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electrochemistry

Monday 10 12.30
Wenesday 13 14.30
Electrochemistry
ENMT 613008
ENMT 603004
Syllabus: basic concepts and application of
electrochemistry, and conductivity solutions,
Faradays law, and their application. Electrode
electrochemical cell (definition, potential,
equation Nernst, electrical double layer, the
polarization, the measurement of potential, free
energy and electrode potential, equilibrium
potential), the reference electrode, construction
Pourbaix diagram and its application.
Electrochemical kinetics, electrode reaction
speed, mixed potential theory, Evans diagram,
the mixed potential diagram
Text Books
- JOM Bockris and AKN Reddy: Modern
Electrochemistry, vol. 1, 2 1997
- Bard, Faulkner and Larry R: Electrochemical
Methods Fundamentals and Application,1980
- Piron, The electrochemistry of corrosion,
NACE, 1991
Pyrometallurgical
Hydrometallurgical
Electrometallurgy Purification or
recovery of metals using electric or
electrolytic processes - Electrochemical
Basic Concepts in
Electrochemistry

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Electrochemical Cell

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Fuel Cell

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Electrolysis Cell

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What is electrochemistry?
Electrochemistry is defined as
the branch of chemistry that examines the
phenomena resulting from combined
chemical and electrical effects.

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Types of processes

This field covers:


- Electrolytic processes:
Reactions in which chemical changes occur on
the passage of an electrical current
- Galvanic or Voltaic processes:
Chemical reactions that result in the production
of electrical energy

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Electrochemical cell
An electrochemical cell typically consists of:
- Two electronic conductors (also called
electrodes)
- An ionic conductor (called an electrolyte)

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Modes of charge transport

Charge transport in the electrodes occurs via the


motion of electrons (or holes),
Charge transport in the electrolyte occurs via
the motion of ions (positive and negative)

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Reactions half cell and overall

At each electrode, an electrochemical reaction


occurs. This reaction is called a half cell
reaction (since there are two electrodes in a
typical cell at which reactions occur)
The overall chemical reaction of the cell is
given by combining the two individual half
cell reactions

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Half cell reaction types

There are two fundamental types of half cell


reactions:
- Oxidation reactions
- Reduction reactions
A reaction is classified as oxidation or reduction
depending on the direction of electron
transfer

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Oxidation and reduction energetics

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Oxidation
Involves the loss of an electron
Involves the transfer of electrons from the
species to the electrode
R = O + ne (1)
Oxidation is an energetic process, and occurs
when the energy of the electrode dips below the
highest occupied molecular orbital of the
compound see figure part b
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Reduction
Involves the gain of an electron
Involves the transfer of electrons from the
electrode to the species
O + ne = R (2)
Reduction is also an energetic process, and occurs
when the energy of the electrode increases
above the lowest vacant molecular orbital of
the compound see figure part a
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Example of electrochemical cell

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Reactions

Zinc metal gets oxidized - goes into solution:


Zn = Zn2+ + 2e (3)
Copper ions in solution reduced; copper metal -
deposited on the copper electrode
Cu 2+ + 2e = Cu (4)
Electrons for reduction obtained from the zinc
electrode - external wire
Sulfate ions [reaction (4)] migrate through the
membrane, -react with the zinc ions [from (3)] -
zinc sulfate

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Convention
Electrode at which the oxidation reaction
occurs is called the anode
Electrode at which the reduction reaction occurs
is called the cathode
Thus in the above example, the zinc electrode
was the anode and the copper electrode was
the cathode

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Determine the EMF of the following
electrochemical cell (galvanic cell):
FeFe2+ Cu2+Cu, in 1M solution of HNO3

Determine the EMF of the following


electrochemical cell (galvanic cell): if the
solution of Fe 0.01M and Cu 3M
Working and counter electrodes
The electrode at which the reaction of
interest occurs is called the working
electrode
The electrode at which the other (coupled)
reaction occurs is called the counter
electrode
A third electrode, called the reference
electrode may also be used
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What gets oxidized?

