Electrochemical Engineering,9783540643869

Electrochemical Engineering

by ;
ISBN13: 9783540643869
ISBN10: 3540643869
Format: Nonspecific Binding
Pub. Date: 2013-03-09
Publisher(s): Springer Nature
List Price: $358.58

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Summary

The particular concern of this book is to close the gap between electrochemical engineering science and electrochemical technology. Electrochemical techniques are fundamental for a few key-products in the chemical process industries, but they are even more frequently used in many other industries such as the metallurgical industries, in metal-surface processing, and semiconductor and electronic processing and they are essential to pollution control of aqueous industrial effluents. Recently electrochemical technologies have begun to play a role in energy systems and their management by fuel cells. For all electrochemists and electrochemical engineers, metallurgists, engineers in chemical process, galvanic, metallurgical and electric power industries.

Table of Contents

The Scope History of Electrochemical Engineering
Carl Wagner and the Beginning of Electrochemical Engineering Science
1(1)
Electrochemistry and Electrochemical Engineering Science
2(1)
Electrochemical Engineering Science and Technology Since the Mid-1960s
3(2)
What Means Electrochemical Engineering Science and Technology Today?
5(3)
References
7(1)
Further Reading
7(1)
Basic Principles and Laws in Electrochemistry
Stoichiometry of Electrochemical Reactions
8(2)
Faraday's Law
10(1)
Production Rates and Current Densities
11(1)
Ohm's Law and Electrolyte Conductivities
12(2)
Parallel Circuits and Cells with Electrolytic Bypass and Kirchhoff's Rules
14(3)
Further Reading
16(1)
Electrochemical Thermodynamics
Equilibrium Cell Potential and Gibbs Energy
17(4)
Electrode Potentials, Reference Electrodes, Voltage Series, Redox Schemes
21(7)
Reaction Enthalpy, Reaction Entropy, Thermoneutral Cell Voltage and Heat Balances of Electrochemical Reactions
28(1)
Heat Balances of Electrochemical Processes
29(2)
Retrieval of Thermodynamic Data and Activity Coefficients
31(4)
Thermodynamics of Electrosorption
35(4)
References
37(2)
Electrode Kinetics and Electrocatalysis
The Electrochemical Double Layer
39(2)
Kinetics of Interfacial Charge Transfer
41(4)
Electrode Kinetics of Multielectron Charge Transfer Reactions
45(4)
Thermal Activation and Activation Energies of Electrochemical Reactions
49(1)
Electrochemical Reaction Orders
49(2)
Current Density/Potential Correlations for Different Limiting Conditions
51(6)
Micro- and Macrokinetics of Electrochemical Reactions
51(1)
Mass Transfer Controlled Current Potential Curves
52(2)
Reaction Controlled Current Voltage Curves
54(1)
Charge Transfer Controlled Current Voltage Correlation
55(1)
Combined Activation and Mass Transport Control
56(1)
Reaction Controlled Current Voltage Curves
57(4)
Introductory Remarks
57(1)
Fast Preceding Reaction of an Electroactive Minority Species
58(2)
Fast Consecutive Reactions
60(1)
Electrocatalysis
61(7)
Principles of Electrocatalysis
61(1)
Heterogeneous Electrocatalysis in Cathodic Evolution and Anodic Oxidation of Hydrogen
61(1)
The Volcano Curve
62(2)
Electrocatalysis in Anodic Oxygen Evolution and Cathodic Oxygen Reduction
64(2)
Redox Catalysis
