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Catalysis in Organic Chemistry This is a digital copy of a book that was preserved for generations on library shelves before it was carefully scanned by Google as part of a project to make the world's books discoverable online. It has survived long enough for the copyright to expire and the book to enter the public domain. A public domain book is one that was never subject to copyright or whose legal copyright term has expired. Whether a book is in the public domain may vary country to country. Public domain books are our gateways to the past, representing a wealth of history, culture and knowledge that's often difficult to discover. Marks, notations and other marginalia present in the original volume will appear in this file - a reminder of this book's long journey from the publisher to a library and finally to you. Usage guidelines Google is proud to partner with libraries to digitize public domain materials and make them widely accessible. 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About Google Book Search Google's mission is to organize the world's information and to make it universally accessible and useful. Google Book Search helps readers discover the world's books while helping authors and publishers reach new audiences. You can search through the full text of this book on the web at http : //books . google . com/ CATALYSIS jj'f[: IN ORGANIC CHEMISTRY BT PAUL fjABATIER MEMBXR OF THB INBTITUTB DEAN OF THB FACUIAT OF BCIBNCBS OF TOULOUSB Translated by E. EMMET REID PBOFB880R OF ORGANIC CHBMISTBT JOHNB HOPKINB UNTVBBSITT NEWYORK D. VAN NOSTRAND COMPANY EIGHT WABBBN STOUT 1022 C* • • • • • •" CX)PYBIQHT; 1032 BY D. YAN NOSTBAND COMPANY Printed in the United States of America PREFACE BY his remarkable investigations on catalysis. Professor Sabatier has opened up new fields rich in scientific interest and fruitful in technical results. Catalytic hydrogenation will ever be an important chapter in chemistry. He is a teacher as well as an investigator and has done an important service in collecting from scattered sources a vast amount of information about catalysis and bringing the facts together in convenient and suggestive form in his book. I deem it a privilege to render his masterly work more accessible to English* speaking chemists. The text and the unsigned footnotes represent Professor Sabatier's work as closely as I can make them. I have retained the charac­ teristic italics. I have added a few notes which are signed by those responsible for them. In this connection I wish to thank my friends, among them Dr. Gibbs, Dr. Ittner, Dr. Adkins, and Dr. Richardson, for assistance, Professor Gomberg for verifying a number of Russian references, and Professor H. H. Lloyd for aid in proofreading. To the chapter on the theory of catalysis, I have added an illumi­ nating extension by Professor Bancroft, Chairman of the Committee on Catalysis of the National Research Council. In order to make the vast amount of detailed information in the book more readily available, I have prepared a subject index of some seven thousand entries and an author index of about eleven hundred names. It is a pleasure to present a brief sketch of his life and abounding activities. I have taken great pains to check the hundreds of references, but doubtless errors will be found. Corrections of any kind will be appreciated if sent me. E. EMMET REID. JOHNS HOPKINS UNIVERSITY, BALTIMORE, MD. August, 1021. 