Introduction to Electrochemistry

(電化學概論)

Introduction
2023/2/24
 General Information
• Lecturer:
⚬ 羅世強
• 辦公室︓工綜454
• email: shyhchyang@ntu.edu.tw
• Office Hour: Please send me an email to make an
appointment
• Lecture schedule:
⚬ Friday 2,3,4 (綜 ???)

• Lecture materials: NTU COOL

 Electrochemistry
• The study of chemical reactions which take place at the
interface of an electrode, usually a solid (metal or a
semiconductor), and an ionic conductor, the electrolyte
• These reactions involve electric charges moving
between the electrodes and the electrolyte (or ionic
species in a solution)
• Thus, electrochemistry deals with the interaction
between electrical energy and chemical change

• -en.wikipedia.org
 Who Should Take This Course?
• The focus of electrochemistry class:
⚬ 林招松教授(MSE)：材料電化學
⚬ 何國川教授(ChemE)：電催化、電極動力學
⚬ Others…
⚬ This one: general electrochemistry and focused on
energy issues (lithium ion battery, LIB)
• Specific and final Goals
⚬ Material scientists are the key players in the field
⚬ Being able to study papers related to LIB by yourself
☛ Team presentations
• prerequisite
⚬ Physical chemistry (Thermodynamics is a MUST)
 Course Content (Tentative)
第1週 2/24 Introduction, History of Electrochemistry Basic
第2週 3/03 Electrochemical Cells
第3週 3/10 Electrolyte Conductivities, Activity Ionic System
第4週 3/17 Electrode Potential, Nernst equation, EMF series
Thermodynamics
第5週 3/24 Liquid Junction, ISE
第6週 3/31 Double Layer, Electrified Interfaces, Potential vs. Current Interface
第7週 4/07 Kinetics Kinetics
第8週 4/14 <Midterm>
第9週 4/21 Experimental Techniques
第10週 4/28 Energy Topic/ Lithium Battery
Applications
第11週 5/05 Presentation Solid-State (Lithium) Battery
第12週 5/12 Presentation Spectroelectrochemistry
第13週 5/19 Presentation DSSC, SECM Electrosynthesis Show time!
第14週 5/26 Presentation Electrocatalysis
第15週 6/02 Presentation Electrochemical Analysis and Sensing
第16週 6/09 <Final> 包含presentation的內容！
 Textbook and Reference
Main Textbook
• [1] Peter Atkins, Julio de Paula, James Keeler "Atkins'
Physical Chemistry" 11e
• [2] M. Teresa Fernández Abedul "Laboratory Methods in
Dynamic Electroanalysis” accessible online
Reference
• [1] C. H. Hamann, A. Hamnett, W. Vielstich
“Electrochemistry” 2007, Wiley-VCH
• [2] A. J. Bard and L. R. Faulkner, “Electrochemical
Methods: Fundamentals and Applications,” 2nd ed.,
2000, Wiley
 Score
(%)
Midterm Exam 35
Final Exam 35
Quiz 10
Presentation / Report 20

Presentation / Report
• 原則上3人一組
• 報告時每個組員都要報告，各自需要準備一個題目問聽眾同學
• 我會請聽眾提問、我自己也會發問
• Report: 把報告用的PPT、準備的問題/答案、同學及老師發問的問
題/答案，在報告後三天內email給我
HISTORY OF
ELECTROCHEMISTRY
 Reference
• https://en.wikipedia.org/wiki/History_of_electrochemistry

YouTube- The Voltaic Pile

https://www.youtube.com/watch?v=edMN7P5oCaY
Italy 10000 Lire

Alessandro Volta, 1745 ~ 1827

 Alessandro Volta

Italian physicist Alessandro

Volta showing his "battery" to
French emperor Napoléon
Bonaparte in the early 19th
century

en.wikipedia.org
Voltaic Pile

en.wikipedia.org
Galvani's Experiment on Frog Legs

Luigi Galvani “animal electricity”

en.wikipedia.org
 Galvanism
• Galvani is properly credited with the discovery of
bioelectricity
• In biology, galvanism is the contraction of a muscle that
is stimulated by an electric current
• Today, the study of galvanic effects in biology is called
electrophysiology, the term galvanism being used only
in historical contexts
en.wikipedia.org
 William Nicholson and Anthony Carlisle

