None
Wiener klin. Wocbenscbr. Wiener landw. Ztg. Wiener Med. Wocbenscbr. Wiener Mittb. Pbot. Wiener Mus. Ann. Wiener Poly. J. Wiener Ztg. Wiener Zts. Pbysik. Wild, Rep. Meteorol. Wihia, Collect. Med. Cbir. Wilts, Arcbaeol. Natur. Hist. Mag. Wimereux I^ab. (Stat.) Zool. Wincbester, J. Sci. Soc. Wisconsin Acad. Trans. Wisconsin Natur. Hist. Soc Bull. Wisconsin Natur. Hist. Soc. Pap. Wisconsin Natur. Hist. Soc. Proc. Wisconsin Univ. Bull. Sci. Wiss. Abb. Pbys.-Tecb. Reicbsanstalt IViss. Meeresuntersucb. Sitzungsbericbte der Matbematiscb-naturwissenscbaft- li<:ben Classe der Kaiserlicben Akademie der Wissen- scbaften Jabres-Bericbt des Sotmblick-Vereines. Wien Wiener tecbnologisbe Blatter Scbriften des Vereins zur Verbreitung Naturwissen- scbaftlicber Kexmtnisse in Wien Verbandlungen der k. k. Gesellscbaft der Aerzte zu Wien Verbandlungen des Neiderosterreicbiscben Gewerb- Vereins Wocbenblatt der k. k. Gesellscbaft der Aerzte in Wien Zeitscbrift der k. k. Gesellscbaft der Aerzte zu Wien Pestscbrift zur Feier des funftmdzwanzigjabrigen Bestebens der k. k. Zoologiscb-Botaniscben Gesell- scbaft in Wien Verbandltmgen der k. k. Zoologiscb-Botaniscben Gesellscbaft in Wien Arbeiten aus dem Zoologischen Institute der Uni- versitat Wien ind der Zoologiscben Station in Triest Wiener Entomologiscbe Monatscbrif t Jabresbericbt des Wiener Entomologischen Vereins Wiener Entomologiscbe Zeittmg Wiener kliniscbe Wocbenscbrift Wiener landwirtscbaftlicbe Zeitung Wiener mediciniscbe Wocbenscbrift Wiener Mitteilungen (Pbotograpbiscben Inbalts) Annalen des Wiener Museums der Naturgescbicbte Allgemeines Wiener polytecbniscbes Jotunal Wiener Zeitung Zeitscbrift fur Pbysik, Cbemie, tmd Mineralogie RepcTtorium fur Meteorologie, berausg. von der kaiserlicben Akad. der Wissenscbaften Collectanea medico-cbirurgica Caesarea Academiae Medico-Cbirurgicae cura edita Magazine of tbe Arcbaeological and Natural History Society of Wiltsbire See Lille Inst. Zool. Trav. Journal of Proceedings and Annual Reports of tbe Wincbester and Hampsbire Scientific and Literary Society Transactions of tbe Wisconsin Academy of Sciences, Arts, & Letters Bulletin of tbe Wisconsin Natural History Society Occasional Papers of tbe Natural History Society of Wisconsin Proceedings of tbe Natural History Society of Wis- consin * Bulletin of tbe University of Wisconsin. Science Series Wissenscbaftlicbe Abbandlungen der Pbysikalisb- Tecbniscben Reicbsanstalt Wissenscbaftlicbe Meeresuntesucbtmgen berausge- geben von der Kommission zur wissenscbaftlicben Untersucbung der deutscben Meere in Kiel tmd der biologiscben Anstalt auf Helgoland CXXll LIST OF ABBREVIATIONS TO LITERATURE Wochenbl. Archit. Ver. Wochenbl. Papierfabr. Wochensch. Brau. Wochenschr. Centr.-Ver. Rubezuker-ind. Wochenschr. osterr. Ing. Ver. Wochenschr. Ver. deut. Ing. WoUen-Gewerbe WoUen Ztg. Wombat Woods Holl Mar. Biol. Lab. Btdl. Woods Holl Mar. Biol. Lab. Lect. Woolhope Field Club Trans. Woolwich, Proc. World's Paper Trade Rev. Wimderlich, Archiv. Heilk. Wiirttemberg. Aerzt. Ver. Mitth. Wiirttemberg, Jahresh. Wiirzburg, Arb. Hot. Inst. Wiirzburg, Arb. Phys. Lab. Wurzburg. Med. Zts. Wiirzburg. Naturwiss. Zts. Wurzburg Phys. Med. Festschr. Wiirzburg, Phys. Med. Sitzber. Wiirzburg, Phys. Med. Verb. Wiirzburg, Zool Inst. Arb. Year Book Pharm. Year-book of Pharm. Yn X'ioar Manninagh Yokohama, Mitth. Deut. Ges. Yonne Yonne,' Bull. Yorksh. Natur. Union Trans. Yorksh. Phil. Soc. Report Wochenblatt, herausgegeben von mitgliedem des Architekten-Vereins zu Berlin Wochenblatt der Papierfabriken Wochenschrift fur Brauerei Wochenschrift des Central- Vereins fiir Rubenzuker- industrie in der Oe.sterr-Ung-Monarchie Wochenschrift des osterreichischen Ingenieur und Architekten Vereins Wochenschrift des Vereins deutscher Ingenieure Das Deutsche WoUen-Gewerbe Wollen Zeitung The Wombat. The Journal of the Geelong Field Naturalists' Club, and the Gordon College Amateur Photographic Association Biological Bulletin. Edited by the Director and Members of the Staff, of the Marine Biological Laboratory, Woods Holl, Mass. Biological Lextures delivered at (from) the Marine Biological Laboratory (of) Woods Holl (Mass.) Transactions of the Woolhope Naturalists' Field Club Minutes of Proceedings of the Royal Artillery Insti- tution World's Paper Trade Review See Roser imd Wunderlich Mittheiltmgen des Wiirttembergischen Aerztlichen Vereins Jahreshef te des Vereins fiir vaterlandische Naturkunde in Wiirttemberg Arbeiten des Botanischen Instituts in Wiirzburg Arbeiten aus dem Physiologischen Laboratorium der Wiirzburger Hochschule Wiirzburger medicinische Zeitschrift Wiirzburger Naturwissenschaftliche Zeitschrift; Herausgegeben von der Physikalisch-Medicinischen Gesellschaft Festschrift zur Feier ihres funfzigjahreign Bestehens herausgegeben von der Physikalisch-Medizinischen Gesellschaft zu Wiirzburg Sitzimgsberichte der Physikalisch-Medicinischen Gesellschaft zu Wiirzburg Verhandlimgen der Physikalisch-Medicinischen Gesell- schaft Arbeiten aus dem Zoologisch-Zootomischen Institut in Wiirzbiu"g See Brit. Pharm. Confer. Proc. Year-book of Pharmacy Yn Lioar Manninagh. The Journal of the Isle of Man Natural History and Antiquarian Society Mittheilungen der Deutschen Gesellschaft fiir Natur und Volkerkunde Ostasiens See Auxere Bulletin de la Soci^td des Sciences Historiques et Naturelles de 1' Yonne The Transactions of the Yorkshire Naturalists' Union Annual Report of the Council of the Yorkshire Philo- sophical Society LIST OF ABBREVIATIONS TO LITERATURE CXXIU Yorksh. Proc. Phil. Soc. Zach, Corresp. Zach, Monat. Corresp. Zahntech. Zantcdeschi. Ann. Fis. Zeeuwsch Genootsch. Nieuwe Verh. Zeeuwsch Genootsch. Wet. Archief Zentr. Biochem. Biophys. Zentr. exp. Med. 2^entr. inn. Med. Zentr. oesterr - ungar Papierind. Zentr. Physiol. • Zentr. Physiol. Path. Stoff- wech. 2^tmer, Civilingenietir Ziva Zool. Anz. Zool. Beitr. Zool. Bull. Zool. Congr. Zool. Jahr. Zool. J. Zool. Soc. Proc. Zool. Soc. Trans. Zool. Vortr. Zoologica Zoologist Ztg. Blechind. Zts. Akklimat. Zts. allg. Erdkunde Zts. allg. osterr. Apoth. Ver. Zts. allg. Physiol. Zts. anal. Chem. Zts. Anat. Zts. ang. Chem. Zts. ang. Mikr. Zts. anorg. Chem. Zts. Bauwesen Zts. Berg-Hutten Salmenw. Zts. Biol. Proceedings of the Yorkshire Philosophical Society Correspondence Astronomique, Geographique, Hydro- graphique, et Statistique Monatliche Correspondenz zur Befdrderung der Erd- und Himmels-Kunde Die Zahntechnische Reform Annali di Fisica Nieuwe Verhandelingen van het Zeeuwsch Genootschap