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Anodic Stripping Voltammetry (ASV)
- Combines two techniques discussed previously
- the purpose of preconcentrating species of interestThe first step is Electrodeposition at constant potential for Done in stirred solution to enhance mass transfer
electrodeEither plate 100% of material (usually a metal) onto or into the
plate a constant fraction each run (most common approach)Or plate with reproducible stirring for a known time interval to
- direction to reoxidize or strip out the plated materialThe second step is a linear potential sweep in the anodic
Unstirred solution during stripping step
Linear Scan
ASV
time
E
cathodic
fixed time interval reducing Mpotential is applied for aA cathodic or reducing
n+
E
anodic
anodicI
M n+
↔-^ (^) M o
M
↔^ - M^ (^) n+
direction to strip out Min anodic or oxidizingPotential is scanned
o
backward scanpeaks withupside downrequires plottingConvention
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any electrodeASV can be done with
DropMercury Hanging
- Can improve by use differential pulse stripping step)waveform during anodic scan (i.e.,
- Measure current at points indicated
time
E
cathodic
- A thin film mercury electrode (TFME or MFE) the surface of a carbon electrodecan also be prepared by plating mercury onto
- This is usually accomplished by adding a the analyte ionsplating out the mercury simultaneously withsolution of mercury ions to the sample and
- The other metals strip out first and mercury last
- Mercury oxidation wave- Hydrogen wave- Extremely sensitive- Several metals in scanDifferential Pulse ASV
- Can also do cathodic stripping voltammetry species on the surface of the electrodeusing an anodic potential to adsorb anionic(CSV) or adsorptive stripping voltammetry
- Ions like MoO
(^4) 2- and CrO^
(^4) 2-
- Stripping step is a cathodic scan
Square Wave Voltammetry
- One of the most modern electroanalytical techniques (approximately 20 years old)
- Can be used with a preconcentration step• Can be used with all types of electrodes• Very fast (1 Volt scan in 0.5 sec)• Very sensitive as in ASV (square wave stripping)
- I = n F A D• Uses large amplitude square wave
½ C^
½
τ^
½
ψ^
(E
s ,E
p)
C = differenceB = anodic currentA = cathodic current
- Voltammogram is obtained in 0.5 to 3 sec depending on frequency
- If using DME, the entire scan is done in the last half of a single drop
- For a reversible reaction, size of pulse is direction and oxidation on reverse pulselarge enough to cause reduction in one
- Get forward current (cathodic) and reverse current (anodic) combine to get 2 x current
- Gives peak at E
½
M, without plating^
FIA/HPLC flow cells – use low volume cell with
counter electrode downstreamworking electrode upstream, reference and
- Several possible types of measurements
flow stream as in ion chromatography (IC)Conductance – measure conductivity of
solutes reach electrodewith fixed potential measuring current asAmperometry – like chronoamperometry
Voltammetry – need fast method like SWV
coulombs as solutes go by (not efficient)Coulometry – fix E (or I) and count
Frontiers in Electrochemistry
Hydrodynamic electrochemistry
- e.g. using Rotating Disk Electrode (RDE)
improved mass transport
reproducible convection
- Rotating Ring Disk Electrode (RRDE)
reduce something at the disk
reoxidize it as it passes the ring
similar to cyclic voltammetry
disk
ring
electrodeAnnimated rotating
- (^) Membrane covered electrodes
over the surface of the electrode for selectivityput dialysis membrane or other membrane
mass transport is hindered
- modify surface of electrode by attachingChemically modified electrodes
that are electroactivereduced themselves or that bind other speciesfunctional groups that are either oxidized or
Conducting polymers as electrodes
