Introduction to

Electroanalytical Chemistry
Potentiometry, Voltammetry,
Amperometry, Biosensors
Applications
Study Redox Chemistry
electron transfer reactions, oxidation,
reduction, organics & inorganics, proteins
Adsorption of species at interfaces
Electrochemical analysis
Measure the Potential of reaction or process
E = const + k log C (potentiometry)
Measure the Rate of a redox reaction; Current
(I) = k C (voltammetry)
Electrochemical Synthesis
Organics, inorganics, materials, polymers
Electrochemical Cells
Galvanic Cells and Electrolytic Cells
Galvanic Cells power output; batteries
Potentiometric cells (I=0) read Chapter 2
measure potential for analyte to react
current = 0 (reaction is not allowed to occur)
Equil. Voltage is measured (E
eq
)

Electrolytic cells, power applied, output meas.
The Nernst Equation
For a reversible process: Ox + ne- Red
E = E
o
(2.303RT/nF) Log (a
red
/a
ox
)
a (activity), related directly to concentration
Voltammetry is a dynamic
method
Related to rate of reaction at an electrode

O + ne = R, E
o
in Volts

I = kA[O] k = const. A = area
Faradaic current, caused by electron transfer

Also a non-faradaic current forms
part of background current
Electrical Double layer at Electrode
Heterogeneous system: electrode/solution
interface
The Electrical Double Layer, es in electrode;
ions in solution important for voltammetry:
Compact inner layer: d
o
to d
1,
E decreases linearly.
Diffuse layer: d
1
to d
2,
E decreases exponentially.

Electrolysis: Faradaic and Non-Faradaic
Currents
Two types of processes at electrode/solution
interface that produce current
Direct transfer of electrons, oxidation or reduction
Faradaic Processes. Chemical reaction rate at
electrode proportional to the Faradaic current.

Nonfaradaic current: due to change in double layer
when E is changed; not useful for analysis

Mass Transport: continuously brings reactant from the
bulk of solution to electrode surface to be oxidized or
reduced (Faradaic)
Convection: stirring or flowing solution
Migration: electrostatic attraction of ion to electrode
Diffusion: due to concentration gradient.

Typical 3-electrode
Voltammetry cell
Counter
electrode
Reference electrode
Working electrode
End of Working electrode
O
R
O
R

e
-

Bulk solution
Mass transport
Reduction at electrode
Causes current flow in
External circuit
Analytical Electrolytic Cells
Use external potential (voltage) to drive
reaction
Applied potential controls electron energy
As E
o
gets more negative, need more
energetic electrons in order to cause
reduction. For a reversible reaction:
E
applied
is more negative than E
o
, reduction
will occur
if E
applied
is more positive than E
o
, oxidation
will occur
O + ne- = R E
o
,V

electrode reaction
Current Flows in electrolytic cells
Due to Oxidation or reduction
Electrons transferred
Measured current (proportional to reaction
rate, concentration)

Where does the reaction take place?
On electrode surface, soln. interface
NOT in bulk solution

Analytical Applications of Electrolytic Cells
Amperometry
Set E
applied
so that desired reaction occurs
Stir solution
Measure Current

Voltammetry
Quiet or stirred solution
Vary (scan) E
applied
Measure Current
Indicates reaction rate
Reaction at electrode surface produces concentration
gradient with bulk solution
Mass transport brings unreacted species to electrode surface
E, V
time
Input: E-t waveform
potentiostat
Electrochemical cell
counter
working electrode
N
2
inlet
Figure1
reference
insulator
electrode
material
Cell for voltammetry, measures I vs. E
wire
Output, I vs. E, quiet solution
reduction
Polarization - theoretical
Ideally Polarized Electrode
Ideal Non-Polarized Electrode
No oxidation or reduction
reduction
oxidation
Possible STEPS in electron transfer processes
Rate limiting step may be mass transfer
Rate limiting step may be chemical reaction
Adsorption, desorption or crystallization polarization
Charge-transfer may be rate limiting
Overvoltage or Overpotential
= E E
eq
; can be zero or finite

E < E
eq
< 0
Amt. of potential in excess of E
eq
needed to make
a non-reversible reaction happen, for example
reduction
E
eq

NERNST Equation: Fundamental Equation
for reversible electron transfer at electrodes
O + ne
-
= R, E
o
in Volts
E.g., Fe
3+
+ e- = Fe
2+
If in a cell, I = 0, then E = E
eq
All equilibrium electrochemical reactions obey the
Nernst Equation


Reversibility means that O and R are at equilibrium at all times, not all
Electrochemical reactions are reversible

E = E
o

- [RT/nF] ln (a
R
/a
O
) ; a = activity

a
R
= f
R
C
R
a
o
= f
o
C
o
f = activity coefficient, depends on ionic strength

Then E = E
o

- [RT/nF] ln (f
R
/f
O
) - [RT/nF] ln (C
R
/C
O
)
F = Faraday const., 96,500 coul/e, R = gas const.
T = absolute temperature







Ionic strength I = z
i
2
m
i,

Z = charge on ion, m = concentration of ion

Debye Huckel theory says log f
R
= 0.5 z
i
2
I
1/2

So f
R
/f
O
will be constant at constant I.

And so, below are more usable forms of Nernst Eqn.

E = E
o

- const. - [RT/nF] ln (C
R
/C
O
)
Or
E = E
o

- [RT/nF] ln (C
R
/C
O
); E
o

= formal potential of O/R

At 25
o
C using base 10 logs

E = E
o

- [0.0592/n] log (C
R
/C
O
); equil. systems