66(2)
Catalyst Morphology and Utilisation
68(3)
Structural Features and Catalyst Morphology of Electrocatalysts for Gas Evolving and Gas Consuming Electrodes
68(1)
Utilisation of Porous Electrocatalyst Particles
69(2)
Electrocatalysis in Electroorganic Synthesis
71(10)
Introduction into the Field of Electroorganic Synthesis
71(1)
Mediated Electrochemical Conversions of Organic Substrates
71(1)
Direct Anodic and Cathodic Electrochemical Conversions of Organic Substrates
72(1)
Electrocatalytic Oxidations by Oxides of Multiply-Valent Metals
72(2)
The Heterogeneously Catalysed Benzene Oxidation at Pb/PbO2 Electrodes in Sulfuric Acid
74(1)
Electrocatalytic Hydrogenation and Electrocatalyzed Mediated Reduction
74(1)
The Electrode Surface as Medium Catalysing Chemical Reactions of Electrogenerated Reactive Organic Intermediates
75(3)
Electrocatalytic Action of Electrosorbed Non-Reactant Species --Electrocatalysis of the Second Kind
78(1)
Kinetics and Selectivity of Homogeneous Chemical Consecutive Reactions Following Charge Transfer
79(1)
References
80(1)
Further Reading
80(1)
Mass Transfer by Fluid Flow, Convective Diffusion and Ionic Electricity Transport in Electrolytes and Cells
Introduction
81(1)
Fluid Dynamics and Convective Diffusion
81(3)
Fluid Dynamics of Viscous, Incompressible Media
84(6)
Laminar vs Turbulent Flow
86(1)
Velocity Distributions for Laminar Flow
87(1)
Singular Electrode; Unidirectional Laminar Flow Along a Plate
87(1)
Pair of Planar Electrodes
88(1)
Circular Capillary Gap Cell
89(1)
Mass Transport by Convective Diffusion
90(17)
Fundamentals
90(2)
Dimensionless Numbers Defining Mass Transport Towards Electrodes by Convective Diffusion
92(1)
Hydrodynamic Boundary Layer and Nernst Diffusion Layer: Planar Electrodes
93(2)
Mass Transport Towards a Singular Planar Electrode Under Laminar Forced Flow
95(2)
Channel Flow and Mass Transfer to Electrodes of Parallel Plate Cells for Free and Forced Convection
97(1)
Free Convection at Isolated Planar Electrodes and between Two Vertical Electrodes
97(1)
Convective Mass Transfer for Parallel Plate Cells with Forced Convection: Planar Plate Cells
98(3)
Mass Transfer in Circular Capillary Gap Cells
101(1)
Convective Mass Transfer Toward Rotating Electrodes
102(1)
Rotating Cylinder
102(1)
Rotating Disc Electrode
102(1)
Mass Transfer at Gas Evolving Electrodes
103(2)
Calculating km, bubble According to the Penetration Model or Model of Periodic Boundary Layer Renewal
105(1)
Calculating Bubble-Enhanced Mass Transfer According to Flow Model
105(1)
Mass Transfer in Three-Dimensional Electrodes
106(1)
Summary
107(1)
Heat Transport
107(3)
Chilton--Colburn Analogy of Mass and Heat Transfer
107(1)
General Description of Heat Generation and Heat Transfer in Electrolyzers and Fuel Cells
108(1)
Heat Balance and Steady State-Temperature of Cells
109(1)
Ionic Charge and Mass Transport in Electrolytes
110(1)
Strong Electrolytes
110(1)
Temperature Dependence of Electrolyte Conductivities
111(2)
Molten Salt Electrolytes
113(1)
Segregation in Stagnant Electrolytes of Binary Molten Carbonates in Fuel Cells
114(3)
Current Density Distribution in Cells and Electrochemical Devices
117(2)
Primary Current Density Distribution
119(2)
Secondary Current Density Distribution
121(1)
