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Reading Material
Cazes:
Ch. 25
Chapter 17
Voltammetry
Polarography:
Amperometry:
Polarization
More on Polarization
Overvoltage:
DC Polarography
www.drhuang.com/.../polar.doc_files/image008.gif
A variable potential
excitation signal is applied
to the working electrode
Different voltammetric
techniques use different
waveforms
A linear sweep
voltammogram for the
following reduction of A
into a product P is shown
A + n e- P
A + n e- P
Half-wave potential
Limiting current
Remember, E is scanned
linearly to higher values as
a function of time in linear
sweep voltammetry
Hydrodynamic Voltammetry
Hydrodynamic Voltammograms
Example:
the
hydrodynamic
voltammogram of
quinone-hydroquinone
OH
+ 2H+ + 2e
OH
quinone
hydroquinone
Cathodic wave
Anodic wave
Diagram from Stroebel and Heineman, Chemical Instrumentation, A Systematic Approach 3 rd Ed. Wiley 1989.
Environmental Studies
Sewage Treatment
Fermentation Process
Medicine
O2
O2
dissolved
O2
id - measured current
O2
analyte solution
electrolyte
O2 permeable membrane
(O2 crosses via diffusion)
id = 4 F Pm A P(O2)/b
F - Faraday's constant
Pm - permeability of O2
A - electrode area
P(O2) - oxygen concentration
b - thickness of the membrane
platinum electrode
(-0.6 volts)
Cyclic Voltammetry
Cyclic Voltammetry
Cyclic Voltammetry
Spectroelectrochemistry (SEC)
transparent electrodes
This allows for analysis of the mechanisms involved in
complex electrochemical reactions
Example: ferrocene oxidized to ferricinium on a forward CV
sweep (ferricincium shows UV peaks at 252 and 285 nm),
reduced back to ferrocene (fully reversible)
Y. Dai, G. M. Swain, M. D. Porter, J. Zak, New horizons in spectroelectrochemical measurements: Optically transparent carbon electrodes, Anal. Chem., 2008, 80, 14-27.
Further Reading:
C. Amatore and E. Maisonhaute, When voltammetry reaches
nanoseconds, Anal. Chem., 2005, 303A-311A.
Y. Dai, G. M. Swain, M. D. Porter, J. Zak, New horizons in
spectroelectrochemical measurements: Optically transparent
carbon electrodes, Anal. Chem., 2008, 80, 14-27.