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`Our reference
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`reference
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`Item
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`PUBLIC AVAILABILITY DATE REQUEST
`
`Janelle Beitz
`Fredrikson & Byron, P.A
`200103-2
`
`£90.00
`
`Electrochemical engineering: science & technology in chemical and
`other industries, Hartmut Wendt, Gerhard Kreysa, Springer/Verlag
`Berlin Heidelberg (1999), ISBN 3-540-64386-9.
`Shelfmark(s): Document Supply 99/19145; Science Technology &
`Business (B) LG 80.
`
`British Library Research Service
`Tel: +44 (0) 20 7412 7903 bipc-research@bl.uk
`
`Tennant Company
`Exhibit 1018
`
`Exhibit 1018_0001
`
`
`
`I .
`
`Janelle K. Beitz, J.D., M.L.I.S.
`Research Librarian
`Fredrikson & Byron, P.A.
`200 South Sixth Street, Suite 4000
`Minneapolis, Minnesota 55402
`USA
`
`18th December 2020
`
`Dear Janelle
`
`“Title: Electrochemical engineering: science & technology in chemical and
`other industries, Hartmut Wendt, Gerhard Kreysa, Springer/Verlag Berlin
`Heidelberg (1999), ISBN 3-540-64386-9. Shelfmark(s): Document Supply
`99/19145; Science Technology & Business (B) LG 80”.
`
`According to our records, this item was receipted by The British Library on 29th March
`1999, when it would have been available for public use from this date.
`
`A scan of the cover pages showing the date stamp on page two indicating the date of
`availability has been attached, together with the table of contents.
`
`Please note that we can only provide the date that the British Library made this item
`available for public use; for the actual date of publication, please contact the
`publisher.
`
`Yours sincerely
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`Ms S Rampersad
`
`British Library Research Service
`Tel: +44 (0) 20 7412 7903 bipc-research@bl.uk
`
`Exhibit 1018_0002
`
`
`
`...........,.,,-· E;lectrochemicaf
`Engineering
`Science
`andTe~hnology
`in Chemical
`and Other
`Industries
`
`'S~ringer
`
`Exhibit 1018_0003
`
`
`
`Hartmut Wendt and Gerhard Kreysa
`
`Electrochemical
`Engineering
`
`Science and Technology in Chemical and Other Industries
`
`With 177 Figures and 45 Tables
`
`BRITISH LIBRARY
`DOCUMENT SUPPL'< CENTRE
`
`Springer
`
`Exhibit 1018_0004
`
`
`
`Prof. Dr. Hartmut Wendt
`Institut for Chemische Technologie
`TU Darmstadt
`Petersenstraf3e 20
`D-64287 Darmstadt
`Germany
`
`Prof. Dr. Gerhard Kreysa
`Karl Winnacker Institut
`DECHEMA e. V.
`Theodor-Reuss-Allee 25
`D-60486 Frankfurt am Main
`Germany
`
`ISBN 3-540-64386-9 Springer-Verlag Berlin Heidelberg New York
`
`Library of Congress Cataloging-in-Publication Data
`Wendt, Hartmut, 1933-
`Electrochemical engineering : science and technology in chemical and other industries / Hartmut Wendt,
`Gerhard Kreysa.
`p.cm.
`Includes bibliographical references.
`ISBN 3-540-64386-9 (hardcover: alk. paper)
`1. Electrochemistry, Industrial. I. Kreysa, Gerhard. IL Title.
`TP255.W46 1999
`660' .297--dc2 l
`
`This work is subject to copyright. All rights are reserved, whether the whole part of the material is concerned,
`specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction
`on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof
`is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current ver(cid:173)
`sion, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecu(cid:173)
`tion under the German Copyright Law.
`
`© Springer-Verlag Berlin Heidelberg 1999
`Printed in Germany
`
`The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply,
`even in the absence of a specific statement, that such names are exempt from the relevant protective laws and
`regulations and therefore free for general use.
`
`Typesetting: MED IO, Berlin
`Coverdesign: Design & Production, Heidelberg
`
`SPIN: 10675807 2/3020 - 5 4 3 2 1 0 - Printed on acid-free paper.
`
`Exhibit 1018_0005
`
`
`
`Preface
`
`)lications. The authors
`nfined to the relatively
`dustries, but that elec(cid:173)
`re money in the metal(cid:173)
`J the electronic indus(cid:173)
`m of processes to these
`
`!merging fuel cell tech-
`1 engineering are more
`rochemical process.
`-ipt of the two authors,
`agen, who so patiently,
`Mr. Bottiger, who with
`>k and whose quality is
`er programs.
`
`H. Wendt
`
`Contents
`
`Chapter 1
`The Scope and History of Electrochemical Engineering
`
`1.1
`
`1.2
`1.3
`
`Carl Wagner and the Beginning of Electrochemical
`Engineering Science . . . . . . . . . . . . . . . . . . . . . . . .
`Electrochemistry and Electrochemical Engineering Science .
`Electrochemical Engineering Science and Technology
`Since the Mid-1960s .. .. . . . . . . . . . . . . . .
`1.4 What Means Electrochemical Engineering Science
`and Technology Today?
`References . . . .
`Further Reading
`
`Chapter 2
`Basic Principles and Laws in Electrochemistry
`
`2.1
`2.2
`2.3
`2.4
`2.5
`
`Stoichiometry of Electrochemical Reactions
`Faraday's Law . . . . . . . . . . . . . . . . .
`Production Rates and Current Densities ..
`Ohm's Law and Electrolyte Conductivities .
`Parallel Circuits and Cells with Electrolytic Bypass
`and Kirchhoff's Rules
`Further Reading.
