《物理化学实验》课程教学资源（书籍文献）Thermochemical Data of Pure Substance，Third Edition，in collaboration with Gregor Platzki

Ihsan BarinThermochemical Dataof Pure SubstancesThird Editionin collaboration withGregor PlatzkiAg - KrLa - ZrWeinheimNew YorkBaselCambridgeVCHTokyo

Ihsan Barin Therrnochernical Data of Pure Substances Third Edition in collaboration with Gregor Platzki Volume I Ag -Kr rrrl Weinheim New York Base1 Cambridge VCH Tokyo La - Zr

Foreword to the First EditionThe Barin tables are far more complete in coverageMetallurgical, materials, ceramic and chemicalthan any of the sources described above. All of theengineers worldwide will welcome this new compila-natural elements and their compounds are included.tion of thermochemical data by Professor Barin. HereIn addition to the substance types listed in USBMthey will find the most comprehensive tables yet avail-Bull 677, the Barin tables include a large number ofableforthe thermodynamic properties of pure sub-ternary oxides --aluminates,arsenates,borates, chro-stances asa function of temperatureat 100°intervals.mates,molybdates,nitrates,oxy-halides,phosphatesAlmost twenty-four hundred substances are includedtitanates, tungstates, selenates,vanadates, zirconates,the elements, and compounds of two, three, andetc. as well as cyanides, hydroxides, complex sili-four elements.The vast majority of substances are in-cates and inter-metallic compounds. The only sub-organic, but Dr.Barin has included a generous selec-stances not included by Barin, for which tables can betion of the more common hydrocarbons, car-found elsewhere, are the ionized-gas species and abohydrates,and afew chlorinated hydrocarbons.Thelimited numberof gas species important only at veryformat of the tables conforms to that of the JANAFhigh temperatures, which are listed in the JANAFtables, and SI units are employed.tables. For each table Dr. Barin gives references forTo better appreciate the value of Dr. Barin's work,each of the major thermochemical values employedI have compared it below with other compilations that(enthalpy of formation and entropy at 298 K, andI regularly use.heat capacity). Like the USBM Bulletins, no attemptJANAF tables.These tables are critically evaluated,is madeto discuss the choice between conflicting dataeach table is accompanied by a text that describes thesources,data considered and reasons for the choice betweenRegarding quality of the values listed, Dr.Barin hasconflicting values.The effort is directed at substanceswisely relied heavily on critically evaluated dataofimportancetothesponsorsof theproject(U.S.Air(CODATAandJANAF)incaseswheresuchvaluesForce and Department of Energy). As a result theareavailable.For other substanceshehasdrawn onastress is on substances of importance to fuel combus-wide variety of sources, including the USBMtion, jet and rocket propulsion, and air pollution.Bulletins, other compilations, the periodical litera-Many elementsandcompoundsofimportancetoture, and his own estimation of some thermochemicalmetallurgy and related fields have not yet been includ-data. As new measurements are made, and as newed. For example, there are no tables for the elementscritical evaluations becomeavailable,many of theand compounds of Ag, As, Au, Bi, Cd, Ce, In, Ir, LaBarin tables will require revision, but this is a charac-Pd,Pt,Se,Sn,Te,Y,and U;moreover,many com-teristic of any attempt to compile thermochemicalpounds essential to metallurgical calculations, such asCu2S, NiO, NisO4, PbsO4,ZnO and ZnS have yet todata. Anyonemaking thermochemical calculationsbe included.who insists on thebest possibledata,will usea com-U.S. Bureau of Mines Bull. 672, 674, and 677.pilation,suchasthat of Barin orJANAF,as a startingBulletins 672 and 674 cover the elements, binary ox-place, but he will then check the recent periodicalliterature for new measurements that may have ren-ides and binary halides in a very complete fashion.Bulletin 677, summarizes thevalues from Bulletinsdered the compiled values obsolete.This in no way672 and 674, and adds a modest selection of tables fordetracts from the value of the compilation by Dr.Barin, which offers a starting place that is far morearsenides, antimonides, borides, carbides, carbonates,comprehensive