In previous example:
- Zn was oxidized
- Cu was reduced
For a given set of two reversible redox reactions,
Thermodynamics predicts which reaction
proceeds as an oxidation and which proceeds
as a reduction

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Competing reactions

F or a set of 2 competing reactions:


The reaction with the lower standard reduction
potential gets oxidized -
the other reaction proceeds as a reduction
Zn = Zn2+ + 2e (3) Ered = - 0.7618 V
Cu2+ + 2e = Cu (4) Ered = 0.341 V
Thus, in the above example, Zn is oxidized, and
Cu is reduced
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Standard electrode potential (E0)
- the anode oxidation half-reaction is then:
Zn(s) Zn2+(aq) + 2e-
- the reduction half-reaction occurs as follows:
2H+(aq) + 2e- H2(g)
Where concentration of H+ is 1 M and
pressure of H2 gas is at 1 atm. The line
notation for this cell is:
Zn(s) | Zn2+(aq),(1M) || 2H+(aq) | H2(g),(1atm)
If Eocell> 0, we have a spontaneous process
(galvanic cell)
If Eocell< 0, we have a nonspontaneous process
(electrolytic cell))

G0cell is related to E0cell by the equation:


G0cell = -nFE0cell
where n is number of moles of electrons per
mole of products
F is the Faraday constant, ~96,485 C/mol =
96500 C/mol
Thus in order to have a spontaneous reaction
(-G0), Eocell must be positive, where
Eocell= Eoanode + Eocathode
where E0anode is the standard potential at the
anode (reverse the sign of the standard
reduction potential value for the electrode)
and E0cathode is the standard potential at the
cathode as given in the table of standard
electrode potential.
Electrochemical cell
Electrochemical Thermodynamics
Every substance has a unique propensity to contribute to a systems energy. We
call this property Chemical Potential.

m
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.

m=m+nFf
These are perhaps the most fundamental measures of thermodynamics.
Gibbs Free Energy
The free energy function is the key to assessing the way in which a chemical
system will spontaneously evolve.

dG SdT V dP mi dni dA f dl

constant T dont stretch it


constant P dont change
shape

dG mi dni
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 n F E

Note how a measurement of a cell potential directly calculates the Gibbs


free energy change for the process.
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)
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 Reference states are
volume changes with T 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 P
a a
C 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:

m m RT ln a
Reaction Quotient
wA xB yC zD
In order to analyze a chemical process mathematically, we form this reaction
quotient.

aCy a zD
Q
aw a
A B
x

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.


Concentration Dependence
How does Gibbs free energy change with activity (concentration)?

Same dependence as with the chemical potential. We have

G G RT ln a

When we apply this to a reaction, the reaction quotient comes into to play,
giving us

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

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

0 G R T ln Q*
G RT ln Q* 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.
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 ln Q
The relation between cell potential E and free energy gives

n F E n F E R T ln Q
Rearrange and obtain the Nernst Equation.

RT
E E ln Q
nF
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 ln Q
n
0.0592
E E log Q
n

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 2 e Cu s Zn s Zn 2 aq 2 e

Cu 2aq Zn s Zn 2aq Cu s

Note that n=2 for this reaction. =1

RT aCu a
Zn 2
Zn2
EE ln
nF a 2 aZn
Cu =1
Activity for solid materials is 1; replace activities with concentrations.

EE
RT
ln
Zn 2
1.10 0.01285 ln
Zn 2
2 F Cu 2
Cu 2
Example continued

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

1.00
E 1.10 0.01285 ln 1.10 0.01285 ln 100
0.01
1.10 0.01285 4.6052 1.041V
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

RT a 2Hg a 2 a 2
Cd SO4
EE ln
nF aCd a Hg2 SO4

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?