`
`Chapter 3
`Electrochemical Thermodynamics
`
`3.1
`3.2
`
`3.3
`
`3.4
`
`Equilibrium Cell Potential and Gibbs Energy . . . . . . . .
`Electrode Potentials, Reference Electrodes,Voltage Series,
`Redox Schemes . . . . . . . . . . . . . . . . . . . . . . . . .
`Reaction Enthalpy, Reaction Entropy, Thermoneutral Cell
`Voltage and Heat Balances of Electrochemical Reactions
`. . . . . . . . .
`Heat Balances of Electrochemical Processes
`
`1
`2
`
`3
`
`5
`7
`7
`
`8
`10
`11
`12
`
`14
`16
`
`17
`
`21
`
`28
`29
`
`Exhibit 1018_0006
`
`
`
`VIII
`
`Contents
`
`I
`
`Retrieval of Thermodynamic Data and Activity Coefficients
`3.5
`Thermodynamics of Electrosorption.
`3.6
`References . . . . . . . . . . . . . . . . . . . .
`
`Chapter4
`Electrode Kinetics and Electrocatalysis
`
`4.1
`4.2
`4.3
`4.4
`
`4.5
`4.6
`
`4.7
`
`4.8
`
`4.9
`
`4.10
`
`4.6.2
`4.6.2.1
`4.6.3
`
`The Electrochemical Double Layer . . . . . . . . . . . . . . . . .
`Kinetics of Interfacial Charge Transfer
`. . . . . . . . . . . . . .
`Electrode Kinetics of Multielectron Charge Transfer Reactions.
`Thermal Activation and Activation Energies of
`Electrochemical Reactions
`. . . . . . . . .
`Electrochemical Reaction Orders . . . . . .
`Current Density/Potential Correlations for
`Different Limiting Conditions
`. . . . . . . . . . . . . . .
`4.6.1
`Micro- and Macrokinetics of Electrochemical
`Reactions . . .... .. . . .. . . . ... . . . .
`Mass Transfer Controlled Current Potential Curves
`Reaction Controlled Current Voltage Curves
`Charge Transfer Controlled Current Voltage
`Correlation .. . . . . . . . . . . . . . . . . . .
`Combined Activation and Mass Transport Control
`4.6.4
`Reaction Controlled Current Voltage Curves . . . . . .
`4.7.1
`Introductory Remarks .. . .. . ... . . . .
`4.7.2
`Fast Preceding Reaction of an Electroactive
`Minority Species . . . . . .
`4.7.3
`Fast Consecutive Reactions
`Electrocatalysis . . . . . . . . . . . . . .
`4.8.1
`Principles of Electrocatalysis
`4.8.2
`Heterogeneous Electrocatalysis in Cathodic
`Evolution and Anodic Oxidation of Hydrogen
`The Volcano Curve . . . . . . . . . . . . . . . .
`Electrocatalysis in Anodic Oxygen Evolution
`and Cathodic Oxygen Reduction
`Redox Catalysis . . . . . . . . . . . . . . . . . .
`4.8.4
`Catalyst Morphology and Utilisation
`. . . . . . . . . . .
`4.9.1
`Structural Features and Catalyst Morphology
`of Electro catalysts for Gas Evolving and Gas
`Consuming Electrodes . . . . . . . . . . . . . .
`Utilisation of Porous Electro catalyst Particles .
`4.9.2
`Electrocatalysis in Electro organic Synthesis . . . . . . ..
`4.10.1
`Introduction into the Field of Electroorganic
`Synthesis . .. . . . . . . . . . . . . . . . . .
`4.10.1.1 Mediated Electrochemical Conversions of
`Organic Substrates . . . . . . . . . . . . . .
`
`4.8.2.1
`4.8.3
`
`31
`35
`37
`
`39
`41
`45
`
`49
`49
`
`51
`
`51
`52
`54
`
`55
`56
`57
`57
`
`58
`60
`61
`61
`
`61
`62
`
`64
`66
`68
`
`68
`69
`71
`
`71
`
`71
`
`Exhibit 1018_0007
`
`
`
`Contents
`
`Contents
`
`:fficients . . . .
`
`.... .. .
`. ..... .
`r Reactions.
`
`. . . ...
`
`nical
`
`ial Curves
`ves
`1ge
`
`·t Control
`
`ive
`
`die
`ogen
`
`tion
`
`fogy
`3as
`
`:ides.
`
`anic
`
`if
`
`. .....
`
`.. .. . . ..
`
`31
`35
`37
`
`39
`41
`45
`
`49
`49
`
`51
`
`51
`52
`54
`
`55
`56
`57
`57
`
`58
`60
`61
`61
`
`61
`62
`
`64
`66
`68
`
`68
`69
`71
`
`71
`
`71
`
`4.10.2
`
`4.10.2.1
`
`4.10.3
`
`4.10.4
`
`4.10.1.2 Direct Anodic and Cathodic Electrochemical
`Conversions of Organic Substrates . . .
`Electrocatalytic Oxidations by Oxides
`of Multiply-Valent Metals .. . ..... .. . .. .. .
`The Heterogeneously Catalysed Benzene Oxidation
`. . . . . . . .
`at Pb/PbO 2 Electrodes in Sulfuric Acid
`Electrocatalytic Hydrogenation and Electrocatalyzed
`Mediated Reduction . . . . . . . . . . . . . . .
`The Electrode Surface as Medium Catalysing
`Chemical Reactions of Electro generated
`Reactive Organic Intermediates
`. . . . . . . . . . . . . .