than others, particularly for thosehydrides, nitrides,phosphides,selenides,silicates,concerned with metallurgical and similar systems.silicides, sulfates, sulfides and tellurides. The coverageThe accomplishment of Dr. Barin in producing thisof these added compound types, however, isfar fromvolumeismoreremarkablein that itis largelyanincomplete:forexample,therearenotablesforPbsO.SnsO4, GaS and LizS. The only ternary compoundsdividual effort. The writer appreciates, from his ownmodest efforts to accumulate thermochemical data,includedare the carbonates, sulfates and silicates,andthe magnitude of the effort represented by this work.no quaternary compounds are listed except for alimited number of hydrated compounds.Only briefFebruary, 1989Herbert H. Kelloggreferences are given to the data sources, without at-ColumbiaUniversitytempt to explain the choice between conflictingNewYork,N.Y.,10027values

Foreword to the First Edition Metallurgical, materials, ceramic and chemical engineers worldwide will welcome this new compila￾tion of thermochemical data by Professor Barin. Here they will find the most comprehensive tables yet avail￾able for the thermodynamic properties of pure sub￾stances as a function of temperature at 100" intervals. Almost twenty-four hundred substances are included - the elements, and compounds of two, three, and four elements. The vast majority of substances are in￾organic, but Dr. Barin has included a generous selec￾tion of the more common hydrocarbons, car￾bohydrates, and a few chlorinated hydrocarbons. The format of the tables conforms to that of the JANAF tables, and SI units are employed. To better appreciate the value of Dr. Barin's work, I have compared it below with other compilations that I regularly use. JANAF tables. These tables are critically evaluated, each table is accompanied by a text that describes the data considered and reasons for the choice between conflicting values. The effort is directed at substances of importance to the sponsors of the project (U.S. Air Force and Department of Energy). As a result the stress is on substances of importance to fuel combus￾tion, jet and rocket propulsion, and air pollution. Many elements and compounds of importance to metallurgy and related fields have not yet been includ￾ed. For example, there are no tables for the elements and compounds of Ag, As, Au, Bi, Cd, Ce, In, Ir, La, Pd, Pt, Se, Sn, Te, Y, and U; moreover, many com￾pounds essential to metallurgical calculations, such as Cu2S, NiO, NiS04, PbS04, ZnO and ZnS have yet to be included. US. Bureau of Mines Bull. 672, 674, and 677. Bulletins 672 and 674 cover the elements, binary ox￾ides and binary halides in a very complete fashion. Bulletin 677, summarizes the values from Bulletins 672 and 674, and adds a modest selection of tables for arsenides, antimonides, borides, carbides, carbonates, hydrides, nitrides, phosphides, selenides, silicates, silicides, sulfates, sulfides and tellurides. The coverage of these added compound types, however, is far from complete; for example, there are no tables for PbS04, SnS04, Gas and Li2S. The only ternary compounds included are the carbonates, sulfates and silicates, and no quaternary compounds are listed except for a limited number of hydrated compounds. Only brief references are given to the data sources, without at￾tempt to explain the choice between conflicting values. The Barin tables are far more complete in coverage than any of the sources described above. All of the natural elements and their compounds are included. In addition to the substance types listed in USBM Bull 677, the Barin tables include a large number of ternary oxides - aluminates, arsenates, borates, chro￾mates, molybdates, nitrates, oxy-halides, phosphates, titanates, tungstates, selenates, vanadates, zirconates, etc. - as well as cyanides, hydroxides, complex sili￾cates and inter-metallic compounds. The only sub￾stances not included by Barin, for which tables can be found elsewhere, are the ionized-gas species and a limited number of gas species important only at very high temperatures, which are listed in the JANAF tables. For each table Dr. Barin gives references for each of the major thermochemical values employed (enthalpy