Electrode Processes and Electrochemical Engineering

ISBN-13: 9781475701111 / Angielski / Miękka / 2012 / 426 str.

Fumio Hine

Opis

This book has been planned and written by Dr. Hine with his knowledge and experience in electrochemical science and engineering for over thirty years since he joined with me at Kyoto University in 1948. This book is unique and is useful for engineers as well as scientists who are going to work in any interdisciplinary field connected with elec- trochemistry. Science is sure to clarify the truth of nature as well as bring prosperity and an improvement to the welfare of human beings. The origin of the word "science" is the same as of "conscience," which means the truth of our heart. When we consider a scientific and technological subject, first we classify it into the components and/or factors involved, and then we clarify them individually. Second, we combine them to grasp the whole meaning and feature of the subject under discussion. Computers may help us greatly, but how to establish the software that will be most desirable for our purposes is of great importance. We need to make these efforts ourselves, and not decorate with borrowed plumes. With this concept in mind, this book is attractive because the author describes the basic science in electrochemistry and practice, and discusses the electrochemical engineering applications as a combination of science and technology.

Spis treści

I. Introduction to Electrochemistry.- 1. Concept and Role of Electrochemical Engineering.- 1.1. Electrochemical Science and Technology.- 1.2. Features of Electrochemical Processes.- 2. Thermodynamics of Electrochemical Processes.- 2.1. Electromotive Force and Decomposition Voltage.- 2.1.1. Example 1: Formation and Electrolysis of Hydrochloric Acid.- 2.1.2. Example 2: Electrolysis of Water.- 2.2. Reversible Potential.- 2.2.1. Example 1: Anodic and Cathodic Reactions of HCl Electrolysis.- 2.2.2. Example 2: Hydrogen Electrode Reaction versus Oxygen Electrode Reaction.- 2.2.3. Example 3: Chlorine Electrode Process.- 2.2.4. Example 4: Sodium Amalgam Electrode.- 2.2.5. Example 5: Solid - Phase Electrodes of Mercury Compounds.- 2.2.6. Example 6: The Pourbaix Diagram for the Iron-Water System.- 3. Kinetics of Electrochemical Processes.- 3.1. The Rate of Electrochemical Process.- 3.2. Electrode Processes Controlled by a Reaction Step.- 3.2.1. Example 1: Hydrogen Electrode Process.- 3.2.2. Example 2: Oxygen Electrode Process.- 3.2.3. Example 3: Chlorine Electrode Process.- 3.2.4. Example 4: Iron Electrode Process.- 3.3. Electrode Processes Controlled by a Mass Transfer Step.- 3.3.1. Example 1: Copper Electrode Process.- 3.3.2. Example 2: Oxygen Cathode Reaction.- 3.3.3. Example 3: Fe2+ /Fe3+ Redox System.- 3.3.4. Example 4: Sodium Amalgam Electrode.- 3.4. More Complicated Electrode Processes.- 3.4.1. Electrode Process Controlled by Chemical and Mass Transfer Steps.- 3.4.2. Dimensional Analysis of Mass Transfer on an Electrode.- 4. Voltage Balance and Energy Balance in an Electrolytic Cell.- 4.1. Conductivity of Electrolytic Solutions.- 4.1.1. Specific Conductance, Molar and Equivalent Conductivities.- 4.1.2. Example 1: Conductivity of Concentrated KCl Solutions.- 4.1.3. Example 2: Conductivity of the Mixed Solution of HCl and CuCl2.- 4.1.4. Example 3: Conductivity of the Electrolyte Solutions Containing Gas Bubbles.- 4.2. Current Efficiency and Energy Efficiency.- 4.2.1. Current Efficiency.- 4.2.2. Energy Balance.- 4.3. Voltage Balance.- 4.3.1. Example 1: Electrolysis of NaCl Solutions— Comparison between the Amalgam Process and the Diaphragm Process.- 4.3.2. Example 2: Electrorefining and Electrowinning of Copper.- 4.3.3. Example 3: Application of the Oxygen Cathode to HCl Electrolysis.- II Electrochemical Industries.- 5 Water Electrolysis.- 5.1. Water Electrolyzer.- 5.2. Production of Heavy Water.- 5.3. Prospects of Water Electrolysis.- 6. Electrolysis of Hydrochloric Acid Solution.- 6.1. HCl Electrolyzers.- 6.2. Recovery of Chlorine from Hydrochloric Acid.