`4.10.4.1 Electrocatalytic Action of Electrosorbed Non-Reactant
`Species - Electrocatalysis of the Second Kind . . . . .
`Kinetics and Selectivity of Homogeneous Chemical
`Consecutive Reactions Following Charge Transfer .
`
`4.10.5
`
`References . .
`Further Reading
`
`Chapter 5
`Mass Transfer by Fluid Flow, Convective Diffusion and Ionic Electricity
`Transport in Electrolytes and Cells
`
`5.1
`5.2
`5.3
`
`5.4
`
`. . . ... .
`
`Introduction. . . . . . . .
`Fluid Dynamics and Convective Diffusion . . . . .
`Fluid Dynamics of Viscous, Incompressible Media.
`Laminar vs Turbulent Flow . ...... .
`5.3.1
`Velocity Distributions for Laminar Flow
`5.3.2
`Singular Electrode: Unidirectional Laminar
`5.3.2.1
`Flow Along a Plate . . . . .
`Pair of Planar Electrodes ...
`5.3 .2.2
`Circular Capillary Gap Cell . .
`5.3.2.3
`Mass Transport by Convective Diffusion
`Fundamentals
`. . . ..... .
`5.4.1
`Dimensionless Numbers Defining Mass Transport
`5.4.2
`Towards Electrodes by Convective Diffusion .
`Hydrodynamic Boundary Layer and Nernst
`Diffusion Layer: Planar Electrodes . . . . .
`Mass Transport Towards a Singular Planar
`Electrode Under Laminar Forced Flow . . . . . . . . .
`Channel Flow and Mass Transfer to Electrodes
`of Parallel Plate Cells for Free and Forced Convection
`Free Convection at Isolated Planar Electrodes
`and between Two Vertical Electrodes . . . . . . .
`Convective Mass Transfer for Parallel Plate Cells
`with Forced Convection: Planar Plate Cells . . . .
`
`5.4.3
`
`5.4.4
`
`5.4.5
`
`5.4.5.l
`
`5.4.5.2
`
`IX
`
`72
`
`72
`
`74
`
`74
`
`75
`
`78
`
`79
`80
`80
`
`81
`81
`84
`86
`87
`
`87
`88
`89
`90
`90
`
`92
`
`93
`
`95
`
`97
`
`97
`
`98
`
`Exhibit 1018_0008
`
`
`
`X
`
`Contents
`
`5.4.5.3
`5.4.6
`
`5.4.6.1
`5.4.6.2
`5.4.7
`5.4.7.1
`
`5.4.7.2
`
`5.5.2
`
`5.6
`
`Mass Transfer in Circular Capillary Gap Cells.
`Convective Mass Transfer Toward Rotating
`Electrodes . . . . . . . .
`Rotating Cylinder . . . . . . . . . . . . . . .
`Rotating Disc Electrode ....... ... .
`Mass Transfer at Gas Evolving Electrodes .
`Calculating km, bubble According to the Penetration
`Model or Model of Periodic Boundary Layer Renewal .
`Calculating Bubble-Enhanced Mass Transfer
`According to Flow Model. . . . . . . . . . . . . . .
`Mass Transfer in Three-Dimensional Electrodes .
`5.4.8
`Summary. . . . . . . . . . . . . . . . . . . . .
`5.4.9
`5.5 Heat Transport . . . . . . . . . . . . . . . . . . . . . . .
`5.5.1
`Chilton- Colburn Analogy of Mass and Heat
`Transfer. . . . . . . . . . . . . . . . . . . . . .
`General Description of Heat Generation and Heat
`Transfer in Electrolyzers and Fuel Cells . . . . . . . .
`Heat Balance and Steady State-Temperature of Cells .
`5.5.2.1
`Ionic Charge and Mass Transport in Electrolytes
`. . . .
`5.6.1
`Strong Electrolytes . . . . . . . . . . . . . . . .
`Temperature Dependence of Electrolyte Conductivities .
`5. 7
`5.8 Molten Salt Electrolytes . . . . . . . . . . . . . . . . . .
`5.9
`Segregation in Stagnant Electrolytes of Binary Molten
`Carbonates in Fuel Cells . . . . . . . . . . . . . . . . . .
`5.10 Current Density Distribution in Cells and Electrochemical
`Devices . . . . . . . . . . . . . . . . . . . .
`5.11 Primary Current Density Distribution . . . . . . . . . . . . . . . .
`5.12 Secondary Current Density Distribution. . . . . . . . . . . . . . .
`5.13 Secondary Current Density Distribution and "Throwing Power"
`in Electrodeposition and Electrocoating
`5.14 The Wagner Number . . . . . .
`5.15 Tertiary Current Distribution .
`References . . . .
`Further Reading
`
`. . . . . . . . . . . .
`
`Chapter 6
`Electrochemical Reaction Engineering
`
`Introductory Remarks
`6.1
`6.2 Microkinetic Models .
`6.3 Mode of Operation ..
`6.4
`Electrical Control of Cells
`6.5 Macrokinetic Models . . .
`6.5.1
`Stirred-Batch Tank Reactor
`6.5.2
`Continuously Stirred Tank Reactor
`
`101
`
`102
`102
`102
`103
`
`105
`
`105
`106
`107
`107
`
`107
`
`108
`109
`110
`110
`111
`113
`
`114
`
`117
`119
`121
`
`122
`124
`125
`127
`127
`
`128
`128
`129
`131
`131
`131
`132
`
`Exhibit 1018_0009
`
`
`
`Contents
`
`Contents
`
`Cells.
`ing
`
`!S
`.
`)enetration
`,ayer Renewal .
`nsfer
`
`ectrodes .
