Introduction to Electroanalytical Chemistry

Potentiometry, Voltammetry, Amperometry, Biosensors

Current (I) = k C (voltammetry) • Electrochemical Synthesis Organics. polymers . materials. 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.Applications • Study Redox Chemistry – electron transfer reactions. organics & inorganics. inorganics. reduction. oxidation.

batteries • Potentiometric cells (I=0) read Chapter 2 – measure potential for analyte to react – current = 0 (reaction is not allowed to occur) – Equil.→ Red • E = Eo – (2. – The Nernst Equation • For a reversible process: Ox + ne.Electrochemical Cells • Galvanic Cells and Electrolytic Cells • Galvanic Cells – power output. output meas.303RT/nF) Log (ared/aox) • a (activity). power applied. related directly to concentration . Voltage is measured (Eeq) • Electrolytic cells.

caused by electron transfer Also a non-faradaic current forms part of background current .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.

Electrical Double layer at Electrode • Heterogeneous system: electrode/solution interface • The Electrical Double Layer. ions in solution – important for voltammetry: – Compact inner layer: do to d1. – Diffuse layer: d1 to d2. E decreases exponentially. E decreases linearly. e’s in electrode. .

Chemical reaction rate at electrode proportional to the Faradaic current. . – Nonfaradaic current: due to change in double layer when E is changed. oxidation or reduction • Faradaic Processes. 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.Electrolysis: Faradaic and Non-Faradaic Currents • Two types of processes at electrode/solution interface that produce current – Direct transfer of electrons.

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 .

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

interface – NOT in bulk solution . soln.• 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.

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. E wire potentiostat insulator electrode material reference N2 inlet counter working electrode Electrochemical cell Output. E. V time . measures I vs. quiet solution Input: E-t waveform reduction E. I vs.

theoretical Ideal Non-Polarized Electrode Ideally Polarized Electrode reduction No oxidation or reduction oxidation .Polarization .

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 .

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

[RT/nF] ln (CR/CO) F = Faraday const. Eo in Volts •E. not all Electrochemical reactions are reversible E = Eo .= R.500 coul/e. T = absolute temperature . a = activity f = activity coefficient.g.[RT/nF] ln (aR/aO) aR = fRCR ao = foCo . then E = Eeq All equilibrium electrochemical reactions obey the Nernst Equation Reversibility means that O and R are at equilibrium at all times. 96...= Fe2+ If in a cell.[RT/nF] ln (fR/fO) . Fe3+ + e. depends on ionic strength Then E = Eo .NERNST Equation: Fundamental Equation for reversible electron transfer at electrodes O + ne. I = 0. R = gas const.

Z = charge on ion.Ionic strength I = Σ zi2mi.0592/n] log (CR/CO).const. Eo’ = formal potential of O/R At 25 oC using base 10 logs E = Eo’ . And so.[0. E = Eo . m = concentration of ion Debye Huckel theory says log fR = 0. below are more usable forms of Nernst Eqn.[RT/nF] ln (CR/CO).5 zi2 I1/2 So fR/fOwill be constant at constant I. . equil. systems .[RT/nF] ln (CR/CO) Or E = Eo’ .

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