Chapter 25.

Voltammetry

z Excitation Signal in Voltammetry

z Voltammetric Instrumentation
z Hydrodynamic Voltammetry
z Cyclic Voltammetry
z Pulse Voltammetry
z High-Frequency and High-Speed
Voltammetry
z Application of Voltammetry
z Stripping Methods
z Voltammetry with Microelectrodes

Voltammetry

z Voltammetry: measurement of current (I) as a function

of applied potential (E). Under condition with
polarization (η). Negligible consumption of analyte
– Amperometry: measure I at a fixed E
– Potentiometry: measure E when I Æ 0, no polarization
– Coulometry: measure C, polarization is compensated, all
analyte is consumed
z Polarography: voltammetry at the dropping mercury
electrode (DME)
– DA: Hg (poison), apparatus (cumbersome), better techniques
z Application:
– Oxidation and reduction process
– Adsorption processes on surfaces
– Electron transfer mechanism
Jaroslav Heyrovsky
1890-1967

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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

Voltammetric Working Electrode

z Disk electrode: A small flat disk in a
rod of an inert materials like Teflon,
glass or Kel-F.
z HMDE: hanging mercury drop
electrode
– Large negative E, fresh metallic HMDE
surface, reversible reaction
z UME: microelectrode, r: < 25 µm, wire Disk electrode
in glass, tip polished WE
z Flow cell WE: in flowing stream,
PEEK (polyethertherketon)
z Emin: reduction of water (H2), Emax:
oxidation of water (O2)

UME Flow electrode

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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

Circuit Model of a Working Electrode

Double

A. Randles circuit: layer

Diffusion
Bulk electrolyte layer
– RΩ, solution resistance
– Cd, double layer capacity
WE

– Zf, faradaic impedance Æ f dependence

B. Faradaic impedance:
– Rs, electron transfer resistance
– Cs, pseudocapacitance, mass transfer A Cd
C. Faradaic impedance:
RΩ
– Rct, charge transfer resistance Zf
– Zw, Warburg impedance

B
C Cd
Cd
RΩ
RΩ
Zw Rs Cs
Rct

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 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

4
Voltammograms

z Voltammetric wave: an ∫-shaped wave of I-E

z Limiting current, il: the current plateau observed at the
top, ∝ cA il = kc A Linear-sweep voltammogram
– cA = 0 at electrode surface at slow scan rate
– maximum mass transfer rate
z Current in American way: E0 = -0.26 V
– Reduction current +
– Oxidation current -
z Half-wave potential:
– E1/2 at i = il/2, ≠ E0
– Relative to E0
– Identification
vs. SCE

Volumetric Currents

z A planar electrode: Nernst diffusion layer δ control

n : electron / analyte

∂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

z Based on the kinetics of the reaction:

– Reversible systems: obey Nernst ∆E = 0.1 V
equation ∆E = 0.2 V
– Totally irreversible system: either the
cathodic or anodic reaction is too slow as
to be negligible
– Partially reversible system: the reaction in
one direction is much slower than the
other one.
– like organic system, i = kc, E = f(v, c, il)
z Voltammogram for mixture:
– ∆E ≥ 0.1 V
z Anodic/Cathodic Voltammogram:
– A: oxidation current –
– B: both reaction
– C: reduction current +

Clark electrode

Oxygen Wave and Sensors

z Oxygen wave:
– I is proportional to n
– Sparging: deaerate the solution with inert
gas, N2, Ne and He
– Highly depends on the pH of the solution
z Clark electrode: volumetric sensor
– Cathodic Pt electrode: O2 + 4H+ + 4e ↔
2H2O
– Anodic Ag electrode: Ag + Cl- ↔ AgCl (s) + e
– Diffusion across membrane ( ~ 10 µm)
– Diffusion cross the thin electrolyte solution (
~ 10 µm)
– Steady-state current Æ I is dependent on
electrochemical equilibrium, [O2] Æ 10 ~ 20 s
and dm+s < 20 µm