`
`Heat
`
`t and Heat
`
`ture of Cells .
`
`.vities .
`
`,lten
`
`chemical
`
`rowing Power"
`
`101
`
`102
`102
`102
`103
`
`105
`
`105
`106
`107
`107
`
`107
`
`108
`109
`llO
`110
`lll
`113
`
`114
`
`117
`119
`121
`
`122
`124
`125
`127
`127
`
`128
`128
`129
`131
`131
`131
`132
`
`6.5.3
`6.5.3.1
`6.5.3.2
`
`6.5.4
`6.5.5
`6.5.6
`6.5.7
`
`. . . . . . . . . . . . . . . . . .
`Plug-Flow Reactor (PFR)
`Plug Flow Electrolyzer with Uniform Current Density .
`PFR Operated at Mass Transfer Limited and
`Higher Current Density . . . . . . . .
`Cell Cascades . . . . . . . . . . . . . .
`Extended Modelling of Electrolyzers.
`Residence-Time Distribution . . . . .
`The Selectivity Problem of Consecutive Reactions
`in Batch Reactors . . . . . . . . . . . . . . . . . .
`Coupling of Electrochemical and Chemical Reactors . .
`Electrolyzer Design and Chemical Yield Losses Due To
`Parasitic Chemical Reactions . . . . . . . . . . . . .
`Performance Criteria of Electrochemical Reactors
`6.8.1
`Fractional Conversion, X . . . . . . .
`Relative Amount of Charge-Qr . . . .
`6.8.2
`Overall Conversion Related Yield 0P .
`6.8.3
`Current Efficiency <I> e . . . .
`6.8.4
`. . . . .
`6.8.5
`Parameters for Energy Considerations
`References .
`Further Reading
`
`6.6
`6.7
`
`6.8
`
`Chapter 7
`Electrochemical Engineering of Porous Electrodes and Disperse
`Multiphase Electrolyte Systems
`
`7.1
`7.2
`
`Introduction. . . . ..
`Three-Dimensional Electrodes ..
`7 .2.1
`General Considerations
`7.2.2
`Fundamental Equations . .
`7.2.2.1
`Nanoporous Electrode Particles
`7.2.2.2
`Microporous Electrodes . . . . .
`7.2.2.3
`Packed and Fluidized Bed Electrodes
`7.2.3
`Gas Consuming Nanoporous Electrodes for
`Fuel Cells and Nanoporous Catalyst Particles
`and Layers for Gas E.vol.ving Electrodes . . . .
`Physical Structure of Particulate, Gas Consuming
`Nanoporous Gas Diffusion Electrodes . .. .
`Physical Structure of Raney Nickel Coatings
`for Hydrogen Evolving Cathodes . . . . . . .
`Modelling Hydrogen Concentration Profiles
`and Catalyst Efficiencies for Hydrogen Consuming
`Fuel Cell Anodes or Other Gas Diffusion Electrodes .
`Modelling of Hydrogen Concentration Profiles
`and Catalyst Efficiencies for Hydrogen Evolving
`Nanoporous Raney-Nickel Catalyst Coatings . . .
`
`7.2.3.3
`
`7.2.3.4
`
`7.2.3.1
`
`7.2.3.2
`
`XI
`
`133
`135
`
`135
`136
`138
`139
`
`142
`146
`
`148
`149
`150
`150
`150
`151
`152
`152
`152
`
`153
`154
`154
`155
`156
`156
`157
`
`157
`
`157
`
`159
`
`160
`
`165
`
`Exhibit 1018_0010
`
`
`
`XII
`
`f
`I
`
`Contents
`
`7.2.4
`7.2.5
`
`7.3
`
`Porous Battery Electrodes . . . . . . . . . .
`Packed Bed and Fluidized Bed Electrodes
`Composed of Coarse Particles . . . . . . . .
`Fluidized Bed Electrodes ....... . .. .
`7.2.5.1
`Ionic Conductivity of Electrolytes Containing Dispersed
`Gas Bubbles in Gas Evolving Electrolyzers.
`Electrolyzers with Gaseous Reactants .
`7.4
`Electrochemical Liquid/Liquid Systems
`7.5
`References . . . .
`Further Reading
`
`. . . . . . . . . . . . . .
`
`Chapter 8
`Electrochemical Cell and Plant Engineering
`
`8.2
`
`8.3
`
`8.4
`
`8.1 Materials Choice and Corrosion Problems.
`8.1.1
`Metals ...
`8.1.2
`Carbon .....
`Electrode Materials . . . .
`8.2.1
`Stainless Steel .
`8.2.2
`Nickel . . .
`8.2.3
`Lead . . .. . .
`Titanium .. .
`8.2.4
`8.2.5
`Noble Metals.
`8.2.6
`Massive Carbon .
`Electrode Design . . . . . .
`8.3.1
`Gas Evolving Electrodes
`8.3.2
`Gas Consuming Electrodes, Gas Diffusion Electrodes ..
`Separators: Membranes and Diaphragms
`8.4.1
`Membranes .... ... . .... . .. ... .. . .. . . .
`8.4.2
`Diaphragms . . . . . . . . . . . . . . . . . . . . . . . . ..
`Polymeric Materials for Cell Bodies and Electrolyte Loops . . . . .
`Gaskets ..... . ........ .
`Electrodes . . . . . . . . . . . . . . .
`8.7.1
`Horizontal Electrodes .
`8.7.2
`Membrane Electrolyzer. .
`Cell and Electrode Design . . . . . .
`8.8.1
`Zero Gap Electrolysis Cells.
