LECTURE NOTES FOR CHEMICAL STUDENTS: EMBKACING MINEEAL AND ORGANIC CHEMISTRY. BY EDWARD FRANKLAND, F.R.S., FOR. SEC. C.S., COEEESPONDING MEMBER OF THE IMPERIAL INSTITUTE OF FRANCE, PEOFESSOE OF CHEMISTRY IN THE ROYAL INSTITUTION OF GREAT BRITAIN, AND IN THE GOVEENMENT SCHOOL OF MINES. ;: .; ; , o -. ^,;:o LONDON: JOHN VAN VOORST, PATERNOSTER ROW. MDCCCLXVI. PEINTED BY TAYLOR AND FRANCIS, RED LION COURT, FLEET STREET. PKEFACE. THE contents of this little book are to a great extent a transcript of the notes of my lectures delivered at the Royal College of Chemistry during the Winter Session of 1865-66. These notes have been considerably amplified only in the earlier chapters, on nomenclature, notation, and the atomicity of elements subjects which, in their modern developments, have undergone such profound changes as to render their somewhat more extended treat- ment necessary to the comprehension of the remainder of the book. To render the work as concise as possible, all formal description of the properties of the bodies treated of has been, for the most part, entirely omitted. Such a descrip- tion (which is moreover easily accessible elsewhere) would, even if brief, have swollen the book to more than double its present size. For the same reason I have been compelled to treat the metallic elements in a manner which will doubtless seem, to many, unworthy of their importance ; but their number is so great, that any attempt to give more than the names and formulae of their chief com- pounds would have extended the work far beyond the limits I had assigned to it. My aim has been to classify and systematize rather than to describe, and I have endea- voured to furnish the student with a kind of skeleton of IV PREFACE. the science, which it is intended he should himself clothe with the%already known and daily increasing facts of expe- rimental research. To aid him in this, he has the choice of numerous standard treatises, amongst which may be mentioned Watts' s v ( Dictionary of Chemistry/ Gmelin's ' Handbook of Chemistry/ Graham's ' Elements of Che- mistry/ Miller's ' Elements of Chemistry/ (Ming's ' Manual of Chemistry/ Gerhardt's < Traite de Chimie Organique/ ' Traite de Chimie Generale ' by Pelouze and Fremy, Kolbe's ' Lehrbuch der organischen Chemie/ and Kekule's ' Lehrbuch der organischen Chemie/ I have often noticed with regret the great amount of labour which an earnest student expends in noting down the reactions and the names and formulse of substances which are presented to his notice in the lecture-theatre. He is thus greatly interrupted in following the arguments and explanations of the speaker, and he often loses more important generalizations in securing a record of details. One of my chief objects in the preparation of this book has been to relieve him from such distractions. For this purpose very full lists of names and formulse are given, and a comparatively large amount of space is devoted to equations expressing the reactions occurring in the for- mation and decomposition of the substances treated of. Such being the chief objects of the book, it would obviously have been impossible to give in all, or even in many cases the reasons which have induced me to adopt such views of the constitution of both mineral and organic compounds as are either novel or not generally recognized. Thus, I am aware that the atomicity which is assigned to many of the elements may be called in question; but it is hoped that, in thus giving for the first time a thorough and consistent scheme of the combining-powers of atoms, PREFACE. the advantages of the simplicity of symbolic expression, thereby secured, will more than outweigh the evil resulting from the few errors which future research may reveal. Whilst tlie rapid progress of organic chemistry has 011 the one hand enormously increased the number of organic compounds, it has, on the other, revealed new relations between the different groups of these compounds, and opened up many new paths, both from one group to another and from member to member of the same group. The relative importance of individual compounds has thus gradually diminished in comparison with that of the family to which they belong ; and the time has now arrived for recognizing this condition of things, by so classifying organic bodies as to make the description of the individual members subsidiary to that of the family to which they are attached. The student can thus more easily gain a general view of the otherwise almost hopelessly vast array of organic substances. To illustrate important constitutional formulae, I have extensively adopted the graphic notation of Crum Brown, which appears to me to possess several important advan- tages over that first proposed by Kekule. Graphic notation affords most valuable aid to the teacher in rendering intel- ligible the constitution of chemical compounds, especially when it is supplemented by what may be called the glyptic formulae of Hofmann. The system of symbolic notation, which I have explained in Chapter III., is so framed as to express the same ideas, of the chemical functions of atoms, as the graphic and glyptic formulae, with which, therefore, it harmonizes completely; whilst it enables the student gradually to dispense with the last two forms of constitutional notation. I am aware that graphic and glyptic formulae may be VI PREFACE. objected to, on the ground that students, even when spe- cially warned against such an interpretation, will be liable to regard them as representations of the actual physical position of the atoms of compounds. In practice I have not found this evil to arise ; and even if it did occasionally occur, I should deprecate it less than ignorance of all notion of atomic constitution. In conclusion, I have much pleasure in thanking my assistant, Mr. Herbert M c Leod, for his valuable help, both in compilation and in the revision of the proofs. Mr. M c Leod has devoted much attention to the consti- tutional formulae of minerals ; and most of the symbolic and graphic expressions for these compounds are from his pen. To my assistant, Mr. W. Valentin, I am also much indebted for aid in the laborious work of revising proofs. In a book which is so full of formulae, it would be too much to expect entire freedom from errors; but every care has been taken to reduce their number as much as possible. E. F. Royal College of Chemistry, London, September 15, 1866. TABLE OF CONTENTS. CHAPTER I. INTRODUCTORY. Page Definition of chemistry 1 Simple and compound matter 1 Mooes of chemical action 1 Atomic weight "2 Atoms and molecules 2 Chemical affinity 4 CHAPTER II. CHEMICAL NOMENCLATURE. Names of elements f> Names of binary compounds 7 Systematic and trivial or irregular names 8 I Names of acids 9 / Names of bases 11 Normal, acid, and basic salts 12 CHAPTER III. CHEMICAL NOTATION. Symbolic notation 14 Chemical formulae 14 Chemical equations 15 Use of the bracket 16 Use of thick letters 16 Rational and empirical formulae 17 Atomicity of elements 17 Chemical bonds . . 18 Vlll TABLE OF CONTENTS. Page Monatomic and polyatomic molecules 19 Absolute, latent, and active atomicity 21 Graphic notation 23 CHAPTER IV. COMPOUND RADICALS. Simple and compound radicals 26 Definition of a compound radical 27 Inorganic compound radicals 28 CHAPTER V. ATOMIC AND MOLECULAR COMBINATION. Atomic union 30 Molecular combination . . 30 CHAPTER VI. CLASSIFICATION OF ELEMENTS. Metals and non-metals 31 Chlorous or negative and basylous or positive elements 31 Monads, dyads, triads, tetrads, pentads, and hexads 32 CHAPTER VII. WEIGHTS AND MEASURES. French and English systems 32 Conversion of French into English weights and measures .... 33 The. crith 34 CHAPTER VIII. MONAD ELEMENTS. Section I. HYDROGEN 36 Preparation of hydrogen 36 Section II. CHLORINE 37 Preparation of chlorine 37 Preparation of hydrochloric acid 39 Reactions of hydrochloric acid 39 TABLE OF CONTENTS. IX Page CHAPTER IX. DYAD ELEMENTS. Section I. OXYGEN .30 Preparation of oxygen 4 ) Allotropic oxygen or ozone 41 Formation and reactions of water 43 Preparation and reactions of hydroxyl 44 Oxides and ox-acids of chlorine 45 CHAPTER X. TRIAD ELEMENTS. Section I. BORON 51 Amorphous, graphitoidal, and diamond boron 51 Compounds of boron with chlorine, bromine, and fluorine .... 53 Boric anhydride and acids 54 Boric sulphide and nitride 56 CHAPTER XI. TETRAD ELEMENTS. Section 1. CARBON 57 Compounds of carbon with oxygen 57 CHAPTER XII. PENTAD ELEMENTS. Section I. NITROGEN 60 Oxides and ox-acids of nitrogen 61 Compounds containing nitrogen, chlorine, and oxygen 6(5 Compounds of nitrogen with hydrogen 67 Compound of nitrogen with chlorine 69 Compound of nitrogen with iodine and hydrogen 69 CHAPTER XIII. HEXAD ELEMENTS. Section I. SULPHUR (59 Compounds of sulphur with basylous elements 70 Compounds of sulphur with oxygen and hydroxyl 74 SELENIUM 84 Compounds of selenium with hydrogen and chlorine 84 Compounds of selenium with oxyg - en and hydroxyl 85 TELLURIUM 85 Compounds of tellurium 86 a ~> TABLE OF CONTENTS. Page CHAPTER XIV. MONAD ELEMENTS (continued). II. (continued). BUOMINE 86 Hydrobromic acid 87 Compounds of bromine with oxygen and hydroxyl 88 IODINE 90 Hydriodic acid 91 Compounds of iodine with oxygen and hydroxyl' 93 FLUORINE , 96 Hydrofluoric acid 97 CHAPTER XV. TETRAD ELEMENTS (continued). Section I. (continued). SILICON 97 Silicic hydride 99 Silicic chloride 99 Silicic bromide and fluoride 100 Compounds of silicon with oxygen and hydroxyl 101 Silicates 102 Silicic sulphide 104 TIN 104 Compounds of tin 104 TITANIUM 106 Compounds of titanium 106 CHAPTER XVI. PENTAD ELEMENTS (continued). Section I. (continued). PHOSPHORUS 107 Compounds of phosphorus with hydrogen 108 Compounds of phosphorus with chlorine Ill Phosphoric oxytrichloride 112 Phosphoric sulphotrichloride 113 Compounds of phosphorus with oxygen and hydroxyl 114 ARSENIC 119 Arseniuretted hydrogen 120 Arsenious chloride 121 Compounds of arsenic with oxygen and hydroxyl 122 Compounds of arsenic with sulphur and hydrosulphyl 124 ANTIMONY 125 Antimoniuretted hydrogen 126 Compounds of antimony with chlorine 128 Oxides and acids of antimony 130 Antimonious oxydisulphide 135 TABLE OF CONTENTS. XI Compounds of antimony and sulphur 136 Sulphantimonites 137 BISMUTH 139 Bismuthous chloride 139 Bismuthous bromide, iodide, and fluoride 140 Compounds of bismuth with oxygen and hydroxyl 140 Compounds of bismuth with sulphur 144 CHAPTER XVII. MONAD ELEMENTS (continued). Section HI. POTASSIUM 145 Compounds of potassium with chlorine, bromine, iodine, and fluorine 147 Compound of potassium with hydroxyl 147 Compounds of potassium with oxygen 148 Compounds of potassium with hydrosulphyl and sulphur .... 149 Potassic carbonate 151 SODIUM 151 Sodic carbonate 151 LITHIUM 152 CAESIUM and RUBIDIUM 153 Section IV. THALLIUM 153 Compounds of thallium 153 SILVER 154 Compounds of silver with oxygen 155 CHAPTER XVHI. DYAD ELEMENTS (continued}. Section II. BABIUM 155 Compounds of barium with oxygen 156 Compound of barium with hydroxyl 159 STRONTIUM 159 Strontic peroxide and carbonate 160 CALCIUM 160 Compounds of calcium with oxygen and hydroxyl 161 Calcic chloro-hypochlorite or bleaching-powder 161 Dihydric calcic dicarbonate 161 MAGNESIUM 162 Magnesic sulphate and carbonate 163 Magnesia alba 164 ZINC , 164 Zincic oxide 165 Other compounds of zinc 166 Xll TABLE OF CONTENTS. Page CHAPTER XIX. DYAD ELEMENTS (continued). Section IV. CADMIUM 167 Cadinic oxide, hydrate, and sulphate 167 MERCURY 168 Compounds of mercury with chlorine, oxygen, and sulphur . . 168 Salts of mercury 169 COPPER 170 Compounds of copper with hydrogen, chlorine, oxygen, and hydroxyl 170 Copper minerals and salts of copper 171 CHAPTER XX. TRIAD ELEMENTS (continued). Section II. GOLD 174 Compounds of gold 174 CHAPTER XXL TETRAD ELEMENTS (continued). Section II. ALUMINIUM 175 Compounds of aluminium with chlorine, oxygen, and hydroxyl 17o Aluminic minerals and salts 176 CHAPTER XXII. TETRAD ELEMENTS (continued). Section III. PLATINUM 178 Principal compounds of platinum 179 CHAPTER XXIII. TETRAD ELEMENTS (continued). SectionlV. LEAD 180 Compounds of lead with chlorine, oxygen, and hydroxyl 181 Plumbic minerals and salts . 182 TABLE OF CONTENTS. Xlll Page CHAPTER XXIV. HEXAD ELEMENTS (continued). Section IV. CHROMIUM 185 Chromous and chromic compounds 185 Chromic minerals and salts 186 MANGANESE 188 Manganous and manganic compounds 188 Manganous and manganic minerals and salts 189 IRON 192 Ferrous and ferric compounds 192 Ferrous and ferric minerals and salts 193 COBALT 195 Cobaltous and cobaltic compounds 195 Cobalt bases , 19(5 NICKEL 197 Nickelous and nickelic compounds 197 Nickelous and nickelic minerals and salts 198 CHAPTER XXV. ORGANIC CHEMISTRY. Introductory 199 Compound organic radicals 200 Notation of organic compounds 201 Types of organic compounds 202 Reduction and development of formulae 204 Classification of organic compounds 206 CHAPTER XXVI. ORGANIC RADICALS. Class I. Basylous or positive radicals 207 Monad radicals of the methyl series 207 Normal, secondary, and tertiary monad radicals . 208 Ethyl 210 Monad radicals of the vinyl series 210 Monad radicals of the phenyl series 211 CHAPTER XXVII. ORGANIC RADICALS (continued). Dyad basylous radicals of the ethylene series 212 Isomerism of ethylene and ethylidene compounds 215 XIV TABLE OF CONTENTS. Ethylene 216 Dyad basylous radicals of the acetylene series 217 Dyad basylous radicals of the phenylene series 220 Triad basylous radicals 220 CHAPTER XXVin. ORGANIC RADICALS (continued). Class II. Chlorous or negative radicals 221 Cyanogen 222 Hydrocyanic acid 223 Single and double cyanides 224 Other compounds of cyanogen 227 Oxatyl 228 Relations between methyl, oxatyl. and cyanogen 228 Oxalic acid 229 Oxamic acid and oxamide 231 CHAPTER XXIX. HYDRIDES OF THE COMPOUND RADICALS. Class I. Hydrides of the basylous radicals 232 Hydrides of the radicals of the methyl series 232 Relations of the basylous monad radicals to their hydrides .... 233 Methylic hydride, or marsh-gas 234 Ethylic and amyHc hydrides 236 Paraffin : 237 Hydrides of the radicals of the phenyl series 237 Benzol 238 Substitution derivatives of benzol 239 Class H. Hydrides of chlorous radicals 243 Cyanic hydride or hydrocyanic acid 243 Oxatylic hydride or formic acid 243 CHAPTER XXX. THE ALCOHOLS. Definition of alcohols 243 Classification of alcohols 244 Normal monacid alcohols of the methyl series 246 Relations of these alcohols to the monad C n H 2n +i radicals 246 dyad CH 2re radicals 247 hydrides of the C tt H 2n+1 radi- cals 248 radical cyanogen. Ascent of the series 248 Methylic alcohol 249 EthyHc alcohol 250 TABLE OP CONTENTS. XV Page Mercaptan 251 Propylic, butylic, and amylic alcohols 252 Secondary monacid alcohols 252 Isopropylic, pseudamylic, and pseudohexylic alcohols 253 Tertiary monacid alcohols 254 Pseudobutylic alcohol 255 CHAPTER XXXI. THE ALCOHOLS (continued}. Monacid alcohols 255 Vinylic series 255 Vinylic alcohol 256 Allylic alcohol 257 CHAPTER XXXII. THE ALCOHOLS (continued). Monacid alcohols 258 Phenylic series 258 Normal alcohols of this series 260 Benzoic alcohol 260 Secondary alcohols 260 Phenylic alcohol or carbolic acid 260 Cresylic alcohol or creosote 262 CHAPTER XXXIII. THE ALCOHOLS (continued). Diacid alcohols or glycols 262 Ethylic glycol 264 Derivatives of ethylic glycol 265 Polyethylenic glycols 266 CHAPTER XXXIV. THE ALCOHOLS (continued). Triacid alcohols 267 Glycerin 268 Relation of glycerin to isopropylic alcohol 268 allylic alcohol 268 Relations of glycerin to propylic glycol 268 glyceric and tartronic acids 269 acrylic acid 270 Other polyacid alcohols 270 XVI TABLE OF CONTENTS. Page CHAPTER XXXV. THE ETHERS. Classification of ethers 272 Ethers of the monacid alcohols, methyl series 272 Methylic and ethylic ether 274 Ethylic sulphide 27G Ethers of the vinyl and phenyl series 276 Ethers of the diacid" alcohols 276 Ethylenic oxide 277 Ethers ojf the triacid alcohols 279 Glycylic ether 279 CHAPTER XXXVI. THE HALOID ETHERS. Classification of haloid ethers 280 Haloid ethers of the monad positive radicals 282 Methylic chloride and chloroform ... 285 Ethylic chloride and iodide 286 Haloid ethers of the dyad positive radicals 287 Classification of these ethers 287 Ethylenic bromide 288 Ethylenic cyanide 289 Haloid ethers of the triad positive radicals 289 Classification of these ethers 289 CHAPTER XXXVII. THE ALDEHYDES. Classification of aldehydes 290 Formation and reactions of aldehydes 291 Aldehydes derived from the C M H 2n -j-iHo series of alcohols .... 292 Acetic aldehyde 293 Aldehydes derived from the CnH 2w _iHo series of alcohols .... 294 Acrolein or acrylic aldehyde 294 Aldehydes derived from the C n II 2w _ 7 Ho series of alcohols .... 295 Benzoic aldehyde or oil of bitter almonds 295 CHAPTER XXXVIII. THE ACIDS. Classification of organic acids 296 Monobasic acids and their classification 296 Acetic or fatty series 297 Normal acids of this series 298 Formation of normal fatty acids 300 TABLE OF CONTENTS. XV11 Page Relations of these acids to the C M H 2n+ i series of radicals 302 C M 'H 2n +iHo series of alcohols . . 303 each other. Ascent of the series . . 303 Formic acid 304 Acetic acid 306 Propionic and butyric acids 308 Valeric acid 309 Secondary fatty acids 310 Dimethacetic or isobutyric acid 311 Tertiary fatty acids 311 Trimethacetic acid 312 CHAPTER XXXIX. THE ACIDS. Acrylic or Oleic Series. Classification of these acids 312 Formation of normal acids 313 Formation of secondary and olefine acids 314 Relations of the acrylic to the acetic series of acids 314 Acrylic acid 315 Oleic acid . 316 CHAPTER XL. THE ACIDS. Lactic Series. Definition of an acid of this series 316 Classification of these acids 317 Normal acids 317 Etheric normal acids 319 Secondary acids 319 Etheric secondary acids 320 Normal olefine acids 321 Etheric normal olefine acids 322 Secondary and etheric secondary olefine acids 322 Relations of the lactic to the acetic series of acids 324 Relations of the lactic to the acrylic series of acids 324 Lactic acid 325 Isomerism in the lactic series 325 CHAPTER XLI. THE ACIDS. Pyruvic Series. Relation of these acids to oxalic acid 333 "Relation of these acids to the lactic series 334 Glyoxylic series. Relation of these acids to the glycerin series of alcohols 335 XV111 TABLE OF CONTENTS. Page CHAPTER XLIL THE ACIDS. JBenzoic or Aromatic Series. Constitution of these acids 336 Acryloid and lactoid acids of the benzoic series 336 Benzoic acid 337 CHAPTER XLIH. THE ACIDS. Dibasic Acids. Constitution of these acids 337 Classification of dibasic acids 338 Succinic series 339 Relations of the succinic to the lactic series and to the glycols 340 Relations of the succinic series to the dyad radicals 340 Relations of the succinic to the acetic series 341 Succinic acid 342 Salts of succinic acid 344 CHAPTER XTJY. THE ACIDS. Fumaric or Acryloid Series. Constitution of these acids 345 Isomerism in this series 346 Fumaric, maleic, and isomaleic acids 345 Itaconic, citraconic, and mesaconic acids 348 CHAPTER XLV. THE ACIDS. Malic or Lactoid Series. Tartronic and malic acids 350 Tartaric or glyoxyloid series 351 Tartaric and homotartaric acids j Varieties of tartaric acid > 351 Racemic, inactive tartaric, and metatartaric acids ) CHAPTER XLVI. THE ACIDS. Tribasic Acids. Constitution and classification of the tribasic acids 352 Tricarballylic or acetoid series 352 Aconitic or acryloid series ) Citric or lactoid series [ 353 Desoxalic or glyoxyloid series ) TABLE OF CONTENTS. XIX Page CHAPTER XLVII. THE ANHYDRIDES. Constitution and classification of the anhydrides 354 Anhydrides of monohydric monobasic acids 356 Anhydrides of dihydric monobasic acids 357 Anhydrides of dihydric dibasic acids 357 CHAPTER XLVHI. THE KETONES. Derivation and constitution of the ketones 357 Formation of the ketones 358 Isomerism in the ketone family 360 CHAPTER XLDL ETHEREAL SALTS. Definition and constitution of the ethereal salts 361 Ethereal salts of monobasic, dibasic, and tribasic acids 362 Ethereal salts of monacid, diacid, and triacid alcohols 362 CHAPTER L. ORGANIC COMPOUNDS CONTAINING TRIAD AND PENTAD NITROGEN AND THEIR ANALOGUES. Classification of these compounds 363 Positive section. The amines 364 The natural alkaloids 370 The phosphines, arsines, and stibines 370 The oxybases 371 CHAPTER LI. ORGANIC COMPOUNDS OF TRIAD NITROGEN (continued). Neidral section. The amides 372 The alkalamides 375 The trichlorinated and tribrominated amines 376 The haloid compounds of oxybases 376 Negative section. The imides and nitrides 376 XX- TABLE OF CONTENTS. Page CHAPTER LII. COMPOUNDS OF PENTAD NITROGEN AND ITS ANALOGUES. Classification of these bodies 377 Positive or basylous compounds 377 Caustic nitrogen, phosphorus, arsenic, and antimony bases .... 377 Oxyarsenic and oxyantimonic bases 377 Neutral compounds 378 Salts of amines, normal, monacid, and diacid 378 Salts of phosphines, arsines, and stibines 379 Salts of oxyarsenic and oxyantimonic bases 380 Negative or chlorous compounds 380 Organic arsenic acids, oxychlorides, and chlorides 380 Organic antimonic acids " 380 CHAPTER LIH. ORGANOMETALLIC BODIES. Definition of these compounds 381 Formation of organometallic bodies 382 Reactions of organometallic bodies 384 Constitution of organometallic bodies 388 Organo- compounds containing monad and dyad metals 391 Organo- compounds containing triad, tetrad, and pentad metals. 392 ERRATA. Page 12, line 3 from bottom, and in a few other places, the atomicity marks ought to be placed to the left of atom coefficient. Thus loc. cit. for " Ca 3 "" read "CaV 45, top line, for " OXIDES AND ACIDS OF CHLOKINE " read " OXIDES AND OXACIDS OF CHLORINE." 46, line 16 from bottom,./br " 79'4 criths " read " 39 - 7 criths." 244, 17 from top, for "Ethyl series " read "Methyl series." 292, 5 from bottom, for " (Enanthic " read " CEnanthylic." LECTUKE NOTES FOR CHEMICAL STUDENTS. CHAPTER I. INTRODUCTORY. DEFINITION. Chemistry is the science which treats of the atomic composition of bodies, and of those changes in matter which result from an alteration in the relative position of atoms. SIMPLE AND COMPOUND MATTER. All kinds of matter are divided into two great classes, simple substances, and com- pound substances. A simple substance is one out of which it is impossible to obtain, by any known process, two or more essen- tially different kinds of matter. A compound substance, on the other hand, is one which can be resolved into two or more simple substances. The simple substances at present known are sixty-two in number, and are termed elements. By the combination of these elements with each other, all the infi- nitely varied forms of terrestrial matter are produced. MODES or CHEMICAL ACTION. Matter undergoes chemical change in five different ways, viz. : 1st. By the direct combination of elements or compounds with each other. 2nd. By the displacement of one element or group of ele- ments in a body by another element or group of elements. 3rd. By a mutual exchange of elements or groups of elements in two or more bodies. -' : ''. / ' > v- ATOMS AND MOLECULES. 4th. By the re-arrangement of the elements or groups of elements already contained in a body. 5th. By the resolution of a compound into its elements, or into two or more less complex compounds. ATOMIC WEIGHT. Chemists assign to every element a number called its atomic weight. This number is made to represent, as far as possible, 1st. The smallest proportion by weight in which the element enters into or is expelled from a chemical compound, the smallest weight of hydrogen so entering or leaving a chemical compound being taken as unity. 2nd. The weight of the element in the solid condition which, at any given temperature, contains the same amount of heat as seven parts by weight of solid lithium at the same temperature. 3rd. The weight of the element which, in the form of gas or vapour, occupies, under like conditions of temperature and pressure, the same volume as one part by weight of hydrogen. The atomic weight of a compound is the sum of the atomic weights of its elements. The atomic weights of the elements are given in the Table at page 6. ATOMS AND MOLECULES. The proportional amount of any element represented by its atomic weight, as above described, is commonly called an atom of that element. When an element is isolated, or separated from every other kind of matter, its atoms still exist, except in a few cases, in combination with each ether. In many instances the atoms of isolated elements are associated in pairs when thus combined. Such an isolated atom or group of atoms constitutes an elemen- tary molecule. It follows from what has been said that the bulk of a mole- cule, or the molecular volume of an element in the gaseous or vaporous condition, must be the same as the molecular volume of hydrogen at the same temperature and pressure, and that the molecular weight of an element is in a large number of cases twice its own atomic weight. MOLECULAR VOLUME. The following is a list of those elements whose molecular volumes have been determined. Molecules containing of the element One atom. Two atoms. Three atoms. Four atoms. Six atoms. Monatomic Diatomic Triatomic Tetratomic Hexatomic Molecules. Molecules. Molecules. Molecules. Molecules. Mercury. Cadmium. Hydrogen. Oxygen. Oxygen (as Ozone). Phosphorus. Arsenic. Sulphur. Zinc. Chlorine. Bromine. Iodine. Fluorine. Nitrogen. Sulphur. Selenium. It will be perceived from the above Table that an element may have two distinct molecular weights. This is known to be the case with oxygen and sulphur. The molecular weight of a compound is, with very few excep- tions, identical with its atomic weight. The molecular volume or the space occupied by the combining proportion of a com- pound is, with very few exceptions, equal to that occupied by two combining proportions, or one molecule, of hydrogen. Hence the law equal volumes of all gases and vapours contain, at the same temperature and pressure, an equal number of mole- cules. With very few exceptions, therefore, the molecules of all compounds, no matter how great may be the aggregate volume of their constituents, occupy, when compared at the same tem- perature and pressure, one uniform volume, which is exactly the same as that filled by one molecule of hydrogen. Thus : vol. vol. vols. 1 of Hydrogen + 1 of Chlorine form 2 of Hydrochloric acid. 1 of Hydrogen + 1 of Bromine vapour 2 of Hydrogen + 1 of Sulphur vapour 2 of Hydrogen + 1 of Oxygen 3 of Hydrogen + 1 of Nitrogen 4 of Hydrogen +x of Carbon vapour 6 of Hydrogen +1 of Oxygen +2x of Carbon vapour 12 of Hydrogen -f 1 of Oxygen +5* of Carbon vapour 2 of Hydrobromic acid. 2 of SulphurettedHydrogen. 2 of Steam. 2 of Ammonia. 2 of Marsh-gas. 2 of Alcohol vapour. 2 of Amylic alcohol vapour. 4 CHLOROUS AND BASYLOUS ELEMENTS. CHEMICAL AFFINITY. The force or power which holds to- gether the elements of a compound is termed chemical affinity. Elements which readily combine with each other, and develope much heat on combination, are said to have a powerful affinity for each other. The elements which thus exhibit toward^ each other a great affinity are possessed of widely different properties ; and when their compounds are decomposed by an electric cur- rent, the constituents are evolved at the opposite poles. Those elements which, under such circumstances, make their appearance at the positive pole are termed electro-negative or negative elements, whilst those disengaged at the negative pole are called electro-positive or positive elements. For reasons which will appear hereafter, the negative are sometimes called chlorous, and the positive basylous elements. It must be re- membered, however, that the difference between these two classes is one of degree only ; they insensibly merge into each other, since the members of both classes exhibit a graduated intensity of the positive or negative quality. Thus potassium is more positive than sodium, and oxygen more negative than sulphur, whilst mercury is negative to sodium but positive to iodine. The following eight elements are negative or chlorous to- wards the remaining fifty-four elements, which are more or less positive or basylous : Fluorine. Oxygen. Chlorine. Sulphur. Bromine. Selenium. Iodine. Tellurium. Although two positive or two negative elements can combine together chemically, yet their union is rarely attended with such striking phenomena as are manifested when the combi- nation takes place between a positive and a negative element. NAMES OF ELEMENTS. CHAPTER II. CHEMICAL NOMENCLATIVE. THE study of every science necessitates an acquaintance with the system of names and peculiar modes of expression which have been found most convenient to denote the materials and to describe the phenomena which form its objects. Such names and modes of expression form the groundwork of the language of every science, upon the right employment of which depend the precision and accuracy of scientific definition. The nomenclature of a science ought to be distinguished for its clearness and simplicity ; but it is by no means easy to secure these conditions in a science like chemistry, where the rapid progress of discovery necessitates the continual addition of new and the frequent alteration of old names. The che- mical name of a substance should not only identify and indi- vidualize that substance, but it should also express the compo- sition and constitution of the body, if a compound, to which it is applied. The first of these conditions is readily attained ; but the second is much more difficult to secure, inasmuch as our ideas of the constitution of chemical compounds the mode in which they are built up as it were require frequent modi- fication. On this account all attempts to frame a perfectly consistent system of chemical nomenclature have hitherto been only partially successful. It has been already mentioned that the number of elements at present known is sixty-two. These have received the names given in the following Table, in which the twenty-one most important elements are distinguished by the largest type, those next in importance by medium type, whilst the names of elements which are either of rare occurrence, or of which our knowledge is yet very imperfect, are printed in the smallest type. CHEMICAL NOMENCLATURE. Name. Sym- bol. Atomic weight. Name. Sym- bol. Atomic weight. ALUMINIUM ANTIMONY ARSENIC Al Sb As 27-5 122 75 Molybdenum . . NICKEL Niobium Mo Ni Nb 92 58-8 97-6 BAEIUM BISMUTH Ba Bi 137 208 NITROGEN .. Osmium N Os 14 199 BOBON B 11 OXYGEN .. 16 BROMINE Cadmium Caesium CALCIUM CARBON Cerium . Br Cd Cs Ca C Ce 80 112 133 40 12 92 PALLADIUM . . PHOSPHORUS PLATINUM .... POTASSIUM... RHODIUM Rubidium Pd P Pt K Rh R,b 106-5 31 197-4 39 104 85-5 CHLORINE ... CHROMIUM COBALT Cl Cr Co 35-5 52-5 58-8 Ruthenium...... Selenium SILICON Ru Se Si 104 79 28-5 COPPER Cn 63-5 SILVER A" 108 Didymium T) 96 SODIUM .. . Na 23 FLUORINE ... Grluciiium F (1 19 14 STEONTIUM ... SULPHUR. Sr S 87-5 32 GOLD ... Au 196-7 Tantalum Ta 137-5 HYDROGEN ... Indium H Tn 1 74 Tellurium Thallium Te Tl 128 204 IODINE T 127 Thorium Th 231-5 IRIDIUM Tr 198 TIN Sn 118 IRON . TV 56 TITANIUM Ti 50 Lanthanium . . . LEAD L ?b 92 207 TUNGSTEN UEANIUM W 17 184 120 Lithium Li 7 Vanadium . V 137 MAGNESIUM ... MANGANESE Mg Mn 24 55 Yttrium ZINC Y 7tr\ 68 65 MERCURY ... Hg 200 Zirconium Zr 90 These elementary substances have been long divided into two great classes metals and non-metals, the latter being also sometimes termed metalloids. The metals are by far the most numerous, the non-metals numbering only the following thirteen elements:- Boron, Bromine, Carbon, Chlorine, Fluorine, Hy- drogen, Iodine, Nitrogen, Oxygen, Phosphorus, Selenium, Silicon, Sulphur. NAMES OF ELEMENTS. 7 The names of the elements can scarcely be said to have been given according to any rule ; many of them are derived from the most prominent property of the bodies themselves, whilst others have a mythological origin. An attempt has been made to distinguish the metals by the termination urn., as potassium, sodium, &c. ; but the common metals, such as gold, copper, iron, &c., still retain their original names ; and one substance, selenium, which at the time of its discovery was regarded as a metal, has had no change made in its name, although further research has divested it of all metallic attri- butes. An important group of electro-negative non-metals fluorine, chlorine, bromine, and iodine have received the termi- nation ine ; three are distinguished by the terminal syllable on, viz. carbon, silicon, and boron ; and three others have gen for their final syllable, viz. oxygen, hydrogen, and nitrogen, these last names being derived from Greek words denoting the pro- perty possessed by these elements of generating respectively acid, water, and nitre. When two elementary bodies unite together, they form a chemical compound of the first order, to which the name Unary compound has been applied. The names of these com- pounds are formed from those of their constituents, the. name of the positive constituent with the terminal ic, or some abbre- viation thereof, preceding that of the negative constituent, which is made to terminate in ide, thus : Potassium and Sulphur form Potassic sulphide. Sodium Oxygen Sodic oxide. Silver Chlorine Argentic chloride. Zinc Iodine Zincic iodide. Calcium Chlorine Calcic chloride. But the same elements frequently form with each other two compounds, in which case the one which contains the smaller proportion of the negative element is distinguished by changing the terminal syllable of the name of its positive constituent into ous, the terminal ic being retained for the compound con- O CHEMICAL NOMENCLATURE. taining the larger proportion of the negative element. Thus, One atom of tin and two atoms of chlorine form Stannous chloride. One atom of tin and four atoms of chlorine form Stannic chloride. Sometimes, however, the same elements form with each other more than two compounds. In these cases the prefixes hypo and per are employed as marks of distinction ; but their use is very rarely required. If a binary compound contains oxygen, and forms an acid when made to unite with water, or a salt when added to a base, it is termed an anhydride or anhydrous acid. Thus, One atom of carbon and two atoms of oxygen form carbonic anhydride. Two atoms of nitrogen and five atoms of oxygen form nitric anhydride. Two atoms of nitrogen and three atoms of oxygen form nitrous anhydride. One atom of sulphur and three atoms of oxygen form sulphuric anhydride. One atom of sulphur and two atoms of oxygen form sulphurous anhydride. In the following cases, the systematic names have not dis- placed the trivial and irregular names used for the same sub- stances : Systematic name. Trivial or irregular name. Hydric oxide Water. Hydric sulphide Sulphuretted hydrogen. Hydric selenide Seleniuretted hydrogen. Hydric telluride Telluretted hydrogen. Hydric chloride Hydrochloric acid. Hydric bromide Hydrobromic acid. Hydric iodide Hydriodic acid. Hydric fluoride Hydrofluoric acid. Hydric carbide . .. { Marsh-gas or light carburetted I hydrogen. Hydric nitride Ammonia. Hydric phosphide Phosphuretted hydrogen. Hydric arsenide Arsenuretted hydrogen. Hydric antimonide Antimonuretted hydrogen. The term acid was originally applied only to substances pos- sessing a sour taste like vinegar ; but analogy has necessitated the application of the same name to a large number of com- NAMES OF ACIDS. 9 pounds which have not this property. In the modern accepta- tion of the name, an acid may be defined as a compound con- taining one or more atoms of hydrogen, which become displaced by a metal when the latter is presented to the compound in the form of a hydrate. The hydrogen capable of being so displaced may be conveniently termed displaceable hydrogen. An acid containing one such atom of hydrogen is said to be monobasic, two such atoms dibasic, &c. Acids of a greater basicity than unity are frequently termed polylasic acids. Thus nitric acid gives, with sodic hydrate, sodic nitrate : N0 3 H + ONaH == N0 3 Na + OH 2 . Nitric acid. Sodic hydrate. Sodic nitrate. Water. Sulphuric acid gives, with potassic hydrate, potassic sulphate : SO 4 H 2 + 20KH = S0 4 K 2 + 20H 2 : Sulphuric acid. Potassic hydrate. Potassic sulphate. Water. and hydrochloric acid gives, with potassic hydrate, potassic chloride : HC1 + OKH = KC1 + OH 2 . Hydrochloric Potassic Potassic Water. acid. hydrate. chloride. When an acid contains oxygen, its name is generally formed by adding the terminal ic either to the name of the element with which the oxygen is united, or to an abbreviation of that name ; thus sulphur forms, with oxygen, sulphuric acid ; nitro- gen, nitric acid ; and phosphorus, phosphoric acid. But it frequently happens that the same element forms two acids with oxygen ; and when this occurs, the acid containing the larger amount of oxygen receives the terminal syllable ic, whilst that containing less oxygen is made to end in ous. Thus we have sulphurous acid, nitrous acid, and phosphorous acid, each containing a smaller proportion of oxygen than that necessary to form respectively sulphuric, nitric, and phosphoric acids. In some instances, however, the same element forms more than two acids with oxygen, in which case the two Greek words hypo, under, and hyper, over, are prefixed to the name of the 10 CHEMICAL NOMENCLATIVE. acid. Thus an acid of sulphur containing less oxygen than sulphurous acid is termed hyposulphurous acid ; and another acid of the same element containing, in proportion to sulphur, more oxygen than sulphurous acid and less than sulphuric, might be named either hypersulphurous acid, or hyposulphuric acid ; but the latter term has been universally adopted. The prefix per is frequently substituted for hi/per ; thus in the case of chlorine, which forms the following four acids with oxygen, viz. hypochlorous acid, chlorous acid, chloric acid, and hyper- chloric acid, the latter is generally named perchloric acid ; but per can only be used as a prefix to the acid containing the largest proportion of oxygen. Some acids do not contain oxygen amongst their constituents, but consist of sulphur or hydrogen united with other elements. This peculiarity of composition is expressed in their nomen- clature by the prefixes sulplio or sulph, and hydro or hydr : thus sulpharsenic acid and sulphostannic acid denote acids composed respectively of sulphur, hydrogen, and arsenic, and sulphur, hy- drogen, and tin ; whilst the names hydrochloric acid and hydri- odic acid are given to acids composed, the first of hydrogen and chlorine, and the second of hydrogen and iodine. The terminals ous and ic are also applied to these acids in exactly the same manner as to the oxygen acids : thus we have sulph- arsenious and sulpharsenic acid, the latter containing a larger proportion of sulphur than the former ; but the appli- cation of the second of these terminals has not hitherto been found necessary in the case of hydrogen acids, since no ele- ment has yet been observed to form more than one acid with hydrogen. The term anhydride or anhydrous acid is applied to the residue obtained by the abstraction of water from one or two molecules of an oxygen acid. Thus, S0 4 H 2 - OH 2 = S0 3 : Sulphuric acid. Water. Sulphuric anhydride. 2N0 3 H - OH 2 = N a O B . Nitric acid. Water. Nitric anhydride. NAMES OF BASES. 11 The term base is applied to three classes of compounds, all of which are converted into salts b y the action of acids. These are 1st. Certain compounds of metals with oxygen, such as sodic oxide (Na 2 0), zincic oxide (ZnO), &c. 2nd. Certain compounds of metals with the compound radical hydroxyl (HO), such as sodic hydrate (OHNa or Na(HO)), zincic hydrate (Zn(HO) 2 ), &c. 3rd. Certain compounds of nitrogen, phosphorus, arsenic, and antimony, such as ammonia (NH 3 ). There are also some organic compounds to which the name base is sometimes given, but which are not included in the above classes ; it is, however, unnecessary further to allude to them here. The bases of the first class are named in accordance with the rules already given for compounds of two elements. The following bases, however, still retain their irregular names : Systematic names. Irregular names. Baric oxide Baryta. Strontic oxide Strontia. Calcic oxide Lime. Magnesic oxide Magnesia. Aluminic oxide Alumina. Grlucinic oxide Grlucina. Zirconic oxide Zirconia. The names of the bases belonging to the second class are formed by changing the terminal syllable of the metal into ic or ous, and the word hydroxyl into hydrate. Thus cesium and hydroxyl form ca3sic hydrate (Cs (HO)) ; barium and hydroxyl, baric hydrate, (Ba (HO) 2 ) ; and iron and hydroxyl, ferric hy- drate (Fe 2 (H0) 6 ). A few of these bases have trivial or irregular names, which are almost invariably used instead of the systematic names : Systematic names. Irregular names. Potassic hydrate Potash. Sodic hydrate Soda. Lithic hydrate Lithia. 12 CHEMICAL NOMENCLATURE. The bases of the third class are distinguished by the terminal syllable ine, except nitrine, (NH 3 ), which retains its trivial name ammonia. These bases belong almost exclusively to the department of organic chemistry, and their nomenclature could not be advantageously discussed here. It has been already mentioned that by the mutual action of an acid and a base upon each other, a salt is produced. If the salt be free from oxygen and sulphur, like common salt, (NaCl) , it is termed a haloid salt ; if it contain oxygen it is termed an oxysalt ; and if this oxygen be replaced by sulphur, it is distin- tinguished as a sulphosalt. The haloid salts are named according to the rules for binary compounds above given, thus : Name. Formula. Sodic chloride NaCl. Calcic iodide CaI 2 . Ferrous bromide EeBr 2 . Ferric bromide Fe 2 Br 6 . Oxy salts are divided into normal, acid, and basic. A normal salt is one in which the displaceable hydrogen of the acid (see page 9) is all exchanged for an equivalent amount of a metal or of a positive compound radical. The following examples will serve to illustrate this definition of a normal, or as it is sometimes incorrectly called, a neutral salt, the displaceable atoms of hydrogen in the acid, and the metal by which they have been displaced in the salt, being printed in italics : Acid. Normal salt. XT ., . ., ATrk TT / Sodic nitrate NO.,.ZVa. Nitric acid NCX^ST \ _ . . . I Calcic nitrate (NO 3 ) 2 Ca". Sulphuricacid SO 4 #, f Potassic sulphate SO^. I Calcic sulphate SO 4 Ca". .-,- TT / Potassic phosphate ... PCvfiT,. Phosphoric acid PO.J91 1^,i- i i . I Calcic phosphate (PO 4 ) 2 Ca 3 ". Hypophosphorous acid . . PO 2 H 2 # . . . Sodic hypophosphite . . I Phosphorous acid PO 3 HZ? 2 ... Potassic phosphite ...I NAMES OF SALTS. 13 Acid. Normal salt. Metaphosphoric acid . . . PO 3 # ...... Lithic metaphosphate . PO 3 Zi Pyrophosphoric acid ... P 2 O 7 # 4 ... Calcic pyrophosphate .. P 2 O 7 Ca t ". CSO.iff ( SO.JVa Nordhausen sulphuric Q ^ Sodic bisulphite ...... \O . acid ..................... \S0 3 H lsO,JV T a O 3 H f CrO 3 K Unknown acid ............ -I O ...... Potassic bichromate An acid salt is one in which the displaceable hydrogen of the acid is only partially exchanged for a metal or positive compound radical. The following examples illustrate the constitution and nomen- clature of these salts : Acid. Acid salt. Sulphuric acid ... SO 4 # 2 Hydric sodic sulphate ...... SO+HNa. Carbonic acid ... CO 3 H. 2 ? Hydric potassic carbonate. . CO 3 HK. r Hydric disodic phosphate. . PO 4 .fflVa. 2 . Phosphoric acid... ~POH 3 I Dihydric sodic phosphate... ~POH. 2 Na. - [ Microcosmic salt ............ FO^NH, )Na. (Hydric ammonic sodic phosphate.) Acid salts are produced almost exclusively from polybasic acids. When the number of bonds* of the metal or compound positive radical contained in a salt exceeds the number of atoms of displace- able hydrogen in the acid, the compound is usually termed a basic salt as, for instance, Acid. Basic salt. rr . /Malachite ........................ CO 5 H 2 CV'. Carbonic acid ......... CO 3 R 2 \ . * ^ 2 I Blue cupric carbonate ......... C 2 O f< H 2 C'M 3 // . _ f Tribasic cupric sulphate ...... SO..H.CK". SulphuncacKl ...... K> These and most, if not all, other basic salts do not differ essentially in their constitution from the normal and acid salts. This will be seen from the arrangement of their atoms given under the different metals entering into their composition. * For an explanation of this term see Chap. III. p. 18. 14 CHEMICAL NOTATION. The nomenclature of organic bodies is founded upon the same principles as that of inorganic compounds ; but its discus- sion could not be conveniently introduced here. CHAPTER III. CHEMICAL NOTATION. SYMBOLIC NOTATION. Every element is represented by a symbol, which is frequently the initial letter of the name of the element ; but as in some cases the names of two or more elements begin with the same letter, it is necessary to distinguish them by the use of a second letter in small type, which is either the second letter of the word, or some other letter prominently heard in its pronunciation ; thus carbon, cadmium, cobalt, and cerium all begin with the same letter ; but they are distinguished by the symbols C, Cd, Co, and Ce. In the use of the single letters, the non-metallic elements have the preference ; thus oxygen, hydrogen, nitrogen, sulphur, phos- phorus, boron, carbon, iodine, and fluorine are expressed by the single letters O, H, N, S, P, B, C, I, and F ; whilst the metals osmium, mercury, nickel, strontium, platinum, bismuth, cobalt, iridium, and iron are symbolized by two letters each ; thus Os, Hg (hydrargyrum), Ni, Pt, Bi, Co, Ir, and Ee (ferrum). In the selection of the single letter for other cases, preference is given to the most important element ; thus sulphur, selenium, and silicon are all non-metallic elements, beginning with the same letter, but sulphur being the most important, the single letter S is assigned to it ; whilst selenium and silicon are de- noted respectively by Se and Si. The symbols of compounds are formed by the simple juxta- position of the symbols of their constituent elements. Such a group of two or more symbols is termed a chemical formula. FORMULA AND EQUATIONS. 15 Thus: Argentic chloride AgCl. Zincic oxide ZnO. The symbols not only represent the elements for which they are used, but they also denote a certain definite proportion by weight of each element ; the formula HC1, for instance, does not merely denote a compound of hydrogen and chlorine, but it signifies a molecule of that compound containing one atom (1 part by weight) of hydrogen, and one atom (35'5 parts by weight) of chlorine. When, therefore, the molecule of a com- pound contains more than one atom or combining proportion of any element, it is necessary to express such fact in the for- mula : this is done by the use of a coefficient placed after the symbol of the element : Zincic chloride ZnCl 2 . Ferric chloride Fe.,Cl 6 . Stannous chloride SnCl 2 . Stannic chloride SnCl 4 . When it is necessary to denote two or more molecules of any compound, a large figure is placed before the formula of the compound ; such a figure then affects every symbol in that formula : thus 3S0 4 H 2 means three molecules of the compound S0 4 H 2 . The changes which occur during chemical action are expressed by equations, in which the symbols of the elements or compounds, as they exist before the change, are placed on the left, and those which result from the reaction on the right. Thus, taking an example from each of the five kinds of chemical action above mentioned, we have (1) Zn + C1 2 = ZnCl 2 . Zinc. Chlorine. Zincic chloride. (2) 2HC1 + Na 2 = 2NaCl + H 2 . Hydrochloric acid. Sodium. Sodic chloride. Hydrogen. (3) S0 4 Cu + (N0 3 ) 2 Ba = SO 4 "Ba + (N0 3 ) 2 Cu. Cupric sulphate. Baric nitrate. Baric sulphate. Cupric nitrate. 16 CHEMICAL NOTATION. (4) (CN)O(NHJ = N 2 H 4 (CO). Ammonic cyanate. Urea. (5) 20H 2 = 2 + 2H 2 . Water. Oxygen. Hydrogen. The sign .+ , as seen from the foregoing examples, is placed between the formulae of the molecules of the different substances which are brought into contact before the reaction, and of those which result from the change. This sign must never be used to connect together the constituents of one and the same chemical compound. The sign is only very rarely used in chemical notation, but when employed it has the ordinary signification of abs- traction; thus, S0 4 H 2 - H 2 = S0 3 . Sulphuric acid. Water. Sulphuric anhydride. Use of the bracket. The bracket has been employed in various senses in chemical formulae ; but in the following pages it is used in notation for one purpose only, viz. for expressing chemical combination between two or more elements which are placed perpendicularly with regard to each other and next to the bracket in a formula. Thus in the following cases, I. II. III. ( CH 3 ( CH 3 COO } \CH 3 \0 ' Bal [CH 3 COOj the formula No. I. signifies that two atoms of carbon are directly united with each other, No. II. that two atoms of car- bon are linked, as it were, together by an atom of oxygen, the latter being united to both carbon atoms, whilst in like manner No. III. expresses the fact that one atom of oxygen in the for- mula of the upper line is linked to another atom of oxygen in the formula of the lower line, by an atom of barium. Use of thick letters. As a rule, the formula in this book are so written as to denote that the element represented by the first symbol of a formula is directly united with all the active ATOMICITY OF ELEMENTS. 17 bonds of the other elements or compound radicals following upon the same line : thus the formula S0 2 Ho 2 (sulphuric acid) signifies tha$ the hexad atom of sulphur is combined with the four bonds of the two atoms of oxygen, and also with the two bonds of the two atoms of hydroxyl. Such a formula is termed a rational formula*. Occasionally, however, owing to the atomic arrangement of a compound not being known, its formula cannot be written according to this rule ; and in order to prevent such more or less empirical formula from being mistaken for rational for- mulae, the first symbol of a rational formula will always be printed in thick type whenever the element has more than one bond. It deserves also to be mentioned that, as a rule, the ele- ment having the greatest number of bonds will occupy this prominent position. Thus, Sulphuric acid S0 2 Ho 2 . Water OH 2 . Mtricacid . . NO Ho. Microcosmic salt POHo AmoNao. ATOMICITY OF ELEMENTS. It has been already stated that the atomic weight of an element is the smallest proportion by weight in which that element enters into or is expelled from a chemical compound. The atoms of the various ele- ments, the relative weights of which are thus expressed, exhibit very different values in chemical reactions. Thus an atom of zinc is equivalent to two atoms of hydrogen ; for when zinc is brought into contact with steam at a high tempera- ture, one atom of zinc expels from the steam two atoms of hydrogen and occupies their place thus, OH 2 + Zn = OZn + H 2 . Water. Zincic oxide. Again, when zincic oxide is brought into contact with hydro- chloric acid, the place of the zinc becomes once more occupied * For further information on this subject see ATOMICITY OF ELEMENTS below. 18 CHEMICAL NOTATION. by hydrogen, but two atoms of hydrogen are found to be neces- sary to take the place of one atom of zinc : OZn + 2HC1 = ZnCl a + ' OH 2 . Zincic oxide. Hydrochloric acid. Zincic chloride. Water. In like manner one atom of boron can be substituted for three atoms of hydrogen, one atom of carbon for four, one of nitrogen for five, and one atom of sulphur for no less than six atoms of hydrogen. To give a concrete expression to these facts, the atom of hydrogen may be represented as having only one point of attachment or bond by which it can be united with any other element, zinc as having two such bonds, boron three, and so on. Thus the atoms of these elements may be graphically represented in the following manner : Hydrogen ........................ Zinc .................... .......... Boron Carbon Nitrogen Sulphur In symbolic notation, the same idea is conveyed by the use of dashes and Roman numerals placed above and to the right of the symbol of the element ; thus, Hydrogen ......... H', Carbon ............ C 1V , Zinc ............... Zn", Nitrogen ......... N v , Boron ............ B"', Sulphur ......... S vi . No element, either alone or in combination, can exist with any of its bonds disconnected ; hence the molecules of all ele- MONATOMIC AND POLYATOMIC MOLECULES. 19 ments with an odd number of bonds are generally diatomic, and always polyatomic ; that is, they contain two or more atoms of the element united together. Thus, Symbolic. Graphic. Hydrogen ............ H 2 .. @ Chlorine ............ C1 2 ................. Nitrogen ............ N 2 V ............... Phosphorus ......... P 4 V .................. An element with an even number of "bonds can exist as a monatomic molecule, its own bonds satisfying each other. Thus, Symbolic. Graphic. Mercury ............... Hg" ............... Cadmium ............... Cd" ............... Zinc ..................... Zn" ............... r^ It is nevertheless obvious that such an element may also exist as a polyatomic molecule. Oxygen furnishes us with an example of this ; for, in its ordinary condition it is a diatomic molecule, and in the allotropic form of ozone, a triatomic molecule : Symbolic. Graphic. Oxygen ............... O 2 " ............... = - Ozone .................. O 3 " ............... \ / This combining value of the elementary atoms is usually termed their atomicity or atom-fixing power. An element with 20 CHEMICAL NOTATION. one bond is termed a monad, with two bonds a dyad, with three a triad, with four a tetrad, with five a pentad, and with six a Jiexad. Elements with an odd number of bonds are termed perissads, whilst those with an even number are named artiads. In order to avoid the unnecessary use of atomicity -marks in symbolic notation, I shall never attach them to a monad or to oxygen, which, it must be remembered, is always a dyad. Neither will the atomicity-coefficient be attached to the tetrad element carbon, in the formulae of organic bodies, unless this element plays the part of a dyad an occurrence of extreme rarity. When not otherwise marked, therefore, carbon must always be understood to be a tetrad. It will also, as a rule, be unnecessary to mark the atomicity of the elements which are expressed by symbols in thick type, because their atomicity is clearly indicated by the sum of the atomicities of the elements or compound radicals placed to their right, or connected with them perpendicularly by a bracket. Thus in the formula /CC1 3 |ccy each atom of carbon is united with three atoms of the monad chlorine, whilst the bracket indicates that the two atoms of carbon are also united, thus stamping C as a tetrad element. From what has just been said with regard to carbon, it is evident that the atomicity of an element is, apparently at least., not a fixed and invariable quantity : thus nitrogen is sometimes equivalent to five atoms of hydrogen, as in ammonic chloride, (N V H 4 C1), sometimes to three atoms, as in ammonia (N'"H 3 ), and sometimes to only one atom, as in nitrous oxide (N 2 0). But it is found that this variation in atomicity always takes place by the disappearance or development of an even number of bonds : thus nitrogen is either a pentad, a triad, or a monad ; phosphorus and arsenic, either pentads or triads ; carbon and tin, either tetrads or dyads ; and sulphur, selenium, and tellu- rium, either hexads, tetrads, or dyads. These remarkable facts can be explained by a very simple ABSOLUTE, LATENT, AND ACTIVE ATOMICITY. 21 and obvious assumption, viz. that one or more pairs of bonds be- longing to one atom of the same element can unite and, having saturated each other, become, as it were, latent. Thus the pentad nitrogen becomes a triad when one pair of its bonds becomes latent, and a monad when two pairs, by combination with each other, are, in like manner, rendered latent, conditions which may be graphically represented thus : Pentad. Triad. Monad. And in the case of sulphur : Hexad. Tetrad. Dyad. Adopting this hypothesis, it will be convenient to distinguish the maximum number of bonds of an element as its absolute atomicity, the number of bonds united together as its latent atomicity, and the number of bonds actually engaged in linking it with the other elements of a compound as its active atomicity. The sum of the active and latent atomicity of any element must evidently always be equal to the absolute atomicity. Thus in sulphuric acid (S vi 2 Ho 2 ) the absolute and active atomicities are both =vi, therefore the latent atomicity =0. In sulphu- rous acid ("S iv OHo 2 ) the active atomicity =IY, and conse- quently the latent =YI iv=ii ; whilst in sulphuretted hydro- gen ( IV S"H 2 ) the active and latent atomicities are respectively ii and iv. The apparent exceptions to this hypothesis disappear on investigation : thus iron, which is a dyad in ferrous compounds (as FeCl 2 ), a tetrad in cubical pyrites (FeS 2 "), and a hexad in ferric acid (FeO 2 Ho 2 ), is apparently a triad in ferric chlo- ride (FeCl 3 ) ; but the vapour-density of ferric chloride shows that its formula must be doubled that, in fact, the two atoms of the hypothetical molecule of iron (Fe 2 ) have not been com- CHEMICAL NOTATION. pletely separated. The formulae of the ferrous and ferric chlorides and of ferric acid then become Symbolic. Ferrous chloride, . iv Fe"C! 2 . Ferric chloride ... "Te'" 2 Cl 6 . -=-(3 Ferric acid Fe vi 2 Ho 2 . Again, mercury is apparently a monad in mercurous chlo- ride (calomel, HgCl) and a dyad in mercuric chloride (cor- rosive sublimate, Hg"Cl 2 ); but there are strong reasons for believing that the formula of calomel ought to be doubled, in which case mercury would assume the dyad form in both com- pounds : Mercurous chloride ... 'Hg' 2 Cl 2 . Mercuric chloride Hg"Cl 2 . It w r ill be remarked that the number of bonds supposed to be combined with each other in the atom of iron in ferrous chloride is expressed in the above symbol by the atomicity numeral rv placed to the left of the symbol, whilst the analo- gous union of three bonds of each atom of iron in ferric chlo- ride is expressed by the three dashes'" to the left of the symbol Pe 2 . I shall not, however, use these coefficients of latent ato- micity in the case of the single atom of an element, the student being supposed to have made himself acquainted with the abso- lute atomicity of every element as expressed in the Table at GRAPHIC NOTATION. 23 page 32. For a similar reason, it will also rarely be necessary to express the same idea in graphic notation : thus, for instance, ammonia will be drawn It will be necessary, however, to employ these coefficients in symbolic formula, where two or more atoms of the same ele- ment are joined together under such circumstances, that the number of bonds uniting them cannot be found by subtracting the coefficient of active atomicity from the absolute atomicity of the element ; as in hydric persulphide ('S' 2 H 2 ) , for instance, which might otherwise be viewed as '"S' 2 H 2 , or V S' 2 H 2 . In rare cases, in which oxygen links together two elements or radicals in the same line, a hyphen is placed before and after the symbol 0, thus : CH -O-CMeO CH 2 -0-CMeO' Diacetic glycol. GRAPHIC NOTATION. This mode of notation, although far too cumbrous for general use, is invaluable for clearly showing the arrangement of the individual atoms of a chemical com- pound. It is true that it expresses nothing more than the symbolic notation of the same compound, if the latter be written and understood as above described ; nevertheless the graphic form affords most important assistance, both in fixing upon the mind the true meaning of symbolic formulas, and also in making comparatively easy of comprehension the internal arrangement of the very complex molecules frequently met with both in mineral and organic compounds. It is also of especial value in rendering evident the causes of isomerism in organic bodies. 24 CHEMICAL NOTATION. Graphic notation, like the above method of symbolic notation, is founded almost entirely upon the doctrine of atomicity, and consists in representing, graphically, the mode in which every bond in a chemical compound is disposed of. Inasmuch, however, as the principles involved are precisely the same as those already described under the heads of SYMBOLIC NOTATION and ATOMICITY OF ELEMENTS, it is unnecessary here to do more than give the following comparative examples of symbolic and graphic for- mulae : Water Symbolic. .. OH,. Nitric acid Ammonic chloride . Sulphuric anhydride ... N0 2 Ho. NH 4 C1. S0 3 . Sulphuric acid S0 2 Ho 2 . Carbonic anhydride CO 2 . Potassic carbonate C OKo 3 . GRAPHIC FORMULAE. Symbolic. Graphic. 25 Marsh-gas CH 4 . Ammonic carbonate, COAmo 2 . Zincic nitrate N0 2 It must be carefully borne in mind that these graphic for- mulae are intended to represent neither the shape of the mole- cules, nor the relative position of the constituent atoms. The lines connecting the different atoms of a compound, and which might with equal propriety be drawn in any other direction, provided they connected together the same elements, serve only to show the definite disposal of the bonds : thus the for- mula for nitric acid indicates that two of the three constituent atoms of oxygen are com- bined with nitrogen alone, and are conse- quently united to that element by both their bonds, whilst the third oxygen atom is com- bined both with nitrogen and hydrogen. The lines connecting the different atoms of a compound are but crude symbols of the bonds of union between them ; and it is scarcely necessary to remark that no such material con- nexions exist, the bonds which actually hold together the atoms of a compound being in all probability, as regards their nature, much more like those which connect the members of our solar system. It may also be here mentioned that graphic, like symbolic 26 COMPOUND RADICALS. formulae, are purely statical representations of chemical com- pounds, they take no cognizance of the amount of potential energy associated with the different elements. Thus in the formulae for marsh- gas and carbonic anhydride, -- == Marsh-gas. Carbonic anhydride. Ihere is no indication that the molecule of the first compound contains a vast store of force, whilst the last is comparatively a powerless molecule. CHAPTER IV. COMPOUND EADICALS. THE term compound radical may be applied to any group of two or more atoms, which takes the place and performs the functions of an element in a chemical compound. In practice, however, it is only applied to any such group when the latter is met with in numerous chemical compounds. An element is a simple radical, and enters into combination in the following manner, a, ft, c, and d being monad elements, a" a dyad, a" a triad, and a a tetrad element : a + b=ab, a" +2b = a"b z , a'" + 3b=a'"b 3 , &c. &c. A group of elements replacing a, ", or a' n in the above equa- tions is a compound radical, as in the following examples. COMPOUND RADICALS. 27 (a"b) + b= (a"b)b, =('"ft)"i 2 , = (a'"bc)b, The group of elements (&" &) constitutes a compound monad radical equivalent to one atom of hydrogen or chlorine. The group (a'"b)" is a compound dyad radical, &c. It is there- fore evident that a polyad element is essential to every com- pound radical ; in fact a compound radical consists of one or more atoms of a polyad element in which one or more bonds are unsatisfied; and it is either a monad, dyad, triad, fyc. radical, ac- cording to the number of monad atoms required to satisfy its active atomicity. Such a radical, when a monad, triad, or pentad, cannot exist as a separate atom ; like hydrogen or nitrogen, when isolated, it combines with itself, forming a diatomic mole- cule. It is only by the union of two atoms that the vacated bonds can in these cases be satisfied. From the above definition of a compound radical, it is evi- dent that an almost infinite number of such bodies must exist ; for in the compounds of every polyad element it is only neces- sary to vacate successive bonds to create each time a new com- pound radical. Thus marsh-gas (CH 4 ) minus one atom of hydrogen gives the compound radical methyl (CH 3 ); minus two atoms of hydrogen, it forms methylene (CH 2 )", and by the abstraction of three hydrogen atoms it is transformed into the triad radical formyl (CH)'"; but, except in a few cases, it is not advantageous thus to incorporate, as it were, compound radicals, which, instead of simplifying notation and nomencla- ture, would, if thus multiplied, only embarrass them. No compound radical, therefore, ought to receive a recognition as such unless it can be shown to enter into the composition of a large number of compounds. The following are the names and formulae of the chief inor- c2 28 COMPOUND RADICALS. game compound radicals recognized in the notation of this book : Abbreviated Molecular formulae. Atomic formulae. atomic formulas. Hydroxyl (H0) 2 HO Ho. Hydrosulphyl (HS) 2 HS Hs. Ammonium (NH 4 ) 2 NH 4 Am Ammonoxyl (NH 4 O) 2 KH.O Amo. Amidogen (NH 2 ) 2 ]N T H 2 Ad. In addition to these, certain compounds which metals form with oxygen are also regarded as compound radicals for instance, Molecular Atomic Abbreviated formulae. formulae. atomic formulae. Potassoxyl (K0) 2 KO Ko. fO Zincoxyl (ZnO 2 ) 4 Zn" Zno". lo The essential character of these last compound radicals is that the whole of the oxygen they contain is united with the metal by one bond only of each oxygen atom, as seen in the following graphic formulae : Hydroxyl Potassoxyl Zincoxyl (o) (z n ) (o The metal thus becomes linked to other elements by these dyad atoms of oxygen. The functions of such compound radicals will be sufficiently evident from the following examples of compounds into which they enter, and in which their position is marked by dotted lines. Nitric acid FUNCTIONS OF RADICALS. 29 Potassic sulphate Baric nitrate Zincic sulphate It is not necessary to dignify all these metallic compound radicals with names ; the chief point of importance about them is their abbreviated notation, in which the small letter o is attached to the symbol of the metal, the atomicity of the radical being marked in the usual manner. It must be borne in mind that the number of atoms of oxygen in any radical of this class depends upon its atomicity : thus a monad contains only one atom of oxygen, a dyad two, and a triad always three atoms of oxygen. The use of any but monad and dyad metallic compound radicals is very rare. 30 ATOMIC AND MOLECULAR COMBINATION. CHAPTER V. ATOMIC AND MOLECULAE COMBINATION. IN all the cases of chemical combination considered in the above Chapters, a union of atoms has been invariably contem- plated. This atomic union is generally attended by the breaking up of previously existing molecules two such molecules, by the mutual exchange of their atomic constituents, producing two new and perfectly distinct molecules. Thus when chlorine unices with, hydrogen to form hydrochloric acid, a molecule of chlorine and one of hydrogen yield up their constituent atoms, forming two molecules of hydrochloric acid, C1 2 + H 2 =2HC1. In comparatively rare cases, two molecules combine to form only one new molecule ; thus a molecule of carbonic oxide and one of chlorine combine to form one molecule of carbonic oxydichloride or phosgene gas : but the union is even here essentially atomic ; for after combination both the oxygen and chlorine are directly united with the atom of carbon : C"0 + C1 2 = C iy OCl 2 . Carbonic oxide. Chlorine. Phosgene gas. Chemists are, however, compelled to admit an entirely dif- ferent kind of union, which not unfrequently occurs, and which may be appropriately termed molecular union or molecular com- bination. In the formation of such compounds, no change takes place in the active atomicity of any of the molecules. It is this kind of combination which holds together salts and their water of crystallization, as, for instance, Sodic chloride crystallized at 10 C NaCl, 2OH 2 . Sodic bromide crystallized below +30C....NaBr, 2OH 2 . Sodic iodide crystallized below + 50 C....NaI, 2OH 2 . Alum S,0 8 ('A1 2 '"0 6 ) vi Ko 2 , 24OH 2 . CLASSIFICATION OF ELEMENTS. 31 The researches of Tyndall upon the absorption of radiant heat by different vapours, render it more than probable that aqueous vapour does not consist of an assemblage of single and separate molecules of the compound OH 2 , but of groups of these molecules of great complexity, united without contraction of volume. Numerous other instances of molecular combination might be adduced ; but it is only necessary here to point out that such molecular unions will be distinguished from atomic combi- nations by the use of the comma, as in the above and following examples : Tetramethylammonic tri-iodide NMe 4 1, 1 2 . Tetramethylammonic pentiodide NMe 4 1, 2I 2 . Tetramethylammonic iodo-dichloride . NMe 4 1, C1 2 . In all cases molecular combination seems to 'be of a much more feeble character than atomic union ; for, in the first place, such bodies are generally decomposedwithfacility ; and secondly, the properties of their constituent molecules are markedly per- ceptible in the compounds. Thus the above so-called perio- dides of the organic bases present in appearance great resem- blance to iodine. CHAPTER VI. CLASSIFICATION OF ELEMENTS. IT has already been mentioned that the elements may be divided into two great classes, the metals and the non-metals or metalloids. A second division into positive or basylous and negative or chlorous elements has also been explained. A third and still more important classification is founded upon the atomicity of the elements. In the following classified Table all three methods are embodied, the metalloids being printed 32 WEIGHTS AND MEASURES. in red type, and the metals in black, whilst the positive or basylous elements are printed in Roman characters, and the negative or chlorous in italics. In addition, the different classes are also divided into sections, consisting of elements closely related in their chemical characters. Monads. Dyads. Triads. Tetrads. Pentads. Hexads. 1st Section. Hydrogen. 1st Section. Oxygen. 1st Section. Boron, 1st Section. Carbon. Silicon. Tin. Titanium. 1st Section. Nitrogen. Phosphorus. Arsenic. Antimony. Bismuth. 1st Section. Sulphur. Selenium. ' Tellurium. 2nd Section. Fluorine. Chlorine. Bromine. Iodine. 2nd Section. Barium. Strontium. Calcium. Magnesium. -Zinc. 2nd Section. Gold. 2nd Section. Tungsten. Vanadium. Molybdenum. 2nd Section. Thorinum. Niobium. Tantalum. Zirconium. Aluminium. 3rd Section. Caesium. Rubidium. Potassium. Sodium. Lithium. 3rd Section. Didymium. Lanthanum. Yttrium. Glucinum. 3rd Section. Osmium. - Iridium. Ruthenium. - Rhodium. 3rd Section. Platinum. Palladium. 4th Section. Chromium. Manganese. - Iron. Cobalt. Nickel. Uranium. Cerium. 4th Section. Thallium. Silver. 4th Section. Cadmium. Mercury. Copper. 4th Section. Lead. CHAPTER VII. WEIGHTS AND MEASURES. THE weights and measures employed in this book are chiefly those of the French decimal system. The following Tables, published by Messrs. De la Rue and Co., will enable the student to convert these into their English equivalents when- ever this may be necessary. WEIGHTS AND MEASURES. 33 French Measures of Length. In English inches. In English feet =12 inches. In English yards =3 feet. In English fathoms =6 feet. In English miles = 1760 yards. Millimetre Centimetre Decimetre Metre Decametre Hectometre Kilometre Myriometre 0-03937 0-39371 3-93708 39-37079 393-70790 3937-07900 39370-79000 393707-90000 0-003281 0-032809 0-328090 3-280899 32-808992 328-089920 3280-899200 32808-992000 0-0010936 0-0109363 0-1093633 1-0936331 10-9363310 109-3633100 1093-6331000 10936-3310000 0-0005468 0-0054682 0-0546816 0-5468165 5-4681655 54-6816550 546-8165500 5468-1655000 O-OOOOOOo 0-0000062 0-0000621 0-0006214 0-0062138 0-0621382 0-6213824 6-2138244 1 inch =2-539954 centimetres. 1 yard=0'9143S35 metre. 1 foot =3-0479449 decimetres. 1 mile =1-6093149 kilometre. French Measures of Surface. In English square feet. In English square yards =9 square feet. In English poles = 272-25 sq. feet. In English roods = 10890 sq. feet. In English acres = 43560 sq. feet. Centiare or sq. metre Are or 100 sq. metres Hectare or 10,000 1 square metres ... j 10-764299 1076-429934 107642-993418 1-196033 119-603326 11960-332602 0-0395383 3-9538290 395-3828959 0-0009885 0-0988457 9-8845724 0-0002471 0-0247114 2-4711431 1 square inch=6'4513669 square centimetres. 1 square foot =9-2899683 square de'cimetres. 1 square yard=0'83609715 square metre or centiare. 1 acre ' =0-40467102 hectare. French Measures of Capacity. In cubic inches. In cubic feet= 1728 cubic inches. In pints 34-65923 cubic inches. In gallons =8 pints =277-27384 cubic inches. In bushels =8 gallons = 2218-19075 cubic inches. Millilitre or cubic cen- 1 0-06103 ' 0-61027 6-10271 61-02705 610-27052 6102-70515 61027-05152 610270-51519 0-000035 0-000353 0-003532 0-035317 0-353166 3-531658 35-316581 353-165807 0-00176 0-01761 0-17608 1-76077 17-60773 176-07734 1760-77341 17607-73414 0-0002201 0-0022010 0-0220097 0-2200967 2-2009668 22-0096677 220-0966767 2200-9667675 0-0000275 0-0002751 0-0027512 0-0275121 0-2751208 2-7512085 27-5120846 275-1208459 Centilitre or 10 cubic \ centimetres / Decilitre or 100 cubic i centimetres J Litre or cubic de'cimetre Decalitre or centistere. . . Hectolitre or de'cistere.. Kilolitre, or Stere, or 1 cubic metre / Myriolitre or decastere.. 1 cubic inch= 16-386176 cubic centimetres. 1 cubic foot =28-315312 cubic de'cimetres, or litres. 1 gallon =4-543358 litres. c5 WEIGHTS AND MEASURES. French Measures of WeigJit. In English grains. In troy ounces = 480 grains. In avoirdu- pois lbs.= 7000 grains. In cwts. = 1121bs.= 784000 grs. Tons = 20 cwts.= 15680000 grs. Milligramme Centigramme De'cigramme Gramme 0-01543 0-15432 1-54323 15-43235 154-32349 1543-23488 15432-34880 154323-48800 0-000032 0-000322 0-003215 0-032151 0-321507 3-215073 32-150727 321-507267 0-0000022 0-0000220 0-0002205 0-0022046 0-0220462 0-2204621 2-2046213 22-0462126 o-ooooooo 0-0000002 0-0000020 0-0000197 0-000191)3 0-0019684 0-0196841 0-1968412 o-ooooooo o-ooooooo o-ooooooi o-oooooio 0-0000098 0-0000984 0-0009842 0-0098421 De'cagramme Hectogramme Kilogramme Myriogramme 1 grain =0'064799 gramme. 1 Ib. avoir. = 0-453593 kilogr. 1 troy oz. = 31-103496 grammes. 1 cwt. =50-802377 kilogrs. Temperatures are expressed upon the Centigrade scale, and barometric measurements are given in millimetres. For the ready conversion of gaseous volumes into weights, I have adopted the crith, or standard multiple proposed by Dr. Hofmami. The crith is the weight of one litre or cubic deci- metre of hydrogen at C. and at a pressure of 760 millimetres of mercury. The following is Dr. Hofmann's description of the value and applications of this unit. " The actual weight of this cube of hydrogen, at the standard temperature and pressure mentioned, is O0896 gramme ; a figure which I earnestly beg you to inscribe, as with a sharp gra- ving tool, upon your memory. There is probably no figure in chemical science more important than this one to be borne in mind, and to be kept ever in readiness for use in calculation at a moment's notice. For this litre- weight of hydrogen = 00896 gramme (I purposely repeat it) is the standard multiple, or coefficient, by means of which the weight of one litre of any other gas, simple or compound, is computed. Again, therefore, I say, do not let slip this figure 0'0896 gramme. So important, indeed, is this standard weight unit, that some name the simpler and briefer the better is needed to denote it. For this purpose I venture to suggest the term crith, de- rived from the Greek word KpiQri, signifying a barley-corn, and figuratively employed to imply a small weight. The weight of 1 litre of hydrogen being called 1 crith, the volume- weight THE CRITH. 35 of other gases, referred to hydrogen as a standard, may be ex- pressed in terms of this unit. " For example, the relative volume-weight of chlorine being 35*5, that of oxygen 16, that of nitrogen 14, the actual weight of 1 litre of each of these elementary gases, at C. and O m> 76 pressure, may be called respectively 35 '5 criths, 16 criths, and 14 criths. " So, again, with reference to the compound gases ; the rela- tive volume-weight of each is equal to half the weight of its product-volume. Hydrochloric acid (HC1), for example, con- sists of 1 vol. of hydrogen + 1 vol. of chlorine = 2 volumes ; or, by weight, 1 + 35-5=36-5 units ; whence it follows that the relative volume-weight of hydrochloric acid gas is ^ = 18* 25 units ; which last figure therefore expresses the number of criths which one litre of hydrochloric acid gas weighs at C. temperature and O m '76 pressure ; and the crith being (as I trust you already bear in mind) 0*0896 gramme, we have 18-25 x 0-0896=1-6352 as the actual weight in grammes of hydrochloric acid gas. " So, once more, as the product-volume of water-gas (H 2 0) (taken at the above temperature and pressure) contains 2 vols. of hydrogen + 1 vol. of oxygen, and therefore weighs 2 + 16 =18 units, the single volume of water-gas weighs ^ 8 =9 units ; or, substituting as before the concrete for the abstract value, 1 litre of. water-gas weighs 9 criths; that is to say, 9x0'0896 gramme =0*8064 gramme. " In like manner the product-volume of sulphuretted hydro- gen (H 2 S)=2 litres of hydrogen, weighing 2 criths, +1 litre of sulphur-gas, weighing 32 criths, together 2 + 32=34 criths, which, divided by 2, gives % 4 =17 criths =17 X 0*0896 gramme = 1-5232 gramme = the weight of 1 litre of sulphuretted hydro- gen at standard temperature and pressure. " And so, lastly, of ammonia (NH 3 ) ; it contains in 2 litres 3 litres of hydrogen, weighing 3 criths, and 1 litre of nitro- gen, weighing 14 criths ; its total product-volume-weight is 36 HYDROGEN. therefore 3 + 14=17 critlis, and its single volume or litre weight is consequently y =8-5 criths=8'5 x 0'0896 gramme =0'7616 gramme. " Thus, by the aid of the hydrogen-litre-weight or crith = 0*0896 gramme, employed as a common multiple, the actual or concrete weight of 1 litre of any gas, simple or compound, at standard temperature and pressure, may be deduced from the mere abstract figure expressing its volume-weight relatively to hydrogen." CHAPTER VIII. MONAD ELEMENTS. SECTION I. HYDROGEN, H 2 . Atomic weight =1. Molecular weight =2. Molecular volume I I I. 1 litre weighs 1 crith. Atomicity ', being the standard of comparison. Occurrence. In combination, as water, in very large quan- tities in nature. In almost all vegetable and animal sub- stances, and in many minerals. In the free state in the gases of volcanoes. In certain stars and nebula ? Preparation. 1. By the action of sodium upon water: 2OH 2 + Na, = 2(XNaH + H 2 . Water. Sodium. Sodic hydrate. Hydrogen. 2. By the action of sodium upon dry hydrochloric acid : 2HC1 + Na 2 = 2NaCl + H 2 . Hydrochloric acid. Sodium. Sodic chloride. Hydrogen. CHLORINE. 37 \ 3. By the action of zinc, iron, or certain other metals on hydrochloric acid : 2HC1 + Zn = ZnCl 2 + H 2 . Hydrochloric acid. Zincic chloride. 4. By the action of zinc or certain other metals on dilute sulphuric acid : S0 2 Ho 2 + Zn = S0 2 Zno" + H 2 . Sulphuric acid. Zincic sulphate. 5. By passing steam over iron heated to redness : Fe 3 + 40H 2 = iv (Fe 3 ) viii 4 + 4H 2 . Water. Triferric tetroxide. 6. By the action of zinc on a boiling solution of potassic hydrate : 2OKH + Zn = ZnKo 2 + H 2 . Potassic hydrate. Potassic zinc oxide. 7. By the electrolysis of water and of some other liquids containing hydrogen. 8. By the action of intense heat upon water. 9. In the destructive distillation of some organic substances. SECTION II. CHLORINE, C1 2 . Atomic weight =35' 5. Molecular weight =71. Molecular volume P I I. 1 litre weighs 35'5 criths. Has not been solidified. Liquefies at 15 0< 5 C., under a pressure of 4 atmospheres. Atomicity '. Evidence of atomicity, HC1. Occurrence. Always in combination with sodium and other metals in sea-water, and in the solid state in the salt-beds of Cheshire, Worcester, &c. Evolved from volcanoes in the form of hydrochloric acid. Preparation. 1. By heating certain metallic chlorides, as platinic and auric chlorides : PtCl 4 = 2C1 2 +Pt. Platinic chloride. 38 CHLORINE. 2. By gently heating a mixture of manganic oxide and hy- drochloric acid, when the reaction takes place in two stages : Mn0 2 + 4HC1 = MnCl 4 + 2OH 2 ; Manganic oxide. Hydrochloric acid. Manganic chloride. Water. MnCl 4 = MnCl 2 + C1 2 . Manganic chloride. Manganous chloride. 3. By heating a mixture of sulphuric acid, sodic chloride, and manganic oxide, when the whole of the chlorine present is liberated : Mn0 2 + 2S0 2 Ho 2 + 2NaCl = SO 2 Nao 2 + Manganic oxide. Sulphuric acid. Sodic chloride. Sodic sulphate. SO 2 Mno" + 2OH 2 4- CJ 2 . Manganous sulphate. Water. If in the second process a mixture of manganic oxide, hydrochloric acid, and sulphuric acid be employed, the whole of the chlorine is evolved : Mn0 2 + S0 2 Ho 2 + 2.HC1 = Manganic oxide. Sulphuric acid. Hydrochloric acid. S0 2 Mno" + 2OH 2 + C1 2 . Manganic sulphate. Water. 4. By the electrolysis of hydrochloric acid. Reactions. 1. A mixture of chlorine and hydrogen unite instantly, with explosion, under the influence of sunlight, or of powerful artificial light, or on the application of a burning body to the mixture. A burning jet of hydrogen continues to burn when plunged into chlorine, H 2 + C1 2 = 2HC1. 2. Chlorine has so great an attraction for hydrogen, that it removes the latter from its compounds with carbon. "When a rag moistened with turpentine is plunged into chlorine, the chlorine and hydrogen unite, with evolution of heat and light, carbon being liberated : C 10 H 16 + 8C1 2 = 16HC1 + IOC. Turpentine. Hydrochloric acid. OXYGEN. 39 HYDROCHLORIC ACID, Chlorhydric Acid, Muriatic Acid. HC1. Molecular weight =36'5. Molecular volume FTl- 1 litre weighs 18'25 criths. Has not l)een solidified. Condenses at 10 under a pressure of 40 atmospheres. Occurrence. Evolved from volcanoes. Preparation. 1. Prom its elements, as above described. 2. By gently heating sodic chloride with sulphuric acid, pre- viously diluted with a small quantity of water : S0 2 Ho 2 + NaCl = S0 2 HoNao + HC1: Sulphuric acid. Sodic chloride. Hjdric sodic sulphate. Hydrochloric acid. or S0 2 Ho 2 + 2NaCl = S0 2 ^ T ao 2 + 2HC1. Sulphuric acid. Sodic chloride. Sodic sulphate. Hydrochloric acid. Reactions. Hydrochloric acid may be converted into salts termed chlorides by the action of certain metals as described above, and also by that of the metallic hydrates or oxides : OKH + HC1 = KC1 + OH 2 . Potassic hydrate. Hydrochloric acid. Potassic chloride. Water. ZnO + 2HC1 = ZnCl 2 + OH 2 . Zincic oxide. Hydrochloric acid. % Zincic chloride. Water. For the remaining monad elements of this Section, see Chapter XIV. CHAPTER IX. DYAD ELEMENTS SECTION I. OXYGEN, O 2 . Atomic weight =16. Molecular weight =32. Molecular volume \ I I. 1 litre weighs 16 criths. Atomicity". Evidence of atomicity : 40 OXYGEN. Water OH 2 . Potassic hydrate OKH. Argentic oxide OAg 2 - Hypochlorous anhydride OC1 2 . Occurrence. In the free state in the atmosphere. In the combined state in water, in most mineral bodies, and in almost all animal and vegetable compounds. Preparation. 1. If metallic mercury be heated to its boiling- point with access of air, it gradually absorbs oxygen, being converted into mercuric oxide, Hg"0. This compound, when more strongly heated, is resolved into its elements, 2HgO = 2Hg + 2 . Mercuric oxide. Mercury. Oxygen. 2. By heating native manganic oxide (pyrolusite) a portion of its oxygen is liberated : 3Mn0 2 = iv (Mn 3 )0< + O 2 . Manganic oxide. Trimanganic tetroxide. 3. Oxygen is evolved in nature in a remarkable manner by the decomposition of carbonic anhydride, CO 2 , by the green leaves of plants, the vegetable assimilating the carbon, whilst the oxygen escapes into the atmosphere : C0 2 = C + 2 . Carbonic anhydride. 4. By the action of heat upon potassic chlorate . roci (Atomic) \ = KC1 + 30, or [OK roci (Molecular) 2 \ O =2KC1 -f 30 2 . I OK Potassic chlorate. Potassic Oxygen, chloride. 5. By mixing the potassic chlorate with manganic oxide, the oxygen is evolved at a much lower temperature ; the man- ganic oxide appears to take no part in the reaction. 6. By dropping concentrated sulphuric acid into a red-hot OZONE. 41 platinum retort, the acid is decomposed into oxygen, sulphu- rous anhydride, and water : (Atomic) SO 2 Ho 2 = SO 2 + OH 2 + O, or (Molecular) 2S0 2 Ho 2 = 2SO 2 + 2OH 2 + O 2 . Sulphuric acid. Sulphurous Water, anhydride. 7. By the electrolysis of water. 8. By the action of heat upon a mixture of manganic oxide and sulphuric acid : (Atomic) MnO 2 + S0 2 Ho 2 = SO 2 Mno" + OH 2 +O, or (Molecular) 2MnO 2 + 2SO 2 Ho 2 = 2SO 2 Mno'' + 2OH 2 -fO 2 . Manganic Sulphuric Manganous Water, oxide. acid. sulphate. 9. By heating a mixture of potassic bichromate and sulphuric acid : fCr0 2 Ko 2 JO + 8S0 2 Ho 2 = 2S0 Ko I Cr0 2 Ko Potassic bichromate. Sulphuric acid. Potassic sulphate. + 2S 3 6 ('Cr 2 '"0 6 ) vi + 30 2 + 80H 2 . Chromic sulphate. Water. 10. By passing steam and chlorine through a red-hot porce- lain tube, hydrochloric acid and oxygen are formed : 2OH 2 + 2C1 2 = 4HC1 + 2 . Water. Chlorine. Hydrochloric acid. Reaction. A mixture of two volumes of hydrogen and one volume of oxygen explodes at a red heat, water being produced. >The same compound is formed when hydrogen is burnt in oxy- gen or oxygen in hydrogen : (Molecular) 2H 2 + O 2 = 2OH 2 . ALLOTROPIC OXYGEN or OZONE, 3 . Molecular weight =48. Molecular volume I I I. 1 litre weighs 24 criths. Preparation. 1. When electric sparks are passed through air or oxygen, a peculiar odour, which is due to ozone, is observed. 42 OZONE. 2. By placing phosphorus in moist air at about the ordinary temperature for a few hours. 3. By passing an electric current through dilute sulphuric or chromic acid. Thus obtained, ozone is always mixed with a large proportion of air or oxygen. Properties. Powerfully oxidizing. It oxidizes the metals silver and mercury, and organic matters at ordinary tempera- ture. When oxygen is converted into ozone, contraction of volume takes place ; and when the ozone is heated to 290, it is retraiisformed into the original volume of ordinary oxygen, in- , dicating that the molecule of ozone contains more atoms than the molecule of ordinary oxygen. In most cases of oxidation by ozone no diminution of the vo- lume of gas takes place, the additional atoms previously intro- duced into the molecules of oxygen being removed, and ordinary oxygen becoming free. But it has been recently shown by Soret, that oil of turpentine absorbs the whole molecule of the ozone, leaving untouched the oxygen which was previously pre- sent in the state of admixture. By observing the contraction during the production of the ozone and the diminution of volume produced by absorbing it with oil of turpentine, the density of ozone may be readily calculated, and consequently its atomic constitution. By this means the specific gravity of ozone has been shown to be 24, the molecular weight being therefore 48, which is the weight of 3 atoms of oxygen. In ordinary oxygen, the molecule is composed of two atoms of oxygen, and is represented by weighing 32. In ozone the molecule contains 3 atoms of oxygen, and is re- presented by ' o }( o , weighing 48. WATER. 43 WATER, Hydric Oxide. 0--0 QH 2 . Molecular weight = 18. Molecular volume \ \ \. 1 litre of water-vapour weighs 9 critlis. Fuses at 0. Soils at 100. Occurrence. Most abundantly in nature. Formation. 1. By the direct union of Hydrogen and oxygen, as above. 2. As a secondary product in numberless chemical reactions, as, for instance, in the action of hydrochloric acid on potassic hydrate : OKH + HC1 = OH 2 + KC1. Potassic hydrate. Hydrochloric acid. Water. Potassic chloride, Reactions. 1. By its action many metallic oxides are con- verted into hydrates : OK, 4- OH 2 = 20KH. Potassic oxide. Water. Potassic hydrate. BaO + OH 2 = BaHo 2 . Baric oxide. Water. Baric hydrate. 2. By its action on anhydrides it transforms them into acids : NA + Nitric anhydride. OH 2 Water. = 2NO 2 Ho. Xitric acid. S0 3 + Sulphuric anhydride. OH 2 Water. = S0 2 Ho 2 . Sulphuric acid. P,0, + 3OKL = 2POHo,. Phosphoric anhydride. Water. Phosphoric acid. 3. It also unites molecularly with many compounds as water of crystallization (see Chapter V.), as in the following instances : BaCl 2 , 2OH 2 .................. Baric chloride. SO 2 A T ao 2 , 10OH 2 ............... Sodic sulphate. S 4 O 8 Ko 2 ('Al 2 "'0 6 ) vi , 24OH 2 . . . Alum. 44 HYDROXYL. HYDROXYL, Hydric Peroxide. OH H 2 O 2 or(HO) 2 orHo 2 or Probable molecular weiglit = 34. Preparation. By passing a current of carbonic anhydride through water in which baric peroxide is suspended : {o Ba " + CO 2 + OH 2 = COBao" Baric peroxide. Carbonic anhydride Water. Baric carbonate. Hydroxyl. Reactions. 1. By heat it is decomposed into water and oxygen : Hydroxyl. Water. Oxygen. 2. Hydroxyl is transformed into water by the action of nas- cent hydrogen: if hydroxyl be introduced into an apparatus generating hydrogen, the gas ceases to be evolved : S0 2 Ho 2 + Zn + = S0 2 Zno" + 2OH 2 . Sulphuric acid. Hydroxyl. Zinoic sulphate. Water. 3. Hydroxyl liberates iodine from potassic iodide : 2KI + {OH = 20KH + ^ Potassic iodide. Hydroxyl. Potassic hydrate. Iodine. 4. Hydroxyl is a powerful oxidizing agent ; it converts, for instance, plumbic sulphide into plumbic sulphate : PbS" + 4 = S0 2 Pbo" + 40H 2 . Plumbic sulphide. Hydroxyl. Plumbic sulphate. Water. OXIDES AND ACIDS OF CHLORINE. 45 OXIDES AND ACIDS OF CRLOEINE. Oxygen forms many compounds with chlorine and with chlorine and hydroxyl ; but none of them can be produced by direct combination. The following list contains all that are known : Hypochlorous 1 OC1 anhydride ...... J roci Chloric oxide r ... j QQI ' Chlorous anhy- { OC1 dride ............ oca Chloric peroxide -- -0-0- _0_0_0_ oci OC1 Chloric hyper- oxide? ^ ~ . O ( OC1 Hypochlorous acid, OC1H, or ClHo. Chlorous acid ... OClHo, or j OC Chloric acid... { QHo' or roci Perchloric acid -JO , or [OHo 46 OXIDES OF CHLORINE. HYPOCHLOROUS ANHYDEIDE. OC1 2 . Molecular weight = 87. Molecular volume \ \ \. 1 litre of liypoclilorous anhydride vapour weighs 43 '5 criths. Soils at about 20. Preparation. By passing chlorine over mercuric oxide at a low temperature : [HgCl 2HgO -1- 2C1 2 = Jo + OC1,. [HgCl Mercuric Mercuric Hypochlorous oxide. oxychloride. anhydride. CHLOROUS ANHYDRIDE. OC1 o . OC1 Molecular weight =119. Molecular volume anomalous L III. 1 litre weighs 79'4 criths. Preparation. By gently heating in a water-bath a mixture of potassic chlorate, nitric acid, and arsenious acid. Four dif- ferent reactions are to be distinguished in this operation : L oKo + N * H O = OHO + NO * Ko ' Potassic chlorate. Nitric acid. Chloric acid. Potassic nitrate. 2. AsHo 3 + N0 2 Ho = NOHo + AsOHo 3 ; Arsenious acid. Nitric acid. Nitrous acid. Arsenic acid. 3. Q + NOHo = OClHo + N0 2 Ho; Chloric acid. Nitrous acid. Chlorous acid. Nitric acid. roci 4. 2OClHo = \ O + OH 2 . [oci Chlorous acid. Chlorous anhydride. Water. HYPOCHLOROUS ACID. 47 CHLORIC PEROXIDE. OC1 o o OC1 Molecular weight = 135. Soils at 20. Preparation. By the action of sulphuric acid on potassic chlorate : fOCl f C1 3 + 2SOaHo = +2SO a HoKo + OH Potassic Sulphuric Potassic Hydric potassic Water. Chloric chlorate. acid. perchlorate. sulphate. peroxide. HYPOCHLOROUS ACID. OC1H, or ClHo. Molecular weight = 52 '5. Preparation. 1. By the action of water on hypochlorous anhydride : OC1 2 + OH 2 2ClHo. Hypochlorous anhydride. Water. Hypochlorous acid. 2. By the action of chlorine upon mercuric oxide in the pre- sence of water : fHgCl 2HgO + OH 2 + 2C1 = J O + 2ClHo. {HgCl Mercuric oxide. Water. Chlorine. Mercuric Hypochlorous oxychloride. acid. Reactions . 1. By the action of hydrochloric acid, chlorine is evolved from both the hydrochloric acid and hypochlorous acid : ClHo + HC1 = C1 2 + OH 2 . Hypochlorous acid. Hydrochloric acid. Chlorine. Water. 48 ACIDS OF CHLORINE. 2. By the action of argentic oxide, oxygen is evolved from both compounds : OAg a + 2ClHo = 2AgCl -f OH 2 + O 2 . Argentic Hypochloroua Argentic Water. oxide. acid. chloride. 3. By the action of hypochlorous acid, metallic oxides or hy- drates are converted into hypochlorites : OKH + ClHo = CIKo + OH 2 . Potassic hydrate. Hypochlorous Potassic Water, acid. hypochlorite. It was formerly supposed that hypochlorites, together with chlorides, were formed when chlorine acted upon certain me- tallic oxides and hydrates : 2C1 2 + 2CaHo 2 = CaCl 2 + Cao"Cl 2 + 2OH 2 . Calcic hydrate. Calcic chloride. Calcic hypochlorite. Water. But the so-called chloride of lime or bleaching powder does not contain calcic chloride, and the true reaction appears to be CaHo 2 + C1 2 = Ca(001)Cl + OH 2 . Calcic hydrate. Bleaching powder *. Water. By the action of acids this compound yields free chlorine : Ca(OCl)Cl + S0 2 Ho 2 = S0 2 Cao" + OH 2 + C1 2 . Bleaching powder. Sulphuric acid. Calcic sulphate. Water. CHLOROUS ACID. OClHo or { Molecular weight =68'5. Preparation. By the action of water upon chlorous anhy- dride : OC1 O + OH 2 = OC1 Chlorous anhydride. Water. Chlorous acid. \OHo Molecular weight =84*5. CHLORATES. 49 CHLOEIC ACID. roci roci 1 I OH Preparation. By the action of dilute sulphuric acid upon baric chlorate : roci I + SO a Ho, = 2 {g Baric chlorate. Sulphuric acid. Chloric acid. Baric sulphate. Decomposition. By boiling, it is decomposed into perchloric acid, water, chlorine, and oxygen : fOCl f C1 3 |OHo + OH 2 + C1 2 4 20, Chloric acid. Perchloric acid. Water. Preparation of Chlorates. 1. Potassic chlorate may be pre- pared by the action of chlorine upon a concentrated solution of potassic hydrate : 60KH + 3C1 2 = 5KC1 + + 3OH 2 . Potassic Chlorine. Potassic Potassic Water. hydrate. chloride. chlorate. 2. Calcic chlorate is made by passing chlorine through boiling milk of lime : roci |o 6CaHo 2 + 6C1 2 = ^ Cao" + 5CaCl 2 + 6OH 2 . OC1 Calcic hydrate. Calcic chlorate. Calcic chloride. Water. By the addition of potassic chloride to the calcic chlorate, D 50 PERCHLORIC ACID AND PERCHLORATES. potassic chlorate is formed ; the latter is then separated from the calcic chloride by crystallization : 2KC1 = 2/gg, + CaCla . Potassic Potassic Calcic chloride. chlorate. chloride. PERCHLORIC ACID. Molecular weight = 100*5. Preparation, Potassic perchlorate is distilled with about three times its weight of sulphuric acid : roci roci 2^0 + S0 2 Ho 2 = 2^0 + S0 2 Ko 2 . [OKo JQHo Potassic perchlorate. Sulphuric acid. Perchloric acid. Potassic sulphate, The impure perchloric acid is then carefully rectified, when pure perchloric acid passes over as an oily liquid towards the end of the operation. It forms with water a white crystalline hydrate. % Preparation of Potassie Perchlorate. 1. Potassic chlorate is heated gradually, and the process arrested when one-third of the oxygen present has been evolved ; the residue then con- tains potassic chloride and perchlorate : oci f ocl + KO Potassic chlorate. Potassic chloride. Potassic perchlorate. BORON. 51 By crystallization the two salts are separated. 2. When potassic chlorate is gradually introduced into boiling nitric acid, chlorine and oxygen are evolved, potassic nitrate and perchlorate being formed : 3 I2S 1 +2N0 2 Ho==2N0 2 Ko-fOH 2 + <{ + CL + 2CL fl K n ^ ^ I * OKo Potassic erchlorat These salts are then separated by crystallization. Potassic Nitric acid. Potassic nitrate. Water. Potassic chlorate. perchlorate. CHAPTER X. TEIAD ELEMENTS. SECTION I. BOKON, B 2 . Atomic weight =11. Probable molecular weight = 22. Sp.gr., diamond variety, 2'68. Atomicity '". Evidence of ato- micity : Boric chloride B"'C1 3 . Boric fluoride B'"F 3 . Boric ethide B'"Et 3 . Occurrence. Pound only in combination with oxygen. Preparation : a. Amorphous boron. 1. By igniting boric anhydride with sodium : B 2 3 + 31Sra 2 = 3OlS T a 2 + B 2 . Boric anhydride. Sodium. Sodic oxide. 2. By passing boric chloride over heated potassium : 2BC1 3 + 3K a = 6KC1 + B 2 . Boric chloride. Potassic chloride. D2 52 BORON. /3. Graphitoidal boron. By passing boric chloride over fused aluminium : A1 2 + 2BC1 3 = 'A1 2 '"C1 6 + B 2 . Boric chloride. Aluminic chloride. y. Diamond boron. By fusing boric anhydride with alumi- nium : A1 2 + B 2 3 = 'A1 2 '"0 3 + B a . Boric anhydride. Aluminic oxide. Reactions : a. Amorphous boron. 1. Decomposes hot sulphuric acid : B 2 + 3S0 2 Ho 2 = B 2 3 + 3OH 2 + 3S0 2 . Sulphuric acid. Boric anhydride. Water. Sulphurous anhydride. 2. Decomposes nitric acid : B 2 + 6N0 2 Ho = 2BHo 3 + Nitric acid. Boric acid. Nitric peroxide. 3. Decomposes alkaline carbonates, sulphates, and nitrates : B 2 + 3CONao 2 = 2BNao 3 + 3C"0. Sodic carbonate. Trisodic borate. Carbonic oxide. B 2 + 3SO 2 Ko 2 = 2BKo 3 + 3SO 2 . Potassic sulphate. Tripotassic borate. Sulphurous anhydride. B 2 + 6N0 2 Ko = 2BKo, + 3'N 2 *0 4 . Potassic nitrate. Tripotassic borate. Nitric peroxide. 4. Boron is one of the very few elements which unite directly with nitrogen : B 2 + N 2 = 2B / "N / ". Boric nitride. y. Diamond boron. 1. When fused with hydric potassic sul- phate, boric anhydride is formed : 6S0 2 HoKo + B 2 = B 2 3 + 3S0 2 Ko 2 + 3OH 2 + 3SO 2 . Hydric potassic Boric Potassic sul- Water. Sulphurous sulphate. anhydride. phate. anhydride. No compound of boron with hydrogen has been obtained ; but the chloride, bromide, and fluoride are known. COMPOUNDS OF BORON. 53 BORIC CHLORIDE. BC1 3 . Molecular weight = 117'5. Molecular volume \~\ |. 1 litre of boric chloride vapour weighs 58*75 criths. Sp. gr. 1'35 at 7. Boils at 17. Preparation. By passing chlorine over a mixture of boric anhydride and charcoal heated to redness : B 2 3 + 3C1 2 + C, = 2BC1 3 + SCO. Boric anhydride. Boric chloride. Carbonic oxide. Reaction. In contact with water it forms hydrochloric and boric acids : BC1 3 + 3OH 2 = 3HC1 + BHo 3 . Boric chloride. Water. Hydrochloric acid. Boric acid. BORIC BROMIDE. BBr 3 . Molecular weight =251. Molecular volume \ \ \. 1 litre of boric bromide vapour weighs 125'5 criths. Sp.gr, of liquid =2-69. Soils at 90 C. Prepared and decomposed in exactly the same way as the chloride. BORIC FLUORIDE. BF, Molecular weight = 68. Molecular volume [~~\~\. 1 litre iveighs 34 criths. Preparation. 1. By strongly heating boric anhydride with calcic fluoride : 2B 2 3 + 3CaP 2 = B 2 Cao 3 " + 2BF 3 . Boric anhydride. Calcic fluoride. Calcic borate. Boric fluoride. 54 COMPOUNDS OF BORON. 2. By heating together boric anhydride with calcic fluoride and sulphuric acid : B 2 3 + 3CaF a + 3S0 2 Ho 2 = 3SOHo 2 Cao" + 2BF 3 . Boric Calcic Sulphuric Dihydric calcic Boric fluo- anhydride. fluoride. acid. sulphate *. ride. Reaction. By contact with water boric fluoride forms a peculiar acid, the hydrofluoboric acid, the constitution of which is not well understood : 4BF 3 + 3OH 2 = 3(BF 3 , HF) + BHo 3 . Boric fluoride. Water. Hydrofluoboric acid. Boric acid. This acid acts upon metallic hydrates, forming salts : BF 3 , HF + OKH = BF 3 , KF + OH 2 . Hydrofluoboric Potassic Potassic Water, acid. hydrate. borofluoride. Possibly the boron in these compounds is pentadic ; thus B T HF and BORIC ANHYDRIDE AND ACIDS. Boric anhydride B 2 O 3 . Monobasic boric acid ] Tr\-rr .., . , ., r JSU-tLo. Metaboric acid J Tribasic boric acid ... } n-rr Boric acid . . . . J 3 BORIC ANHYDRIDE, Boracic anhydride. B 2 3 . Molecular weight = 70. Sp. gr. 1*83. Preparation. By fusing boric acid at a red heat : 2BHo 3 = B 2 3 + 3OH 2 . Boric acid. Boric anhydride. Water. * See sulphuric acid, Chap. XIII. page 81. BORATES. 55 BORIC ACID, Boracic Acid, Orthoboric Acid. BHo 3 . Molecular weight =62. Sp. gr. 1/479. Occurrence. Contained in the steam which escapes from the suffioni in some parts of Tuscany. Preparation. By the addition of hydrochloric acid to a hot saturated solution of borax, when the acid crystallizes out on cooling : B 4 O 5 Nao a + 2HC1 + 5OH 2 = 4BHo 3 + 2NaCl. Borax. Hydrochloric Water. Boric Sodic acid. acid. chloride. Reactions. 1. At the temperature of 100 it loses water, being converted into metaboric acid : BHo 3 = BOHo + OH 2 . Boric acid. Metaboric acid. Water. 2. By the action of metallic hydrates, oxides, or carbonates, borates are formed. The mineral tincal contains borax, an abnormal sodic borate, B 4 5 Nao 2 , 100H 2 . A trimagnesic octoborate is known as the mineral loracite :- 56 COMPOUNDS OF BORON. BORIC SULPHIDE. B 2 S 3 ". Molecular weight =118. Preparation. By passing carbonic disulphide over a mixture of carbon and boric anhydride heated to bright redness : 2B 2 O 3 + 3CS 2 " + 30 = 2B 2 S 3 " + 6C"O. Boric Carbonic Boric Carbonic anhydride. disulphide. sulphide. oxide. Reaction. Boric sulphide is readily decomposed by water, giving sulphuretted hydrogen and boric acid : B 2 S 3 " + 6OH 2 = 3SH 2 + 2BHo 3 . Boric Water. Sulphuretted Boric sulphide. hydrogen. acid. BORIC NITRIDE. BUT'". Molecular weight =25. Preparation. 1. By heating boron in nitrogen (see p. 52). 2. By heating together borax and ammonic chloride : B 4 O.]S T ao 2 + 4NH 4 C1 = 4BN'" + Borax. Ammonic chloride. Boric nitride. Sodic chloride. 7OH 2 + 2HC1. Water. Hydrochloric acid. Reaction. When fused with potassic hydrate, boric nitride yields tripotassic borate and ammonia : BN'" + 3OKH = BKo 3 + NH 3 . Boric Potassic Tripotassic Ammonia. nitride. hydrate. borate. COMPOUNDS OF CARBON. 57 CHAPTER XI. TETRAD ELEMENTS. SECTION I. CARBON, C. Atomic weight = 12. Atomicity " and 1V . Evidence of atomi- city : Carbonic oxide C"0. Carbonic tetrachloride ... C 1V C1 4 . Marsh-gas C iv H 4 . Chloroform C iv HCl 3 . Occurrence. In large quantities in nature, but chiefly in combination. Manufacture. By the carbonization of animal and vegetable matters. COMPOUNDS OF CAEBON WITH OXYGEN. CARBONIC ANHYDRIDE. C0 2 . Molecular weight = 44. Molecular volume I I I. 1 litre weighs 22 criths. Fuses at 57. Soils below its melting- point. Occurrence. In the atmosphere, and dissolved in water. Formation. By the combustion of carbon and of carbona- ceous substances in air or oxygen. In respiration, decay, putre- faction, and fermentation. During the formation of coal. E?olved from volcanoes. Preparation. 1. By burning carbon in air or oxygen : C + 2 = C0 2 . Carbonic anhydride. D 5 58 OXIDES OF CARBON. 2. By the action of acids upon metallic carbonates : COKo 2 + Potassic carbonate. S0 2 Ho 2 Sulphuric acid. = C0 2 + Carbonic anhydride. OH 2 + Water. S0 2 Ko. 2 . Potassic sulphate . COKoHo Hydric potassic carbonate. + N0 2 Ho Nitric acid. = C0 2 Carbonic anhydride. f- OH 2 - Water. f N0 2 Ko Potassic nitrate. COCao" Calcic carbonate. + 2HC1 Hydrochloric acid. CO 4~ Carbonie anhydride. OH 2 + Water. CaCl 2 . Calcic chloride. Reactions. 1. Carbonic anhydride is decomposed by heated potassium : 3C0 2 + 2K 2 = 2COKo 2 + C. Carbonic anhydride. Potassic carbonate. 2. It acts upon metallic hydrates, forming carbonates : C0 2 + 2KHo = COKo 2 + OH 2 . Carbonic anhydride. Potassic hydrate. Potassic carbonate. Water. CO 2 Carbonic anhydride. CaHo 2 = Calcic hydrate. COCao" Calcic carbonate. OH 2 . Water. Carbonic acid, COHo 2 , is not known. CARBONIC OXIDE, CO. Molecular weight =28. Molecular volume {"T"l. 1 litre weighs 14 criths. Formation. In the combustion of carbon or carbonaceous matter with a limited supply of air. In destructive distilla- tion of many organic substances containing oxygen. Preparation. 1. By passing carbonic anhydride over red-hot charcoal : C0 2 + C = 2CO. Carbonic anhydride. Carbonic oxide. CARBONIC OXIDE. 59 2. By passing carbonic anhydride over red-hot iron : 4C0 2 + Fe 3 = iv (Fe 3 ) viii 4 + 4CO. Carbonic anhydride. Triferric tetroxide. Carbonic oxide. 3. By heating iron or carbon with a carbonate : COCao" + C = CaO + 2CO. Calcic carbonate. Lime. Carbonic oxide. 4. By heating oxalic acid with sulphuric acid (by which water is removed from the former), and then separating the carbonic anhydride by washing with sodic hydrate : Oxalic acid. Water. Carbonic Carbonic oxide. anhydride. 5. By heating formic acid or a formate with sulphuric acid : Formic acid. Water. Carbonic oxide. 6. By heating potassic ferrocyanide with sulphuric acid: Fe"C 6 N 6 K 4 + 6OH 2 + 6S0 2 Ho 2 = 6CO Potassic ferrocyanide. Water. Sulphuric acid. Carbonic oxide. + 2S0 2 Ko 2 + S0 2 Feo" + 3S0 2 (NH 4 O) 2 . Potassic sulphate. Ferrous sulphate. Ammonic sulphate Reactions. 1. It burns in air and oxygen, producing car- bonic anhydride : CO + O = C0 2 . Carbonic Carbonic oxide. anhydride. 2. Carbonic oxide and chlorine unite under the influence of light (p. 30), forming carbonic oxydichloride or phosgene gas, COCL, The compounds of carbon with chlorine, nitrogen, and hy- drogen will be studied in connexion with organic compounds. 60 NITROGEN. CHAPTER XII. PENTAD ELEMENTS. SECTION I. NITROGEN, Azote, N a . Atomic weight = 14. Molecular weight = 28. Molecular volume r~[~1- 1 foVre weighs 14 critJis. Atomicity v , which, by the mutual saturation of pairs of bonds, becomes reduced to '" or to ' (see p. 20). Evidence of atomicity : Nitrous oxide .................. OJST 2 . Ammonia ..................... N'"H 3 Ammonic chloride Occurrence. In the free state in the atmosphere. In some nebulae ? In combination, in animal and vegetable bodies. Preparation. 1. By burning phosphorus in air, whereby the oxygen is removed from the latter. 2. By passing air over ignited copper, when the oxygen unites with the copper. 3. By heating ammonic nitrite, or a mixture of ammonic chloride with potassic or sodic nitrite : N"'0(N V H 4 0) = N 2 + 2OH 2 . Ammonic nitrite. Water. NH 4 C1 + NONao = NaCl + N 2 + 2OH 2 . Ammonic chloride. Sodic nitrite. Sodic chloride. Water. 4. By passing chlorine through an excess of solution of ammonia : 8NH 3 + 3C1 2 = 6NH 4 C1 + N 2 . Ammonia. Ammonic chloride. NITRIC ACID. 61 GUIDES AND OX-ACIDS OF NITROGEN. N> {O} oT Nitrous oxide ON 2 . Nitric oxide * Nitrous anhydri Nitric peroxide Nitric anhydride Nitrous acid NOHo. Nitric acid NITRIC ACID, Aquafortis. N0 2 Ho. Molecular weight =63. Molecular volume \~\~\, 1 litre of nitric acid vapour weighs 31'5 criths. Fuses at 50. Soils at 84-5. * This compound is anomalous ; for its molecule, deduced from the spe- cific gravity, is represented by NO. The dissociation which in the case of | jJ Q 2 is very imperfect at C., but almost complete at 100 C., is probably nearly complete in the case of N 2 O 2 at the lowest temperature to which this gas has hitherto been exposed. 62 NITRIC ACID. Production. 1. By the slow oxidation of nitrogenized orga- nic matter in the presence of powerful bases. 2. By the passage of electric sparks through moist air. Manufacture. By distilling potassic nitrate (nitre) or sodic nitrate (cubic nitre) with concentrated sulphuric acid : N0 2 Ko + S0 2 Ho 2 = S0 2 HoKo + NO 2 Ho. Potassic Sulphuric Hydric potassic Nitric acid, nitrate. acid. sulphate. By employing two molecules of potassic nitrate and one of sulphuric acid a saving of sulphuric acid is effected, but a higher temperature is required, which destroys some of the nitric acid. The reaction takes place in two stages : 1. 