der Wetenschappen Archief Vroegere en Latere Mededeelingen voor- namelijk in Betrekking tot Zeeland, uitgegeven door het Zeeuwsch Genootschap der Wetenschappen Zentralblatt fur Biochemie tmd Biophysik Zentralblatt der experimentellen Medizin (former name Zentralblatt ftir die gesamte Physiologie und Pathologie des Stoffwechsds) Zentralblatt fur innere Medizin Zentralblatt fiir die oesterr-ungar Papierindustrie Zentralblatt fur Physiologie Zentralblatt fiir die gesammte Physiologie und Patho- logie des Stoffwechsels, Berlin und Wien Der Civilingenieur, Zeitschrift fur das Ingenieurwesen fiva: Casopis prirodnicky oologischer Anzeiger 2^oologische Beitrage 2^oological Bulletin See Congr. Int. Zool. C. R. Int. Congr. Zool. Proc. Zoologische Jahrbiicher. Zeitscluift fiir Systematik, Geographic und Biologic der Thiere The Zoological Journal Proceedings of the Scientific Meetings (General Meet- ings for Scientific Business) of the Zoological Society of London Transactions of the Zoological Society of London Zoologische Vortrage Zoologica. Original- Abhandltmgen aus dem Ges- ammtgebeite der Zoologie The Zoologist; a monthly Journal o( Natural History Illustrierte Zeitimg fiir Blechindustrie Zeitschrift fiir Akklimatisation : Organ des Akklima- tisations-Vereins in Berlin Zeitschrift fiir allgemeine Erdkunde Zeitschrift des allgemeinen dsterreichischen Apotheker- Vereins Zeitschrift fiir allgemeine Physiologie Zeitschrift fiir analytische Chemie Zeitschrift fiir Anatomic und Entwickelungsgeschichte Zeitschrift fiir angewandte Chemie, imd Zentralblatt fiir technische Chemie Zeitschrift fur angewandte Mikroskopie mit besond- erer Riicksicht auf die mikroskopischen Unter- suchungen von Nahnmgs- tmd Genussmitteln, technischen Produkten, Krankheitsstoflen, etc. Zeitschrift fiir anorganische Chemie Zeitschrift fiir Bauwesen Zeitschrift ftir das Berg-Hiitten und Salinenwesen im Preussichen Staate Zeitschrift fiir Biologie CXXIV UST OF ABBREVIATIONS TO LITBRATURB Zts. Hot. Zts. Chem. Zts. chem. Apparat. Zts. Chem. Jnd. Zts. chem. Ind. Kolloide Zts. Chemotherap. Zts. deut. geol. Ges. Abh. Zts. deut. Landw. Zts. Dreschler Zts. Diingerw. Zts. Hlectrochem. Zts. Entom. (Breslau) Zts. Ethnol. Zts. exper. Path. Therap. Zts. Farben-Ind. Zts. Feuerwehr. Zts. Fischerei Zts. Fleisch. Milchhyg. Zts. Geburtsh. Zts. Geburtsh. Gynakol. Zts. ges. Brauw. Zts. ges. Getreidew. Zts. ges. Naturwiss. Zts. Ges. Omith. Zts. ges. Textilind. Zts. ges. Wasserwirts. Zts. Heilk. Zts. Hyg. Zts. Immunit. Abt. I. 13. Abt. Ref. Zts. Induk. Abst. Vererb- ungslehre Zts. Instrumentenk. Zts. Klin. Med. Zts. Krebsforsch. Zts. Kryst. Mineral. Zts. landw. Versuchsw. Zts. Malakozool. Zts. Math. Phys. Zts. math. Unterf. Zts. Mikro. Tek. Zts. Morphol. Anthrop. Zts. Nahr. Genuss. (Z. genuss) Zts. Naturwiss. Zeitschrift fiir Botanik Zeitschrif t fiir Chemie Zeitschrift fur chemische Apparatenkunde (Discon- tinued) Zeitschrift fiir die Chemische Industrie mit besonderer Beriicksichtigung der chemisch-technischen Unter- suchungsverfahren 1887; later Zts. ang. Chem. Zeitschrift fiir Chemie und Industrie der Kolloide Zeitschrift fiir Chemotherapie tmd verwandte Gebiete. (formerly Folia Serologia) Zeitschrift der deutschen geologischen Gesellschaft Abhandltmgen Zeitschrift fiir deutsche Landwirthe Zeitschrift fiir Dreschsler, Elfenbdngraveure und Holzbildhauer Zeitschrift fiir Diingerwesen Zeitschrift fiir Electrochemie Zeitschrift fiir Entomologie im Auftrage des Vereins fur schlesische Insektenkimde zu Breslau Zeitschrift fflr Ethnologie Zeitschrift fiir experimentelle Pathologic und Therapie, Berlin Zeitschrift fur Farben-Industrie lUustrirte Zeitschrift fiir die deutsche Feuerwehr Zeitschrift fur Fischerei Zeitschrift fiir Fleisch- und Milchhygiene Zeitschrift fiir Geburtshiilfe tmd Frauenkrankheiten Zeitshrift fiir Gebtutshiilfe und Gynakologie lUustrirte Zeitschrift das gesammte Branwesen Zeitschrift fiir das gesamte Getreidewesen Zeitshrift fiir die Gesammten Naturwissenschaften Zeitschrift fur die gesammte Omithologie Zeitschrift fdr die gesamte Textilindustrie Zeitschrift fiir die gesamte Wasserwirtschaft Zeitschrift fur Heilkimde, als Fortsetzung der Prager Vierteljahrsschrift fur praktische Heilkunde Zeitschrift fiir Hygiene und Infektionskrankheiten Zeitschrift fiir Immunitatsforschtmjg und experimen- telle. Therapie. Abteilung I. 13. Abteilung II. or Ref. 1 vol. Zeitschrift fiir Induktive Abstammungs- und Vererb- ungslehre Zeitschrift fiir Instrumentenkunde Zeitschrift fiir Klinische Medizin Zeitschrift fiir Krebsforschung Zeitschrift fiir Krystallographie und Mineralogie Zeitschrift fiir das landwirtschaftliche Versuchswesen in Oesterreich Zeitschrift fiir Malakozoologie Zeitschrift fiir Mathematik und Physik Zeitschrift fiir mathematischen und naturwissenschaft- lichen Unterrricht Zeitschrift fiir Mikroscopischen Teknik. Zeitschrift fiir Morphologie und Anthropologie Zeitschrift fiir Untersuchung der Nahrungs und Genussmittel, sowie der Gebrauchsgegenstande Zeitschrift fur Naturwissenshaften. . .im Auftrage (Organ) des NaturwissenschafHichen Vereins fOr Sachsen und Thiiringen LIST OF ABBREVIATIONS TO LITERATURE CXXV Zts. offentl. Chem. Zts. Ohrenheilk. Zts. osterr. Ing. Ver. Zts. paraf. Ind. Zts. Parasit. Zts. Pflanzenkrankheiten Zts. physik. Chem. Zts. Physik. Chem. Unterr. Zts. Physiol. Chem. Zts. prakt. Geol. Zts. PsychoL Zts. ration. Med. Zts. Reprodiikt. Zts. Rubenzuckeiind. Zts. Schiess Spreng. Zts. Spiritusind. Zts. Telegr. Ver. Zts. Thiermed. Zts. Tuberkulose Zts. Ver. deut. Ingen. Zts. Ver. Rubenzuckerind. Zts. Ver. Zuckeiind. Zts. Wiss. Geogr. Zts. wiss. Mikro. Zts. wiss. Photochem. Zts. wiss. Zool. Zts. Zuckerind. Zts. Zuckerind. Bdhm. Zurich Denkschr. Med. Chir. Ges. Zurich Mitth. Zurich, Monats. Zurich natw^. Ges. Zurich Physik. Ges. Jahr. Zurich, Schweiz. Ges. Neue. Denkschr. Zurich, Sec. Hntom. Zurich, Unters. Physiol. Lab. Zurich, Verh. Zurich, Vierteljahrschr. Zwickau Ver. Naturk. Jahr ZwoUe. Vooruitgang. Zeitschrift fur dffentliche Chemie Zeitschrift fur Ohrenheilkimde in deutscher tmd englischer Sprache Zeitschrift des dsterreichischen Jngenieur und Archi- tekten Vereins Zeitschrift fur Parafin Industrie Zeitschrift fur Parasitenkunde Zeitschrift fur Pflanzenkrankheiten Zeitschrift ftir physikalische Chemie, Stdchiometrie und Verwandschaftslehre Zeitschrift fur dem physikalischen imd chemischen Unterricht Zeitschrift fur physiologische Chemie (Hoppe-Seylers) Zeitschrift ftir praktische Geologie Zeitschrift fur Psychologic