of formation and entropy at 298K, and heat capacity). Like the USBM Bulletins, no attempt is made to discuss the choice between conflicting data sources. Regarding quality of the values listed, Dr. Barin has wisely relied heavily on critically evaluated data (CODATA and JANAF) in cases where such values are available. For other substances he has drawn on a wide variety of sources, including the USBM Bulletins, other compilations, the periodical litera￾ture, and his own estimation of some thermochemical data. As new measurements are made, and as new critical evaluations become available, many of the Barin tables will require revision, but this is a charac￾teristic of any attempt to compile thermochemical data. Anyone making thermochemical calculations who insists on the best possible data, will use a com￾pilation, such as that of Barin or JANAF, as a starting place, but he will then check the recent periodical literature for new measurements that may have ren￾dered the compiled values obsolete. This in no way detracts from the value of the compilation by Dr. Barin, which offers a starting place that is far more comprehensive than others, particularly for those concerned with metallurgical and similar systems. The accomplishment of Dr. Barin in producing this volume is more remarkable in that it is largely an in￾dividual effort. The writer appreciates, from his own modest efforts to accumulate thermochemical data, the magnitude of the effort represented by this work. Herbert H. Kellogg February, 1989 Columbia University New York, N.Y., 10027

Preface to the Third EditionR.H. Eijkelberg (Eindhoven, Netherlands) amongothers. The number of tables has risen to 2518, in-cluding more than 230 organic substances. The wholeIt has become necessaryto producea third editionbook contains 3297 data sets for the thermodynamicafter a relatively short time. There have been no sig-description of substances and substance phases.nificant changes in the existing preliminary text. InI would particularly like to thank my co-workers atpart IV and in the subsequent sections the inclusionthe ZEUS Institute, especially Mr. F-R. Zenz, Mr. M.ofnatural materials,suchasminerals,ores,coal,andWestphal, and Mrs.D.Dokupil for their valuable sup-waste,inthethermodynamiccalculationshasbeenex-port.plained in detail. In the tables some errors have beenThe new edition has been greatly supported bycorrected and new substances listed. Here, substantialVCH Verlagesgesellschaft, in particular by Dr. Ebel,support was given by thefollowing experts: W.HartelMrs. K. Sora and Mr. Maier.(Freiburg, Germany), H. Kleykamp (Karlsruhe, Ger-many), K. Supiyama (Kamihama Tsu, Japan),H.Aachen/Duisburg,1994/95Ihsan BarinNielson (Copenhagen, Denmark), F.J.J. van Loo,Preface to the Second EditionThe work has been supported by VCH Verlagsge-sellschaft, in particular by Dr. Ebel, Dr. G. Schulz,Mr, Maier, and Ms. Hillenbrand, Dipl.-Ing. F. Sauert,The first edition of this book has found wide-spreadBergisch-Gladbach, deserves special thanks for per-acceptance and been received with a great deal of in-forming the calculations. I would also like to thankterest. The constructive advice and criticism of col-my co-workers at the ZEUS Institute. My family hasleagues from various countries have been of valuablegiven me immense support throughout the entire pro-help in preparing the second editionject.The preliminary text, an introduction to chemicalFinally, I would like to gratefully acknowledgethermodynamics, has been corrected, revised, and ex-Thyssen Engineering GmbH, Essen, Gesellschaftpanded toprovide a sound basis for the calculation ofDeutscher Metallhutten und Bergleute (GDMB),the tabulated functions and their scientific/technicalClausthal, and Stifterverband Metalle, Dusseldorf,application.for their financial support.The enthalpy H and Gibbs energy G have beenmore accurately defined and several errors in theDuisburg,1993Ihsan Barintables have been corrected

