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V.S.MURALIDHARAN
CSIR EMERITUS SCIENTIST
Electro analytical Methods
Potentiometry Potential at 0 current Quantitative analysis of Defined by 100 mg 10-2 -102 ppm Measures activity rather than
(potentiometric ions in solutions, pH. electrode (e.g., concentration.
titration) F-, Cl-, Ca2+)
(chronopotentiometry)
Coulometry Current and time as Exhaustive electrolysis Little qualitative 100 mg 10-9 -1 g High precision possible.
number of Faradays identification
information
Anodic Stripping Weight Quantitative trace Oxidation 100 mg 10-3 -103 g Electro deposition step
Voltammetry analysis of potential permits 10 ng provides improved detection
(Electrodeposition) electrochemically identification of limits over normal
reducible metals that metal. voltammetry.
form amalgams with
mercury
Reactions which affect working range for
polarisable electrodes
Solvent
2 H+ + 2 e - H2 E° = 0.00 V
O2 + 4 H+ + 4 e ---- >2 H2O E° = +1.23 V
O2 + 2 H+ + 2 e ---- > H2O2 E° = +0.70 V
Electrode
Hg2+ + 2 e --- Hg E° = +0.80 V
Hg2Cl2 + 2 e ---2 Hg + 2 Cl – E° = +0.27 V
Pt2+ + 2 e --- Pt E° = +1.20 V
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Working Range for Polarizable Electrodes
SCE = +0.244 V
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Summary of Voltammetric Techniques
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POLAROGRAPHY
V.S.MURALIDHARAN
7 V.S.MURALIDHARAN 2/6/2018
Voltammetric Methods
•Historical
•Electrolysis at DME -1920’s
•Usually 3-electrode cells
8 V.S.MURALIDHARAN 2/6/2018
Polarography uses mercury
droplet electrode that is regularly
renewed during analysis.
Applications:Metal ions
(especially heavy metal
pollutants) - high
sensitivity.Organic species able to
be oxidized or reduced at
electrodes: quinones, reducing
sugars and derivatives, thiol and
disulphide compounds, oxidation
cofactors (coenzymes etc),
vitamins,
pharmaceuticals.Alternative when
spectroscopic methods fail.
9 V.S.MURALIDHARAN 2/6/2018
History
Jaroslav Heyrovský was the inventor of the
polarographic method, and the father of
electroanalytical chemistry, for which he was the
recipient of the Nobel Prize. His contribution to
electroanalytical chemistry can not be
overestimated. All modern voltammetric methods
used now in electroanalytical chemistry originate
from polarography.
On February 10, 1922, the "polarograph" was born as Heyrovský recorded the current-voltage curve
10 V.S.MURALIDHARAN
for a solution of 1 M NaOH. Heyrovský correctly interpreted the current increase between -1.9 and -
2/6/2018
+
2.0 V as being due to deposition of Na ions, forming an amalgam.
Typical polarographic curves (dependence of current I on the voltage E applied to the
electrodes; the small oscillations indicate the slow dropping of mercury): lower curve
- the supporting solution of ammonium chloride and hydroxide containing small
amounts of cadmium, zinc and manganese, upper curve - the same after addition of
small amount of thallium.
iav = 607nD1/2m2/3t1/6C
13 V.S.MURALIDHARAN 2/6/2018
The diffusion current is determined by subtracting away the residual
currentFurther improvements can be made by reducing charging currents
Usually D’s are similar so half wave potential is similar to formal potential.
Also potential is independent of concentration and can therefore be used
as a diagnostic of identity of analytes. For example
Class Functional Group E1/2 (v
SCE)
Azo -N=N- -0.4
carbonyl >C=O -2.2
Nitro NO2 -0.9
Quinone C=O -0.1
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•Organic reductions often involve hydrogen ions
•R + nH+ + ne RHn
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Charging Currents : first look
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Charging current sets limit of detection
Various ways of reducing it
e.g., Sample current at end of drop life (TAST
polarography)
19 V.S.MURALIDHARAN 2/6/2018
VOLTAMMETRY
A.) Comparison of Voltammetry to Other Electrochemical Methods
21 VSMuralidharan vsm
Apply Linear Potential with Time Observe Current Changes with Applied Potential
B.) Theory of Voltammetry
Apply
Potential
1) Differences from Other Electrochemical Methods
a) Potentiometry: measure potential of sample or system at or near zero
current.