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Enzyme-based Sensors

• Glucose detection: largest selling chemical instruments

• A polycarbonates film (glucose permeable, not for protein and
other blood constitutes): diffuse through
• An immobilized enzyme layer (glucose oxidase): glucose
reduction Æ H2O2
• A cellulose membrane layer for H2O2 diffusion: H2O2 oxidation
Æ O2
– Amperometric detection (I ∝ c) or volumetric detection (E ∝ c) of
sucrose, lactose, ethanol and L-Lactate

glucose oxidase
glu cos e + O2 ⎯⎯⎯⎯⎯ ⎯
⎯→ gluconic acid + H 2O2
H 2O2 + 2OH − → O2 + H 2O + 2e −

Amperometric Titration

z At least one species is Analyte is reduced

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

The ripples are caused by the

constant forming and dropping of
Polarography the mercury electrode

z WE: DME, diffusion control, no

convection
z Residue current: current
observed in the absence of an
electroactive specie Polarogram
z Diffusion current: limiting
current which is limited by the
diffusion
z A: DL ~ 10-5 M, Faster
equilibrium + new electrode
surface Æ reproducible current; 0.5 mM Cd2+ in 1 M HCl
High η for H2 evolution Æ low E
window
z DA: new surface Æ large
charging current

(id ) max = 708nD1 / 2 m 2 / 3t1 / 6c

n : electron / analyte
1 M HCl
D : diffusion coefficient, cm 2 /s
m : rate of flow of Hg throug the capillary, mg/s
c A : mol / cm3
t : time, s

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Cyclic Voltammetry

z CV: forward scan,

switching potential,
reverse scan
z Application of CV: 6.0 mM Fe(CN)63-
– Study of redox reaction
– Detection of reaction Reversible
intermediates (reduction)
– Observation of follow-up
reactions
(+) (-)
z Reaction: (oxidation)
– A: H2O oxidation Æ O2
– B-H: reduction
Irreversible or rapid removal of Red
– B-D: cA0 Æ 0 (reduction)
– D-F: cA0 = 0, δ ↑
– F-H: reduction
(+) (-)
– H-K: oxidation
E (vs SCE)

CV- Fundamental Studies

z Peak potential: Epc and Epa ∆E p = E pa − E pc =

0.0592
– Reversible: ∆Ep = 0.0592 /n n
– Irreversible: ∆Ep > 0.0592 /n
z Peak current: n : electron / analyte
D : diffusion coefficient, cm 2 /s

5 3/ 2 1/ 2 1/ 2 A : electrode surface area, cm 2

i p = 2.686 × 10 n AD v c c : mol / cm3 Parathion in 0.5 M
v : scan rate, V/s
acetate buffer in 50%
z Qualitative information in organic and ethanol, pH = 5
inorganic chemistry
– first choice
– reaction intermediate

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

z Digital simulation: DigiSim, DigiElk

– Fast implicit finite difference methods
– 1st or 2nd order homogeneous chemical reaction
– Generate dynamic concentration profiles
– The exact current may be offset as the nonfaradaic current is
not easily simulated

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Differential Pulse Polarography

z DPP: increasing sensitivity

– Lower DL: ~ 10-7 to 10-8 M (2
∆t
~ 3 order lower than CV)
– Enhancing faradic current:
diffusion current (id) + Nernst
contribution due to ∆E,
several times larger than id, 0.36 ppm
∆t is small enough tatrecylineHCl in 0.1
– Decrease in nonfaradic M acetate buffer,
pH=4
current: charging current
decays exponentially with
time, is small at the late
lifetime of the drop, ∆t is large
enough
– Trace heavy metal detection

Square-wave Polarography

z SWP: increasing sensitivity

– Great speed: step < 10 ms, signal average is 10 mV

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

Guanine, adenine, thymine

forward

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

12
Homework

z 25-2 (a, b, c, e), 25-5

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