A TEXT-BOOK OF PRACTICAL ORGANIC CHEMISTRY INCLUDING QUALITATIVE ORGANIC ANALYSIS By ARTHUR I. VOGEL, D.Se.(Lond.),D.1.C.,F.R.LC. Formerly Head of Chemistry Department, Woolwich Sometime Beit ScieatiGe Research Fellow of the Imperial With diagrams and 8 photographs THIRD EDITION LONGMANLONGMAN GROUP LIMITED Associated companies, branches and representatives Throughout the world First published 1948 New impression with minor corrections, October 1948 ‘Second Eivion 1951 [New impression with addition of Chapter Nil on Semimiro Technique 138 Third Edition, 1986 New impression wlth corrections and ‘dons 1987 [New impressions 1939, 1961, 1962, 1964, "1865, 1967, 1970, 1972, and 1974 Ison 0 582 44245 1 LOWE AND BRYDONE (PRINTERS) LTDPREFACE TO THIRD EDITION ‘Tae favourable reception accorded to previous editions by reviewers, students and practising organic chemists has encouraged the author to undertake an exhaustive revision of the entire text in the light of the numerous developments in practical organic chemistry since the book was first written (1945-46). ‘The net result has been an increaso in the length of the volume by some 150 pages, a figure which gives some indi- cation of the now matter incorporated in the present edition. It ia impossible within the limitations of a short preface to give a de- tailed list of the numerous changes and additions. Some of the more important new preparations include 1. Chapter IIT. \-Heptene (111,10) ; alkyl iodides (KI-H,PO, method) (U1,38) ; alkyl fluorides (KF ethylene glycol method) (IIL41) ; keten (nichrome ‘wire method) (ITI,90) ; ion exchange resin eatalyst method for esters (111,102) ; acetamide (urea method) (111,107); ethyl -bromopropionate (11,126) ; fcetoucetatic ester condensation using sodium triphenylmethide (111,151) 2. Chapter IV. a-Chloromethyinaphthalene (1V,23) ; benzylamino (Gabriel synthesis) (1V,39) ; NN-dialkylanilines (from amines and trialky! orthophos- hates) (IV,42) ; a-naphthaldehyde (Sommelet reaction) (LV,120) ; «phenyl: innamic acid (Perkin reaction using triethylamine) (IV,124);_6-nitrostyrene (1V,128) ; S-bromonaphthalene and §-naphthoic acid (from 2-naphthylamine-1- rulphonic acid) (IV,62 and IV,164); diphenic acid (from phenanthrene) UV.165). 3. Chapler ¥- Quinaldine (V,2); 2-methyl., 2: S-dimethyl- and 2-acetyl- thiophene (V,8-V.10) ; 2: 5-dimethyl- and 2 :4-dimethyl-dicarbethoxy-pyrrole (WA2-V,13} ? 2-amino- and ie (Vi15-V,16) ; 3: 5-dimethyl- pyrzole (V7); -ethylpyridine (from pyridine) (V,19);n-amylpyridines {rom picolines) (V.28) ; pleolinie, nieotinie and isonicotinic acid (V.21-V.22) ; (ethyl nicotinate and §-eyanopytidine (V,23-V,24) ; uramil (V.25);" 4-methyl- (coumarin (V,28) ; 2shydroxylepidine (V.29). 4. Chapter VI.” Reductions with potassium borobydride (VI.11) ; Oppen- suet oxidation (VI3) ;_ epoxidation and hydroxylation of ethylenic com- pounds (VI,18) ; Amdt-Eistert reaction (VII7) ; Darzens glycidic ester con. ensstion (VI,18) ; Erlenmeyer azlactone reaction (VI,19) ;, Mannich reaction (VI20) ; Michael reaction (Vi,21) ; Schmidt reaction (VI23) ; Stobbe con- entation (Vi24) ; Willgerodt_ reaction (VI25) ; unsymmetrical diaryls (VI27); syntheses with organolithium compounds (VI,28); syntheses with organosodium compounds (Vi,29) ; syntheses with organocadmium compounds (WE30);) some electrolytic syntheses (VI,31) ; chromatographic adsorption (VE33) ; ing enlargement with diazomethane (VI,34). 5. Chapters VIE-LX. Diazomethane (p-tolylsalphonylmethylnitrosamide method) {VIL20); Girard’s reagents“ ‘T” and“ P” (VIL25) ; psoudo- saccharin chlotide (VI26) ; 2: 2-dipyridyl (VIII,13) ; ninhydrin (VIIL14) ; Sindoleacetic acid. (1X14). ‘A new feature is ths account of the electronic mechanisms (in outline) of the numerous reactions desoribed in the text. Although some of these mechanisms may be modified in the near future, itis hoped that the brief treatment scattered throughout the volume will stimulate the student's interest in this important branch of organic chemistry. Tt will be noted that many reactions are designated by name; this may be undesirable on pedagogical grounds but, in most cases, established usage and the example set by the various volumes of Organic Reactions (J. Wiley) may be put forward in justification.vi PREFACE TO THIRD EDITION Chapter XII is concerned with Semimioro Technique. ‘There ean be little doubt that preparations on a smaller seale than has hitherto heen customary have many advantages ; partioular reference may be made to cont, time and bench space, all of which are important factors in teaching laboratories and also in training for research. Once the student has mastered the special technique, no difficulty should be experienced adapting most of the preparations described in the book to the sem miero scale. A few examples of small-scale preparations are included together with a suggested list of experiments for an elementary course. Section A7, “Applications of infrared and ultraviolet absorption spectra to organic chemistry,” should provide a brief introduction to tho subject. Tt is regretted that the size of the volume has rendered the insertion of literature references impossible : the Selected Bibliography (A,5) may partly compensate for this omission. Section numbers are now included in the headings of the pages—a feattire introduced in response to requests by many readers. ‘The volume comprises virtually at least three books under one cover, viz., experimental technique, preparations, and qualita- tive organic analysis. Tt should therefore continue to be of value as a ‘one-volume reference work in the laboratory. Students at all levels will find their requirements for laboratory work (excluding quantitative organie analysis) adequately provided for and, furthermore, the writer hopes that the book will be used as a souree of information to supplement their theoretical studies, ‘Tho author wishes to thank Dr. G. H. Jeffery, C. , Cresswell, B.Se., ©. M. Ellis, M.Se., Dr. J, Leicester and C. Kyte, B.So., for assistance with the proof reading and for helpful suggestions ; Dr. G. H. Jeffery for invaluable assistance in numerous ways; and C, Kyte, BSe, and R. Grezskowiak, B.Se., for a number of original preparations and also for ‘hooking and improving many of the new experimental procedures. Criticisms and also suggestions for improving the book are weleomed. ARTHUR 1. VOGEL. Woolwich Pelytechnie, London, 8.E. 18. ‘September 1958, PREFACE TO FIRST EDITION ‘Tre present volume is an attempt to give to students of practical organie chemistry the benefit of some twenty years’ experience in research and teaching of the subject. ‘The real foundations of the author's knowledge of the subject were lnid in 1925-1929 when, as a research student at the Imperial College under the late Professor J. FP. Thorpe, F.RS., he was introduced to the methods and experimental technique employed in a large and flourishing school of research in organic chemistry. Since that period the author and his studenta have been engaged inier alia in researches on Physical Properties and Chemical Constitution (published in the Journal of the Chemical Society) and this has involved the prepara: tion of over a thousand pure compounds of very varied type. Many ofPREFACE TO FIRST EDITION vii the new procedures and much of the specialised technique developed and employed in these researches are incorporated in this book. Further- ‘more, new experiments for the elementary student have emanated from these researches ; these have been tried out with large classes of under- {graduate students over several sessions with gratifying success and have now been included in the present text-book. In compiling this book, the author has drawn freely from all sources of information available ‘to him—research notes, original memoirs in scientific journals, reference works on organic chemistry, the numerous text-books on practical organic chemistry, and pamphlets of manufac turers of specialised apparatus, Whilst’ individual acknowledgement cannot obviously be made—in many cases the original source has been lost track of—it is a duty and a pleasure to place on record the debt the writer owes to all these sources. Mention must, however, be made ‘of Organic Syntheses, to which tho reader is referred for farther details of many of the preparations described in the text. ‘The book opens with @ chapter on the theory underlying the technique of the chief operations of practical organic chemistry : it is considered that proper understanding of these operations cannot be achieved without a. knowledge of the appropriate theoretical principles. Chapter II is devoted to a detailed discussion of experimental technique; the inclusion of this subject in one chapter leads to economy of space, par- ticularly in the description of advanced preparations. It is not expected that the student will employ even the major proportion of the operations described, but-a knowledge of their existence is thought desirable for the ‘advanced student so that he may apply them when occasion demands, Chapters IIL and IV are confined to the preparation and properties of Aliphatic Compounds and Aromatic Compounds respectively. This division, although perhaps artificial, falls into line with the treatment in many of the existing theoretical text-books and also with the author's own lecture courses, A short theoretical introduction precedes the detailed preparations of the various classes of organic compounds: it is recommended that these be read coneurrently with the student's lecture course and, it is hoped, that with such reading the subject will become alive and possess real meaning. The partition of the chapters in this manner provides the opportunity of introducing the reactions and the methods of characterisation of the various classes of onganic compounds the foundations of qualitative organic analysis are thus laid gradually bbut many teachers may prefer to postpone the study of this subject w ‘ representative number of elementary preparations has been carried ‘out by the student. ‘The division into sections will facilitate the intro- duction of any scheme of instruction which the teacher considers desirable, Chapters V-X deal respectively with Heterocyclic and Alieyelie Com- pounds ; Miscellaneous Reactions ; Organic Reagents in Inorganic and Organic’ Chemistry ; Dyestuffs, Indicators and Related Compounds ; Some Physiologically-Active Compounds; and Synthetic Polymers. Many of these preparations are of course intended for advanced students, but a mere perusal of the experimental details of selected preparations by those whiose time for experimental work is limited may assist to impress them on the memory. Attention is particularly directed to the chaptervil PREFACE TO FIRST EDITION upon Organic Reagents in Inorganic and Organic Chemistry. It is always @ good plan to set advanced students or adequately-trained laboratory assistants on the preparation of those compounds which aro required in the laboratory for organic and inorganic analysis ; the result- ing cost is comparatively low (for o-phenanthroline, for example, itis less than one-tenth of the commercial price) and will serve to promote the use of these, otherwise relatively expensive, organic reagents in the laboratory. Chapter XI is devoted to Qualitative Organic Analysis, ‘The eubject is discussed in moderate detail and this, coupled with the various Sections and Tables of Physical Constants of Organic Compounds and their Derivatives in Chapters III and IV, will provide « satisfactory course of study in this important branch of chemistry. No attempt has been made to deal with Quantitative Organic Analysis in this volume. ‘The text-book is intended to meet the requirements of the student of chemistry throughout the whole of his training. Considerable detail is given in those sections of particular interest to the elementary student ; in the author's opinion it is the duty of a writer of a practical text-book to lay secure foundation of sound experimental technique for the beginner. ‘The subject matter of the book is sufficiently comprehensive ‘to permit the teacher to cover any reasonable course of instruction. Tt will be observed that the scale of the preparations varies considerably ; the instructor can easily adapt the preparation to a smaller scale when such a step is necessary from considerations of cost. and time or for other reasons. Quantities of liquid reagents are generally expressed as weights ‘and volumes : the latter refer to a temperature of 20°. ‘The book will be suitable for students preparing for the Pass and Honours (General and Special) B.Sc. of the Universities, the A.R.I.C. and the F.R.LC. (Organic Chemistry). It will also provide an introduction to research methods in organic chemistry and, itis hoped, may serve as an intermediate reference book for practising organic chemists. Attention is directed to the numerous references, particularly in Chapter II on Experimental ‘Technique, to firms supplying specialised apparatus, The author has usually had first-hand experience ‘with this apparatus and he feels that some readers may wish to know the present source of supply and also from whom to obtain additional information. Te must be mentioned that most of tho specialised apparatus has been introduced to the market for the first time by the respective firms after much development research and exhaustive tests in their laboratories. A reference to such a firm is, in the writer's opinion, equivalent to an original literature reference or'to a book. During the last decade or two much development work has been carried out in the laboratories of the manufacturers of chemical apparatus (and also of industrial chemicals) and some acknowledgement of the great help rendered to practical organic ‘chemists by these industrial organisations is long overdue; it is certainly no exaggeration to state that they have materially assisted the advancement of the science. A shortlist of the various firms is given on the next pago. ARTHUR 1. VOGEE. Wookwich Polytochnie, London, S.E. 18 December 1646.110. Ta. 112, 113. ni 115. 116. 17. Lis. 119. E20. 121. 122, m1. m2. 13. is. ms. us. CONTENTS CHAPTER I THEORY OF GENERAL TECHNIQUE ‘THEORY OF DISTILLATION Vapour prorsure . Calculation of the boiling point wc selooted prossuies 2 *. Superheating and bumping Fractional distillation ‘The breaking up of azeotropie mi Steam detiation, "Ditton of «pair of unmicible iid Distillation with superheated stenrm SOLUTIONS OF LIQUIDS IN LIQUIDS Partially miscible liquide. Critical solution temperature Influence of added subetances upon the critical salution tomparaturo THEORY OF MELTING AND FREEZING Melting point and vapour pressure. Efiect of impurities upon the melting point. ‘System in which the solid phasea consist of the pure components and ‘the components are completely miscible in tho liquid phase Construction of equilibrium diagrams System in which the two components form a compound possessing & ‘congruent melting point System in which tho two compononta form a compound with an ‘incongruent molting point - Syitom in which the’ two components form a continu olid solutions Mixed melting points Systom in which the solid phases eonsist of the pure components and ‘the componente are only partially miscible in the liquid state. series of "Theory of sublimation oe - iwory ofthe action of drying agents’ SS fot Deliquesoence and eMlorescence = Polof tt Extraction with solvents Dot Dot CHAPTER II EXPERIMENTAL TECHNIQUE, Common laboratory apparatus. Cleaning and drying of glassware Uso of cork and rubber stoppers Gutkng and banding of glo tubing Heating baths «= Cooling bathe 2 2 23 Pa 26 a 2 En 6 n 30 3CONTENTS ‘Mechanical agitation =. : Gas absorption traps! Calibration of thermometers | Experimental determination of the melting point Miseellaneous forma of molting point appuratus ixperimental determination of the boiling point» ‘Typical assemblies of apparatus for distillation and relluxine Piro hazards attending the distillation of inflainmabe solvents retinal dalton, “Distilaion with afraconatingcoivon 1 ‘Simple apparatus for fractionation : 23 Improved apparatus for fractional distillation o Stil heads for fractionating colina 103 Distillation under diminished pressure (" vacuum” distillation) | 108 Eractional distillation under diminished prossure 2 tos Water pumps - : : : Ho Oil pumps : io Masiometors and manostata ne Refinements in the technique of distillation under’ diminished ‘pressure ne Precision fractional distillation under diinished pressiro 19 Molecular distillation = 130 Parifieation of wolid organi compounds by erystallisntion. General considerations. Experimental details for reerystaliation Proparation of a fated Sltor papor Removal of traces of colouring mattor and resinoiss prowuets! Uso ‘of deeolourising carbon " Dilfieulties encountered in reerystallisition Filtration with sution Drying of the recrystallised material | Filtration of small quantities of material with suctiot | Miscellaneous apparatus for filtration with suction ‘Reerystallisation in an atmosphiero of inott Evaporation of the salvent Drying of solid organie compouncls Drying of liquids oF of solutions of organic compounds in organis folventa : 7 oe ‘Technique of steam distillation Moaifaton of th loam tation appa. ‘Technique of extraction with solvents traction by chemically netive solvents Continuous extraction of liquids or solids by solvents Technique of sublimation Chromatographie adsorption Purifleation of the common organie solvents Inorganie reagonts—gases s Tnonganie reagents— liquids Inorgunie reagents solids Cateutation of yields : Dot General instrustions for wrk in the laboratory : Safoty precaution vee eS APPARATUS WITH INTERCHANGEABLE, GROUND GLASS JOH Interchangeable ground glass joints . 208 ‘Types of ground glass joints 21) Apparatus with interchangoablo ground ginss joints ‘suitaiily for eneral use i. preparative organte chemistry [Blectrie heating inuntles (for use in fractional distillation, ate.)CONTENTS sil PAGE 1188, Apparatus for the continuous extraction of solids or liquids by olvents oS 38 11,59. sbriention of grounil glass joints > : ia 160, ‘Typient assemblies ee Dol ff me CHAPTER UT PREPARATION AND REACTIONS OF ALIPHATIC COMPOUNDS PRELIMINARY LABORATORY OPERATIONS. Determination of malting points Puriication of solid organic compounds by reerystaliaati SATURATED ALIPHATIC HYDROCARBONS. Keactions and charncteriaion of aturatd aliphatic hydrocarbons 284 mOetano (Wurtz reaction)» : 236 icHexane (hydrocarbon from Grignard reagent) Dot ar reOctane (Clemnmensen reduction oy a Betone) 238 ETHYLENIC HYDROCARBONS (ALKENES) Amyleno 239 Reactions and characterisation of ethylenic hydrocarbor 2a cyloHexene ss es BRB ACETYLENIC HYDROCARBONS (ALKYNES) 13. Acetylene . ALIPHATIC ALCOHOLS 27 UL,14. n-Amsl alcohol (from ethyl n-valerae) 240 HUIS. Tetrumethylone glyool (I4-butanediol) 250 HN16. n-Heptyl aleohol (from n-heptaldehyde) 251 MII7, eyelotTexylearbinol (from eyclokery! chloride) 252 HIEAB, eHlexpl aleohol (from n-butyl bromide). 