Fundamentals of

Electrochemistry
CHEM*7234 / CHEM 720
Lecture 1

Course Overview
Date

Topic

Instructor

Thurs 8
Fri 9
Mon 12
Tues 13
Wed 14
Thurs 15
Fri 16
Mon 19
Tues 20
Wed 21
Thurs 22

Thermodynamics, Cell Potentials, Nernst equation

The Electrode/Solution Interface
Electrode Kinetics and Mass Transport
Instrumentation
Voltammetric Methods
Chronometric Methods
Impedance Methods
Victoria Day Holiday
Industrial Applications, Sensors
Organic Electrochemistry
Industrial Applications: Hydrothermal Electrochemistry
Industrial Applications: Fuel Cells and Batteries
Imaging/ Surface Analytical Methods

D. Thomas
J. Lipkowski
J. Lipkowski
G. Szymanski
M. Baker
I. Burgess
J. Noel

Fri 23

N. Bunce
A. Houmam
P. Tremaine
D. Malevich
D. Thomas

Course Evaluation
Assignments: Five Assignments, about every other day. Each will consist of three
questions. These assignments will count for 60% of the course grade.
Final Exam: May 30 in AXEL 259. There will be eight questions. You will choose to answer
six of them. It will count for 40% of the course grade.

Energy Levels

Energy

E=0

Empty
States

LUMO

Filled
States

HOMO

An Atom

A Small
Molecule

Vacuum
Level

A Large
Molecule

Fermi
Level

Bulk
Material

Chemistry is controlled
by the states around the filled/empty transition.

Band Structure
Infinitesimal
spacing
between
filled and
empty states

Large
spacing
between
filled and
empty states

Small but
non-zero
spacing
between
filled and
empty states

Valence
Band

Band Gap

Core
Bands

Metal

Semiconductor

Insulator

Our focus in this course is on metals.

Fermi Level
focus on the electrons near the filled/empty boundary.
each materials energy state distribution is unique; different EF.
Minimum
energy to
remove
electron
from
sample

E=0 (vacuum level)

EF (Fermi level)
EF (Fermi level)

Metal 1

Metal 2

the closer an electron is to the vacuum level, the weaker it is bound to the solid

or,themoreenergeticistheelectron

Two Conductors in Contact

+
+
+
+
+

electron flow
leads to charge separation

Contact potential difference

sample
Fermi level the same throughout

An Ion in Solution
ions electronic structure: HOMO, LUMO, HOMO-LUMO gap.

Lowest Unoccupied Molecular Orbital

HOMO-LUMO Gap

Fermi level

Highest Occupied Molecular Orbital

Metal in an Electrolyte Solution

Fermi levels
are aligned

Charge is transferred to
equilibrate Fermi levels,
producing a charge
separation and a contact
potential difference.

+
+
+

Two Electrolyte Solutions

Fermi level

A charge separation
arises to align the
Fermi level and
produces a potential
at the interface.

+
+
+

Junction Potentials
In any circuit there are junction potentials
whenever two dissimilar materials come into
contact.
We focus on the metal-solution interface in
electrochemistry

Electrochemical Thermodynamics
Every substance has a unique propensity to contribute to a systems
energy. We call this property Chemical Potential.

When the substance is a charged particle (such as an electron or an ion)

we must include the response of the particle to an electrical field in
addition to its Chemical Potential. We call this Electrochemical
Potential.

=+zF
These are perhaps the most fundamental measures of thermodynamics.

Chemical Potential
Chemical potential (or electrochemical potential if it is charged) is the
measure of how all the thermodynamic properties vary when we
change the amount of the material present in the system. Formally we
can write

=
n T,P

=
nT,V

H
=
n S,P

U
=
n S,V

Gibbs Free Energy

The free energy function is the key to assessing the way in which a
chemical system will spontaneously evolve.

dG =SdT +VdP + i dni + dA+ f dl

constantT
constantP

dontchange
shape

dG = i dni

dontstretchit

Gibbs Function and Work

Start with the First Law of Thermodynamics and some standard thermodynamic
relations. We find

dU =dq+dw

dq=T dS
dw =P dV +dwelectrical

dU =T dSP dV +dwelectrical
dGT =dHT T dS

dH P =dU P +P dV

=dUT,P +P dV T dS
=T dSP dV +dwelectrical+P dV T dS
dGT,P =dwelectrical
And therefore, the Gibbs function is at the heart of electrochemistry, for it
identifies the amount
from a system.
of work we can extract electrically

Gibbs and the Cell Potential

Here we can easily see how this Gibbs function relates to a potential.

welectrical=V Q
since Q =nF
=nF E
By convention, we identify work which is negative with work which is
being done by the system on the surroundings. And negative free
energy change is identified as defining a spontaneous process.