- 7. Amalgam-Type Chlor-Alkali Industry.- 7.1. Flowsheet.- 7.2. Amalgam Cell.- 7.3. Amalgam Decomposition.- 7.3.1. Minimum Sectional Area.- 7.3.2. Minimum Height.- 7.3.3. Notes for Convenience.- 7.4. Effects of Impurities and Necessity of Brine Purification.- 8. Chlor-Alkali Industry Using Diaphragm Cells.- 8.1. Diaphragm-type Chlorine Cells.- 8.2. Ion-Exchange Membrane Cells.- 8.3. Amalgam Process vs. Diaphragm Process.- 9. Fused Salt Electrolysis and Electrothermics.- 9.1. Background of Fused Salt Electrolysis.- 9.2. Production of Aluminum.- 9.2.1. The Bayer Process for Production of Alumina.- 9.2.2. The Hall-Heroult Process for Aluminum Production.- 9.2.3. Production of High-Purity Aluminum by Means of Electrorefining.- 9.3. Electrolytic Production of Magnesium.- 9.4. Electrochemical Production of Sodium.- 9.5. Production of Calcium Carbide.- 10. Electrorefining and Electrodeposition of Metals.- 10.1. Electrochemical Production of Copper.- 10.1.1. Electrorefining of Copper.- 10.1.2. Electrochemical Winning of Copper.- 10.2. Electrodeposition of Less Noble Metals.- 10.3. Electrolytic Production of Pure Zinc.- 10.4. Initiation, Growth, and Morphology of Electrodeposited Metal.- 11. Batteries.- 11.1. Leclanché-Type Batteries.- 11.2. Lead-Acid Batteries.- 11.3. Alkali Storage Batteries.- 11.4. Fuel Cells and Application of Fuel Cell Concepts to Chemical Processes.- III. Electrochemical Engineering.- 12. Configuration of Electrolyzers.- 12.1. Configuration and Type of Electrolyzers.- 12.1.1. Case Study of Configuration of Chlor-Alkali Cells.- 12.1.2. Monopolar Cells vs. Bipolar Cells.- 12.1.3. Some Cell Configurations of Interest.- 12.2. Diaphragms and Separators.- 12.2.1. Electrochemical Systems Having Liquid Junction Potential.- 12.2.2. Mass Transfer through a Diaphragm.- 12.3. Anode Materials.- 12.3.1. Example 1: Graphite Anode for Chlorine Evolution.- 12.3.2. Example 2: Precious-Metal-Coated Anodes.- 12.3.3. Example 3: The Oxide-Coated Metal Anodes.- 12.4. Cathode Materials.- 12.4.1. Effects of Brine Impurities on the Amalgam Cathode.- 12.4.2. Low Hydrogen Overvoltage Cathodes in Alkali Solutions.- 12.4.3. Oxygen Cathodes for Chlor-Alkali Cells.- 13. Current Distribution and Potential Distribution.- 13.1. Primary Current Distribution.- 13.1.1. Example 1: Effects of the Side Wall of an Electrolytic Cell on the Current Distribution.- 13.1.2. Example 2: Effects of the Back Wall of an Electrolytic Cell on the Current Distribution.- 13.2. Effect of the Electrode Resistance.- 13.3. Secondary Current Distribution.- 13.3.1. Effect of the Overvoltage on the Current Distribution on a Resistant Electrode.- 13.3.2. Effect of the Overvoltage on the Current Distribution on a Finite-Plate Electrode.- 14. Optimum Design of an Electrolytic Cell.- 14.1. Size of Electrolyzer and Optimum Current Density—A Case Study.- 14.1.1. Optimum Size and Number of Cells.- 14.1.2. Optimum Current Density.- 14.1.3. Optimum Number of Stand-by Electrolyzers.- 14.2. Energy Saving in the Chlor-Alkali Industry.- 14.2.1. Use of off-peak Electricity.- 14.2.2. Reduction of Consumption of the Overall Energy for Processing.- 14.2.3. Reduction of the Power Consumption for Electrolysis.- 14.2.4. Voltage Balance.- 14.2.5. Bubble Effects.- 14.2.6. New Technology.- 14.3. Use of Computers.- 15. Feasibility of Electrochemical Processes.- 15.1. Production of Chlorate.- 15.1.1. Capacity, Production, and Market.- 15.1.2. Technology.- 15.1.3. Reaction Mechanisms for Electrolytic Production of Chlorate.- 15.1.4. Anode Materials.- 15.2. Electrolytic Production of Organic Compounds.- 15.2.1. Introduction.- 15.2.2. Electrochemical Synthesis of Adiponitrile: an Example of Electroorganic Chemistry.- 15.3. Safety Problems and Environmental Protection in Electrochemical Industries.- 15.3.1. Safety Problems in Electrochemical Industries.- 15.3.2. Abatement of Mercury Discharge from Chlor-Alkali Plants.- 15.4. Feasibility and Prospects of Electrochemical Processes— Conclusion.