摘要:

QUARTERLY JOURNAL OF THE CHEMICAL SOCIETY. ~IT.-Chernical Composition of the Waters of the Metropolis during the Autumn adWinter of 1854 By ROBERTDUNDAS M.D. F.R.S. L.& E. THOMSON THEimportant bearing of the composition of the waters supplied to the inhabitants of the metropolis on the public health may serve as a sufficient apology for the addition of another to the many previous investigations which have been instituted on this subject. The valu-able report communicated to this Society in 1851 details researches which were made under particular circumstances during the winter season and at a time when the diluting influence of recent rain had tended to modify the constitution of the metropolitan watei+s. In the present paper it is intended to coniprise a summary of an extensive series of analyses which were made from the 1st of September 18549 to the beginning of the present year.From these results it is apparent that the waters supplied to London possess in many respects a fluctuating character which may tend in some measure to explain the antagonistic views that have at different times been entertained with regard to their adaptation to domestic purposes. In order to determine the composition of the waters as supplied to the inhabitants specimens of water were taken from houses generally in which the epidemic had proved fatal and these were compared VOL. V1II.-NO. XXX. H DR. R. D. TIIOMSON ON THE CHEMTCAL whcn the object could be conveniently accomplished with samples obtained from the sources of supply.In the course of the inquiry it was observed that the composition of the Chelsea and Southwark Companies' waters depended so much on the state of the river under different circumstances that it was found necessary to examine the Thaines at various periods of the tidal flow so as to obtain a basis for the explanation of remarkable apparent discrepancies. The following table gives the composition of the river in different parts of its course at high and low waters the Vauxhall samples having been obtained at a point intermediate between those from which the Chelsea and Southwark Companies derive their supply. The amounts are stated in grains per gallon convertible into degrees of impurity.* TABLEI. High Water.London Vauxhall. Hungerford. Bridge. Greenwich. --_I_- Mechanical impurity Organic impurity Inorganic impurity Total impurity . . . . . . . . . 60950 5.28 3G.64 102-42 .- Gii fi4 5-80 45.24 Gg44 -4-72 -45.08 -115-68 1 113.24 - Chlorine . . . . 22'00 24-00 I 21.00 A Mechanical impurityOrganic impurity . Inorganic impurity . . . 1 10-26 434 12'54 Low Water. 8'40 23.64 21.20 29 44 72.54 27.14 In collecting these specimens care was taken that each series should be obtained on the same day and as nearly as possible at each locality at the corresponding periods of the tide. When this table is compared with that which now follows the varying composition of the Thames waters taken from the lower portion of the river's course obviously depends on the chemical state * I have proposed in concurrence with the opinion of some eminent engineers of water-works to designate pure distilled water by 0 and to express by degrees equi- valent to grains per gallon tM mechanical and soluble matters contained in water.COMPOSITION OF THE WATERS OF THE METROPOLIS. of the water in the river as affected by the tidal flow at the period when the Company’s engines are in action. TABLE 11. Total Residue in Thames Waters. Grand West 1 Lsmbeth Junction Middlesex Chelsea /Southwarh Company. Company. Company. Company. Company. -I--August 1854 . . --56.26 September , . . 13.37 14.42 19.04 60.17 48’18 October , . . . --43.50 November , . . . 17.40 17.92 18.97 -4 2-78 December , . . .--36-96 -hfarch 1855. . . . --23-15 According to these data which are the means of many experiments the Southwark and Vauxhall water is more than twice as impure in August as in March. These numbers however do not convey a correct idea of the highest extreme obtained since in September the water has been found to contain 72-66grains per gallon on om occasion in Walworth. A similar observation applies to the water of the Chelsea Company. But it will be observed that the higher sources of supply from the river afford the purest water during the dry seasons and the largest amount of matter in solution during the wet seasons as the rains bring down the soluble constituents of the soil from the agricultural districts and add to the total amount both of earthy and alkaline salts.In the following series the analyses are divided into two groups Tables 111 and IV. the first comprising the Thames waters and the second those obtained from other sources The total water supplied to the metropolis by the various companies in 1853 amounted to 60,614,420 gallons of which 28,638,576 gallons were derived from the Thames. Considerable modifications in these works have been introduced by some of the water companies within a recent period which have contributed to improve the quality of the waters. Thus the Lambeth Company’s water is now obtained from Thames Ditton while important new cuttings have been made by the East London Company so as to avoid the influence of con4 taminating sewage. As the object in view in making the present investigation was to determine the nature of the water as used in the DR.W. D. THOMSOM OX THE CHEMTCAL several localities from which the samples werc taken the specimens were usually collected from the cisterns if possitde at the time when the service-pipe was delivering the supply. This may account for some differences in the amount of carbonate of lime which is well known to precipitate to some extent by exposure. In all the waters collected during the courseof the inquiry abund- ance of animal and vegetable life was detected in inechanical suspension and although the experiments were in some measure in abeyance before the cold weather set in remarkable examples were incidentally noticed during the severest frost of the persistence of vitality among some of the larger animal forms familiar to those who bdve micro- scopically examined the Southwark water.The fibrine of the faxes has also constantly been obtaincd from service-pipes of the Southwark Company,-a fact which has led to further investigation in reference to the presence of other products of animal origin in the Lambeth and Southwark waters these two waters being derived from the two extremes of the rirer so far as the Thames Companies are involved. The rcsults of these inquiries are included in Table ILL under the head of carbonate of ammonia and under Table V. -As the waters from Thames Ditton and from the Thames at Vauxhall were tested for ammonia on the same day the difference in the amount of am-monia in favour of Vauxhall water is obviously due to the influence of human excretions.And it would also appear from experiments on other rivers not subject to the reception of sewage that the Thanies Ditton water is supplied with an excess of ammonia due to the influence of different sources of pollution. In a chemical paper no attempt to discuss the nature of the organised matter diffused through the waters has been made. The analyses were made from quantities of the residual ash obtained by evaporation. COMPOSITION OP THE WATERS OF THE NETBOYOLIS. 101 TABLES 111. and IV. Composition of Metropolitan Waters. _.__-Grains per Imperial Gallon. Thames Waters. Other Waters. -r. rr. 111. IV. 111.-A& t! tA 'C ;.$ 1 4$$i is .ba $ sg Eg$ QJ; L -a gE 32.E 25 2 "44 x? us q 40 Organic mattcr.......... Silica ....................... Sesquioxidesof iron alu mina and phosphates lnvoluble lime ........... 1.39 *351 *21E 5.68C 1-92! .09( -73C 4967 2*08(*52( -4GC 5.555 5*41( 1-51] -63Y 5.348 1.480 *420 *130 5,342 Soluble lime .............. Insoluble magnesia ..... Soluble magnesia ........ Nodium .................... 944 '281 *26C -37 -975 '342 *22E '372 *868 -342 '*157 -643 2-648 '209 1.283 11.708 1.254*loo *400 -343 Potassium.. ............... Ammonia ................. -38E *023 249 - .25Y - 1.304 - ,518 - Sulphuric acid ........... Chlorine ................. Nitric acid ................. 1.596 1-020 - 1.647 0.980 - 1-504 1.160 _- 6.043 19.554 - 2'3& 1'240 - Carbonic acid ...........9.55a 8560 9SSO 9.10G 8.616 --. -Organic matter.. .......... 1.390 1.920 2.080 5410 1.480 Silica ....................... ,350 *090 -520 1.511 '420 fiesquioxide of iron ah. minn and phosphates. *215 "730 -460 *639 -130 Carbonate of lime......... 0 144 8.870 9.919 9.550 9.540 Sulphate of lime ........ 2-149 2.368 2-1 09 6.432 3.085 Nitrate of lime ............ trace trace trace trace Lracc -Chloricle of calcium ...... --Carbonate of magnesia... ,592 '720 *720 +438 -210 -Sulphate of niagiiesia . . --1-390 Chloride of magnesium.. . -617 -542 .360 1.947 '94s9 Sulphate of potash ...... '730 '553 ,577 2.903 1.153 Chloride of potassium ... ----trace Sulphate of soda ......... --- -Carbonate of soda......... - Cliloride of sodium ......,966 -947 1.637 19.797 -874 Total ........................ '-153 3740 3.443 '-841 Reaidue by evqiowt,ion .17'440 3.920 3.970 "760 Cai.bonate of ammonia... -Of344 --Hardness ..................13.2 36 !'2 DR. R. D. THOMSON ON THE CHEMICAL AMMONIA i~ THE LAMBETH AND SOUTHWARK COMPANIES’ WATERS. As the absolute and relative amount of ammonia present in water in addition to the quantity of nitric acid is a question of vital im- portance in regard to the sources of the contaminating influences to which waters are subjected it seemed desirable to make the experiments upon such a scale of magnitude that minor difficulties occurring on the small scale of operations might be obviated. In the subsequent tables exhibiting the amount of ammonia present in Southwark water the quantity operated on was always 50 gallons which were introduced into a copper still and boiled for a considerable time in order to precipitate the carbonate of lime.About 2 gallons of distilled water were usually drawn o& and were never found alkaline; from which it might be inferred that no carbonate of ammonia existed in the water but the distillation was scarcely protracted sufficiently long to decide this question. About half a pint of strong caustic soda was then poured into the boiler and the 2 gallons of distilled water returned. When the amount of ammonia present in the water was considerable the distilled fluid gave evidence of an alkaline reaction in about two minutes after the addition of the soda which accounts for the facts exhibited in the table of the largest amount of ammonia being found to exist in the second half gallon as in Nos.1 and 2. When the quantity of ammonia was feeble as in No. 4,no alkalinity was detected till the fourth half gallon was distilled The rate at which the ammonia distilled was found to depend in a great measure on the mode of the application of the heat to the still the higher the temperature the more rapid being the evolution of the ammonia as in Nos. 1 and 2; while in No.5 the gradual application of the heat caused the alkalinity to be appreciable even in the eighteenth half-gallon of distilled water. The alkalinity was neutralised in all the experiments in the table by sulphuric acid diluted to such a degree that 100 alkalimeter mea- sures saturated 38-46 of soda or 21.112 of ammonia.Each 100 measures therefore contained 49.67 parts of sulphuric acid. In Order to check the numbers determined by the neutralising acid the whole of the fluids after the addition of a slight excess of acid were evaporated to dryness and the residual sulphate of ammonia freed from a small portion of lime with which it was usually contaminated dried cautiously in a dry atmosphere and weighed. The controlling numbers thus obtained are exhibited in Table VT. Generally they exceed the quantity procured by means of the acid process because eeveral additional gallons which were drawn off although destitute of COMPOSITION OF THE WATERS OF TUIE IClETlWPOLlS.103 any appreciable alkalinity were acidified and boiled down to obtain their residue which was added to the rest of the sulphate. The Southwark and Vauxhall water was examined on this extensive scale because the operation could be conveniently performed; but in the case of theLambeth water as the fluid required to be brought from a distance the &stillation was made with 10 gallons; acid was added to the distillate until the reaction indicated an excess; the water was cautiously evaporated ; and the ammonia determined as platino-sal- amruoniac. In the case of the St. Thomas's Well the amount distilled from was 50 gallons. TABLEV. South wark. St. Thomas's Measures of Acid. Well. IV. Half-Gallons. March 17 1855. 1st 2d 3a 4th 5th 8th 7th 8th 9th 10tll 1 Lth 12th 13th 14th 15th 16th 17th 18th 48.0 10.0 104 DR TEFOMSON ON THE WATEXS OF THE METROPOLIS.TABLE VI. Amount of Ammonia in Southwark and Lambeth Waters. It.Tho. Well. Nov. 30 Dec.22 Jan. 5 gar. 17 aar. 17 1854. 1854. 1855. 1855. 1855. Southmark and Vauxtiall Water and St. Tliomas's Well :-Ammonia (NH,) in 60 gallons deter- mined by an acid . . . . 10.134 14.881 8.441 2.111 11-717 Ditto by evaporation as sulpliate . . --2'575 11.874 Ammonia (NH,) per gallon determined by acid . . . . . . -203 -298 -109 -042 234 Ditto by evaporation as sulphate . . --4515 *28i5 Carbonate of ammonia (NH CO HO) -119 -661 I c SOFTENING PROCESS FOK WATERS.Having had an opportunity of witnessing on an extended scale at Ylumstead under the management of Rlr. Homersham the efficiency of Dr. Clark's so€tening process it may be satisfactory to subjoin analyses of two chalk-waters in their natural and softened conditions :-Watford. Plumdead. Hard. Soft. 11 Hard. Organic matter . . . 1'400 Silica. . . . . . *480 Alumina and phosphates . . . -240 Carbonate of lime . . . . 14.131 Carbonate of magnesia . . . *870 Sulphitte of lime . . . . I *8S7 Nitrate of lime . . . . . 1.521 Sulphate of potash . . . . a309 -. Sulphate of soda . . . . Chloride of sodiuni . . . 1.153 Total . . . . . . 22-251 7.327 30.577 Residue by evaporation . . . 22.400 8.030 30.900 11 These data are sufficient if any were reqnired to demonstrate that practically the softening process is as successful as theory would indicate.

ISSN:1743-6893    

DOI:10.1039/QJ8560800097

出版商:RSC    

年代:1856

数据来源: RSC

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105 Dlt. J. STENHOUSE ON PLATlNISED CHAKCOAL VIII.-On Ylutinised Charcoal. By DR.JOHNSTENHOUSE, LLD. F.R.S. THE lighter kinds of wood charcoal owing to the nine volumes of oxygen gas contained in their pores possess a considerable power of oxidising the greater number of easily alterable gases and vapoura. The absorbent power of charcoal however is comparatively much greater than its capacity for inducing chemical combination. In this respect charcoal presents a remarkable contrast to spongy platinum which though inferior as an absorbent for some gaseous substances,- such for instance as ammonia of which spongy platinum absorbs only 30 volumes while charcoal absorbs 90,-is ncvertheless immensely more effective both as an oxidiser and as a promoter of chemical combination generally.As it is desirable for some purposes while retaining the absorbent power of charcoal unimpaired to increase its oxidating influences it struck me that this important object might be easily effected by combining the charcoal with minutely divided platinum. In this way a combination is produced to which I have given the name of platinised cbarcoal which possesses the good pro- perties of both of its constituents. In order to platinise charcoal nothing more is necessary than to boil the charcoal either in coarse powder or in large pieces in a solution of bichloride of platinum and when the charcoal has become thoroughly impregnated with the platinum which seldom requires more than ten minutes or a quarter of an hour to heat it to redness in a close vessel-a capacious plati- num crucible being very well adapted for this purpose.When 150 grains of charcoal were impregnated with nine grains of platinum by the process just described the charcoal was found to have under- gone no change in its external appearance though its properties Bad been very essentially altered. When a few grains of this platinised charcoal were passed up into a mixture of dry oxygen and hydrogen in the proportions to form water over mercury the two gases rapidly combined in the course of a few minutes precisely iu the same way as when a clay ball of spongy platinum is 2myloyed. When how-ever a fragment of charcoal containing a considerably larger propor- tion of platinum was passed up into a sirnilar gaseous mixture the gases instantly combined with explosive violence just as if platinum-black had been used.If pieces of cold platinised charcoal are held in a jet of hydrogen they specdily become incandescent and inflame thc gas. l’latinised charcoal when slightly warnled likewise rapidly lQ6 DR. J. STENHOUSE ON PLATINISED CHARCOAL. becomes incandescent in a current of coal gas but the jet of gas is not inflamed owing to the very high temperature a white heat which is required for this purpose. In the vapour of alcohol or wood-spirit platinised charcoal becomes red hot and continues so till the supply of vapour is exhausted. In the course of a few hours spirits of wine in contact with platinised charcoal and air is converted into vinegar.I find that two per cent of platinum is sufficient to platinise charcoal for most purposes. Charcoal containing this small amount of platinum causes a mixture of oxygen and hydrogen tocombine perfectlyin about a quarter of an hour and this is the strength of platinised charcoal that seems best adapted for charcoal disinfectant respirators. Charcoal containing one per cent. of platinum causes a mixture of oxygen and hydrogen to combine in about two hours ;and charcoal containing the extremely minute quantity of & per cent. platinum produces the same effect in from ti to 8 hours. Ylatinised charcoal seems likely to admit of various useful applications one of the most obvious of these is its excellent adaptability to air-filters and respirators for disinfectant pnr- poses.It is plain that no easily alterable organic vapours such as effluvia or miasmata can remain in contact even for a few minutes with platinised charcoal without being destroyed their carbon being converted into carbonic acid and their hydrogen into water. Platinised charcoal also seems likely to prove a highly useful appli- cation to malignant ulcers and similar sores on which I confidently expect froni its powerful oxidating properties that it will act as a mild but effective caustic. Perhaps however as an application to sores platinised asbestos either alone or in combination with platinised charcoal might be found more manageable. In those diseases also where the internal use of charcoal has been found beneficial I should think that platinised chazcoal may be advantageously substituted. In Bunsen’s carbon battery also the employment of platinised charcoal may I think be advantageously tried. It is clear that the amount of platinum in the charcoal may be varied almost at pleasure according to the strength of the platinum solution employed in its preparation and the purposes to which the charcoal is intended to be applied. Almost any form and even very considerable dimensious may be given to the platinised charcoal,- circumstances which greatly extend the range of its applications.

ISSN:1743-6893    

DOI:10.1039/QJ8560800105

出版商:RSC    

年代:1856

数据来源: RSC

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DR. A. MATTHIESSEN ON STRONTIUM AND MAGNESIUM. 107 1X-h the Preparation of Strontium and Magnesium. By A. MATTHIESSEN, PH.D. INmy paper on the preparation of calcium I confirmed Bunsen’s statement. concerning the action of the density of the current employed in the electrolytic deconiposition of metallic salts. Since then in pursuing the research further in the Heidelberg Laboratory I have found that the same conditions are necessary for the preparation of metallic strontium. The best method by which pieces weighing half a gramme are sometimes obtained is as follows :-A small crucible with a porous cell is filled with the anhydrous chloride of strontium mixed dth some chloride of ammonium so that the level of the fused chloride in the cell is much higher than in the crucible.The negative pole placed in the cell consists of a very fine iron wire wound round a thicker one and then covered with a piece of tobacco-pipe stem so that only about the one-sixteenth part of an inch appears below; the positive is an iron cylinder placed in the crucible round the cell. It is easy to regulate the heat during the experiment so that a crust may form in the cell; the metal will then collect under this crust without coming in contact with the sides. I have found this method very advantageous also for the preparation of calcium. Strontium resembles calcium in colour being only a shade darker. It 0xidise.smuch more quickly than that metal. The specific gravity of the metal obtained from pure chloride of strontium gave in two experiments 2.5041 and 2.5796 the mean of which is 2.5418.Its atomic volume is 216 being 18 greater than that of calcium. The specific gravity of calcium from pure chloride of calcium gave in three experiments 1.5843,1.5656 and 1.5835 the mean of which is 1.57‘18. The atomic volume is 158. The place of strontium in the electrical series water being used as the exciting liquid is not the same as has hitherto been supposed but is as follows :-k Nay Li Cay Sr Mg &c. Strontium burns like calcium and also acts similarly to it when heated in chlorine oxygen bromine or iodine or on boiling sulphur or when thrown into water or acids. I next proceed to describe a method of preparing magnesium with- out the necessity of making the anhydrous chloridc out of which 108 DR.A. MATTHIESSEN ON STRONTIUM AND MAONESlUM. Bunsen reduces it.* Instead of the anhydrous chloride the pre- paration of which is so very difficult it is simpler to use a mixture of the chlorides of potassium and magnesium in nearly equal pro- portions viz. three equivalents of chloride of potassium to four of chloride of magnesium. The solution of the chloride of magnesium can be evaporated almost to dryness and analysed to find the amount of anhydrous salt present. After having mixed the two salts in the proper proportions with some chloride of ammonium the mixture may be fused and electrolysed by Bunsen’s method the pockets not being required as the metal is specifically heavier than the fused mixture. A very simple and convenient way of reducing the metal especially for the lecture table is in a common clay tobacco-pipe over a Berzelius’ spirit-lamp the negative pole being an iron wire put ,up the pipe-stem and the positive being a piece of gas-coke just touching the surface of the fused chlorides. * Ann. Ch.Pharm. lxxxii. 137.