2N0 2 Ko + S0 2 Ho 2 = S0 2 HoKo Potassic nitrate. Sulphuric acid. Hydric potassic sulphate. + N0 2 Ko + N0 2 Ho: Potassic nitrate. Nitric acid. 2. S0 2 HoKo + N0 2 Ko = SO 2 Ko 2 + N0 2 Ho. Hydric potassic sulphate. Potassic nitrate. Potassic sulphate. Nitric acid. Decompositions. 1. The decomposition which the nitric acid undergoes by heat is expressed in the following equa- tion : 4N0 2 Ho = 2OH 2 + 2'N 2 iv O 4 + O 2 . Nitric acid. Water. Nitric peroxide. Oxygen. 2. By the action of metallic oxides or hydrates, nitric acid produces nitrates : OKH + NO 2 Ho = N0 2 Ko + OH 2 . Potassic hydrate. Nitric acid. Potassic nitrate. Water. fN0 2 PbO + 2NO 2 Ho = \ Pbo" + OH 3 . (NO, Plumbic oxide. Nitric acid. Plumbic nitrate. Water. NITROUS ACID. DO NITRIC ANHYDRIDE. N 2 0, Probable molecular weight =108. Probable molecular volume m- Fu*es at 29-5. Soils at 45. Preparation. By passing dry chlorine over argentic ni- trate : 4N0 2 Ago + 2C1 2 = 4AgCl + 2IST 2 3 + O f Argentic nitrate. Argentic Nitric chloride. anhydride. Reaction. By the action of water it forms nitric acid : N 2 5 + OH 2 = 23NT0 2 Ho. Nitric anhydride. Water. Nitric acid. NITROUS ANHYDRIDE. N 2 3 , Probable molecular weight = 76. Probable molecular volume ED- Preparation. 1. By heating together nitric acid and starch. 2. By gently heating nitric acid with arsenious anhydride : As 2 3 + 2N0 2 Ho = As 2 5 + N 2 3 + OH 2 . Arsenioua Nitric acid. Arsenic Nitrous Water, anhydride. anhydride. anhydride. 3. By the action of nitric acid on silver : 6N0 2 Ho + 2Ag 2 = 4N0 2 Ago + N 2 3 + 3OH 2 . Nitric acid. Argentic nitrate. Nitrous anhydride. Water. NITROUS ACID. NOHo. Molecular weight =47. . Preparation. By mixing liquefied nitrous anhydride with a small quantity of water : N 2 3 + OH 2 = 2NOHo. Nitrous anhydride. Water. Nitrous acid. 64 OXIDES OP NITROGEN. Decompositions. 1. In the presence of much water, nitric acid and nitric oxide are formed : GNOHo = 2N0 2 Ho + 2'N" 2 O 2 + 2OH 2 . Nitrous acid. Nitric acid. Nitric oxide. Water. 2. Nitrous acid acts as a reducing agent under some circum- stances : 2NOHo + 2 = 2N0 2 Ho; Nitrous acid. Nitric acid. and as an oxidizing agent under others : 4NOHo = 2'N" 2 2 + 2OH 2 + O 2 . Nitrous acid. Nitric oxide. Water. Oxygen. 3. By the action of metallic oxides or hydrates, nitrous acid forms nitrites : OKH + NOHo = NOKo + OH 2 . Potassic hydrate. Nitrous acid. Potassic nitrite. Water. NITROUS OXIDE, Laughing Gas. Molecular weight = 44. Molecular volume ["TV 1 litre weighs 22 criths. Fuses at 101. Soils at 88. Preparation. 1. By the action of dilute nitric acid on zinc : |NO a 10N0 2 Ho + Zn 4 = ON 2 + 4 \ Zno" +5OH 2 . a N0 2 Nitric acid. Nitrous oxide. Zincic nitrate. Water. 2. By heating ammonic nitrate : T H 4 0) = 2OH 2 + ON 2 . Ammonic nitrate. Water. Nitrous oxide. OXIDES OF NITROGEN. 65 NITRIC OXIDE. f NO .,, n { N0 ' or N A- Molecular weight =60. Molecular volume anomalous \~\~\ 1 Zitfrtf weighs 15 critJis. Preparation. By the action of nitric acid upon mercury or copper : fN0 2 3Cu -f 8N0 2 Ho = 3 \ Cuo" + 'N" 2 2 + 4OH 2 . Nitric acid. [ N"0 2 Nitric oxide. Water. Cupric nitrate. Reaction. Unites directly with oxygen : 2'N" 2 2 + 2 = 2N'" 2 3 : Nitric oxide. Nitrous anhydride. 'N" 2 2 + 2 = 'N^O,. Nitric oxide. Nitric peroxide. NITRIC PEROXIDE. Molecular weight =46 to 92. Molecular volume |"T1 t \" 1 litre weighs 23 to 46 criths. Preparation. 1. By the union of nitric oxide with oxygen (see above). 2. By the action of nitric acid upon tin : Sn 5 + 20N0 2 Ho = Sn 5 O 5 Ho 10 + 5OH 2 + 10'N* 2 O 4 . Nitric acid. Metastannic acid. Water. Nitric peroxide. Decomposition. By the action of metallic hydrates and oxides it produces nitrites and nitrates : 'N iv 2 O 4 + 2OKH = N0 2 Ko + NOKo + OH 2 . Nitric Potasaic Potassic Potassic Water, peroxide. hydrate. nitrate. nitrite. 66 COMPOUNDS OF MTROGEN. COMPOUNDS CONTAINING NITBOGEN, CHLO- RINE, AND OXYGEN NITROUS OXYCHLORIDE, CUoronitrous Gas. NOC1. Molecular weight =65*5. Molecular volume I I I. 1 litre weighs 3275 criths. Soils at C. A mixture of nitric and hydrochloric acids possesses the property of dissolving gold, and is therefore called aqua regia ; wheii heated it evolves chlorine and nitrous oxychloride : N0 2 Ho + 3HC1 = NOC1 + 2OH 2 + C1 2 . Nitric acid. Hydrochloric Nitrous Water, acid. oxychloride. NITRIC DIOXY-TETRACHLORIDE, CUoronitric Gas. 'N 2 iv 2 Cl 4 . Prepared, together with nitrous oxychloride, by heating a mixture of nitric and hydrochloric acids : 2N0 2 Ho + 6HC1 = 'N iv 2 2 Cl, + 4OH a -f Cl a . Nitric acid. Hydrochloric acid. Chloronitric gas. Water. NITRIC DIOXYCHLORIDE, CUoropernitric Gas. N0 2 CL Preparation. By mixing phosphoric oxytrichloride and plumbic nitrate : fN0 2 3 \ Pbo" + 2PC1 3 = P 2 2 Pbo" 3 + 6N0 2 C1. N0 2 Plumbic nitrate. Phosphoric Triplumbic Nitric oxytrichloride. diphosphate. dioxychloride. AMMONIA. 67 COMPOUNDS OF NITROGEN WITH HYDROGEN. AMMONIA. NH 3 . Molecular weight =17 '. Molecular volume \ | ~|. IL litre weighs 8-5 crMs. JW? a 75. .StA a 38'5. Occurrence. In the atmosphere in very minute quantities. Formation. By the decay of animal and vegetable matters containing nitrogen. Manufacture. By the destructive distillation of animal matter, as horn or bones, and of vegetable matter, as coal. Preparation. By heating a mixture of lime and ammonic chloride (sal-ammoniac) : 2NH 4 C1 + CaO = CaCl 2 + 2NH 3 + OH 2 . Ammonic Lime. Calcic Ammonia. Water, chloride. chloride. Reactions. 1. Decomposed by chlorine (see p. 60). 2. Unites directly with acids, forming the ammonium salts in which the atomicity of nitrogen is v : N'"H 3 + HC1 = N V H 4 C1. Hydrochloric acid. Ammonic chloride *. N'"H 3 + N v 2 Ho = N V O 2 (N V H 4 0). Nitric acid. Ammonic nitrate t . 2N'"H 3 + S0 2 Ho 2 = SO 2 (N V H,0) 2 . Sulphuric acid. Ammonic sulphate J. : -0-0-0-0-- 68 AMMONIC AMALGAM. AMMONIUM. JNH 4 INK; This monad radical has never been obtained in the free state, but its compounds are perfectly analogous, in crystalline form and other properties, to those of potassium. These facts have induced some chemists to consider the group NH 4 as a metal, to which they have given the name ammonium an hypo- thesis which is considered to receive support from the production of an unstable amalgam of this radical. All the compounds of mercury with metals are found to possess metallic lustre ; and this is also the case with the amalgam of ammonium. It may be prepared by two different processes. 1. If a solution of ammonic chloride be electrolyzed, the negative electrode being mercury and the positive a platinum plate, the mercury is observed to swell up, owing to the forma- tion of a spongy metallic mass. 2. By preparing an amalgam of potassium or sodium, and pouring it into a slightly warmed solution of ammonic chloride, the amalgam is found to swell enormously, potassic or sodic chloride being simultaneously formed : Hg n Na m + mNH 4 Cl = H gn (N T H 4 ) m + mNaCl. Sodic amalgam. Ammonic chloride. Ammonic amalgam. Sodic chloride. Ammonic amalgam rapidly decomposes into mercury, am- monia, and hydrogen, the ammonia and hydrogen being liberated in the proportions of 2NH 3 to H 2 : 2Hg n (]Sr v H 4 ) m = 2nHg + 2mNH 3 + mH 2 . Ammonic amalgam. Mercury. Ammonia. Ammonium plays the part of a compound monad radical, and its salts are isomorphous with those of potassium; they are all volatile, unless the acid from which they are derived be fixed. SULPHUR. 69 COMPOUND OF NITROGEN WITH CHLORINE. NITROUS CHLORIDE. NC1 3 ? Preparation. By the action of chlorine upon ammonic chloride : N V H 4 C1 + 3C1 2 = N'"C1 3 + 4HC1. Ammonic chloride, Nitrous chloride. Hydrochloric acid. The formula of this compound is not fixed with certainty ; it may contain hydrogen, and it is possible that the two compounds intermediate between ammonia and nitrous chloride may exist: NH 3 , NH 2 C1, NHC1 2 , NC1 3 . COMPOUND OF NITROGEN WITH IODINE AND HYDROGEN. NITROUS HYDRODINIODIDE. Preparation. By the action of ammonia on iodine a brown substance is obtained, which has the composition NHI 2 . It is formed according to the following equation : 3NH 3 + 2I 2 = NHI 2 + 2NH 4 I. Ammonia. Nitrous Ammonic hydrodiniodide. iodide. CHAPTER XIII. HEXAD ELEMENTS. SECTION I. SULPHUR, S 2 . Atomic weight =32. Molecular weight =64. Molecular volume f"Tl at 1000 C., but only one-third of this at its boiling- 70 COMPOUNDS OF SULPHUR. point. 1 litre of sulphur vapour weighs 32 criths. Atomi- city " iv and vi . Evidence of atomicity : Hydrosulphuric acid ............ S"H 2 . Triethylsulphine iodide ......... S iv Et 3 I. Sulphuric dioxydichloride ...... S v5 O 2 Cl 2 . Sodic nitrosulphate ............... S vi O (NO) 2 lN"ao 3 . Occurrence. Found in the free state in volcanic districts, and widely diffused in combination with metals and oxygen, as sulphides and sulphates. Manufactured from native sulphur, and from Iron pyrites ........................ FeS" 2 . Copper pyrites ..................... (FeCu)S 2 ". Character. Sulphur is capable of existing in several allo- tropic forms, of which the following are the most important : Condition. Specific gravity. a. Octahedral ...... 2'05 Soluble. /3. Prismatic ......... 1'98 Transformed into a. y. Plastic ............ 1*95 Insoluble. & Powder ............ T95 Insoluble. When united exclusively with basylous elements or radicals, sulphur is almost invariably a dyad ; and it is then the analogue of oxygen, as will be seen from the following formulae : Oxygen compounds ... OK 2 , OKH, C0 2 , COKo 2 . Sulphur compounds ... SK 2 , SKH, CS 2 ", CSKs 2 . COMPOUNDS OF SULPHUR WITH BASYLOUS OR POSITIVE ELEMENTS. Sulphuretted hydrogen SH 2 . Hydrosulphyl 'S' 2 H 2 , or Hs 2 . Carbonic disulphide CS 2 ". SULPHURETTED HYDROGEN. 71 SULPHURETTED HYDROGEN, Hydrosulpliuric Acid, Sulphhydric Acid. SH, -- Molecular weight = 34. Molecular volume \ \ \. 1 litre weighs 17 criths. Solid at 85'5 C. Liquid under a pressure of 17 atmospheres at 10 C. Occurrence. Evolved with other gases from volcanoes and fumaroles. Found also in hepatic mineral waters, and frequently in waters which contain both organic matters and sulphates. Preparation. 1. By direct union of its elements : H 2 + S = SH 2 . 2. By the action of hydrochloric or dilute sulphuric acid on ferrous sulphide : FeS" + 2HC1 = SH 2 + FeCl 2 . Ferrous Hydrochloric Sulphuretted Ferrous sulphide. acid. hydrogen. chloride. FeS" + S0 2 Ho 2 = SH 2 + SO 2 Feo". Ferrous Sulphuric Sulphuretted Ferrous sulphide. acid. hydrogen. sulphate. 3. By the action of hydrochloric acid on antimonious sulphide with the aid of a gentle heat : Sb 2 S 3 " + 6HC1 = 3SH 2 + 2Sb01 3 . Antimonious Hydrochloric Sulphuretted Antimonious sulphide. acid. hydrogen. chloride. Reactions. 1. It is immediately decomposed by chlorine, thus : SH 2 + C1 2 = 2HC1 + S. 2. It is also rapidly decomposed by many metallic compounds rich in oxygen, such as ferric oxide : 'Fe 2 '"0 3 + 3SH 2 = 2FeS" + S + 3OH a . Ferric oxide. Sulphuretted Ferrous Water, hydrogen. sulphide. 3. The sulphhydrates and sulphides of the metals are produced COMPOUNDS OF SULPHUR. by the action of hydrosulphuric acid on the hydrates and oxides, thus : OKH Potassic hydrate. + SH 2 = SKH + Sulphuretted Potassic hydrogen. sulphhydrate. OH, Water. BaHo 2 Baric hydrate. 4- 2SH 2 = BaHs 2 4 Sulphuretted Baric hydrogen. sulphhydrate. - 2OH 2 . Water. Argentic oxide. + SH 2 = SAg 2 + Sulphuretted Argentic hydrogen. sulphide. OH 2 . Water. CuO Cupric oxide. + SH 2 = CuS" + Sulphuretted Cupric hydrogen. sulphide. OH 3 . Water. HYDROSULPHYL, Hydric Persulphide. 'S 'H 2 , or Hs 2 . Probable molecular weight = 66. Sp. gr. T769. Preparation. By pouring a solution of calcic disulphide into hydrochloric acid : 'S 2 'Ca" + 2HC1 Calcic disulphide. Hydrochloric acid. Character. It is the analogue of hydroxyl in composition and functions. 'S 2 'H 2 Hydrosulphyl. CaCl 2 . Calcic chloride. CARBONIC BISULPHIDE, Bisulphide of Carbon. CS 2 . Molecular weight =76. Molecular volume \ \ \. 1 litre of carbonic disulphide vapour weighs 38 criths. Specific gravity 1-26. Soils at 45. SULPHO-CARBONIC ACID. 73 Preparation. 1. By passing sulphur over strongly ignited charcoal : C + S 2 = CS" 2 . Carbonic disulphide. 2. By heating together charcoal and iron- or copper-py- rites : C + 2PeS" a = CS" 2 + 2FeS". Iron pyrites. Carbonic Ferrous Ferric disulphide. disulphide. sulphide. Decompositions. 1. Heated potassium burns in the vapour of carbonic disulphide, with formation of potassic sulphide and liberation of carbon : CS" 2 + 2K 2 = 2SK 2 + C. Carbonic disulphide. Potassic sulphide. 2. "When brought into contact with a solution of an alkaline hydrate, carbonic disulphide is decomposed, a carbonate and a sulpho-carbonate being formed : 6OKH + 3CS" 2 = 2CS"Ks 2 + COKo 2 + 3OH 2 . Potassic Carbonic Potassic Potassic Water, hydrate. disulphide. sulpho-carbonate. carbonate. 3. In contact with solutions of alkaline sulphides, carbonic disulphide also forms alkaline sulpho-carbonates : SK 2 -f CS" 2 = CS"Ks 2 . Potassic sulphide. Carbonic disulphide. Potassic sulpho-carbonate. SULPHO-CARBONIC ACID. CS"Hs 2 . Preparation. By the action of hydrochloric acid on ammonic sulpho-carbonate : CS"(NH 4 S) 2 + 2HC1 = CS"Hs 2 + 2NH 4 C1. Ammonic Hydrochloric Sulpho-carbonic Ammonic sulpho-carbonate. acid. acid. chloride. 74 SULPHUR COMPOUNDS. COMPOUNDS OF SULPHUR WITH OXYGEN AND HTDEOXTL. In these compounds the sulphur is either a dyad, a tetrad, or a hexad. Sulphurous anhydride SO 2 . Sulphurous acid SOHo 2 . Sulphuric anhydride S0 3 . Sulphuric acid. (Hydric 1 S0 Ho sulphate.) J Nordhausen sulphuric r so Ho acid. (Dihydric di- < O sulphate.) [S0 2 Ho Hyposulphurous acid. \ gg"OHo (Sulphosulphuric acid.) J Dithionic 1 , QT Trithionic acid. (Sul- phodithionicacid.)... 1 gQ jj^ SULPHUROUS ANHYDRIDE. /O Tetrathionic acid. (Vi-\S* (u^\- sulphoditU- 1 S" onicacid.)... [S0 2 Ho Pentathionic f ^ acid. (2H- I S" 2 71 7 J Cl" sulphodi- < & thionic ' S " -- SULPHUROUS ANHTDRIDE. so a . Molecular weight =64. Molecular volume fTI- li litre weighs 32 criths. Solid at 76. Liquid under the pressure of ttvo atmospheres at 7 C. Occurrence. 1. As a volcanic product. 2. In the air of towns. 3. Evolved in the roasting of copper pyrites and other sul- phureous ores. Preparation. 1. By the combustion of sulphur in air or in oxygen : S + O 2 = S0 2 . 2. By heating sulphuric acid with copper or mercury: 2S0 2 Ho 2 Sulphuric acid. 2S0 2 Ho a Sulphuric acid. 3. By heating charcoal with sulphuric acid : Cu = S0 2 - Sulphurous anhydride. t- SO 2 Cuo" + Cupric sulphate. 2OH 2 . Water. Hg = S0 2 + Sulphurous anhydride. S0 2 Hgo" 4 Mercuric sulphate. - 20H 2 . Water. 2S0 2 Ho 2 Sulphuric acid. 2S0 2 Sulphurous anhydride. C0 2 Carbonic anhydride. 2OH 2 . Water. E2 76 SULPHUROUS ANHYDRIDE. 4. By heating a mixture of about three parts by weight of sulphur (two atoms) with four of manganic oxide (one atom) : S 2 + Mn0 2 = S0 2 + MnS". Manganic oxide. Sulphurous anhydride. Manganous sulphide. Reactions. 1. Dissolved by water, producing an acid liquid which, when cooled to 0, deposits white cubical crystals of sulphurous acid : S0 2 + OH 2 = SOHo 2 . Sulphurous anhydride. Water. Sulphurous acid. 2. Sulphurous anhydride, when passed into solutions of the metallic hydrates, produces sulphites. If the sulphurous anhy- dride be in excess, an acid sulphite is obtained : OKH + S0 2 = SOHoKo. Potassic hydrate. Sulphurous anhydride. Hydric potassic sulphite. 3. If the metallic hydrate be in excess, the normal sulphite is formed, thus : 2OKH + S0 2 = SOKo 2 + OH 2 . Potassic hydrate. Sulphurous anhydride. Normal potassic Water. sulphite. 4. Sulphurous acid, when acted upon by metallic hydrates, pi oduces the same salts : OKH + SOHo 2 = SOHoKo + OH 2 : 2OKH + SOHo 2 = SOKo 2 + 2OH 2 . 5. Sulphurous anhydride, when passed over metallic peroxides, produces sulphates: Pb0 2 + S0 2 = S0 2 Pbo". Perplumbic oxide. Sulphurous anhydride. Plumbic sulphate. Detection. Sulphites are recognized by the pungent odour of sulphurous anhydride which they evolve on the addition of a strong acid, such as sulphuric acid : SOKo 2 + S0 2 Ho 2 = S0 2 Ko 2 + S0 2 + OH 2 . Potassic Sulphuric Potassic Sulphurous Water, sulphite. acid. sulphate. anhydride. SULPHURIC ANHYDRIDE. 77 "When solutions of sulphites are mixed with solutions of argentic nitrate, a white precipitate of argentic sulphite is formed : SOKo 2 + 2NO 2 Ago = SOAgo 2 + 2NO 2 Ko. Potassic Argentic Argentic Potassic sulphite. nitrate. sulphite. nitrate. When this argentic sulphite is boiled with water, it becomes black, owing to the separation of metallic silver : SOAgo a + OH 2 = S0 2 Ho 2 + Ag 2 . Argentic sulphite. Water. Sulphuric acid. SULPHURIC ANHYDRIDE. so, Molecular weight = 80. Molecular volume I I I. 1 litre of sulphuric anhydride vapour weighs 40 criths. Fuses at 24-5. Boils at 52'6. Preparation. 1. By passing a mixture of sulphurous anhy- dride and oxygen over ignited spongy platinum: S0 2 + O S0 3 . Sulphurous anhydride. Sulphuric anhydride. 2. By heating Nordhausen sulphuric acid : S0 2 Ho = S0 2 Ho 2 -f S0 3 . S0 2 Ho Nordhausen Sulphuric acid. Sulphuric sulphuric acid. anhydride. 3. By heating the so-called anhydrous sodic bisulphate (disodic disulphate) : SCXNao O = S0 2 Nao 2 -f SCL , Anhydrous sodic bisulphate Sodic sulphate. Sulphuric (Disodic disulphate). anhydride. 78 SULPHURIC ACID. 4. By heating sulphuric acid with phosphoric anhydride S0 2 Ho 2 + P 2 5 = S0 3 + 2P0 2 Ho. Sulphuric Phosphoric Sulphuric 'Meta-phosphoric acid. anhydride. anhydride. acid. SULPHURIC ACID. S0 2 Ho 2 . Molecular weight = 98. Molecular volume ' H L Dissociation. 1 litre of sulphuric acid vapour weighs 24'5 criths. Sp. gr. 1-85. Soils at 325. Preparation. 1. By the action of hydroxyl upon sulphurous anhydride : 50 2 + Ho 2 = S0 2 Ho 2 . Sulphurous anhydride. Hydroxyl. Sulphuric acid. 2. By the exposure of sulphurous acid or metallic sulphites to air or oxygen : SOHo 2 + O S0 2 Ho 2 . Sulphurous acid. Sulphuric acid. SONao 2 + O S0 2 Nao 2 . Sodic sulphite. Sodic sulphate. 3. By the addition of water to sulphuric anhydride : 50 3 + OH 2 = S0 2 Ho 2 . Sulphuric Water. Sulphuric acid, anhydride. 4. By the action of nitric peroxide and oxygen on sulphurous anhydride and subsequent decomposition by water of the white crystalline compound thus produced (Briining and De la Provostaye) : rso 2 (]sx) 2 ) 2S0 2 + 'N- 2 4 + O=^0 (S0 2 (N<0 2 ) Sulphurous Nitric White crystalline anhydride peroxide. compound. SULPHURIC ACID. 79 O^ + 20H 2 = 2S0 2 Ho 2 + N 2 3 . White crystalline Water. Sulphuric Nitrous compound*. acid. anhydride. In the manufacture of sulphuric acid on the large scale, the nitrous anhydride is again acted on by water and transformed into nitric acid and nitric oxide : 3N 2 3 + OH 2 = 2N0 2 Ho + 2'N" 2 O 2 . Nitrous Water. Nitric acid. Nitric oxide, anhydride. The nitric oxide by the action of oxygen reproduces nitric peroxide, which is then ready to undergo the same processes a second time. The nitric acid is at the same time reduced to nitric peroxide by the action of sulphurous anhydride : S0 2 + 2N0 2 Ho = S0 2 Ho 2 + 'N^O,. Sulphurous Nitric acid. Sulphuric Nitric anhydride. acid. peroxide. The crude sulphuric acid may be freed from traces of nitrous anhydride (which it always contains) by the addition of some ammonic sulphate : S0 2 (NH 4 0) 2 + N 2 3 = S0 2 Ho 2 + 3OH 2 + N 4 . Ammonic sulphate. Nitrous Sulphuric Water, anhydride. acid. Character. Sulphuric acid forms several classes of salts : Hydric potassic sul- 1 phate J 80 SULPHATES. Potassic sulphate . . . S0 2 Ko 2 . Anhydrous sodic bi- f SO Nao sulphate. (Disodic * f*.WoM- MOM- Zincic sulphate S0 2 Zno". Tetrabasic zincic sul- ^ phate. (Dizincic I SOZno" 2 . fe.) J Hexabasic zincic sul- -j phate. . (Trizincic I SZno'V sulphate.) J Crystallized gyp- sum. (Tetrahydric I SHo 4 Cao"- calcic sulphate.) . . . J & HYPOSULPHUROUS ACID. 81 G-ypsum dried at "] 100. (Dihydric I SOHo 2 Cao". calcic sulphate?) ... J Gypsum dried at 260. (Calcic sul- } S0 2 Cao". phate.) HYPOSULPHUROUS ACID, Sulphosulphuric Acid SS"OHo 2 (hypothetical). Preparation of Hyposulphites (Sulpho sulphates) . 1. By boil- ing a solution of sodic sulphite with sulphur : SONao 2 + S = SS"ONao 2 . Sodic sulphite. Sodic hyposulphite (Sodic sulphosulphate). 2. By exposure of an alkaline persulphide to the air : 'S' 2 Ca" + O 3 = SS"OCao". Calcic Calcic persulphide. hyposulphite. Reaction. The hyposulphites, when acted upon by acidt^, evolve sulphurous anhydride, whilst sulphur is precipitated : SS"ONao 2 + 2HC1 = 2NaCl + OH 2 + S + SO 2 . B5 Sodic hyposulphite Hydrochloric Sodic Water. Sulphurous (Sodic sulpho- acid. chloride. anhydride. sulphate). 82 ACIDS OF SULPHUR. DITHIONIC ACID, Hyposulphuric Acid. 'Sv 2 4 Ho, Preparation. Powdered manganic oxide is suspended in water and a current of sulphurous anhydride passed through the liquid, when the manganic oxide gradually dissolves. The solution contains manganous dithionate or hyposulphate : Mn0 2 + 2S0 2 = 'S v 2 O 4 Mno". Manganic Sulphurous Manganous oxide. anhydride. dithionate. This solution is next treated with baric sulphide, which pre- cipitates manganous sulphide, baric dithionate existing in the solution : 'S v 2 O 4 Mno" + BaS" = MnS" + 'S v 2 4 Bao". Manganous dithionate. Baric sulphide. Manganous sulphide. Baric dithionate. By adding sulphuric acid to a solution of the baric dithio- nate, baric sulphate is precipitated and dithionic acid remains in solution : 'S v 2 O 4 Bao" + SO 2 Ho 2 = S0 3 Bao" + 'S v 2 4 Ho 2 . Baric Sulphuric Baric sulphate. Dithionic acid, dithionate. acid. TKITHIONIC ACID, SulphoditUonic Acid, Sulphuretted Hyposul/phuric Acid. S0 2 Ho S" S0 3 Ho Preparation. By digesting hydric potassic sulphite with sulphur, potassic trithionate and potassic hyposulphite (sul- pliosulpJiate) are formed : rso 2 Ko GSOKoHo + 2S = 2 \ S" + SS"OKo 2 + 3OH 3 . [S0 2 Ko Hydric potassic Potassic Potassic Water, sulphite. trithionate. Hyposulphite. ACIDS OF SULPHUR. 83 The two salts so produced, when decomposed by hydrofluo- silicic acid,yield trithionic acid, sulphurous acid, and sulphur: fS0 2 Ko SS"OKo 2 + 2 \ S" + 3H 2 Si iv F 6 = 3K 2 Si iv F 6 [SO.Ko Potassic Potassic Hydrofluosilicic Potassic hyposulphite. trithionate. acid. silicofluoride. rso 2 Ho + 2 I S" + SOHo 2 + S. S0 2 Ho Trithionic acid. TETRATHIONIC ACID, DisulphoditUonic Acid, Bisulphuretted HyposulpJiuric Acid. S0 2 Ho S" S" S0 2 Ho Preparation. When iodine is added to baric hyposulphite (sulpJiosulpliate) , baric iodide and baric tetrathionate are pro- duced : rsp 2 -, 2SS"OBao" + I 2 = BaL -f j |'' Bao". [soj Baric hyposulphite. Baric iodide. Baric tetrathionate. This salt, when decomposed by sulphuric acid, yields tetra- thionic acid. PENTATHIONIC ACID, TrisulpJioditJiionio Acid, Trisulphwretted Hyposulphuric Acid. S0 2 Ho S" 84 SELENIUM Preparation. This acid is obtained by the action of hydro- sulphuric acid on sulphurous anhydride : fS0 2 Ho S" 5SH 2 + 5S0 2 = 4 S" + 4OH 2 + S 5 . I S" Sulphuretted Sulphurous _ ^- , . 2 . hydrogen. anhydride. Pentathiomc acid. Water SELENIUM, Se 2 . Atomic weight =79. Molecular weight =158. Molecular vo- lume p[~|- 1 litre of selenium vapour weighs 79 criths. Sp. gr. 4-3. Fuses a little above 100. Soils at about 700. Atomicity ", iv , and vi . Evidence of atomicity : Hydroselenic acid Se"H 2 . Selenious chloride Se iv Cl 4 . Selenic acid Se vi 2 Ho 2 . Occurrence. In small quantities in some mineral sulphides. COMPOUNDS OF SELENIUM WITH HYDROGEN. SELENIURETTED HYDROGEN, Hydroselenic Acid. SeH 2 . Molecular weight =81. Molecular volume \ \ |, 1 litre weighs 40*5 criths. Preparation. By the action of hydrochloric acid upon fer- rous selenide : FeSe" + 2HC1 = SeH 2 + PeCl 2 . Ferrous selenide. Hydrochloric Hydroselenic Ferrous chloride, acid. acid. Character. Like hydrosulphuric acid, it produces precipi- tates in solutions of most of the heavy metals. There are two chlorides of selenium : 'Se' 2 Cl 2 and SeCl 4 . TELLURIUM. 85 COMPOUNDS OF SELENIUM WITH OXYGEN AND HYDEOXYL. Selenious anhydride Se 2 . Selenious acid SeOHo 2 . Selenic acid Se0 2 Ho 2 . These bodies closely resemble the corresponding sulphur compounds. Selenious anhydride is formed by burning selenium in oxy- gen: Se 2 + 2O 2 = 2SeO 2 . Selenious anhydride. Selenious acid is formed by dissolving the anhydride in boil- ing water and crystallizing. Potassic seleniate is prepared by fusing selenium or metallic selenides with nitre. The acid is obtained by transforming the potassic salt into a plumbic salt, and subsequently decompo- sing the latter with hydrosulphuric acid. TELLURIUM, Te 2 . Atomic weight = 128. Probable molecular weight =256. Sp. gr. 6-2. Fuses at 490-500. Atomicity ", iv , and vi . Evi- dence of atomicity : Hydrotelluric acid Te"H 2 . Tellurous chloride Te iv Cl 4 . Telluric acid Te vi O 2 Ho 2 . This element is of even less importance than selenium, which it closely resembles. 86 BROMINE. The following compounds are known : Hydrotelluric acid (telluretted hydrogen) TeH 2 . Hypotellurous chloride TeCl 2 . Tellurous chloride TeCl r Tellurous anhydride TeO 2 . Telluric anhydride TeO 3 . Tellurous acid TeOHo 2 ? Telluric acid Te0 2 Ho 2 . CHAPTER XIV. MONAD ELEMENTS. SECTION II. (continued from Chap. VIII.). BROMINE, Br 2 . Atomic weight = 80. Molecular weight = 160. Molecular vo- lume III. 1 litre of bromine vapour weighs 80 criths. Sp. gr. 318. Fuses at 20. Soils at 63. Atomicity '. Evidence of atomicity : Hydrobromic acid HBr. Potassic bromide KBr. Argentic bromide AgBr. Occurrence. In small quantities in some saline mineral waters. In sea- water, and the waters of the Dead Sea. Preparation. 1. By the treatment, with chlorine, of the mother-liquors of saline waters containing bromides, and ex- tracting the liberated bromine by ether : 2KBr + C1 2 = 2KC1 + Br 2 . Potassic bromide. Potassic chloride. HYDROBROMIC ACID. 87 2. By heating together sulphuric acid, sodic bromide, and manganic oxide : 2JSTaBr + Mn0 2 .+ 2S0 2 Ho 2 = Br 2 Sodic bromide. Manganic oxide. Sulphuric acid. + S0 2 Nao 2 + SO 2 Mno" + 2OH 2 . Sodic sulphate. Manganous sulphate. Water. Character. Bromine unites with several metals directly, and with great energy. Antimony and arsenic burn in it with bril liancy. At bromine combines with water, forming a crystalline compound, Br 2 , 10OH 2 . HYDROBROMIC ACID. HBr. Molecular weight = 81. Molecular volume fT~l- 1 litre of hydrobromic acid weighs 4O5 criths. Fuses at 73. Soils at -69. Preparation. 1. By passing a mixture of hydrogen and bromine vapour through a red-hot tube, or by burning hydro- gen in a mixture of bromine vapour and air : H 2 + Br 2 = 2HBr. Hydrobromic acid. 2. By heating potassic bromide with phosphoric acid : 3KBr + POHo 3 = POKo 3 + 3HBr. Potassic Phosphoric Potassic Hydrobromic bromide. acid. phosphate. acid. Sulphuric acid cannot be employed for this operation, as a portion of the hydrobromic acid is then decomposed, bromine being liberated : S0 2 Ho 2 + 2HBr = Br 2 + 2OH 2 + S0 2 . Sulphuric acid. Hydrobromic Water. Sulphurous acid. anhydride. 3. By the action of water upon phosphorous tribromide : P'"Br 3 + 3OH 2 = P v OHHo 2 + 3HBr. Phosphorous Water. Phosphorous Hydrobromie tribromide. acid. acid. 88 COMPOUNDS OF BROMINE. 4. By gradually dropping bromine into water containing amorphous phosphorus : P 2 + 3Br 2 + 6OH 2 = 2P v OHHo 2 + 6HBr. Water. Phosphorous Hydrobromic acid. acid. 5. By passing sulphuretted hydrogen through water con- taining bromine : 2SH 2 + 2Br 2 = 4HBr + S a . Sulphuretted Hydrobromic hydrogen. acid. Reactions. 1. Decomposed by chlorine with liberation of bromine : 2HBr + C1 2 = 2HC1 + Br 2 . Hydrobromic Hydrochloric acid. acid. 2. By the action of atmospheric oxygen a small quantity of bromine is liberated, but the decomposition is soon arrested : 4HBr + 2 = 2OH 2 + 2Br 2 . HVdrobromic Water. Bromine, acid. 3. In contact with metallic oxides, hydrates, and salts, bro- mides are formed. COMPOUNDS OF BROMINE WITH OXYGEN AND HYDROXYL. Hypobromous anhydride OBr 2 . Hypobromous acid OBrH. fOBr Bromic acid { O . [OH The graphic formulae of these compounds are analogous to those of the corresponding chlorine compounds, given at page 45. BROMIC ACID. 89 HYPOBROMOITS ANHYDRIDE. OBr 2 . Preparation. By passing bromine vapour over dry mercuric oxide : HgO + 2Br 2 = HgBr 2 + OBr 2 . Mercuric Mercuric Hypobromous oxide. bromide. anhydride. HYPOBROMOUS ACID. OBrH. Preparation. 1. By passing hypobromous anhydride into water : OBr 2 + OH 2 = 2OBrH. Hypobromous Water. Hypobromous anhydride acid. 2. By agitating mercuric oxide with bromine- water : fHgBr 2HgO + OH 2 + 2Br 2 = 2OBrH + \ IHgBr Mercuric Water. Hypobromous Mercuric oxide. acid. oxybromide. BROMIC ACID. JOBr \OHo' Preparation. By acting upon a solution of baric bromate with sulphuric acid : fOBr S0 2 Ho 2 = 2 + SO 2 Bao". Baric bromate. Sulphuric Bromic Baric acid. acid. sulphate. 90 IODINE. Reaction. By boiling, bromic acid decomposes into water, bromine, and oxygen : 4 {oHo = 2Br * + 20H > + 50 >- Bromic acid- Water. Preparation ofbromates. 1. By adding bromine to a solu- tion of a metallic hydrate, and separating the bromate by crys- tallization: 6KHo + 3Br 2 = 5KBr + + 3OH 2 . Potassic Potassic Potassic Water. hydrate. bromide. bromate. 2. By the action of potassic hydrate on bromine pentachlo- ride: 6KHo + BrCl 5 = 5KC1 + Potassic Bromine Potassic Potassic Water. hydrate. pentachloride. chloride. bromate. Character ofbromates. Some of the bromates when heated lose oxygen, being transformed into bromides : 2 {lo = 2KBr + 30 >- Potassic Potassic bromate. bromide. Others evolve bromine and a portion of their oxygen,' leaving metallic oxides : fOBr Mgo" = 2MgO + 2Br 2 + 50 2 . r Magnesic oxide. IODINE, I 2 . Atomic weight =127. Molecular weight =254. Molecular vohtme I I I. 1 litre of iodine vapour weighs 127 criths. Sp. gr. 4-95. Fuses at 107. Soils at 180. Atomicity '. Evidence of atomicity : HYDR10DIC ACID. 91 Hydriodic acid HI. Potassic iodide KI. Argentic iodide Agl. Occurrence. In mineral springs, in sea-water, and in con- siderable quantities in sea-plants. Manufacture. Sea-weeds are burnt and the ash is ex- tracted with water. The liquid is evaporated, and, after a con- siderable quantity of sodic carbonate and chloride has crys- tallized out, the mother-liquor, which contains potassic iodide, is distilled with sulphuric acid and manganic oxide : 2KI + Mn0 2 + 2S0 2 Ho 2 =S0 2 Ko 2 +S0 2 Mno" + I 2 +2OH 2 . Potassic Manganic Sulphuric Potassic Manganous Water, iodide. oxide. acid. sulphate. sulphate. Reactions. 1. Iodine is precipitated from its solutions by chlorine and bromine : 2KI + C1 2 = 2KC1 + I 2 . Potassic Potassic iodide. chloride. 2KI + Br 2 = 2KBr + I 2 . Potassic Potassic iodide. bromide. 2. Iodine unites directly with many metals. HYDRIODIC ACID. HI. Molecular weight =128. Molecular volume I I I. 1 litre of Jiydriodic acid weighs 64 critJis. Fuses at 55. Preparation. 1. By passing iodine vapour and hydrogen througha red-hot tube or over spongy platinum gently heated: H 2 + L = 2HI. 92 HYDRIODIC ACID. 2. By the action of dilute sulphuric acid on baric iodide, or of phosphoric acid on any iodide : BaI 2 + S0 2 Ho 2 == 2HI + S0 2 Bao". Baric Sulphuric Hydriodic Baric iodide. acid. acid. sulphate. 3. By decomposing phosphorous triiodide by water : PI 3 + 3OH 2 = POHHo 2 + 3HI. Phosphorous Water. Phosphorous Hydriodic triiodide. acid. acid. 4. By heating together water, potassic iodide, iodine, and phosphorus : 4KI + P 2 + 5I 2 + 8OH 2 = 14HI + 2POHoKo 2 Potassic Water. Hydrio iodide. acid. Potassic Water. Hydriodic Hydric dipotassic phosphate. 5. A solution of hydriodic acid is obtained by passing sulphu- retted hydrogen through water in which iodine is suspended: 2SH 2 + 2I 2 = 4HI + S 2 . Sulphuretted Hydriodic hydrogen. acid. Reactions. 1. Decomposed by chlorine and bromine, with liberation of iodine : 2HI + C1 2 = 2HC1 + I 2 . Hydriodic Hydrochloric acid. acid. 2HI + Br 2 = 2HBr + L, Hydriodic Hydrobromic acid. acid. 2. It is gradually but completely decomposed by atmospheric oxygen ; the iodine, which at first remains dissolved in the hydriodic acid, is after a time deposited in crystals : 4HI + 2 = 2OH 2 + 2I 2 . Hydriodic Water. acid. 3. With metallic oxides, hydrates, and some salts it forms iodides. Even argentic chloride is transformed by hydriodic acid into argentic iodide : AgCl + HI = Agl + HC1. Argentic Hydriodic Argentic Hydrochloric chloride. acid. iodide. acid. COMPOUNDS OP IODINE. 93 4. Hydriodic acid is rapidly decomposed by mercury, with liberation of hydrogen : 2HI + 2Hg = 'Hg' 2 I 2 + H 2 . Hydriodic Mercurous acid. iodide. COMPOUNDS OF IODINE WITH OXYGEN AND HTDEOXTL. lodic anhydride lodicacid {OHO* Periodic anhydride <( O . Periodic acid The graphic formulae of these compounds are analogous to those of the corresponding chlorine compounds given at p. 45. IODIC ANHYDRIDE. foi 1 IA, or OI 94 IODIC ACID. Preparation. By heating iodic acid to 170, when it sepa- rates into iodic anhydride and water : f01 . = OH + s O OI Iodic acid. Iodic anhydride. Reaction. When strongly heated, it decomposes into iodine and oxygen. IODIC ACID. roi \OHo* Preparation. 1. By the action of sulphuric acid upon baric iodate : OI O fOT Bao" + S0 2 Ho 2 = 2 1 g^o + so , Ba "- LOI Baric iodate. Sulphuric Iodic acid. Baric sulphate, acid. 2. By oxidizing iodine with strong boiling nitric acid : 6N0 2 Ho + I 2 = 2*. + 20H 2 + 2N 2 O 3 + 'N^O,. Nitric acid. Iodic acid. Water. Nitrous Nitric anhydride. peroxide. 3. By acting upon iodine and water with chlorine : I 2 + 60H 2 + 5C1 2 = 2 {2* + 10HCL Water. Iodic acid. Hydrochloric acid. Reactions. 1. In contact with hydriodic acid it forms water and iodine : + 5HI - 30H > + 3I ' Iodic acid. Hydriodic Water, acid. PERIODIC ANHYDRIDE. 95 2. It is reduced by many other deoxidizing agents. Preparation oflodates. 1. By treating solutions of metallic hydrates with iodine, and separating the iodate by crystalliza- tion : GKHo 4- 3I 2 = 5KI + + 3OH 2 . Potassic Potassic Potassic Water. hydrate. iodide. iodate. 2. By dissolving iodine in potassic hydrate and treating the mixture with chlorine : 12KHo + I 2 + 5C1 2 = 10KC1 + 2 + 6OH 2 . Potassic Potassic Potassic Water. hydrate. chloride. iodate. 3. By heating together potassic chlorate and iodine : roci TP1 roi T * + JOKO + \OKo Potassic Iodine Potassic chlorate. monochloride. iodate. Character of Mates. Some of the iodates when heated split into iodides and oxygen, others into metallic oxides, iodine, and oxygen. lodic acid gives several well-defined anhydro-salts. PEKIODIC ANHYDRIDE. fOI O I 2 7 , or X O . Preparation. By heating periodic acid to 160 oi Periodic Periodic Water. acid. anhydride. 96 FLUORINE. Reaction. When heated it is decomposed into oxygen and iodic anhydride, and ultimately into iodine and oxygen. PERIODIC ACID. 01 O . OHo Preparation. By decomposing plumbic periodate with sul- phuric acid : Plumbic periodate. S0 2 Ho 2 Sulphuric acid. OI OHo Periodic acid. S0 2 Pbo". Plumbic sulphate. Preparation ofPeriodates. Sodic periodate may be prepared by passing chlorine through mixed solutions of sodic hydrate and sodic iodate : fOI ONao Sodic iodate. Sodic hydrate. f 01 1 (ONao Sodic periodate. Water. Sodic chloride. FLUORINE, F 2 . Atomic -weight =19. Molecular weight =38 (?). Molecular volume f"T~|. 1 litre weighs 19 criths (?). Atomicity '. Evidence of atomicity: Hydrofluoric acid HF. Occurrence. In combination with metals in fluorspar, cryo- lite, apatite, and other minerals. Little is known of fluorine in the uncombined condition. SILICON. 97 COMPOUND OF FLUORINE WITH HYDROGEN. HYDKOFLUOEIC ACID. HF. Molecular weight =20. Molecular volume \~~[~\. 1 litre weighs 10 criths. Preparation. By heating calcic fluoride with sulphuric acid in a leaden or platinum vessel : CaF 2 + S0 2 Ho 2 = 2HF = SO 2 Cao". Calcic Sulphuric Hydrofluoric Calcic fluoride. acid. acM. sulphate. CHAPTER XV. TETEAD ELEMENTS. SECTION I. (Continued from Chapter XI.) SILICON, Silidum, Si. Atomic iveight =28'5. Sp.gr. (grapMtoidal) =2'49. Atomicity 1 *. Evidence of atomicity : Silicic chloride SiCl 4 . Silicic fluoride SiF 4 . Occurrence. Silicon is one of the most widely diffused ele- ments. It is found, in combination with oxygen and metals, in a very large number of minerals. a. Amorphous Silicon. Preparation. 1. By heating potassic silicofluoride with potassium : SiK 2 F G + 2K 2 = Si + 6KF. Potassic Potassic silicofluoride fluoride. 98 SILICON. 2. By heating sodium in a current of the vapour of silicic chloride : SiCl 4 + 2]S T a 3 = Si + Silicic Sodi chloride. chloride. Reactions. 1. Silicon is dissolved by aqueous hydrofluoric acid, and converted into hydrofluosilicic acid : Si + 6HF = SiH 2 F 6 + 2H 2 . Hydrofluoric . Hydrofluosilicic acid. acid. 2. When fused with potassic hydrate, or boiled in its solu- tion, it yields potassic silicate : Si + 4KHo = SiKo 4 + 2H 2 . Potassic Potassic hydrate. silicate. 3. Heated in the air, it burns, producing silicic anhydride. /3. GrapJiitoidal Silicon. Preparation. By fusing amorphous silicon with alumi- nium, and boiling the compound in hydrochloric or hydrofluoric acid, which dissolves the aluminium, leaving the silicon in the form of hexagonal plates with a metallic lustre. Character. May be heated to whiteness in oxygen without burning. Is gradually oxidized by a mixture of nitric and hydro- fluoric acids. Is slowly attacked by fused potassic hydrate. y. Adamantine Silicon. Preparation. By heating aluminium very strongly in a current of the vapour of silicic chloride. The aluminic chloride which is formed volatilizes, leaving the adamantine silicon be- hind : 3SiCl 4 + 2A1 2 = 2'A1'" 2 C1 6 + Si 3 . Silicic Aluminic chloride. chloride. COMPOUNDS OF SILICON. 99 SILICIC HYDRIDE. SiH 4 . Molecular weight =32 '5. Has not been obtained free from hydrogen. Preparation. 1. By decomposing dilute sulphuric acid by a feeble electric current passing from electrodes of aluminium containing silicon, when the silicic hydride is evolved at the negative pole. 2. By decomposing magnesic silicide with hydrochloric acid : SiMg" 2 + 4HC1 = 2MgCl 2 + SiH 4 . Magnesic Hydrochloric Magnesic Silicic sihcide. acid. chloride. hydride. Reaction. Inflames spontaneously in air, producing water and silicic anhydride : SiH 4 + 20 2 = Si0 2 + 20H 2 . Silicic Silicic Water, hydride. anhydride. SILICIC CHLORIDE. SiCl 4 . Molecular weight =170'5. Molecular volume (""[""I- 1 litre weighs 85'25 criths. Sp. gr. of liquid 1'52. Soils at 59. Preparation. 1. By burning silicon in chlorine. 2. By heating a mixture of carbon and silicic anhydride in a stream of chlorine : Si0 2 + 2C + 2C1 2 = SiCl 4 + 2CO. Silicic Silicic Carbonic anhydride. chloride. oxide. Reaction. By contact with water it produces silicic and hy- drochloric acids : SiCl 4 + 4OH 2 = SiHo 4 + 41IC1. Silicic Water. Silicic Hydrochloric Chloride. acid. acid. F2 100 COMPOUNDS OF SILICON. SILICIC BROMIDE. SiBr 4 . Molecular weight =348'5. Sp. gr. 2'813 at 0. Soils at 153. Preparation. By the same method as that employed for making the chloride, bromine vapour being substituted for chlo- rine. Reaction. Decomposed by water in the same manner as the chloride. SILICIC FLUORIDE. SiF 4 . Molecular weiglit =104'5. Molecular volume f"T~l- 1 litre weighs 52' 25 critJis. Fuses at 140 C. Condensable gas. Preparation. By heating together silicic anhydride, calcic fluoride, and sulphuric acid : Si0 2 + 2Car 2 + 2S0 2 Ho 2 = SiF 4 Silicic Calcic Sulphuric Silicic anhydride. fluoride. acid. fluoride. + 2SOHo 2 Cao". Dihydric calcic sulphate. Reaction. By contact with water it produces silicic and hydrofluosilicic acids : 3SiP 4 + 4OH 2 = SiHo 4 + 2SiH 2 F 6 . Silicic Water. Silicic Hydrofluosilicic fluoride. acid. acid. By contact with metallic oxides, hydrates, and salts, hydrofluo- silicic acid produces silicofluorides, some of which, as the potassic and baric compounds, are insoluble in water : SiH 2 ]F 6 + 2KHo = SiK a F e + 2OH 2 . Hydrofluosilicic Potassic Potassic Water. acid. hydrate. silicofluoride. SILICIC ACID. 101 COMPOUNDS OF SILICON WITH OXYGEN AND HYDEOXYL. Silicic anhydride Si0 2 . Silicic acid SiHo 4 and SiOHo 2 . Chryson Si G H 6 O 4 - Leukon Si 3 H 4 5 . SILICIC ANHYDRIDE. Si0 2 . Molecular weight =60'5. Sp. gr. 2'69. Occurrence. In the pure state in many minerals, as quartz, agate, Okenite. Tetrahydric calcic disilicate. J 7? (^ " d n r i ^ L/tlO . ...... SiHo-J Serpentine. Dihydric trimagnesic disi- focate. See fig. 4.. (SiHoMgo"' Steatite. Trimagnesic tetrasilicate. } . ^ .,.. See fig. 5 .. ....................... } Sl AMgo 3 . fSiHoMgo" Meerschaum. Tetrahydric dimagnesicj 2-rr trisilicate. See fig. 6 ............... |Q 2 o^ Pyropbyllite. Dihydric aluminic tetr a- SiO i I y} ' See fig. 7 .................. SiO SiOHo J Anortnite. Aluminic calcic disilicate. ,~ Seefig.8 Ca ' SiO Labradorite. Aluminic calcic trisilicate. SiCao"-Al o 71 See fig. 9 ............................... SiO ^J 2 Grossularia. Aluminic tricalcic trisili- j ao '' . See fig. 10 Emerald. Triqlucinic aluminic Jiexa- } . ^ . , 17 ,^ ll . .,. . o .,., h- Si O 6 ALo vi Grlo silicate. See fig. 11 ............... J Chloropal. Jfemc trisilicate. See c ^-n %. 12 .................................... e2 ' " Felspar. Orthose. Dipotassic alumi- \ nic hexasilicate. See fi ff . 13 ... J 104 TIN. SILICIC SULPHIDE. SiS" 2 . Preparation. By passing the vapour of carbonic disulphide over silicic anhydride heated to redness : Si0 2 + CS" 2 = SiS" 2 + C0 2 . Silicic Carbonic Silicic Carbonic anhydride. disulphide. sulphide. anhydride. Reaction. By the action of water, hydrosulphuric acid is evolved, and the solution contains silicic acid : SiS 2 + 4OH 2 = SiHo 4 + 2SH 2 . Silicic Water. Silicic Sulphuretted sulphide. acid. hydrogen. TIN, Sn. Atomic weight = 118. Molecular weight unknown. Sp. gr. 7 '28. Fuses at 228. Atomicity" and iv , also pseudo-triatomic. The following are the names and formulae of the principal compounds of this metal : Stannous chloride SnCl 2 . Stannic chloride Sn C1 4 . Stannous oxide SnO. Stannic oxide or anhydride. Sn 2 . rsnci Distannous oxydichloride. . \ O [SnCl Stannous hydrate SnHo 2 . - Stannic acid SnOHo 2 . (K'UvQ 0i$ ^ ov\, ' V\ Qju. Dipotassic stannite SnKo 2 . Dipotassic stannate SnOKo 2 , 4OH 2 . COMPOUNDS OF TIN. 105 Distannic trioxide or 8 Stannous sta nnate SnOSno". 0z(sn) SnHo 3 O SnHo Metastannic acid (dried at 100) SnHo a O Dipotassic metastannate . Stannous sulphide Stannic sulphide Distannic trisulphide .... or Stannous sulphtistannate. . SnSSns". 'SnHo 2 Ko O SnHo 2 SnO O SnHo a O ^SnHo 2 Ko SnS". SnS'' \ / \ \ 106 COMPOUNDS OF TITANIUM. Stannous sulphate SO 2 Sno". TITANIUM, Ti. Atomic weight =50. Molecular weight unknown. Sp. gr. 5'3. Atomicity " and iv , also pseudo-triatomic. The following are the names and formulae of the chief com- pounds of titanium : Titanic tetrachloride TiCl 4 . f TiPl Dititanic hexachloride ... \ X I Titanous oxide ............... Titanic oxide or anhydride ^ (Eutile, Anatase, Brook- L Ti0 2 . ite) ........................ J Titanic acid .................. TiOHo 2 . Titanic sulphide ............ TiS" 2 . -r.-^^ j- M. -j fTiN"' Dititanic dmitride ......... j TIN'"' @ -(Tr) fri \^y \Zy s in PHOSPHORUS. 107 CHAPTER XVI. PENTAD ELEMENTS. SECTION I. {Continued from Chapter XII.) PHOSPHORUS, P 4 . Atomic weight =31. Molecular weight =124. Molecular volume I I I. 1 litre of phosphorus vapour weighs 62 criths. Sp. gr. TS3. Fuses at 44-45. Boils at 290. Atomicity '" and*. Evidence of atomicity : Phosphorous trihy dride P'"H 3 Phosphorous trichloride P'"C1 3 . Phosphoric chloride P V C1 5 . Phosphonic iodide P V H 4 I. Occurrence. In combination as a constituent of several minerals, and in small quantities in most rocks and soils. In plants, and in the brain, nerves, urine, and bones of animals. Manufacture. Calcined bones or Sombrerite, both of which consist chiefly of calcic phosphate, are digested with sulphuric acid, by which the tricalcic diphosphate is converted into tetra- hydric calcic diphosphate : P 2 2 Cao" 3 + 2S0 2 Ho 2 = P a O a Ho 4 Cao" + 2SO 2 Cao". Tricalcic diphos- Sulphuric Tetrahydric calcic Calcic phate (Bone-ash). acid. diphosphate. sulphate. The tetrahydric calcic phosphate is extracted with water from the calcic sulphate, evaporated, mixed with charcoal, dried and distilled, when phosphorus, carbonic oxide and tricalcic diphosphate are produced : 3P 2 4 Cao" + C 10 = P 2 2 Cao" 3 + 10CO + P 4 . Calcic meta- Tricalcic Carbonic phosphate. diphosphate. oxide. 108 PHOSPHOKETTED HYDROGEN. AMORPHOUS PHOSPHORUS. Allotropic Phosphorus. Red Phosphorus. Obtained by heating common phosphorus to 230-250 in close vessels. Neither the number nor the arrangement of the atoms in the molecule of this variety of phosphorus is known. COMPOUNDS OF PHOSPHORUS WITH HYDROGEN. Phosphorus forms three compounds with hydrogen, which cannot be obtained by the direct combination of their elements. f Pf ~P'"TTV Solid phosphoretted hydrogen... j p! > P" / HY' ^ Liquid ditto 'P" 2 H 4 . Graseous ditto .. PEL. GASEOUS PHOSPHORETTED HYDROGEN. Molecular weight =34. Molecular volume I I i. 1 litre weighs 17 critlis. Preparation. 1. By heating hypophosphorous acid : 2POH 2 Ho = PH 3 + POHo ? . Hypophosphorous Phosphoretted Phosphoric acid. hydrogen. acid. 2. By heating phosphorous acid : 4POHHo 2 = PH 3 + SPOHo,. Phosphorous Phosphoretted Phosphoric acid. hydrogen. acid. PHOSPHORETTED HYDROGEN. 109 3. By heating phosphorus with solution of sodic or potassic hydrate : SONall + P 4 + 3OH 2 = 3POH 2 Nao + PH 3 . Sodic Water. Sodic Phosphoretted hydrate. hypophosphite. hydrogen. The gas prepared by this process contains free hydrogen and the vapour of liquid phosphoretted hydrogen. Reactions. 1. By combustion in oxygen it yields phosphoric acid : PH 3 + 20 2 = POHo 3 . Phosphoretted Phosphoric hydrogen. acid. 2. "When passed through a solution of cupric sulphate, it causes a black precipitate of cupric phosphide : 2PH 3 + 3S0 2 Cuo" = P 2 Cu" 3 + 3SO 2 Ho 2 . ilphur acid. Phosphoretted Cupric Cupric Sulphuric hydrogen. sulphate. phosphide. 3. When passed through a solution of argentic nitrate, me- tallic silver and nitric and phosphoric acids are formed : PH 3 + 8NO a Ago + 4OH 2 = Phosphoretted Argentic Water. Phosphoric Nitric hydrogen. nitrate. acid. acid. 4. It unites directly with hydriodic and hydrobromic acids when they are presented to it in the nascent state, forming compounds isomorphous with the corresponding substances in the nitrogen series : PH 3 + 3I 2 = PI 3 + SHI; hosphoretted Phosphorous Hydriodi hydrogen. triiodide. acid. 3PH 3 + 3HI = 3PH 4 L Phosphoretted Hydriodic Phosphonic hydrogen. acid. iodide. In this behaviour phosphoretted hydrogen bears a striking analogy to ammonia, although, unlike the latter compound, it does not unite with other acids. 110 COMPOUNDS OP PHOSPHORUS. LldUID PHOSPHORETTED HYDROGEN. Molecular weiglit =66. Preparation. By the action of water or very dilute hydro- chloric acid upon calcic phosphide, 'P" 2 Ca" 2 , the gas evolved being transmitted through a freezing-mixture : 'P" 2 Ca" 2 + 4OH 2 = 'P" 2 H 4 + 2Ca"Ho a . Calcic Water. Liquid phos- Calcic phosphide. phoretted hydrate. hydrogen. The calcic phosphide is prepared by passing the vapour of phosphorus over lime heated to redness : 14P + 14CaO = 2P 2 3 Cao" 2 + 5'P" 2 Ca" 2 . Lime. Calcic Calcic pyrophosphate. phosphide. Reaction. Decomposed by sunlight into solid and gaseous phosphoretted hydrogen . 5'P" 2 H 4 = 6PH 3 + Liquid phospho- Gaseous phospho- Solid phosphorette retted hydrogen. retted hydrogen. hydrogen. SOLID PHOSPHORETTED HYDROGEN. fP(F"H)" ? \ P(F"H)" ' Molecular weight =126 ? Preparation. By dissolving calcic phosphide in concen- trated hydrochloric acid, or by the action of light upon the liquid phosphoretted hydrogen. COMPOUNDS OF PHOSPHORUS. Ill COMPOUNDS OF PHOSPHORUS WITH CHLORINE. Phosphorus forms two compounds with chlorine : Phosphorous trichloride ^C1 3 . Phosphoric chloride PC1 5 . PHOSPHOROUS TRICHLORIDE. -- Molecular weight =137 '5. Molecular volume \ I I. 1 litre of phosphorous trichloride vapour weighs 68 '75 criths. Sp.gr. 1-45. Soils at 74. Preparation. By the action of chlorine upon phosphorus : P 2 + 3C1 2 = 2PC1 3 . Reaction. By the action of water it yields hydrochloric and phosphorous acids : PC1 3 -f 3OH 2 = 3HC1 + POHHo 2 . Phosphorous Water. Hydrochloric Phosphorous chloride. acid. acid. PHOSPHORIC CHLORIDE. PC1 5 . Molecular weight =208*5. Molecular volume |"T1 to | 112 COMPOUNDS OF PHOSPHORUS. 1 litre of phosphoric chloride weighs 52*1 to 104*25 criths. Volatilizes lelow 100. Preparation. By the action of chlorine upon phosphorous chloride : PC1 3 Phosphorous chloride. C1 2 = PCL, Phosphoric chloride. Reactions. 1. By the action of an excess of water it. pro- duces hydrochloric acid and phosphoric acid : PCI, + Phosphoric chloride. 4OH 2 = 5HC1 + Water. Hydrochloric acid. POHo 3 . Phosphoric acid. 1 CH 2 Ho Ethylic alcohol. T *^1 5 Phosphoric chloride. J'CH 3 ICOHo Acetic acid. Phosphoric chloride. 2. When submitted to the action of alcohols and acids, the chlorides of the radicals of the alcohols and acids are obtained, thus : HC1 Ethylic Hydrochloric Phosphoric chloride. acid. oxytrichloride. + HC1 + POC1 3 . Hydrochloric Phosphoric acid. oxytrichloride. \COC1 Acetylic chloride. COMPOUND OF PHOSPHORUS WITH CHLORINE AND OXYGEN. PHOSPHORIC OXYTRICHLORIDE. POC1 3 . Molecular weight =153'5. Molecular volume fTI. 1 litre of COMPOUNDS OF PHOSPHORUS. 113 phosphoric oxytrichloride vapour weighs 76'75 criths. Sp. gr. 1-7. Soiling-point 110. Preparation. 1. By the action of a limited quantity of water on phosphoric chloride : PC1 5 + OH 2 = POC1, + 2HC1. Phosphoric Water. Phosphoric Hydrochloric chloride. oxytrichloride. acid. 2. By passing oxygen through boiling phosphorous trichlo- ride : PC1 3 + O = POC1 3 . Phosphorous Phosphoric trichloride. oxytrichloride. 3. By heating phosphoric chloride with phosphoric anhy- dride : P 2 O 5 + 3PC1 5 = 5POC1 3 . Phosphoric Phosphoric Phosphoric anhydride. chloride. oxytrichloride. 4. It is formed as a secondary product in the preparation of the chlorides of alcohol and acid radicals as above described (p. 112). Reactions. 1. By contact with water it is transformed into hydrochloric and phosphoric acids : POC1 3 + 3OH 2 = POHo 3 + 3HC1. Phosphoric Water. Phosphoric Hydrochloric oxytrichloride. acid. acid. 2. By distillation with the salts of organic acids it yields the cliloracids : + POC1 = 3 {COC1 + PONao *- Soctic Phosphoric Acetylic Sodic acetate. oxytrichloride. chloride. phosphate. COMPOUND OF PHOSPHORUS WITH CHLORINE AND SULPHUR. PHOSPHORIC SULPHOTRICHLORIDE. PS"C1 3 . Molecular weight =169'5. Boils at 128. 114 COMPOUNDS OF PHOSPHORUS. Preparation. By the action of sulphuretted hydrogen upon phosphoric chloride : PC1 SH 2 = PS"C1 3 2HC1. Phosphoric Sulphuretted Phosphoric Hydrochloric chloride. hydrogen. sulphotrichloride. acid. Reaction. When boiled with sodic hydrate, it yields sodic chloride and trisodic sulphophosphate : PS"C1 3 SNaCl Sodic Phosphoric Sodic hydrate. sulphotrichloride. chloride. PS"Nao 3 + 3OH a . Trisodic Water. sulpho- phosphate. COMPOUNDS OF PHOSPHORUS WITH OXYGEN AND HYDROXYL. Phosphorous anhydride... P 2 3 . Phosphoric anhydride ... P 2 O 5 . Hypophosphorous acid . . . POH 2 Ho. Phosphorous acid POHHo 2 . (5)_( O ) [ O COMPOUNDS OF PHOSPHORUS. 115 Phosphoric acid 1 pQHo (tribasic) ... J Metaphosphoric 1 j / t. \ i acid (monobasic)- J ------ Pyrophosphoric acid (tetra- basic) ......... Hexabasic phosphoric acid ......... P 4 7 Nao 6 . Sodium salt (Fleitmann and Henneberg) (Hexasodic tetra- phospliate): ---------- P I0 19 Nao 12 . Dodecabasic phosphoric acid Sodium salt (Fleitmann and Henneberg) (Dodecasodic deca- pJiospTiate): 116 PHOSPHOROUS ACID. PHOSPHOROUS ANHYDRIDE. Molecular weight =110. Preparation. By the slow oxidation of phosphorus in a gentle current of dry air. Reaction. In contact with water it produces phosphorous acid : P 2 3 + 3OH 2 = 2POHHo 2 . Phosphorous Water. Phosphorous anhydride. acid. PHOSPHOROUS ACID, POHHo 2 . Molecular weight = 82. Preparation. 1. By the action of water on phosphorous anhydride as above. 2. By the slow oxidation of phosphorus in moist air. 3. By the action of water upon phosphorous chloride (see p. 111). 4. By passing chlorine through phosphorus under hot water. Reactions. 1. "When heated, it yields phosphoric acid and phosphoretted hydrogen : 4POHHo 3 = 3POHo 3 + PH 3 . Phosphorous Phosphoric Phosphoretted acid. acid. hydrogen. 2 It absorbs oxygen from the air, yielding phosphoric acid : 2POHHo 2 + O 2 = 2POHo 3 . Phosphorous acid. Phosphoric acid. METAPHOSPHORIC ACID. 117 PHOSPHORIC ANHYDRIDE. PA- Molecular weight =142. Preparation. By burning phosphorus in excess of dry air or oxygen. Eeaction. By contact 'with water it forms metaphosphoric acid : P 2 5 + OH 2 = 2P0 2 Ho. Phosphoric Water. Metaphosphoric anhydride. acid. METAPHOSPHORIC ACID. P0 2 Ho. Molecular weight =80. Preparation. 1. By dissolving phosphoric anhydride in water (see above). 2. By heating phosphoric acid to redness POHo 3 = P0 2 Ho + OH 2 . Phosphoric Metaphos- Water. acid. phoric acid. Preparation ofmetapJiospliates. The metaphosphates may be produced 1. By igniting a dihydric phosphate with a fixed base : POHo 2 Nao = P0 2 jSFao + OH 2 . Dihydric sodic Sodic Water, phosphate. metaphosphate. 2. By igniting a monohydric phosphate which contains one atom of a volatile base : POHoNao(N v H 4 0) = P0 2 Nao + NH 3 + OH 2 . Hydrio sodic ammonic Sodic Ammonia. Water. phosphate. metaphosphate. 3. By igniting a dihydric pyrophosphate : P 2 O 3 Ho 2 JN T ao 2 = 2P0 2 Nao + OH 2 . Dihydric disodic Sodic Water, pyrophosphate. metaphosphate. 