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SEPTEMBER, 1905. Vol. XXX., No. 364. THE ANALYST. PROCEEDINGS OF THE SOCIETY OF PUBLIC ANALYSTS. NOTES ON THE HISTORY OF DISTILLED SPIRITS, ESPECIALLY WHISKY AND BRANDY. BY T. FAIRLEY, F.R.S.E., F.I.C. (Read at the Meeting, May 3, 1905.) BEVERAGES, liquids obtained by fermentation of the juices of fruits or other parts of plants, have been in use all over the world from the earliest times. It is even said that there is evidence of the use of malted barley long back in the prehistoric period, during the Stone Age, and in the lake dwellings of Switzerland, etc. Failing saccharine juices from plants, the milk of animals has been used for this purpose, as shown in the koumiss of the Tartars in Central Asia and the kephir of the inhabitants of the Caucasus. I t is not so generally accepted that the art of distilling fermented liquids to obtain a more concentrated alcoholic liquid is also of unknown antiquity.In many works on the chemical history of Modern Europe the Arabians are credited, not only with having conveyed the knowledge of distillation to Southern Europe, but also that Geber (about A.D. 800) invented the process. Certainly Rhases, one of Geber’s followers, used the process in the distillation of fermented materials; and about a century later Albucasis, a physician of Cordova, gave an exact description of a, distillation apparatus as applied in the preparation of medicines, among which l’eau de vie de vin was reckoned one of the most valuable. For some centuries this was the chief application of the spirit from wine, and the knowledge was spread into France and other countries by Arnaud de Villeneuve, Raymond Lully, and others who lived at that time.I n ancient times such processes were often kept secret* in the hands of the priests or religious houses, and later wines and spirits specially flavoured were produced by these houses, some of which survive to the present day. Distillation is seldom referred to by Greek or Roman writers, though Aristotle in his Meteorology ” says : ‘‘ Sea-water can be rendered potable by distillation ; wine and other liquids can be submitted to the same process. After they have been converted into humid vapours they return to liquids.”? Aristotle also explains the formation of dew by the condensation of the vapour of water suspended in the air. If these views of Aristotle were ever applied in practice it was done secretly, and the first exact description of apparatus for distillation in this part of the world is by Zosemus of Alexandria (about the fourth century).He quotes the figures as taken from the ancient temple of Memphis in Egypt.: * Kept secret under the most severe penalties, Hoeffer’s “ Histoire de Chimie,” vol. i., p. 38. t Aristotle’s “ Meteorology,” lib. ii., chap. ii.; Hoeffer’s ‘‘ Histoire de Chimic,” vol. i., p. 98. : Hoeffer’s “ Histoire de Chimie,” vol. i., p. 262.294 THE ANALYST. But not merely in Egypt, but over a great part of the Eastern world, the know- ledge of distillation prevailed from times of an unknown antiquity. I append a table showing some of the alcoholic beverages obtained by fermenta- tion and the distillates obtained from them.I n India and some other countries a number of different materials were used for these purposes, as they are to this day. Only the more important ones are shown on the table : TABLE OF FERMENTED AND DISTILLED LIQUIDS USED IN VARIOUS COUNTRIES. Country. China. Japan. India. Ceylon. Thibet. Tart ary. Caucasus. Peru. Mexico. South Sea Islands. Continent of Europe and Egypt. British Islands. Raw Material. Rice, millet, etc. Rice. Rice and other grains. Flower s p a t h e s of various palms. Flowers of Muowha-tree. Palm-tree (Go- cis nuci feral. Rice, w h e a t , etc. Milk !of mares, etc. Milk of mares, etc. Maize and manioc. Agave. Ti or Tee root. Barley or other grains . Honey. Grape. Barley. Honey, etc.Fermented Liquor. Tar-asun o r Sake. tchoo. Toddy a n d other names. Toddy. Chong. Koumiss. Kephir. Chica, sora. Pulque, octli. Beer and other names. Mead, etc. Wine. Beer. Mead. Distilled Liquor. 3aut choo. Sochu. Arrack. Arrack. Arra. Arika and other names. Skhou a n d other names. Puichiu. Mexical, agua a r d i e n t e de maguey. Ava . ? ? Eau de vie de Uisque beatha: “ M e a d d i s - vin, etc. whisky. tilled.” Period of Discovery. Long before Christian era. Very ancient. At least 800 B .C. “ T i m e imme- Ancient. morial.” Very ancient. Unknown, but in use soon after Spanish Conquest. 1 ? ? ? Ninth century. Before twelfth Ancient British. century. ~UTHORITIES QUOTED IS TABLE : “ Encyclopedia Britannica,” and Supplement, ninth edition, vol. ii., p. 628 ; vol.iv., p. 216 ; vol. vii., p. 264 ; vol. xiii., p. 263 ; vol. xvi., pp. 213, 305 ; vol. xxxii., p. 808 ; articles by Dittmar, Paton, Schidrowitz, etc. Cyrus Redding’s ‘‘ History of Modern Wines:,” Appendix XXIX., p. 836 ; More~ood’s “ Inebriating Liquors,” second edition ; Muspratt‘s “ Chemistry ; Scarisbrick’s ‘‘ Spirit Manual,” 1884 ; Scarisbrick’s (‘ Spirit Assaying ”; Valpy French’s (‘ Nineteen Centuries of Drink in England”; Hoeffer’s “ Histoire de ,Phimie,” 1866 ; Skeen’s “Wines and Other Fermented Liquors ”; Tovey’s I‘ Wine and Wine Countries.THE ANALYST. 295 The following illustrations show some of the ancient forms of stills. ALEMBIC AND RECEIVER FIGURED BY Zosmrx THE PASOPOLITAIN, OF ALEXANDRIA, SAID TO HAVE BEEN COPIED FI:OM THE ANcrwr TEMPLE O F h~EMPHIS, IN EGYPT.He wrote in Greek, and a copy of part of his writing is preserved in the “ Bibliothbque Imperiale ” in Paris, and is quoted and transcribed by F. Hoeffer in his “ Histoire de Chimie,” vol. i., p. 252 and appendix. In this connection it is interesting to note that the word “ alembic ” is really a Greek word appig with the Arabian article ‘‘ a1 ” prefixed. Our word “ beaker ” may also be derived from up&$, gen. ap@itcor, a cup, etc., from PLKOS. STILL USED IN CHISA. This is probably one of the earliest forms of still without the worm-tub. The head of the still is generally globular, and is enclosed in the lower part of the cylinder kept filled with cold water. The neck from the head of the still projects outside the cylinder, whence a small gutter or tube conveys the condensed liquid t o the receiver.-From Du Halde’s ‘ ‘ Description g&ographique, historique et physique de l’empire de la Chine et de la Tartaric Chinoise,” vol. i., p. 303 ; and in Morewood’s “ Inebriating Liquors,” 1835 edition, p. 228. See also Dr. H. Gray’s “ China,” p. 141.296 THE ANALYST. ASCIENT STILL USED IN CESTRSL INDIA. In use, a hole is dug in the ground suitable for the size of the body of the still, with room for the fire below, and level with the bottom there is underground commmlication with a second excavation for the purpose of feeding the fire. A fire is first kindled in the pit, and the ground thoroughly heated (as in the ancient mode of haking bread in the East). A chininey is also provided near the edge of the hole.Then the still is charged wit11 the fermented liquid from rice, molasses, thejuice of the cocoanut-tree, etc., and fixed in the pit and enclosed with earth round the top of the still, SO that no heat can escape. On boiling, the vapour is condensed by a stream of cold water constantly applied by the attendant, running off a t g , while the condensed liquid runs off a t a. These stills may be of metal or earthenware.-Buchanan’s ‘‘ Journey through the Mysore,” vol. i., p. 39 :. Morewood’s “ Inebriating Liquors, ” p. 159. ANCIENT STILL USED IPT CEYLON OF THE SIMPLEST CONSTRUCTIOS, AND STILL IN USE BY THE NATIVES. a., b., is the alembic and capital luted together ; d., e., a refrigerator and receiver of one piece, and the latter connected with the head by a bamboo, c.The still eniployed for this purpose is of earthenware and of the simplest construction. The above is a true representation of the one in general use.-Morc~*ood’s “ Inebriating Liquors,” p. 186 ; Muspratt’s “Chemistry,” vol. i., p. 115.THE ANALYST. 297 STILL USED IX TH~EET AKD ROOTAN. A , An earthen vessel, in which the chong is placed, immediately over the fire ; B, another vessel without a bottom ; C, a smaller earthen vessel, which is the recipient ; D, an iron basin filled with cold water, renewed occasionally as it grows warm, which may be termed the condenser ; e, e, e, the three cross staves of mood on which the recipient is placed. The junction of the three vessels ( A , B, and B) being secured with cotton bandages and clay lute, a fire is lighted under A , which contains the chong.The spirit rises though B, is condensed upon the convex bottom of the basin (B) and is received into the smaller vessel (C). f, The fireplace ; g , g , g, openings over the fire for the reception of similar apparatus.-Turner’s L L Embassy ” (1800), pp. 26 and 343 ; Morewood’s “ Inebriating Liquors,” p. 172. ANCIEXT STILL USED BY THE KALRIUCIC TM:TAIX, CONSTRUCTED OF COARSE CLAY, CONNECTED WITH THE RECEIVER 1 ; ~ A TUBE OF CAXE OR WOOD. The head of the still is kept cool by coating with wet mud and the application of cold water. The ltouniiss gives a t first a weak spirit, which may be further concentrated by a second or third distillation. They have separate names for these distillates, according t o the number of times the liquid has been distilled.-Clarke’s ‘ Travels in Asia,” etc. ; Morewood’s ‘ ‘ Inebriating Liquors,” p. 147.298 THE ANALYST. STILL USED BY THE TRIBES OF THE CAUCASUS. The pot is made of earthenware or of copper, covered with a lid luted on, and carrying a tube connected This apparatus gives a nearer approach to the worm-tub than any with the condenser overhead. other primitive form of still.-Morewood’s “ Inebriating Liquors,” p. 507. ANCIEXT F o m OF STILL USED BY THE PERUVIANS. The fermented liquor to be distilled is put into a deep earthen pot having a hole in the side near the top, through which passes a wooden gutter of the form shown, connecting with the receiver. Over the top a pan filled with cold water and luted to the pot with clay is placed. This acts as the condenser, and the spirit flows along the groove into the bottle or receiver.-Morewood’s (‘Inebriating Liquors ” (1838), pp.138 and 306. An apparatus similar in arrangement but generally made of copper is in use in Japan.