und Physiologic der Sinnes- organe Zeitschrift ftir rationelle Medidn Zeitschrift fur Reproduktiontechnik Neue Zeitschrift ftir Rtibenzuckerindtistrie ^ Zeitschrift ftir das gesammte Schiess- und Spreng- stoffwesen Zeitschrift ftir Spiritusindustrie Zeitschrift des deutsch-osterreichischen Telegraphen- Vereins Zeitschrift fur Thiermedicin Zeitschrift ftir Tuberktilose tmd Heilstattenwesen Zeitschrift des Vereins deutscher Ingenieiu'e Zeitschrift des Vereins ftir die Rtibenzucker-Industrie des deutschen Reichs Zeitschrift des Vereins der deutschen Zuckerindustrie Zeitschrift ftir wissenschaftliche Geographic Zeitschrift fiir wissenschaftliche Milo'oscopie Zeitschirft fur wissenschaftliche Photographic, Photo- physik, tmd Photochemie Zeitschrift fur wissenschaftliche Zoologie Zeitschrift fur Zuckerindustrie Zeitschrift ftir Zuckerindtistrie in Bdhmen Denkschrift der medizinisch-chirurgischen Gesell- schaft des Kantons Zurich Mittheilungen der Naturforschenden Gesellschaft in Zurich Monatsschrift des wissenschaftlichen Vereins in Zurich Viertdjahrschrift der nattu^orschenden Gesellschaft in Zurich . . . Jahresbericht der physikalischen Gesellschaft in Zurich Neue Denkschriften der allgmeinen Schweizerischen Gesellschaft fiir die gesammten Natiuwissen- schaften Sodetas Entomologica. Organ fiir den intemationalen Entomologenverein. Ziirich Untersuchtmgen aus dem Physiologischen Labora- torium der Ziiricher HochschtUe Verhandltmgen der Medicinisch-chinirgischen Gesell- schaft des Kanton Ziirich im Jahr 1826 Vierteljahrsschrift der Naturforschenden Gesell- schaft in Ziirich Jahresbericht des Vereins fiir Nattu-kunde zu Zwickau De Vooruitgang; Tijdschrift voor Wetenschap CHAPTER I. CELLULOSE. » Comprehensive knowledge of the nature, limitations and inner mechanics of cellulose esterification and etherification presupposes a thorough understanding of the substituent groups or aggregates entering into and comprizmg those esters and ethers, including an intimate fimdamental acquaintance with the various normal and modified celluloses and cognate carbohydrates — ^the predominating constituent of plant tissues, and the structural basis of the vegetable world. Comparatively speaking, there are few substances more intricate in composition, complex in constitution, or ramified in 1. For general information upon the subject of cellulose development, see T. Anderson, N. Ed. Phil. J. 1849, 47, 132; J. prakt. Chem. 1849, 47, 449; Jahr. Chem. 1849, 2, 484. Barreswil and Rilliet, N. J. Pharm. 21, 205; J. prakt. Chem. 1852, 56, 334; abst. Jahr. Chem. 1852, 5, 657. v. Baumhauer, Scheik. Onderzoek, 2, 62, 194; abst. Ann. 1843, 48, 356; J. prakt. Chem. l&H, 32, 204, 210; N. Br. Arch. 53, 68; Berz. Jahr. 1846, 25, 585. A. Bechamp, Compt. rend. 1853, 37, 134; 1856, 42, 1210; Inst. 1853, 261; Ann. Chim. Phys. 1856, (3). 48, 461; Ann." -4856, 100, 367; J. prakt. Chem. 1856, OS, 449; Jahr. Chem. 1856, 9, 670, 674. Blondeau de Carolles, Rev. Sci. 1843, 14, 476; abst. J. prakt. Chem. 1844, 32, 427; Berz. Jahr. 1846, 25, 582. Boettger, J. prakt. Chem. 1843, 30, 257; Ann. 1843, 47, 329; Berz. Jahr. 1845, 24, 464. Braconnot, Ann. Chim. Phys. 1819, (2), 12, 172; Schw. J. 1819, 27, 328; Gilb. Ann. 1847, 03, 347; abst. Berz. Jahr. 1822, 1, 107. Chodnew, Ann. 1844, 51, 393. C. Cramer, J. prakt. Chem. 1858, 73, 1; abst. Chem. Centr. 1858, 60. P. Damis, Dingl. Poly. 1855, 137, 376; Mon. Ind. 1855, No. 1986; abst. Jahr. Chem. 1855, 8, 901. L. de Koninck, Dingl. Poly. 1857, 144, 359; Rev. univ. 1857, 131; abst. Jahr. Chem. 1857, 10, 648. DuUo, Dinel. Poly. 1860, 158, 392; Chem. Centr. 1860, 25; abst. Jahr. Chem. 1860, 13, 715; J. Emmet (SiU.), Am. Jour. Sci. 1837, 32, 140; J. prakt. Chem. 1837, 12, 120; abst. Berz. Jahr. 1839, 18, 275. O. Erdmann and M. Mittenzwey, J. prakt. Chem. 1859, 70, 386; Chem. Centr. 1859, 642; abst. Jahr. Chem. 1859, 12, 541. A. Franchimont, Compt. rend. 1879,89,711, 713, 755; Ber. 1879, 12, 1939; abst. Jahr. Chem. 1879, 832. E. Fremy, Compt. rend. 1859, 48, 202; N. J. Pharm. 35, 81; abst. Rep. Chim. Pure, 1859, 1, 269; Compt. rend. 1859, 48, 325, 360, 667, 862; J. Pharm. 35, 321, 401; abst. Inst. 1859, 121. 151; Rep. Chim. Pure, 1859, 1, 357, 433; Pharm. Vierteljahr. 9, 221. N. J. Pharm. Inst. 1&59, 357; Rep. Chim. Pure, 1869, 1, 602; Chem. Centr. 1860, 4. Compt. rend. 1859, 49, 661; Jahr. Chem. 1859, 12, 529, 530, 532, 533, 534, 537, 540. E. Fremy and Terrell, J. Pharm. Chim. 1868, 7, 241; Chem. Centr. 1868, 616; abst. Jahr. Chem. 1868, 762. Fromberg, Scheik. Onderzoek, 2, 36; abst. Ann. 1843, 48, 353; J. prakt. Chem. 1844, 32, 198; Mulder, Physiol. Chem. 1844, 2 TECHNOLOGY OF CELLULOSE ESTERS reactivity, or about which it is more difficult to arrive at tangible, definite conclusions than with the celluloses. This is partially accountable from the fact that what we call "cellulose" is not the distinctive name of a definitely characterized chemical individual, but rather the collective name of a closely interrelated series of allied members, which often by imperceptible gradations merge one into another. Their ready susceptibility to oxidation and reduction; hydrol3rsis and dehydration; condensation and depol3anerization; either before, dtuing or after alkylation or acidylation, thus 198; Berz. Jahr. 1845, 24, 462. Fourcroy, Systeme des Connaissances chim- iques, 8, 87. J. Gladstone, Mem. Chem. Soc. 1850, 3, 412. E. Gilson, La Cellule, 1893, 9, 397; abst. J. C. S. 1894, 66, i, 107; Chem. Centr. 1893, II, 530; Jahr. organ. Chem. 1893, 1, 265; J. S. C. I. 1894, 13, 1106; Bull. Soc. Chim. 1894, 11, 590; Jahr. Chem. 1893, 881. Gay-Lussac, Ann. Chim. Phys. 1829, (2), 41, 398; Pogg. Ann. 1829, 17, 171 ; Schw. J. 1830, 58, 87; abst. Berz. JahA 1831, 10. 183. Gmelin, Schw. J. 1830, 58, 374, 377. W. Henneberg, Ann. 1868, 146, 130; abst. BuU. Soc. Chim. 1868, (2), 10, 414; Jahr. Chem. 1868, 761. Compare Ritter, Jahr. Chem. 1868, 761. Harting, Scheik. Onder- zoek. 3, 17; abst. Berz. Jahr. 1847, 26, 613; J. prakt. Chem. 1846, 37, 329; Annuaire de Chim. 1847, 606. W. HofFmeister, Landw. Versuchstat. 1886, 33, 153; abst. Jahr. Chem. 1886, 2103; 1891, 39, 461; 1897, 48, 401; 1901, 55, 115; Undw. Jahr. 1888, 17, 239; 1889, 18, 767; J. C. S. 1886, 50, 954; 1890, 58, 581; 1892, 62, 129; 1898, 74, ii, 148, 544; 1901, 80, ii, 205; Ber. 1893, 26, R, 497; Jahr. Chem. 1898, 1368; 1901, 889; Chem. Centr. 1890, I. 112; 1897, 1, 1004; 1901, 1, 862; J. S. C. 1. 