118 PHOSPHORIC ACID. PYROPHOSPHORIC ACID. P 2 3 Ho, Molecular weight =178. Preparation. By decomposing plumbic pyrophosphate by hydrosulphuric acid : P 2 3 Pbo" 2 + 2SH 2 = 2PbS" + P a O 8 Ho 4 . Plumbic Sulphuretted Plumbic Pyrophosphoric pyrophosphate. hydrogen. sulphide. acid. Pyrophosphates are prepared by heating monohydric phos- phates containing two atoms of a fixed base : 2POHoNao 2 = P 2 3 Nao 4 + OH 2 . Hydric disodic Sodic Water, phosphate. pyrophosphate. PHOSPHORIC ACID, OrtJiopJiospJioric Acid. POHo 3 . Molecular weight =98. Preparation. 1. By boiling a solution of phosphoric anhy- dride or of metaphosphoric acid in water: P 2 5 + 3OH 2 = 2POHo 3 . Phosphoric Water. Phosphoric anhydride. acid. 2. By the oxidation of amorphous phosphorus with nitric acid, and then boiling the product with water. 3. By the action of water upon phosphoric chloride and phosphoric oxytrichloride (see pp. 112 and 113). 4. By the combustion of phosphoretted hydrogen in air or oxygen : PH 3 + 20 2 = POHo 3 . Phosphoretted Phosphoric hydrogen. acid. ARSENIC. 119 5. By decomposing tricalcic diphosphate (bone-ash) with a large excess of sulphuric acid : P a O a Cao" 3 + 3S0 2 Ho 2 + 6OH 2 = 2POHo 3 Tricalcic Sulphuric Water. Phosphoric diphosphate. acid. acid. + 3SHo 4 Cao". Gypsum. Tetrahydric calcic sulphate. Reaction. When heated to 213, it produces pyrophos- phoric acid ; 2POHo 3 = P 2 3 Ho 4 + OH 2 . Phosphoric Pyrophosphoric Water, acid. acid. The phosphates are a numerous and important class of salts. The following list contains some of the most interesting : Common sodic phosphate j PO HoNao 2! 12OH, (Hydnc disodic phosphate) J Trisodic phosphate ' PONao 3 , 12OH 2 . Hydric sodic potassic phosphate POHoNaoKo, OH 2 . Apatite (Francolite) P 3 O 3 Cao"/^Ca" ) Triple phosphate (Diammonic dimagnesic diphosphate) ... Yivianite P 2 Feo" 3 , 8OH 2 . Wavellite . P 4 O('Ar" 2 O 6 ) vi 3 , 12OH 2 . Pyromorphite P 3 3 Pbo"/$l Pb " )' ARSSNIC, As 4 . Atomic iveight =75. Molecular weight =300. Molecular volume \ I I. 1 litre of arsenic vapour weighs 150 criths. Sp.gr. 5-6 to 5'9. Volatile at 180. Atomicity'" and\ Evidence of atomicity : 120 ARSENIURETTED HYDROGEN. Arseniuretted hydrogen As'"H 3 . Arsenious chloride As'"Cl 3 . Tetrethylarsonic chloride As v Et 4 Cl. Occurrence. In nature, in various ores, and sometimes in the free state. In some mineral waters, and in the mud of rivers. Preparation. By reducing, with charcoal, arsenious anhy- dride, which is produced in the roasting of many ores : As 2 3 + 30 = As 2 + SCO. Arsenipus Carbonic anhydride. oxide. COMPOUND OF ARSENIC WITH HYDROGEN. ARSENIURETTED HYDROGEN, Arsenious Hydride. AsH 3 . Molecular weight = 78. Molecular volume I I I. 1 litre weighs 39 critlis. Soils at 40. Preparation. 1'. In the pure state by the action of sulphuric acid on an alloy of arsenic and zinc : As 2 Zn" 3 + 3S0 2 Ho 2 = 3S0 2 Zno" + 2AsH 3 . Arsenioua Sulphuric Zincic Arseniuretted zincide. acid. sulphate. hydrogen. 2. By the action of nascent hydrogen upon soluble arsenic compounds, as by the introduction of arsenious acid into an apparatus evolving hydrogen : AsHo 3 + 3H 2 = AsH 3 + 3OH 2 . Arsenious Arseniurefcted Water, acid, hydrogen. Reactions. 1. "When burnt with free access of air, it gives water and arsenious anhydride : 2AsH 3 + 30 2 = As 2 3 + 3OH a . Arseniuretted Arsenipus Water, hydrogen. anhydride. ARSENIOUS CHLORIDE. 121 2. When burnt with a limited supply of air, it yields water and free arsenic : 4AsH 3 + 30 2 = As 4 + 6OH 2 . Arseniuretted Water, hydrogen. 3. When exposed to a red heat, it is decomposed into arsenic and hydrogen. 4. Passed through a solution of argentic nitrate, it yields a precipitate of metallic silver, arsenious and nitric acids re- maining in solution : 6N0 2 Ago + 3OH 2 + AsH 3 = 6N0 2 Ho Argentic nitrate. Water. Arseniuretted Nitric acid. hydrogen. . + AsHo 3 + 3Ag 2 . Arsenious acid. COMPOUND OF ARSENIC WITH CHLORINE. ARSENIOUS CHLORIDE. AsCl 3 . Molecular weight =181*5. Molecular volume I I I. 1 litre of arsenious chloride vapour weighs 90'75 criths. Sp. gr. 2'205. Soils at 132. Preparation. 1. By the action of dry chlorine upon arse- nic : As 2 + 3C1 2 = 2AsCl 3 . Arsenious chloride. 2. By distilling arsenic with mercuric chloride (corrosive sublimate) : As 2 + 6HgCl 2 = 3'Hg' 2 Cl 2 + 2AsCl 3 . Mercuric Mercurous Arsenious chloride. chloride. chloride. 3. By distilling sodic chloride, arsenious anhydride, and sul- phuric acid : As 2 3 + 6NaCl + 6S0 2 Ho 2 = 2AsCl 3 Arsenious Sodic Sulphuric Arsenious anhydride. chloride. acid. chloride. + 6S0 2 HoNao + 3OH 2 . Hydric sodic Water, sulphate. 122 ARSENIOUS ACID. Reaction. "With excess of water it forms arsenious and hydrochloric acids : AsCl 3 + 3OH 2 = 3HC1 + AsHo 3 . Arsenious Water. Hydrochlo- Arsenious chloride. ric acid. acid. COMPOUNDS OF ARSENIC WITH OXYGEN AND HYDROXYL. Arsenious anhydride As 2 3 . Arsenic anhydride As 2 5 . Arsenious acid AsHo 3 . Arsenic acid AsOHo v ARSENIOUS ANHYDRIDE. As,0, Molecular weight =198. Molecular volume D- 1 litre of arsenious anhydride vapour weighs 198 criths (anomalous). Sp. gr. 3-7. Occurrence. Very rare in nature. Preparation. 1. By burning arsenic in air or oxygen. 2. By roasting arsenical ores in certain metallurgical opera- tions. ARSENIOUS ACID. AsHo 3 . Molecular weight =126. Only known in solution. Arsenious acid forms many salts, of which the following are examples : Dihydric pqtassic arsenite (Fowler's solution) AsHo 2 Ko. Hydric cupric arsenite (Scheele's green) AsHoCuo". Triargentic arsenite AsAgo 3 . ARSENIC ACID. 123 A monobasic arsenious acid, AsOHo, corresponding to ni- trous acid, appears to exist, one of its compounds, AsOAmo, being known. Arsenious acid when boiled with cupric ace- tate yields Schweinfurt green, 3As 2 2 Cuo", Cu(C 2 H 3 2 ) 2 . ARSENIC ANHYDRIDE. As 2 5 . Molecular weight =230. Preparation. By heating arsenic acid nearly to redness : 2AsOHo 3 = 3OH 2 + As 2 5 . Arsenic acid. Water. Arsenic anhydride. ARSENIC ACID. AsOHo 3 . Molecular weiglit = 142. Preparation. By treating arsenious anhydride with nitric acid : As 2 3 + 2N0 2 Ho + 2OH 2 = 2AsOHo 3 + N 2 0,. Arsenious Nitric acid. Water. Arsenic acid. Nitrous anhydride. anhydride. Salts are known derived from acids of the three following formulae : As0 2 Ho, AsOHo 3 , As 2 O 3 Ho 4 , Metarsenic acid. Arsenic acid. Pyrarsenic acid. corresponding corresponding corresponding to to to P0 2 Ho POHo 3 . P 2 3 Ho r Metaphosphoric Phosphoric Pyrophosphoric acid. acid. acid. and N0 2 Ho. Nitric acid. 124 SULPHIDES OF ARSENIC. COMPOUNDS OF ARSENIC WITH SULPHUR AND HYDROSULPHYL. " 'As"S". Sulpharsenious anhydride (Arsenious 1 A _ a" sulphide) .............................. J Sulpharsenic anhydride {Arsenic sul- 1 A _ -@--@ The corresponding baric and strontic chloro-hypochlorites Ba^ C1 and Sr^ 01 , are known. Barium, strontium, and calcium all form soluble dihydric dicarbonates : They are produced by passing an excess of carbonic anhy- dride through solutions of baric, strontic, arid calcic hydrates. The compounds are decomposed at 100, carbonic anhydride being evolved and carbonates precipitated : fCOHo \ Cao" = COCao" + OH 2 + CO 2 . 'COHo Dihydric calcic Calcic Water. Carbonic dicarbonate. carbonate. anhydride. 162 MAGNESIUM. MAGNESIUM, Mg. Atomic weight =24. Probable molecular weight =24. Sp.gr. 1'75. Fuses at a red heat. Volatilizes at a bright-red heat. Atomicity ". Evidence of atomicity : Magnesic chloride Mg"Cl 2 . Magnesic oxide Mg"O. Magnesic hydrate Mg"Ho a . Occurrence. In nature in dolomite, the calcic magnesic di- carbonate, in hrucite or magnesic hydrate, MgHo 2 , and in many minerals containing silicon. Preparation. 1. By electrolyzing fused magnesic chloride. 2. By fusing a mixture of magnesic chloride, potassic chlo- ride, and sodium. Eeactions. 1. It very slowly decomposes water at the ordi- nary temperature, but more rapidly at a boiling heat. 2. It readily burns when heated to redness in the air. Character. Magnesium only forms one compound with oxy- gen, MgO, magnesia. It is obtained by burning magnesium in air, or by heating the carbonate to redness. Magnesic hydrate (MgHo a ) is formed by the action of water upon magnesic oxide, or by precipitating magnesic sulphate by potassic hydrate : S0 2 Mgo" + 2OKH = S0 2 Ko 2 + MgHo 2 - Magnesic Potassic Potassic Maenesic sulphate. hydrate. sulphate. hydrate. It scarcely dissolves in water. Crystallized magnesic sulphate (SOHo 2 Mgo", 6OH 2 ) is pre pared by treating dolomite, the magnesic calcic dicarbonate, with COMPOUNDS OF MAGNESIUM. 163 sulphuric acid, filtering from the nearly insoluble calcic sul- phate, and crystallizing : 2S0 2 Ho 2 = SOHo 2 Cao" Dolomite, calcic magnesic dicarbonate. Sulphuric acid. Dihydric calcic sulphate. SOHo 2 Mgo" Dihydric magnesic sulphate. + 2C0 2 Carbonic anhydride. Magnesic sulphate is very soluble in water, thus differing from the baric, strontic, and calcic sulphates. Magnesic sulphate, when mixed with potassic or ammonic sulphate, forms a disulphate, as, for instance, Mgo". S0 2 Ko S0 2 Ko Dipotassic magnesic disulphate. Many magnesic phosphates are known. Diammonic dimagnesic diphosphate, ^r M g POAmo occurs in the seeds of some of the cereals, and sometimes in urine, and in the form of calculi: it is found in nature as guanite and struvite. Magnesic carbonate (COMgo") is found in nature as mag- nesite. 164 ZINC. MAGNESIA ALBA, Tetrahydric tetramagnesic tricarlonate. r 2 Mgo" 2 C 3 Mgo" 4 Ho 4 , or -< C M g" 2 This compound is formed by boiling a solution of magnesic sulphate with sodic carbonate (Berzelius) : 4SO 2 Mgo" Magnesic sulphate. 4CONao 2 Sodic carbonate. 4S0 2 Nao 2 Sodic sulphate. L 2 Water. h C0 2 . Carbonic anhydride. C 3 Mgo" 4 Ho 4 Magnesia alba. ZINC, Zn. Atomic weight =65. Molecular weight =65. Molecular and atomic volume I I I. 1 litre of zinc vapour weighs 32 '5 criths. Sp. gr. 6'8 to 7'2. Fuses at 500. Distils at a red heat. Atomicity". Evidence of atomicity : Zincic chloride Zn"Cl 2 . Zincic oxide Zn"O. Zincic hydrate Zn"Ho 2 . Occurrence. In nature as oxide (ZnO) in red zinc, as sulphide (ZnS") in the mineral zinc blende, carbonate (COZno") ZINCIC OXIDE. 165 in calamine, and as silicate in electric calamine, williamite, or zinc glass. Manufacture. Zinc blende or calamine is roasted in a current of air, whereby it is converted into zincic oxide : COZno" = ZnO + C0 2 . Zincic carbo- Zincic Carbonic nate (calamine). oxide. anhydride. 2ZnS" + 3O 2 = 2ZnO + 2SO 2 . Zincic sulphide Zincic oxide. Sulphurous (Zinc blende). anhydride. The roasted and powdered mineral is then heated with pow- dered coal, when the zinc is reduced and distils over : ZnO + C = Zn + CO. Zincic Carbonic oxide. oxide. Reactions. 1. It slowly decomposes aqueous vapour at 100: OH 2 + Zn = ZnO + H 2 . Water. Zincic oxide. 2. Zinc is attacked by almost every acid at the common temperature. 3. When boiled in potassic, sodic, or even ammonic hydrate, hydrogen is evolved, and a mixed oxide formed : 2OKH + Zn = ZnKo 2 + H 2 . Potassic Dipotassic hydrate. zincic oxide. COMPOUND OF ZINC WITH OXYGEN. ZINCIC OXIDE. ZnO. Preparation. 1. Zincic oxide is obtained by burning zinc in air. 2. By passing steam over heated zinc. 3. By heating the precipitate formed by ammonic carbonate in solutions of zinc salts. 166 COMPOUNDS OF ZINC. OTHER COMPOUNDS OF ZINC. Zincic hydrate (ZnHo 2 ) is obtained as a white precipitate by the action of potassic hydrate on solutions of zinc salts : S0 2 Zno" Zincic sulphate. 2OKH = ZnHo 2 + S0 2 Ko 2 Potassic Zincic ' Potassic hydrate. hydrate. sulphate. The precipitate is dissolved by excess of potassic hydrate. Crystallized zincic sulphate is isomorphous with crystallized magnesic sulphate, and contains seven molecules of water, six of which are easily expelled at a moderate heat, the last only being driven off at a somewhat high temperature. It also resembles magnesic sulphate in forming double salts with potassic and ammonic sulphates : Zincic sulphate (crystallized) SOHo 2 Zno", 6OH 2 . [SOKo Dipotassic zincic disulphate (crystallized) ^ Zno" , 6OH 2 . I SO 2 Ko Zincic carbonate (CO Zno") occurs in nature as calamme. The precipitate obtained by adding a solution of sodic car- bonate to a solution of a salt of zinc has a variable constitution. The reaction usually takes place thus : fCHo(OZn"Ho) 2 5S0 2 Zno" + 5CONao 2 + 3OH 2 = \ Zno" [CHo(OZn"Ho) 2 Zincic sulphate. Sodic carbonate. Water. + 5SO 2 Nao 2 H Sodic sulphate. Dihydric pentazincic dicarbonate tetrahydrate *. 3C0 2 . Carbonic anhydride. COMPOUNDS OF CADMIUM. 167 CHAPTER XIX. DYAD ELEMENTS. SECTION IV. CADMIUM, Cd. Atomic weight =112. Molecular weight =112. Molecular and atomic volume I I 1. 1 litre of cadmium vapour weighs 56 criths. Sp.gr. 87. Fuses below 260. Easily volatile. Atomicity ". Evidence of atomicity : Cadmic chloride Cd"Cl 2 . Cadmic oxide Cd"O. Occurrence. In nature in small quantities, associated with zinc ; and in the form of sulphide as greenockite. Preparation. By distilling fractionally the more volatile part of the metal obtained in the manufacture of zinc, and then dissolving this more volatile product (which consists of zinc, cadmium, and a little copper) in hydrochloric or dilute sulphuric acid, precipitating the cadmium and copper with sulphuretted hydrogen, dissolving the mixed sulphides in dilute sulphuric acid, and adding an excess of solution of aminonic carbonate, which precipitates both cadmium and copper, but redissolves the latter. The cadmic carbonate is then ignited, and the resulting oxide reduced by charcoal. Cadmic oxide (CdO) is prepared by heating the hydrate, carbonate, or nitrate. Cadmic hydrate (CdHo 2 ) is obtained by precipitating a solu- tion of a cadmic salt by sodic or potassic hydrate. Cadmic sulphate (S0 2 Cdo",4OH 2 ) is obtained by dissolving cadmic oxide or carbonate in sulphuric acid. By heating this compound, or by partially decomposing it with alkaline hydrates, it is transformed into Dicadrnic sulphate dihydrate S0 2 (OCd"Ho) 2 168 COMPOUNDS OF MERCURY. MERCURY, Hg. Atomic weight =200. Molecular weight =200. Molecular and atomic volume \ \ |. 1 litre of mercury vapour weighs 100 criths. Sp. gr. 13'59. Fuses at -40. Soils at 360. Atomicity ", also a pseudo-monad. The following list contains the principal compounds of this metal : Mercurous chloride 1 'jj c ' ni / HgCl (horn-mercury) ... J Mercuric chloride ... HgCl 2 . Mercurous oxide . . . Mercuric oxide HgO. f Mercurous sulphide. . 'Hg' 2 S",or \ Mercuric sulphide 1 (vermilion, cinna- > HgS". *) J Mercurous sulphate, . S0 2 Hg 2 o". Mercuric sulphate ... S0 2 Hgo". Trimercuric sulphate! g-g- (Turpeth mineral). J g 3< COMPOUNDS OF MERCURY. 169 Tetrahydric mercurous dinitrate... N 2 2 Ho 4 Hg 2 o". )NOHg 2 o" Dimercurous dinitrate ... 4 Q (NOHg 2 o" Hexahydric trimercu- j N o 4 Ho.Hg 1 o",. rous tetranitrate . . . J Mercurous dimercuric j N 2 O a Hg,o"Hgo",. dinitrate ........... . J Tetrahydric mercuric | N 0jr Ho 4 Hgo". dinitrate ............ J Tetrahydric dimercu- j N OHo Hgo 2 . ric dinitrate ......... J Dihydric trimercuricj N OH H - dinitrate ............ J / \ Trimercuric carbonate... CHgo"(Hg" 2 O 3 )". @ Tetramercuric carbonate. CHgo y '(Hg" 3 O 4 )". -- -- Mercurosodiammonic *| NH 3 ClHg ) dichloride J NH.ClHg/- 170 COMPOUNDS OF COPPER. Mercurosomercurodi- ammonic dichloride. Mercurammonic chlo- ride. (White preci-\ NH 2 Hg"Cl. pitate.) Trimercuric diamide ... N Hg" 3 . COPPER, Cu. Atomic weight =63'5. Probable molecular weight =63'5. Sp.gr. 8'8. Fuses at about 780. Atomicity' 1 ; also a pseudo -monad. The following are the principal compounds of this metal : Cuprous hydride ......... Cuprous chloride ...... 'Cu' 2 Cl 2 or Cud' Cupric chloride ......... CuCl 2? 2 OH 2 . CuHo Cu Q Cu Cuprous hydrate, 4'Cu' 2 0, OH 2 , or 1 Cu [Cu ICuHo COMPOUNDS OF COPPER. 171 Cupric hydrate CuHo. Cuprous quadrantoxide. Cu Cu' 3. : Cuprous oxide. (Bed copper ore, or ore.) e \ n% I 'Cu' 2 O or | J (o) Cupric oxide CuO. Cuprous sulphide. \ ,Q^, g, f (Copper glance.) ... J Cupric sulphide. (In- "j digo copper or Hue I CuS". copper.) J Cupric sulpho-hydrate. . 5 CuS", CuHo 2 , or CuHo S" Cu." S" Cu" S" Cu" S" Cu" S" CuHo Cupric nitrate "NT) 2 ^ U0 "' Dihydriccupric sulphate SOHo 2 Cuo", 4OH . Hydric tricupric BU!- 1 SOHo(OCu Ho) phate trihydrate ... J i2 172 COMPOUNDS OF COPPER. Dihydric tetracupric "j sulphate tetrahy- I SHo 2 (OCu"Ho) 4 . ite. J x Hydric pentacupric "\ 'sulphate pentahy- [ SHo(OCu"Ho) B ,2OH a . drate J Ammoniocupric sul- - phate. (Dfy* diammonic cuprodi- ammonic sulphate.) Dipotassic cupric disul- ( SO 2 Ko <> Dicupric carbonate. 1 QQ UO " (Mysorin.) ......... J Dicupric carbonate di- j cO(OCu"Ho).,. hydrate. (Malachite.) J COMPOUNDS OF COPPER. Dihydric tricupric dicar- 173 azurite, mountain-Hue f | CHoCuo" or copper-azure.) ...... J Cuprodiainmonic carbo--| nate. (Ammoniocupric I CO ivj y TT 3 ^ u "^ 2 "' carbonate.) := Hydric cupric silicate! S iOHo(OCu"Ho) hydrate. (Dioptase) ] 174 COMPOUNDS OF GOLD. CHAPTER XX. TRIAD ELEMENTS. SECTION II. GOLD, Au 2 . Atomic weight =196*7. Probable molecular weight =393*4. Sp. gr. 19-3 to 19*5. Fuses at about 1100-1200. Atomi- city ' and '". The following are the names and formulse of the chief com- pounds of gold : Aurous chloride AuCl. (AA-(a)" Auric chloride AuCl 3 . @ Aurous iodide Aul. Auric iodide AuI 3 . Aurous oxide Au a O. Auric oxide. (Auric anhy- \ ~ U T . 1 N ^ V/ I Potassic aurate AuOKo, 3OH 2 . Aurous sulphide Au 2 S". fAuS" Auric sulphide ... ... < S" AuS" COMPOUNDS OF ALUMINIUM. 175 CHAPTER XXI. TETEAD ELEMENTS. SECTION II. ALUMINIUM, Al. Atomic weight = 27'5. Molecular weight unknown. Specific gravity 2*6. Fuses at about 450. Atomicity iv , but is always a pseudo-triad. Evidence of atomicity : Analogy with iron and chromium. Annexed are the names and formulae of the .most important compounds of this metal : (cT) (c\\ Aluminic chloride ... 'A1'" C1 6 or \ AlfV (c\\ (c\\ \. 3 (c Aluminic oxide ...... A1 2 O 3 or Aluminic hydrate. | r AlHo 3 (Gibbsite.) ...... } A1 * H * or \ AlHo; C^ C^) ----- <) 176 COMPOUNDS OP ALUMINIUM. Aluminic oxydi- >v hydrate. (Di- I Al 2 2 Ho 2 or j {AIS" AIS"^"' Dipptassic aluminate Al 2 2 Ko 2 or j ^JOKo' Magnetic alumi-l ^ o M - or |^0 2 Mgo". nate. (Spinelle.} J [ Al 5 Aluminic sulphate . . . S 3 O 6 ('Ar" 2 O 6 ) vi ,18OH 2 or SO Aluminic sulphate ~| tetrahydrate. I S0 2 ('Ar" 2 O 2 Ho 4 )",7OH 2 . (Aluminite.) ... ) Allophane SiHo 2 ('Al'" 2 Ho 4 O 2 )", (2 or 4)OH : Prehnite Si 3 Ho 2 Cao 2 "('Al'" 2 B ) vi . / f'Al'V Zoisite Si 4 Cao" 3 ( i O V l'Al'" a ( Spodumene Si 15 15 Lio 6 ('A1'" 2 O 6 ) vi 4 . Petalite Si 30 O 45 N a o 2 Lio 4 ('Al'" 2 6 ) Vi 4 . COMPOUNDS OF ALUMINIUM. 177 SOHoKo,, Alunite, alum-1 SOHo stone . K . L Collyrite. Pig. 2.... SiHo 2 ('Al'" 2 Ho 5 0) 2 ,4OH 2 . Dipotassic alumi- ^ gQ j nic tetrasul- SO 2 r o ^ phate. (Common f SO 2 - ( A1 ^ U ^ alum.) Fig. 3. J SO 2 Ko Worthite. Fig. 4... Miloschine. Fig. 5. SiHo 2 ('Al'" 2 Ho. 4 O 2 )". Porcelain clay of) SiHo 2 ,, A1 ,,, -rr o Vr Passau. Pi.6.J SiHo 2 ^ ! ^OJ Pig. Cimolite, kaolin of) N - n 3 Ellenbogen. \ ^ Pig. 7 ............. -' SiHo 3 I SiOHo , csn i Agalmatolite. Pig. 8. SiOHo J Buchholzite, xeno- 1 ^('Al'" 2 O 6 ) vi lite. Pig. 9. ...J |i('Al'" 2 6 )vi. T, 1-1 fSiHo , Porcelain clay. He. 10. ] -"- v ^" 2J Andalusite, chias- "j tolite, cyanite, I JO , , o y/ m TJ -IT r 5>*w( iiJ. 2 v/ 4> ; fibrolite, sillima- [ nite. Pig. 11. J Wernerite. Pig. 12. Si 2 Cao"('Al'" a O 6 ) vi . i5 178 PLATINUM. Saponite. Fig. 13. Si 7 Mgo" 6 Ho 10 ('Al'" 2 O 6 ) vi . Lepidolite. Fig. 14. Si 9 O 8 Ko 2 Lio t ('Ar" 2 6 ) ri 2 ('Al'" 2 F 4 O 2 )". SiHo 2 Nao O es Analcime. Fig. 15. } sj('Al'" 2 O 6 ) vi . O SiHoNao Eazoumoffskin. i aiEo^'M" O V Kg- 16 J 5 Jl UJ ' Malthacite. Fig. 17. Si 8 O u Ho 4 ('Ar" 2 O 6 )". SiONao , SiO Albite. Fig. 18. ... L f :i('Ar,0 6 )*. io i0 ~ "I [SiO 1 I SiONao ' CHAPTER XXII. TETRAD ELEMENTS. SECTION III. PLATINUM, Ft. Atomic weight =197*4. Molecular weight unknown. 8p.gr. 21 '5. Atomicity" and' 1 ". To faff page- 1'/ COMPOUNDS OP PLATINUM. 179 The following compounds will serve to illustrate the ato- micity and general character of this metal : V X (C?H^ 6 Platinous chloride . . . PtCl 2 . Platinic chloride . . . PtCl 4 - Platinous oxide PtO. Platinic oxide Pt0 2 . Platinous hydrate . . . PtHo 2 . Platinic hydrate PtHo 4 . -"($ M) Platinosodiammo- . rWTTni nic dichloride. |NH 3 C1 (JX' .,'/ (Green salt off [NH 3 C1 / \ / X ) Magnus.) J Q ('n) White compound of ( Eeiset \W' lNH a l ^-1^1 %^ (^ ^ 180 LEAD. Platoso-diammon di- fNH 2 (N v H 4 )Ho ammonium dihy- -j Pt" drate . <) /* T^TTT Diplatosammonic ox- I _ , sn .-, 1 Pt " O. ide .................. }NH J (> & Platinous sulphide . . . PtS". Platinic sulphide ... PtS" 2 . CHAPTER XXIII. TETEAD ELEMENTS. SECTION IY. LEAD, Pb. Atomic weight =207. Molecular iveiglit unknown. $p. gr. 11-445. Fuses at 335. Soils at a white heat. Ato- micity " and 1Y . Also sometimes pseudo-triatomic. The following list contains the names and formulas of the most interesting compounds of this metal : Plumbic chloride ... PbCl 2 . COMPOUNDS OF LEAD, 181 i O. Plumbic oxide. 1 {Litharge.) ...... J Plumbic peroxide. 1 (Plattnerite.) ... J Diplumbic tri oxide Tri plumbic \ rS X tetroxide J ^3 PbPbo" . X ' ' : Tetraplumbic | pbpb() ,, (pb ,, Q y , pentoxide J Plumbic chlorohy- drate Plumbic hydrate ... PbHo a - Diplumbic drate O PbHo Diplumbic oxydichlo- J Q ride. (MatlocMte.) [pbCl 182 COMPOUNDS OF LEAD. Triplumbic oxydi- chloride. ( Mendi- pite.) . Diplumbic oxychlo-j bH rohydrate ......... [ Octoplumbic hept- 1 p, Q oxydichloride . . . J ^K5)-(^---(^-(^--- Plumbic sulphide. 1 pbS" (Galena.) J , , ,. fPbOl Diplumbic sulphodi- I chloride ( Pbci Plumbic sulphate. 1 Q p, (Lead vitriol.) J CNO Plumbic dinitrite ... -j Pbo". [NO Plumbic nitrite hy- j NO( p b HoO ). drate J Diplumbic nitrite- j N p bo (Pb H oO) . hydrate J , Xi)- COMPOUNDS OF LEAD. 183 fN0 2 Plumbic dinitrate . .. Pbo NO "' Dihydric diplum- bic nitrate hy- drate . NOHoPbo "- NHo 2 Pbo"(PbHoO). ----( Y$) Dihydric diplumbic nitrate nitrite. I p^ " (Basic hyponitrate I ]\fQ o/ 1 lead.) ............ Plumbic carbonate ^ (Lead spar, white > COPbo". lead ore.) J 184 COMPOUNDS OF LEAD. Triplumbic dihy- 1 CO(OPbHo) p , drate dicarbonate J CO(OPbHo) r ' H >-( O V- PbW W C V-f W Pb W O V-f C V-f O WPbW O Dihydric triplum- 1 CHoPbo"p, bic dicarbonate J CHoPbo" 7 v Diplumbie sul- phate carbonate. (Lanarkite.) . . . co . Pbo" 2 . = Tetraplumbic tri- \ QQ 1 carbonate sul- CO phate. (Lead- | CO Ullite.) J S0 viy -0--(o Diplumbie chromate. CrOPbo" 2 . Triplumbic di- f^ r 9 Pb "^ ^ x Pbo O. chromate . . . | CrOPW u Dipotassic plumbate ... COMPOUNDS OF CHROMIUM. 185 CHAPTER XXIV. HEXAD ELEMENTS. SECTION IV. CHEOMIUM, Cr. Atomic weight =52*5. Molecular weight unknown. Sp. gr. 6. Atomicity ", iv , and VI ; also a pseudo-triad (and a pseud-octad) . Evidence of atomicity : See the annexed compounds. The following are the most important compounds of this metal : Chromous chloride CrCl . Chromic chloride ... ! Q Qi 3 . ~ Cr ) ( Cr ) ( Cl Chromic perfluoride. CrF 6 . (c*Y 0/ Chromous oxide CrO. Chromous hydrate . . . CrHo 2 . f Chromic oxide j CrO' 186 COMPOUNDS OP CHROMIUM. Chromous dichromic f tetroxide ............ I ~H Dichromic ferrous ~\ tetroxide. f CrO p (Chrome iron f 1 CrO ' 0= ore.) J Chromic dioxide Cr O 2 . Chromic anhydride. Cr0 3 . Dipotassic chro- > mate. (Normal potassic ckro-\ mate.) J Dipotassic dichro- i CrO Ko mate. (Potassic \ O bichromate.) [ Cr0 2 Ko Cr0 2 Ko Dipotassic trichromate. J CrO (Potassic terchromate.) \ O t,Cr0 2 Ko = v^ \^f 7)-0_0_0_0_(o Pig. 4. Pie', b COMPOUNDS OP CHROMIUM. 187 Dipotassic cliromous ] disulphate. Fig. 1. i S0 2 Ko n ,, SOKo Cl Cr0 2 Pbo". Tetrapotassic dichro- mosulphate.Fig.8.... | CrOKo-O 2 J Dipotassic dichromic -\ gQ j tetrasulphate. I SO* I , o , vi (Pota88ium chrome \ SO - ^, Cr ^^ alum.) Fig. 3 ....... J SO 2 KoJ Dichromic hexani- ) n ( , r , o Vv trate. Fig. 4 ....... j W eO 13 (< r 2 O 6 ) . Octochromic carbo- nate dihydrate. Fig. 5 ................ Plumbic chromate. (Red lead ore, crocoisite.) Fig. 6. Sulphochromic acid. fSO Ho (Dihydric sulphate < O chromate.) Fig. 7. ... I CrO 2 Ho Chromic hydrate . . j Perchromic acid 188 COMPOUNDS OF MANGANESE. n Potassic chlorochro- mate nilr (JiJlo. Chromic dichlorodi- "j oxide. (Chloro- I Cr0 2 Cl 2 . -- chromic acid.} J JX Chromous sulphide.... CrS". Dichromic trisul- f CrS", phide |CrS" b Sulphochromic anhy- ) c dride .. J 3 ' MANGANESE, Mn. Atomic weight =55. Molecular weight unknown. Sp. gr. 7' to 8. Atomicity ", iv , w^/ vi ; /50 pseudo-triad and a pseud-octad. Evidence of atomicity : Manganic perfluoride Mn vi F 6 . Analogy with chromium. The following are some of the more important compounds of this element : Manganous chloride. MnCl 2 . Manganic chloride . . . Mn Cl r Dimanganic hexa- J MnCl 3 chloride \ MnCl 3 * Manganous hydrate . MnHo 2 . -0--~ COMPOUNDS OF MANGANESE. 189 Manganous oxide ... MnO. Trimanganic tetr- | MnO^ oxide. (Hausma- \ Mn Q = mto.) Manganous diman- j MnO Mn() ,, anic tetroxide ... I MnO ' Dimanganic trioxide. f (Braunite.) I MnO Dimanganic dioxydi- OHo hydrate. (Manga- j fMnO-O n Tarvicite ............ \ Mno" (Mn iv Ho" 2 ) . [MnO-0 J Manganic oxide. 1 (Pyrolusite.) ...... J Manganous diman- -\ ganic tetroxide di- I Mnllo hydrate. (Psilome- lane, Hartmangan?) ___ M ,, M ^ vc/\ ^) @-~ Dipotassic manganate Mn0 2 Ko 2 . -()-~~ 190 COMPOUNDS OF MANGANESE. Dipotassic per- j f Mn0 2 (OKo) manganate J \ MnO 2 (OKo)' Manganous sul- phide. (Man- [ MnS. MnK S ,, o) Disulphopotassic trimanganous disulphide Manganous carbo- nate. (^Manga- nese spar.) Dihydric manga- 1 nous sulphate... J Dipotassic nianga- 1 nous disulphate J Aluminic manga- ^j nous tetrasul- I phate. (Manga- nese aluminium alum.) j Dirnanganic trisul- 1 phate j Dipotassic diman-"l ganic tetrasul- I phate. (Potas- V siu/ni manganese | Mn g , COMno". SOHo 2 Mno",(3, 4 or 6OH 2 ). S0 2 , Mno"' 7 ( / Ar" 2 6 ) vi ,24OH 2 . S0 2 J SO , S0 2 -('Mn'" 2 6 )-. SO 2 J SO 2 Ko-i In 2 (!'Mn'" a 6 r,240H 2 . S0 2 , S0 2 KoJ COMPOUNDS OF MANGANESE. Dihydricdimanga-j p o H Mno ;,. nous dipnospnate J Manganous sili- cate. (Silicife- rous manganese, red manganese, ) SiOMno". rotfier Mangan- I kiesel, Rotli- braunsteinerz.) ) Dimanganous sili- cate. (TepliTO- ite.) Dihydric dinianga- ] nic silicate dihy- drate. (Scliwar- zer Manqanlcie- 7 Hexmanganic mo- nosilicate. (He- \ Si('Mn'" O u ) iT . terocline.) 1-91 SiMno" SiHo 2 (OMnHo) 2 . Trilucinic tetraman- (^ f ganous trisilicate I M . no ", ; /f^, 11 " ' ' SiGrc" I Mno' sulphide. (Hel- F no / n\ iG f ( 1 1' ,_ ) ' Mno \ ! Mn O/ Aluminic manganous J * ^~), ,,, . disilicate | SJ ( , Ai 2 6)V1 ' * COMPOUNDS OF IRON. IRON, Fe. Atomic weight =56. Molecular iveight unknown. Sp. gr. 7*8. Atomicity ", iv , and vi . Evidence of atomicity : Analogy with chromium. The following is a list of the chief compounds of iron : Ferrous chloride ... FeCl 2 . Ferric chloride . Ferrous oxide Fe . Ferrous hydrate FeHo 2 . Ferric oxide. (Red h&matite, micace- ous iron, oligist, \ p e / : \O. specular iron or iron glance.) Diferric hexahydrate. J FeHo 3 FeHo; Tetraferric trioxy- hexahydrate.((7 FeS" 2 . martial pyrites.) ) -- 194 COMPOUNDS OF IRON. f FeS" Diferric trisulphide j " Diferric dicupric te- trasulphide. (Cop- j p^(Cu 2 S" 2 )''- per pyrites.) Diferric hexani- trate. Fig. 1 ... Hexahydric di- -\ ferric diphos- I P H o 6 ('Fe'" 2 Ho 2 O 4 ) iv . phate dihydrate. | > J Ferrous sulphate. lg- o ............ . ,. fS0 2 Ko Dipotassic ferrous di- I -p eo 2 " 6QH sulphate. Pig. 4. [ S0 2 Ko'. Diferric trisul- ^ SO 2 | phate. (Coquim- I SO 2 -(Te'" 2 6 ) vi ,9OH 2 . bite.) Tig. 5. ) s 2 Dipotassic diferric^ S0 2 Ko tetrasulphate. I SO- (Fe '" o.)*24OH,. (Potassium iron Pi- 6. Tetraferric sul- V SO (Te'" 4 O 7 )",6OH a . phate. Fig. 7. J Tetrahydric tetra-^. ferric sulphate | octohydrate. > SHo 4 (Te'" 4 OHo 8 O 2 )". (Vitriol ochre) I Fig.8 ............ J KH oH s Ho WreWoH* HoHK COMPOUNDS OF COBALT. aferric octo- \ phide. (Mag- > 'ic pyrites.) ... J Heptaferric octo- sulphide. netic pyrite Fe 7 S" 8 . Ferrous carbonate, "j (Spathic iron I COFeo". ore.) ) fNO Ferrous nitrate ...... { Feo". lNO r 195 COBALT, Co. Atomic weight = 58'8. Molecular weight unknown. Sp.gr. 8'5. Atomicity ", iv , and ^ ? also pseudo-triatomic. For evidence of the atomicity of cobalt see the following list of the chief compounds of this metal : Cobaltous chloride CoCl 2 . Cobaltic chloride {coCr Cobaltous oxide .. CoO. Cobaltic oxide Cobaltous dicobaltic f CoO tetroxide \ CoO ; hept- ) Coo". Hexacobaltic hept- oxide -- 0=0 196 COMPOUNDS OF COBALT Cobaltous hydrate CoHo 2 . Cobaltic oxy-dihydrate j Cobaltous sulphide .%... CoS". Cobaltic sulphide. (Cobalt f CoS" g ,, pyrites?) 1 CoS" Dipotassic cobaltous disul- } SO Ko i TI- r phate. Fig. 1 J Dihydric pentacobaltous ] ^-p- /nr , ,. , , , CHo(OCo 2p " dicarbonatetetrahydrate. > CHo(OCo"Ho ; ) ' .Kg. a J Dicobaltous carbonate di- 1 r*f\/r\n "TT \ L v^UfUCo Ho).,, hydrate. Tig. 3 J Dipotassic cobaltous dicar- 1 COKo^ i/ bonate. Kg. 4 J COKo C< ' fNH 4 Cobaltoso-diammon-diammo- I p 2 nic dichloride. Fig. 5. ... " Dicobaltic hexammon-hexam- f Co-NH 2 (NvH 4 )Cl monic hexachloride. (!M- \ TXTH flY v R 4; !rr teo-cobalt chloride?) Fig. 6. I Co NH 2 (N V H 4 )C1 Dicobaltic tetrammon-hexam- f Co-NH 2 (]N" V H 4 ) Cl monic hexachloride. (Ro- J NH 3 C1 1 T\TTT C*\ seo-cobalt or purpureo-colalt \ M-TT/TVTVTT \m chloride.) Fig. 7 I C 3 -WH 2 (J H 4 )C INTO Cobaltous dinitrate JJjyCoo",6OH 2 . Tb fa* vage. 196. COMPOUNDS OF NICKEL. Cobaltic disulphide CoS 2 . 197 Dicobaltous oxysulphide Co Co OS". Dihydric cobaltous sulphate.. SOHo 2 Coo",6OH 2 . NICKEL, Ni. Atomic weight =58*8. Molecular weight unknown. Sp. yr. 8'7. Atomicity ", iv , and " ? Trimethylated methyl. (Molecule.) CLASSIFICATION OF ORGANIC COMPOUNDS. The most important organic compounds can be conveniently divided into the following twelve families : 1. Organic radicals. 2. Hydrides of organic radicals. 3. Alcohols. 4. Ethers. 5. Haloid ethers. 6. Aldehydes. 7. Acids. 8. Anhydrides. 9. Ketones. 10. Ethereal salts. 11. Organic compounds containing triad or pentad nitrogen. 12. Organo-metallic bodies. MONAD BASYLOUS RADICALS. 207 CHAPTER XXVI. ORGANIC RADICALS. This family of organic compounds is divided into two classes : Class I. Basylous or positive radicals. Class II. Chlorous or negative radicals. CLASS I. BASYLOVS OR POSITIVE RADICALS. Monads. Methyl or (CJ3 2n+1 ) 2 Series. Vinyl or (C M H 2n _i) 2 Series. Phenyl or (C n H 2/l _ 7 ) 2 Series. Dyads. Ethylene or C n H 2n Series. Acetylene or C M H 2n _ 2 Series. Phenylene or C n H 2n _ 8 Series. Triads. Glyceryl or (CJH^O"^ Series. CLASS I. BASYLOUS RADICALS. MONADS. METHYL or (C M H 2n+1 ) 2 SERIES. These radicals are divided into three sections, viz. Normal, Secondary, and Tertiary : General formula. 1. Normal Eadicals 208 ORGANIC RADICALS. * General formube. 2. Secondary Radicals { C(C H^IT 3. Tertiary Eadicals . In the first of the above formula? n may =0, but in the others it must be a positive integer. Examples of the secondary and tertiary series of radicals may be seen in the secondary and tertiary fatty acids. They have not yet been isolated. It is evident that, besides the three series of radicals shown above, three other series, containing, in the same molecule, normal and secondary, normal and tertiary, and secondary and tertiary radicals, may exist ; but up to the present time they have not been obtained. 1. Normal Radicals. This series contains the radicals of the methylic series of alcohols. These radicals also enter into the composition of the normal series of fatty acids. The following list contains all the radicals of this section that have been hitherto obtained : Boiling- points. Methyl I M ' or I CH 3 not known. fCH 3 E %> jit' or {S' or cl: about-23. ^ {pr'-fcEti;'- cl + 68 CH CH CH CH CH NORMAL MONAD RADICALS. 209 Boiling- points. Butyl JBu n JCPrH 2 V -r> , OP "\ r*-n TT 119 Amyl \ Bu' \ CPrH 2 ' f Ay f CBuH 2 i A , OP i *NT) TT 159. Caproyl \ Ay' \ CBuH 2 ' f Cp J CAyH 2 < r* OF 1 J~ A J TT 202 \Cp' \CAyH 2 Preparation. 1. By the action of zinc on the iodides of the normal radicals : 2C( C>1 H 2 ,, +1 )I + Zn = Znl, + Part of the liberated radical is at the same time decomposed into the hydride of the radical and the corresponding dyad radical : f C(C M H 2M+ i)H a f C(C n H 2/l+1 )H 2 , rnrr TT \ C(C n H 2n+1 )H 2 { H L^(^n-ti A remarkable special method for preparing ethyl consists in exposing mercury and ethylic iodide to the influence of sun- light: 2EtI + Hg = HgT 2 + Et 2 . Ethylic Mercuric Ethyl, iodide. iodide. 2. By the electrolysis of the salts of the normal fatty acids. In this process nascent oxygen acts upon the fatty acid, con- verting its oxaty] into carbonic anhydride, the positive radical being set free : 2 fC(C,,H 2) , +l )H, fO(C.H kH )H, 2 ICOHo |C(CH 2n+1 )H 2 Fatty acid. Eadical. + 2C0 2 + OH 2 . Carbonic Water, anhydride. 3. By acting with zinc upon the iodides of two radicals simul- taneously, the so-called double or mixed radicals are produced: Mel 4- EtI + Zn = Znl a + | ^ fc e . Methylic Ethylic Zincic Methyl iodide. iodide. iodide. ethyl. 210 ORGANIC RADICALS. ETHYL. f CMeH 2 \ CMeH 2 * Molecular weight =58. Molecular volume \ I I. 1 litre of ethyl gas weighs 29 criths. Soils at about 23 C. Preparation. By digesting together at 120 ethylic iodide and zinc, the reaction being exactly similar to that between hydriodic acid and zinc : Zn + 2HI = ZnI 2 + Hydriodic acid. Zincic iodide. Zn + 2EtI = ZnL Ethylic iodide. Zincic iodide. H ydrogen. Et Ethyl. VINYL SERIES. General formula... ( n2n _ 1 The first member of this series vinyl has not yet been isolated. ALLYL. C 3 H rC(CMe"H)H 2 C 3 H 5 01 \ C(CMe"H)H 2 ' Molecular weight =82. Molecular volume II I. 1 litre of allyl vapour weighs 41 criths. Sp. gr. 0'684. Soils at 59. PHENYL SERIES OF RADICALS. 211 Preparation. By digesting allylic iodide with sodium, and then distilling : Na 2 + 2C(CMe"H)H 2 I = + 2NaI. Allylic iodide. Allyl. Sodic iodide. Character . Bromine and iodine unite directly with allyl, producing allylic tetrabromide and tetriodide. In these com- pounds the molecule of allyl plays the part of a tetrad radical. In allylic tetrabromide, four latent carbon bonds in the mole- cule of allyl have become active, and are united with four atoms of bromine : f C(CMe"H)H 2 -p, f C[C(CH Br)BrH]H 2 \ C(CMe"H)H 2 Br4 \ C[C(CH;Br)BrH]H; Allyl. Allylic tetrabromide. An analogous case is met with in ferric chloride, where two tetrad atoms, united by one bond of each, become together hexa- tomic : {%** Allylic monobromide can only be obtained by the action of phosphorous tribromide on allylic alcohol : 3C(CMe"H)H 2 Ho -f PBr 3 = 3C(CMe"H)H 2 Br Allylic alcohol. Phosphorous Allylic monobromide. tribromide. + POHHo 2 . Phosphorous acid. PRENTL SEEIES. General formula... { Sp n 5 2M ~ 7 S 2 . I C(C n -U 2n _ 7 )H 2 These radicals are but very imperfectly known, phenyl alone having been investigated. 212 ORGANIC RADICALS. PHENYL. fC(C 5 H 3 )H 2 C(C 5 H 3 )H; Molecular weight =154. Molecular volume \ \ I. 1 litre of phenyl vapour weighs 77 criths. Fuses at 70. Soils at 240. Preparation. By the action of sodium on phenylic bro- mide : 2C(C 5 H 3 )H 2 Br + Phenylic bromide. Phenyl. Sodic bromide. Reaction. By treatment with bromine, pheuyl produces bromphenyl and hydrobromic acid : fC(C 5 H 3 )H a rC(C f H 3 )HBr 9HB \C(CXX 4 \C(C 5 H 3 )HBr + 2HBr " Phenyl. Bromphen)'!. Hydrobromic acid. CHAPTER XXVII. BASYLOITS RADICALS. DYADS. ETHYLENE or C M H 2n SERIES. Preparation. These compounds are produced as follows : 1. In many cases of destructive distillation, where, however, the reaction cannot be traced. ETHYLENE SERIES. 213 2. By the abstraction of the elements of water from the normal monacid alcohols of the methylic series, as for in- tance: f CH 3 f CH ftTT |CH:HO = {CH; + OH >- Ethylic alcohol. Ethylene. Water. 3. By passing the vapours of the haloid compounds of the nor- mal monad radicals of the C n H 2w+ i series over heated lime, thus : 3 _ CH 2 , CHC1 CH Ethylic Ethylene. Hydrochloric chloride. acid. 4. By the transformation of the monad radicals at the mo- ment of liberation from their compounds, when they split into dyad radicals and the hydrides of monad radicals : fC(CH 3 )H 3 . ,,fOH, |CH 3 1 C(CH 3 )H 2 1 CH 2 t CH; Ethyl. Ethylene. Ethylic hydride. 5. By the action of the iodide of a monad radical on the sodium compound of a monad radical : CH 3 f CH 3 ^ T , f CH 2 f CH 3 3 + JCH 2 Ethylic Sodic Sodic Ethylene. Ethylic iodide. ethide. iodide. hydride. Character. The lower members of this series of dyad radicals are gaseous, the higher solid, and the intermediate ones liquid. The following list includes the known dyad radicals of this series, together with their fusing- and boiling-points : Fusing- Boiling- point. point. Ethylene ........................ C 2 H 4 ...... - Propylene ........................ C 3 H 6 ...... -- 17'8 Butylene ........................ C 4 H 8 ...... - - -f-35'0 Amylene ........................ C 3 H 10 ...... 55'0 Hexylene ........................ C fi H 12 ...... - 39'0 Heptylene or OEnanthylene... C 7 H U ...... - 55'0 Octylene or Caprylene ......... C 8 H 16 ...... - 95'0 214 ORGANIC RADICALS. Fusing- Boiling- point. point. Nonylene ........................ C 9 H 18 ...... -- 125 Paramylene ..................... C 10 H 20 ...... -- Cetene ........................... C 16 H 32 ...... - Cerotene ........................ C 27 H 54 ...... 57 275 Melene ........................... C 30 H 60 ...... 62 375. Reactions. 1. The dyad radicals of this series all unite directly with chlorine, bromine, and iodine, producing com- pounds which, in the case of ethylene, are represented by JCH 2 C1 JCH 2 Br f CH 2 I \CH 2 C1 t CH 2 Br [CH 2 r Ethylenic Ethylenic Ethylenic dichloride. dibromide. diiodide. These compounds, when treated with alcoholic solution of potassic hydrate, furnish one molecule of a hydracid, thus : f CH Cl , TT-TT TT^ II f CHC1 ^ \CH 2 C1 GH Ethylenic Potassic Potassic Vinylic chloride, Water. dichloride. hydrate. chloride. or chlorinated ethylene. The monochlorinated radical thus obtained again unites with two atoms of chlorine, producing chlorinated ethylenic dichlo- ride, JCHCICI \CH 2 C1 ' which, by further treatment with alcoholic potash, yields dichlo- rinated ethylene ; and so, by alternate treatments with chlorine and potassic hydrate, ethylene becomes transformed into tetra- chlorinated ethylene. The following formulae show the first, intermediate, and final compounds : JCH 2 J"CH 2 C1 JCHC1 fCHClCl f CHC1 \CH 2 \CH 2 C1 \CH 2 \CH 2 C1 \ CHC1 J CHC1C1 f CC1 2 f CCLC1 J CC1 2 \CHC1C1 \CHC1 \CHC1C1 \CCV ETHYLENE AND ETHYLIDENE. 215 Tetrachlorinated ethylene absorbs two additional atoms of chlorine, producing the solid dicarbonic hexachloride : /CC1 3 . \CC1 3 Dicarbonic hexachloride. 2. The dyad radicals of the ethylene series can be transformed into the monad radicals from which they are derived. If ethylene be digested with hydriodic acid for 50 hours at 100 C., it is transformed into ethylic iodide : TTT J CH 3 + HI = icBfr Ethylene. Hydriodic Ethylic acid. iodide. From this, ethyl may be prepared, as shown at p. 210. Isomerism of ethylene and ethylidene compounds. The chlorides of the dyad radicals are isomeric : 1. With the chlorides of the monochlorinated normal monad radicals. 2. With the chlorides derived from the aldehydes, w r hich, however, are identical with the chlorides of the monochlorinated normal monad radicals : fCH 2 ci |CH 3 rcH 3 \CH 2 C1 \CHC1 2 \CHCy Ethylenic Ethylidenic dichlo- Monochlorinated dichloride. ride (obtained from ethylic chloride. aldehyde.) These substances, when treated with alcoholic potash, all yield the same vinylic chloride : f CH C1 ICH'CI + Ethylenic Potassic Vinylic Water. Potassic dichloride. hydrate. chloride. chloride. Monochlorinated Potassic Vinylic Water. Potassic ethylic chloride, or hydrate. chloride. chloride. Ethylidenic dichlo- ride. But certain compounds of ethylene yield paralactic acid, 216 ORGANIC RADICALS. whilst the corresponding compounds of ethylidene give lactic acid. The boiling-points of their chlorides also differ, ethy- lenic dichloride boiling at 85, whilst ethylidenic dichloride boils at 64 ; on the other hand, ethylenic oxide boils at 13-5, whilst ethylidenic oxide (aldehyde) boils at 20. The oxides of the dyad radicals are isomeric 1. With the corresponding aldehydes. 2. With the alcohols of the vinylic or C M H 2n _iHo series. The nature of this isomerism is seen from the following for- mulae : JCH 20 fCH, ,,JCH 2 \CH 2 U ICOH \CHHo- Ethylenic Acetic Vinylic oxide. aldehyde. alcohol. ETHYLENE. {Si:- --- \-J Molecular weight =28. Molecular volume \ \ I. 1 litre weighs 14 criths. Preparation. See general methods (p. 213). Reactions. 1. Decomposed into carbon and marsh-gas by passing through a red-hot tube : Ethylene. Marsh- gas. 2. Burns in chlorine with deposition of carbon : "{cl 2 + 2Cl < = c * + 4HC1 - Ethylene. Hydrochloric acid. Ethylidene, the isomer of ethylene, has not yet been isolated, ACETYLENE. 217 unless the hydrocarbon C 2 H 4 derived from the transformation of ethyl be this body. The formula of ethylidene is doubtless CH 3 "OH' ACETYLENE or C M H 2 ,,_ 2 SERIES. Acetylene is the only radical belonging to this series which is well known. The series comprises the following members : Acetylene C H 2 . Allylene c" 8 H 4 - Crotonylene Cyi 6 . These radicals stand in the same relation to the alcohols of the vinylic series as ethylene bears to ethylic alcohol. They are also probably capable of assuming tetrad functions. ACETYLENE. ,,, r , p f "CH C 2 H 2 orj,, CH . Molecular weight =26. Molecular volume \ \ I. 1 litre weighs 13 criths. Preparation. 1. By synthesis from its elements. When an electric arc from a powerful voltaic battery passes between car- bon poles in an atmosphere of hydrogen, acetylene is produced. 2. By the action of water on potassic carbide : C 2 K 2 + 2OH 2 = C 2 H 2 + 2KHo. Potassic Water. Acetylene. Potassic carbide. hydrate. 218 ORGANIC RADICALS. 3. By the action of heat upon olefiant gas or the vapours of alcohol, ether, or wood-spirit, or by passing induction sparks through marsh-gas : = C 2 H 2 3H 2 . 2CH 4 Marsh-gas. Acetylene. 4. By heating the vapour of methylic chloride to low red- ness : 2CH 3 C1 = Methylic chloride. C 2 H 2 Acetylene. 2HC1 Hydrochloric acid. H 2 . 5. By passing the vapour of chloroform over ignited copper: 2CHC1 3 Chloroform. Cu C 2 H 2 Acetylene. 3'Cu' 2 Cl 2 . Cuprous chloride. 6. By the action of calcic carbide upon water : C 2 Ca" Calcic carbide. 20H 2 = Water. C 2 H 2 Acetylene. CaHo 2 . Calcic hydrate. 7. From vinylic bromide, one of the derivatives of ethylene, acetylene may be obtained by the action of alcoholic potash : C 2 H 3 Br + KHo = C 2 H 2 + KBr + OH 2 . Vinylio bromide. Potassic hydrate. 22 Acetylene. Potassic bromide. Water. 8. By the incomplete combustion of bodies containing car- bon and hydrogen : 3O 2 4CH 4 Marsh-gas. 2C 2 H 4 Olefiant gas. = 2C 2 H 2 Acetylene. 2C 2 H 2 Acetylene. 60H 2 : Water. 20H 2 . Water. The crude acetylene, obtained by any of these processes, is best purified by passing it through an ammoniacal solution of cuprous chloride, with which it -forms a red precipitate con- taining X O COMPOUNDS OF ACETYLENE. 219 C 2 'Cu' 2 H 2'Cu' 2 Cl a + 2C 2 H 2 + OH 2 = 40 + 4HC1. , C 2 'Cu' 2 H Cuprous Acetylene. Cuprosovinylic Hydrochloric chloride. ether. (Acetylide acid of copper.) If ethylene have been present in the crude acetylene, the liquid containing the red precipitate is next heated to boiling, in order to decompose a compound which ethylene forms with copper. The cuprosovinylic ether is then collected upon a filter and washed. On heating cuprosovinylic ether with hydrochloric acid, pure acetylene is evolved : O + 4HC1 = 2C H + 2'Cu' 2 Cl 2 + OH.,. [C 2 'Cu' 2 H Cuprosovinylic Hydrochloric Acetylene. Cuprous Water. ether. (Acetylide acid. chloride. of copper.) Reactions. 1. When cuprosovinylic ether is heated with zinc and dilute ammonia, the nascent hydrogen evolved by the action of the zinc upon the ammonia unites with acetylene, producing ethylene : rc 2 'Cu' 2 H ^O + 2H 2 = 2C,H 2 + 4Cu + OH. 2 ; ( c;cu' 2 H Cuprosovinylic Acetylene. Water. ether. Acetylene. Ethylene. 2. Acetylene is absorbed by sulphuric acid, producing vinyl- sulphuric acid : C 2 H 2 + S0 2 Ho 2 = S0 2 (C 2 H 3 0)Ho. Acetylene. Sulphuric Vinyl-sulphuric acid. acid. 3. Acetylene unites with bromine, forming acetylenic dibro- mide : '"C'H 2 + Br 2 = "C" 2 H 2 Br 2 . Acetylene. Acetylenic dibromide. L2 220 ORGANIC RADICALS. BROMACETYLENE. CJSBr. By boiling together dibromethylenic dibromide with alco- holic potash, a spontaneously inflammable gas is evolved, which is bromacetylene. JCHBrBr -o-r, ^ r TTR,. JGHBrBr = Br * + C ^ HBr ' Dibromethylenic Hydrobromic Bromaoetylene. dibromide. acid. PHENYLENE or C M H 2n _ 8 SERIES. The dyad radicals of this series are very little known. The following has alone been isolated : Phenylene, C 6 H 4 . EASYLOUS RADICALS. TRIADS. These radicals are unknown in the separate state, unless they are identical with the dyad radicals of the acetylene series: f(CH)"' Acetylene. Formyl. They are, however, well known in a numerous class of com- pounds belonging to families which will be studied hereafter. CYANOGEN AND OXATYL. 221 CHAPTER XXVIII. OEGANIC EADICALS. CLASS II. CHLOROUS OR NEGATIVE RADICALS. Every positive or basylous radical may be looked upon as the source of a chlorous or negative radical, which is generated by displacing a portion of the hydrogen of the former by oxygen. Thus : Ethyl {gg yields acetyl {ggg. Allyl {gag- acryl { ggg. Ethylene (C 2 H 4 )" glycolyl (C 2 H 2 O)". Propylene (C 3 H 6 )" lactyl (C 3 H 4 O)". malonyl (C 3 H 2 O 2 )". The constitution of the so-called compounds of these negative radicals may, however, be more simply explained from another point of view ; and, in fact, it will only be necessary for us to establish the existence of two negative radicals, in order to inves- tigate the whole range of chlorous organic compounds. These are Cyanogen { Oxatyl, the molecule of which is dry j J ( oxalic acid. These two radicals are the acidifying principles of nearly all organic acids ; they are therefore highly important compounds. The atom of each consists of an atom of carbon, one bond of which 222 ORGANIC RADICALS. is free to combine with other elements or groups of elements, the other three bonds being saturated, in cyanogen by triad nitrogen, and in oxatyl by one atom of oxygen and one of hydroxyl. In the molecules of both, the two free bonds of the carbon saturate each other. These radicals are also closely related to each other. Thus, if cyanogen be dissolved in water, it is soon transformed into ammonic oxalate : , ON'" Cyanogen. Water. Ammonic oxalate. In the presence of potassic hydrate, cyanogen evolves ammonia and produces potassic oxalate : CN "' 20H JCOKo 20H2 ~ GOKo "" Cyanogen. Potassic Water. Potassic Ammonia. hydrate. oxalate. From these salts oxalic acid, or the molecule of oxatyl, may of course be readily obtained by the action of sulphuric acid. In the converse manner, oxatyl may be converted into cya- nogen, by transforming it into ammonic oxalate and submitting the salt to the action of heat : fCOCN'H.O) QH (OS'" \ CO(]SIXH 4 O) "* \ ON"" Ammonic oxalate. Water. Cyanogen. CYANOGEN. f ON"' n | C]sr orCy 2 . Molecular weight =52. Molecular volume Mi. 1 litre weighs 26 criths. Fuses at 34. Soils at 207. Occurrence. Amongst the gases of blast furnaces, a proof of its withstanding an extremely high temperature. HYDROCYANIC ACID. 223 Preparation. By the action of heat on mercuric cyanide : HgCy, = Hg + Cy, Mercuric Cyanogen, cyanide. This equation only partially expresses the reaction, as a brown non-volatile compound (paracyanogen), Cy n , is simultaneously produced. Reaction. Cyanogen unites directly with potassium: Cy 2 + K 2 = 2KCy. Cyanogen. Potassic cyanide. HYDROCYANIC ACID. orHCy. Molecular weight =27. Molecular volume I I I. 1 litre of hy- drocyanic acid vapour weighs 13*5 criths. Sp. gr. of liquid 0-7058. Fuses at 15. Soils at 26'5. Preparation. 1. In the anhydrous condition, by passing hydrosulphuric acid over mercuric cyanide : HgCy 2 + SH 2 = HgS" + 2HCy. Mercuric ' Sulphuretted Mercuric Hydrocyanic cyanide. hydrogen. sulphide. acid. 2. By distilling potassic cyanide, or ferrocyanide, with dilute sulphuric acid : 2KCy + S0 2 Ho 2 = 2HCy + SO 2 Ko 2 . Potassic Sulphuric Hydrocyanic Potassic cyanide. acid. acid. sulphate. 3. By passing nitrogen over an ignited mixture of potassic carbonate and carbon : COKo 2 + C 4 + N 2 = 2CN'"K + SCO. Potassic Potassic Carbonic carbonate. cyanide. oxide. The potassic cyanide thus formed is then treated according to process No. 2. Reactions. 1. Hydrocyanic acid in contact with water slowly 224 ORGANIC RADICALS. passes, partly into ammonic oxalate as mentioned at p. 222, and partly into ammonic formate : CN"'H + 20H 2 = Hydrocyanic Water. Ammonic acid. formate. 2. If hydrocyanic acid be mixed with concentrated hydro- chloric acid, formic acid and ammonic chloride are produced : + 20H 2 + HC1 = Hydrocyanic Water. Hydrochloric Formic Ammonic acid. acid. acid. chloride. 3. The displacement of the hydrogen in hydrocyanic acid by metals gives rise to a very extensive series of single and double cyanides. The following is a list of the most important of these compounds : Single Cyanides. Potassic cyanide ................................. KCy. Zincic cyanide .................................. ZnCy 2 . Cadmic cyanide ................................. CdCy 2 . Nickelous cyanide .............................. NiCy 2 . Argentic cyanide .............................. AgCy. Mercuric cyanide .............................. HgCy 2 . Aurous cyanide ................................. AuCy. Cuprous cyanide .............................. 'Cu' 2 Cy 2 . Ferrous cyanide ................................. FeCy 2 . Cobaltous cyanide .............................. CoCy 2 . Double Cyanides. Dipotassic zincic tetracyanide ............... K 2 Zn", Cy 4 . Dipotassic cadmic tetracyanide ............ K 2 Cd", Cy 4 . Dipotassic nickel ous tetracyanide ......... K 2 Ni", Cy 4 . Potassic argentic dicyanide .................. KAg, Cy 2 . Potassic aurous dicyanide .................. KAu, Cy a . Potassic auric tetracyanide .................. KAu'" Cy 4 . Dipotassic cuprous tetracyanide ........... K 2 'Cu' 2 , Cy 4 . Dipotassic platinous tetracyanide ......... K 2 Pt", Cy 4 . DOUBLE CYANIDES. 225 Tetrapotassic diplatinic decacyanide K 4 ,'Pt"' 2 Cy 10 . Tetrapotassic ferrous hexacyanide. (Po- tassic ferrocyanide.) K 4 , Fe"Cy 6 . Hexapotassic diferric dodecacyanide. (Po- tassic ferricyanide.) K 6 , Te'" 2 Cy 12 . Hexapotassic dicobaltic dodecacyanide. (Potassic cobalticyanide.) K 6 , 'Co'" 2 Cy ]2 . Hexapotassic dichromic dodecacyanide ... K 6 , 'Cr'" 2 Cy 12 . Hexapotassic dimanganic dodecacyanide... K 6 'Mn'" 2 , Cy la . The cyanides of the alkali metals when fused in contact with air, absorb oxygen, producing cyanates : KCy + O = CyKo. Potassic Potassic cyanide. cyanate. Some of the single cyanides, as potassic cyanide, are readily decomposed by acids ; others, as ferrous and aurous cyanides,, may be boiled with moderately strong acids without decom- position. Most of the insoluble single cyanides dissolve in solutions of the alkaline cyanides, forming double cyanides. Some of these double compounds, when acted upon by hydrochloric acid, evolve hydrocyanic acid, producing chlorides of both metals, as in the case of dipotassic zincic tetracyanide. These are called easily decomposable cyanides, and are indicated in the above Table by the comma being placed between the cyanogen and the metals. Other double cyanides do not evolve hydrocyanic acid under the influence of hydrochloric acid, but produce a chloride of one of the metals, the remaining elements of the compound uniting with hydrogen to form a complex acid. In the above Table the double cyanides of this class are indicated by the comma being placed between the metals. The most important of these double cyanides are the po- tassic ferrocyanide K 4 , Fe"Cy 6 , and the potassic ferricyanide K 6 ,Te'" 2 Cy 12 . L5 226 ORGANIC RADICALS. POTASSIC FERROCYANIDE. K 4 , W'Cy e or K 4 Cfy. Preparation. 1. By placing a mixture of iron filings with solution of potassic cyanide in contact with the air, oxygen is absorbed and potassic ferrocyanide produced : Fe + 6KCy + OH 2 + = K 4 Fe"Cy 6 + 2KHo. Potassic Water. Potassic Potassic cyanide. ferrocyanide. hydrate. 2. By digesting potassic cyanide with ferrous sulphide : FeS" + 6KCy = K 4 Fe"Cy e + SK 2 . Ferrous Potassic Potassic Potassic sulphide. cyanide. ferrocyanide. sulphide. 3. On a manufacturing scale it is prepared by fusing nitroge- nous animal matter with potassic carbonate and iron filings in iron vessels, lixiviating the resulting mass with water, and crys- tallizing. Reactions. 1. Potassic ferrocyanide, when fused with po- tassic carbonate, forms potassic cyanide and cyanate : Pe"Cy 6 K 4 + COKo 2 = 5KCy + CyKo + Fe + CO 2 . Potassic Potassic Potassic Potassic Carbonic ferrocyanide. carbonate. cyanide. cyanate. anhydride. 2. By mixing solution of potassic ferrocyanide with ether and hydrochloric acid, hydroferroeyanic acid is precipitated : Ee"Cy 6 K 4 + 4HC1 = 4KC1 + Fe"Cy 6 H 4 . Potassic Hydrochloric Potassic Hydroferrocyanic ferrocyanide. acid. chloride. acid. 3. Potassic ferrocyanide produces, with solutions of ferrous salts, a light-blue precipitate, which rapidly becomes dark blue in contact with the air : Fe"Cy 6 K 4 + S0 2 Feo" = Fe"Cy 6 Fe"K 2 + S0 2 Ko 2 . Potassic Ferrous Light-blue Potassic ferrocyanide. sulphate. precipitate sulphate. POTASSIC FERRICYANIDE. 