NOTICES PAPERS CONTAINED IN British and Foreign Journds. Chemical Report on the cause of the Fire in the ‘Amazon.’ By Professor Graham. February 17th 1852 MY LORDS In reply to the questions arising out of the disastrous loss of the I Amazon’ by fire which are proposed to me for a Chemical opinion I beg to submit to your Lordships the following statements and con- clusions. The practice of mixing together the various stores of the engineer consisting of oils tallow soft-soap turpentine cotton waste and tow and placing them in heated store-rooms contiguous to the boilers must be looked upon as dangerous in no ordinary degree for several reasons. Although oil in bulk is not easily ignited particularly when preserved in iron tanks still when spilt upon wood or imbibed by tow and cotton waste which expose much surface to air the oil often oxidates and heats spontaneously and is allowed to be one of the most frequent causes of accidental fires.The vegetable and drying oils used by painters are most liable to spontaneous ignition but no kind of animal or vegetable oil or grease appears to be exempted from it ;and instances could be given of olive-oil igniting upon sawdust; of greasy rags from butter heaped togetber taking fire within a period of twenty-four hours; of the spontaneous combustion of tape-measures which are covered with an oil-varnish when heaped together; and even of an oil-skin urribrella put aside in a damp state The ignition of such materials has been often ob- served to be greatly favoured by a slight warmth such as the heat of the sun.I am also informed by Mr. Braidwood that the great proportion of fires at railway-stations have originated in the lamp- store and that in coach-works also when the fire can be traced it is most frequently to the painters’ department the fire having arisen spontaneously from the ignition of oily matters. Lamp-black and ground charcoal are still more inflammable when the smallest quan- PROFESSOR GRAHAM'S REPORT ON THE FIRE IN THE 'AMAZON.' 35 tity of oil obtains access to them and should not be admitted at all among ships' stores. The stowing metallic cans or stoneware jars of either oil or turpen- tine in a warm place is also attended with a danger which is less obvious namely the starting of the corks of the vessels or the actual bursting of them by the great expansion of the liquid oil which is caused by heat.These liquids expand in volume so much as one upon thirty by a rise of not more than 60" of temperature or by such a change as from the ordinary low temperature of 40" to a blood-heat; the latter temperature may easily be exceeded in an engine-room. It is remarkable that the burning a few years ago of a large steamer on the American lakes which even surpassed in its fatality the loss of the cAmazon,' was occasioned by the bursting in the manner described of a jar of turpentine placed upon deck too close to the funnel by a party of journeymen painters who were passengers. This steamer was also on her first voyage and being newly varnished the flames spread over her bulwarks and extended the whole length of the vessel in a few minutes.The bulkheads of coal-holds appear to admit of obtaining consi- derable security from fire by being constructed double where close to the boiler with a sheet of air between the two partitions. The tendency of coals to spontaneous ignition is increased by a modera e heat such as that of the engine-room from which they would be protected by the double partition. I have obtained instances where coals took fire in a factory on two different occasions by being heaped for a length of time against a heated wall of which the tern- perature could be supported by the hand ; also of coals igniting after some days upon stone flags covering a flue of which the temperature was not known to rise above lSO' and of coals showing indications of taking fire by being thrown in bulk over a steam pipe.These were LancaRhire coals which are highly sulphureous; but the same accident occurred with Wallsend coals at the Chartered East Com- pany's works in London where the coals were twice ignited through a two-feet brick wall of which the temperature was believed by 'falr. Croll not to exceed 120" or 140'. The surface of deal in the partition opposed to the boiler would probably be better protected from fire by impregnating the wood with a saline solution which diminishes combustibility such as the zinc solution of Sir W. Burnett rather than by coating the wood on the side next the boiler with sheet iron.Indeed this use of iron appears to introduce a new danger. The iron being a good conductor of heat the wood below is heated nearly as much as if uncovered and wood in contact with iron appears to be brought by repeated heating to an extraordinary degree of combustibility and to become peculiarly liable to spontaneous ignition. Mr. Braidwood who has been led to that conclusion gave an D2 PROFESSOR GRAHAM’S REPORT instance of wood covered by sheet iron igniting spontaneously in a wadding manufactory. The numerous occasions also on which wood and paper have been ignited by Perkins’ heated water-pipes equally exemplify the dangerous consequences which may arise from mode- rately heated iron in long contact with combustible matter.The most obvious precautions for guarding against the sponta- neous ignition of coal stowed in ships’ bunkers appear to be the taking the coal on board in as dry a condition as possible and the turning it over if there is room for doing so as soon as the first symptom of heating is perceived. An obnoxious vapour is described as always preceding the breaking out of the fire and affords warning of the danger. The ignition of Newcastle coals in store is not an unfrequent occurrence at the London gas-works. It appears always to begin at a single spot and is met by cutting down upon and removing at once the heated coals. Long iron rods are placed upright in the coal heap which can be pulled out and indicate by their warmth the exact situation of the fire.Steam can be of little avail for extinguishing fire among coals in bulk; and water although it may extinguish the fire for the time is too apt to induce a recur-rence of the evil. For extinguishing a fire occurring in berths or cabins in the im-mediate vicinity of the boiler and engine-room steam might be more advantageously applied means of turning on the steam being pro-vided upon the upper deck or other distant place of safety. Steam however can only be said to be efficient in extinguishing flame or a blaze from light objects and is not to be relied upon beyond an early stage of a fire. Upon a mass of red-hot cinders the extinguishing effect of steam is insensible. An essential condition of applying steam with success to the extinction of a fire in the engine-room would be to prevent the rapid ingress and circulation of air at the same time which is occasioned by the draught of the fires.This could only be done completely by valving the chimneys for the quantity of heated air passing off by the funnels greatly exceeds in volume the steam produced by the boilers in the same time and would rapidly convey away the steam thrown into the atmosphere of the engine-room and prevent any possible advantage from it. The fire in the ‘Amazon’ appeared to the witnesses to take its rise either in the small oil store-room situated over the boiler or in a narrow space of from three to eleven inches in width between a bulk- head and the side of the boiler immediately under the same store- room.No substance remarkable for spontaneous ignition such as oiled cotton waste was actually observed in the store-room or the space referred to. The wood itself of the bulkhead which was within a few inches of the boiler may have been highly dried and sensibly heated by its proximity to the latter but is not likely to have acquired ON THE FIRE IN THE ‘AMAZON,’ 37 any tendency to spontaneous ignition ;for when that property results from low heating it is an effect of time requiring weeks or months to develop it The same observation applies to the decks in con-tact with the steam-chest which incased the base of the funnel. Nor does it appear probable that the coals in the coal-hold of the vessel gave occasion to the fire by heating of themselves and then burning through the wooden partition of the oil-store with which they were in contact.These coals were from Wales) and not remarkable for this pro-Pe*Y * They are also said to have been shipped in a dry and dusty state and not damp a month or two previously. Their ignition would also have been preceded by the strong odour before referred to which does not appear to have been remarked although the coal-hold communicated directly with the boiler-room Oil was seen to drop from the floor of the store-room upon the top of the boiler but not in greater quantity than might be acci- dentally spilt in drawing the oil from the tank for the use of the en gineere. A parcel of twenty-five newly-tarred coal-sacks which had been thrown upon the boiler also obtained it is supposed some of the same oil.This oil appears to be the matter most liable to the possi- bility of spontaneous ignition which was noticed near the spot where the fire commenced. But the sudden and powerful burst of flame from the store-room which occurred at the very outset of the conflagration suggests strongly the intervention of a volatile combustible such as tixrpen- tine although the presence of a tin can of that substance in the store-room appears to be left uncertain. It was stated to be there by two witnesses but its presence is denied by a third witness. I find upon trial that the vapour given off by oil of turpentine is sufficiently dense at a temperature somewhat below 3 loo to make air explosive upon the approach of a light.Aay escape of turpentine from the heated store-room would therefore endanger a spread of flame by the vapour communicating with the lamps burning at the time in the boiler-room or even with the fire of the furnaces. The fire appears not to have begun in the tarred sacks lying upon the boiler although from their position which was close to the store-room they must have been very early involved in the confla- gration and contributed materially to its intensity. The sacks appear to have been charged each with about two pounds of tar thus furnishing together fifty pounds of that substance in a condition the most favourable that can be imagined for rapid combustion. The freshness of the tar and its high temperature would make it ignite by the least spark of flame although riot prone to spon-taneous ignition.The burning of a group of newly-tarred cottages PROFESSOR GR14HAM’S KEPORT in Deptford which came under the notice of Mr. Braidwood arose from their being set on fire by lightning while the sun was shining upon them and the tar liquefied by the heat. The origin of the fire must remain I believe a subject of specula- tion and conjecture; but the extreme intensity and fearfully rapid spread of the combustion are circumstances of scarcely inferior inte- rest which are not involved in the same obscurity. The timber of the bulkheads and decks near the engine-room is reported to have been of Dantzic red wood or Riga pine and such was the character of a portion of the Amazon’s timber which was supplied to me for chemical examination.The wood has had its turpentine drawn off and differs in that respect from pitch pine. The Dantzic red wood is in consequence less combustible than pitch pine but more porous and spongy. Oil-paint is absorbed and dries more quickly upon this porous wood than upon oak and other dense woods. After their paint is well dried pixie and other woods certainly acquire from it some protection from the action of feeble and transient flames which might kindle the naked wood. But the effect of paint especially of fresh paint appears to be quite the reverse when the wood is exposed to a strong although merely passing burst of flame. The paint melts and emits an oily vapour which nourishes the flame and soon fixes it upon the wood.There can he no doubt therefore that the timber of the rAmazon’ was in a more inflarnmable state than ship-timber usually is from being recently painted and also probably from its newness and compara- tive dryness. But the circumstance which appears above all others to give a character to the fire in the ‘Amazon’ was its occurrence not in a close hold or cabin but in a compartment of the vessel where a vigorous circulation of air is maintained by the action of the boiler- fires and their chimneys. The air of the engine-room must be renewed under this influence every few minutes and would be so although full of flames rising above deck through the hatchways; for a portion of these flames would always escape by the funnels and add to their aspirating power instead of diminishing it.The combustion of bulkheads or decks once coiiimenced in this situation would therefore be fanned into activity and powerfully supported. The destruction of the floor of the oil store-room and the over-turning in consequence of the oil-tanks and combustibles into the well of the boiler-room was probably the crisis of the fire. A mass of combustible vapour would speedily be generated and shot about on all sides of which the kindling power upon the new and painted timber of the bulkheads and decks would be wholly irresistible. The burning of the ‘Amazon’ imprcsses most emphatically the dangerous and uncontrollable character of a firc arising in the engine or boiler room where the combustion is miniated by a stcady and ON THE FIRE IN THE ‘AMAZON.’ powerful circulation of air and the danger of collecting combustible matter together in such a place.The removal of the oil stores to a safer locality is fortunately generally practicable and is the measure best calculated to prevent the recurrence of any similar catastrophe. I have the honour to remain &c. &c. THOS. GRAHAM. To the Lords of the Committee of Privy Council for Trade. Contributions to the knowledge of the Manufacture of Gas. By E. Frankland Ph.D. (Read before the Manchester Literary and Philosophical Society January 13 1852.) (ABSTRACTED BY THE AUTHOR.) The constituents of purified gas as used for illuminating purposes are hydrogen light carburetted hydrogen carbonic oxide olefiant and other gases having the general formula C H, the vapours of hydro-carbons of the form C Hn+ and other hydrocarbons the formulzx! of which are unknown; in addition to these coal-gas usually contains small quantities of nitrogen oxygen and bisulphide of carbon vapour ; but these for our present purpose may be entirely disregarded Tt has always been asserted that hydrogen and carbonic oxide possess no illuminating power and that the light emitted by coal- gas is due to light carburetted hydrogen olefiant gas and other hydrocarbons ; I hope however to prove by the experiments detailed below that light carburetted hydrogen is for all practical; purposes also entirely devoid of illuminating power; and that therefore the whole of the light giving effect is due to the olefiant gas and hydro-carbons.This is an important point as we shall find that it much simplifies the estimation of the illurriinating power of any gas and teaches us that the nature of the combustible diluents of the olefiant gas and hydrocarbons has no effect whatever upon the quautity of light emitted by the mixture. The constituents of coal-gas may therefore be divided into two classes viz. illuminating and non-illuminating constituents. To the first will belong olefiant gas and the other hydrocarbons above-mentioned ; and to the second hydrogen light carburetted hydrogen and carbonic oxide. To the first class alone the illuminating power of the gas is due; but one member at least of the second class is also indispensable as a diluent without which we should find great diffi- culty in consuming the hydrocarbons without the production of much smoke.The members of the first class are all decomposed at a white heat instantaneously at a red heat more slowly depositing the whole or the greater part of their carbon in the form of very fine particles which become so many centres for the radiation of light in a Dpt. FRANKLAND ON THE gas Aatne ;and the greater the number of particles existing in a flame at the same time the greater will be the light emitted by that flame. It is therefore evident that the value of these hydrocarbons for the production of ligbt depends directly upon the quantity of carbon contained in a given volume and is altogether independent of the hydrogen with which this carbon is combined ; consequently the densest or most easily condensible of these gases and vapours of the first class are those which possess the highest illuminating power.All the compounds belonging to this class are as before stated decomposed more or less rapidly at a red heat; in the ordinary process of gas-making the interior walls of the retorts soon become coated with a stratum of carbon derived from this source. Now the extent of this decomposition must depend first upon the length of time during which they are exposed to the heated materials and secondly upon the number of particles which are in contact with the red-hot surface; consequently it will be diminished first by re-moving the gases rapidly from the retort and secondly by the mixture of the illuminating constituents with the non-illuminating ones :for it is evident that the