ISSN:1743-6893    

DOI:10.1039/QJ8560800107

出版商:RSC    

年代:1856

数据来源: RSC

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REPORT OF THE COUNCILj MARCH 30 1855. THECouncil have the satisfaction to announce that there is a steady increase in the numbers of the Chemical Society. At the last Anniversary meeting the number of Fellows was-Eesident and Non-resident . . . 247 Deduct Deaths b a . 3 L_.l 244 Add Elected since . . ' . 17 Present number of Fellows . . . 261 The Fellows who have died in the last year are Mr. Richard Prosser of Birmingham; Mr. John Thomas Cooper; and Mr. Charles Blachford Mansfield. R i c hard Pro sseF was an engirteer of high original faculties and great attainments. He was the inventor of many mechanical improve- ments and among other inventions of the process of forming pottery from dry clay-dust by the application of powerful pressure a process which gave rise to the manufacture of those coloured mosaic tiles manufactured by M in ton which have attained so great a celebrity.To the exertions of Mr. Prosser the late reform in the Patent Law was mainly owing. At the time of his death he was sedulously pursuing a work of importance to the Ordnance Board-an appendix to the volume now issuing from the office of Mr. Woodcroft con- taining an account of all the patented inventions on the subject of Gunnery from the earliest periods. He died at the age of 50. John Thomas Cooper was born at Greenwich June 29 1790. In early life he studied for the niedical profession ;but Chemistry was his favourite science and we find him at 20 years of age delivering popular lectures on that subject in Moant Street Lambeth.He was XEPORT OF THE COUNCIL. subsequently appointed Lecturer on Chemistry at the Russell hstitu- tion and he was afterwards teacher of the aame science at the Aldersgate School of Medicine. At one time Rlr. Cooper was the sole manufacturer of Iodine in this country. He was also a very successful preparer of Potassium and Sodium by the process of Gay Lussac and Thhard at a time when those metals were sold for ten and twelve guineas the ounce. Among the published results of Mr. Cooper’s scientific investigations we may mention the fol- lowing :-r‘ On some Combinations of Platinum” (Q. J. S. iii. 119) ; “Analysis of Zinc Ores” (Q. J. S. ix. 19);An Examination of the Ancient Ruby Glass (Ann. Phil. vii. 105) ; “Improvements in the Instruments invented hy Dr.Wollaston for ascertaining the Refracting Indices of Bodies’’ (Mem. of Chern. Sjoc. April 1843); “ On Cate-chuic Acid” (Mem. Chew Soc. Dec. 1843) ; “On the Baroscope an Instrument for Measuring Heights” (read before the Royal Society Feb. 1839). He also discovered the Sesquioxide of Carbon but from delay in his investigation Mr. Serullas who also discovered it had the priority of publication. In the year 1823 Mr. Cooper received two of the medals of the Society of Arts for an improved Hydrometer for Saline Solutions and for an Apparatus for the Analysis of Animal and Vegetable Substances (Journ. Soc. Arts xli.) In 1835 he perfected his Oxyhydrogen Microscope and in con-junction with Mr. Carey the Optician produced it for public exhibi- tion.He first employed the Canada balsam for mounting microscopic objects an invention of great practical utility. He died Sept. 24 1854 in his 65th year. Charles Blachford Mansfield was the son of a clergyman and was born at Rowner in Hampshire in the year 1819. His interest in natural science exhibited itself at a very early age in an intense fondness for natural history which he always retained. I-Ie was edu- cated at Winchester School and at the University of Cambridge. Subsequently he placed himself as one of the first pupils at the College of Chemistry under the guidance of Dr. Hofmann. After passing through the ordinary training of the College he undertook the investigation of the constituent volatile cils of coal-tar among which he discovered the presence of benzol in considerable quantity.He invented and patented a process for obtaining benzol from coal-tar and for producing a new light by charging air with its vapour. His researches on this subject appear in Vol. 1 of the Journal of the Chemical Society and in the volume of the Researches of the Chemical REPORT OF THE COUNCIL. College as well as in a pamphlet. The Institute of Civil Engineers awarded to him for them the Telford premium. In the year 1851 he was invited to deliver a course of lectures on the Chemistry of the Metals at the Royal Institution. The earlier lectures of this course were remarkable for some broad and Griginal generalisations which were afterwards developed by hini in a manu- script work unfortunately left unfinished.During the last seven years of his life he was much occupied with efforts for the ameliora- tion of the condition of the working classes; and his interest in those matters by which science connects itself with social life may be instanced by some striking letters on the subject of the consumption of smoke contained in late numbers of the ‘‘Mechanics’ Magazine.” On his return from a voyage to tropical South America he devoted much time to the preparation of a work on the constitution of salts which he completed and placed in a publisher’s hands a few days before the accidcnt which put an end to his career. He had been officially invited to prepare specimens of the products he had extracted froin coal tar for the French Exhibition then about to be opened.In carrying out this purpose the accidental boiling over of the naphtha from a small still which he had long been using inflicted injuries on his assistant and set his own clothes on fire The still itself was in flames and the only chance of preventing them from extending to the premises was in removing the whole apparatus. High courage and presence of mind were never wanting to him. He seized the still in his hands and bore it a sheet of fire to the door. This he was unable to open and had to escape through the window It was on the 17th of February the coldest day of the present year ; the ground was covered with snow and he extinguished the flames with which he was enveloped by rolling himself upon it.The thought of another’s danger now flashed on his mind and he was with diffi- culty hindered from re-entering the building to rescue his assistant by a person who had come to his aid. He did not escape however without complicating hisinjuries by a violent blow on the head whilst passing through a low wicker door leading into the street. With his hands burnt almost to the bone his fa:“ and head a mass of injuries his countenance unrecognisable by his dearest friends besides slighter wounds on ths knees and feet he had to walk a mile supported by a woman to a cab and had himself carried to the Middlesex Hospital which he reached almost in state of collapse from the intensity of the cold. There he terminated his life after nine days of lingering agony.It would be wrong to estimate the man by what he had actually REPORT OF THE COUNCIL. given to the world. He was cut off at an age when with his varied gifts it would have been easy for him to have completed an ordinary life’s work. He had proposed to himself a task so broad that the time failed him to do more than lay the foundation for it. How broad that foundation was his manuscript works and fragments which are mostly preparing for publication may possibly show to the world. The following are the Fellows and Associates of the Chemical Society elected since March 30 1854:-April 3 1854.-A. Kekule‘ Ph.l). Reinhold Hoffmann Ph.D. Associates. May 1.-Robt Railton Esq. University College; Patrick Duffy Belfast Fellows.May 15.-Hugo W. Muller Ph.D. 110 Bunhill Row; Charles Greville Williams Esq. 3 Oxford Court Cannon Street Associates. November 6.-Robert Mortimer Glover M.D. F.R.S.E. Royal Free Hospital Gray’s Inn Lane; J. Taylor Esq. 5 Burchfield Terrace East India Road; Newton Samuelson Esq. 11 Temple Court Liverpool; Henry M. Noad Ph.D. Bark Place Bayswater ; Robert Hunt Jun. Esq. Government School of Mines; Isaac Newton Loomis M.D. of Macao in the State of Georgia U.S. Fellows. Messrs. Henry Buff and Richard Tuson of St. Bartholo- mew’s Hospital Associates. November 2O.-Mr. James Taylor Fellow. December l8.Tohn S. Abel Esq. Coquimbo Chili ; Charles Loudon Bloxam Esq. King’s College; Chas. W. Heaton Esq.,26 Lime Street; Fletcher Norton Esq.5 Stanhope Street Harnpstead Road Fellows. January 15 1855.-H. J. Smith Esq. B.A. Oxford; Mathew Warton Johnson Esq.; Charles Tookey Esq. 3 Mitre Street Claremont Square,. Fellows. February 5.-Messrs. Frederick Stohmann and Frederick Versniann of University College Associates. March 5.-John James Bancroft Esq. Ruthen North Wales Fellow. REPORT OF THE COUNCIL. The followiiig is the List of Papers read before the Chemical Society froni March 30 1854 to March 30 1855:-April 17 1854.-Mr. Frederick Field communicated a paper “On the Composition of a Specimen of Atacamite from the Province of Copiapo Chili. May 15.-‘{On the Occurrence of Ozone and Peroxide of Hydrogen in the Electrolysis of Sulphuric Acid :” by Heinrich Meidinger.“On the Corrosive Action of Sugar on Iron and other Metals :” by Dr. J. H. Gladstone. June 19.-“.Preliminary Notice on the Action of Ammonia on the Oils and Fats :” by J. H. Rowney Yh.D. “On the Action of Iodine on Calomel :” by Dr. R. M. Glover. “On an unexpected Source of Nitrobenzol:” by Arthur H. Church. ‘‘ On the Substitution-compounds obtained by the Action of Nitric Acid on Cotton :” by Edward Ash Hadow. November ‘6.-“ On the Analysis of a Surface-Soil from the Desert of Atacama :” by Frederick Field. December 4.-“ On the Preparation of Pure Pyroxylic Spirit :” by W. Gould. December 18.-“ On the Produce of Barley Sown in Rocks of various ages :” by Dr. Daubeny. “ Notice of further Experiments as to the Reduction of Metallic Oxides by Peroxide of Barium :” by B.C. Brodie. January 15 1855.-“ On Thernio-Electric Joints formed with the metals Antimony Bismuth and Palladium :” by Richard Adie. “ Investigation of the Vegetable Tallow from a Chinese Plant the ‘Stillingia Sebifera :’” by N. S. Maskelyne M.A. F.G.S. “On the Absorption of Chlorine in Water:” by H. E. Roscoe B.A. Ph.D. February 5 ,-On a peculiar Eiflorescence of Chloride of Potassium :” by Robert Warington. “On the Preparation of the Metals of the Earths by Electrolysis :” by A. Matthiessen Ph.D. February 19.-<< On the Thermo-Electrical Currents generated in Elements where Bismuth is used to Form the Joint :” by Richard Adie. VOL. VII1.-NO. XXX. I REPORT OF THE COUNClL. The Society is also indebted to Professor Miller of King’s Col- lege for an able and interesting discourse ‘‘On the Action of Waters on Lead,” delivered at the last Meeting of the Society.The Council have during the past year entered into an arrange- ment with the Rdyal Society by reason of which the Fellows of this Society receive the ‘‘Proceedings of the Royal Society” free of charge. The Council wish to record their sense of the liberal spirit in which the Royal Society with a view to the diffusion of scientific intelli- gence has met their wishes upon this point. Several valuable additions have been made to the library of the Society; and the Council beg to call to it the attention of Fellows as a place of deposit for curious works upon Chemistry and for pamph- lets upon chemical subjects which collected are of great interest but separately are often of little or no value to the possessor.Dr. ROBERT PORRETT (TREASURER) IN ACCOUNT WITH TEE CHEMICAL SOCIETY. CT. 1854. March 27. To Balapce from last Account ........................ 1855. March 28. , Subscriptions since received ........................ , Admission Fees from Thirteen New Members.. ,Y 2 , One Year’s Dividend on 2300 Three per Cent. Y YY Consols minus Property Tax .................. ,? Rent for the Use of the Rooms by the Ethno- 2 2 logical Society to November 1854 and by the Chess Club to Christmas last ............... 9 ,> , Proceeds of Sale of “Memoirs” .................. 32 London 28th March 1855 d2 s.d. 105 2 lo& 265 2 0 26 0 0 8 9 5 30 15 0 1 14 4 427 3 7+ .€ s. a. By Payment of One Year’s Salary to the Librariar 15 0 0 , Ditto of One Year’s Rent t,o Polytechnic In. stitution ............................................ 120 0 0 , Ditto to Henry Watts for One Year’s Salary as Editor of the Society’s Journal ............... 50 0 0 , Ditto to H. Baillidre for Publishing the So-ciety’s Journal .................................... 116 8 0 , Ditto for Attendance and for Tea and Coffee. . 23 19 11 , Ditto to Henry Watts for Translations ......... 516 2 , Ditto for Petty Cash Postage Stamps &c. ... 5 511 , Ditto to Imperial Gas Company for Gas.. ....... 779 , Ditto to Cavendish Society Subscription 1855 110 , Ditto to Walton and Maberly for Books ......330 ,,Ditto to H. Baillikre for Books .................. 717 0 , Ditto to Taylor and Francis for Philosophical Magazine. ............................................ 115 0 , Ditt.0 to Charles Whiting for Printing ......... 500 , Ditto to the Collector for Poundage ............ 11 14 0 , Ditto to Royal Society for “Proceedings” sent to theMembers of this Society .................. 20 0 0 , Ditto to Doorkeeper of Polytechnic Institution 100 ),Balance carried to new Account ................. 31 15 lo+ f 427 3 7+ R. PORRETT Treasurer. Examined and found correct J. H. GILBERT WM. ODLINGC.

ISSN:1743-6893    

DOI:10.1039/QJ8560800109

出版商:RSC    

年代:1856

数据来源: RSC

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YROCEEDINGS AT THE MEETINGS OF THE CHEMICAL SOCIETY. April 2,1855. Dr. WARREN DE LA RUE Vice-president in the Chair. Specimens of a deposit formed during the preparation of extract of rhubarb were presented by Mr. George Whipple accompanied by a note in which the deposit is described as consisting of several undetermined organic substances together with a considerable pro-portion of chrysophanic acid. The caustic alkalies dissolve the greater part of the deposit forming intense crimson solutions which stain paper of a crimson colour are changed to yellow by most acids and yield a crimson lake of great beauty on the addition of alum. Mr. Whipple suggests that this substance may admit of useful application in the arts. A paper was read :-“On the Chemical Composition of the Waters of the Metropolis during the Autumn and Winter of 1854:” by Dr.R. n. Thomson. April 16 1865. Dr. W. A. MILLER,Presidcnt in the Chair. The following donations were annouiiced :-‘‘Miller’s Elements of Chemistry :” from the President. cr The Literary Gazette :” from the Publishers. “ The Proceedings of the Royal Society? from the Society. PROCEE1)INCS 014’ THE CHEMICAL SOCIETY. Mr. Warington delivered a discourse “On the Maintenance of a Permanent Balance between the Animal and Vegetable Kingdoms in a Medium of Fresh or Sea Water.” May 7 18%. Dr. W. A. &II LLER President in the Chair. David Gamble Esq. and T. N. Keates Esq. were admitted Fellows of the Society. Williain Go~ild Esq. was duly elected a Fellow of the Society.The following donations were announced :-“The Jouriial of the Society of Arts :” from the Society. ‘‘ The Journal of the Photographic Society :” from the Society. ‘‘The Literary Gazette :” from the Publishers. ‘I The Pharmaceutical Journal :” from the Editor. Dr. Williamson delivered a discourse On certain Processes ‘I recently proposed for the Decomposition of Pats by Water at High Ternperat iires.” May 21 1855. Dr. G. D. LONGSTAFF, Vice-President in the Chair. Dr. Noad was admitted a Fellow of the Society. The following donations were announced :-‘‘ The Literary Gazette :” from the Publishers. ‘(The Journal of the Society of Arts :” from the Society. The Journal of the Franklin Institute :” from the Institute Dr.J. H. Gladstone made a short verbal communication on the Influence of Magnetism on Salts in Solution. Dr. Gilbert delivsred a discourse “ On the Chemical Statistics of the Animal Body.” After which A paper was read :-I( On Platinised Charcoal :” by Dr. Stenhouse. PROCEEDINGS OF THE CHEMICAL SOCIETY. June4 1855. Dr. W. A. MILLER,President in the Chair. The following donations were announced :-‘(Tractatus varii:” by Robert Boyle. 1611-10. London 1676. “ Opuscules Chiiniques :” by M. de Margraf. Tomes 1and 2 12mo. Paris 1762. “Metallurgie :” by A. M. Grassin. Tomes 1 and 2 12mo. Paris 1751. ‘< Institute de Chymie :” by Jacques-Reinhold Spielmann. Tomes 1 and 2 12mo. Paris 1770. “Rudiments of Chemistry:” by Samuel Parkes.121110. London 1822. “An Essay on Fire:” by Mark Augustus Pictet. 12mo. London 1791. ‘I Ele‘mens de Chimie Pratique:” by M Macquer. Tomes 1 and 2. l2mo. Paris 1756. ‘‘Opuscules Chimiques :” by Pi e r r e B aye n . 8vo. Paris. “Philosophical Tracts :” by Stephen Hales D.D. F.R.S. 8170. London 1739. “Essay on the Disinfecting and Medicinal Chlorurets :” by Thos. Alcock. “ Chimie du Fer :” by Le ChevaIier Hervk. 8vo. Paris 1826. “Experiments on Bleaching:” by Francis Horne M.D. 8v0. Edinburgh 1756. Chimie Min6rale et Analyses de Substances Midrales :” by M. P. Berthier. 8vo. Paris 1835. “Description of Chemistry:” by J. F. A. Gottling. 8vo. London 1791. “ Course of Chemistry :” by M. Lemery. 8vo. “Pyritologia; or a History of the Pyrites:” by J.F. Henckel. 8170. London 1757. “De I’Analyse des Corps Inorganiques:” by J. J. Berzelius. 8vo. Paris 1827. “Lectures on Chemistry read at Guy’s Hospital by William Babington Alex. Marcet and W. Allen.” 8vo. LondonJ1816. “Chemical Lectures delivered at Guy’s Hospital by W. Allen John Bostock and Arthur Aikin. 8vo. London 1822. “Elements of the Art of Dyeing:” by M. Berthollet. 8vo. Edinburgh 1792. “ Recherche9 sur les Bois :” by M. Eugsne Chevandier. 8vo. Paris 1844. PROCEEDINGS OF THE CHEMICAL SOCIETY. “Elements of Chymistry:” by M. Macquer. Vols. 1 and 2. 8vo. London 1758. ‘I Elements of Chemistry :’ by Joseph Francis Jacquin. 8vo. London 1803. “Experiinents on Animal Heat :” by A.Crawford M.D. 8170. London 1’788. “Experiments in Chemical Philosophy :,’ by Bryan Higgins M.D. 8vo. London 1786. “A Treatise on the Nature and Properties of Air :” by Tiberius Cavallo F.E.S. 4to. London 1781. “ Complete Works on Chemistry :” by J. Rudolph Glauber. Folio London 1689. From Dr. Faraday. ‘(On the Object of the Salt Condition of the Sea:” by E. J. Chapman. From the Author. “A Dream of the New Museum.” From Dr. Daubeuy. Gustav Magnus and Charles Gerhard t were duly elected Foreign Members of the Society. Communications were read :-“On the Preparation of Strontium and Magnesium:” by A. Matthiessen Ph.7). ‘I On the Preparation of Lithium :’ by Professor Bunsen. Dr. Longstaff delivered a discourse “On the Explosion at Gateshead in October 1854.” June 18 1855. Dr. W. A. MILLER,President in the Chair. The following donations were announced :-‘‘ The Journal of the Society of Arts :” from the Society. “The Literary Gazette :” from the Publishers. The following papers were read :-“ On the Colwr of Chloride of Copper in different states of Hy-dration:” by J. H. Gladstone Ph.D. F.R.S. ‘I On the Proximate Constitution of Chemical Compounds :” by John Joseph Griffin.

