voltammetry mass transport

methods that measure current Working Electrode

as a function of applied
voltage Solution is well mixed (e.g., by stir Stagnant solution (Nernst Diffusion Layer)
bar or flowing stream)
- i.e., monitoring Faradaic
current from an electrochemical Nernst Diffusion Layer viscous drag
reaction causes a thin film of solution to Bulk Solution
become stagnant at the electrode (well mixed)
Working Electrode electrode at surface
which the reaction of analytical = 10-2-10-3 cm depending on stirring and solution viscosity
interest occurs. Electrode is small - mass transport only by diffusion in film
(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 The characteristics of the linear sweep voltammogram depend on a
cA = analyte concentration in bulk solution 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, SCANNING-
TUNNELING-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
(1) Preconcentration step
Stripping analysis is an analytical
(2) Stripping step
#$%&that involves (i) pre
technique
!"
concentration of a metal phase Edep
'" $(& (1)
onto a solid electrode surface or

!
tdep
)" *+,-./+,0123.453.-6/"

Potential, V
into Hg (liquid) at negative (2)
potentials and (ii) selective
!7 89 61.!78: #;<'.+==-=.>1,.
oxidation of each metal phase Eclean
/18?-6+@.=-A1BC6C12"
species during an anodic potential
sweep. Time, s Working electrode: Electrode at which the reaction of
interest occurs. (Reduction or Oxidation)
E1o Electrode materials: Hg, Hg-film, gold, carbon
&@-/6,1=-A1BC6C12 B6-A3.&=3. M1n+
/+,,C-=.156.C2.+.B6C,,-=. E2o
pre concentration occurs via Parameters of interest
Current, A

B1@56C12.+6.+.A16-26C+@.B-D-,+@.
adsorption or electrochemical M2n+ Peak potential
6-26EB.1>.+.D1@6.?1,-.2-;+6CD-.
reaction Peak current
6E+6.6E-.&1 >1,.6E-.@-+B6.-+BC@F. Peak charge
stripping can be either cathodic Peak width
,-=5/-=.?-6+@.C12" Potential, V
(reduction) or anodic (oxidation)
The metals strip off near their respective E0.
 Deposition Step Stripping Step
1) The stripping peak current ( and charge) is proportional to the
Hg: spherical droplets Thin-film of spherical Hg concentration of the metal in or on the electrode, and therefore to its
Mn+ + ne- ! M(Hg) 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), Thin films of Hg: Peak current (Ip) is given by, where A = Area, l = thickness,
to be calculated: Ip = k C A = n2F2 !1/2 A l CA CA = concentration, ! = scan rate
CM = iL td / nF VHg 2.7 RT

iL: limiting current for the deposition of the metal 35.0

Cd(II)
F: Faraday
Deposition times Variation of peak currents vs.
7.5 m 30.0
30s
deposition time

Current(A)
25.0
VHg: Volume of the Mercury electrode 60s

Control Parameters 20.0

90s
120s
td: Deposition time
! Film morphology and architecture 15.0 150s

Incase of a metallic film deposited on a inert 10.0

180s

! Deposition potential solid electrode, the amount, in moles, of metal 5.0

deposited on the surface (M) is: 0.0

! Deposition time -5.0
M = iL td / nF -1000 -900 -800 -700 -600 -500

Potential (mV vs. Ag/AgCl)

Applications of ASV
Advantages of Stripping Voltammetry 1) Environmental Analysis: Water, soil samples etc.
2) Clinical Analysis: Blood, Urine samples
1) Linear Dynamic Range: 4-5 orders of magnitude
3) Food Analysis
2) Limits of Detection: (S/N = 3), high ppt to low ppb range
4) Gasoline and Oil analysis
3) Response precision: < 2-3 % is common
5) Pharmaceutical analysis
4) Sensitive to oxidation states
5) Low cost for instrumentation and running
6) Allows Standard addition: no matrix effects
7) Compact

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