258 HILI9. ":Nonyl aleohel (Jrom ncheptyl Bromide) 254 T1120. Methyl n-amnyl carbinol rom methyl n-amyl Ketone) 254 Meth n-butyl earbinol (from methyl n-butyl Ketone) Df pss TIT22, Methst foo-propyl earbinal : 255 TIN23. Dicm-butyl earbinol (from n-butyl bromide) * Dot 256 M28. Dimethyl nebutyl earbinel. : Df ar HIL25. Triethyl earbinol Dolo 258 HL26. Dimethyl n-propyl carbinel 2 250 27, Reuetions and chareeterisation of aliphatic alcohsls | 260 ALKYL HALIDES: 210 1128, n-Butyl chloride (ZnCl, -HCL method) : 22 MIE29. fee-Butyl chlorida (ZnCl, - HCL method) 213 NO. UosButel shlonde (SOCIe. Pyridine mitiod) oan HIBI. n-Hexyl chloride (SOCI, method) at | i i xiv CONTENTS PAGE HII,32. cycloFfoxyl ehloride (HC1-CaCl, method) 278 TM33._tertButyl chloride (HCI method) Dot 26 UN34. ieoPropyl bromide (HBr method) > 207 TI1,38. n-Dutyl bromide (HBr -H,S0, method) 277 TI;36. Butyl bromide (KBr-H1580, method) 280 MIN,37.n-Butyl bromide (red P= firy method) | 281 MIL38.1:4-Diiodobutano (KT-H,20, methed) 284 MI1,39.isoPropyl iodide (211 method) | Dot 2 285 MIAO. n-Butyl fodide (red P'and T, method) 2 28s USI) nHexyl fuoride* : 288 MII42! Resetions and charucterisation of alky! halides Dt a0 POLYHALOGEN COMPOUNDS 207 M143. Chloroform - : 207 MIN44. Bromoform 1) | Dot ert) TM45. Todoform | : : Df f69 TIT46. Mathylone bromide | : : Df 300 TIN47. Methylene iodide? : Dot 300 UNAS. 12273 Tribromopropane’ |) 301 ESTERS OF INORGANIC ACIDS 302 mButyl sulphite : - 303 ‘mButyl phosphate | 306 n-Butyl borate : 308 n-Propyl thioeysnats —) 305 Amp nitrite tot : 308 LNitto-n-butane (4gNO, inethod) —)S 2 307 Nitromethane 2 bor ALIPHATIC ETHERS MESS. Dietiylother HL'S2. Din Bugler : TE38. Rihyl mesg! ether MES9. qylotosyl sthsh ether 11160, Renctiona and charactriation of liphati sthors ALIPHATIC ALDEHYDES mButyraldehyde MHexaldehyde eatayet mithody” | MHoxaldenyde (ethyl ortheformate method) | iHoealdehvde(Jrom mam cyan) ‘cetaldelyo (rom paraldchyde) Formaldehyde.” MC) Hexamethylonctotemine (hexathino) | Acetal (acetaldehyde detylacetal) Resctions and characterisation of totale”, Resotions and charecteriation of aliphatic aidehyites ALIPHATIC KETONES 335 HIL71. Methyl n-hexyl kotone oe se 386 HL72. Disthy!ketone | Pol of ff as TIL73. eyctoPentanone 340 TIN74. Reactions and characterisation of aliphatic ketones |] at HIL75. Acetone eyanohydrin aCONTENTS: xv Pace, 11176, n-Hoptaldoxime - marry MINI7. Pinacol and pinecolone * fot Dol ye TIL78. Diacotone alcohot fol : Dot as M79. Mesityloxide St fol Dasa SATURATED ALIPHATIC MONOBASIC 4 364 MM,80. izo-Butyricacid =. ee - 888 MESI. mitepteicacid Dot ase MIL,82. n-Butyl n-butyrato - : Dot as MIN,83. n-Valorio acid (hydrolysis of n-butyl eyanide) D387 MINS. di-Methylothylacetic acid (carbonation of a Grignard reagent): | 358 TI185. Reetions ancl charactorisation of aliphatic carboxylic aide 360 ACID CHLORIDES OF ALIPHATIC CARBOXYLIC ACIDS 367 I11,86. Acetyl chloride : - foe 807 TIN,87. n-Butyry! chloride | D308 TIT,S8, Reactions and characterisation of acid chlorides of aliphatic acida | 369 ACID ANHYDRIDES OF ALIPHATIC CARBOXYLIC ACIDS 371 Acetic anhydride. 32 Keton ar n-Caproie anhydride au Buceinie anhydride. ious Maloic anhydeido ° 376 ‘Renctions and characterisation of acid anhydrides (aliphatic) 316 ALIPHATIC ESTERS 9 111,95. n-Butyl acetate fone : - 388 T1196. tert. Butyl ecotate | Pott Dol ass M197. nButylformato§ 2 SDD Dol ase MN 98, eyeloHoxyl acetate : Dol aes MI1.99. Diethyl adipate (azcotropic mixture method) > ° Dot aes MIT,100. Diethyl adipato (benzene method) = Dot ae HOI. »-Propyl n-valerate toot ase ME 102: ihoPropy! lactate (im exchange rein catalyst method) Dot ser UIE{103. Diethyl maleate (silver sale method) Daas HIEL04. Ethyl n-valorato (from n-butyl cyanide) Lt 380 HIE105. Ethyl vinylacotata (acid ehloride method) : 389 11,106, Reactions wnd characterisation of aliphatic esters 300 ALIPHATIC AMIDES «or 11,107. Acetamide (from ammonium aceate or from acetic acid). «401 UIL108. Acatamide (from ethyl aceite) 403 HI109. n-Capreamide » Lt foe HEAY0, Reactions and characterisation of aliphatic amides : to ALIPHATIC CYANIDES (NITRILES) ‘or MUL 111. Acotonitrile - 407 MIL12, -Aroyl eyanide (n-eapronitite) | Dot 408 HILLS, Butyl eyanide (n-valeronitrilo) : 08 HII1$, Trimethyleno dicyanide (glutaroniteile) 00 HILLIS, Reactions and characterimation of aliphatic cyanides (nitriles) a0xvi CONTENTS ALIPHATIC AMINES 111,116. Methylamine hydrochloride (from acetamide) HI-LIZ. Mothylumine hydroshiride from formalin) HI118. Dimethylamine hydrochloride : TI.119. Trimethylamine hydrochloride | 119,120. n-Amylamine : TILA21. n-Heptylamine 111,122. Di-r-butylamine 111,123. Reactiona and charsctorisation of aliphatic amines TIN,124. N:Nitrosoditoothylamine (dimethylalteosamine) SUBSTITUTED ALIPHATIC MON II1,125. Monochloroacetio acid - 111,126. Monobromonoatio cid and ethyl brosioncetate 111,127. Dichloroacetic acid... HIL128. Trichlorowcotio weld | 111,129. Glyeine faminowcotic acid)! 111,130. cAmino-neaproic acid (notloucine) HN 131. Ethyl eyanoncetate T1132. Reactions and characterisation of amino acids MIT 133. Uren TI 134, Thiourea (thioearbusiide) | (OBASIC ACIDS POLYHYDRIC ALCOHOLS, FATS AND SOAPS HI1,135. Saponification of a fat. Soap. TIT,136, Reuctions and chareoterisation of polyhydi aleohots CARBOHYDRATES: 111,137. a. and @-Glucose pente-acctate « MIN138. Mucio acid TI1,139. Reactions and characterization of eastiohydiates Photographs of osazonoe : : UNSATURATED ALIPHATIC COMPOUNDS. 111,140. Allyl aleoho! MIN141, Grotonaldehyds | MII,142. G-Dimethylacrylic asia T143. Mloio and fumeric ncids |! IIM,144. Crotonie acid and vinylacetic seid TIL145. Sorbie acid : TI,146. Dally! (hoxadione-1,5) ML147, 223-Dimethyl-1 : Sbutadione HIL148. Dimethylethynyl earbinol HI,149. 10-Undecynoie seid TIT,150. Catalytic reduction with Adams’ platinum oxide Catalyst ETHYL ACETOACETATE 111,151. Ethyl acotonontate LI,152, Ethyl n-propylacetoacotats and mothyl n-butyl ketone DIETHYL MALONATE, UII,183. Diethyl malonate HIN 154. Ethyl n-butylmalonate HEISE. Capra aed rm ty tuyinalnate TIN186. m-Propylmalonie seid me 49 451 402 453 455 59 460 460 451 463 $66 460. 487 457 408 470 415 an 451 483 484 485 486 488CONTENTS xvii PAGE SOME ALIPHATIC DICARBOXYLIC ACIDS 480 TI1,187. Malonio acid. : : 490 MIE 158, Glutaric acid (from trimethylene dieyanide) 49 TIN 159. Pimelio acid (from benzoyl piperidine) 492 L160. uta acd (rom eyelopentanone) < 1 493 ME161. Adipic acid i 5 aoe MN 162! aa-Dimethylavceinie acid || 495 ALIPHATIC SULPHUR COMPOUNDS 496 111,163. n-Hoxyl morcaptan (whoxyl thio) ©. sor HI{164. Din-propyl rulphide Pol tf ar HIj165, Diethyl disulphide : 1 498 HII,166. Potassium ethyl xanthato - Dot LD a9 TIN167. Ethyl S-ethyl xanthato St 400 HI168, Reactions and eharnctorisation of moreaptans (thiols) < 2 500 RESOLUTION OF A RACEMIC COMPOUND 111,169. Determination of the rotatory power ‘503 HIII70, Resolution of wec-oetyl alcool (-2-cetanol) into ite optically ‘etive components (d- and I-2-octano!) 505 CHAPTER IV PREPARATION AND REACTIONS OF AROMATIC COMPOUNDS AROMATIC HYDROCARBONS 508 Wik. nBatylbonsine (Wate Fi ayes) 5 - 1V.2) iao-Propylbenzene (eumene) Dot on 133. tert-Butylbenzono » - : : : 51a IVA. Diphenylmethane Dot Dt as I'S. ‘Triphenylmethane fol 515 IVi6.Etliylbenzene Dol any IVi7. wPropylbenzone Dolo D518 IV,8. tcAmylbenzene : Doar 1V'9 Characterisation of aromatic hydrocarbons | I ose NITRATION OF AROMATIC HYDROCARBON: 523 Nitrobenzene tone 525 eNitronaphthalone | Pol tf eae ‘n-Dinitrabenzene 2 526 2; 4Dinitrotoluene : 527 p-Bromoniteobenzen : : oon 2Pe-Dinitrodiphenyl | Dosa [Ronetions and characterisation of aromatic nitro compounds 538 Reactions and eharseterisation of aliphatic nitro compounds 631 HALOGENATION OF AROMATIC HYDROCARBONS 632 1V17. Chlorobenzone =. oe 535 IVi18. Bromobenzene : Dot 535 IVA9. mDromonitrobonzene— * folot ot Dostxviii CONTENTS PAGE 1V,20. «-Bromonaphthalne 837 1Vi21. Todobenzene 538 1V;22. Benzyl chloride (eMorination of toluene) | 538 28. Renal chon (Mormathylation of enon [of se IV,24. Todobonzene dichloride : Bal 1V,25. Todosobenzene Bal 1V.26. _Todoxybenzene 542 IV;27. Diphenyliodonium iodide | | 542 1V,28. Reactions and. characterization ‘carbons ee 42 SULPHONATION OF AROMATIC HYDROCARBONS st 1V,29. Sodium benzenesulphonate oe : 549 1V;30. Sodium p:toluonesulphonate > en) 1V;31. Sodium frnaphthalenecuiphonate |; : 351 1V/32.__p-Tolueneeulphonic acid D552 1V;33.Renetions and charaoteriantion of arvinatie sulphonic acids | 582 1V,33A. Reactions and charecterisation of aromatic sulphonmides [ase AROMATIC AMINES AND THEIR SIMPLE DERIVATIVES 559 1V,34. Aniline : - 563 1V,35. B-Phenylothylamine | : : 566 1V36. = Phenylethylamine fot 567 1V,37. eNaphthylamine 568 1Vj38, f:Naphthylamine Polo lft ses 1Vi39. Benzylamine (Gabriel eyriheri) | | ft 509 1V40. Puro mothylaniling from commercial methylamine 370 IVi41. Benzylaniline Se 512 IV\42.Dimethyleniling | : Doan IVA43._p-Nitrosodimothylanitine | : Daa TVi48. eeNitroaniling ny Dot Doon ACETYLATION OF AROMATIC AMINES 578 1s. foe si avia6. : 578 avia7. : o10 1V\48. p-Bromoacetanilide - 580 1V49. p-Bromoaniling | : 2580 1V,50. p-Nitroacetanilide Dot f pat IVS1. p-Nitroaniline 51 BENZOYLATION OF AROMATIC AMINES 082 1V,52, Benzanilide (Sehotten- Baumann reaction). ‘5R2 1V{53.Benzanilide et 583 1V(54. Hippuric acid (benzo! glycine) 584 SULPHONATION OF AROMATIC AMINES 585 1,55. Sulphanilio acid =. 586 1V{56: Naphthionic acid 586 IV157. Orthanilio aid 587 TV{58. Metenilic acid 5801v,59. 1V,60. Ivo. 1v62, 1,63. 1.66. Iver. 168. 1,69: 1,70. wy wy. 1wy73. Wir wys. 1,76. ivi: 1wy78. wir. v.80. Ist. W82. 1V,83. Wiss. v.85. 1,86. w,s7. 1,88. CONTENTS DIAZONIUM SALTS Sold phenslaiaoniur ehorite Todobenzene peChlorotoluens p-Bromotoluene (Sandmeyer reaction) fn-Bromotaluene o-Bromotoluene (Gatiermann reaction} Dot Baaaneuipine eed ‘olunitrile (p-tolyl eyanile) Fiuorobenzene o-Dinitrobonzene Phenol (from aniline) m-Nitrophenol ‘Toluene (from p-tluidine) aym.tTribromobonzene 3: '-Dimethyldiphony! Diphonie eid (jrom anthranitic aid) Phenylarsonio acid : SOME AZO DYESTUFES Phenyl-uzo-$-naphthol foe Chrysoidine Polo fof ott AMothy! orange Orange If G-naphthel orange) Methyl red a Diazoaminobenzene | p-Amino-azobenzone E PRODUCTS IN THE REDUCTION OF NITRO COMPOUNDS f-Phenythydroxylamine . [Nitrosobenzane : Azoxybenzone Dot : ‘Azobenzane : : Hyurazabenzen (yicdiphmnytigdenine) © : Benzidine Dolo INTERMEDIAT. REDUCTION OF DIAZONIUM COMPOUNDS. ARYL HYDRAZINI Wwe, 195. 196. 1v97. 1398. 1.99, 1,100. Phonylhydrazine p-Nivrophenylhydrazino 2 P'¢ Diniteophenylnydeazine AROMATIC DIAMINES o-Phonylenediainine « foe mPhetylenediaming =) FS MISCELLANEOUS COMPOUNDS DERIVED FROM PRIMARY AMINES. ‘Thiocarbanilide (eym.-diphenylthioures) - Phonylieo-thioeyanate (from tiocarbanilide) > : Phenyl igo-thiocyanate (from aniline) « : Phienglurea (eyanate method) Pop tit Phenglarea (urea method) tt pelodoaailine Rosstions aad characterisition of arorastie winines PAGE: "500 a7 08 600 2 608 606 607 00 ei 813, els 815 815 616 sit 67 20 eae 823 eat 825 825 826 827 ora 620 630 eal eal 32 633 635 636 637 638 40 640 ea wae 62 63 ous was er roxx CONTENTS pace PHENOLS OH AV,101. p.Cresol : : 687 IVi102. f:Naphthot 658 IV{103. Phenyl acetate : 69 IVi104. Anisolo : 880 Wit05. Phony n-butyl ether 871 ‘Reactions and characterisation of aromatic ethers ert * -Propiophenol and p-propiophencl 676 6: and p-nitrophencls : err 2'4-Dimitrophenol - Dare : Pieri acid (2 + 4 6-trinitrophenal) olf ats pBromophenel : 670 1 S-Bromophenol fold 679 . p-lodophenal Poll D 680 Reactions and chacacterisation of phenole |! esi AROMATIC ALDEHYDES 689 IV,115. Benzaldohyde : : oe - 093 IVI116. p-Bromobensaldehydo fo 694 IVJLI7. p-Nitrobonsaldehyde pol 695 IVi118, p-Tolunldehydo : fot aor GNaphthaldehyde arty 4 Naphthaldetiyde (Sommelet reaction) 5 700 . fol ff mr Salieylaldohyds SD DD tas CONDENSATION REACTIONS OF AROMATIC ALDEHYDES 700 i 1,123. m1 \ haere m2 1 1vi125. ne | i126, ns 1 | qvy27. : : ns 1V,128. Benzalacetone | Popol t : 18 1 : B-Niteoatyrene : id Bencalactophenone (chalone) : m3 i Ethyl einnamate Doms EDiperonylacrylic acd (3? methylenedionycinsamic ast): 718 i - and 8-Benzaldoximes m9 i Hydrobenzamide no | Reactions and charactorisation of aroimatio aldehydes! || 720 | AROMATIC KETONES 725 5 . Acetophenone ; Butyrophonone ‘ | pelbromoneetophenone | Bonzophenone . Benzylaoetaphenone Methyl benzyl Ketone Phioroacetophenone a-Tetralone 6-Benzoylbenzoie acid ‘Anthraquinone Anthrone Benzophenone oxime and Beckmann rearrangement Reactions and charueteriaation of aromatic ketonesCONTENTS xxi PAGE QUINONES 45 1,149. p-Bonzoquinone(“quinone™) . . es HB 1Vj150. 1: 2-Naplithoguinone : oma IVi151. Quinhydrone Dolo 1V,152, Reactions and characterisation of quinones”) ) tT AROMATIC CARBOXYLIC ACIDS 1,153. Benzoie acid . IV\154.p-Nitrobenzoie acid . IVSS. 2: 4: G:Trnitrobenzoie acid 1V}156. 2: 4-Dinitrophenylacetie acid IV}187. o.Chlorobenanio acid 1,158. ‘Terephthalic acid 1Vi159. o-Toluie acid IV;160. Phonylactc ac (from bene egenie) IVi161. p-Nitrophenylacotic acid : 1V,162. p-Aminophenylacetic acid : : IV}163. @-Nephthoic acid IV,164. BNaphthoic acid > WWil65. Dipheni aid rom penivene) IVy166. Hydrocinnamie acid IV\167. m:Nitrobenzoie acid IV 168. 3: 5-Dinitrobenzoie acid 1,169, Homophthalie acid IV,170. Anthranilie acid IV,A71. Diphonylacetic acid IV72, Mandelie neid IV,173. Salicylic acid IW,17$. Phenylpropiolic acid” : IVI75. Reactions and characterisation of aromatie carboxylic lds AROMATIC ESTERS 780 IV,176. Methyl benzoate. : - 781 IVAT7. Methyl salicylate > 2 rez IV,178. Bonzyl acotato > : Doss IV\179. Ethyl phenylacotate Dot Drea IV180. Phenyl cinnamate : : Dl eM IVIISI. Phenyl benzoate Do Poll lf re IVUS2, Ethylanaphthoate |] : 185 IVII83. Reactions and characterisation of aroinatio ators’ || L785, AROMATIC ACID CHLORIDES 701 1,184. pNitrobonzoyl chloride ©. - ToL IVi185. Benzoyl chloride. S Pot ff ff me AROMATIC ACID ANHYDRIDES 798 704 1V,186. p.Chlorobenzoic anhyari ee . jon of acid chlorides of aromatic acide 795 1Vj187. Reactions and character AROMATIC ACID AMIDES 197 WAS. Benzamido 2. - : 707 1Vy189. Moreury banzamide | Dot : 97 1V}190, o-Toluamide * 708 IVJI91, Reactions and characterisation of primary aromatic amides 708 1V}192, Roastions and characterisation of substituted aromatic amides (aromatic acylated bases) Se 8011v,193. IVi194. 1V1195; 1,196. 1Vj197. IVj198, 1V,199. 1V,200. 1V201 1,202. 1V'203, 1Vj208, Tv.205. 1,206. 1207. Ivi208, 1vi209: ato. Iwan. Iva12, CONTENTS AROMATIC NITRILES Bonzonitle © 0. ee Verstronitrile. | Reactions and characterisation of aromatio nitriles SOME AROMATIC PEROXIDES AND PER-ACIDS Benzoyl peroxide p-Nitrobenzoy! peroxide Fensenaci asi tmpzoy Hydrgun prone) Monoporphthalio acid AROMATIC ALCOHOLS .Toll embina (p-methy! bene alee!) « Fonchydrat iphinylarina) ‘Triphenylearbinel ‘Triphenylehloromethane | @-Phenylethy! aloohot Reactions and characterisation of aromatic uleoliols COMPOUNDS DERIVED FROM AROMATIC SULPHONIC ACIDS Benzonesulphony] cblorid p-Toluenostlphons] chloride Dichioramine-T and chloramine: Sacoharin . n-Butyl p-toluenesulphonste Sodium ptoluonsulphinat Thiophenol CHAPTER V PAGE 803 803 505 $05 807 807 508 808 810 siz 812 813 815 816 si7 820 saz 822 823 824 525 828 827 SOME HETEROCYCLIC AND ALICYCLIC COMPOUNDS vas, v9. Quinoline Quinatdin Furfury! alcobel and furoie acid 2.Furfuralacetone . Furylericacid Farin Rul 2:54 eT ne 2 Acetone 2:4 Dime 3: oartnthonyryerste Succinimide 2Aminothiazola | 2: 4-Disnethylthiazoio 2: 5.Dimethylpyrazole 5: 5.Dimethylhydantoin 4-Ethylpyridine (from pyridine) | 20 831 832 833 a4 #35 835 $36 836 837 837 838 830 840 Bal saz 843 esCONTENTS xxiii PAGE pAprpitoes om rnin - As Picolinie acid. fol : sar Nicotinie acid” | fold ary Ethyl nicotinate | fold 40 B.Cyanopyridine : 2 850 Uramil fot : 2 880 2-Phenylindole” Dot : Das Bantimidazolo — ) )] Pol ft asa “4Methyleoumarin 2 yarosslpidine (-matyleabontya) Phonylbenzoyldiazomethane 2.Carbethoxyeyelopentanor : : cyeloButane-1 * I-dicarboxylic ‘acid “und” eyelabutanceartoxyio ‘acid an : 857 V3. eyeloPropanecarboxylic acid Dot er) 856 CHAPTER VI MISCELLANEOUS REACTIONS Acotylacctone =. sw ar Bonzoylacctone |] fo Df es Phenylglyoxal - fot Dt see Appa for Factions undorprewure S| Df 566 Raney nickel (catalyst) : 870 Copper chromium oxide eatalyst : : om Hexamethylone glyeol (1:6-Hexanodiol) | : 873 Ethyl S-phenylshydroxypropionate osm £8-Dimethylglutarie acid. Bolt 816 Reductions with lithium aluminium hydride Dot ai Reductions with potassium (or sodium) borohydride : sal Reductions with aluminium alkoxides : 882 ‘The Oppeniavor oxidation 586 Oxidation of unsaturated compounds with ozonizad oxygen (ozon0- isis) . Epoxidation and hydroxylation of othylenis compound Jicctions in guid ammonia. Soon actin ompovnds ‘The Arde ‘The Darsens gl Erlenmeyer aslactone feection : ‘The Mannich reaction es | : ‘The Michael vention =|? Cyanoethylation The Behmide eatin o arrangomonit ‘The Stabbe condensation = : ‘The Willgerodt reaction ‘The Wohi-Ziegler reaction. Applications of -bromesuocinimide Synthesia of unsymmetrical diatyls Synthesos with organolithium compounds Syntheses with organosodium compounds. ‘Syntheses with organoeadmium somponnda Some electrolytic rmnthesoe : ‘The dione syathesis (Diole-Alder reaction) Some applications of chromatographic adsorption ing "Stlegoment with “dnsretiane tHoptinon fo ‘cyclohexanone. is Deh in of hiydroarormetic compounds | Preparation of palladium catalysts for hydrogenation | Oxidation with oad totrw-acntate. m Buty! lyonyiatevia. vine. CONTENTS CHAPTER VIT ORGANIC REAGENTS IN INORGANIC AND ORGANIC CHEMISTRY Dimothylelyoxime Semieurbazide hydrochloride Diphenylearbezide Diphenylearbazono ” Biticoe phen Cupferron : Salicylaldoxim Benzoinoxime a-Nitroao-f-naphthol Ammonium eale of aurin ti p Nitrobonano azpanaph P-Bromophenaey! bromide p-Nitrobonzyl bromide» p-Phenylphenseyl bromide jouw ‘boxylie acid ( aluminon ") anthiydeot 8 Beasyhigothiurenion citorte S.Nitrophthalic anbydride Diazomethane + ‘4: 8Triiodobenzoy! chloride 3: S-Dinitrobenzoyl chloride 1: 2ycloHexanedione-dioxime (nioxime) Quinaldinie neid Girard’s reagents “7 and P* Peoude-saccharin chloride S-DimathyL I: Syloexanelion timothy toreorsina) 970 980 CHAPTER VIII DYESTUFFS, INDICATORS AND RELATED COMPOUNDS Congo red Indigo ‘Aliznrin vn. vara: vars. vans, van vu. vung. Vun0, vara: viini2: wnins3. vim, Ceyatal violet Sepperpitintcyanin (Monnet ie) Phonolphthalein Fluorescein and eosin, pp Totramethyldiaminodiphenylmethane | 2Sulphobenzoie anhydride Sulphoneplithalaine N-Bhenylanthranilio acid | 1: 10-Phenanthroline 2:2Dipyridyl Ninhydrin (indsne-1 +2: 2-trioné hydrate) CHAPTER IX SOME PHYSIOLOGICALLY ACTIVE COMPOUNDS {eps gots ie eidy Phonaootin ‘Antipyrine Bromural (2-bromo-igo-valerylures) Benzocaine (ethyl p-amninobenzoate) Barbiturie acid. os 982 985 oss 985 987 987 989 991 901 902 993 996 906 998 809 1000 1001xu. X12. x3. xt. xs. xe. xi7. ra. x19, xi. xm. xar3. xara. CONTENTS xxv PAGE Diothylbarbitorie acid (veronal) - «1002 Phenylothylberbitarie acid (phenobarbitone) 5 100s ‘p-Aminobenzenesulphonamide (sulphanilaride) 5 1005, Pp Aminobensenesuiphonasiso) pyridine (euphapyeiiney | + 1007 Sulphagusnidine 1009 }Thepslquinlinetcnrboxylo eid (aophan) 1010 js¢p-Chlorophenyl)-1 1 I-tricbloroethane (D-D:i:) Sion S-Indoletcetio acid oe Dio CHAPTER X SYNTHETIC POLYMERS Brief introduction to subject 1014 Phenol-formaldehyde resin 1022 Depolymerisation of methyl methaeryiate resin 1023 Formation of a glyptal resin. 