`8.8.2
`Vertical/Horizontal Electrodes
`8.8.3
`Divided/Undivided Monopolar/Bipolar Cells
`and Modes of Electrolyte Flow
`8.8.4
`Special Cell Designs.
`8.8.5
`Capillary Gap Cells . . . . . . .
`8.8.6
`Swiss Roll Cell . . . . . . . . . .
`Cells with Three-Dimensional Electrodes .
`8.8.7
`Power Supply for Electrochemical Plants . . . . . . .
`
`8.5
`8.6
`8.7
`
`8.8
`
`8.9
`
`171
`
`173
`178
`
`179
`183
`186
`186
`186
`
`187
`188
`192
`193
`194
`194
`195
`195
`195
`196
`196
`196
`197
`199
`201
`203
`203
`205
`206
`206
`207
`208
`208
`209
`
`209
`210
`216
`216
`217
`218
`
`Exhibit 1018_0011
`
`
`
`Contents
`
`Contents
`
`Rectifiers. . . . . . .
`8.9.1
`Transformer Wiring
`8.9.2
`8.9.3
`Further Equipment.
`Further Reading
`. . . . . . . . . . . . .
`
`Chapter9
`Process Development
`
`es
`
`persed
`
`ion Electrodes ..
`
`yte Loops ....
`
`Lr Cells
`
`des .
`
`171
`
`173
`178
`
`179
`183
`186
`186
`186
`
`187
`188
`192
`193
`194
`194
`195
`195
`195
`196
`196
`196
`197
`199
`201
`203
`203
`205
`206
`206
`207
`208
`208
`209
`
`209
`210
`216
`216
`217
`218
`
`XIII
`
`218
`218
`219
`220
`
`221
`222
`
`222
`222
`223
`223
`
`225
`226
`230
`230
`230
`
`231
`233
`233
`235
`236
`236
`236
`236
`237
`238
`
`239
`239
`
`9.2.1.1
`9.2.1.2
`9.2.1.3
`9.2.1.4
`
`9.2.1.5
`9.2.2
`9.2.2.1
`9.2.2.2
`9.2.2.2.1
`
`9.1
`
`9.2
`
`9.3
`
`9.5
`
`Scope and Purpose of Laboratory and Pilot Plant
`Measurements
`. . . . . . . . . . . . . . . . . . . .
`Laboratory Methods . . . . . . . . . . . . . . . . .
`Steady-State Measurements of Current Density
`9.2.1
`Potential Correlations
`General Remarks . . . . . . . . . ...... .
`Measuring Devices . . . . . . . . . . . . . . .
`Evaluation of Rotating Disc Measurements .
`Current-Voltage Correlation for Competing
`Reactions by Non-Electrochemical Methods
`The Ring Disc Electrode ..
`Non-Steady State Methods ..... . ... .
`General Remarks . . . . . . . . . . . . . .
`Potentiodynamic Polarisation Curves . .
`Cyclic Voltammetry and Linear Potential
`Sweep Method
`. . . . . . . .
`9.2.2.2.2
`Initial Polarisation Curves
`9.2.2.3
`Square-Wave Pulses . . .
`9.2.2.4
`Eliminating the IR Drop . .
`9.2.2.4.1
`Galvanostatic Methods
`. .
`9.2.2.4.2 Potentiostatic Procedures .
`Pilot Plant Methods
`. . . . . . . . . .
`9.3.1
`General Considerations . .
`9.3.2
`Mass-Transfer Measurements.
`9.3.3
`Determination of Residence-Time Distributions.
`9.4 Mathematical Modelling and Optimisation by Factorial
`. . . . . . . . . . . . . . . . .
`Design of Experiments
`9.4.1
`Introduction
`. . . . . . . . . . . . . . . . .
`9.4.2
`General Procedure for Optimum Finding
`by Experiment . . . . . . . . . . .
`239
`240
`Factorial Design of Experiments . . . . . .
`9.4.3
`243
`Cost Analysis . . . . . . . . . . . . . . . . . . . . . . .
`243
`9.5.1
`Composition of Productions Costs
`. . . . .
`9.5.2
`Total and Specific Investment Costs . . . . . . . . . . . . 244
`9.5 .3
`Cost Optimisation with Respect to Current Density . .
`245
`9.5.4
`Optimisation of Non-Selective Electrolysis Processes .
`248
`9.5.4.1
`Current Density Against Current Efficiency. . . . . . .
`249
`
`Exhibit 1018_0012
`
`
`
`XIV
`
`Contents
`
`r
`
`Temperature vs Current Efficiency . . . . . . . . . . . .
`Examples Including Influences of Process Parameters
`on the Equipment for Non-Electrochemical
`Unit Operations and Corresponding Costs . . . . . . .
`250
`Further Reading
`. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
`~
`
`250
`
`252
`
`253
`255
`
`255
`257
`258
`
`260
`
`260
`260
`
`261
`261
`
`261
`262
`
`263
`264
`265
`265
`
`265
`265
`
`266
`
`266
`268
`
`268
`
`268
`
`9.5.4.2
`9.5.5
`
`Industrial Electrodes
`
`10.5.3
`10.5.4
`
`10.5.5
`10.5.6
`
`10.1 Catalytically Activated Electrodes.
`10.2 Functioning, Longevity and Application of
`Electrocatalyst Coatings . . . . . . . . . . .
`10.3 Design oflndustrial Electrodes . . . . . . .
`10.3.1 Monopolar Electrodes and Current Density
`Distribution on Their Surface . . . . . .
`Electrodes for Bipolar Electrode Stacks . . .
`10.3.2
`Gas Evolving Electrodes . . . . . . . . . . . .