ISSN:1743-6893    

DOI:10.1039/QJ8560800116

出版商:RSC    

年代:1856

数据来源: RSC

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NOTICES OF PAPERS CONTAINED IN OTHER JOURNALS. BYHENRY B.A. F.C.S. WATTS Report on the Supply of Spirit of Wine Free from Duty for Utie in the Arts and Manufactures. By Professors Graham Hofmann and Redwood. ADDRESSED TO THE CHAIRMAN OB INLUD REVENUE. SIR,-We have now the honour to report on the practicability of supplying for commercial purposes R mixed spirit free from duty without injury to the revenue,-a subject proposed to us for investi-gation in your letter of March 25 in the following terms :-'' The attention of Government has for some time been directed to the iiiiportance of allowing spirit of wine free of duty for use in the arts and manufactures. In order that such a privilege may be granted with safety to the revenue it is ahsolutely necessary that means should be devised by which such spirit may first be rendered unfit for human consumption.It is also indispensable-1st. That spirit after being thus treated should still be so pure as to be generally available for the purposes to which it is applied in the arts or manufactures. 2nd. That it should not be capable of puri- fication by any simple process of rectification or otherwise so as to be made palatable by the addition of sweetening or flavouring ingredients. (( It is also highly desirable that while the mixed spirit should be rendered as offensive as possible to the taste or smell no decidedly poisonous properties should be communicated. 'C Some preliminary inquiries have been made into this subject. Mr. Phillips one of our surveying-general examiners has suggested a substance to be mixed in certain proportions with spirit which would interfere very little with its use in the arts while it would REI'!)R'L' ON THE SUPPLY OF SPLRlT OF WlNE PILEE FROM DUTY.121 render it highly unpalatable although not unwholesonie. Dr. Hofuiann as you are aware has made a number of experiments on spirits mixed in the manner suggested and obtained very promising results. It is therefore desirable that the subject should be more fully investigated. '' With this view your attention is directed to the points already indicated viz. :-"Whether and by what nieails spirit produced in the ordinary niode can be rendered so offensive to the taste or smell as to make it unfit for human consumption as a beverage without materially itlipairing it.either for the manufacture of ethers or as a solvent of gum-resins or for any of the ynrposes in the arts to which it is usually applied. "Whether and to what extent the mixed spirit would resist any process for its purification or might be so compounded as to make it palatable ? '' To what branches of the arts or manufactures it would be safe or desirable to limit the privilege of using such mixed spirit ? '' In what manner under what superintendence and with what precautions the spirit should be mixed ? "The Board will also be glad to hear of any suggestions of a practical nature although not falling within the scope of this com-mission which may occur to you in the course of your investigation," Of the volatile substances which first suggested themselves as proper to be added to alcohol in order to attain the object proposed the greater number were soon eliminated as unsuitable upon a close consideration or actual trial of their properties.Snlphide of ethyl and volatile sulphur-compounds analogous to it communicate their repulsive taste and odour when they are added to alcohol even in a proportion so minute as 1to 100,000; and are not removed from the alcohol by rectification or filtration through charcoal. But the sulphide of et.hyl was easily separated from the alcohol by means of distillation after the addition of a little alkali which is conclusive against its use. The neutral volatile oils or essences are too easily removed from alcohol by nieans of dilution with water and distillation The same objection applies to ordinary ether and to the compound ethers of all classes the compound ethers being further readily decomposed by distillation with an alkali.The mixed oils procured from wood and various other organic sribstances by the agency of destructive distillation promised better results. The liquid distilled from caoutchouc and known as Caout-chicene which is distinguished by a powerful and highly characteristic odour has the advantage of being composed entirely of neutral hydrocarbons and is thcrcfore not likely to bo acted upon by either 122 PROFESSORS GRAHAM HOFMANN AND REDWOOD ON acids or alkalies. These hydrocarbons are also of various degrees of volatility some of them boiling at a lower and some at a higher point than alcohol itself which must increase the difficulty of their separation from alcohol by the process of rectification.Fer experi-ments in mixing caoiitcliicene was prepared by distilling cao~xtchouc in a glass retort by a heat gradually rising to redness. The oil was redistilled till its temperature of ebullition rose to 250' centigrade ; and the portion which came over below that temperature amounting to about three-fifths of the original distillate was alone employed. The caoutchicene so prepared when mixed with a large proportion of alcohol evaporates completely in air and when used as a solvent of resins leaves on drying an inodorous varnish. The proportion of caoutchicene which it was found most advan- tageous to use was one part to 400 parts of strong alcohol or 0.35 per cent.of caoutchicene. The spirit used in all the expe-riments to be described was of specific gravity0.828. Such a mixed spirit becomes milky and opaque when diluted with water but it is remarkable that the caoutchicene exhibits no disposition to separate as an oil and come to the top even when allowed to stand at rest for many days. Nor was the oil removed from the diluted mixture by agitation with tlie solvents of caoutchicene such as benzole and colza oil. Filtration of the diluted mixture through wood charcoal removes the oil in part but the caoutchicene odour remains seemingly unreduced in intensity. This mixed spirit when distilled with one-eighth of its weight of potash still retained the taste and odour of caoutchicene unaltered.When distilled with the same proportion of sulphuric acid the odour of the mixed spirit was slightly modified but still remained very decided. The odour of cacutchicene was not removed from the mixed spirit by chlorine. 500 measures of this mixed spirit were diluted with 250 measures of water which produced hrbidity and distilled by a water-bath. The distillate first collected amounting to 166 measures was of specific gravity 0.869; it became turbid by water had the rank odour of caoutchicene and was quite unpotable. The second portion of the distillate amounting to 380 measures of sp. gr. 0.888 was less offensive but its odour was still peculiar and disagreeable; the taste of caoutchicene was also sensible and persistent.This distillate became milky with water and the odour was then more repulsive. The third portion of the distillate which contained all that remained of the alcohol amounted to 62 nieasures of sp. gr. 0.955. It was turbid from the more fixed oils having distilled over and possessed the strong taste and odour of caoutchicene. The second distillate described above as amounting to 380 measures of sp. 0.888,was again diluted with half its bulk of water and re-distilled at 212'. The first portion of distillate amounting to 166 measures of spagr. 0.893 became very turbid with water and had THE SUPPLY OF SPIRIT OF WINE FREE FROM DUTY. 123 a highly decided odour and flavour of caoutchicene becoming insup- portable on the tongue after evaporation of the alcohol.The second portion of the distillate amounting to 177 measures of sp. gr. 0,930 was still decidedly marked by the odour of caoutchicene particularly on dilution when it became only slightly opalescent This which was the most highly purified portion of the distillate was evidently a spirit which would not be saleable as a beverage. In another experiment 500 measures of the mixed spirit containing caoutchicene were first distilled and 420 measures drawn off. This distillate became turbid with water and had the offensive odour of caoutchicene. Mixed with half its bulk of water the liquid was redis- tilled and three fractions collected. The first distillate amounting to 182 measures of sp.gr. 0.875 became milky with water and retained the repulsive odour and taste of caoutchicene in a stiiking degree of intensity. The second fraction amounting to 297 measures of sp. gr. 0.905 became opalescent with water and had a distinct odour not very unpleasant and a taste allied to that of a minthy essential oil. The odour and taste became more highly marked on the addition of water. The third distillate amounting to 288 measures of density 0.987 and very aqueous was offensive in taste and odour. The second fraction above which was the most highly purified portion of the liquid was itself submitted to a new distillation and brought over in three portions of sp. gr. 0.865 0,866 and 0.905 respectively. All of them retained a decided taste and odour of caou tchicene.These experiments show that much of the caoutchicene in the mixed spirit can be separated by repeated distillations but that a portion adheres to the alcohol with considerable pertinacity. Enough of the caoutchicene appears to be retained in all circunmtances to render the alcohol unpalatable as a beverage. On the other hand the intense and disagreeable odour of spirit so mixed would considerably limit its applications. The odour would not be tolerated in dwelling- houses nor in shops and warehouses frequented by the public and the use of the mixed spirit would probably therefore be confined to manufactories. Our attention has been particularly directed to wood-naphtha (crude pyroxylic or methylic spirit) as the substance to be added to alcohol by the previous experiments of Mr.G. Phillips and of Dr. Hofmann on the use of that liquid. The application of crude wood-naphtha depends partly upon the empyreumatic oils which it contains and partly upon the methylic spirit and other substances miscible with water which constitute the mass of the liquid. It was necessary to examine separately the influence of these two classes of constituents and first of the enipyreumatic oils. In one series of experinients a specimen of the oils which had been 124 PROFESSOItS GRAHAM HOFMANN AKD HEDWOOD ON separated from wood-spirit in the process of purifying that liquid was used as the flavouring substance. Two per cent of these oils were dissolved in spirits of wine.This mixed spirit had the strong charac- teristic odour of crude wood-naphtha became milky when mixed with water and was highly unpalatable. When this mixed spirit without any addition was simply distilled by the heat of a water-bath a mall quantity of' a dark-brown tarry matter was left behind in the retoyt aiid the proportion of oils in the distilled spirit was greatly reduced. The inixcd spirit appeared to be further purified when distilled froiti anhydrous sulphate of copper frotn the protosulphate of iron or from persulyhate of iron. But none of these distillates was potable aid all became turbid with water. The flavour of the same mixed spirit was iniprovecl by distillation with one-eighth of its weight of sulphuric acid but the liquid was still not potable.When the last distillate was again rectified from one-twentieth of its weight of potash the raiik orlour of the oils dis- appeared in a great measure the odour now retained resenibling that of benzole. An attempt was mide to rcmovc the odour last described. by diluting the liquid with water and passing it in the state of' vapour over animal charcoal ; but the liqnid still retained the benzole odour and was precipitated by water. The greatest amount of puritication was obtained by distillation from potash or lime the alkali keeping back the creosote; but the mixed spirit still retained the tarry smell of benzole and was turbid with water. When the mixed spirit so far purified by means of alkali was diluted with water and again distilled tlic first half of the new distil- late was turbid with water and even forliied a layer of oil on the surface.But the second half of the distillate did not become turbid with water showing that the benzole product comes off first. This last portion of the alcohol appearing to be restored to a fair degree of purity it became doubtful whether much dependence could be placed upon the oils of wood-naphtha for the purpose of mixing apart from the methylic spirit of the naphtha. An experiment was made with pure benzole itself mixed in the proportion of one part of benzole to ninety-nine parts of strong alcohol. A considerable portion of benzole was separated from this mixture by dilution with water the benzole forming an oily film on the surface of the liquid.The liquid how-ever continued milky and retained a strong odour of benzole. When this mixed spirit was diluted with three times its volume of water and slowly rectified the first part of the distillate contained much benzole and became milky with water ; while the second half of the distillate did not become turbid with water and appeared to contain very little benzole. This result affords a very strong presumption that benzole is removable by rectification from alcohol when diluted with water. Three additional and still more extensive series of experiments were j~dc by ineans of different varietics of crude wood-naphtha as this substance varies considerably in coin posit ion. Two of the varieties were procured from Rlessrs.Turnbull and Co. of Glasgow one of' which was described as '' of full strength but concentrated without dcstroying the oils ;" the other described as taken '(at an earlier stage of the process half strength and containing more oils than the last." The third material operated upon was a mixture of strong alcohol with five per cent of crude naphtha prepared at the laboratory of Inland Revenue by XIr. Phillips. But after what has been already said it is unnecessary to enter into the details of these experi- ments as the results were similar to the first series. The oils were in a great measure removed from the mixed spirit by simple distillation or by distillation from potash and the distilled spirit was chiefly characterised by the taste and comparatively mild odoiir of methylic spirit or pure wood-spirit.The specimens became as little offensive as alcohol mixed with Tu rn b ull's purified wood-naphtha ; and there appeared therefore to be no great advantage in using the crude naphtha for mixing in preference to a purer wood-spirit. The question reduced itself to the applicability of pure wood-naphtha for the object in view. The wood-naphtha hereafter used for niixing with alcohol was of the comparatively pure quality in which it is supplied to the public by Messrs. Turnbull and Co. at the price of 8s. 6d. per gallon. This wood-naphtha was nearly colourless ; it mixed with water without bcconiing turbid in the least degree and contained no more than a small trace of the oils which givea rank and repulsive odour to inany specimens of wood-naphtha.The odour of this purified wood-naphtha was not disagreeable although well marked and characteristic being due principally to methylic spirit. The specific gravity of tbis naphtha was 0.815 and its boiling point 151' F. When thoroughly dehydrated by being distilled three times from half its weight of anhydrous sulphate of copper one gallon of the liquid gave by frac- tional distillation the following series of liquids each amounting to about a pint :-1st distillate of sp. gr. 0.8067; boiling point 14Y.6' F. , 2nd Y ) 0.8047 ,) 143.3' ,, 3rd ? ) 0.8031 , 146.5' ), 4th 9 ) 0.8028 , 146.5' , y 99 5th ) 0.8016 , 1-1.8' 6th , , 0.8008 ) 15O0 y Y> 7th , , 0-8009 151O > 9, 8th , 0.8015 151' , Fractions 1 and 2 distilled again together from anhydrous sulphate of copper retained the low boiling point 143*5O,and had the mean density 0,8057 which is a liquid possessing the lowest boiling point that has been assigned to niethylic spirit but with a somewhat higher 126 PROFESSORS GRAHAM HOFMANN AND REDWOOD ON specific gravity the specific gravity of pure methylic spirit being about 0.800.None of the fractional portions appears to be a single substance. The methylic spirit is probably accompanied in the earlier fractions with acetone of sp. gr. 0.792 aud boiling at 132*8O and acetate of methyl of sp. gr. 0908 and boiling at 144O; while some third liquid of which the nature is unknown must be present to impart the high boiling point combined with a low specific gravity which distinguishes the later fractions of the distillate The presence of five per cent.of this purified wood-naphtha in strong alcohol is easily recognised by its taste and odour and is more than sufficient. to render spirit unsaleable as a beverage as has been ascer- tained upon good authority. At the same time the odour of the niixed spirit on evaporating in air is by no nieaus offensive. In solvent power such a niixed spirit is undistinguishable from pure alcohol ; and varnishes made by means of it dry readily and acquire no odour or peculiar character from the menstruum. Farther no practicable means of separating the methylic spirit again and recover- ing the spirit of wine in a state of purity and suitable as a beverage appear to exist ; while the substance which destroys the potability of the mixed spirit without impairing its value for many useful purposes is not itself poisonous or unwholesome,-wood-naphtha as is well known having been used to some extent in medicine.The purified wood-naphtha appears indeed to be singularly well adapted for the preparation of a mixed spirit such as the Government desires to supply duty-free to manufacturers. At the same time a mixed spirit containing ten per cent. of the purified wood-naphtha appears to be preferable to a five per cent. mixture from the greater facility of recognising the wood-naphtha in the larger proportion particularly when disguised by the presence of other volatile and odorous substances.A ten per cent. mixture might therefore be issued in the first instance and the proportion of wood-naphtha be reduced at a later period if it was found that the change could be made with safety to the revenue. It is accordingly a ten per cent mixture which we have had tested for the various useful applications of alcohol because if this mixture was found to meet the requirements of trade the suitability for the same purpose of any mixture containing a less proportion of wood-naphtha might be easily assumed. Although wood-naphtha (methylic spirit) and alcohol are of unequal volatility there being a difference of about thirty degrees between their boiling points yet no sensible separation of these liquids can be effected by distillation.Both the five and ten per cent. mixtures described were submitted to fractional distillation ;but wood-naphtha was found in all the fractions. Even the last eighth portion of the five per cent. mixture which was not distilled over .but was left behind in the retort contained abnndance of wood-naphtha the more volatile constituent. In another experiment to be described in the THE SUPPLY OF SPIRIT OF WINE FREE FROM DUTY. 127 sequel rectification repeated several times failed equally to eliminate the smallest portion of pure methylic spirit from the mixed spirit. The reason of this is that alcohol which boils at the higher temperature has a denser vapour than methylic spirit in the proportion of 1.600 to 1.125.The less volume of alcohol vapour which distils over at the boiling point of the mixed spirit is compensated for by the greater weight of that vapour YO that the proportion between the constituents of the niixed spirit appears to be little if at all disturbed during the progress of the distillation. The similarity in chemical constitution of methylic spirit and spirit of wine both being alcohols is attended with a remarkable analogy in properties between the two substances which appears to render their separation by chemical means also a problem of great if not insuperable difficulty. Methylic spirit forms a solid crystalline compound with chloride of calcium,-a property which is taken advantage of in purifying methylic spirit for scientific purposes from the other liquids by which it is accompanied in wood-naphtha.Our mixed spirit being first carefully dehydraied by means of sulphate of copper and reduced to a specific gravity of 0.801 was then mixed with chloride of calcium in excess so as to form a thin paste and distilled by a water-bath heat. Methylic spirit was easily discernible by its odour in the distillate which came over ; so that the presence of ordinary alcohol in a large relative proportion appears to prevent the combination of methylic alcohol with chloride of calcium or to decompose such a compound when formed for ordinary alcohol as well as methylic alcohol has a considerable affinity for the salt in question. When water was sub- sequently added to the chloride of calcium nearly dry in the retort and the heat renewed a liquid came over which possessed a peculiar and disagreeable odour but appeared to be chiefly composed of ordinary alcohol.This liquid should have been methylic spirit if the experiment of separation had been successful. The attempt was also made to purify the alcohol of our mixed spirit from its accompanying methylic spirit by passing the vapour of the two liquids through a long glass tube containing fragments of chloride of cdlcium which was kept at a temperature of 212' during the experiment. No absorption however of the methylic spirit by the chloride of calcium occurred but the salt remained unaltered and the alcohol distilled over and condensed with its original proportion of methylic spirit. Several experiments were also made on the oxidation of the mixed spirit by means of various proportions of the mixture of bichromate of potash and sulphuric acid with the view of oxidising andremoving the methylic spirit ;but without success.The oxidation products were acetic acid and formic acid accompanied by much aldehyde and indi- cated the decomposition of the alcobol as well as of the niethylic spirit. 128 PROFESSORS GRAHAM HOFFMASN AND REtbWOOD ON Sulphuric acid is very useful for discovering the presence of common alcohol when mixed with wood-spirit from the ready production of ordinary sulphuric ether. But for the converse problem of separating a small proportion of wood-spirit from a large proportion of alcohol sulphuric acid appeared to be wholly inapplicable.Oxalic acid employed to etherise the mixed spirit seemed at first to promise better results as the methylic oxalic ether appeared to form more easily than the corresponding ethylic ether. After the cohoba- tion of the dehydrated mixed spirit with oxalic acid for several hours the liquid which came over on distilling was alcohol with the propor- tion of methylic spirit apparently considerably reduced. This alcohol always contained portions of the oxalic ethers and was liable to become acid from the gradual decomposition of these ethers. The flavour of the methylic spirit which is at first covered by the rum-like flavour of these ethers would no doubt come out with time and prove as usual highly disagreeable. No economical process for the purifi- cation of the mixed spirit could we believe be founded on the action of oxalic acid.The conclusion from much investigation is that the removal of wood-naphtha from the ten per cent. mixed spirit and the restoration of its potability by any simple and economical process is a most un- likely occurrence. We apprehend no danger whatever to the revenue from this source. The mixture of spirits of wine with ten per cent. of purified wood-naphtha or methylic spirit which we commend may be designated nzetli ylatrd spirit for convenience. The quantity of wood-naphtha which can be commanded appears to be amply sufficient for the new conteniplated application of that sub- stance. We are indebted to Mr. John Turnbull for his valuable opinion on this point.“My calculation regarding wood-spirit,’’ that gentleman states “is a produce of two gallons and a half from a ton of average dry wood and the production of the United Kingdom amounts annually to 66,000 gallons. This I take as the proceeds of nineteen manufacturers of pyroligneous acid although you must re- ceive it as a rough guess still I believe it is not very far from the truth.” Much wood-naphtha is also attracted to this country from the continent owing to the high price which that liquid obtains here as a substitute for alcohol. We have been favoured with the opinion of Mr. G. Smith of Whitechapel one of the most extensive London distillers on the application of our methylated spirit as a beverage. He pronounces the methylated spirit to be quite unfit for the use of the rectifier.He believes also that publicans would never use such a spirit for mixing with their liquors even in a small proportion. A mixture of byin with one-eighth part of the methylated spirit was found to be nauseous and unpalatable. In gin mixed with one-sixteenth of me-thylated spirit the flavour of the latter was still very strongly marked. THE SrPFLY OF SPIRlT OF WINE FREE FROM DUTY. 129 In gin with one part of methylated spirit in thirty-two the flavour of the methylic spirit became faint but it was still perceptible in a tiiis- ture of one to sixty-four. The largest proportion of the methylatcd spirit which it was thought a publican might venture upon adding to his gin was one.in thirty-two. Now the saving to him would be the same fraction of the spirit duty or proportion of 6s. 3d. per gallon the duty on spirits of the strength of gin-that is a profit of 2id. per gallon. So small a profit mould be no compensation for the deterioration in the quality of the gin. The disagreeable odour of the methylic spirit is brought out strongly on mixing the gin with hot water. The consumption of sweetened and highly-fla\ oured cordials appears to be greatly inferior to that of gin ; a puhlican in large business who map retail 1200 gallons of gin per month not disposing of' more than ten or twelve gallons of cordials in the same time. 'he substances chiefly used in flavoixring cordials are caraway cloves and aniseed. The methylated spirit could not be used for any of these liquors.Indeed from their being generally made use of to give an extempore flavour to gin at the option of the customer more. than usual atten- tion must be paid to their own purity of flavour. The flavour of brandy is too delicate to be tampered with by the addition of the smallest proportion of methylated spirit. The addition of the latter substance to whisky would require to be guarded against from the predilection of the consumers of that spirit for a smoky flavour. An experiment has been related to us in which methylic spirit was employed for the sake of its fla\our by a Scotch distiller and mixed with spirits in the minute proportion of one gallon to 1000 gallons. The flavour although not objected to in the whisky when newly mixed became rank and disagreeable in the course of two months.The mixing of rnethylated spirit with that low quality of' ruin known as Leeward Islands rum is also to be apprehended from the great impurity of that spirit which would render any additional contamination less obvious to the palate. But when the liquid is deliberately examined the presence of methylic spirit could not escape detection. Strong alcohol of not more than 0.830 specific gravity should be employed as the basis of the methylated spirit. As the uniformity in quality of the wood-naphtha employed for mixing is important it should be approved of by the Excise and also added to the spirit under tbe inspection of an excise officer. It appears to us that it would be proper to mix the spirit in the distillery and to declare illegal the possession of the methylated spirit by a rectifier or publican.The retail sale of the methylated spirit would then fall into the hands of oilmen and druggists who would-be supplied directly by the distiller or through the agency of a wholesale druggist or drysalter. VOL. VII1.