Two methods:
Stirred - hydrodynamic voltammetry
Unstirred - polarography (dropping Hg electrode)
0.0592log [Mred]s
Eappl = Eo - at surface of electrode
n [Mox]s
Applied potential
If E appl = Eo:
0.0592
[Mred]s
Eappl = E0 - log
[Mox]s
n
[Mox]s = [Mred]s
Apply
Potential
E << Eo
dx
where:
n = number of electrons in ½ cell reaction
F = Faraday’s constant
A = electrode area (cm2)
D = diffusion coefficient (cm2/s) of A (oxidant)
dx
dCA
As time increases, push banding further and further out.
Results in a decrease in current with time until reach point where convection of analyte takes over and
diffusion no longer a rate-limiting process.
Thickness of Diffusion Layer (d):
nFADox
i= (cox, bulk – cox,s)
d
so:
i = kcox,bulk
therefore:
current is proportional to bulk concentration
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3.) Combining Potential and Current Together
Limiting current
Related to concentration
E½ at ½ i
Half-wave potential : E1/2 = -0.5 . E0 - Eref
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How to calculate peak currents?
Current is a function of concentration gradient
FOR SECOND
PEAK
CURRENT FUNCTION FOR A REVERSIBLE
PROCESS
(t )
mv mv
120 0.009 0.008 -5 0.400 0.548
100 0.020 0.019 -10 0.418 0.596
120 0.016 0.041 -15 0.432 0.641
110 0.024 0.087 -20 0.441 0.685
100 0.035 0.124 -25 0.445 0.725
90 0.05 0.146 -28.5 0.4463 0.7516
80 0.073 0.173 -30 0.446 0.763
70 0.104 0.208 -35 0.443 0.796
60 0.145 0.236 -40 0.438 0.826
50 0.199 0.273 -50 0.421 0.875
40 0.264 0.314 -60 0.399 0.912
35 0.300 0.375 -80 0.353 0.957
30 0.337 0.403 -100 0.312 0.980
25 0.372 0.451 -120 0.280 0.991
20 0.406 0.499 -150 0.245 0.997
i nFAC00 D0 (t ) nFAD0 C00 (t ) r0
The second term in the right hand side is for spherical diffusion. This correction
is small when the electrode radius is large Then
0
nFAD0 C
i P i planar (0.725 10 ) 5 0
r0
1.857 RT 47.7
EP EP 2 mV
cF c
Cyclic Voltammetry
1) Method used to look at mechanisms of redox reactions
in solution
2) Looks at i vs. E response of small, stationary electrode
in unstirred solution using triangular waveform for excitation
Cyclic voltammogram
Excitation Cyclic Voltammetry
E2
(CV)
Eapp, V
Important parameters:
E1 Epa and Epc
Time, s
ipc and iac
Response Epa E’
DE = |Epa - Epc|
I, A
E1 E2
Epc
R - ne -=O
Eapp, V
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Analysis of an Example K3Fe(CN)6
• Starting at an initial voltage (A), the
potential is scanned in the negative
direction.