number of particles of olefiant gas in contact with a given surface would only be half so great if this gas were diluted with an equal volume of hydrogen as it would be without such an admixture.Besides the use of the second class or non-illuminating gases which has been already stated they are of value as forming a medium for the solution of the vapours of such hydrocarbons as exist in the liquid or even solid state at the ordinary temperature of the atmosphere ;and they thus enable us to convert an additional quantity of illuminating materials into the gaseous form which they retain permanently unless the temperature fall below the point of satu-ration.The gain in illuminating power which is thus obtained will be perhaps better seen from the following example. If 100 cub. in. of olefiant gas being allowed to saturate itself with the vaponr of a volatile hydrocarbon containing three times the amount of carbon in a given volume of its vapour as that contained in an equal volume of olefiant gas took up or dissolved in this way 3 cub. in. of hydro- carbon vapour then if we express the value in illuminating power of 1 cub. in. of olefiant gas as unity the illuminating power of the 103 cub. in. of the mixture of olefiant gas and hydrocarbon vapour will be 109; now if we mix these 103 cub. in. with 100 cub. in. of hydrogen the mixture will be able to take up an additional 3 cub.in. of the hydrocarbon vapour and the illu- minating power of the 206 cub. in. will then become 118. Thus the hydrogen produces a gain in illuminating power equal to 9 cub. in. of olefiaiit gas or nearly 4-5per cent upon the total volume of mixed gases. When we consider that coal-naphtha contains hydrocarbons of grcat volatility and which are no doubt the surplus remaining after the saturation of the gas from which MANUFACTURE OF GAS. they have condensed the importance of this function of the non- illuminating class of combustible gases will be sufficiently evident. I may here remark that incombustible gases could not be employed for this purpose since their cooling influence upon the flame during the subsequent burning of the gas would diminish the light to a far greater extent than the hydrocarbon vapour could increase it.It is evident that all the three non-illuminating gases forming the second class would perform both the offices I have assigned to them equally well; and therefore we have as yet seen no reason for giving our preference in favour of any one of these diluents. If however we study their behaviour during combustion we shall find that where the gas is to be used for illuminating purposes hydrogen has qualities which give it a very decided preference over the other two. When gas is used for lighting the interior of public buildings and private houses it is very desirable that it should deteriorate the air as little as practicable or in other words it should consume as small a quantity of oxygen and generate as little carbonic acid as possible ;the oppressive heat which is often felt in apartments lighted with gas also exemplifies the great advantage of its generating a minimum amount of heat.1 cub. ft. of light carburetted hydrogen at SO' F. and 30 in. Bar. consumes 2 cub. ft. of oxygen during its combustion and generates 1 cub. ft. of carbonic acid yielding a quantity of heat capable of heating 5 lbs. 14 oz. water from 32' to 212'. 1 cub. ft. of carbouic oxide consumes 4 a cub. ft. of oxygen generates 1 cub. ft. of carbonic acid and affords heat capable of raising the temperature of 1 lb. 140z. of water from 32' to 212'. 1 cub. ft. of hydrogen consumes 4 a cub.ft. of oxygen generates no carbonic acid and yields heat capable of raising the temperature of only 1lb. 13 oz. water from 32' to 212'. Thus light carburetted hydrogen is very objectionable as a diluent not only on account of the carbonic acid which it gene-rates and the large quantity of oxygen it consumes but also by reason of the very great amount of heat which in relation to its volume it evolves on cornbustion the absolute thermal effect being more than three times as great as that of either of the other gases. The quantity of heat evolved by the combustion of equal volumes of carbonic oxide and hydrogen is nearly and the amount of oxygen consumed quite the same but the quantity of carbonic acid evolved by the first gives a decided preference to hydrogen as the best diluent.The same comparison also shows that where the gas is to be used for heating purposes arid the products of combustion are carried away light carburetted hydrogen is by far the best diluent. The experiments of Dulong on the absolute thermal effect of DR. FRANKLAND ON THE hydrogen light carburet ted hydrogen and carbonic oxide are taken as the basis of the foregoing calculations. These remarks indicate the objects that should be chiefly regarded in the generating department of the nianufacture of gas for illu- minating purposes these are 1. The formation of a due proportion of illuminating and non-illuminating constituents so that on the one hand the combustion of the gas shall be perfect and without the production of smoke or unpleasant odour and on the other the volume of gas required to produce a certain amount of light shall not be too great.2. The extraction of the largest possible amount of gaseaus illu- minating compounds from a given weight of material. 3. Tbe presence of the largest possible proportion of hydrogen amongst the non-illuminating constituents to the exclusion of light carburetted hydrogen and carbonic oxide so as to produce the least amount of atmospheric deterioration in the apartments in which the gas is consumed. I have not introduced these preliminary observations to show the inductive reasoning by which the process of gas-making described below was arrived at for I believe that so far as these considerations are concerned that process was accidentally adopted; but I bring them forward to illustrate and explain the principles involved in it and also to show that a close study of the chemistry of gas-manu- facture would have led to the discovery of this more phllosophical method of gas -generation long ago.Various attempts have been made to estimate the illuminating power of coal and other gases from the analytical results they yield but hitherto no certain method of acconiplishing this has been esta- blished. Dr. Henry regarded and not unjustly the consuniption of oxygen by a given volume of gas to be a rough estimation of its illiiminating power ; but it is evident that although generally those gases which have the highest illuminatirg poq-er consume most oxygen yet this is not always the case ; for a gas containing 10 per cent of olefiant gas 20 per cent of light carburetted hydrogen and 70 per cent of hydrogen would consume much less oxygen during cornbustion than one containing only 5 per cent of olefiant gas and in which the proportion of light carburetted hydrogen and hydrogen were reversed although its illuminating power would be twice as great.It will be seen from what has been already said respecting the illuminating power of carbo-hydrogens that the more dense these are the greater does that illuminating power become. This important fact was first pointed out in reference to coal-gas by Mr. Leigh,* * Memoirs of the Manchester Lit. and Philosoph. Soe. IX. (new series) 303. MANUFACTURE OF GAS.who was also the first to make an approach towards estimating the illuminating power of gas from its analysis. Mr. Leigh regards the illuminating power of coal-gas as due to light carburetted hydrogen olefiant gas and hydrocarbons and that the value of the latter is directly proportional to the quantity of oxygen required for their combustion. If we leave the light carburetted hydrogen entirely out of the calculation as I shall prove that this gas has practically no illuminating power this method generally gives results not far from the truth but which are nevertheless liable to very considerable error from the fact that the amount of oxygen consumed does not depend alone upon the luminiferous ingredients of the carbon but also upon the amount of hydrogen combined with that element and which is necessarily a variable quantity being in some of the hydrocarbons in the proportion C :H=n :n; in others C :H=n :n-6; and in others even C :H =n :n-10.If however we estimate the volume of carbon vapour contained in the luminiferous hydrocarbons and make that the basis of our calculation we avoid this source of error and obtain a correct expression for the illuminating power however much the composition of the hydrocarbons may vary. I have already pointed out a method for accomplishing this;* and Mr. Leigh in the memoir to which I have already alluded also describes a similar plan which he employs for the determination of the consumption of oxygen by these bodies. The method which I have adopted in the annexed experiments is the following A known quantity of the gas previous to the action of sulphuric acid is exploded with an excess of oxygen and the volume of carbonic acid produced accurately noted.Another known volume of the same gas after the withdrawal of the hydrocarbons by sulphuric acid is then similarly exploded with oxygen and the carbonic acid formed also estimated. Thus the percentage amount of hydrocarbons plus the volume generated by the non-luminous gases alone being known it is easy to calculate the amount of carbonic acid generated by 1 volume of the hydrocarbons. Thus if we designate the percentage of hydrocarbons absorbed by sulphuric acid by A the volume of carbonic acid generated by 100 volumes of the originalgas by R the carbonic acid formed by the residual gas after absorption of hydro-carbons by C and the volume of carbonic acid generated by the combustion of 1 volume of the hydrocarbons alone by X we have the following equation X=C-B and therefore the amount of carbonic acid generated by 1 volume of the hydrocarbons is represented by C-B A * Chem.SOC. Qu. J. IE. 225. Dfl. PRANKEAND ON THE but ae one volume of ‘carbon vapour generates one volume of carbonic acid this formula also expresses the quantity of carbon vapour in 1 volume of the luminiferous constituents. For the purpose of comparison however I represent the value of these hydrocarbons in their equivalent volume of olefiant gas one volume of which contains 2 volumes of carbon vapour; for this purpose the last expression need only be changed to C-B ftA Thus if a gas contains 10 per cent of hydrocarbons of which one volume contains 3 volumes of carbon vapour the quantity of olefiant gas to which this 10 per cent is equivalent will be 15.The illuminating power of the coal gases mentioned below has also been practically tested by Bunseii’s photometer and the results are corrected to those which would have been obtained by using a sperm candle burning 120grs. per hour ; and one of these candles burning for ten hours is taken as the standard of comparison for the total quantity of light yielded by a given volume of gas; thus when it is stated that the total quantity of gas produced from 1 ton of coal is equal to 4816 candles it is intended that the light afforded by the gas is equal to that yielded by 4816 sperm candles each burning 10 hours and at the rate of 120grs.per hour. The following experiments which I lately made at the request of two merchants of this town upon a new process of gas-rnaking known as White’s hydrocarbon process serve to illustrate the prin- ciples laid down in the preceding pages. Mr. White’s process consists essentially in the generation of non-illuminating combustible gases by the action of steam upon charcoal coke or other substances in a separate retort and the introduction of thesegases along with an excess of watery vapour into the retort in which the illuminating gases are being generatdJd and in such a manner that these latter gases shall be swept out of the retort as rapidly as possible and removed from the destructive influence of a high temperature.The excess of steam accompanying the water-gases into the second retort? performs there a remarkable office; it reacts upon the tar and fuliginous matter in a manner that will be described below and gives rise to the formation of a great additional quantity of gas a very large proportion of which is pure hy!rogen. That this reaction of the steam should be confined entirely to the tar and other refuse matters and should not affect the luminiferous gases generated in the same retort is scarcely con- ceivable since the constitution of tar and gaseous hydrocarbons is so nearly alike ; yet any destruction of illuminating principles that may be thus caused is iminensely overbalanced by the quantity of these principles which are saved from decomposition by their rapid removal MANUFACTURE OF GAS.from the influence of a high temperature and by the vapours of volatile hydrocarbons with which the water-gases remain more or less saturated. WHITE’S PROCESS APPLIED TO RESIN. I. PRACTICAL RESULTS. 4th Exp. Average. 1st Exp. 2nd Exp. 3rd Exp. Gasproduced per ton ofresin . . 26000 cbc. ft. 28120 cbc. ft. 36820 cbc. ft. 29300cbc. ft. 30060 cbc. ft. Resin-oil produced per ton of resin . . 88 9 galls. 64 galls. 41 8 galls 84.8 galls. 69 9 galls. Coal consumed in heat- ingretorts . . 13% lbs. 1396 lbs 1399 lbs. 1406 lbs. 1399 lbs. Charcoal for water-gas p.3 ss 100 Is 111 3* 97 ss 98 w Waterused .. 606 I* 790 #s 606 s9 660 *. 89 11. ANALYTICAL RESULTS. PEECENTAGE COMPOSITION OF PUHIFIED GASES. I 2nd Exp. 3rd Exp. -1st Exp. -4th Exp. Average. Olefiant gas and hydrocarbons . 8.27 7.94 7.78 8.53 8.13 Light carburetted hydrogen . . 18.76 45-06 22.79 32.25 29.71 Hydrogen . . . . . 42.03 37.59 50.27 43.62 43.38 Carbonic oxide . . . . 30.93 -.-15.60 18.78 9.41 19.16 10000 100*00 10000 100~00 10000 ILLUMINATING VALUE OF OLEFIANT GAS AND HYDROCARBONS EXPRESSED IN EQUIVALENT QUANTITY OF OLEFIANT GAS. 1st. Experiment. 2nd Experiment. 3rd Experiment. 4th Experiment. Average. 11-58per cent. 11.11 per cent. 10.89 per cent. 11.94 per cent. 11.38 per cent. i 1 I I WHITE’S PROCESS APPLIED TO COALS AND CANNELS.In order to obtain a fair comparison of the results yielded by the various coals when distilled alone (as in the usual process of gas-making) with those obtained from the same coals when treated with water-gas according to the hydrocarbon process each coal was distilled first by itself and then with the addition of water-gas equal weights being used for each experiment DR. FRANKLAND ON THE I. PRACTICAL RESULTS. Cnbic feet of gas p,',b~~~:~:6ii process. White's process. Gain per ton by White's Gain per cent by Name of coal. I-i per ton* I sperm candles. I----By old process 11,340 21,308 1 1 ........ 20,688 ~ I Wigan camel (Iiice Hall) 10,900 Wigan 1 1 dItto '(Bat .. 10,440 15,500 4,156 5,920 5,060 1,764 '2:; ;;% 13,934 18,560 6,314 11,088 16,840 5,772 108-6 carres). Boghead caanel . . 13;240 3,160 Ditto 2nd exp. . -. .. .... 51.720 Lermahago cannel . gi2 ~ 10,620 9,560 7,620 5,316 29,180 26,46)0 Methyl canuel . QUANTITY OF COAL OR CANNEL REQUISITE FOR PRODUCING LIGHT EQUAL TO 1000 SPERM CANDLES EACH BURNING TEN HOURS AT THE RATE OF 120 GRS. PER HOUR. Name of coal. Weight of coal. By old process. By White's process. Wigan cannel (Ince Hall) . * . 465.1 lbs. 347.4 lbs. Wigan cannel (Balcarres) . .. 539.0 )) 378.4 ,, Boghead cannel . . . .. 197'5 , 104.8 , Lesmahago cannel . . .. 293.9 ) 160.7 ) Methyl cannel . . . .. 443.9 ,) 396.T ,, Newcastle coal (Pelton) .* . 745.7 , 11. ANALYTICAL RESULTS. PERCENTAGE COXPOSITION OF GASES. 1 1 1 1 Wigan cannel Boghead cannel ~ ~ ~ ~Methyl cannel. o (Ince Hall). f g Byold By new Byold By new Byold By new Byold process./ process.1 process./ process./ process./ process] process. Hydrocarbons and 1 olefiant gas . . 10.81 1@55 1 Carbonic acid . . 