr' + VO•• + 3OO
Y2O3 ⎯ZrO
⎯
http://pubs.rsc.org/en/content/articlelanding/2005/jm/b4171
Nafion® 43h/unauth#!divAbstract

▪ Charged species of H+ and -SO3‒ (on backbone)

https://en.wikipedia.org/wiki/Nafion http://www.orientjchem.org/vol32no5/proton-exchange-membranes-based-on-sulfonated-polymers/
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 13
 Electrode

❑A substance that primarily conducts electrons e- (can also be electron

holes h•) in an electrochemical system.
▪ Connects electrolyte with the external circuit
▪ At the electrode/electrolyte interface, the reduction or oxidation reactions (or
simply redox reactions) occur

❑Categories
▪ Metallic electrode
− Ni, Au, Pt, Cu …

▪ Non-metallic electrodes
− Ceramics:
• Carbon (as graphite or carbon black)
• Conducting oxides: La1-xSrxMnO3, etc.
− (Conducting) polymers
• PEDOT, PANI…

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 14

 Electrochemical Cell & Cell Potential

❑A basic electrochemical cell consists of “two electrodes separated by at

least one electrolyte” V
▪ Example 1
Zn & Cu immersed in a ZnCl2 + CuCl2 mixed solution Zn Rext Cu
and connected through an external circuit (can
be open circuit)
▪ Example 2
H2O
Zn immersed into ZnCl2 solution, while Pt immersed Zn2+ Cl- Cu2+
into dilute HCl solution with bubbling H2, with the
two metal connected through an external circuit and
H2
the two solutions are connected by a KCl salt bridge. V
❑Electrochemical cell potential Rext
▪ Without applying any external power source, a Zn Pt
potential difference could often be measured
between the two electrodes
▪ The measured cell potential depends on cell
construction (e.g., materials, concentration, T, P) Zn2+ H+
& the external circuit resistance Rext Bard & Faulkner (2001) KCl salt bridge
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 15
 H2
V
Rext
Zn Pt

Zn2+ H+
KCl salt bridge

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 16

 Half Cell & Overall (Full Cell) Reactions

❑Electrochemical reaction V
Once an electrochemical cell is formed (either
intentionally or naturally), the electrochemical Zn Rext Cu
reaction(s) might happen, in certain way.
❑Two half (cell) reactions H2O
The overall electrochemical reaction always involve/
consists of two half (cell) reactions with each half Zn2+ Cl- Cu2+
(cell) reaction at one of the electrode/electrolyte interfaces
Reduction/cathodic half (cell) reaction: Overall/Full cell reaction
e.g., Cu2+ + 2e- = Cu
Zn + Cu2+ = Zn2+ + Cu
Oxidation/anodic half (cell) reaction:
Full cell and both half cell reactions must
e.g., Zn = Zn2+ + 2e-
satisfy BOTH mass & charge balance!
❑Overall/full cell reaction
Combination of the reduction (cathodic) half (cell) and oxidation (anodic) half (cell)
reaction with elimination of electrons in the formula
❑Electrochemical reaction vs. general chemical reaction
▪ Always involve oxidation/reduction or change of valence
▪ e- must go from the anode where oxidation occurs through an “external”
circuit (at least for a short distance) to the cathode where reduction occurs
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 17
 Half Cell & Full Cell Reactions -
Class Examples
For the given pair of reduction (cathodic) and oxidation (anodic) half (cell)
reactions, write the overall or full cell reactions
Notes: (1) Mass & Charge balance (2) Elimination of electrons!
Anodic: Fe → Fe2+ + 2e- 1 An + 1 Cat
Cathodic: 2H+ + 2e- → H2 Fe + 2H+ = Fe2+ + H2