1897, IS, 940. Hermann, J. prakt. Chem. 1841, 23, 380; 1842, 27, 165; abst. Berz. Jahr. 1843, 22, 499; 1844, 23, 315. Johnson, Bot. Gaz. 1895, 20, 16. John, Chem. Schriften, 4, 204. G. Kindt, Dingl. Poly. 1846, Utt, 334; 1847, 105. 189; Chem. Centr. 1865, 320; Ann. 1847, 61, 253; Phil. Mag. 1847, (3), 31, 157; J. Pharm. (3), 11, 324; Jahr. Chem. 1847-8, 1, 1122. F. Koch, Pharm. Zts. Russ. 25, 619, 635, 651, 667. 683, 699, 730, 747, 763; abst, Ber. 1887, 20, 145. W. Kirchner and B. ToUens, Ann. 1875, 175, 221; abst. J. C. S. 1875, 28, 1179; Jahr. Chem. 1875, 799; Jahr. rein Chem. 1875, 3, 381. H. Kopp, Ann. 1840, 35, 39. Mitscherlich, Berl. Akad. Ber. 1850, 102; Ann. 1850, 75, 305; J. prakt. Chem. 1850, 50, 144; abst. Pharm. Centr. 1850, 385; Chem. Gaz. 1851, 61; Instit. 1850, 228; Jahr. Chem. 1850, 3, 541. H. v. Mohl, Flora, 1840; Vermischte Schriften, 1845, 335; Bot. Ztg. 1847, 497. A. Morin, Ann. Chun. Phys. 1832, (2), 49, 311 ; Bull, univers. 50, 337; Schw. J. 66, 362; abst. Berz. Jahr. 1834, 13, 77. G. Mulder, Scheik. Onderzoek. 2, 76; abst. J. prakt. Chem. 1844, 32,336; Ann. 1841, 39, 150. A. Miintz, Compt. rend. 1882, 94, 453; abst. Jahr. Chem. 1882, 1151; Bull. Soc. Chim. 1882, (2), 37, 409; Ber. 1882, 15, 937; J. C. S. 1882, 42, 707; Chem. News, 1882, 45, 99. Compt. rend. 1886, 102, 624, 681; abst. J. C. S. 1886, 50, 575; BuU. Soc. Chim. 1886, (2), 46, 486; Ber. 1886, 19, 299; J. S. C. 1. 1886, 5, 386; Chem. News, 1886, 53. 167, 180; Jahr. Chem. 1886, 1809. A. Payen, N. Ann. Sc. Nat. Bot. 1839, 11, 21, 27;l4,37; Compt. rend. 1840, 10, 941 ; 1844, 18, 271 ; 1859, 48, 210, 275. 319, 326, 328, 358, 362, 772, 893 ; abst. Rep. Chim. Pure, 1859, 1, 270, 359, 434; N. J. Pharm. 35, 88, 185. Jahr. Chem. 1859, 12, 530, 531, 532, 533, 534, 536, 539; Ann. Sc. Nat. 1839, (2), 2, 21; 1840, (2), 3, 73. E. Peligot, Compt. rend. 1839, 9, 135; 1858, 47, 1037; abst. Berz. Jahr. 1841, 20, 541; abst. Jahr. Chem. 1858,11,574. See also C. Gerbardt, Ann. Chim. Phys. 1839, (2), 72, 208, (Cuprammonium). J. Pelouze, CBW.UU>SE . 3 giving rise to an indeterminate number of products often similar in appearance, analogous in properties yet differing from the original cellulose, only complicates the subject. Especially is this true, where the elementary composition remains the same and the chemical changes are analytically indistinguishable. All plant tissues — ^from the minute imicellular organism to the giant conifers of California — are comprised of cells, and the envelope or investing matrix of these cells is composed of cellulose. In the higher plants the individual cells co-apt and coalesce in such a manner that their walls are broken up with the formation of Compt. rend. 1859, 48, {310, 327; N. J. Pharm. 35, 88; Rep. Chim. Pure, 1859' 1, 272; Dingl. Poly. 1859, lO, 394; Jahr. Chem. 1859, U, 532. A. Poggiale' N. J. Pharm. 36, 121; Compt. rend. 1859, 49, 128; abst. Rep. Chim. Pure, 1859, 1, 521: Chem. Centr. 1859, 844; Jahr. Chem. 1859, 12, 733. J. Porter, Ann. 1849, 71, 115; Am. J. Sci. (Sill.) 1850, (2), 9, 20; abst. Pharm. Centr 1849, 777; Chem. Gaz. 1849, 469; Jahr. Chem. 1849, 2, 474. L. Pozzoz, Compt. rend. 1858, 47, 207; J. prakt. Chem. 1859, 7G, 314; abst. Jahr. Chem. 1858, 242. J. Poumarede and O. Piguter, Memoire sur le Ligneux, etc. Paris, 1847; N. J. Pharm. U, 458; 12, 81 ; J. prakt. Chem. 1847, 42, 25; Compt. rend. 1846, 23, 918; 1847, M, 17: Ann. 1847, 64, 387; Repert. Pharm. (2), 47, 344; Jahr. Chem. 1847-8, 1, 795, 797. J. Proust, J. Phys. 48, 469; Schw. J. 7, 707. L. Radikofer, Ann. 1855, 94, 332; abst. J. prakt. Chem. 1855, 66, 127; Pharm, Centr. 1855, 26, 566; Dingl. Poly. 1855, 138, 152; Jahr. Chem. 1855, 8, 821. T. Ransome, Phil. Mag. 1887, 30, 4. J. Reade, Lon. Ed. Phil. Mag. 1837, 11, 421. H. Reinsch, Jahr. Pr. Pharm. 14, 25; Dingl. Poly. 1860, 156, 156; Chem. Centr. 1860, 491; Bayer. Gewerbeztg. 1860, No. 8; Jahr. Chem. 1859, 12, 746. R. Reiss, Ber. 1889; 22, 609; Jahr. Chem. 1889, 2086; 1890, 2183. Landw. Jahr. 1889, 18, 707; Chem. Centr. 1889, I, 541; 1890, I, 165; Bot. 7, 322; J. S. C. I. 1889, 8, 406; J. C. S. 1889, 56, 687; 1891, 60, 366; BuU. Soc. Chim. 1890, (3), 3, 713; Rev. g€n. Sd. 1890, 1, 244. F. Rochleder and W. Heidt, Ann. 1843, 48, 8; abst. Berz. Jahr. 1845, 24, 382; J. Pharm. 1844, 5, 89. P. Rochleder, Ann. 1844, 50, 225; abst. Berz. Jahr. 1846, 25, 864; Ann. 1846, 59, 300; 1847, 63, 193; J. prakt. Chem. 1846, 39, 367; J. Pharm. 1844, 6, 161; 1848, 14, 445. J. Rossignon, Compt. rend. 1842, 14, 873; B. Rumford, Schw. J. 8, 160. F. Sacc, Ann. Chim. Phys. 1849, (3), 25, 218; J. prakt. Chem. 1849, 46, 430; Pharm. Centr. 1849, 235; Chem. Gaz. 1849, 274; Jahr. Chem. 1849, 2, 473. N. Saussure, N. AUg. J. Chem. (Gehl.) 1804, 4, 681. Ann. Chim. Phys. 1804, 50, 225; Ann. Phys. (Gilb.) 1804, is, 208; J. de Phys. 1804. 58, 393; PhU. Mag. 1805, 20, 307. Schaefer, Ann. 1871, 160, 312; abst. Jahr. Chem. 1871, 789; Bull. Soc. Chim. 1872, 17, 371; J. C. S. 1872, 25, 309. J. Schlossberger, Ann. 1858, 107, 22; J. prakt. Chem. 1868, 73, 370; N. Br. Arch. 95, 145; Ann. 1859, HO, 246; N. Jahr. Pharm. 12, 6; abst. J. prakt. Chem. 1859, 77, 508; Rep. Chim. Pure, 1859, 1, 432; Chem. Centr. 1858, 474; Jahr. Chem. 1858, 11, 199; J. prakt. Chem. 1859, 78, 370; abst. Rep. Chim. Pure. 1860, 2, 142; Jahr. Chem. 1859, 12, 542; see also J. prakt. Chem. 1859, 78, 372. J. Schrader. Schw. J. 33, 410. E. Schweizer, Chem. Centr. 1858, 49; J. prakt. Chem. 1857, 72, 109; 1859, 78, 370; Rep. Chim. Pure, 1860, 2. 142; Vierteljahrsch. Zurich, naturforsch. Gess., abst. Dingl. Poly. 1857, 146, 361; Jahr. Chem. 1857, 10, 246. M. Schleiden, Berz. Jahr. 1841, 20, 342; Wiegm. Arch. 1838, 59; Pogg. Ann. 1838, 43, 391; Grundz. d. wissensch. Botanik, Leipzig. 1849, 1, 172; Ann. 1836, 17, 139; 1839, 30, 2660; 1842, 42, 306; Flora, 1^2, 237. J. Schlossberger and O. Doep- 4 TECHNOLOGY OF CELI^UI^OSE ESTERS tubular structures, which often attain extraordinary lengths — i. e. , several hundred times their diameter. Carbohydrates are a widely distributed and numerous class of bodies, found in the vegetable kingdom primarily, although carbohydrates of animal origin are not unknown. Strictly speaking, they contain six or a multiple of six carbon atoms, and from the fact that they always contain carbon,' and the ratio of the hydrogen and oxygen atoms is the same as in water, accounts for their name. The carbohydrates form the basis of alcoholic drinks and ping, Ann. 1844, S2, 113; abst. Berz. Jahr. 1846, 25, 588; Annuaire Chim. 1846, 636. E. Schmidt and Hecker, J. prakt. Chem. 1847, 40, 257; abst. Jahr. Chem. 1847-8, 1, 1130; Poly. Centr. 