GT,P =welectrical=nF E
Note how a measurement of a cell potential directly calculates the Gibbs
for the process.

free energy change

Standard Reference States

All thermodynamic measurements are of differences between states;
there is no absolute value for any property (exception: entropy does
have an absolute measure from theory, but its the only one).
In order to quantify thermodynamics, we choose by convention a
reference state. Most common choice is called Standard Ambient
Temperature and Pressure (SATP).
Temperature = 298 K (25 C)
Pressure = 1 bar (105 Pa)
Concentration = 1 molal (mol of solute/kg of solvent)
BUT

Standard Reference States

atmosphere is a widely used unit of pressure.
1 atm = 1.0134 bar
Reference State for Pressure is usually 1 atm
molality better than molarity
solvent density is T dependent
volume changes with T

Reference states are

indicated by superscript
C or P

But
volume is easier to measure than mass
density of water (the most common solvent) is close to 1
The most commonly used reference state is that of 1 M (mol/liter).

Activity
The propensity for a given material to contribute to a reaction is measured
by activity, a.
How active is this substance in this reaction compared to how it would
behave if it were present in its standard state?
activity scales with concentration or partial pressure.
a C/C OR a P/P
BUT
intermolecular interactions
deviations from a direct correspondence with pressure or concentration

Activity Coefficients
Definition of activity

C
a = o
C

P
a = o
P

Activity coefficients close to 1 for dilute solutions and low partial

pressures.
it changes with concentration, temperature, other species, etc. Can be
very complex.
Generally, we ignore activity coefficients for educational simplicity, but
careful work will require its consideration.

Approximate Activity
activity is unitless
activity coefficient is complex over wide ranges of conditions
Since
activity coefficients are close to 1 for dilute solutions
reference states for partial pressure and concentration have
numerical value of 1
Therefore, we often approximate activity by concentration (M) or partial
pressure (atm).

Solids, Solvents, Liquids

SOLID: reference is itself
PURE LIQUID: reference is itself
SOLVENT: reference is itself

a = 1 for all of these materials

Increase amount of these : reaction goes longer, but not faster.

Chemical Potential and Activity

How does chemical potential change with activity?
Integration of the expressions for the dependence of amount of material
on the Gibbs function, leads to the following relationship:

=o +RT lna

Reaction Quotient
wA+xB yC +zD
In order to analyze a chemical process mathematically, we form this
reaction quotient.
aCy azD
Q= w x
aA aB
it always has products in the numerator and reactants in the
denominator
it explicitly requires the activity of each reaction participant.
each term is raised to the power of its stoichiometric coefficient.

Simplifying Approximations
Leave out terms involving solids, pure liquids, and solvents
Solutes appear as the concentration (in M).
Gases appear as the partial pressure (in atm).

REACTION QUOTIENT IS UNITLESS.

But its value does depend upon the chosen reference state.

Concentration Dependence
How does Gibbs free energy change with activity (concentration)?
Same dependence as with the chemical potential. We have

G =G +RT lna
When we apply this to a reaction, the reaction quotient comes into to play,
giving us

G =G +RT lnQ

Equilibrium
G =Go +RT lnQ
When all participants have unit activity (a=1), then Q=1 and ln Q = 0.

G =Go

(duh! As designed.)

Reaction proceeds, Q changes, until finally G=0. The reaction stops. This
is equilibrium.

0=Go +RT lnQ*

Go =RT lnQ*

Q* Keq

This special Q* (the only one for which we achieve this balance) is renamed
Keq, the equilibrium constant.