1033 Thiokol A polyethylene polyulphie) 1028 Phonylethylene (etyrene) = 1 124 Polystyrene 1025 Euhivlenodiamine -adipie acta polymer 1026, Depelyreration of « hexarbthylenediamine alii eid palyner Nylon 68") 1026 CHAPTER XI QUALITATIVE ORGANIC ANALYSIS Basia of qualitative organic analysis. oe 1026 Determination of physical constants | * to2s Qualitative analysia for the elements 1038 ‘The solubilities of organic compounds: 1035, The solubility groups. 1050 Determination of the solubilities of organic compounds (for group ° 1085, (reactions for functions! groups) 2 0st mn of derivatives 1081 Qualitative analysis of mixturee of organic compounds 000 CHAPTER XII SEMIMICRO TECHNIQUE Introduction and general considerations 1101 Some typical operetions on the semmimicro # 103, Semimict spparets with interchangeable round gis jaa ° 1109 Small-scale preparations. : 110 APPENDIX LITERATURE OF ORGANIC CHEMISTRY Beiltein's * Handbuch * Original souroee of cheraidl information : Sectnary sore of choral irnaton. Abatrasting oor ‘Locating an organie compound Selecta reference works on ongene cieistry Laboratory accidents and fist id “Applications of infrared and ulraviola epecira to onganse chemistry Densities and porcentage compositions of various solutions. + 1 Density and vapour pressure of water : 0° to 35" C. Atoms weighta :NAME INDEX OF ORGANIC REACTIONSt ‘Acetoacetic ester condensation. +. 475, 4768, ‘Amdt-Bistert reaction 51 '902, 203, 904° 005, 908 Bert reaction. Dot : 597, 617, B18 Beckmann rearrangement : "738, 741 Bentidine rearrangement « Dol S_ o3oe) oa Benailic acid rearrangement, | 709%, 716, 716 Benzoin reaction (condensation) > : goss) 714 Blane chloromethylation reaction 534, 639) 540 Bouveault-Blane reduction st 2, 249,250, 812, B16 Bochorr hydantoin synthesis aOR Bucherer reaction : 2 61%, 568, 550 Gannizzero reaction joes, 711, 712, 811; 812, 832 Clason aldol condensation — > : : ‘now, 718 Claisen condensation : 477, 801", 862°, 863-865 Glaisea-Sehimidt reaction : 709, T10*, 716-718 Clommonson reduction 5S '2as, 610 15, 10,728,738 Darzons glyeidic eater condensation | 908 907 Dinscrno-eminato earangemont 623, 626, 627 Dieekmana reaction ot 856, 857 DieleAlder reaction | 961, 9408, 043 Doebner reaction : Dot 463, 405, 710, 7116, 719, Erlenmeyer azlactono synéhos : ~ "907, 908%, 909, 910, Fischer indole eynthesis 851", 862 Fisoher.Spoior esterifeation —_ +1 870%, 80%, 382383, eg. Friedel Crafts renction 508, 509%, 512, 013, S18, 725, 720°, 728, 120-738), SL, 815 Fries rowction : 604°, 055°, 676, 6 Gabriel synthesis | : Gattormann aldehydo reaction Gattermann reaction : Gattermann-Koch reaction 237 Grignard reaction Pol lf esi, 268, 255-260, 358-350, 304, 511, 616-517, 752, 750-781," 705, 781, 811, 813-818 Guareschi reaction fone 870, 877 Haworth reaction : Dot 726, 1284, 737, 738 Hell-Volherd-Zalinsky reaction | + 4279, 430) 430, Hoosch reaction ss) 1 rere) 136, 137 Hofmann reaction | | : Do aise, ata) 154; 773, Knoovenagel reaction | : 2 “400,710, 711°) 719. Knore pyrrole synthesis : : : 8309, 840 KolboSchiitt rosstion | : 2 164, 108, 774-776 Louckart reaction. Dot : 561, 567 Mannich resction | 910, 811¢, 912, 1012, 1013, Mecrsein-PonndoctVerey reduction” : 2882, 383-836, Michael reaction. : D912, o13%, O14 Oppenoucr oxidat 880, 887°, B88 + A number of rourrangemonta and also the aeetoncotie ester condensation aro included in the Namo Index for the convenience of the reader, Other reactions (including ring enlargement with diazomethane) for which mechanisms are given, ‘ill be found in the Index. ‘The asterisk indicates the page where the techaniama (ia outline) is described.NAME INDEX OF Pechmann restion « Perkin rencton Pinscol-pinacolone rearrangement Preshajew epoxidation reaction Reformataiy reaction Reimer Tieshann reaction Reeoamund redaction Scnmayer eacton Scheme resoton | SShmiot reaction or rearrangemont SShotten-Baursann reaction Scmuprotion Sommrlot renetion Stephen reaction Stabbe contianniion mann reaction Wilgerodt reaction Willameon synthesis Wohi Zigler reaction Wolf reetrangemone Wolf Rise rection Warts reaction Wart Fitlg reaction ORGANIC REACTIONS xxvii PAGE 853%, 854, 855 700, 107°, 708, 712-713 ‘340%, 350, 351 803", 604 8148, 875, 816 661, 692+, 708-705 =" 691, 609, 5028, 504, 600-603, 751 504°; 595, 609-612, 618 «917, 918%, 919 ‘582, 584, 780, 784 sige, 820, 830, 091, 902 ‘92,693, 700, 701 BIS*, 324, 691, 698 919, 920%, 92: 524, bon, 236, 237 508, 811, 512CHAPTER 1 ORY OF GENERAL TECHNIQUE ‘THEORY OF DISTILLATION _,l. Vapour pressure, If a liquid is admitted into a closed vacuous Space, it will evaporate or give off vapour until the latter attains a definite fresstire, which depends only upon the temperature, ‘The vapour is then said to be saturated. Experiment shows that at a given temperature TH Fressure inn cf Hercury a Temper Fig. 1,1. the vapour pressure of a liquid substance in contact with its own liquid isa constant quantity and is independent of the absolute amount of Liquid fand of vapour present in the system, ‘The vapour pressure is usually 12 PRACTICAL ORGANIC CHEMISTRY a expressed in terms of the height of @ mercury column which will produce an equivalent pressure, ‘The vapour pressure of a liquid increases with rising temperature. A few typical vapour pressure curves aro collected in Fig. 1,1, 1. When the vapour pressure becomes equal to the fotal pressure exerted on the surface of a liquid, the liquid boils, ic, the liquid is vaporised by bubbles formed within the liquid. When tho vapour pressure of the liquid is the same as the external pressure to which the liquid is subjected, the tem~ perature does not, asa rule, rise further. Ifthe supply of heat is increased, ‘the rate at which bubbles are formed is increased and the heat of vaporisa, tion is absorbed. ‘The bolling point of a liquid may be defined as the temperature at which the vapour pressure of the liquid is equal to the external pressure exerted at any point upon the liquid surface, ‘This extemal pressure may be exerted by atmospheric air, by other gases, by vapour and air, ete. ‘The boiling point at a pressure of 760 mm. of mercury, ‘orone standard atmosphere, may be termed the normal boiling point. If the pressure on the surfuce is reduced, say by connecting the vessel containing the liquid with a pump, the boiling point is lowered ; tho exact valuo may be obtained by reference to a vapour pressure curve (see, for example, Fig. J, 1,1). It is therefore necessary to specify the pressure in recording a boiling point: unless this is done, 760 mm, is understood. Advantage is taken of the lower boiling point under diminished pressure in the distillation of substances which decompose upon heating to the boiling point under atmospheric pressure ; thus, ethyl acetoacetate, which boils with decomposition at 180° under 760 mm. pressure, boils without de- ‘composition at 78° under 18 mm. pressure (usually written as 78°/18 mm.). 1,2. Calculation of the boiling point at selected pressures. One sometimes requires the boiling point of a liquid at a pressure which is nob recorded in the literature. ‘This can best be ealeulated from the vapour pressure temperature curve. For most practical purposes this may be assumed to have the form : logp= 4 42 where p is the vapour pressure, 7’ is the temperature on the absolute scale, and A and B are constants, If log p is plotted as ordinates against 1s abucsae, sought nw ie obtained, ‘Two vn of with the corresponding values of 7’ suffice. Values of p corresponding to any absolute temperature or vice versa can be obtained from the graph. A 111 was constructed, are shown in Fig.I,2,1; it will be seen that they approximate to straight lines. For distillations conducted at atmospheric pressure, the barometric pressures are rarely exactly 760 mm. and deviations may be as high as 20 mm. ‘To correct the observed boiling point to normal pressure (780 mm.), the following approximate expression may be used : At = 0-0012 (760 — p) (t+ 273), where At is the correction in degrees Centigrade to be applied to the tow typleal log p-2 diagrams, axing the data ftom which Fy3) THEORY OF GENERAL TECHNIQUE 3 observed boiling point t, and p is the barometric pressure, For water, alcohols, acids and other associated liquids, it is better to use the expression : ‘At =0-0010 (760 — p) (¢ +273). 1,3. Superheating and bumping. If a liquid is heated in a flask by means of a Bunsen burner and wire gauze placed below it, the formation of bubbles of vapour at the lower surface of the liquid in contact with the heated glass is facilitated by the presence of air dissolved in the liquid or adhering as a film to the glass and by roughness on the surface of the 49 ad 1 -Acetone lt mater W~Bromobenzene Fig. 12,1. glass, Ifa minute bubble of air is formed (this will be at atmospheric pressure), it will serve ns a nucleus for a larger bubble of vapour. At the boiling point the liquid (at 760 mm. vapour pressure itself) will deliver vapour in relatively large quantity to the air bubble, With the heat supply at hand, the total pressure inside the bubble soon rises above that of the atmosphere and is sufficient to overcome the pressure due to the column of liquid; a vapour bubble is then expelled. Hence, if a source of minute air bubbles or other nuclei is available in the liguid, boiling will proceed quietly. If, however, the liquid is largely free ftom air and ifthe walls of the flask are clean and very smooth, bubbles are formed with ‘greater difficulty and the temperature of the liquid may rise appreciably above the boiling point ; it is then said to be superheated. When a4 PRACTICAL ORGANIC CHEMISTRY it bubble does eventually form, the vapour pressure corresponding to the temperature of the liquid far exceeds the sum of the pressures of the stmosphere and of the column of liquid, hence ‘vapour is evelved, the Dubble increases in size rapidly and at the same time the temperature of the liquid falls slightly. ‘These experimental eonditions end. to irregular eballition and the liquid is sai to burp. Various methods are available for preventing, or at least considerably reducing, Bumping ina liquid, An Obvicus method is to surround the flask containing the liguid by a bath charged with a a temperature of which is not allowed to tise more than 20° above the boiling Point of the liquid Bubbles of vapour may now ns from points around The edge ofthe liquid and not only from the bottom ofthe flask. Further- tore, the danger of superheating is considerably reduced. ‘The procedure most frequently employed to prevent bumping of a liquid during distilation under atmospheric presoure is to adda Tow fragments of unglazed porous. porcelain (often termed “porous pot,” “boiling stones” or * boling chips "the term "porous pot wll be used frequently in this book).+ ‘These emit small quontities of air and promote regular ebulliion, Tt must be emphasised. that the. porous pot” iv added (othe cold liquid before distillation is commenced. ‘Under ho circumstances should “ porous pot” be dropped into a liquid which has already been heated to boiling : the sudden evolution of vapour may result in spray and sometimes of « large proportion of the Tuid being ejected from the mouth of the flask. “if the distillation has been interrupted, it is recommended thet two or three small fragments of fresh ‘porous pot” be added before the heating is resumed ; the “ porous pot "intially added, from which the ait has been pastialy removed by Heating, will probably be largely ineffective owing to their absorption of the liquid on cooling. ‘A usefil device to prevent bumping of liquide during distillation consists of a glass tube, 2-3 mm. fn diameter, bent in a U-form with one arm some: what shorter than the other; it should be long ‘enough to extend from the bottom of the flask for S short distance into the neck in order that it should remain in an upright position (Fig. 1,3, 1, a). IPfor ny reason a shorter U-tube i desied, a glass rod may be sealed on as in Fig- 1.3, 1,0. ‘the shor! frm of the U-tube should be jist above the lovel ofthe liquid in the lask, whilst the long arm should @—_«_Teston the bottom ofthe flask just above the source Fig.t.3,1. oF heat, With a large flask it ip advantageous to employ two or three U-tubes, the short arin of one should be just above the fluid lovel at the start of the distillation. the short arms of the other U-tubes should be of different lengths and below the initial level of the liquid saint Oi nd thor akan er ne eterna hi See le ae end apn pa ey pu ce Fe cla pha favo e mpercoled lige eps of hn ntasuperseced water MY4) THEORY OF GENERAL TECHNIQUE 5 Other aids for promoting regular boiling include the addition of the following :—fragments of pumice stone or of carborundum ; small strips of Teffon (a tetrafluoroethylene polymer) tape, ca. }" wide, or of shredded Teton (the strip may be washed with an organic solvent, dried and re- used) ; small pieces of platinum wire (use is made of the well-known property of platinum in absorbing large quantities of gases) ; sufficient glass wool to fill the flask and to rise 4-5 mm. above the surfuco of the liquid ; long capillary tubes sealed at a point about 0-5 mm. from the end (the short. capillary end is immersed in the liquid, thus filling the small cavity with air, which is evolved in fine bubbles when the liquid is heated). The boiling point of a pure liquid, if properly determined, has a definite and constant value at constant pressure, say, that of the atmosphere. ‘The boiling point of an impure liquid will depend to a large extent on the physical nature of the impurities. If all the impurities are non-volatile, {he liquid will have x constant boiling point and the impurities will remain behind when the liquid has been distilled. If, however, the impurities are themselves volatile, the boiling point may rise gradually as the liquid distils or it may remain constant at a particular stage of the distillation due to the formation of a constant boiling point. mixture of two oF more substances. ‘The separation of liquids by distillation forms the subject of tho next Section, 1,4. Fractional distillation. ‘The aim of distillation is the separation of & volatile liquid from a non-volatile substance or, more usually, the separation of two or moro liquids of different boiling point. ‘The latter is usually termed fractional distillation. ‘The theoretical treatment of fractional distillation requires a knowledge of the relation between the boiling points, or vapour pressures, of mixtures of the substances and their composition ;’if these curves are known, itis possible to predict whether the separation is dificult o easy or, indeed, whether it will be possible. ‘At the outset it wil be profitable to deal with an ideal solution possess- ing the following properties : (i) there is no heat effect, when the com- ponents are mixed ; (ii) there is no change in volume when the solution is formed from its components ; (iil) the vapour pressure of each com- ponent is equal to the vapour pressure of the pure substances multiplied by its mol fraction * in the solution. ‘The last-named property is merely an expression of Raoult’ law, viz.,the vapour pressure of a substance is pro- portional to the number of mols of the substance present in unit volume of the solution, applied to liquid-liquid systems, ‘Thus we may write : pam Kay @, where p, is the vapour pressure of the substance and z, is its mol fraction inthe solution. If, = I, i., we are dealing with the pure substance A, then p, = K = p,’, the vapour pressure of the puro substance at the given temperature. ' Substituting this value in equation (1), we have : M= 7 2 @. i.e, the vapour pressure of a component of a solution at a given temperature is equal to the vapour pressure of the pure substance multiplied by its mol fraction in the solution. This is another form of Raoult’s law. + Tho mol fraction of any co ato in defined aa the number of mols, or gram moleolea, ofthat constituent divided by the total number ef rls, or grain mle: len the mixta 26 PRACTICAL ORGANIC CHEMISTRY fia Let us consider a mixture forming an ideal solution, that is, an ideal liquid pair. Applying Raoult’s law to the two volatile components A and B, we have : marie and pe ‘The total pressure p will be P= Pat Pam Pa 24 Pe Boe ‘The vapour pressures are proportional to the mol fractions in the vapour ‘phase, hence the composition of this phase will be given by : a=? Pm er at Pe ‘The relative concentrations of either constituent, say B, in the vapour and liquid phases will be: (a. and ay Pa_ Pa Beth Pe -—___ , we et Pe be 1ce in the liquid phase x, -} 25 = 1. mn of B will be greater inthe vapour phase, and if py’ < py’, it will be less. ‘This may, perhaps, be made clear with the aid of an example. Let us assume that the two components A and B have vapour pressures of 60 and 100 mm. of mercury respectively, and that the mol fraction of A is 0-25 and of B is 0-75. ‘Then for the solution : Px =0-25 x 60 =15 mm. (Hg) and pp = 0-76 x 100 = 76 mm. (Hg). ‘The total pressure will be : p=. + px = 90 mm, (Hg). ‘The composition of the vapour phase will be 3° = 15/90 =0-167 and 7" = 75/90 = 0-893. ‘Thus a solution containing mol fractions of 0-25 and 0-76 of A and B respectively is in equilibrium with a vapour containing 16-7 and 88-3 mol per cent. of A and B respectively. ‘The component B with the higher vapour pressure is relatively more concentrated in the vapour phase than in the liquid phase. If the compositions of the vapour phaso for vatious mixtures of the same two components are calculated and plotted against the vapour pressures, a diagram having the general features shown in Fig. 1, 4,1 is obtained. The abscissae represent the composition of both the liquid and the vapour phases, and the ordinates the total vapour pressure of the liquid. ‘The curve labelled vapour gives tho composition of the vapour in equilibrium with the solution having the vapour pressure corresponding to the ordinate. ‘Thus the liquid with composition /, and vapour pressure pp represented by the point m is in equilibrium with vapour of composition 1’. Since the mixture is an ideal solution of the two liquids, the vapour Pressures are additive and the liquid vapour pressure- composition curve AmB is a straight line. ‘The composition of the vapour in equili-4] THEORY OF GENERAL TECHNIQUE 7 brium with the various mixtures is given by Am’B, falling below the liquid vapour pressure-composition line. Figure J, 4, 1 is therefore the vapour pressure diagram for an ideal liquid pair. ‘The diagram shows clearly that the vapour in equilibrium with the ideal solution of two liquids is richer in the more volatile component than is the solution ; it follows, therefore, that the two components could be separated’ by fractional distillation. Only a limited number of examples are known of mixtures which obey Raoult’s law over the whole range of concentration and give straight line plots of the vapour pressure (ordinates) against the composition of the liquid expressed in mol fractions (abscissae). ‘These include mhexane and n-heptane at 30°; ethyl bromide and ethyl iodide at 30°; n-butyl chloride and n-butyl bromide at 50°; and ethylene dibromide and_propy- Jono dibromide at 85°. In most | eases, however, li deviate from Raoult’s law. ‘The deviations may be either positive or negative, ie, the vapour pressure may be either greater or Jess than that calculated. If both components exhibit positive deviations (eg., carbon disulphide and acetone at 35°), the total vapour pressure curve will be greater than that calculated and the curve passes through a maxi- mum. If the two components show negative deviations (eg., ‘acetone and chloroform at 35°), 6 Yopou Pressure of A Vapour Pressure of the total vapour pressure curve Wo fraction of 8 vill be less than that calculated +—Mo! fraction ofA and the curve will pass through a Fig. 1.41. minimum. Itean be shown that ‘when the vapour pressure is a maximum or a minimum, the composition ofthe vapour is tho same as that ofthe liquid with which itisinequilibrium, The normal boiling point of a liquid is the temperature at which the vapour pressure of the liquid is equal to the pressure of the atmosphere. Hence for the study of fractional distillation it is better to construct diagram in which the boiling points are ordinates and the compositions tre abseissae at constant (i.., atmospheric) pressure. In the vapour pressure composition curves the vapour pressure is plotted against. the ‘composition at constant temperature, whereas in the boiling point~ composition curves the boiling point is plotted against. the composition at constant pressure. ‘The two curves are similar in type except that they are inverted (soe Figs. 1, 4,2 and I, 4,3 below). In the boiling point-composition diagram two’ curves are obtained, one giving the composition of the liquid and the other that of the vapour with which it's in equilibrium at the boiling point. ‘The vapour phase is relatively8 PRACTICAL ORGANIC CHEMISTRY a, richer in the component which results in lowering of the boiling point when added to the mixture, or, altematively, the liquid phase is richer in the component which raises the boiling point. ‘Three classes of curves will be considered : those in which (1) the boiling point rises steadily with change of composition from the moro volatile to the less volatile component, (2) the boiling point reaches a minimum, and (3) the boiling point reaches a maximum, (1) The boiling point increases regularly. The boiling point eom- position diagram for such a system is shown in Fig.., 4,2 (the eomple- mentary vapour pressure - composition diagram is depicted in Fig. Z,4, 3 for purposes of comparison only). Let us consider the behaviour of such 4 liquid pair upon distillation. If @ solution of composition Zy is heated, the vapour pressure will rise until at the point J it is equal to the pressure of the atmosphere, and boiling commences at temperature f.. ‘The eom= 5 B g £ é aber po ee om mis Canpetn Compton Fig. 14.2 Fig. 4,3 position of the vapour first distilling is V,; it is richer in A, the lower boiling point component, than was the original solution. As the boiling proceeds, the residue becomes increasingly richer in B, the higher boiling point component ; consequently the boiling point will rise, say, to f, and the composition of the residue will gradually change to Lg, whilst that of the distillate (vapour) will change from V, to V3. ‘Thus from a solution of initial concentration L,, a distillate is obtained of composition approxi mating to (V, + V,)/2 and a residue of composition Ly. ‘The distillation has thus effected a partial separation of A and B, and it is clear that by repeated distillation an almost complete separation of the two components can be made. For this purpose, each fraction collected between suitable temperature limits is redistilled ; with each fractionation the separation of the two components is improved. It is evident that the greater the slope of the boiling point curve, the greater is the difference in composition between the liquid and the vapour ; hence the greater the difference in tthe boiling points of the two liquids forming the mixture, the more easily can they be separated by distillation. In practice, it is usual to employ a fractionating column to reduce the4) THEORY OF GENERAL TECHNIQUE 9 number of distillations necessary for reasonably complete separation of the two liquids. A fractionating column is designed to provide @ con- timuous series of partial condensations of the vapour and partial vapor sations of the condensate and its effect is, indeed, similar to a number of istilations. The effect of partial condensation will bo evident 1, 4,2. Ifthe temperature of the vapour is lowered, it will partly condense giving a liquid richer in B and leaving the vapour richer in A. ‘The vapour passing up the column will accordingly contain more of A than did the vapour which left the boiling liquid, Similarly the liquid returning to the flask will contain relatively more of the less volatile component B. A fractionating column consists essentially of a long vertical tube through which the vapour passes upward and is partially condensed ; the condensate flows down the column and is returned eventually to the flask. Inside the column the returning liquid is brought into intimate contact with the ascending vapour and a heat interchange occurs whereby the vapour is enriched with the more volatile component A at the expense of the liquid in an attempt to reach equilibrium. ‘The conditions necessary for a good separation are :—(i) there should be a comparatively large amount of liquid continually returning through the column ; (ii) thorough, mixing of liquid and vapour ; and (iti) a largo active surface of contact, between liquid and vapour. "Excessive cooling should be avoided ; this dificulty is particularly apparent with liquids of high boiling point and may be overcome by suitably insulating or Ingaing the outer surface of the column or, if possible, by surrounding it with a vacuum jacket or an electrically heated jacket. Various types of laboratory fractionating columns are described in Sections 11,15-11,18. (2) Minimum boiling point. ‘Typical boiling point- composition curves for systems of this kind aro shown in Fig.,4,4. If a solution of composition L, is heated, the vapour pressure will rise until at the point jit i equal to the pressure of the atmosphere and boiling commences at ty. ‘The composition of the vapour first distilling is V,. As the boiling proceeds the temperature rises from f, to fy, and during this period dis- tilates with compositions ranging from V; to V, will be obtained. If the distillate be redistlled, the vapour approaches the composition of the nminimum boiling point system, as can be seen from the figure. Hence fractional distillation will result in a distillate of composition Zyg, although the final residue will approach A. Similarly, a solution of composition 1 when distilled commences to boil at f', ic., at a temperature 4’ the ‘vapour (and therefore the distillate) will have the composition V,’. As the distillation continues the composition of the vapour changes to V,’ and the liquid to L,’. Fractional distillation will, in this ease, yield a solution ‘of composition Lay, and the residue will approach B. ‘Tho liquid mixture can then be separated only into the component present. in excess (either A or B) and the mixture of minimum boiling point. ‘Phe liquid repre- tented by Ly, will distil over completely without change of composition since at the boiling point the vapour has the same composition as the liquid. Such systems which distil unchanged are called azeotropic mixtures (Greek : to boil unchanged). ‘The composition and boiling point of auch constant boiling point. mixtures vary with the pressure and consequently they are not chemical eompounds,lo PRACTICAL ORGANIC CHEMISTRY a Composition Fig. 1,4, 4. ‘Examples of azeotropic mixtures of minimum boiling point are collected in Table, 4, A. ‘Tame J,4,A. Azgormorio Mrxronss oy Mnmeow Boru Poner f Br.or | % oF A Commoner A Courowmxr B | Azzormorro (ot wr) | | |Mrcrome | Mocrone | Water, 100-0° | ethyl alcohol, 78-3" 78-15" | Water, 100-0" | eobopyialoshel, 82:4* foe Water, 100:0° Props alah, 97:2" ar | Water, 100-0 Totetlatyl alconsh 82:0 | 19: qo0-0" Srisine, 118" Ethyl iodide, 72-3° Methyl aootate, 57:0° Ethyl avotate, 77-2" Butyrie aoid, 163-5 Propionic acid, 140-7" cyeloHiexane, 80:8° Bonzeno, 80:2 ‘Toluene, 110-6" | Methyl elechét, 647" | Chloroform, 61-2° Ethyl aleohol, 783" | Chloroform, 61:2" Ethyl aleohol, 38-3 | Methyl ethyl ketone, 79-6* Methyl aleohcl, 64:7" | Methylal, 42-2" Aste seid, 16-6" | Tone, 110-6" 2, Methyl iodide, 44-9" 30. | (3) Maximum boiling point. A typical boiling point - composition diagram is shown in Fig. /, 4,5. By reasoning analogous to that given4) THEORY OF GENERAL TECHNIQUE. n ander (2), it is evident that fractional distillation of a liquid mixture of composition D, will yield ultimately @ specimen of almost pure A and a residue of composition Ly, which will eventually distil unchanged. Simi larly, a liquid mixture of composition 1,’ will give ultimately pure B and a residue Zy,, which will itself distil unchanged, Thus distillation will afford ultimately the component present in exeess of the constant boiling point mixture and the constant boiling point mixture itself. Te Lo. Temperstare va Composition Fig. 14.5. wwe Tg WW ete Examples of azeotropic mixtures of maximum boiling point aro tabulated below; these are not as numerous as those of minimum boiling point, Tastx 1,4, B. Azeomorro Mexronus or Maxncox Bou Ponce Water, 100-0" Formic noid, 100-8" 06 | Water, 100-0" Hydroftuorio acid, 19-4° 37 Water, 100°0" | Hydrochlorio acid, — 84. 2022 | Water, 100-0" | Mydrobromie eaid, — 73° 08 7 10:0" Hydriodie acid, — 51-0 Water, 100-0" | Nitric wetd, 86:0" ot ‘Water, 100-0" | Shlplhurie de mp, 10-9" oes | | Water, 100-0° | Porehtoric wcid, 110-0" 18 | Aettone, 584° Chloroform, 61:3 80 ‘enti eeid, 118:5° | Pyridine, 113-5" 85 | Chloroform, 61-2" | Mothyl wostate, 57-0" 2 Phenol, 181°5° | Aniline, 184-4" 582 PRACTICAL ORGANIC CHEMISTRY a 1,5. The breaking up of azeotropic mixtures. The behaviour of constant boiling point mixtures simulates that of a pure compound, because the composition of the liquid phase is identical with that of the vapour phase. ‘The composition, hiowever, depends upon the pressure at shih the distillation is conducted and also rarely corresponds to stoichio- metric proportions. ‘The methods adopted in practice will of necessity depend upon the nature of the components of the binary azeotropic mixture, and include :-— (1) Distillation with @ third substance which alters the vapour pressure ratios in the azeotrope. This method is of particular value in industry for the production of absolute ethyl alcohol from the azeotropic mixture containing 95-6 per cent. of alcohol or from aqueous alcohol. Upon the addition of benzene and distillation through a suitable fractionating apparatus, a temary azcotropic mixture of water, alcohol and benzene ‘of minimutn boiling point, 64:85°, and containing 7-4 per cent. of water, 18-5 per cent. of alcohol and 74-1 per cent. of benzene passes over first, followed by @ second azeotropie mixture of benzene and alcohol (b-p. 68-25", containing 32-4 per cent. of benzene), and finally absolute ethyl alcohol. By carrying out the fractional distillation under pressure, the water content of the ternary mixture is increased. (2) Chemical methods may be employed if the reagent attacks only one of the components. ‘Thus quicklime may be employed for the removal of water in the preparation of absolute ethyl alcohol. Also aromatic and unsaturated hydrocarbons may be removed from mixtures with saturated hydrocarbons by sulphonation. (3) Preferential adsorption of one of the components may be used for the same purpose. Charcoal or silica gel may be employed to adsorb one of the constituents of an azeotrope in preference to the other. If the adsorbate is readily recoverable, the process will have practical applications. (4) Fractional extraction may sometimes find application, since the ‘components distribute themselves in a different proportion in the solvent (compare Section 11,44). (6) Fractional erystallisation is occasionally employed. ‘The mixture is dissolved in o suitable solvent, the whole frozen, and then allowed to melt slowly in a centrifuge in order that the successive fractions may be removed as they are formed. The various melts are then fractionally distilled. If necessary, the fractional erystallisation may be repeated. 1,6. Steam Distillation, Distillation of a Pair of Immiscible Liquids. Steam distillation is a method for the isolation and purification of substances, It is applicable to liquids which are usually regarded as completely immiscible or to liquids which are miscible to only a very limited extent. In the following discussion it will be assumed that the liguids are completely immiscible. ‘The saturated vapours of such completely immiscible liquids follow Dalton's law of partial pressur (1801), which may be stated : when two or more gases or vapours which do not react chemically with ono another are mixed at constant tempera- ture each gas exerts the same pressure as if it alone were present and that6 THEORY OF GENERAL TECHNIQUE 13 the sum of these pressures is equal to the total pressure exerted by the system. This may be expressed Pepmtmt. . + +h where P is the total pressure and p,, py, ete., are the partial pressures of the components. Ifa mixture of two immiscible liquids be distilled, the boiling point will be the temperature at which the sum of the vapour pressures is equal to that of the atmosphere. ‘This temperature will bo lower than the boiling point of the more volatile component. Since one of the liquids is water, steam distillation at atmospheric pressure will result in the reparation of the higher boiling component at a temperature below 100°—a considerable advantage if the compound decomposes at or neat its own individual boiling point ; the process woild also be useful for teparation from non-volatile or from undesirable (e.., tarry) substances. When a mixture of immiscible liquids is distilled, the boiling point of the nixture remains constant until one of the components has been almost completely removed (since the total vapour pressure is independent of the relative amounts of the two liquids) : the boiling point then rises to that of the liquid remaining in the flask. ‘The vapour passing over from such a mixture contains all the components in proportion by volume to the relative vapour pressure of each. ‘The composition of the vapour can easily be calculated as follows :— Assuming that the gas laws are applicable, it follows that the number of molecules of each component in the vapour will be proportional to its partial pressure, i.e., to the vapour pressure of the pure liquid at that temperature. If p, and py are the vapour pressures of the two liquids Avand B at the boiling point of the mixture, then the total pressure P is given by PaptPe Me ‘and the composition of the vapour by = Tyla = Pala @, where n, and ng are the number of mols of the two substances in a fiven volume of the vapour phase. But m,— 4/M, and m, = 104/Myy there w is the weight of substance in a given volume of the vapour, and Mis tho molecular weight. Hence : wy Amy _ Map wy Many Mops ‘The relative weights of the two components of the vapour phase will be identical with the relative weights in the distillate, i.e, the weights of the two liquids collecting in the receiver are directly proportional to their vapour pressures and their molecular weights. ‘Equation (3) indicates the great value of steam distillation, since the smaller the product M,p,, the langor is the value of wy. Water has a mall molecular weight’ and a comparatively moderate vapour pressure, fo that its value of 4Y,p, is low. This permits substances of high mole- falar weight and of low vapour pressure to be separated economically onthe technical scale. ‘The following figures are given by 8. Young (1922), @).“ PRACTICAL ORGANIC CHEMISTRY ts Ls carne. | 150 | za | om eetale ue | aie | Rm: L _ ‘As an example of steam distillation, let us consider bromobenzene which has a normal boiling point of 155°. ‘The vapour pressures of water and bromobenzene at different temperatures are given in the following table. | Varoon Passavn | Teurmnarons | Waren (p,) Baowonexzewe | Mexrume es) (wae tps) aor 32 mm em. | o 55 min. inn | oor 22 mm: tom, oo 149 mm, 2m, | ter 239 min ten ar 38 mim, Strom, oor 628 um, $8 rm, a 34 man, ue mn 00 10 an. Mi i. If we plot these as in Fig. J, 6, 1 we find that the vapour pressure of the mixture attains 760 mm. at a temperature of 95-3°; this is there- fore the boiling point of the mixture. At this temperature Pp, = 641 mm, and p, = 119 mm, ‘The molecular weights of the two liquids are 18 and 157 respec- tively. Substituting these values in equation (3), we havc wy 64 x 18 _ 6-2 vw, = 119 x 157 = 10-0 ‘Thus for every 6-2 grams of water collectedinthereceiver 10-Ograms of bromobenzene are obtained (or the distillate contains 62 per cent. by weight of bromobenzene) in spite of the fact that bromo- Zo’ benzene has only 119/641 of the Tempercture nC vapour pressure of water at Fig. 1,6, the boiling point of the mixture, s Pressure in mm of Mercury Bes gs gea THEORY OF GENERAL TECHNIQUE 6 Similarly it is found that for chlorobenzene the boiling point of the mixture (Tyogun) 18 90°3°, py = 530, py = 230, Mf, = 112-5, and the distillate contains 71 per’ cent. of chlorobenzene by weight ; for iodobenzene, the boiling point of the mixture is 98-2", p, = 712, py 48, M, = 204, giving a distillate containing 43 per cent. by weight of fodobenzene, For aniline Tye i 98°5°, p, = 711, py = 43, My = 93, fand the calculated value is 23 per cent. of aniline by weight: the proportion found experimentally is somewhat lower because aniline is appreciably soluble in water and the vapour pressure is slightly reduced. 