-Roscoe and Schoelemmer’s “Chemistry,” vol. iii., part i., p. 296. It is probable that the Peruvians used this apparatus long before the date of the Spanish Conquest.THE ANALYST. 299 PRIMITIVE STILL USED IN TAHITI, THE LARGEST OF THE GEORGIAPIT ISLANDS. In many of the South Sea Islands the knowledge of distillation and of distilled liquors has been intro- duced by Europeans. But Captain Cook, when he first visited the Georgian Islands, found then1 already in possession of this knowledge, with an apparatus which, from its most primitive form and materials, may have been known for many centuries.The body of the still is a large stone hollowed to form a pot, placed on stones with spaces between for the fire. In this is inserted a long bamboo cane, which passes through a trough or gutter filled with cold water t o serve as a condenser.-Ellis’s “ Polynesian Researches,” vol. i., p. 230 ; “ Encyclopzdia Kritannica,” ninth edition, vol. vii., p. 264 ; Morewood’s “ Inebriating Liquors ” (1838), p. 256. To the top of this pot is placed a head formed of the hollowed-out trunk of a tree. ILLICIT STILL AS USED IN IRELARD (EIGHTEENTH CENTURY). Up to 1556 the distillation of spirits was carried on in Ireland without license or taxation. The attempt to raise revenue by granting monopolies or licenses, and, later, by taxation on the liquids produced were long opposed and resented by the people, and the illegal manufacture often exceeded th amounts on which taxes were paid.The common black pot of the kitchen supplied the body c the still, to which were attached simple fittings such as could be replaced in case of seizure a a small cost. Failing an authentic drawing of a still used by the natives centuries ago, I give fror Morewood, p. 675, a view of an Irish illicit distillery. Watchers are posted on the hills, and t h police or revenue officers are to be seen approaching on the left. Thc apparatus was of the simplest kind.300 THE ANALYST. The great crisis which arose about twenty years ago in France and other wine-growing countries was due to the ravages of a minute insect figured above.The destruction was verygreat, and in the Charente district the vines were almost exterminated by the exceeding voracity and enormous reproductive powers of the species. The winter egg (magnified) is seen in the left top corner, and to the right of this egg the wingless (aptera) insects developed from i t in the spring, mostly females. Each of these produces an enormous number of eggs, hatching again, mainly to feniales, and so on for eight to ten generations during the summer. In August or September the winged insect appears-male and female-living only a short life, but easily transported by the wind to settle on the leaves and lay three or four eggs under the bark. The peculiar sexual arrangement common to certain species of only requiring fertilization from the male once in so many generations facilitates rapid multiplication (parthenogenesis, meaning ‘‘ virgin birth ”).The insects feed mainly on the roots of the vine, and the wounds they make cause loss of sap and rapid decay. In view of the great importance of the subject, I have ventured to add this illustration and description, from Tovey’s “ Wines and Spirits,” p. 284. In each case the fermentable material most convenient or available in the country is used for the purpose of fermentation and distillation. There is no evidence that there ever was a period when all alcoholic spirit was obtained from wine, as applied generally over the world, and certainly not as applied to the British Islands. The British, like other Northern nations, made a fermented liquor from honey (mead and other names), and in the 6 6 Mead Song,” written in the sixth century by Taliesin, a British poet, the words occur : L L Mead distilled I praise, its eulogy is everywhere,”* etc.I have not found any other reference to distilled mead. WHISKY. This spirit was probably first prepared in the East. Barley was especially fermented in those countries subject to inundation, such as the greater part of fertile Egypt, where the vine does not flourish, I n India the fermentation of barley was forbidden in times of scarcity or famine. They distilled these fermented liquors from rice and other grains from a period before the Christian era. This knowledge gradually came to the Arabians, and Rhases, in Hoeffer’s Histoire de Chimie 7 7 jvol.i., p. 342), describes a process for preparation of * Sharon Turner’s ” Vindication of the Ancient British Poets,” 1803 ; Valpy French, “ Nineteen Centuries of Drink in England,” p. 15.THE ANALYST. 301 eau-de-vie by a simple process from I t occulti,” or secret thing, which Hoeffer explains to have been wheat allowed to germinate in the ground. When the knowledge of distillation first came into the British Islands is uncertain, but such knowledge was independent of the distillation of a spirit from wine, seeing that the process was in use in Ireland before the latter came into Europe. The Irish legend states that St. Patrick taught the art of distillation as applied to ‘1 potheen,” which is said to take its name from that of the saint.” Whether or not the date of the distillation of whisky be as old as this legend would make it, it is certain that when the English first invaded Ireland, 1170-1172, the manufacture of whisky was a matter of common knowledge among the people of the country.Like the process of brewing, it was carried on as a domestic art, and was not subject to any legal restrictions till some centuries later. As on the Continent, the Irish distilled liquor was used largely as a, medicinal agent, and its Celtic name, uisque beatha,” English ‘( usquebaugh,” means ‘‘ water of life.” This name is found in the old writings and songs of the country. By dropping the last syllable, usquebaugh has been transformed into the modern word ‘‘ whisky.” The various Esks-names of rivers in England and Scotland-and the Usk in South Wales, are forms of the same word-meaning water.In the early times of the Christian era Ireland was a more civilized country than a great part of Europe, and there is proof that the Irish had direct intercourse with the East. The Phcenicians traded with Cornwltll and the adjacent parts of Ireland, and in all probability the knowledge of distillation came direct into Ireland from the East. The modern word ‘‘ Fenian ” expresses the claim of the Irish to be related to the ancient ‘‘ Phcenicians.” In the time of Henry VIII., Irish settlers came over into Pembroke and established distilleries,i and no doubt the soldiers of Henry II., 300 years before, brought back with them the knowledge of whisky. The population in the islands, etc., of the South-West of Scotland has been largely recruited from Ireland, and distilling has been carried on there probably almost as early as in Ireland itself.I n the time of the Tudor Kings Scotch whisky attained considerable reputation in England. Legal documents referring to aqua vita? made from malt in 1494; are extant, and the manufacture was common at that time, and had been carried on long before as a domestic art, and in the religious houses. Most large houses had their stillroom- ‘‘ stillatory.” From the time that the manufacture of spirits was made a source of revenue either by licenses to use stills (Tudor and Stuart period) or by excise duties on the amount manufactured (middle of seventeenth century and onwards), we have no difficulty in tracing the history of distilled spirits.The dispersion of the religious houses at the time of the Reformation helped to diffuse more generally the knowledge of the arts practised by the monks-among them that of distillation. In Scotland and in Ireland in former times, whisky was prepared from * Chambers’ “ Book of Days,” vol. i., p. 384, and vol. ii., p. 64. + Valpy French, “Nineteen Centuries of Drink in England,” p. 133. 1 “Accounts of the Lord High Treasurer of Scotland,” edited by Thomas Dickson, 1877, vol. i., p. ccxiii.THE ANALYST. malted barley, and the genuine small-still whisky in Scotland is still prepared in this wcy. In Ireland the malted barley is mixed with a certain proportion of unmalted barley or other grain, though there are distilleries in Ireland which use malt only.‘: I n modern times the manufacture of spirit has obtained an immense development in the patent stills so largely used, These give a spirit containing much less of the other substances which go over with the spirit in the small stills, and to which, after ageing, the special flavour of the small-still whisky is due.I n certain parts of England this plain patent-still spirit, after diluting and colouring, is sold as whisky, but much of it is used for blending with the small-still whisky, which costs more to produce, and some of the best of these blends are only usable after ageing for a certain number of years. Like t4e best brandies, some of the best whiskies are scarcely usable when new, but when kept for a sufficient time their character changes greatly.So far as my observation goes, the genuine small-still whisky, properly aged, is less injurious than one would expect an alcoholic liquid to be of the same strength. blending ” of spirits may save a certain time in the ageing, when its value is locked up for so many years; it also saves the difference in cost between the smrtll- still whisky and the patent-still spirit. If the patent-still spirit used be obtained from grain the evil of mixing is less than if it is obtained from potatoes, which gives a spirit more difficult to purify. The Let us now trace the variations in the trade meaning of ‘‘ whisky.” 1. The small-still distillate from malt only. 2. The small-still distillate from a mixture of malted barley and some other grain. 