1 1-19 I 0.00 I 100-00 I 10000 ILLUMINATING VALUE OF OLEFIAN1' GAS AND HYDROCARBONS EXPRESSED IN EQUIVALENT QUANTITY OF OLEFIANT GAS. Wigan Wigan Boghead Boghead Lesmaha- Lesmaha- Methyl Methyl Pelton camel by cannel by camel bl cannel by go cannel go cannel cannel by cannel by 1 coal by old pro-new pro- old pro- new pro-by old by new old pro- new pro- old pro- 1 1 1 1 1 cess. cess. I cess. _-cess. procesr. process.cess. cess. cesr. ~ --1 I----per cent. percent. per cent. I per cent I per cent. per cent. I per cent. 1 per cent. 16.13 13.72 31 11 W84 28'60 p?9~~t'l 18-58 14.04 1 7-16 MANUFACTURE OF GAS. The foregoing results bring to light several circumstances highly favourable to the hydrocarbon process of gas-making which could scarcely have been predicted previous to the actual trials being made. The first and most important of these is the disappearance of the carbonic acid contained in the water-gas during its passage through the coal retort ;this disappearance is so complete that the resulting gaseous mixture actually contains a much smaller percentage than does the gas obtained by the distillation of the coal alone. There is little doubt that this removal of the carbonic acid depends upon its conversion into carbonic oxide by the carbonaceous matters in the coal retort ; and of these the coke is probably the most active since the volatile matters do not differ materially from those produced during the distillation of resin; and these we have seen fail to remove the acid gas.Anotber favourable circumstance occurring in the process consists in the relatively small quantity of carbonic oxide that is produced. A large proportion of this gas would be equally objectionable with a high percentage of light carburetted hydrogen on account of the quantity of carbonic acid formed during its subsequent combustion. A reference to the composition of the foregoing gases shows us how- ever that in all cases the amount of carbonic acid generated is less than that formed by the combustion of an equal volume of the gas obtained from the same coals by the ordinary process of manufacture and in some cases it is even less than that produced by a pure coal- gas-flame giving an equal light.The favourable position which the hydrocarbon gases occupy in the above comparison would not have been attained if the whole or even a very large portion of the water- gas had been generated in the charcoal retort; for when water-gas alone is generated it is found to consist of hydrogen and carbonic oxide mixed with quantities of carbonic acid varying from 0 to 15 per cent according to the heat employed and other circumstances. When the percentage of the acid-gas is 0,then the volumes of hydrogen and carbonic oxide are equal; and as no important quantity of carbonic acid was ultimately present in the gases produced in the foregoing experiments the whole of that gas entering the coal retort must be converted into carbonic oxide and therefore we may consider the water-gas entering the coal retort as being composed of equal volumes of hydrogen and carbonic oxide.Now if the increase in the total quantity of gas produced by the application of the hydrocarbon process to any given coal or camel were due only to the water-gas formed in the charcoal retort it is obvious that the gaiu in carbonic oxide ought to be equal to the gain in hydrogen; but a glance at the analytical results shows that this is far from being the case.Thus for instance with Boghead gas the proportion is Gain in H gain in C0=3 5 :1 DR FRANKLAND ON THE and with Lesmahago cannel Gain in H gain in C0=4 6 :1 It is therefore evident that a large quantity of water-gas must be generated by the action of steam upon the carbonaceous materials in the coal retort and that this water-gas contains a very much greater percentage of hydrogen than that produced in the charcoal retort. Although we are not yet sufficiently acquainted with the action of watery vapour upon organic substances at high temperatures to state positively the cause of this excess of hydrogen yet there can be little doubt that it is derived from the action of steam upon the hydro- carbons of the tar.For as watery vapour in acting upon carbon transfers its oxygen to that element forming carbonic oxide and an equal volume of hydrogen so also when steam acts upon a compound of carbon and hydrogen it produces carbonic oxide but in doing so sets at liberty not only its own hydrogen but that of the carbo- hydrogen also; and thus the volumes of hydrogen and carbonic oxide remain no longer equal but the volume of the former becomes double treble or even fourfold that of the latter. An important feature in the history of a gas for illuminating purposes is its behaviour when exposed to cold I have therefore submitted several of the above gases to a temperature of 32' and carefully ascertained the loss of vohme by liquefaction of hydro-carbons.These experiments as might be expected show that the gases made by the new process suffer less loss by this refrigeration than those made from the same material by the old process. Cubic feet of hydrocarbons condensed Name of gas. from 100 cubic feet of gas on expo-sure to B cold of 320 F. Boghead by old process . . . . 4.42 cubic feet. Ditto by new process . . . . -24 ?I Methyl by old process . . . . . -33 1) Ditto by new process. . . . . 47 9f Ince Hall by old process . . . . -37 If MANUk’AC’CURE OF GAS. constituents not condensible either by fuming sulphuric acid or by chlorine; the nature of these constituents and the cause why they cannot be detected by our present methods of gas analysis I have already pointed out.* The following table exhibits this difference between the value of olefiant gas in coal-gas compared with that in cannel-gas and shows also that in the case of the latter the illu- minating power is always directly proportional to the amount of olefiant gas to which the percentage of condensible hydrocarbons is equivalent.The establishment of this rule with regard to gases having such different percentages of light carburetted hydrogen as the Boghead gas with and without water-gas I hold to be conclusive evidence that light carburetted hydrogen has no higher illuminating power than hydrogen or carbonic oxide. Vaiue of 1cub. ft. of the olefiant gas contained in the following gases expressed in sperm candles e&h burning ten hours at thi rate of 120 grs.per hour. CANNEL GASES. Candles. Ince Hall cannel . . 2.96 Boghead cannel . Lesmahago cannel . Ramsay’s Newcastle cannel . Methyl cannel . ’Y with water-gas 9 with water-gas 7 with wa ter-gas 3’ with water-gas ,? with water-gas . . . . . . . . . . 2.96 2.80 2.86 2.58 2-54 2-88 2.86 3-04! 3.03 COAL GASES. Canaes. Pelton coal . 4.23 City Company’s gas {coal) . . 3.73 3.92 Great Central Company’s gas (coal) In conclusion the advantages resulting froni the application of Mr. White’s hydrocarbon process to coals and cannels may be thus summed up 1. It greatly increases the produce in gas from a given weight of coal or cannel the increase being from 46 to 290 per cent according to the nature of the material operated upon.2. It greatly increases the total illuminating power afforded by a given weight of coal the increase amounting to from 12 to 108 per * Chem. SOC. Qu. J. 111,42. VOL. V.-NO. XVII. E DR. BNIIERSON ON THE DESTEUCTIVE cent being greatest whcn coals afforciiiig highly illumiaating gases are used. 3. It diminishes the quantity of tar formed by convertiug a portion of it into gases possessing a considerable illuminating power. 4. It enables us profitably to reduce the illuminating power of tbe gases produced from such materials as Boghead and Lesmahago cannels &c. so as to fit them for burning without smoke and loss of light. 5. In addition to these positive advantages the use of this process does not incur any additional expense in the working of the appa- ratus the wear and tear of retorts or the purification of the gas; and beyond a change of retorts it involves no alterations in the construction of furnaces and apparatus at present employed in gas manufactories conducted on the old system.On the Products of the destructive distillation of Animal Substances Part 11. BY Thomas Anderson M.D. F.R.S.E.* (ABSTRACTED BY THE AUTHOR) In a former paper on this subject I announced the discovery among the products of the destructive distillation of animal substances of picoline and described one new base to which I gave the name of petinhe and indicated the existence of several others. In examining these substances I found that the quantity of material though obtained from 300 pounds of bone oil was much too small to admit of satisfactory results; the process m,s therefore repeated with a similar quantity of the oil but I was again foiled by deficiency of material.The experience obtained in these preparations having enabled me to see that success could only be obtained by the use of very large quantities I once more commenced the tedious preparation of the bases froin no less than 250 gallons of the crude bone-oil. The oil was rectified in a large cast-iron retort furnished with a good condenser kept cold by a current of ice-cold water. A gentle heat was applied and the first 20 gallons which consisted of equal bulks of a very volatile oil and water charged with sulphide of ammonium carbonate and hydrocyanate of ammonia were collected apart and the rest of the oil received in a succession of casks which were numbered as they were filled.The watery fluid was separated from the oil supersaturated with sulphuric acid and boiled for a considerable time in a large copper boiler. It was then allowed to * Edinburgh Phil. Trans. SS 2 2-17. DISTILLA TI0N (13’ AN I 11A Id SUBSTANCES . cool slaked lime added in excess a copper head and condenser attached and heat again applied. The distillate was collected in a large glass receiver connected by a doubly bent tube with a second containing hydrochloric acid for the purpose of condensing ammonia and any of the very volatile bases which might be carried along with it. The distillate which had a powerfully arnrnoniacal and putrid odour was treated with sticks of caustic potash which caused ammo- nia to escape with effervescence while a small quantity of volatile bases collected on the surface which were separated and preserved.The oil of which only the more volatile half was used was agitated with dilute sulphuric acid. After two or three days during which the agitation was frequently repeated more water was added and the solution drawn off. The fluid after the addition of more acid was then boiled for the separation of Runge’s pyrrol. In my previous experiments I had neglected this substance but observing now that a very powerful odour was evolved when the fluid began to boil the head of the boiler was attached for the purpose of endeavouring to obtain it.The distilled fluid carried over with it a small quantity of a colourless oil which rapidly became red and in the course of a few days absolutely black and proved to be a mixture of an oil insoluble in acids and a series of bases of very remarkable properties obviously related to one another and which I designate provisionally by the name of pyrrol bases. When these substances had been entirely expelled for which long- continued ebullition is requisite slaked lime was added and the bases which had been retained by the acid distilled over. A watery solution was obtained from which the bases were separated as an oily layer by the addition of solid caustic potash. The potash solution still containing a considerable quantity of the more volatile bases which could only be separated by the use of a very large quantity of potash was distilled in glass vessels and the product collected in a succession of three receivers the first kept cold by water the second by a freezing mixture and the third containing hydrochloric acid for the purpose of condensing ammonia and another gaseous base by Rhich it was accompanied.The first receiver contained the oily bases which could now be separatedby a comparatively small expen- diture of potash ;in the second only a few drops of fluid were found; while the hydrochloric acid in the third was saturated with ammonia ad another gaseous base. This last solution was evaporated; the chloride of amtnonium,jwhich deposited in succession crops of crystals was separated ;and at length there was obtained a dark mother-liquor which on cooling solidified into a mass of foliated crystals deliques- cent in moist air.These were dissolved in absolute alcohol for the separation of traces of sal-ammoniac and purified by animal charcoal They were thus obtained in long transparent and colourless plates with a pungent and bitter taste. Treated with potash they evolved a E2 DR. AN1)ERSON ON THE DCSTli.lTCTIVE gaseous base having ail ainnioiiiacal and putrid odour. They gave a platinum-salt in fine golden-yellow scales the analysis of which cor- responded completely with the formula C H N . HCl. PtCI,; the base is consequently methylamine. The oily bases were dried by means of caustic potash and distilled in a retort with a thermometer.Ebullition commenced at about 150' F.; at 212' the receiver was changed and the oil distilling above that temperature collected in fractions of 10' each. The por-tion boiling under 212' each which were nearly equal in bulk. 5' was rectified and collected in fractions of They were all very similar in properties possessing a high refractive power and a pungent odou r very like .that of ammonia in the lower fractions. Exposed in the anhydrous state to a mixture of snow and salt they remain perfectly fluid but if a little water be added cryetals of a hydrate are depo- sited. The quantity of those bases which I obtained was too small to admit of complete separation by fractionated distillation ;I there-fore converted portions of those fractions which I had reason to believe corresponded to particular bases into platinum salts.selected in the first instance the most volatile fraction which boiled under 150° and obtained from it a beautiful yellow salt readily soluble in cold .v\.ater still more so in boiling water and depositing in golden scales which gave analytical results corresponding with the formula C H N . HC1 . PtC1,. The base is therefore propylamine which I have already obtained by the action of potash upon codeine. Having obtained these bases etbylamine the intermediate term of the same series was next sought for ;and by collecting the first few drops of the lowest fraction apart a platinum-salt was obtained which was obviously a mixture of those of ethylamine and propylamine but of which the quantity was too small to admit of purification by re-crys- tallization.The occurrence of these bases enables us to establish satisfactorily the constitution of petinine which mist obviously be C N and not C H, N as I formerly supposed it. Indeed the analysis of the platinum-salt contained in the first part of this paper fully agrees with the latter formula though that of the base itself differs from it; but much less reliance is to be placed upon that analysis as it is difficult to obtain the base itself sufficiently pure. It thus appears that the products of destructive distillation contain ammonia and the first four members of the series of bases homo- logous with it ; but it is probable that that series does not end here as distinct indications of the presence of amylamine were found; and it is possible that caproamine may also be detected; but here the series ends as when we reach a temperature of about 240° the character of the bases alters arid we enter rrpon an entirely different series.The separation of the bases boiling above 240° has been attended with great difficulties ;but after a trial of many different processes such as converting them into salts exposure to cold partial satura- DISTTLLATIOS OP ANIXAL SUBSTAKCES. tion &c. fractionated distillation was found the most advantageous though even that was extremely troublesome arid I was by 110 means so successful in obtaiuing rixed boilingpoints as I had been when operating on a smaller scale.A11 the oils boiling above 212O mere submitted to a systematic course of fractionation each fraction being distilled alone and the product collected in a fresh series of receivers which were changed at every 10'. After fourteen rectifications the fractions which had at first spread themselves at each successive dis-tillation over a very large number of degrees were confined to a comparatively sinall range and it was obvious that a separation was being effected although with extreme slowness. At this point 1 endeavoured by examination of the platinum salts obtained at diffe- rent temperatures to ascertain the constitution of the bases which those fractions contained and knowing from previous experiments that that boiling between 270" and 280' consisted of picoline I had indications of where these were likely to be found and have thus been enabled to determine the existence of two bases homolosous with that substance.Pyridine.-The first of these bases to which I give the name of pyridine occurs in the fraction boiling about 240'. It is a perfectly transparent and colourless oil which is not coloured by exposure to the air. Its odour is siinilar to that of picoline but more powerful and pungent. It dissolves in water in all proportions and is also readily soluble in the fixed and volatile oils. Acids dissolve it with the evolution of much heat aid the formation of highly soluble salts. With bichloride of platinum it gives a double salt in the forir~of flattened prisms tolerably soluble in boiling water less so in alcohol and entirely insoluble in ether.When these crystals are boiled for a considerable time in water they appear to undergo decomposition with the formation of a platinurn-salt crystallizing in golden yellow scales. The analysis of this salt gave results corresponding with thc formula C, H N . HC1 .PtCl,. The forinula of the base itself must consequently be C, H N. a member of the picoline eeries. I have not yet extended my investiga-tion of this base further as the phenomena observed in the exaniina- tion of the next substance showed that much difficulty would still be experienced in its purification. Latidine.