-NO. XXX. K 130 PROFESSORS OEAHAM HOFMANN AND REDWOOD ON Although it appears scarcely probable that the titethylated spirit will ever find its way into public-houses it is nevertheless desirable to possess means by which in cases of misapplication the presence of wood-naphtha could be readily detected and proved in the suspected liquid. The methylated spirit which was operated upon consisted of ninety measures of spirits of wine of density 0-828,mixed with ten measures of wood-spirit of density 0.815 and had a density of 0-823,as has been alreated stated and boiled about 170'.When the methylated spirit was deprived of all water by distillation from anhydrous sulphate of copper it boiled at 169'. These temperatures are both very sensibly under lf2'5 the lowest temperature at which absolute alcohol or any mixture of pure alcohol and water can boil. The possession by a sample of spirits of a lower boiling point than the last would indicate sophistication particularly if the low boiling point was retained after rectification of the spirits from sulphate of copper and the fwt would suggest the existence of wood-naphtha in the spirits.The attempt to identify wood-naphtha in spirits by means of chemical tests must obviously be attended with great difficulties ; for the very applicability of wood-naphtha for the purpose of producing an unpotable mixture which can be given to the public without fear of endangering the revenue excludes the possibility of an easy separation of the two substances; and it may be at once stated that the experi- ments made with tbe view of finding an efficient chemical process for the identification of methylic spirit have been unsuccessful and deserve to be noticed chiefly as affording additional illustrations of the safety of the mixture which is proposed. Fortunately methylic spirit even when highly purified,* so as to become deprived of all the tarry and empyrcumatic smell which it generally exhibits posscsses so characteristic and persistent an odour and taste that after a little experience it is not difficult to detect its existence even when it is highly diluted or masked by the presence of other flavours.Among the properties of the two alcohols on which possibly a separation might be founded the different volatility of the two liquids at once suggested itself absolute boiling alcohol at 173' Pahr. whilst absolute methylic spirit boils at 143' Fahr. In order to test this process half a gallon of the methylated spirit was submitted to distil- lation at a comparatively low temperature and in an apparatus which allowed the less volatile liquid to condense. The first quart which passed over was again distilled the first part being collected apart and so on until at last one-sixteenth of the original bulk of the liquid was obtained as the most volatile portion.This liquid va,s repeatedly distilled over anhydrous sulphate of copper to remove any water which it might retain ;it was found to boil between 168O and 169' showing * By conversion into methyl-oxalate decomposing this substance by ammonia concentrating the reproduced spirit and rectifying over anhydrous sulphate of copper which retaina also the ammonia. THE SUPPLY OF SPIRIT OF WINE FREE FROM DUTY. 131 that the methylic spirit had been scarcely concentrated by this process. This fact which at the first glance appears contrary to general expe- rience has been already explained; it is due to a certain extent to the difference of the vapour-densities of the two alcohols; for it is obvious that the smaller amount of alcohol-vapour which forms during distillation on account of the higher bailing point of alcohol must be compensated within certain limits by the greater weight this vapour possesses when compmed With that of an equal bulk of methylic spirit vapour.The isolation of the methylic spirit by a series of fractional distil- lations having proved impossible the mixture mas now boiled for several hours with dehydrated oxalic acid in order to produce the osalates of methyl and ethyl. The difference in the boiling point of the two ethers (363°-3321=420) is not much greater than that which is observed with the alcohols from which they are derived.Oxalate of methyl being at the common temperature a solid crystalline substance while oxalate of ethyl (true oxalic ether) is a liquid it was hoped that the fractionation of the mixture of the two ethers might be more successful and that by repeated distillation at last a product might be obtained in which the more volatile methyl-oxalic ether should predominate to such an extent as to crystallise. Experiment however showed that the presence even of a minute quantity of the former ether prevents the latter from assuming the solid form. In studying the action of oxalic acid upon the methylic spirit it had been observed that if a smaller amount of oxalic acid be used than is necessary for the etherisation of the entire quantity of the mixture the methylic spirit appeared to be converted into ether with greater facility than the alcohol.Experiments were accordingly made with the view of isolating the methylic spirit by means of this reaction. The mixture was partially etherised by oxalic acid and then submitted to distillation in order to separate the alcohol which had not been acted upon by the acid. The residuary liquid consisting chiefly of methyl-oxalic ether was decomposed by distillation with water. Thc reproduced spirit certainly contained a larger amount of methylic spirit than the original mixture ; nevertheless the quantity of alcohol which it retained was so considerable that the advantages gained by the process did not appear to be in proportion to the amount of time and labour which its practice requires.A further concentration might be obtained by a repetition of the process; but this would render it so tedious and troublesome an operation as to preclude the possibility of using it as a routine test for the purpose of recognising the presence of pethylic spirit in a suspected liquid although the process might be available for identifying and isolating that substance in cases of dispute. Under the influence of oxidising agents methylic spirit furnishes together with other products a considerable amount of formic acid 152 PROFESSORS GRAHAM HOFMANN AND REDWOOD ON whilst alcohol under these circumstances yields principally acetic acid. Formic and acetic acids although closely allied in composition and general characters still offer a greater number of points of diffe- rence than the two alcohols which they represent.Formic acid may be readily distinguished from acetic acid by the facility with which the former precipitates the metals from the solutions of the more easily reducible metallic oxides such as oxide of silver or oxide of mercury which are not affected by acetic acid. Unfortunately this method of testing became inapplicable since it was found that alcohol free from methylic spirit when sizbmitted to the action of oxidising agents invariably yields in addition to aldehyde which can be resinified and removed by potash a small quantity of formic acid; so that the presence of formic acid among the products of oxidation of a suspected liquid cannot with certainty be regarded as an evidence of the existence of methylic spirit in the original liquid.It is well known that ordinary alcohol when heated with an excess of concentrated sulphuric acid furnishes in addition to sulphurous acid a considerable amount of olefiant gas. Methy!ic spirit under the same circumstances Fives rise to the formation of a heavy oily liquid which is insoluble in water and consists chiefly of the neutral sulphate of methyl. The same liquid was obtained together with olefiant gas and sulphurous acid when the methylated spirit was dis- tilled with eight or ten times its weight of concentrated sulphuric acid. But on careful examination it,was found that alcohol alone when submitted to similar treatment yields likewise in addition to olefiant gas the chief product of the reaction a small quantityof oily products (heavy oil of wine &c.) ; so that the production of an oily substance from a suspected liquid by the action of an excess of sul- phuric acid ceases to be an indication of the presence of methylic spirit in such liquid.The action of sulphuric acid upon the two alcohols produces a very different result if the latter are iu excess. Alcohol and methylic spirit under these circumstances exhibit the same deportment the former yielding ether (common sulphuric ether) while the latter is converted into methyl-ether. It is however well known that the etherisation of common alcohol proceeds with far greater ease than that of me-thylic spirit.Accordingly the methylated spirit. was snbmitted to the ordinary continuous etherisation-process (ten parts of wood-spirit being successively exposed to one part of sulphuric acid). It was expected that after the evolution of the ether capable of being formed under these circumstances the methylic spirit woiilcl remain behind as sulphomethylic acid. But the residue neutralised with lime and distilled with water or with solution of potash furnished no spirit, but an aqueous liquid in which no methylic spirit could be detected. When anhydrous baryta is dissolved in dehydrated metliylic spirit a combination is formed which crystallises in lustrous needles and THE SUPPLY OF SPIRIT OF WlNE FREE FROM DUTY. 233 consists of equal equivalents of rnethylic spirit and baryta.This substance was found to resist the action of water ; even when boiled with water it gave up no rnethylic spirit. It was possible that alcohol might differ in this respect; but although no crystals were observed nevertheless a similar corn pound with analogous properties appeared to bc formed a solution of anhydrous baryta in abso- lute alcohol when distilled with water yielding scarcely a trace of alcohol. Lastly a few experiments were made with the view of establishiug the presence of methylic spirit in alcoholic mixtures by the dark yellowish-brown colour wood-spirit assumes when left for some time iu contact with either solid hydrate of potash or soda. But it was found that the brown coloiir assumed by niethylic spirit was only little niore intense than that which alcohol shows when similarly treated.Moreover it seems to be chiefly clue to the impurities the colouration becoming less and less marked the greater the care bestowed upon the purification of the rnethylic spirit; the pure inethylic spirit obtained by decoinposing methyl-oxalic ether show-ing within a moderate time no colouration whatever either wher left in contact in the cold or when boiled with solid hydrate of potash or soda. The principal uses to which spirit of wine is or may be applied independently of its use as a beverage appear to be the following:- As a solvent of resinous substances which when thus dissolved are used in the manufacture of hats and otherwise as varnishes.As a solvent employed in the manufacture of many chemical preparations including the alkaloids and other organic products which are prin- cipally used in medicine. For the production of ether chloroform sweet spirit of nitre and fulminating mercury. For burning in spirit-lamps as a source of heat and for mixing with 011 of tur-pentine or other hydrocarbons for burning in lamps as a source of light. As a solvent and menstruum for administering the active constituents of animal and vegetable substances used in medicine in the form of tincture spirit &c. As a solvent of essential oils and other odorous substances used in perfumery. 1. Spirit of wine is largely used for dissolving the resins employed by hatters and varnish-makers. In the manufacture of hats shellac dissolved either in spirit of wine or in impure methylic spirit (known as wood-naphtha) is used for giving stiffness and elasticity to the felt or other foundation of the hat and for causing the adhesion of the nap.When wood- naphtha is used for this purpose it is necessary to make a selection of those commercial samples which are found to be most suitable. Some varieties of wood-naphtha are imperfect solvents of the resins and are therefore inapplicable for the purpose but even among those 134 PROFESSORS QNAHAM HOPMANN AND REDWOOD ON samples which freely dissolve the resins there is much difference in quality commercial methylic spirit being always a mixed and very variable product some of the coristituerits of which exert an injurious effect in the varnishes made with it.Spirit of wine is preferivd to wood-naphtha for hat-making being in the state in which it is met with in comnierce more uniform in quality and less conteami- natd with foreign matters. Hatters state that when the felt has been stiffened with shellac dissolved in spirit of wine the felt retains its elasticity after it has been dried and hardened without being much affected by atmospheric changes or exposure to wet and it does not readily crack or break on being bent. But when the felt has been stiffened with shellac dissolved in naphtha the hat while it retains its stiffness is liable to crack on being bent and it readily loses its stiffness and elasticity when wetted or exposed to a damp atmo-sphere.Wood-naphtha is therefore used only on account of its low price the quality of the hats in the manufacture of which it has been used being inferior to that of hats made with solution of shellac in spirit. In those instances in which from competition in price the hat-maker is obliged to use wood-naphtha it is found necessary to use more shellac than would be required if spirit of wine were the solvent in order to give the required stiffness and elasticity. The weight of the hat is thus increased wmetinies to the extent of several ounces in order to compensate for the deteriorating effect produced by the naphtha. English hatters generally complain that they have to compete with foreign makers under a disadvantage in consequence of the high price of spirit in this country.In the manufacture of spirit vurnishes which are applied to other purposes than that of hat-making both spirit of wine and naphtha are used for dissolving the resins. Among the varnishes of this description are included French polish and lacquer the consumption of which as also of other spirit varnishes is very great. Varnishes made with spirit of wine are considered to be better in quality than those made with naphtha. With regard to French polish tho% who are practically engaged in the use of this varnish say that when it is made with wood-naphtha it is not so easily worked and does not afford so durable and serviceable a polish as that made with spirit of wine. The disagreeable smell evolved during the evaporation of the wood-naphtha is also objected to especially when the polish has to be applied to furniture in private houses or in the warehouses of upholsterers which are visited by customers.In the manufacture of lacquer for brass and other metals and of other sorts of spirit varnish there are also equally strong objections to the use of wood-naphtha as a substitute for spirit of wine. Hitherto the French have been considered to excel us in lacquered goods which may no doubt be ascribed to the superiority of their lacquer in the manufacture of which the. always use spirit of wine for dissolving the resins. Euglish THE SUPPLY OF SPIRIT OF WINE FREE FROM DUTY. 135 manufacturers on the other hand notwithstanding the inferiority of lacquer and other varnishes made with wood-naphtha use large quan- tities of that solvent ; in proof of which an extensive varnish-maker informed us that his consumption of wood-naphtha was equal to that of spirit of wine.There is reason to believe that if spirit were sup- plied to manufacturers duty-free the use of spirit-varnishes would be greatly extended and varnished ornamental woods would frequently be substituted for painted deal. Among the purposes to which spirit varnishes would be more generally applied if spirit were cheaper may be mentioned the mmu-facture of paper-hangings and especially those in which imitation gold leaf ('I leaf metal") is used which unless protected with varnish soon become tarnished by the sulphuretted hydrogen always present in a town atmosphere.Not only for gilt papers however but fol* many others and especially t,hose used iu staircases would the appli- cation of a good spirit varnish be advantageous. Another application of spirit-varnish woiild be in the production of' waterproof papers to be used as wrapping-paper for steel goods for the construction of envelopes for transmission by sea for the manu- facture of military cartridges &c. Among the productions of' ornamental stationery there is a class of paper with embossed patterns originally called Morocco paper but which on account of the variety of the patterns now appear under the more general designation of varnished papers which are very extensively used especially for book-binding and for cardboard box-making; and in the production of these papers the English manu-facturer is at present precluded by the high price of spirit of wine from the use of spirit varnish.It is admitted that this manufacture would be greatly improved by the employment of spirit varuish as the papers when made as at present with oil varnish are not aclaptcd for exportation on account of their liability to become heated and to adhere together. In some of the applications of leather the employment of spirit varnish would be a great advantage especially in book-binding. At present its use is restricted. by the high price of spirit to the better class of bound books; but its ernyloynient not only increases the beauty of the work but serves to protect the leather; and there can be no doubt that if spirit were cheaper its use for this purpose would be greatly extended.In the application of spirit of wine as a solvent of resinous subr stances for the purposcs already referred to it is not necessary that the spirit should be pure; but it is important that whatever foreign inatter my be mixed with it shall volatilise without producing a very disagreeable odonr and that the resins shall be left after the drying of the varnishes uriinipnired it1 quality and free from any offcnsive sniell dcrived from thc solveiit. 136 PROFESSORS GRAHAM HOPMANK AKD REDWOOD ox There is reason to believe that a considerable quanity of illicit spirit is supplied to a certain class of hatters and varnish-makers to the injury of the revenue and of the honest manufacturer.We are informed that this illicit spirit is sold for about 1:h per gallon at 60 overproof. As the employment of spirit for dissolving resinous substances appears to be the most extensive and important of its applications in the arts and manufactures it was necessary to ascertain whether spirit mixed in the manner proposed in this Report is applicable for such purposes. With the view of determining this point experiments were made by ourscIves and were also kindly undertaken at our request by gentlemen practically engaged in the several departments of matlufacture referred to. The results have fully satisfied us that the metliylated spirit is suitable for all these applications. We are indebted for much valuable assistance in reference to this part of our inquiry to Xfessrs.J. T. and E. Christy and Co. and Messrs. Cooper Box and Co. hatters; to Mr. Rea and Mr. Heywood \arnish-~nalws and to Mr. Warren De la Rue. 2. Spirit of wine is employed as a solvent iii the manufacture of nimy chemical preparations including the alkaloids and other organic products which are principally used in medicine. In manufacturing the alkaloids derived from the cinchona barks spirit is used in one part of the process. Indeed alcohol appears to be the bcst and most general solvent for this class of substances. It is used in the IIIanufacture of veratrine and is required for crystallising morphine although this alkaloid may be prepared from opium without spirit. It has hitherto been the object of English manufacturers to discover processes for the preparation of chemical products without the use of spirit and such processes are sometimes adopted to the injury of the product.Spirit of wine may be advantageously used in the pre- paration of some inorganic salts such as protosulphate of iron which when precipitated from its aqueous solution by means of alcohol is less subject to change from exposure to the air than it is when crystalliaed in the usua1 way. The resinous constituents of jalap and scammony which are used in medicine are separated from the drugs by means of spirit of wine and the use of this solvent might no doubt be greatly extended for siniilar purposes with advantage. In some cases the manufacture of chemical products has been lost to English mantifacturers in consequence of the high price of alcohol or of ether which is made from alcohol.Thus pure tannin the prepa- ration of which involves the loss of a large quantity of ether is imported from abroad at a price at which it cannot be produced at home. Among this class of productions involving the use of spirit of wine as a solvent may be mentioned transparent soap a pure and elegant preparation for the toilet which is much used in those countries in which alcohol is cheap but which from the THE SUPPLY OF SPIRIT OF WINE FREE YROM DUTY. 137 high price of the solvent is but rarely made and little used in this country. For all the purposes here referred to the methylated spirit appears to be applicable.In addition to our own experiments we have been favoured with a statement of results obtained by Mr. T. N. R. Morson in the preparation of chemical products and by Mr. Pears in the manufacture of transparent soap. 3. Spirit of wine is used as an ingredient for the production of ether chloroform sweet spirit of nitre and fulminating mercnry. These are important articles of manufacture t.he first three articles being valuable medicinal agents and the last-named being used for making percussion caps for fire-arms. Ether and chloroform are also made use of on account of their solvent power especially the former. Sweet spirit of nitre is used exclusively in medicine but being a popular remedy the quantity used is very considerable. We map state with reference to this article that it is made by distilling a mixture of spirit of wine and nitric acid and that when properly prepared it consists of a solution of a sniall quantity of nitrous ether in spirit of wine.The proportion of nitrous ether present is extremely variable and in some commercial samples is so small as merely to impart a slight favour to the spirit which flavour moreover is by no means disagreeable. From information derived from those practically acquainted with the conimerce of this article it may be inferred that a large proportion of the sweet spirit of nitre now used is made from illicit spirit the price at which the wholesale dealer can purchase sweet spirit of nitre being less than that at which it can be produced with spirit on which t>he duty has been paid.It is scarcely to be expected that spirit which has been rendered permaneritly unpotable can be used for making sweet spirit of nitre as the peculiar and unobjectionable flavour of that compound is the popular test of its good quality. When made with the methylated spirit the compound acquires a disagreeable flavour which is more especially developed on diluting it with water ; and it is impossible to recovei. the alcohol again in a pure state from such sweet spirit of nitre. On the other hand the separation of pure alcohol from good potable sweet spirit of nitre such as the public are accustomed to use and require is attended with no difficulty. It appears improbable therefore that any regulations could be devised for the preparation of sweet spirit of nitre from duty-free spirit which could be adopted with safety to the revenue.Ether and chloroform may be made with the methylated spirit and when the products have been purified in the usual way they do not appear upon a superficial examination to differ from those made with pure spirit. Upon allowing them slowly to evaporate however a peculiar and disagreeable odour becomes perceptible towards the end of the evaporation. This impurity would probably preclude their 138 PROFESSORS GR.4HAR1 HOFMANN AND REDWOOD ON application for most medicinal purposes for which they are required to be pure or at least to be free from any foreign flavour either in taste or smell. When used as solvents the same degree of purity is not generally essential and we believe that ether and chloroform pro.duced from the mixed spirit are perfectly applicable for most manu- facturing purposes. Fulminating mercury is produced from mercury nitric acid and alcohol and in consequence of the large quantity of alcohol consumed in the process the price of the product is greatly influenced by the cost of this ingredient so that the English manufacturer has found it difficult to compete with those who can command cheap spirit. We are informed that most of the fulminating mercury now used in this country is either made from illicit spirit or is brought from the Channel Islands where the low price of spirit offers an advantage to the manufacturer. The rnethylated spirit is applicable for this manufacture.We have been aided in this part of our inquiry by the informtiou kindly afforded to us by Mr. Alfred White Mr. Charles Davy and Mr. F. Joyce. 4. A considerable quantity of spirit of wine is sold by retail dealers chiefly chemists and druggists for burning in lanips as a source of' heat including its application for singeing horses. It is also mixed with oil of turpentine or other hydrocarbons for burning in lamp as a source of light. The methylated spirit is quite suitable for such applications . 5. Spirit of wine is used as a solvent and menstruum for ad- ministering the active constituents of animal and vegetable substances used in medicine in the form of tincture spirit &c. These pre- parations being intended for the treatment of disease and their efticacy frequently depending upon the association of substances which from long experience have been found to contribute to the required result the unauthorised introduction into their composition of a new substance and especially one of so marked a character as methylic spirit cannot in any way be sanctioned.There is a large number of pharmaceutical preparations of the sort here referred to most of which are made according to formula given in the Pharma- copoeias a strict compliance with which is enjoined upon those who compound them. We cannot recommend the substitution of any mixture for the pure spirit directed to be used in making these preparations. 6. Spirit of wine ie employed 8.3 a solvent of essential oils and other odorous substances used in perfumery and it is scarcely necessary to say that the addition of anything to the spirit imparting to it an uu- pleasant odour must render it unfit for purposes of that description The methylated spirit therefore cannot be used for the preparation of perfumes.THE SUPPLY OF SPIRIT OF WINE FREE PROM DUTY. 139 7. The employment of spirit of wine in the manufacture of acetic acid by the German process of oxidation has been suggested as a possible result of the entire removal of the duty on pure spirit; but this appli- cation could not obviously be made of a mixed spirit such as has been contemplated in this inquiry. 8. The methylated spirit would serve for the preservation of objects of natural history and also for the purposes generally to which alcohol is applied in chemical research.It would remove an impediment to the prosecution of science in this country created by the high price of alcohol which has long been complained of. To recapitulate briefly the results of this inquiry- It has appeared that means exist by which spirit of wine produced in the usual way may be rendered unfit for human consumption as a beverage without materially impairing it for the greater number of the more valuable purposes in the arts to which spirit is usually applied. To spirit of wine of not less strength than corresponds to density 0.830,it is proposed to make an addition of 10 per cent. of purified wood-naphtha otherwise known as wood-spirit pyroxylic spirit and methylic spirit and to issue this mixed spirit for consump-tion duty free under the name of ‘I Methylated Spirit.” It has been shown that methylated spirit resists any process for its purification the removal of the substance added to the spirit of wine being not only difficult but to all appearance impossible ; and further that no danger is to be apprehended of the methylated spirit being ever com- pounded so as to make it palatable.The privilege of using such mixed spirit should be open to all branches of the arts and manu- factures without restriction; but it may be expedient to prevent the sale of methylated spirit in licensed public-houses or the preparation and sale of it by the licensed rectifiers of spirits. The wood-naphtha employed in mixing should be supplied by the Inland Revenue in order to ensure uniformity in its quality and that substance be mixed with the spirit at the distillery under Government inspection.The permission to use pure spirit of wine for any purpoae of manufacture under a bond of security or in presence of a revenue deer may reasonably be withheld till the methylated spirit now proposed has had a fair trial. It may be found safe to reduce eventually the pro-portion of the mixing ingredient to 5 per cent. or even a smaller proportion although it is recommended to begin with the larger proportion of 10 per cent. The present supply of wood-naphtha is amply sufficient for the application contemplated of that substance for mixing with the spirits used in the arts and manufactures of the country.The command Pf alcohol at a low price is sure to suggest a multitude of improved processes and of novel applications which can be scarcely anticipated at the present moment. It will be €eek far beyond the 140 PROFESSOILS GRAHAM HOFMANN AND REDWOOD ON limited range of the trades now more immediately concerned in the consumption of spirits ; like the repeal of the duty on salt it .will at once most vitally affect the chemical arts and cannot fail ultimately to exert a beneficial influence upon many branches of industry. The same measure also practicaIly removes one of the last anomalies in the duties imposed €or revenue; alcohol having as a raw material of manufacture a claim to exemption from duty according to sound principles of taxation.We have the honour to remain Sir Your very obedient Servants THOMAS GRAHAM. A. W. HOPMANIN. THEOPHILUS REDWOOD. London July 24 1854. JOHN Esq., WOOD Chairman of the Board of Inland Revenue. Inland Revenue 2d November 1854. C:E NTLEv EN,-= As I am informed that it is your intention to add some remarks to your report on the supply of spirit of wine duty-free for use in the arts and manufactures I take the opportunity of requesting your attention to the passage in page 8 of the Report in which you state in effect that as the oils in crude naphtha are removable from the mixed spirit by a process not very difficult the question is reduced to the applicability of pure wood-naphtha for the object in view I am not entirely convinced that the question is thus narrowed.We have two objects first to prevent the recovery of spirit of wine from the mixture in such a state of purity as to render it potable ; and second to render tbe mixed spirit so offensive as to prevent. any temptation to its use among the workpeople who will necessarily have access to it in the. manufacturing processes in which it will be em-ployed. Now it is obvious that the use of crude naphtha produces a more offensive mixture than that of the pure naphtha ; and that it would probably be so offensive as to preclude its consumption by workpeople ; arid this would be an important point gained. It is also obvious that any attempt to render it potable (as an article of conimerce) would be more troublesome and expensive.THE SUPPLY OF SPIR.IT OF WINE FREE FROM DUTY. 141 The question then remains whether the crude mixture would be generally available in. arts and manufactures. This is a subject of great practical importance and I shall be much obliged by your attention to it and by the communication of the result of your inquiries. I am &c. Thomas Graham Esq. F.R,.S.A. 1..Hofmann Esq. F.R.S. Tlieophilua Redwood Esq. (Signed) JOHN WOOD. London 8th January 1855. SIR,-The observations which we desired to add to our “Report on the Supply of Spirit of Wine free from Duty for use in the Arts and Manufactures,” have reference to the mode in which the public is to be supplied with the spirit.On a review of the subject and after further inquiries among manufacturers and others we doubt whether it would prudent to permit at first the retail sale of the methylated spirit. It has been represented to us that the unrestricted sale of the spirit would cause it to get into the hands of individuals of perverted tastes who in extreme cases may use it for producing intoxication. Although we are satistied that such a misapplication of the methy- lated spirit could only occur in some isolated instances among persons of confirmed habits of intemperance yet it may be feared that even such cases would cause a public outcry against the measure before it had received a fair trial. We would therefore recommend that the niethylated spirit should be issued by agents duly authorised by the Board of Inland Revenue to none but manufacturers who should themselves consume it and that application shonld always be made for it according to a recognised form in which besides the quantity wanted the applicarrt should state the use to which it is to be applied and undertake that it should be applied for that purpose only.The maiiufacturer might be permitted to retail varnishes and other products containing the methylated spirit but not the niethylated spirit itself in pn unaltered state. in thus suggesting a restriction upon the sale of the rnethylated spit we must however express our belief that this limitation may eveiitually be removed with safety when the measure has been fairly and fully introduced.Our attention having been directed by your letter of the 2d Novem-ber 1834 to that part of our Report in which we recommend theuse of purified wood-naphtha rather than crude naphtha for preparing the methylated spirit we have instituted new inquiries on this part of the subject. 