1847, 36. F. Schulze, Beitrage zur Kenntniss des Lignins, Rostock, 1856; abst. Chem. Centr. 1857, 321; Jahr. Chem. 1855, 702, 1019. E. Schulze and E. Steiger, Ber. 1887, 20, 290; abst. Jahr. Chem. 1887, 2270; Bull. Soc. Chim. 1887, 48, 280. J. C. S. 1887, 52, 460; Chem. News, 1889, 59, 377; J. S. C. 1. 1887, 6, 446. C. Schmidt, J. prakt. Chem. 1846, 38, 433. L. SchaflFner, Ann. 1^44, 50, 148; abst. Berz. Jahr. 1846, 25, 586. P. Schuetzenberger, Zts. Chem. Pharm. 1861, 4, 65; abst. Bull. Soc. Chim. 1861, (1), 3, 16. P. Thenard, Compt. rend. 1861, 52, 444; Rep. Chim. Pure, 1861, 3, 207; BuU. Soc. Chim. 1861, (1), 3, 33; Jahr. Chem. 1861, 14, 908; Chem. News, 1861, 4, 136. G. Staedeler, Ann. 1859, 111, 27; J. prakt. Chem. 1859, 78, 169; Chem. Centr. 1859,705; J. Pharm. (3), 36, 229; Rep. Chim. Pure, 1859, 1, 569; Tahr. Chem. 1859,12, 598. J. Stenhouse, Phil. Mag. 1841, 18, 122; Ann. 1840, 35, 301. J. Thomson, Ann. 1849, 69, 128; J. prakt. Chem. 1840, 19, 146; Phil. Mag. 1834, 5, 365. L. Vauquelin, Schw. J. 12, 2530. F. Versmann and A. Oppenheim, Pharm. J. Trans. (2), 1, 385, 422; Chem. News, 1860, 1, 20; Jahr. Chem. 1860, 13, 715; Br. Assoc. Rep. No. 29, 86; J. prakt. Chem. 1860, 80, 433; Dingl. Poly. 1860, 158, 66; Zts. Chem. Pharm. 1860, 240; see also Dingl. Poly. 1860, 156, 157; abst. Chem. Centr. 1860, 352; Rep. Chim. Appl. 1860, 2, 59. M. Vincent, Compt. rend. 1847, 24, 542; abst. Pharm. Centr. 1848, 500; Jahr. Chem. 1847-8, 1, 1122; see also Gaudichaud, Boussingault and Payen; Compt. rend. 1849, 29, 491; abst. Instit. 1849, 353; Mon. ind. 1849, No. 1397; Dingl. Poly. 1850, 115, 150; Pharm. Centr. 1849, 909; Jahr. Chem. 1849, 2, 711. Weiss, Chem. Centr. 1871, 179; Mon. Sci. 1869, 11, 342; 1870, 12, 23; Bull. Soc. Chim. 1870, 13, 93 ; Jahr. Chem. 1869, 1 ia3. H. Weber, Pharm. Viertelj, 7, 538 ; Pharm. Centr. 1858, 864 ; Jahr. Chem. 1858, U, 577. E. Winterstein, Ber. 1893, 26, 362; abst. Chem. Centr. 1893, I, 602; Jahr. organ. Chem. 1893, 1, 266; Zts. Physiol. Chem. 1893, 18, 43; Bull. Soc. Chim. 1893, 10, 699; J. C. S. 1893, 64, i, 380, 497 ; Meyer Jahr. Chem. 1893, 3, 236 ; J. S. C. I. 1893, 12, 702. F. Winkler, J. prakt. Chem. 1839, 17, 65. Bachet, Jahr. Chem. 1866, 663. N. Basset, Belg. P. 138952, 1898. J. Batka, Chem. Centr. 1859, 865; abst. Poly. Notiz. 1860, 15, 3; Dingl. Poly. 1859, 154, 395; Vierteljarhsch. Pharm. 9, 275; Rep. Chim. Pure, 1860, 2, 142; Jahr. Chem. 1859, 12, 543. E. von Baumhauer and P. Fromberg, Ann. 1^43, 48, 356; J. prakt. Chem. 1844, 32, 204. Chem. Gazz. 1847, 5, 413; J. prakt. Chem., 1844, 32, 210. A. Bacycr, Ber. 1869, 2, 54; abst. Bull. Soc. Chim. 1869, 12, 292. F. Bayer & Co. Belg. P. 220582, 1910; F. Beltzer Rev. gen. Chim. 1910, 13, 20; abst. Chem. Zentr. 1910, I, 1596; C. A. 1910, 4, 1369. C. Beadle, J. Frank. Inst. 1894, 138, 100; abst. Jahr. Chem. 1894, 1134; Chem. Trade J. 1894, 128; J. S. C. I. 1894, 13, 900. J. Beggaard and B. Gott- schalk, Norw. P. 20847, 1909. R. Boettgcr, Chem. Centr. 1874, 309; Dingl. CELLULOSE 5 the majority of foodstuffs, starch being the chief ingredient of flour, from which bread is made. Cellulose, related to it, is of interest in this work from the fact that organic and inorganic esters may be prepared therefrom, of increasing interest both m the peaceful and warlike arts. According to the older system of carbohydrate classifica- tion three groups were recognized, one containing isomeric Poly. 1874, 213, 362; Jahr. phys. Ver. Frankfurt, 1872-73, 70; Zts. anal. Chem. 1874, U, 246; Jahr. Chem. 1874, 1031. A^folassi. Caout. Guttap. 1918, 15, 9604; abst. J. S. C. 1. 1918, 37, 686- A. T. Chaudhuri, Modern Chemistry and Chemical Industry of Starch and Cellulose, 156 pages. C. Cross and E. Bevan, J. Soc. Arts, 1896-7, 45, 225, 684, 703.716 ; Proc. U. S. Nav. Inst. 1886, 12, 624; Chem. News, 1889, 60, 163, 254; abst. Chem. Centr. 1889, II, 790; 1890, I, 21; Jahr. Chem. 1889, 2066; 1890, 2152. J. C. S. 1890, 57, 1. Compagnie Industrielle des alcools de I'Ardeche, Swiss P. 53961, 1910; A. Deiss, Span. P. 47327, 1910; Port. P. 7164, 1910. A. Deiss and C. Foumier, Aust. P. Anm. 6861, 1909. K. Dimcan, Sci. Amer. Suppl. Apr. 28, 1900. E. Durin, Ber. 1876, 9, 1430, 1446; Compt. rend. 1876, 83, 128; abst. Chem. News, 1876, 34, 63; J. C. S. 1877, M, 106; Jahr. Chem. 1876, 947. E. Jandrier, Schw. Wochensch. f. Pharm. u. Chem. 1899, 489; abst. Amer. J. Pharm. 1900, 72, 497; Compt. rend. 1899, 128, 1407; Chem. Centr. 1899, II, 184; Bull. Soc. Chim. 1899, (3), 21, 895; Jahr. Chem. 1899, 1295, 1297; J. A. C. S. 1899, 21, 1175; J. C. S. 1899, 76, i, 788; 1900, 78, ii, 177; Chem. News, 1899, 80, 11. C. KeUner, U. S. P. 773941, 1904; abst. J. S. C. I. 1904, 23, 1159; F. P. 326313, 1902, abst. J. S. C, I. 1903, 22, 817, 1304; Mon. Sci. 1904, 81, 46. A. Klein, Papier Ztg. 31, 4286; Chem. Ztg. 1906, 30, 1259; abst. C. A. 1907, 1, 485, 2492; Wochenbl. Papierfabr. 38, 1813; Zts. ang. Chem. 1907, 20, 610; Bull. Soc. Chim. 1907, (4), 2, 905; Chem. Centr. 1907, I, 381. W. Massot, Zts. ang. Chem. 1909, 22, 241, 299; 1911, 24, 433; abst. Kunst. 1911, 1, 452; Chem. Zentr. 1909, I, 801; 1911, I, 1259; C. A. 1910, 4, 1240; 1911, 5, 1995. P. Marino, Ital. P. 302/5/101627, 1909. P. Michela, Ital. P. 30024, 1892. H. Mork, J. Frank. Inst. 1917, 184, 353; abst. C. A. 1917, U, 3430. A. Sander, Fortschritte Chem. 4, 293; abst. C. A. 1912, 6, 153. C. Schwalbe, Chem. Zts. 1908, 32, 287; abst. J. C. S. 1908, 84, i, 260, 321; Mon. vSci. 1910, 72, 825; J. Frank. Inst. 170, 371; Papier Ztg. 36, 2496, 2531, 2667. 2699, 2735, 2769; abst. C. A. 1911, 5, 3908; Papier Ztg. 36, 2599, 2631; abst. C. A. 1911, 5, 3729; Papier Ztg. 39, 2486, 2543; abst. C. A. 1915, 9, 713. J. Schmitt, F. P. 377979, 1907; abst. J. S. C. I. 1907, 26, 1088; Mon. Sci. 1908, 69, 29; C. A. 1908, 2, 1368. F. Schulz, Zts. physiol. Chem. 1900, 29, 124; abst. J. C. S. 1900, 78, ii, 292; Chem. Centr. 1900, I, 729; Bull. Soc. Chim. 1901, 26, 32. Societe Thirion et Bonnet, F. P. 308446, 1901. W. Walker, Mon. Sci. 1908, 69, 461; J. Frank. Inst. 1907, 164, 131; abst. C. A. 1908, 2, 318, 2619. W. Whitney, U. S. P. 923745; abst. J. S. C. I. 1909, 28, 743; see also U. S. P. 923227; abst. J. S. C. I. 1909, 28, 743; C. A. 1909, 3, 2091. Wichelhaus, Inter. Cong. London, abst. Zts. ang. Chem. 1909, 22, 1119. Ber. 1910, 43, 2922; abst. J. S. C. I. 1910, 29, 1369; Chem. Zentr. 1910, II, 1961; J. C. S. 1910, 98, i, 868; Meyer Jahr. Chem. 1910, 20, 317; Bull. Soc. Chim. 1911, (4), 10, 1054; C. A. 1911, 5, 2953; Rep. Chim. Appl. 1911, 11, 138. W. Viewer, Wochenblatt fiir Papier fabrikat ion, 1911, 3541, 3729; abst. Kunst. 