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UNIVERSITY OF SO PAULO / SO CARLOS CHEMISTRY INSTITUTE

GROUP OF ELECTROCHEMISTRY MATERIALS AND ELECTROANALYTICAL METHODS

ELECTROCHEMISTRY TOOLS:
Basic concepts
MSC. JAQUELINE RUIZ MALUTA
http://gmeme.iqsc.usp.br/

WHAT IS ELECTROCHEMISTRY?

Interrelation of electrical and chemical effects.

Study of chemical changes caused by the passage of an


electric current

Types of research

The production of electrical energy by chemical reactions

Phenomena: Corrosion, electrophoresis

Devices: electrochromic displays, electroanalytical sensors,


batteries, and fuel cells

Technologies: the electroplating of metals and the large-scale


production of aluminum and chlorine

PRODUCTION OF CHLORINE

WHICH TYPE OF INFORMATION


DO YOU HAVE?

Thermodynamic data about a reaction;

Analyze a solution for trace amounts of metal ions or organic


species;

The design of a new power source;

Electro-synthesis of some product;

Electro-degradation of some molecule;

REQUIRES AN UNDERSTANDING OF THE FUNDAMENTAL PRINCIPLES OF


ELECTRODE REACTIONS AND THE ELECTRICAL PROPERTIES OF
ELECTRODE-SOLUTION INTERFACES.

MY FIELD OF RESEARCH

ELECTROANALYSIS Electrochemistry in analytical context

Useful for quantitative purposes, based on measurements of the


peak current

The current is proportional to the concentration;

Environmental monitoring, industrial quality control, or biomedical


analysis.

Advantages

high sensitivity (~10-9 mol L-1), selectivity toward electroactive species, a


wide linear range, portable and low-cost instrumentation.

PORTABLE AND LOW-COST


INSTRUMENTATION
Home testing of blood glucose

Electrochemical test strips have


electrodes where a precise
voltage is applied and a current
proportional to the glucose in the
blood is measured as a result of
the electrochemical reaction on
the test strip.

http://www.docstoc.com/docs/69965634/Accu-Chek-AdvantageElectrochemistry-for-Diabetes-Management

SELECTIVITY TOWARD
ELECTROACTIVE SPECIES

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WHAT DO YOU NEED?

Voltammetric analyser

Cell:

conductive sample solution

Analyte:

working, reference, auxiliary/counter;

Electrolyte:

Covered beaker of 550 mL volume;

Three electrodes:

Potentiostatic circuitry and a voltage


ramp generator

electroative species

Plotter

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ELECTROCHEMICAL CELL
Flow cell

Electrolysis Cell

Temperature control

UV-vis Cell

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WORK ELECTRODE

The working electrode is the electrode at which the investigated


processes occur.

Electrode materials:

solid metals (e.g.,Pt, Au),

liquid metals(Hg, amalgams),

carbon

and semiconductors (indium-tin oxide).

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COUNTER ELECTRODE

The current flows between the working and the counter


electrode.

Material: usually platinum or titanium

The area of the counter electrode should be larger than that of


the working electrode.

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REFERENCE ELECTRODE

The reference electrode is keep at a constant potential.

It is used to control the potential of a working electrode

Saturade calomelane
electrode

Ag/AgCl electrode

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ELECTROLYTE

Electrolyte phase charge is carried by the movement of ions;

Ionic species ( H+, Na+, Cl-) in either water or a nonaqueous solvent

Electrolyte is usually added to the test solution to ensure sufficient


conductivity.

Migration mass transport influence is eliminated

Unstirring There is no convection mass transport

Just diffusion mass transport

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POTENTIAL WINDOW

The available potential window is determined by the currents of


reduction/oxidation of the supporting electrolyte/solvent

We should avoid entering potentials where these processes visibly


occur

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-

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POTENTIAL WINDOW

Surfaces are partially oxidized;

Thin layers of oxides are formed at gold and platinum;

Functional groups (C=O; OH) are attached to the carbon materials.

The voltammograms of solid phases are specific fingerprints, even when the
assignment of signals is not obvious.

Martnez-Huitle, J. Brazilian Chem Society, 2008, 19: 150-156.

Maluta, J.P., J Solid State Electrochem. 2014, 18:24972504

VARIABLES AFFECTING THE RATE


OF AN ELECTRODE REACTION

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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

pH influence, all the


others parameters are
the same.

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WHAT IS HAPPENING?

*O Oxidized specie
*R Reduced specie

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WHAT IS HAPPENING?

Oxidation reaction

R O + ne-

The e- formed will be received by an electrode

Reduction reaction

O + ne- R

The electrode is the source of the electrons

REDOX
REACTIONS

Redox changes current passage

The amout of material electrochemical oxidized or reduced is


proportional to the current passage

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TECHNIQUES

POTENTIOMETRY: difference in electrode potentials is measured

COULOMETRY: the cell's current is measured over time

VOLTAMMETRY: the cell's current is measured while actively altering


the cell's potential.

CYCLIC VOLTAMMETRY

SQUARE WAVE VOLTAMMETRY

DIFFERENCIAL PULSE VOLTAMMETRY

THE ANALYTICAL SENSITIVITY


CAN BE IMPROVED

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(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

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CYCLIC-VOLTAMMETRY

Cyclic voltammetry is often the first experiment performed in an


electroanalytical study:

Qualitative information about electrochemical reactions

Thermodynamics of redox processes

Kinetics of heterogeneous electron transfer reactions

Location of redox potentials

Effect of media on the redox process

The occurrence of chemical reactions, that precede/succeed the


redox process

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CYCLIC-VOLTAMMETRY

[Fe(CN)6]4-

[Fe(CN)6]3-

+ e-

[Fe(CN)6]3- + e- [Fe(CN)6]4-

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ELECTROCHEMICALLY
REVERSIBILITY

a) Reversible

Ep = independent of scan rate

IPA / IPC = 1

IP vs scan rate = linear

Current is controlled by mass transport

Described by Nerst Equation

b) Quasi-reversible:

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Depend of both electron transfer and mass


transport

c) Irreversible

The electron transfer is slow

EFFECTS DUE TO CAPACITANCE


AND RESISTANCE

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a) Reversible cyclic voltammogram


b) With the effect of capacity
c) With additional resistance

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COMPLICATIONS

The electrode reaction is rarely simple;

The product is either insoluble, or partly adsorbed at the electrode


surface.