3. In the United States and Canada the spirit distilled from fermented maize, 4.Blended mixtures of small-still malt whisky and patent-still spirit. the latter 5. Small-still spirit with patent-still spirit from potatoes, molasses, beetroot, etc. 6. Patent -still spirits, slightly coloured, flavoured or unflavoured. The consumer ought to have the right to obtain either the pure malt small-still whisky or any of the others mentioned above to suit his requirements. The selling of a liquid which costs less in the name of one which costs more must ultimately lead, when it becomes known and understood, to a diminution in the demand and sale. rye, etc., often, therefore, called corn whisky. generally obtained from grain. BRANDY. Early in the fourteenth century Genoese traders brought arrack from the East into England and this is the first known importation of foreign spirits by sea.In Queen Elizabeth’s time the trade in brand-wine from France had attained consider- able dimensions. The trade was in the hands of the French, English, and Dutch. The distillation of brandy began to take form in France as a manufacturing industry * See Allen on “Whisky,” J. S. C. I., 1891, p. 305.THE ANALYST. 303 early in the fourteenth century, It became subject to legal restriction and control about 1619 in France and in 1590 in Spain.::: The extension of the term “ brandy ” to include distillates not made from wine, though flavoured and coloured to imitate the genuine wine distillate, practically began in France, and received enormous development during the latter half of last century.The modern English word “brandy”is quite as old as any of its Continental equivalents. As shown by the following examples, it was formerly spelt brandewine, brand-wine, and brandy wine. The word “brand” is common to all the Teutonic languages of Northern Europe,t and means a thing burning, or that has been burnt, so that brandy or brandy wine, meaning burnt wine, is as old as the High German branntwein, the Dutch brande- wijn, or the old French brandevin. In Spain and other countries, when wine goes off in quality so as not to be sale- able, it is sent to be “ burnt ”-that is distilled. Examples of the meaning and application of “ brand ”: English Bible : l 6 A brand plucked out of the fire.’, Modern English : ‘‘ Brandnew,” originally applied to castings, forgings, etc., fresh from the fire.l L To brand,” to mark or burn with a hot iron. “Brand,” the mark made by a hot iron, or the hot iron itself, etc. ’‘ Brand,” a flashing sword, is from the same root, through the Romaic and Italian (( brando,” whence our word L c brandish,” and the French word ‘‘ brandon,” a torch, etc. Examples from Murray’s “ Etymological Dictionary ” and other sources showing the changes in the word c c brandy.” Brandwine: and Braizdewine.--1622, Fletcher’s d ( Beggar’s Bush ” : Buy brand wine.” Brandywine.-l652, Proc. Parl., No. 132, 2,391 : ‘( Laden in wools, brandywine, and salt.” 1697, View Penal Laws, 173 : ‘( No aqua vitae or brandywine shall be imported into England.” 1729, D’Urfey’s ‘‘ Pills,” etc., v.23 : ‘ I I was entertained with kisses fine and brandywine.” Brandy.-In familiar use this word came in about 1657 by dropping the last syllable from brandywine, but the latter was retained in legal documents down t o 1702. The best early description which I have been able to find of the distillation of wine is given by Ortholain, who lived in Paris about the middle of the fourteenth century. He published in 1358 ‘( Practica Vera Alchemica per magistrum Ortholanim, Parisiis probata et experta, sub anno Dom. 1358. Theatr. Chem., 4 p., 1028.” Hoeffers quotes from him and says : ‘( In a remarkable chapter on the distillation of wine he describes the manufacture of eau de vie de vin of different degrees of concentration, and he indicates how to obtain absolute spirit of wine.The process which he describes is not greatly dis- similar to that in use in the small-shill distilleries at the present day.” Brandy, up to r?l comparatively modern period, was the spirit obtained from wine Shakespeare apparently thought these words insuffizent : Othello, Act II., Scene 3 : ( ( 0 thou Some authors give 1313, others 1343. 1650, Roxburgh ‘( Ballads ”: ‘‘ It is more fine than brandewine.” * hlorewood, “ Inebriating Liquors, ” p. 366. .t. Iilurre’s “ Etyniological German Dictionary. ” invisible spirit of wine, if thou hast no name t o be known by, let 11s call thee devil.” Q *‘ Histoire do Chimie,” 441-443.304 THE ANALYST. and from wine only. During the last fifty years the manufacture of factitious brandy has attained an enormous development both in France and in other countries. I quote from official sources statistics of the brandy trade in France from 1840 to 1900.It is seen that ‘‘ trade brandy,” which in 1850 formed 10 per cent. or less of the total production, in 1893 formed 90 per cent. or over of the whole production. The brandy exported into the British Islands as pure eau de vie de vin from France, exceeds the total production of brandy from wine in France. The brandy exported into this country as cognac similarly exceeds the total pro- duction of genuine cognac in France. Other fruits by similar processes give alcoholic distillates-apple, pear, peach, prune, giving apple brandy, etc.-but during the last twenty-five years any distilled spirit suitably coloured and flavoured is sold in the name and place of the old eau de vie de vin or brandy wine.We have the following meanings of the word as used in trade : 1. Brandy, a distillate from wines grown in France, including “ distillation des 2. Brandy, distillates from wines grown in any country. 3. Brandy, distillates from fruits other than grape, which may or may not have 4. Brandy, distillates from grains, roots, molasses, etc. (“trade brandy ”). In 1850 the trade brandy amounted to one-tenth of the total wine and fruit I n 1893 the trade brandy amounted to ten times the amount of the wine and vins altdr6s ou malade.” the special characters indicative of their origin. brandy. fruit brandy. These facts are well shown in the following table : STATISTICS OF FRENCH BRANDY FROM 1840 TO 1900.(The numbers in each of these tables refer to 1,000 gallons.) 1840 1850 18.52: 1860 1870 18765 1880 1886 1893 1900 Natural (grapc and other fruits).” ( a ) 17,600 17,950 8,800 - - 14,410 1,100 1,144 5,434 7,106 Trade (maize, beet, etc.).? ( b ) 2,200 1,661 8,800 - - 23,188 34,100 44,000 49,060 51,326 Total. 19,800 19,611 17,600 10,206 27,214 37,598 35,100 45,144 54,494 58,432 Approximate Proportion. ( a ) (1)) 8 : l 10 : 1 1 : 1 - - 1 : 1.5 1 : 30 1 : 40 1 : 10 1 : 7 * From French official sources, chiefly through the Boc~rd of Trade Jozwml. See also “Encyclo- 9 See also United States Consular Report, quoted in JO~LIW. SOC. C’hem. I X ~ S ~ T I J , 1889, p, 827, referring $ Oidium disease. § Phylloxera set in, 1876 t o 1890. p d i a Britannica,” vol. xxxii.. p.807. t o the very large exportation of “ cognac ” as compared with the total production of wine brandy,THE ANALYST. 305 In 1900 the following analysis is given of the production of brandy in France : ... [ F n e ... ... ... 3,278 3,828 ILees, etc. } * a * 7,106 ’Maize and other grains, etc. ... 12,386 ... ... ... 17,534 Beetroot ... ... ... ... 21,406 Wine, fruit, etc. Cider ... ... .- .. ... 51,326 - ~ _ _ _ Total of all kinds ... ... 58,432 One-seventh of the total is exported as eau de vie de vin, but the amount so classed exceeds the total production from wine in the proportion of two to one. It also exceeds the total production from wine and other fruits in the proportion of seven to six. This is taking no account of the genuine eau de vie de vin used in France.[NOTE.-It may be that part of this ‘‘ trade brandy )’-so termed in the official journals-is really alcohol destined for industrial purposes other than human con- sumption, and that these applications of spirit have much increased during the last thirty years. The returns I have been able to consult so far do not enable me to make allowance for these diflferent applications of ‘‘ trade brandy. ”1 The effect of this large sale of “trade brandy ’’ as genuine eau de vie de vin is well shown in the following table of imports into the United Kingdom.“ 1872 ... ... ... ... ... 3,945 1882 ... ... ... ... 3,013 1892 ... ... ... ... ... 2,670 1902 ... ... ... ... ... 2,355 The fall has been gradual and continuous, and the new certificates of origin issued by the French Government from March 30, 1903, are evidently a proof of zl desire to regain trade by restoring confidence.The following is a quotation from the Distillers Brewers and Spirit Merchants Mugnzine, referring to the proceedings of the Committee of the Wine and Spirit Association in a recent case: “If it were to go forth on the authority of the Association that ‘brandy ’ is a meaningless term, applicable to any kind of spirit, the public would be less disposed than ever to ask for anything bearing that name.” To extend the meaning of the term “brandy” so a8 to include almost any alcoholic distillate is, in my opinion, calculated to absolutely destroy the confidence that a great part of the British public have had in the use of brandy, either as a superior spirit or as a medicinal agent. That this fear is well grounded is shown by the fact that, in spite of increased population and wealth, the importation and con- sumption of brandy has gone down about 40 per cent. during the last thirty years. Some who defend the extension of the term “brandy” to other alcoholic distillates do not approve of the extension of the term “ cognac,” which they say * Abbreviated from the Distillers Brewers apllcl Spirit JhrcJmits Magcmine, 1904, p. 232.306 THE ANALYST., should be strictly limited to the distillates from the wines of the Cognac district, and possibly of those districts immediately adjacent. During the past twenty years a process of extension of the application of the term “ cognac ” has been going on, and it is now claimed that cognacs may be made in any part of France. This claim has been supported in a French court of law. Further, it is claimed that cognacs may be made in any other country where a product of a more or less similar character can be produced. We now have German and other cognacs. I n Murray’s ( ( New English Dictionary ” now being issued it is stated that the term “ cognac ” is being ‘( extended for trade purposes to mean brandy in general.” This definition conforms with my own observation, both in this country and on the Continent. I gladly thank Messrs. Scarisbrick, Nettleton, Squire, Stanley Smith, Murphy, and others for their kind assistance in collecting information ; Mr. B. A. Burrell for kindly taking photographs and preparing slides, and Mr. Clifford for exhibiting the lantern slides.