Preface to the Third Edition It has become necessary to produce a third edition after a relatively short time. There have been no sig￾nificant changes in the existing preliminary text. In part IV and in the subsequent sections the inclusion of natural materials, such as minerals, ores, coal, and waste, in the thermodynamic calculations has been ex￾plained in detail. In the tables some errors have been corrected and new substances listed. Here, substantial support was given by the following experts: W. Hartel (Freiburg, Germany), H. Kleykamp (Karlsruhe, Ger￾many), K. Supiyama (Kamihama Tsu, Japan), H. Nielson (Copenhagen, Denmark), F. J. J. van Loo, Preface to the Second Edition The first edition of this book has found wide-spread acceptance and been received with a great deal of in￾terest. The constructive advice and criticism of col￾leagues from various countries have been of valuable help in preparing the second edition. The preliminary text, an introduction to chemical thermodynamics, has been corrected, revised, and ex￾panded to provide a sound basis for the calculation of the tabulated functions and their scientific/technical application. The enthalpy H and Gibbs energy G have been more accurately defined and several errors in the tables have been corrected. R. H. Eij kelberg (Eindhoven, Netherlands) among others. The number of tables has risen to 2518, in￾cluding more than 230 organic substances. The whole book contains 3297 data sets for the thermodynamic description of substances and substance phases. I would particularly like to thank my co-workers at the ZEUS Institute, especially Mr. F.-R. Zenz, Mr. M. Westphal, and Mrs. D. Dokupil for their valuable sup￾port. The new edition has been greatly supported by VCH Verlagesgesellschaft, in particular by Dr. Ebel, Mrs. K. Sora and Mr. Maier. AachedDuisburg, 1994/95 Ihsan Barin The work has been supported by VCH Verlagsge￾sellschaft, in particular by Dr. Ebel, Dr. G. Schulz, Mr. Maier, and Ms. Hillenbrand, Dip1.-Ing. F. Sauert, Bergisch-Gladbach, deserves special thanks for per￾forming the calculations. I would also like to thank my co-workers at the ZEUS Institute. My family has given me immense support throughout the entire pro￾ject. Finally, I would like to gratefully acknowledge Thyssen Engineering GmbH, Essen, Gesellschaft Deutscher Metallhutten und Bergleute (GDMB), Clausthal, and Stifterverband Metalle, Dusseldorf, for their financial support. Duisburg, 1993 Ihsan Barin

Preface to the First EditionThermodynamic calculations are often used for theture of the tables.A relatively large amount of spaceanalysis and description of the changes of state asso-is devoted to the examples in orderto demonstrate theciated with the transfer of matter and energy. Theseuse of tables to those who are not well acquaintedcalculations are an indispensablepart of today'swith thermodynamic calculations.technical and scientific investigations in various fieldsThe data listed in the tables in Part VII also formthedatabasefor EQUITHERM,a software systemsuch as chemistry, metallurgy, chemical engineering,energy technology, and environmental technology.authored by I. Barin, G. Eriksson, F. Sauert, M.The recent improvement in computer capabilities hasZeitler, B. Wittig, and W. Schmidt, which is availableenhanced the application of thermochemical calcula-fromthepublishers of thebook,EQUITHERM cantionsinthedevelopemntofnewprocessesaswellasbe used to carry out thermodynamic calculations onfor the improvement of existing techniques.multi-component, multi-phase systems made up ofThe reliability of the results of thermochemicalany of the substances listed in this work.Thus, thecalculations depends, in the first instance, on the ac-publishers are in the unique position of being able tocuracy of the thermochemical data used. On the otheroffer both a printed compilation of thermodynamichand, the practical relevancy of the results is deter-data for pure substances and a software package formined by the comprehensiveness of inclusion of thethe calculation of equilibria in multi-species systems.various species which are often quite numerous in realsystems.Cologne/Aachen,1988Ihsan BarinInthissensethepresentworkmaycontributetotheapplication of thermochemical calculations to a widevariety of substances. The values of the thermochemi-cal functions of 2372 pure substances [including 91elements and the electron e"(gas) are tabulated atAcknowledgmenttemperature intervals of 100K.The substances in-clude about 100 