`10.3.3
`10.4 Structural Features of Electrocatalysts for Gas Evolving and
`Gas Consuming Electrodes . . . . . . . . . . . . . .
`10.5 Electrocatalytically Activated Dimensionally Stable
`Chlorine-Evolving Electrodes . . . . . . . . . . . . .
`Technological History . . . . . . . . . . .
`10.5.1
`Electrocatalysis and Selectivity of Anodic
`10.5.2
`Chlorine Evolution at RuO 2-Anodes . . . .
`Preparation and Formulation of the Coatings .
`Improvement of Adhesion and Strength
`of the Coatings . . . . . . . . . . . . . . . .
`Design of Cells Using DSAs . . . . . . . . .
`Lifetime of Dimensionally Stable Chlorine
`Evolving Anodes . . . . . . . . . . . . . . .
`DSAs for Chlorate and Hypochlorite Production.
`10.5.7
`10.6 Oxygen Evolving Anodes. . . . . . . . . . . . . . . , . . . . .
`Technical Processes
`. . . . . . . . . . . . . . . . .
`10.6.1
`Electrocatalysis of Oxygen Evolution in Advanced
`10.6.2
`Alkaline Water Electrolysis. . . . . . . . . . . . . .
`10.6.2.1 Coatings Containing Cobalt and Iron Oxides . . .
`Electro catalysis of the Anodic Oxygen Evolution
`10.6.3
`by Raney-Nickel Coatings . . . . . . . . . . . . . .
`Catalyst-Coated Titanium Electrodes for Oxygen
`Evolution From Acid Solutions . . . . . . . .
`10.7 Hydrogen Evolving Cathodes . . . . . . . . . . . . . . .
`Technoeconomical Significance of Cathodic
`10.7.l
`Hydrogen Evolution . . . . . . . . . . . . . .
`Electrocatalyst Coatings for Hydrogen Evolution
`from Alkaline Solution . . . . . . . . . . . . . . . .
`
`10.6.4
`
`10.7.2
`
`Exhibit 1018_0013
`
`
`
`Contents
`
`Contents
`
`10.8.3
`
`10.8.4
`10.8.5
`
`10.8
`
`,s Parameters
`ical
`sts .... . . .
`
`tsity
`
`Jlving and
`
`le
`
`lie
`
`atings.
`1
`
`ine
`
`·eduction .. . ..
`
`tAdvanced
`
`>xides . . ..
`Evolution
`
`:,r Oxygen
`
`10dic
`
`Evolution
`
`250
`
`250
`251
`
`252
`
`253
`255
`
`255
`257
`258
`
`260
`
`260
`260
`
`261
`261
`
`261
`262
`
`263
`264
`265
`265
`
`265
`265
`
`266
`
`266
`268
`
`268
`
`268
`
`10.7.2.1 Technically Applied Coatings .
`10.7.2.2 Nickel Sulfide Coatings
`. . . .
`10.7.2.3 Raney-Nickel Coatings .. . .
`10.7.2.3.1 Precursor Alloys and Fabrication
`of Coated Cathodes
`. . . . .
`10.7.2.3.2 Utilisation of the Catalyst in
`Raney-Nickel Coatings ...
`10.7.2.3.3 Performance and Ageing of Raney-Nickel Coatings .
`Coatings of Platinum Metal Oxides
`. . . . . . .. . .
`10.7.3
`Active Coatings of Flame Sprayed, Doped Nickel Oxide.
`10.7.4
`Platinum and Platinum Metal Cathodes in Membrane
`10.7.5
`Water Electrolyzers
`. . . . . . . . . . .
`Fuel-Cell Electrodes .. .. .. .. . . . . . . . . . . . . . .
`Low- and High-Temperature Fuel Cells ... . .
`10.8.1
`Structural Design of Gas-Diffusion Electrodes
`10.8.2
`in Low-Temperature Fuel Cells .
`Oxygen Reduction Catalysts in
`Low-Temperature Cells
`. . . . .
`Catalysts for Anodic Hydrogen Oxidation
`Properties, Preparation and Improvement
`of Electrocatalysts in Gas Diffusion Electrodes
`for Low Temperature Cells
`. . . . . . . . . . ..
`10.8.5.1 Pt-Activated Active Carbon . . ... .. .. .. .
`Particle Size of Pt Nanocrystals on Active Carbon
`10.8.5.2
`and Their Effective Catalytic Activity . .
`Pt-Alloy Catalysts ..... . ...... .
`Morphology and Structure of Complete
`PTFE-Bonded Active-Carbon Electrodes
`Ageing of Pt-Catalysts . .... . .... .
`Electrocatalysis of Anodic Methanol Oxidation
`Technoeconomic Significance of the Process . . .
`Self-Poisoning of Methanol Oxidising Pt-Catalyst
`by Oxidation Products of Methanol . . . . . . .
`Anodic Methanol Oxidation at Alloy Catalysts .
`Gas-Diffusion Electrodes in Membrane (PEM)
`. ... .. . . . . . . . . . . . . . . . .
`Fuel Cells
`Rationale of Developing a Method of Internal
`Wetting for Membrane Fuel Cell Electrodes
`Improving Catalyst Utilisation by Ionomer
`Impregnation of Gas-Diffusion Electrodes .
`The Preparation of Membrane Electrode
`Assemblies (MEAs) for Membrane Fuel Cells
`Electrodes for High-Temperature Fuel Cells
`Stability of Electrode Structures
`at High Temperatures . . . . . . . . . . . . .
