Beruflich Dokumente
Kultur Dokumente
ELECTROCHEMISTRY TOOLS:
Basic concepts
MSC. JAQUELINE RUIZ MALUTA
http://gmeme.iqsc.usp.br/
WHAT IS ELECTROCHEMISTRY?
Types of research
PRODUCTION OF CHLORINE
MY FIELD OF RESEARCH
Advantages
http://www.docstoc.com/docs/69965634/Accu-Chek-AdvantageElectrochemistry-for-Diabetes-Management
SELECTIVITY TOWARD
ELECTROACTIVE SPECIES
10
11
Voltammetric analyser
Cell:
Analyte:
Electrolyte:
Three electrodes:
electroative species
Plotter
12
ELECTROCHEMICAL CELL
Flow cell
Electrolysis Cell
Temperature control
UV-vis Cell
13
14
WORK ELECTRODE
Electrode materials:
carbon
15
COUNTER ELECTRODE
16
REFERENCE ELECTRODE
Saturade calomelane
electrode
Ag/AgCl electrode
17
ELECTROLYTE
18
POTENTIAL WINDOW
The products generated at the potential limits may interfere with the
system under investigation and may affect the electrode surface.
Too positive:
H2O(l) O2 + 2 H+ + 2 eToo negative:
2 H2O(l) + 2 e- 2 H2 + OH-
19
POTENTIAL WINDOW
The voltammograms of solid phases are specific fingerprints, even when the
assignment of signals is not obvious.
20
21
EXEMPLE: pH INFLUENCE
-3
1,80x10
pH 2
pH 3
pH 4
pH 5
pH 6
pH 7
pH 8
-3
I / mA cm
-2
1,35x10
-4
9,00x10
-4
4,50x10
0,00
0,60
0,65
0,70
0,75
0,80
0,85
E / V (vs Ag/AgCl)
0,90
0,95
1,00
NO detection in
phosphate buffer solution
22
WHAT IS HAPPENING?
*O Oxidized specie
*R Reduced specie
23
WHAT IS HAPPENING?
Oxidation reaction
R O + ne-
Reduction reaction
O + ne- R
REDOX
REACTIONS
24
TECHNIQUES
CYCLIC VOLTAMMETRY
25
26
(A) Cyclic voltammograms obtained at the OMC electrode with, 0.5, 1, 1.5 mM CySH (from top
to bottom) in the PBS pH 7.16
(B) Currenttime response curves of the OMC electrode in PBS pH 7.16 with successive addition
of 0.1 mM CySH
27
CYCLIC-VOLTAMMETRY
28
CYCLIC-VOLTAMMETRY
[Fe(CN)6]4-
[Fe(CN)6]3-
+ e-
[Fe(CN)6]3- + e- [Fe(CN)6]4-
29
ELECTROCHEMICALLY
REVERSIBILITY
a) Reversible
IPA / IPC = 1
b) Quasi-reversible:
30
c) Irreversible
31
32
COMPLICATIONS
In situ UV-vis
33
Run experiments in which you selectively vary the potential scan rate;
Plot the peak current versus the square root of the scan rate;
For a reversible system, the peak height will increase linearly with the square root of
the scan rate. Also, de current is controlled by diffusion transport
The slope of the resulting line will be proportional to the diffusion coefficient
(Randles-Sevcik equation)
n = number of electrons
A = area (cm2)
F = Faraday constant
34
suggesting a adsorption-controlled
process
35
36
COUPLED REACTIONS
The
product
R
is
chemically
removed from the surface
OH
+
N-phenylhydroxylamine
0,0
2H
37
nitrosobenzene
OH
i / mA
2 e-
2 e-
2H
N-phenylhydroxylamine
nitrosobenzene
-0,2
O
O
+
1
2
3
4
5
OH
H
N
4 e-
4H
N-phenylhydroxylamine
nitrobenzene
-0,6
0,0
E / V (vs Ag/AgCl)
0,6
PROGRESSIVE ADSORPTIVE
ACCUMULATION
indicating progressive
adsorptive accumulation at
the surface.
38
INCREASE OF ANALYTE
CONCENTRATION
39
40
MODIFIED ELECTRODES
41
Possess electroactivity;
42
not electroactive,
43
SAMPLE PREPARATION
44
SAMPLE PREPARATION
45
CARBON ELECTRODES
Carbon electrodes: graphite, glassy carbon, graphite powder with liquid or
solid binders, carbon fibers, carbon nanotubes, boron-doped diamond,
titanium carbide, ordered mesoporous carbon, graphene
Carbon nanotubes:
Boron-doped Diamond
46
ELECTRODE PRETREATMENT
47
ELECTRODE PRETREATMENT
http://www.basinc.com/mans/LC_epsilon/Maintenance/Working/working.html
48
REMEMBER...
Pay attention in all variables which may affecting the electrode reaction
49
REFERENCES
http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical_Chemistry_2.0
/11_Electrochemical_Methods/11D_Voltammetric_Methods