Summary

The Basic Electrochemistry Lecture 1

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Faradic process

The current flow to and from electrodes is the results of Faradaic and Non-Faradaic processes. These processes can occur alone or simultaneously. A Faradaic process involves the transfer of electrons across the electrode-electrolyte interface.
A Non-Faradaic process involves charging of the interface (double layer), much like that of capacitor, without the transfer of electrons.

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Faradic process

Charge Transfer Electrodes: electrodes at which Faradaic process occur. Electrons are either gained or given up depending on their energy.
By driving the potential of the electrode more negative, the energy of the electrons in the electrode increases thereby given the electrons sufficient energy to occupy vacant states on the species in the electrolyte. By driving the potential more positive, the electrons in the electrode loose energy, thereby making it possible for electrons from species in the electrolyte to lower their energy by transferring to the electrode.

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Faradays Law of Electrolysis

Faradays Law of Electrolysis: The extent of the electrochemical reaction is proportional to the charge passed to the electrode. This can be demonstrated by the dissolution of metal: M Mn+ + neThe charge Q (in coulombs) passed to the electrode is represented as: t I= current (amps) to the electrode Q Idt t= duration (seconds) of the current

Moles of electrons passed are obtained by dividing Q by Faraday constant: F = 96487 C/mol e Mols of metal dissolved are obtained by dividing the mols of electron by n: I *t I *t M M * AW (g) AW = atomic weight (g) n * F (mol) Then mass: n* F

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Faradays Law of Electrolysis

Electrolysis is a Faradaic process where electrons are transferred across the electrode-electrolyte interface resulting in transformation of chemical spices. Water electrolysis is electrochemical water splitting, where Reduction reaction proceeds on Cathode, in which electrons are consumed: 4H+ + 4e 2H2

Oxidation reaction proceeds on Anode, in which electrons are given: 2H2O O2 + 4H+ + 4e
Overall reaction: 2H2O O2 + 2H

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Galvanic & Electrolytic Cell

Galvanic cell: Reactions occur spontaneously, chemical energy can be converted into electrical energy. Examples: Discharging batteries. Electrolytic cell: Reactions driven by external power source. A sufficient potential is applied across the two electrodes to induce the electrochemical reactions. Cathode potential is more negative than anode potential. Examples: Charging batteries, electrolysis, electroplating.

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Non-Faradaic process & Double Layer

In some cases, it might be thermodynamically or kinetically unfavorable for Faradaic charge transfer processes to occur even if electrode is polarized through a range of potentials. Current, however may still flow to the electrode.

Non-Faradaic Current - Double Layer Charging The current originates from charging of the electrode, which is analogous to charging of a capacitor. During charging, species in the electrolyte may absorb or desorb from the interface, and therefore, the structure of the interface may change.

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Double Layer

Interphase region: The transitional region going from the electrode phase to the electrolyte phase. The interphase region is also called the electric double layer due to the two layers of excess charge.

Double layer represents a capacitor is describes by capacitance Cd ranging from 10 to 40 mF/cm2. However, since the capacitance is a function of potential, the double layer does not behave as an ideal capacitor.

Basic Electrochemistry: Lecture 1 Summary CPE690: Power Sources for Portable, Automotive, and Renewable Energy Systems

Vojtech Svoboda, January 2010

Summary: Double Layer

Double layer models:
Helmholtz model
Helmholtz proposed there is one layer of excess charge in the electrode and another layer of excess charge in the electrolyte separated by a fixed distance to give a linear potential profile.

Goy-Chapman model

Stern model: Stern proposed a hybrid of

Helmholtz and Goy-Chapman models.

Hamann, C. et al.: Electrochemistry, Wiley-VCH Verlag, 2007, page 117