227 4. "With ferric salts it gives prussian blue : 3Fe"Cy 6 K 4 + 2Fe 2 Cl e = 3Fe"Cy 2 , 'Fe'" 4 Cy 12 + 12KC1. Potassic Ferric Prussian blue. Potassic ferrocyanide. chloride. chloride. 5. "With cupric salts it gives a red precipitate of cupric ferro- cyanide : K 4 Fe"Cy 6 + 2SO 2 Cuo" = Cu" 2 Fe"Cy 6 + 2S0 2 Ko 2 . Potassic Cupric Cupric Potassic ferrocyanide. sulphate. ferrocyanide. sulphate. POTASSIC FERRICYANIDE. K 6 Te'" 2 Cy 12 or K 6 Cfdy. Preparation. By the action of oxidizing substances, such as chlorine and nitric acid, on potassic ferrocyanide : 2K 4 Ee"Cy 6 + C1 2 = K' 6 Fe'" 2 Cy 12 + 2KC1. Potassie Potassic Potassic ferrocyanide. ferricyanide. chloride. Reaction. Potassic ferricyanide produces no precipitate with solutions of ferric salts, but causes a deep-blue precipitate with ferrous compounds : K' 6 Fe"' 2 Cy 12 + 3S0 2 Feo" = Fe" 3 Te'" 2 Cy I2 + 3SO 2 Ko 2 . Potassic Ferrous sulphate. TurnbulTs blue. Potassic ferricyanide. sulphate. OTHER COMPOUNDS OF CYAYOGEN. There are three isomeric chlorides of cyanogen : CyCl. Cy 2 Cl 2 . Cy 3 Cl 3 . Gaseous. Liquid. Solid. The molecular volume of all three cyanogen chlorides is II I. 1 litre of gaseous cyanogen chloride weighs 61*5 criths. 1 litre of vapour ofliqidd cyanogen chloride weighs 123 1 litre of vapour of solid cyanogen chloride weighs 184*5 Cyanogen produces, with hydroxyl, three isomeric acids and an isomeric neutral body : 228 ORGANIC RADICALS. Cyanic acid Cy OH or CyHo. Cyanuric acid Cy 3 3 H 3 or Cy 3 Ho 3 . Fulminuric acid Cy 3 O 3 H 3 or Cy 3 Ho 3 . Cyamelide Cy B O n H n or Cy n Ho n . When potassic cyanide is boiled with sulphur, the latter is dissolved and the solution contains potassic sulphocyanate : CyK Potassic cyanide. + s = CyKs. Potassic sulphocyanate. This compound produces with ferric salts a blood-red colour. OXATYL, JCQHo { COHo" This radical, in the isolated condition, constitutes dry oxalic acid ; and in combination with hydrogen and other radicals it enters into the composition of nearly all organic acids. Acids containing one atom of oxatyl are monobasic, those contain- ing two atoms are dibasic, and those containing three are tri- basic. The relations between methyl, oxatyl, and cyanogen are very simple : OH, Cyanogen , fCOHo J |COHO : Oxatyl. OXATYL AND OXALIC ACID. 229 In methyl the two carbon atoms are united together by one bond of each, the remaining three bonds of each atom being satu- rated by three atoms of hydrogen. In cyanogen the carbon atoms are united in the same manner, but the three remaining bonds of each carbon atom are saturated by triad nitrogen ; whilst in oxatyl the three remaining bonds are saturated with the dyad oxygen and the monad radical hydroxyl. Oxatyl has not been united with chlorine to produce oxatylic chloride (COHoCl) ; nor has its hydroxyl been replaced by chlo- f COP! rine to form QQQI- When treated with phosphoric chloride, it yields carbonic oxide and carbonic anhydride : + C0 a + 2HC1 + POC1, Oxatyl. Phosphoric Carbonic Carbonic Hydrochloric Phosphoric chloride. oxide. anhydride. acid. oxy trichloride. OXALIC ACID. Occurrence. In the form of the hydric potassic salt in Oxalis acetosella, and in the form of different salts in many other plants, and also in the animal organism. Preparation. 1. Eroni its elements through the medium of cyanogen. (See p. 222.) 2. By the oxidation of a large number of organic compounds. Most organic substances are converted by oxidizing agents into oxalic acid before their final transformation into carbonic anhydride and water : thus sugar is transformed into oxalic acid by the action of nitric acid. 3. By heating sawdust with a mixture of potash and soda, oxalates of these bases are formed. Transformations. 1. By the action of heat, oxalic acid is trans- 230 ORGANIC RADICALS. formed into carbonic anhydride and oxatylic hydride, or formic acid : JCOHo ro JH | COHo OU * t COHo* Oxalic acid. Carbonic Formic acid. anhydride. A portion of the formic acid is at the same time decomposed into water and carbonic oxide : Formic acid. Water. Carbonic oxide. 2. Substances having a strong attraction for water, as sul- phuric acid, transform oxalic acid into water, carbonic oxide, and carbonic anhydride : {colo = CO + C0 2 + OH 2 . Oxalic acid. Carbonic Carbonic Water. oxide. anhydride. 3. Heated with an excess of alkali, oxalic acid (or an oxalate) yields hydrogen and a carbonate : {colo + 2KHo = 2C OKo 2 + => Potassic Potassic Potassic oxalate. hydrate. carbonate. 4. Argentic oxalate explodes when heated, producing silver and carbonic anhydride : Argentic Carbonic oxalate. anhydride. Salts of Oxalic acid. Oxalic acid forms three series of salts: Normal. Acid. Superacid. ( COKo f COHo J COHo f COHo \COKo- \COKo' \COKo' \COHo' fCOHo co I CO l^COHo OXAMIDE. 231 OXAMIC ACID. H ) f COAd 1 COHo T 1 COHo- Preparation. By heating liydric ammonic oxalate to 230 : 2 COHo Hydric ammonic Oxamic acid. Water. oxalate. Reaction. By boiling oxamic acid with water it is retrans- formed into liydric ammonic oxalate. OXAMIDE. JCO(N'"H 2 ) JCOAd t CO (N'"H 2 ) or \COAd" Preparation. 1. By distilling normal ammonic oxalate : 1 CO (N"'H a )' Normal ammonic Water. Oxamide. oxalate. 2. By acting upon ethylic oxalate by ammonia : JCOEto 2MTT fCO(N"'H 2 ) \COEto + 2NH ^ - \CO(N'"H 2 ) Ethylic Ammonia. Oxamide. Alcohol. oxalate. Reactions. 1. Oxamide, when heated with phosphoric anhy- dride, evolves cyanogen : fCO(N'"H a ) 2QH JCN'" \CO(N"'H 2 ) J01i ^ \CN"" Oxamide. Water. Cyanogen. 2. Dilute acids convert it into oxalic acid and ammonic salts : fCO(N'"H a ) SQH QH f COHo \CO(N"'H 2 ) >U ' M ' 20M ' \COHo Oxamide. Sulphuric acid. Water. Oxalic acid. + S0 2 (N'H 4 0) 2 . Ammonic sulphate. 232 HYDRIDES OF COMPOUND RADICALS. By distilling the oxalates of the compound ammonias instead of ammonic oxalate, compound oxamides are obtained : / CO(N v MeH 3 O) 9mr f CO(N'"MeH) | CO (N v MeH 3 0) ^ U12 { CO (N'"MeH)' Methylammonic oxalate. Water. Dimethyloxamide. JCO(N v PhH 3 0) 90TT fCO(N"ThH) |CO(N v PhH 3 0) a |CO(N"ThH)' Phenylammonic oxalate. Water. DiphenyloxamiJe. CHAPTER XXIX. HYDEIDES OF THE COMPOUND RADICALS. This family is divided into two classes : Class I. Hydrides of the Basylous or Positive Radicals. Class II. Hydrides of the Chlorous or Negative Radicals. CLASS I. HYDEIDES OF THE SASYLOUS Oil POSITIVE RADICALS. Two series of hydrides belonging to this class are well known they are : 1. Hydrides of the Radicals of the Methyl series. 2. Hydrides of the Radicals of the Phenyl series. 1. HYDEIDES OF THE RADICALS OF THE METHYL SERIES, Marsh-gas, or C n H 2 ,+ 2 Series. There is some difference of opinion as to whether these com- pounds are identical or isomeric with the radicals of the methvl HYDRIDES OF THE MARSH-GAS SERIES. 233 series. Thus methyl and ethylic hydride both contain C 2 H 6 , and ethyl and butylic hydride both contain C 4 H 10 . The graphic formulae exhibit no difference between these pairs of bodies re- spectively. Thus : HI ( c -h Methyl or ethylic hydride. Ethyl or butylic hydride. These formulas do not show us whether the molecule of methyl or ethylic hydridewill separate at a and so berepresented by the formula ! -rj 3 ' 2 ; or at b, and so be written thus, I CR 3 ' or wne ^ ner the molecule of ethyl or butylic hydride will separate at c and so be formulated j TT 3 a ; or at d, when it should be represented by ! crfH^H 2 ' Some experi- ments in connexion with this subject appear to show that these compounds are isomeric. A difference between methyl and ethylic hydride can only be conceived on the supposition that the four bonds of carbon have not equal values in combination, an hypothesis which is not altogether unsupported by facts. Preparation. 1. There is only one process of general applica- tion for preparing these hydrides ; it consists in bringing water into contact with the zinc compounds of the respective radi- cals: f r\ f) I ^71 Zinc compound of radical. 2OH 2 = Water. ZnHo 2 Zincic hydrate. Hydride of radical. The corresponding compounds containing more positive metals might doubtless be substituted for those of zinc. 2. There are several special processes which may be used for preparing these hydrides. Thus all the hydrides above that of 234 HYDRIDES OF COMPOUND RADICALS. methyl may be obtained, together with the corresponding dyad radical, by acting upon the iodide of the monad radical by zinc : C M H 2n+1 + Zn = Znla + CwH ^ + f C n H 2n+1 Iodide of the monad Zincic Dyad Hydride of radical. iodide. radical. monad radical. Methylic hydride, or marsh-gas, is produced during putre- faction, and by the distillation of potassic acetate with excess of potassic hydrate. The destructive distillation of coal and of allied substances also furnishes a large number of the members of this series. Character. They are all distinguished by their great chemical indifference, and by their forming substitution compounds con- taining chlorine, bromine, &c. The following list contains the hydrides of the monad radicals at present studied : Boiling-points. Methylic hydride, or Marsh-gas MeH or C H 4 Ethylic hydride EtH or C 2 H 6 Propylic or tritylic hydride PrH or C 3 H 8 Buty lie or tetry lie hydride BuH or .C 4 H 10 slightly above Amy He or pentylic hydride Ayll or C 5 H 12 30 Hexylic or caproylic hydride CpII or C 6 H u 68 Heptylic hydride C 7 H le 92-94 Octylic hydride C 8 H 18 116-118 Nonylic hydride C 9 H 20 136-138 Decatylic hydride C 10 H 22 160-162 Endecatylic hydride C n H 24 180-184 Dodecatylic hydride C 12 H 26 196-200 Tridecatylic hydride C 13 H~ 8 216-218 Tetradecatylic hydride C U H 30 236-240 Pentadecatylic hydride C I5 H 32 255-260 METHYLIC HYDRIDE, Marsh-gas, Light Carluretted Hydrogen, Mr e- damp. CH 4 or MeH. MARSH-GAS, OR METHYLIC HYDRIDE. 235 Molecular weight = 16. Molecular volume \ \ |. 1 litre weighs 8 criths. Occurrence, 1. As a product of the decomposition of organic substances out of contact with air. 2. Evolved in coal-mines. 3. The gas of the mud- volcano at Bulganak in the Crimea is nearly pure marsh-gas. Preparation. 1. By the action of water on zincic methide. (See general reaction, p. 233.) 2. By distilling two parts of potassic acetate, two of potassic hydrate, and three of lime : {coko + KHo = COZo * + CH - Potassic Potassic Potassic Methylic acetate. hydrate. carbonate. hydride. 3. By the reduction of carbonic chloride or of chloroform with sodium amalgam and water : CC1 4 + H 8 = 4HC1 + CH 4 : Carbonic Hydrochloric Methylic chloride. acid. hydride. CHC1 3 + H 6 = 3HC1 + CH r Chloroform. Hydrochloric Methylic acid. hydride. 4. By passing carbonic disulphide and hydro sulphuric acid, or carbonic disulphide and steam, over ignited copper : CS" 2 + 2SH 2 + 4Cu = 4CuS" + CH 4 . Carbonic Sulphuretted Cupric Methylic disulphide. hydrogen. sulphide. hydride. 5. By the destructive distillation of organic substances, such as wood, coal, &c. Reaction. "When equal volumes of methylic hydride and chlorine are exposed to diffused daylight, methylic chloride is formed : CH 4 + Cl a = HC1 + CH 3 C1. Methylic Hydrochloric Methylic hydride. acid. chloride. 236 HYDRIDES OF COMPOUND RADICALS. ETHYLIC HYDRIDE. C 2 H 6 or CMeH 3 . Molecular weight = 30. Molecular volume FTI. 1 litre weighs 15 critTis. Preparation. 1. By the action of water on zin-cic ethide (see p. 233). 2, By the action of ethylic iodide on sodic ethide, ethylene being simultaneously produced : CMeH 2 Na + CMeH 2 I = Nal + C 2 H 4 + CMeH 3 . Sodic ethide. Ethylic Sodic Ethylene. Ethylic iodide. iodide. hydride. Reactions. 1. When equal volumes of ethylic hydride and chlorine are exposed to diffused daylight, the following action takes place : CMeH 3 + C1 2 = CMeH 2 Cl + HC1. Ethylic /3 Ethylic Hydrochloric hydride. chloride. acid. A small portion of the body CMeH 2 Cl is ordinary ethylic chloride, which is a liquid, boiling at 12'5 ; but the rest is a gas which does not condense at 18. 2. When a mixture of two volumes of chlorine and one of ethylic hydride is exposed to the action of diffused daylight, an oily liquid having the composition of ethylenic dichloride is formed : CMeH 3 + 2C1 2 = C 2 H t Cl 2 + 2HC1. Ethylic Hydrochloric hydride. acid. AMYLIC HYDRIDE. C 5 H 12 or CBuH 3 . Molecular weight =72. Molecular volume [~]~|. 1 litre of amylic hydride-vapour weighs 36 criths. Soils at 30. HYDRIDES OF RADICALS OF THE PHENYL SERIES. 237 Occurrence. In petroleum and coal-oil. Preparation. By digesting zinc and amylic iodide with water or alcohol at 100 : 2CBuH 2 I + 2Zn + 2OH 2 = 2CBuH 3 Amylic Water. Amylic iodide. hydride. + ZnHo 2 + ZnI 2 . Zincic Zincic hydrate. iodide. PARAFFIN. This body is produced, together with numerous other com- pounds of a like nature, by the destructive distillation of bog- head coal and similar substances. It is also found in petro- leum and asphalt. If chlorine be passed into melted paraffin, the latter is slowly attacked, hydrochloric acid being evolved. In this reaction paraffin resembles the hydrides of the monad radicals, and differs from the dyad radicals, to which class it was formerly considered to belong. In the formula C n H 2n+2 for paraffin, the value of n has not yet been satisfactorily deter- mined ; in fact it is probable that several distinct hydrides of the class now under consideration are confounded under this name. 2. HYDRIDES OF THE RADICALS OF THE PHENYL SERIES. The following five members of this series are known, viz. : Boiling- Formula, point. Sp. gr. Benzol C 6 H 6 80*5 0'85 Toluol C 7 H 8 110-0 0-87 Xylol C 8 H 10 128-5 Cumol C 9 H 12 148-5 0'87 Cymol C 10 H U 171'4 0-86 Preparation. 1. These hydrides are produced by the distilla- 238 HYDRIDES OF COMPOUND RADICALS. tion of the alkaline salts of the acids containing the same posi- tive radicals, with excess of potassic hydrate : {cOKo" 7 + KHo = COKo * + Potassic salt. Potassic Potassic Hydride of hydrate. carbonate. radical. 2. By the destructive distillation of various organic sub- stances, such as coal. Properties. These hydrides are distinguished from those of the radicals of the C n H 2n +i series by being less indifferent to chemical agents. By treatment with strong nitric acid they yield nitro-compounds : Thus Benzol, C 6 H 6 , gives nitrobenzol, C 6 H 3 (N V O 2 ). Toluol, C 7 H 8 , nitrotoluol, C 7 H 7 (N V O 2 ). Xylol, C 8 H 10 , nitroxylol, C 8 H 9 (N V 2 ). Cumol,C 9 H 12 , nitrocumol, C 9 H U (N V 2 ). Cymol,C 10 H u , nitrocymol, C 10 H 13 (N V O 3 ). Under the influence of reducing agents, these nitro-com- pounds yield aniline and its homologues. BENZOL, Benzene, 'Benzine, Phenylic Hydride, Bicarburet of Hydrogen. C 6 H 6 or C(C 5 H 3 )H 3 , or PhH. Molecular weight =78. Molecular volume ["T"1 1 litre of benzol-vapour weighs 39 criths. Fuses at 5*5. Boils at 80'5. SUBSTITUTION PRODUCTS FROM BENZOL. 239 Occurrence. In Rangoon petroleum and in coal-tar. Preparation. 1. By heating benzole acid with excess of lime or baryta : Benzoic acid. Lime. Benzol. Calcic carbonate. 2. By heating the vapour of benzoic acid to redness, when it splits into benzol and carbonic anhydride : Benzoic acid. Carbonic Benzol. anhydride. 3. By heating phthalic acid with lime : C 8 H 6 O 4 + 2CaO = C rt H e + 2COCao". Phthalic Lime. Benzol. Calcic acid. carbonate. 4. By passing fats through red-hot tubes. 5. By the destructive distillation of coal. 6. In small quantity, when the vapour of acetic acid or of alcohol is passed through a red-hot tube. SUBSTITUTION DERIVATIVES OF BENZOL. I. Eromo Compounds. MONOBROMBENZOL. C 6 H 5 Br. Soils at 150. Preparation. By acting with two atoms of bromine on boil- ing benzol : C 6 H 6 + Br a = C 6 H 5 Br + HBr. Benzol. Monobrombenzol Hydrobromic >r phen; bromu or phenylic acid, ide. DIBROMBENZOL. OABr r Fuses at 89. Soils at 219. 240 HYDRIDES OF COMPOUND RADICALS, Preparation. By treating monobrombenzol with excess of bromine. TRIBROMBENZOL HYDROBROMATE. C 6 H 6 Br 6 . Preparation. By exposing a mixture of benzol and bromine to the action of sunlight. TRIBROMBENZOL. C 6 H 3 Br, Preparation. By boiling the previous compound with alco- holic potash. The following graphic formulae show the probable atomic relations subsisting between benzol, tribrombenzol hydrobro- mate, and tribrombenzol : Benzol. Tribrombenzol. NITROBENZOL. 241 II. Chloro-compounds. Benzol forms three chloro- substitution compounds, similar to the bromo-compounds just described. State of Fusing- Boiling- aggregation, point. point. Sp. gr. Monochlorbenzol... C 6 H 5 C1, Liquid... 136. Dichlorbenzol C 6 H 4 CJ 2 , Solid... 89. Trichlorbenzol C 6 H 3 C1 3 , Oily ... 210 1-457. III. Nitro-compounds. Two only have hitherto been produced. Nitrobenzol 0^(1^0,) or N(C 6 H 5 )O 2 . Dinitrobenzol C 6 H 4 (N V O 2 ) 2 or N 2 (C 6 H 4 )"0 4 . NITROBENZOL. N(C 6 H 5 )0 2 orNPh0 2 . Molecular weight =123. Molecular volume II I. 1 litre of nitrobenzol vapour weighs 61'5 critJis. Fuses at 3. Soils at 220. Preparation. By the action of nitric acid on benzol : C(C 5 HJH 3 + N0 2 Ho = N(C 6 H 5 )0 2 + OH 2 . Benzol. Nitric acid. Nitrobenzol. Water. Reactions. 1. By the action of reducing or hydrogenating agents, as zinc and hydrochloric acid, sulphuretted hydrogen, acetic acid and iron, or potassic arsenite, nitrobenzol is con- verted into aniline : N(C 6 H 5 )0 2 + 3SH 2 = N(C 6 H 5 )H 2 + 2OH 2 + S 3 or C 6 H 5 (Nv0 2 ) + 3SH 2 = C 6 H 5 (N'"H 2 ) + 2OH 2 + S 3 . Nitrobenzol. Sulphuretted Aniline. Water, hydrogen. M 242 HYDRIDES OF COMPOUND RADICALS. The relation between nitrobenzol and aniline will be seen in the following graphic formulae : Aniline. 2. By the action of sodium amalgam and water, nitrobenzol is converted into azobenzol, and finally into benzidine : 2N'(0 6 H 5 )0 2 Nitrobenzol. ,,{N(C e H s ) \N(C 6 H 5 ) Azobenzol. _ ,,|N(C 6 H S ) \N(C.H.) Azobenzol. fN(C 6 H s )H JN(C 6 H 5 )H- Benzidine. 4OH 2 . Water. DINITROBENZOL. N 2 (C 6 H 4 )"0, Fuses lelow 100. Preparation. By treating nitrobenzol with a mixture of concentrated nitric and sulphuric acids. Reaction. By the action of sulphuretted hydrogen, dinitro- benzol is converted into nitraniline : N0 N 2 (C 6 H t )"0 4 Dinitrobenzol. 3SH 2 = Sulphuretted hydrogen. 4)" Nitraniline. 2OH Water. S a . THE ALCOHOLS. 243 CLASS II. HYDRIDES OF CHLOROUS OR NEGATIVE RADICALS. Only two of these are known : Cyanic hydride or Hydrocyanic acid. Oxatylic hydride or Formic acid. The first has already been considered (p. 223); and the second will be more conveniently studied in connexion with the fatty acids (p. 304). CHAPTER XXX. THE ALCOHOLS. THE alcohols form one of the most important of the families of organic compounds. The simplest member of this family is methylic alcohol, which is derived from marsh-gas by the sub- stitution of one atom of hydroxyl for one of hydrogen. CH 4 . CH 3 Ho. (*>- -6-0- Marsh-gas. Methylic alcohol. The alcohols have been termed the hydrated oxides of the basylous radicals ; but this is erroneous, as they do not contain water. . They may more correctly be defined as the compounds of hydroxyl with the basylous organic radicals, whence it follows that each series of basylous radicals forms a correspond- ing series of alcohols. The alcohols act upon and saturate acids, forming a family of compounds termed ethereal salts. M2 244 THE ALCOHOLS. The acidity or acid- saturating power of the alcohols depends upon the number of atoms of hydroxyl which they contain : the monad radicals give monacid alcohols, the dyad radicals diacid alcohols, &c. We have thus the annexed three principal subdivisions of the alcohol family. Monacid. Methyl or C n H 2n+ iHo series. Vinyl or C n H 2n _iHo series. Phenyl or C n H 2n _ 7 Ho series. Diacid. Triacid Glycol or C M H 2n Ho 2 Glycerin orC n H 2n _iHo 3 The following symbolic and graphic formulae will exemplify the arrangement of the bonds in these three subdivisions : Monacid Alcohols. Propylic alcohol. ) (Ethyl series.) J J C ( CH 3 ) H 2 or { CH 2 Ho ' Allylic alcohol. \ (Vinyl series) J Benzoic alcohol. 1 (Phenyl series) J MONACID ALCOHOLS. 245 Propylenic alco-| hol,orpropylic glycol ......... J G-lycerin Diacid Alcohols. C 3 H 6 Ho 2 or Triacid Alcohols. fCH 2 Ho = C 3 H 5 Ho 3 or \ CHHo 33 ^ .^.^-^ -^-^ CH 2 Ho MONACID ALCOHOLS: Methyl or C n It 2n+1 Ho series. These alcohols may be divided into three classes viz. : 1. Monacid normal alcohols 2. 3. secondary tertiary C(C n H 2M+1 )H 2 CH 2 Ho |C(C M H 2n+1 )H 2 t C(C m H 2m+1 )HHo- JC(C n H 2n+1 )H 2 I C(C w H 2m+1 ) 2 Ho' In the general formula of the normal alcohols n may =0, and even the whole radical C(C w H 2n+ i)H 2 may be replaced by hydrogen, as is the case in methylic alcohol. In the formulae of the secondary and tertiary alcohols n may also =0, but m must always be a positive integer. 246 THE ALCOHOLS. NORMAL MONACID ALCOHOLS. General formula { ^ ^+i) H 2. The following is a list of the members of this class : Fusing- Boiling- points, points. Methylic alcohol (cH 2 Ho 66 ' 5 ' Ethylic alcohol 1 OTOTn * 78 ' 4 ' [ 2 96 o. ff 2 1090. Caproylic or hexylic f CBuH 2 fC(C 4 H 9 )H 2 alcohol ............. :....\CH 2 Ho or \ CH 2 Ho OEnanthylic or heptylic f CAyH f C(C 5 H n )H 2 alcohol .................. \CH 2 H8 or \CH 2 Ho Cetylic alcohol ........................... cH 292 49 - 50 - Cerotic alcohol ........................... {cH 2 ao 51 ^ H2 79 ' Melissic alcohol ........................... 257)H2 85 ' The lower members of the class are liquid, and the higher solid. There is a rise of about 19 in the boiling-point for every addition of CH 2 . They are produced in a variety of operations, such as destructive distillation, fermentation, and animal secretion, but by reactions which cannot usually be traced. Relations of the normal C n H 2n+ iHo alcohols to the monad C n H 2H+1 radicals. 1. The radicals C n H 2n+ i which are combined with hydroxyl in the normal alcohols may be separated, by first converting the alcohol into an iodide (see p. 283), and subsequently acting on the iodide by zinc (see p. 209). RELATIONS OF ALCOHOLS TO DYAD RADICALS. 247 2. The radical next lower in the series, than that contained in the alcohol, may be obtained by converting the alcohol into the corresponding fatty acid, and then submitting a salt of this acid to electrolysis (see p. 209). 3. Inversely, the normal alcohols may be obtained by acting upon the radicals with chlorine under the influence of light, when one atom of hydrogen in the radical is displaced by chlorine. Thus in the case of methyl we have Methyl. Chlorinated Hydrochloric methyl. acid. by the action of potassic hydrate upon this chlorinated me- thyl, ethylic alcohol is formed, thus : KHo = Chlorinated Potassic Ethylic Potassic methyl. hydrate. alcohol. chloride. This reaction requires further investigation (see p. 248). Relations of the normal C n H 2 n+iHo alcohols to the dyad C n H 2M radicals. 1. The CJETj* radicals are obtained from the normal C w H 2/t+1 Ho alcohols by the abstraction of the elements of water : CH 3 ftTr f CH 2 ~ = |CH; Ethylic Water. Ethylene. alcohol. 2. Inversely, the normal alcohols are obtained from these radicals by first uniting the latter with hydrochloric, hydro- bromic, or hydriodic acid, and then treating the product with potassic hydrate : CH 2 wpl f CH 3 CH 2 + = |cH 3 2 cr Ethylene. Hydrochloric Ethylic acid. chloride. f CH , TTTT _ J CH \CH 2 Ci lCH 2 Ho Ethylic Potassie Ethylic Potassic chloride. hydrate. alcohol. chloride. 248 THE ALCOHOLS. Or by uniting the dyad radicals with sulphuric acid, and distilling the product with water : S0 2 Ho 2 + C 2 H 4 = S0 2 Ho(C 2 H 5 0): Sulphuric Ethylene. Sulphovinie acid, acid. S0 2 EtoHo + OH 2 = S0 2 Ho 2 + EtHo. Sulphovinie Water. Sulphuric Ethylic acid. acid. alcohol. Relations of the normal C n H 2rt+1 Ho alcohols to the hydrides of the C n H 2n+1 radicals. 1. "When the alcohols are converted into iodides (see p. 283) and the latter digested with zinc and water at 100, the corre- sponding hydrides are produced (see p. 237). . 2. When the hydrides of the C M H 2n+1 radicals are acted upon by chlorine under the influence of light, they produce the chlorides of the radicals, from which the alcohols may be obtained by the action of potassic hydrate : EtH + C1 2 = EtCl + HC1. Ethylic Ethylic Hydrochlo- hydride. chloride. ric acid. EtCl + KHo = EtHo + KC1. Ethylic Potassic Ethylic Potassic chloride. hydrate. alcohol. chloride. The greater quantity of the chlorine compound so formed is isomeric with the chloride of the radical, and possibly gives a corresponding isomeric alcohol. Relations of the normal C n H 2n+1 Ho alcohols to the radical cya- nogen. Ascent of the alcohol series. Mendius's reaction. By the dry distillation of potassic sulphovinate and its homo- logues with potassic cyanide, the cyanides of the radicals are produced: S0 2 EtoKo + KCy = SO 2 Ko 2 + EtCy. Potassic Potassic Potassic Ethylic sulphovinate. cyanide. sulphate. cyanide. METHYLIC ALCOHOL. 249 By treatment with nascent hydrogen, this cyanide is con- verted into propylamine : NC(CMeH 2 ) + H 4 = N[C(CMeH 2 )HJH 2 or NPrH,. Ethylic cyanide. Propylamine. By the action of nitrous anhydride, propylamine is trans- formed into propylic alcohol : 2NPrH 2 + N 2 3 = 2PrHo + OH 2 + 2N 2 . Propylamine. Nitrous Propylic Water, anhydride. alcohol. It is obvious that by repeating these reactions on propylic alcohol, butylic alcohol would be obtained, the homologous series of alcohols being ascended one step at each repetition of the process. METHYLIC ALCOHOL, Wood Spirit, Pyroxylic Spirit. CH 3 HoorMeHo. Molecular weiglit = 32. Molecular volume \ I I. 1 litre of metJiylic alcohol vapour weighs 16 criths. Sp. gr. 0*798. Boils at 66-5. Preparation. 1. From marsh-gas, by the action of chlorine and subsequent treatment with potassic hydrate : + HC1; Hydroehlo- ric acid. + KC1. Potassic chloride. 2. Prom the essential oil of Gaultheria procumbens, by the action of potassic hydrate C 7 H 4 OMeoHo + KHo = C 7 H,OHoKo + MeHo. Oil of Gaultheria pro- Potassic Potassic salicylate. Methylic cumbens. (Metno- hydrate. alcohol, salicylic acid.) 3. By the destructive distillation of wood. Reactions. 1. Methylic alcohol unites with some salts in the capacity of water of crystallization, as, for instance, CaCl 2 , 2MeHo. M5 CH 4 Marsh- gas. + 01, = CH 3 C1 Methylic chloride. CH 3 C1 Methylic chloride. + KHo = Potassic hydrate. OH,Ho Methylic alcohol. 250 THE ALCOHOLS. 2. By the action of potassium and sodium, methylates are formed with elimination of hydrogen : CH 3 Ko. CH 3 Nao. Potassic Sodic methylate. methylate. 3. By oxidation it is transformed into formic acid : Methylic Formic acid. Water. alcohol. 4. "When distilled with calcic chloro-hypochlorite (chloride of lime) and water, chloroform is produced. 'CaCl O Ca" 2CH 3 Ho + 4Ca(OCl)Cl = 2CHC1 3 +<< O + 3OH 2 . Ca" O Methylic Calcic chloro- Chloroform. Calcic oxy- Water. alcohol. hypochlorite. chloride. ETHYLIC ALCOHOL, Alcohol, Spirit of Wine. Molecular weight =46. Molecular volume I I I. 1 litre of ethylic alcohol vapour weighs 23 criths. Sp. gr. O792 at 20. Boils at 78'4. Preparation. 1. From ethylene (p. 247). 2. By the fermentation of grape-sugar with yeast at about 22: C 6 H 12 6 = 2C 2 H 5 Ho + 2C0 2 . Grape-sugar. Ethylic Carbonic alcohol. anhydride. At the same time, however, other products are formed, but in very small quantities. Reactions. 1. Treated with potassium or sodium, alcohol forms ethylates : 3 CH 2 Ko* CH 2 Nao' Potassic Sodic ethylate. ethylate. |CH 3 t CH 2 MERCAPTAN. 251 2. When passed through a red-hot tube, alcohol is decom- posed into marsh-gas, hydrogen, and carbonic oxide : C 2 H 5 H = CH 4 + H 2 + CO. Ethylic Marsh- Carbonic alcohol. gas. oxide. Small quantities of ethylene, benzol, and naphthalin are simultaneously produced, whilst carbon is deposited. 3. By oxidation, ethylic alcohol is converted first into alde- hyde, and then into acetic acid : I CH 4. o I 3 \CH 2 Ho \COH Ethylic Aldehyde. Water. alcohol. f CH 3 n I cok + = Aldehyde. Acetic acid. 4. Distilled with chloride of lime, ethylic alcohol produces chloroform. AlcoJiolates are salts containing alcohol in the place of water of crystallization j they are mostly decomposed immediately by water. The following are known : ZnCl 2 , 2C 2 H 5 Ho. CaCl 2 , 4C 2 H 5 Ho. N 2 4 Mgo", 6C 2 H 5 Ho. MERCAPTAN, Sulphur Alcohol, Ettylic sulphhydrate, HydrosulpJiate of Ethyl. Molecular weight =62. Molecular volume I VI. 1 litre of mercaptan vapour weighs 31 criths, Sp> gr. 0'835. Boih 252 THE ALCOHOLS. Preparation. By distilling potassic sulphovinate with po- tassic sulphhydrate : S0 2 EtoKo + KHs = EtHs + S0 2 Ko 2 . Potassic Potassic Mercaptan. Potassic sulphovinate. sulphhydrate. sulphate. Reactions. 1. By the action of potassium and sodium on mercaptan, an atom of hydrogen is displaced by the metal, pro- ducing mercaptides : fCH 3 \ CH 2 Ks' Potassic Sodic mercaptide. mercaptide. 2. Mercaptan acts upon mercuric oxide with great energy, a white crystalline mercuric mercaptide being formed : Mercaptan. Mercuric Mercuric Water. oxide. mercaptide. Propylic alcohol, \ QTT TT 2 , is obtained from the fusel oil of the marc brandy of the south of France. Butylic alcohol, j QJJ jj^, is contained in the fusel oil pro- duced in the preparation of spirit from the molasses of beet- root sugar. f CPrTT Ami/lie alcohol, \ QTT -u- 2 is the chief constituent of the fusel oil obtained in the manufacture of alcohol from potatoes or grain. As far as these alcohols have been studied, they resemble, in their chemical relations, the two previously described. SECONDARY MONACID ALCOHOLS. General formula... The secondary alcohols differ from the normal in yielding by oxidation ketones instead of acids. ISOPROPYLIC ALCOHOL. 253 Three secondary alcohols are at present known : {CTT CMeHHo- {CTT 3 f CPrTT Pseudohexylic alcohol ......... The first is obtained by the action of nascent hydrogen on acetone : / CH 3 J CH 3 \ COMe ^ 1 CMeHHo' Acetone. Isopropylic alcohol. The relation existing between ethylic alcohol, propylic alcohol, and isopropylic alcohol, will at once be evident from the following formulae : CH 3 J C(CH 3 )H 2 f CH 3 CH 2 Ho- [ CH 2 Ho \ C(CH 3 )HHo' Ethylic alcohol. Propylic alcohol. Isopropylic alcohol. From these formulae it is seen that propylic alcohol is ethylic alcohol in which one atom of hydrogen in the methyl (or non- oxygenated part of the compound) is displaced by methyl ; whereas isopropylic alcohol is ethylic alcohol in which one atom of hydrogen, in the oxygenated part of the compound, is dis- placed by methyl. Ethylic alcohol boils at ... 78'4 Propylic alcohol ... 96 Isopropylic alcohol ... 87 Thus, by substituting an atom of methyl for one of hydro- gen in the non-oxygenated part of the alcohol, the addition of CH 2 raises the boiling-point 17'6 ; whilst, if an atom of hy- drogen in the oxygenated part be similarly displaced, the same addition only raises the boiling-point 8'6. Isopropylic alcohol yields by oxidation a ketone, and not an acid. The radical oxatyl being a necessary constituent in 254 THE ALCOHOLS. organic acids, it will be seen from the following equations that, although propylic alcohol can be converted into an acid without the disruption of its carbon atoms, isopropylic alcohol cannot be so transformed : I'CH 3 \CO(CH 3 ) ' Acetone. Water. + OK TERTIARY MONACID ALCOHOLS. Greneral formula... VINYL SERIES OF MONACID ALCOHOLS. 255 One of these alcohols has recently been obtained, but little is yet known of its reactions. {^*TT CM 3 H ' ^ as keen P r duced by acting with zincic methide on acetylic chloride, and submitting the product thus obtained to the action of water : = {Se 2 (Zn"MeO) Acetylic chloride. Zincic inethide. Zincic chlor- methide. \CMe/Zn"MeO) + CH 4 JCH 3 \CM( Water. eHo Pseudobutlic alcoh uty ol. Methylic hydride. ZnHo 2 . Zincic hydrate. or JCH 8 1 C(CH 3 ) 2 Ho- Pseudobutylic alcohol. CHAPTER XXXI.. MONACID ALCOHOLS : Vinyl or C w H 2n _iHo series. The normal alcohols only of this series are known ; and of 256 THE ALCOHOLS. these but two have been obtained : Vinylic alcohol "|cjj 2 Ho or CMe"HHo. AH r i v i CMe"H AUylic alcohol ... Vinylic alcohol. Allylic alcohol. VINYLIC ALCOHOL. Preparation. By combining acetylene with sulphuric acid and distilling the product with water, in the same manner as in the preparation of ethylic alcohol from ethylene (p. 248) : S0 2 Ho 2 Sulphuric acid. S0 2 (C 2 H 3 0)Ho Sulphovinylic acid. C 2 H 2 Acetylene. OH 2 = Water. S0 2 (C 2 H 3 0)Ho. Sulphovinylic acid. S0 2 Ho 2 Sulphuric acid. CMe"HHo. Vinylic This alcohol is isomeric with aldehyde and with ethylenic oxide : CH 2 CHHo Vim alcoJ Vinylic hol. | OH, \COH Aldehyde. f'CH CH CH 2 0. Ethylenic oxide. If the above, and not I QTT TT , be the true formula for vinylic alcohol, it is obvious that this body could not yield an acid by oxidation ; but if the latter formula represent vinylic f " alcohol, this alcohol ought to yield on oxidation an acid, \ homologous with acrylic acid. REACTIONS OF ALLYLIC ALCOHOL. 257 ALLYLIC ALCOHOL. Soils at 103. Preparation. Grlycerin, when submitted to the action of di- phosphorous tetriodide, yields allylic iodide : fCH 2 Ho ,, +2CMeOA S ' \CH 2 -0-CMeO + Ethylenic Argentic acetate. Ethylenic diacetate. Argentic dibromide. (Diacetic glycol.) bromide. The ethylenic diacetate is now acted upon by potassic hydrate, when it yields potassic acetate and glycol : f CH 2 -0-CMeO 9lrTT f CH 2 Ho \CH 2 -0-CMeO \CH 2 Ho ' Ethylenic diacetate. Potassic Glycol. Potassic acetate, hydrate. Reactions. 1. Grlycol is easily oxidized, the first product of its oxidation being glycollic acid : JCH 2 Ho r 2 |CH 2 Ho + 2 = JGOHo Glycol. Glycollic Water. acid. 2. By further oxidation oxalic acid is formed : \CH 2 Ho 4 = GOHo Glycol. Oxalic Water. acid. 3. Oxalic acid is also produced by heating glycol and po- tassic hydrate together to 250 : JCH 2 Ho 91 n JCOKo H + 2KHo = JCOKO H - Glycol. Potassic Potassic hydrate. oxalate. DERIVATIVES OF GLYCOL. 265 4. Treated with potassium or sodium, the hydrogen of the hydroxyl in glycol is replaced in two successive stages : f CH 2 Nao \CH 2 Ho ; Monosodic glycol. f CH 2 Nao \ CH 2 Nao' Disodic glycol. The following list contains some of the principal derivatives of glycol : CH 2 Ho CH 2 Ho' Glycol. / CH 2 Hs \ CH 2 Hs' Sulphur glycol. J CH 2 Ho 1 CH 2 C1 ' Chlorhydric glycol. / CH 2 Ho 1 CH 2 Br Bromhydric glycol. f CH 2 Eto [ CH 2 Br Bromethylic glycol. CH 2 Eto ( CH 2 Ho ' Hydric ethylic glycol CH 2 Eto CH 2 Eto' Diethylic glycol. fCH 2 Ho I CO ICH, / CH 2 Ho r I CH 2 -O-CMeO ' Monaceti glycol. CH 2 Br CH -0-CMeO' CH 2 -0-CMeO CH r O-CMeO- Diacetic glycol. 266 THE ALCOHOLS. fCH 3 CO J CH 2 J CH 2 -0-CMeO < CH 2 or \ CH 2 -0-CPrO ' O CO V C(C 2 H 5 )H 2 Acetobutyric glyeol. POLYETHYLENIC GLYCOLS. Poly ethylenic Alcohols. These bodies are produced by heating ethylenic oxide with glyeol in sealed tubes, and by other processes. They may be regarded as formed by the addition of ethylenic oxide to glyeol. Diethylenic glyeol Triethylenic glyeol 'CH.HO CH 2 fCH 2 Ho JC 2 H 4 CH 2 or o 2 4 ,CH 2 Ho [CH 2 Ho fCH 2 Ho CH 2 fCH 2 Ho CH 2 j C 2 H 4 O or 1 o )CH 2 1 C 2 H 4 CH 2 o o ^CH 2 Ho fCH 2 Ho Tetrethylenic glyeol CR or O OH, CH 2 O Pentethylenic and hexethylenic glycols have also been termed. TRIACID ALCOHOLS. 267 CHAPTER XXXIV. TEIACID ALCOHOLS. THESE alcohols contain three atoms of hydroxyl united with three separate atoms of carbon ; consequently the lowest term contains three atoms of carbon. Only two of these alcohols have been obtained : ( CH 2 Ho Glycerin \ CHHo . [CH 2 Ho (CH 2 Ho Amylglycerin ... \ CEtHo . [CH 2 Ho The constitution of amylglycerin is not at present established. Its formula may possibly be fCEtHHo ^CHHo . I CH 2 Ho The action of oxidizing agents on amylglycerin will pro- bably throw light upon its internal structure. 268 THE ALCOHOLS. GLYCEEIN. fCH 2 Ho 4 CHHo . [CH 2 Ho Sources. Most animal and vegetable fats consist of mixtures of the glycerin ethereal salts of the fatty and of the oleic series of acids. Glycerin is liberated from these by water at high temperatures, or by bases giving salts insoluble in water : rcH 2 -o-C(c 17 H 35 )o rcH 2 Ho rcrc H \ CH -0-C(C 17 H 35 )0 + 30H = \ CHHo +3 { ^Mn 1 CH 2 -0-C(C 17 H 35 )0 1 CH 2 Ho Stearin. Water. Glycerin. Stearicacid. Relation of Glycerin to Isopropylic Alcohol. By the action of hydriodic acid, glycerin is converted into isopropylic iodide : f CH 2 Ho ^CHHo + SHI = C w H 2n _iCl. HI. C M H 2n _ 7 Cl. The following will serve as examples of the three series : Propylic iodide . . . C 3 H 7 I or C(C 2 H,)H 2 L Allylic iodide . . . Phenylic iodide . . . or C(C 2 H 4 )"HI. or CfC s H 3 )HJ. HALOID ETHERS OF DYAD AND TRIAD RADICALS. 281 Haloid Ethers of the Dyad Positive Radicals. As the diacid alcohols contain two atoms of hydroxyl, it follows that there are two classes of haloid ethers derivable from them. The first is formed by the substitution of one of the hydroxyl atoms by chlorine, bromine, &c., and the second by the like displacement of both atoms of hydroxyl : I. Haloid ethers of the form C n H 2n HoCl. II. 5, )j j, C ro H 2n Cl 2 . The following examples will suffice to illustrate the consti- tution of both these classes of haloid ethers : Chlorhydric glycol or ethy- lenic chlorhy drate C 2 H 4 Ho Cl or f CH 2 Ho I CKC1 ' Ethylenic dichloride C 2 H 4 C1 2 or f CH 2 C1 1 CH 2 cr Haloid ^Ethers of the Triad Positive Radicals. There are three classes of haloid ethers which are derived from the triacid alcohols, by the successive substitution of the three atoms of hydroxyl contained in these alcohols by chlorine, bro- mine, &c., and a fourth class, which stands intermediately between the ethers and the haloid ethers, and which is formed by the substitution of one of the atoms of hydroxyl in the alcohol 282 THE HALOID ETHERS. by a monad negative radical, such as chlorine, bromine, or cyanogen, and the remaining two atoms of hydroxyl by the dyad atom of oxygen: I. Haloid ethers of the form II in. The following are examples of each of these classes : fCH 2 Ho Chlorhydrin. I CHC1 [CH 2 Ho , CH 2 C1 Dichlorhydrin..J CHHo. 1 CH 2 C1 rcH 2 ci Trichlorhydrin. . \ CHC1 . [CH 2 C1 Hydrochloric f CH 2 C1 glycide or epi- < CH chlorhydrin . . I HALOID ETHERS OF THE MONAD POSITIVE RADICALS. Preparation. These ethers are produced by the following general reactions : HALOID ETHERS OF MONAD RADICALS. 283 1. By the action of the hydracids upon the alcohols : C n H w Ho + HC1 = C M H 2W+1 C1 + OH 2 . Alcohol. Hydrochloric Haloid ether. Water, acid. 2. By the action of phosphorous trichloride on the alcohols : 3C n H 2M+1 Ho + PC1 3 = 3C w H 2n+1 Cl + POHHo 2 ' Alcohol. Phosphorous Haloid ether. Phosphorous trichloride. acid. 3. By the action of chlorine on the hydrides of the radi- cals: CJB^H + C1 2 = C n H 2n+1 Cl + HC1. Hydride. Haloid ether. Hydrochloric acid. -i> It is obvious that in these reactions bromine and iodine may be used instead of chlorine. These reactions apply equally to the C n H 2 n-i and C n H 2n _ 7 series. For the preparation of the cyanides of the radicals, two special reactions are employed. 1. The distillation in the dry state of a mixture of the po- tassic sulphate of the radical with potassic cyanide : S0 2 Ko(C n H 2n+1 0) + KCy = SO 2 Ko 2 + C n H 2 ,, +1 Cy. Potassic sulphate of Potassic Potassic Cyanide, the radical. cyanide. sulphate. 2. The fatty acids are converted into ammonium salts and distilled with phosphoric anhydride, when the cyanides of the positive radicals which they contain are produced : |C n H 2n+1 2po fCJff^ 4P0 2 Ho. \CO(N'H 4 0) 2P * 5 \CN'" Ammonium Phosphoric Cyanide. Metaphosphoric salt. anhydride. acid. Reactions. 1. Treated with alcoholic solution of potash, all the haloid ethers of the C w H 2n+1 series, except the cyanides, are reconverted into alcohols : C M H 2 , l+1 Cl + KHo = C w H 2n+1 Ho + KC1. Haloid ether. Potassic Alcohol. Potassic hydrate. chloride. 284 THE HALOID ETHERS. 2. The cyanides under similar circumstances are converted into potassic salts of the acids which contain the positive radi- cal of the cyanide : + KHo -f OH 2 Cyanide. Potassic Water. Potassic Ammonia, hydrate. salt. 3. "When the iodides are digested with zinc or magnesium, the radicals are either liberated or unite with the metal : 2C n H 2n+ I + 2Zn = Zn(C n H 2n+1 ) 2 + ZnI 2 , Iodide. Organo-zinc Zincic compound. iodide. or 2C n H 2n+1 I + Zn = Iodide. Free Zincic radical. iodide. 4. "When the iodides are submitted to the action of sodic ethylate, a mixed ether (or a simple ether if ^=2) is formed : f C n H 2rt+1 C 2 H 5 lSrao + C n H 2n+1 I = j O + Nal. Sodic Iodide. Ether, ethylate. 5. The haloid ethers are the representatives of the hydracids of mineral chemistry, and unite directly with ammonia, pro- ducing salts which, when treated with potassic hydrate, yield compound ammonias containing the basylous radical of the haloid ether in the place of one atom of hydrogen : NH 3 + EtI = NH 3 EtI. Ammonia. Ethylic Ethylammonic iodide. iodide. NH 3 EtI -f KHo = NEtH 2 + KI + OH 2 . Ethylammonic Potassic Ethylamine. Potassic Water, iodide. hydrate. iodide. CHLOROFORM. 285 METHYLIC CHLORIDE. CH 3 C1 or MeCl. Molecular weight =50*5. Molecular volume II I. 1 litre of metJiylic chloride vapour weighs 25*25 criths. Soils at 21. Preparation. By heating together sodic chloride, methylic alcohol, and sulphuric acid : S0 2 Ho 2 + MeHo = SO 2 MeoHo + OH 2 . Sulphuric Methylic Snlphomethylic Water, acid. alcohol. acid. SO 2 MeoHo + NaCl = MeCl + S0 2 HoNao. Sulphomethylie Sodic Methylic Hydric sodic acid. chloride. chloride. sulphate. Reaction. By the action of chlorine, methylic chloride pro- duces three substitution derivatives: Boiling- points. Monochlorinated methylic chloride, CH 2 C1 2 . 31 Dichlorinated CHC1 3 . 60'8 Trichlorinated CC1 4 . 78 CHLOROFORM, Dichlorinated Methylic Chloride. CHC1 3 . Molecular weight =119'5. Molecular volume [""[""] 1 litre of chloroform vapour weighs 59'7 '5 criths. Sp.gr. 1'48. Soils at 60-8. Preparation. This compound is manufactured in large quantities by heating alcohol with -a solution of calcic chloro- hypochlorite (chloride of lime). It may also be made by treat- ing methylic alcohol in the same manner. For the reaction see p. 250. Reactions. 1. Chloroform is transformed into potassic for- mate by boiling with alcoholic potash : CHC1 3 + 4KHo = CHOKo + 3KC1 + 2OH 2 . Chloroform. Potassic Potassic Potassic Water, hydrate. formate. chloride. 286 THE HALOID ETHERS. 2. When acted upon by chlorine in the presence of sunlight, the hydrogen is displaced by chlorine, and carbonic tetrachlo- ride (CC1 4 ) formed. ETHYLIC CHLORIDE. C 2 H 5 C1 or EtCl. Molecular weight =64*5. Molecular volume II I. 1 litre of ethylic chloride vapour weighs 32*25 criths. Sp. gr. 0*874. Soils at 11'5. Preparation. Ethylic alcohol is saturated with hydrochloric acid, and digested in sealed tubes at 100 for one or two hours, when the mixture separates into two layers, the upper one being the ethylic chloride : EtHo + HC1 = EtCl + OH 2 . Alcohol. Hydrochloric Ethylic Water, acid. chloride. ETHYLIC IODIDE. C 2 H 5 I or EtI. Molecular weight =156. Molecular volume II I. 1 litre of ethylic iodide vapour weighs 78 criths. Sp. gr. 1*9464. Soils at 72*2. Preparation. By placing in a retort two parts by weight of alcohol and one of amorphous phosphorus, and then introducing five parts of iodine and distilling in a water-bath : 3C 2 H 6 Ho + P + I 3 = 3C 2 H 5 I + POHHo 2 . Alcohol. Ethylic Phosphorous iodide. acid. HALOID ETHERS OF THE DYAD RADICALS. 287 Reaction. Ethylic iodide, when heated with water in a sealed tube, produces ether and hydriodic acid : fC 2 H 5 2C 2 H 5 I + OH 2 =^0 + 2HL IC 2 H 5 Ethylic Water. Ether. Hydriodic iodide. acid. The methylic and amylic iodides are similar liquids, and ob- tained by analogous processes ; the methylic iodide, CH 3 I, has a sp. gr. 2-237, and boils at 42 C. Amylic iodide, C 5 H U I, has a sp. gr. 1-511, and boils at 146. The haloid compounds of the allylic and phenylic series are of comparatively little importance. HALOID ETHERS OF THE DYAD POSITIVE RADICALS. I. Haloid ethers of the form C^TLoCl. Preparation. These ethers are prepared by the action of the hydracids on the glycols. The following will serve as examples of this class : {CTT TTo CH 2 C1 ' Ethylenic iodhydrate or iodhydric glycol ... | ciT 2 T ' Treated with potassic hydrate, both these bodies give ethy- lenic oxide, as previously described (p. 277). II. Haloid ethers of the form C n H 2w Cl 2 . Preparation. These ethers are generally formed by the direct union of the dyad radicals with the chlorous elements. The following list comprises the chief members of this class: Boiling-points. Methylenic chloride CH 2 C1 2 40 iodide CH 2 I 2 181 Ethylenic chloride C 2 H 4 C1 2 85 288 THE HALOID ETHERS. Boiling-points. Ethylenic bromide C 2 H 4 Br 2 129 iodide C 2 H 4 I 2 Propylenic chloride C 3 H 6 C1 2 103 bromide C 3 H 6 Br 2 144 iodide C 3 H 6 I 2 Butylenic chloride C 4 H 8 C1 2 127 bromide C 4 H 8 Br 2 160 Amylenic chloride C 5 H 10 C1 2 bromide C.H 10 Br 2 175 By the action of potassium, sodium, or zinc, the radicals are again liberated, except in the case of the methylene compounds. The bromides are the most important members of the series. ETHYLENIC BROMIDE. C 2 H 4 Br 2 or or Et"Br 2 . Molecular weight =188. Molecular volume I I I. 1 litre of efhylenic bromide vapour weighs 94 criths. Sp. gr. 2'16. Fuses at 9. Soils at 129. Preparation. By agitating bromine and water with ethy- lene. Reactions. 1. Boiled with alcoholic potash it yields brom- ethylene or vinylic bromide : C 2 H 4 Br 2 + KHo = C 2 H 3 Br + KBr -f OH 2 . Ethylenic Potassic Vinylic bromide Potassic Water. bromide. hydrate. or bromethylene. bromide. 2. Heated with an alcoholic solution of potassic acetate, it yields monacetic glycol. JCH 2 Br ocMpOlTn OH fCH -0-CMeO lCH 2 Br + 2CMeOKo + OH * = |CH 2 "Ho Ethylenic Potassic Water. Monacetic glycol. bromide. acetate. + CMeOHo + 2KBr. Acetic Potassic acid. bromide. HALOID ETHERS FROM GLYCERIN. 289 ETHYLENIC CYANIDE. Fuses at 37. Preparation. By heating ethylenic bromide with potassic cyanide to 100 for sixteen hours : + 2CN-K = + 2KBr. Ethylenic Potassic Ethylenic Potassic bromide. cyanide. cyanide. bromide. Reaction. "When boiled with alcoholic potash, ethylenic cyanide yields potassie succinate : fCH 2 (CN'"), 9TrHn 90H fCH a (COKo) 1CH 2 (CN'") + 2KHo + 20H * = Ethylenic Potassic Water. Potassic Ammonia. cyanide. hydrate. succinate. HALOID ETHERS OF THE TRIAD POSITIVE RADICALS. I. of the form C n H 2a _ l 'Bio,fll. Boiling- point. fCH 2 Ho Chlorhydrin .. . J CHC1 ............ 227. I CH 3 Ho fCH 2 Ho Bromhydrin ... { CHBr ............ 180 in vacuo. { CH a Ho II. Of the form C fCH 2 Cl Dichlorhydrin... ^ CHHo ............ 180. [CH 3 C1 III. Of the form CBCl. fCH 2 Cl ydrin. . \ ( Trichlorhydrin. . 4 CHC1 155. [CH 2 C1 o 290 THE ALDEHYDES. IV. OftheformC w H 2 n-iOCl. Boiling- point. Hydrochloric ( CH n glycide or epi- 1 CR L 118. chlorhydrin ... 1 CH 2 C1 Preparation. The ethers of the first three forms are obtained by the action of the hydracids upon glycerin ; whilst those of the fourth are produced by the action of alkalies upon the second form of compounds. CHAPTER XXXVII. THE ALDEHYDES. THESE compounds are intermediate between the alcohols and the acids. They are formed from alcohols by the abstraction of hydrogen ; hence the name, which is an abbreviation of alcohol dehydrogenatum. Three series of aldehydes are known, corresponding to the three series of monacid alcohols, viz. : A. Aldehydes derived from C n H 2rt+ iHo alcohols. B% C w H2 W _!Ho C. C w H 2w _ 7 Ho Preparation. 1. The aldehydes are formed by the oxidation of the alcohols ; ethylic alcohol, for instance, yields acetic alde- hyde : j CH, i n i ^^3 4- OH \ CH 2 Ho { COH UM2> Ethylic Acetic Water, alcohol. aldehyde*. 2. Aldehydes are also formed by distilling a mixture of equiva- REACTIONS OF ALDEHYDES. 291 + COKo, lent quantities of the potassic salt of a fatty acid and of potassic formate : / CH, / H r CH, I COKo 1 COKo \ COH Potassic Potassic Acetic acetate. formate. aldehyde. carbonate. This is an important reaction, as by its means the series of fatty acids can be ascended; for the aldehyde may next be transformed into an alcohol by nascent hydrogen, then the alcohol converted into a cyanide, which by treatmentwith potassic hydrate gives the potassic salt of the next higher acid. Thus : fCH, JCH 3 1 CH 2 Ho Ethylic alcohol. S0 2 HoEto Sulphovinic acid. f CMeH, {COH Acetic aldehyde. CH Ho Ethylic alcohol. S0 Ho = SO, + OH 2 Sulphuric acid. Potassic cyanide. Sulphovinic acid. SO 2 KoHo Hydric potassic sulphate. Water. f CMeH, ION" 1 ' ' Ethylic cyanide. + OH Potassic hydrate. 2 Water. JCMeH 2 - COKo Potassic propionate. Ammonia. 1 CN'" Ethylic cyanide. Starting again with potassic propionate, instead of potassic acetate, the same series of reactions can be performed, resulting in potassic butyrate, and so on. Reactions. 1. By direct absorption of oxygen, the aldehydes are transformed into the corresponding acids : {COH Aldehyde. Acid. 2. Also heated with ammoniacal solution of argentic oxide, the aldehydes are converted into acids, metallic silver being deposited : , \ COH \COHo Aldehyde. Argentic oxide. Acid. 3. When heated with potassic hydrate, the aldehydes yield the potassic salts of the corresponding acids, with evolution of hydrogen : o2 292 THE ALDEHYDES. J C n H 2n +i I TTTT^ -rr COH KHd - \COKo H *' Aldehyde. Potassic Potassic hydrate. salt. 4. Treated with nascent hydrogen, they are converted into the corresponding alcohols : ra i -a 2ra+1 COH " 1 CH 2 Ho ' Aldehyde. Alcohol. 5. Most aldehydes combine directly with ammonia, forming crystalline compounds : J C n ll2n+l _i_ TVTTT J \COH w3 \ Aldehyde. Ammonia. Ammonium compound. 6. Aldehydes also combine with the alkaline hydric sulphites, producing crystalline compounds : +l SOKoHo = SOKoHo , +1 Hydric potassic sulphite. Aldehyde. A. ALDEHYDES DEE1VED FROM THE C n H 2n+1 Ho SERIES OF ALCOHOLS. The following are known : Fusing- Boiling- point. point. Acetic aldehyde ...... {cOH ................................. - 21 ' Propionic aldehyde . . | ^* or j g^ ^ ......... - (55-65). Butyric aldehyde -. 2 or 15 ^ 2 ......... - (68-75). Valeric aldehyde . . . or ......... - 93. (Enanthic aldehyde., j ^OH* 2 or {c^ U ^ below -12 8 . 152. Capric aldehyde ...... {c^OU'"^ ........................... ~ 2 ' 228 ? Euodic aldehyde ...... { % ( H~ 1 ^ H * ........................... + 7. 213. Laurie aldehyde ...... {^cm 3 " 31 ^ 2 ........................ - 232 ' Palmitic aldehyde... H ^ H 3 ........................ 52. REACTIONS OF ACETIC ALDEHYDE. 293 ACETIC ALDEHYDE, Aldehyde. J 3 \COH Molecular weight = 44. Molecular volume ["Tl- 1 litre of aldehyde vapour weighs 22 criths. Sp. gr. 0*79. Boils at 21 0> 8. Preparation. 1. By oxidizing alcohol with chromic acid, chlorine water, or manganic oxide and sulphuric acid : + = {cok + Ethylic Acetic Water. alcohol. [aldehyde. 2. By oxidation, casein, fibrin, and albumen also yield alde- hyde. 3. Aldehyde is formed when the vapour of alcohol or ether is passed through a tube heated to dull redness. Reactions. 1. It gradually absorbs oxygen from the air, forming acetic acid, into which it is also readily converted by oxidizing agents : CH 3 Q f CH 3 COH \ COHo' Acetic Acetic aldehyde. acid. 2. It reduces silver salts, depositing lustrous metallic silver on the sides of the vessel. 3. When submitted to the action of potassium, one atom of hydrogen is substituted by an atom of the metal, the compound V COK being formed. 4. Hydrocyanic acid transforms aldehyde into alanin : JCH 3 rivr/l/1T OTT JCMeHHo \COH ^ tCO(N'"H 2 )' Acetic Hydrocyanic Water. Alanin. aldehyde. acid. 294 THE ALDEHYDES. By the action of nitrous anhydride, alanin is converted into lactic acid : f CMeHHo N _ 2 f CMeHHo w 2 { CO(N'"H 2 ) ' " W 33 " 2 { COHo h JJN * Alanin. Nitrous Lactic acid. Water, anhydride. There are three isomeric modifications of aldehyde : Metaldehyde, crystalline, subliming at 120. ParaldeJiyde, liquid, boiling at 125. Elaldehyde, crystalline, fusing at 2, boiling at 94. B. ALDEHYDES DERIVED FROM THE ALCOHOLS. ACROLEIN. Acrylic Aldehyde. f CMe"H JCOH Molecular weight =56. Molecular volume [~[~]. 1 litre of acrolein vapour iveiglis 28 critJis. Boils at 52'4. Preparation. 1. By the action of phosphoric anhydride or of sulphuric acid on glycerin : f CH,HO f ^ . X O = i {CH 2 H Glycerin. Water. Acrolein. 2. By the oxidation of ally lie alcohol : f CMe"H f CMe"H ICBTHo + = {COH + Allylic Acrolein. Water. alcohol. 3. By the action of heat on the product of the union of ace- tone with bromine : f COMe -R r f CMeBr 2 1CH 3 Br ^ ^ lCH 2 Ho : Acetone. CMeBr, f CMe"H 9TTT , o = ICOH + 2HBr - Acrolein. Hydrobromic acid. BENZOIC ALDEHYDE. 295 Reaction. By oxidation, acrolein yields acrylic acid : f CMe"H n f CMe"H JCOH t COHo * Acrolein. Acrylic acid. C, ALDEHYDES DERIVED FROM THE C n H 2n _ 7 Ho ALCOHOLS. Benzoic aldehyde ...... j Cuminic aldehyde . . . j Q^^^ - - - 229-4. BENZOIC ALDEHYDE, Oil of Bitter Almonds, Hydride of Benzoyl. Molecular weight =106. Molecular volume II I. 1 litre of benzoic aldehyde vapour weighs 53 critJis. Sp. gr, 1*04:3. Boils at 180. Preparation. 1. By the oxidation of amygdalin by nitric acid, and by the action of a mixture of manganic oxide and sul- phuric acid on albumen, fibrin, casein, and gelatin. 2. By digesting bitter almonds with water for five or six hours at 30-40. The synaptase present acts as a ferment on the amygdalin, converting it into glucose, benzoic aldehyde, and hydrocyanic acid : Amygdalin. Water. Benzoic Hydrocyanic Glucose. aldehyde. acid. Reactions. 