142 REPORT ON THE SUPPLY OF SPIRTT OF WINE FREE FROM DUTY. We have in the first place to state that the distinction of crude and purified wood-naphtha is not generally recognised in commerce. The term “crude wood-naphtha,” when used is understood to desig- nate a very impure sort of naphtha not in the state in which that substance is first produced but in a partially although very imper- fectly purified state. This product which is of a brown colour and contains tarry matter and oils which are not easily volatilized after being further purified constitutes the wood-naphtha generally met with in commerce and which we have referred to as purified wood- naphtha.The terms ‘(crude ” and “purified,” as thus applied have not any definite signification ; they we used to indicate an undefinable difference of purity the principal feature of which consists in the presence of more difficultly volatilized matter in the less pure than in the more highly purified article. We have further to state that the purification of crude naphtha to the extent to which this is effected for commercial purposes is not attended with any difficulty. Methylated spirit prepared with crude naphtha may also be rendered as free from taste and smell as that made with purified wood-naphtha by simple and inexpensive means.We have had a methylated spirit prepared (No. 1 of the specimens sent herewith) containing 10 per cent. of the crudest wood-naphtha we could procure and which was quite unsaleable. Now by a simple distillation from 10per cent. of potash this (as seen in No. 2) is highly purified so as to be quite equal if not superior to the rnethylated spirit made with Turnbull’s purified wood-naphtha as recommended in the Report. The cost of applying this purification of methylated spirit would be less than 1s. a gallon. We believe that if very impure wood-naphtha be used for making the methylated spirit the spirit so prepared will not fulfil the requirements of any class of manufacturers referred to in our Report unless the purification of the spirit before its use be permitted and such we presume would not be deemed advisable; if this purification was forbidden the honest manufacturer would obey the law and work to a great disadvantage as compared with his less scrupulous competitors who would resort to illicit purification.This of itself would be a great evil and one we fear quite beyond the powers of the Excise to pre-vent. We admit that the methylated spirit made with crude naphtha mould be more unpalatable than that made with purified wood-naphtha and that the latter would be more likely than the former to be drunk by the workmen employed in manufactories where such spirit was used; but as already stated we can only conceive it possible that such use would be made of methylated spirit by individuals of perverted taste and confirmed habits of intemperance; and in such instances we doubt if even the use of crude wood-naphtha would be sufficient entirely to prevent the evil.The conclusions we have come to as the result of our investigations BUNSEN ON THE PREPARATION OF LITHIUM. on this subject are that methylated spirit made with a very impure wood-naphtha could not be advantageously used as a solvent for resins by hatters and varnish-makers as the less volatile parts of the naphtha would be retained by the resins after the spirit had evaporated and the quality of the resins would be thus impaired and that such me-thylated spirit woulcl be almost wholly inapplicable for chemical and pharmaceutical purposes and for the preservation of objects of natural history.The benefits anticipated from the proposed measure would thus be greatly limited without as we believe any adequate advantage resulting either in increased security to the reveuue or otherwise. It is purified wood-naphtha and not the impurity which crude naphtha contains that presents the great and insuperable difficulty we have indicated to its separation froin spirit of wine with which it has been mixed ; in fact the more highly purified the naphtha is with which the spirit is mixed the more difficult it will be to effect an alte-ration of this mixture in the way contemplated by any chemical process ; and in proportion as this condition is fulfilled the mixed spirit will be more valuable for use in the arts and manufactures as a substitute for spirit of wine on the other hand the impurity which constitutes the difference between crude and purified wood-naphtha presents little or no difficulty in the way of its separation whilst for all purposes referred to it reiiders the mixed spirit contained in it less applicable and for some of those purposes it entirely precludes its applicaiion.We are therefore unable to recommend any alteration in the mode of preparing the methylated spirit suggested in our Report. THOMAS GRAHAM. A. W. HOFMANN. T. REDWOOD. To John Wood Esq. Chairman of the Board of Inland Revenne. On the Preparation of Lithium.* (Copy of a Letter addressed to Professor Liebig by Professor Bunsen.) DR.MATTHIESSEN is still engaged with the preparation of the metals of the alkaline earths.Out of the chloride of lithium which you had the kindness to send me I have with him reduced the metal. This which is more easily obtained than the other metals belonging to the same group can be preparea at the lecture-table with the greatest success. The method by which we prepare it is the follow- ing :-Pure chloride of lithium is fused over a Berzelius’s spirit lamp in a small thick porcelain crucible and is decomposed by a zinc coke battery consisting of four to six cells. The positive pole is a * Ann. Ch. Pharm. xciv. 10’7. BUNSEN ON THE PREPARATION OF LITHIUJM. small splinter of gas coke (the hard carbon deposit in the gas retorts) and the negative an iron wire about the thickness of a knitting needle.After a few seconds a small silver-white regulus is formed under the fused chloride round the iron wire and adhering to it which after two or three minutes attains the size of a small pea to obtain the metal the wire pole and regulus are lifted out of the fused mass by a small flat spoon-shaped iron spatula. The wire can then be withdrawn from the still melted metal which is protected from ignition by the chloride of lithium with whicii it is coated. The metal may now be easily takcn off the spatula with a pen-knife after having been cooled under rock-oil. As this operation can be repeated every three minutes an ounce of chloride of lithium may be reduced in a very short time.Lithium on a fresh cut surface has the colour of silver but tar- nishes after having been exposed for a fern seconds to the air and becomes slightly yellow. The melting point is 180' C. A piece of it at that temperature if pressed between two glass surfaces exhibits the colour and brightness of polished silver. Lithium is harder than potassium or sodium but softer than lead and therefore can be pressed out like that metal to wire. The specimen I enclose about a foot in length weighs only nine milligrammes. It tears much more easily than a lead wire of the same dirnensions. By pressure lithiuiii can be welded at ordiiiary temperatures it swims on rock-oil and is the lightest of all solid bodies. Its specific gravity is 0.5936 bcing the mean of two experiments.The first in which the chloride of lithium used was precipitated twice with carbonate of ammonia gave as result 0.5983; in the second the chloride was three times precipitated and gave 0.5891. If the atomic weight of lithium be taken at 81.7 its atomic volume is 13.7 being nearly the same as that of calcium. Lithiuni is much less oxidisable than potassium or sodium. All these metals mark paper. Potassium marks it whitish-grey and disappears first; then sodium which gives a bluish-grey tint ; and last of all lithium which marks it lead-grey. Lithium ignites at a temperature much higher than its fusing point ; it burns tranquilly with an intense white light. It burns when heated in chlorine oxygen bromine iodine or dry carbonic acid and on boiling sulphur with uncomnion brilliancy.When thrown on water it oxidises but does not fuse as sodiuni does. Fuming and common nitric acid act on it so violently that it fuses and often ignites. Concentrated sulphuric acid attacks it slowly but diluted sulphuric and hydro- chloric acids quickly. Silicic acid,- glass and porcelain are attacked by lithium at a temperature even below 200OC. BERTHELOT AND DE LUCA ON THE ACTION &C. On the Action of Iodide of Phosphorus upon Glycerine." By MM. Berthelot and De Luca. WHEN1part of crystallised biniodide of phosphorus and 1part of syrupy glycerine are mixed together a very energetic action soon takes place ;propylene C,H, is evolved in the form of gas ;water and liquid ioclopropy,Ze?ie C6H5I distil over; and there remains in the retort a solid mass composed of iodine undeconiposed glycerine a small quantity of an organic compound containing iodine together with oxygen-acids of phosphorus and a trace of red phosphorus.With 1eq. iodide of phosphorus and variable quantities of glycerine the products are 1 eq. iodopropylene and 4 eq. water. To obtain 1eq. of prdpylene-gas it is necessary to use from 9 to 18 eq. of iodide of phosphorus; hence the formation of propylene is but of secondary importance as compared with that of iodopropplene. The residue in the retort is of variable composition When 100 parts of iodide of phosphorus are niadc to act on 100 parts or moye of gly-cerine the products just nientioiied are formed and the residue consists mainly of glycerine; but when only 64 parts or a snialler quantity of glycerine is used to 100 iodide of phosphorus the residue in the retort consists of a black non-volatile insoluble mass ; the point at which this change in the reaction takes place corresponds nearly to the proportion of 2 eq.glycerine to 1 eq. iodide of phosphorus. Half the iodine of the iodide of phosphorus used contributes rather to the formation of the iodopropylene but reniains in the residue under various forms chiefly however in the free state. 'l'he prin-cipal reaction which iodide of phosphorus exerts npon glycerine appears to be that which is represented by the following equation :-PI,+2C,H,O,=P,H51+4 HO+I + (C6HY06+P0,-H0) the portion within the brackets representing the oxygen-acids of phosphorus mixed and combined with the excess of glycerine.The formation of iodopropylene is clue to a reducing action exerted by the iodide of phosphorus on the oxygen of the glycerine. Iodopropylene C6H,I constitutes the greater part of the dis- tillate obtained in this decomposition. The latter is rectifid and the liquid which passes over at 101' received in a separate vessel. Iodopropylcne thus obtained is a colourless liquid haviiip an ethereal and afterwards atliaceous odour insoluble in water solubll in alcohol and ether and of specific gravity 1,789 at 16O. * Compt. rend. xxxix. 745 j Ann. (211. Phys. [3] rliii. 257. VOL. VII1.-NO. xxx. L 146 BERTHELOT AND DE LUCA OX THE ACTION Or Fonnd.Calculnt ed. Carbon . . . 21.5 21.4 Hydrogen Iodine . . 3.2 75.7- 3.0 75*6- 100.6 100.0 Under the influence of air and light it quickly turns brown and then emits extremely irritating vapours. By the action of aqueous ammonia at IOO" coqtinued for forty hours iodopropylene is completely decomposed ; and if the resulting mass be distilled with potash a very volatile base is obtained which is insoluble in water and smells of ammonia and also like sea-fish. This base forms a hydrochlorate which is soluble in anhydrous alcohol and deliquescent ; and the hydrochlorate forms with bichloride of platinum a double salt which crystallises in yellow 'needles dis- solves in boiling water and lias the composition of chloroplatinate of propylamine C,H,N HCl PtCI,.Found. Calculated. ---.. Carbon . . 13.2 13.0 13.1 -18-6 Hydrogen . 3.9 3.8 3.8 -3.8 Platinum . -37.5 37% 37-9 37.3 This double salt when gently hcated with potash is suddenly decomposed with formation of an inflammable gas which smells like ammonia and sea-fish and dissolves in water,-and of a liquid which has a similar odour a strong alkaline reaction and on addition of lumps of solid caustic potash or on being heated to 50" or 60° boils and gives off an inflammable ammoniacal vapour. Tt appears then that the action of aqueous ammonia at 100' produces hydriodate of propylene but this is not the only product formed. If the liquid containing potash from which the propylamine has been driven out by boiling is mixed with a slight excess of' hyclro-chloric acid and evaporated in the water-bath long violet-black needles are produced which fuse when heated and are decomposed with evolution of iodine leaving a residue of charcoal; they are insoluble in water somewhat soluble in a hot solution of iodide of potassium scarcely or not at all in sulphide of carbon and but sparingly in anhydrous alcohol and in ether.The composition of the dark needles recrystallised from ether was iiot ascertained with cetainty but two analyses gave the following results :-Carbon . . 26.0 23.0 Hydrogen . . 4.1 2.4 Nitrogen . . 1.5 0.3 Iodine . . 61-6 69.8 IODIDE OF PHOSPHORUS UPON GLYCERINE. 14'7 Fuming nitric acid instantly decomposes iodopropylene with sepa- ration of iodine.Sulphuric acid does not act on iodopropylene in the cold; but on the application of heat it carbonises the latter and a small quantity of propylene gas is evolved. By the action of hydrogen-gas in the nascent state iodopropylene is converted into propylene. When iodopropylene is added to a small quantity of zinc and dilute sulphuric acid and the mixture gently heated the iodopropylene is decomposed and a gas is evolved the fourth part of which consists of propjlene C,H,I + 2 Zn + HO=C,H + ZnI + ZnO. When a sinall quantity of iodopropylene and dilute eulphuric or better strong hydrochloric acid are introduced into a test-tube standing over mercury the latter is attacked and pure propylene gas is evolved.Propylene gas may be obtained in the pure state by collecting either the gas evolved in the action of iodide of phosphorus upon glycerine or that which is produced by the decompositicn of iodo-propylene with mercury and hydrochloric acid as just described. The gas obtained by the former method contains a certain quantity of phosphuretted hydrogen ; the second method yields propylene-gas mixed with a little hydrochloric acid gas and a small quantity of the vapour of a chloruretted or ioduretted body which latter rnay be completely condensed by passing the gas through a tube cooled to -40'. Large quantities of propylene gas may be readily ob- tained by mixing in a tubulated retort 50 grms. of biniodide of phosphorirs PI (prepared by dissolving phosphorus together with eight times its weight of iodine in sulphide of carbon and evapo- rating thc solution in a stream of carbonic acid gas) with 50 grms.of syrupy glycerine and inducing the action by a gentle heat; 30 grms. of iodopropylene then collect in the receiver. This product is introduced into a small flask with 150 grms. of mercury and 50 to 60 grrns. of fuming hydrochloric acid and gently heated ; propylene-gas is then immediately evolved and may be collected to the amount of about 3 litres. The eudioinetric analysis of propylene-gas gave numbers corresponding with the forinula C,H ; the specific gravitv was found to be =1.498 while the density calculated from the formula for a condensation to 44 volumes is 1.478. Pure propylene-gas has a peculiar and somewhat phosphorous odour like that of purified oletiant-gas; its taste is sweetish and suffocating.It is not condensed by cooling down to -40'; but when it was introduced into the narrow neck of a glass tube the body of which was filled with mercury its condensation was effected by the expansion of the mercury in heating at a pressure which appeared to be intermediate between those which are required for the con-densation of ammonia and of carbonic acid respectively. Water 148 BERTHELOT ON absorbs from one-tenth to one-sixth absolute alcohol twelve to thir- teen times and glacial acetic acid five times its volume of propylene- gas. Fuming or concentrated sulphuric acid absorbs propylene-gas readily bromine absorbs and combines wit,h it.When a small quantity of iodine is introduced into a glass globe filled with propylene-gas and the globe exposed to sunshine for an hour or heated for some tinie to 50' or 60° a liquid product is formed which may be purified by agitation with potash. This liquid has a density of .2.4490at 18.5' ; when recently prepared it is colour- less and has an ethereal odour but becomes coloured by the action of the air and more especially of light and then exerts an extremely irritating action on the eyes. It is the biniodide of yropylene C$&Ip-Carbon . . 12.4 12.2 Hydrogen . 1.9 2.0 Iodine . . 85.8 85.8 100.1 100.0 This liquid does not solidify at -10". Heated with potash and alcohol it reproduces propylene-gas together with a few drops of a volatile compound different from iodopropy he and probably con- taining oxygen.On the Formation of Alcohol from Oleflant Gas. By M. serthelot. A LARQE glass globe of 31 or 39 litres capacity was exhausted of air and filled with olefiant gas; 900 gramrnes of pure and boiled sul- phuric acid poured into it in several separate portions; then a few kilogrammes of mercury; and the whole submitted to violcnt and continued agitation the gas was then gradually absorbed. After 53,000 agitations the absorption became too slow and the operation was discontinued ; the quantity thus absorbed amounted to 30 litres. The sulphuric acid was then mixed with five or six times its bulk of distilled water and after repeated distillation and subsequent sepa-rations with carbonate of potash 52 grammes of hydrated alcohol were obtained which by its density corresponded to 45 grammes of absolute alcohol.This weight amounts to three-fourths of the olefiant gas absorbed the rest was lost in the several manipulations The alcohol thus obtained exhibited all the characters of ordinary alcohol produced by fernmitation having a spirituous taste and odour distilling without residae at 7Yo to 81' C. yielding olefiant THE PORMATION OF ALCOHOL FROM OLEFIANT GAS. i49 gas when heated with sulphuric acid and acetic ether when distilled with sulphuric and acetic acids together. To obtain further confirmation of this result defiant gas obtained by the action of hydrochloric acid and mercury on the iodide of ethylene (C4H412+ 4Hg= C,H + 2 Hp,I) was absorbed by sulphuric acid and the liquid saturated with carbonate of baryta or carbonate of lime ; in this manner the snlphovinates were obtained.The baryta-salt distilled with acetate of soda yielded acetic ether ; with butyrate of potash butyric ether ; and with benzoate of potash benzoic ether C14H604,C4H4. This latter product boiled at ZIOoC. and yielded benzoic acid and alcohol when treated with potash. Lastly to show that the same results may be obtained with olefiaiit gas not originally derived from alcohol coal-gas was subjected to the action of iodine and the resulting iodide of ethylene decomposed by heating it with potash. The pure olehant gas thence obtained was absorbed by sulphuric acid as before and by the series of operatioiis above described benzoic ether was obtained which when distilled with potash yielded benzoic acid and alcohol.This is the first time that alcohol has been produced without fermentation. Formation qf Propyh Alcohol C6H8O2 from Propylene C&&. -Propylene gas is absorbed by strong sulphuric acid almost as rapidly as carbonic acid by potash ; and on subsequently diluting the acid with water filtering and distilling propylic alcohol is obtained in the form of a spirituous liquid having a peculiar pungent odour soluble in water but precipitated from the solution by carbonate of potash This liquid in a state of concentration but .still mixed with a certain quantity of water has a density of 0.817 and begins to boil at 81' to 82' C.It mixes in all proportions with water and forms with crystallised chloride of calcium either a homogeneous solution or two distiuct stxata according to the proportion of the salt. It burns with a brighter flame than common alcohol; mixed with sulphuric acid and sand and heated it blackens decomposes rapidly and yields propylene-gas mixed with about &th of another combustible gas probably hydride of propyl C,H8. Distilled with a mixture of sulphuric and butyric acids it yields propylo-butyric ether C,H,04 C,H6 which is a neutral liquid lighter than water volatile below 130' C. and having an odour like that of butyric ether but more unpleasant ; it is demmposed at loo6 by potash yielding buty- rate of potash and propylic alcohol.The alcohol distilled with sul- phuric and acetic acid yields propylacetic ether analogous to ordinary acetic ether but volatilising at about 90' C. A mixture of propylic alcohol and sulphuric acid gently heated and then saturated with carbonate of baryta yields a crystaliisable salt the sulphopropylate of baryta S,O6,~,H6,HO,BaO + 6 Aq. This salt parts with its water of crystallisation in vacuo. With benzoate of potash it forms propylo- NATANSON ON THE SUBSTITUTION OF benzoic ether. By immediately saturating with carbonate of baryta the solution of propylene in sulphuric acid two saltswere obtained con- taining different quantities of water viz. S,06,C6H6,HO BaO -I-6 Aq. identical with the salt obtained f'rom propylic alcohol S20,,C6H,H0 BaO + 2 Aq.corresponding with the sulphovinate. These two hydrates exhibit the same degree of stability and behave in the same manner with various salts both producing the acetate butyrate and benzoate of propy1.s Propylene is likewise absorbed by hydrochloric acid. When this gas is left to stand at ordinary temperatures over a stratum of the fuming acid it is slowly taken up and disappears after some weeks this reaction takes place even in a sealed tube. At 100' C. the ab- sorption is complete in 30 hours. The product is a neutral liquid lighter than water and insoluble in that fluid. After being purified with potash and distilled it consists for the most part of hydrochlorate of propylene C6H,,HC1 which volatilises at about 40' c.and has the odour taste and flame of hydrochloric ether. On the Substitution of the Aldehyde Radicals in Arnm0nia.t' By J. Natanson. Oside of Acetylammonium C4H3' 13 I NO . H0.-This compound or rather the corresponding chloride is obtained by the action of chloride of ethylene (C,H,C12 or C,H,Cl. HC1) on ammonia at high tem-peratures :-G4E13Cl. HCl + 2H,N=NH4C1 + ',',IN. GI. 113 When one part of chloride of ethylene and five parts of strong ani- monia are placed together in a sealed tube and heated in an oil-bath to 150' (no action takes place a€ loo') the chloride of ethylene is com- pletely absorbed in the course of a few hours and the whole converted into a homogeneous yellow watery liquid. On opening the tube the odour of chloride of ethylene is no longer perceptible j and if the liquid be left to evaporate over sulphuric acid or in a warm place sal-amnioniac separates out and a mother-liquid is obtained which yields nothing but water and ammonia by distillation with hydrate of lime and therefore does not appear to contain any volatile organic base; but on treating it with recently precipitated oxide of silver evaporating * The compound formed with pi-opylene and fuming sulphuric acid does not re-produce these ethers.t Ann. Ch. Pharin. xoii. 48. 'PIIE -4LDEHYDE RADICALS IN AMRIONIA. the filtrate to dryness at a gentle heat to expel the ammonia and extracting the residile with water a solution is obtained having a strong alkaline reaction and therefore indieatins the presewe of a nou-voZnti2e base.The aqueous solution blackened on exposure to the air and deposited reduced silver; and on removing the silver by sulphuretted hydrogen expelling the excess of that gas from the filtrate by heat neutralising the remaining liquid with sulphuric acid decomposing the sulphate with caustic baryta (taking care to avoid an excess of that reagent) and extracting with alcohol the base was obtained in the free state. Great difficulty was experienced in fixing the composition of this base by analysis because none of its salts could be made to crystallise the only mode of obtaining them in a state approaching to purity being to precipitate them from their aqueous solutions by alcohol. They are then obtained in the form of white flocculent precipitates which in drying aggregate together in yellow viscid masses rendering it inipossible to dry them conipletely; moreover in the dry state they are highly hygroscopic.The sulphate prepared in the manner just described gave in two analyses 40.77 and 41.13 per cent. sulphuric acid; the formula C4H3 INO. SO requires 43.47. The chloroplatinate which ac-H3 cording to theformula C4H3 NC1. PtCl should contain 39.57 per H3 I cent. platinum yielded only 38-22per cent. These results not being sufficiently accurate to establish the formula without further con-firmation such confirmation was sought in the proportion of carbonic acid and nitrogen obtained by combustion of the sulphate. Experi-ment gave N CO,= 1 :3-91,which does not differ much from the ratio given by calculation viz.1 :4. These results viewed in connection with the two following reactions which show that. the base contains the radical of aldehyde may be regarded as sufficient evidence that it is really the oxide of acelylamn~onium.-l. When nitrate of silver is added to a solution of the chloride and the liquid heated aldehyde is copiously evolved especially if a few drops of dilute sulphuric acid be added:-'4'3 NO + N03=C4H30.HO + 2N + 2HO. H3 f 2. When ammonia and nitrate of silver are added to a solution of the base or of either of its salts and the liquid boiled for some time an extremely beautiful specular deposit of silver is formed indicating the presence of a considerable quantity of aldeh yde-ammonia.This reaction is slower with the chloride than with other salts because the separated chloride of silver is difficult to reduce. The base separated from the sulphate by means of baryta forms a yellowish inodorous viscid mass,Awhich dissolves readily in water and SATANSON ON THE SUBSTITUTION OF alcohol. The aqueous solution has a strong alkaline reaction a slightly caustic taste and when boiled gives off the faint characteristic odour of alkaline solutions. It easily expels ammonia from ammoniacal salts. It absorbs carbonic acid from the air and afterwards effervesces witti acids. When heated it becomes carbonised giving off vapours which have a faint but characteristic odour. When aqueous ethyla- mine is added at ordinary temperatures to a salt of acetylammonium its odov is ininiediately destroyed a proof that ethylamine separates acetylamine from its compounds ; on boiling however the ethylamine is expelled its volatility then coming into play.Hydrated oxide of acetylammonium does not dissolve alumina ; it dissolves oxide of silver with great facility but the silver is quickly reduced on beating the liquid Solution of chloride of gold produces an orange-yellow amorphous precipitate which dissolves readily when the liquor is heated but is almost sirniiltaneously decomposed with reduction of gold. Bichloride of platinam forms a deep orange-yellow filmy pre- cipitate which afterwards aggregates together. Chloride of mercury forms a white precipitate very sparingly soluble in cold watcr but dissolving with tolerable facility in hot water and separating out again on cooling ; it is insoluble in alcohol.Stdphate of' acetylammonium is precipitated from a moderately coucentrattd aqucwis solntion by alcohol in white flakes ; from a stronger solution as a non-niiscible yellow stratum of liquid. It has a slight acid reaction even if tile aqueous solution before precipitation with alcohol has been made alkaline by excess of base. When dried it forms a viscid yellow mass. The uitrute is similar to the sulphate. The oxaEate is precipitated by alcohol from the ayneous solution in the form of a white gelati- nous precipitate which if the solution is concentrated converts the liquid into a pasty mass. The aqncous solution of the chloride does not niix in the concentrated state with alcohol but remains as a heavy stratum at the bottom ; but in the dilute state the chloride unlike the other salts is not precipitated by alcohol.The salts of acetylam- tnonium are very hygroscopic becoming nioist in a few seconds after drying. They are all insoluble in ether Hydrated oxide of acetylammonium C4H3N} NO. HO is iso-H3 meric with aldehyde amnionia C,H,02. H,N ; and though it has certain properties io common with that compound e. g. th_e reaction with silver-salts it is nevertheless sufficiently distinguished therefrom by. its fixity its basic qualities and its permanency in presence of acids and alkalies. The most remarkable and interesting point con- nected with this base is its non-volatility.It is in fact a fixed alkali like the bases of Hofmsnn's fourth series ; and though much less complex than those bases is neverthless permanent at ordinary THE ALDEHYDE RADICALS IN AM3tO.NIA. temperatures arid is not resolved into water and acetylamine even when heated. Its existence affords one more argument in favour of the ainmonium-theory tending in fact to show that t.he amnioniurn- oxides are the trne bases while ammonia and the conipound ammonias ale merely products resulting from their decomposition. It is very probable that by treating the aqueous solution of oxide of acetylammonirim with fresh quantities of chloride of ethylene a greater number of equivalents of hydrogen may be replaced by acetyl and that by treating it with alcohol-radicals a series of new fixed alkaloids may be formed.Investigations in the same directions as them of Natan son above de- scribed but with somewhat different results have beenmade by Cloez.