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Ch. 25
Chapter 17
Voltammetry
Polarization
More on Polarization
Overvoltage:
DC Polarography
The first voltammetric technique
(first instrument built in 1925)
If an electroactive species is
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A variable potential
Different voltammetric
A linear sweep
A + n e- P
Half-wave potential
Limiting current
proportional to analyte
concentration
and is used for
quantitative analysis
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
obtained depending on
the starting sample
OH
+ 2H+ + 2e
OH
quinone
hydroquinone
Cathodic wave
Anodic wave
Diagram from Stroebel and Heineman, Chemical Instrumentation, A Systematic Approach 3rd Ed. Wiley 1989.
O2
Ag + ClO2
dissolved
O2
id = 4 F P
AgCl + em
A P(O2)/b
id - measured current
O2
analyte solution
4OH-
F - Faraday's constant
Pm - permeability of O2
electrolyte
A - electrode area
P(O2) - oxygen concentration
b - thickness of the membrane
O2 permeable membrane
(O2 crosses via diffusion)
platinum electrode
(-0.6 volts)
Cyclic Voltammetry
Cyclic Voltammetry
Cyclic Voltammetry