-In the fraction boiling about 310° occurs a base which has exactly the constitution of toluidine.The fraction obtained at 305O to 310' in the distillation of the mixed bases gives more distinct indications of a fixed boiling point than that obtained at any other temperature. It is much less soluble than those of lower boiling points and when dropped into a small quantity of water floats on thc surface and is only slowly dissolved on agitation. It is leas soluble DR. AND'EKSON OX THE 1)ESTKUCTiV.E in hot than in cold water and separates as an oily layer when its cold saturated solution is gently heated. Its odoiir is more aroniatic than that of picoline. It unites with the acids and forms highly soluble salts. Its analysis gave results corresponding closely with the formula C, H N. Notwithstanding the close correspondence of the analy- tical results it appeared on further experiment that in some of thc portions analyzed appreciable quantities of picoline were present ; for when a portion was converted irito platinum-salt the first crystals which deposited were found to contain 32.8 per cent of platinum, which is the number for the picolinc-salt ;biit on evaporating furthcr crystals were deposited containing 32.5 and 32.0 per cent of platinum ; and the mother-liquor of these in addition of alcohol and ether .gave a salt in flattened tables which analysis pored to be the pure lutidine salt.This salt crystallizes in square tables sometimes very regular at other times confused and imperfect. It is very soluble in cold and still more so in hot water and is also extremely soluble in excess of hydrochloric acid.The analysis of the pure salt corresponded with the forniula C, H N . HCI . PtCI,. It is clear that this salt is that of the base of which the analysis has been given; but it is equally obvious that notwithstanding the close approximation of the results to theory the base had never been obtained absolutely pure but had retained more or less picoline. In the course of this investigation I have been frequently struck with the fact tbat when the fraction corresponding to any particular base is analyzed results closely approximating to theory are obtained even when the substance is very far from being pure. I found for in- stance that the portion boiling between 270' and 280° after one 01-two rcctifications gave exactly the numbers for picolinc although when again rectified it commenced boiling at about 250° and a sinall quantity remained in the retort at 300'.But it is readily intelligible that this should be the case where we have to deal with a series of" homologous bases in which the percentage of earbon increases as the boiling point rises so that we have the excess of carbon in the less volatile counterbalancing the deficiency in the more volatile and as each rectification renioves equal quantities of the more and the less volatile bases the percentage composition of the intermediate sub- stance must remain unchanged. Hydrwgochloride of Luttdine.-1 directed niy attention to this compound in the bope that it might prove suited to the purification of the base but soon abandoned it as I found it impossible to obtain invariably the same compound.tVhen a solution of corrosive subli- mate in alcohol is added to an alcoholic solution of Intidine a curdy white precipitate falls immediately unless the solutions be highly dilute in which case it is depositcd slowly in groups of radiatcd DISTILLATION OF ANlhiAL SUBSTANCES. needles. It dissolves in boiling water with partial decomposition and is still more soluble in spirit from which it is deposited in crystals on cooling. Its analysis corresponded with the formula 2HgC1+ C, H N. In another preparation a salt was formed which corresponded nearly with the formula SHgCI +C, II N and inter-mediate results were also obtained; but as the existence of these different compounds appeared fatal to their employment as a means of purifying the bases I did not pursue their examination further.It appears then that Dippel's oil contains two series of bases one homologous with ammonia the other peculiar to the oil homologous with one another and ,remarkable for their isomerism with the series of which aniline is the type. Thus we havc Pyridine . C, H Pl Yicoline . . C, H N . . . Aniline Lutidine . . C, H N . . . Toluidine. And it is probable that the series does not cease here as I have found that the fractions of base with higher boiling points give a steadily decreasing percentage of platinum. It is impossible in the present state of the investigation to give any opinion as to the intimate con- stitution and relations of these two series of what may be called iso- homologous bases.The most obvious explanation would be to suppose thc new bases to be irnidogen or nitrile bases; but into those ques- tions I shall not now enter but reserve their consideration ior a future paper. Pyrrol bases.-I have already referred to another series of bases which I call provisionally pyrrol bases wbich distil away from the acid by which the others are retained. They are obtained iii the form of an oil insoluble in water and which though at first colourless soon becomes red and finally black and gives with hydrochloric acid and a piece of fir wood the peculiar purple-rcd colour which Runge describes as characteristic of pyrrol. I imagined at first that I had actually obtained this substance which had escaped me in my pre- vious experiments but soon found I had to deal with a mixture of several bases; for when distilled with the thermometer it began to boil about 212O and gave a series of fractions up to above 370'.These oils were all bases with a peculiar and disgusting odour quite different from and much more disagreeable than the picoline bases. They dissolve easily in a small qtiantity of hydrochloric acid and give with bichloride of platinum a yellow precipitate which is rapidly :onverted into a black substance. When heated with an excess of acid they present a very remarkable character; the solution at a certain tempcArature becomes filled with red flocks so abundant and bulky that if not too dilute it becomes perfectly solid and the vessel may be inverted without anything escaping.The same change takes place though more slowly in the cold. When this substaiice is MR. SCI-IUNCK ON 1tUHIBPr’ collected on a filter washed and:dried it forins a reddish-brown porous mass insoluble in water acids and alkalies but soluble in alcohol. The acid Auid separated from this substance by filtration when supersaturated with an alkali evolves the odour of the picoline bases whence I infer that the pyrrol bases are in all probability coupled substances containing the picoline series in combination with some substance which yields the red matter. I have not as yet paid much attention to the non-basic portion of bone-oil but T have found that by repeated recifieations it improves in odour and that benzine is contained in the more volatile por-tions.It is probable therefore tbat the series of ho!nologous carbo- hydrogens to which benzine belongs may constitute a part but not the whole of the oil as I have found that when boiled with potash ammonia is gradually evolved; and on saturating the potasb solutiori with sulphuric acid the odour of butyric acid or at least one of the fatty acids is evolved; whence I conclude that it also contains the nitriles of those acids. On Rubian and fts Products of Deco~uyosition By Edward Sehnnek,F.R.S. (ABSTRACTED BY THE AUTHOR.) PART 1. Among the many discussions to which the snbject of madder has given rise among chemists there is none which is calculated to excite so inuch interest as that concerning the state in which the colouring matter originally exists in the root and there is no part of this extensive subject which is at the same time involved in such obscurity.It is a well-known fact that the madder-root is not well adapted for the purposes of dycins until it has attained a growth of from eighteen months to three years and that after being gathered and dried it gradually improves for several years after which it again deteriorates. During the time when left to itself especially in a state of powder it increases in weight and bulk (in consequence probably of absorption of moisture from the air) and some chemical change is effected which though not attended by any striking phenomena is sufficiently well indicated by its results.There are few chemical investigations that have thrown any light on the nature of the process which takes place during this lapse of time and in €act most of the attempts to do so have merely consisted of arguments based on analogy* It has been surmised that the process is one of oxidation and that the access of atmospheric air is consequently necessary ; but a more general supposition is that the process is one of fermentation attended perhaps by oxidation. What the substance is however on which this AND 1‘1% YSODUCTS OF DECOBl€’OSfTION. process of oxidation or fermentation takes effect and what the products are which are formed by it are questions which have never been satisfactorily answered.It has indeed been suspected by several chemists that there exists originally some substance in madder which by the action of fermentation or oxidation is decomposed and gives rise by its decoinposition to the various substances endowed either with a red or yellow coloui; which have been discovered during the chemical investigations of this root ;and to this view Yersoz in his u Trait6 de 1’Impression des Tissus,”* gives his assent. To Mr. J. Higgint is due the merit of having first called attention to the fact that important changes take place during the process of‘ dyeing with madder which can only be explained by supposing that an actual formation of colouring matter takes place during the process. Mi*. Higgin concluded from his experinients that a formation of part of the colouring matter during the dyeing process is due to the peculiar Substance called by Kuhlmann XarJthine.A very simple experiment suffices to prove that madder in its dry state contains very little if any alizarine ready formed. If an extract of madder be made with cold water it will be found that the brownish- yellow liquid thus obtained when gradually heated will dye as well and as strongly as the madder from which it has been pressed. Now if the colouring matter were originally present in the forin of alizarine this could not take place since alizarine is almost insoluble in cold water ; and in employing it for the purpose of dyeing it is necessary to dissolve it in warm or boiling-water before it begins to exert any effect as is plainly seen in the case of garancine which contains alizariiie ready formed.Uy adding a variety of substances to an extract of madder with cold water I was enabled to ascertain under what circumstances and by what means the tinctorial power of the liquid is destroyed and consequently what is the general character of the substance or substances to which it is due. I found that by adding sulphuric or muriatic acid to the extract and heating the liquid after neutrali- sation of the acid was no longer capabte of dyeing. The tinctorial power was also destroyed by the addition of hydrate of alumina magnesia protoxide of tin and various metallic oxides but not by carbonate of lime or carbonate of lead. In all cases in which the property of dyeing in the extract was destroyed I invariably found that its bitter taste and bright yellow colour were lost.In my former papers on this subject I have shown that the intensely bitter taste of madder and its extracts is due to rubian ;and hence it follows that this substance though itself no colouring matter is in some way concerned in the changes when by a formation of colouring matter is induced in aqueous extract of madder. * T. I. 501. f-On the Colourittg Matters of Madder ly J. IIiggin Phil. Trans. for Oct. 1848. MK. SCHUNCK ON RUUIAN The preparation of rubian in a state of purity is attended with difficulties in conseyrrence of the facility with which it is decomposed by most reagents. There is also another circunistance which presents obstacles to almost all attempts to obtain it pure.There is no investi-gation of madder which does not make niention of a substance which when its watery solution is mixed with sulphuric or niuriatic acid and boiled gives rise to the formation of a dark green powder. To this substance which possesses no bitter taste and is in fact devoid of any characteristic property except the one mentioned I havc restricted the name xanthine. The xanthine of most other chemists is however a mixture of rubian with this substance and possesses therefore the bitter taste of the former while showing the characteristic behaviour of the latter towards acids. To avoid confusion I shall no longer employ the name of xanthinc and I shall call the substance which gives the green powder with acids chlorqgenine.Now these two substances though of very different nature behave similarly towards many reagents. Chlorogenine for instance is iiot precipitated by basic acetate of lead when it is contained alone in solution ; but it is partly precipitated thereby when rubian is present at the saiiie time. After numerous experiments I discovered a property of rubian which is perhaps more characteristic of it than any other and that is the remarkable attraction which is manifested by it towards ail substances of a porous or finely-divided nature; and it was this property by nicans of which I was enabled to obtain it in a state of purity. If to a watery extract of madder a quantity of protochloride of tin be added a light purple-lake is precipitated.Most ofthe rubiaii remains in the solution which still retains its yellow colour and bitter taste. If however after filtering sulphuretted hydrogen be passed through it then provided the quantity of tin still in soltition be sufficiently large the sulphuret of tin at the moment of precipitation carries down the whole of the rubian and the solution loses its bitter taste and the greater part of its yellow colour. The whole of the chlorogenine reinailis in solution aiid may easily be detected in the filtered liquid by means of acids. If the sulphuret of tin after being collected on a filter and vvell washed with cold water until the percolating liquid no longer gives a green colour on being mixed with acid and boiled be treated with boiling alcohol a yellow solution is obtained which on evaporation gives pure rubian tvithou t any admixturc of chlorogcniiie in the shape of a dark yellow brittle substance.The same effcct is produced by sulphuret of lead. If sugar of lead be added to an extract of madder a dark reddish-brown precipitate falls the liquid still containing the rubian of the extract as seen by its deep yellow colour and bitter taste. If sulphuretted hydrogen be now passed through the filtered liquid a great part of the rubian goes down with the sulphurct of lead and mag again hc separated from it by incans of boiling alcohol. AND ITS PRODUCTS OF DECOMPOSITION. This attraction of surfacc exerted towards rubian by bodies in a state of minute division is not confined to metallic srdphurets.A very small quantity of animal charcoal is sufficient to deprive an aqueous extract of madder of its bitter taste and its tinctorial power. Lamp-black acts in the same manner though much less powerfully. Wood ciiarcod however has no absorbent effect whatever on rubian. ,411 these substances attract rubian alone leaving the other substances contained in the extract such as chlorogenine sugar and pectine untouched. By means of boiling alcohol part of the riibian in combination with them is again removed and thus an easy and efficient means is given of obtaining rubian in a state of purity. The following method of operation I have found best adapted for the purpose. A weighed quantity of madder being placed on a piece of calico or fine canvas stretched on a wooden frame boiling.water is poured on it in the proportion of 4quarts of water to 1 of madder. Lp. dark yellowish-brown liquor is obtained to which there is added while hot for every pound of madder taken 1 02. of animal charcoal. The liquid being well stirred with the charcoal the latter is allowed to settle which it does in a very short time and the liquid which still retains a brown colour is decanted. The charcoal is then placed on a piece of calico or on a paper filter and washed with cold water until the percolating liquid when mixed with muriatic acid and boiled no longer acquires a green colour nliich is a sign that the chlorogenine is removed. The animal charcoal is now treated with boiling alcohol uhich is filtered boiling hot and the treatment is repeated until it no loriger communicates to the alcohol any gellow colour.The alcohol is now evaporated. During evaporation a small quantity of a dzrk flocculent substance is depo- sited which is separated by filtration. Thc solution still contains a sniall quantity of another substance which is a product of decompo-sition of rubian itself and is probably formed by the application of too great a heat in the process of drying the madder. This sub-stance niay be removed by adding sulphuric acid to the cold solution after the greatest part of the alcohol has been removed. The sul- phuric acid completely decomposes the foreign substance provided a sufficient quantity is employed and converts it into a siibstancc which renders the solution milky and then falls in the shape of brown resin-like drops.The sulphuric acid being neutralized with carbonate of lead thc filtered solution which is yellow and now contains pure rubian is carefully evaporated to dryness. From 1cwt. of madder I obtained in this manner about 1000 grs. of rubian. As thus prepared rubian has the following properties. It is a hard dry brittle shining perfectly uncrystalline substance similar in appearance to gun1 or dried varnish. It is not deliquescent as xanthine is described to be. In thin layers it is perfectly transparent AlK SCHUNCK ON 1tUBIlN and of a beautiful dark yellow colour. In large masses it is dark brown. It is very so'iuble in water and alcohol it:ore so in the former than the latter but insoluble in ether.Its soiutions have an intensely bitter taste. Its watery solutiou gives 110 precipitates with the mineral or organic acids nor with salts of the alMi or alkaline earths. The only metallic salt which precipitates it from its solution is basic acetate of lead. The precipitate is light red. Concentratcd sulphuric acid dissolves ritbian with a blood-red colour ;on boiling the solution it becomes black and disengages sulphurous acid. Dilute sulphuric and muriatic acids decompose it on boiling in a manner to be described below. Nitric acid changes it into the acid which I called in my former papers alizaric acid and which Laurent and Gerhardt consider as identical :vith naphthalic acid.Phos-phoric oxalic tartaric and acetic acids produce no effect on rubian. Whcn a stream of chlorine gas is passed through a watery solution of rubian the solution immediately becomes milky and begins to de- posit a lemon-yellow powder into which. on continuing the action the whole of the rubian is conaerted the liquid becoining colourless. Caustic soda turns the colour of a solution of rubian from yellow to blood-red which on boiling the liquid again changes to purple. When heated on platinum-foil rubian melts swells up very much burns with a flame and leaves a carbonaceous residue. When heated gradually in 8 tube it begins to undergo decomposition accompanied by loss of water at a temperature of about 130' C. When heated still further it gives fumes of an orange colour which condense on the colder parts of the vessel to a crystalline mass con-sisting chiefly of alizarine.The composition of rubian is expressed by the formula C56H31030 that of its lead-compound by C, H, O, +6 YbO. Action of sulphuric and nwriatic acid on rubian.