organic compounds. The data ofThe present work is the result of an individual effortgaseous species are tabulated separately.without any support from public authorities. TheComplete sets of basic data needed for the calcula-facilities of KHD Humboldt Wedag AG, Cologne,tion of thermochemical functions are available onlywere used in the compilation of the tables. The sup-for a relatively small number of substances.Veryport of the management of the company and staff ofoften the datahaveto be completed by analysingthe research and development center is gratefullyvalues from different sources as well as by appropriateacknowledged. The input of data was carried out overestimations before they can be used for calculationsa long period by Ms. Wang Shu Sheng outside theand they may well then be less accurate. Suchestimates have been made especially for S (298.15)working hours. Dipl. Ing.F. Sauert and Dr. E.and C, (T).Schultze-Rhonhof provided computer methods andaided in the examination of the consistency of selectedThelayout ofthetablesand thefunctions quoteddata.correspond to conventions which are also used inKind encouragement was provided during thestandard works such as the JANAF Tables and theTables of the U.S.Bureau of Mines.The followingcourse of the work by Dr. N.A. Gokcen, US Bureauof Mines, Albany, Oregon, and Dr. N. Themelis, Co-thermochemical functions are tabulated:heat capaci-lumbia University, New York, N.Y., and by manytyCp,entropyS,Gibbsenergyfunction-Gef-other colleagues and friends-[G-H(298.15)]/ T, enthalpy H, enthalpy incrementVCHVerlagsgesellschaft,Weinheim,has supportedH-H(298.15), Gibbs energy G=H-TS, and thethe work in all its phases.formation quantities AH,G and logK,.The for-mation reactions refer to the reference states of theDr. F. and Mrs. J.A. Hampson, Saarbrucken, areacknowledged for the translation of the introductoryelements, which are given in a separate table.text.Apreliminarytext serves to introduce the subject ofI particularly wish to thank my family for their pa-thermodynamics and includes a short description oftience, help, and understanding while I was preparingthe fundamental relations of chemical thermody-this book.namics.Thecalculationofthermochemicalfunctionsis elucidated on the basis of these relations. This isAachen,1988Ihsan Barinfollowed by a description of the contents and struc-

Preface to the First Edition Thermodynamic calculations are often used for the analysis and description of the changes of state asso￾ciated with the transfer of matter and energy. These calculations are an indispensable part of today’s technical and scientific investigations in various fields such as chemistry, metallurgy, chemical engineering, energy technology, and environmental technology. The recent improvement in computer capabilities has enhanced the application of thermochemical calcula￾tions in the developemnt of new processes as well as for the improvement of existing techniques. The reliability of the results of thermochemical calculations depends, in the first instance, on the ac￾curacy of the thermochemical data used. On the other hand, the practical relevancy of the results is deter￾mined by the comprehensiveness of inclusion of the various species which are often quite numerous in real systems. In this sense the present work may contribute to the application of thermochemical calculations to a wide variety of substances. The values of the thermochemi￾cal functions of 2372 pure substances [including 91 elements and the electron e- (gas)] are tabulated at temperature intervals of 100 K. The substances in￾clude about 100 organic compounds. The data of gaseous species are tabulated separately. Complete sets of basic data needed for the calcula￾tion of thermochemical functions are available only for a relatively small number of substances. Very often the data have to be completed by analysing values from different sources as well as by appropriate estimations before they can be used for calculations and they may well then be less accurate. Such estimates have been made especially for S (298.15) and C, (T). The layout of the tables and the functions quoted correspond to conventions which are also used in standard works such as the JANAF Tables