William Nicholson (1753-1815) English physicist

and inventor and Anthony Carlisle (1768-1840),
English surgeon
In 1800, Nicholson made a voltaic pile constructed
which he and Carlisle used for experiments
They took a small tube, mounted vertically, filled
with water then sealed, into which at either end was
inserted a platinum wire connected to one of the
two battery terminals
As the tips of the wires were gradually advanced
towards each other they observed that a stream of
bubbles was produced from each tip, one found to
be of oxygen, the other hydrogen
The electric current decomposed the water into the
two gases of which it is made
Nicholson and Carlisle had discovered electrolysis
www.sciencephoto.com from which developed the science of
electrochemistry
 Humphry Davy
Humphry Davy used electrolysis to isolate
the metallic element in alkalis and alkaline
earths
Davy used a combination of Voltaic
batteries to give the highest electrical
power he could obtain and ran an electrical
current through a solution of potash which
caused the isolation of potassium
This was the first metal to be isolated by
electrolysis
Davy isolated sodium in the same year by
passing an electric current through molten
sodium hydroxide
www.sciencephoto.com Davy discovered calcium in 1808 by
electrolyzing a mixture of lime and
mercuric oxide
He worked with electrolysis throughout his
life and was first to isolate magnesium,
boron, and barium
en.wikipedia.org
 Michael Faraday
Faraday's laws of electrolysis
Faraday's 1st Law of Electrolysis
• The mass of a substance altered at an electrode
during electrolysis is directly proportional to the
quantity of electricity transferred at that electrode
• Quantity of electricity refers to the quantity of
electrical charge, typically measured in coulomb

Faraday's 2nd Law of Electrolysis

• For a given quantity of electric charge, the mass of
an elemental material altered at an electrode is
directly proportional to the element's equivalent
weight
• The equivalent weight of a substance is equal to its
(22 Sept. 1791 – 25 Aug. 1867)
An English scientist who molar mass divided by the change in oxidation
contributed to the fields of state it undergoes upon electrolysis (often equal to
electromagnetism and its charge or valence)
electrochemistry en.wikipedia.org
 Faraday's Laws of Electrolysis

! Q $! M $
m = # &# &
" F %" z %
where:
m: the mass of the substance liberated at an electrode in
grams
Q: is the total electric charge passed through the substance
F = 96,485 C mol−1 is the Faraday constant
M: the molar mass of the substance
z: the valence number of ions of the substance (electrons
transferred per ion)
 Faraday's Laws of Electrolysis

! Q $! M $
m = # &# &
" F %" z %
In the case of constant-current electrolysis, leading to
Q = It
" I ⋅ t %" M %
m =$ '$ '
# F &# z &
" I ⋅ t %" 1 %
n =$ '$ '
# F &# z &
n is the number of moles, liberated: n = m/M
 George Johnstone Stoney

• In 1874, after studying the phenomenon

of electrolysis, Irish physicist George
Johnstone Stoney suggested that there
existed a “single definite quantity of
electricity”, the charge of a monovalent
ion
• He was able to estimate the value of this
elementary charge e by means of
Faraday’s laws of electrolysis
• In 1891, he proposed the term 'electron'
to describe the fundamental unit of
electrical charge, and his contributions to
research in this area laid the foundations
for the eventual discovery of the particle
by J. J. Thomson in 1897 (1826 – 1911)
 William Whewell
• William Whewell (1794-1866), English
polymath
• He was gifted at inventing words to
describe new discoveries, and brought
words such as scientist and physicist
to the language for the first time
• Whewell suggested the terms ion,
dielectric, anode, and cathode… to
Michael Faraday

“A polymath (Greek: πολυμαθής,

polymathēs, "having learned much”) is a
person whose expertise spans a significant
number of different subject areas”
en.wikipedia.org
 Svante August Arrhenius
• Published his thesis in 1884, Recherches
sur la conductibilité galvanique des
électrolytes, and proposed theory of
electrolytic dissociation
• Arrhenius' explanation was that in forming a
solution, the salt dissociates into charged
particles (to which Michael Faraday had
given the name ions many years earlier)
• Faraday's belief had been that ions were
produced in the process of electrolysis;
(1859 – 1927) was a Arrhenius proposed that, even in the
Swedish scientist. He
absence of an electric current, solutions
received the Nobel Prize
for Chemistry in 1903 of salts contained ions
• He thus proposed that chemical reactions
en.wikipedia.org
in solution were reactions between ions
 Chemical Activity
• “The ions were supposed to be the carriers of not only
the electric current as in electrolysis but also the
chemical activity”
• “The relation between the actual number of ions and
their number at great dilution (when all the molecules
were dissociated) gave a quantity of special interest
("activity coefficient")”