ISSN:0003-2654    

DOI:10.1039/AN9053000293

出版商:RSC    

年代:1905

数据来源: RSC

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306 THE ANALYST., ON THE REDUCING ACTION OF HYDROGEN. (Preliminary Note.) BY ALFRED C. CHAPMAN AND H. D. LAW. NOTWITHSTANDING the great theoretical and practical importance attaching to a, more intimate knowledge of the properties of the hydrogen evolved during the solution of metals in acids, very little attention appears to have been devoted to this subject until quite recently, the employment of the expressions ‘‘ nascent ” and free ” being apparently considered sufficient to cover all the known facts. If the conceptions of atomic or active and moleculur or inactive hydrogen were all-suficient, the source of the hydrogen in any reduction process should be a matter of indifference so far as the reducing action is concerned; but yet it is quite well known that this is by no means the case, and that the reducing agent to be employed must be chosen in careful relation to the reduction which it is desired to bring about.This is well seen in connection with the Marsh-Berzelius test for arsenic, for not only does the hydrogen formed at the surface of a platinum cathode in the electrolytic method fail to reduce arsenates, but quite different results may be obtained in the zinc method by the employment of various samples of zinc. Before alluding to the results of our experiments, we may perhaps be permitted to refer very briefly to the following elementary theoretical considerations : When a rod of zinc is immersed in dilute sulphuric acid, the zinc of course tends to pass into solution and to ‘‘ force out ” the hydrogen. On the other hand, a hydrogen electrode placed in a solution of zinc sulphate tends to cause the deposition of metallic zinc.Thus in the case we are considering (dilute sulphuric acid and zinc) hydrogen will be liberated only when the solution tension of the metal is greaterTHE ANALYST. 307 than that of hydrogen. The solution tension of hydrogen is about 1 volt, whilst that of zinc is about 1.7 volts, so that an evolution of hydrogen might be expected. There is, however, another important factor which comes into play-vie., the ‘‘ retaining ” effect which every metal exerts on the hydrogen formed at its surface-and so in many cases a potential far in excess of that of the hydrogen electrode is necessary before any free hydrogen is obtained-that is, before the hydrogen is liberated. This excess of potential is known as (‘ supertension,” and in the case of zinc amounts to about 0.7 volt above that of the hydrogen electrode.From this it will be seen that in the case of pure zinc and sulphuric acid little or no evolution of hydrogen is to be expected. Other metals, however--e.g., platinum-have smaller supertensions, and consequently emall quantities of such metals deposited on the surface of the pure zinc will allow the gas to come off freely and at 8 lower potential, its activity being in consequence sometimes reduced to a point which renders it incapable of bringing about the reduction of difficultly reducible substances. The application of these considerations to the explanation of the insensitiveness of zinc in the Marsh- Berzelius test will, we think, be obvious.The metal, as used in our laboratories, is necessarily more or less impure, frequently containing particles of metals of low supertension-such, for example, as iron. Hydrogen is therefore liberated rapidly, and at a potential too low to permit of the reduction of arsenious acid to arsenic hydride under the conditions of the experiment. Thus we have been able to show that such low supertension metals as palladium, platinum, copper, nickel, cobalt, silver, and iron all render zinc insensitive, whilst cadmium, lead, and tin, which are possessed of high supertensions, have no effect on the reducing power of sensitive zinc. Starting with a sensitive sample of this metal, we have been able to render it exceedingly insensitive by depositing on its surface small quantities of iron, cobalt, etc. ; and, conversely, we have succeeded in rendering the highly insensitive metal fully sensitive by the use of metals of high supertension. In the near future we hope to publish a detailed account of our work in this field. Throughout the investigation the Marsh-Berzelius arsenic process has been used merely as a convenient and delicate method of determining the amount of reduction taking place, and in a future paper we hope to extend the inquiry to other and widely differing substances.

ISSN:0003-2654    

DOI:10.1039/AN9053000306

出版商:RSC    

年代:1905

数据来源: RSC

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THE ANALYST. 307 ABSTRACTS OF PAPERS PUBLISHED IN OTHER JOURNALS. FOODS AND DRUGS ANALYSIS. Detection of Formaldehyde in Milk. Utz. (Chm. Zeit., 1905, xxix., 669.) -A reagent, consisting of vanillin and hydrochloric acid, is recommended for the detection of formaldehyde in milk. This reagent has been previously used by Winckel as a test for enzymes. Equal volumes of milk and hydrochloric mid (epecific gravity 1.19) together with a few crystals of vanillin, are mixed and heated. Should formaldehyde be present in the milk, a violet or raspberry-red coloration308 THE ANALYST. ' J appears. If the milk contain mere traces of formaldehyde, the mixture is coloured yellow. Similar reactions can be obtained by substituting piperonal or p-hydroxy- benzaldehyde for the vanillin, but the latter is the best.The author also shows that the presence of formaldehyde only interferes with reactions employed to distinguish raw from heated milk when the quantity of formaldehyde is largely in excess of that usually used for preservative purposes. w. P. s. ' shaking, 2.5 C.C. of 80 per cent. acetic acid and an equal volume of con- centrated sulphuric acid are added, and the contents of the flask well mixed. The flask is then placed in hot water until the contents turn a coffee colour. It is now removed and cooled, 4 C.C. of ether added, mixed, and boiled off' by again placing the flask in warm water. The layer of fat floating on the surface of the liquid in the flask is brought into the graduated neck of the latter by pouring in hot water through the side tube.The graduations give direct percentages when 5 C.C. of milk are used, so that in using The volume of fat is then read off. > 1.72 grams (one-third of the weight of 5 C.C. of milk) of the food the result must be multiplied by 3 to obtain the percentage of fat in the food. The apparatus and process may also be employed for the deter- Corned Beef containing Flour. H. Matthes. (Zeit. Untersuch. Nahr. Genussmittel, 1905, ix., 732.)-During the examination of a number of tins of corned beef one sample was found to contain about 1.5 per cent. of flour. This was probably added to '' bind " the pieces of beef together, and the author points out that, whilst fresh, tender beef readily forms a solid block of corned beef, tough beef from old animals requires the addition of some such material as flour.None of the w. P. s. samples were found to contain preservatives. The Detection of Artificial Colour in Mustard. P. Suss. (Pharnz. Zentralh., 1905, xlvi., 291 ; Chem. Zeit., 1905, xxix. [Rep.], 123.)-About 50 grams of the mustard are mixed with about 75 C.C. of 70 per cent. alcohol, allowed to stand for ten minutes, and filtered. A piece of unmordanted wool yarn is dipped in one portion of the filtrate, and then washed and dried in a porcelain basin over a small flame. Another portion of the filtrate is used for dyeing a '' capillary strip " of the wool, which is immersed for twenty-four hours in the liquid and then dried. If the wool fibre shows a dirty yellow colour which speedily fades, artificial coloration is indicated, even when moistening the wool with hydrochloric acid or ammoniaTHE ANALYST.309 solution does not give a reaction-bluish-red (methyl orange), brownish-red (turmeric). A coal-tar dyestuE, which the author was unable to identify, dyed the wool lernon- yellow. In the case of the capillary strip, yellow edges are only observed when a coal-tar dyestuff is present. The usual tests with hydrochloric acid, ammonia, and boric acid must also be made here. The natural colouring matter of mustard either gives no coloration with hydrochloric acid, or at most a faint brown shade. It becomes intensely yellow on the addition of ammonia.. C. A. M. Occurrence of Boric Acid in Common Salt. R. Hefelmann. Zeit. 6fentZ. Chem., 1905, xi., 231-234.)-Although some common salt, more particularly that mined in Italy and certain districts in Germany, undoubtedly contains boric acid, the quantity of the latter present is extremely small, varying from 0.0006 to 0.003 per cent.When this salt is used for flavouring meats or for salting butter and margarine, the amount of boric acid thus introduced is too small to be detected. W. P. S. The Detection of Iodoform. Stortenbeker. (Rec. Trav. Chim. des Pays-Bas, 1905, xxiv., 67; Chem. Zeit., 1905, xxix. [Rep.], 197.)-The following method is recommended for the detection of traces of iodoform in organs of the body : The substance is rendered slightly acid and distilled in a current of hydrogen. The distillate is treated with a few drops of alkali solution to dissolve any fatty acid present, which might interfere with the subsequent crystallization, and then shaken out with ether.The ethereal extract is allowed to evaporate spontaneously in the dark, and the residual drop of water taken up with filter-paper. The residue is now dissolved in a little hot glacial acetic acid, and the residue left on evaporation of a, portion of the solution examined under the microscope. Well-marked crystals are obtained in the presence of iodoform. The colour reaction given by iodoform with sodium phenolate is not interfered with by the presence of chloroform or bromoform. C. A. M. A New Method of Analyzing Pyramidon. G. Pattein. (BzbZZ. SOC. Chim., 1905, xxiii., 845-847.)--This is based upon the fact that pyramidon (dimethylamido- antipyrin) gives no insoluble derivative with formaldehyde, whereas antipyrin gives a, nearly insoluble compound- N - C,H5 N - C6H5 CH3 - N<)CO C O O N - CH, CH, - C=C - CH2 - C=C - CH3, which the author terms diantipyrin methane. If 1 gram of pure pyramidon be treated with 5 C.C.of water, 5 C.C. of hydrochloric acid, and 2 C.C. of a 40 per cent. solution of formaldehyde, and left in a corked tube for four days, the liquid remains absolutely clear after the addition of 10 C.C. of water and sufficient ammonia to make the reaction alkaline. But if antipyrin is present a crystalline deposit (melting point 177" to 179" C.) is formed as the liquid cools. I t can be collected on a, filter, dried in310 THE ANALYST. the oven, and weighed. Theoretically, 0.2 gram of antipyrin should yield 0.214 gram of the compound, but in practice the amount varies from 0.18 to 0.20 gram.In the case of a mixture the filtrate from the crystals can be extracted with chloroform, and the extract allowed to evaporate spontaneously, when crystals of uncombined pyramidon (melting point 104' to 106O C.) will be left. If time is limited the tube may be left for four hours on the water-bath at 100" C., and the liquid then cooled and treated as above described. C. A. M. The " Manipulated " Opiums of Smyrna. V. Masson. (Joum. Pharm. Chzim., 1905, xxi., 529-534.)-For several years past certain dealers have supplied opiums manufactured at Smyrna in place of the natural product. These opiums are stated by the author to be extensively met with in commerce under the name of Smyrna opium, 10 per cent., or '( manipulated " opium, and consist of a mixture of the natural juice with substances more or less inert.The proportion of foreign substances varies considerably, and alters considerably the composition of the com- ponents that contain morphine as their base. The products differ in physical character- istics from natural opiums, and may be described as pastes, the only standard of which is that they contain not less than 10 per cent. of morphine. They give an alkaline reaction in contradistinction to true opiums which give an acid one, and the whole of the morphine they contain does not pass into the aqueous extract. This may be owing to a portion of the morphine meconate having been decomposed by added calcium carbonate, or to morphine, and not one of its salts, having been added to an exhausted marc. The following analyses represent the compositions of five different types of these preparations and of samples of pure opium examined by the author.The extract is calculated on the basis of opium containing 10 per cent. of water, whilst the morphine is calculated on the substance dried at 100" C. Smyrna manipulated opium, 1 ,? 9 , ,¶ 2 8 , 9 9 1, 3 9 ; 9 9 $ 9 4 $ 9 , 9 9 , 5 Pure opium, Yerli ... ... Salonica . . . ... ,, Smyrna ... ... 9 1 9 , ... $ 9 - * - Water. Per Cent. 14.5 9-24 8.31 19.11 21.17 26-1 24.97 17-62 20.93 Aqueous Extract. Per Cent. 20.0 20.20 27.80 44.52 57-30 53.95 49.17 46.35 44.83 Morphine. Yer Cent. 10.2 13-0 12.19 10.62 10.12 13.51 12.18 10-53 10.82 Ash. Per Cent. - 5.88 5.71 9.25 5.05 - - - - Morphine i n Aqueous Ex- tract.Per Cent. - 22.28 29.96 18-67 12.0 - - - The gum in the extract of No. 5 was 21.50 per cent., as against 2.50 per cent. in natural opium. C. A. M. A Hethod of Distinguishing Dionin from Codein. N. D. Rudionon. (Chem. Zeit. Rep., 1905, xxix., 187.)-Dionin (hydrochloride of mono-ethylmorphine) has the same colour reactions as codeine (mono-methylmorphine), but their dissimilar behaviour towards ammonia may be used to distinguish between the two. TheTHE ANALYST. 311 author also finds a difference in their reactions with Wagner’s reagent (12-7 grams of iodine and 10 grams potassium iodide in 1,000 C.C. of water). When 10 drops of this reagent are added to 2 C.C. of a 1 per cent. hydrochloric acid solution of codeine, a pulverulent dark red-brown precipitate is obtained.On violent shaking this precipitate does not change its colour, and immediately settles again to the bottom. If a 1 per cent. dionin solution is treated in the same way, a precipitate of the same kind and colour is obtained ; but on vigorous shaking it becomes flocculent, acquires a brown-orange colour, and rises to the surface of the liquid. The reactions take place in neutral as well as in sulphuric or hydrochloric acid solutions. As very vigorous shaking is necessary, it is best to use test-tubes with glass stoppers. E. K. H. Identification of Rheum Rhaponticum. A. Tschirch. (Schzoeiz. Wochenschy., xliii., 253,)-The rhizome of R. rhaponticum (common English rhubarb) contains a crystalline substance, called rhaponticin, rhapontin, or ponticin, which is characterized by its insolubility in ether, separating from its aqueous solution when shaken with that liquid. The following method €or detecting R. rhaponticum is based on this peculiarity: Ten grams of the sample are boiled with 50 C.C. of dilute alcohol for fifteen minutes, then filtered, and the filtrate concentrated to about 10 C.C. The latter is shaken with from 10 to 15 C.C. of ether. On allowing the mixture to stand, a considerable quantity of a minute crystalline deposit will be formed if R. rhaponticum be present. The deposit, after being collected on a filter, washed with water, and dried, is coloured purple-red by sulphuric acid. Chinese rhubarb, similarly treated, gives no such crystalline deposit. w. P. s.

