CHEM 558 - Electrochemistry – Syllabus – Fall 2023

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-Noon, TR 9:30-11:30. TWR 1:30 – 3:00 pm

Text: Understanding Voltammetry, 2nd 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 (SHESCEAg/AgCl)

Review * Daniell Cell * The Nernst Equation

Standard Electrode Potentials * Electrochemical Series (Link 2)

Connection between Ecell, ∆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)

 

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”

 

  

 

            4.2 Emphasis on Coupled Homogeneous ReactionsChapter 7

A study of an EC’ Mechanism from my research group, Digisim Examples, rev CV, radial, CE, EC, EC')

Digisim in J. Chem. Ed.            Digielch

An Open Source Simulator

A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms Chem Sci. 2019 Jul 14; 10(26): 6404–6422

Literature – A manual for modeling

Nicolson’s Paper, Analytical Chemistry, 37, 1965, 1351

A Review Article: Chem. Sci., 2019, 10, 6404-6422

An example of a CE mechanism: Organometallics, 1999, 18 (10), pp 1854–1861

EC Mechanism CV of Dopamine, Libretext

ECE mechanism J. Phys. Chem. 76, 1972, 2439. Anal. Chem. 37, 1965, 190.

EC’ Mechanisms J. Phys Chem C. 2011, 115, 11204, PNAS 2017, 114, 11303.

 

            4.3 Adsorbed Species  https://pubs.acs.org/doi/pdf/10.1021/acs.jpcc.8b05484

4.4 Thin-Layer Cells Wolfram Research Demo

 

5.0 Hydrodynamic Methods – Chapter 8

 

            Mathematical models at Wolfram Research

                        RDE Levich Equation

                        RDE  Ox + ne- = Red

            Special Topic – analysis of fuel efficiencies.

 

6.0 Pulse Voltammetric Methods – Chapter 9

 

7.0 Recent Topics

 

7.1 Carbon Electrodes: Glassy Carbon, Graphene, Graphite, and GUITAR Electrodes

                        Electron Transfer at the Basal vs. Edge Planes

                        J. Phys. Chem C, 2019, 123, 11677

                        Chem. Rev. 2008, 108, 2646

                        Band Theory, Youtube Video

Raman spectroscopy of carbon

                        Potential Windows

 

7.3 Batteries (An Overview of Batteries from Powerstream)

                        Li ion

                        Lead-Acid

                        Redox Flow Batteries

            7.4 Fuel Cells

 

8.0 AC Techniques

 

Exam Schedule