Coupled chemical reactions can happen

The results should be carefully analyzed

In situ UV-vis

Scan rate test

Change the window potential

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SCAN RATE TEST

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)

Ip = 269 n2/3 AD1/2 v1/2 C

ip= peak height (amp)

n = number of electrons

A = area (cm2)

D = diffusion coefficient (cm2/sec)

v = scan rate (V/sec)

C = concentration of solution (M)

F = Faraday constant

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SCAN RATE TEST

The current linearly increases with


scan rate (not scan rate)

suggesting a adsorption-controlled
process

NOT controlled by diffusion transport

D. Zheng et al. / Journal of Electroanalytical Chemistry 625 (2009) 8287

SOME MECHANISMS INVOLVING COUPLED CHEMICAL REACTIONS

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COUPLED REACTIONS

The
product
R
is
chemically
removed from the surface

Smaller reverse peak

In the extreme case, the chemical


reaction may be so fast that all of R
will be converted, and no reverse
peak will be observed.

In faster scan rates, we can see the


reverse peak

OH

+
N-phenylhydroxylamine

0,0

2H

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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

Repetitive CV for riboflavin in a


sodium hydroxide solution.

A gradual increase of the


cathodic and anodic peak
currents

indicating progressive
adsorptive accumulation at
the surface.

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INCREASE OF ANALYTE
CONCENTRATION

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Run experiments in which you selectively


vary the analyte concentration;

Plot concentration versus peak current

Check the concentration where the graphic


is linear

The equation can be used to determine an


unknown solution concentration

Maluta, J.P., J Solid State Electrochem (2014) 18:24972504

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MODIFIED ELECTRODES

Methods based on attaching a certain compound, or a specific


chemical group, to the surface of electrode

by adsorption, by chemical reaction or by formation of a polymer film

Electrocatalytic modified electrodes contain attached electrontransfer mediators

They accelerate electrode reactions

The catalyst is readily regenerated by the fast and reversible electrode


reaction

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WHAT COMPOUNDS AND


MATERIALS CAN BE STUDIED?

Highly insoluble in the electrolyte solution used;

Possess electroactivity;

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the ability to be either oxidized or reduced in the accessible potential


window of the experiment.

Three different kinds of compounds:

not electroactive,

irreversibly destroyed in the electrochemical reactions,

can be reversibly reduced and oxidized.

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SAMPLE PREPARATION

Physical casting in a base electrode:

Prepare a solution in a volatile solvent (Usually alcohols or


DMF);

Put a drop and let it dry;

Nafion or glutamin can be use together as binder;

The compound should be stable under ambient


conditions.

Impurities, which may be electrochemically active,


should not be introduced by this procedure.

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SAMPLE PREPARATION

Bojorge, N., & Alhadeff, E. Graphite-Composites Alternatives for


Electrochemical Biosensor.

Chen, J. Adv. Mater. 2012, 24, 45694573

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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

The glassy carbon:

Synthesis: Very slow carbonization in inert atmosphere at 300C to 1200C.

Inside a pre-modeled polymeric resin body

With the base polished to a mirror

Carbon nanotubes:

Synthesis: arc discharge, laser ablation, or chemical vapor deposition


They appear either as multi-walled, or as single-walled.

Boron-doped Diamond

Synthesis: Low-pressure chemical vapor deposition or high pressure and high


temperature

Wide window potential

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ELECTRODE PRETREATMENT

A solid electrode requires very careful pretreatment.

The best cleaning method has to be chosen from applying either


inorganic or organic solvents.

If necessary, the electrode surface should be clean and polished on


a very wet pad to mirror gloss.

Often, the solid electrode needs an electrochemical


activation/regeneration.

Using abrasive powders (such as diamond and alumina)

Cycling the potential in an appropriate range and in an appropriate


solution.

Modified solid cannot be treated by polishing.

The only way is the electrochemical treatment

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ELECTRODE PRETREATMENT

http://www.basinc.com/mans/LC_epsilon/Maintenance/Working/working.html

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REMEMBER...

Before carrying out voltammetric experiments with analytes:

Check the available potential window

Check if there are no peaks of unwanted impurities in that range

After use, the working electrode should be thoroughly rinsed and


dried

Pay much attention to the reproducibility of results!

Each set of experiments should start and end with a blank


voltammogram in order to verify the cleanliness of the electrode itself

Pay attention in all variables which may affecting the electrode reaction

The starting potential should be carefully set to a value where no


reaction is expected.

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REFERENCES

Scholz, F. (2009). Electroanalytical methods: guide to experiments and


applications. Springer.

Wang, J. (2006). Analytical electrochemistry. John Wiley & Sons.

Bard, A. J., & Faulkner, L. R. (1980). Electrochemical methods: fundamentals


and applications. New York: Wiley.

Monk, Paul M.S., Fundamentals of Electroanalytical Chemistry (2002). John


Wiley & Sons.

http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical_Chemistry_2.0
/11_Electrochemical_Methods/11D_Voltammetric_Methods