-The action of these two acids is precisely the same; but for the purpose of study-ing it it is better to eniplop sulphuric acid. as it is more easily removed again afterwards. On adding sdphuric acid in considerable quantity to a watery solution of rubian and boiling the liquid no perceptible change takes place at first except that the solution loses a little of its transparency and becomes slightly opalescent. After boiling for some time the rubian is entirely decomposed.On allow- ing to cool a quantity of orange-coloured flocks are deposited while the liquid becomes almost colourless. The orange-coloured flocks are separated by filtration and washed with co!d water until all the acid is removed. They now consist of four different substances viz. firstly Alizarine ;secondly the substancc which in my former papers I have called abhn-resin but to which I prefer giving the name of Rubiretine ; thirdly the substance \T hich I formerly termed beta-o*esin but which I shall now call Vernntine from Vernntia the name applied to madder in the middle ages. The fourth substance has AND ITS PRODUCTS OF DECOJIPOSITION not hitherto been observed. I shall call it Rubianine. On dissolving the mixture of these four substances in a small quantity of boiling alcohol the rubianine separates on the solution cooling as a brownish- yellow crystalline mass and is purified by recrystallization from boiling alcohol.On adding acetate of alumina to the alcoholic liquid a dark red precipitate falls which consists of alizarine and verantine in combination with alumina. The compound is decom- posed with acid; the mixture of alizarine and verantine is again dissolved in alcohol; and the verantine is precipitated by means of acetate of copper a compound of alizarine and oxide of copper re- maining dissolved in the alcohol and forming a dark purple solution. The rubiretine is contained in the liquid from which the alizarine and verantine have been precipitated by acetate of alumina.The acid liquid from which the orange-coloured flocks were deposited, contains a species of sugar; which is obtained by neutralising the acid with carbonate of lead and evaporating. The analysis of the alizarine formed in this process led to the sanie formula at which I had previously arrived viz. C, H 0, and this formula receives a new confirmation from the relation in which it stands to that of rubian. The formation of alizarine from rubiaii admits of a very easy explanation. By simply losing 14 equivs. of water 1 equiv. of rubian is converted into 4 equivs. of alizarine; for C, H, 0, = 4C, H,O + 14 HO. The properties of verantine are identical with those of the sub-stance to which I formerly gave the name of the beta-resin of madder.Its composition is expressed by the formula C, H 0, which was confirmed by the analysis of the baryta and copper com- pounds. The most probable formula for rubiretine is C, H 0,. If there- fore 2 equivs. of verantine 2 equivs. of rubiretine and 12 equivs. of water be added together the sum will be equal to 1 equiv. of rubian ;for 2 C, H50 + 2C, H 0,+ 12 NO = CS6H3 0, Rubianine is soluble in boiling alcohol and water from which it crystallizes on the solutions cooling in bright lemon-yellow silky needles which when dry form an interwoven mass. When heated it is carbonised without being volatilised. It is not decomposed by boiling nitric acid. It dissolves in solutions of alkalies with a blood- red colour but after some time is again deposited unchanged.Its alcoholic solution gives no precipitate with sugar of lead. It is not converted into rubiacic acid by means of persalts of iron by which it is chiefly distinguished from rubiacine. Its composition is expressed by the formula C, H, Ol,. The sugar mentioned above as the fifth product of the action of 31. PASTEUlt ON acids on rubian is obtained in the form of a yellow transparent syrup which neither crystallises however long its solution may be left to stand nor becomes dry unless heated to 100' C. Its taste is sweetish accompanied by a bitter after-taste like that of burnt sugar. Tt is easily decomposed by caustic alkalies; but not so easily by dilute sulphuric acid. Nitric acid converts it into oxalic acid. By fermentation it yields alcohol.Its composition is identical with that of grape-sugar its formula being Ci H, O12. Hence it follows that 1 equiv. ofrubian takes up 9 equivs. of water and then splits up into 1 equiv. of rubianine and 2 equiva. of sugar for In the opinion of most chemists who have examined madder this root contains two distinct colouring matters viz. alizarine and another to which the nanies of purprine oxylixaric acid and madder-purple have been applied by different chemists. I have however reason to suppose that the latter is in fact no distinct colonrin6 matter but a mixture of alizarine and verantine. As a charactei*isticof parpurine is mentioned its property of forming when treated with boiling alum-liquor a red opalescent solution from which it separates again in orange-coloured flocks on the solution cooling.Pure alizarine is not more soluble in boiling alum-liquor than in water; it only communicates to the liquor a yellow colour. Verantine is still less soluble in alum-liquor. If however a mixture of alizarine and verantine be dissolved in caustic alkali and they be then precipitated together by means of a solution of alum added in excess then on boiling the precipitate with the liquid a bright red solution is obtained and on filtering and allowing to cool orange- cofoured flocks are deposited while the liquid still remains red but gives a yellow precipitate on the addition of acid. From this expe- riment I arn inclined to infer that alizarine and verantine are capable of forming a double compound with alumina soluble in boiling water and that a mixture of the two in the proportion in which they exist in this compound constitutes what has been called purpurine.In a former memoir the author has shown that aspartic and malic acids have the power of turning the plane of polarization of luminous rays and that this power likewise extends to all their saline com- pounds ; moreover that fumaric acid as formed in nature and likewise Compt. rend. XXXITI 217; Ann. Ch. Phys. [3] XXXIV 30. ASPAltTtC AND MALIC ACIDS. as it is obtained by the dry distillation of malic acid does not possess this property. About the same time M.Dessaignes announced the transformation of acid fumarate of ammonia into malic acid. On comparing the results obtained by Dessaignes with those of Pasteur it would appear that aspartic acid a substance possessing rotatory power may be obtained artificially from acid fumarate of ammonia a substance which is destitute of that property.Now as such a result would be contrary to all previous experience the author was disposed to conclude that the aspartic acid formed by Dessaignes differed from natural aspartic acid-that namely which is formed from asparagine-by the absence of molecular rotatory power. Accordingly he obtained from %!I. Dessaignes a specimen of the aspartic acid prepared from fumarate of ammonia and on examining it found that it was really destitute of' rotatory power although in its chemical properties it exhibited the most exact resemblance to natural aspartic acid.It became therefore peculiarly interesting to examine the trans- formation of this substance into malic acid. It is well known that malic acid may be readily formed from asparagine and aspartic acid; and the author has shown that the acid thus obtained is identical in its chemical crystallographical and optical properties with the nialic acid of the service-tree the apple and the grape. Now on treating the new aspartic acid of Dessaignes by a method exactly similar to that by which Piria obtained malic acid from asparagine a nialic acid was produced which was likewise destitute of rotatory power. The author proposes to distinguish these acids and their derivatives by the names actually in use with the addition of the epithets active and passive; e.g. active ma& acid active aspartic acid tnactive malic acid inac-tive aspartic acid. A comparison of the properties of these active and passive com- pounds presents very curious and unexpected results. With the exception of a few dissimilarities for the most part of minor import- ance these substances are chemically speaking undistinguishable. Every reaction which can be produced by one of the active acids may likewise be obtained under similar circumstances with the cor- responding passive acid ; and the resulting compounds have always the same ultimate coinposition and the same chemical properties. Thus active malic acid when heated to nearly 15OoC. is trans- formed into two volatile acids the wtuZeic and furnaric.The same phenomenon is presented by inactive nialic acid. Active malate of lead fuses at a temperature below 100'; so likewise does the inactive malate. Active malate of lead which is amorphous when first precipitated subsequently crystallizes in silky tufts ; inactive malate of lead exhibits the same property. All the active malates and aspartates without exception have their analogues among the inactive malatea which latter are obtained by exactly the same processes as the active 31. PAS'I'EITR ON salts. Lastly the corresponding salts have always the same cheuiical formula. The crystalline forms of the corresponding active and inactive com- pounds present some remarkable peculiarities being sometimes totally distinct and incompatible sometimes sensibly the same and with the same angles.Thus active aspartic acid and aspartate of soda crys- tallize in the system of the right prism with a rhombic base whereas the corresponding inactive compounds crystallize in the system of the oblique prism with rectangular base which is incompatible with the preceding. On the other hand thc active bimalates of lime and ammonia crystallize in the system of the right prim with rhombic base and the corresponding inactive bimalates not only crystallize in the same system but likewise with the same angles; there is this difference however that the active substances always exhibit hemi- hedral faces which the inactive compounds never do. It appears then that the molecular coiistitution of the inactive substances is not incompatible with a crystalline form identical with that of the cor-responding active compounds ; and we may presume with tolerable certainty that where the forms appear incompatible the incompati- bility is due to dimorphism.The phenomena above described might induce the supposition that the inactive varieties of aspartic and malic acid might each be sepa- rated into two other acids one of which would turn the plane of polarization to the right and the other to the left in the same manner as racemic acid is separated into dextroracemic and lzevo- racumic acid. This supposition however is untenable. For in the first place the difference between racemic and tartaric acid is much greater than that which exists between active and inactive malic acid.Thus the chemical cotnposition of a racemate is rarely identical with that of the corresponding tartrate; and in the few cases in which this identity of composition exists the racemate is separable by crys- tallization into a dextro- and a 12evo-tartrate. But the chief objcc- tion to the above-mentioiied supposition is derived from the mode of production of inactive aspartic and malic acids. Inactive aspartic acid is in fact derived from maleic and funiaric acids. If then it possesses a binary constitution an analogous constitution must be supposed to exist in the acids from which it is derived-unless indeed we suppose that the maleic and fumaric acids are transformed by heat into binary syminetrZcaZ groups-a change which there is even greater difficulty in conceiving.Now to suppose a binary constitution in fumaric and maleic acids is to admit that the action of heat transforms a inolecule of active malic acid into binary groups of two active molecules identical in form but not superposible. On the other hand it is reasonable to suppose that a molecular arrange- ment unsymmetrically constituted may when exposed to an elevated temperature be changed into another molecular arranpment in which the peculiar disposition which produced thc want of synlrnetry in the first arrangement has disappeared.* The results above described throw a new light on the niolecular constitution of bodies. The author had shown in former researches that sizbstances capable of acting on polarized light niay be com-pared to those groups so frequent in the vegetable and animal king- doms in which the want of symmetry is of that nature that we may imagiue other groups identical with them in form but not super-posible; e.g, the right and left members of the body and those plants in which the points of insertion of the leaves form a right-hand or a left-hand spiral. In one case (that of tartaric acidj the left-hand modification corresponding to the right-hand variety previously known mas actually discovered. In the present instance we see that com- pounds exerting a rotatory power on polarized liFht may be so little altered in their molecular grouping as to retain without exception all their chemical properties and merely to lose that peculiar unsym- metrical molecular grouping which produces the right or left- handed character.The only known substances which can be compared with those just considered are ordinary active oil of turpentine and the inactive .variety obtained by the action of heat and caustic lime on the arti- ficial solid camphor of turpentine. It is highly probable however that this new kind of isonierism is a general property of substances possessing the rotatory power and that examples of the same kind will be multiplied now that the attention of chemists has been drawn to this new class of compounds. A remarkable similarity appears to exist between thc molecular constitution of ordinary malic acid and that of tartaric acid. Biot it is well known has discovered several remarkable peculiarities in the action of tartaric acid upon light viz.1. That its rotatory power increases with the proportion of water which it contains; 2. That this power is increased by elcvation of temperature; 3 By the presence of boracic acid; 4. That the mode of dispersion of the planes of pola- rization does not follow the law of the inverse squares of the lengths of the wave which is found to be very nearly true in quartz and in most substances possessed of molecular rotatory power. These four exceptional laws have hitherto liccn considered qnitc peculiar to * Bimalate of ammonia beconics iuactive by the abstraction of 5 atoms of water at 2060 c. and aspartic acid bp the loss of 3 atoms. Tile loss of rotatory power may be attributed to several causes 1.The action of heat. 2. The expulsion of water the moIecular c1;ronp before the loss of water being unsymmetrical in consequence of the disposition of the atoms of water in the midst of it. 3. We may suppose that the rotatory power was due to the relatire arrangement of the molecules of water and of the &-hydrated substance. It would he very useful towards the solution of this important question to abstract the molecules of watcr from the active groups at lorn* temperatures and asrcrtain \diet her the rotatory power is destroyed nnder those circumstances. VOL V.