Anodic: In → In3+ + 3e- 2 An + 3 Cat

Cathodic: 2H+ + 2e- → H2 2In + 6H+ = 2In3+ + 3H2

Anodic: Fe → Fe3+ + 3e- 4 An + 3Cat

Cathodic: 2H2O + O2 + 4e- → 4(OH)- 4Fe + 3O2 + 6H2O = 4Fe(OH)3

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 18

 Active Electrode vs. Inert Electrode

❑The actual electrode material (electron conductor) may or may not be

the actual species going through the oxidation (for anode) or reduction
(for cathode) half (cell) reaction V
❑Active electrode - electrode material is also
the substance that goes through the Zn Rext Cu
electrode reactions:
▪ Zn anode: Zn = Zn2+ + 2e- H2O
▪ Cu cathode: Cu2+ + 2e- = Cu
Zn2+ Cl- Cu2+
❑Inert electrode - the species that goes through H2
half cell reaction (cathodic or anodic) is V
NOT the electrode material
▪ On Pt cathode: Zn
Rext
Pt
Actual reduction/cathodic reaction: 2H+ + 2e- = H2
▪ Pt remains inert (does NOT change valence).
It only conducts electrons and provides
the (catalytic) interface between ionic (electrolyte) Zn2+ H+
and electronic (electrode) conductors
KCl salt bridge
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 19
 Separation of Oxidation & Reduction in
an Electrochemical Cell
❑Electrochemical cell, e.g., Zn(s)/Zn2+, Cu2+, Cl-/Cu(s) cell
❑Anode - where oxidation or anodic half (cell) reaction occurs
❑Cathode - where reduction or cathodic half (cell) reaction occurs
❑Two half-cell reactions (reduction/cathodic vs. oxidation/anodic) are
geometrically separated!

V
e- e-
Anode Zn Rext Cu Cathode
M
e
H2O e- Cl- m Cl- Cl-
e-
b
Zn 2+
r
Oxidation/ Zn a
2+ Cu2+
Reduction/
anodic half n cathodic half
Zn → Zn2+ + 2e- - Cu2+ + 2e- → Cu
Cl e (cell) reaction
(cell) reaction
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 20
 Transition between Electronic and Ionic
Conduction at Electrode/Electrolyte Interface
❑Electronic condition in electrode vs. Ionic conduction in electrolyte
▪ In an electrochemical cell, both the cathode (e.g., Cu) and the anode (e.g., Zn),
conduct primarily electrons, while, in between the two electrodes, the electrolyte
(e.g., ZnCl2-CuCl2 water solution here) primarily conducts charged ions
▪ For the electrochemical reaction to occur, there must be transition(s) from
electronic conduction to ionic conduction, which occur through the half (cell)
reaction(s) across the electrode (cathode or anode)/electrolyte interface(s)

e-
V Alan C West (2012)
e-
Zn Rext Cu

H2O e-
Zn2+
e- Cu2+
Cl-
Zn2+
Zn → Zn2+ + 2e- Cu2+ + 2e- → Cu
at the Zn/solution Cu2+ at the Cu/solution
interface interface
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 21
 Electrochemical Reactions -
Additional Features
❑Always involve electrical current
& work e- V
Zn bulb Cu
❑Direct measurement of reaction rate
(from current) possible H2O

❑Control of direction and rate of Zn2+ Cl- Cu2+

reaction
▪ Use vs. charging of an Li ion battery

▪ Electroplating vs. electropolishing

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 22

 Open Circuit & Equilibrium Cell Potential

Without applying an external power source, when the external circuit connecting the
two electrodes is open (open circuit or when external resistance Rext goes to infinity),
the resulting external current is zero.
If the followings can also be assumed:
▪ Reversible reactions at both electrodes
▪ No internal electronic leakage through the electrolyte
▪ Only a single electrochemical reaction occurs at each electrode
Then ‒ Eeq +
▪ The electrochemical cell will Zn Cu
reach equilibrium
▪ A reversible & stable potential M
between the two electrodes is e
H2O e- - m - Cl-
obtained, called equilibrium Cl Cl- e
Cl- b
(cell) potential Eeq Zn2+ Cu2+
r Cu2+
Zn2+
Cl- a Cl-
Cl- Zn  Zn2+ + 2e- n - Cu2+ + 2e-  Cu
e Cl
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 23
 Galvanic Cell

With out applying any external power source, while the external resistance is finite,
the overall electrochemical reaction would proceed in a spontaneous way:
e- flow out from anode where oxidation half (cell) reaction occurs through the external
circuit to the cathode where the reduction half (cell) reaction occurs.
▪ Such a cell is called a galvanic cell
▪ In a galvanic cell, (stored) chemical energy converts to electrical work
▪ Encountered in the discharge of a battery or fuel cell
If I is net current through the cell, e- e-
based on Ohm’s Law and Rext
addition of potential: Zn Cu
Eeq = I (Rint + Rext) M
Rint and Rext are cell internal -
e
H2O e Cl -
m - - Cl-
resistance and external circuit Cl e
resistance, respectively Cl- b
Zn2+
r Cu2+ Cu2+
Zn2+
Cell (external circuit) potential a Cl-
Eext = IRext = Eeq - IRint Cl- Zn → Zn2+ + 2e- Cl- n Cl- Cu2+ + 2e- → Cu
e
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 24
 Electrolytic Cell