17. Distillation with superheated steam. Consideration of ¢ tion (3) (Section 1,6) indicates that the proportion of the higher boiling point component in the steam distillate can be raised by increasing the Fig J, 7,1. ‘vapour pressure of this component relative to water. ‘This may be done with superheated (or high pressure) steam. ‘The effect of superheated steam may be illustrated by reference to benzaldehyde, which boils at 178° at 760 mm. It distils with steam at 91-9° (p, = 703-5 mm. and p, = 66-5 mm.) and the distillate contains 32-1 per cent, of benzaldehyde by weight. If one employs steam super- heated to 133°, tho vapour pressure of benzaldehyde (extrapolated from the boiling point pressure curve) is 220 mm.: hence p, = 540 (water), , = 220 (benzaldehyde), and wy _ 540 x 18 _ 41-7 w, ~ 220 x 106 ~ 100 ie, the distillate contains 70-6 per cent. of benzaldehyde by weight. ‘This compares with 31-4 per cent. with steam at 100° and one atmosphere,18 PRACTICAL ORGANIC CHEMISTRY a, ‘The use of superheated steam has the advantage that less condensation takes place thus obviating the use of supplementary heat in the vessel containing the substance; beyond this no advantage over steam used under ordinary pressure will result 60 long as condensed water is present. If all condensation of the steam is prevented (e4., by surrounding the flask by a bath of liquid at the same temperature as the superheated steam), the higher temperature of the superheated steam will result in an increase in the proportion of the higher boiling point. component in the distillate In practice superheated steam is generally employed for substances with a low vapour pressure (< 5-1 mm.) at 100°. ‘Thus in the recovery of the products of nitration or aromatic compounds, the ortho derivative (eg., enitrophenol) ean be removed by ordinary steam distillation ; the temperature may then be raised, and the para compound distilled. ‘The upper limit of temperature will of course be controlled by the stability of the compound. A convenient apparatus for distillation in superheated steam (due to A. A. Morton) is shown in Fig. 1,7, 1. ‘The Pyrex tube B, of 10 mm, diameter or larger, is wrapped with a few layers of wire gauze and heated with a wing-topped bumer, the gauze being supported by a clamp to prevent sagging of the tube at the high temperature ; C is a thermometer and A is a trap for condensed water. »‘The flask is heated in an oil bath to approximately the same temperature as the superheated steam, Tt will be observed that the superheater is close to the steam inlet tube, thus reducing the cooling of the steam, before it enters the flask, to a minimum. A commercial apparatus, constructed of metal (the Fisher superheater), is shown in Fig. 1, 7, 2.8) THEORY OF GENERAL TECHNIQUE " SOLUTIONS OF LIQUIDS IN LIQUIDS 18. Partially miscible liquids. Critical solution temperature. Some liquids are practically immiscible (e.g., water and mercury), whilst others (eg., water and ethyl alcohol or acetone) mix with one another in all proportions. Many examples are known, however, in which the liquids ate partially miscible with one another. If, for example, water be added to ether or if ether be added to water and the mixture shaken, solution will take place up to a eertain point ; beyond this point further addition of water on the one hand, or of ether on the other, will result in the formation of two liquid layers, one consisting of a saturated solution of water in ether and the other a saturated solution of ether in water. ‘Two such mutually saturated solutions in equilibrium at a particular temperature are called conjugate solutions. It must be mentioned that there is no easential theoretical difference between liquids of partial and complete miscibility for, as will be shown below, the one may pass into the other with change of experimental conditions, such as temperature and, Jess frequently, of pressure. ‘Three types of liquid/liquid systems are commonly encountered. ‘The first type hheniol and water) is characterised by increasing mutual solubility with rise of temperature. ‘Thus when phenol is added to water at the ordinary temperature, a homogeneous liquid is produced. When the concentration of the phenol in tho solution has risen to about 8 per cent., the addition of more phenol results in the formation of a second liquid phase, which may be regarded as @ solution of water in phenol. If now the temperature is raised, the second liquid phase will disappear tand more phenol must be added to produce « separation of the liquid into two layers. By increasing the amount of phenol in this way and observ- ing the temperature at which the two layers disappear, the so-called solubility curve of phenol in water may be determined.’ In a similar manner the solubility curve of water in liquid phenol may be obtained, and it is found that the solubility also increases with rise of temperature Its clear that since, with rise of temperature, the concentration of water in the phenol layer and also of phenol in the water layer increases, tho compositions of the two conjugate solutions become more and more nearly the same, and at « certain temperature the two solutions become identical in composition. ‘The temperature at which the two layers become iden- tical in composition and are, in fact, one layer is known as the critical solution temperature (D. 0. Masson, 1891) or the consolute tempera- ture (W. D. Bancroft, 1894) of the system. Above this temperature the two liquids are miscible in all proportions. Some experimental results for the mutual solubility of phenol in water are plotted in Fig. I, 8,1; these lead to a critical solution temperature of 69-9" and a. critical concentration of 34-0 per cent. of phenol. Fig. 1, 8,1 enables one to predict the effect of bringing together phenol and’ water in any given quantities at any temperature. If the resulting mixture is represented by a point in the arca enclosed by the solubility curve, separation into two layers will take place, whereas if the total composition of the mixture and the temperature is expressed by a point lying outside the solubility curve a clear homogeneous solution will result,18 PRACTICAL ORGANIC CHEMISTRY a, Other pairs of liquids which exhibit an upper consolute temperature are methyl alcohol cyclohexane (CS.T. 491°; critical composition 29 per cent. by weight of methyl alcohol) ; isopentane - phenol (63-5° ; ‘81 per cent. of isopentane); and carbon disulphide- methyl alcohol (40-5° ; 80 per cent. of carbon disulphide : g Two liquid phases a & i ‘er cent Phono! Fig. 1,8, ‘The second type of system is characterised by decreasing mutual solu- bility with rise of temperature. As the temperature is lowered the mutual solubilities increase and below a certain critical temperature the two liquids become miscible in all proportions. A typical example triethylamine and water. ‘The behaviour of this system with reapect to We Tuo Liquld phoses Tempercture One tiguid phase Per cant Triethylamine Fig. 1, 8, 2. concentration and temperature is shown in Fig., 8,2; the critical solition temperature is 18-5°. Other pairs of liquids which exhibit a lower critical solution temperature are : diethylamine - water (C.8.T. 43°; 13 per cent, by weight of diethylamine) ; -col cent.) ; I-methylpiperidine - water (48° ; 5 per cent.).8 THEORY OF GENERAL TECHNIQUE 19 ‘The third type of system gives a closed solubility curve and therefore possesses both an upper and lower critical solution temperature. The first ease of this type to be established was that of nicotine and water ; the solubility curve is illustrated in Fig.1, 8,3. ‘The lower and upper consolute temperatures are 60-8° and 208" respectively ; below the former and above the latter the two liquids are completely miscible. One Liquid phase “ Tuo ligand phases, Temperoture as One Liguia phase a Per cont Meotine Fig. 1.8, 3. Tt should be noted that the modern viow is that all partially miscible liquids should have both a lower and upper critical solution temperature so that all tuch systems really belong to one class. A closed solubility curve is not obtained in all cases because thé physical conditions under normal pressure prevent this. ‘Thus with liquids postessing a lower C:8.T., the critical tem- perature (the critical point for the liquid - vapour systemn for each component, fe, the maximum temperature at which liquefaction is possible) may be reiched before the consolute temperature, Similarly for liquids with an upper CST, one or both of the liquids may freeze before the lower C.S:T. is attained, Many pairs of partially miscible liquids possess neither a lower nor an upper G87 for reasons outlined in the previous paragraph... ‘Thus consider the two liguid phases from the two components water and diethyl ether. Upon cooling the system at constant pressure, a point will be reached when a third phase, jee, will form, thus rendering the production of a lower C.8.T. impossible. Likewise, if the temperature of the two layers is raised, the eritical point for the ether-rich layer will be reached while the two liquid phases have different ‘compositions. Above the eritical point the ether-rich layer will be converted into vapour, and hence the system will be converted into a water-rich liquid and an ether-rich vaponr; the upper CST. cannot therefore be stiainod.20 PRACTICAL ORGANIC CHEMISTRY is A few systems with both lower and upper critical solution temperatures are tabulated below. Svere (4,2) Lower C3 Water :2:mothylpiperidine . 0° Water : S-methylpiperidine ~ 50" Water: -methylpiperidina sr Water :f-picoling Water: aaclutiding || : 45 Glyeorol:m-toluidine > : P 1,9. Influence of added substances upon the critical solution temperature. For a given pressure the C.S.T. is a perfectly defined point. Tt is, however, affected to a very marked extent by the addition of quite a small quantity of a foreign substance (impurity), which dis- solves either in one or both of the partially miscible liquids. "The deter- mination of the consolute temperature may therefore be used for testing the purity of liquids. ‘The upper consolute temperature is generally employed for this purpose, If the third substance dissolves in only one of the liquids, it is found that their mutual solubilities are decreased and the UST. is generally raised. For example, a concentration of 0-15 mol of potassium chloride per litre of water raises the C.8.1.. of the water - phenol system by about. 12°; a similar concentration of naphthalene in the phenol produces a rise of about 30°, If the third substance dissolves in both liquids (and the solubility in each of the liquids is of the same order), the mutual solubility of the liquids will be increased and an upper C.-T, will be lowered, as is the ease when succinic acid or sodium oleato is added to the phenol - water system. A 0-083 molar solution of sodium oleate lowers the C.8.T. by 86-7° this lange effect has been applied industrially in the preparation of the disinfectant sold under the name of “Lysol.” Mixtures of tar acids (phenol -+ cresols) do not mix completely with water at the ordinary temperature, but the addition of a small amount of soap (= sodium oleate) lowers the miscibility temperature so that “Lysol” exists as a clear liquid at the ordinary temperature. ‘An important application of the critical solution temperature is to the determination of the water content in such substances as methyl and ethyl alcohols. Here the system is usually the alcohol and a hydro: carbon, such as n-hexane or dicyelohexyl; the water is, of course, insoluble in the hydrocarbon. Thus, the methyl aleohol - cyclohexane system has a C.S.T. of 45+5° and even 0-01 per cent. of water produces a rise of 0-15" in the C.8.T. The experimental details are given below. For methyl alcohol, two volumes of synthetic n-hexane, b.p, 03:6-69-0° (uncorr.), and one volume of the alcohol to be tested are mixed and the homogeneous mixture is cooled in ice until the appearance of a cloudiness. A thermometer is placed in the solution, which is allowed to warm gradu ally to the temperature at which the second phase disappears. ‘The10) THEORY OF GENERAL TECHNIQUE a1 temperature at which the solution just becomes homogeneous is taken as the critical solution temperature. ‘The same result is obtained by observing the temperature at which the second phase appears. ‘The water content may then be deduced with the aid of the following table, and checked, if desired, by a determination of the density (Section X12). Powis ov CHAOHL (%) ose. I ay 100-0 0-79578 99-80. | 0-79634 99-65, | 0-70676 99-50 | o-79i18 99-35, 41-00 | 0.79760 99-45 45-00 | 9-70845, 98-69) 45-00 | o-70047 usar 46. | 9-S0026 88-01 48-05, | v-S0140, 74s 50-15 -s0292 713 a 0-80390 For ethyl alcohol, two volumes of dicyelohexyl * are mixed with one volume of the alcohol, a thermometer is introduced, and the mixture heated until it becomes clear. 'The solution is then slowly cooled, with constant stirring, and the temperature is determined at which the opales- cent solution suddenly becomes turbid so that the immersed portion of the mercury thread of the thermometer is no longer clearly visible. This, is the C.S.T. ‘The water content may then be evaluated by reference to the following table, Poniry oF GyH,0H (%) csr, ae 100-0 aaa 078984 90-9 264 0.78968 an ara 078987 a7 20:3 079028 99-6 51.0 0-79059 99-5, B28. 0-70089 99:0 a0 0-79243 98:5 20 o-79348 ‘THEORY OF MELTING AND FREEZING 1,10, Melting point and vapour pressure. ‘The melting point of a crystalline solid is the temperature at which the solid begins to change into liquid under a pressure of one atmosphere. For pure substances, the change from the solid to the liquid stato is quito sharp (within 0-5°), hence the temperature is valuable for purposes of identification. More- over, the melting point is considerably infhienced by the presence of other ‘+ Thinmaay bo propared by the catalytic reduction of pure diphunyl c0e Section 1,150)22 PRACTICAL ORGANIC CHEMISTRY a substances, and it is therefore an important criterion of purity. If the liquid is cooled, solidification will occur at the same temperature,* and for a pare substance the melting point and freezing point ate identical, ‘The freezing point is usually defined as the temperature at which both liguid and solid ean exist in contact with each other under a total pressure of one atmosphere. ‘The reason for the constancy and sharpness of the melting point of a pure orystalline solid can be appreciated upon reference to Fig. , 10, 1, in which (a) is the vapour pressure curve of the solid and (b) that of the liquid form of the substance. Let us imagine a vessel, maintained at constant temperature, completely filled with a mixture of the above liquid ‘and solid. ‘The molecules of the solid can only pass into the liquid and the molecules of the liquid only into the solid. "We may visualise two com- petitive processes taking place : (i) the solid attempting to “ evaporate” but it can only pass into the liquid, and (ii) the liquid attempting to “distil” but it ean only pass into the solid. If process (i) is faster, the solid will melt, whereas if process (ii) proceeds with greater speed the sod Se guid é i é i : , z 3 § 2 _ we SO Temparctare Temperet 8 ‘Temperature (0) ) «) Fig. 1, 10, 1. substance would completely solidify. ‘To decide which process is likely to occur at particular temperature, curve (a) must be superimposed ‘upon curve (6) thus giving curve (¢). ‘The rate of riso of vapour pressure ‘with temperature is greater for the solid than for the liquid, consequently the two curves will intersect. At the intersection (and only at this tem- perature), both solid and liquid ean cooxist ; this is therefore the freezing point or melting point since these two constants are identical for a pure substance. Provided the pressure is atmospheric, the temperature A is tan absolute constant. If the temperaturo is less than A, the liquid will pass more rapidly into solid than the solid into liquid ‘and hence the substance will remain solid, whilst for temperatures greater than M the id, having the greater vapour pressure, will pass more rapidly into the liquid phase. It is only at the temperature IM, ‘at which the vapour pressures of the liquid and the solid are equal in magnitude, tnat the Fates of transformation are identical and both liquid and solid can co- exist, provided the temperature is maintained constant. As soon as the + A liquid ean sometimes be supercooled, i, the tomperstire can be reduced below the freering point without said separating, bit aa enon as asd dows ppoar ie tomperceare ‘immediately rise tothe tru freeding pose,ny THEORY OF GENERAL TECHNIQUE 23 temperature is raised even a fraction of a degree above Mf, the solid will be completely converted into the liquid phase, assuming of course that suffi- cient time is allowed for the transformation to take place. This is why the rate of rise of temperature in the vicinity of the melting point must be small (say, 1-2° per minute) for an accurate determination of this constant. It is a well-known fact that substances like water and acetic acid can be cooled below the freezing point : in this condition they are said to be supercooled (compare supersaturated golution). Such supercooled sub- stances have vapour pressures which change in a normal manner with temperature: the vapour pressure curve is represented by the dotted line AEZ/—a continuation of ML. ‘The curve ML/ lies above the vapour pressure curve of the solid and it is apparent that the vapour pressure of the supersaturated liquid is greater than that of the solid. ‘Tho super- cooled liquid is in a condition of metastability. As soon as crystallisation seta in, the temperature rises to the truo freezing or melting point. Tt will be observed that no dotted continuation of the vapour pressure carve of the solid is shown ; this would mean a suspended transformation in the change from the solid to the liquid state. Such a change has not been observed nor is it theoretically possible. I11. Effect of impurities upon the melting point. Let us take a specific example and examine the effect of the addition of a small quantity of naphthalene to an equilibrium mi ture of pure solid and liquid «-naphthol at the temperature of the true melting point (95-5°) at atmospheric pressure. ‘The naphthalene will dissolve in t liguid anaphthol and, according to Raoult’s law, the vapour pressure of the latter will bo reduced. Hence eenaphthol will pass preferentially into tho liquid phase and, if the external temperature is maintained at 95-65°, the ultimate result will bethe complete melt Vopour Pressure ing ofthe solid «-naphthol; since melting ° Temperature requires heat and no heat is imparted to the aystem, the temperature will fall. Fig. 1, 1,14 ‘The effect can easily be interpreted by reference to Fig. J, 1,1. ‘The initial state of the system is represented by M. Upon the’ addition of a small amount of the second substance, the vapour pressure of the liguid first falls to A. Now a solid phaso with vapour pressure M cannot coexist with a liquid phase with lower vapour pressure A. ‘The solid represented by A will therefore melt and tend to pass into the condition expressed by A. However, in melting heat is absorbed, and the temperature will consequently fall. ‘Thus the vapour pressures of the solid Mf and the liquid will fall along their respective vapour pressure curves, which will intersect at M,. At Mf, equilibrium results and no further change will take placo; here tolid e-naphthol and the solution of naphthalene in «naphthol may coexist indefinitely—this, it will be observed, is below the melting point of the pure substance («-naphthol). Further addition of naphthalenem PRACTICAL ORGANIC CHEMISTRY a will result in the depression of the melting point of a-naphthol to points represented by M,, My, ete. ; the curve through these points indicates the temperatures at which solid «naphthol can cocxist with solutions of increasing naphthalene content. It is natural to enquire as to how far the melting point may be depressed by additions of the second substance. The limiting temperature M, is known as the eutectic point ; it is the temperature below which not even the impure liquid can exist. Further cooling merely resulta in both components solidifying completely. ‘A somewhat different method of plotting the results will help the reader to appreciate the significance of tho eutectic temperature, In Fig. J, 11, 2 melting points are plotted against composition.