-NO. XI-11. F ORGANIC BASES CONTAINING ANTIMONY. tartaric acid. Pasteur however finds that active malic acid exhibits the same peculiarities.There must therefore be some intimate rela- tion between the molecular constitution of tartaric and of nialic acid; and it must be especially remarked that this analogy of constitution is shown by a dissymmetric phenomenon viz. the optical rotatory power. Hence it follows independently of any theoretical generaliza- tions of the facts relating to right and left-handed substances-that since there are two varieties of tartaric acid the one right and the other left-handed there must likewise exist two corresponding varie- ties of malic acid. It matters little whether the variety of malic acid which is symmetrical to the ordinary malic acid known to chemists exists or not in any particular plant. That which we may safely assert is the possible existence of this variety of malic acid sym-metrical or non-superposible to the acid of the service-tree of the apple and the grape.The ordinary active variety of malic acid corresponds to deztrod tartaric acid a fact which might have been predicted from the con- stant simultaneous existence of malic acid and dextro-tartaric acid in all acid fruits. It is very probable that when the kind of grape which yielded tartaric acid containing racemic acid shall have been redisco- vered this same grape will be found to contain the Zevo-rnalic acid symmetrical to ordinary malic acid. Another consequence which may be deduced from the preceding facts is the possible existence of an inactive asparagine corresponding to the inactive malic and aspartic acids; and when we shall have dis- covered the mode of preparing ordinary active asparagine from active malic or aspartic acid the same reaction applied to the corresponding inactive acids will doubtless produce inactive asparagine.There are also strong reasons for presuming the existence of an inactive tartaric acid corresponding to inactive malic acid. This acid would be neutral to polarized light like racemic acid but would differ from the latter in molecular constitution and would not be separable into two symmetric acids. Organic Bases containing Antimony.* The compounds of this class discovered up to the present time are as follows Stibmethyl . . . SbMe = Sb ,3(C H3) Stibmethylium . . SbMe = Sb .4 (C H ) * Lowig and Schweitzer Ann. Ch. Pharm.LXXV 315 327; J. pr. Chem. XLIX 385 ; L 321 ; Pogg. Ann. LXXX 338 ; Chem. Gaz. 1850 201,372,395,420. -Landolt Ann. Ch. Pharm. LXXVIII 91 ; Lowig Grundriss der Organischen Cliemie Braunschweig 1852 S. 383. ONGANIC BASES CONTAINING ANTIMONY. Stibethyl . . . SbAe = Sb .3 (C H,) Stibethyliuni . . . SbAe = Sb .4 (C H5) Stibamyl . . . . XbAm,= Sb . 3 (CloHll) The compounds SbMe, SbAe, and SbAm are obtained by dis- tilling the iodide of methyl ethyl or amyl with antimonide of potassium. They all oxidize very rapidly; and therefore in preparing them the same precautions must be taken as in the preparation of cacodyl viz. to exclude the air completely and conduct the whole operation in an atmosphere of carbonic acid. These compounds have remarkably strong combining tendencies and unite at ordinary temperatures with oxygen sulphur selenium and the halogens the act of combination being attended with conL siderable evolution of heat sufficient in the case of stibmethyl and stibethyl to produce inflammation.The compounds formed with the elements just named resemble in all their relations the correspoiiding potassium-compounds and may be transformed one into the other by mutual decomposition. The so-called basic radicals however containing 3 cq. of methyl &c, combine with 2 eq. of oxygen sulphur chlorine &c. a character by which they also differ from cacodyl. The compounds containing 4 eq. of methyl or ethyl are precisely analogous to ammonium combining only with 1 eq. of oxygen sulphur chlorine &c.These last-mentioned compounds are formed by the action of iodide or bromide of methyl or ethyl on stibmethyl or stibethyl in which case the haloid-compounds SbMe T SbAe I &c. are produced. Stibmethyl SbMe,.-This compound is a colourless heavy liquid which has peculiar odoui; is insoluble in water but. dissolves sparingly in alcohol and readily in ether. When exposed to the air it gives off thick white vapours takes fire and burns with a blue flame with separation of metallic antimony. Xtibrnethyliurn Sb&fe,.-Not yet obtained in the separate state. Oxide of Xtibmethyhum (SbMe,) 0i-H0.-This conipound is obtained by agitating an aqueous solution of iodide of stibmethylium (SbMe,) I with recently precipitated oxide of silver filtering from the iodide of silver and evaporating the filtrate in vacuo over sul- phuric acid.White crystalline mass having a highly caustic alkaline taste and analogous in all its relations to caustic potash. Dissolves rcadily in water and alcohol but very sparingly in ether. Volatilizes unchanged at a high temperature Heated with potas- sium it gives off a spontaneously inflammable gas. This base saturates acids completely forming salts precisely corresponding to the salts of potash; it likewise expels ammonia and even baryta and lime as well as all the heavy metallic oxides from their combinations. The F2 ORGANIC BASES CONTAINING ASTIMONY. precipitate which it forms in solutions of zinc and alumina dissolves in excess of the precipitant.From copper-salts it throws down hydrated oxide of copper insoluble iD excess of the base and does not dissolve a trace of oxide of silver. All its salts have a bitter taste. SulphatP of Slibmethylium.-L?r. Netdral. (SbMe,) 0 . SO or SbRle . SO,.-Obtained by adding sulphate of silver to an alco-holic solution of the iodine-compound filtering from the iodide of silver and treating the filtered liquid with a mixture of alcohol and ether; or by adding the oxide of stibmethylium to a concen-trated solution of the acid salt till the acid reaction disappears and then mixing the aqueous solution with alcohol containing ether. It first separates in oily drops which however soon solidify and form rhombic prisms. P. Acid subhate (SbMe,) 0 .HO .2SO or SbllCJle SO +HSO,.-Obtained by evaporating a solution of the neutral salt over the water-bath. Crystallizes in very beautiful square tables with trun- cated summits; they are very hard dissolve readily in water and with tolerable facility in alcohol ; their taste is first sharp and after- wards bitter. Nitrate qf Stibmeth:yZium.-Formcd by treating a solution of the iodide with nitrate of silver. It is soluble in water ; has a rough and bitter taste ; crystallizes in small needles ; and detonates when heated. Bicarbonate of Stibmethylium (SbMe,) 0 .NO .2 CO or SbMe . CO +HCO,.-Formed by completely saturating the pure base with carbonic acid. Crystallizes in small needles arranged in stellate groups. Dissolves easily in water has a slightly alkaline and bitter taste and gives no precipitate with neutral magnesia-salts.Iodide oj Sfibmethylium SbMe I.-Formed as above-nien tioned by bringing stibmethyl in contact with iodide of methyl. Crystal-lizes in very beautiful six-sided tables easily soluble in water and alcohol sparingly in ether. Its taste is first saline afterwards bitter. When heated in a test-tube it gives off vapours which take fire spontaneously in the air antimonious acid being separated at the same time. Acids separate iodine froni this conipouiid; the iodine may also be precipitated by silver-salts. Iodide of SfiClmelhyletllyliurrz,SbMe Ae . I.-Obtained by mixing stibmethyl with iodide of ethyl ; it closely resembles the preceding compound. C,Y,Joride of Stibmethylium SbMe C1.- Obtained by evaporating the iodine nitli strong hydrochloric acid and evaporating or by decomposing the iodide with corrosive sublimate ;but the best mode of obtaining it is to saturate a solution of pure oxide of stibmethy-lium with hydrochloric acid and evaporate.This compound forms 69 0 ILGANIC BASl3 S CON TAI N I K 0 ANTI M 0N Y . wliite crystals which are easily soluble in water less soluble in alcohol and quite insoluble in ether; they have a bitter taste and in other respects are precisely analogous to the iodine-compound. Stitrethyl SbAe = 4 vol. gas.-This cornpound forms a trans-parent colourless extremely mobile liquid having a strong refracting power and a disagreeable alliaceous odour which however is wry transient.It is insoluble in water but dissolves readily in alcohol and ether. Does not solidify at -29' C. boils at 158*5'. Spec. grav. =1.3244. Vapour-density = 7.44. Oxide of Stibethyl (SbAe,) 0,+2 H0.-When stibethyl is intro- duced in a fine jet into oxygen gas it immediately takes fire and burns with a dazzling white light ; the same effect is produced in the air excepting- that the ignition does not take place till after several seconds and is preceded by the formation of a thick white fume. If however the oxidation proceeds slowly a transparent syrupy mass is obtained consisting of (SbAe,) 0,+2 SbOd* (the so-called efhylo-stybelic acid). The oxide is obtained in a state of purity by precipi- tatins the sulphate with baryta-water and separating the baryta which still remains in the filtrate by carbonic acid.On eraporating the liquid the oxide remains in the form of a viscid transparent and perfectly colourless mass presenting no traces of crystallization. It dissolves readily in water and alcohol sparingly in ether ;has a bitter taste is not poisonous and does not excite vomiting. It is not volatile. Oxide of stibethyl behaves like an inorganic base and forms with acids a number o€ crystallizable salts which are very soluble in water. Sulphute qf Stibethyl (SbAe,) 0 . 2 SO, is obtained by decom- posing sulphide of stibethyl with sulphate of copper. Crystallizes in small white prisms which are inodorous have an acid reaction a bitter taste and are soluble in water and alcohol. Nitrate qf Xtibethyl (SbAe,) 0,.2NO,.-Stibethyl takes fire with explosion when brought in contact with fuming nitric acid. In dilute nitric acid it dissolves like a metal with evolution of nitric oxide gas. This salt crystallizes from its aqueous solution by spon-taneous evaporation in large transparent rhomboidal crystals which dissolve easily in water and alcohol have an acid reaction a bitter taste and fuse at 62.5'. It deflagrates when heated. * This is the formula given in Lowig's recently publislied Grundriss der Org. Chern. But in the original paper by Lijwig and Schweitzer (Ann. Ch. Pharm. LXXV) it is stated that the slow oxidation of stibethyl yields two products viz. a syrupy nias coirsibting of oxide of stibethyl (SbAe,) O, and a white powder i~~soluble in ether consistiiig of (ShAe) 0,.This latter compound is called Aethylsfihylsiiure the radical Sbde Iieiirg called Aethylstibyl. ORGANIC BASES CONTAINING ANTI1\IONY. Sukhide of StibethyZ (SbAe,) S,,-When an ethereal solution of stibethyl is boiled with washed flowers of sulphur and the warn1 ethereal solution decanted from the excess of sulphur the whole liquid solidifies in a few minutes forming a mass of dazzling white crystals which smell like nmcaptan dissolve easily in water and alcohol and when heated above looo fuse into a colourless liquid. The introduction of a piece of potassium into the fused sulphide of stibethyl causes an immediate evolution of vapours of stibethyl. The solution of siilphide of stibethyl precipitates all metallic salts as sul- phides ; dilute acids immediately decompose it with evolution of sulphuretted hydrogen.Sulphide of stibethyl is not volatile. With SbS it forms a yellow insoluble compound which smells like mer- captan and contains (SbAe,) S2+2 SbS,. Selenide of SkibethyZ.-SimiIar in composition and properties to the sulphicle ; it suffers decomposition however when exposed to the air seleniuni being separated. Iodide of Stibeihyl (SbAe,) I,.-Formed by adding iodine in small quantities to an alcoholic solution of stibethyl as long as its colour disappears and then diluting the alcoholic solution. Crys-tallizes in long perfectly colourless needles; has a faint odour a bitter taste and is easily soluble in water alcohol and ether; fuses at 70° and may be siiblimed by careful heating.With chlorine bromine acids and metallic salts it behaves exactly like iodide of potassium ; nitrate of silver immediately forms with it a precipitate of iodide of silver. Bromide of StibethyZ (SbAe,) Br2.-When bromine is added drop by drop to stibethyl each drop produces combustion. But by adding bromine in very small quantities as long as its colour disappears to an alcoholic solution of stibethyl which must be kept cold and theii mixing the solution with a large qiiantity of water bromide of sti-bethyl scparatcs in the form of a perfectly colourless transparent liquid which at --fO0 solidifies in a snow-white crystalline mass. It has an unpleasant odour like that of turpentine excites a copious flow of tears when heated; is insoluble in water but dissolves readily in alcohol and ether; it is not volatile.In its chemical relations it is precisely analogous to bromide of potassium. Chloride of Stibethyl (SbAe,) Cl,.-When stibethyl is dropped from a narrow tube into a flask filled with chlorine it takcs fire at the instant of contact Hydrochloric acid gas is decomposed by stibethyl with evolution of hydrogen and formation of chloride of stibethyl; the same action takes place when strong hydrochloric acid is poured upon stibethyl. On mixing a solution of nitrate of stibethyl with strong hydrochloric acid chloride of stibethyl immediately scparates in the form of a colourless strongly refracting liquid. It smells like turpentine tastes bitter is insoluble in water but dissolves readily in alcohol and ether; does not liquefy at -12'.Sp. gr.=1*540. MR. MALLET ON TELLURIDE OF ETHYL. It is not volatile. In its chemical relations it resembles chloride of potassium. Stibethylium SbAe,.-Known as yet only in the form of iodide which is obtained by adding iodide of ethyl to stibethyl. The iodide crystallizes in long beautiful needles which are easily soluble in water and alcohol. StibamyZ SbAm,.-Clear colourless liquid which fumes in the air but without taking fire. It forms compounds analogous to those of stibethyl but they are all liquid and insoluble in water. BismethyZ or Bismuthide of Ethyl:" BiAe,. Bismethyl is ob-tained in the same manner as stibethyl bismuthide of potassium being substituted for the antimonide.Forms a slightly yellow very mobile liquid9 of sp gr. 1.80 which can only be distilled with water. Has a disagreeable odour like that of stibethyl and produces even if only traces of it are inhaled an extremely un- pleasant burning sensation on the tongue. When exposed to the air it emits dense vapours and takes fire diffusing a thick yellow smoke of oxide of bismuth. With oxygen the halogens and sulphur it combines in the same proportions as stibethyl; but the resulting compounds are less permanent ;for instance when an alcoholic solu- tion of iodide of bismethyl is left to stand for awhile pure iodide of bismethyl separates out. Bismethyl when heated alone is decom- posed with separation of bismuth and evolution of gaseous products.If suddenly exposed to a high temperature it explodes with great violence. Observations on Telluric Ethyl or Tellurhle of Ethyl. By W. Mallet.? Wohler in his notice upon telluride of ethy1,f states that it is dissolved by nitric acid with evolution of nitric oxide and that on adding hydrochloric acid to this solution a heavy colourless liquid is precipitated in oily drops. The nature of this liquid was not €urther investigated. Mallet in pursuing this subject has found that telluride of ethyl * LSwig. Grundriss rier Organischen Chemie. S. 386. t Ann. Ch. Phano. LXXIX 223. Ibid. YXXV 112. MIA MALLET ON TELLUKIDE OF ETH1L. behaves like an organic radical. The substance was prepared by Wohler's process viz.by distilling a concentrated solution of sulphovinate of baryta with telluride of potassium. Its vapour has an intense yellow colour. In attempting to prepare a telluric memaptan C €I Te, by dis- solving in water a mixture of sulphovinate of baryta and telluride of potassium in a flask previously filled with hydrogen gas then satu- rating the solution with telluretted hydrogen and distilling the only product at first obtained was monotelluride of ethyl C,H,Te. But on continuing the distillation at a stronger heat another liquid passed over with the water distinguished from the former by much greater density higher boiling-point and an intense red colour so that even in small masses it appeared black and opaque like bromine; it had an offensive odour.Analysis showed it consisted of hitelluride of ethyl C H Te,. Nitrate of Telluric Ethyl.-C H TeO . NO5.