An Electrochemical Cell
The Weston Cell

Saturated CdSO4
solution

CdSO4 (s)

Hg2SO4 (s)

Cd(Hg) (l)

Hg (l)

Weston Cell Reactions

Here are the two reactions that are occurring. In the left-hand cell we find
Cd(Hg) Cd2+(aq) + 2e
Cd is being oxidized (its oxidation number is going from 0 to +2)
In the right-hand cell we find
Hg2SO4(s) + 2e 2 Hg(l) + SO42(aq)
Hg is being reduced (its oxidation number is going from +1 to 0)
The overall reaction is the sum of these two reactions
Cd(Hg) + Hg2SO4(s) 2 Hg(l) + Cd2+(aq) + SO42(aq)
This reaction occurs spontaneously as written. Its free energy change G is
therefore ive and its cell potential E is +ive.

Cell Notation
A shorthand cell notation has been developed for convenience. The
Weston cell is written as
Cd(12.5% Hg amalgam) | CdSO4(aq, sat) | Hg2SO4 (s) | Hg(l)
write components in sequence
separate phases with a single vertical line |
a salt bridge or membrane is represented by a double vertical line ||
included a specification of the species concentration
note that the solid CdSO4 is necessary to maintain a saturated solution,
but it does not participate directly in the reaction so it is not included in
the cell definition

Electrode Convention
The electrode at which oxidation is occurring is called the anode.
The electrode at which reduction is occurring is called the cathode.
write the anode on the left and the cathode on the right.
a cell operating spontaneously in this configuration is said to have a
positive total cell potential.
when connecting a voltmeter, connect the positive terminal to the
positive electrode. If it reads a positive potential, you have correctly
identified all the terminals. If you read a negative potential, then you
have misidentified the reactions in the cells, and you have hooked it up
backwards. Reverse your assignment of anode and cathode.
in a galvanic cell the cathode is +ive
in an electrolytic cell the cathode is ive.

Daniell Cell
Anode (oxidation)
ive

salt bridge

Cathode (reduction)
+ive

Zn metal

Cu metal

ZnSO4 (aq)

CuSO4 (aq)

Zn(s) Zn2+(aq) + 2e

Cu2+(aq) + 2e Cu(s)

Salt Bridge
What is the role of the salt bridge?
Daniell Cell without salt bridge

Liquid-liquid interface

Carefully merge
two solutions.
Make CuSO4
more dense
than ZnSO4.
Sheath Cu
electrode in
glass.

Salt bridge makes cell

construction and
operation easier.

Pack tube with a viscous, aqueous

solution of KCl or KNO3. The
viscosity prevents mixing with
the electrolytes. The ions permit
exchange of charge. The chosen
ions have similar mobility to
minimize
junction potentials.

Flow of Charge
How does charge flow in a cell?
V+

Zn

Cu

Zn2+
Cl
NO3

Cu2+

K+
NO3

If concentrations are
1M, then the cell is
at standard
conditions and the
measured potential
is +1.10 V.

Electrolytic Cell
What about running the cell in reverse?
DC V +

Zn

apply an external voltage of

opposite polarity.
magnitude must exceed the +1.10
V that the cell produces on its
own.
Cu electrode now dissolves and
Zn now plates out on its
electrode.

Cu

Zn2+
Cl
NO3

K+

Cu2+

NO3

Nernst Equation
Take the expression for the Gibbs dependence on activity and turn this around for
an expression in terms of the cell potential.

G =G +RT lnQ
The relation between cell potential E and free energy gives

nF E =nF E +RT lnQ

Rearrange and obtain the Nernst Equation.

RT
E =E
lnQ
nF
o

Nernst Equation

continued

The equation is sometimes streamlined by restricting discussion to T = 25 C and

inserting the values for the constants, R and F.

0.0257
E =E
lnQ
n
o 0.0592
E =E
logQ
n
o

Note the difference between using natural logarithms and base10

logarithms.
Be aware of the significance of n the number of moles of electrons
transferred in the process according to the stoichiometry chosen.

Example: Daniell Cell

Cu is cathode (it is reduced). Zn is anode (it is oxidized).