* ‘The curve AC portrays the decreasing melting point of s-naphthol as naphthalene is added up to a mol fraction of 0-605. ‘The curve BC represents the 05 5 & ie melting points of naphthalene with x-naphthol regarded as the “ foreign ingredient” up to a mol fraction of 0-395 of «naphthol. ‘The curves intersect at C giving a eutectic temperature of 61-0°. 1,12. System in which the solid phases consist of the pure com- ponents and the components are completely miscible in the liquid phase. We may now conveniently consider the general case of a system in which the two components A and B are completely miscible in the liquid state and the solid phases consist of the pure components. ‘The equilibrium diagram is shown in Fig.1, 12, 1. Here the points A and B are the melting points of the pure components A and B respectively. If the freezing points of a series of liquid mixtures, varying in composition from pure A to pure B, are determined, the two curves represented by AC and BC will bo obtained. ‘The curve AC expresses the compositions of solutions which are in equilibrium, at different temperatures, with the solid component A, and, likewise, the curve BC denotes the compositions * Froqueatly composition i exprossed in rol fractions of in, mol Grastions x 100, ‘ie, molecular composition x 100 compare footnote to Section LV).2 THEORY OF GENERAL TECHNIQUE 25 of solutions in equilibrium with the solid B. At the point of intersection 4 liquid solution of definite composition corresponding with the point C. This point is called the eutectic point (reek : easy melting), and rep sents the temperature and composition at which the system liquid - solid A-solid B can exist in equilibrium ; in short, it gives the temperature and composition of the system when both components erystallise out simultaneously. This solid mixture is known as the eutectic mixture. Tt has a fixed composition and melts and freezes, like a pure substance, at a definite temperature. This temperature is the eutectic temperature and ia always the lowest freezing point of the whole series of mixtures of A and B. The eutectic mixture is not, however, a definite chemical compound because (i) separate crystals of the two components can be seenunder themicroscope and (ii) it rarely corre- sponds to the exact com- position of a simple chemical compound; itis, in fact, an intimate mechanical mixture or conglomerate of the two solid components. If a liquid solution having a composition represented bya point lying to the left of the eutectic point C be cooled, the solid com- — .oza aie ponent A will erystallise 8 Composition oA out (it is assumed that Fig. 1.12, supersaturation is ex- cluded) when the temperature reaches the point on the curve AC corre- sponding with the initial composition of the solution, If the cooling be continued, more and more of the component will separate and the compo- sition of the solution will change in the direction of . When the composition corresponding to the point C is reached, solid B, also, can crystallise out. Ifwithdrawal of heat from the system be continued, both solid. and solid B will separate while the temperature remains constant. Since, according tothe phase rule (compare Section 1,20), the composition of the solution at the point must remain constant, it follows that the components 4 and B must crystallise from the eutectic solution in constant proportions. In a similar manner, if a liquid having a composition represented by a point to the right.of C be cooled, the solid B will separate and the composition of the solution will change in the direction of C. At G, solid A will also crystallise out, and the temperature and composition of the solution will, remain constant whilst the solid components crystallise out as a eutectic ure. If a liquid mixture of composition denoted by the eutectic point C be cooled, no solid will separate until the eutectic temperature D is reached and then the eutectio mixture will crystallise out. Lguia Temperoture Aetiguia Ae Eutectic B+ Eutectic6 PRACTICAL ORGANIC CHEMISTRY n It is convenient, when dealing with mixtures, to call the temperature ‘at which the solid commences to crystallise from the liquid, the freezing int of the mixture, and to term the temperature at which the solid mixture begins to liquefy the melting point of the mixture. ‘The com- plete equilibrium diagram usually includes two curves, which are called liquidus and solidus respectively. ‘The liquidus (or liquidus curve) is the temperature - composition curve of the liquid phase and is therefore the freezing point curve; it represents “the beginning of freezing.” ‘The solidus (or solidus curve) is the temperature - composition curve of the solid mixture and is therefore the melting point curve ; it corresponds to the “beginning of melting ” on heating or to the “ end of freezing ” on cooling the system. In Fig. f, 12, 1 the liquidus curvo is ACB, whilst the solidus curveis ADCEB. ‘These curves divide the figure into regions which contain the phases indicated in the diagram, and the composition of the system represented by any point can be easily ascertained. ‘Thus the point (Fig. J, 2, 1) is a mixture of solid B (= y) and liquid of composition 2 : the proportion of liquid to solid is given by the ratio of the distance zy/z2. 1,13. Construction of equilibrium diagrams. It is interesting to consider how a complete equilibrium diagram (including solidus and a fron oy reeng (est, ay seca [se eras Temperotare Temperature Temperature ¥ | Tine Time Time a w ay Fig. 1,28, 1. liquidus curves) may be constructed. For simplicity, only the system considered in the previous Section will be studied. ‘The procedure is known as the cooling curve method. When o pure substance is allowed to cool slowly and the temperature observed at definite intervals of time, cooling curve may be constructed, eg., ab in Fig. 1, 13, 1,1, When the freezing point is reached, if supercooling is absent, solid will commence to separate out and the ‘temperature will remain constant until all the liguid has solidified (6c in Fig.1,13,1,i). With further cooling of the solid phase, the temperature will fall’ steadily as indicated by ed. If, however, agolution is allo;sed to cool slowly and the cooling curve similarly determined, a continuous curve ef (Fig. I, 13, 1, ii) is obtained as long a the solution is entirely liquid. When a solid phase commences to form, the heat of fusion will be liberated so that at the point f the rate of cooling will be checked. Since the composition of the solution changes with the separation of the solid phase, the temperature will not remain constant but will gradually fall until the eutectic is reached (fg). At the eutectic13) THEORY OF GENERAL TECHNIQUE 7 point both components crystallise out as a eutectic mixture and the temperature remains constant until complete solidification has occurred (line gh). After complete solidification of the mixture the fall in tempera- ture of the system becomes uniform (lino hi) until the room temperature is reached. It is clear from what has already been said that the cooling curve of the eutectic mixture will be similar to (i)-—that of a pure sub- stance, ‘The pointa 6, f and g at which a “break ” occurs in the cooling curve are called “‘arreats ” or “ arrest points " of the cooling curve. ‘The separation of the solid phase does not occur readily with some liquid mixtures and supereooling is observed. Tnstead of an arrest in the cooling curve at f', the cooling co long a continuation of ef’ and then rises tuddenly to meet the line f'9 which it subsequently follows (Fig. J, 3, 1, The correct freezing point may be obtained by extrapolation of the two parts of the curve (as shown by the dotted line). To avoid supereooling, « few small crystals of the substance which should separate may be added (the provess is called “seeding ") ; these act aa nuclei for crystallisation. Per cont & g Time @ g 2 fercentae 80 Composition tb) Fig. 1,13, 2 By constructing cooling curves for several mixtures of different com- mn, the total weight of the mixture being kept the same in each ‘ease, a series of cooling curves may be obtained which may be employed for the construction of the equilibrium diagram. ‘Thus in Fig. I, 13, 2, a,28 PRACTICAL ORGANIC CHEMISTRY a the cooling curves obtained with various mixtures of the t..0 components A and Bare shown, The first and last eurves refer to pure A and pure I respectively, whilst the other curves are for mixtures’ of 80 per cent. A and 20 per cent. B, 00 per cent. A and 40 per cent, B, 40 per cont. d and 60 per cent. B, and 20 per cent. A and 80 per cent. B. By joining the first arrest points (represented by crosses) the liquidus curve is obtained. whilst the solidus curve is obtained by drawing a line through the second arrest points (denoted by circles; see Fig. , 13,2,)). In practico, itis only necessary to plot the arrest temperatures against the composition, but it is believed that Fig. 1, 13, 2 brings out clearly the connexion between cooling curves and the equilibrium diagram for thesystem under discussion, and is therefore of considerable interest. Another procedure, known as the thaw-melt method, is available for the construction of equilibrium diagrams; it involves heating, instead of OY 8 g y q v - le aa ome more ore Composition on Fig, 1, 13, 3, cooling, mixtures of known composition, This has certain advantages over the cooling curve method, particularly in those eases where suger. cooling is serious and also where the quantity of material is limited. ct us consider, for example, a system of composition represented by the line ad (Fig. 1,13, 8), where d denotes the system completely. soliifed and a the same system completely liquefied, i.e., above its melting point. If the temperature of the solid expressed by d is slowly raised, no charge will ovour until the point c, the eutectic temperature, is reached + liq of composition C will then commence to form. As the temperature ts faised from ¢ to 6, the quantity of liquid increases and its composition changes from C to b; at 6 the last trace of sold is about to dgappear and above d the aystem is completely liquid. ‘This forms the basis of the thaw-melt procedure, A mixture of known composition—made by melt, ing (to ensure thorough mixing), cooling and then powdoring-is placed in a wide capillary tube (of about 2 mm, diameter) and the powder well pressed down with a thin glass rod or platinum wire so that the material4) THEORY OF GENERAL TECHNIQUE 29 occupies 3-5 mm. at the bottom of the tube. ‘The tube is then placed in a well-stirred bath of a suitable liquid and the temperature slowly raised. ‘The temperature at which the first minute drops of liquid appear (i¢., at c), the so-called thaw point, is the eutectic temperature for the given mixture, ‘The mixture is heated further and the temperature at which the last trace of solid just disappears (.c., at which the fused mass becomes perfectly clear) is taken as the melting point (6). ‘The thaw points and melting points of other mixtures, as well as of the pure components, are determined in the same way. ‘Thaw points and melting points are then plotted against composition. ‘Tho curve obtained by joining the thaw points is the solidus and that obtained by joining the melting points is the liguidus. Only a pure substance, or a mixture having the composition of the eutectic, melts sharply at a definite temperature. ‘The thaw-melt procedure demonstrates very clearly why an impure substance may melt over a considerable range of temperature. The system (Section 1,12), just studied in considerable detail, in which the components are completely niscible in the liquid state and the solid phases consist of the pure com- ponents, is very common with many pairs of organic and inorganic substances, Examples are given in the following table. B Evrrene ‘Naphthalene, m.p. 80° Naphthalene, m.p. 80° Diphonyimethano, m.p, 27° | Naphthalono, m.p. 80° Benzoio acid, mp. 122° | Cinmamie acid, mp. 183° ap. 8 eNitrophencl, mp. 48° | p-Toluidine, mp. 43° Mp. 15-3" ‘Antimony, m-p. 630° Losd, mp. 827" Bip. 246" Bismuth, m.p. 271 Cadnniuro, m.p. 321° Mp. 146 Gold, mp 108" | ‘halium, mp. 300 Mp. 1st 1,14. System in which the two components form a compound possessing a congruent melting point. This system, which occurs less frequently than that of Section 1,12, is of considerable interest. ‘The equilibrium diagram depicted in Fig. 7, 14,1 (for benzophenone and diphenylamine) isan illustration ofa system in which the two components form a compound possessing a congruent melting point, ic., capable of ‘existing as a solid compound in equilibrium with a liquid of the same composition. Point A is tho melting point of benzophenone (47-7°) and B that of diphenylamine (52-8°). - When diphenylamine is added to benzophenone, the freezing point is lowered along the cure AC. At € (31-9°) there is the first eutectic point where benzophenone and the addition compound {(CgH,),CO.(C,H,),NH)} = D separate together as sutectic mixture. Further addition of diphenylamine raises the freezing point to a maximum at D (40-2°). At D, the composition of the liquid and solid phases are identical, and this maximum temperature is therefore the congruent melting point of the addition compound. In a similar manner the freezing point of diphenylamine (B) is lowered by the addition of benzophenone as indicated by the curve BE. ‘The point is the second ‘euteotio point, where a eutectic mixture of diphenylamine and the addition30 PRACTICAL ORGANIC CHEMISTRY t compound separates. Further addition of benzophenone results in the freezing point rising along BD to a maximum at D, the melting point of the addition compound, ‘The liquidus consists of the curves AC, CDE and BB; the solidus ‘comprises the horizontal lines FCG and I/EJ as well as the vertical es, Tempecature Solid ASard © Solid B+ Soli fd vB iter percon biatenionne Molecular Composition Fig. 1. 14,1. lines PA, JB and GD. The areas have the significance indicated in the figure.” Tho details of the phase diagram can be best understood and the behaviour of various systems on cooling or heating readily predicted by regarding it as composed of two diagrams of the simple eutectic type (Big. 7, 12, 1) placed side by side with the dividing line at DK. To the 8 ® o 3 = le & $4 & g E . al . ce ic Composition Gomposion (a (b) Fig. 1,142 left of the dividing line the figure gives the equilibria of the two com- ponent system A and compound D, whereas to the right of the line the components may be regarded as D and B. It is clear from the figure that the presence of a stable compound i characterised by (i) a maximum point on the liquidus, (ii) a meeting15] THEORY OF GENERAL TECHNIQUE 31 point of the solidus and liquidus, and (ii) the existence of eutectic Point on either side of the maximum. ‘The melting point of the compound may be above, below or between those of the two components. If the compound is not completely stable but tends to decompose (dissociate) into its components in the liquid state, the melting point will be lowered by the products of decomposition. The shape of the middle branch of the curve will therefore give a rough indication of the stability of the compound. ‘The greater the stability of the compound the sharper is the maximum and, usually, the larger is the contral branch CDE of the curve as in Fig. 1, /4,2,a (eg., phenol and piorie acid). A flat maximum ‘and a small GDB curve indicate considerable decomposition of the addi- tion compound into ite components as in Fig. Z, 14, 2,6 (eg. naphthalene and m-dinitrobenzene). Other examples of this system are collected in the following table. | Eureence ,,| AB, mp. 28:8" | 16-0" (60-5 % A) - ” 24-0" (32 % 4) Phenol, p-Toluidine, AB, mp. 28-8 | BO" (10 % 4), ‘mp. 40-4° ‘mp. 43° ao-9° (31 & 4) Phenol, Piorie acid, | 4B, mp. asi | 36° (949 4), ‘mp. 40-4" mp. 122-5 | | 80-0" (42 46 4) aNaphthol, —p-Toluidine, | AB, m.p. 68-7" | 60-2° (60 % A), mp. 05-9" mp ase | 0-3" (19 ¢ 4) 1,15. System in which the two components form a compound with an incongruent melting point. In this system the compound formed ve e Sold 8 e + Liquid Sold ax8, | Solis se biguid | 480d Ar By ad AS By composition Fig. 1,15, 1.se PRACTICAL ORGANIC CHEMISTRY a is 20 unstable that it decomposes completely at a temperature below its melting point, so that the solid eannot be in equilibrium with a liquid of the same composition as itself—in other words, it has no true melting point. Such a eystem is exemplified by benzene and picrie acid: the ‘equilibrium diagram is shown in Fig. 1, 15,1 (for clarity, the illustration is not drawn to scale). ‘The point. A is the melting point of benzene, B that of picrie acid, and C that of the eutectic composed of solid benzene and the addition compound (represented by the symbol 4,B,). ‘The curve (CB is the equilibrium curve for the compound 4,B,—in the example under consideration x1 and y = 1—with the submerged maximum at D. ‘The point D is not realised in practice beeause the compound decomposes completely at # into solid picric acid and liquid benzene. ‘The point £ is spoken of as the incongruent melting point of the compound (since the ‘composition of the liquid is not the same as that of the original compound) cor as the transition point, "Tho curve EB represents the equilibriuin between solid B and the liquid. This system is rarely encountered anong compounds, but other examples are acetamide - salicylic acid and di- methylpyrone - acetic acid ; it is, however, comparatively common in alloy systems (eg., gold - antimony, AuSb,). 