-When a solution of monotelluride of ethyl in nitric acid is evaporated to dryness at a gcn tle heat there remains a white crystalline mass which dissolves perfectly in water and burns away like gunpowder when heated. Alkalies produce no precipitate in solutions of this salt because the base C Bj TeO is soluble in water. Sulphurous acid on thc contrary immediately reduces the radical which separates in dark- red drops. Sulphuretted hydrogen produces an orange-coloured pre- cipitatc which on heating the liquid fuses into heavy black drops doubtless consisting of the sulphur-compound of telluride of ethyl = C 11 TeS. Chloride of TeZZuric Ethyl C H,TeCl separates in the form of a colourless oil on the addition of hydrochloric acid to a solution of telluride of ethyl in nitric acid.At fimt the liquid becomes milk- white but the compound soon collects in large transparent drops which sink in the water. It has an offensive odour. It may be distilled without decomposition bizt its boiling-point appears to be very high for when distilled with water it passes over very slowly. By analysis it vas found to contain 50.55 per cent of tcllurium and 27.07 of chlorine the calculated numbers being 49.81 Te and 27.63 C1. Oxide of Telluric Ethyl C H TeO is formed by treating the chloride immersed in water with recently precipitated oxide of silver. The liquid becomes warm and chloride of silver is formed.The filtered liquid is a solution of the oxide of telluric ethyl in water ; and on evapomtion at a gentle heat the oxide remains in the form of a colourless highly crystalline mass. The aqucous solution exhibits an alkaline reaction with turmeric. The oxide when heated in a tube is decomposed with separation of metallic tellurium and formation of an oil having an offensive odour. When heated in the zir it burns with B blue flame like tellurium. Sulphurous acid decomposes the solution RIESSRS. SLCOLOPF AND STBECKEE ON HIPPURIC ACID. 73 and separates the telluride of ethyl in red drops. Hydrochloric acid throws down the chloride in colourless drops. The oxide is likewise formed by direct oxidation of an alcoholic solution of telluric ethyl in the air; the process is however too slow to be practically available.It is likewise obtained in the form of a sulphate by treating telluride of ethyl with peroxide of lead and dilute sulphuric acid. The solution of the oxide gives a yellow precipitate with chloride of platinum and white with corrosive sublimate. When it is mixed with chloride of ammonium-the solutions not being too dilute-ammonia is set free and after a short time a salt separates in small crystals arranged in stellate .groups and having exactly the form and the angles of gypsum. This salt dissolves readily in hot water and crystallizes out again unaltered on cooling. By analysis it was found to contain 26.73 per cent of tellurium and 15.45 of chlorine numbers which appear to agree only with the formula C H TeCl+ 2 NH*Cl and with the supposition that in the decomposition with the silver- salt only one-third of the chlorine is separated.But whether this is really the case and what other compound is thereby formed the author was unable to decide for want of material. Examination oicertain products obtained from Hippuric Acid. By N. Socoloff and A. Strecker.* There are few organic acids whose rational constitution has given rise to so many different opinions as that of hippuric acid. From the decomposition which this acid undergoes by the action of per-oxide of lead whereby it is converted into benzamide and carbonic acid Pchling regarded it as a compound of benzamide with ail acid (fumaric acid) convertible into carbonic acid by addition of oxygen thus This view of the decomposition however is not quite satisfactory inasmuch as fumaric acid is not altered by boiling with water and peroxide of lead.Pclouze regarded the composition of hippuric acid as follous C, 11 NO = C, H 0,+ C HN + C H 0,. L-y-d C-”l %--J L-Y-Hippuric acid. Bitter almond Hydrocy-Formic acid. oil. ariic acid. * Ann. Ch. Yhaim LUX 17. I\IESSRS. SOCOLOPP AND STRECKEB ON CERTSIN This view of its constitution is based principally on the evolution of hydrocyanic acid in the dry distillation of hippuric acid and on the formation of benzoic acid carbonic acid and ammonia on treating hippuric acid with sulphuric acid and peroxide of manganese. Since however the acids composed of formic acid conjugated with aldehydes (lactic mandelic acid &c.) give up the aldehydes in the free state under similar circumstances it follows that the constitution of hippuric acid assigned by Pelouze is not in accordance with its decomposition.After Dessaignes had found that hippuric acid is resolved by the action of strong boiling acids and alkalies into benzoic acid and glycocol the majority of chemists were iriclined to regard it as a conjugated compound of those two substances. But upon that sup- position as correctly observed by Berzelius the transformation effected by peroxide of lead becomes unintelligible. These different views of the constitution of hippuric acid suppose that there exists in this acid a group of atoms containing 14 equivs.of carbon-that is to say a benzoyl group-together with a second group which contains 4 equivs. carbon and under particular circuui- Btances may be resolved into two other bodies each containing 2 equivs. of carbon. Since however the nitrogen may be transferred to the one or the other group of atoms according to the action to which the hippuric acid is subjected it appears more confcrmable with the behaviour of this acid to regard the nitrogen as more intimately combined not with either of these groups of atoms alone but with the conjugated compound resulting from their union and consequently to regard hippuric acid as an amide of the conjugated acid C, H 08. This acid cannot well be separated by the action of alkalis or acids on the amidogen-acid because the conjugated acid thereby suffers decomposi- tion.Nitrous acid however separates the non-nitrogeaeous acid (as previously shown by one of the authors of this paper*) acting in fact in this instance as it does upon other amidogen-compounds. To this acid whose composition is expressed by the formula jiist stated the authors give the name of Benxoglycolic acid. The present me-moir contains a more particular examination of this acid together with its salts and products of decomposition. The hippuric acid used in the preparation was obtained from horses’ urine by Gregory’s process somewhat modified viz. by boiling the urine for a short time with milk of lime then straining the liquid carefully neutralizing it with hydrochloric acid concen-trating at a boiling heat and adding hydrochloric acid after cooling.The hippuric acid thus obtained after being washed with cold water’ awas nearly white with only a faint tinge of red. * Ann. Ch. Phariu. LXVIII 54. PRODUCTS OBTAINED FROM HIPPURIC ACID. Hippuric acid does not act upon an aqueous solution of nitrate of potash neither is any action produced by dissolving it in strong sul- phuric acid and passing nitrous acid (evolved from nitric acid and starch) through the solution. But when nitrous acid is passed into a warm aqueous solution of hippuric acid in mhich powdered hippuric acid is suspended decomposition takes place attended with evolution of nitrogen. This method however is not advantageous because a large portion of the nitrous acid is resolved into nitric oxide and nitric acid which latter substance decomposes the new acid at the temperature of the liquid.The followiiig method was found to yield the best results. The hippuric acid dried in the air and pulverized was mixed in a mortar with a quantity of commercial nitric acid sufficient to form it into a thin paste. The mass was then put into a tall glass cylinder (so as to form a long column of liquid) and nitric oxide gas (evolved from copper and nitric acid) passed through it at a moderate rate. As a strong effervescence takes place the cylinder must not be more than half filled with the liquid. The hippuric acid then dissolves and bubbles of nitrogen are evolved from the liquid.The termination of the action cannot be very accurately observed but the passage of the gas may be continued till the liquid assumes a distinct green colour; an excess of nitric oxide is not injurious but rather beneficial inas- much as it removes a portion of the solvent. The operation is com-plete in five or six hours and does not require the application of heat. Part of the benzoglycolic acid separates from the solution even during the passage of the gas but the greater portion is precipitated on the addition of water. The liquid which has become warm is then left to cool and filtered through a paper filter doubled at the apex and the benzoglycolic acid is washed on the filter with water as cold as can be obtained. The benzoglycolic acid thus produced is impure and has a slight yellow colour.It is purified by converting it into a lime-salt and decomposing this salt with hydrochloric acid. For this purpose the crude acid is suspended in water and neutralized with milk of lime. It then solidifies in a few minutes to a solid mass; but on the appli- cation of heat the lime-salt dissolves and separates out from the filtered liquid on cooling in very long fine needles which are yellow at first from enclosed mother-liquor but after washing with cold water and strong pressure become perfectly colourless. The nitric acid diluted with water retains a considerable quantity of benzogly- colic acid in solution. This portion may be separated by neutralizing with carbonate of potash ;concentrating at a boiling heat ;decanting the liquid from the nitrate of potash which separates out on cooling ; concentrating again ;and mixing this last mother-liquid which con- tains nearly all the benzoglycolate of potash with strone nitric acid.The crystals which separate consist of benzoglycolic acid generally MKSSRS. SWOLOFY AND STlCECKER ON CERTAIN contaminated with benzoic acid to remove which one half of the mixture is neutralized with milk of lime the other half then added and the mixture evaporated to dryness. The benzoglycolic acid then remains in combination with the lime while the benzoic acid is set free and may be dissolved out by ether in Payen's extraction-appa- ratus. The benzoglycolate of lime which remains is perfectly pure and white.To obtain the pure acid the lime-salt is dissolved in water and mixed in the cold with hydrochloric acid whereupon the acid sepa- rates in the form of a light perfectly white powder. Larger crystals are obtained by dissolving the lime-salt in alcohol adding sulphuric acid filtering and leaving the liquid to evaporate freely. The acid then separates in tolerably large colourless prisms with dihedral angles of 37' 40' and 142' ZO' and flattened into thin tables by the excessive development of two of the prismatic faces. The crystals separated from the alcoholic solution lost no weight at 100' ;their analysis yielded the following results Calculation. Mean of experiments. Cl 108 60.00 60-09 HE3 8 4.44 4.66 64 35.56 35.25 08 Cl H 08 180 1oo*oo 100~00 Benzoglycolic acid is very sparingly soluble in cold water but dissolves wore readily in hot water by which also it is gradually decomposed.Heated with a quantity of water not sufficient to dis- solve it it fuses into oily drops. It dissolves readily in alcohol and ether. When heated on platinum-foil it fuses and solidifies again iii the crystalline state in cooling. When strongly heated it gives off vapours which excite coughing and smell of benzoic acid leaving a coaly residue which easily burns away at a red heat. SALTS OF BENZOGLYCOLLC ACID. These salts are mostly soluble in water and many of them also in alcohol. They have a neutral reaction and a faint but peculiar taste. From the aqueous solutions most of the stronger acids and even acetic acid throw down benzoglycolic acid in small crystals.Benzoglycolate of potash is obtained by exactly saturating the acid with carbonate of potash or by decomposing the lime-salt with car-bonate of potash. It dissolves readily in water and alcohol and crystallizes with difficulty and indistinctly. From a solution satu- rated while hot it crystallizes on cooling in extremely thin and very broad tables. By spontaneous evaporation it is obtained in cauli- flower-like masses. PRODVCTS OBTAINED PROM HIPPUHIC ACID. '17 Benzoglycolate of soda crystallizes much more readily than the potash-salt and separates on cooling from a hot saturated solution in tolerably large rhombic tables whose composition is NaO . €3 07+6Aq.The whole of the water is given off at 100'. The ammonia-sa2t is prepared like the potash-salt; it gives off ammonia when evaporated. Benxoylycotate of 2ime is obtained as already described by satu- rating the free acid with milk of lime. It possesses in the highest degree the property of forming super-saturated solutions so that sometimes perfectly cold solutions from which part of the salt has already crystallized out become turbid while being strained through a fine cloth and in a few minutes solidify to a thick jelly. If the liquid be then filtered the mother-liquor generally solidifies again after a while. The salt forms fine silky needles grouped like Wavellite. The crystals are permanent in the air lose no weight at loo' but give off 1 atom water at 12OOC.Their formula is CaO . c] 13 0 + Aq. 100 parts of water dissolved 2.36 parts of the salt at w'c. and 13.26 parts at 1000. Benxoylycolate of baryta crystallizes like the lime-salt in silky crystals. It contains 2 atoms water of crystallization which it gives off at looo. Benzoglycolate of magnesia is obtained by mixing the boiling solutions of benzoglycolate of lime and sulphate of magnesia and exhausting the solidified mass with absolute alcohol. The salt crys- tallizes by evaporation and cooling in extremely fine soft needles and consequently forms a very bulky mass. Benzoglycolate qf ferric oxide.-When soltition of benzoglycolnte of lime is mixed with sesquichloride of iron a bulky non-crystalline flesh-coloured precipitate is obtained which becomes darker on the surface when exposed to the air.It is perfectly insoluble in water. When dried in the air it contains 28 atoms water which are all driven off at looo. The formula is 2 Fe 0 . 3(C!8 H 0,)+28 Aq. Benxoglycolate of zinc is obtained on mixing the lime-salt with chloride of zinc in long thin colourless needles grouped in stellate masses. The crystals contain ZnO .CI8H 0 +4 Aq. ; the whole of the water escapes at looo. Renxogtycolate of copper is obtained by mixing a boiling solution of the lime-salt with nitrate of copper. It crystallizes in beautiful blue rhombic tables very sparingly soluble in cold water somewhat more soluble in hot water. On heating the crystals with a quantity of water not sufficient to dissolve them the undissolved portion is con- verted into a green powder probably consisting of the anhydrous salt.At 100' the crystals become green and opaque but the faces retain their lustre. Lead-salts.-a. Sespzciba~ic.-~Q cold solution of benzogl ycolate of lime is precipitated in curdy flakes by neutrd acetate of lead The 7'8 MESSRS. SOCOLOFF AND STRECKEK ON CERTAlX precipitate is sparingly soluble in cold water ; when heated with water it first melts then dissolves completely and Beparates again on cooling. The first deposit is amorphous but after cooling the lead-salt separates in crystals. On digesting the original curdy pre- cipitate in a large quantity of cold water filtering and leaving the solution to spontaneous evaporation the salt was obtained after a few days in crystals united in dense hemispherical masses.These crystals contain 3 atoms water which are given off at looo the anhy- drous salt fusing at the same time. Their composition is 3PbO. 2v1 H 0,)+3 Aq. P. Monobasic.-The mother-liquor from which the preceding salt had separated yielded after long standing a quantity of thin short soft needles grouped in stellate masses. These crystals were easily separated from the former salt by levigation. They are anhy- drous their formula being PbO .C, H 0,. y. Xexbasic.-A boiling solution of the lime-salt mixed with neutral acetate of lead yields an amorphous white precipitate which is almost wholly soluble in acetic acid it is a mixture of several basic salts.But when a cold solution of benzoglycolate of lime is mixed with basic acetate of lead a flocculent precipitate is formed which does not fuse when boiled in water and is but very slightly soluble in water. The precipitate after partial washing was immersed in cold water the solution filtered and then left to stand. In a few days crystals were separated having the appearance of the neutral salt and mixed with a small quantity of carbonate of lead from which they were separated by levigation. Their coniposition was found to be 6Pb0. C, H O,+Z HO; the water was given off at looo. The lead precipitates obtained by direct precipitation are always mixtures of several basic lead-salts. Benxoglycolate of siher.-Wheu a neutral solution of the lime-salt is mixed with nitrate of silver the resulting precipitate washed with a small quantity of cold water then dissolved in boiling water and the solution left to cool fine white microscopic crystals are ob-tained which soon blacken when exposed to daylight.When pre- pared by artificial light the salt is perfectly white. Its formula is Ago * c, H 07. Benxoglycolzc ether.