Introduction to Electroanalytical Chemistry

Potentiometry, Voltammetry, Amperometry, Biosensors

Applications
Study Redox Chemistry
electron transfer reactions, oxidation, reduction, organics & inorganics, proteins Adsorption of species at interfaces

Electrochemical analysis
Measure the Potential of reaction or process E = const + k log C (potentiometry) Measure the Rate of a redox reaction; Current (I) = k C (voltammetry) Electrochemical Synthesis Organics, inorganics, materials, polymers

Electrochemical Cells
Galvanic Cells and Electrolytic Cells Galvanic Cells power output; batteries Potentiometric cells (I=0) read Chapter 2
measure potential for analyte to react current = 0 (reaction is not allowed to occur) Equil. Voltage is measured (Eeq)

Electrolytic cells, power applied, output meas.

The Nernst Equation
For a reversible process: Ox + ne- Red E = Eo (2.303RT/nF) Log (ared/aox) a (activity), related directly to concentration

Voltammetry is a dynamic method

Related to rate of reaction at an electrode

O + ne = R,

Eo in Volts

I = kA[O] k = const. A = area Faradaic current, caused by electron transfer

Also a non-faradaic current forms part of background current

Electrical Double layer at Electrode

Heterogeneous system: electrode/solution interface The Electrical Double Layer, es in electrode; ions in solution important for voltammetry:
Compact inner layer: do to d1, E decreases linearly. Diffuse layer: d1 to d2, E decreases exponentially.

Electrolysis: Faradaic and Non-Faradaic Currents Two types of processes at electrode/solution interface that produce current
Direct transfer of electrons, oxidation or reduction Faradaic Processes. Chemical reaction rate at electrode proportional to the Faradaic current.
Nonfaradaic current: due to change in double layer when E is changed; not useful for analysis

Mass Transport: continuously brings reactant from the

bulk of solution to electrode surface to be oxidized or reduced (Faradaic) Convection: stirring or flowing solution Migration: electrostatic attraction of ion to electrode Diffusion: due to concentration gradient.

Typical 3-electrode Voltammetry cell

Reference electrode Counter electrode Working electrode

O eR
End of Working electrode Mass transport

O
R
Bulk solution

Reduction at electrode Causes current flow in External circuit

Analytical Electrolytic Cells

Use external potential (voltage) to drive reaction Applied potential controls electron energy As Eo gets more negative, need more energetic electrons in order to cause reduction. For a reversible reaction:
Eapplied is more negative than Eo, reduction will occur if Eapplied is more positive than Eo, oxidation will occur O + ne- = R Eo,V electrode reaction

 Current Flows in electrolytic cells

Due to Oxidation or reduction Electrons transferred Measured current (proportional to reaction rate, concentration)

Where does the reaction take place?

On electrode surface, soln. interface NOT in bulk solution

Analytical Applications of Electrolytic Cells Amperometry

Set Eapplied so that desired reaction occurs Stir solution Measure Current

Voltammetry
Quiet or stirred solution Vary (scan) Eapplied Measure Current
Indicates reaction rate Reaction at electrode surface produces concentration gradient with bulk solution Mass transport brings unreacted species to electrode surface

Cell for voltammetry, measures I vs. E

wire
potentiostat
insulator electrode material

reference N2 inlet counter

working electrode

Electrochemical cell
Output, I vs. E, quiet solution
Input: E-t waveform

reduction

E, V

time

Polarization - theoretical
Ideal Non-Polarized Electrode Ideally Polarized Electrode
reduction

No oxidation or reduction oxidation

Possible STEPS in electron transfer processes

Charge-transfer may be rate limiting

Rate limiting step may be mass transfer

Rate limiting step may be chemical reaction Adsorption, desorption or crystallization polarization

Overvoltage or Overpotential
= E Eeq; can be zero or finite
E < Eeq < 0 Amt. of potential in excess of Eeq needed to make a non-reversible reaction happen, for example
reduction

Eeq

NERNST Equation: Fundamental Equation for reversible electron transfer at electrodes

O + ne- = R, Eo in Volts E.g., Fe3+ + e- = Fe2+ If in a cell, I = 0, then E = Eeq All equilibrium electrochemical reactions obey the Nernst Equation
Reversibility means that O and R are at equilibrium at all times, not all Electrochemical reactions are reversible

E = Eo - [RT/nF] ln (aR/aO)
aR = fRCR ao = foCo

a = activity

f = activity coefficient, depends on ionic strength

Then E = Eo - [RT/nF] ln (fR/fO) - [RT/nF] ln (CR/CO) F = Faraday const., 96,500 coul/e, R = gas const. T = absolute temperature

Ionic strength I = zi2mi, Z = charge on ion, m = concentration of ion

Debye Huckel theory says log fR = 0.5 zi2 I1/2 So fR/fOwill be constant at constant I. And so, below are more usable forms of Nernst Eqn. E = Eo - const. - [RT/nF] ln (CR/CO) Or E = Eo - [RT/nF] ln (CR/CO); Eo = formal potential of O/R At 25 oC using base 10 logs E = Eo - [0.0592/n] log (CR/CO); equil. systems