voltammetry

mass transport

methods that measure current

as a function of applied
voltage

Working Electrode

Solution is well mixed (e.g., by stir

bar or flowing stream)

- i.e., monitoring Faradaic

current from an electrochemical
reaction

Stagnant solution (Nernst Diffusion Layer)

Nernst Diffusion Layer viscous drag

causes a thin film of solution to
Bulk Solution
become stagnant at the electrode
(well mixed)
surface
= 10-2-10-3 cm depending on stirring and solution viscosity
- mass transport only by diffusion in film

Working Electrode electrode at

which the reaction of analytical
interest occurs. Electrode is small
(microelectrode, mm2) to very
small (ultramicroelectrode, m2)

analyte experiences resistance to mass transfer (i.e., diffusion-limited

transport) across the Nernst film

Diffusion current

linear sweep voltammetry

current observed when the rate

of electrode reaction is limited
by the rate of diffusion of the
analyte to the electrode surface

n = number of electrodes in half reaction

F = Faradays constant
A = surface area of electrode
DA = diffusion coefficient of analyte
! = thickness of Nernst diffusion film
cA = analyte concentration in bulk solution

The characteristics of the linear sweep voltammogram depend on a

number of factors:
*The rate of the electron transfer reaction(s)
*The chemical reactivity of the electroactive species
*The voltage scan rate

cyclic voltammetry

atomic microscopy and CV

varying the applied potential at a working electrode in both forward

and reverse directions (at some scan rate) while monitoring the
current

rarely used for quantitative determinations

widely used for the study of redox processes
! for understanding reaction intermediates
! for obtaining stability of reaction products

relative to the onset of bulk Bi deposition which is

190 5 mV vs SHE in 0.1 M HC104.
CHEN CH, KEPLER KD, GEWIRTH AA, et al.
ELECTRODEPOSITED BISMUTH MONOLAYERS ON AU(111) ELECTRODES - COMPARISON OF SURFACE X-RAY-SCATTERING, SCANNINGTUNNELING-MICROSCOPY, AND ATOMIC-FORCE MICROSCOPY LATTICE STRUCTURES
JOURNAL OF PHYSICAL CHEMISTRY 97 (28): 7290-7294 JUL 15 1993

stripping voltammetry

Experimental Details

Anodic Stripping Voltammetry

(reduction) or anodic (oxidation)

(2) Stripping step

Potential, V

Edep

(1)

tdep
(2)
Eclean

Working electrode: Electrode at which the reaction of

Time, s
M1n+

interest occurs. (Reduction or Oxidation)

E1o

Current, A

&@-/6,1=-A1BC6C12 B6-A3.&=3.
/+,,C-=.156.C2.+.B6C,,-=.
pre concentration occurs via
B1@56C12.+6.+.A16-26C+@.B-D-,+@.
adsorption or electrochemical
reaction
6-26EB.1>.+.D1@6.?1,-.2-;+6CD-.
6E+6.6E-.&1 >1,.6E-.@-+B6.-+BC@F.
stripping can be either cathodic
,-=5/-=.?-6+@.C12"

(1) Preconcentration step

Stripping analysis is an analytical

technique
!"
#$%&that involves (i) pre
concentration of a metal phase
'"
$(&
onto a solid electrode surface or
)"
*+,-./+,0123.453.-6/"
into
Hg (liquid) at negative
potentials and (ii) selective
89 61.!78: #;<'.+==-=.>1,.
!7
oxidation
of each metal phase
species during an anodic potential
/18?-6+@.=-A1BC6C12"
sweep.

Electrode materials: Hg, Hg-film, gold, carbon

E2o
M2n+

Potential, V

Parameters of interest
Peak potential
Peak current
Peak charge
Peak width

The metals strip off near their respective E0.

Deposition Step
Hg: spherical droplets

Stripping Step

Thin-film of spherical Hg
Mn+ + ne- ! M(Hg)

1) The stripping peak current ( and charge) is proportional to the

concentration of the metal in or on the electrode, and therefore to its
concentration in the sample solution
2) Peak potentials serve to identify the metal ions in the sample

Application of Faradays law enables the

concentration of the metal in the amalgam, (CM),
to be calculated:
CM = iL td / nF VHg

Control Parameters
! Film morphology and architecture
! Deposition potential
! Deposition time

Ip = k C A =

iL: limiting current for the deposition of the metal

35.0

F: Faraday

30.0

VHg: Volume of the Mercury electrode

td: Deposition time

Incase of a metallic film deposited on a inert

solid electrode, the amount, in moles, of metal
deposited on the surface (M) is:
M = iL td / nF

n2F2

!1/2

A l CA

where A = Area, l = thickness,

CA = concentration, ! = scan rate

2.7 RT

Current(A)

7.5 m

Thin films of Hg: Peak current (Ip) is given by,

Cd(II)
Variation of peak currents vs.
deposition time

Deposition times
30s

25.0

60s
90s

20.0

120s

15.0

150s
180s

10.0
5.0
0.0
-5.0
-1000

-900

-800

-700

-600

-500

Potential (mV vs. Ag/AgCl)

Applications of ASV
Advantages of Stripping Voltammetry
1) Linear Dynamic Range: 4-5 orders of magnitude
2) Limits of Detection: (S/N = 3), high ppt to low ppb range
3) Response precision: < 2-3 % is common
4) Sensitive to oxidation states
5) Low cost for instrumentation and running
6) Allows Standard addition: no matrix effects
7) Compact

1) Environmental Analysis: Water, soil samples etc.

2) Clinical Analysis: Blood, Urine samples
3) Food Analysis
4) Gasoline and Oil analysis
5) Pharmaceutical analysis

Major Interferences in ASV

1) Overlapping stripping peaks caused by similarity in oxidation potential
2) Presence of surface-active organic compounds that adsorb on the Hg surface
and inhibit metal deposition
3) Formation of intermetallic compounds (e.g., Cu-Zn) which affect peak size and
position
Source: http://www.icsu-scope.org/downloadpubs/scope51/images/fig13.1.gif