By applying an external potential Eapp in the reverse direction w/ value larger than Eeq
cell current will be reversed →
the overall electrochemical reaction would proceed in the reverse direction
▪ Such a cell is called an electrolytic cell
▪ Electrical energy (consumed) converts to chemical energy (stored)
▪ Encountered in battery charging or electrolytic production of chemicals/metals
If I is the net current flowing through e- - + e-
the electrolytic cell,
based on Ohm’s Law and Zn Cu
addition of potential:
the applied potential Eapp M
e
Eapp = Eeq + IRint H2O e-
Cl- Cl- m Cl- e- Cl-
Rint is cell internal resistance Cl- b Cl-
Zn2+
2+
r Cu2+ Cu2+
Zn
a
Zn2+ + 2e- → Zn Cl- n Cl- Cu → Cu2+ + 2e-
e 25
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts
 Faraday Constant & Faraday’s Law

❑For a simple electrochemical cell, the amount of charge transferred in

the reaction is linearly related to the amount of product generated or
reactant consumed
1 coulomb (or 1 C) = 6.24x1018 of e- e- = 1/(6.24x1018) C
1 mole of e- = 6.02 x 1023 of e-
Faraday constant: the electrical charge (in C) per mole of electron
F = 1/(6.24x1018) C × 6.02 x 1023/mol = 96485 C/mol

❑Faraday’s Law
The mass (of metal) deposited in a simple electrolytic reaction is given by
𝑀𝑄
𝑚=
𝑧⋅𝐹
M atomic mass, g/mol
Q total passed charge, C
z valence of the metal ion, unitless
F Faraday constant 96485C/mol

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 26

 An Example of Faraday’s Law

For electrolytic deposition of Cu from Cu2+ solution, assuming no other species got
reduced, if the reduction current is constant at 1 A and the total time is 1 min,
what is the amount of Cu deposited, in mole?
𝑄 𝐼⋅𝑡 1𝐴 ⋅ 60sec
𝑛𝐶𝑢 = = = = 3.1 × 10−4 𝑚𝑜𝑙
𝑧⋅𝐹 𝑧⋅𝐹 2 ⋅ 96485𝐶/𝑚𝑜𝑙

Cu has atomic mass of 63.55 g/mol →

The mass of Cu deposited will be 3.1x10-4 mol x 63.55 g/mol = 0.0197 g = 19.7 mg

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 27

 Faradaic Efficiency

❑Actual electrode might e- - + e-

have additional half-cell
reactions in addition to Zn Cu
the desired one
❑Example of an M
electrolytic cell e
H2O e- - Cl- Cl-
Zn|Zn2+, Cl-|KCl|Cu2+, Cl-|Cu Cl Cl- m e-
Primary cathodic/reduction Cl- b Cl-
Zn2+
half cell reaction: 2+
r Cu2+ Cu2+
Zn
Zn2+ + 2e- = Zn a
Additional (parasitic) cathodic/ Zn2+ + 2e- → Zn Cl- n Cl- Cu → Cu2+ + 2e-
reduction half cell reaction: e
H+ + e- = H2

❑Faradaic efficiency
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝜂𝐹 =
𝐴𝑚𝑜𝑢𝑛𝑡 𝑡ℎ𝑎𝑡 𝑐𝑜𝑢𝑙𝑑 𝑏𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑐ℎ𝑎𝑟𝑔𝑒 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 28
 Faradaic Efficiency Example

Example
Nickel is electrodeposited from NiSO4 solution. A constant current of 1 A is
passed for 1 h and 1.05 g of metallic Ni was deposited. What is the Faradaic
efficiency of the deposition?
Solution
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
𝜂𝐹 =
𝐴𝑚𝑜𝑢𝑛𝑡 𝑡ℎ𝑎𝑡 𝑐𝑜𝑢𝑙𝑑 𝑏𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑡𝑜𝑡𝑎𝑙 𝑐ℎ𝑎𝑟𝑔𝑒 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑
From Faraday’s Law, the amount of Ni that could be produced under ideal condition
𝑀𝑁𝑖 ∙ 𝑄
𝑚𝐹𝑒_𝑖𝑑𝑒𝑎𝑙 =
𝑧𝑁𝑖 ⋅ 𝐹
Therefore,
𝑚𝑁𝑖_𝑎𝑐𝑡𝑢𝑎𝑙 𝑚𝑁𝑖_𝑎𝑐𝑡𝑢𝑎𝑙
𝜂𝐹 = =
𝑚𝑁𝑖_𝑖𝑑𝑒𝑎𝑙 𝑀𝑁𝑖 𝑄/𝑧𝑁𝑖 𝐹
1.05𝑔 1.05𝑔
= = = 0.959 or 95.9%
1𝐴 ∙ 3600𝑠 1.095𝑔
58.69𝑔/𝑚𝑜𝑙 ∙
2 ∙ 96485𝐶/𝑚𝑜𝑙
EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 29
 Lecture 1 Homework