and the Tables of the U.S. Bureau of Mines. The following thermochemical functions are tabulated: heat capaci￾ty Cp, entropy S, Gibbs energy function -Gef = - [G- H(298.1 5)] / 7; enthalpy H, enthalpy increment H-H(298.15), Gibbs energy G = H-TS, and the formation quantities AHf, AGf and log Kf. The for￾mation reactions refer to the reference states of the elements, which are given in a separate table. t\ pi.cliininary text serves to introduce the subject of thermodynamics and includes a short description of the fundamental relations of chemical thermody￾namics. The calculation of thermochemical functions is elucidated on the basis of these relations. This is followed by a description of the contents and struc￾ture of the tables. A relatively large amount of space is devoted to the examples in order to demonstrate the use of tables to those who are not well acquainted with thermodynamic calculations. The data listed in the tables in Part VII also form the database for EQUITHERM, a software system authored by I. Barin, G. Eriksson, F. Sauert, M. Zeitler, B. Wittig, and W. Schmidt, which is available from the publishers of the book. EQUITHERM can be used to carry out thermodynamic calculations on multi-component, multi-phase systems made up of any of the substances listed in this work. Thus, the publishers are in the unique position of being able to offer both a printed compilation of thermodynamic data for pure substances and a software package for the calculation of equilibria in multi-species systems. Cologne/Aachen, 1988 Ihsan Barin Acknowledgment The present work is the result of an individual effort without any support from public authorities. The facilities of KHD Humboldt Wedag AG, Cologne, were used in the compilation of the tables. The sup￾port of the management of the company and staff of the research and development center is gratefully acknowledged. The input of data was carried out over a long period by Ms. Wang Shu Sheng outside the working hours. Dipl. Ing. F. Sauert and Dr. E. Schultze-Rhonhof provided computer methods and aided in the examination of the consistency of selected data. Kind encouragement was provided during the course of the work by Dr. N.A. Gokcen, US Bureau of Mines, Albany, Oregon, and Dr. N. Themelis, Co￾lumbia University, New York, N.Y., and by many other colleagues and friends. VCH Verlagsgesellschaft, Weinheim, has supported the work in all its phases. Dr. F. and Mrs. J.A. Hampson, Saarbriicken, are acknowledged for the translation of the introductory text. I particularly wish to thank my family for their pa￾tience, help, and understanding while I was preparing this book. Aachen, 1988 Ihsan Barin

ContentsVolume 11.81-15List of chemical symbols and namesChemical potential1.8.11-15of substances in the orderOpensystemsXIIof tabulation (Formulae index)1.8.2Definition of the chemical potential,.....1-15Gibbs fundamental equationList of chemical symbols for substances1.8.3Standard state for chemical potential,1-15according to the alphabetical orderdefinition of activity.............of elements (modified Hill indexing1.9Chemical equilibrium1-16.....XXXVIIsystem)....1.9.1Gibbs fundamental equationI-16for closed systems1.9.21-16Conditions for chemical equilibriumPartI Basic Principles1.9.31-16Equilibrium constant...............1Thermodynamic functions and1-171.10MixturesI-1relations ..1.10.1 Gibbs-Duhem equation1-171.10.2 Standard states for activitiesI-11.1The basic concepts[-17and activity coefficients1.1.1I-1Thermodynamic system..I-11.1.2State functions1-181.11Gibbs phase ruleI-11.1.3Changes in state+.+++-..1.12Electrochemical reactionsI-18I-21.1.4The Zeroth Law of thermodynamics1-181.12.1Electrochemical work.1.1.51-2Equations of state++-1-191.12.2 Electrochemical potential1.2I-3The First Law of thermodynamics...1-19°1.12.3 Electrochemical equilibrium.1.2.1I-3Work1.13References for chapter 11-201-4..1.2.2Energy and heat1.2.31-4 Internal energy21.2.4I-5EnthalpyCalculation of thermochemical1.2.51-5Heat capacitiesfunctionsI-211.2.6Changes in U and H of closed2.1Units and conventions1-6systemsI-21(seeSections 10.1-10.3)+1.31-7Joule-Thomson effect2.2Calculation of the thermochemical1.4The Second Law of thermodynamics.1-7I-21functions of pure substances...