500141 V TABLE OF CONTENTS [References are to Paragraphs] CHAPTER I CATALYSIS IN GENERAL DvnrarBON or CATALTBIB 1 HISTORICAL 4 DIVERSITY IN CATALTBIB 5 Homogeneous systems 8 Heterogeneous systems 7 AtTTOGATALTBIB 8 NBOATTVB CATALTBIB 9 Stabilisers 13 Reversal of Catalytic Reactions 14 Reversible reactions, Limits 19 Velocity of Catalytic Reaction* 23 Influence of Temperature 24 Influence of Pressure 80 Influence of Mass of Catalyst 82 CHAPTER U ON CATALYSTS Solvents 88 DIWBSB MATBBIALB CAN GAUSS CATALTBIB 41 Element* a* Catalysts 42 Non-metals 48 Metals 80 Nickel, Conditions of Preparation 83 Copper 89 Platinum, Various Forms used 81 Colloidal Metals, Methods of Preparation 87 Oxide* a* Catalyst* 73 Water 73 Metallic Oxides 78 Influence of their Physical State 78 Mineral Acid* 81 Bases 83 Fluorides, Chlorides, Bromide*, Iodide* 84 Cyanides 96 Inorganic 8alt* of Oxygen Acid* 98 Various Compound* 104 DURATION or THE ACTION OF CATALYSTS Ill Poisoning of Nickel 112 Poisoning of Platinum 118 Fouling of Catalysts 118 Regeneration of Catalysts 123 Mixture of Catalysts with Inert Material* 128 vu viii CONTENTS CHAPTER IH MECHANISM OP CATALYSIS Ideas of Berzelius 120 Physical Theory of Catalysis 131 Properties of Wood Charcoal 131 Heat of Imbibition 133 Absorption of Gas by finely divided Metals 136 Physical Interpretation of their Catalytic Role 138 Insufficiency of the Physical Theory 141 Chemical Theory of Catalysis 145 Reciprocal Catalysis 146 Induced Catalysis 149 Auto-oxidations 150 Oxidation Catalysts 152 Catalysis with Isolatable Intermediate Compounds 156 Action of Iodine in Chlorination 156 Catalysis in the Lead Chamber 158 Action of Sulphuric Acid on Alcohols 159 Method of Squibb 161 Use of Copper in Oxidations 162 Action of Nickel on Carbon Monoxide 163 Catalysis without Isolatable Intermediate Compounds 164 Hydrogenation with Finely Divided Metals 165 Dehydration with Anhydrous Oxides 169 Decompositions of Acids 171 The Friedel and Crafts Reaction 173 The Action of Acids and Bases in Hydrolysis 175 Advantages of the Theory of Temporary Combinations 180 Theories of Catalysis by W. D. BANCROFT 180a CHAPTER IV ISOMERIZATION — POLYMERIZATION — DBPOLYMBRIZATION —CONDENSATIONS BY ADDITION |1. Isomcrization 181 Changes of Geometrical Isomers 182 Changes of Optical Isomers 186 Migration of Double and Triple Bonds 190 Decyclizations 193 Cyclisations and Transformations of Rings 194 Migration of Atoms 199 12. Polymerizations 209 Ethylene Hydrocarbons 210 Acetylene Hydrocarbons 212 Cyclic Hydrocarbons 216 Aldehydes 218 Aldolisation 219 Polyaldehydes 222 Passage into Esters ' 225 Ketones 229 Nitrites and Amides 230 13. Depolymerizations • 234 14. Condensation by the Addition of Dissimilar Molecules 236 CONTENTS ix Aldehydes and Nitrocompounds 236 Ketones 238 Acetylation of Aldehydes 240 Hydrocarbons 241 CHAPTER V OXIDATIONS L Direct Oxidation with Gaseous Oxygen 244 Classification of Direct Oxidations 244 Platinum and Related Metals 245 Copper 253 Various Metals 254 Carbon 257 Metallic Oxides 258 Metallic Chlorides 263 Manganese Salts 264 Oxidation of Oils 265 Silicates 267 11. Oxidation effected by Oxygen Compounds 268 Hydrogen Peroxide 268 Nitric Acid 269 Hypochlorites 270 Chlorates 271 Sulphur Trioxide 272 Permanganates 275 Persulphates ? 276 Nitrobenzene 277 CHAPTER VI VARIOUS SUBSTITUTIONS IN MOLECULES S 1. Introduction of Halogens 278 Chlorination 278 Iodine 278 Bromine 279 Sulphur 280 Phosphorus 281 Carbon 282 Metallic Chlorides 283 Aluminum Bromide 289 Brominatiork 290 Iodine 291 Manganese 292 Metallic Chlorides or Bromides 293 Iodtnation 294 12. Introduction of Sulphur 295 8 3. Introduction of Sulphur Dioxide 297 S 4. Introduction of Carbon Monoxide 298 S 5. Introduction of Metallic Atoms 299 Formation of Alcoholates 299 Formation of Organo-magnesium Complexes 300 X CONTENTS CHAPTER Vn Hydration Classification of Hydrations 905 Addition of Water 306 Ethylene Compounds 306 Acetylene Derivatives 308 Nitriles and Imides 311 Addition of Water with Decomposition, in Liquid Medium 313 Hydrolysis of Eaten 313 Use of Acids 313 Use of Bases 318 Hydrolysis of Chlorine Derivatives 320 Ethers 321 Acetals 322 Polysaccharides 323 Olucosides 327 Amides and their Analogs 331 Addition of Water with Decomposition, in Gaseous Medium 337 Hydrolysis of Esters 337 Ethers 338 Carbon Disulphide 339 Alcoholysis 340 CHAPTER VHI HYDROGENATION Hydrogenation in Gaseous System, Generalities, Use of Nickel 342 Historical 342 Method of Sabatier and Senderens 343 Hydrogen Generator 346 Reaction Tube 347
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