《精细有机合成单元反应》课程教学参考文献：《Unit Processes In Organic Synthesis》书籍原版PDF电子版（Philip Herkimer Groggins，第五版，1958）.pdf_大学文库

PREFACEAquarterofacentury has elapsed since the frst editionof "Unit Proc-esses in Organic Synthesis"went to press.During that span of years thedomestic synthetic organic chemical industry has grown enormously.Theproductionofpetrochemicals,plastis,potectiecoatings,sufactanchlorinated solvents,and elastomerall involving organic synthesishasmultiplied many times.New technics have been developed, and chemicalengineers have contributed much to make production processes moreefficient.Ifadoptionasateachingtoolanduse asaplantreference workmayserveas criteria,“Unit Processes in Organic Synthesis"has apparently serveda useful purpose.Acceptance of the work has been world-wide, snd it iswith gratification that the authors note that the book has been or is cur-rently being translated into fve foreign languages.Apparently this refects the need for such a textbook in a growing technological economy.In the preface tothefirst edition, the editor distinguished between thenow well-established terms unit processes and unit operalions and showedhow they are intimately related in the chemical engineering aspects oforganic synthesis.The prime objective of the present volume continuesto be the presentation of the industrial technic used in converting organicraw materials into usable products by various processes.Accordingly,theunderlying principlesandfactorsforeachunitprocesareorganizedinsystematicmanner with most of theemphasis onfundamental scientific andtechnologicalprinciplesDetaileddiscussionofmanufacturing processesisincluded only to the extent required for the elucidation of these basicprinciples.Thus it is expected that the present volume willcontinue toserve asa“semiworks course"to facilitate the student's transition fromthe university classroom to an industrial environment.In keeping with the modern trend toward the so-called chemical engi-neering sciences,theauthorshavestressedfundamentaladvnes intheryas wellas in industrial practice.Thus, thermodynamicsandkinetics havereceived increased emphasis.These subjects are inextricably associatedwith allchemicalreactions and,therefore,areparticularlyimportant intheBtudyand practice ofunit procsses.Inthisfth edition, threenewiptroductory chapters are devoted to these subjects.vii

CONTENTS444;Designof reactors and auxilisriee,447;Technical manufactureof aminocompounds,450;Controloftheammonia-recoverysystem,482.Oxidation486Types of oxidstive reactions, 486; Oxidizing agents,488; Liquid-phsse oxids-tion with oxidizing compounds, 503;Liquid-phase oxidation with oxygen,507;Vapor-phase oxidation of aliphatic compounds,517;Vapor-phase oxidation ofsromatichydrocarbons, 534;Kineticsand thermochemistry,542; Apparatusfor oxidations, 549.10.Hydrogenation555Introduction,555;Hydrogen:production snd properties, 560; Catalytichydrogenation and hydrogenolysis: type reactions, 574; Kinetics and ther-modynamics of hydrogenstion reactions, 590; General principles concerninghydrogenationcatalysts,600;Apparatusandmaterialsof construction,608;Industrialprocesses,612.11.HydrocarbonSynthesisandHydroformylation651Introduction, 651;Technology of Fischer-Tropsch operation, 654; Catalyets,658; Thermodynamics snd kinetics of the Fischer-Tropsch resction, 661;Reactordevelopment,664;Commercialoperation,671;EconomicsofFischerTropschoperations,675;Methanstion,675;ProcessesrelatedtotheFischerTropchsynthesis,67869412.EsterificationEsterificationbyorganic acids,695;Esterification of carboxylic acid deriva-tives,710;Esters by addition td unaaturated eystens, 720; Esters of inor-ganic acids,723; Esterification practice, 726.75013.HydrolysisDefinition and scope,750;Hydrolyzing agents,752;Materials susceptibletohydrolysis, 756; Kinetics, thermodynamics, and mechanism of hydrolysis,76l:Equipmentforhydrolysis,772;Technicaloperationsinvolvinghydroly-sis, 773.80414.AlkylstionIntroduction,804;Typesof alkylation,806;Alkylatingsgents,815;Factorscontrolling alkylation, 819;Equipment for alkylations, 825; Effect of alkyla-tion,828;Technical alkylations,829.856Part1.Principles of PolymerChemistry15.Introduction, 856;Chemistry of polymerization reactions,858;Methodeofpolymerization, 892;Polymerization kinetics,904;Solution properties ofpolymers, 913; Polyelectrolytes, 923; Influence of molecular characteristicsonpolymer properties,939;Infuenceof intermolecular arrangement onpolymer properties,941.943Part2.PolymerizationPracticeIndustriallyimportantpolymerizations andpolymers,943.1037Indez