1911, 1, 452; C. A. 1911, 5, 3907. Papier Ztg. 1907, 32, 309. 398; Chem. Ztg, 1907, 31, 85; Chem. Zentr. 1907, I, 677; C. A. 1907, 1, 1319. E. Vitrebert, Papier, 1914, 17, 134; abst. C. A. 1915, 9, 148. Worlds Paper Tr. Rev. 67, No. 8, p. 32; No. 12, p. 22. See Caout. et Guttap. 1919, 16, 9888; C. A. 1919, 13, 3314. 6 TECHNOUKJY OF CEl<I.ULOSE ESTERS compounds of the type CeHuOa termed the glucose or grape sugar group; a second containing compounds of the formula CisHasOii and designated as the saccharose or cane-sugar group; while a third division was made of the highly complex, crypto- crystalline or amorphous compounds, to which starch and cellu- lose are t3rpes. This classification, although inadequate is still retained, the word "glucose" being now reserved for the dextro and laevo enantiomorphs of grape sugar to take the place of the older word **dextrose," wt4^ became unsuitable after the discovery of the laevo enantiomorphic form. As a comprehensive class- ification, the three older groups of carbohydrates may be distin- guished by the names: Monosaccharoses, Monosaccharides, Monoses (formerly glucoses). Disaccharoses, Disaccharides, Saccharobioses (formerly saccharoses). Polysaccharoses, Polysaccharides (formerly amyloses). After E. Fischer had succeeded in synthesizing a number of new sugars containing more or less than six carbon atoms, a further subdivision of the monosaccharoses became necessary. Many new compounds were synthesized, containing two to nine carbon atoms and possessing the general characteristics of the monosaccharoses, and being distinguished by the names biose, triose, tetrose, etc. Inasmuch as some of the monosaccharoses combine the properties of alcohol and aldehydes, while others partake of the properties of alcohols and ketones, the fiuther distinction of "aldose" and "ketose" has been necessary. ToUens* has devised the following comprehensive scheme of classification of the carbohydrates: I. Monosaccharides (Glycoses). (a) Monose, Formaldehyde. (b) Diose, Glycolaldehyde, Glycolose. (c) Triose, Aldotriose (Glycerose), Ketotriose (Dioxy- acetone). (d) Methyltriose, Methylglycerolaldehyde. 1. "Kurtz Lehrbuch der Kohlenhydrate," 1914. E. v. Lippmann, "Die Chemie der Zuckerarten," 1904. L. Macquenne, "Les Sucres et leurs principaux derives," 1900. E. Armstrong, "The Simple Carbohydrates," 1910. E. Fischer, "Untersuchungen ueber Kohlenhydrate 1884r-1908/' 1909. CELLULOSE 7 (e) Tetrose, Aldotetrose (Er3rthrose), Ketotetrose (Ery- thrulose). (f) Pentose, Arabinose, Xylose, Ribose. (g) Methylpentose, Rhanmose, Rhodeose, Fucose. (h) Hexose, Glucose, Mannose, Galactose, Fructose, Sorbose, (i) Glycose with 7 carbon atoms, Rhamnohexose. (]) Glycose with 8 carbon atoms, Rhanmoheptose, Mannooctose. (k) Glycose with 9 carbon atoms, Rhamnooctose, Mannononose. (1) Glycose with 10 carbon atoms, Glucodecose. II. Di- and Poly-saccharides. (a) Disaccharide, Arabiose, Saccharose, Maltose, Cel- lose, Lactose. (b) Trisaccharide, Rhamnotriose, Raffinose, Melezitose, Triamylose. (c) Tetrasaccharide, Lupeose, Stachyose, Manneo- tetrose. III. Polysaccharide (Saccharo-coUoids). (a) Pentosan-coUoids, Araban, Xylan. (b) Arabin, Tragacanth, Bassorin, Pectins. (c) Starch, Dextran, Glycogen, Hemicellulose, Amyl- oid, Lichenin. (d) Paramanan, Seminin. (e) Gelactan, Gelose, Gelan. (f) Levulosin, Fructosan, Inulin, Asparagose. (g) Glucosamine. (h) Cellulose, Hydrocellulose, Oxycellulose, Cellulose Esters. In general, the molecular magnitude is the basis of arrangement of these polyhydroxy-aldehydes and ketones, and to the sub- stances which give these when hydrolyzed by heating with mineral acids. Nearly all of the naturally occurring carbohydrates are optically active, the specific rotatory power being influenced not only by the temperature and concentration of their solutions, but also not infrequently by the presence of optically inactive 8 TECHNOU)GY OF CELLULOSE ESTERS bodies.^ Some representatives also exhibit the phenomena of birotation and semirotation. By heating the solutions for a brief period, constant rotation is usually obtained. The deter- mination of the rotatory power of the carbohydrates by means of the saccharometer, not only aseertains their purity, but may be made quantitative. As to their general characteristics. The members may be either soluble or insoluble, in water, those soluble being usually of a sweet taste, and the insoluble carbohydrates may be trans- formed into soluble by hydrolytic treatment. The mono- saccharoses are colorless crystalline compoimds, reducing alka- line solutions of the heavy metals as copper. Characteristic compoimds are formed with phenylhydrazine. The di- and poly-saccharoses are converted into simple car- bohydrates when hydrolyzed, either by mineral acids or by enzymes. The complicated carbohydrates of which cellulose is a type are amorphous, tend to form colloidal solutions, and relatively speaking, are chemically inert. By virtue of the hydroxyl groups which they contain, they react with nitric acid, organic acids and alkylating agents, forming esters, and ethers, the detailed descrip- tion of which forms the subject matter of the volumes in this series. Classification of Celluloses. E. Premy,^ who has classified the celluloses and allied bodies, has distinguished them according to their chemical basis as follows: (a) Celluloses proper, including normal cellulose, meta- cellulose and para-cellulose. (b) Vasculose, identical with lignocellulose and found chiefly in woody fiber. (c) Cutose, and (d) Pectose, found in unripe, fleshy fruits and roots, and transformed under the influence of acids into pectins 1. R. Pribram, Ber. 1888, 21, 2599; Wien. Akad. Ber. II b, $7, 375; Monatsh. $, 395; abst. J. C. S. 1888, 54, 1229; Bull. Soc. Chim. 1889, (3), 1, 782; Chem. Ind. 1888, 11, 554; Jahr. Chem. 1888, 2580; J. S. C. I. 1888, 7, 594. 2. Compt. rend. 1859, 48, 667; abst. J. Pharm. (3), 35, 321; Instit. 1859, 121; Rep. Chim. Pure, 1, 351; Jahr. Chem. 1859, 534. Compt. rend. 1876, 83, 1136; abst. Bull. Soc. Chim. 1877, 28, 174; Ber. 1877, 10, 90. His classification has not found favor with some critical writers. CELLULOSE 9 There are a large number of substances, more or less, intimately related to cellulose, to which the term "compound-celluloses** has been applied. These compoimd celluloses are usually sub- divided into the three following groups: I. Pectocelluloses, which include most of the vegetable textile fibers with the exception of cotton, which forms a class by itself, and jute, which is a lignocellulose. The non-cellulose constituents are usually pectic substances, characterized as vegetable extractive bodies of an acid nature which readily gelati- nize.