CHEM 558

CHEM 558 - Electrochemistry – Syllabus – Fall 2024

Frank Cheng, Renfrew 003, ifcheng@uidaho.edu, tel. (208) 885-6387, Cheng Group Web Site

Lecture: MWF 9:30-10:20 am

Office Hours: MWF 10:30-11:30, TR 9:30-11:30.

Text: Understanding Voltammetry, 2^nd Ed. Richard G. Compton, Craig E. Banks

This course will also use web links and handout lecture notes.

Electrochemistry Basics*Cambridge University Lecture Notes*MIT

1.0 Equilibrium Electrochemistry – Chapter 1 (Do Homework Set 1, Review Problems from Chem 454)

1.1 Nernst Equation

Reference Electrodes (SHE, SCE, Ag/AgCl)

Review * Daniell Cell * The Nernst Equation

Standard Electrode Potentials * Electrochemical Series (Link 2)

Connection between E_cell, ∆G, and K

Single Electrode Potentials, Precipitation Reactions on Electrodes

Potentials for sums of half reactions

1.2 Ion-selective Electrodes

1.3 Advanced Aspects of Nernst Equation (Lecture Notes, Transformation of Halogenated Compounds ES&T 21, 1987, 722, Henry's Law Constants
J. Phys. Chem. Ref. Data. 10, 1981, 1175)

1.5 Pourbaix Diagrams; (Lecture Notes, Wikipedia, Fe, Chem. Soc. Rev. 2013, Google Search)

1.6 Special Topics – ZVI based remediation of halocarbons, TCE (Reactive Iron Barrier, link 2, 3) Video

2.0 Electrode Kinetics – Chapter 2 (Do Homework Set 2)

2.1 Introduction

2.2 Butler–Volmer Kinetic (Text: Chapter 3.3 – 3.5) National Association of Corrosion Engineers, Wolfram Research Demo

2.3 Tafel Analysis (University of Cambridge, Example of Corrosion Inhibition, Gamry.com

Corrosion of Alaska Oil Pipeline, NYT

2.4 Marcus Theory (Text: Chapter 3.6, Rudolph Marcus 1992 Nobel Prize DOE tech docs)

2.5 Special Topic - Redox Flow Batteries, improvement of kinetics.

3.0 Diffusion and Controlled Potential Methods – Chapter 3 (Homework Set 3 Part 1, Homework Set 3 Part 2)

3.1 Mass Transport – Diffusion, Migration and Convection

3.2 Introduction

3.3 Potential Step – Diffusion Control

3.4 Potential Step – Kinetic Control

3.5 Chronocoulometry (Text: 5.8, Glucose Sensor: Talbott and Jordan Microchemical J. 1988, 37, 5, Patent)(more sensors based on chronoamp)

3.6 Pulse Methods – Chapter 9 (Libretext)

Polarography (Jaroslav Heyrovský Electrochemistry Encyclopedia

Pulse Polarography/Voltammetry (AC 50, 1978, 1489-1496)

Stripping Analysis (Text: 11.8 EPA Method 7063)

4.0 Cyclic Voltammetry – Chapter 4 Practical Guide

4.1 Introduction Wikipedia, Anal. Chem. 36:706-23, 1964., Wolfram Research Demo, Irving Shain Obituary.

New – Power buffering. Vanadium Redox Flow Battery. Measurement of electrode kinetics by cyclic voltammetry.

4.1.1 Radial vs Semi-infinite liner diffusion. Example of both contributing to the CV.

4.1.2 Osteryoung’s Equation.

“Linear sweep voltammetry at very small stationary disk electrodes. Aoki, Koichi; Akimoto, Koji; Tokuda, Koichi; Matsuda, Hiroaki; Osteryoung, Janet. Tokyo Inst. Technol., Grad. Sch. Nagatsuta, Yokohama, Japan. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry (1984), Vol. 171, p219”