ISSN:0003-2654    

DOI:10.1039/AN9053000307

出版商:RSC    

年代:1905

数据来源: RSC

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THE ANALYST. 311 ORGANIC ANALYSIS. Detection of Methyl Alcohol. H. Scudder. (Joum. Anzer. Chem. SOC. 1905, xxvii. 892-906.)-1n comparing the tests for methyl alcohol the author takes as the standard of delicacy that quantity of methyl alcohol which can be detected in ethyl alcohol. Most of the tests will show very much smaller quantities of methyl alcohol in water but their use for such a purpose is practically unknown. The Mulliken-Scudder test (ANALYST 1901 74) will show the presence of 8 to 10 per cent. of methyl alcohol whilst the United States Pharmacopceia test will indicate 2 per cent. Trillat’s test (ANALYST 1899 211) is somewhat more delicate. If only traces of methyl alcohol be present it is advisable to concentrate by fractional distillation before testing.The value of the resorcinol (Mulliken-Scudder) test is in the positive evidence given and the advantage of having a rough idea of the quantity of formal-dehyde present. In testing mixtures any formaldehyde present must be previously removed. For this purpose various methods may be employed (see ANALYST 1891, 113 ; 1901 74). Other aldehydes are removed by digestion with resorcinol and sulphuric acid or aniline and phosphoric acid. Phenols and bases will combine with any formaldehyde produced in the course of the test and must be removed by distil-lation with potassium hydroxide in the case of phenols and with sulphuric acid in the case of bases. Colouring matters can be removed by distillation or filtration through animal charcoal. w. P. s 312 THE ANALYST. Determination of Glycerol in Crude Glycerines etc.K. Braun. (Chem. Zeit. 1905 xxix. 763-'765.)-In the process described the glycerol is oxidized by means of potassium bichromate (chromic acid) and the resulting carbon dioxide collected and determined. A weighed portion of the sample is diluted with water. Should carbonates be present they must be decomposed by boiliDg the diluted and acidified solution. A measured quantity of this solution is transferred to a round-bottomed flask of about 1 litre capacity an excess of standard bichromate solution is added and also about 10 C.C. of sulphuric acid. The flask is connected with a Liebig's condenser the lower end of which is drawn out and passed into a receiver containing a known volume of A small flame is used for heating the flask and the distillation carried on for about thirty minutes.Hot barium chloride solution is then added to the contents of the receiver the precipitated barium carbonate being collected on a filter and washed until free from alkali. Both filter and precipitate are now placed in a flask more than sufficient & hydrochloric acid to dissolve the barium carbonate is added and the excess titrated back with & potassium hydroxide. One C.C. of ;& acid is equivalent to 0.001533 gram of glycerol. The method is The latter is then made up to a known volume. potassium hydroxide solution. stated to give results which agree well with those obtained by other methods. w. P. s. Gasometric Determination of Formaldehyde. G. B. Frankforter and R. West. (Joum. Amer.Chenz. SOC. 1905 xxvii. 714-719.)-The process described is based on the fact that when formaldehyde is brought into contact with sodium or potassium hydroxides in the presence of hydrogen peroxide potassium formate is formed and hydrogen liberated according to the formula-2CH,O + 2KOH = 2HCOOK + 2HZO + H,-I n the absence of hydrogen peroxide methyl alcohol is formed and no hydrogen set free. The authors measure the volume of the liberated hydrogen and from it calcu-late the amount of formaldehyde present. The details of the process are 1 C.C. of the formaldehyde solution of known specific gravity is placed in the side tube of a Schiebler-Finkner calcimeter and 10 C.C. of hydrogen peroxide and 20 C.C. of potas-sium hydroxide solution are placed in the body of the generator.The latter is closed and the water in the measuring-tube brought to the zero mark. After the temperature has become constant the solutions are gradually mixed. When the reaction is completed the temperature is again allowed to become constant and the volume of hydrogen read off. The presence of alcohol and formic acid has no influence on the results provided that a good excess of hydrogen peroxide be present. Sodium peroxide previously dissolved in water may be used instead of hydrogen peroxide but slightly too high results are obtained probably due to dissolved oxygen. With barium peroxide the reaction is slow and incomplete in the cold. Manganese and lead peroxides are practically without action on formaldehyde. The authors describe experiments to prove that the gas liberated in the above reaction consists of pure hydrogen.w. P. s THE ANALYST. 313 The Polarimetrie Determination of Sucrose. F. Watts and H. A. Tem-pany. (W. Indian Bull. 1905 vi. 52-60.)-The authors have investigated the influence of alterations of temperature on the optical activity of sucrose. They find that changes of temperature up to about 30" C. cause a lowering of the reading on the Ventzke scale which may be corrected by the formula Polarization + (0*00023t)N, where t is the difference of temperature of observation from that at which the instrument was standardized and N is the scale reading observed. A correction must also be made for the influence of temperature on the quartz wedge of Schmidt and Haensch instruments and may be expressed by the formula (Jobin's): Polarization + (0.00016t)N ; or the two corrections may be combined Polariza-tion + (0-0003Yt)N.Of course where the temperature of observation is below that at which the instrument was standardized the correction becomes a negative one. For solutions requiring no clarifying reagents the authors recommend that 26 grams of the sugar be dissolved in 100 trae C.C. This is equivalent to 26.048grams in 100 Mohr C.C. The true cubic centimetre is taken as being the volume of 1 gram of water weighed in vacuo at 4O C. whilst 100 C.C. Mohr are defined as being 100 grams of water at 1'7.5" C. in air no correction being made for displacement of air ; under these conditions 100 C.C. Mohr become equal to 100.228 C.C. true. The correction of the volume of lead precipitate in solutions which require clarifying varies for almost each class of sugar owing to the varying density of the precipitate.I t is better instead of adding basic lead acetate solution to the sugar solution and diluting the mixture to a known volume to dissolve 26 grams of the sugar in distilled water make up to 100 true c.c. and clarify by adding anhydrous basic lead acetate avoiding an excess. w. P. s. Note on a Fluid Portion obtained from Cacao Butter. F. Strube. (Zed. ofentl. Chem. 1905 xi. 215 216.)-By slowly cooling large blocks of '' Samana " cacao butter a fluid portion occasionally separated out which on examination yielded chemical and physical constants differing considerably from those given by ordinary cacao butter. For instance various specimens of this fluid portion were found to have iodine values of from 53.08 to 58.80 and gave refractorneter readings of 50.45 at 40" C.The melting-point was very low-about 12" C.; at 17.5" C. the specific gravity of the specimens was 0.906. w. P. s. The Detection of Oil extracted by Carbon Bisulphide in Expressed Olive Oil. G. Halphen. (dourn. Pharm. Chim. 1905 xxi. 54-56.)-The method depends on the conversion of residual sulphur compounds into thiosulphates which remain in solution when the soap is salted out by sodium sulphate or chloride. Fifty C.C. of the olive oil are heated to 110" C. in a basin and treated with 12 C.C. of a solution of 100 grams of pure sodium hydroxide in 75 C.C. of water. The heating is then continued for about seven to ten minutes until the mass ceases to froth the temperature being then about 160" C.The flame is now withdrawn and the mass continually stirred until the temperature has fallen to llOa C. and the soap is finely granulated. It is then treated with 200 C.C. of hot water and constantly shaken until cold when practically the whole of the soap should have dissolved. Thi 314 THE ANALYST. solution is shaken with 100 C.C. of a saturated solution of sodium sulphate after which 20 C.C. of a 33 per cent. solution of copper sulphate are introduced and the liquid thoroughly stirred and filtered. The object of adding the copper sulphate is to convert into insoluble copper salts impurities in certain expressed olive oils which give a slight brown precipitate with silver nitrate.The filtrate should be faintly green and if not it should be treated with an additional 0.2 C.C. of the copper aulphate solution and again filtered. To 100 C.C. of the clear filtrate are added 5 C.C. of a solution consisting of 1 part of a 5 per cent. solution of silver nitrate with 5 parts by volume of glacial acetic acid and the whole gently heated to the boiling-point then cooled and rendered slightly alkaline with ammonia. If the oil had been extracted with carbon bisulphide a brown or black precipitate will be formed although in some cases it is necessary to collect it on a filter before it can be detected. The author states that the black precipitate is invariably obtained even when only small quanti-fies of the extracted oil are present. It is of course necessary to insure the absence of the oils of cruciferous plants which normally contain sulphur.C. A. M. The Refractometer Values of Castor Oil Cod-liver Oil and Neat's Foot Oil. H. C. Lythgoe. (Journ. Amer. Chem. SOL 1905 xxvii. 887-892.)-The following results were obtained from the examination of a number of pure samples of these oils : Castor Oil. Cod-liver Oil. Neat's Foot Oil. Number of samples . . . 44 20 4 Maximum variation of reading . . . to-5 +_ 1.3 20.2 Average butyro-refractometer (Zeiss) reading at 20" C. . . . 81.2 80.6 63.5 The average polarization of fifteen samples of castor oil when read in a 200-millimetre tube at 20" C. was + 24.1' Ventzke. Tables are also given showing lthe refractometer values of these oils for each 0.5 degree of temperature from 15.0" it0 35.0" C.w. P. s. A New Reaction of Substances containing a Phenolic Group. J. Aloy and F. Laprade. (Bull. SOC. Chim. 1905 xxxiii. 860 861.)