Secondary Current Density Distribution and ``Throwing Power'' in Electrodeposition and Electrocoating
122(2)
The Wagner Number
124(1)
Tertiary Current Distribution
125(3)
References
127(1)
Further Reading
127(1)
Electrochemical Reaction Engineering
Introductory Remarks
128(1)
Microkinetic Models
128(1)
Mode of Operation
129(2)
Electrical Control of Cells
131(1)
Macrokinetic Models
131(15)
Stirred-Batch Tank Reactor
131(1)
Continuously Stirred Tank Reactor
132(1)
Plug-Flow Reactor (PFR)
133(2)
Plug Flow Electrolyzer with Uniform Current Density
135(1)
PFR Operated at Mass Transfer Limited and Higher Current Density
135(1)
Cell Cascades
136(2)
Extended Modelling of Electrolyzers
138(1)
Residence-Time Distribution
139(3)
The Selectivity Problem of Consecutive Reactions in Batch Reactors
142(4)
Coupling of Electrochemical and Chemical Reactors
146(2)
Electrolyzer Design and Chemical Yield Losses Due to Parasitic Chemical Reactions
148(1)
Performance Criteria of Electrochemical Reactors
149(4)
Fractional Conversion, X
150(1)
Relative Amount of Charge-Qr
150(1)
Overall Conversion Related Yield Θp
150(1)
Current Efficiency Φe
151(1)
Parameters for Energy Considerations
152(1)
References
152(1)
Further Reading
152(1)
Electrochemical Engineering of Porous Electrodes and Disperse Multiphase Electrolyte Systems
Introduction
153(1)
Three-Dimensional Electrodes
154(25)
General Considerations
154(1)
Fundamental Equations
155(1)
Nanoporous Electrode Particles
156(1)
Microporous Electrodes
156(1)
Packed and Fluidized Bed Electrodes
157(1)
Gas Consuming Nanoporous Electrodes for Fuel Cells and Nanoporous Catalyst Particles and Layers for Gas Evolving Electrodes
157(1)
Physical Structure of Particulate, Gas Consuming Nonoporous Gas Diffusion Electrodes
157(2)
Physical Structure of Raney Nickel Coatings for Hydrogen Evolving Cathodes
159(1)
Modelling Hydrogen Concentration Profiles and Catalyst Efficiencies for Hydrogen Consuming Fuel Cell Anodes or Other Gas Diffusion Electrodes
160(5)
Modelling of Hydrogen Concentration Profiles and Catalyst Efficiencies for Hydrogen Evolving Nanoporous Raney-Nickel Catalyst Coatings
165(6)
Porous Battery Electrodes
171(2)
Packed Bed and Fluidized Bed Electrodes Composed of Coarse Particles
173(5)
Fluidized Bed Electrodes
178(1)
Ionic Conductivity of Electrolytes Containing Dispersed Gas Bubbles in Gas Evolving Electroylyzers
179(4)
Electrolyzers with Gaseous Reactants
183(3)
Electrochemical Liquid/Liquid Systems
186(1)
References
186(1)
Further Reading
186(1)
Electrochemical Cell and Plant Engineering
Materials Choice and Corrosion Problems
187(6)
Metals
188(4)
Carbon
192(1)
Electrode Materials
193(3)
Stainless Steel
194(1)
Nickel
194(1)
Lead
195(1)
Titanium
195(1)
Noble Metals
195(1)
Massive Carbon
196(1)
Electrode Design
196(3)
Gas Evolving Electrodes
196(1)
Gas Consuming Electrodes, Gas Diffusion Electrodes
197(2)
Separators: Membranes and Diaphragms
199(4)
Membranes
201(2)
Diaphragms
203(1)
Polymeric Materials for Cell Bodies and Electrolyte Loops
203(2)
Gaskets
205(1)
Electrodes
206(2)
Horizontal Electrodes
206(1)
Membrane Electrolyzer
207(1)
Cell and Electrode Design
208(10)
Zero Gap Electrolysis Cells
208(1)
Vertical/Horizontal Electrodes
209(1)
Divided/Undivided Monopolar/Bipolar Cells and Modes of Electrolyte Flow
209(1)
Special Cell Designs
210(6)