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Start at E >> E0 Mox + ne- Mred
- in forward scan, as E approaches E0 get current due to
Mox + ne- Mred
driven by Nernst equation
concentrations made to meet
Nernst equation at surface
eventually reach i max
< solution not stirred, so d grows with time and
see decrease in i max
- in reverse scan see less current as potential increase until
reduction no longer occurs
< then reverse reaction takes place (if
reversible reaction)
< important parameters
Epc – cathodic peak potential
Epa – anodic peak potential
ipc – cathodic peak current
ipa – anodic peak potential
< ipc . ipa
< d(Epa – Epc) = 0.0592/n,
where n = number of electrons in reaction
< E0 = midpoint of Epa Epc
Voltammetric Parameters
The peak potential,
is offset about 28 mV at 25°C
RT
E p E1 2 1.1 i p kn AD cv
32 12 12
nF
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For Nernstian CV
DEp = |Epa - Epc| = 59/n mV at 250C
independent of n
Eo = (Epa + Epc)/2
Ipc/Ipa = 1
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For Nernstian Process
Potential excitation controls [R]/[O] as in Nernst equation:
Eapp = E0- 0.059/n log [R]/[O]
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Quasi-reversible or Irreversible
Quasi-reversible:
DEp > 59 mV and DEp increases with increasing n
iR can mascarade as QR system
Irreversible:
chemically - no return wave
slow ET - 2 waves do not overlap
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Criteria for Nernstian Process
Ep independent of scan rate
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Some schemes
E A+e=B
EE A + e = B; B + e = C; 2B = A + C
EC A1 + e = B1; B1 = B2
EC’ A + e = B; B + P = A + Q
EC2 A + e = B; 2B = B2
CE Y = A; A + e = B
ECE A1 + e = B1; B1 = B2; B2 + e = C2;
B1 + B2 = A1 + C2
v.s.muralidharan 2/6/2018
Adsorption Phenomena
Non-specifically adsorbed
No close-range interaction with electrode
Chemical identity of species not important
Specifically adsorbed
Specific short-range interactions important
Chemical identity of species important
VSMuralidharan 50
Applications of CV
Many functional group are not reducible so we can derivatize
these groups
convert them into electroactive groups by chemical
modification
EXAMPLES:
alcohols + chromic acid = aldehyde group
phenyl + nitration = nitro group
21/05/1439 VSMuralidharan 51
CV and Adsorption
If electroactive adsorbed species:
Ep = Eo - (RT/nF) ln (bo/bR)
ip = (n2F2/4RT) A o* n
90 mV If ideal Nernstian,
I Epa = Epc and DEp/2 = 90.6 mV/n at
Eapp 250C
VSMuralidharan 52
UME’s Radial vs. Planar Diffusion
Radial Diffusion Planar Diffusion
Redox wave: Redox wave:
sigmoidal shape normal shape
Iss = 4nFrDoCo* Ip n1/2 Do1/2 C
Iss scan rate independent
DoCo*
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EXAMPLE 1: UME’s
in Sol-Gels
Learn Do from CA
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20 mV/s EXAMPLE 2: No
Electrolyte!
20 mV/s [S2Mo18O62]4- + e- = [S2Mo18O62]5-
+ e- = [S2Mo18O62]6-
BAS 100-A
100 mV/s 3-electrode cell:
GC macrodisk/Pt wire/ Pt wire
ACN with no electrolyte
vsm VSMuralidharan 55
Ultra micro electrodes
Fast scan rates Slow scan rates
30 V/s 5 mV/s
planar diffusion radial diffusion
Fe3+
0.1 mm 0.1 mm
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EXAMPLE 2: Oxidation
of Cysteine at BDD
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Stripping Analysis or Stripping
Voltammetry
Cathodic (CSV)
Good for anions and oxyanions
Anodic (ASV)
Good for metal cations
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Stripping Voltammetry - Steps
1. Deposition
2. Concentration
3. Equilibration
4. Stripping
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Example of ASV: Determination of Pb
at HDME
Deposition (cathodic) reduce Pb2+
Stir (maximize convection)
Pb Pb2+ + 2e-
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Stripping Voltammetry - Quantitation
I p Co *
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HDME ASV
Usually study M with Eo more negative than
Hg
Ex: Cd2+, Cu2+, Zn2+, Pb2+
Study M with Eo more positive than Hg at GC
Ex: Ag+, Au+, Hg
Can analyze mixture with DEo 100 mV
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CSV
Anodic deposition
Form insoluble, oxidized Hg salt of analyte anion
Stir (maximize convection)
Equilibrate (stop stirring)
Scan potential in opposite sense (cathodic)
Reducing salt/film and forming soluble anion
Record voltammogram
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Stripping Voltammetry
For cations of amalgam-forming metals and anions of
sparingly soluble Hg salts
First step is electrochemical deposition (preconcentration)
at the Hg electrode
Second step is anodic or cathodic potential sweep, in which
peak currents are measured
Extremely sensitive (nM or ppb range) depending on
preconcentration time
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Anodic Stripping Voltammagram
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audience
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