-Uranyl nitrate gives ,a coloration usually red with bodies containing a phenolic group. The reagent is prepared by dissolving 10 grams of uranyl nitrate in about 60 C.C. of water adding a dilute solution of ammonia until the liquid is exactly neutral filtering it and diluting the filtrate to 100 c.c Other uranyl salts can be used in place of the nitrate but it is essential to neutralize the solution exactly. In testing for a phenoloid substance the liquid is first neutralized and the reagent added drop by drop until the intensity of colour no longer increases. The presence of one COOH NH or NO group does not interfere with the reaction but several groups in the molecule may prevent it.The colour is destroyed by mineral acids and by alkalies. The reaction is capable of detecting 1 part of phenol or less in 1,000. C. A. M. On the Determination of Nitrogen by Kjeldahl's Method. S. P. L. Sorensen and C. Pedersen. (Comptes Rend. des Trav. d u Lab. de Carlsberg 1905, vi. 126-136.)-1t has been asserted by Kutscher and Steudel that Kjeldahl's metho THE ANALYST. 315 is not applicable in the case of certain compounds such as creatine creatinine lysine, and uric acid. The authors have therefore made experiments to determine this point. They show that one source of error on the part of Kjeldahl’s critics is that, in the oxidation with potassium permanganate they add this salt to the cooled liquid, which is then heated to the boiling-point.This is quite contrary to Kjeldahl’s directions and makes a loss of ammonia inevitable. The results show that the nitrogen in creatine is converted rapidly and completely into ammonium salts when boiled with concentrated sulphuric acid but that lysine compounds are only trans-formed slowly even after the addition of phosphotungstic acid as advocated by Henderson. The general conclusion is that Kjeldahl’s method is quite applicable t o these compounds although the results are very slightly too low. Thus the ‘( racemic chloride of lysine ” gave 12-63 per cent. of nitrogen by Dumas’ method and 12.52 per cent. by Kjeldahl’s method. (c.f. Abstract 1904 xxix. 124.) C. A. M. On the Determination of Nitrogen in Lysine and Similar Compounds.S. P. L. Sorensen and A. C. Andersen. (Comptes Rend. des Trav. du Lab. de CarZsberg 1905 vi. 193-208.)-Certain derivatives of lysine are particularly resistant to the action of sulphuric acid. Thus lysuric acid after havlng been boiled for twenty-four hours yielded only 7-56 per cent. of nitrogen by Kjeldahl’s method as against the theoretical 7.93 per cent. Hence it is recommended that in the analysis of the decomposition products of proteids parallel determinations should be made by Kjeldahl’s and by the Gunning-Arnold method ; and should concordant results be obtained only the former simpler method need be used subsequently. If however, too little ammonia is obtained there must be present compounds only decomposed with difficulty and in which the nitrogen is in ring-formed combination-e.g.deriva-tives of pyridine or piperidine. The compounds may thus be divided into two groups -viz. ( A ) compounds containing or capable of forming five membered rings com-posed of 4 atoms of carbon and 1 of nitrogen. All these can be analysed by Kjeldahl’s method-e.g. a-pyrrolidine carboxylic acid a-amino-8-hydroxyvaleric acid a-8-diamino-adipic acid; ( B ) compounds containing or capable of forming six membered rings, consisting of 5 atoms of carbon and 1 of nitrogen-e.g. pyridine piperidine lysuric acid u-E-dianiinopimelic acid. Tho last-named compound forms a piperidine ring when boiled with strong sulphuric acid and behaves like piperidine itself yielding lower results by Kjeldahl’s method than by the modifications of Gunning or Gunning and Arnold.C. A. M. The Determination of Nitrogen in Azo- and Similar Compounds by Kjeldahl’s Method. @. Flamand and B. Prager. (Berichzte 1905 xxxviii., 559,56O.)-From 0.15 to 0.2 gram of the substance is dissolved in 10 C.C. of alcohol in a 500 C.C. flask with a long neck and the solution heated with 0.5 to 1 gram. of zinc dust and 2 to 5 C.C. of sulphuric acid (specific gravity 1.19) until colourless which usually takes a few minutes. Ten C.C. more of the concentrated sulphuric acid and 0-5 gram of crystallized copper sulphate are then introduced and the flask heated until white fumes appear after which 5 grams of potassium sulphate are added and the heating continued until the liquid has become clear and light green in colour 316 THE ANALYST.which is usually the case after fifteen minutes. The ammonia is then distilled in the usual way. Phenyl-hydrazine benzalphenyl-hydrazine and formazyl compounds did not give satisfactory results by this method although the theoretical amount of nitrogen was obtained in the case of various azo- hydrazo- and azoxy-derivatives. C. A. M. Determination of the Organic Nitrogen in Potable Waters. J. C. Brown. (Proc. Chem. Soc. 1905 xxi. 208 209.)-Details are given of a process for the determination of the whole of the organic nitrogen in water and sewage effluents, The process essentially consists in the distillation to dryness and subsequent ignition of a mixture of a portion usually 200 c.c. of the sample without previous evaporation, with potassium hydroxide and potassium permanganate.The operation is carried out either in a Jena glass or in a copper retort and the evolved ammonia is determined by Nessler's reagent as usual. The process is found to be convenient and rapid. The results obtained by this process on a variety of waters compare well with those determined by the Frankland Wanklyn and Forscharnmer methods. The total organic carbon may be determined as carbon dioxide in the residue remaining in the retort but owing to the large amount of carbon dioxide found by blank experiments, and which has to be deducted from the total quantity the results are not as accurate as in the case of nitrogen. w. P. s. The Determination of Alkaloids by Means of Potassium Bismuth Iodide. H. Thoms.(Ber. deutsch. Pharm. Ges. 1905 85; Journ. .€'harm. Chim. 1905 xxi., 605.)-The reagent is prepared by dissolving 80 grams of bismuth subnitrate in 200 grams of dilute nitric acid (specific gravity 1-18> and pouring the solution into an aqueous solution containing 272 grams of potassium iodide. The bulk of the potassium nitrate formed crystallizes out and the decanted liquid is evaporated down to a litre. For the valuation of extract of belladonna 2 grams of the sample are dissolved in 50 C.C. of water containing 10 C.C. of dilute sulphuric acid (1 lo) and 5 C.C. of the reagent added little by little with continual stirring. The resulting precipitate is collected on a filter and washed twice with 5 C.C. of sulphuric acid (I 10). The filter and precipitate are then shaken in a stoppered flask with 0.3 gram of sodium sulphite and 30 C.C.of a 15 per cent. solution of sodium hydroxide until the alkaloids are liberated after which 15 grams of sodium chloride and 100 C.C. of ether are intro-duced and the shaking continued until the alkaloids have been taken up by the ether. The mixture is left to separate 50 C.C. of the ethereal layer then removed by means of a pipette and the amount of alkaloids it contains determined by titration with a i%G hydrochloric acid iodeosin being used as indicator. The number of C.C. used multiplied by 0.289 gives the weight of total alkaloids in terms of atropine. Test experiments showed that 97 per cent. of the alkaloid present was determined by this method. C. A. M. The Extraction of Tannin Materials with Various Extractors.F. P. Veitch. (Journ. Amer. Chem. SOC. 1905 xxvii. 724-729.)-To prevent possible oxidation o THE ANALYST. 317 tannin by prolonged boiling and to provide for the extraction of certain materials from which maximum results are only obtained at low temperatures a number of forms of apparatus have been used for the laboratory extraction of tanning materials. The two extractors at present in general use are the Koch and a modified Soxhlet, known as the Weiss extractor. With the Koch extractor the extract amounting to 2 to 4 litres has to be evaporated thus encouraging the very oxidation it was designed to prevent. The apparatus however enables the temperature during the extraction to be controlled. The Weiss extractor is used in most tannery labora-tories in America for extracting woods and barks but the prolonged boiling of the materials is regarded by some authorities as inadmissible.The author prefers to use a continuous extractor and describes one shaped like an ordinary Soxhlet but without the siphon tube and with the lower central tube in direct communication with the body of the apparatus. The powdered material is made into a paste with water and poured into the extractor a perforated porcelain disc being placed at the bottom of the body of the extractor and a similar disc on the top of the material. The turbid liquid which runs through at first is returned to the extractor which is then connected with a condenser. The lower end of the condenser should reach below the side tube of the apparatus.The results obtained by these three extractors are compared and show that the highest tannin results are yielded with the con-tinuous extractor except in the case of sumach where the Hoch apparatus gives the highest result. With the exception of sumach there is nothing to indicate that there is any serious loss of tannin with any of the extractors. w. P. s. The Determination of Ash in Vegetable Substances. E. Gutzeit. (Chem. Zed. 1905 xxix. 556.)-The powdered substance is intimately mixed with a known weight of freshly-ignited basic calcium phosphate and very gently heated in an open platinum crucible until the organic substance is carbonized after which it is ignited at a moderate heat eventually with the crucible partially covered until the residue appears white when it is weighed as rapidly as possible. The ash thus obtained is quite free from carbon particles and carbon dioxide. After each determination the crucible and its contents are ignited more strongly and can then be used again for a new determination The basic calcium phosphate is prepared by mixing pure finely-powdered calcium chloride and sodium phosphate in such quantities that the ratio of calcium oxide to phosphoric anhydride corresponds to the formula of basic calcium phosphate 3Ca0.2P2O,[zOH ?] and igniting the mixture. The mass is digested with hot water thoroughly washed and dried. C. A. M