1. When exposed to the air, benzoic aldehyde absorbs oxygen and is converted into benzoic acid : f C(C,H 3 )H a Q f C(C 5 H 3 )H 2 \ COH \ COHo Benzoic aldehyde, Benzoic acid. 2. Heated with solid potassic hydrate, it gives hydrogen and potassic benzoate : + KHo = Benzoic Potassic Potassic aldehyde. hydrate. benzoate. 296 THE ACIDS. CHAPTER XXXVIII. THE ACIDS. THE acids form the most numerous family of organic com- pounds. Many of them are contained in plants in the free state, or in combination as metallic or ethereal salts. Others are produced by the action of chemical agents on organic matters. Some are formed in the animal organism, as, for instance, formic, paralactic, oleic, and stearic acids. The organic acids are divided into three great classes, accord- ing to their basicity. 1. Monobasic acids. 2. Dibasic acids. 3. Tribasic acids. The basicity of organic acids is determined by the following simple law : an organic acid containing n atoms of oxatyl is n-basic. MONOBASIC ACIDS. The monobasic acids, which always contain a single atom of oxatyl (COHo), include the six following series : Q-eneral formulas. f C TT 1. Acetic or fatty series ...... | cOHo" 1 ' 2. Acrylic or oleic series ...... g^|H 2n )"(C m H 2m+1 ) 3. Lactic series 4. Pyruvic series ............... { 5. Glyoxylic series ............... j 6. Benzoic or aromatic series j COH 2 " 2 ' ACETIC SERIES OF ACIDS. 297 The 1st, 2nd, 3rd, 5th, and 6th of these series may be regarded as the derivatives from corresponding series of alcohols. 1. The Acetic series from the Methyl series of alcohols. 2. Acrylic Allyl 3. Lactic Ethylene 5. Glyoxylic G-lycerin 6. Benzoic Benzoic The acids of the first, second, fourth, and sixth series are termed monoJiydric as well as monobasic ; whilst the acids of the third series are termed dihydric and monobasic, indicating their origin from the diacid alcohols, and that they contain two atoms of hydroxyl, one of which is in the oxatyl, and the other in the positive part of the compound. The hydrogen of the latter hydroxyl may be displaced by very positive metals, in the same manner as the hydrogen of the hydroxyl in alcohols ; but it cannot be displaced by double decomposition with bases in the same manner as the hydrogen in the oxatyl may be sub- stituted. The acids of the fifth series are termed trihydric and mono- basic, indicating that they are derived from the triacid alcohols, and that they contain, besides the hydroxyl in the oxatyl, two other atoms of hydroxyl in the positive part of the compound. 1. ACETIC OR FATTY SERIES OF ACIDS. General formula ... These acids may be conveniently arranged under three divi- sions, viz. : A. Normal acids. General formula . . . j General formula ... 1 B. Secondary acids. ula ... 1 2{3f?* l+1 ) H . [ CfOJio o5 298 THE ACIDS. C. Tertiary acids. General formula .. A. NOEMAL ACIDS OF THE ACETIC OE FATTY SEEIES. G-eneral formula . In formic acid, which is generally considered to be the first term of this division, the radical C(C n H 2n+ i)H 2 is replaced by H ; and in acetic acid the value of n=0. The following is a list of the normal fatty acids : Fusing- Boiling- point, point. f TT Pormicacid I COHo +1- 100. .-, [Me f CH 3 , ,,- ,-,,,0 Acetic acid { C OHo or \ COHo + 17 ' T, . M JCMeH 2 JC(CH 3 )H 2 14 , Propiomc acid . j COHo 2 or j c v OHo 3 ' ., JCEtH 2 JC(C 2 H.)H 2 below 1ftlo Butyric acid ...| COHo 2 {oo4o "' -20. T71 . ., JCPrH 2 JC(C 3 H 7 )H 2 17 - Yaleric acid { COHo or 1 COHo r ^T? -,TJ r (** f c* TT ^TT /^i *i I ^-DUn o I Vy I vy. i-iq ) -Lin I ro i r\oo Caproic acid ... j QQHo or I COHo "^ ' /"N T T I ^^ V^ U JLL I ^^( ^L! Jtl-i o )xl -1 A Q OO/^O Caprylic acid ... j QQJJ 2 or j COHo ' ' Pelargonic acid .. j Sk C T 7 T Hl5)H3 ... +18? 260. Melissic acid NORMAL FATTY ACIDS. 299 Fusing- point. Capric acid ..................... { oOHo" )Ha 2 7'2(30). Laurie acid ..................... 2 43 ' 6 ' Myristic acid 2 53 ' 8 ' Arachidic acid .................. 372 75 - Behenic acid .. J JftX'r 1 * 1 ' 11 ' 70. Ceroticacid 5l2 7S Palmitic acid .................. cOm 62 * Margaricacid .................. (3l)H2 59 ' 9 ? Stearicacid 50 300 THE ACIDS. Occurrence. The greater number of the acids of this series are met with ready formed in nature, some in the free state, as formic acid in ants and nettles, valeric acid in the valerian root, pelargonic acid in the essential oil of the Pelargonium roseum, and cerotic acid in bees-wax. Others are met with as the ethereal salts of monacid alcohols. Thus spermaceti is cetylic palmitate, and Chinese wax cerylic cerotate. A large number exist as natural fats in the form of the ethereal salts of glycerin : this is the case with butyric, pal- mitic, and stearic acids, which, united with glycerin, form respectively butyrin, palmitin, and stearin. Formation. 1. By the oxidation of the normal alcohols of the methyl series, as in the conversion of alcohol into acetic acid by heating it with a solution of chromic acid : CH 2 Ho Alcohol. - \COHo Acetic acid. + OH 2 . Water. 2. By the action of alkalies or acids upon the cyanides of the C n H 2 ,, + i series of radicals : ON'" Cyanide. and + KHo + OH = Potassic hydrate. f C n H 2n+1 \COKo Water. Potassic salt. NH, s ' Ammonia. ON'" Cyanide. + HC1 + Hydrochloric acid. OftTT J n**2n+l ^ u1 2 - IcOHo Water. Acid. 3XTH 4 C1. Ammonic chloride. Instances of these reactions are seen in the treatment of ethylic cyanide by a boiling solution of potassic hydrate, when it is converted into potassic propionate, ammonia being evolved, thus FORMATION OF NORMAL FATTY ACIDS. 301 CMeH. -^-p- OTT JCMeH 2 ' KHo + OH > COKo Ethylic Potassio Water. Potassic Ammonia. cyanide. hydrate. propionate. and in the conversion of ethylic cyanide, by the action of hydro- chloric acid, into ammonic chloride and propionic acid fCMeH. -p-pn OOT T JCMeH 2 ivm- n JCN"' ^ + 20H > = \COHo + NH * CL Ethylic Hydrochloric Water. Propionic Ammonic cyanide. acid. acid. chloride. 3. By the action of the potassium or sodium compound of the C n H 2 ,, +1 radicals upon carbonic anhydride C0 2 + CH 2ntl Na = {'oN + ao> Carbonic Sodium Sodie anhydride. compound. salt. as, for example, in the formation of sodic propionate by the ab- sorption of carbonic anhydride by sodic ethide : CO, + CMeH,Na = { Carbonic Sodic ethide. Sodic anhydride. propionate. 4. By the oxidation of aldehydes C n H 2n+1 Q J C n H 2w+1 COS \ COHo ' Aldehyde. Acid. as in the conversion of acetic aldehyde into acetic acid by the absorption of atmospheric oxygen : / CH 3 f 3 jcok + {coko Acetic Acetic aldehyde. acid. Besides these reactions of general application, there are numerous special methods for the production of certain mem- bers of this series. In most of these methods, however, the reactions cannot be clearly traced. Thus, by the oxidation of albumen, fibrin, casein, and other similar substances, there are produced formic, acetic, propi- onic, butyric, valeric, and caproic acids. 302 THE ACIDS. Propionic and butyric acids are produced in some kinds of fermentation ; and acetic acid is obtained by the destructive distillation of wood and other similar substances. Relations of the Normal Fatty Acids to the C n H 2n+1 Series of Radicals. 1. "When these acids are submitted to the action of nascent oxygen evolved by electrolysis, the negative radical oxatyl is converted into carbonic anhydride and water, the positive radical being set at liberty : o f C w H 2n +i if) f CVHWi , 2 COHo C Acid. Positive Carbonic Water. radical. anhydride. On electrolyzing a solution of potassic valerate, hydric po- tassic carbonate and the normal radical butyl are formed : {c'(?K O = Potassic Water. Butyl. Hydric potassic Talerate. carbonate. 2. When the ammonic salts of these acids are heated with phosphoric anhydride, they are converted into cyanides of the radicals of the CH 2n + \ series {C n H 2n +l , op r\ f nzn+i CO(N V H 4 0) Z ^ 5 \CN'" Ammonic salt. Phosphoric Cyanide. Metaphosphoric anhydride. acid. as in the transformation of ammonic acetate into methylic cyanide by distillation with phosphoric anhydride : Ammonic Phosphoric Methylic Metaphosphoric acetate. anhydride. cyanide. acid. These cyanides are converted into normal monacid alcohols by Mendius's reaction (see p. 248). From the alcohols so obtained, the CH 2n+1 radicals are iso- lated as described at page 246. ASCENT OF THE SERIES OF FATTY ACIDS. 303 Relations of the Normal Fatty Acids to the C n H 2n +iHo Series of Alcohols. 1. By oxidation the normal alcohols yield these acids, as #bove shown. 2. Conversely, the normal fatty acids can be converted into the normal C n H 2w+ iHo alcohols, 1st, by Mendius's reaction (see p. 248) ; 2nd, by Piria and Wurtz's reactions, viz. : Distillation of the potassic salt of the fatty acid with an equivalent quantity of potassic formate, by which the acid is converted into the aldehyde J CH 2n +i , f H f Cn^^nti ( COKo \ COKo \ COH Potassic Potassic Aldehyde. Potassic salt. * formate. carbonate. and subsequent treatment of the aldehyde by nascent hy- drogen J C w H 2n +i i TT J C w H 2ra +i \ COH ^ \ CH 2 Ho ' Aldehyde. Normal alcohol. Relations of the Normal Fatty Acids to each other. Ascent of the Series. If the hydrogen constituting the positive part of formic acid were substituted successively by methyl, ethyl, &c., the whole series of normal fatty acids would be obtained : Formic acid { GOHo' Acetic acid . . I w (O TT COHo- Butyric acid .... This substitution has not yet been accomplished ; but an analogous series of reactions has been effected with acetic acid. THE ACIDS. 304 By the action of sodium on acetic ether, one of the hydrogen atoms in the positive part of the compound becomes substituted by sodium, producing Monosodacetic ether J 5^7;dr a \ COEto' By acting on this body with the iodides of the C n H 2n+1 radicals, ethylic salts of the higher acids are produced. On submitting monosodacetic ether to the action of methylic iodide, for instance, propionic ether is formed f CH 2 Na ^ T / C(CH 3 )H 3 1 COEto + CH 3 I = { COEto Monosodacetic] Methylic Propionic Sodic ether. iodide. ether. iodide. and by the action of ethylic iodide, butyric ether is produced f CH 2 Na c T f C(C 2 H 5 )H a T { COEto + 'W = { COEto Monosodacetic Ethylic Butyric Sodic ether. iodide. ether. iodide. FORMIC ACID. Molecular weight = 46. Molecular volume [""[""! 1 litre of formic acid vapour weighs 23 criths. Sp.gr. T2353. Fuses at 1 C. Boils at 100 C. Occurrence. If red ants be made to pass over blue litmus- paper and be at the same time irritated, they leave a red streak behind them, produced by the formic acid which they eject. By placing the hand on an ant-hill, a tingling sensation is felt from the same cause, and the hand acquires the powerful and pleasant odour of formic acid. Formic acid also occurs in the hairs of certain caterpillars, and in the sting of nettles. Formation. 1. Eormic acid is produced in a very large num- ber of chemical reactions, as in the oxidation of many organic FORMIC ACID. 305 matters (such as starch, woody fibre, or tartaric acid) by a mix- ture of sulphuric acid and manganic oxide, or by potassic hy- drate or chromic acid. 2. By the action of potassic hydrate on chloroform, potassic formate is generated : CHOI, + 4KHrf = CHOKo + 3KC1 ]+ 2OH 2 . Chloroform. Potassic Potassic Potassic Water. hydrate. formate. chloride. 3. By the oxidation -of methylic alcohol : Methylic Formic Water. alcohol. acid. 4. By heating equal weights of dry oxalic acid and glycerin together to 75 C., when the oxalic acid splits into formic acid and carbonic anhydride : fCOHo fH \COHo \COHo + Oxalic Formic Carbonic acid. t acid. anhydride. 5. By digesting together at 100, for forty-eight hours, potassic hydrate and carbonic oxide : K;H O + co fH \ COKo' Potassic Carbonic Potassic hydrate. oxide. formate. Eormic acid from any of these sources is obtained in the concentrated state by decomposing plumbic formate with sul- phuretted hydrogen, and afterwards rectifying the acid over plumbic formate : Plumbic Sulphuretted Formic Plumbic formate. hydrogen. acid. sulphide. 306 THE ACIDS. Character. When heated with concentrated sulphuric acid, formic acid splits into water and carbonic oxide : = CO + OH, , Formic Carbonic Water. acid. oxide. Chlorine converts formic acid into hydrochloric acid and car- bonic anhydride : C1 > = 2HC1 + C0 - Formic Hydrochloric Carbonic acid. acid. anhydride. When heated with excess of mercuric oxide, it is converted into carbonic anhydride and water, the mercury being reduced to the metallic state : Formic Mercuric Carbonic Water. acid. oxide. anhydride. ACETIC ACID. Molecular weight =60. Molecular volume II I. 1 litre of acetic acid vapour weighs 30 critJis. Sp. gr. 1/064. Fuses at +17. Boils at 117. Occurrence. Found in small quantities in the juices of plants and in animal fluids. Manufacture. 1. By the destructive distillation of wood, a liquid is obtained which contains acetic acid ; the acid is pu- rified by being converted first into a calcic, and then into a sodic salt, the latter being afterwards decomposed by sulphuric acid. 2. By the oxidation of ethylic alcohol : {ci-.no + > = {COHO + OH >- Ethylic Acetic Water. alcohol. acid. ACETIC ACID. 307 Preparation. Pure acetic acid may be obtained by distilling potassic diacetate : f CH 3 I CH 3 \ COKo' \ COHc Potassic diacetate. 1 COKo Potassic acetate. JCH 3 \COHo' Acetic acid. Character. Chlorine acts on acetic acid in sunlight, pro- ducing three chlorinated acids, in which chlorine is substituted for hydrogen : COHo Acetic acid. rcH 2 ci \COHo Monochloracetic acid. J CHC1 2 \COHo Dichloracetic acid. + 01, = + ci, + 01, CH.C1 COHo Monochloracetic acid. / CHC1 3 I COHo Dichloracetic acid. /CO, \COHo Trichloracetic acid. + HC1. Hydrochloric acid. + HC1. Hydrochloric acid. + HC1. Hydrochloric acid. The salts of acetic acid in which the hydrogen of the oxatyl is replaced by monad metals have the general formula JCH 3 1 COMo' The acetates of the dyad metals have the constitution repre- sented by the following general formula : rcH 3 rco-o- \CH 3 CMe0 . or \ Mo" or CTV/r _ o o - [CMeO ^ MeUJ By the action of phosphorous trichloride, acetic acid yields acetylic chloride: Acetic acid. Phosphorous trichloride. ofCH, 6 \ COC1 Acetylic chloride. -f POHHo, Phosphorous acid. THE ACIDS. PROPIONIC ACID, Methacetic Acid. f CMeH 3 \ COHo ' Molecular weight = 74. Molecular volume I I I 1 litre ofpro- pionic acid vapour weighs 37 critlis. Soils at 141. Preparation. 1. By the oxidation of metacetone a liquid obtained by the distillation of a mixture of sugar and lime. 2. By the action of concentrated solution of potassic hydrate on sugar. 3. By the fermentation of glycerin, and also of sugar, by means of putrid cheese in the presence of calcic carbonate. 4. By the action of potassic hydrate or hydrochloric acid on ethylic cyanide (see p. 300). 5. By the action of carbonic anhydride on sodic ethide (see p. 301). 6. By the action of hydriodic acid on lactic acid : JCMeHHo 9TTT JCMeH a . \COHo \COHo + OH > + T - Lactio Hydriodio Propionic Water, acid. acid. acid. 7. By the action of m ethylic iodide on sodacetic ether (see page 304). BUTYRIC ACID, Ethacetic Acid. j CEtH 2 \COHo' Molecular weight = 88. Molecular volume I I I. 1 litre of butyric acid vapour weighs 44 criths. Sp. gr. 0'9886. Fuses below 20. Soils at 161 C. Occurrence. In butter, juice of flesh, perspiration, and many animal secretions. Preparation. 1. By the fermentation of sugar with putrid cheese. ISOMERS OF VALERIC ACID. 309 2. By the action of ethylic iodide on sodacetic ether (for reaction, see page 304) . VALERIC ACID, Valerianic Acid. fCPrH Molecular weight =102. Molecular volume I I 1. 1 litre of valeric acid vapour weighs 51 critks. Sj). gr. 0*937. Soils at 175. Occurrence. In many plants, as in the roots of valerian and angelica. Preparation. By the oxidation of amylic alcohol with a mix- ture of sulphuric acid and dipotassic dichromate : 0, - Amylic ale Valeric acid. OH, Water. Isomeric forms. There are four possible isomers of valeric acid : Normal valeric acid or f CPrH a()p f CH 2 (CH 2 [CH 2 (CH 8 )]) propvlacetic acid ... I COHo ( COHo ^ropylaceticacid ... 310 THE ACIDS. Methethacetic acid ... *) Tritnethacetic acid .. . . I f^^-rr or \ ^Jx-n- [ V/w-tLO [ wU-CLO -- Of these, the normal, the /3 propylacetic, and the trimetha- cetic acid are known. B. SECONDARY FATTY ACIDS. General formula... Formation. By the action of the iodides of the C n R 2n+l radicals on disodacetic ether, the ethereal salts of these acids are produced. SECONDARY AND TERTIARY FATTY ACIDS. 311 DIMETHACETIC ACID, or Isolutyric Acid. JCMe 2 H I COHo ' Molecular weight =88. Molecular volume I I I. 1 litre of dimetJiacetic acid vapour weighs 44 critJis. Soils at 152. Isomeric with liutyric or ethacetic acid. Preparation. As a potassic salt, by the action of methylic iodide on disodacetic ether and the subsequent decomposition, by alcoholic solution of potash, of the ethereal salt so formed : GOEto Disodacetic ether. Methylic iodide. fCMe 2 H JGOEto Dimethacetic ether. + 2NaL Sodic iodide. JCMe 2 H ICOEto + Dimethacetic ether. Potassic hydrate. JCMe 2 H (cOKo Potassic dimethacetate. Alcohol. Diethacetic acid, TT isomeric with caproic acid, and diamylacetic acid, \ QQJ| O , isomeric withlauric acid, have been prepared by the substitution of ethylic and amylic iodides in the above reaction. C. TERTIARY FATTY ACIDS. General formula... { Formation. As ethereal salts, by the action of the iodides of the C M H2n + i radicals on trisodacetic ether. 312 THE ACIDS. TBIMETHACETIC ACID. CMe. COHo' Molecular weight =102. Molecular volume I I I. 1 litre of trimethacetic acid vapour weighs 51 criths. Isomeric with voter ianic acid. For the graphic formula of trimethacetic acid see p. 310. Preparation. As an ethereal salt, by the action of methylic iodide on trisodacetic ether : Trisodacetic Methylic Trimethacetio Sodic ether. iodide. ether. iodide. CHAPTER XXXIX. THE ACIDS. 2. ACRYLIC OR OLEIC SERIES OF ACIDS. General formula of normal and f C(C n H 2M )"(C m H 2m+1 ) secondary acids { COHo This series is divided into normal, secondary, and olefine acids. In the normal acid m=0; in the secondary it must be a positive integer. Most of the normal acids exist as glycerin ethers in natural fats and oils. The following is a list of the acrylic series of acids : A. NORMAL ACIDS. or |C(CH /H NORMAL AND SECONDARY ACIDS OF THE ACRYLIC SERIES. 313 or 2 . Dainaluric acid ................................. C 7 H 12 O Damolic acid .................................... C 13 H 24 O 2 . Moringic acid ............ 1 PTTO Cimicicacid ............ I Physetoleic acid ......... ^ Hypogaeic acid ......... I .................. C 16 H 30 O a . Gaidic acid ............... J Oleicacid . " 1 Elaidicacid ....................................... CH 34 2 . Doeglicacid C 19 H 36 O 2 . rassic acid.) Brassic acid. (Erucic 1 J B. SECONDARY ACIDS. Met^otonicaeid ...... Qr acid ......... { g { C. OLEFINE ACIDS. fCMe"H fC(CH 2 )"H /3 Crotonic acid ............ \ CH 2 or X CH 2 [ COHo [ COHo Formation of Normal Acids. 1. By the oxidation of the alcohols of the vinyl or C n H 2n _iHo series : fC(C.H 2n )"H Q rC(C,,H 2 ,,)"H (CH a Ho u > \COHo Alcohol. Acid. Water. 2. By the oxidation of the aldehydes of the acrolein or + . Aldehyde. Acid. 314 THE ACIDS. Formation of Secondary Acids. By the action of the phos- phorus chlorides or of phosphoric anhydride upon the ethereal salts of secondary acids of the lactic series, the elements of water are removed and the ethereal salts of the acrylic secon- dary division of acids produced : f C(C M H 2M+1 ) 2 Ho pcl 3 f C(C n H 2n )"(C n H 2n+1 ) d { COEto ^ 3 d 1 COEto Ethereal salt of Phosphorous Ethereal salt of the lactic series. trichloride. the acrylic series. + POHHo 2 + 3HC1. Phosphorous Hydrochlo- acid. ric acid. Formation of Olefine Acids. By the action of potassic hydrate upon the cyanides of the C n H 2n _i family of radicals : fCMe"H fCMe"H \ CH 2 + KHo -f OH 2 = \ CH 2 + NH 3 . I ON'" [COKo Allylic cyanide. Potassic Water. Potassic Ammonia, hydrate. /3 crotonate. Relations of the Acrylic to the Acetic Series of Acids. The normal and secondary acids of the acrylic series, when treated with fused potassic hydrate, yield the potassic salts of two normal acids of the acetic series : + 2KHo = Acid of the acrylic series. Potassic Potassic salt of acid hydrate. of the acetic series. i f C(C n _ 2 H 2rt _ 3 )H TT + JGOKo ^ Potassic salt of acid of the acetic series. All the members of the acrylic series found in nature give acetic acid as one of the acids produced in this reaction. From this and other considerations it is believed that their ACRYLIC ACID. 315 basylous radicals all contain one atom of hydrogen and a dyad radical. They are normal acids ; and by the action of fused potassic hydrate the dyad radical becomes substituted by two atoms of hydrogen. Thus : / CMe"H \COHo Potassic + 2KHO J 3 ICOKo fH COKo Acrylic acid. f CEt"H \COHo Crotonic acid. f CPr'H \COHo Angelic Potassie hydrate. 2KHo = Potassic hydrate. acetate. Potassic formate. COKo Potassic acetate. acid. Methacrylic acid. J CEf'Me \COHo Methylcro- tonic acid. f CEf'Et \COHo 2KHo = Potassic hydrate. 2KHO = Potassic hydrate. 9TrTTn 2KHo = Potassic hydrate. nTT-TT., 2KH J, \COKo Potassic acetate. CMeH, COKo + propionate. COKo Potassic formate. f CH 3 \00ko Potassic acetate. -f fCH 3 \COKo Potassic acetate. Some of the secondary acids also give acetic acid when treated with fused potassic hydrate ; but this can only happen when the dyad radical is ethylene, thus : f CMeH 2 \COKo Potassic propionate. f CMeEL \COKo Potassic propionate. , JCH 3 ' [COKo Potassic acetate. fH 1C |CEtH 2 COKo H Ethylcro- tonic acid. Potassic hydrate. Potassic butyrate. ACRYLIC ACID. J CMe"H \COHo ' Molecular weight =72. Boils at about 100. Preparation. By the oxidation of acrolein with argentic ox- ide: rCMe"H ftA JCMe"H . ICOH OA ^ \coHo Acrolein. Argentic oxide. Acrylic acid. P2 316 THE ACIDS. Reactions. 1. Acrylic acid, under the influence of nascent hydrogen, produces propionic acid : JCMe"H JCMeH, | COHo -^ 1 COHo ' Acrylic acid. Propionic acid. 2. Acrylic acid also combines directly with bromine, pro- ducing dibromopropionic acid. OLEIC ACID. fC(C 16 H 32 )"H \COHo Preparation. Obtained in the purification of stearic acid. Reaction. Heated with potassic hydrate, it gives potassic acetate and palmitate : Oleic acid. Potassic Potassic Potassic palmitate. hydrate. acetate. CHAPTER XL. THE ACIDS. 3. LACTIC SERIES OF ACIDS. G-eneral formula of normal and secondary acids : \COHo In the normal acids m in this formula =0 ; but in the secon- dary acids it must be a positive integer. The members of the lactic series may be defined as acids containing one atom of oxatyl, the fourth bond of the carbon ACIDS OF THE LACTIC SERIES. 317 of which is united with the carbon of a basylous group, con- taining one atom, and one only, of hydroxyl, or of the peroxide of a monad radical, either alcoholic or acid. The following examples will serve to illustrate this definition : The acids of this series at present known, or which could be obtained by obvious processes, are classified into the fol- lowing eight divisions : 1. Normal Acids. 2. Etheric Normal Acids. 3. Secondary Acids. 4. Etheric Secondary Acids. 5. Normal Olefine Acids. 6. Etheric Normal Olefine Acids. 7. Secondary Olefine Acids. 8. Etheric Secondary Olefine Acids. 1st. Normal Acids. A normal acid of the lactic series may be defined as one in which an atom of carbon is united with 318 THE ACIDS. oxatyl, hydroxyl, and at least one atom of hydrogen. The general formula of these acids is therefore f CEHHo \COHo ' In this formula E may be either hydrogen or any monad alcohol radical ; and the number of acids possessing the same atomic weight, and belonging to this division, is determined by the number of isomeric modifications of which the alcohol radical is susceptible. Thus, of the acids containing two, three, or four atoms of carbon, there can be only one of each belong- ing to this division, because these acids cannot contain an alcohol radical higher in the series than ethyl, and this radical is not susceptible of isomeric modification ; but a normal acid containing propyl can have one isomer in this division, the two acids containing respectively propyl (CEtH 2 ) and isopropyl (CMe 2 H). For acids of this division containing normal alco- hol radicals only, the following general graphic formula may be given : In the case of gly collie acid n=Q. The following are the acids at present known belonging to this division : G-lycollic acid JCH 2 Ho COHo ' T ,. ., JCMeHHo Lactlcacid COHo ' Oxybutyric acid JCEtHHo \COHo ' ACIDS OF THE LACTIC SERIES. 319 Valerolactic acid f CPrHHo \ COHo ' T . ., fCBuHHo Leucicacld \COHo ' 2nd. EtTieric Normal Acids. An etheric normal acid of the lactic series is constituted like a normal acid, but contains a monad organic radical, chlorous or basylous, in the place of the hydrogen of the non-oxatylic hydroxyl. The following is there- fore the general formula of these acids : in the graphic formula ft, as before, may =0. or / CEHSo \COHo ' The number of possible isomers belonging to this division is very great ; for, in addition to those of which the normal acids containing E of the same value are susceptible, a host of others + must result from the complementary variation of E and E. The lowest member of the division, methylglycollic acid (iso- meric with lactic acid), is the only one incapable of isomeric modification. The following examples will serve to illustrate the constitu- tion of the acids belonging to this division : Methylglycollic acid Ethyl-lactic acid Aceto-lactic acid . ,. J CMeHAco* \COHo 3rd. Secondary Acids. A secondary acid of the lactic series * Aco = peroxide of acetyl, 320 THE ACIDS. is one in which an atom of carbon is united with oxatyl, hy- droxyl, and two atoms of a monad alcohol radical. The general formula of these acids is / -N fCE-Ho or COHo- In the graphic expression, the values of n and m may differ ; but both are positive integers, and neither may =0. In the symbolic formula E. must be a monad alcohol radical. The following examples will serve to illustrate their constitution : Dimethoxalic acid Ethomethoxalic acid / CEtMeHo { COHo ' Diethoxalic acid {cOHb- The number of acids possessing the same atomic weight, and belonging to this division, is determined, first, by the comple- mentary variation of the two alcohol radicals, and, secondly, by the number of possible isomers of these radicals. The two lowest terms of the series are alone incapable of isomeric modi- fication by either of the causes mentioned. 4th. MJieric Secondary Acids. These acids stand in the same relation to the secondary as the etheric normal to the normal acids; they consequently contain a monad organic radical in the place of the hydrogen of the non-oxatylic hy- ACIDS OF THE LACTIC SERIES. 321 clroxyl. The following is therefore the general formula of these acids : . JCE 2 Eo or \COHo- 5th. Normal Olefine Acids. A normal olefine acid belonging to the lactic series is one in which the atom of carbon united with oxatyl is not combined with hydroxyl, and in which the atom of carbon united with hydroxyl is combined with not less than one atom of hydrogen. The following are the general graphic and symbolic formulae of the acids belonging to this division : -0- & HSKs) or CEHHo In both these formulae n must be a positive integer and cannot =0, but E may be either hydrogen or a monad alcohol radical. The olefines of these acids may belong either to the ethylene or ethylidene series. The following are the only acids at present known belonging to this division : fCH 2 Ho Paralactic acid \ CH 2 iCOHo CH 2 Ho Paraleucic acid \ (C 4 H 8 )". COHo 322 THE ACIDS. The number of isomers in this division will obviously depend, first, upon the complementary variations of E and (CH 2 ) n ; secondly, upon the isomeric modifications of which E is sus- ceptible ; and thirdly, upon the isomeric modifications of (OH,).. 6th. Etheric Normal Olefine Acids. These acids only differ from the normal olefine acids in having the hydrogen of the non-oxatylic hydroxyl replaced by an organic monad radical, positive or negative ; their general formula is therefore, rCEHEo or j(CH 2 )" n . COHo As in the fifth division, n must be a positive integer and cannot + =0, whilst B may be either hydrogen or a monad alcohol + radical ; but E must be a monad compound radical, either acid or alcoholic. 7th. Secondary Olefine Acids. A secondary olefine acid of this series is one in which the atom of carbon united with oxatyl is not combined with hydroxyl, and in which the atom of carbon united with hydroxyl is also combined with two monad alcohol radicals, as shown in the following formulae : CE 2 Ho (CH 2 )" M . COHo In both of these formulae n must be a positive integer and cannot =0, and E must be a monad alcohol radical. 8th. Etheric Secondary Olefine Acids. These acids are related to the secondary olefine acids in the same way as the sixth division to the fifth. No member of the seventh or eighth division has yet been formed. ACIDS OP THE LACTIC SERIES. 323 Formation of the Normal Acids. 1. By the oxidation of the glycols, or diacid alcohols. fCH 2 Ho fCH 2 Ho \CH 2 Ho + s \COHo + G-lycol. G-lycollic Water. acid. 2. By the oxidation of the C n H 2n+1 Ho alcohols : , n /CH 2 Ho , |CH 2 Ho + 3 = | COHo Ethylic Glycollie Water, .alcohol. acid. 3. From the fatty acids, by converting them first into chlo- ro-substitution acids, and then acting upon these compounds with potassic hydrate : |cOHo 2n " + Cl2 - {cOHo 2 *" 1 + HC1; Fatty acid. Chlorofatty acid. Hydrochloric acid. {C(C n H 2n+1 )HCl KH fC(C M H 2n+1 )HHo \COHo \COHo Chlorofatty acid. Potassic Normal acid of the Potassic hydrate. lactic series. chloride. Formation of Secondary Acids. By the action of the zinc compounds of the monad radicals upon ethylic oxalate, and the subsequent addition of water : / COEto \COEto Ethylic Zinc compound of oxalate. monad radical. + Zn(C n H 2n+1 )Eto; " |C(C n H 2n+1 ) 2 (Zn"C n H 2n+1 0) { COEto ^ ^^ = \COEto Water. Secondary acid. j* H 2+i + ZnHo 2 . Hydride of Zincic radical. hydrate. 324 THE ACIDS. Formation of Olefine Acids. By uniting a dyad radical with carbonic oxydichloride (phosgene gas) under the influence of sun- light, and subsequently acting upon the product with potassic hydrate : { CH 3 COP1 f CH 2 C1 CH 2 s CH 2 (COC1) Ethylene. Carbonic oxydi- /3 Chlorpropionylic chloride. chloride. (Phosgene gas.) /S Chlorpropionylic Potassic Potassic Potassic chloride. hydrate. paralactate. chloride. Water. Relations of the Lactic to the Acetic Series of Acids. 1. The transformation of the acetic or fatty into the normal lactic series of acids has been mentioned above (p. 323). 2. The converse operation is effected with the normal and secondary acids of the lactic series by means of hydriodic acid : f C(C M H 2n+1 )(C m H 2w+1 )Ho HJ _ f C(C n H 2n+1 )(C M H 2w+1 )H \ COHo - \ COHo Acid of lactic series. Hydriodic Acid of acetic series. acid. + OH 2 + I,. Water. If m does not =0 the fatty acid will' be a secondary one, like the member of the lactic series from which it is derived. Relations of the Lactic to the Acrylic Series of Acids. If the ethereal salts of the secondary acids of the lactic series be treated with phosphorous trichloride, the ethereal salts of the secondary acids of the acrylic series are produced : o JC(C, f H 2M+1 )(C M H 2m+1 )Ho pn _o fC(C n H 2n+1 )(C m H 2M )" 6 \ COEto +**U3=d | CGEto Ether of lactic series. Phosphorous Ether of acrylic series, trichloride. + POHHo 2 + 3HCI. Phosphorous Hydrochloric acid. acid. LACTIC ACID. 325 This reaction has not yet been produced in the case of the normal acids of the lactic series. A secondary lactic acid minus OH 2 = an acrylic acid. The reverse of this operation has not been performed. LACTIC ACID. f CMeHHo \ COHo ' Sp. gr. 1-215. Occurrence. In sour milk, Sauerkraut, fluids of muscular tissue, gastric juice, saliva of diabetic patients. In the acid liquor of starch-factories, in blood, urine, tears, bile, &c. It is also a general product of putrefactive fermentation. The acid contained in animal fluids isparalactic acid (see p. 327). Preparation. By fermenting sugar with putrid cheese. For other processes, see pages 329 and 330. Its salts have the following general formulae : f CMeHHo ( CMeHHo 1 CO-O,, 1 COMo ' j CO-0 M ' \ CMeHHo Salts of monad metals. Salts of dyad metals. Isomerism in the Lactic Series. The synthetical study of the acids of this series affords an insight into numerous and interesting cases of isomerism. Commencing with the lowest member of the series, we have for glycollic acid the formula 326 THE ACIDS. An inspection of this formula shows that, glycollic acid admits of no isomeric modification, except with a total change of type. The part of the formula below the dotted line repre- sents oxatyl, which cannot be altered without sacrificing the acid character of the compound ; there remains therefore only the part of the formula above the dotted line, which admits of the following modification : The acid represented by the formula so modified no longer comes within the definition of the lactic series. It is carbo- methylic acid, and differs essentially from glycollic acid and the lactic series in general, inasmuch as the carbon of its chlorous radical, oxatyl, is linked to the carbon of the basylous radical by oxygen*. * Bearing this constitution of carbomethylic acid in mind, we have only to go one step further in order to perceive the constitution of carbonic acid itself, and the anomalous basicity of this acid ; for if, in the above graphic formula for carbomethylic acid, we replace the methyl by hydrogen, we have Carbomethylic acid. Carbonic acid. It is thus evident that the radical oxatyl, when united with hydroxyl, has sufficient chlorous power to produce a feebly dibasic acid ; but inasmuch as carbonic acid is not included in the category of organic acids, it forms no exception to the law that an organic acid containing n atoms of oxatyl is w-basic. ISOMERISM IN THE LACTIC SERIES. 327 There being no decisive evidence that homolactic acid differs from gly collie acid, experiment and theory both agree in asserting that the formula C 2 H 4 O 3 represents only one acid in the lactic series. Proceeding now one step higher in this series, we have in the formula of lactic acid an expression capable of the following three variations without quitting the lactic type : Or, expressed symbolically : No. 1. No. 2. f CMeHHo 1 COHo ' CHHo CH 2 Ho No. 3. CH 2 M COHo belongs to the normal division ( I \ [ All the acids represented by the above formulae are known. The first expresses the constitution of lactic acid, which ^ ) of the series, COHo / described at page 317 ; the second shows the atomic arrange- ment of paralactic acid ; whilst the third represents methyl- glycollic acid. The proof that the first two of these acids are so constituted is afforded by the synthetic processes sometimes employed to produce them ; for ethylidene cyanhydrate is con- verted by ebullition with potash into a salt of lactic acid, whilst ethylene cyanhydrate is transformed under similar cir- 328 THE ACIDS. cumstances into paralactic acid. It has also been mentioned above that by the action of phosgene gas upon ethylene, para- lactic acid is produced. Now the formation of ethylidene, or rather of its compounds, scarcely leaves a doubt that this body, if isolated, would have the following atomic constitution : HJ or 3 CH it would consist of an atom of methyl and an atom of hydrogen, both united with an atom of carbon, two of whose bonds satisfy each other. Thus the formation of ethylidene dichloride from aldehyde and phosphoric chloride takes place as follows : {gib + PCI, = .^ + FOCI,, Aldehyde. Phosphoric Ethylidene Phosphoric chloride. dichloride. oxytrichloride. the oxygen in the aldehyde being simply replaced by chlorine. There now only remains one possible formula for ethylene, viz. Such, then, being the constitution of ethylidene and ethylene, it follows that the former ought to give rise to an acid of the constitution shown in formula No. 1, whilst ethylene should produce an acid agreeing with formula No. 2. The acids actually produced from these sources are lactic and paralactic acids ; hence No. 1 is the constitutional formula of lactic acid, and No. 2 that of paralactic acid, a conclusion which harmo- nizes perfectly with all the reactions in which the production ISOMEBISM IN THE LACTIC SERIES. 329 of these acids can be traced. Thus in the formation of lactic acid by the oxidation of propylic glycol, we have JCMeHHo n JCMeHHo \CH 2 Ho " \COHo + Propylic glycol. Lactic acid. Water. Again, in the production of this acid from ethylidene cyan- hydrate, Ethylidene Potassic Water. Potassic lactate. Ammonia. cyanhydrate. hydrate. The formula given for potassic lactate in this equation is only apparently different in type from that previously used for lactic acid, since 3 r-TUVFTTT^rrnr^ JCMeHHo \CHko(COKo) ; JGOKo ' In the reaction by which chloropropionic acid is transformed into lactic acid we have the following change : fCMeHCl 2KH fCMeHHo Kn QH \COHo \COKo + OH - Chloropropionic Potassic Potassic lactate. Potassic Water. acid. hydrate. chloride. The production of lactamic acid (alanin), and that of lactic acid from the latter by the action of nitrous acid, are also clearly confirmatory of the above view. J CH 3 , C N '".4-OTT O-TTPl / CMeH ( N "' H 2 )_LTVTT PI CONvH + H + OH 2 + I =cOHo +NH 4 C1: Ammonic Hydrocyanic Water. Hydro- Lactamic acid Ammonio aldehyde acid. chloric (alanin). chloride. acid. JCMeH(N'"H 2 ) , wnTT /CMeHHo jCOHo \COHo Lactamic acid Nitrous Lactic acid. Water. (alanin). acid. Not the least interesting reaction illustrative of the consti- 330 THE ACIDS. tution of lactic acid is the formation of this acid by the action of nascent hydrogen upon pyruvic acid : fCOMe JCMeHHo \COHo ** ICOHo Pyruvic acid. Lactic acid. By an analogous reaction, glyoxalic acid, which is the next lower homologue of pyruvic acid, has been transformed into glycollic acid. /con rcH,Ho I COHo 2 I COHo ' Glyoxalic acid. Glycollic acid. In a similar manner it can be demonstrated that the above formula No. 2 expresses the constitution of paralactic acid, which belongs to the fifth or olefine division of these acids, CKHHo (CH 2 )" n (COHo) ' That paralactic acid possesses this constitution is proved, first, by its production from cyanhydric glycol fCH 2 Ho + KHo + OH * - jg* ko + NH *; Cyanhydric Potassic Water. Potassic Ammonia. glycol. hydrate. paralactate. and secondly, by its formation from phosgene gas and ethylene (see p. 324). By the action of water upon the chloride of /3 chlorpropionyl, a body of the composition of chloropropionic acid is obtained ; but inasmuch as this body yields paralactic acid by ebullition with potash, whilst chloropropionic acid gives under the same circumstances lactic acid, it follows that the former chloro-acid must be isomeric, and not identical, with the latter. Now, although the formula of propionic acid does not admit of any isomer, yet that of chloropropionic acid does, as is seen in the following graphic formulae : ISOMERISM IN THE LACTIC SERIES. 331 A comparison of these formulae with those of lactic and para- lactic acids (p. 327) shows at a glance that No. 1 is the chloropropionic acid which yields lactic acid, whilst No. 2 is iso-chloropropionic acid, which, by the substitution of its chlorine by hydroxyl, must yield paralactic acid. By the action of nascent hydrogen, both isomeric chlorides will obviously produce the same propionic acid. The cause of the isomerism of methyl-glycollic acid (No. 3, p. 327) is so obvious as to require no further explanation. Proceeding to the next higher stage in the series, such is the rapid increase of isomerism, that we now encounter no less than eight possible isomers, all within the lactic family. Etheric normal. No. 1. CEtHHo COHo No. 2. / CMe 2 Ho \COHo No. 3. / CH 2 Eto ICOHo * No. 4. ( CMeHMeo \COHo Normal oleflne. Etheric normal oleflne. No. 8. fCH 2 Meo JCH 2 . COHo No. 5. fCH 2 Ho CH 2 ]CH 2 ' [COHo No. 6. fCH 2 Ho 1 CMeH. (COHo No. 7. fCMeHHo ^CH 2 - [COHo Of these acids, Nos. 1, 2, and 3 are known. No. 1 is oxy- butyric acid ; No. 2 is dimethoxalic acid, which is probably identical with acetonic acid. On this assumption, the forma- 332 THE ACIDS. tion of the latter by the action of hydrocyanic and hydrochloric acids upon acetone is easily intelligible : { COke + CN '" H + 20H * + HC1 = { g^ o Ho + HH.CL Acetone. Hydrocyanic Water. Hydro- Acetomc or acid. cMoric acid, dimethoxalic acid. The third of the above formulae is that of ethyl-glycollic acid. Of the possible acids containing five atoms of carbon, only two, viz. ethomethoxalic acid and valerolactic acid, are known. The cause of the isomerism of these two acids is seen at once from an inspection of their constitutional formulae : Ethomethoxalic acid ...... Valerolactic acid Of acids containing six atoms of carbon, the following three are known : I-icacid Diethoxalic acid ............ { \ CH 2 Ho Paraleucic acid ............ \ (C A)". [COHo The above formula for leucic acid is founded upon a reaction for the synthetical production of this acid from valeric aldehyde and hydrocyanic acid. Valeric acid contains butyl; conse- quently valeric aldehyde has the constitution expressed by the formula < QQ-m and the reaction in question may therefore be explained by the following equation : fBu * + NH Cl \COHo 4 L Ammonic Hydro- Water. Hydro- Leucin. Ammonic valeric aldehyde. cyanic chloric chloride. acid. acid. PYRUVIC SERIES. 333 Such being the rational formula of leucin, its transformation into leucic acid by nitrous acid determines the constitution of leucic acid : f CBuH(N'"H 2 ) fCBuHHo , OH , N \COHo -\COHo - cm, -J JN a . Leucin. Nitrous acid. Leucic acid. Water. CHAPTER XLI. THE ACIDS. 4 PYEUVIC SERIES. General formula ...... / CO(C n H 2n+1 ). In this formula n may = 0. The following list contains all the known members of this series : Glyoxalic acid ............ { COHo* Pyruvicacid ............ { COHo' Boils at 165. Convolvulinoleic acid . . . j l23 ]Fuses at 42 ' Jalapinoleic acid ......... j Eicinoleic acid ......... { COHo ^^ ' The first two members only of this series are well known. These acids are the semialdehydes and semiketones of oxalic acid, and they stand in much the same relation to this acid as that which acetic aldehyde occupies with regard to acetic acid : fCH 3 . fCH 3 \COHo' \COH- Acetic acii Acetic aldehyde. 334 THE ACIDS. J COHo f COH 1 COHo : 1 COHo' Oxalic acid. Glyoxalie acid. The same chemical change, when repeated upon the other half of oxalic acid, converts this acid into a true aldehyde, viz. Glyoxal ...{gg= Both glyoxal and glyoxalic acid are produced by the oxidation of ethylic alcohol by nitric acid : Q fCOH \CH 3 Ho \COH + Ethylic Glyoxal. Water. JCOH n JCOH \COH \COHo' Glyoial, Glyoxalic acid. Glyoxalic acid reduces silver salts like an aldehyde, and is transformed into oxalic acid : J COH n / COHo t COHo \ COHo- Glyoxalic Oxalic acid. acid. These reactions show clearly the relations of the pyruvic series to oxalic acid. The pyruvic series is also closely related to the lactic series the first two members of the former absorbing hydrogen and being converted into glycollic and normal lactic acids respec- tively : f COH f CH 2 Ho \COHo ^ \COHo' Glyoxalic Glycollic acid. acid. fCOMe JCMeHHo \ COHo -^ \ COHo Pyruvic Lactio acid. acid. BENZOIC OR AROMATIC SERIES. 335 5. THE OLTOXYLIC SERIES OF ACIDS. ( General formula... n+i-, ^ c H Ho< ~ [cOHo~ In the second formula n may =0. The two following acids of this series are known : Formula. Physical condition. Glyoxylic acid ... \ QQjj^ 2 - Syrupy, crystalline hydrate. f CH 2 Ho Gly eerie acid . . . < CHHo. Syrupy. [COHo These acids are dihydric, but monobasic, and are related to the glycerin series of alcohols in the same way in which the members of the lactic series are related to the glycols : f CH 2 Ho f CH 2 Ho { CH 2 Ho' { COHo ' G-lycol. Glycollic acid. CHHo 'CHHo 2 CHHo . CHHo. ( CH 2 Ho [ COHo Glycerin. Glyceric acid. Glvceric acid has hitherto been but little investigated. CHAPTER XLIL THE ACIDS. 6. THE BENZOIQ OR AROMATIC SERIES OF ACIDS. General formula . . . { 336 THE ACIDS. The following terms of this series are known : Phencic acid 1 f C 5 H 3 Puses at 60. CollinicacidJ { COHo' Fuses at 100. Benzoic acid ...... j Q$^** Ha . Fuses at 121'4. Toluylicacid ...... Cuminic acid ...... 98 ' Fuses at 92 ' These acids have the same constitution as those of the acetic series, but contain the C n H 2n _ 7 radicals. They have been much less studied than the acetic series, and further investigation will probably bring to light other series holding towards them the same relation as the acrylic, gly collie, pyruvic, and glyoxylic series bear to the acetic series. Already an acryloid acid of this section is known corresponding to an unknown homologue of benzoic acid : |C(C,H 7 )H 2 fC(C,H,)"H \COHo jCOHo Unknown acid. Cinnamic acid. Cinnamic acid is decomposed, like the acids of the acrylic series, when treated with fused potassic hydrate ; it gives, under these circumstances, potassic acetate and benzoate. For the analogous reaction in the acrylic series see p. 314. Salicylic acid is the lactic acid of benzoic acid : fC(C,H 3 )H 2 fC(C 5 H 3 )HHo. \ CO Ho \ COHo Benzoic acid. Salicylic acid. and the oil of meadow-sweet (Spircea, ulmaria) is generally re- garded as the aldehyde of salicylic acid : JC(C 5 H 3 )HHo ICOH DIBASIC ACIDS. 337 BENZOIC ACID. fC(C 5 H 3 )H 2 \COHo Molecular weight =122. Molecular volume [~]~\. 1 litre of benzoic acid vapour weighs 61 criths. Fuses at 121'4. Soils at 239. Occurrence. In many balsams and gums. In putrid urine. Preparation. 1. By the oxidation of oil of bitter almonds (p. 295). 2. By the action of fused potassic hydrate on cinnamic acid : Cinnamic Potassic Potaseic Potassic acid. hydrate. acetate. benzoate. 3. By boiling hippuric acid with hydrochloric acid : C 9 H,N0 3 + OH 2 = C 2 H S N0 2 + Hippuric Water. Grlycocin. Benzoic acid. acid. 4. By the action of oxidizing agents on casein or gelatin. 5. Prom gum benzoin, by sublimation, or by extraction with potassic hydrate and subsequent precipitation of the acid by hydrochloric acid. CHAPTER XLIIL THE ACIDS. DIBASIC ACIDS. General formula... A(COHo) 2 or A and B being dyad radicals containing These acids all contain two atoms of oxatyl ; and if in the Q 338 THE ACIDS. general formula n, m, and I = 0, oxalic acid will be the first term of the series. Formation. Many of the dibasic acids are produced by the oxidation of substances richer in carbon, such as oils and fats. Others are found ready formed in nature. Reactions. 1. By the action of dehydrating substances, and even sometimes by heat alone, these acids lose water, forming anhydrides : fA(COHo) QTT J A ( co rA iB(COHo) = OH <> \B(CO/ Acid. Water. Anhydride. 2. If the anhydride be submitted to the action of phosphoric chloride, an atom of oxygen is replaced by two of chlorine : A(C0\ JA(COCl) PU * \B(COC1) Anhydride. Phosphoric Chloride. Phosphoric chloride. oxytrichloride. 3. Both the anhydrides and the chlorides are reconverted nto the acids by the action of water: JA(COCl) 9QTT JA(COHo) IB(COCI) + 20H * = JB(COHo) Chloride. Water. Acid. Hydrochloric acid. The dibasic acids may be divided into the four following series : 1. Succinic or acetoid series ......... ! Q"JJ (COHo) ' In the first member of the series m =0. 2. Fumaric or acryloid series ...... " | C H" f COHoV 3. Malic or lactoid series . . . . j 1 4. Tartaric or glyoxyloid series ... { gfc The first and second series are dibasic and dihydric, the third, dibasic and trikydric, and the fourth, dibasic and tetraJiydric. DIBASIC ACIDS. 339 1. THE SUCCINIC OR ACETOID SERIES. fCOHo rroTT \ r\ TT C/U-bio General formula... X XTT or \ C, t H 2n . COHo The following members of this series are known : fCOHo Malonic acid ^ CH 2 . Fuses at 140. [COHo fCOHo Succinic acid i C 2 H, . Fuses at 180. Boils at 235. I COHo fCOHo Pyrotartaric acid ... 4 C 3 H 6 . Fuses at 112. Boils at 200. [COHo fCOHo Adipic acid X C 4 H 8 . Fuses at 140. I COHo fCOHo Pimelic acid \ C 5 H 10 . Fuses at 134. [COHo [COHo Suberic acid 4 C 6 H 12 . Fuses at 125. [COHo fCOHo Anchoic acid . . . ! C JL . Fuses at 116. I COHo* fCOHo Sebacic acid \ C 8 H 16 . Fuses at 127. [COHo fCOHo Eoccellicacid.. .. J CUL, Fuses at 132. Boils at 200. It is obvious that there may be several modifications of each of these acids. Thus there may be two succinic acids, one containing ethylene, and the other ethylidene (see p. 346) : JCH (COHo) , JCH 3 \CH" 2 (COHo) and \CH(COHo); Q2 340 THE ACIDS. 1. Relations of the Succinic to the Lactic Series of Acids and to the Grlycols. These acids are related to the lactic series and to the glycols in the same way as the fatty acids are related to the monacid alcohols : f CH 2 Ho J CH 2 Ho f COHo \ CH 2 Ho' \ COHo ' \ COHo' Grlycol. G-lycollic acid. Oxalic acid. This relation, however, does not strictly extend beyond the first member, although it may be partially traced in the rela- tions of malonic and adipic acids to paralactic and paraleucic acids : CH 2 (CH 2 Ho) f CH 2 (CH 2 Ho) / CH 2 (COHo) CH 2 Ho \COHo ' \COHo Isopropylic glycol. Paralactic acid. Malonic acid. known.) (Un f C 4 H 8 (CH 2 Ho) f C 4 H 8 (CH 2 Ho) f C 4 H 8 (COHo) \ CH 2 Ho ( COHo \ COHo Unknown glycol. Paraleucic acid. Adipic acid. 2. Relations of the Succinic Series to the Dyad Radicals. 1. The succinic series is intimately related to the dyad radicals, the cyanides of which are readily converted into dibasic acids by ebullition with potassic hydrate or hydrochloric acid : C M H 2n (CN'") C M H 2w (CN'") Cyanide of the Potassic Water. Potassic salt of the Animo- dyad radical. hydrate. dibasic acid. nia. 2. Some of these acids, when heated with excess of caustic baryta, give up two atoms of carbonic anhydride, yielding the hydrides of the dyad radicals : COHo C 6 H I2 = 200, + (C 6 H 12 )"H 2 . COHo Suberic acid. Carbonic anhydride, fCOHo JC 8 H 16 = 2C0 2 + (C 8 H 16 )"H 2 . [COHo Sebacic acid. Carbonic anhydride. RELATIONS OF THE SUCCINIC SERIES. 341 These reactions are the analogues, in the dyad series, of the one by which marsh-gas is obtained from acetic acid. The hydrides of the dyad radicals so obtained are isomeric with those of the corresponding monad radicals. The elimination of carbonic anhydride from a monobasic acid can only take place once, while from a dibasic acid it takes place in two successive stages : In the case of a monobasic acid, {cbi COHo ~ C 2 = C H2 + lR In the case of a dibasic acid, lststa g e...j^(COHo) oo = .COHo f f~\ TT 2nd stage... Jcjl'r - CO 2 = j p n 2n+1 . [COHo lWU 2n+1 3. Relations of the Succinic to the Acetic Series of Acids. 1. By the loss of the elements of carbonic anhydride, the first three members of the succinic series are converted into members of the acetic series, containing one atom of carbon less : JCOHO co JH \ COHo UUa \ COHo' Oxalic acid. Carbonic Formic acid, anhydride. COHo , CH OHo C + l Cok - Malpnic Carbonic Acetic acid, acid. anhydride. CH H CO i CMeH * SbHo 1 COH ' Succinic Carbonic Propionic acid. anhydride. acid. 342 THE ACIDS. In the first two cases the action of heat alone is sufficient to effect the transformation ; but in the third the attraction of lime for carbonic anhydride must be superadded. 2. Conversely, the members of the acetic series may be con- verted into those of the succinic containing one atom of carbon more, by replacing one atom of the methylic hydrogen in acetic acid by cyanogen, and then boiling with potassic hydrate : fCH 2 (CN'") 9 rCH 2 (COKo) I COHo + 2KHo = \COKo Cyanacetic acid. Potassic Potassic malonate. Ammonia. hydrate. The conversion of formic acid into oxalic acid, by heating with potassic hydrate, also belongs to this class of reactions : 2 COHo + 2KHo = co + 20H * + Formic acid. Potassic Potassic Water. hydrate. oxalate. SUCCINIC ACID. rcoHo 1 C 2 H t . [COHo Fuses at 180. Soils at 235. Occurrence. In amber; in some kinds of lignite; in the resin of some kinds of pine ; also in many other vegetable and animal substances. Formation. 1. By the action of potassic hydrate upon ethy- lenic cyanide (p. 289) : this reaction proves that succinic acid contains ethylene, and that its constitutional formula is as above given; but an isosuccinic acid must be capable of formation, though hitherto never obtained. This acid will obviously contain ethylidene in the place of ethylene ; and its \ COHo formula will be 4 CMeH. (See p. 346.) COHo SUCCINIC ACID. 343 2. By the oxidation of butyric acid by nitric acid : fCTW fCOHo j v/!/tii in J r* TT i r\TT JCOHO + jg b H o + OH " Butyric acid. Succinic acid. Water. The nature of this reaction is more clearly seen with fully developed formulae, thus : fCOHo n J ^^ OTT * = ICH* + OH ^ COHo [COHo Butyric acid. Succinic acid. Water. 3. By the reduction of malic acid by fermentation, or by hydriodic acid : (COHo [ COHo CHHo w JCH 2 OTT CH 2 H 2 = ICH + OH - COHo l_COHo Malic acid. Succinic acid. Water. 4. By the reduction of tartaric acid by hydriodic acid : COHo COHo 20H = [COHo [COHo Tartaric Hydriodic Succinic Water. acid. acid. acid. It is evident that this reaction is perfectly analogous to that by which lactic acid is transformed into propionic acid (p. 308). 5. The two isomeric acids, fumaric and maleic acids, are converted by nascent hydrogen into succinic acid : {COHo fCOHo J CH H ' = ]CH 2 " ' [COHo Succinic acid. coHo COHo Buccinic acid. 344 THE ACIDS. The two processes by which succinic acid is always prepared are, the distillation of amber and the fermentation of calcic malate. Reactions. 