Capillary Gap Cells
216(1)
Swiss Roll Cell
216(1)
Cells with Three-Dimensional Electrodes
217(1)
Power Supply for Electrochemical Plants
218(3)
Rectifiers
218(1)
Transformer Wiring
218(1)
Further Equipment
219(1)
Further Reading
220(1)
Process Development
Scope and Purpose of Laboratory and Pilot Plant Measurements
221(1)
Laboratory Methods
222(14)
Steady-State Measurements of Current Density Potential Correlations
222(1)
General Remarks
222(1)
Measuring Devices
223(1)
Evaluation of Rotating Disc Measurements
223(2)
Current-Voltage Correlation for Competing Reactions by Non-Electrochemical Methods
225(1)
The Ring Disc Electrode
226(4)
Non-Steady State Methods
230(1)
General Remarks
230(1)
Potentiodynamic Polarisation Curves
230(1)
Cyclic Voltammetry and Linear Potential Sweep Method
231(2)
Initial Polarisation Curves
233(1)
Square-Wave Pulses
233(2)
Eliminating the IR Drop
235(1)
Galvanostatic Methods
236(1)
Potentiostatic Procedures
236(1)
Pilot Plant Methods
236(3)
General Considerations
236(1)
Mass-Transfer Measurements
237(1)
Determination of Residence-Time Distributions
238(1)
Mathematical Modelling and Optimisation by Factorial Design of Experiments
239(4)
Introduction
239(1)
General Procedure for Optimum Finding by Experiment
239(1)
Factorial Design of Experiments
240(3)
Cost Analysis
243(9)
Composition of Productions Costs
243(1)
Total and Specific Investment Costs
244(1)
Cost Optimisation with Respect to Current Density
245(3)
Optimisation of Non-Selective Electrolysis Processes
248(1)
Current Density Against Current Efficiency
249(1)
Temperature vs Current Efficiency
250(1)
Examples Including Influences of Process Parameters on the Equipment for Non-Electrochemical Unit Operations and Corresponding Costs
250(1)
Further Reading
251(1)
Industrial Electrodes
Catalytically Activated Electrodes
252(1)
Functioning, Longevity and Application of Electrocatalyst Coatings
253(2)
Design of Industrial Electrodes
255(5)
Monopolar Electrodes and Current Density Distribution on Their Surface
255(2)
Electrodes for Bipolar Electrode Stacks
257(1)
Gas Evolving Electrodes
258(2)
Structural Features of Electrocatalysts for Gas Evolving and Gas Consuming Electrodes
260(1)
Electrocatalytically Activated Dimensionally Stable Chlorine-Evolving Electrodes
260(5)
Technological History
260(1)
Electrocatalysis and Selectivity of Anodic Chlorine Evolution at RuO2-Anodes
261(1)
Preparation and Formulation of the Coatings
261(1)
Improvement of Adhesion and Strength of the Coatings
261(1)
Design of Cells Using DSAs
262(1)
Lifetime of Dimensionally Stable Chlorine Evolving Anodes
263(1)
DSAs for Chlorate and Hypochlorite Production
264(1)
Oxygen Evolving Anodes
265(3)
Technical Processes
265(1)
Electrocatalysis of Oxygen Evolution in Advanced Alkaline Water Electrolysis
265(1)
Coatings Containing Cobalt and Iron Oxides
265(1)
Electrocatalysis of the Anodic Oxygen Evolution by Raney-Nickel Coatings
266(1)
Catalyst-Coated Titanium Electrodes for Oxygen Evolution From Acid Solutions
266(2)
Hydrogen Evolving Cathodes
268(6)
Technoeconomical Significance of Cathodic Hydrogen Evolution
268(1)
Electrocatalyst Coatings for Hydrogen Evolution from Alkaline Solution
268(1)
Technically Applied Coatings
268(1)
Nickel Sulfide Coatings
269(1)
Raney-Nickel Coatings
269(1)