ISSN:0003-2654    

DOI:10.1039/AN9053000311

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

THE ANALYST. 317 INORGANIC ANALYSIS. The Separation of Platinum and Iridium. L. Quennessen. (Chem. News, 1905 xcii. 29 30.)-The alloy under examination is dissolved in aqua regia com-posed of 1 part by volume of nitric acid of specific gravity 1.32 with 2 parts of hydrochloric acid of specific gravity 1.18 and the excess of nitric acid afterwards expelled by heating the solution at first gently and finally at 120' C. in an oven. The residue is then treated with water the metals precipitated by means of magne 318 THE ANALYST. sium and the precipitate dried ignited and heated a t a dull red heat in a ciirrent of hydrogen. The excess of magnesium is subsequently removed by means of dilute sulphuric acid (1 lo) and the residue treated with the aqua regia diluted with three times its volume of water.This dissolves only the platinum which is then converted into the double chloride of ammonium and ignited at as low a temperature a8 possible so as to prevent appreciable loss in the form of platinous chloride. The use of a reducing agent such as oxalic acid or glucose is advisable or the filter-paper containing the dried precipitate may be placed upside down in the covered crucible in the furnace and the charred paper then acts as a reducing agent its combustion being subsequently completed in the air after the operation is over. The iridium precipitated by the magnesium is soluble while still in a moist condition in acetic and dilute sulphuric acids and does not lose this property when dried at 100" C. It imparts a yellow colour to the sulphuric acid which gradually changes to violet, while the acetic acid solution is green.After being heated in the air to 440" C. the oxide gives a violet colour with sulphuric acid and a blue colour when the tempera-ture has been raised to BOO" C . C. A. M. On the Separation of Tungsten Trioxide and Silieon Dioxide by Means of Gaseous Hydrogen Chloride and the Analysis of Silico-Tungstates. Carl Friedheim W. H. Henderson and Alfred Pinagel. (Zeits. anorg. Chem., 1905 xlv. 396.)-Tungsten trioxide and silica may be separated by heating the dehydrated mixture contained in a platinum boat in a glass tube in a current of dry hydrogen chloride. The tungsten is volatilized partly as chloride which is caught in a receiver containing strong hydrochloric acid and partly as tungstic acid which sublimes into the cooler parts of the glass tube and may be detached with a platinum wire.A fairly bright red heat is necessary for the separation which proceeds the more slowly the more strongly the oxides have been heated previously. The method gives exceedingly exact results as the test analyses quoted show and is of especial use in those cases where the silica cannot be removed from the mixture by treatment with hydrofluoric acid-that is when the anhydrides have been obtained by ignition of the mixed salts e.g. mercury or quino-line salts of the two acids. In applying the method to the analysis of silico-tungstates the salt is evaporated to dryness with hydrochloric acid in a platinum boat the residue being ignited and treated as above.The presence of potassium or sodium chloride does not interfere with the volatilization of the tungsten but the platinum boat is seriously attacked, especially with potassium salts if the hydrogen chloride carries any air with it. On the other hand if no air is present the tungsten trioxide occasionally suffers reduc-tion and is then not further acted on by the hydrogen chloride. I t is therefore, best to fit the combustion tube with a T-inlet tube through which either dry hydrogen chloride or air may be introduced. The reaction is carried out as far as possible in air-free hydrogen chloride. Should the mixture in the boat become green indicating reduction of the tungsten trioxide the current of gas is stopped the heating inter-rupted and air led through the tube for some little time after which the air is shut off and the heating in hydrogen chloride resumed.The residual silica in the The silicon remains behind as dioxide THE ANALYST. 319 boat is weighed after evaporating to dryness with acid and extraction of the residue with acid. As it may contain platinum it is then volatilized with hydrofluoric acid. The tungsten is determined as usual in the liquid in the receiver. A. G. L. Rapid Method for the Estimation of Potash. E. H. Schultze. (Chem. Zeit. 1905 xxix. 509.)-The method is one especially adapted for kainite and the so-called “40 per cent. salt.” It is carried out as follows Twenty grams of kainite or 10 grams of “40 per cent. salt” are boiled in a 500 C.C. flask with about 250 C.C. water and 10 C.C. hydrochloric acid for ten minutes.The sulphuric acid is then precipitated by a not too large excess of barium chloride whilst boiling and the boiling continued for one minute. For kainite 100 c.c. and for ‘‘ 40 per cent. salt ” 10 c.c. of 10 per cent. barium chloride should be used. The precipitate is allowed to settle and then a few drops of barium chloride are added. If no further precipitate is caused the process is continued; if a precipitate again forms 20 C.C. more barium solution are added and the liquid again boiled. When the whole of the sulphate has been precipitated the solution is cooled made up to 500 c.c. shaken and then filtered ; 10 C.C. of the filtrate (=0*4 gram kainite or 0.2 gram ‘ I 40 per cent. salt ”) are treated in a beaker of 300 to 400 C.C.capacity with 5 C.C. of a solution of platinic chloride (10 C.C. = 1 gram platinum) and 120 C.C. of hot 96 per cent. alcohol added in small portions. It is then stirred continuously for fifteen minutes the beaker being placed in an outer vessel through which a current of water flows. This method in addition to securing purity and completeness of the precipitation result9 in the formation of the largest possible crystals. Immediately after the stirring (more easily after the precipitate has settled) it can be filtered off. It is washed with 82 per cent. of alcohol containing a little ether and then dried to constant weight in an oven at about 120° C. E. K. H. On the Determination of Ammonia in Water. Cavalier and Artus. (BUZZ. SOC. Chim. 1905 xxxiii. 745-747.)-Quantitative experiments with the nitrogen iodide method of Trillat and Turchet (ANALYST xxx.218 273) have shown that the new method is much less sensitive than that of Nessler no coloration being per-ceptible until the proportion of ammonia is as much as 3 mgms. per litre. Hence, in the case of drinking-water containing only 0.2 mgm. it is necessary to evaporate 500 C.C. of the water (in the presence of a small amount of sulphuric acid) in order to obtain the 20 C.C. required for a colorimetric determination ; and this evaporation is as tedious as the distillation in Nessler’s process. A more serious drawback is that the black coloration of the iodide is very unstable. After the lapse of a minute the colour of water containing 10 mgms. is fainter than that immediately given by water containing 5 mgms.and it disappears almost completely after two or three minutes. C. A. M. The Reduction of Chlorates Bromates and Iodates for the Determina-tion of the Halogen. P. Jannasch and A. Jahn. (Berichte 1905 xxxviii. 1576-1592.)-Chlorates and bromates are reduced quantitatively by fuming nitric acid 320 THE ANALYST. but iodates are only reduced when heated with it under pressure. Hydrogen peroxide cannot be used as a reducing agent in an alkaline solution but if used in a dilute nitric acid solution it gives a quantitative reduction of chlorates certain pre-cautions being necessary. Bromates are also reduced (though the nitric acid possibly plays a part in the process) but there is no reduction in the case of iodates. Iodates and bromates are completely reduced by hydrazine sulphate in alkaline solution but not chlorates and formic acid has a similar action.Neither acetalde-hyde nor dextrose effect reduction either in a nitric'acid or acetic acid solution but chlorates are quantitatively reduced when heated under pressure with dextrose and acetic acid. The best results are obtained by the use of hydroxylamine sulphate, which effects the reduction in either an acid or ammoniacal solution the latter being preferable for iodates. I n determining the halogen in chlorates or bromates about 0.25 gram of the salt is dissolved in 50 C.C. of water and treated with 5 grams of hydroxylamine sulphate after which the liquid is rendered strongly acid with nitric acid and heated and the halogen precipitated by means of silver nitrate.Other salts of hydroxylamine or hydrazine such as the acetate can be used so as to eliminate the disturbing influence of the sulphates on the precipitation of silver chloride. When the reduction is to be effected in an alkaline solution an excess of ammonia solution is introduced prior to the addition of the hydroxylamine salt. C. A. M. Volumetric Determination of Nitrous Acid by Means of Ceric Sulphate. (Chem. Zeit. 1905 xxix. 668 669.)-Nitrous acid is completely G. Barbieri. oxidized in the cold by ceric salts according to the equation-2Ce(S04) + KNO + H,O = Ce,(SO,) + KNO + H,S04. The most accurate results are obtained when the nitrite solution is treated with more than the required quantity of ceric sulphate solution the excess of the latter being afterwards decomposed by the addition of potassium iodide and the liberated iodine titrated as usual.The ceric sulphate solution must be previously titrated to ascertain its oxidizing value. The presence of considerable quantities of nitrates does not interfere with the reaction nor is it necessary that the ceric sulphate be free from lanthanum praseodymium or neodymium. w. P. s. Rapid Method for the Estimation of Phosphorie Acid. E. H. Schultze. (Chent. Zeit. 1905 xxix. 509.)-The process depends upon the solubility of ammonium phosphomolybdate in alkalies. Solutions of potassium hydroxide are used approximately normal in strength and these are standardized against phoe-phate solutions of known strength. The analysis is carried out as follows A solution of the substance is obtained in the case of superphosphate by simply shaking 10 grams of the substance with 1,000 C.C.of water. Insoluble phosphates are dissolved in dilute sulphuric acid in the usual way. A quantity of the solution corresponding to from 0.2 gram to 1.2 grams of the substance according to its expected percentage of phosphoric acid is run into an Erlenmeyer flask and potash solution added till a turbidity is just produced. Fifteer C.C. of nitric acid (specific gravity 1.40) an THE ANALYST. 321 20 C.C. ammonium nitrate (1 2) are added and the whole made up to 80 to 100 c.c., and heated over wire gauze to about 80" C. To the hot solution 40 C.C. of the molybdate solution A are added the mixture shaken up and kept on a water-bath at 80" C.for five minutes. After filtration the precipitate is washed by decantation once with water containing 1 per cent. nitric acid and then twice with cold water, it is then transferred to the filter without removing the last residues in the Erlen-meyer and further washed six to eight times. The filter funnel is then placed on the Erlenmeyer flask in which the precipitation was first made the filter-paper pierced, and the precipitate washed into the flask and the filter finally put into the flask also. Exactly 25 C.C. of the normal KOH solution which has been standardized against phosphoric acid solution are then run in from a burette the flask is shaken up to get the whole of the precipitate into solution and then the excess of KOH estimated by normal HCl using phenolphthalein as indicator.Knowing the phosphoric acid equivalent of the potash solution (for the dissolving of ammonium phosphomolybdate) by the standardization experiment the percentage of phosphoric acid in the sample can be calculated. Solution A is made by dissolving 800 to 900 grams of ammonium molybdate in 1,700 to 1,800 grams concentrated ammonia (specific gravity 0.91) and 10 litres of water and then pouring into 10 litres concentrated nitric acid. I t is filtered after standing for one day. E. K. H. On the Alleged Volatility of Silicon Dioxide at the Instant of Pre-cipitation by a Strong Acid. Carl Friedheim and Alfred Pinagel. (Zeits. anorg. Chem. 1905 xlv. 410.)-Kehrmann and Fliirscheiin (Zeits. anorg. Chenz., xxxix. 98 and 106) have ascribed some losses in silica found in their analyses of silico-tungstates to a possible volatility of silicon dioxide at the instant when it is precipitated from its salts by hydrochloric or nitric acid. To test this assumption, they fused some ignited silica with potassium sodium carbonate and evaporated the aqueous solution of the melt twenty times with concentrated hydrochloric acid. In this way a loss of 1-59 per cent. of the silica was found. The present authors have made three similar experiments to check Kehrmann and Flurscheim's statement. From the results obtained they conclude that it is entirely without foundation and that the losses of silica in question were probably caused by dehydrating the silica, at too low a temperature (at 100' C.) and by washing it finally with pure water instead of using dilute acid. A. G. L

