Chemistry 517: Electrochemistry

Textbooks

There are no assigned textbooks for this course. The class notes are based on the Bard  and  Faulkner textbook. You are expected to use the following excellent references.

• “Electrochemistry Methods. Fundamentals and Applications” by Bard and Faulkner (1st or 2nd edition)
• “Physical chemistry of surfaces” by Arthur W. Adamson.

Course Description

Chem 517 is an introduction to electrochemical methods and advanced techniques. After successfully com- pleting this course you will be able to:

• describe the energetics of transferring an electron into or out of a metal or semi-conductor surface
• understand the double layer model of ion distribution within an electrolyte near a charged metal surface
• understand the instrumentation used in electrochemical measurements and experiments
• understand the principles behind the electron transfer reaction and the model describing the effect of potential on the rate of electron transfer (e.g.:  Butler-Volmer, etc.)
• use the Butler-Volmer equation to analyze current-voltage data
• describe the φ₂ effect on electron transfer rates

• describe the current - potential - time surface and use it to rationalize a CV of a redox active species      in solution
• describe the CV for a reversible, quasi-reversible and irreversible electron transfer
• describe other voltammetric methods commonly used (e.g., DPV, ASV, SWV)
• describe the fundamentals behind impedance spectroscopy as applied to an electrochemical system
• describe electrosorption and the models used to describe molecular adsorption and the influence of electrode potential

Evaluation

• Problem Set and Modeling Project: 25%.
  • problem sets are to be handed in during class or on-line
  • solutions will be discussed in class or virtually
• Presentation and Report: 25%
  • Seminar will be evaluated on the following points:

∗ Clarity of presentation - was it clearly outlined a presented in a logical manner, or was it confusing, not well explained, missing important ideas/theory

∗ Material presented - eg did you prepare a lecture that was about a new topic, new method, extending the class material, not just a research seminar, but a lecture!

∗ Report/lecture notes - for distribution to fellow classmates

∗ Ability to answer questions, explanations used to answer questions

• Final Exam: 50%
  • oral final exam scheduled at the end of term, format to be determined

The final examination is scheduled by the registrar. The examination period for this term is given in the UBC Calendar. DO NOT BOOK TRAVEL RESERVATIONS UNTIL THE EXAMINATION TIMETABLE

FOR  THE CURRENT TERM IS FINALIZED. No changes in exam dates will be made to accommodate   travel plans.

During the writing of all examinations in CHEM517, the following University regulations will be strictly enforced:

"Candidates guilty of any of the following, or similar, dishonest practices shall be liable to disciplinary action:

1. Making use of any book, papers, preprogrammed information in calculators, or memoranda other than those authorized by the examiners.
2. Speaking or communicating with other candidates.
3. Purposely exposing written papers to the view of other candidates. The plea of accident or forgetfulness shall not be received."

Identification (AMS card) is required at examinations.

Lecture Schedule

1. Introduction
   • Electrostatics Review, Electrical Work, Nernst equation
2. The Metal Side of the Interface
   • Inner, Outer and Surface Potential, Fermi Level, Work Function, Work Function and Surface Crystallography, Work Function Changes Due to Adsorption, Absolute Scale of Potential
3. The Solution Side of the Interface
   • Helmholtz Model, Extensions to the Helmholtz Model, Gouy-Chapman-Stern Theory, Ionic or Dif- fuse Part of the Double Layer (Gouy-Chapman Model), Capacitance of the polarizable interface, Deficiencies of the GCS theory, The Effect of Solvent
4. Electron  Transfer Reactions
   • Rate of electron transfer, Exchange Current, Tafel Behaviour, Influence of φ₂ on Rates of Electron Transfer Reactions
5. Instrumentation
   • Operational Amplifiers,  Ideal  and  Real  Op  Amps,  Feedback  Circuits,  Voltage  Follower,  Cur-  rent Follower, Inverter or Scaler, Summing Amplifier, Integrator, Three electrode configuration, Difficulties in Potential Control, Measurements using AC signals, AC Signals, Phasor Diagram,

Example using AC Impedance for Measuring Capacitance

6. Electrochemical Techniques
   • Mass Transport, Ficks Laws of Diffusion, Cottrell Equation, Potential Steps at a Planar Electrode, Quasi-reversible or irreversible reactions, Potential Sweep Methods, Linear Sweep Voltammetry, Cyclic Voltammetry, Capacitive Currents, AC Impedance, Constant Phase Element (CPE)

(if time permits, semi-conductor electrochemistry or coupled techniques such as spectroelectrochemical meth- ods (eg. IR, UV-Vis reflectance, Raman) will be discussed)