E E
0.0257 Cu 2
ln

anode


n
Cu
2


cat hode
0.0257 0.001
0 ln 0.089 V
2 1.00
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)

a2Hg a 2
RT SO4
EHg2 SO4 / Hg E Hg ln
2 SO4 / Hg 2 F a Hg2 SO4

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

RT aCd
E E ln
Cd 2 /Cd Cd 2 / Cd 2 F a 2

Cd
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 The standard aspect to this cell is that the


activity of H2(g) and that of H+(aq) are both 1.
Pt 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 choose one reaction for reduction
choose another for oxidation
Co3+ + e Co2+ +1.81
Au+ + e Au +1.69 Au+ + e Au
Cu Cu2+ + 2e
Ce4+ + e Ce3+ +1.61
Br2 + 2e 2Br +1.09 Overall Reaction:
2Au+ + Cu Cu 2+ + 2Au
Ag+ + e Ag +0.80
Cu2+ + 2e Cu +0.34
Cell potential E:
AgCl + e Ag + Cl +0.22
E = +1.69 - 0.34 = +1.35 V
Sn4+ + 2e Sn2+ +0.15
Using the Tables continued

F2 + 2e 2F +2.87 choose one reaction for reduction


choose another for oxidation
Co3+ + e Co2+ +1.81
Au+ + e Au +1.69 Sn4+ + 2e Sn2+
Ce4+ + e Ce3+ +1.61 Ce3+ Ce4+ + e
Br2 + 2e 2Br +1.09 Overall Reaction:
Sn4+ + 2Ce3+ Sn 2+ + 2Ce4+
Ag+ + e Ag +0.80
Cu2+ + 2e Cu +0.34
Cell potential E:
AgCl + e Ag + Cl +0.22
E = +0.15 - 1.61 = -1.46 V
Sn4+ + 2e Sn2+ +0.15
Oxidative Strength
F2 + 2e 2F +2.87 Consider a substance on the left of one of
these equations. It will react as a
Co3+ + e Co2+ +1.81 reactant with something below it and on
the right hand side.
Au+ + e Au +1.69
Ce4+ + e Ce3+ +1.61 higher in the table means more likely to act
Br2 + 2e 2Br +1.09 in a reducing manner.

Ag+ + e Ag +0.80 when something is reduced, it induces


Cu2+ + 2e Cu +0.34 oxidation in something else.

AgCl + e Ag + Cl +0.22
it is an oxidizing agent or an oxidant.
Sn4+ + 2e Sn2+ +0.15
F2 is a stronger oxidant than Ag+.

Cu2+ is a weaker oxidant than Ce4+.


Reductive Strength
F2 + 2e 2F +2.87 Substances on the right hand side of the
Co3+ + e Co2+ +1.81 equations will react so as to be
oxidized.
Au+ + e Au +1.69
Ce4+ + e Ce3+ +1.61 LOWER in the table means a greater
Br2 + 2e 2Br +1.09 tendency to be oxidized.

Ag+ + e Ag +0.80
when oxidized, it induces reduction in
Cu2+ + 2e Cu +0.34 something else. It is a reducing agent
or reductant.
AgCl + e Ag + Cl +0.22
Sn4+ + 2e Sn2+ +0.15
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 n F E 2 96285

0.235 J 45,348
mol mol
This is the free energy change. It leads to the equilibrium constant for the reaction.
45348 J
G mol
ln Keq 18.3034
RT 8.314 J 298 K
K mol
Keq e18.3034 8.89 10 7
Example
Consider the Fe(III)/Fe(II) couple. The Nernst equation reads

EE
RT
ln
a
Fe 2

EFe 3 / Fe 2
RT

ln

Fe 2
Fe
2

Fe 3 /Fe 2 F a 3
Fe
F
Fe
3 Fe3

E
RT
2
ln Fe
RT
Fe
ln 3
2

Fe 3 / Fe 2 F 3 F
Fe
Fe
When the concentration quotient is 1, the last term is 0. This defines the
new formal potential as

' RT Fe 2
E E ln
Fe 3 / Fe 2 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.

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