Precursor Alloys and Fabrication of Coated Cathodes
269(2)
Utilisation of the Catalyst in Raney-Nickel Coatings
271(1)
Performance and Ageing of Raney-Nickel Coatings
272(1)
Coatings of Platinum Metal Oxides
273(1)
Active Coatings of Flame Sprayed, Doped Nickel Oxide
273(1)
Platinum and Platinum Metal Cathodes in Membrane Water Electrolyzers
273(1)
Fuel-Cell Electrodes
274(16)
Low- and High-Temperature Fuel Cells
274(1)
Structural Design of Gas-Diffusion Electrodes in Low-Temperature Fuel Cells
275(1)
Oxygen Reduction Catalysts in Low-Temperature Cells
276(1)
Catalysts for Anodic Hydrogen Oxidation
276(1)
Properties, Preparation and Improvement of Electrocatalysts in Gas Diffusion Electrodes for Low Temperature Cells
277(1)
Pt-Activated Active Carbon
277(1)
Particle Size of Pt Nanocrystals on Active Carbon and Their Effective Catalytic Activity
278(1)
Pt-Alloy Catalysts
278(1)
Morphology and Structure of Complete PTFE-Bonded Active-Carbon Electrodes
279(1)
Ageing of Pt-Catalysts
280(1)
Electrocatalysis of Anodic Methanol Oxidation
281(1)
Technoeconomic Significance of the Process
281(1)
Self-Poisoning of Methanol Oxidising Pt-Catalyst by Oxidation Products of Methanol
281(1)
Anodic Methanol Oxidation at Alloy Catalysts
281(1)
Gas-Diffusion Electrodes in Membrane (PEM) Fuel Cells
282(1)
Rationale of Developing a Method of Internal Wetting for Membrane Fuel Cell Electrodes
282(1)
Improving Catalyst Utilisation by Ionomer Impregnation of Gas-Diffusion Electrodes
282(1)
The Preparation of Membrane Electrode Assemblies (MEAs) for Membrane Fuel Cells
283(1)
Electrodes for High-Temperature Fuel Cells
284(1)
Stability of Electrode Structures at High Temperatures
284(1)
Electrode Kinetics and Electrocatalysis in Molten-Carbonate Fuel Cells
285(1)
Anodic Hydrogen Oxidation
285(1)
Cathodic Oxygen Reduction
285(2)
Electrodes in Solid-Oxide fuel Cells (SOFC)
287(1)
Electrodes and Electrode Structure
287(1)
The SOFC-Anode
287(1)
The SOFC-Cathode
288(1)
References
289(1)
Further Reading
289(1)
Industrial Processes
Introductory Remarks
290(1)
Inorganic Electrolysis and Electrosynthesis
291(1)
Chloralkali-Electrolysis
291(4)
The Electrochemical Reaction
292(1)
Thermodynamics and Energy Demands
292(1)
Anodic Chlorine Evolution
293(1)
The Cathodic Reaction
294(1)
Cathodic Sodium Deposition in the Mercury Process
294(1)
Cathodic Hydrogen Evolution in the Diaphragm and Membrane Process
295(1)
Process Technologies
295(11)
The Amalgam Process
295(2)
The Diaphragm Process
297(1)
The Membrane Process
298(2)
Process-Flow Sheets
300(2)
Brine Recycling
302(1)
Gas Purification and Conditioning
303(1)
Chlorine
303(1)
Hydrogen
304(1)
Comparison of the Three Processes
304(2)
Hypochlorite, Chlorate and Chlorine Dioxide
306(6)
Production of Sodium Hypochlorite
306(1)
Electrolytic Generation of Hypochlorite
306(1)
Current Efficiency Losses
307(1)
Production of Sodium Chlorate
307(3)
Balance of Plant of Chlorate Electrosynthesis
310(1)
Construction Materials
311(1)
Chlorine Dioxide from Sodium Chlorate
311(1)
Perchloric Acid, Perchlorates, Peroxidsulfates
312(3)
Perchoric Acid
312(1)
Sodium Perchlorate
312(1)
Peroxidisulfates
313(2)
Fluorine
315(1)
Hydrogen by Water Electrolysis
316(10)
Technoeconomic Environment
316(1)
Thermodynamics and Technological Principles of Electrolytic Water Splitting