1. By distillation, succinic acid splits almost entirely into succinic anhydride and water : fCOHo fCO , C 2 H 4 = C 2 H 4 + OH, [COHO [co ' Succinic Succinie Water, acid. anhydride. 2. Under the action of nascent oxygen produced by electro- lysis, succinic acid yields ethylene, carbonic anhydride, and water : COHo C 2 H 4 + = C 2 H 4 + 2CO a + OH 2 . COHo Succinic Ethylene. Carbonic Water, acid. anhydride. 3. Succinic acid may be boiled for hours with concentrated nitric acid without suffering any change ; neither is it affected by a mixture of potassic chlorate and hydrochloric acid ; but it produces acetic acid when distilled with sulphuric acid and manganic oxide. 4. Succinic acid forms three kinds of salts, viz. : Neutral. Acid. Superacid. fCOMo J C 2 H 4 [ COMo' rcoHo | COMo' rcoHo [ COMo' rcoHo C 2 H 4 , tCOHo rco , X C H Mo" 1 ^^2 4 J - T - L " 1 CO J ISOMERISM IN THE FUMARIC SERIES. 345 CHAPTER XLIV. THE ACIDS. 2. FUMARIC OE AGRTLOID SERIES. General formula or ^H 2tt _ 2 (COHo) 2 . Formula. aric acid \ >ic acid L "C" 2 H 2 (COHo) 2 ; laleic acidj In this series there are three isomeric acids containing four atoms of carbon, viz. Eumaric acid Maleic Isomaleic and three other isomeric acids containing five atoms of carbon, viz. Itaconic acid ^ Citraconic acid I Ti (C 3 ) Yi H 4 (COHo) 2 . Mesaconic acid J Rational notation predicts the existence of a fourth acid belonging to the four-carbon group. The following are the four possible formulaa for these acids : No. 3. fCOHo \ C("CH)H. (COHo fCOHo \ CMe" . [COHo Q5 346 THE ACIDS. Of these formulae, Nos. 1 and 2 represent fumaric and maleic acids. Data are still wanting to enable its own particular for- mula to be assigned to each of these acids ; but the first two formula must belong to fumaric and maleic acids, because both these acids yield succinic acid under the influence of nascent hydrogen, thus : No. 1. {COHo ,/CH CH iCOHo No. 2. COHo CH "C COHo COHo CH 2 CH 2 COHo COHo CH 2 CH 2 COHo Succinic acid. 0-0-0 Succinic acid. (f ^- jCH 2 (COHo) \COKo Citric acid. Potassic Potassic Potassic Water, hydrate. oxalate. acetate. Desoxalic acid is pentahydric, and contains, like glyoxylic acid, two atoms of non-oxatylic hydroxyl. It is obtained from the product of the action of sodium upon oxalic ether. CHAPTER XLVIL THE ANHYDKIDES. THE anhydrides are compounds obtained from the acids, by the abstraction of the hydrogen of their hydroxyl, together with sufficient oxygen to form water. For every two atoms of hydrogen and one of oxygen thus abstracted from hydroxyl, there will obviously remain one atom of oxygen, which, as a dyad element, exactly satisfies the two bonds vacated by the hydroxyl : 2Ho = OH 2 + 0". Hydroxyl. Water. On this account, two molecules of a monohydric acid are re- quired to form one molecule of anhydride, thus : ( CMeO 2CMeOHo = \ O + OH 2 . [ CMeO Acetic acid. Acetic Water, anhydride. The anhydrides of those monobasic and dibasic acids which contain one and two atoms of hydroxyl have alone been investi- gated. ANHYDRIDES OF THE ACETIC AND BENZO1C SERIES. 355 They may be divided into the following classes : i T -, ., ,, ,, 1. Anhydrides of the j CO I CO monohydric niono-<( O and <( O basic acids ......... CO | CO i v C n H 2n _ 7 2. Anhydrides of the fC(Cja 2n+1 ) 2 dihydric monobasic X O. acids ............... [CO 3. Anhydrides of the C CO _ dihydric dibasic J C w H 2w O. acids CO --- ' 1. ANHYDRIDES OF THE MONOHYDRIC MONOBASIC ACIDS, These are known only in the acetic and benzoic series. They bear the same relation to the acids from which they are derived as the ethers to the alcohols. The residues of different acids can unite to form mixed anhydrides analogous to the mixed ethers. Aceto-benzoic anhy- dride is a body of this class. Formation. By the action of the chloracids, or so-called chlorides, of the monad negative radicals on the potassic salts of the acids : C(C-H 2n+1 )OKo+C(C w H 2w+1 )OCl= O +KC1. C(CJI 2W+1 )0 PotaBBic Bait. Chloracid. Anhydride. Potassic chloride. Reaction. In contact with water they are converted into the corresponding acids : = 2C(C M H 2n+1 )OHo, Anhydride. Water. Acid. 356 THE ANHYDRIDES. The following is a list of the anhydrides belonging to this class : Fusing- Boiling- point, point. Acetic anhydride fCMeO [CMeO fC(CH 3 )0 or {0 [C(CH 3 )0 138. Propionic anhydride ... (CEtO CEtO or ! O lC(C 2 H 5 )0 165. Butyric anhydride fCPrO 1 [CPrO rc(c 3 H 7 )o or \ [C(C 3 H 7 )0 about 190: Valeric anhydride . rcBuO 1 ( C(C 4 H 9 )0 or \ O about 215. [CBuO [C(C 4 H 9 )0 Caproic anhydride fCAyO 1 O I CAyO rc(C 5 H n )o or \ O lC(C 5 H n )0 C(C 6 H 13 )0 rccpo rc(c 6 H 13 )o (Enanthylic anhydride. 4 O or { [ CCpO fC(C 6 H 5 )0 Benzoic anhydride 1 O lC(C 6 H 5 )0 fCMeO Acetobenzoic anhydride \ O I C(C 6 H 5 )0 ( C(C 7 H 15 )0 Caprylic anhydride . . . \ O [C(C 7 H 15 )0 rc(c 8 H 17 )o Pelargonic anhydride. . \ O 10(0 S H 17 )0 rc(c 15 H 31 )o Palmitic anhydride ...sO I C(C 15 H 31 )0 42. 310. 120- below 0. about 290. +5. 530.3. THE KETONES. 357 2. ANHYDRIDES OF THE DIHYDRIC MONOBASIC ACIDS. Formation. By applying heat to a dihydric monobasic acid, thus : JCMeHHo /CMeH n OTT \COHo JCO + OH 3' Lactic acid. Lactide. Water. (Lactic anhydride.) Reaction. Boiled with water, and especially with alkalies, they reproduce the acids from which they were derived : f CMeH n ftTT f CMeHHo JCO + OH * = JGOHo ' Lactide. Water. Lactic acid. 3. ANHYDRIDES OF THE DIHYDRIC DIBASIC ACIDS. Formation. By the action of heat, or of substances having an attraction for water, upon the dihydric dibasic acids : fCOHo fCO , \ 2 H 4 = \ C 2 H 4 O + OH 2 . [COHo [CO ' Succinic Succinic Water, acid. anhydride. Reaction. Like the anhydrides of the first and second classes, they unite with water, reproducing the acids from which they were derived. CHAPTER XLVIII. THE KETONES. THE ketones may be regarded as derived from the fatty acids, 358 THE KETONES. by the substitution of the hydroxyl of the latter by a monad alco- hol radical ; they thus resemble the aldehydes in constitution : |CH 3 fCH 3 |CH 3 \ COHo' I COH- I COMe' Acetic Acetic Acetone, acid. aldehyde. The ketones are also correctly viewed as compounds of car- bonic oxide with monad alcohol radicals, thus : COMe 2 . Acetone. By the- action of nascent hydrogen upon the ketones, they are converted into secondary alcohols, whilst the aldehydes, under the same treatment, yield primary alcohols : f CH 3 f CH 3 { COMe ^ \ CMeHHo' Acetone. Isopropylic Ketones, unlike aldehydes, do not oxidize spontaneously ; neither do they reduce ammoniacal solution of argentic oxide. Like aldehydes, many of them combine with hydric potassic or hydric sodic sulphite. Formation. 1. By the action of the zinc compounds of the positive monad radicals upon chloracids : n J C n ll2+i \-*7~(r\ TT \ _ of ^n*i2n+l , 17 ri] 2 \ COC1 5n(UH 2w+ i) 2 -^ | GO(C n H 2n+1 ) " Chloraeid. Zinc compound. Ketone. Zincic chloride. 2. By the action of sodic ethide and its homologues on car- bonic oxide : CO + 2Na(CH 2B+1 ) = Carbonic Sodium compound. Ketone. oxide. 3. By the distillation of the salts of the fatty acids : 9 f C w H 2 ra+i f 2n +i 2 1 COKo | CO(CH 2n+1 ) Potassic salt Ketone. Potassic of fatty acid. carbonate. FORMATION OF KETONES. 359 4. By distilling together salts of two different fatty acids, ke- tones containing two different basylous radicals are obtained : f CEtH 2 \COKo Potassic butyrate. J 3 \COKo Potassic acetate. f CEtH. \COMe Pr COKo 2 . Potassic carbonate. COEto 5. Ketones are also produced by the consecutive action of sodium and the iodides of the C n H 2n+1 radicals on acetic ether, the product so obtained being subsequently boiled with alco- holic solution of potassic hydrate : CH 3 + 2EtHo + H Alcohol. Nal; Sodic iodide. C CH on 3 1 nm*- + 2KHo = -I co + EtHo + COKo 2 . OUlit rTH-rr COEto I CEtH ^ Acetic ether. Ethylic sodacetone carbonate. fCH 3 ICH I CO 1 CHNa EtI = co 3 CHEt [ COEto COEto Ethylic sodacetone carbonate. Ethylic iodide. Ethylic ethacetone carbonate. Ethylic ethacetone Potassic carbonate. hydrate. Ethylated acetone Ethylated Alcohol. Potassic acetone. carbonate. CEtH, JCEtH 2 I COMe' In this compound one atom of hydrogen in acetone has been displaced by ethyl. A second atom may be displaced in the following manner : 2 fCH 3 2 \ COEto Acetic ethe Jeer + 1 COEto Ethylic disodace- tone carbonate. EtHo + Alcohol 360 THE KETONES. CO CO J 1 1 CN"a 2EtI = i w^ 1 CEt 2 + 2NaI : [ COEto [ COEto Ethylic disodace- tone carbonate. Ethylic iodide. Ethylic diethace- tone carbonate. Sodic iodide. | CEt 2 + 1 COEto 2KHo = jco 3 + [ CEt 2 H EtHo + COKo 2 . Ethylic diethace- Potassic Diethylated Alcohol. Potassic tone carbonate. hydrate. acetone. carbonate. f OTT Diethylated acetone CJ1 3 \CO = f CEt 2 H \^N/^v~n IT * .' CEt H COMe The following is a list of the names, constitutional formulae, and boiling-points of those ketones which are best known : Acetone COMe Boiling- point. 56. o g, a< Methylated actone. (Ethyl acetyl, me- { ^MeH 2 thyl acetone.) I COMe Diinethylated ace- tone. tone) 93 ' 5 - Ethylated acetone... f CEtK Propione. (Ethyl f CMeH 2 , m [^ propionyl.) \COEt J 6 f Methyl valeral . . J S^ 1 " 1 ^ .. 120 g I \COMe o ] Ethyl butyral M L \COBu r 128. 138. .3* [Diethylated acetone. | COMe JJButyrone {gEtH 2 M4 o. ETHEREAL SALTS. 361 Little is known of the ketones of the CH 2n -7 series. Two of them have been obtained : /C IT \ BenzopJienone ( QQ(C H )) *^ e ketone f benzoic acid, is obtained by heating potassic benzoate. aCTT N CO/C H w * s P re P are( l by distilling together calcic acetate and beiizoate. CHAPTER XLTX. ETHEEEAL SALTS. THESE compounds correspond to the metallic oxysalts of the acids. The acids from which they are derived may be either mineral or organic ; but the base must always be organic. The haloid ethereal salts are excluded from this family ; they have been already described as haloid ethers. The ethereal salts are produced by reactions analogous to those employed for the preparation of metallic salts : {cOHo + KHo = {coko + OH v Acetic acid. Potassic Potassic Water. hydrate. acetate. + EtH = cofeto + Acetic acid. Ethylie Ethylic Water. hydrate. acetate. But as the hydrates of the organic radicals do not act upon acids so energetically as potassic hydrate, it is often advisable to employ the acid in the form of a potassic salt, and the radi- cal as a sulphoacid, thus, with acids of the acetic series : S0 2 Ho(C,,H 2ll+1 0).+ P salt. sulphate. Sulphoacid. Potassic Ethereal salt. Hydric potassic hat 362 ETHEREAL SALTS. Monobasic acids form only one ethereal salt with each monacid alcohol ; and this salt is always neutral. With diacid alcohols they each form two ethereal salts, and with triacid alcohols three ethereal salts. These are also neutral. Thus with acetic acid we have : Acetic salt of a monacid alcohol : { COEto' Ethylic acetate. Acetic salts of a diacid alcohol : f CH 2 Ho f CH -0-CMeO \ CH 2 -0-CMeO' \ CH 2 -0-CMeO* Monacetic glycol. Diacetic glycol. Acetic salts of a triacid alcohol : fCH 2 Ho fCH 2 -0-CMeO fCH 2 -O-CMeO \ CHHo . J CHHo . I CH"-O-CMeO. I CH 2 -O-CMeO [ CH 2 -0-CMeO [ CH 2 -O-CMeO Monacetin. Diacetin. Triacetin. Dibasic acids form, with monacid alcohols, two series of ethereal salts : 1. Acid ethereal salts, as : f COEto Succinethylic acid <| C H 4 . [COHo 2. Neutral ethereal salts, as : f COEto Ethylic succinate 4 C 2 H 4 . [ COEto In the same manner, tribasic acids form with monacid alcohols three series of ethereal salts, the first two of which are acid, and the third neutral. Prolonged contact with water generally decomposes the ethereal salts, liberating the radicals of the bases in the form of alcohols : S0 2 Meo 2 + 2OH 2 = SO 2 Ho 2 '+ 2MeHo. Methylic Water. Sulphuric Methylic sulphomethylate. acid. alcohol. COMPOUNDS OF TRIAD NITROGEN, &C. 363 Ebullition with potassic hydrate, especially when the latter is dissolved in alcohol, effects this transformation very speedily: + KHo = + EtH ' Ethylic Potassic Potassic Ethylic acetate. hydrate. acetate. alcohol. CHAPTER L. ORGANIC COMPOUNDS CONTAINING TRIAD AND PENTAD NITROGEN OR THEIR ANALOGUES. THIS numerous family may be divided into two great classes : 1. Compounds of triad nitrogen, phosphorus, arsenic, and antimony. 2. Compounds of pentad nitrogen, phosphorus, arsenic, and antimony. I. COMPOUNDS OF TRIAD NITROGEN AND OF ITS ANALOGUES. This class may be again subdivided as follows : Positive. Neutral. Negative. 1. Amines. 1. Amides. 1. Imides and 2. Phosphines. 2. Alkalamides. nitrides. 3. Arsines. 3. Trichlorinated and tribrominated amines. 4. Stibines. 4. Haloid compounds 5. Oxybases. ofoxybases. Of these the Amines and Amides are the most important. R2 364 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. POSITIYE OB BASYLOTTS SECTION. 1. THE AMINES. The Amines are commonly termed organic bases or artificial alkaloids ; they are divided into A. Monamines. B. Diamines. C. Triamines. D. Tetramines. The last two have been but little investigated. A. MONAMINES. There are three kinds of monamines : a. Primary monamines. /3. Secondary monamines. y. Tertiary monamines. a. Primary Monamines. General formulae. Methyl or C w H 2n+1 series N(C M H 2tt+1 )H 2 . Vinyl or Cjak-i series N^H^S,. Phenyl or C n H 2n _ 7 series N(CJE 2n _ 7 )H 2 . Formation. 1. By the reduction of the nitro-substitution compounds of the hydrides of the radicals by sulphuretted hydrogen, ammonic sulphide, zinc and sulphuric acid, or iron and acetic acid: N(C.H 5 )O a + 3SH 2 = N(C 6 H 5 )H 2 + 2OH 2 + S 8 . Nitrobenzol. Sulphuretted Aniline. Water, hydrogen. 2. By treating cyanic ethers with boiling solution of potassic MONAMINES. 36 hydrate. The reaction is perfectly analogous to the decom- position of cyanic acid with potassic hydrate : CN'"Ho H Cyanic acid. h 2KHo = Potassic hydrate. COKo 2 Potassic carbonate. CN'"Eto H Ethylic cyanate. - 2KHo = Potassic hydrate. COKo 2 Potassic carbonate. Ammonia. NEtH 2 . Ethylamine. 3. By the action of the haloid ethers of the monad positive radicals upon ammonia, and subsequent action of potassic hy- drate upon the product so formed : NH 3 + EtI = NEtH 3 I. Ammonia. Ethylic Ethylammonic iodide. iodide. NEtHJ + KHo = NEtH 2 + KI + OH 2 . Ethylammonic Potassic Ethylamine. Potassic Water. iodide. hydrate. iodide. The following are a few of the primary monamines : Methylamine ............ NMeH 2 or N(CH 3 )H 2 . Ethylamine ............ NEtH 2 or N(C 2 H 5 )H 2 . Amylamine ............ NAyH 2 or N(C 5 H U )H 2 . Allylamine ............... NA11H 2 or N(C 3 H 5 )H 2 . Phenylamine (Aniline) NPhH 2 or N(C 6 H.)H 2 . Reaction. Treated with nitrous acid, they evolve nitrogen and yield the corresponding alcohols : NPhH 2 + NOHo = PhHo + N 2 + OH 2 . Phenylic Phenylamine. Nitrous acid. alcohol. Water. /3. Secondary Monamines. General formula. Methyl or C n H 2n+1 series ......... N(C n H 2w+1 ) 2 H. Vinyl or CA^ series ............ N(C n R 2n _ l ) 2 K. Phenyl or C n H 2n _ 7 series ......... N(C n H 2n _ 7 ) 2 H. The secondary monamines are derived from ammonia by the displacement of two atoms of hydrogen by monad positive radicals. They are sometimes called Imidog en bases. Formation. By the action of the haloid compounds of the 366 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. monad positive radicals on the primary monamines, and subse- quent treatment with potassic hydrate : NEtH 2 + EtI = NEt 2 H 2 I. Ethylamine. Ethylic Diethylammonic iodide. iodide. NEt 2 H 2 I + KHo = NEt 2 H + KI + OH 2 . Diethylammonic Potassic Diethylamine. Potassic Water, iodide. hydrate. iodide. By using the iodide of a radical different from that already contained in the primary monamine, secondary monamines may be formed containing two different radicals, thus : NPhH 2 + EtI = NEtPhH 2 I. Phenylamine. Ethylic Ethylphenylammonic (Aniline.) iodide. iodide. NEtPhH 2 I + KHo = NEtPhH + KI + OH 2 . Ethylphenylam- Potassic Ethylphenylamine. Potassic Water, monic iodide. hydrate. (Ethylaniline.) iodide. The following secondary monamines are known : Dimethylamine NMe 2 H orN(CH 3 ) 2 H. Diethylamine NEt 2 H orN(C 2 H 5 ) 2 H. Methylethylamine NMeEtHorN(CH 3 )(C 2 H 5 )H. Ethylamylamine NEtAyH or N(C 2 H 5 )(C 5 H n )H. Ethylphenylamine NEtPhH or N(C 2 H.)(C 6 H.)H. Piperidine N(C 5 H 10 )"H. Conine N(C 8 H u y ; H. y. Tertiary monamines. Formation. By acting upon the secondary monamines with the iodides of the monad positive radicals, and subsequent treatment with potassic hydrate : NEt 2 H + EtI = NEt 3 HI. Diethylamine. Ethylic Triethylammonic iodide. iodide. NEt 3 HI + KHo = NEt 3 + KI + OH 2 . Triethylammonic Potassic Triethylamine. Potassic Water, iodide. hydrate. iodide DIAMINES. 367 By varying the radicals, tertiary monamines with several different radicals may be formed. The following are a few of the known tertiary monamines : Trimethylamine NMe 3 or N(CH 3 ) 3 . Triethylamine NEt 3 or N( C 2 H 5 ) 3 . Triamylamine NAy 3 or N ( C 5 H n ) 3 . Methyl-ethyl-phenylamine NMeEtPh or N(CH 3 )(C 2 H 5 )(C 6 H E ). Pyridine N(C 5 H 5 )"'. Picoline N(C 6 H 7 )"'. Lutidine N(C 7 H 9 )'". Collidine N(C 8 H n )'". Parvoline N(C 9 H 13 )'". The constitution of the triad radicals contained in the last five bases is not known. Tertiary monamines, when acted upon by the iodides of monad positive radicals, yield iodides which are not decomposed by potassic hydrate. In this manner tertiary monamines may be distinguished from primary and secondary monamines. The three may be distinguished from each other by the alternate action of ethylic iodide and potassic hydrate : thus, as we have just seen, tertiary monamines are recognized by producing im- mediately iodides which are not decomposed by potassic hy- drate ; a secondary monamine, however, produces an iodide decomposable by potassic hydrate ; but the base thus liberated is tertiary, and will therefore be transformed immediately into the stable iodide by a second application of ethylic iodide. A primary monamine requires three applications of ethylic iodide and potassic hydrate to produce the same result. B. DIAMINES. Formation. The diamines are formed by coupling together two atoms of nitrogen in two molecules of ammonia, or of a pri- 368 COMPOUNDS or NITROGEN AND ITS ANALOGUES. mary or secondary monamine, by a dyad radical, which at the same time takes the place of two atoms of hydrogen ; thus : NH 2 fNH IN fNEt" Et" . X Et" i Et", or 4 Et" . NH 2 INK IN [NET Primary Secondary Tertiary diamine. diamine. diamine. This reaction is effected by treating ammonia or a primary or secondary monamine with the haloid salt (preferably a bro- mide) of the dyad radical, thus : ( NH 3 Br 2NH 3 + Et"Br 2 = J Et" [NH 3 Br Ammonia. Ethylenic Ethylene-diammonic dibromide. dibromide. When the salts of ethylene diammonium are decomposed by potassic hydrate, an oxide of the basylous radical is produced, thus : OH 2 + 2KBr. Water. Potassic bromide. In this respect the diamines differ from the monamines. Urea and its derivatives belong to the class of diamines. These compounds are produced by boiling a solution of ammonic cyanate or ethylammonic cyanate, or a homologue of the latter. In these compounds, the two atoms of nitrogen are held together by the dyad radical carbonyl, CO : fNH 2 CN"'(N V H 4 0) = 4 CO . j'NH 3 Br \ Et" + [ NH 3 Br Ethylene-diam- monic dibromide. 2KHo Potassic hydrate. INH.-J Ethylene-diam monic oxide. Ammonic cyanate. Urea. fNHEt CN"'(N v EtH 3 0) = J CO . Ethyl-ammonic Ethylurea. cyanate. UREA. 369 Ureas in which ethyl and other monad basylous radicals are substituted for hydrogen may also be obtained by the action of ammonia or a monamine on the cyanic ethers, thus : fNHEt CN'"Eto + NH 3 = ICO . JNH 2 Ethylic Ammonia. Ethylurea. cyanate. fNHEt CN'"Eto + NH 2 Et = JCO . [NHEt Ethylic Ethylamine. Diethylurea. cyanate. Reaction. Urea is decomposed by nitrous anhydride : fNH 2 \ CO + N 2 3 = C0 2 + 2N 2 + 2OH 2 . Urea. Nitrous Carbonic Water. anhydride. anhydride. The following is a list of the best-known diamines : NH 2 Ethylene diamine ..................... X Et" . fNHEt Ethylene diethyl diamine ............ \ Et" . [NHEt fNH 2 Urea .................................... X CO. INH 2 fNHEt Ethylurea .............................. \ CO . [NH 2 fNHPh Sulphophenylurea ..................... \ CS" . INK, E5 370 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. THE NATURAL ALKALOIDS. Of the constitution of these organic bases very little is known. The following is a list of the chief of them, with the sources whence they are derived : Alkaloids from Opium. Morphine C 17 H 19 lSr0 3 . Codeine C 18 H 21 ]S T 3 , OH 2 . Thebaine C 19 H 21 NO 3 . Papaverine C 20 H 21 NO 4 . Narcotine C 22 H 23 NO r Nareeine C 23 H 29 NO 9 . From Cinchona Bark. Quinine C 20 H 24 N 2 O 2 . Cinchonine C 20 H 24 N 2 O. Aricine C 23 H 26 N 2 O 4 . From Tobacco. Nicotine : C 10 H 14 N a . From Nux vomica. Strychnine C 21 H 22 N 2 2 . Brucine C 23 H 26 N 2 O 4 . 2, 3, 4. THE PHOSPH1NES, ARSINES, AND STIBINES. These bases cannot be obtained, like the amines, by the dis- placement of hydrogen in phosphuretted, arseniuretted, and antimoniuretted hydrogen. The tertiary compounds only are OXYBASES. 371 known ; and they are produced by reactions of which the follow- ing may be regarded as types : + 3EtI = AsEt 3 + Sodic Ethylic Triethyl- Sodic arsenide. iodide. arsine. iodide. 3ZnEt 2 + 2PC1 3 = 2PEt 3 + 3ZnCl 2 . Zincic Phosphorous Triethyl- Zincic ethide. trichloride. phosphine. chloride. Unlike the amines, these bodies have a powerful affinity for oxygen, in consequence of which they are generally sponta- neously inflammable. 5. OXYBASES. These compounds are only known in the arsenic series. Arsenious oxybases. Only one of these, cacodylic oxide, has been carefully in- vestigated. By the distillation of potassic acetate with arsenious anhy- dride, a compound known as cacodyi, 'As" 2 Me 4 , is produced. This substance may also be prepared by the action of methylic iodide upon an alloy of sodium and arsenic containing 'As" 2 Na,:- 'As" 2 Na 4 + 4MeI = 'As" 2 Me 4 + 4NaI. Sodic Methylic Cacodyi. Sodic arsenide. iodide. iodide. By allowing cacodyi to absorb oxygen slowly, an oily liquid containing cacodylic oxide (As 2 Me 4 O) is formed. This oxybase does not appear to unite with oxygen acids, but it is attacked by hydrochloric acid, forming cacodylic chlo- ride : f AsMe 2 Jo + 2HC1 = 2AsMe 2 Cl + OH.. I AsMe 2 Cacodylic Hydrochloric Cacodylic Water, oxide- acid. chloride. 372 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. Cacodylic oxide, when exposed to moist air, absorbs water and oxygen, forming cacodylic acid : As 2 Me 4 O + O 2 + OH 2 = 2AsMe 2 OHo. Cacodylic Water. Cacodylic oxide. acid. CHAPTER LI. ORGANIC COMPOUNDS OF TRIAD NITROGEN AND OF ITS ANALOGUES (continued). NEUTRAL SECTION. 1. THE AMIDES. THESE compounds are formed by the substitution of amidogen (NH 2 ) for the oxatylic hydroxyl of organic acids. They are most conveniently written on the diadelphic type, but may also be formulated upon the ammonia type. If the acid contain only one atom of oxatyl, a monamide is the result ; if two atoms of oxatyl are present in the acid, a diamide is generally formed, &c. Secondary and tertiary com- pounds can also be produced, as in the case of the amines ; but they belong to the negative section of this family. Acetamide : A. MONAMIDES. I. Primary Monamides. Chloracetamide : JC(CH 2 C1)0 ^ WTT rrvrTT mm . / CH 2 C1 i TVTTT or JMxi I v^((JJtL a Cl)UJ, or < -- (^ iilj 2 Benzamide : 'orNH 2 [C(C 6 H 5 )0],or MONAMIDES. 373 Formation. 1. By the distillation of the ammonic salts of the monobasic acids : ran, ran, \CO(N'H 4 0) \CO(N'"H 2 ) Ammonic Acetamide. Water. acetate. 2. By the action of ammonia upon the chloracids : {COCI + =. = {CO(N'"H 2 ) + HC1 - Acetylic Ammonia. Acetamide. Hydrochloric chloride. acid. 3. By the action of ammonia on the ethereal salts of the monobasic acids : Ethylic Ammonia. Acetamide. Alcohol. acetate. Reactions. 1. Boiled with aqueous solutions of acids, the primary monamides yield ammonic salts and acids : {CO(N"'H 2 ) + HC1 Acetamide. Hydrochloric Water. Ammonic Acetic acid. chloride. acid. 2. Boiled with potassic hydrate, ammonia is evolved, and a potassic salt, corresponding to the amide, is formed. JCH 3 -^ T r ft -KTTr fCH 3 1CO(N'"H 2 ) + NH3 + ICOKo- Acetamide. Potassic Ammonia. Potassic hydrate. acetate. II. Secondary Monamides. fCH 3 I CO Diacetimide ... N(CMeO) 2 H or <( NH . I CO rrco -i" rco n Succinimide ...... NH \ C 2 H 4 or \ Et" (N'"H)". [I CO [ 374 COMPOUNDS OP NITROGEN AND ITS ANALOGUES. These bodies possess a negative character, and are treated of under the negative section of this class as imides (p. 376). Tertiary monamides are little known. They are the nitrides (see p. 376). B. DIAMIDES. The diamides may be regarded as derived from two molecules of ammonia, by the substitution of a dyad negative radical for two atoms of hydrogen ; or they may be considered as formed by the substitution of amidogen for the hydroxyl contained in the two atoms of oxatyl in dibasic acids : Primary Diamides. Oxamide ... " or rrcoY rcoAd Succinamide... N 2 H 4 (C 4 H 4 2 )" or N 2 H 4 1 J Et" I or \ Et" . COAd Formation. 1. By the action of heat upon the neutral am- monic salts of dibasic 'acids: f CO(N V H 4 0) f CO(N'"H 2 ) \ CO(N V H 4 0) { CO(N'"H 2 ) Ammonic oxalate. Oxamide. Water. 2. By the action of ammonia on the ethereal salts of dibasic acids : GOEto 3 = cO(N'"H 2 ) Ethylic Ammonia. Oxamide. Alcohol. oxalate. 3. By the action of ammonia on the chloro-dibasic acids : fCOCl fCO(N'"H 2 ) 4NH 3 + XBt" = 4W + 2NH 4 CL ( COC1 [ CO(N"'H 3 ) Ammonia. Succinylic Succinamide. Ammonic chloride. chloride. The secondary and tertiary diamides are but little known. */ 7 ALKALAMIDES. 375 C. TRIAMIDES. Primary Triamides. The primary triamides may be regarded as derived from tribasic acids by the substitution of amidogen for the hydroxyl contained in the three atoms of oxatyl of these acids, or as derived from three molecules of ammonia by the displacement of three atoms of hydrogen by the residue of a tribasic acid. A gd example of a triamide is f CHHo(COAd) Citramide \ CH(COAd) or N 3 H 6 (C 6 H 5 O 4 )'". I CH 2 (COAd) Citramide is formed by the action of ammonia on ethylic citrate. Secondary and tertiary triamides have not yet been formed. 2. THE ALKALAMIDES. These compounds are intermediate between the amines and the amides. They are derived from ammonia by the substi- tution of part of the hydrogen by positive, and part by negative radicals ; and inasmuch as two atoms at least of hydrogen must be so substituted, no primary alkalamide can exist, Secondary and tertiary inonalkalamides, dialkalamides, and trialkalamides are known. Ethyl acetamide NHEt(CMeO). Ethyl diacetamide NEt(CMeO) 2 . Diethyl oxamide N 2 H 2 Et 2 (C 2 O 2 )". Diphenyl-carbonyl-oxalyl diamide . N 2 (C 6 H 5 ) 2 (CO)"(C 2 2 )". Citryl-triphenyl-triamide N 3 H 3 (C 6 H 5 ) 3 (C 6 H 5 O 4 )'". The alkalamides incline towards basicity in their character, their degree of alkalinity being about equal to that of urea. 3. -THE TRIGHLORINATED AND TRIBROMI- NATED AMINES. If the hydrogen in an amine be gradually substituted by 376 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. . chlorine or bromine, the basic power of the amine gradually diminishes, and finally a neutral compound is obtained. This reaction has been studied in the case of aniline, which loses basic energy by the successive displacement of two atoms of hydrogen, and finally becomes neutral by the substitution of three atoms of chlorine or bromine for three of hydrogen : MH,(CA). NH 2 (C 8 H 4 C1). NH 2 (C 6 H 3 C1 2 ). NH 2 (C 6 H 2 C1 3 ). Aniline. Chloraniline. Dichloraniline. Trichloraniline. 4. THE HALOID COMPOUNDS OF OXYBASES. These bodies are only known in the arsenic series ; they are formed by the action of chlorine, bromine, or iodine upon cacodyl and its homologues, or of hydrochloric acid, hydro- bromic acid, or hydriodic acid upon the oxybases. G-eneral formula As(CH 2n +i) 2 Cl. NEGATIVE SECTION. THE IMIDES AND NITRIDES. General formula (ofimides... NH(C n H 2n _>()),, I of nitrides. Formation. By the action of chloracids (the so-called chlo- rides of negative radicals) upon amides : NH 2 (CMeO) + CMeOCl = NH(CMeO) a + HC1. Acetamide. Acetylic Diacetimide. Hydrochloric chloride. acid. A repetition of this reaction gives acetylic nitride. An imide may also be formed by the substitution of a dyad negative radical for two atoms of hydrogen in ammonia, thus : Succinimide ......... NH(C 4 H 4 2 )", or NH Et" coJ These bodies have hitherto received but little attention. CAUSTIC NITROGEN BASES. 377 CHAPTER LIT. II. COMPOUNDS OF PENTAD NITROGEN AND OF ITS ANALOGUES. This class of compounds contains the following series : Positive. 1. Caustic Nitrogen bases. 2. Phosphorus bases. 3. Arsenic bases. 4. Antimony bases. 5. Oxyarsenic bases. 6. Oxyantimonic bases. Neutral. 1. Salts of Amines. 2. Phosphines. 3. Arsines. 4. Stibines. 5. Oxyarsenic bases. 6. Oxyantimonic bases. Negative. 1. Organic arsenic acids, oxychlo- rides, ana chlo- rides. 2. Organic antimo- nic acids. POSITIVE or BASYLOUS COMPOUNDS. 1. Caustic Nitrogen Bases. General formula N(C n H 2 +i) 4 Ho. In each radical n must be a positive integer. The radicals need not be all of the same atomic weight. Formation. By the action of argentic hydrate upon the iodides of the compound ammoniums : NEt 4 I + AgHo = NEt 4 Ho + Agl. Tetrethylammo- Argentic Tetrethylammo- Argentic nic iodide. hydrate. nic hydrate. iodide. 2. Caustic Phosphorus Bases. 3. Caustic Arsenic Bases. 4. Caustic Antimony Bases. By displacing the N in the above general formula and in the equation by P, As, and Sb, the constitution and formation of these three series of compounds will be expressed. 5. Oxyarsenic Bases. These bodies, which are diacid bases, are obtained by the slow oxidation of the tertiary monar- sines : As(C n H 2ra+1 ) 3 + = As(C n H 2n+1 ) 3 0. Tertiary monarsine. Oxyarsenic base. 378 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. 6. OxyantimonicBases. These are formed in a manner exactly analogous to that in which the oxyarsenic bases are produced. NEUTRAL COMPOUNDS. 1. Salts of Amines. Q-eneral formulae : In the first formula m may = ; in the second, C TO H 2JW may be displaced by H 2 ; and in the third, C OT H 2m _ 1 may be substituted by H 8 - Formation. Like the analogous compounds of ammonia, the salts of the amines are formed by the direct union of acids with the amines without elimination of water, thus : NEtH 2 + HC1 = NEtH 3 Cl. Ethylamine. Hydrochloric Ethylammonic acid. chloride. The haloid salts of the amines may also be produced by the union of the haloid ethers of the monad positive radicals with the amines (for reaction see p. 365). Character. The salts of the diamines and triamines are often found to contain only one molecule of acid, instead of two or three as shown in the above general formulas, which indicate the composition of the normal salts. The nitrogen atoms are in such cases united together by one of the bonds of each, besides being linked by the polyad radicals, thus : The difference between these two classes of salts will be ren- dered more evident by a comparison of the following graphic and symbolic formulae : SALTS OF NITROGEN BASES. 379 Normal Salts. \ / J -0 or N 2 H 6 Et"Cl 2J or -I Et" . 5X~ X ' 0/ x xj) I"" Ethylene-diammonic dichloride. 3 \ / NH Cl NH 3 C1 Diethylene-triammonic trichloride. fNH 3 Cl | Et" or N a H 8 Et",Cl 8 or < NH 2 C1. | Et" ^NH 3 C1 Monacid Salts. or 'N iv H,Et"Cl or Ethylene-diammonic monochloride. \ / ^ ---- 7 Diethylene-triammonic monochloride . or iv (N 3 ) xi H 6 Et" 2 Cl or \ NH m [NH 2 Cl Diacid Salt. f X -- (g) - 0/X5) Diethylene-triammonic dichloride. or "(N 3 ) xiii H 7 Et" 2 Cl 2 or f NH 2 **,. 1 NH 2 Cl Et 380 COMPOUNDS OF NITROGEN AND ITS ANALOGUES. 2. Salts of PliospJiines. 3. Salts of Ar sines. 4. Salts ofStibines. These three series of salts all present close analogies with the salts of the amines both in constitution and in the mode of their formation. 5. Salts of Oxy arsenic Bases. As(C n H 2n+1 ) 3 Cl 2 . Formation. By the action of acids on the oxy arsenic bases : AsMe 3 O + 2HC1 = AsMe 3 Cl 2 + OH 2 . Arsenic Hydrochloric Arsenic trimetho- Water, trimethoxide. acid. dichloride. 6. Salts of Oxyantimonic Bases. These resemble the previous salts in formation and consti- tution. NEGATIVE or CHLOROUS COMPOUNDS. 1. Organic Arsenic Acids, Oncy chlorides t and Chlorides. The following are the principal bodies of this class : Monomethylarsenic acid AsMeOHo 2 . Arsenic oxy dichlormethide AsMeOCl 2 . Arsenic tetrachlormethide AsMeCl 4 . Cacodylic acid AsMe 2 OHo. Cacodylic trichloride AsMe 2 Cl 3 . 2. Organic Antimonic Acids. No exploration of this series has yet been made. The members of it will doubtless be found to present close analogies with the corresponding series of arsenic compounds. ORGANOMETALLIC BODIES. 381 CHAPTER LIIL ORGANOMETALLIC BOBIES. THIS term is applied to a family of compounds in which an organic radical is united directly with a metal ; and it serves to distinguish them from other organic compounds containing metals, in which the metal and organic radical are indirectly united or linked to each other. Thus zincic ethide is an organometallic body, while zincic ethylate and zincic succinate are organic bodies containing metals : Zincic ethide . . . ZnEt 2 . Zincic ethylate . . . ZnEto 2 . I I e -. rco , Zincic succinate . . . -j C 2 H 4 Zn [CO ' Many organic compounds containing metals are the deriva- tives of organometallic bodies ; thus zincic ethide by oxidation yields zincic ethylate ZnEt a + O 2 = ZnEto 2 ; Zincic Zincic ethide. ethylate. 382 ORGANOMETALLIC BODIES. and by further oxidation zincic ethylate can be converted into zincic acetate Zincic ethylate. Zincic acetate. Water. Another instance of the derivation of organic bodies con- taining metals from organometallic bodies is seen in the for- mation of potassic propionate by the action of potassic ethide upon carbonic anhydride : CMeH 2 K + C0 2 = Potassic Carbonic Potassic ethide. anhydride. propionate. Formation of organometallic bodies. Organometallic bodies are produced in a large number of reactions, which may, however, be classed under the following four heads : I. By the union of monad positive radicals in statu nascenti with a metal, or by the coalescence of a metal with the iodide of a monad positive radical. Thus, when zinc and ethylic iodide are heated together to 100 in closed vessels, zincic ethide is formed : 2EtI + Zn 2 = ZnEt 2 + ZnI 2 . Ethylic Zincic Zincic iodide. ethide. iodide. Sometimes light may be employed instead of heat to effect this change, as in the case of the organo-tin compounds. In the formation of organo-mercury compounds by this method, light is indispensable to the reaction : EtI + Hg = HgEtl. Ethylic Mercuric iodide. ethiodide. II. By the action of the respective metals alloyed with potas- sium or sodium upon the iodides of the monad positive radicals. FORMATION OF ORGANOMETALLIC BODIES. 383 By this process there is less tendency to form compounds containing both positive radicals and negative elements. Potas- sium or sodium compounds are never produced in this reaction, because they cannot exist in the presence of ethylic iodide or its homologues. This process is well adapted for the formation of arsenic, antimony, tin, mercury, lead, bismuth, and tellurium compounds: 4EtI Ethylic iodide. 2EtI Ethylic iodide. Tin sodium alloy. HgNa 2 Sodium amalgam. = SnEt 4 + Stannic Sodic ethide. iodide. HgEt 2 Mercuric ethide. Sodic iodide. III. By the action of the zinc compounds of the monad positive radicals upon the haloid compounds, either of the metals themselves, or of their organo- derivatives. For the production of organometallic bodies containing less positive metals than zinc, this method is generally the most convenient, and is of most universal application. Compounds containing mercury, tin, lead, antimony, and arsenic have been thus produced ; but the process has failed when applied to the haloid compounds of copper, silver, platinum, and iron ; for, although these bodies are violently acted upon, the organic radicals do not unite with the metal : SnCl 4 - Stannic chloride. SnCl 4 Stannic chloride. 2HgEtI Mercuric ethiodide. ZnEt 2 = Zincic ethide. 2ZnEt 2 = Zincic ethide. ZnEt 2 Zincic ethide. SnEt 2 Cl 2 Stannic dichlor- ethide. = SnEt 4 Stannic ethide. 2HgEt 2 Mercuric ethide. ZnCl 2 . Zincic chloride. 2ZnCl 2 . Zincic chloride. ZnI 2 . Zincic iodide. IV. By the displacement of a metal in an organometallic compound by another and more positive metal. This method has been successfully employed for the forma- 384 ORGANOMETALLIC BODIES. tion of the organo-compounds of potassium, sodium, lithium, aluminium, and zinc. In the first three cases the reaction takes place at ordinary temperatures, some of the original compound entering into the composition of the resulting organometallic body : 3ZnEt 2 Zincic ethide. 3HgEt 2 + A1 2 = Mercuric ethide. HgAy 2 -f Zn = Mercuric amylide. = 2ZnNaEt Sodic zincic ethide. 'Al'" 2 Et 6 Aluminic ethide. Zincic amylide. Zn. 3Hg. ZnAy 2 + Hg. Reactions of organometallic bodies. 1. The most interesting reaction of the organo- compounds of the monad metals \&, their transformation into salts of normal fatty acids by the action of carbonic anhydride (see p. 301). 2. The organo- compounds of potassium and sodium decompose the iodides of the monad positive radicals in the cold, forming hydrides and dyad radicals : C 2 H 4 . Ethylene. C 2 H 5 Na Sodic ethide. C 2 H 5 I = Ethylic iodide. Nal Sodic iodide. C 2 H 5 H Ethylic hydride. 3. The organo- compounds of zinc are decomposed by water, with formation of the hydrides of the radicals : ZnEt 2 Zincic ethide. 2OH 2 Water. ZnHo 2 Zincic hydrate. 2EtH. Ethylic hydride. 4. By the slow action of dry oxygen, they pass through two stages of oxidation : ZnEt 2 + O = Zincic ethide. ZnEtEto -f Zincic ethide ethylate. O ZnEtEto; Zincic ethide ethylate. = ZnEto a . Zincic ethylate. REACTIONS OF ZINCIC ETHIDE. 385 5. Monad negative elements, such as iodine, remove succes- sively the two atoms of ethyl : ZnEt 9 + L = ZnEtl + EtI : Zincic ethide. Zincic ethiodide. Ethylic iodide. ZnEtl + I 2 = ZnI 2 + EtI. Zincic ethiodide. Zincic iodide. Ethylic iodide. 6. The organo-zinc compounds are extremely useful for the displacement of chlorine or its analogues by ethyl or its homo- logues : 2PC1. + 3ZnEt 2 = 2PEt 3 + 3ZnCl 2 . Zincic ethide. 3 Phosphorous trichloride. SiCl 4 Silicic chloride. rc 2 H 4 ci 2\ O lC 2 H 4 Cl Chlorether. ,C 2 H 4 C1 Ethylo- chlorether. Triethyl- phosphine. 2ZnEt = SiEt Zincic ethide. ZnEt 9 = Zincic ethide. + ZnEt 9 = 2 Zincic ethide. Zincic chloride. 2ZnCl . Zincic chloride. fC 2 H 4 Et + ZnCl 2 : I C 2 H 4 C1 Ethylo- Zincic chlorether. chloride. fC 2 H 4 Et 1 + ZnCl 2 . Diethylated Zincic ethylic ether. chloride. Diethylated ethylic ether is isomeric with butylic ether, and contains the radical methylo-ethylated methyl (see p. 205). By oxidation it would doubtless give methylated acetone (p. 360). 7. Oxygen may also be displaced in a similar manner. Thus : NJEtO, 2'N" 2 2 + Nitric oxide. ZnEt Zincic ethide. NOEt-O-J Zn" Zincic dinitro-ethylate. This compound is analogous to zincic propionate, the latter containing two atoms of tetrad carbon in the place of the two tetrad pairs of nitrogen atoms : COEt-0 i CWO Zincic propionate ... 386 ORGANOMETALLIC BODIES. 8. An analogous reaction is observed with sulphurous anhy- dride : Z.M, . Sulphurous Zincic Zincic methyldithionate. anhydride. methide. 9. When ethylic borate is acted upon by zincic methide, the ethoxyl becomes replaced by methyl : BEto 3 + 3ZnMe 2 = BMe 3 + SZnMeEto. Ethylic Zincic Boric Zincic methide borate. methide. methide. ethylate.J 10. "When ethylic oxalate is heated with zincic ethide, and water afterwards added, diethoxalic ether is formed : { Colto Ethylic Zincic Water. Diethoxalic Zincic Alcohol. oxalate. ethide. ether. hydrate. 11. By the action of ammonia, or of certain amines and amides, zincic ethide exchanges its zinc for hydrogen : ZnEt 2 + 2NH 3 = ZnAd 2 + 2EtH. Zincic Ammonia. Zincic amide. Ethylic ethide. hydride. 12. The organo-zinc compounds, by losing one of their organic radicals, become monad radicals, as shown by the fol- lowing formulae : Methylozincic dinitrome- 1 w , Me-O-(ZnMe). thylate .................. J Ethylozincic dinitroethy- f W OEt _ .(ZiiEt). late ........................ I Ethylic ethylo-zincic di- f CEt 2 -0-(ZnEt) ethoxalate ............... \ COEto 13. Mercuric ethide, when treated with bromine, loses one- half of its ethyl, which is displaced by the negative element HgEt 2 + Br = HgEtBr + EtBr. Mercuric Mercuric Ethylio ethide. ethobromide. bromide. REACTIONS OF ORGANOMETALLIC BODIES. 387 14. Mercuric methide, when submitted to the action of mer- curic iodide, yields mercuric methiodide : HgMe 2 + HgI 2 = 2HgMeI. Mercuric Mercuric Mercuric methide. iodide. methiodide. The hydrates corresponding to the mercuric ethobromide and methiodide have been produced. They are powerful caustic- bases, of the formulae HgEtHo and HgMeHo. Mercuric Mercuric ethohydrate. methohydrate. 15. The organo-stannous compounds unite directly with negative elements, passing into stannic bodies : SnEt 2 + I 2 = SnEt 2 I 2 . Stannous Stannic ethide. iododiethide. 16. Hypostannic organo-compounds undergo a similar trans- formation : 'Sn'" 2 Et 6 -f I 2 = 2SnEt 3 I: Hypostannic Stannic ethide. iodotriethide. SnEt 3 I + I 2 = SnEt 2 I 2 + EtI. Stannic Stannic Ethylie iodotriethide. iododiethide. iodide. 17. Hypostannic ethodiniodide is formed by the action of iodine upon stannic ethodimethide : 2SnEt 2 Me 2 + I 6 = 'Sn'" 2 Et 4 I 2 + 4MeL Stannic Hypostannic Methylic ethodimethide. ethodiniodide. iodide. 18. Stannic eihide, when treated with hydrochloric acid, yields stannic chlorotriethide and ethylic hydride : SnEt 4 + HC1 = SnEt 3 Cl + EtH. Stannic Hydrochloric Stannic Ethylic ethide. acid. chlorotriethide. hydride. The oxide and hydrate corresponding to the stannic chloro- triethide are known ; their formula are : SnEt 3 Oxide... -[O ; Hydrate... SnEtJIo. SnEt 3 388 ORGANOMETALLIC BODIES. These compounds, and the salts which they form, correspond in composition, constitution, and, to a certain extent, in pro- perties, with the compounds of methyl : Alcohol. Haloid ether. Ether. rcH 3 Methylic CH 3 Ho. CH 3 C1. 4 O . ICH 3 TSnEt 3 Stanntriethylic ... SnEt,Ho. SnEt 3 Cl. O [SnEt 3 19. Stannic chlorodietUde is readily reduced to stannous ethide by the action of zinc : SnEt 2 Cl 2 + Zn = SnEt 2 + ZnCl 2 . Stannic Stannous Zincic chlorodiethide. ethide. chloride. 20. Perplumbic ethide resembles stannic ethide in its re- actions ; thus with hydrochloric acid it yields perplumbic chlorotriethide and ethylic hydride : PbEt 4 + HC1 = PbEt 3 Cl + EtH. Perplumbic Hydrochlo- Perplumbic Ethylic ethide. ric acid. chlorotriethide. hydride. 21. Perplumbic trietholiydrate (PbEt 3 Ho) is a powerful base, forming salts with acids. 22. The organo-tellurium compounds form oxides and salts. The following are the formulae of tellurium ethide and some of its compounds : Tellurium ethide TeEt 2 . Tellurous diethoxide TeEt 2 O . Tellurous diethiodide TeEt 2 I 2 . Tellurous diethosulphate TeEt 2 (S vi 4 )". Constitution of Organometallic Bodies. The organometallic compounds are constituted on the types of the metals they contain. It was, in fact, the study of these bodies which first led to the doctrine of the atomicity of elements. They afford striking examples of monad, dyad, triad, tetrad, pentad, and hexad types. CONSTITUTION OF ORGANOMETALLIC BODIES. 389 The organic derivatives of the monad metals are formed on the type of potassic chloride (KC1) : HJ (H o/ v_> Potassic ethide. Potassic chloride. The organo-zinc, cadmium, magnesium, and mercury com- pounds are formed upon the type of zincic chloride (ZnCl 2 ): 0-0-0 Zincic chloride. H ) I H <~s \^> Mercuric iodethide. The organo-aluminic compounds are formed upon the type of aluminic chloride ('A1'" 2 C1 6 ) : - -- Aluminic chloride. Aluminic methide. The organo-tin compounds are formed upon the three types "Sn"Cl 2 , 'Sn'" 2 Cl 6 , and SnCl 4 , the first resembling the zincic 390 ORGANOMETALLIC BODIES. chloride type, and the second the aluminic chloride type (see p. 389) : Stannic chloride. Stannic iododiethide. Stannic ethide. Stannic iodotriethide. <-x ^-^ Et) (Et) (Et I I Stannic triethohydrate. Distannic hexethoxide. The inorganic types of the organo-tellurium series are TeCl 2 andTeO == Tellurous oxide. (SH5K5) Tellurium chloride. 0-0-0 (Et) II)' '(Et, Tellurium ethide. Tellurous diethoxide. Tellurous diethiodide. The organo-arsenie, antimony, and bismuth compounds are derived from the types 'As" 2 S" 2 , AsCl 3 , AsOHo 3 , SbCl 3 , SbCl 5 , BiCl 3 , and Bi0 2 Ho (see pp. 370, 377, and 380) : 'O '- Cacodylie acid. Monomethylarsenic acid. (Me) (As) (Me) Arsenic oxytrimethide. ORGANO- COMPOUNDS OF MONAD AND DYAD METALS. 391 The effect of the substitution of positive for negative radicals in compounds is well exhibited in the case of arsenic acid, AsOHo 3 , as illustrated in the above graphic representations. By the substitution of one atom of methyl for hydroxyl, a well-defined acid (less negative, however, than arsenic acid) is produced, monomethyl arsenic acid, AsOMeHo 2 . By the replacement of a second atom of hydroxyl by methyl, a very feeble acid, cacodylic acid, AsOMe 2 Ho, is obtained. By the replacement of the third atom of hydroxyl by methyl, the acid properties are completely destroyed, a feeble base, the arsenic oxytrimethide, being formed, AsOMe 3 . Finally, by the substitution of methyl and hydroxyl for the remaining atom of oxygen there is produced a powerful base, tetramethylarsenic hydrate, AsMe t Ho. The following is a list of the principal organometallic bodies at present known : I. Organo- compounds containing monad metals : Potassio-zincic methide KMe,ZnMe 2 . Potassio-zincic ethide KEt,ZnEt 2 . Sodio-zincic ethide NaEt,ZnEt 2 . Lithio-zincic ethide LiEt,ZnEt 2 . Lithio-mercuric ethide LiEt,HgEt 2 . II. Organo- compounds containing dyad metals : Magnesic ethide MgEt 2 . Zincic methide ZnMe 2 . Zincic ethide ZnEt 2 . Zincic amylide ZnAy 2 . Mercuric methide HgMe 2 . Mercuric ethide HgEt 2 . Mercuric methiodide HgMel. Mercuric ethonitrate HgEt (N V 3 ) . Stannous ethide .. .."Sn"Et.,. Tellurium methide TeMe 2 . 392 ORGANOMETALLIC BODIES. III. Organo- compounds containing triad metals : These compounds belong to the llth family of organic bodies, and have been treated of at p. 370. IV. Organo- compounds of tetrad metals : Stannic methide SnMe 4 . Stannic iodotrimethide . . SnMe Q L Stannic iododimethide SnMe 2 I 2 . Hypostannic ethide 'Sn'" 2 Et 6 . Stannic ethylodimethide SnEt 2 Me 2 . Hypostannic ethodiiodide 'Sn'" 2 Et 4 I 2 . Perplumbic ethide PbEt 4 . Perplumbic chlorotriethide PbEt 3 Cl. V. Organo- compounds of pentad metals : These bodies belong to the llth family of organic com- pounds, and have been already treated of at p. 377 and 380. INDEX. Absolute atomicity, 21. Acetamide, 372. Acetic series of acids, 297. series of acids, relations of, to acrylic series, 314. series of acids, relations of, to lactic series, 324. Acetic series, relations of succinic series to, 341. Acetone, 360. diethylated, 360. dimethylated, 360. ethylated, 360. methylated, 360. Acetyl, 221. Acetylene, 217. series of radicals, 217. Acetylic nitride, 376. Acetylide of copper, 218, 219. Acid, acetic, 306. aceto-lactic, 317, 319. ace tonic, 331. aconitic, 353. acrylic, 270, 315. adipic, 339. amidodinitrophenylic, 262. anchoic, 339. angelic, 312. aposorbic, 271. arachidic, 299. arsenic, 123. arsenious, 122. behenic, 299. benzoic, 337. boracic, 55. boric monobasic, 54. boric tribasic, 54. boric, 55. brassic, 313. bromic, 89. bromphenylic, 261. butyric, 308. capric, 299. caproic, 298. Acid, caprylic, 298. carbolic, 259. carbomethylic, 326. carbonic, 58, 326. cerotic, 299. chlorhydric, 39. ,, chloric, 49. chlorochromic, 188. chloropropionic, 329. ,, chlorous, 48. cimicic, 313. cinnamic, 336. ,. citraconic, 345. citric, 270, 353. collinic, 336. ,, convolvulinoleic, 333. ,, crotonic, 312. /3 crotonic, 313. cuminic, 336. cyanic, 228. cyanuric, 228. damaluric, 313. damolic, 313. desoxalic, 271, 353. dextrotartaric, 351. diamylacetic, 311. dibromosuccinic, 347. dichlorphenylic, 261. diethacetic, 311. diethoxalic, 320. dimethacetic, 311. dimethoxalic, 320. dinitrophenylic, 261. disulphodithionic, 75, 83. disulphuretted hyposulphurie, 83. dithionic, 74, 82. doeglic, 313. elaidic, 313. erucic, 313. ethacetic, 308. ethomethoxalic, 320. ethylcro tonic, 313. ethylglycollic, 332. 394 INDEX. Acid, ethyl-lactic, 319. formic, 243, 304. ,, fulminuric, 228. ,, fumaric, 345. gai'dic, 313. glyceric, 269, 335. glycollic, 264, 278, 318. glycomalic, 351. glyoxalic, 333. glyoxylic, 335. hi ippuric, 337. homolactic, 327. homotartaric, 351. hydriodic, 91. hydrobromic, 87. hydrochloric, 39. hydrocyanic, 223, 243. hydroferrocyanic, 226. hydrofluoric, 97. hydrofluoboric, 54. hydroselenic, 84. hydrosulphuric, 70. hypobromous, 89. hypochlorous, 47. hypogseic, 313. hypophosphorous, 114. hyposulphuric, 82. hyposulphurous, 74, 81. iodic, 93, 94. isobutyric, 311. isochloropropionic, 331. isodibromosuccinic, 347. isomaleic, 345. itaconic, 345. jalapinoleic, 333. lactamic, 329. lactic, 325, 327, 329. lasvotartaric, 351. lauric, 299. leucic, 319. maleic, 345. malic, 350. malonic, 339. margaric, 299. melissic, 299. mesaconic, 345. metabismuthic, 140, 143. metabismuthous, 140, 142. metaboric, 54. metantimonic, 131, 134. metantimonic, of Fre'my, 135. metantimonious, 131, 132. metaphosphoric, 115, 117. Acid, metarsenic, 123. ,, metastannic, 105. ,, metatartaric, 351. methacetic, 308. methacrylic, 313. ,, methethacetic, 310. methylcrotonic, 313. methylglycollic, 319. methyl-lactic, 317. moringic, 313. mucic, 271. ,, muriatic, 39. myristic, 299. nitric, 61. nitric, manufacture of, 62. nitrophenylic, 261. nitrous, 61, 63. oananthylic, 298. oleic, 316. orthantimonic, 130, 131. orthobismuthous, 142. orthoboric, 54. orthophosphoric, 118. oxalic, 229. oxamic, 231. oxybutyric, 318. palmitic, 299. paralactic, 321. paraleucic, 321. parantimonic, 135. pelargonic, 298. pentathionic, 75, 83. perchloric, 50. perchlorphenylic, 261. perchromic, 187. periodic, 93, 96. phenoic, 336. phenylic, 260. phosphoric, 115, 118. phosphoric dodecabasic, 115. phosphoric hexabasic, 115. phosphorous, 114, 116. physetoleic, 313. picramic, 262. picric, 262. pimelic, 339. propionic, 308. propylacetic, 309. /3 propylacetic, 309. pyrantimonic, 131, 135. pyrarsenic, 123. pyrophosphoric, 115, 118. pyrotartaric, 339, 349, INDEX. 395 Acid, pyroterebic, 313. pyruvic, 333. ,, racemic, 351. ricinoleic, 333. roccellic, 339. saccharic, 271. salicylic, 336. sebacic, 339. selenic, 85. selenious, 85. silicic, 101. stannic, 104. stearic, 299. suberic, 339. succinethylic, 362. succinic, 342. sulphamylic, 275. sulpharsenic, 124. sulpharsenious, 124. sulphhydric, 71. sulphocarbonic, 73. sulphochromic, 187. sulphodithionic, 74, 82. sulphomethylic, 274. sulphosulphuric, 74, 81. sulphovinic, 275. sulphuric, 74, 78. sulphuric, manufacture of, 79. sulphuric (Nordhausen), 74, sulplmrous, 74. tartaric, 270, 351. tartaric (inactive), 351. tartronic, 269, 350. tetrathionic, 75, 83. titanic, 106. toluylic, 336. tricarballylic, 353. trichlorphenylic, 261. trimethacetic, 310, 312. trinitrophenylic, 262. trisulphodithionic, 75, 83. trisulphuretted hyposulphuric, 83. trithionic, 74, 82. valerianic, 309. valeric, 309. valerolactic, 319. Acid salts, definition of, 13. Acids, acetic or fatty series of, 297. acetoid series of, 339. acrylic series of, 312. anhydrous definition of, 8, 10. Acids, benzoic or aromatic series of, 335. classification of, 296. definition of, 8. derivation of, from alcohols, 297. dibasic, 337. dibasic, definition of, 9. dibasic, formation of, 338. dibasic, reactions of, 338. dibasic, succinic or acetoid series of, 339. dibasic, fumaric or acryloid series of, 345. ,, dibasic, tartaric or glyoxyloid series of, 351. formation from anhydrides, 43. fumaric or acryloid series of, 345. glyoxylic series of, 335. lactic series of, 316. lactic series of, classification of, 317. lactic series of, definition of, 316. lactic series of, relations to acetic series, 324. lactic series of, relations to acrylic series, 324. law of basicity of, 296. malic or lactoid series of, 349. monobasic, 296. monobasic, definition of, 9. nomenclature of, 9. normal fatty, ascent of the series, 303. ,, normal fatty, relations of, to C M H 2n +iHo alcohols, 303. normal fatty, relations of, to C n H 2 +i radicals, 302. normal fatty, relations of, to each other, 303. normal, of acetic series, 298. normal, of acrylic series, 312. normal, of acrylic series, for- mation of, 313. normal, of fatty series, for- mation of, 300. normal, of fatty series, occur- rence of, 300. normal, of lactic series, for- mation of, 323. 