Cu2+(aq) +2e Cu( s)

Zn(s) Zn2+(aq) +2e

Cu2+(aq) +Zn( s) Zn2+(aq) +Cu(s)

=1

Note that n=2 for this reaction.

aCu aZn2+

o RT
E =E
ln
nF a

2+ aZn

Cu

2+
[Zn ]
o

[]

=1

Activity for solid materials is 1; replace activities with concentrations.

2+
2+
Zn
Zn
RT [
]
[
]
o
E =E
ln
=1.100.0128
5 ln
2+
2+
2F [Cu ]
Cu
[
]

Example

continued

What is the potential in the cell if [Cu2+] = 0.01 M and [Zn2+] = 1.00 M?

1.00
E =1.100.0128
=1.100.0128
5 ln
5 ln(100)
0.01
=1.100.0128
) =1.041V
5(4.6052

Note that the cell potential decreased by about 60mV. This was a change in
concentration of TWO orders of magnitude, but since it was also a TWO
electron process, we saw the same 60 mV change in potential.

Example: Weston Cell

Recall that the total cell reaction is
Cd(Hg) + Hg2SO4(s) 2 Hg(l) + Cd2+(aq) + SO42(aq)
and it is a two electron process. The Nernst equation is

a2Hg a

2+ a 2
RT
Cd
SO4
E =E o
ln
nF
aCd aHg2SO4

The activity of liquid Hg is 1; that for solid Hg2SO4 is 1; that for Cd2+ and
SO42 will be constant since the solution remains saturated (continual
precipitation or dissolution of solid CdSO4 as necessary). The Cd
concentration in the amalgam (at 12.5%) will not change much if the
cell current is kept low.
E = 1.0180 V at 25 C (NOT standard state, but a very stable output).

Concentration Cell
Nernst equation demonstrates that potential depends upon concentration.
A cell made of the same materials, but with different concentrations, will
also produce a potential difference.
Cu | Cu2+ (0.001 M) || Cu2+ (1.00 M) | Cu
What is standard cell potential E for this cell?
What is the cell potential E? What is n, the number of electrons
transferred? Which electrode, anode or cathode, will be in numerator?

2+

Cu
[
]
o 0.0257
anode
E =E
ln
[Cu2+]

cathode

0.0257 0.001
=0
ln
=+0.089V
1.00
2

Half-Cell Potentials
It is best to think of a cells operation in terms of the two reactions taking
place at the two electrodes separately.
can understand each half-cell reaction in isolation
makes classifying and tabulating data easier
Hg

CdSO4 solution

1.018 V

Cathode Potential DIfference

Anode Potential Difference

Cd(Hg)

Standard Reduction Potentials

Convention: We discuss half-cell reactions from a point of view of their
being reduction processes.
Weston Cell Cathode:
Hg2SO4(s) + 2e 2 Hg(l) + SO42(aq)
This is a reduction and is the half-cell process we consider.
Weston Cell Anode:
Cd(Hg) Cd2+(aq) + 2e
This is an oxidation. We must consider the reverse process in our
convention.
Cd2+(aq) + 2e Cd(Hg)

Nernst and Half-Cells

The Nernst equation can be accurately applied to the half cell reactions.
The same rules of products over reactants applies to forming the
activity ratio in the logarithm. The number of electrons is as specified
by the stoichiometry.
The reactions in the Weston Cell:
Hg2SO4(s) + 2e 2 Hg(l) + SO42(aq)

a
a 2
Hg
RT
SO4
EHg2SO4 /Hg =EoHg SO /Hg
ln

2 4
2F aHg2SO4

Cd2+(aq) + 2e Cd(Hg)

RT aCd
E 2+
=E 2+
ln

Cd /Cd
Cd /Cd
2F a 2+
o

Cd

So What Is The Half-Cell E?

To complete each Nernst equation we need to know the potential
difference between each electrode and the solution. This we cannot
measure directly.

?
Hg

?
CdSO4 solution

Solution: Adopt an
arbitrary reference
electrode.

Cd(Hg)

Standard Hydrogen Electrode

The convention is to select a particular electrode and assign its standard
reduction potential the value of 0.0000V. This electrode is the Standard
Hydrogen Electrode.
2H+(aq) + 2e H2(g)

H2
Pt

The standard aspect to this cell is that the

activity of H2(g) and that of H+(aq) are both 1.
This means that the pressure of H2 is 1 atm
and the concentration of H+ is 1M, given that
these are our standard reference states.