* This chemist has examined the action of ammonia in the state of alcoholic solution on bromide of ethylene C,H,Br or C,H,Br .HBr. He finds that these bodies do not act upon another in the cold but that when the mixture is enclosed in sealed tubes and heated fa two or three holm in boiling water a copious deposit of bromide of ammo- nium is formed which increases on cooling. The action is completed in twelve hours ; and if the ammoniacal liquid be then filtered from the saline deposit arid evaporated there remains a solid deliquescent residue which when heated with a mixture of lime and potash gives off first a very caustic transparent liquid having a decided ammo-niacal odour afterwards a viscid and at last a thick glutinous liquid.If the distillate be left for twenty-four hours in contact with fused caustic potash and then rectified about one-third passes over between l$Oo and 145O C. the rest at a temperature above 350'. The more volatile portion is a transparent colourless liquid having a faint ammoniacal odour and very caustic taste; it has an alkaline reaction neutralises acids and forms with them salts most of which crystallise readily. The formula of this base is C,H,N. Cloez calls it Formiline (better perhaps Formylamine) inasmuch as it may be regarded as ammonia in which 1 eq.H is replaced by 1eq. formyl C,H. For-mylamine acts even at ordinary temperatures upon the bromides of methyl ethyl and amyl forming new liquid bases whose composition may easily be predicted. The crude product from which the formylamine has been distilled yields a second base which boils at 200° and is regarded by Cloez as Acetyliac or Acetylamine although the analyses which have been made of it do not establish the formula very precisely. * Iustitut 1853,213;Liebig and Kopp's Jahresbericht 1853,468. 154 THE COMPOUNDS OF KETONES WlTH ALKALINE BISULPHITES. Compounds of the Ketones with Alkaline Bisulyhites." By Dr. Limpricht. THEKetones form with alkaline bisulphites crystalline compounds similar to those which Bertagnini has obtained with the aldehydes.1. Pure acetone agitated with a concentrated solution of bisulphite of soda dissolves with considerable evolution of heat aud the liquid on cooling yields lamime of the sulphite of acetone and soda. These crystals dissolve pretty easily in water less readily in alcohol ;when they are heated alone empyreumatic products are evolved; on clis-tilling them with an alkaline carbonate pure acetone passes over. For analysis they were freed from the mother-liquor by pressure between paper and dried over sulphuric acid :-Calculated. Found. 6C . . . 36 /- 22.2 21.3 7H ... 7 4.3 4.1 30 . . .24 14.8 15.7 NaO . .-31 19.1 19.2 2 so,. . . 64 39.6 39.7 NaO .C6H6O2.2SO2+Aq. 162 100.0 100.0 2. The compound of acetone with bisulphite of potash is prepared like the soda-compound and resembles it in all its properties.It gave by analysis 27.21 per cent. of potash a5reeing very nearly with the forrnula KO .C6H60 .2S02 which requires 27.81 per cent. 3. When acetone is mixed with a very strong solution of bisulphite of ammonia it dissolves with so great a rise of temperature that the mixture begins to boil ; nevertheless it does not deposit any crystals on cooling. After evaporation the compound remains in the solid form but still mixed with bisulphite of ammonia. The author has not yet obtained it in the pure state. Sulphite of acetone and ammonia distilled with excess of lime (as in Gijssmanii's process see page 160) yields a volatile base which may be separated from the ammonia that passes over with it by treating the dry hydrochlorates with absolute alcohol.When the salt which remains on evaporating the alcoholic solution is treated with potash a strong ammoniacal odour is evolved and an inflam- mable vapour given off. By. agitating a concentrated solution of an alkaline bisulphite with the liquid containing butyral and butyrone obtained by distilling butyrate of lime or with the mixture of valeral and valerone pro- duced in a similar manner from valerate of lime results were cbtained showing first that butyrone and valerone behave with alltaline * Ann. Ch.Pliarm. xciii. 238. LIMI'RICRT ON CAPBYLIC ALDEHYDE. 155 bisulphites in the same manuer as acetone arid consequently tbat the same may very probably be predicted of all ketones; secondly that butyral and valeral which on accouiit of their boiling-points and their reaction with ammonia have been re5arded as not identical with the aldehydes of butyric aiid valerianic acids at least resemble the aldehydes in their behaviour with alkaline bisulphites.The connpouiidu of ketones with alkaline bisulphites may perhaps throw some light on their rational formulze. Gerhardt derives the aldehydes from the type hydrogen ] ,by substituting 1atom of the oxygen-radical of the corresponding acid (othyl or acetyl C,H302 for example in the cast of acetic acid) for 1 atom hydrogen thus common aldehyde = c '4 €I 3 0 2 1 Xow in the compounds of the alde- H J' hydes with alkaline bisulphites the other atom of hydrogen is replaced 2'21 by the alltali-mctal e.g. '4 S,O,. The ketones are derived from the same type and are regarded as aldehydes in which the second atom of hydrogen is replaced by an alcohol-radical thus acetone =C4H302 ]* This mode of representation however does C,H3 not explain the formation of compounds of ketones with the alkaline bisulphites because the place of the atom of hydrogen which should be replaced bythe alkali-metal is already occupied by an alcohol-radical. But if the formula of acetone be written thus C4H3(C2H3)02) ,which H anionnts to snppositig that an atom of hydrogen in the oxygen-radical itself is replaced by methyl (as in gaultheria-oil) the difficulty just iiieiitioned will he removed and the rational formula of sulphite of acetone and soda will be- On Caprylic Aldehyde.* By Dr.Limpricht. THEliquid product obtained by distilling castor-oil or its soaps with hydrate of potash is stated by Bouis,? Cahours,f Mosclinin 6 and Squire,(] to be caprylic alcohol CI6Hi8O2; Wills and Railton,v * Ann. Ch. Pharm. xciii. 242. t Compt. rend. xxxviii. 935; Ann. Ch. Phye. [3] xliv. 77; Chem. SOC.Qu. J. vii. 286. 5 Compt. rend. xxxix. 254. 0 Ann. Ch. Pharm. lxxxvii. 111, 11 Chem. SOC.Qu. 3. vii. 108. a Ibid. vi. 208 307. LII\.IPRLCHT ON CAPHYLIC ILDEHYDE. on the other hand regard it as cenanthylic alcohol C,,H1602. According to Linipricht however it is not an alcohol at all but caprylic aldehyde C16HlG02. This couclusion is based on the fact that the liquid in question when mixed with a concentrated solution of bisulphate of potash or soda yields a large quantity of a crystalline compound (a property belonging to the aldehydes and acetones but not to the alcohols) ; and that this compound when freed from the mother-liquor by pressure between paper washed with cold alcohol dried over sulphuric acid and then dissolved in hot water yields pure caprylic aldehyde.In fact the liquid thus obtained after being dried over chloride of calcium and rectified till it boiled constantly at 175' yielded by analysis 74.65 (wean) per cent. of carbon and 12.76 of hydrogen numbers agreeing very nearly with the formula of caprylic aldehyde which requires 75.0 per cent. carbon and 12.5 of hydrogen. The crystalline compounds of this aldehyde cannot be purified by cry stallisation ; moreover they undergo a slow spontaneous decom- position continually giving off sulphurous acid hence they are not well adapted for analysis.The potash-salt when purified as completely as possible exhibited too great a quantity of potash and too little sulphurous acid to agree with the formula CHO 2 S,O + 3Aq. ; 16K15 but the proportions of carbon and hydrogen found by combustion agreed very closely with that formula. Caprylic aldehyde turns acid on exposure to the air like other aldehydes,-a fact which explains the result obtained by H a il t o n who by passing oxygen gas through his supposed cenanthylrc alcohol obtained a large quantity of acid. [The experiments just described certainly show that caprylic alde- hyde occurs among the products of the distillation of castor-oil with hydrate of potash and that it may be separated out by combination with alkaliue bisulphiteu; but they by no means prove that it is the only product.On the other hand the very exact analytical results obtained by Bouis and the numerous derived compounds obtained by himself and others establish beyond doubt that caprylic alcohol is not only a product but one of the chief products of the decom- position ; and the experiments of Wills and Railton also render it probable that oenanthylic alcohol is sometimes obtained by the same process.-E D.] LIMPRICHT’B CHEMICAL XOTICES. By H. Limyricht. 1. Preparation of Leucin .from the AZdehyde cf Vderianic Acid.-The reaction on which this mode of preparing leucin depends is similar to that by which Strecker obtained alanine from the alde- hyde of acetic acid.The ammoniacal compound of valeral is boiled in a retort with hydrocyanic and hydrochloric acid till the oily layer consisting of the fused ammonia-compound has completely dis-appeared. The greater part of the sal-ammoniac is then left to crystallise out ; the hydrochloric acid removed by hydrated oxide of lead; the lead by sulphuretted hydrogen; and lastly the residue which remains after evaporating the filtrate crystallised from hot dilute alcohol. The larninz thw obtained exhibit the reaction and composition of leucin viz. :-Calculated. Found. -12 C . . . 72 54-9 54-9 13H .. . 13 9.9 10.0 N . . . 14 10.7 4 0 . . . 32 24.5 Cl,H,,NO 131 100.0 2. On the Metaldehyde of Valerianic Acid.-It is stated by Parkinson,? that an isonieric modification of valeral is obtained (1) in the preparation of that body by the action of sulphuric acid and chromate of potash on fusel-oil ; (2) when valeral is heated above its boiling point ; (3) by heating the sulphite of valeral arid soda with dry carbonate of soda. Acccjrding to Limpricht however no such inodification is obtained by either of these processes. 3. Easy Method of‘ Preparing Chloride of Ethylene.-A tubulated retort is half filled with a mixtiire of 2parts black oxide of manganese, 3 parts comimon salt 4 parts water and 5 parts sulpliuric acid and loosely connected with a flask to serve as receiver.Olefiant gas is then passed into the mixture by means of a tube passins through thc cork of the tubulure and dipping half an inch below the surface of the liquid. So long as the gas is passing through the mixture the retort must be only very gently heated,-as by placing under it a single red-hot coal,-;ind the resultiiig chloride of ethylene afterwards distilled over at a higher temperature. If this precaution be attended to in heating the chlorine-mixture the operator will not be annoyed by escape of chlorine. Where coal-gas is at hand it will naturally furnish the readiest * Ann. Ch. Phsrm. scir. 243. t Ibicl. xc. 114. ZININ AND MOLDENHAUER ON source of ethylene; but when that is not the case the olefiant gas may be readilyprepared from alcohol and sulphuric acid by adopting Wohler's method of adding sand to the mixture in sufficient qiiantity to make it into a thick paste this addition completely preventing the frothing which otherwise causes so much inconvenience.The crude product thusobtained in an hour and a half from 2 ounces of alcohol yielded 1ounce of pure chloride of ethylene. The arrangement just described is peculiarly well adapted for con- densing the gases homologous with ethylene when it is desired to submit them to further examination for which purpose they were formerly collected in gasometers over water and converted into liquid bromides by contact with bromine. If for example we wish to examine the hydrocarbons homologous with ethylene which are obtained by heating valerate of baryta the retort eontaining that sa?t may be coiinected air-tight with a tubulated and \vell-cooled receiver to condense the liquid products and the gases not condensed in the receiver made to pass into the chlorine-mixture.4. The following compounds usually regarded as aldehydes and ketones do not combine with alkaline bisulphites either when agitated and heated with an aqueous solution of the potash or soda-salt 01' when thcir alcoholic solution is mixed with an alcoholic solution of the ammonia-salt. Myristone prepared by dry distillation of myristate of lime ; a mixture of Palmitone and Stearone obtained by quickly heating margaric acid with excess of lime; Benzophenone prepared in a similar nianner from benzoate of lime ;Yhorone from caniphorate of lime; Palmitic aldehyde obtained by oxidising ethal with a mixture of chromate of potash and sulphuric acid.Hence it appears that thc property of combining with alkaline bisulphites does not belong to all aldehydes and ketones,-oiD per-haps thc bodies just mentionecl do not belong to either of these groups. On Compouiid Ureas. By N. Zinin* and F. Moldenhau@r.'f THEresearches of Chancel Wurtz and Hofmann have brought to light a number of compounds which may be regarded as urea in * J. pr. Chem.1xii. 355 Ann. Ch. fhys. [3] xliv. 5'7. f-Ann. Ch. Pharm xciv. 100. The experiments of Zinin and Moldenliauer appear to have been made about the same time and independentlv of each other.Zinin's paper however was published first containing B full description of t,he acetyl and benzoyl ureas and a slight notice of the other two compounds. The description and analysis of these latter is due to Moldenli~uer. COM POU N I) UR.E.A S. which one or more equivalents of hydrogen are replaced by a corre- sponding number of equivalents of a hydrocabon. The following experiments show in like manner that the hydrogen in urea may be replaced by oxygen-radicals :-1. Acetureid Acetyl-urea or Otliyl-urea C :so N 0,. -432 When chloride of othyl C4€I,02. GI is poured upon dry urea the action commences immediately ; the mixture becomes spontaneously heated ; the chloride of othyl volatilises ; and the liquid is gradually converted into a white viscous mass.When this substance is kept for some minutes at a temperature of 120' C. it loses altogether the odour of chloride of othyl and if treated with ether after cooling does not yield anything to that solvent. The residue dissolved in hot alcohol crystallises from that solution in long needles with rectangular base generally striated and having a bright white colour and silky lustre. One part of this body dissolves in 10 parts of boiling alcohol but requires 100 parts of cold alcohol to dissolve it. Hot water dissolves it more readily than alcohol and deposits it on cooling in stellate groups of prisms with rhomboidal bases and dihedral summits. In the formation of this compound the reaction takes place between 1 eq. of chloride of othyl and 1 eq.urea :-C,H4N20 + C4H,0 . C1 = HCI + C,c i30] N,O,. 432 An excess of urea appears however to be advantageous in the pre- paration. According to Zinin the best proportions are 2 eq. urea to 1 eq. chloride of othyl. The composition of othyl-urea is as follows :-Calculated. Zinin. Moldenhauer. 6 C . . . 36 35.29 35.56 35.29 GH.. . 6 5.88 5-92 5-88 2N . . . 28 2745 27.05 40 . . . 32 31-38 31.47 C6H6N,04 I02 100*00 100.00 When othpl-urea is heated on platinum-foil white vapours are evolved and the crystals become covered with a woolly sublimate. At a higher temperature the whole volatilises. When it is heated in a tube the sublimate makes its appearance at 16OoC. and at 200' the substance melts to a transparent liquid which on evaporation is converted into a crystalline mass soluble in water and alcohol.The spirituous solution yields by evaporation crystalline nodules composed 160 ZININ AND MOLDENHAUER ON COMPOCND UREAS. of thick shortened rhomboidal prisms. At a still higher temperature othyl-urea is resolved into othylaniide and cyanuric acid :----.u Othyl-urea. Cyanuric acid Ot!iylamide. Potash decomposes othyl-urea into carbonic acid acetic acid and ammonia. -.-the preceding by the action of chloride of butyryl on urea Crystal-lises readily from water in small crystalline scales ; from alcohol in very thin somewhat elongated highly lustrous laiiiiuz which appear to belong to the rhombic system. It is inodorous and tasteless and melts at 176' to a yellowish liquid which solidifies again in the crys- talline form on cooling; at a high temperature it decornposes like othyl-urea.This cornpound in the state of aqueous solution is not precipitated either by nitric and oxalic acid or by mercuric nitrate. The mean of two analyses gave 45-68 per cent. of carbon and 7-53 hydrogen; the formula requires 46.15 C. and 7.69 H. 3. VaZeryZ-urea Cl,H12N204= C2c-,0~~0 f N 0,. -Obtained ~.-by the action of chloride of valeryl on urea.* It is nearly in- soluble in cold water and alcohol. Froin the hot aqueous solution it is deposited in microscopic laminz having a pearly lustre and soft and unctuous to the touch the alcoholic solution yields thin needles which under the microscope appear like transparent four-sided prisms.It melts at 19l0C. and when cai-efully heated in a tube yields a crystalline sublimate of broad iridescent lamin=. Analysis gave 49.57 per cent. carbon; and 8.79 hydrogen; the formula requires 50.00 C. and 8.33 H. is obtained by heating a mixture of 2 eq. urea and 1 eq. chloride of benzoyl in an oil-bath to 150 or 155O care beius taken that thc tem- perature which increases as soon as thc action coir~~nences, does not rise above 160" for this reason it is best iiot to operate on more than I2 or 15 gi-ammes at once. On tr2ating the cooled and pidvcrised mass * Cliloride of valeryl not previously 'mown was obtained by the action of oxy-chloride of phosphorus on valerate of ozda. It is a colourless very mobile liquid which fumes strongly in the air and is resolred by water irito Iydrorhlorir and valerianic acids (M o Iden liaue r).G~~SSJZANN ON ETHYLAMINE AMARINE AND LOPHINE. 161 with cold alcohol hydrochloric acid and the excess of urea dissolve and there remains a crystalline powder which when dissolved in boilinp alcohol yields on cooling thin rectangular laminre of benzoyl- urea often with pnintcd summits. These crystals are very brilliant and resemble those of beuzoic acid but are distinguished therefrom bg their solubility in alcohol. One part of benzoyl-urea dissolves in 10 parts of boiling and 100 parts of cold alcohol ; in water and ether it is still less soluble. Hot hydrochloric acid dissolves the crystals without alteration and deposits them on cooling.Nitric acid decom-poses benzoyl-urea with formation of benzoic acid. Ammonia does not alter it. Potash dissolves it in the cold and decomposes it at a boiling heat with evolution of ammonia. Heated in a tube to 200"C. it melts without alteration of weight into a colourless liquid which on cooling solidifies in a crystalline maw having the same composi- tion a8 benzoyl- urea but different properties dissolving more readily in water and crystallising differently. Benzoyl-urea heated above its melting point froths up becomes filled with crystals of benzzamide and leaves a residue of cyanuric acid :-On a new Mode of Formation of Ethylsmine Amarine and &ophiue.* By A. Gossmann. 1. EthyZumine.-When bisulphite of aldehyde-ammonia is heated with lime ethylamine is evolved and the sulphurous acid is converted into sulphuric acid :-C4H40 .NH . 2 SO = 2S0 + C4H,N. To obtain ethylamine by this decomposition it is by no means necessary to go through the troublesome process of preparing crystallised aldeh yde-am monia; it is sufficient to take the crude distillate containing aldehyde which is obtained by acting on alcohol with sulphuric acid and peroxide of manganese (or bichromate of potash); mix it with the requisite quantity of bisulphite of ammonia; evaporate to dryness; mix the perfectly dry saline mass with four times its weight of a mixture of quick and slaked lime; and distil it in a retort provided with a bent tube for conveying the evolved gas into dilute hydrochloric acid. The distillation must be performed immediately after the mixture is made and the mass must be heated as quickly and as strongly as possible; otherwise aldehyde and ammonia pass over the latter is always evolved when an excess of bisulphite of ammonia has been * Ann.Ch.Pharm. xci. 122; xciii. 329. VOL. \'liI.-NO. xxx. M 162 GOSSMANN ON A NEW NODE OF FORMATION OF added. The sal-ammoniac thus formed is however easily removed by a mixture of alcohol and ether which dissolves the hydrochlorate of ethylamine but leaves the sal-ammoniac undissolved. 2. Formation of Rmarine and Lophine.-Since as shown by Ber- tagnini it is a general property of aldehydes to unite with alkaline bisulphites producing compounds similar to that formed by ordinary aldehyde it appeared probable that they would also when treated in the manner just described yield organic bases.This expectation has been verified with regard to bitter almond oil. The sulphurous acid compound was prepared by mixing a concentrated alcoholic solution of acid sulphite of ammonia with a sufficient quantity of bitter almond oil collecting the resulting crystalline mass after it had ceased to in- crease in quantity and drying it The perfectly dried mass was then mixed with three or four times its volume of very dry and recently prepared hydrate of lime; the mixture introduced into a capacious retort and covered with a thin layer of lime ;and the retort after being connected with a well-cooled receiver was surrounded as quickIy as possible with hot coals and heated to 18O0-2OOc C.The cool part of the neck of the retort then immediately became covered with a white amorphous-looking mass which as the beat increased ran down into the receiver in oily drops. This substance is arnarine. The heating was continued as long as oily stris appeared in the neck of the retort and the sublimate in the hottest part of it continued to increase. When the operation is properly conducted the amarine is found partly in the receiver suspended in an ammoniacal liquid rendered turbid by the presence of a small quantity of bitter almond oil partly in the lower part of the neck of the retort. Tn the upper part there is always found another substance partly detached in tuft-like groups of needles partly coating the glass in radiating masses.This second body is Lophim. To collect the amarine and separate it from a small quantity of oily products it is rinsed into the receiver with a sniall quantity of cold alcohol dissolved by addition of alcohol and hydrochloric acid precipitated by ammonia and purified by recry stallisation and treat- ment with animal charcoal. The hydrochlorate of this base yielded the following results by analysis :-Calculated. Found. 42 C .. .292.0 75.33 75.15 19 H ...19.0 5.68 5.62 2N ...%3*0 8-37 c1 . . .35.5 10.62 -. --C,,H IsN .HCI 3745 100~00 ETHYLAMINE AMARINE AND LOPHTNE. The chloroplatinate left on ignition 19.8 per cent. of platinum; the formula C,,H,,N,Cl . PtCl requires 19-58per cent. The lophine which collected in the upper part of the retort and of its neck was dissolved in hot alcohol,.treated with animal charcoal and recrystallised. It was in most cases so pure that after one recrystallisation it exhibited the appearance of dazzling white needles. It melted at 265"C volatilising at the same tinie unchanged and solidifying on cooling in a beautiful is a8 follows :- radiated mass. Its composition Calculated. Found. 46 C . . 276 85-98 85-69 17 H . . 17 5.30 5.5 2N . . 28 8.72 321 The chloroplatinate left after ignition 18.89 per cent. of platinum ; the formula CaHl,N,C1. PtCl requires 18-72per cent. The formation of lophine begins only when the retort has attained a very high temperature and probably arises from the amarine formed in the interior of the mass not being able to escape before the tempe- rature of the outer parts has risen high enough to decompose it.It may therefore be greatly promoted by using a capacious retort heating it very strongly and suddenly and covering the upper part immediately with red-hot coals beginning from the front so as to fulfil as quickly as possible all the conditions which are essential to cause the amarine to pass through a strongly heated space. By attending to these direc- tions needles of lopbine more than an inch long may be obtained even with small quantities of material. In the preparation of amarine and lophine as in that of ethylamine it is not absolutely necessary first to prepare the crystallised com-pound of the aldehyde with acid sulphite of ammonia; it is sufficient to mix a highly concentrated solution of acid sulphite of ammonia with the corresponding quantity of bitter almond oil dissolved in a little alcohol; evaporate to dryness as quickly as possible over the water-bath ; and [nix the resulting mass immediately with recently prepared and perfectly dry hydrate of lime if the mass Ee used before it is thoroughly dry or if the hydrate of lime be very moist the compound is for the most part resolved during the distillation into ammonia and bitter almond oil.As however this mode of proceeding always gives rise to the formation of a certain quantity of benzoic acid in the mass a quantity of benzol corresponding to this admixture of benzoic acid is always found in the distillate; an impurity however which is not very difficult to remove inasmuch as it volatilises very quickly when the product of the distillation is heated to SO" or 90" C.164 W~HLERANI) DEAN OH en Tell~romethyl.~ By F. Wohler and J. Dean. THIScompound is obtained by a process exactly sirnilar to that which is adopted for the preparation of tellurethy1,t namely by distilling tellaride of potassium with a tolerably strong solution of sulphome-thylate of baryta the reaction goes on very easily. The distillation was continued as long as drops of oil continued to pass over with the water. Telluromethyl is a pale yellow mobile liquid which sinks in water and docs not mix with it. Its odour is extremely unpleasant like that of garlic very intense and so persistent that even the breath of the operator becomes affected by it.It was found to boil at 92' (3.1 Its vapour is yellow like that of tellurium itself. It fumes slightly in the air from oxidation. When set on fire it burns with a light bluish white flame giving off a thick vapoiir of tellurons acid. Tellwornethyl C,H,Te like tellurethyl has the chemical relations of a radical or nietd. It form a basic oxide and corresponding haloYd cornpoiinds. Oak% of Tellurornethyl C2F1,Te0.-Formecl by heating telluro- methyl with iiioderateiy strong nitric acid. At first a portion dis-solves with reddish yellow colonr ;then suddenly a violent action takes place nitric oxide is evolved and a coloiirless solution is formed con- taining nilrate of telhromethyl which on carefully evaporating the solution is obtafned in large colourless prisms.This salt dissolves readily in watcr and in alcohol; when heated it decomposes with detonation. It is the material froin which all the other compounds of tellnromethyl we obtained. The ozide however is most conve-nien tly prcpared not dircbctly from the nitrate but hy decomposing the cllloridc or iodide with oxide of silver. Oxide of telluromethyl in the dried st:ite is indistinctly crystalline. When exposed to the air it deliqucsces like potash and absorbs carbonic acid. It has a most nauseous taste but is destitute of odour. Its solution exhibits a strong alkaline reaction with litmus paper. It is so strong an alkali that it separates ammonia from sal-ammoniac even at ordinary temperatuws and forms a blue precipitate with sulphate of copper.From its solution sulphurous acid immediately throws down telluro-methyl in the form of an oily stinking liquid :hydrochloric acid pre- cipitates the white cbloride ; hpdriodic acid the red iodide. Jt Ann. Ch. Pharm. xoiii. 233. t Ibid. Ixxxiv. 79; Chem. SOC.Qu. J. ri. 40. 1 The red bciling-point is probably 80" for in thc experiment the telluromethyl was covered with a thin layer of water and the thermometer did not dip into it immediately but into oil in which the very thin tube containing the telluromethvl was immersed. If the boiling-point bc 80° that of tellurethyl which has not y;t been debcrmiiird b~ exprrinrent mwt nccoi4ing to Kopp's lam be 99".TE 1 LUl%OMETBY L. Su/phate of I%lluromethyZ formed by directly saturating the base with the acid crystallises in transparent cnbes very regular and of considerable size. It dissolves readily in water birt is insoluble in alcohol. The oxalate tartrate acetate and formiate are easily soluble. Chloride of Telluromethy Z C,H,TeCl is fortried as a thick white precipitate resembling chloride of lead when hydrochloric acid is dropt into the solution of the nitrate. It redissolves when heated and crystallises on cooling in long thin prisms resembling corrosive sub- limate. Melts at 97.5' C. but appears not to be capable of volatilising completely without decornpovition. Although it eannot be distilled with water its solution has nevertheless a faint alliaceous odour when heated.It solidifies in a very dietiiictly crystalline form. Dissolves readily in alcohol. When prepared from the amorphous nitrate it contailis tellurous acid either admixed or in combination. Dues not form any precipitate with bichloride of platinum. The Oxycitloride C2H,TeC1 + C,H,TeO is formed by dissolving the chloride in ammonia. The solution when evaporated yields a mixture of sal-ammoniac and the oxychloride which may be separated by alcohol. The oxychloride forms short colourless prisms. Hydro-chloric acid added to its solution precipitates the chloride. Bromide of Tellwornethyl C2H,TeBr.-Produced like the chloride to which it bears a strong resemblance and with which it is probably isomorphous. Forms shining colourless prisms and melts at 89' C.Iodide of Tel/uromethyl.-Colourless hydriodic acid or solution of iodide of potassium dropped into a solution of nitrate or chloride of telluromethyl forms a bright lemon-yellow precipitate which after a while changes to vermilion-red. If the solutions are warm when mixed the precipitate is immediately red and crystalline. Aftey drying it forms a vermilion-coloured the iodide is as follows :- powder. The composition of Found. Calculated. Carbon . . 5.40 5.81 Hydrogen Tellurium . . . 1.61 . 31-24 1-45 31.12 Iodine . . 61-54 61-62 99.79 100.00 Iodide of telluromethyl dissolves very sparingly in cold much more readilv in warm water. Hot alcohol dissolves it in 1arie quantity formi& a reddish-yellow solution.From both solutions the iodide crystallises in small shining vermilion-coloured prisms the alcoholic solution yielding the larger crystals. The crystals yield an orange- yellow powder. Under the microscope they appear orange-yellow by transmitted light and certain faces exhibit a beautiful blue surface- colour. 166 KRAUT ON When the cooled alcoholic solution is mixed with about an equal bulk of water the iodide is thrown down as a lemon-yellow preci- pitate. But after a few minutes a movement takes place among the particles and in a short time the eiitire precipitate is converted into glimmering crystalline laminae of the dour of vermilion. Iodide of telluromethyl therefore like chloride of mercury exhibits two states a yellow and a red connected most probably as in the latter substance with dimorphism.The yellow modification however has not yet been obtained in a fixed and crystalline form. The alcoholic solution in which the iodide clearly exists in the yellow form deposits it by spontaneous evaporation in red crystals; and it cannot be melted without decomposition being converted into black iodide of tellurium even at 13OoC. A solution of the oxide of telluromethyl dissolved in aqueous hydrocyanic acid did not yield any cyanogen compound the base separating out quite unaltered when the liquid was evaporated. When sulphuretted hydrogen is passed into a solution of chlo-ride of telluromethyl a white flocculent precipitate is formed. (C,H,TeS +C,H,TeCl ?) which afterwards becomes yellowish the liquid acquiring an intensely disgusting odour.If it be then distilled there passes over with the water a very offensive heavy oily reddish- yellow body which when oxidised with aqua-regia,. yields sulphuric acid. When a solution of oxide of telluromethyl is saturated with sulphuretted hydrogen a slight whitish turbidity is produced. On distilling the liquid white sulphur separates out as soon as the heat begins to act and a yellow oil passes over which appears to bemerely reduced telluromethyl. On Cuminic Alcohol.