1,16. System in’ which the two components form a continuous series of solid solutions. Tn all the preceding examples the individual components (A or B or A,B) form separate crystals when solidifying from the melt. ‘There are, however, a number of oxamples of the separation ofa homogeneous solid solution of 4 and B (or A and A,B, etc). Before studying the equilibrium diagrams of these systems, the significance of the term solid solution must be made clear. A solid may dissolve com- pletely in another solid to form a solid solution in a manner analogous to the dissolution of ono liquid in another to yield a liquid solution. ‘The solid thus ‘obtained is perfectly homogeneous and has been called mized crystals ot isomorphous mixtures ; theso two terms may suggest heterogeneity and it is therefore better to employ the expression solid solution, proposed by van't Hoff in 1890. The phenomenon is different from the process of ordinary solution in a liquid sinee a liquid has no space lattice of ts own, ‘The formation of a solid solution involves the structural dissolution of one solid by another crystalline solid : this process entails, particularly for inorganic compounds, the spatial marshalling of the one in the other with respect to a definite space lattice, and the resulting solid solution therefore behaves as a single entity. ‘The physical properties of solid solutions are continuous functions of their percentage composition. ‘The conditions which must generally be satistied in the case of pairs of non-polar organio compounds are: (a) their chemical constitution must be analogous, (b) their molecular volumes must be approxi= mately equal, and (c) their crystal structures must be similar. ‘Tho general case of two compounds forming a continuous scries of solid solutions may now be considered. The components are completely miscible in the solid state and also in the liquid state, ‘Three different types of curves are known. ‘The most important is that in which the freezing points (or melting points) of all mixtures lie between the freezing points (or melting points) of the pure components. The equilibrium diagram is shown in Fig., 16,1. ‘The liquidus curve portrays the com- position of the liquid phase in equilibrium with solid, the composition of ee16) THEORY OF GENERAL TECHNIQUE 33 which is given by the solidus curve. ‘The composition of the solid phase changes continuously with that of the liquid from which it separates. Tt is found experimentally, and can also be deduced theoretically, that at ‘any temperature the concentration of that component by the ‘addition Temperature Solid Solution one oa one Composition 08 Fig. , 16,1. of which the freezing point is depressed is greater in the liquid than in the tolid phase. It is evident from the figure that upon cooling a fused mixture of two substances capable of forming solid solutions, the tom- perature of solidification (freezing point) will not remain constant during the separation of the solid, nor will the tempera- ture of liquefaction (melting point) of the solid solution be constant. ‘Thus, for example, if a liquid solution of composition a is allowed to cool very slowly (so as to ensure equilibrium, conditions as far as possible), a solid of compo- sition f will separate at 6. As the temperature continues to fall, more and more solid will be deposited and, since the solid phase is relatively © richer in B, the liquid will become richer in A. ‘The composition of the liquid will therefore pass along bg; the composition of the solid will ot the same time follow the curve fe. At Tine the point ¢, the last traces of liquid of compo- Fig. 1, 16, 2 sition g are just disappearing and solidification iscomplete, ‘The cooling curve will have the shape shown in Fig. I. slid commences to separate at.b and solidification is complete atc. is no complete arrest, only a change in the rate of cooling during the separation of the solid. If a mixture of composition d is slowly heated (as in the thaw-melt emperature34 PRACTICAL ORGANIC CHEMISTRY a method), it will commence to melt at the temperature ¢ (i.e., the first drops of liquid will appear) with the production of liquid of composition g. ‘Thereafter, as the temperature of the masa rises, more of the solid will melt and the composition of the solid and liquid will change as represented. by the curves of and gb respectively. Finally, when the temperature has reached }, complete liquefaction will have’ occurred. ‘The process of melting or freezing thus extends over the temperature interval bc. Examples of this system are g-naphthol, m.p. 122°- naphthalene, m.p. 80°, and q-monochlorocinnamic aldehyde, m-p. 31-2°- «-monobromo- cinhamic aldehyde, m.p. 69-6", ‘Two other types of equilibrium curves are occasionally encountered with the system of two components forming a continuous series of solid solutions. These are shown in Figs. I, 16, 3 and I, 16,4. In the former the freezing or melting curve passes’ through a ‘ainimum (examples: p-ehloroiodobenzene, m.p. 67°- p-dichlorobenzene, m.p. 53°; naphtha- Liquid Soutian Temperoture Sold Sutton woop oe Composition — FB RE Eampysitign soa Fig. 1, 16,3 Fig. 1,1 lene, m.p. 80°- @-naphthylamine, m.p. 112°), and in the latter it passes through o maximum (example : d- and l-earvoxime, m.p. 72°). 117, Mixed melting points. In the majority of cases the presence of a" foreign substance ” will lower the melting point of a pure organic compound, This fact is utilised in the so-called mixed melting point test for the identification of organic compounds. Let us suppose that an unknown compound X is supplied which is suspected to be o-chlorobenzoie ‘acid sinco its melting point is 140°. ‘This is tested for by intimately mixing together approximately equal weights of X and an authentic specimen of o-chlorobenzoie acid (A) and determining the melting point of the mixture. If the melting point is still 140°, then X is o-chloro- benzoic acid, but if the melting point is depressed by several degrees A and X cannot be identical. It is recommended that at least three mix- ‘tures containing, say, 10 per cent. X + 90 per cent. A, 50 per cent. X + 60 per cent. A, and 90 per cent. X + 10 per cent be prepared, and the melting points be determined. Alternatively, if time permits, the com- plete melting point curve (i.., the temperature at which the mixture18) THEORY OF GENERAL TECHNIQUE 35 liguefies completely) may be determined by the thaw point method (Section 1,13)—this will supply more information than mere evidence of non-identity, should this be desired. Cases may arise in which the melting point of certain mixtures aro higher than the individual components, ¢., if an addition compound of higher melting point is formed (compare Fig. I, 14, 1) or if the two com- pounds are completely soluble in the solid state forming solid solutions (compare Figs./, 16,1 and I, 16,4). Furthermore, for certain optical isomers, e., d- and L-camphoroximes and for d and /-borneol, there is no depression in the melting point, the freezing or melting points of all mixtures being the same as the pure components, It will be seen, therefore, that the mixed melting point test, although of great practical value, is not infallible and should accordingly be used with reasonable regard to these possibilities. [18. System in which the solid phases consist of the pure com- ponents and the components are only partially miscible in the liquid state. In concluding the discussion on the theory of melting and freezing, the system in which the two components are only partially miscible in the liquid state and the solid phases consist of the pure com- ponents will be considered. In all the previous cases the components ‘were completely miscible in the liquid state, but examples are known (eg. euccinonitrile and water) where, over a limited range of concentra- tion, the liquids are partially miscible and two liquid phases are formed. ‘The equilibrium diagram of a such a system is presented in Fig. f, 18, 1 (for the sake of clarity, this has not been drawn to scale ; the salient features have been exaggerated). Point is the melting point of suecino- nitrile and B that of ice. If succinonitrile (A) is added to ice at B, the freezing point will fall along BC, ice (solid B) separating ; ultimately the temperature of the eutectic C (—1-2°) will bo reached. If the temperature is now raised slightly so that the eutectic mixture just melts ‘and the addition of A is continued, the concentration of A in the solution will increase (curve CD) and the solid phase in equilibrium with the solutions denoted by CD will be A (succinonitrile). At the point D (18-8), solid A melts and two liquid phases make their appearance. This is the ‘well-known phenomenon of melting under the solvent or the separation ‘of an “oil” during the recrystallisation of a pure substance from a solvent. ‘The compositions of the two liquid phases are represented by the points D and F and there will be, in addition to the vapour, three phases present, A (the solid stccinonitrile), solution of liquid 4 in B (water) and of Bin liquid A, ‘The temperature ¢, is therefore a quadruple point (i.e., four phases coexist). ition of more A will result in a change of the relative amounts of the two layers—increased amount of B in liquid A, decreased amount and eventual disappearance of liquid A in B—the temperature remaining constant (DE). At B only one liquid phase is present; with further addition of A, the equilibrium temperature rises as expressed by EA. If the system represented by the point D be heated, the solid A will disappear and two partially miscible liquids will remain. The curve ETD is the ordinary solubility curve for two partially miscible liquids (compare Section 1,8, Fig. 1, 8, 1). As the temperature rises, the mutual36 PRACTICAL ORGANIC CHEMISTRY a, solubility of the two components increases until at the oritical solution, temperature 1’ (65:5°) they become miscible in all proportions. At all temperatures above the curve BCDTEA there is only one liquid phase; at temperatures between D and 7’, mixtures of total composition denoted by points inside the area D7'F will separate into two liquid phases. ‘The equilibrium diagram expresses in shorthand form the behaviour of all mixtures upon heating or cooling. Thus, let us examine the effect of cooling a homogeneous liquid mixture of composition expressed by the point a. ‘Two layers (conjugate solutions) commence to form at 4, the compositions of which are given by b and 6”; with further eooling, the compositions follow the curves bE and 6’D respectively. V ‘composition of the system as a whole is expressed by the poi One Liquid 1 tore Temoer to B Soa 6 igus Sota Liquid F| ¥ 6 ab Sold As Sond 8 ‘om On Composition we Fig. 1, 18, 1. ‘compositions of the liquid layers are at H and D: solid A then commences to separate, the relative amount of the liquid layer richer in B (i.e., D) inereases and eventually the layer E disappears. ‘The temperature remains constant, up to the point of the disappearance of the two layers, ‘Thenceforth the temperature falls gradually from ¢ to d, and the com: position follows DC, solid A soparating. At C, the eutectic point, the other solid B deposits and the temperature again remains constant ‘until the liquid has disappeared. The solid mixture of A and B then cools slowly along de. ‘The behaviour of any other system to the left of the curve ABTD will be obvious from what has already been said ; systems to the right of D behave normally like those of whieh the components are completely miscible in the liquid state and the solid phases consist of pure components (Section 1,12). For this reason the recrystallisation of a substance which tends to “melt under the solvent” should be confined to the area of composition to the right of the point D.19) THEORY OF GENERAL TECHNIQUE cd Examples of solid liquid systems with two liquid layers are given below : the temperature f, is the temperature at which the two layers ‘separate or the quadruple point, Water, mp. 0° Phenol, m.p. 43" Benzene, m.p. 5° Resoreinol, in.p. 110° 119. THEORY OF SUBLIMATION ‘The processes of distillation and sublimation are closely related. There are three ways in which the vaporisation of a thermally stable substance may take place on heating :— (i) Tf the substance is liquid under ordinary conditions, it may boil at ‘definite temperature depending upon the pressure, (ii) If the substance is solid under ordinary conditions, it may first melt at a definite temperature and, upon rise of temperature, boil like an ordinary liquid. (ii) Tf the substance is solid under ordinary conditions, it may volatilise without melting, at a definite temperature depending upon the pressure. ‘The condensation of the vapour of a stable substance may, likewise, take place in three ways (j) ‘There may be liquefaction only. (ii) Liquefaction may take place frst, followed by solidification. (ii) The vapour may pass directly, without the intermediate formation of a liquid, into the solid state. The term distillation is applied to vaporisation and subsequent con- densation according to (i); it should also be applied to (ii) since it is really the liquid which is converted into vapour and is first formed by condensation. Strictly speaking, the term sublimation should be applied to changes according to (iii). However, in practice, a substance when heated may first melt and then boil, but on cooling it may pass directly from the vapour to the solid : the process is then also called sublimation. Indeed the mode of vaporisation, whether directly from solid to vapour or through the intermediate formation of a liquid, is of secondary import- ‘ance ; it is the direct conversion of vapour to solid which is really the outstanding feature of sublimation in the laboratory. ‘To understand the conditions which control sublimation, itis necessary to study the solid - liquid - vapour equilibria. Tn Fig. 1,19, 1 (compare Fig. 1, 10, 1) the curve 1'W is the vapour pressure curve of the liquid (i.., represents the conditions of equilibrium, temperature and pressure, for stem of liquid and vapour), and T'S is the vapour pressure curve of the tolid (ie. the conditions under which the vapour and solid are in equili brium). ‘The two curves intersect at 7’: at this point, known as the triple point, solid, liquid and vapour coexist. ‘The curve 7'V representa the38 PRACTICAL ORGANIC CHEMISTRY a. temperatures and pressures at which the solid and liquid can be in equilibrium, that is, it indicates the influence of pressure upon the melting point. ‘This curve meets the other curves at the triple point 7. ‘The normal melting point of a substance is the temperature at which solid and liquid are in equilibrium at atmospheric pressure. At the triple point, the pressure is the equilibrium vapour pressure of the system (eolid - liquid vapour) and the temperature differe from the melting point. The difference is, however, quite small—usually only a fraction Of a degree—since the line TV departs only slightly from the vertical within reasonable ranges of pressure. It is clear that if the vapour at a pressure below the triple point is Pressure Yopour reduced sufficiently in temperature, it will condense direetly to the solid form, or, sublimation will ensuo. Tn order that a solid may pasa directly into vapour without. the inter- v w_ Mediate formation of a liquid phase, — the pressure of the vapour must not be allowed to exceed that of the triple point. This can easily be done if the vapour pressure at the triple point is fairly high and con- Sous sequently tho rate of vaporisation will be considerable ; the conditions are then favourable for the puri- fication of the solid by sublimation at atmospheric pressure. camphor (triple point, 170°; equili- brium pressure, 370 mm.) is slowly heated below 179°, it will vaporise without melting and, if the vapour is deposited on a cooled surface, the pressure will be kept below 370 mm. Temperature so that. vaporisation will continue Fig. 1,29, 1. ‘until the solid has disappeared. Condensation takes place on the cold surface directly as the solid because the pressure is below that at the triple point. If the triple point pressure of a solid is below one atmosphere, it will melt if the heating is conducted rapidly go that the vapour pressure can ‘exceed that at the triple point. If camphor is heated in a closed space, the vapour pressure increases and when the value of 360 mm. is reached, the solid will melt ; further heating results in an increase in the vapour pressure and the camphor will boil when the vapour pressure is 760 mu. For substances with a moderate triple point pressure (eg., benzoic acid, 6 mm., m.p. 122°; naphthalene, 7 mm., mp. 80°*), the simple process described above for camphor will not give a satisfactory yield of sublimed product, ‘Thus, for example, if naphthalene ia heated it will ‘melt at 7’ (80°), and will boil when the vapour pressure is 760 mm. (218°) ; = Yor most practical purposes the teraperature and preegure at the tiple point may be ‘peered ot dering appreciably fom the main pint andthe vapous prema et ‘Ge melting point rempoctively.20) THEORY OF GENERAL TECHNIQUE 30 it will be necessary to maintain the compound at about this temperature if any substantial quantity is to be completely converted into vapour. Upon cooling the vapour, naphthalene will deposit as « liquid until the temperature 7” (Fig. 1, 19,1) is reached (the vapour pressure is then mm.) and thenceforth as a solid. To improve the yield of sublimate, the pressure in the system must be reduced ; this may’ be done by exhaus ting the apparatus with a pamp. In the present and similar cases, a sintpler procedure isto dilute the vapour with an inert gas (carbon dioxide ornitrogen). ‘This dilution will reduce the partial pressure ofthe substance fand also simultaneously cool the vapour; the sublimed crystals are clected ina cooling chamber, where they deposit usually in a finely- divided form. ‘True sublimation can occur only when the partial pressure of the vapour of the substance is lower than its triple point pressure. Substances with low vapour pressures at their melting points can only be satisfactorily eublimed under greatly diminished pressure. ‘Two cases of direct eublimation at atmospheric pressure are worthy of mention. Hexachlorocthane has « triple point temperature of 186” ‘and a triple point pressure of 780 mm. Complete sublimation ean there- fore be easly effected by merely heating to about 186° (the vapour pressure {s 760 mm, at 185°). ‘The melting point of this gubstance is most satis- factory determined in a sealed capillary tube. ‘The triple point tempera. ture and pressure of carbon dioxide aro — 58-4° and 6-11 atmospheres respectively. This means that liquid carbon dioxide can only be formed if the pressure exceeds 5-11 atmospheres. If liquid earbon dioxide, from a eylinder, is allowed to escape into the air (best into a cloth bag tied to the nozzle of the cylinder), it absorbs so much heat during the rapid evaporation that part of it is frozen into a snow-like solid. Com- mercially, the carbon dioxide “snow” ia compressed hydraulically into slabs of Dry Ice or Drikold. The solid evaporates comparatively slowly, owing to its high latent heat (87-2 cal. per gram), its high density (1-56), and the fact that itis surrounded by an insulating layer of heavy vapour. The solid will pass directly into the gas since atmospheric pressure is vrell below the triple point pressure. Solid carbon dioxide (Dry Tee ; Drikold) has the following advantages over ice as a ref (1) As already stated, it passes directly into the vapou (2) It ean produce a lower temperature (— 78°). (8) It occupies less space. (4) It forms excellent freezing mixtures with many organie liquids, eg., with alcohol, — 72°; with ether, — 77° ; and with chloroform, — 77°, (6) It has a higher latent heat and a greater density producin, over-all cooling effect which is about twice as efficient as ordinary ive, 120. THEORY OF THE ACTION OF DRYING AGENTS Drying agents may be divided broadly into (a) those which combine with water reversibly and (b) those which react chemically with water by a nonreversible process giving rise to a now water-free compound. Sodium, calcium carbide and phosphorus pentoxide belong to the latter class and will be discussed in Section 11,39.0 PRACTICAL ORGANIC CHEMISTRY a, To appreciate the action of a drying agent of class (a), let us imagine ‘some anhydrous copper sulphate in an evacuated vessel provided with a pressure gauge, and water is allowed to enter slowly ; the temperature 4s assumed constant at 26°, ‘The results may be best expressed by means of @ vapour pressure - composition diagram (Fig. 1,20, 1). ‘The initial system is represented by the point A; the pressure will rise along AB until the monohydrate CuS0,,H,O commences to form at B. A —] 3 “Jal s, Fo —| £ —s6lnm : a 5 i éy — ay ! 