H+

Standard as a Reference
Once chosen, this reference cell is employed as one half-cell with all other
cells. Since its potential is assigned the value of 0.000 V, all of the
potential difference measured experimentally is attributed to the other,
test electrode.
Since we are cataloguing reduction potentials, the cells are formed by
connecting the Standard Hydrogen Electrode (SHE) as the anode and
the other half-cell as the cathode.
Consider:
Pt | H2 (1.00 atm) | H+ (1.00 M) || Cu2+ (1.00 M) | Cu
Measured potential = +0.340 V
Since the activity of all components in the Cu cell are standard, +0.340 V
is the STANDARD REDUCTION POTENTIAL of the Cu2+/Cu couple.

By Contrast
Consider the Zn2+/Zn half-cell.
Pt | H2 (1.00 atm) | H+ (1.00 M) || Zn2+ (1.00 M) | Zn
Measured Cell Potential = -0.7626 V
This is the Standard Reduction Potential for this couple.
negative potential means it really is being oxidized
convention accounts for that with the negative sign when written as a
reduction.
will make for easier use of tables.

Standard Potential Tables

All of the equilibrium electrochemical data is cast in Standard Reduction
Potential tables.
F2 + 2e 2F

+2.87

2H+ + 2e H2

0.0000

Co3+ + e Co2+

+1.81

Pb2+ + 2e Pb

-0.13

Au+ + e Au

+1.69

Sn2+ + 2e Sn

-0.14

Ce4+ + e Ce3+

+1.61

In3+ + 3e In

-0.34

Br2 + 2e 2Br

+1.09

Fe2+ + 2e Fe

-0.44

Ag+ + e Ag

+0.80

Zn2+ + 2e Zn

-0.76

Cu2+ + 2e Cu

+0.34

V2+ + 2e V

-1.19

AgCl + e Ag + Cl

+0.22

Cs+ + e Cs

-2.92

Sn4+ + 2e Sn2+

+0.15

Li+ + e Li

-3.05

Using the Tables

F2 + 2e 2F

+2.87

Co3+ + e Co2+

+1.81

Au+ + e Au

+1.69

Ce4+ + e Ce3+

+1.61

Br2 + 2e 2Br

+1.09

Ag+ + e Ag

+0.80

Cu2+ + 2e Cu

+0.34

AgCl + e Ag + Cl

+0.22

Sn4+ + 2e Sn2+

+0.15

choose one reaction for reduction

choose another for oxidation
Au+ + e Au
Cu Cu2+ + 2e
Overall Reaction:
2Au+ + Cu Cu 2+ + 2Au
Cell potential E:
E = +1.69 - 0.34 = +1.35 V

Using the Tables

F2 + 2e 2F

+2.87

Co3+ + e Co2+

+1.81

Au+ + e Au

+1.69

Ce4+ + e Ce3+

+1.61

Br2 + 2e 2Br

+1.09

Ag+ + e Ag

+0.80

Cu2+ + 2e Cu

+0.34

AgCl + e Ag + Cl

+0.22

Sn4+ + 2e Sn2+

+0.15

continued

choose one reaction for reduction

choose another for oxidation
Sn4+ + 2e Sn2+
Ce3+ Ce4+ + e
Overall Reaction:
Sn4+ + 2Ce3+ Sn 2+ + 2Ce4+
Cell potential E:
E = +0.15 - 1.61 = -1.46 V

Calculating Cell Potential

Because we tabulate reduction potentials, the cell potential is calculated
(from those tabulated numbers) as

Ecell = Ecathode - Eanode

The minus sign is present only because we are using reduction potential
tables and, by definition, an anode is where oxidation occurs.

Example
Fe2+ + 2e Fe
V2+ + 2e V

-0.44
-1.19

To get a final positive cell potential,

the more negative half-reaction
(V) must act as the anode.

Sn2+ + 2e Sn

-0.14

Ag+ + e Ag

+0.80

More negative potential reaction is

the anode.
Multiply the Ag reaction by 2, but
dont modify the cell potential.