+....2.2.11.4.11-7I-21EntropyC,(T), heat capacity...1.4.22.2.21-22Entropychanges,thermodynamicH(T), enthalpy1-92.2.3S(T), entropy[-24temperature.+.+.+.+.+.........+..++++-++2.2.41.4.31-9G(T), Gibbs energyI-24Temperature dependence of entropy.:2.2.5Gef(T),Gibbs energy function1.5The Third Law of thermodynamicsI-25(free enthalpy function)1-10(Nernst Heat Theorem) ....2.2.6△H,(T), △G(T), log K,(T) Molar1.6Fundamental relations ofquantities of formation reactionI-25++.+1-11thermodynamics2.31-27Equilibrium calculations1.6.1Helmholtz energy, Gibbs energyI-11....2.3.11-27K(),equilibriumconstant1.6.2Temperature and pressure dependence2.3.2p(7),vaporpressureI-27........I-12of Gibbsenergy2.3.3E(T), standard emfI-271.6.3Natural changes and equilibrium state2.4[-12in a closed systemEntropy production and “exergy"I-28+++I-132.4.11.6.4Characteristic functionsEntropy production ..1-282.4.21-29Exergy1.7I-13Closed system with reactions2.4.3Exergy losses by irreversibilitiesI-291.7.1Reaction equation and conventions[-132.4.4References for exergy relations ....1-301.7.2Reaction quantities1-14.,..2.51.7.3Enthalpy and entropy of naturalEnthalpy and entropy of transition,Clausius-Clapeyron equationI-14materialsI-30

Contents Volume 1 List of chemical symbols and names of substances in the order of tabulation (Formulae index) . XI11 List of chemical symbols for substances according to the alphabetical order of elements (modified Hill indexing system) . XXXVII Part I Basic PrinciDles 1 1 . 1 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5 1.2 1.2.1 1.2.2 1.2.3 1.2.4 1.2.5 1.2.6 1.3 1.4 1.4.1 1.4.2 1.4.3 1.5 1.6 1.6.1 1.6.2 1.6.3 1.6.4 1.7 1.7.1 1.7.2 1.7.3 Thermodynamic functions and relations . The basic concepts . Thermodynamic system . State functions . Changes in state . The Zeroth Law of thermodynamics . Equations of state . The First Law of thermodynamics . Work . Energy and heat . Internal energy . Ent halpy . Heat capacities . . Changes in U and H of closed systems . Joule-Thomson effect The Second Law of thermodynamics . Entropy . Entropy changes. th temperature . Temperature depend The Third Law of thermodynamics (Nernst Heat Theorem) . Fundamental relations of thermodynamics Helmholtz energy Temperature and pressure dependence of Gibbs energy . . Natural changes a in a closed system . Characteristic functions . Closed system with reactions Reaction equation and conventions . . Reaction quantities . Enthalpy and entropy of transition. Clausius-Clapeyron equation . 1-1 I- 1 I- 1 I- 1 I- 1 1-2 1-2 1-3 1-3 1-4 1-4 1-5 1-5 1-6 1-7 1-7 1-7 1-9 1-9 1-10 1-1 1 1-1 1 1-12 1-12 1-13 1-13 1-1 3 1-14 1-14 1.8 Chemical potential . 1-15 1.8.1 Open systems . 1-15 1.8.2 Definition of the chemical potential. Gibbs fundamental equation . 1-15 1.8.3 Standard state for chemical potential. definition of activity . 1-15 1.9 Chemical equilibrium . I- 16 1.9.1 Gibbs fundamental equation for closed systems . 1-16 1.9.2 Conditions for chemical equilibrium . 1-16 1.9.3 Equilibrium constant . 1.10 Mixtures . 1.10.1 Gibbs-Duhem equation . 1.10.2 Standard states for activities and activity coefficients . 1 . 11 Gibbs phase rule . 1.12 Electrochemical reactions . 1.12.1 Electrochemical work . : . 1.12.2 Electrochemical potential . 1.12.3 Electrochemical equilibrium . 1.13 References for chapter 1 . 2 Calculation of thermochemical functions . 2.1 Units and conventions (see Sections 10.1 - 10.3) . 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 Calculation of the thermochemical functions of pure substances . C, (T). heat capacity . H( T). enthalpy . S( T). entropy . G(T). Gibbs energy . Gef(T). Gibbs energy function (free enthalpy function) . AHf(T). AGf(T). logKf(T) Molar quantities of formation reaction . 2.3 Equilibrium calculations . 2.3.1 K( T). equilibrium constant . 2.3.2 po(T). vapor pressure . 2.3.3 Eo(T). standard emf . 2.4 Entropy production and “exergy” . 2.4.1 Entropy production . 2.4.2 Exergy . 2.4.3 Exergy losses by irreversibilities . 2.4.4 References for exergy relations . 2.5 Enthalpy and entropy of natural materials . 1-16 1-17 1-17 1-17 1-18 1-18 1-18 1-19 1-19- 1-20 1-21 1-21 1-21 1-21 1-22 1-24 1-24 1-25 1-25 1-27 1-27 1-27 1-27 1-28 1-28 1-29 1-29 1-30 1-30