ISSN:0003-2654    

DOI:10.1039/AN9053000317

出版商:RSC    

年代:1905

数据来源: RSC

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THE ANALYST. 321 APPARATUS. An Electrical Method for the Combustion of Organic Compounds. H. N. Morse and L. S. Taylor. (Amer. Chzsm. Joum., 1905, xxxiii., 591.)-The apparatus described is strongly recommended as being very compact, wasting but little heat, and allowing a combustion to be made in much less time than in the ordinary way. A glass combustion-tube, closed at one end, of a length of 350 mms. and an in- ternal diameter of 15 mrns., is fitted with a rubber stopper at its open end. Through this stopper there pass: the porcelain tube c, 250 mms. long and 6 mms. in diameter; the glass tube k , through which the products of the com- In Fig. 1 the simplest form of the apparatus is represented.328 THE ANALYST. bustion enter the absorption apparatus ; and the rather stout platinum wire, which extends from f to j .The porcelain tube c is joined by rubber tubing to the branched tube d. The latter is fitted with a stopper g, through which passes the stout platinum wire e, which extends into the porcelain tube to the point h, where it is joined to a thinner platinum wire. This wire, extending from h to j , has a length of 1.75 metres, and weighs about 2.5 grams. I t passes through the porcelain tube, and then returns outside in a series of loose coils. The thicker wire at the ends is necessary to avoid overheating of the rubber stoppers. A roll of copper PIG. 1. P wire gauze (b), about 60 mms. in length, is inserted between the boat and the porcelain tube. This last is made (by the Royal Berlin Porcelain Works) of unglazed porcelain. Clay-pipe stems may also be used, but are very hygroscopic, and require careful burning out before each combustion.In making a determination, oxygen or air is admitted at d, and a gradually increasing current is sent through the platinum wire, The maximum current used amounts to about 3.6 ampikes at 54 volts. At the same time, the roll of copper gauze and the boat are heated by a lamp held in FIG. 2. 1 the hand. The part of the glass tube into which the porcelain tube extends is protected by an asbestos trough below and an inverted mica trough above. I t is also useful to invert an asbestos trough some little distance above the copper gauze. During the cooling the current should be shut off very gradually, and it is advisable to protect the exposed parts of the combustion-tube by covering them with soot from a smoky flame.Care must also be taken that none of the platinum loops touch the glass at any point, as this leads to cracks. The objections to this form of the apparatus are that the whole of the heating apparatus, as well as the copper gauze, must be removed before each combustion, and that it requires a little time to sweep out the products of combustion from theTHE ANALYST. 323 closed end. A tube open at both ends is therefore to be preferred, and is shown in Fig. 2. The procedure is practically the same as before, except that a current of air or oxygen is admitted from the rear of the tube as well as at d throughout the entire combustion, and that an additional roll of copper gauze, heated by a second lamp, is placed behind the boat.For substances containing halogens, nitrogen, or sulphur, the usual modifications in the packing of the tube are made. The authors use lead chromate in the form of a cartridge made by filling a shell of fine copper gauze with granular lead chromate. A large number of excellent test analyses made with the apparatus described above are given. For substances containing carbon and hydrogen, or carbon, hydrogen, and oxygen only, the time required was usually only thirty minutes or less, Halogen and sulphur compounds also burnt readily, but with nitrogen com- pounds it was found wise to allow about one and a half hours for the combustion. A. G. L. A New Filtering Apparatus. (Chm. Zed., 1905, sxix., 511.)-The firm of Ernst. W.Hiibner, of Ammendorf b. Halle a. S., have introduced a small apparatus, constructed on somewhat similar lines to their larger filter-presses, for filtering. As some substances can be filtered only under the natural pressure given by a column of water a few metres in height, others can at once have pressure applied to them by means of a special pressure-pump. There are also cases where it is desirable to com- mence filtering under natural pressure, and afterwards to apply pressure. The apparatus under notice is specially designed to meet the last-mentioned cases, but it can be equally well used for filtering either with or without additional pressure. There is also an arrangement by which the liquid to be filtered can be cooled or heated to any temperature desired by means of a current of water or steam.All this is attained in a fairly simple manner by the proper arrangement of pipes and taps as shown in the figure. Tap I. is connected with a reservoir of water, when open, filtration proceeds at the pressure of a column of water the height of the reservoir; when the tap is closed pressure by mean8 of the pump can be applied. Taps 11. 11. provide for the egress of the filtrate, tap 111. for the addition of wash- water, 1111. for the admission of air. Taps V. V. and VI. can be connected either with a steam or a cold water supply. E. K. H. On a Difficulty in Dissolving the Fused Mass out of Platinum Crucibles. (Zeits. angew. Chem., 1905, 1025.)-The author recommends that all C. Bender.324 THE ANALYST. platinum crucibles should be polished with sea-sand between every few, at mos four, alkaline fusions.difficult to dissolve off the fused mass. this simple precaution is often neglected. Failure to do so results in the formation of a rough surface, from which it is The irregular shape of crucibles in constant use show, that in many laboratories A. N. C. A New Apparatus for the Supply of Gases. Emil Geisel. (Chem. Zeit., 1905, xxix., 726.)-The problem 9 (two only shown in section). obtained. of obtaining a steady and continuous supply of various gases, especially hydrochloric acid and sulphur dioxide, is one entirely of the apparatus to be used. The author refers to two previous attempts to solve the question: First, that of Bender, which apparatus the author considers defective in detail, and high in price, owing to its requiring a large amount of skilled glass-working in its construction ; second, that of McCoy, which has the objection that it has a rubber cork as an essential part of its interior fitting, which would come into contact with the sulphuric acid used in both the important cases mentioned above.The apparatus designed by the aathor is of fairly simple construction, and the method in which it works can be clearly seen from the accompanying figure. The vessel a contains one of the liquids used for obtaining the gas, in the case of sulphur dioxide a concentrated solution of sodium bi- sulphite. In b is concentrated sulphuric acid. In action, the acid passes down the stem c, up the outer jacket d, and through the four fine holes of Thus a very steady current of gas can be There is a stopper at the base of a by which d can be emptied and cleaned, the acid being retained meanwhile in b by inserting a well-fitting cork in g. The apparat.us can be used for almost any gas, and the author recommends it as especially convenient for the production of a steady stream of air-free carbon dioxide in nitrogen estimations-in this case a should contain solid sodium bicarbonate as well as a saturated boiled solution of it, whilst b is filled with boiled hydrochloric acid. The apparatus is supplied by the firm of Victor Lietzau, Danzig. E. K. H.

ISSN:0003-2654    

DOI:10.1039/AN9053000321

出版商:RSC    

年代:1905

数据来源: RSC