3] t aan \ —e se Mos MO to 10150 Fig. Z, 20,1 \ At this point the system has throo phases (CuSO, CuS0,,0 ; 1,0 vapour) ‘and the number of components is tro (aihydrous salt i Phase Tule, Pk P= O4 2, ity BpP Od E2, of consequently univariant, in other words, only one varisble, eg. bo fixed to define the aystem completely : tho preasure af water vapous in coat brium with CuSO, and CuSO, H,O should bo constant at constant tomperutis, As more water vapour is absorbed by the system, the pressure remains constant along BC until the anhydrous salt is completely converted into the monohydrate. ‘The conversion ia complete at 0: the preseure then rises along CD until the trihydrate is formed at D. Two solid phases (Cu80,,3H,0; CuS0,,H,0) are now ‘present and the pressure remains constant until all the monohydrate is transformed into the trihydrate at E. The pressure again rises to F, and when it attains tho value denoted by F, the pentahydrate commences to form and the system has a constant pressure until all the trihydrate has passed into the pentahydrate at 0. ‘The same curves are obtained if copper sulphate pentahydrato is dehy. arated at constant temperature (25°): here the powdered erystals of the Pentahydrate are contained in a vessel and the water vapour is gradually removed by means of a pump. ‘The pressure remains constant along GF whilst. the pentahydrate is being converted into trihydrate; at F only the trihydrate is present. A sharp drop in pressure to then occurs and along ED the trihydrate passes at constant pressure into the mono hydrate. This change is complete at D, the pressure falls again to C, at which point dissociation of the monohydrate to the anhydrous salt occurs. ‘This transformation is complete at B, and, with the complete removal of the water, the pressure drops to almost zero at A.20) THEORY OF GENERAL TECHNIQUE a Itis evident from these results that threo equilibria are to be considered, CuSO, ++ H,O=CuSO,H,O; 0-8 mm, at 25" (i) CuS0,H,O + 2H,0 <* CuS0,3H,0; 5-6 mm. (i CuS0,3H,0 + 2H,0 = CuS0,,5H,0; 7-8 mm. (iii) Furthermore, it is the system, Hydrate I/Hydrate II (or Anhydrous Salt), that possesses a definite pressure at a particular temperature ; this is independent of the relative amounts, but is dependent upon the nature of the two components in equilibrium. It is incorrect, therefore, to speak of the “vapour pressure of a salt hydrate.” Similar results are obtained at other temperatures, ¢g., at 60°, the above three systems give equilibrium vapour pressures of 4:5, 30-9 and 45-4 mm, respectively. There is some evidence for the existence of a tetrahydrate CuSO,,4H,0, but this does not affect the general nature of the change described above. At temperatures higher than about 102°, the pentahydrate is unstable and CuSO,3H,O is the first stable hydrate. We may now understand the nature of the change which occurs when an anhydrous salt, say copper sulphate, is shaken with a wet organic solvent, such as benzene, at about 25°. ‘The water will first combine to form the monohydrate in accordance with equation (i), and, provided sufficient anhydrous copper sulphate is employed, the effective concen- tration of water in the solvent is reduced to a value equivalent to about, Imm. of ordinary water vapour. ‘The complete removal of water is im- possible ; indeed, the equilibrium vapour pressures of the least hydrated system may be taken as a rough measure of the relative efficiencies of ‘such drying agents. If the water present is more than sufficient to convert’ the anhydrous copper sulphate into the monohydrate, then reaction (i) will be followed by reaction (i), i.c., the trihydrate will be formed ; the water vapour then remaining will be equivalent to about 6 mm, of ordinary water vapour. Thus the monohydrate is far less effective than the anhydrous compound for the removal of water. Magnesium sulphate is a useful drying agent as can be seen from the following table of equilibrium vapour pressures of the various possible ystems at 25°; MgSO, + _H,O=MgSO,H,O ; 1mm. Mg80,H,0 + 1,0 = MgS0,2H,0; 2mm. MgSO,,2H,0 + 2H,0 = MgSO,4H,0; 5mm. MgSO,4H,0 + H,0 = MgSO,5H,0; 9mm. MgSO,,5H,O + H,O > Mg80,6H,0 ; 10 mm. ‘MgSO,.6H,0 + HO = Mg80,7H,0 ; 11-3 mm. Another valuable drying agent. of general application is anhydrous calum sulphate, marketed uncer the nsme of“ Drienle”” Tex rapid in its action, but has only a limited drying capacity because it forms the hydrate 2CaS0,,H,O and thus combines with only 6-6 per cent. of its weight of water. ‘The vapour pressure of the system : 2CaS0, ++ H,0 <* 2Ca80,,H,02 PRACTICAL ORGANIC CHEMISTRY i is only 0-004 mm. at about 25°. The residual water content is therefore very low, and the substance may be employed for drying alcohols, esters, ketones, acids, etc. If the water content of the organic substance is somewhat high, a preliminary drying with another desiccant such as anhydrous magnesium or sodium sulphate, which can absorb a higher proportion of water, is recommended. ‘A rough method for comparing the drying powers of the common desiccants consists in passing moist air over the drying agent maintained fat a constant temperature and then determining the residual moisture with phosphorus pentoxide—the most efficient drying agent known Some resulta, due largely to Bower (1934), are tabulated below. Rasiovat, Waree Varous pik LIne oF Atm at 30°6° Resovas, Resear | Wain (0) Waren (x) 0-08 0-08 o-ot 0-005 0-003 0-003 0-002 0-002 0-007 2 2 1 NaOH, sticks CaCl, anhydrous (fused) HB0e 85% | “S Approsimate eomposiion? GoO,1R0. As a rough approximation it may be assumed that one mg. of water contained in one litre of gas at 25-30° exerts a 1 mm. partial vapour pressure. Obviously, the lower the residual water content or the vapour pressure, the more intense is the ultimate drying capacity of the substance. ‘The vapour pressures of the various hydrate systems increase with temperature (compare the figures for the threo copper sulphate - water ayatems of equations (i), (i) and (iil) at 25° and 50° already given). It follows, therefore, that the efficiency of desiccants decreases with rise of temperature and, indeed, at high temperatures certain desiccating agents may actually undergo dehydration. ‘Thus the vapour pressures of some calcium chloride- water systems exceed atmospheric pressure at high temperatures, as ean be seen from the following table. Varour Puxssunm or Caucus CHionip Systems 7 Approximate composition? 4CaClyH0. [ rawsavone | rameous ony sour Pus | | Toe — Cucl,6H,0 Cati,6H,0'~ $ Cac, AHO Gach,SH130 — 2 CaCly nti B.Catitti,0 2 3i1,0 — caCt.fi,0"2) ‘THEORY OF GENERAL TECHNIQUE 3 It follows that liquids of high boiling point should not be distilled from drying agent systems which have appreciable vapour pressures. An tetreme case of this action is the dehydration of oxalic acid dihydrate by distillation over toluene or over carbon tetrachloride. LAL. Deliquescence and efflorescence. A substance is said to deliquesce (Latin : to become liquid) when it forms a solution or liquid phase upon standing in the air. ‘The essential condition is that the vapour pressure of the saturated solution of the highest hydrate at the ordinary Temperature should be less than the partial pressure of the aqueous vapour in the atmosphere. Water will be absorbed by the substance, which gradually liquefies to @ saturated solution ; water vapour will continue to be absorbed by the latter until an unsaturated solution, having the same vapour pressure as the partial pressure of water vapour in the air, is formed. In order that the vapour pressure of the saturated solution may be sufficiently low, the substance must be extremely soluble in water, and it is only such substances (eg., calcium chloride, zine chloride and potassium hydroxide) that deliquesce, Tn the British Isles ihe atmosphere is normally about two-thirds saturated and tho partial vapour pressure of a well-ventilated laboratory fs 12-14 mm. at about 20°. The vapour pressure of ealeium chloride (CaCl, 6H,0- CaCl, 4H1,0) at room temperature is about 4 mm., that of the saturated solution about 7-8 mm., and 100 grams of water will dissolve 74-5 grams of the hydrate at 20°; it is therefore deliquescent. Sodium and potassium hydroxides possess similar properties. Copper sulphate pentahydrate, on the other hand, is not deliquescent as the vapour of the saturated solution is about 16 mm. at 20° and that of the CuS0,,5H,0 - CuSO,3H,O system is considerably less than this (Gee Fig. 1, 20, 1). ‘A salt hydrate is said to effloresce (Latin : to blossom) when it loses water and falla to a powder upon exposure to the atmosphere, Efflores- ‘cence will occur when the vapour pressure of the hydrate system is greater than that of water vapour in the atmosphere; dehydration will then occur in the effort for equilibrium to be attained between the hydrate system and the surroundings. A good example is washing toda, Na,CO,,10H,0, which gives off water vapour with the production of the monohydrate, Na,CO,H,0. Other examples aro the systems containing Na,SO,,10H,0 and Na,HPO, 12H ‘It must be emphasised that deliquescence and efflorescence are relative properties, since they depend upon the actual presence of water vapour in the atmosphere, which varies considerably with place and time. ‘A substance is said to be hygroscopic when it attracts moisture from the atmosphere. All deliquescent compounds are consequently hygro- seopie, but there are many hygroscopic substances which absorb water vapour without deliquescing. Most dry substances, particularly it in a fine powder form, are slightly hygroscopic. Substances which aro commonly regarded as hygroscopic inelude quicklime and cuprie oxide. The term is also applied to liquids: thus concentrated sulphurio acid, absolute methyl and ethyl alcohols, and deuterium oxide (“heavy water”) have hygroscopic properties.“ PRACTICAL ORGANIC CHEMISTRY u 1,22. EXTRACTION WITH SOLVENTS ‘The process of extraction with solvents is generally employed either for the isolation of dissolved substances from solutions or from solid mixtures or for the removal of undesired soluble impuritios from mixtures. ‘The latter process is usually termed washing. ‘The theory of the process can best be illustrated by considering the operation, frequently carried out in tho laboratory, of extracting an organic compound from its aqueous solution with an immiscible solvent. ‘We are concerned here with the distribution law or partition law which, states that if to a system of two liquid layers, made up of two immiscible or slightly miscible components, is added a quantity of a third substance soluble in both layers, then the substance distributes itself between the two layers so that the ratio of the concentration in one solvent to the concentration in the second solvent remains constant at constant tem- perature. It is assumed that the molecular state of the substance is the same in both solvents.* If c, and cy are the concentrations in the layers A and B, then, at constant temperature : alee = constant = K. ‘Tho constant K is termed the distribution or partition coefficient. As a very rough approximation the distribution coefficient may be ‘assumed equal to the ratio of tho solubilities in the two solvents, Organic compounds are usually relatively more soluble in organic solvents than in water, hence they may be extracted from aqueous solutions. If electrolytes, ¢., sodium chloride, are added to the aqueous solution, the solubility of the organic substance is lowered, ie, it will be salted out: this will assist the extraction of the organic ‘eompound. ‘The problem that arises in extraction is the following. Given a limited juantity of the solvent, should this be used in one operation or divided into several portions for repeated extractions in order to secure the best result? A general solution may be derived as follows. Let the volume, v ml,, of the aqueous solution containing 1) grams of the dissolved substance be repeatedly extracted with fresh portions of s ml. of tho organic solvent, which is immiscible with water. If w, grams is the weight of the solute remaining in the aqueous phase after the first extraction, then the concentrations aro w,/o g. per ml. in the aqueous phaso and (w»—1w,)/6 g. per ml. in the organic solvent layer. ‘The partition coefficient K is given by : wie (wy — wie + For s theoretical teatmant involving atusitin or dismcaton In one solvent, se, for example, 8: Glastono, Tere Book of Phynsal Chemisty, Second Baition YO0l, fe 13 (Wan Nosteaod Macmillan.ny THEORY OF GENERAL TECHNIQUE 5 in the aqueous layer after the second extraction, = wie = aw, o “Ky ba Ke yt ligt) ‘Similarly if , grams remain in the aqueous layer after the nth extraction : wy (gt) o. We desire to make w, as small as possible for a given weight of solvent, ive, the product of m and ¢ is constant, hence » should be large and # small; in other words, the best results are obtained by dividing the extraction solvent into several portions rather than by making a single extraction with the whole quantity. It must be emphasised that the expression deduced above applies strictly to a solvent which may be regarded as completely immiscible with water, such as benzene, chloroform ‘or carbon tetrachloride ; if the solvent is slightly miscible, e.., ether, the ‘equation (1) is only approximate, but is nevertheless useful for indicating the qualitative nature of tho results to be expected. ‘Let us consider a specific example, viz., the extraction of a solution of 4-0. of n-butyric acid in 100 ml. of water at 15° with 100 ml. of benzene at 16°. ‘The partition coefficient of the acid between benzene and water may be taken as 3 (or 4 between water and benzene) at 15°. For a single extraction with benzene, we have : For threo extractions with 33-3 ml. portions of fresh benzene : waa) Hence one extraction with 100 ml. of benzene removes 3-0 g. (or 76 pet cent.) of the n-butyrio acid, whilst threo extractions remove 3:5 g. (or 87-5 per cont.) of the total acid, This clearly shows the greater efficiency of extraction obtainable with several extractions when the total volume af solvent is the same, Moreover, the smaller the distribution coefficient between the organic solvent and’ the water, the larger the number of extractions that will be necessary. The above considerations apply also to the removal of a soluble im- purity by extraction (or washing) with an immiscible solvent. Several rashings with portions of the solvent give better results than a single ‘washing with the total volume of the solvent.CHAPTER 11 EXPERIMENTAL TECHNIQUE 11. COMMON ORGANIC LABORATORY APPARATUS Ir will be useful at the very outset to introduce the student to the apparatus that is commonly employed in the organic laboratory. Whether he will personally handle all the types of apparatus to be described will, of course, depend (i) upon the duration of the course in practical organic chemistry and (i) upon the facilities provided by the laboratory. Never. theless, it is deemed advantageous that the student should, at least, now of their existence, Flasks. Various types of flasks are shown in Fig. II, 1, 1, a- SOOO Fig. 1, 1,1. (a) Flat-bottomed flask (the so-called Florence flask) with vial mouth. ‘The sizes vary between 60 ml. and 40 litres, (6) This is similar to (a) except that it is provided with a ring neck, which increases the mechanical strength, prevents breakage when a stopper is inserted, and provides a means for wiring a stopper in place. The upper rim is ground flat. (©) Round-bottomed flask. ‘The common sizes range between 25 ml and 50 litres, (d) Round-bottomed flask with short ring neck (the so-called bolt- head flask). ‘This is widely used, particularly in advanced work, and possesses the advantages given under (6). ‘The common sizes range botweon 60 ml. and 20 litres, (¢) This is the familiar Erlenmeyer or conical flask. ‘The common sizes range between 25 ml. and 6 litres, Beakers. The usual Griffin form with spout, Fig. I, 1,2,a, are widely used. Sizes between 7 30 ml.’ and 6 litres are available. The tall form without spout (Fig. I, 1, 2 6) oceasionally finds ig. 11.1.2. application in organic laboratories. “a) EXPERIMENTAL TECHNIQUE a Distilling flasks. Fig. 1/,1,3,a is the ordinary distilling flask. ‘The sizes vary between 25 and 6,000 ml. (0) is the so-called Claisen flask, a distilling flask with two necks ; the thermometer is placed in the neck carrying the side arm. Sizes ‘vary between 25 ml. and 2,000 ml. It is of particular value in distillations there foaming or bumping occurs, and is widely employed in distillations under diminished pressure. (c) is identical with (0) except that it is provided with a second long and indented neck (which is essentially a Vigreux column—see Section 11,15). tis sometimes termed a Claisen flask with fractionating side arm. In (d) the side arm outlet extends @ short distance into the long neck of the flask, thus preventing any vapour which has been in contact with cork or rubber stoppers from condensing and flowing down the side arm. ee er @ Wig. 11, 1,3. which attack cork or rubber It is usually employed for those liqui stoppers. ‘Condensers. ‘The various types in common use are shown in Fig IL, 1,4, 0-1. (@) is a typical Liebig condenser, which consists of an inner glass tubo surrounded by a glass jacket through which water is circulated. ‘The inner jacket is fitted into the outer jacket by means of rubber stoppers ; rubber tubing, formerly used, is less durable and is not recommended. (6) is an all-glass Liebig condenser of similar design to (a) ; the jacket, is sealed to the condenser tube. ‘Two convenient sizes of condensers, suitable for general use, have jackets of 20 and 40 cm. length. In the Pyrex glass West condenser greater efficiency of cooling is obtained by having a light-walled inner tube and a heavy-walled outer tube with a minimum space between them. (©) is the inner tube of a Liebig condenser. It is used as an air-con- denser when the boiling point of the liquid is above 140-150", (d) is an all-glass Allin condenser. ‘The condensing tube is made with ‘a series of bulbs ; this increases the condensing surface and lessens the resistance to the passage of vapoura when the condenser is employed for