* By C. Kraut. GERHAHDT and CAHOURSt have shown that the volatile oil con-tained in the seeds of Cuminum Cyminurn and known in commerce by the name of Roman cumin oil is a mixture of two compounds viz.a compound free from oxygen called Cymene and an oxygenised body called Curninol. This latter substance is homologous with bitter almond oil and stands in the same relation to cuniinic acid as bitter almond oil to benzoic acid,-that is to say it is the aldehyde of cuminic acid. The two constituents of the Boman cumin-oil were separated by the following process :-After the whole of the cymene together with a portion of the cuminol had been removed from the commercial oil * Ann. Ch. Pharm. xoii. 66. t Ibid. xxxviii. 67. CUMINIC ALCOHOL. by distillation at 200' C. the residue was converted by agitation with a concentrated solution of bisulphite of soda into a crystalline double salt insoluble in saline solutions; this salt completely freed from the mother-liquor by pressure was then diffused in water and the cuminol obtained from it in a state of purity by addition of carbonate of soda and distillation with vapour of water.The cuminol which bad dis- tilled over with the cymene was separated therefrom by agitation with solution of bisulphite of soda so dilute that the resulting double salt remained in solution. Cuminol becomes sensibly heated when mixed with several times its volume of a concentrated solution of hydrate of potash in alcohol*;and if the mixture be kept for an hour in a state of ebullition and regularly concentrated by allowing the condensed vapourv to flow back again the cuminol is completely decomposed and there are formed without any evolution of hydrogen a large quantity of cuminate of potash and two liquid compounds cymene and cuminic alcohol which on addition of water separate in the form of oil.Although these two bodies arc always produced simultaneously the author is disposed to think from experiments hereafter to be described and from the analogous beha- viour of benzoic alcohol that the cymene is formed not from the cuminol but by the action of potash on cuminic alcohol. On this supposition the decomposition of cuminol by potash as above may be represented by the following equation :-f2C2,Hl2O2 + KO. HO = C2,-,H,,02 + C20H,,K0 '-\--Cuminol. Cuminic Cuminete Alcohol. of Potaek When the mixture after being diluted with water was distilled the cuminic alcohol and the cymene passed over with the aqueous vapour ; they were removed from the surface of the distillate ; agitated with bisulphite of soda to free them from adhering cuminol; then dehydrated and finally separated by fractional distillation.The cuminic alcohol gave the following results by analysis :-Calculated. Found. 1--I 20 C . . 120 80.00 79-63 79.62 79.56 79.49 14 H . . 14 9.33 9-33 9.36 9.35 9.39 2 0 . . 16 16.67 C20H1402 150 100.00 Cuminic alcohol is a colourless liquid having a very faint but agreeably aromatic odour and burning spicy taste ; boils without decomposition at 243O and does riot turn acid even by long exposure to the air. It is ineohble in water but diseolves in all progorhm- 168 KRAUT ON CUMINlC ALCOHOL. in alcohol and ether and is not altered by agitation with solutions of a1 kaline bivul phi tes.When heated with potassium it gives off hydrogen and forms a solid granular mass which is decomposed by water yielding potash and curninic alcohol. Strong nitric acid heated with cumiiiic alcohol converts it into cuminic acid without the simultaneous formation of any other acids. Weaker nitric acid would probably first form cuminol. Concentrated sulphuric acid converts cuminic alcohol without formation of any conjugated acid into a resinous mass which is brittle and friable when cold but becomes semifluid when immersed in boiling water. Of the compounds of cuminic alcohol corresponding to the com-pound ethers only the benzoate has yet been examined. This compound is obtained by heating cuminic alcohol or its potassiurn- compound with chloride of benzoyl and forms a buttery indistinctly crystalline mass which cannot be distilled without decomposition is decomposed by potaah-solution even in the cold and when washed merely with water continually renders that liquid acid.It has been assumed above that the formation of cymene from cuminol is due to the-action of potash on the cuminic alcohol already formed. This assumption is supported by the fact that pure cuminic alcohol when continuously boiled with alcoholic solution of potash is decomposed in the manner denoted by the following equation :-a 3C9oH1402 + KO HO = C2,H,,KO + 2C2oH14 + 4HO. -' -Cuminic Cuminate of Cyrnene. Alcohol. Potash. The cymene thus produced is identical with that which is formed by natural-processes and boils like the latter at 171k" C.It gave the following results by analysis :- Calculated. Found. 20 c . . 120 89.56 88.91 88.92 14 H . . 14- 10.44 11-01 10.62 '2OHl4 134 100*00 The decomposition just cited does not depend upon the presence of alcohol; for cymene is likewise formed when cuminol or cuminic alcohol is treated with melted hydrate of potash and especially when the potash is either not heated strongly enough to oxidise the cuminol at the first contact or when individual particles of the fused salt are cooled down by too rapid addition of the cuminol. It is possible that similar processes may determine the simultaneous formation of cymene and cuminol in the living plant ; at all events CANNlZ2,IRO ON BENZOIC ALCOHOL.the assumption that a hydrocarbon is produced by the decomposition of an oxygenised constituent is inore strongly supported by analogy than that of a direct reduction or oxidation. From the cymene obtained in the processes above described the author prepared the hitherto unknown compound Dinitrocymene. This body was obtained by cautiously dropping cymene into a mixture of 2 parts concentrated sulphuric and 1 part fuming nitric acid heating the mixture to about 5OoC. and leaving it to stand for a day or two. On subsequently diluting it with water a brown substance separates liquid at first but becoming solid and crystalline after some t itne ; this substance is a mixture of dinitrocyrnene and certain un- crystallisable products formed in consequence of the action of the acids having been carried too far.From the solution in boiling alcohol the non-crystallising bodies separate on cooling whereas the ctinitrocy mene does not crystallise out till the liquid is evaporated. The crystals are colourless beautifully iridescent rhombic tables which melt at 54' C. dissolve in ether and alcohol but not in water and separate from the saturated solution in the form of an oily liquid. When heated in the air they detonate and leave a very slody com- bustible charcoal. The results of their analysis are as follows :-Calculated. Found. -0. --. 20 c . . 120 53.57 32-13 53.39 12 H . . 12 5.36 5.28 6-04 2 NO . 92 41.07 -I. On Berlzoic Alcohol." BY 8.Cannizzsro. A NOTICE of the author's firat observations on benzoic alcohol was given in vol. vii. p. 192 of this Journal. It was there stated that when the vapour is passed over red-hot spongy platinum an oil is formed lighter than water and having probably the composition C,H6. Subsequent observation however has shown that this is not the case the oil in question being a mixture of several products among which benzene could be distinguished and separated j it contains also a solid body not yet examined. Benzoic alcohol in contact with sulphuric acid or when heated with chloride of zinc or anhydrous phosphoric acid is converted into * Ann. Ch. Pharm. xc. 252 ; xcii. 113. 170 CANNIZZARO ON a resinoiis substance which is insoluble in water alcohol and ether dissolves but sparingly in fuming sulphuric acid and softens in boiling water (vid.seq.) Benzoic alcohol when treated with potash yields benzoate of potash and a hydrocarbon (toluol Deville's benzoene).Under the influence of reducing agents therefore the alcohol is converted into a hydrocarbon which stands to it in the same relation as marsh-gas to wood-spirit :-C14H802 + KHO2 = C14H5K04 + H 2C14H802 + H = 2C14H8 + 4HO. To obtain this hydrocarbon the alcohol is distilled with a strong alcoholic solution of potash; as soon as all the alcohol has passed over and the residue has become solid the hydrocarbon begins to pass over mixed with undecomposed berizoic alcohol. To obtain the hydrocarbon pure the liquid which has passed over is again distilled the portion which goes over at 116' being collected apart ; this dis- tillate is mixed with strong sulphuric acid which resinises the benzoic alcohol and the decanted liquid is washed with water and rectified over anhydrous phosphoric acid.The product thus obtained does not solidify ill a freezing mixture ; it boils at 114O ; has an agreeable odour like that of benzin. Its analysis gave 91.223 per cent. carbon and 8.738 hydrogen (rneau) which agrees very nearly with the formula Cl,H8 that formula requiring 91.305 C. and 8.695 H. The boiling point 114* corresponds with that which Gerhardt found for toluol; the odour is exactly the same. Just as acetic ether obtained from common alcohol is polymeric with aldehyde and probably isomeric with metaldehyde so likewise is thc benzoic acid ether of benzoic alcohol polymeric with the aldehyde of this alcohol viz.bitter almond oil and isomeric with benzoin. This ether is obtained by distilling equal equivalents of chloride of benzoyl and benzoic alcohol or by distilling benzoic alcohol with Gerhardt's anhydrous benzoic acid. As tlie distillate cools the ether crystallises out surrounded with a yellow oil which does not alter its composition to any great extent. It crystallises in snow-white needles often in rhorubohedrons ; above 20' C. it melts to a colourless oil which remains liquid for a day and solidities only when exposed to a freezing mixture. Its formula is C,,H,,O,. Fluoride of silicium has no action on benzoic alcohol.Fluoride of boron on the contrary attacks it vigorously forming boracic acid hydrofluate of boracic acid and a resinous substance. After being washed first with alkaline water then with pure water alcohol and ether dried at 170° dissolved in sulphide of carbon m in chloroform separated from the solvent by evaporation and fusion it forms an amorphous translucent amber-coloured substance which is insoluble in water nearly insoluble in alcohol dissalves very sparingly in BENZOIC ALCOHOL. ether but very readily in oil of turpentine sulphide of carbon and chloroform ;becomes soft and melts wheii heated and decomposes at a higher temperature yielding both solid and fluid volatile products and leaving a residue of charcoal.It gave by analysis 92.860 per cent. carbon and 6.817 hydrogen agreeing nearly with the formula C14H6; but its physical properties show that its true formula is a multiple of C14H6 probably C,H12 which would make it isomeric with stilbene. Fused boracic acid acts on benzoic alcohol in two different ways. Between 100" and 12OoC. it converts the alcohol into the coi're- sponding ether C28H1402 and at a higher temperature into the resinous substance C28H12. This latter body is also formed by the action of anhydrous phosphoric acid. The ether corresponding to benzoic alcohol may be prepared as follmvs :-The alcohol is made into a paste with fused and pulverised boracic acid and the mixture heated to 120' or 125' for several hours in a sealed tube immersed in an oil-bath.The mixture hardens and turns brown. It is treated with boiling water and with a solution of alkaline carbonate till all the boracic acid is dissolved arid a greenish brown oil floats on the surface of the liquid. This oil is distilled ;the portion which goes over below 300' C. contains unaltered benzoic alcohol; but that which distils over between 300' and 315' contains the benzoic ether. In the retort there reniains a quantity of the resinous hydrocarbon saturated with the ether which cannot be sepa- rated from it without decomposition. Benzoic ether is a colourless oily liquid,which when viewed in certain directions exhibits a slight indigo- colour. It boils between 310' and 3 I 5'. It gives by analysis 84.5 per cent.carbon and 7.3 hydrogen the formula C2,H1402 requiring 84.5 C and 7.1. 1-1. Benzoic ether treated with sulphuric or phosphoric acid yields a resinous substance probably identical with that which is obtained from the alcohol. When heated in a scaled tube to a few degrees above 315' the ether decomposes becoming am ber-coloured and yielding a yery small quantity of the resinous body together with bitter-almond oil (which may be separated by bisulphite of soda) and a light oil probably consisting of toluol. A small portion of the ether appears therefore to be resolved into water and the hydrocarbon C28H12 C28H,402 = C,,H12 + 2 HO; while the greater part is resolved into hydride of beneoyl and toluol C2SH1402 = C14H602 + C14HW 172 AKYPE ON On the Anilides of Pyrotartaric Acid.By E. Arype. Pyrotartaail C,,II,,NO (= C,,H7N C,,Hs0,-4 HO).-When crystallised pyrotartaric acid is fused with aniline in the proportion of 2 eq. of the acid (C,H,O,) to 1eq. of aniline (CI2€I7N) and the inixture kept for about ten minutes at a temperature a few degrees above loo" a brown viscid mass is obtained which when stirred with a glass rod begins to crystallise and assumes the form of a dirty-red solid mass consisting of impure Pyrotartanil. This substance after being twice heated with animal charcoal in a boiling aqueous solution separates on cooliiig in the form of a perfectly white tasteless inodorous crystalline powder which under the microscope exhibits the appearance of delicate needles.Pyrotartanil melts at 98' C. and runs in boiling water like an oil which on cooling solidifies in a crystalline fatty mass. It volatilises without decomposition ; at 140" C. it sublimes pretty quickly giving off a vapour which has a faint odour and adheres to cold bodies in the form of a very hard crystallisation. By boiling during which the temperature may gradually rise to 300° it is partially decomposed the greater part however collecting in the neck of the retort in the form of a tolerably pure and more or less distinctly crystalline sub- limate of unaltered pyrotartanil. Hence very impure pyrotartanil nlay be conveniently purified by slow distillation. Pyrotartanil dissolves but sparingly in water even at a boiling heat. Alcohol dissolves it readily and moreover greatly assists the solvent power of boiling water without hindering the subsequent separation in cooling; hence weak spirit is the best solvent to use when impure pyrotartanil is to be decolorised by animal charcoal.Pyrotartaiiil is also readily soluble in ether and in the ordinary acids Alltaliev dissolve it without alteration ; but on heating the solution the pyrotartanil is first converted into pyrotartanilic acid and then resolved by the action of the fixed alkali into aniline and pyrotartaric acid. Very strong nitric acid converts it into pyrotartonitranil. The composition of pyrotartanil is as follows :-Calculated. Found. 22 C . . 132 69-84 69-81 11 H . . 11 5.82 5.93 N ..14 7-41 - 40 . . 32- 16.93 C2lHlPO* 189 100~00 2.Pyrotartanilic acid C2,H,,N06 (= C,,H,N. Cl,H80,-2 HO). -When aniline is added by drops and with stirring to pyrotartaric THE ANILIDES OF PYROTARTAHIC ACID. anydride (the watery oil obtained by distilling pyrotartaric acid may be used for the purpose) the mass becomes very bot and solidifies to a reddish crystalline magma of pyrotartanilic acid which ultimately crumbles to pieces and becomes nearly dry; it may he purified by boiling with weak alcohol and animal charcoal in the manner described far the purification of pyrotartariil. Pyrotartanilic acid separates on cooling from a boiling solution in a bulky mass of shining crystalline needles which if the solution is not very concentrated are arranged in stellate groups and exhibit under the microscope the appearance of rectangular prisms with perpendicular terminal faces.Tt bears a heat of 140' C. almost without loss; melts at 14i0 giving off water and being partially converted into the more easily fusible yyrotartanil ; hence the acid after one fusion melts at 140". It dissolves rather slowly iu water though in greater quantity than pyrotartanil ; alcohol however dis- solves it readily and froin the alcoholic solution it is precipitated in the crystalline form by water. With ether and with acids it behaves like pyrotartanil. It is deconiposed by boiling with excess of potash. Neither pyrotartanil nor pyrotartanilic acid gives the characteristic reaction of aniline with solution of chloride of lime. Pyrotartanilic acid is a ~erystable though rather weak acid.It reddens litmus paper expels carbonic acid from carbonates forms several crystallisabIe salts but is precipitated in the crystalhe fornr from its solutions by other acids even by acetic acid The pyro- tartanilates of the alkalies and earths are easily soluble; those of the heavy metallic oxides sparingly soluble. In a solution of the neutral ammonia-salt no precipitate is formed by chloride of barium or cal-cium or by baryta or lime-water ; sulphate of zinc produces a tur- bidity after a while; sulphate of copper forms a bluish-green and sesquichloride of iron a yellowish-red precipitate. The analysis of the acid dried at 14.0' and at 100' gave the fol-lowing resiilts :-Found. me-. Calculated.At 140°. At 100". 22 C . . . 132 63.77 63.84 63-60 13 TI . . . 13 6.28 6.54 6-32 N.. . 14 6.76 60.. . 48 23.19 C,,H,,NOti 207 100~00 Pyrotartanilate of ammonia dries up to a radiated crystalline mass easily gives up its ammonia and is decomposed by water with the aid of heat; in the cold it is readily dissolved if perfectly neutral. It is likewise fortncd by boiling pyrotartanil with ammonia. The potash- 174 AltPPD OX THE ANILIDES OF PYROTARTARTC ACID. salt resembles the ammonia-salt and dissolves readily in water. The soda-salt dries up to a confused crystalline mass. The baryta-salt becomes granular and crystalline when thoroughly dried. The linzo-salt forms needles having a dull silky lustre. The lead-salt PbO C2,H1,N0 - forms a white precipitate which becomes pasty by boiling but when left to itself assumes a granular crystalline character and melts at a higher temperature; it dissolves in acetate of lead and in boiling water.The silver-salt Ago C22H12N05,is a white pulverulent body which dissolves in water and separates again on evaporation in sniall round crystalline nodules. It contains 34-36 per cent. silver. 3. Pyrotartonitranil C, (H,,NO,) NO,. -This compound in which 1 eq. of the hydrogen in pyrotartanil is replaced by 1eq. of hyponitric acid is produced with the greatest facility by dissolving pyrotartanil in the very strong nitric acid obtained by distillation with sulphuric acid. The solution assumes a red colour for a while but afterwards becomes yellow and on addition of water deposits a gradually solidifying oil which after being resolved in boiling alcohol decolorised by aninial charcoal and filtered yields pure pyrotartonitranil in crystalline needles arranged in spherical groups.Pyrotartonitranil melts at 155' and solidifies in the crystalline state at 153' ;sublimes without decomposition when carefully heated dissolves in alcohol and ether; but is nearly insoluble in water. By boiling with ammonia it is converted into an acid which is likewise produced by the action of the fixed alkalies but is readily transformed by the latter into a yellow crystalline substance. Yyrotartonitranil yields the following results by analysis :-Calculated. Foun (I. 22 C . . 132 56.41 5G.35 10 H . . 10 4-27 2N .. 28 11.97 80 . . 64 27.35 C221-IloN,O 234 100.00 4. Pyrotartoizitranilic acid C22(H,,NO,) NO -When pyro-tartonitranil is added to a somewhat dilute solution of carbonate of soda it is quickly dissolved while the solution assumes il yellow colour and a slight evolution of carbonic acid becomes perceptible. If the yellow solution be cooled yellow crystals of nitranilirie (vid.in$) separate out from it. The clear yellow solution consists chicfly of pyrotartonitrauilic acid which on the addition of nitric acid in excess is precipitated in yellow flakes. It is decolorised partly by animal charcoal partly by recrystallisation but is not easily obtained in a state of perfect purity. 443*~14 ARPPE ON NITRANILINE AND PARANITRANILINE.175 This acid dissolves very sparingly in water even at a boiling heat but readily in alcohol and ether; from a saturated solution it separates in a distinctly crystalline form and when examined by the microscope appears to consist of rhombic tables having angles of 60' and 120'. It is so weak an acid that it is scarcely able to expel carbonic acid. After drying over sulphuric acid it gave the following results by analysis :-Calculated. Found. 22 C . . 132 52.38 52.46 12 H . . 12 4-76 4.89 2N . . 28 11.11. 10 0 . . 80 31.75 100.00 The salts of this acid are very unstable and uncrystallisable. The potash-salt scarcely exists in the solid state the solution of the acid in potash quickly decomposing and assuming mi intense yellow colour.The ammonia-salt dries up to a syrup. The siher-salt precipitates in white flakes and is found by analysis to contain 30.13 pcr cent. silver the formula requiring 30.10 per cent. On Nitraniline and Paranitraniline.+ By E. Arppe. THE yellow body produced by the action of alkalies on pyrotartoni- tranilic acid is identical in composition with the nitraniline which I-lofmann and Muspratt obtained from diuitrobenzol C,,fl,N,O,.t The two bodies however differ remarkably in many of their proper- ties; and as the substance produced by Arp p e is produced directly from an aniline-compound he proposes to assign to it the name of Nitraniline,and to designate as Paranifralinethe isomeric compound produced from dinitrobenzol. 1. N itr a n il in e.-This base is most readily obtained by boiling pyrotartanitril or pyrotartonitrilic acid in a solution of carbonate of soda mixed with a little caustic soda; tbe decomposition is then com-pleted in a quarter of an hour and the solution on cooling deposits nitraniline in yellow laminae which may be purified by recrystalli- sation.From a slowly cooled aqueous solution nitraniline separates in long needles; but if the cooling be accelerated small tabular or needle- shaped crystals are obtained having angles of 69O and lll' bnt with * Ann. Ch.Pliarm. xc. 147; xciii. 357. f' Ibid. lrii. 215. 176 ARPPE ON the smaller angle so much truncated as to convert the crystal into a six-sided table with angles of 111' and 138'. An alcoholic solution on the other hand yields unaltered rhombic tables as well as these six-sided crystals ; from ether the compound separates partly in tables partly in capillary needles; from carbonate of soda in tables of 55' and 125'; by.sublimation it is obtained partly in needles partly in irregular laminze. Nitraniline melts (according to the latest determination) at 141' volatilises at about the same temperature and sublimes very beauti- fully when carefully heated between two watch-glasses. It dissolves readily in alcohol and ether but requires 43 parts of boiling water and no less than 1250 parts of water at 18.5' to dissolve it completely. Its analysis gave 52.03 per cent. carbon and 4-44 hydrogen agreeing very nearly with the formnla CI2Ii6N2O4 which requires 52.17 per cent.carbon and 4.35 hydrogen. Hgdrochlorate of Nitraniline C,,H,N20 .HC1. -Nitraniline forms with boiling hydrochloric acid a yellow or if the acid is in great excess a colourlees solution which on cooling yields tolerably large colourless tabular crystals the simplest forms of which are four-sided tables of 95' and 85' (u),or of 65' and 115' (b) ; by the combina- tions of these whereby the acute angles of (a) are truncated by (b) six-sided tables are produced and by truncation of all the angles of (a) eight-sided tables. The salt is easily decomposed both when heated whereby it loses part of its acid and turns yellow and also by the action of' water by which the base is almost completely precipitated ; alltalies precipitate the nitraniline in the crystalline form but it is redissolved when heated with an excess of the precipitant.The hydrochlorate gives by analysis 20.20per cent. chlorine the formula reyniring 20.34. PZatinum-salts.-I7fyd~~cl~lorateof nitraniline forms two double salts with bichloride of platinum; but that which has the normal coinposition C,,I16N,0,. HCl .PtCl, is difficult to obtain. 1. The best mode of preparing this normal salt is to mix a concen-trated aqueous or alcoholic solution of bichloride of platinum with a warm concentrated solution of nitraniline in hydrochloric acid collect the resulting precipitate in an empty glass funnel leave the mother- liquor to drain 08 and wash the precipitate first with an alcoholic solution of nitraniline and afterwards with ether ;or to mix the con- centrated alcoholic solutiorls of the two chlorides wash the precipitate with a small quantity of water and remove the mother-liquor as com-pletely as possible by pressure.This salt when dry has a yellow colour ; it crystallises with the greatest facility from a concentrated alcoholic solution separating almost instantly in capillary needles arranged in stellate groups ;it may be heated considerably above 100' without decomposition but burns away with slight detonation at a higher temperature The aqueous solution is decomposed by evapo- NITRAN 1LIN E A N D PARA N I TR A N I LI N E . ration; the solution in alcohol is more permanent. The salt gave by analysis 28.22 per cent. platinum ;the formula requires 28.72 per cent.(Pt=98*5). As this salt is much more soluble in alcohol than in water an abundant crystalline precipitate is obtained on adding water to a concentrated alcoholic solution. This precipitate dried at 100' contained 28.45 per cent. platinum and consisted therefore of the unaltered double salt. 2. If the double salt obtained as above be washed with a mixture of alcohol and ether it is decomposed and there remains a less soluble yellow compound C,,H,W,O .HCl +2PtCI, in which the quantity of platinum given by analysis IS 38.16 the formula requiring 38.36. This salt is partially dissolved with red colour by alkalies the rest being left in the form of a brick-red powder which dissolves with red colour in water and alcohol. From the aqueous solution crystals were once obtained having the form of small red regular octohedrons; but from want of material they were not further examined.Subhate of Nitraniline.-A solution of nitraniline in dilute sul- phuric acid yields by gentle evaporation large shining laminae the smaller crystals of which exhibit under the microscope the form of square tables. The salt has a strongly acid taste is depomposed by water but remains unttltered in the acid. The biacid salt C,,H,N,O, +2(HO.SO,) contains by calculation 33-90 per cent. sulphuric acid ; analysis gave 34.41 per cent. Bitrate oj Nitraniline.-The base dissolves very easily in warm nitric acid and the salt crystallises in shining needles several lines long and perpendicularly truncated :it is decomposed by water.The oxalate crystallises in delicate needles and laminae; it is an acid salt sparingly soluble in water and forming a yellow solution. The tartrate forms a yellow solution which deposits yellow needles ; potash does not precipitate but dissolves it with red colour. When a recently prepared solution of tannic acid is added to a solution of hydrochlorate of nitraniline and afterwards a little potash- solution poured in a copious flocculent or almost gummy precipitate is formed which is decomposed by an excess of potash part of the base separating in the crystalline form. 2. Paran it raniline.-This substance was prepared, according to Hofmann and Muspratt'e directions by the action of sulphqretted hydrogen on an alcoholic solution of dinitrobenzol saturated with ammoniacal gas.After treating the solution with animal charcoal the base was obtained in very beautiful yellow highly lustrous long flattened needle-shaped crystals. These crystals gave by analysis 52.01 per cent. carbon and 4.37hydrogen the formula C,,H6N204 requiring 52-17 C and 4.35 H. Paranitraniline melts at 108' (Hofmann and Muspratt fix the melting point at 110') and volatilisev at about the same temperature VOL. VII1.