317(1)
Process Technologies
318(2)
Conventional Alkaline Water Electrolysis
320(1)
Monopolar Technology
320(1)
Bipolar Technology
320(3)
Improval Alkaline Technologies
323(1)
New Technologies
324(1)
Membrane Water Electrolysis
324(1)
Steam Electrolysis
324(1)
Economic Implications of Technical Innovations for Alkaline Water Electrolysis
325(1)
Electrowinning and Electrorefining of Metals
326(9)
Metal Electrowinning and Refining from Aqueous Electrolytes
326(4)
Copper Electrowinning and electrorefining
330(1)
Nickel Electrowinning
331(2)
Nickel from the Chloride Leach Process
333(1)
Nickel Refining
334(1)
Zinc Electrowinning
334(1)
Lead Electrorefining
335(1)
Metal Electrowinning from Molten Salt Electrolytes
335(10)
General Considerations
335(1)
Aluminium Production -- the Hall--Heroult Process
336(1)
The Malt
336(2)
Electrode Reactions
338(1)
The Cell
339(2)
Alkali Metals from Chloride Melts
341(1)
Magnesium Electrolysis
342(1)
Production of the Feed Salt
343(1)
Magnesium Electrolysis Cells
344(1)
Organic Electrosynthesis Processes
345(12)
General Overview
345(2)
Cell Type Used in Commercial Electroorganic Synthesis
347(2)
Process and Reaction Techniques of Some Examples of Industrial Organic Electrosyntheses
349(1)
Adipodinitrile Production by the Monsanto/Baizer Process
349(3)
Electrosynthesis of Sebacic Diesters by Kolbe Synthesis
352(1)
Benzaldehydes by Direct Anodic Oxidation of Toluenes
353(1)
The Selective Anodic Oxidation of L-Sorbose in Commercial Vitamin C Synthesis
353(2)
Anodic Formation of Perfluoro-Propylene Oxide
355(2)
Selected Electrochemical Procedures Outside the Chemical and Metallurgical Industries
357(13)
Electrochemical Wastewater Treatment by Electrodeposition and by Electroosmosis
357(1)
General Considerations
357(1)
Particular Cells for Removal of Metal Ions from Effluents
358(3)
Electrodialysis
361(1)
Electrochemical Surface Treatment and Shaping of Metals
362(1)
Electrochemical Shaping
362(1)
Electropolishing
363(2)
Electrochemical Machining (ECM)
365(1)
Electrochemical Grinding
366(2)
Electroreforming of Microdies and Microtools by the LIGA-Process
368(1)
References
369(1)
Further Reading
369(1)
Fuel Cells
Fuel Cells as Gas Supplied Batteries
370(1)
Theoretical Efficiency of Hydrogen/Oxygen Fuel Cells
371(2)
Fuel Cell Types
373(12)
Low-Temperature Fuel Cells -- Their Technological State
375(1)
Phosphoric-Acid Cells
375(1)
Membrane Cells
376(1)
Direct and Indirect Methanol-Combusting Membrane Cells
377(1)
Process Principles of the PAFCs and PEMFCs with Proton Conducting Electrolyte
378(1)
High-Temperature Fuel Cells
379(1)
Molten-Carbonate and Solid Oxide Fuel Cells
379(1)
Process Schemes of MCFCs and SOFCs
379(1)
Internal Reforming in High-Temperature Fuel Cells
380(1)
Cell Technologies of MCFCs and SOFCs
381(1)
Molten-Carbonate Fuel Cells
381(1)
Solid Oxide Fuel Cells
382(1)
The Westinghouse Technology
382(2)
Flat Plate Solid Oxide Cells
384(1)
Current Voltage Curves of Different Fuel Cells
385(2)
Fuel-Cell Systems
387(8)
Phosphoric-Acid Fuel Cell/PC 25
387(3)
Molten Carbonate Cells
390(1)
ERC-2 MW Plant
390(1)
Hot Module of MTU
390(1)
Proton Exchange Membrane Cells
391(1)
The Ballard Cell
392(2)
De Nora's Cell
394(1)
Further Reading
394(1)
Subject Index 395

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