`
`10.8.5.3
`10.8.6
`
`10.8.7
`10.8.8
`10.8.8.1
`10.8.8.2
`
`10.8.8.3
`10.8.9
`
`10.8.9.1
`
`10.8.9.2
`
`10.8.9.3
`
`10.8.10
`10.8.10.1
`
`xv
`
`268
`269
`269
`
`269
`
`271
`272
`273
`273
`
`273
`274
`274
`
`275
`
`276
`276
`
`277
`277
`
`278
`278
`
`279
`280
`281
`281
`
`281
`281
`
`282
`
`282
`
`282
`
`283
`284
`
`284
`
`Exhibit 1018_0014
`
`
`
`XVI
`
`10.8.11
`
`10.8.11.1
`10.8.11.2
`10.8.12
`10.8.12.l
`10.8.12.2
`10.8.12.3
`References . . .
`Further Reading
`
`Electrode Kinetics and Electrocatalysis in
`Molten-Carbonate Fuel Cells
`Anodic Hydrogen Oxidation . ...... . .
`Cathodic Oxygen Reduction
`. . . . . . . .
`Electrodes in Solid-Oxide Fuel Cells (SOFC)
`Electrodes and Electrode Structure.
`The SOFC-Anode . .
`The SOFC-Cathode .
`
`11.1
`11.2
`11.3
`
`11.4
`
`11.5
`
`11.6
`
`Introductory Remarks . . . . ..... . .. .
`Inorganic Electrolysis and Electrosynthesis .
`Chloralkali-Electrolysis
`. . . . . . . . . . . .
`The Electrochemical Reaction . ..
`11.3.1
`Thermodynamics and Energy Demands .
`11.3.2
`Anodic Chlorine Evolution ....... .
`11.3.3
`The Cathodic Reaction .. . . .. .. .. .
`11.3.4
`11.3.4.1 Cathodic Sodium Deposition in the Mercury Process
`11.3.4.2 Cathodic Hydrogen Evolution in the
`Diaphragm and Membrane Process
`Process Technologies . . . . . . . .
`The Amalgam Process .
`11.4.1
`The Diaphragm Process
`11.4.2
`The Membrane Process.
`11.4.3
`11.4.3.1 Process-Flow Sheets
`. .
`11.4.3.2 Brine Recycling . . . . .
`Gas Purification and Conditioning .
`11.4.4
`11.4.4.1 Chlorine . . . . . . . . . . . . . . ..
`11.4.4.2 Hydrogen . . ... . .. . . . . ... .
`Comparison of the Three Processes
`11.4.5
`Hypochlorite, Chlorate and Chlorine Dioxide.
`Production of Sodium Hypochlorite .
`11 .5.1
`11 .5.1.1 Electrolytic Generation of Hypochlorite
`11.5.1.2 Current Efficiency Losses
`. . . . . . . . .
`Production of Sodium Chlorate
`. . . . .
`11.5.2
`11.5.2.1 Balance of Plant of Chlorate Electrosynthesis
`11.5.2.2 Construction Materials . . . . . . . . . ..
`Chlorine Dioxide from Sodium Chlorate.
`11.5.3
`Perchloric Acid, Perchlorates, Peroxidsulfates .
`Perchloric Acid . . .
`11.6. l
`Sodium Perchlorate
`11.6.2
`
`. . . . . . . . .
`
`Contents
`
`285
`285
`285
`287
`287
`287
`288
`289
`289
`
`290
`291
`291
`292
`292
`293
`294
`294
`
`295
`295
`295
`297
`298
`300
`302
`303
`303
`304
`304
`306
`306
`306
`307
`307
`310
`311
`311
`312
`312
`312
`
`Exhibit 1018_0015
`
`
`
`Contents
`
`Contents
`
`?C)
`
`rcury Process
`
`:e
`
`1thesis
`
`te ..
`
`285
`285
`285
`287
`287
`287
`288
`289
`289
`
`290
`291
`291
`292
`292
`293
`294
`294
`
`295
`295
`295
`297
`298
`300
`302
`303
`303
`304
`304
`306
`306
`306
`307
`307
`310
`311
`311
`312
`312
`312
`
`Peroxidisulfates . . . .
`11.6.3
`11. 7 Fluorine . . . . . . . . . . . . . .
`11.8 Hydrogen by Water Electrolysis
`Technoeconomic Environment .
`11.8.1
`Thermodynamics and Technological Principles
`11.8.2
`of Electrolytic Water Splitting
`. . . . . . .
`Process Technologies
`. . . . . . . . . . . .
`11.8.3
`Conventional Alkaline Water Electrolysis .
`11.8.4
`11.8.4.1 Monopolar Technology . . . . . .
`11.8.4.2 Bipolar Technology
`. . . . . . . .
`Improved Alkaline Technologies .
`11.8.4.3
`New Technologies ...... .
`11.8.5
`11.8.5.1 Membrane Water Electrolysis ..
`11.8.5.2 Steam Electrolysis . . . . . . . . .
`Economic Implications of Technical
`11.8.6
`Innovations for Alkaline Water Electrolysis .
`11. 9 Electrowinning and Electrorefining of Metals
`. . .
`11.9.1 Metal Electrowinning and Refining from
`Aqueous Electrolytes
`. . . . . . . . . . .
`Copper Electrowinning and Electrorefining
`11.9.2
`Nickel Electrowinning . . . . . . . . . . .
`11.9 .3
`Nickel from the Chloride Leach Process .
`11.9.4
`Nickel Refining ... .
`11.9.5
`Zinc Electrowinning . . . . . . . . . . . .
`11.9.6
`Lead Electrorefining . . . . . . . . . . . .
`11. 9. 7
`11.10 Metal Electrowinning from Molten Salt Electrolytes
`11.10.1 General Considerations . . . . . . . . . . .
