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Indicator Electrodes, Potentiometry, Electrochemistry, Electrode Kinetics, Electrogravimetry, Polarography, Square Wave Voltammetry, Wavelength Selection, Types of Spectroscopy, Detectors, Theory of Molecular Absorption, Absorption by Organic Molecules, Applying UV-vis Spectroscopy are major topics of this course. Main points from these slides are: Voltammetry, Oxidation and Reduction Reactions, Electrochemical Cell, Electrolytic Cell, Electrode Kinetics, Mass Transport Or Mass Transfer, Diffusi
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transport-limited current limiting current
nFADC bulk
δ
Nernst controlled current RT (^) [Red]
E = Eo nF - ----- ln --------^ [Ox]
informationGives quantitative
Linear Scan Voltammetry (stirred)
E
½ E= Half wave potentialL^ I= Limiting currentC I= Capacitive current
Linear Scan Voltammetry (stirred)
E
Half wave potential (E
½ (^) )
is E when I = I L (^) /
Linear Scan Voltammetry (stirred)
E
When I = I L/2, then ½E = E[Red] = [Ox] and
nF - ------ ln ---------- I
Linear Scan Voltammetry (stirred)
E
reversible irreversible
irreversiblemost irreversiblemore
Can assign rate constants (k) for irreversible processes
Linear Scan Voltammetry (stirred)
E
of the first specieslarge concentrationin the presence of athe second speciesit is difficult to measureFor a two component system
first speciesset by thethe range issmall sinceL IbecomesThe second
This problem is inherent for techniques that produce waves
Linear Scan Voltammetry (unstirred)
E
P E= Peak potentialP I= Peak current
of the curvecontrolled regionLargely Nernstian
from Cottrell Eq.controlled regionPrimarily diffusion
irreversible
reversible
time
Slope = scan rate in mV/sec
Convention for plotting current & potential
to oxidationCurrent due to reductionCurrent due
potentialsreducing
potentialsoxidizing
cathodicE
anodicI^ cathodicI^
anodicE
Ox + e- (^) Red^
Red - e (^) (^) Ox-
Convention for plotting current & potential
cathodicE
anodicI^ cathodicI^
anodicE Ox + e (^) Red-^ Red - e (^) (^) Ox-
scanning in one directionin an unstirred solutionis the same as for LSVGoing from A to B to C to D