Fe2+ + V Fe + V2+
2 Ag+ + Sn 2 Ag + Sn2+
Ecell = -0.44 - (-1.19) = +0.75 V
Ecell = +0.80 - (-0.14) = +0.94 V

Oxidative Strength
F2 + 2e 2F

+2.87

Co3+ + e Co2+

+1.81

Au+ + e Au

+1.69

Ce4+ + e Ce3+

+1.61

Br2 + 2e 2Br

+1.09

Ag+ + e Ag

+0.80

Cu2+ + 2e Cu

+0.34

when something is reduced, it induces

oxidation in something else.

AgCl + e Ag + Cl

+0.22

it is an oxidizing agent or an oxidant.

Sn4+ + 2e Sn2+

+0.15

Consider a substance on the left of one of

these equations. It will react as a
reactant with something below it and
on the right hand side.
higher in the table means more likely to
act in a reducing manner.

F2 is a stronger oxidant than Ag+.

Cu2+ is a weaker oxidant than Ce4+.

Reductive Strength
F2 + 2e 2F

+2.87

Co3+ + e Co2+

+1.81

Au+ + e Au

+1.69

Ce4+ + e Ce3+

+1.61

Br2 + 2e 2Br

+1.09

Ag+ + e Ag

+0.80

Cu2+ + 2e Cu

+0.34

AgCl + e Ag + Cl

+0.22

Sn4+ + 2e Sn2+

+0.15

Substances on the right hand side of

the equations will react so as to be
oxidized.
LOWER in the table means a greater
tendency to be oxidized.
when oxidized, it induces reduction in
something else. It is a reducing
agent or reductant.
Ag is a stronger reductant than Au.
Co2+ is a weaker reductant than Sn2+

Cell Potentials, Gibbs Free Energy and

Equilibrium Constants
The equations we have allow is to relate measured cell potentials to
Standard Gibbs Free Energies of reaction. These in turn are related to
a reactions equilibrium constant.
Consider the cell
Pt | I (1.00 M), I2 (1.00 M) || Fe2+ (1.00 M), Fe3+ (1.00 M) | Pt
Standard Cell Potential is (from tables) = 0.771 V - 0.536 V = +0.235 V

C
J

G =nF E =2 96285
(0.235J ) =45,348

mol
mol
o

This is the free energy change. It leads to the equilibrium constant for the reaction.

45348
Go

mol
lnKeq =
=
=18.3034
J
RT
8.314
(298K )

K mol

=8.89107
Keq =e18.3034

Formal Potentials
standard states are impossible to achieve
theoretical calculations of activity coefficients possible below 10 -2 M.
formal potential is that for the half-cell when the concentration quotient
in the Nernst equation equals 1.
solution with a high concentration of inert electrolyte, activity coefficients
are constant. Use formal potentials which are appropriate for that
medium and molar concentrations for very accurate work.
often specified as occurring in 1.0 M HClO4, 1.0 M HCl, or 1.0 M H2SO4.

Example
Consider the Fe(III)/Fe(II) couple. The Nernst equation reads
2+

Fe
2+
2+
RT
RT
[
]
o
o
Fe
Fe
E =E Fe3+/Fe2+ ln
=EFe3+/Fe2+ ln

3+

F a 3+
F 3+[Fe ]

Fe
Fe
2+

Fe
2+
]
RT
RT [
o
Fe
=EFe3+/Fe2+ ln

ln
F 3+ F [Fe3+]
Fe

When the concentration quotient is 1, the last term is 0. This defines the new
formal potential as

o'

RT Fe2+
o
=E 3+ 2+ ln

Fe / Fe
F 3+
Fe

This new reference potential is constant, because the activity coefficients are constant
because they are controlled
by the huge excess of inert

ions.

Example

continued

The standard reduction potential for the Fe(III)/Fe(II) couple is

E = 0.771 V
In 1.0 M HClO4 it is
E(1.0 M HClO4) = 0.732 V
In 1.0 M HCl it is
E(1.0 M HCl) = 0.700 V

Some Extra Work For You

First Year Chemistry Textbook
read chapter on electrochemistry.
lots of examples and problems in using standard reduction potential
tables
interrelating E, E, concentrations (Nernst equation)
interrelating E, G, and Keq.