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Electrochemistry:
Definition and Historical Background
a branch of chemistry that studies
the reactions which take place at
the interface of an electronic
conductor and an ionic conductor
(the electrolyte).
English chemists John Daniell (left) and Michael
Faraday (right), both credited to be founders of
electrochemistry as known today
Theory
where
a: reversible
b: quasi-reversible
c: irreversible
Electrochemistry Set-up
This schematic figure shows a classic setup
for an electrochemical measure system
build up by a potentiostat with three
electrodes: the working (WE), the counter
(CE) and the reference (RE), all of them
dipped into the solution to analyze.
Types of Electrodes
Working electrode is the electrode on which the reaction of interest is
occurring.
Counter electrode, also called an auxiliary electrode, is used only to
make a connection to the electrolyte so that a current can be applied to
the working electrode.
Reference Electrode
Ag/AgCl (3 M NaCl) for aqueous
Ag/Ag+ (0.1 M AgNO3) for organic solvent
Ag, Pt quasi-reference for dry solvent (internal standard: Fc)
Analytical Electrochemistry by Joseph Wang
Terminologies
Potential window range of potential over which
it can be used in a given medium
Cathodic limit ( - side) usually limited reduction
of supporting electrolyte or solvent
Anodic limit ( + side) usually limited by
oxidation of supporting electrolyte or electrode
material itself
Anodic potential limit of metallic solid electrodes and
C electrodes up to a range of +1.2V - +1.6V vs SCE)
Voltammogram - plot
Cathodic peak
Potential window
cathodic limit
Anodic limit
(+) E
oxidation
anodic peak
(-) E
reduction
Hg at very + potential
0.3V and higher, the solid Hg will be the one oxidized
Not useful for oxidative voltammetry
KCl 1M
NH3/NH4Cl
1M
NH4Ac/Hac
2M
-0.3V
-0.5V
electrons
+
+
Cd ions
+
+
+
Bulk solution
Freely
deposited Cd
atoms
mass transport
electron transport
mass transport
Oelectrode
Relectrode
Rbulk
Phase formation
Multiple electron transfer
Absorption spectroscopy
Read out
Plot of I vs E
Plot of A vs
Important parameters
Id = kC
A = bc
E1/2 = f (structure,
medium)
max = f (structure,
medium)
Depends on nature of
electrode process
Depends on nature of
electronic transitions
Shape of curve
Electrochemical methods
Two general types:
Potentiometry
- is a static (zero current) technique.
- sample information is obtained from the measured
potential.
Potentiostatic (also called controlled potential)
- is a dynamic (non zero current) technique.
- sample information is obtained from the measured current.
- Advantages: high sensitivity, selectivity toward an
electro active species, wide linear range, portable and low
cost instrumentation, speciation capability, wide range of
electrode selection.
Potentiostatic Technique:
Cyclic Voltammetry
Linear Sweep
Eswitching
Einitial
Efinal
Triangle Sweep
Formal potential : E0=( Ep,c + Ep,a)/2
Potentiostatic Technique:
Cyclic Voltammetry
Randles-Sevcik Equation:
iP=(2.69x105)n3/2AD1/2Cv1/2
n number of electron in redox reaction
A electrode surface area, cm2
D diffusion coefficient of redox molecule,
cm2/s
C concentration of redox, mol/L
v scan rate, V/s
ipa/ipc
Diagnostic Criteria:
1.
Thus, Nernstian behavior.
2.
3.
2. Quasi-reversible Reaction
Diagnostic Criteria:
3. Irreversible Reaction
Diagnostic Criteria:
1. Broad peak on
1. Broad anodic and
forward scan
cathodic peak separation.
2. No reverse peak on
2. I Ep,c-Ep,aI > 59/n mV
backward scan
Potentostatic Technique:
Chronoamperometry
Steady-state
2C
C
D 2
Ficks 2nd law:
t
x
1/ 2
nFAD
APP C
Cottrell Equation: i
1/ 2t 1/ 2
Electrochemistry-SPR
SPR Phenomenon
ksp k ph
EC-SPR Set-up
Electrochemistry-QCM
EC-QCM Set-up
RE
WE
CE
A q q
Spectroelectrochemisty
A. Film deposition
measurements using EC-SPR
-*
bipolaron
Spectroelectrochem Set-up
Electropolymerization
Electrochemistry-SPR-AFM
EC-SPR-AFM Set-up
AFM
PEDOT
EDOT
Electropolymerization