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Electroanalytical Chemistry

Dahlia C. Apodaca, Ph. D.

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

Faradays law of electrolysis:


The mass of a substance produced at an electrode during electrolysis is
proportional to the number of moles of electrons (the quantity of electricity)
transferred at that electrode.

In modern form, Faraday's law states:

where

m is the mass of the substance produced at the electrode (in grams),


Q is the total electric charge that passed through the solution (in coulombs),
q is the electron charge = 1.602 x 10-19 coulombs per electron,
n is the valence number of the substance as an ion in solution (electrons per
ion),
F is Faraday's constant,
M is the molar mass of the substance (in grams per mole), and
NA is Avogadro's number = 6.022 x 1023 ions per mole.

Product yield vs. charge transferred insight into mechanism

Kinetics of Electrode Reaction


Butler-Volmer equation:
Fundamental relationship between current flowing and applied voltage

i0=exchange current density


E=applied potential
Eo=formal potential
=symmetry factor

a: reversible
b: quasi-reversible
c: irreversible

Experimental Setup and Instrumentation

Voltage scan generator (VSG) or ramp generator outputs potential


as a linear function of time

Potentiostat (constant potential source) controls the potential


between WE and RE; ensures that the potential applied to the WE is
equal to that of the output of the VSG.
Electrochemical cell solution and three electrodes; applied
potential generates a current through the cell between the WE and
AE
Current measuring device converts the generated current to a
voltage signal
Electronic integrator amplifier
Recorder records the voltammogram (I vs E)

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 maintains the value of the fixed voltage at the


working electrode.
Analytical Electrochemistry by Joseph Wang

Some Experimental Consideration


Solvent: dissolve both monomers and electrolyte,
electrochemically stable
Supporting electrolyte (Bu4NClO4, Et4PF6) at least 50 time
more concentrated than redox species, electrochemically
stable
Working Electrode: materials (Au, Pt, C, SnO2, Hg, ), shape
and size
e. g. Hg for cathodic rxn in H2O due to large hydrogen overpotential
(toxic, though)
Shape (wire, film, disk, ): current density distribution
Size (macro vs. micro) : comparable with solution volume

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

Choices of Working Electrode, Solvent and


Supporting Electrolyte

Analytical Electrochemistry by Joseph Wang

Hg at very + potential
0.3V and higher, the solid Hg will be the one oxidized
Not useful for oxidative voltammetry

For ascorbic acid determination, use solid


electrode or glassy carbon electrode but not Hg
Cathodic potential limit: Pt and Au up to -0.4
0.7V vs SCE; C electrode up to -1.0V vs SCE
Electrode solution interface where the desired
electrode reaction would take place

Choice of supporting electrolyte


(complexing agents)
Allows signal enhancement of required metal
species to be determined (can eliminate
undesired species also)
Allows the additional use of one or more
complexing agents to increase selectivity
Allows masking of higher concentration
elements when determining traces in the
same medium (ppb trace detn in a g/l bulk
concn soln)

KCl 1M

NH3/NH4Cl
1M

NH4Ac/Hac
2M

-0.3V

-0.5V

Nature of Electrode reactions


Nernst Diffusion layer
Electrode

electrons

+
+

Cd ions
+

+
+

Bulk solution

Freely
deposited Cd
atoms

3 steps involved in the


electrode reaction
Obulk
Oelectrode
Relectrode

mass transport
electron transport
mass transport

Oelectrode
Relectrode
Rbulk

3 modes of mass transport


Diffusion movement of species under the influence of a concentration
gradient
Migration movement of charged species due to electrostatic forces;
made negligible by addition of a large excess of an inert electrolyte
(supporting electrolyte like potassium nitrate or sodium chloride)
Convection movement of species due to external mechanical forces;
eliminated by carrying out electrolysis in a thermostat in absence of
stirring or vibration. Ex. Hydrodynamic voltammetry
Flow through cell diffusion and convection

In polarography, the only mode of mass


transfer is diffusion, and current arises solely
from diffusion (diffusion current)
The rate of chemical charge (current density)
is determined by slowest step
Complications
Adsorption
Chemical reactions
In electrolyte medium
On electrode surface

Phase formation
Multiple electron transfer

Chemical charge at the electrode surface always


leads to diffusion
Reactant to the electrode
Product away from the electrode

Flowing solution, moving electrode, gas sparging,


etc. lead to convection
In a cell there is always a potential gradient
between anode and cathode. Reactant and/or
product is always a charged species; migration
always occurs
Minimized for reactant/product by addition of
inert electrolyte

Analogy bet. Polarography and


absorption spectroscopy
DC polarography

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

Limiting current diffusion-controlled current rate of


electrode process limited by rate of diffusion
Half-wave potential (E1/2) potential on polarographic
curve at which current reaches half of its limiting value;
depends on the nature of electrolyed substance and
composition of solution; used for qualitative
characterization of substances

Diffusion current (id) depends on the concentration of


electroactive substances in solution; quantitative
parameter

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.