CHAPTER1APPLICATIONSOF THERMODYNAMICSINUNITPROCESSESBYTHOMASE.CORRIGANANDKENNETHA.KOBE"Unit Processes in Organic Synthesis" deals with the major chemicaltransformations which are of importance to the chemical industry.Oneof the most important tools that can be used to predict the behavior ofthese chemical reactions is chemical thermodynamics.Whether certainchemical reactions can take place, to what extent chemical conversionscan occur, the effect of temperature and pressure on the behavior of achemical reaction, the composition of reactor effluents if cquilibrium isreached, the driving force of each of several competing reactions takingplace, and the amount of heat released are some of the aspects of chemicalprocesses which can be determined from thermodynamic calculations alone.Thermodynamics cannot, however, tell anything about the speed of thereaction, the effect of the shape of the reactor used, or the relative speedsof competing reactions.If these questions are to be answered, it will beby the use of experimental kinetic data.Not only is a knowledge of thermodynamics necessary to an understand-ing of unit processes, but also it is a prerequisite to the application of ki-netics.Aknowledge of both thermodynamics and kinetics is fundamentalto a completeunderstanding of the unit organic processes.Theprocessengineer finds that before the kinetics of a chemical reaction can be utilizeditsthermodynamicsmustbeknown.Beforebecomingconcernedwithhowfast a reaction will go, one must know if it can go at all and, if so, how far.For a more thorough discussion of the principles reviewed here, the readeris referred to some of the standard texts on chemical engineering thermo-dynamics.!Energy Relations-First Law.The subject of thermodynamics dealsalmost exclusivelywith energy relationships.Manyproblems such as the.IDoDGE,“Chemical Engineering Thermodynamics" MeGraw-Hin Book Company.Inc., NewYork,1944; HouGEN, WArsoN,and RAGATz,"Chemical Process Principles,parts I and II, John Wiley & Sons, Inc., New York, 1954 and 1947; SirH,"Introduc-tion to Chemical Engineering Thermodynamica," MeGraw-Hill Book Company, Inc.,NewYork,1949.1

2UNITPROCESSESINORGANICSYNTHESISequilibrium conversion in an adiabatic reactor or the heat requirementsand quantity of catalyst needed in a catalytic reactor depend upon energybalances for their solution. Energy balances are based upon the first lawof thermodynamics, which states that energy cannot be created or destroyedduring a process, although it may change from one form to another. Thetotal energy of a system entering a process plus any addition during theprocess must equal the total energy of the system leaving the process.Classificationof Energy.Theforms of energy can beclassified intotwogroups: (1) the first is related to the system and (2) the second is associatedwith the process.Theformer includesenergy possessed by material of thesystem; the latter includes energy produced ortransferred by the process-ing.GroupIGroup IIPropertics of a system:Properties of a process:HeatInternal energyWorkFlow or pressure energyKinetic energyPotential energySurface energyMagnetic energyInternal energy (U) is that which a,substance possesses because of themotionand configurationofitsmolecules,atoms,andsubatomicparticles.The flow or pressure energy Py is the product of pressure and volume.It may be regarded as the energy a substance possesses by virtue of thespace it occupies.Kinetic energy is the energy a substance possesses be-cause of its motion and is mu/2, where m and u are the mass and velocityof the substance, respectively.Specific kinetic energy is u/2ge, where g.is the gravitational constant, with 1/g. being the mass of a unit weight.The energy which a material possesses because of its position in relation tosome datum plane is called the potential energy. Two forms of energy,that due to surface tension and that due to magnetic effects, are usuallynegligiblein magnitudecomparedwiththe otherforms andarenot usedin the energy balance.The forms of energy which depend upon the processare heat g and work w.Heat is a termapplied to thatform of energy whichflows as the result of a temperature gradient.Work applies to the expendi-tureof energybymechanical processes.Energy Balance over a Flow System.The first law of thermodynamicswhen applied to two points in a flow system may be expressed by the fol-lowing equation:+*+--D+++%U+PV,+Z+2geThe term q refers to the heat absorbed by the system; w refers to the workdone by the system on the surroundings,In the over-all energy balance

3THERMODYNAMICSINUNITPROCESSESfor chemical processes, the changes in kinetic and potential energy arefrequently negligible compared with internal energy and may be disre-garded.The equations for a flow system then become the same as thosefor a nonflow (orbatch)system.Forthose casesin which the system per-forms nowork upon its surroundings, theequation reduces toU,+PV,+Q=U+PV,or-(U+P,V)-(U,+PV)or-,-AwhereH(enthalpy)isdefinedbytheequationH-U+PVStandard States.To fix exactly the properties of a component in asystem, a standard state must be defined which specifies the temperature,pressure,and physical state of the component.The standard temperatureis25°C (298.15°K); standardpre8sure is 1atm (orunitfugacityf=1.0atm). The physical state must be specified, for the energy of water de-pends on whether it exists as a liquid or a gas; or the energy of carbondepends on whether it existe asβ-graphite or diamond.Heat of Reaction.The change in enthalpy of a system when a reactionoccurs at constantpressure is usually called the heat of reaction, thoughmoreproperly it is the enthalpy change on reaction.The system mayhaveto give off or absorb heat (q) in order to maintain a constant temperaturein the system.ExothermioSystem loses heatAHAH-+EndothermicSystem gains heatWhen reactants and products are in their standard states, the enthalpychange is the standard heat of reaction.If the reaction is a combustionreaction,the enthalpy changeis the standard heat of combustion HIfthe reactants are the elements in their standard state, the product is acompound in its standard state, the enthalpy change is the standard heatofformationHy.For the general reaction aA + bB-→cC + dD, the standard heat ofreaction AHr can be calculated from either standard heat-of-formation orheat-of-combustion data.From heat-of-formation data:H,E(H)produete-(H,)retantse(S))+d(A))Da()A-b()Values for the heat of formations per mole can be found in the referencesfor thermodynamic data listed at the end of this chapter