^ Unlike the adipocelluloses, they are said to be slightly richer in oxygen than normal cellulose, an analysis of raw flax (which is typical of this class) giving C. 43.7, H. 5.9, O. 50.4. On boiling with dilute alkali the pectocelluloses are readily resolved into cellulose, the pectic matters being transformed into soluble derivatives, and this is what takes ^lace in tlie bleaching of linen. Many other fibers contain or consist of pectocelluloses,^ these derivatives having been identified by E- Schunk in the products of the alkaline boiling of raw cotton.' The cellular portion of certain fruits (apple, pear, plum), and roots (turnip, carrot, beet) contain large amounts of pectocellulose. Pectin, found in ripe fruit, is precipitable by alcohol and gelatinizes in boiling water, whereas pectose, found in unripe fruit, is substantially insoluble in water. Both are hydrolyzed by the action of alkalis and acids to intermediate compounds and finally to the hexoses and pentoses. 2. Lignocellulose comprises the main portion of all woody tissues as well as one textile fiber, jute, which in its raw state is richer in carbon than cellulose, and is readily attacked by acids, alkalis and oxidizing agents. Freely soluble in cuproammonium but incompletely precipitated upon acidifying, hence of but little value for the formation of artificial filaments in imitation of silk. Nitric and sulfuric acids, nitrate jute (see nitro-jute), the gain in weight being approximately the same as that of cotton 1. A. Mullcr (Leipzig, 1904), abst. Zts. anorg. Chem. 3$, 121; Jahr. Chem. 1904, 100; Zts. ang. Chem. 1904, 17, 970; has compiled a bibliography of colloids with 350 original publications cited ; and Whitney and Ober (J. A. C. S. 1901, 23, 856; abst. J. C. S. 1902, 82, 65; Jahr. Chem. 1901, 133) have compiled an index to the literature of the same subject. 2. C. Webster, J. C. S. 1883, 43, 23; abst. Jahr. Chem. 1883, 1638; Chem. News, 1882, 46, 240. 3. Proc. Manchester Lit. Phil. Soc. (3), 4, 95. 10 TECHNOLOGY OF CElrLULOSE ESTERS cellulose, and like the cellulose nitrates, give no amido products upon reduction, thus indicating true nitric esters. According to Sachsse lignocellulose consists of about 75 per cent, cellulose and the balance lignin, a body of an aldehydic character. Iodine is absorbed- by jute, the resulting compound being about as un- stable as starch iodide. This reaction has been taken advantage of in the quantitative determination of lignocelluloses in combi- nation with other forms of cellulose. Dilute nitric acid acts upon jute at 80 degrees, forming oxycellulose, oxalic acid, carbon dioxide and a peculiar derivative of imdetermined composition. The lignocelluloses hydrolyze much more readily than the simple celluloses, furftu'ol being obtained in considerable quantity when the temperattu'e is raised to boiling. Glycolignose, the substance of fir and other Abies woods, and glycodrupose, the substance in the stony concretion of pears^ are other forms of lignocellulose. *'Crude fiber," a name applied to the residue obtained by boiling fodder plants with alkaline and acid solutions, has been found in most cases to consist of lignocellulose. C. Cross and E. Bevan^ have drawn attention to certain diversities in the cellulose group as a whole, especially as to the degree of resistance to hydroly tic and oxidizing agents ; the amount of furfural yielded by decomposition with aqueous HCl; and the ratio between carbon and oxygen. The following table has been constructed by them as indicating these points of divergence: Type Cotton Group. Bleached Cotton Wood Cellulose Group. Jute Cellulose Cereal Cellulose Group. Straw Cellulose Carbon content.. Oxygen content.. Furfural Other character- istics 44.0-44.4 0.50 0.1-0.4 No active CO groups 43.0-43.5 0.51 30.-6 Some free CO groups 41.5-52.5 53 12.0-16 CO groups very reactive The lignocelluloses are in general, therefore, compounds of the formula ROCH3 in which "R" represents, probably, aromatic 1. Bcr. 1899, 32, 2493; abst. J. S. C. I. 1899, IS, 940; Chem. Centr. 1899, II, 752; Meyer Jahr. Chem. 1899, 9, 300; J. C. S. 1899, 76, i, 852; Jahr. Chem. 1899, 1290; Bull. Poc. Chim. 1900, 24, 620. 2. J. C. vS. 1895, 67, 433; abst. Jahr. Chem. 1895, 1349; Rev. g^n. sci. 1895, 6, 295; Ber. 1895, 28, R, 645; Wag. Jahr. 1895, 41, 1028. CBLLUI.OSE 1 1 groups. These celluloses are characterized by formmg com- pounds with the halogens and are resolved by chlorination into cellulose and chlorinated derivatives of aromatic compounds which are soluble in alkalis and in dilute sulfite solution, the pure cellulose thus being liberated. 3. Adipocellulose forms the outer or epidermal layer of leaves and fibers, readily transformed by oxidation with nitric acid into products similar to those split off by the oxidation of fats, together with cellulose. They are of a cellular rather than of a fibrous character, richer in carbon and poorer in oxygen than cotton cellulose and comprise the main constituents of the leaves, fleshy fruits and stems of annuals. The chief adipocelluloses are cork and bark, which, when the impurities are removed, leave a neutral body called cutose. Such materials always contain also a large proportion of oils. The chemistry of these bodies as yet has been but imperfectly investigated. The waxes contain lignocellulose and nitrogenous substances. The adipocelluloses and cutocelluloses contain a larger percentage of carbon than pure cellulose, whereas the pectocelluloses have a higher proportion of oxygen. B. Tollens* states that both hydrocellulose and all crude oxycellulose preparations contain cellulose, and that from the action of alkalis upon these bodies the conclusion is drawn that the true products of reaction (e. g., celloxin) are combined with these celluloses somewhat after the manner of esters. Tollens divides the cellulose group into the following four classes: (a) Celluloses. (b) Hydrated celluloses, i. e., hydrocellulose and hemi- celluloses, bodies which are non-reducing, but readily hydrolyzed to reducing compounds. (c) Cellulose with acid, i. e., carboxyl groups; this class includes the pectins, etc. (d) Celluloses with both acid (carboxyl) groups and aldehydic or ketonic groups; this class includes the oxycelluloses which are cupric reducing bodies. The more highly oxidized classes (c) and (d) are distin- 1. Ber. 1901. 