`11.10.2 Aluminium Production - the Hall-Heroult Process . . .
`11.10.2.1 The Melt . . . . . . .
`11.10.2.2 Electrode Reactions . . . . . . . . .
`11.10.3 TheCell....... ...... . ..
`11.10.4 Alkali Metals from Chloride Melts .
`11.10.5 Magnesium Electrolysis . . . .
`11.10.5.1 Production of the Feed Salt . .
`11.10.5.2 Magnesium Electrolysis Cells.
`11.11 Organic Electrosynthesis Processes . . .
`11.11.1 General Overview
`. . . . . . .
`11.11.2 Cell Types Used in Commercial Electroorganic
`Synthesis . . . . . . . . . . . . . . . . . . . . . .
`Process and Reaction Techniques of Some
`Examples of Industrial Organic Electrosyntheses . . .
`11.11.3.1 Adipodinitrile Production by the Monsanto/Baizer
`Process . . . . . . . . . . . . .. ... .
`11.11.3.2 Electrosynthesis of Sebacic Diesters by
`Kolbe Synthesis . . . . . . . . . . . . . .
`
`11.11.3
`
`XVII
`
`313
`315
`316
`316
`
`317
`318
`320
`320
`320
`323
`324
`324
`324
`
`325
`326
`
`326
`330
`331
`333
`334
`334
`335
`335
`335
`336
`336
`338
`339
`341
`342
`343
`344
`345
`345
`
`347
`
`349
`
`349
`
`352
`
`Exhibit 1018_0016
`
`
`
`XVIII
`
`Contents
`
`11.11.3.3 Benzaldehydes by Direct Anodic Oxidation
`of Toluenes. . . . . . . . . . . . . . . . . . . .
`11.11.3.4 The Selective Anodic Oxidation of L-Sorbose
`in Commercial Vitamin C Synthesis . . . . . .
`11.11.3.5 Anodic Formation of Perfluoro-Propylene Oxide.
`11.12 Selected Electrochemical Procedures Outside the Chemical and
`Metallurgical Industries . . . . . . . . . . . . . . . . . .
`11.12.1 Electrochemical Wastewater Treatment by
`Electrodeposition and by Electroosmosis .
`11.12.1.1 General Considerations . . . . . . . . . . .
`11.12.1.2 Particular Cells for Removal of Metal Ions
`from Effluents . . . . . . . . . . . . . . . .
`Electrodialysis
`. . . . . . . . . . . . . . .
`Electrochemical Surface Treatment and
`Shaping of Metals . . . . .
`Electrochemical Shaping. . . . . . .
`Electropolishing. . . . . . . . . . . .
`Electrochemical Machining (ECM) .
`Electrochemical Grinding . . . . . .
`Electroreforming of Micro dies and Microtools
`by the LI GA-Process
`
`11.12.2.1
`11.12.2.2
`11.12.2.3
`11.12.2.4
`11.12.3
`
`11.12.1.3
`11.12.2
`
`References . .
`Further Reading
`
`Chapter 12
`Fuel Cells
`
`12.3.1.4
`
`12.1 Fuel Cells as Gas Supplied Batteries. . . . . . . . . . . . . .
`12.2 Theoretical Efficiency of Hydrogen/Oxygen Fuel Cells. . .
`12.3 Fuel Cell Types
`. . . . . . . . . . . . . . . . . . . . . . . . .
`12.3.1
`Low-Temperature Fuel Cells - Their Technological State
`12.3.1.1 Phosphoric-Acid Cells . . . . . . . . . . . .
`12.3.1.2 Membrane Cells .. ...... .. . : . . .
`Direct and Indirect Methanol-Combusting
`12.3.1.3
`Membrane Cells
`. . . . . . . . . . . . . . .
`Process Principles of the PAFCs and PEMFCs
`with Proton Conducting Electrolyte . . . . . .
`High-Temperature Fuel Cells ... ... ... .
`Molten-Carbonate and Solid Oxide Fuel Cells
`Process Schemes of MCFCs and SOFCs ... .
`Internal Reforming in High-Temperature Fuel Cells .
`Cell Technologies of MCFCs and SOFCs .
`Molten-Carbonate Fuel Cells
`Solid Oxide Fuel Cells
`. . . . .
`The Westinghouse Technology
`
`12.3.2
`12.3.2.1
`12.3.2.2
`12.3.2.3
`12.3.3
`12.3.3.1
`12.3.3.2
`12.3.3.3
`
`353
`
`353
`355
`
`357
`
`357
`357
`
`358
`361
`
`362
`362
`363
`365
`366
`
`368
`369
`369
`
`370
`371
`373
`375
`375
`376
`
`377
`
`378
`379
`379
`379
`380
`381
`381
`382
`382
`
`Exhibit 1018_0017
`
`
`
`Contents
`
`Contents
`
`XIX
`
`Flat-Plate Solid Oxide Cells . . . . . . . . . . . . . . . . . 384
`12.3.4
`12.4 Current Voltage Curves of Different Fuel Cells . . . . . . . . . . . . 385
`12.5 Fuel-Cell Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
`387
`Phosphoric-Acid Fuel Cell/ PC 25 . . . . . . . . . . . . .
`12.5.1
`12.5.2 Molten Carbonate Cells . . .
`. . . . . .
`390
`12.5.2.1 ERC-2 MW Plant . . . . . . . . . . .
`. . . . . . . .
`390
`12.5.2.2 Hot Module of MIU . . . . . . . .
`390
`391
`Proton Exchange Membrane Cells .
`12.5.3
`392
`The Ballard Cel