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Voltammetry
Voltammetry
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Excitation Signals and Instrumentation
z WE: E (relative to
RE); RE: constant E;
CE: Pt wire (current)
z Supporting
electrolyte: a salt
added in excess to
the analyte solution,
like alkali metal salt Measure I, I-to-E converter
– No reaction at the E E follower, high Z, no I
region
– Reduce effect of
migration
Ei Io
– Lower R of the Eo
solution Eo = Ei R Eo = -IiR
Ii
An op amp potentiostat
2
Modified Electrode
z Chemical modification:
– Irreversibly adsorbing substances:
z oxidation of electrode (metal or C) surface
(O- or –OH)
z electrodeposition
– Covalent bonding of components :
z like SAM of thiols with amine or carboxyl
group on the other end
z Organosilanes or amines
– Coating of polymer films
z Dip coating, spin coating
z Application:
– Electrocatalysis
– Smart window: electrode changes color
upon reaction
– Analytical sensor
B
C Cd
Cd
RΩ
RΩ
Zw Rs Cs
Rct
3
Concentration Profile in Unstirred Solution
A planar electrode with potential step
z Reaction: A + e- Æ P reversible and rapid
z Mass transfer: 1. Migration: electric field;
Supporting electrolyte (100×) 2.Diffusion:
concentration gradient 3.Convection:
mechanical
z Potential vs. surface concentration:
0 0.0592 c0
Eappl = E A − log P − Eref
n c0A A
z Current:
∂c A
i = nFAD
∂x
n: #electron P
F: Faraday constant
A: surface area, cm2
D: diffusion coefficient, cm2/s
Concentration distance profile during diffusion controlled reaction
Hydrodynamic Voltammetry
Flow pattern in a flow stream
z the analyte
solution is kept
in continuous
motion
– stir the
solution, 0 0.0592 c0
Eappl = E A − log P − Eref
n c0
– flow A
solution, like
in HPLC
Flow patter near an electrode
10 ~ 100 µm
0
cP = c A − c 0A
convection
A + e- Æ P reversible
and rapid
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Voltammograms
Volumetric Currents
∂c nFADA
A + ne → P
F : 96485C/mol electron
i = nFADA ( A ) = (c A − c 0A ) A : electrode surface area, cm 2
∂x δ D A : diffusion coefficient, cm 2 /s
c A : mol / cm3
z Limiting current: cA0 at the electrode surface =δ 0. : Nernst diffuion layer thickness, cm
nFADA
il = c A = k Ac A
δ
z Reverse current: cP in the bulk solution = 0.
nFADP 0 nFADP 0 0
i= (c P − c P )= cP = k P cP
δ δ
z Half-wave potential, E1/2: i = il/2
0 0.0592 k 0.0592 i
Eappl = E A − log A − log − Eref
n kP n il − i
0 0.0592 k 0
E1 / 2 = E A − log A − Eref ≈ E A − Eref
n kP
5
Voltammetric I-E
Clark electrode
6
Enzyme-based Sensors
glucose oxidase
glu cos e + O2 ⎯⎯⎯⎯⎯ ⎯
⎯→ gluconic acid + H 2O2
H 2O2 + 2OH − → O2 + H 2O + 2e −
Amperometric Titration
electrochemical active
z A WE (rotating Pt) +
RE: confined to product
either a precipitate or a
stable complex.
– Ag+ for X-, Pb2+ for SO42-
– Exception: Br2 (BrO3-)
titration of organics produced is reduced Both analyte
z Two WEs: and products
are reduced
– simple instrument,
determination of a single
specie
– Karl fisher titration for
determining water
BrO3− + 5 Br − + 6 H + → 3Br2 + 3H 2O
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Rotating Electrodes
O2 reduction
z Rotating electrode:
– RDE: rotating disk electrode, affiliate
mass transfer
– RRDE: rotating ring disk electrode,
intermediate detection
Levich equation:
i = 0.620 nFAD ω1 / 2v −1 / 6c
–
l
n : electron / analyte
D : diffusion coefficient, cm 2 /s
ω : angular velocity, radians/s
v : kinematic viscosity, cm 2 /s
c A : mol / cm3
RDE RRDE
8
Cyclic Voltammetry
A : φNO2 + 4e − + 4 H + → φNHOH + H 2O
B : φNHOH → φNO + 2 H + + 2e −
C : φNO + 2 H + + 2e − → φNHOH
9
CV of Modified electrode
z Reversible
surface redox
couple Æ no
mass transfer
effect Æ
symmetrical
peaks + same
peak height ∆E p = E pa − E pc ≈ 0
Digital Simulation of CV
10
Differential Pulse Polarography
Square-wave Polarography
possible
– Lower DL: ~ 10-7 to 10-8 M 50 mV = 2ESW
– Enhancing faradic current + Decrease in
nonfaradic current
– ∆I = If – Ir, the current difference is plotted
difference
reverse
SWP generation
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Stripping Methods
z Stripping methods:
– Anodic stripping methods: C Æ A
for metal
– Cathodic stripping methods: A Æ C
for halides
z Electrodeposition step:
– Stirring the solution: mass transfer
– Only a fraction of analyte is Anodic stripping methods
deposited: accumulation process
– Depends on c, stir rate, deposition
time, electrode surface and
potential Cd
– t < 1 min. for c ~ 10-7 M
– t > 30 min. for c ~ 10-9 M, (higher
sensitivity)
– HMDE or noble metal (Pt, Au, Ag
and C)
Microelectrodes
z Microelectrode: r ~ 1 to 20 µm
– r >> δ, normal electrode, short time
– δ >> r, UME, long time, steady state
z Advantage: 50 µm
– Small current (I ~ pA to nA) Æ small IR
drop Æ no RE
– Capacitor charging current (Inf ∝ A) Æ
Inf ↓ Æ faster scan
– Faradaic current (If ∝ A/r) Æ bigger
contribution from If Ælower DL
– Rate of mass transport increases Æ
steady state is established within µs Æ
⎛ 1 1⎞
faster kinetic study, higher S/N ration i = nFADc 0A ⎜ + ⎟, δ = πDt
– Little disturbance to the system under ⎝δ r ⎠
study
– Small sample volume
– Small current Æsystem with low
dielectric constants, like toluene
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Homework
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