34, 1434; abst. J. S. C. I. 1901, 20, 740; Bull. Soc. Chim. 1902, (3). 28, 269; J. C. S. 1901, 80, i, 453; Jahr. Chem. 1901, 897; Chem. Centr. 1901, II, 39. 12 TECHNOWXJY OF CEW.UU)S^ ESTERS guished from (a) and (b) by elementary analysis, the ratio of H : O being 1 : 8-9, instead of 1 : 8, as in the (a) and (b) classes. G. Bumcke and R. Wolff enstein^ have described a product of the action of hydrogen dioxide on cellulose which they termed **hydralcellulose." They assign a H:0 ratio of 1:8 to this body, but it has been pointed out that their analyses might be equally within the limits of error for a body of the oxycellulose type with a ratio of 1:8.3. Judging from the imdoubted oxycellulose properties of "hydralcellulose/* Tollens regards it as belonging to class (d) and sees no reason for modifying the view that oxycel- luloses are true oxidation products of cellulose. The acid cellulose derivatives and pectins are gelatinous bodies containing an excess of oxygen corresponding to the presence of carboxyl groups, aldehydic or cupric reducing groups being absent. The natural members of this class often contain besides the Ce cellulose aggregate, groups which yield pentoses on hydrolysis. The author also includes gum tragacanth in class (c). Although A. Hilger and W. Dreyfus^ came to the conclusion that the acid properties of tragacanth and oxybassorin could not be due to carboxyl groups, the author taking into account the inconclusive natiu"e of the elementary analyses in this respect, pre- fers to regard both bodies as containing excess of oxygen over the normal carbohydrate 1 : 8 ratio, owing to the presence of carboxyl groups. R. Wolff enstein and G. Bumcke' have shown that in ToUen's classification of the cellulose group of carbohydrates, the hydrocelluloses are recorded as hydrated or hydrolyzed deriv- atives, while the oxycelluloses are merely oxidized products. They contend it is hardly probable that the natural hydrolyzing tendencies of the acid reagents employed should be inhibited by the presence of the oxidizing agents. Tollens suggests that the cellulose in these products may be present combined with the 1. Ber. 1899, 32, 2493; abst. J. S. C. I. 1899, 18, 940; Chem. Centr. 1899, II, 752; Meyer Jahr. Chem. 1899, 9, 300; J. C. S. 1899, 76, i, 852; Jahr. Chem. 1899, 1290; Bull. Soc. Chim. 1900, 24, 620. 2. Ber. 19(X), 33, 1178; abst. J. S. C. I. 1900, 19, 677; Chem. Centr. 1900, I, 1217; Jahr. Chem. 1900, 838; Chem. Ztg. Rep. 1900, 24, 159; Bull. Soc. Chim. 1901, (3), 26, 269; J. C. S. 1900, 78, i, 379. 3. Ber. 1901, 34, 2415; abst. J. S. C. I. 1901, 20, 925; Chem. Centr. 1901, ir. 529; Jahr. Chem. 1901, 888; J. C. S. 1901, 80, i, 582; Bull. Soc. Chim. 1902. (3), 28, 368. CELI<UW)SS 13 oxidized portion in the form of an ester but as this view implies condensation rather than hydrolysis, and the molecule of the product must be at least twice as large as that of the original cellulose, attention is drawn to the fact that if this were so the oxycelluloses ought to be more resistant to hydrolyzing conditions than the celluloses, whereas the reverse is invariably the case. These authors would classify this group of carbohydrates as follows: A. Cellulose B. Hydrated cellulose (hydrocelluloses) (a) Reducing (**Hydralcellulose"); (b) Reducing and with carboxylic groups; (c) With carboxylic groups but non-reducing (acid- cellulose) ; (d) Neither reducing nor with carboxylic groups (lactone configuration). "Hydrocellulose" being produced by so mild a reagent as a 3 per cent, solution of hydrogen peroxide, is regarded as a purely hydrolytic product without the formation of any more highly oxi- dized groupings. Cellulose may be isolated from vegetable raw material by boiling the tissue in solutions of 1 to 5 per cent, sodium hydroxide and after washing, exposure of the moist mass to the vapors of chlorine or fluorine gas or to bromine water at the ordinary temperature. Alkaline hydrolysis, i. e., boiling in alka- line solutions as sodium sulfite, sodium carbonate or sodium hydrate, dissolves away the products formed from the non- cellulose constituents in the preceding treatment. In dealing with unusually refractory materials such as the hard woods, it may be necessary to repeat this cycle of processes several times. The material is finally completely extracted with alcohol and ether in a Soxhlet extractor to remove resinous and fatty prod- ucts not completely saponified by the previous alkaline treatments. From this it follows that the typical celluloses are not sepa- rable from plant tissue in the pure state but in admixture or in intimate chemical union with other compounds or groups of com- pounds, which groups are distinguished by greater reactivity in that they more readily yield to alkaline hydrolysis, such as the pectic bodies; or to oxidation, as the coloring matters or to the action of the halogens. In this latter classification is properly in- 14 TECHNOLOGY OF CELLUI<OSE ESTERS duded the very iniportant group of lignone celluloses which are distmguishedy according to Cross and Bevan, by the presence of cutohexane groups in imion with the cellulose, and therefore capable of directly combining with the halogens. Constitution of Cellulose. The various modifications of cellulose have been extensively investigated and many con- stitutional formulas for the normal cellulose molecule have been suggested. The percentage composition of the purest form of cellulose obtainable is: Carbon 44.2-44.4 per cent., hydrogen 6.2-6.3 per cent., and oxygen 49.4r49.5 per cent. These figures lead to the general formula (C6Hio06)„. It is difficult to deter- mine the molecular weight of cellulose, owing both to its non- crystalline nature, and to the fact that no cellulose derivative is known which has been volatilized without imdergoing chemical change. Although many formulas have been put forward no particular one hitherto has received general acceptation.^ Being a colloid, cellulose — ^like starch — comprises an aggre- gate of reactive constituent groups whose equilibria is continually being modified by the reactive process. It has variously been regarded as a polycydohexane or polyhexose derivative containing CHjOH, CHCOH and CO in addition to OH groups. Their number, as yet, has not been definitely ascertained. 