Lecture 1 Basic Electrochemistry Presentation 2017-1
Lecture 1 Basic Electrochemistry Presentation 2017-1
Lecture 1 Basic Electrochemistry Presentation 2017-1
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
5
Electrochemical Cell
6
Fuel Cell
7
Electrolysis Cell
8
What is electrochemistry?
Electrochemistry is defined as
the branch of chemistry that examines the
phenomena resulting from combined
chemical and electrical effects.
9
Types of processes
10
Electrochemical cell
An electrochemical cell typically consists of:
- Two electronic conductors (also called
electrodes)
- An ionic conductor (called an electrolyte)
11
Modes of charge transport
12
Reactions half cell and overall
13
Half cell reaction types
14
Oxidation and reduction energetics
15
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
16
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
17
Example of electrochemical cell
18
Reactions
19
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
20
Determine the EMF of the following
electrochemical cell (galvanic cell):
FeFe2+ Cu2+Cu, in 1M solution of HNO3
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
23
Competing reactions
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
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
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.
Since
activity coefficients are close to 1 for dilute solutions
reference states for partial pressure and concentration have numerical
value of 1
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
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)
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
0.0257
E E ln Q
n
0.0592
E E log Q
n
Cu2 aq 2 e Cu s Zn s Zn 2 aq 2 e
Cu 2aq Zn s Zn 2aq Cu s
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.
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)
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
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
convention accounts for that with the negative sign when written as a
reduction.
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+.
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.
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.