1. Read textbook Chapter 1 and give an honor statement confirm

reading

2. Questions for the instructor

Raise FOUR (4) question that you don't fully understand for lecture videos
In case you have understood everything and don’t have that many questions, please
give corresponding number of multiple-choice problem (together with your answer)
that you feel can be used to check a student's understanding.

An example multiple-choice problem could be:

Which of the units below can be the unit for current density j?
a) A
b) A/cm2 (Answer)
c) V
d) C

3. Problems (see later, OPTIONAL for EMA4303)

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 30

 Homework 1.1

For electrolytic deposition of silver (Ag) at constant current of 1 A, how

much silver metal could be obtained after 1 sec? Assuming NO parasitic
reactions

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 31

 Homework 1.2

For electrolytic deposition of Mo from a molten salt, 12.85 g are

deposited in 1 hour using a constant current of 7 A. How many electrons
are passed per mole of Mo reacted? What is the oxidation state (or
valence) of Mo in the molten salt? What the assumed Faradic efficiency?

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 32

 Homework 1.3

How much hydrogen gas is needed to operate a hydrogen oxygen fuel

cell for 3 hour at constant power of 50 kW? Knowing during the
operation, the cell voltage is kept constant of 0.7 V, and the anodic half
cell reaction is H2 = 2H+ + 2e-

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 33

 Homework 1.4

Calculate the daily aluminum production of 150,000 A aluminum

electrolytic cell that operates at a Faradaic efficiency of 89%. The overall
cell reaction is 2Al2O3 + 3C = 4Al + 3CO2

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 34

 Homework 1.5

The annual production of Cl2 is about 45 million tons. Assume a typical

plant is operational 90% of a year, and the operating voltage is 3.4 V.
▪ Write down the anodic (or oxidation) half-cell reaction to produce Cl2
▪ Determine the total current needed world wide to generate the global supply of
Cl2
▪ Calculate the electrical power needed

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 35

 Homework 1.6

Continuous sheet copper is made by electrodeposition from a solution

containing CuSO4 onto a rotating drum of lead. For condition given
below, what should be the rotation speed of the drum (revolution per
hour)? Knowing cathodic current density = 1750 A/m2, Faradaic (or
current) efficiency = 95%, desired thickness = 1.22 kg/m2, angle of
cathodic immersion = 165o.

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 36

 Homework 1.7

How many grams of Li are in a 1320 (mAh) cell phone battery? Note 1320
mAh is a unit of charge

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 37

 Homework 1.8

A plate of steel has lost 50 g due to corrosion over the past year.
Estimate the corrosion current that would be associated with this
corrosion rate

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 38

 Homework 1.9

Corrosion of steel in concrete is an important problem. Under

accelerated corrosion testing condition, the current efficiency may be
low. In competition with the oxidation of Fe to Fe2+, oxygen gas can be
evolved following:
2OH- = 0.5O2 + 2 H2O + 2e-
If a current 1.4 mA is passed for 100 h for the corrosion experiment and
the mass loss for Fe is 0.11 g,
▪ What is the Faradaic efficiency for Fe oxidation in the experiment?
▪ How many moles of O2 are evolved?
▪ What is the volume of O2 under standard condition?

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 39

 Homework 1.10

Find out (i) the half cell and full cell reactions, (ii) show how the full cell
reaction is obtained from the half-cell reactions, (iii) identify which is the
anodic (oxidation) and which is the cathodic (reduction) half cell
reaction, for the following processes:
▪ Industrial production of Cl2 and NaOH from NaCl solution
▪ Proton exchange membrane fuel cell running on H2 and air
▪ Discharge of a lead acid battery for automobiles
▪ Alkaline battery

EMA 5305 Electrochemical Engineering Zhe Cheng 1 Basic Concepts 40