𝜇! = 𝜇!" + 𝑅𝑇𝑙𝑛𝑎!
𝑐!
𝑎! = 𝛾! #
𝑐
 Arrhenius Acids and Bases
• The Arrhenius definition of acids and bases is one of the
oldest
• An Arrhenius acid is a substance that when added to
water increases the concentration of H+ ions
• The chemical formulas of Arrhenius acids are written
with the acidic hydrogens first
• An Arrhenius base is a substance that when added to
water increases the concentration of OH- ions
• HCl is an example of Arrhenius acid and NaOH is an
example of Arrhenius base
 Friedrich Wilhelm Ostwald
• In 1894 he gave the first modern
definition of a catalyst and turned his
attention to catalytic reactions
• Ostwald is also known for his
contributions to the field of
electrochemistry, including important
studies of the electrical conductivity and
electrolytic dissociation of organic acids
• Ostwald did significant work on dilution
1853 – 1932 was a Baltic theory leading to his discovery of the
German chemist. He received law of dilution
the Nobel Prize in Chemistry in
1909 for his work on catalysis,
chemical equilibria and reaction
velocities
 Law of Dilution
• A relationship between the dissociation constant Kd and
the degree of dissociation α of a weak electrolyte
• Consider a binary electrolyte AB which dissociates
reversibly into A+ and B- ions.
• Ostwald noted that the law of mass action could be
applied to such systems, and the equation represents
the equilibrium state:
𝐴𝐵 ⇌ 𝐴! + 𝐵"
• If 𝛼 is the fraction of dissociated electrolyte, then αc0 is
the concentration of each ionic species. (1 − 𝛼) must,
therefore, be the fraction of undissociated electrolyte,
and (1 − 𝛼)𝑐# the concentration of the same
 Law of Dilution
• The dissociation constant may therefore be given as
𝐴% [𝐵& ] 𝛼'
𝐾$ = = 𝑐"
[𝐴𝐵] (1 − 𝛼)

• Conductivity measurements determine the value of ‘𝛼’ by

applying the formula Λ/Λ$
Λ
𝛼= (
Λ
Λ' 𝑐"
𝐾$ = ( (
Λ (Λ − Λ)
 Jacobus Henricus van't Hoff
He is best known for his discoveries in
chemical kinetics, chemical equilibrium,
osmotic pressure, and stereochemistry

Van 't Hoff equation

𝑑𝑙𝑛𝐾)* ∆𝐻
=
𝑑𝑇 𝑅𝑇 '
𝐾' −∆𝐻 1 1
1852 – 1911 was a Dutch 𝑙𝑛 = −
physical and organic 𝐾+ 𝑅 𝑇' 𝑇+
chemist and the first winner
of the Nobel Prize in
Chemistry
 Osmotic Pressure
• The osmotic pressure Π of an ideal solution with low
concentration can be approximated:

𝜋 = 𝑖𝑐𝑅𝑇
𝑖: the van, t Hoff factor

• There is a simple relationship the degree of dissociation,

𝛼, and the van't Hoff factor, i
• If a fraction 𝛼 of the solute dissociates into n ions, then

𝑖 = 1 − 𝛼 + 𝑛𝛼 = 1 + 𝛼(𝑛 − 1)
 Walther Hermann Nernst
• Nernst helped establish the modern field
of physical chemistry and contributed to
electrochemistry, thermodynamics and
solid state physics
• He is also known for developing the
Nernst equation

$ 𝑅𝑇
𝐸!"## = 𝐸!"## − 𝑙𝑛𝑄
1864 – 1941 was a German
physicist who is known for his
𝜈𝐹
theories behind the calculation
of chemical affinity as
embodied in the third law of
thermodynamics, for which he
won the 1920 Nobel Prize in
chemistry