-NO. XXX. N 178 ARPPE ON NLTRANXLINE AND PARANITRSNfLINE. forming a sublimate of yellow shining laminae which by micrometricd examination were found to consist of rhombic tables of 51' and l29' having one of their acute angles either perpendicularly truncated or bevelled with two faces but the two obtuse angles either obliquely truncated or unaltered.They often unite in macles with a deep re-entering angle this made-formation being likewise indicated by a feathery striation of the lamellze passing in two different directions. The crystals separated from solutioiis exhibit a similar want of sym- metry. The laminze which separate from the aqueous solution are perpendicularly truncatc d at one end and bevelled at the other with two faces inclined at 98" to one another and 131' to the adjacent faces. Prom the alcoholic solution the base separates by spontaneous evaporation partly in small wedged-shaped four-sided laminze two of whose faces are likewise inclined to one another at an angle of 98O while the other two form a very acute angle,-partly in somewhat large crystals with re-entering obtuse angles.Paranitraniline dissolves sparingly in water requiring 600 times its weight of water at 185O to dissolve it; in boiling water it dissolve8 more readily likewise in alcohol and ether. With hydrochloric acid it forms a colourless solution from which elongated rhombic tables of 120" and 60" separate. This salt dissolves readily in hydrochloric acid is not altered by exposure to the air but is decomposed by water in such a manner that the greater part of the base separates out,-a statement contradictory to that of Hofmann and Muspratt who found their hydrochlorate of nitraniline to dis-solve in water with extraordinary facility. Subhate qf Paranitraniline forms shining microscopic crystals consisting of rhombic tables which have but little taste and form a perfectly colourless solution in water.Potash and ammonia precipi- tate the base in the crystalline form. Nitrate of Parunitraniline is a crystalline powder sparingly soluble in the acid easily in water ; hence the nitric acid poured on the base forms a white crystalline powder which disappears on the addition of water. The author has not been able to confirm the statement of Hofmann and Muspratt that paranitraniline is decomposed with violence by nitric acid. Tartrate of Paranitraniline forms a yellow solution from which yellow. rectangular tables separate ; potash added to the solution throws down the base in the form of a yellow crystalline precipitate insoluble in excess of the reagent.Tan& acid acts with parailitraniline in the same manner as with nitraniline. From the preceding description of nitraniline and paranitraniline it is clear that these two bases are essentially distinct and cannot be easily confounded They are more especially distinguished by their ARPPE ON THE BNILIDES OF TARTARIC ACID. melting points their crystalline forms and _their relations to various solvents ; moreover their sulphates nitrates and tartrates exhibit essential differences. But they also present other points of distinction more easily recognisable. l'aranitraniline has a sweet burning taste whereas nitraniline is nearly tasteless. Paranitraniline has a deeper yellow colour than nitraniline ; its saturated solution is nearly orange- yellow and becomes paler on cooling; the colour of nitraniline as well as that of its solution is always light yellow.Paranitraniline has a strong lustre ; the crystalline needles which it forms are flexible or elastic and therefme difficult to pulverise ; nitraniline has a fainter lustre and its crystalline needles are brittle and easily rendered elec- trical by friction. On the Anililes of Tartaric Acid." By E. Arpye. TARTARIC ACID forms with aniline a crystalline salt which if tartaric acid be regarded as monobasic,' exhibits the composition of a bitartrate. This salt begins to decompose at temperatures a little above looo; if it be kept for some time between 130' and 1No,it turns brown giving off vapours of water and aniline and at the game time a new Crystalline body is formed which covers and penetrates the dark mass.At 150° partial fusion takes place after which the addition of solution of chloride of lime no longer indicates the presence of unaltered aniline. The resulting preparation is thoroughly boiled with water whereby Turtanil is extracted which substance must then be purified by repeated crystallisation and treatrnen t with animal charcoal. The brown mass which remains undissolved by the water is boiled with strong alcohol which dissolves it completely and on cooling yields delicate crystals which may be decolorised by the ordinary methods these crystals consist of Tartunilide. 1. Tartanilide C,,H16N,0 (=BC,,€I,N . c,H601,-4? HO) is insoluble in water sparingly soluble in ether and is not taken up in large quantity even by boiling alcohol.Prom the hot saturated alco- holic solution it is deposited on cooling in fine colourless needles which when collected on a filter and pressed aggregate together in nacreous laminated masses retaining their continuity even after drying. It may be heated to 250' without visible decomposition but is decomposed when fused ; sublimes somewhat above its melting- point; and when carefully heated between two watch glasses yields Ann. Ch. Pharm. xciii. 352. 180 -4RPPE ON a sublimate of shining iridescent lamin= which however not being very volatile remain adhering to the unfused portion. At a higher temperature a dull crystalline or- mealy sublimate is obtained.Tartanilide is a very stable substance; it may be boiled in alkaline solutions without alteration ;hot hydrochloric acid dissolves it with difficulty nitric acid with partial decomposition ;sulpharic acid is the only acid which dissolves it readily. Calculated. Found. 32 C . . 192 64.000 63.61 16H ... 16 5 '334 5.40 2N.. . 28 9-3w 80 . . . 64- 21.332 C32H 1GN208 300 1oo*ooo 2. Tartanil C2,H9N0 (= C,,H,N . C8H60,,-44 HO) dissolves very readily in water and alcohol and separates from hot concentrated solutions either as a dull white fine-grained powder or in laminae having a pearly lustre. Slow cooling and perfect purity in the pre- paration favour the production of the crystalline modification ;and on the other hand sudden cooling and the presence of a small quantity of tartaric acid appear to give rise to the granular variety.Tartanil bears a heat of more than 200' C. without decomposition ; the granular variety however passes at that temperature into the crystalline but without any change of chemical composition ; the sublimate thereby obtained forms an extremely delicate woolly crystallisation of unaltered tartanil. At 230° fusion and decom- position take place. Tartanil has no taste but reddens litmus perceptibly even when perfectly pure. It dissolves but slowly in ether but is readily taken up by other solvents. Calculated. Found. 20 c . . . 120 57.97 57.71 9H ... 9 4'35 4.38 N,.. 14 6.76 80 . . . 64 30.92 C20H9N08 207 100.00 3.Tartanilic Acid C20H11N0,0,is obtained by boiling tartad for about a quarter of an hour with a solution of ammonia evapo- rating the excess of ammonia at a gentle heat adding baryta-water in excess to the solution washing the copious precipitate which is thereby formed and decomposing it with sulphuric acid. From the filtered solution the tartanilic acid separates partly in light red nodular crystalline masses partly in ahining laminae. After purifi- THE ANILIDES OP TARTAltIC ACID. cation with auimal charcoal this acid forms colourless laminze having a strong lustre. It melts at 180"C. and is at the same time par- tially decomposed with loss of water. It dissolves without difficulty in water and alcohol but is much less soluble in ether.Tartanilate of Ammonia after evaporation over sulphuric acid forms a very efflorescent easily soluble crystalline mass. A solution of this salt gives no precipitate with lime-water even after addition of ammonia; but if potash be added a turbidity is produced which increases on boiling and passes into a copious bulky precipitate. Chloride of calcium and chloride of barium form no precipitates not even on addition of excess of ammonia. Baryta-water forms a copious precipitate soluble in sal-ammoniac sesquichloride of iron or yellow precipitate. Tartanilate of Baryta is soluble to a considerable extent in boiling water and separates on evaporation in shining irregular crystalline spangles. It yields by analysis 26.10 per cent. baryta corresponding to the formula BaO .C2,H,,N09 which requires 26.15 per cent.baryta (Ba=68.5). Tartanilaie of Silver forms a white somewhat soluble powder containing 32.66 per cent. silver. The formula Ago. C2,Hl,N0 requires 32.55 per cent. 4. On the action of Nitric Acid upon Tartanil and Tartanilide.-Nitric acid rectified over sulphuric acid acts strongly on these bodies. On mixing them with the acid considerable heat is evolved accom- panied with formation of picpic acid. If the rise of temperature be prevented by immersing the vessel containing the nitric acid in snow and adding the anilides by small quantities a solution is obtained from which water throws down a yellowish body quite insoluble in water very sparingly soluble in alcohol and presenting under the microscope the appearance of a crystalline powder.When this nitro- compound is boiled with carbonate of soda part of it is dissolvecl but the solution does not yield crystals. The. greater portion remains undissolved aud appears to contain picric acid. As these experiments did not lead $0the preparation of nitraniline the author discontinued them and did not examine any further into the chemical relations of tartonitraniline. The Anilides of Racemic Acid appear to be identical with those of tartaric acid ; for the author has obtained from racemate of aniline compounds which do not differ from tartanil and tartanilide at least in their external characters. PIRIA ON SALICYLIC ACID. On Salicylic Acid." By R. Piria THlS acid usually regarded as monobasic nevertheless exhibits the singular anomaly of forming acid ethers analogous rather to the acid ethers of polybasic acids than to neutral ethers.In the course of investigations relating to this matter thc author has succeeded in discovering the causc of' this anomaly or rather he has found that it does not actually exist. The truth is that salicylic acid which has hitherto beel regarded as monobasic is really bibasic and in a very marked degree,-forming with the utmost facility salts with two equivalents of base. The salts with 1 eq. of base which are those already known may for distinction be denominated acid saliqlates ; and the ncwly-discovered salts with 2 eq. of base neutrul salicylntes. The neutral baryta-salt is prepared by adding a concentrated solution of hydrate of baryta to a concentrated boiling solution of the acid salicylate; as the neutral salt is much less soluble than the acid salt it separates out immediately in small white crystalline laminae which may be purified by recI*ystallisation from boiling water.This salt has a very decided alkaline reaction; in the state of aqueous solution it is decomposed by carbonic acid salicylate of baryta being formed and half the Earyta precipitated as carbonate. The composition of the neutral salt is C,,H4Ba,06+ 4 Aq. ; at 100" it gives off 4 eq. water and becomes anhydroim The neutral lime-sa2t is prepared with equal facility. When a solution of lime in sugar-water is added to a solution of acid salicylate of lime the neutral salt separates immediately as a nearly insoluble crystalline sandy precipitate which has an alkaline reaction and is dc composed by carbonic acid like the baryta-salt.The composition of the neutral lime-salt is C,,H4Ca,06 +2 Aq. The neutral lead-salt is anhydrous and forms a heavy white crystalline powder having the composition C,,H4Pb206. It is easily obtained by adding tribasic acetate of lead to a saturated boiling solution of the acid salicylate. If this acid lead-salt be decomposed by ammonia in slight excess and the resulting mixture boiled a pentabasic salicylate C,,H,Pb206 +3 YbO falls dowu as a light insoluble white powder consisting of microscopic laminae which have a pearly lustre. The cupric salts of salicylic acid had not been previously examined.Yiria has prepared the acid salicylate by decomposing the acid sali- cylate of baryta with a solution of cupric sulphate ; it crystallises in long bluish-green needles having the composition C,,H,CuO +4Aq. It gives off its water of crystallisation considerably below 100'. This salt exhibits remarkable properties. When heated in a small quantity of water not sufficient to dissolve it completely it melts below looo f Ann. Ch. P1ix:n. xciii. 262. WILL ON HYDROSULPHATE OF MUSTARD-OIL. and is converted into the neutral salt which remains undissolved and free salicylic acid which dissolves in the water. Ether decomposes it in a similar manner at ordinary temperatures. The neutral copper-salt obtained in th'e manner above described by the decomposition of the acid salt is a light nearly insoluble powder of yellowish-green colonr its formula is C,4H4Cu206 + 2Aq.Piria has likewise obtained two neutral salicylates in which the two equivalents of base are formed by different metals vie. a potassio- cupric sahylate Cl9H,KCuO6 + 4 Aq. which crystdises in beautiful emerald-green lainin= and baryto-cuyric salicylate which forms a crystalline powder containing C,,H,BaCuOG + 4,4q. On some Compounds of Hydrosulphate of Mustard-oil.* By H. Will. INa memoir on the essential oil of black mustard,t the author has demonstrated the existence of a compound of that oil with sulphu- retted hydrogen having the formula C,H,NS . H2S2. Gmelinf denominates this compound Subhosinapic acid ; G e rh ar d t 6 regards it as sulphocarbamic acid in which 1 eq.hydrogen is replaced by ally] C6H,; thus +-Sulphocarbamic acid. Allyl-eulphoctarbamicacid. NH (C S) . S NH (C6H5) (C S)2 . S H.Sl H.6 According to Will's formula it is sulyhocyariide of ally1 combined with sulphuretted hydrogen :-Will formerly obtained the componiid by the action of an alcoholic solution of potash upon oil of mustard it beins theu produced together with carbonic acid and an oily body CI4HlCN2S2O2 in the manner represented by the equation- On separating the oily body ncutralising with acetic acid diluting the * Ann. Ch. Yharin. xcii. 59. t Ibid. lii. 30. ZIundb. d. Cliem. 4. Aufl. v. 207. 8 Trait,d de C'himie Organique ii. 803. 184 WILL ON SOME solution with a large quantity of water and adding acetate of lead a lemon-yellow very unstable lead-salt is thrown down whose analysis HS leads to the formula C,H,NS + PbS).From the author’s more re- cent experiments it appears that the whole of the mustard-oil may be readily converted into the siilphur-acid by treating it directly with alcoholic solutions of metallic hydrosulphates. In this manner the following compounds have been obtained the analyses of which con- firm the composition of the acid previously deduced from the lead- salt :-Oil o$ Mustard with Hydrosulphute vj Ammoniuw When oil of mustard is dropped into a saturated and colourless solu-tion of hydrosulphate of ammonium in strong alcohol its odour is instantly destroyed the liquid becomes strongly heated and in a few seconds solidifies to a crystalline magma composed of colourless needles of the double salt.Calculation. Experiment; dried in vactm 8C . . 48 32.00 ,-31.70 31.36 10 H . . 10 6.66 6-90 6.77 2N4s . . . . 28 64 18.67 42.67 17-40 43.03- 43-30 - 150 100~00 99.03 This salt is not very stable but like the following compounds decomposes spontaneously by keeping. Oil oj’ Mustard with Hydrosut’phate of Potassium An alcoholic or aqueous solutio? of hydrovulphate of potassium to which oil of mustard has been added as long as the odour of the latter disappears yields by slow evaporation in vacuo (provided the quantity of salt present is not too small) large rhombic tables often an inchin diameter ; by quicker evaporation needle-shaped crystals are formed.These crystals while immersed in the liquid are transparent and colourless but on exposure to the air become opaque and yellow 1iJPing their form and becoming partially insoluble in water which then leaves a sulphur-yellow mass. The aqueous solution of the COMPOUNDS OF HYDROSULPHATE OF MUSTARD-OIL. 1% recently-prepared salt may be heated without evolving the odour of. mustard-oil; if it be heated and then mixed with nitrate of silver sulnhide of silver is Dreciuitated and the odour of mustard-oil becomes irnkediately percephle.' The dry compound likewise gives off mustard-oil when heated :-Calculation. Experimeut. 8C . . 48.0 28.04 6H. . 6.0 3.50 - 11'. . 14.0 8.18 - 4s .. 64.0 37.38 38-09 K . 39.2- 22.90 22.50 171.2 100.00 Oil of Mustard with Sulphide of Potassium.-a. C,H,NS +.2KS. -An alcoholic solution of monosulphide of potassium mixed with oil of mustard the former being in slight excess deposits by gentle evaporation a white granular salt which when heated gives off oil of mustard without changing its colour. It gave by analysis 39.2 per cent. of potaesium ;the formula requires 37.4. 6. C,H,NS +KS.-The mother-liquor from which the preceding salt has separated yields when left to stand over sulphuric acid in vacuo needle-shaped crystals having a scarcely perceptible tinge of yellow they behave like the preceding salt, but contain less potas- sium. Analysis gave 25.5 and 25.0 per cent.potassium the formula b requiring 25.4. It appears then that oil of mustard forms crystallisable salts not only with the hydrosulphates but also with the monosulphides of metals and that the combination with the latter takes place in more than one proportion. Oil of Mustard with Hydrosulphate of Sodium C8H5NS2 %}S2+6H0. This compound is readily obtained by mixing a warm alcoholic solu- tion of hydrosulphate of' sodium with oil of mustard till the odour of the latter is no longer destroyed. It separates in nacreous laminz which are greasy to the touch and when heated first melt and then give off a large quadtity of mustard-oil. The salt contains water of crystallisation and like the preceding cannot be preserved without decomposition WILL ON HYDROSULPHATE OF MUSTA R D-OIL.Calculation. -.Experiment. 8C. . 48-0 23.90 23.70 12 11. . 12.0 5.73 5-93 N. . 14.0 -4s. . 64.0 -60. . 48.0 -Na . 23.1 11.10 11.00 114 c_ 209.1 Oil of Mustard with Hydrosubhate of Barium C6H,NS .ElS2+4H0. This salt is produced by adding oil of mustard to a rsolution of sul-phide of barium supersaturated with sulphuretted hydrogen and mixed with a small quantity of alcohol or by passing sulphuretted hydrogen gas through water mixed with alcohol in which hydrate of baryta and oil of mustard are suspended; it is likewise deposited from the mother-liquor of the following less soluble salt containing mono- sulphide of barium. The more soluble salt forms crystalline larninz resembling those of the sodium-salt :-Calculation.Experiment. -8C. . 48-0 20.20 -19-90 10 H. . 10.0 423 -4.60 N. . 14.0 -L 4s. . 64.0 -26.5 40. . 32.0 27.05 -Ba . 68.6 29-00 30.4 30.44 -236.6 Oil of hlustard with Sdphide of Barium C,H5NS . 2BaS +2HO. -When oil of mustard is gradually added to a yellow heated solu- tion of sulphide of barium-such as is obtained by treating crude sulphide of' barium with water-till the odour remains permanent and the liquid filtered the filtrate yields on cooling colourless or slightly yellowish laminae which cru-mble to a white powder on ex-posure to the air. This compound is also precipitated by alcohol. The salt smells of oil of mustard does not melt when heated but burns away with a glimmering light at a higher temperature.Two analyscs made with the sa!t dried by repeated pressure between paper BERTAGNINL ON PFIILLPRIN. gave 49.1 and 47.3 per cent. barium; the above formula requires 41.94. This compound appears to be capable of crystallising with a different amount of water inasmuch as a salt obtained in another preparation gave only 41.6 per cent. barium which corresponds with the formula C H NS .2BaS +GHO (calculated quantity of Ba=42.6). Of,!of Jfustard with Hydrosulphnte of CuZcium.-When milk of lime is mixed with oil of mustard and a little alcohol added to dissolve the latter the mustard odour disappears entirely on passing sulphn- Petted hydrogen through the liquid to supersatiiration. A clear solution is theu obtained which wheu evaporated over the water-bath yields the calcium compound in the form of a slightly yellow trans- parent jelly.When perfectly dried it falls to pieces and gives off abundance of oil of mustard. On Phillyrin.* By C. Bertagnlni. THISsubstance is obtained by treating the decoction of Phitlyrea bark with lime or oxideof lead and evaporating the liquid to a certain point the phiyyrin then separating after a while in the crystalline state. Pure phillyrin is nearly tasteless ; it dissolves very sparingly in cold water with tolerable facility in hot water readily in alcohol but not in ether. Its solutions are not precipitated by those of metallic salts. Ammonia and the fixed alkalies have no action upon phillyrin but mineral acids readily decompose it.When phillyrin is boiled with dilute hydrochloric acid a resinous substance is produced which separates in drops qnd a liquid which when treated with Tro mmer's test-liquid produces an abundant separation of cuprous oxide. Now as phi!lyrin aid the resinous substance separated from it do not act on this test-liquid it appeared probable that phillyrin is a substance of more complex constitution,-like amygdalin ealicin &c.,-and capable like these bodies of yielding sugar as om of its products of decomposition. When phillyrin is heated with a proper quantity of dilute hydro- chloric acid till the separation of resinous matter has ceased the liquid neutralised with carbonate of lead the filtrate evaporated the residue exhausted with alcohol and the alcoholic solution evaporated over the water-bath a sweet syrup is obtained which in a few weeks solidifies into a warty crystalline mass exhibiting all the characters of grape-siigar.* Ann. Ch. I'liarin. xcii. 101). 188 BERTAGNINI ON An attempt was also made to decompose phillyrin with synaptase but that substance does not act upon it. To emure that the substance combined with sugar in phillyrin is not separated by the hydrochloric acid in an altered state,-as is the case in the decomposition of salicin,-the phillyrin was subjected to the lactic acid fermentation whereby it yielded on the one hand the usuaI products of the lactic acid fermentation of sugar and on the other the substauce abovernentioned which may in this manner be readily obtained in the pure state.This substance which may be called Phillygenin is not sensibly altered by acids and is perfectly identical with the resinous body which is produced though not quite pure by the action of hydrochloric acid on phillyrin. Pure philly- genin crystallises readily and forms a perfectly white mass having a pearly lustre. It is insoluble in cold water very sparingly soluble in boiling water but dissolves readily in alcohol and ether. Strong sulphuric acid colours it red. The analyses of phillyrin and of the several products derived from it lead to the formula c54H34022+ 3 Aq. Calculated. Found. y-=/--. Carbon Hydrogen . 57.75 6.63 57.88 6.63 57.66 6.72 57.72 6.52 57.82 f5*7:'3 Oxygen . 35.62 35-49 35.62 35.46 35-45 100~00 100*00 100*00 100+00 100~00 The 3 equivs.of water of crystallisation are given off between 50' and 603 C. and at 100' the substance is perfectly anhydrous. The loss of weight which phiUyrin sustains in drying is 4-7 per cent. ; by calculation it should be 4.8. The formula of anhydrous phillyrin is therefore C,,H,,O,,. Yhillygenin gave by analysis numbers corresponding with the formula C42H24012, as shown by the following table :-Calculated. Found. /--Carbon . . 67.74 67.83 67.60 Hydrogen . 6.45 6.69 6-66 Oxygen . . 25.81 25.48 25.74 -100~00 100-00 100~00 Phillygenin does not dimiuish perceptibly in weight when subjected to further drying; hence the formula just given must be regarded as that of anhydrous phillygenin.Since phillyrin yields by decoinpositioii nothing hut grape-sugar .and phillygcnin -wc arc led to supposc that its coiistitution cor- PHILLYRIN. 189 responds exactly with that of salicin and that it is formed by the union of two groups of atoms with elimination of 2 eq. water as shown by the following equation :-C42H24012 + C12H12012 = 'F~4~34'22 + 'Ho' Phillygenin. Grape-sugar. Anhydrous Phillyrin. This equation is precisely similar to that which expresses the constitution of salicin :-C,,H,04 + C12H12012= C261118014+ 2 HO. Saligenin. Grape-sugar. Salicin. On comparing the formulae of phillygenin and saliqenin we dis- cover a remarkable relation between them. Phillygenin is in fact polymeric with saligenin its formula being exactly treble that of the latter :-C14H804 = C42H24012 3 eq.Saligenin. 1 eq. Phillygenin. Phillyrin is converted by the action of chlorine into chloruretted or bromuretted derivates which crystallise in needles and are less soluble than phillyrin. Their constitution is similar to that of phillyrin and they are decomposed by the same reagents in a cor-responding manner. Thus for example bromophillyrin under the influence of acids or of the lactic-acid fermentation yields grape-sugar or its decomposition-products and bromophillygenin which cr ystallises in shining needles. Nitric acid acts differently on phillyrin according to its temperature and degree of concentration. With a dilute acid in the cold a mas8 of yellow silky crystals is obtained.With strong acid there is formed another product which separates in crystalline grains. Lastly if strong acid be used at a boiling heat carbonic acid and nitrous fumes are evolved and the liquid is found to contain oxalic acid together with a product which crystallises in shining laminae. I90 SCB31ID ON On mangostin.* By W. Schmid. THISname is given to a yellow crystalline substance obtained from the rind of the fruit of the Mangosteen (Garcinia mangostana; Order Guttijem) which is cultivated in the East Indian Islands. This fruit is one of the most delicious of tropical productions and its rind is said to be very efficwcious in the treatment of fevers equalling if not exceeding that of cinchona-bark especially when used in the f'resh state.To extract the active priuciple of this rind a quantity of old dry rinds which were of a brown-red colour thick spongy of astringent taste and lined in the interior with a yellow semi-crystalline sub-stance were finely pulverised and repeatedly boiled with water. The aqueous solution consisted chiefly of tannin which blackened iron-salts. The residue was then treated with hot alcohol which completely dissolved the yellow crystalline body. The filtered liquid which was brown with a greenish lustre did not deposit crystals when left to stand but on evaporation yielded yellow amorphous masses containing the substance which the author calls Mangostin mixed with a large quantity of resin. This resin is very difficult to separate. The best mode of separation is to heat the filtered alcoliolic solution to the boiling point and add distilled water in small quantities from time to time till the liquid becomes opalescent.The resin which is but sparingly soluble in cold dilute alcohol is for the most part deposited first at the bottom of the vessel while the mangostin remains in solution and separates some time after in the form of small yellow silky lamina. Hence if the liquid be decanted from the resinous deposit the mangostin which afterwards separates will be tolerably pure. But to removc the resin completely it is necessary to dissolve the maiigostin in alcohol and precipitate with subacetate of lead suspend the resulting compound of mangostin and lead-oxide in alcohol after thorough washing and pass sulphuretted hydrogen through the liquid while it is kept warm.As the mangostin will not crystallise excepting from solution in dilute alcohol the filtered solu- tion is then mixed at the boiling heat with water till it becomes milky. The niangostin which separates out on cooling and by evaporation of the alcohol is still not quite pure and must therefore be several times recrystallised from dilute alcohol. Mangostin crystallises in thin shining laminae of a beautiful gold- yellow colour ; it is inodorous and tasteless melts at about 190" C. without loss of water and forms a thick dark-yellow liquid which on cooling solidifies in a brittle amorphous transparent mass and is * Ann. Ch. Phsrm. xciii. 83. MANGOST i N. 191 heavier than water.When heated above the melting point it is for the most part decomposed but part of it sublimes unaltered. On platinum-foil it burns away without residue. It is insoluble in water but dissolves readily in alcohol and cther. The solutions have no action on litmus-paper. Dilute acids dissolve mangostin almost completely at a gentle heat and deposit it unchanged on cooling. Strong nitric acid converts it with the aid of heat into oxalic acid. Cold concentrated sulphuric acid dissolves it with partial decomposition forming a deep yellowish- red solution which chars when heated. Mangostin dissolves in alka- lies with a yellow or brownish colour. It is iot precipitated by any metallic salt excepting subacetate of lead. With sesquichloride of iron it produces a dark greenish-black colour which disappears on the addition of acids.The analysis of mangostin dried at looo agrees with the formula C,OH220,0 :-Calculated. Found. ,-40 C 240 . . 70.17 /-69.64 69.63 69.74 22 H . . 22 6-43 6.66 6.37 6-44 10 0 . . 80 23.40 23.70 24.00 23.82 C40W22010 342 100.00 100*00 100~00 100~00 The lead-compound of mangostin prepared by mixing the alcoholic solutions of mangostin and neutral acetate of lead in such proportion that the mangostin was not completely precipitated on the addition of a small quantity of ammonia gave by analysis 44.14 per cent. PbO 38.67 C and 3-45H numbers nearly agreeing with the formula 2(C40H220,0) + 5Pb0 + HO ; it is not however always obtained of the same composition for another sample prepared by the same method gave only 37.46 per cent.of lead-oxide. Certain other bodies obtained from plants of the same natural family as the Garcinia mangostana appear to bear some analogy to mangostin both in composition and in properties. Gamboge from Garcinia gutta has according to Johnston the formula C,H,,O,,. According to this composition it is possible that mangostin may be formed by oxidation of gamboge. And in fact gamboge treated with strong nitric acid yields a crystalline body which appears to bear a very close resemblance to mangostin. Indian yellow (purree) which is said to be obtained from the deposit of camels’ urine after those aniinals have eaten the fruit of Mangostana mungijer consists chiefly of the magnesia-salt of euxanthic acid whose formula is C,H160,,.As this formula stands in near approximation to that of mangostin as well as to that of BERTHEJBT AND DE LUCA OX 1OI)HYDRIN. gamboge it is possible that both these substances may be converted in the living body into euxanthic acid. These considerations induced the author to make some experiments with euxanthic acid whence it appears to be a conjugated compound. In fact when it is treated with strong sulphuric acid and the solution poured into water euxanthone as is well known separates out. The liquid filtered from this deposit. has the property of quickly reducing oxide of copper dissolved in potash,-a property not exhibited by either euxanthic acid or euxanthone.On the Action of Hydriodic Acid upon Glycerine." By MM.Berthelot and De Luca. WHENglycerine is saturated with hydriodic acid gas and heated to 100' in a sealed tube for forty hours and the product treated with potash and with ether a peculiar liquid is obtained to which tbe authors give the name of lodhydrin. This liquid is of a golden yellow colour ; syrupy ; of sp. gr. 1.783; dissolves about one-fifth of its volume of water without itself passing into the state of aqueous solution; dissolves in alcohol even when very dilute and still more readily in ether; has a sweet taste; is not volatile; but burns away without residue giving off vapours of iodine. Its composition is- C,,HllI06 = 2C6H806+ IH -6HO. Found. Calculated. Carbon .. 28 28.2 29.6 - 27.9 Iodine. . . -Hydrogen . 4 48.3 47 49.3 46 48.4 - 49.2 4.3 Aqueous potash decomposes the compound at loo' but the reaction is extremely slow. The products are on the one hand iodide of potassium and a substance similar to or identical with glycerine ; and on the other a rather volatile liquid free from iodine soluble in ether and having the composition- Found. Calculated. Carbon . . 55-2 55.4 Hydrogen . . 1.8 7.7 The iodine in cod-liver oil may perhaps be present in the form of iodhydrin or some analogous compound. * Compt. rend. xxxix. 748 ; Ann. Ch. Phys. C3Jxliii. 279.

ISSN:1743-6893    

DOI:10.1039/QJ8560800120

出版商:RSC    

年代:1856

数据来源: RSC