Analytical Electrochemistry by Joseph Wang

Potentiostatic Technique:
Cyclic Voltammetry

Linear Sweep

Eswitching

Einitial

Efinal

Triangle Sweep
Formal potential : E0=( Ep,c + Ep,a)/2

Analytical Electrochemistry by Joseph Wang

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

electrochemical intermediate stability


Ep=2.3RT/nF, (58/n mV @ 25oC) reaction reversibility
Eo=1/2(Epa+Epc) thermal-dynamic Fermi energy level
Analytical Electrochemistry by Joseph Wang

CV: Mechanism of electron transfer


1. Reversible Reaction

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

Mass Transport Equation ----

2C
C
D 2
Ficks 2nd law:
t
x
1/ 2
nFAD
APP C
Cottrell Equation: i
1/ 2t 1/ 2

Analytical Electrochemistry by Joseph Wang

Vary rate of diffusion

Potential step time, t


CV potential scan rate, v
Microelectrode radius, r
A.C. impedance - frequency

MODERN HYPHENATEDELECTROCHEMICAL TECHNIQUES

Electrochemistry-SPR
SPR Phenomenon

ksp k ph

B. Film deposition kinetic


measurements using EC-SPR

EC-SPR Set-up

Surface plasmon resonance (SPR) refers to the optical


excitation of surface plasmon oscillations at a metal dielectric
boundary by evanescent waves from the base of the prism.
SPR is a collective oscillation of charges at a metal boundary,
which propagates along the interface.
SPR is sensitive to the modification occurring at the thin metal
film interface.

A. Chemical sensing using EC-SPR

Advincula et al. Adv. Funct. Mater. 2006, 16, 2000.

Advincula et al. Langmuir 2008, 24, 9017.

Electrochemistry-QCM

A. Film deposition kinetic


measurements using EC-QCM

EC-QCM Set-up
RE
WE

CE

Advincula et al. Macromolecules 2008, 41, 6703.

Quartz crystal microbalance (QCM) is an


instrument that is sensitive to mass variations
by measuring the change in frequency of a
quartz crystal when it is disturbed by the
addition of a small mass.
Piezoelectric Effect: The ability of certain
crystals to generate electrical potential when
subjected to mechanical stress, and vice-versa.
Sauerbrey Equation:
2mf 2

A q q

f0 is the resonant frequency of the quartz crystal


A is the active area of the crystal between electrodes
q is the density of quartz
q is the shear modulus of quartz

Advincula et al. Langmuir 2007, 23, 908.

Spectroelectrochemisty

A. Film deposition
measurements using EC-SPR

Coupling of a potentiostat set-up to a UV-Vis


spectrometer.
The sample cell includes a cuvette with a three
electrode system (reference electrode, counter
electrode, working electrode (e.g. ITO).
Thus, during a potential sweep, the spectroscopic
measurements can be performed.

-*

bipolaron

Spectroelectrochem Set-up

Electropolymerization

Advincula et al. Chem. Mater. 2008, 20, 4915.

Electrochemistry-SPR-AFM

EC-SPR-AFM Set-up

Atomic force microscopy (AFM) is a


method of measuring
surface
topography.

Film deposition using ECSPR-AFM measurements/


characterization

The technique involves imaging a


sample through the use of a probe, or
a tip. The tip is held several
nanometers above the surface using a
feedback mechanism that measures
the surface-tip interactions.

AFM

Variations in tip height are recorded


while the tip is scanned repeatedly
across the sample, producing a
topographic image of the surface.

Coupling of EC, SPR, and AFM, enables


the simultaneous determination of
chemical and optical properties as well
as surface morphology of films.
Advincula et al. Rev. Sci. Instrum. 2006, 77, 064101.

PEDOT
EDOT
Electropolymerization