396 INDEX. Acids, of acrylic series, relations of, to acetic series, 314. ,, of antimony, 130. of chlorine, 45. of lactic series, isomerism of, 325. of nitrogen, 61. olefine, of acrylic series, 313. olefine, of acrylic series, for- mation of, 314. olefine, of lactic series, for- mation of, 324. oleic series of, 312. organic, 296. polybasic, definition of, 9. pyruvic series of, 333. secondary fatty, 310. secondary, of acrylic series, 313. secondary, of acrylic series, formation of, 314. secondary, of lactic series, 319. secondary, of lactic series, for- mation of, 323. succinic series of, 339. tertiary fatty, 311. tribasic, 352. Acrolein, 270, 294. Acryl, 221. Acrylic series of acids, 312. Acrylic series of acids, relations of, to lactic series, 324. Acryloid or fumaric series of acids, 345. series of acids, isomerism in, 345. Action, chemical, modes of, 1. Active atomicity, 21. Affinity, chemical, 4. Agalmatolite, 177. Alabaster, 160. Alanin, 293, 329. Albite, 178. Alcohol, allylic, 244, 257. amylic, 246, 252. benzoic, 244, 258, 260. butylic, 252. caproylic, 246. caprylic, 246. cerotic, 246. cetylic, 246. cresylic, 259, 262. cumylic, 259. Alcohol, ethylenic, 264. ethylic, 250. heptylic, 246. hexylic, 246. isopropylic, 253. melissic, 246. methylic, 246, 249. octylic, 246. oenanthylic, 246. ,, pentacid, 271. pentylic, 246. phenylic, normal, 258. phenylic, secondary, 260. propylic, 244, 246, 252. pseudamylic, 253. ,, pseudohexylic, 253. stanntriethylic, 388. ,, sulphur, 251. sycocerylic, 259. tetracid, 270. tetrylic, 246, 252. vinylic, 256, 277. Alcoholates, 251. Alcohols, 243. diacid, 245, 262. ,, ethylic series of, 245. monacid, 245, 255, 258. monacid, of vinylic series, 255. ,, normal monacid, of phe- nylic series, 258. normal, of ethylic series. 245, 246. polyacid, 270. relations of, 246. ,, relations of, to fatty acids, 303. ,, secondary monacid, 252. secondary, of ethylic series, 245. ,, secondary, of phenylic se- ries, 259, 260. tertiary monacid, 254. tertiary, of ethylic series, 245. triacid, 245, 267. Aldehyde, acetic, 277, 293. acrylic, 294. benzoic, 295. butyric, 292. ,, capric, 292. cuminic, 295. euodic, 292. INDEX. 397 Aldehyde, lauric, 292. cenanthylic, 292. palmitic, 292. propionic, 292. salicylic, 336. ,, valeric, 292. Aldehydes, 290. definition of, 290. derived from the C n H 2M +iHo alcohols, 292. from the C n H 2n _iHo al- cohols, 294. from the C n H 2n _ 7 Ho al- cohols, 295. ,, preparation of, 290. ,, reactions of, 291. Alkalamides, 363, 375. constitution of, 375. Alkaloids, artificial, 364. from cinchona, 370. ,, from mix vomica, 370. ,, from opium, 370. from tobacco, 370. the natural, 370. Allophane, 176. Allotropic oxygen, 41. ,, phosphorus, 108. ,, varieties of sulphur, 70. Allyl, 210. Allylamine, 365. Allylic iodide, 268. Alum, common, 177. Aluminite, 176. Aluminium, 175. Agalmatolite, 177. Albite, 178. Allophane, 176. Alum, 177. Aluminate, dipotassic, 176. Aluminate, magnesic, 176. Aluminic calcic disilicate, 103. calcic tri silicate, 103. chloride, 175. hydrate, 175. manganous disilicate, 191. ,, manganous tetrasul- phate, 190. methide, 389. oxide, 175. oxyhydrate, 176. sulphate, 176. Aluminium (continued}. Aluminic sulphate tetrahydrate, 176. sulphide, 176. ,, tricalcic trisilicate, 103. Aluminite, 176. Alum, manganese aluminium, 190. potassium chrome, 187. ,, potassium manganese, 190. Alum-stone, 177. Alunite, 177. Analcime, 178. Andalusite, 177. Anorthite, 103. Atomicity of aluminium, 175. Buchholzite, 177. Chiastolite, 177. Cimolite, 177. CoUyrite, 177. Compounds of aluminium, 175. Cyanite, 177. Diaspore, 176. Dihydric aluminic tetrasilicate, 103. Dipotassic aluminate, 176. ,, aluminichexasilicate, 103. ,, aluminic tetrasul- phate, 177. Emerald, 103. Felspar, 103. Fibrolite, 177. Gibbsite, 175. Grossularia, 103. Kaolin of Ellenbogen, 177- Labradorite, 103. Lepidolite, 178. Magnesic aluminate, 176. Malthacite, 178. Miloschine, 177. Orthose, 103. Porcelain clay, 177. ,, clay of Passau, 177. Prehnite, 176. Pyrophyllite, 103. Kazoumoffskin, 178. Saponite, 178. Sillimanite, 177. Spinelle, 176. Spodumene, 176. 398 INDEX. Aluminium (continued). Triglucinic aluminic hexasili- cate, 103. Wernerite, 177. Worthite, 177. Xenolite, 177. Zoisite, 176. Alum, manganese aluminium, 190. potassium crome, 187. potassium manganese, 190. Alum-stone, 177. Alunite, 177. Amides, 363, 372. definition of, 372. Amidogen, 28. Amines, 363, 364. classification of, 364. diacid salts of, 379. monacid salts of, 379. normal salts of, 378. salts of, 378. Ammonia, 60, 67. type, 202. Ammonic chloride, 60, 67. chloride type, 202. salts, 67, 68. Ammoniocupric carbonate, 173. sulphate, 172. Ammonium, 68. amalgam, 68. Ammonoxyl, 28. Amorphous boron, 51. phosphorus, 108. Amoxyl, 203. Amyl, 209. Amylamine, 365. Amylene, 213. Amylenic chloride, 288. bromide, 288. Amyl glycerin, 267. Amylide, antimonious, 128. zincic, 391. Analcime, 178. Anatase, 106. Andalusite, 177. Anhydride, acetic, 356. acetobenzoic, 356. antimonic, 131, 133. antimonious, 130, 131. arsenic, 122, 123. arsenious, 122. auric, 174. benzoic, 356. Anhydride, bismuthic, 139, 140, 142. ,, boric, 54. butyric, 356. carbonic, 57. caproic, 356. caprylic, 356. chlorous, 46. chromic, 186. hypobromous, 89. hypochlorous, 46. iodic, 93. lactic, 357. nitric, 61, 63. nitrous, 61, 63. teiianthylic, 356. palmitic, 356. pelargonic, 356. periodic, 93, 95. phosphoric, 114, 117. phosphorous, 114, 116. propionic, 356. selenious, 85. silicic, 101, 102. stannic, 104. succinic, 357. sulphantimonic, 138. sulphantimonious, 136. sulpharsenic, 124, 125. sulpharsenious, 124. sulphochromic, 188. sulphuric, 74, 77. sulphurous, 74, 75. titanic, 106. valerianic, 356. Anhydrides, 354. , , conversion into acids, 43. definition of, 8, 10, 354. of the dihydric dibasic acids, 357. of the dihydric mono- basic acids, 357. ofthemonohydricmono- basic acids, 355. Anhydrous acid, definition of, 8, 10, 354. Aniline, 241, 365. Anorthite, 103. Antimonic acids, organic, 380. chloride, 125, 128, 129. oxytrichloride, 130. sulphide, 136, 138. sulphotrichloride, 130. tetretho-chloride, 125. INDEX. 399 Antimonious amylide, 128. anhydride, 130, 131. ,, argentide, 127. bromide, 127, 130. chloride, 125, 128. ethide, 128. fluoride, 130. hydride, 126. iodide, 130. oxide, 130, 131. oxybromide, 130. oxy chloride, 129. oxydisulphide, 135. oxyiodide, 130. sulphide, 136. zincide, 128. Antimoniuretted hydrogen, 126. Antimony, 125. ,, compound of, with oxy- gen and sulphur, 135. compounds of, with sul- phur, 136. copper glance, 137. ore, grey, 136. organic compounds of,363 oxides and acids of, 130. red, 135. Apatite, 119. Aquafortis, 61. Are, 33. Argentic compounds (see Silver). . V . or?rk Aricme, 370. Aromatic series of acids, 335. Arsenic, 119. acids, organic, 380. ,, compounds of, with oxygen and hydroxyl, 122. compounds of, with sulphur and hydrosulphyl, 124. organic compounds of, 363. oxydichlormethide, 380. oxytrimethide, 390. sulphide, 124, 125. tetrachlormethide, 380. ,, trimetho-dichloride, 380. ,, trimethoxide, 380. Arsenious chloride, 120, 121. hydride, 120. oxybases, 371. ,, sulphide, 124. Arseniuretted hydrogen, 120. Arsines, 363, 370. salts of, 380. Artiads, definition of, 20. Atomic combination, 30. weight, 2. weights, table of, 6. Atomicity, absolute, 21. active, 21. apparent variation of, 20. latent, 21. law of variation of, 21. marks, 18. of elements, 17. Atoms, 2. Auric compounds (see Gold). Aurous compounds (see Gold). Azote, 60. Azurite, 173. Baric carbonate, 157. chloride, 155. hydrate, 155, 159. nitrate, 157. oxide, 155, 156. peroxide, 156, 158. sulphate, 157. Barium, 155. , , compound of, with hydroxyl , 159. compounds of, with oxygen, 156. Baryta, 156. caustic, 159. Bases, caustic antimony, 377. caustic arsenic, 377. caustic nitrogen, 377. ,, caustic phosphorus, 377. ,, definition of, 11. imidogen, 365. organic, 364. organic, periodides of, 31. oxyantimonic, 378. oxyarsenic, 377. systematic and irregular names of, 11. Basic salts, definition of, 13. Basylous compound radicals, hy- drides of, 232. ,, elements, 4. radicals, dyad, 212. radicals, monad, 207. radicals, organic, 207. radicals, triad, 220. Benzamide, 372. Benzene, 238. 400 INDEX. Benzine, 238. Benzole series of acids, 335. Benzol, 237, 238. chlorocompounds of, 241. substitution derivatives of, 239. Benzophenone, 361. Benzoyl, hydride of, 295. Berthierite, 137. Bicarburet of hydrogen, 238, Binary compounds, 7. Bismuth, 139. ,, compound of, with chlo- rine, 139. compounds of, with oxy- gen and hydroxyl, 140. , , compounds of, with sulphur, 144. glance, 144. ,, ochre, 141. telluric, 145. Bismuthic oxide, 142. Bismuthous bromide, 140. chloride, 139. dichlorethide, 139. ditelluro-sulphide, 145. ethide, 139. fluoride, 140. iodide, 140. nitrate, 141. nitrate dihydrate, 141. oxide, 139, 140, 141. oxybromide, 140. oxy chloride, 140. oxyhydrate, 140, 142. oxyiodide, 140. sulphide, 144. Bismuthylic carbonate, 141. Bleaching-powder, 48, 161. Blende, manganese, 190. Blue copper, 171. malachite, 173. prussian, 227. Turnbull's, 227. Bonds, definition of, 18. nature of, 25. Bone-ash, 107. Boracite, 55. Borates, 55. Borax, 55. Boric bromide, 53. chloride, 53. ethide, 51. Boric fluoride, 53. methide, 386. ,, nitride, 56. sulphide, 56. Boron, 51. amorphous, 51. diamond, 52. graphitoidal, 52. Boulangerite, 137. Bournonite, 137. Bracket, use of, 16. Braunite, 189. Brochantite, 172. Bromacetylene, 220. Bromates, 90. Bromhydrin, 289. Bromine, 86. compounds of, with oxy- gen and hydroxyl, 88. hydrate, 87. Brookite, 106. Brown hematite, 192. iron ore, compact, 192. fibrous, 192. Brucine, 370. Brucite, 162. Buchholzite, 177. Butoxyl, 203. Butyl, 209. Butylene, 213. Butylenic bromide, 288. chloride, 288. Butylic iodide, 271. Butyrone, 360. Cacodyl, 371. Cacodylic acid, 372, 380, 390. chloride, 371. oxide, 371. trichloride, 380. Cadmic chloride, 167. hydrate, 167. oxide, 167. sulphate, 167. Cadmium, 167. Caesium, 153. Calamine, 165, 166. electric, 165. Calc spar, 160. Calcic carbonate, 160. chloride, 160. ,, chlorohypochlorite, 161. dihydric, di carbonate, 161. INDEX. 401 Calcic fluoride, 160. hydrate, 160, 161. magnesic dicarbonate, 162. magnesic disilicate, 103. metaphosphate, 107. oxide, 160, 161. oxysulphide, 152. peroxide, 161. phosphate, 160. phosphide, 110. ,, tetrahydric sulphate, 160. Calcium, 160. Capacity, measures of, 33. Capillary pyrites, 197. Caproyl, 209. Caprylene, 213. Carbon, 57. compounds of, with oxygen, 57. Carbonates, 58. Carbonic disulphide, 72. oxide, 58. ,, oxydichloride, 59. ,, tetrachloride, 57. Carburetted hydrogen, h'ght, 234. Caustic antimony bases, 377. arsenie bases, 377. baryta, 159. nitrogen bases, 377. phosphorus bases, 377. potash, 147. Celestine, 160. Cerotene, 214. Cervantite, 133. Cetene, 214. Chalcedony, 102. Chalk, 160. Chemical action, modes of, 1. affinity, 4. equations, 15. notation, 14. Chemistry, definition of, 1. ,, organic, 199. Chiastolite, 177. Chloracetamide, 372. Chloraniline, 376. Chlorates, preparation of, 49. Chlorhydrate, ethylenic, 281, 287. Chlorhydric acid, 39. Chlorhydrin, 282, 289. Chloride, methylic, 285. of selenium, 84. Chlorides, 39. Chlorine, 37. action of, on the radicals of the ethvlene series, 214. compounds of, with oxy- gen and hydroxyl, 45. ,, oxides of, 45. Chloro-compounds of benzol, 241. Chloroform, 285. Chloronitric gas, 66. Chloronitrous gas 66. Chloropal, 103. Chloropernitric gas, 66. Chlorous elements, 4. elements, table of, 4. organic radicals, 207. Chrome iron ore, 186. potassium alum, 187. Chromium. 185. Chlorochromic acid, 188. Chrome iron ore, 186. Chromic anhydride, 186. chloride, 185. dichlorodioxide, 188. dioxide, 186. hydrate, 187. oxide, 185. perfluoride, 185, Chromium, atomicity of, 185. compounds of, 185. Chromous chloride, 185. dichromic tetroxide, 186. ,, dipotassicdisulphate, 187. hydrate, 185. oxide, 185. sulphide, 188. Crocoisite, 187. Dichromic ferrous tetroxide, 186. hexanitrate, 187. trisulphate, 187. trisulphide, 188. Dihydric sulphate chromate, 187- Diplumbic chromate, 184. Dipotassic chromate, 186. chromous disulphate, 187. dichromate, 186. dichromic tetrasul- phate, 187, trichromate, 186. Normal potassic chromate, 186. 402 INDEX. Chromium (continued). Octochromic carbonate dihy- drate, 187. Perchromic acid, 187. Plumbic chromate, 187. Potassic bichromate, 186. chlorochromate, 188. terchr ornate, 186. Potassium chrome alum, 187. Eed lead ore, 187. Sulphochromic acid, 187. anhydride, 188. Tetrapotassic dichromosul- phate, 187. Triplumbic dichromate, 184. Chryson, 101. Cimolite, 177. Cinchonine, 370. Cinnabar, 168. Citramide, 375. Citryl-triphenyl-triamide, 375. Classification of elements, 31 . organic compounds, 206. Clay, porcelain, 177. porcelain of Passau, 177. Cobalt, 195. Atomicity of cobalt, 195. Cobalt pyrites, 196. Cobaltic chloride, 195. disulphide, 197. oxide, 195. oxydihydrate, 196. sulphide, 196. Cobaltoso-diammon-diammonic dichloride, 196. Cobaltous chloride, 195. dicobaltic tetroxide, 195. dihydric sulphate, 197. dinitrate, 196. dipotassic dicarbo- nate, 196. dipotassic disulphate, 196. hydrate, 196. oxide, 195. sulphide, 196. Compounds of cobalt, 195. Dicobaltic hexammon-hexam- rnonic hexachlo- ride. 196. Cobalt (continued}. Dicobaltic tetrammon-hexam- monic hexachlo- ride, 196. Dicobaltous carbonate dihy- drate, 196. oxy sulphide, 197. Dihydric cobaltous sulphate, 197 pentacobaltous clicar- bonate.tetrahydrate, 196. Dipotassic cobaltous dicarbo- nate, 196. ,, cobaltous disulphate, 196. Hexacobaltic heptoxide, 195. Luteo-cobalt chloride, 196. Purpureo-cobalt chloride, 196. Eoseo-cobalt chloride, 196. Codeine, 370. Colliding 367. Collyrite, 177. Combination, atomic, 30. ,, molecular, 30. Combining proportions, 2. Common sodic phosphate, 119. Compound organic radicals, 200. basylous radicals, hy- drides of, 232. negative radicals, hy- drides of, 232. oxamides, 232. positive radicals, hydrides of, 232. radicals, 26. radicals, chief inorganic, list of, 28. radicals, definition of, 27. radicals, dyad, 27. radicals, monad, 27. radicals, symbols of, 28. radicals, triad, 27. substances, 1. of nitrogen with chlorine, 69. of nitrogen with iodine and hydrogen, 69. of nitrogen with chlorine and oxygen, 66. of nitrogen with hydro- gen, 67. Compounds, 1. binary, 7. INDEX. 403 Compounds of chlorine with oxygen and hydroxyl, 45. organic, 199. of carbon with oxygen,57. ,, of sulphur with basylous elements, 70. of sulphur with positive elements, 70. Conine, 366. Constituents of organic compounds. 199. Copper, 170. Ammoniocupric carbonate, 173. sulphate, 172. Atomicity of copper, 170. Azurite, 173. Blue copper, 171. ,, malachite, 173. Brochantite, 172. Compounds of copper, 170. Copper, acetylide of, 219. azure, 173. glance, 171. pyrites, 194. Cupric chloride, 170. hydrate, 171. nitrate, 171. oxide, 171. phosphide, 109. sulphide, 171. sulphohydrate, 171. Cuprodiammonic carbonate, 173. Cuprosovinylic ether, 219. Cuprous chloride, 170. hydrate, 170. hydride, 170. oxide, 171. quadrantoxide, 171. sulphide, 171. Dicupric carbonate, 172. ,, carbonate dihydrate, 172. Diferric dicupric trtrasulphide, 194. Dihydric cupric sulphate, 171. ,, diammonic cuprodi- ammonic sulphate, 1 72. ., tetracupric sulphate tetrahydrate, 172. ,, tricupric dicarbonato, 173. Dioptase, 173. Dipotassic cupric disulphate, 1 72. Copper (continued). Hydriccupricsilicate hydrate,173. ,, peutacupric sulphate pen- tahydrate, 172. tricupric sulphate trihy- drate, 171. Indigo copper, 171. Malachite, 172. Mountain-blue, 173. Mysorin, 172. Red copper ore, 171. Ruby ore, 171. Coquimbite, 194. Cream of tartar, 132. Crith, 34. use of, 34. Crocoisite, 187. Crystallization, water of, 30, 43. Cubic foot, 33. Cumol, 237. Cupric compounds (see Copper). Cuprous compounds (see Copper). Cyamelide, 228. Cyanic hydride, 243. Cyanides, double, 224. easily decomposable, 225. ,, single, 224. Cyanite, 177. Cyanogen, 221, 222. chlorides of, 227. Cymol, 237. Dark-red silver, 137. Definition of acids, 8. acid salts, 13. anhydrides, 8, 10. anhydrous acids, 8, 10. artiads, 20. ,, bases, 11. basic salts, 13. ,, chemistry, 1. ,, compound radicals, 27. dyads, 20. dibasic acids, 9. haloid salts, 12. hexads, 20. hydrates, 11. monads, 20. monobasic acids, 9. neutral salts, 12. normal salts, 12. oxy salts, 12. pentads, 20. 404 INDEX. Definition of perissads, 20. poly basic acids, 9. salts, 12. sulpho -salts, 12. tetrads, 20. triads, 20. Derivatives of glycol, 265. substitution, of benzol, 239. Development of formulae, 203. Diacetic glycol. 362. Diacetimide, 373, 376. Diacetin, 362. Diacid alcohols, 244, 245, 262. Diadelphic type, 201, 202. Dialkalamides, 375. Diamide, trimercuric, 170. Diamides, 374. constitution of, 374. , , formation of primary, 374. primary, 374. ,, secondary, 374. tertiary, 374. Diamines, 364, 367. formation of, 367. monacid salts of, 379. normal salts of, 379. oxides of, 368. primary, 368. secondary, 368. tertiary, 368. Diamond boron, 52. Diarsenious disulphide, 124. Diaspore, 176. Diatomic molecules, 3, 19. Dibasic acids, 337. acids, anhydrides of, 357. acids, definition of, 9. acids, fumaric or acryloid series of, 345. Dibismuthic tetroxide, 140. Dibismuthous dioxide, 140. disulphide, 144. tetrachloride, 140. Dibrombenzol, 239. Dicadmic sulphate dihydrate, 167. Dichloraniline, 376. Dichlorbenzol, 241. Dichlorethide, bismuthous, 139. Dichlorhydrin, 282, 289. Dichlorinated methylic chloride, 285. Diethylamine, 366. Diethylated acetone, 360. Diethylene triammonic dichloride, 379. triammonic monochlo- ride, 379. triammonic trichloride,379. Diethyloxamide, 375. Diglucinic silicate, 102. Dimethylamine, 366. Dimethylated acetone, 360. Dinitrobenzol, 242. Diopside, 103. Dioptase, 173. Diphenyl-carbonyl-oxalyl diamide, 375. Disodic disulphate, 77. Displaceable hydrogen, 9. Distannic hexethoxide, 390. Disulphide, dibismuthous, 144. Ditelluro-sulphide, bismuthous, 145. Dithionates, 82. Dititanic dinitride, 106. hexachloride, 106. Dizirconic silicate, 102. Dodecasodic decaphosphate, 115. Dolomite, 162. Double cyanides, 224. monadelphic type, 202, 203. Dyad basylous radicals, 212. compound radicals, 27. Dyads, definition of, 19. Dyad elements, 39, 155. Dyads, list of, 32. Dyad positive radicals, haloid ethers of, 281, 287. Elaldehyde, 294. Electric calamine, 165. Electro-negative elements, 4. ,, -positive elements, 4. Elementary molecule, 2. Elements, 1. ,, atomicity of, 17. basylous, 4. chlorous, 4. chlorous, table of, 4. classification of, 31. dyad, 39. electro-negative, 4. electro-positive, 4. hexad, 69. monad, 36. names of, 6, 7. negative, 4. INDEX. 405 Elements, pentad, 60. positive, 4. table of, 6. tetrad, 57. triad, 51. Ellenbogen, kaolin of, 177. Embolite, 154. Emerald, 103. Emetic tartar, 132. Empirical formulas, 17. Enstatite, 102. Epichlorhydrin, 282, 290. Equations, chemical, 15. Erythrite, 270. Erythroglucin, 270. Erythromannite, 270. Ether, 274. allylic, 276. amylic, 273. butylic, 273. cuprosovinylic, 219. diethoxalic, 386. diethylated ethylic, 385. ethylenic, 277. ethylic, 274, 272. ethylic amylic, 273. ethylic butylic, 273. glycylic, 279. methylic, 274, 272. ,, methylic amylic, 272. methylic ethylic, 272. monosodacetic, 304. phenylic, 276. stanntriethylic, 388. sulphomethylic, 362. sulphuric, 274. toluylic, 276. Ethers, 272. formation of, 273. haloid, 280. ,, haloid, of the dyad positive radicals, 281, 287. haloid, of the monad positive radicals, 280, 282. ,, haloid, of the triad positive radicals, 281. of the diacid alcohols, 272, 276. of the methyl series, 272. of the monacid alchols, 272. of the phenyl series, 276. of the triacid alcohols, 272, 279. Ethers of the vinyl series, 276. Ethereal salts, 243, 361. salts, decomposition of, 362. salts, definition of, 361. salts of diacid alcohols, 362. salts of dibasic acids, 362. salts, dibasic acids, acid, 362. salts, dibasic acids, neu- tral, 362. , , salts, monacid alcohols, 362. salts, monobasic acids, 362. salts, triacid alcohols, 362. salts, tribasic acids, 362. ,, salts, tribasic acids, acid, 362. ,, salts, tribasic acids, neu- tral, 362. ,, salts, production of, 361. Ethide, antimonious, 128. boric, 51. bismuthous, 139. hypostannic, 387. lithiomercuric, 391. lithiozincic, 391. magnesic, 391. ,, mercuric, 386. perplumbic, 388. potassic, 389. potassio-zincic, 391. sodio-zincic, 391. stannic, 387. ,, stannous, 387. tellurium, 390. zincic, 389. Ethobromide, mercuric, 386. Ethodiniodide, hypostannic, 387. Ethohydrate, mercuric, 387. Ethonitrate, mercuric, 391. Ethoxyl, 203. Ethyl, 208, 210. acetone, 360. acetyl, 360. butyral, 360. propionyl, 360. urea, 368. acetamide, 375. Ethylamine, 365. Ethylammonic chloride, 378. Ethylamylamine, 366. Ethylated acetone, 360. Ethyl diacetamide, 375. Ethylene, 213. 406 INDEX. Ethylene compounds, 214. diamine, 369. Ethylene-diammonic dichloride, 379. , , monochloride, 379. Ethylene diethyl diamine, 369. series, 212. series of radicals, action of chlorine on, 214. Ethylenic bromide, 288. chloride, 287. chlorhydrate, 281, 287. cyanide, 289. dichloride, 281. ether, 277. iodide, 288. iodhydrate, 287. oxide, 277. oxide, isorners of, 277. Ethylic acetate, 362. chloride, 286. diethacetone carbonate, 360. disodacetone carbonate, 359. ethacetone carbonate, 359. ether, 274. ethylozincic diethoxalate, 386. iodide, 286. sodacetone carbonate, 359. succinate, 362. sulphhydrate, 251. sulphide, 276. Ethylidene and ethylene, isomerism of, 328. compounds, 215. cyanhydrate, 329. Ethylochlorether, 385. Ethylodimethide, stannic, 387. Ethylo-zincic dinitromethylate, 386. ethylic diethoxalate, 386. Ethylphenylamine, 366. Fahl ore, 137. Fatty series of acids, 297. acids, normal, 298. acids, secondary, 310. acids, tertiary, 311. Feather ore, 137. Felspar, 103. Ferric compounds (see Iron). Ferricyanide, potassic, 227. Ferrocyanide, potassic, 226. Ferrous compounds (see Iron). Fibrolite, 177. Fibrous brown iron ore, 192. Fire-damp, 234. Flint, 102. Fluoride, antimonious, 130. ,, bismuthous, 140. boric, 53. .silicic, 100. Fluorine, 96. compound of, with hydro- gen, 97. Foot, 33. cubic, 33. Formulas, 14. development of, 204. empirical, 17. graphic, meaning of, 25. graphic, of organic com- pounds, 205. rational, 17. statical and dynamical, 26. Formyl, 220. Fowler's solution, 122. Francolite, 119. Fumaric or acryloid series of acids, 345. or acryloid series of acids, isomerism in, 345. Galena, 182. Gallon, 33. Gas, chloronitric, 66. chloronitrous, 66. chloropernitric, 66. laughing, 64. phosgene, 59. Gaseous phosphoretted hydrogen, 108. Gaultheria procumbens, oil of, 249. Gibbsite, 175. Glance, bismuth, 144. iron, 192. nickel, 198. silver, 154. Glucose, 271. Glycerin, 267, 268. Glycocin, 337. Glycol, acetobutyric, 266. amylic, 262. bromethylic, 265. bromhydric, 265. butylic, 262. INDEX. 407 Glycol, chlorhydric, 265, 281, 287. derivatives of, 265. diacetic, 265, 362. diethylenic, 266. diethylic, 265. disodic, 265. ethylic, 262, 264. hexethylenic, 260. hydric ethylic, 265. iodhydric, 287. monacetic, 265, 362. monosodic, 265. pentethylenic, 266. propylic, 262. sulphur, 265. tetrethylenic, 266. triethylenic, 266. Glycollic acetobromide, 265. Glycols, 2i':2. polyethylenic 266. relations of succinic series to, 340. Glycolyl, 221. Glyoxal, 334. Glyoxyloid series of dibasic acids, 351. Gold, 174. Atomicity of gold, 174. Auric anhydride, 174, chloride, 174. iodide, 174. oxide, 174. sulphide, 174. Aurous chloride, 174. iodide, 174. oxide, 174. sulphide, 174. Compounds of gold, 174. Potassic aurate, 174. Grain, 34. Gramme, 34. Graphic formulae, meaning of, 25. ,, formulae of organic com- pounds, 205. notation, 23. Graphitoidal boron, 52. Green salt of Magnus, 179. Greenockite, 167. Grey antimony ore, 136. nickel ore, 198. Grossularia, 103. Guanite, 163. Gypsum, 160. Haematite, brown, 192. red, 192. Hair nickel, 197. Haloid compounds of oxybases, 363, 376. ethers, 280. ethers of the dyad positive radicals, 281, 287. ethers of the monad positive radicals, 280. ethers of the triad positive radicals, 281, 289. ,, salts, definition of, 12. Hartmangan, 189. Hausmanite, 189. Heavy spar, 156. Helvine,.191. Hepar sulphuris, 150. Heptylene, 213. Heterocline, 191. Hexad elements, 69, 185. Hexads, definition of, 20. list of, 32. Hexasodic tetraphosphate, 115. Hexatomic molecules, 3. Hexylene, 213. Horn-mercury, 168. ,, silver, 154. Hydrate, argentic, 155. baric, 159. cadmic, 167. calcic, 161. magnesic, 162. potassic, 147. sodic, 151. strontic, 159. zincic, 166. Hydrates, 43. definition of, 11. Hydric oxide, 43. ,, peroxide, 44. persulphide, 72. sulphate, 74. Hydride, anylic, 234, 236. antinionious, 126. butylic, 234. caproylic, 234. cuprous, 170. cyanic, 243. decatylic, 234. dodecatylic, 234. en decatylic, 234. ethylic, 234, 236. 408 INDEX. Hydride, heptylic, 234. hexylic, 234. methylic, 234. nonylic, 234. octylic, 234. oxatylic, 243. pentadecatylic, 234. pentylic, 234. phenylic, 238. propylic, 234. silicic, 99. tetradecatylic, 234. tetrylic, 234. tridecatylic, 234. tritylic, 234. Hydrides of compound basylous ra- dicals, 232. . of compound negative ra- dicals, 232, 243. of compound positive ra- dicals, 232. of the radicals of the me- thyl series, 232. of the radicals of the phe- nyl series, 237. Hydrochloric acid, 39. glycide, 282. Hydrodiniodide, nitrous, 69. Hydrogen, 36. bicarburet of, 238. compounds of, with nitro- gen, 67. displaceable, 9. sulphuretted, 71. Hydrosulphate of ethyl, 251. Hydrosulphyl, 28, 72. Hydroxyl, 28, 44. Hyperoxide, chloric, 45. Hypochlorites, 48. Hypochlorous anhydride, 46. Hypostannic ethide, 392. ethodiiodide, 392. Hyposulphites, 81. Imides, 363, 376. general formula of, 376. Imidogen bases, 365. Indigo copper, 171. Inorganic compound radicals, chief, list of, 28. Introduction to organic chemistry, 199. lodates, 95. Iodides, antimonious, 130. bismuth ous, 140. Iodide, phosphonic, 107, 109. Iodine, 90. ,, compounds of, with oxygen and hydroxyl, 93. lodhydric glycol, 287. lododiethide, stannic, 387. lodotriethide, stannic, 387. Iron, 192. Atomicity of iron, 192. Brown haematite, 192. iron ore, 193. Chrome iron ore, 186. Compact brown iron ore, 192. Compounds of iron, 192. Copper pyrites, 194. Coquimbite, 194. Dichromic ferrous tetroxide, 186. Diferric dicupric tetrasulphide, dioxy-dihydrate, 193. hexahydrate, 192. hexanitrate, 194. oxy-tetrahydrate, 193. trisulphate, 194. trisulphide, 194. Diferrous sulphide, 193. Dipotassicdiferric tetrasulphate, 194. ferrous disulphate, 194. Ferric chloride, 192. disulphide, 193. oxide, 192. trisilicate, 103. Ferrous carbonate, 195. chloride, 192. dichromic tetroxide, 186. diferric tetroxide, 193. dipotassic disulphate, 194. hydrate, 192. nitrate, 195. oxide, 192. sulphate, 194. sulphide, 193. Fibrous brown iron-ore, 192. Heptaferric octosulphide, 195. Hexahydric diferric diphos- phate dihydrate, 194. INDEX. 409 Iron (continued]. Iron glance, 192. ,, micaceous, 192. ore, brown, 193. ore, compact brown, 192. ,, ore, fibrous brown, 192. ore, magnetic, 193. ore, needle, 193. ore, spathic, 195. ,, potassium alum, 194. pyrites, 193. specular, 192. Magnetic iron ore, 193. ,, pyrites, 195. Martial pyrites, 193. Micaceous iron, 192. Needle iron ore, 193. Octoferrous sulphide, 193. Oligist, 192. Potassic ferrate, 193. Potassium iron alum, 194. Eed hematite, 192. Spathic iron ore, 195. Specular iron, 192. Tetraferric sulphate, 194. trioxyhexahydrate, 192. Tetrahydric tetraferric sulphate octohydrate, 194. Triferric tetroxide, 193. Vitriol ochre, 194. Irregular names, 8, 11. names of bases, 11. Isomeric forms of valeric acid, 309. Isomerism of ethylene and ethyli- dene, 328, 346. in the lactic series, 325. Isomerism in fumaric or acryloid series, 345. Isopropylic alcohol, 253. iodide, 268. Kaolin of Ellenbogen, 177. Ketones, 357. formation of, 358. isomerism of, 360. list of, 360. of the C n H 2n _ 7 series, 361. Kobellite, 145. Kupfernickel, 198. Labradorite, 103. Lactic series of acids, relations of, to acetic series, 324. series of acids, relations of, to acrylic series, 324. series of acids, relations of suc- cinic series to, 340. Lactide, 357. Lactoid series of dibasic acids, 349. Lactyl, 221. Lanarkite, 184. Latent atomicity, 21. Laughing gas, 64. Law of volumes, 3. Lead, 180. Basic hyponitrate of lead, 183. Crocoisite, 187. Dihydric diplumbic nitrate hy- drate, 183. diplumbic nitrate ni- trite, 183. triplumbic dicarbo- nate, 184. Diplumbic chromate, 184. nitrite hydrate, 182. oxychlorohydrate, 182. oxydichloride, 181. oxydihydrate, 181. sulphate carbonate, 184. sulphodichloride, 182, trioxide, 181. Dipotassic plumbate, 184. Galena, 182. Hydric plumbic nitrate, 183. Lanarkite, 184. Lead, atomicity of, 180. compounds of, 180. spar, 183. vitriol, 182. Leadhillite, 184. Litharge, 181. Matlockite, 181. Mendipite, 182. Octoplumbic heptoxydichloride, Perplumbic chlorotriethide, 388. ethide, 388. triethohydrate, 388. Plattnerite, 181. Plumbic carbonate, 183. T 410 INDEX. Lead (continued}. Plumbic chloride, 180. chlorohydrate, 181. chromate, 187. dinitrate, 183. dinitrite, 182. hydrate, 181. nitrite hydrate, 182. oxide. 181. peroxide, 181. sulphate, 182. sulphide, 182. Plumbous oxide, 181. Eed lead, 181. ore, 187. Tetraplumbic pentoxide, 181. tricarbonate sul- phate, 184. Triplumbic dichromate, 184. dihydrate dicarbo- nate, 184. oxydichloride, 182. tetroxide, 181. White lead ore, 183. Lead, basic hyponitrate of, 183. ore, red, 187. ore, white, 183. spar, 183. vitriol, 182. Leadhillite, 184. Lead, red, 181. Length, measures of, 33. Lepidolite, 178. Letters, thick, use of, 16. Leucin, 332. Leukon, 101. Light carburetted hydrogen, 234. Lime, chloride of, 48, 161. slaked, 161. Liquid phosphoretted hydrogen, 108, 110. List of dyads, 32. hexads, 32. monads, 32. pentads, 32. tetrads, 32. triads, 32. Litre, 33. Lithia, 152. Litharge, 181. Lithic chloride, 152. hydrate, 152. Lithiomercuric etbide, 391. Lithiozincic ethide, 391. Lithium, 152. Liver of sulphur, 150. Luteo-cobalt chloride, 196. Lutidme, 367. Magnesia, 162. alba, 164. Magnesic aluminate (Spinelle), 176. carbonate, 163. chloride, 162. ethide, 391. hydrate, 162. oxide, 162. sulphate, 162. Magnesite, 163. Magnesium, 162. Magnetic iron ore, 193. pyrites, 195. Magnus, green salt of, 179. Malachite, 172. blue, 173. Malic series of acids, 349. Malonyl, 221. Malthacite, 178. Manganese, 188. Aluminic manganous disilicate, 191. manganous tetrasul- phate, 190. . Atomicity of manganese, 188. Braunite, 189. Compounds of manganese, 188. Dihydric dimanganic silicate di- hydrate, 191. dimanganous diphos- phate, 191. manganous sulphate, 190. Dimanganic dioxydihydrate, 189. hexachloride, 188. trioxide, 189. trisulphate, 190. Dimanganous sih'cate, 191. Dipotassic dimanganic tetrasul- phate, 190. manganate, 189. manganous disul- phate, 190. permanganate, 190. INDEX. 411 Manganese (continued). Disulphopotassic trimanganous disulphide, 190. JTartmangan, 189. Hausmanite, 189. Helvine, 191. Heterocline, 191. Hexmanganic monosilioate, 191. Manganese aluminium alum, 190. blende, 190. potassium alum, 190. siliciferous, 191. spar, 190. Manganic chloride, 188. oxide, 189. perfluoride, 188. Manganite, 189. Manganous aluminic disilicate, 191. chloride, 188. aluminic tftrasul- phate, 190. carbonate, 190. dihydric sulphate, 190. ,, dimanganic tetrox- ide, 189. ,, dimanganic tetrox- idedihydrate,189. ,, dipotassic disul- phate, 190. hydrate, 188. oxide, 189. silicate, 191. sulphide, 190. Potassium manganese alum, 190. Psilomelane, 189. Pyrolusite, 189. Red manganese, 191. Rothbraunsteinerz, 191. Rother Mangankiesel, 191. Siliciferous manganese, 191. Schwarzer Mangankiesel, 191. Tephroite, 191. Triglucinic tetramanganous tri- silicate sulphide, 191. Trimanganic tetroxide, 189. Varvicite, 189. Manganese aluminium alum, 190. blende, 190. Manganese potassium alum, 190. red, 191. spar, 190. Manganite, 189. Mannite, 271. Manufacture of nitric acid, G2. Marble, 160. Marks of atomicity, 18. Marsh-gas, 234. series, hydrides of, 232. ' type, 201. Martial pyrites, 193. Matlockite, 181. Meadow-sweet, oil of, 336. Measures of capacity, 33. length, 33. surface, 33. weight, 34. Measures, weights and, 32. Meerschaum, 103. Melene, 214. Mendipite, 182. Mendius's reaction, 248. Mercaptan, 251. Mercury, 168. Cinnabar, 168. Dihydric trimercuric dinitrate, 169. Dimercurous dinitrate, 169. Hexahydric trimercurous tetra- nitrate, 169. Horn-mercury, 168. Mercurous tetrahydric dinitrate, 169. Mercurammonic chloride, 170. Mercuric amylide, 384. chloride, 168. ethide, 386. ethobromide. 386. ethohydrate, 387. ethon'itrate, 391. iodoethide, 389. methide, 387. methiodide, 387. methohydrate, 387- oxide, 168. sulphate, 168. sulphide, 168. Mercurosodiammonic dichlo- ride, 169. Mercurosomercuro-diammonic dicliloride, 170. T2 412 INDEX. Mercury Mercureus chloride, 168. dimercuricdinitrate, 169. oxide, 168. sulphate, 168. sulphide, 168. Methohydrate, mercuric, 387. Organo-mercuric compounds, 382, 386, 389. Tetrahydric dimercuric dini- trate, 169. mercuric dinitrate, 169. mercurous dini- trate, 169. Tetramercuric carbonate, 169. Trimercuric carbonate, 169. diamide, 170. sulphate, 168. Turpeth mineral, 168. Vermilion, 168. White precipitate, 170. Metaboric acid, 54. Metaldehyde, 294. Metalloids, 6. names of, 6. Metals, 6. Metaphosphates, 117. Metastannic acid, 105. Metasulphantimonites, 137. Metasulphantimonite, sulphargen- tic, 137. sulphocu- prous, 137. sulphofer- rous, 137. sulphoplum- bic, 137. Methide, aluminic, 389. boric, 386. mercuric, 391. potassio-zincic, 391. tellurium, 391. zincic, 386, 391. Methoxyl, 203. Methyl, 208. Methyl acetone, 360. benzone, 361. benzoyl, 361. series,' hydrides of the radi- cals of, 232. series of alcohols, 245, 246. Methyl series, normal alcohols ol, 245, 246. series, secondary alcohols of, 245,252. series, tertiary alcohols of, 245,254. series, normal radicals of, 207, 208. series, preparation of normal radicals of, 209. series, secondary radicals of, 208. ,, series, tertiary radicals of, 208. type, 201. valeral. 360. Methylamine, 365. Methylated acetone, 360. Methylenic chloride, 287. iodide. 287. Methylethylamine, 366. Methylethyl-phenylamine, 367. Methylic chloricK 285. chloride, dichlorinated, 285. chloride, monochlorinated, 285. chloride, trichlorinated, 285. oxide (Methylic ether), 274. Metre, 33. Micaceous iron, 192. Miloschine, 177. Modes of chemical action, 1. Molecular combination, 30. union, 30. volume, 2. volumes, table of, 3. weight, 2. Molecules, 2. diatomic, 3, 19. elementary, 2. hexatomic, 3. monatomic, 3, 19. tetratomic, 3. ,, triatomic, 3, 19. Monacetic glycol, 362. Monacetin. 362. Monacid alcohols, 244, 245. alcohols, secondary, 252. alcohols, tertiary. 254. alcohols, normal, of the phenyl series, 258, 260. INDEX. 413 Monacid alcohols of the phenyl series, 258. alcohols of the vinyl series, 255. Monad basylous radicals, 207. compound radicals, 27. ,, elements, 145, 36. positive radicals, haloid ethers of, 280, 282. Monadelphic type, 201. 202. Monads, definition of, 20. list of, 32. Monalkalamides, 375. Monamides, 372. formation of primary, 373. primary, 372. ,, reactions of primary, 373. ,, secondary, 373. ,, tertiary, 374. Monamines, 364. formation of primary. 364. formation of secondary, 365. formation of tertiary, 366. , , methyl series of primary, 364. phenyl series of pri- mary, 364. methyl series of secon- dary, 365. phenyl series of secon- dary, 365. ,, primary, 364. reaction of primary, 365. recognition of primary, 367. recognition of secondary, 367. recognition of tertiary, 367. secondary, 364. 365. tertiary, 364, 366. vinyl series of primary, 364. vinyl series of secondary, 365. Monatomic molecules, 3, 19. Monobasic acids, anhvdrides of, 355. Monobasic acids, definition of, 9. boric acid, 54. organic acids, 296. Monobrombenzol, 239. Monochlorbenzol, 241. Monochlorhydrin, 2(59. Monochlorinated methylic chloride, 285. propylic glycol, 269. Monomagnesic silicate, 102. Monomethylarsenic acid, 380, 390. Morphine, 370. Mountain-blue, 173. Muriatic acid, 39. Miargyrite, 137. Mysorin, 172. Names of bases, systematic and irregular, 8, 11. of elements, 6, 7. irregular, 8, 11. systematic, 8, 11. trivial, 8, 11. Narceine, 370. Narcotine, 370. Natural alkaloids, 370. Needle iron ore, 193. Needle ore, 145. Negative elements, 4. compound radicals, hy drides of, 232, 243. organic radicals, 207. Nickel, 197. Capillary pyrites, 197. Dihydric nickelous sulphate, 197. pentanickelous dicar- bonate tetrahy- drate, 198. Dinickelous sulphide, 197. Dipotassic nickelous disulphate, 198. nickelous tricarbo- nate, 198. Grey nickel ore, 198. Hair nickel, 197. Kupfernickel, 198. Nickel glance, 198. Nickelic disulphide, 197. hydrate, 197. oxide, 197. tetrarsenide, 198. T3 414 INDEX. Nickel (continued}. Nickelous chloride, 197. diarsenide, 198. dihydric sulphate, 197. dinitrate, 198. dipotassic disulphate, 198. dipotassic tricarbo- nate, 198. hydrate, 197. oxide, 197. sulphide, 197. sulphide diarsenide, 198. Nicotine, 370. Nitraniline, 242. Nitrates, 62. Nitric oxide, 61, 65. peroxide, 65. Nitride, boric, 56. Nitrides, general formula of, 376. negative, 376. Nitrites, 64. Nitrobenzol, 238, 241. Nitrocumol, 238. Nitrocymol, 238. Nitrogen, 60. caustic bases of, 377. compounds of triad, and its analogues, 363. compound of, with chlo- rine, 69. compounds of, with chlo- rine and oxygen, 66. compounds of, with hydro- gen, 67. compound of, with hydro- gen and iodine, 69. compounds of pentad, and its analogues, 377. organic compounds of, 363. oxides and oxacids of, 61. Nitrotoluol, 238. Nitrous chloride, 69. hydrodiniodide, 69. oxide, 61, 64. Nitroxylol, 238. Nomenclature, 5. of acids, 9. Non-metals, 6. names of, 6. Nonylene, 214. Normal acids, 297. acids of the acrylic series, 312. acids of the lactic series, 317. fatty acids, 298. monacid alcohols of phenyl series, 258, 260. olefine acids of the lactic series, 321. radicals of methyl series, 207, 208. ,, radicals of methyl series, preparation of, 209. salts, 12. ,, salts of amines, 379. Notation, 14. chemical, 14. graphic, 23. symbolic, 14. of organic compounds, 201. Ochre, bismuth. 141. vitriol, 194. Octylene, 213. (Enanthylene, 213. Oil of bitter almonds, 295. of Gaultheria procurnbens, 249. Okenite, 103. Olefine type, 202. Oleic series of acids, 312. Oligist, 192. Opal, 102. Organic antimonic acids, 380. arsenic acids, 380. arsenic chlorides, 380. arsenic oxy chlorides, 380. bases, 364. bases, periodides of, 31. chemistry, 199. compounds, 199. ,, compounds, classification of, 206. compounds, graphic for- mulaa of, 205. compounds, notation of, 201. radicals, 200, 207. radicals, basylous, 207. radicals, chlorous, 207, 221. radicals, negative, 207, 221. radicals, positive, 207. Organo-aluminic compounds, 389. antimony compounds, 390. INDEX. 415 Organo-arsenic compounds, 390. ,, bismuth compounds, 390. ., cadmium compounds, 389. lead compounds, 388. magnesium compounds, 389. mercury compounds, 386. potassium compounds, 384. ,, sodium compounds, 384. tellurium compounds, 388. tin compounds, 387. zinc compounds, 384, 389. Organometallic bodies, 381. bodies, constitution of, 388. bodies, definition of, 381. bodies, formation of, 382. bodies, reactions of, 384. bodies, types of, 389. Orthose, 103. Orthosulphantimonites, 137. Ounce, 34. Oxacids of nitrogen, 61. Oxalates, 230. Oxamide, 231, 374. Oxamides. compound, 232. Oxatyl, 221, 228. Oxatylic hydride, 243. Oxide, antimonious, 130, 131. bismuthic, 142. bismuthous, 139, 140, 141. ,, carbonic, 58. chloric, 45. hydric, 43. hyperchlorous, 45. nitric, 61, 65. nitrous, 61, 64. Oxides of antimony, 130. of chlorine, 45. ,, of nitrogen, 61. Oxyantimonic bases, 378. bases, salts of, 380. Oxyarsenic bases, 377. bases, salts of, 380 Oxybases, 363, 371. ,, arsenious, 371. haloid compounds of, 363, 376. Oxygen, 39. * allotropic, 41. Oxygen compounds of carbon, 57. Oxysalts, definition of, 12. Ozone, 41. Papaverine, 370. Paraffin, 237. Paraldehyde, 294. Paramylene, 214. Parvoline, 367. Passau, porcelain clay of, 177. Pentad elements, 60, 107. Pentads, 32. definition of, 20. Peridote, 102. Periodates, 96. Perissads, 20. Petalite, 176. Phenacite, 102. Phenyl, 212. series, ethers of, 276. series, hydrides of the radi- cals of, 237. ,, series, monacid alcohols of, 258. series, normal monacid alco- hols of, 258. series, radicals of, 211. series, secondary alcohols of, 259, 260. Phenylamine, 265. Phenylene series, 220. Phenylic hydride. 238. iodide, 280. Phosgene gas, 59. Phosphate, triple, 119. Phosphates, 119. Phosphines, 363, 370. salts of, 380. Phosphonic iodide, 107, 109. Phosphoretted hydrogen, gaseous, 108. hydrogen, liquid, 108, 110. hydrogen, solid, 108, 110. Phosphoric chloride, 107, 111. oxytrichloride, 112. sulphotrichloride, 113. Phosphorite, 160. Phosphorous trichloride, 107, HI. trihydride, 107. Phosphorus, 107. allotropic, 108. 416 INDEX. Phosphorus, amorphous, 108. compounds of, with oxy- gen and hydroxyl, 114. manufacture of, 107. organic compounds of, S63. red, 108. Phycite, 270. Picoline, 367. Piperidine, 366. Platinum, 178, Diplatosammonic oxide, 180. Green salt of Magnus, 179. Platinic chloride, 179. hydrate, 179. oxide, 179. sulphide, 180. Platinoso-diammon diammo- nium dihydrate, 180. Platinoso-diammonic dichlo- ride, 179. Platinous chloride, 179. hydrate, 179. oxide, 179. sulphide, 180. Platinum, atomicity of, 178. ,, compounds of, 179. White compound of Beiset, 179. Plattnerite, 181. Plumbic compounds (see Lead). Plumbous compounds (see Lead). Polyacid alcohols, 270. Polybasic acids, definition of, 9. Porcelain clay, 177. of Passau, 177. Positive elements, 4. Potash, 147. caustic, 147. Potassium, 145. Dipotassic aluminate, 176. aluminic hexasilicate, 103. chromate, 186. , , chromous disulphate, 187. cobaltous di carbo- nate, 196. ,, cobaltous disulphate, 196. ,, cupric disulphate, 172. dichromate, 186. Potassium (continued). Dipotassic dichromic tetrasul- phate, 187. diferric tetrasul- phate, 194. disulphide, 149. ferrous disulphate, 194. heptasulphide, 149. ,, nickelous disulphate, 198. nickelous tricarbo- nate, 198. pentasulphide, 149, 150. ,, plumbate, 184. sulphide, 149. tetrasulphide, 149. trichromate, 186. trisulphide, 149, 150. Hydric potassic tartrate, 132. sodic potassic phos- phate, 119. Normal potassic chromate, 186. Potassic antimonylic tartrate, 132. aurate, 174. bichromate, 186. carbonate, 151. chloride, 145, 147. chlorochromate, 188. ,, chromate, normal, 186. ethide, 389. dioxide, 148. ferrate, 193. ferricyanide, 227. ferrocyanide, 226. fluoride, 147. hydrate, 145, 147. iodide, 145, 147. oxide, 148. perchlorate, prepara- tion of, 50. peroxide, 149. sulphide, 145. sulphocarbonate, 73. sulphocyanate, 228. sulphhydrate, 149. terchromate, 186. tetroxide, 148, 149. Potassiozincic ethide, 391. Potassiozincic methide, 391. INDEX. 417 Potassium (continued). Potassium chrome alum, 187. compounds of, 147. compounds of, with bromine, 147. compounds of, with chlorine, 147. compounds of, with fluorine, 147. ,, compound of, with hydrosulphyl, 149. ,, compound of, with iodine, 147. compounds of, with oxygen, 148. compounds of, with sulphur, 149. m iron alum, 194. ' manganese alum, 190. Tetrapotassic dichromosulphate, 187. Potassoxyl, 28. Positive compound radicals, hydrides of, 232. dyad radicals, haloid ethers of, 281, 287. monad radicals, haloid ethers of, 280, 282. organic radicals, 207. triad radicals, haloid ethers of, 281. Powder, bleaching, 48. Prehnite, 176. Propione, 360. Proportion, combining, 2. Propoxyl, 203. Propyl, 208. Propylene, 213. Propylenic bromide, 288. chloride, 288. iodide, 288. Propylic glycoi, monochlorinated, Propylic iodide, 280. Proustite, 125. Prussian blue, 227. Pseudorcin, 270. Psilomelane, 139. Purpureo-cobalt chloride, 196. Pyridine, 367. Pyrites, capillary, 197. cobalt, 196. ,, copper, 194. Pyrites, iron, 193. magnetic, 195. martial, 193. Pyrolusite, 189. Pyromorphite, 119. Pyrophosphates, 118. Pyrophyllite, 103. Pyrosulphantimonites, 187. Pyroxylic spirit, 249. Quadrantoxide, cuprous, 171. Quartz, 102. Quicklime, 161. Quinine, 370. Eadicals, acetylene series of, 217. ,, compound, 26. compound basylous, hy- drides of, 232. compound.chiefinorganic, list of, 28. compound, chief inorganic, symbols of, 28. compound, definition of, 27. compound, dyad, 27. ,, compound, monad, 22. compound, triad, 27. dyad basylous, 212. dyad, relations of succinic series to, 340. , , haloid ethers of the dyad positive, 287, 281. haloid ethers of the monad positive, 280, 282. ,, haloid ethers of the triad positive, 281. ,, hydrides of positive com- pound, 232. ,, monad basylous, 207. ,, monad, relations of, to fatty acids, 302. negative, hydrides of, 232, 243. ,, normal, of the methyl se- ries, 207, 208. normal, of the methyl se- ries, preparation of, 209. of the phenyl series, 211. of the phenyl series, hy- drides of, 237. of the vinyl series, 210. organic, 200. 418 INDEX. Eadicals, secondary, of the methyl series, 208. simple, 26. tertiary, of the methyl se- ries, 208. triad basylous, 220. Eational formulae, *17. Razoumoft'skin, 178. Kealgar, 124. Red antimony, 135. copper ore, 171. haematite, 192. lead, 181. lead ore, 187. manganese, 191. phosphorus, 108. silver ore, 154. zinc, 164. Reiset, white compound of, 179. Rock-crystal, 102. Roseo-cobalt chloride, 196. Rothbraunsteinerz, 191. Rother Mangankiesel, 191. Rubidium, 153. Ruby ore, 171. Rutile, 106. Salt cake, 152. Salts, acid, definition of, 13. ammonic, 67. basic, definition of, 13. definition of, 12. ethereal, 243, 361. haloid, definition of, 12. neutral, definition of, 12. normal, definition of, 12. oxy-, definition of, 12. sulpho-, definition of, 12. Sand, 102. Saponite, 178. Scheele's green, 122. Schwarzer Mangankiesel, 191. Schweinfurt green. 123. Secondary alcohols of the phenyl series, 259, 260. monacid alcohols, 252. radicals of the methyl series, 208. Selenite, 160. Selenium, 84. chlorides of, 84. compounds of, with oxy- gen and hydroxyl, 85. Seleniuretted hydrogen, 84. Senarmontite, 131. Serpentine, 103. Signs, use of, 16. Silicates, 102. Aluminic calcic disilicate, 103. calcic trisilicate, 103. . tri calcic trisilicate, 103. Anorthite, 103. Calcic magnesic disilicate, 103. Chloropal, 103. Diglucinic silicate, 102. Dihydric aluminic tetrasilicate, 103. trimagnesic disilicate, 103. Dimagnesic silicate, 102. 'Diopside, 103. Dioptase, 173. Dipotassic aluminic hexasilicate, 103. Dizincic aluminic hexasilicate, 102. Dizirconic aluminic hexasilicate, 102. Emerald, 103. Enstatite, 102. Felspar, 103. Ferric trisilicate, 103. Grossularia, 103. Hydric cupric silicate hydrate, 173. Labradorite, 103. Meerschaum, 103. Monomagnesie silicate, 102. Okenite, 103. Orthose, 103. Peridote, 102. Phenacite, 102. Pyrophyllite, 103. Serpentine, 103. Steatite, 103. Talc, 103. Tetrahydric calcic disilieate, 103. dimagnesic trisi- licate, 103. Tetramagnesic pentasilicate, 103. Triglucinic aluminic hexasili- cate, 103. Trimagnesic tetrasilicate. 103. Willemite, 102 INDEX. 419 Silicates (continued}. Zircon, 102. Silicic bromide, 100. chloride, 99. ethide, 385. fluoride, 100. hydride, 99. sulphide, 104. Sil ciferous manganese, 191. Sil cium, 97. Sil con, 97. adamantine, 98. amorphous, 97. compounds of, with oxygen and hydroxyl, 101. graphitoidal, 98. Sillimanite, 177. Simple radicals, 26. ,, substances, 1. Silver, 154. Argentic chloride, 154, 155. hydrate, 155. iodide, 154, 155. nitrate, 154. oxide, 154, 155. peroxide, 155. sulphate, 154. Argentide, antimonious, 127. Argentous oxide, 155. Silver, compounds of, with oxy- gen, 155. glance, 154. horn, 154. ,, ore, dark-red, 154. Trisulphargentic sulphantimo- nite, 137. Soda ash, 152 Sodic carbonate, 151. chloride, 151. hydrate, 151. oxide, 151. nitrosulphate, 70. ,, pyrantimoniate, 135. sulphide, 152. Sodio-zincic ethide, 391. Sodium, 151. Solid phosphoretted hydrogen, 108, 110. Spar, lead, 183. manganese, 190 Spathic iron ore, 195. Specular iron, 192. Spinelle, 176. Spirit of wine, 250. Spodumene, 176. Stannic compounds (see Tijl). Stannous compounds (see Tin). Statical formula, 26. Stearin, 268. Steatite, 103. Stibines, 363, 370. salts of, 380. Stibnite, 136. Strontianite, 160. Strontic carbonate, 160. chloride, 159. hydrate, 159. oxide, 159. peroxide, 160. sulphate, 160. Strontium, 159. Struvite, 163. Strychnine, 370. Substances, compound, 1. simple, 1. Substitution derivatives of benzol, 239. Succinamide, 374. Succinic series of acids, 339. series, relations of, to acetic series, 341. series, relations of, to dyad radicals, 340. series, relations of, to lactic series and to glycols, 340. Succinimide, 373, 376. Sulphantimonic anhydride, 138. Sulphantimonites, 137. Sulphantimonious anhydride, 136. Sulphargentic metasulphantimonite, 137. sulphursenite, 125. Sulphates, 79, 80. Sulphhydrates, 71. Sulphhydric acid, 71. Sulphide, antimonic, 136, 138. antimonious, 136. arsenic, 124, 125. arsenious, 124. bismuthous, 144. borio, 56. Sulphides, 71. Sulphites, 76. Sulphobismuthites, 145. Sulphocarbonates, 73. 420 INDEX. Sulphocuprosoferrous pyrosulphan- timonite, 137. Sulphocuprous metasulphantimo- nite, 137. Sulphoferrous metasulphantimonite, Sulphohydrate, cupric, 171. Sulphophenylurea, 369. Sulphoplumbio metaaulphantimo- nite, 137. pyrosulphantimo- nite, 137. sulphobismuthite, 145. Sulphosalts, definition of, 12. Sulphosulphates, 81. Sulphur, 69. alcohol, 251. f allotropic varieties of, 70. an analogue of oxygen, 70. compounds of, with basy- lous or positive elements, 70. compounds of, with oxygen and hydroxyl, 74. Sulphuretted hydrogen, 71. Sulphuric dioxydichloride, 70. Surface, measures of, 33. Symbolic notation, 14. Symbols, 6, 14. of chief inorganic com- pound radicals, 28. table of, 6. Systematic names, 8. names of bases, 11. Table of atomic weights, 6. chlorous elements, 4. elements, 6. metalloids, 6, 32. molecular volumes, 3. non-metals, 6, 32. symbols, 6. Talc, 103. Tartar, cream of, 132. emetic, 132. Tartaric or glyoxyloid series of acids, 351. Telluric bismuth, 145. Tellurium, 85. compounds of, 86. ethide, 388. Tellurous diethoxide, 388, 390. Tellurous diethiodide, 388, 390. diethosulphate, 388. Temperatures, 34. Tertiary acids of the fatty series, 298, 311. diamines, 368. monacid alcohols, 254. monamides, 374. monamines, 364, 366. ,, monarsines, 377. radicals of the methyl series, 208. Tetrachloride, carbonic, 57. Tetrad elements, 57, 175, 178, 180. Tetrads, definition of, 20. list of, 32. Tetradymite, 145. Tetramines, 364. Tetratomic molecules, 3. Tetrethylammonic hydrate, 377. Tetrethylarsonic chloride, 120. Tetrethyl stibonic chloride, 125. Thallic carbonate, 153. chloride, 153. nitrate, 153. oxide, 153. perchloride, 153. peroxide, 153. sulphate, 153. sulphide, 153. Thallium, 153. Thebaine, 370. Thick letters, use of, 16. Tincal, 55. Tin, 104. Distannic hexethoxide, 390. Hypostannic ethide, 387. ethodiniodide,387. Stannic acid, 104. anhydride, 104. chloride, 104. chlorodiethide, 388. chlorotriethide, 387. ethide, 387, 390. ethodimethide, 387. iododiethide, 387, 390. iodotriethide, 387, 390. iododimethide, 392. iodotrimethide, 392. methide, 392. oxide, 104. sulphide, 105. triethohydrate,387,390. INDEX. 421 Tin (continued). Stannous chloride, 104. ethide, 387. hydrate, 104. oxide, 104. stannate, 105. sulphate, 106. sulphide, 105. sulphostannate, 105. Stanntriethylic alcohol, 388. chloride, 388. ether, 388. haloid ether, 388. Tin, compounds of, 104. Titanic acid, 106. anhydride, 106. oxide, 106. sulphide, 106. tetrachloride, 106. Titanium, 106. compounds of, 106. Titanous oxide, 106. Toluol, 237. Triacetin, 362. Triacid alcohols, 244, 245, 267. alcohols, ethers of, 279. Triad basylous radicals, 220. ,, compound radicals, 27. elements, 51, 174. ,, positive radicals, haloid ethers of, 281. Triadelphic type, 202, 203. Triads, definition of, 20. list of, 32. Trialkalamides, 375. Triamides, 375. primary constitution of, 375. secondary and tertiary, 375. Triamines, 364. diacid salts of, 379. monacid salts of, 379. ,, normal salts of, 379. Triamylamine, 367. Triamylstibine, 128. Triatomic molecules, 3, 19. Tribasic acids, 352. ,, acids, aconitic or acryloid series, 353. ,, acids, citric or lactoid series, 353. Tribasic acids, desoxalic or glyoxy- loid series, 353. acids, tricarballylic or ace- toid series, 352. Tribrombenzol, 240. hydrobromate, 240. Trichloraniline, 376. Trichlorbenzol, 241. Trichlorhydrin, 282, 289. Trichlorinated &c. amines, 363, 375. ,, methylic chloride, 285. Triethylamine, 367. Triethylarsine, 371. Triethylphosphine, 371, 385. Triethylstibine, 128. Triethylsulphine iodide, 70. Trimercuric diamide, 170. Trimethylamine, 367. Triphylline, 152. Triple phosphate, 119. Trisodic phosphate, 119. sulphophosphate, 114. Trititanic tetranitride, 106. Trivial names, 8. Turnbull's blue, 227. Turpeth mineral, 168. Type, ammonia, 202. ,, ammoriic chloride, 202. condensed diadelphic, 202, 203. diadelphic, 201, 202. ,, double monadelphic, 202, 203. ,, marsh-gas, 201. methyl, 201. monadelphic, 202, 201. olefine. 202. triadelphic, 202, 203. Types of organic compounds, 201. Union, molecular, 30. Urea, 368. a diamine, 369. derivatives of, 368. formation of, 368. ,, reaction of, C69. Use of signs, 16. of the bracket, 16. of the crith, 35. of thick letters, 16. Valentinite, 131. Variation of atomicity, apparent, 20. U 422 INDEX. Variation of atomicity, law of, 21. "Varieties of sulphur, 70. Varvicite, 189. Vermilion, 168. Vivianite, 119. Vinyl series, ethers of the, 272, 276. series, monacid alcohols of the, 255. series, radicals of, 210. Vitriol, lead, 182. ochre, 194. Volume, molecular, 2, 3. Volumes, 3. law of, 3. Water, 43. of crystallization, 30, 43. Wavellite, 119. Weight, atomic, 2. measures of, 34. molecular, 2. Weights and measures, 32. atomic, table of, 6. Wernerite, 177. White compound of Keiset, 179. lead ore, 183. Willemite, 102, 165. Witherite, 156. Worthite, 177. Xenolite, 177. Xylol, 237. Zinc, 164. blende, 164. compound of, with oxygen, 165. glass, 165. Zincic amide, 386. amylide, 391. carbonate, 164, 166. chloride, 164. dinitroethylate, 385. ethide, 381, 389. ethiodide, 385. ethylate, 381. hydrate, 164, 166. methide, 391. methide ethylate, 386. methyldithionate, 386. oxide, 164, 165. propionate, 385. succinate, 381. sulphate, 166. sulphide, 164. Zincide, antimonious, 128. Zincoxyl, 28. Zircon, 102. Zoisite, 176. THE END. Printed by TAYLOE and FBANCIS, Red Lion Court, Fleet Street Students' Class-Books, AN ELEMENTARY TEXT-BOOK OF THE MICROSCOPE, including a Description of the Methods of Preparing and Mounting' Objects. BY J. W. GRIFFITH, M.D., F.L.S., &c. Post 8vo, with 12 Coloured Plates, 7s. Qd. "A capital book." Medical Times, April 16, 1864. MANUAL OF CHEMICAL QUALITATIVE ANALYSIS. By A. B. NORTHCOTE, F.C.S., and ARTHUR H. CHURCH, F.C.S. 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