-An alcoholic solution of benzoglycolic acid left to stand for some time evolves a peculiar odour probably arising from the formation of a compound ether. But on passing dry hydro- chloric acid into an alcoholic solution cf the lime-salt in which a quantity of the solid salt was suspended and afterwards adding water an oily liquid separated which was found to consist almost v\rholly of benzoic ether ; the benzoglycolic acid therefore had been decomposed by the hydrochloric acid.From the preceding description of the salts of benzoglycolic acid PRODUCTS OBTAINED FROM HIPPURIC ACID. it appears that this acid HO . C, H 0 contains 1 equiv. of water which can be replaced by metallic oxides aud moreover saturates the same quantity of base as the hippuric acid from which it is produced. Its production from hippuric acid is expressed by the equation cl*H NO + NO = c, H 0 + HO + ZN -,-J Ly-J Hippunc acid. Benzoglycolic acid. and is therefore perfectly analogous to the formation of other acids from their amides. The saturating power is however remarkable ; for in most cases the amidogen-acid saturates 1 equiv. of base less than the free acid.Nevertheless the case of bonzoglycolic acid is not quite peculiar; for the same relation is observed between aspartic acid and malic acid produced from it by a reaction similar to the above,* also between salicylic acid and its arnide. This saturating power shows a remarkable difference between the ordinary arnides and arnidogen-acids and the bodies which stand nearest to this group viz. hippuric acid alanin anthranilic acid &c. though both exhibit the same deportment towards nitrous acid. PRODUCTS OF DECOIVTPOSITION. It has been already mentioned that benzoglycolic acid is generally decomposed by boiling its aqueous solution with water ; its salts are also decomposed in the same manner but much more slowly. The acid is much more quickly decomposed when heated with dilute acids benzoic acid volatilizing with the watery vapours and a new acid remaining in solution.To examine this new product benzoglycolic acid was boiled for some days with water to which a small quantity of sulphurie acid was added the water being replaced as it evaporated. A large quantity of benzoic acid volatilized with the watery vapour and on concentrating to a small bulk and leaving the solution to cool a further quantity of that acid crystallized out. The mother-liquor was neutralized with carbonate of baryta filtered from the precipi- tated sulphate evaporated to a syrupy consistence and left to stand for several days. A salt then separated in white hard crystalline crusts which gave by analysis results nearly agreeing with the formula BaO .C H 0,. The acid eontained in this salt which in the anhydrous state has the formula C H 0, or in the hydrated state C H 0, agrees * Ann. Ch. Pharm. LXXV 296 MESSRS. SOCOLOFF AND STRECKER ON CEHTAI K with that to which Laureiit+k assigns the name of GZycolic acid because glycocol may be regarded as its amide. C H O6 + NH = C H NO + 2HO. c-y---J c-Y--l Glycolic acid. Glycocol. This acid however had not been previously prepared. To separate the acid from its baryta-salt the aqueous solution of that salt is treated with dilute sulphuric acid filtered and the filtrate evaporated over the water-bath. The syrupy residue dissolves com- pletely in ether and on evaporating the ether the acid is again obtained in the form of a thin syrup which refuses to crystallize.Glycolic acid is miscible in all propertions with water alcohol and ether. It has a strongly sour taste and does not give a precipitate with any metallic salt. In all its properties it bears the closest rc- semblance to lactic acid ; indeed the only reaction which distinguishes the two is that when a solution of glycolic acid is mixed with acetate of lead and ammonia added a white flocculent precipitate is pro- duced whereas lactic acid similarly treated remains clear. Glycolate of zirac was obtained by heating the diluted aqueous acid with carbonate of zinc then filtering and evaporating. As the liquid cooled crystalline crusts separated out having a strong resemblance to lactate of zinc.The individual crystals are small colourless trans- parent prisms arranged in stellate groups round numerous points. The formula of the salt is ZnO . C H 0,+2 Aq. The water is given off at looo. The salt is insoluble in alcohol difficultly soluble in cold water more readily in hot water. 1 part of the anhydrous salt dissolves in 33 pai-ts of water at 20°C. Glycolate of silver appears to be a veiy instable salt. The solution obtained by decomposing glycolate of baryta with sulphate of silver and filtering decomposed and deposited a black insoluble substance even when evaporated in vacuo over sulphuric acid. The addition of alcohol or of ether to the solution produced no precipitate. Glycolic acid as already obseived exhibits an extremely close re- semblance to lactic acid.If the latter may be regarded as a con- jugated cornpound of formic acid with common aldehyde glycolic acid ought perhaps to be considered as a corresponding compound containing the aldehyde of formic acid c H6 06 = C2 I-1 0 + C 13 0 L-.-y-J L.-.-v-J c---’ Lactic acid. Formic acid. Aldehyde. C H 0 = C H 0 -t. C €1 0,. L-yL L-v-d L-T-J Glycolic acid. Formic acid. Fortnic alde- hyde. Formic aldehyde is probably obtained in the cl~ydistillation of glycolic acid or on treating that substance with oxidizing agents * Ann. Ch. Phys. [3] XXTII 112. PBOIIUCTS OBTAINED YROX HIPPURIC ACID. When hippuric acid is treated with peroxide of lead an extremely pungent odour is evolved ;and Schwartz observed that the aqueous distillate gives the reactions of the aldehydes with nitrate of silver.It seems therefore probable that these phenomena are produced by the aldehyde of formic acid which being gaseous at ordinary tempe- ratures has hitherto escaped notice. Glycolic acid is also produced by the action of nitrous acid upon glycocol. This substance in the state of aqueous solution is decom- posed by nitrous acid with evolution of nitrogen. If the solution be then evaporated the glycocol becomes oxidated by the nitric acid pro-duced from the nitrous acid and crystals of oxalic acid are found in the residue. If on the other hand the solution of glycocol after treat- ment with nitrous acid be agitated with ether the ether extracts the glycolic acid from the aqueous solution ;and on evaporating the ether the glycolic acid remains in the form of a syrupy liquid sirnilar in properties to the acid obtained from benzoglycolic acid.The prepa- ration from the last-mentioned acid is however the easier method of the two. The formation of glycolic acid from glycocol is expressed by the equation C H NO + NO = C H 0,+ HO + 2N LU L-Y-Giycocol. Glycolic acid. The same results are therefore obtained whether hippuric acid be first treated with nitrous acid and the benzoglycolic acid afterwards decomposed by boiling with acids or the hippuric acid first resolved into benzoic acid and glycocol and the latter subsequently treated with nitrous acid. It appears from the facts already stated that benzoglycolic acid is easily resolved into benzoic and glycolic acids and there are grounds for supposing that it may be reproduced by the union of its constitu- ents thus C, H6 0,+ C H 0,= C, H 0,+ 2HO.L-Benzoic acid. G Z acid. The authors were prevented by want of material from confirming this theory by experiment but they obtained an analogous result with lactic acid. A mixture of lactic and benzoic acid was heated to 180' C. and kept at that temperature as long as aqueous vapoir continued to escape. The residue solidified on cooling in a resinous mass which was dissolved in water with addition of potash. To the warn1 solu-tion dilute sulphuric was added till benzoic acid no longer crystallized out on cooling and the crystals obtained exhibited a different form.The Eeparated acid was then removed by filtration and the filtrate mixed in the cold with dilute sulphuric acid. An abundant preciyi- VOL. V.-NO. XVII. I rr HEINTZ OX A tate was produced which first fused on being boiled with water theii dissolved in a large quantity of water and on cooling separated partly in drops partly in crystals. This acid was dissolved in ether and recrystallized by evaporation then neutralized with ammonia and precipitated by silver-solution The precipitate yielded 39.7 per cent of oxide of silver a result nearly agreeing with the formula Ago . C, H 0, which requires 38.5 per cent. The excess arose from the presence of benzoic acid. The formation of the new acid which may be called Benzolactic acid is expressed by the following equation.acid. On inew method of separating sitbstances possessing very similar propertics. Ry W. Heintz.' This method is founded on an extension of the principle applied by Lie big? to the separation of certain volatile acids of the sclipic series. It consists in adding to the mixture a substance capable of combining with all the original substances which compose it but in quantity less than sufficient to saturate the whole and subjecting the mixture thus treated to distillation the action of solvents &c. In order that a separation may be effected in this manner it is necessary; first that the substance added possess a decided chemical affinity for the substances contained in the mixture and that the resulting compounds differ so much in their properties from the original substances as to be easily separated from them by the action of solvents or by distillation; secondly that the substance added possess different degrees of affinity for the substances contained in the mixture.If this latter condition be not fulfilled no separation can take place. Experience shows however that perfect equality of affinity of two substances for a third exists only at particular tempe- ratures ; hence by varying the temperature the desired inequality may always be attained. The particular mode of effecting the separation will of course vary with the nature of the substances present. The following is the process which the author has adopted with mixtures of the non- volatile fatty acids stearic margaric acid &c.The separation of these bodies is well known to be a matter of great difficulty on account of the close resemblance existing between them and all their corresponding compounds. * Pogg. Ann. LXXXIV 221. -f Ann. Chem. Pharm. LXXI 325. XEW METfIOD OF SEPARATING FATS. The fatty acids are dissolved in a quantity of boiling alcohol sufficient to retain the whole in solution when the temperature is C. 0' lowered to and a boiling alcoholic solution of crystallized acetate of lead is added drop by drop in quantity sufficient to satu- rate about one-half of the acids with oxide of lead. In most cases as with stearic margaric ethalic and palinitic acid the quantity of sugar of lead required for this purpose amounts to about one-third of the weight of the fatty acids.If the proper quantity of alcohol has been added to the mixture the alcoholic solution remains clear as long as it is kept boiling but becomes turbid on the slightest reduc- tion of temperature; and as the liquid cools the whole of the oxide of lead is precipitated in combination with half the fatty acid. The formation of a precipitate at the boiling temperature shows that the quantity of alcohol used is insufficient ;in that case it is best to add a few drops of acetic acid by which the separated lead-salt is readily dissolved. The liquid is filtered when cold and the precipitate washed till the filtrate is no longer clouded by water ;the washing is very expeditious.The lead-salt saturated with alcohol is then removed from the filter and boiled for a short time with hydrochloric acid. Chloride of lead then separates completely and sinks rapidly to the bottom while the fatty acid remains dissolved in the alcohol. The solution how- ever still contains a portion of the ethyl-compound of the fatty acid. It is therefore super-saturated with caustic potash and boiled till the ethyl-compound is completely decomposed ; after which water is added and the greater part of the alcohol expelled by evaporation. Lastly the acid is separated from the potash-salt by boiling with hydrochloric acid. To separate the acid dissolved in the alcoholic solution acetate of lead also dissolved in alcohol is added in slight excess the precipitate collected on a filter and treated in the manner already described.As the separation thus effected is not complete the lead-precipi- tates instead of being washed may be squeezed by a powerful press and then decomposed by boiling with very dilute hydrochloric acid or better by treating them with alcohol and hydrochloric acid and afterwards with hydrate of potash and hydrochloric acid. The melt- ing points of both portions of the acid are then to be determined. If they are nearly equal and the two portions are otherwise not essentially different in their physical properties it may safely be con- cluded that the substance under examination was not a mixture but consisted essentially of one definite compound possibly contaminated by a small quantity of another.In this case the two portions may be united and purified by one or two recrystallizations from alcohol. If on the contrary the melting points and other physical characters of the two acids differ considerably the process must be repeated upon each and the Same treatment continued till the melting G2 points Src. of the portious last separated are nvarly equal. These last portions are then to be united and crystallized owe or twice from alcohol. This process will serve likewise to separate a mixture of three or more acids provided that not only the extreme portions those namely which contain the strongest and weakest acids but likewise the intermediate portions are subjected to the same trcat- ment.If any of the acids thus separated assume a well-defined crystal- line structure when it passes from the liquid to the solid state it will for the most part be unnecessary to subject it any further to the preceding treatment ; one or two crystallizations from alcohol will yield it in a state of perfect purity. When it is thought that a pure acid has been obtained in the manner above described it is best to subject it once more to the same treatment in order to make sure of its purity. By pursuing this method the author has found 1. That the so-called pure skearine which melts at 61' or 62' C. is 8 mixture of two or more fats containing glycerine. 2. That the substance commonly regarded as pure cetine is a mixture of at least two fats containing ethyl.It does not melt con- stantly at 49' or 49.5' C. ; but by recrystallization from the ethereal solution its melting point may be raised to 53.5'. Another result ofthe autbor's experiments is that spermaceti may be easily saponified by a boiling solution of caustic potash. On the composition of Human Fat. By W. Heintz. The investigations of Chevreul into the composition of human fat showed that it consists of a liquid fat viz. oleine and a solid fat to which Chevreul gave the name of stearine but which as it yields margaric acid by saponification must really consist of margarine. Subsequently Lerch has shown that the volatile portion of the fat contains caprylic acid; and Brucke has found that the solid portion does not yield pure margaric acid by saponification but an acid which melts at 56O and does not crystallize like margaric acid.Hence it would appear that human fat contains besides margarine another solid fat which by saponification yields another fatty acid not separable from margaric acid by crystallization. After various fruitless attempts to obtain the pure margarine by exposing the fat to a very low temperature and crystallizing the solid portion from a solution in ether Heintz resorted to the method of COAX POSITION OP HUMAN FAT. saponifying thc fat with caustic potash; and as the separation of the oleic acid thus produced from the margaric and other solid acids by the usual method of converting them into lead-salts and digesting in ether is very tedious and involves a very large consumption of ether he finally adopted the method of separating the fatty acids from the mixed potash-salts by means of hydrochloric acid and subjecting the liquid portion to the action of powerful press,-then dissolving the resulting hardish mass in a third of its weight of alcohol leaving it to solidify at as low a temperature as possible pressing again and repeat- ing these operations till every trace of oleic acid was removed from the solid acids-a point which was generally attained at the third pres- sure.The mixture of solid fatty acids was then treated by the method described in the preceding paper and was found to contain four different fats. The liquid portion was found to consist princi- pally of oleine.The general results of the investigation are as follovts 1. Human fat does not consist as formerly supposed merely of oleine and margarine but is a mixture of at least six different fats. 2. The first of these fats is present in very small quantity only but appears from an analysis of the fatty acid obtained from it to be identical with Stearophmine the substance which Francis discovered in the berries of Cocculus indicus. The composition and properties of this acid so far as they have been studied agree with those of stearophanic acid the formula of which is C,, H, 0,. 3. The second fat is a new substance to which the author gives the name of Anthropine. The fatty acid obtained from it by saponi- fication is distinguished by its strong tendency to crystalIize.It separates from the alcoholic solution and likewise solidifies from a state of fusion in broad shining lamin=. Its composition appears to agree with the formula C, €I, 0,; but further experiments are necessary to establish this result. 4. The third fat is Margarine which yields niargaric acid by sapo- nification. 5. The fourth substance contained in this solid portion of the fat is PuZmitilze which yields palmitic acid by saponification ;it appears to be the most abundant of the four. 6. The palmitic obtained from human fat is identical with that which is formed by the action of fused potash upon oleic acid and to which Varrentrapp gave the name of OZidic acid 7. The liquid portion of human fat is composed essentially of OZeine ;but it likewise contaiiis a small quantity of another fat which by saponification yields an acid whose baryta-salt differs from oleate of baryta not only by its physical properties but likewise by the quantity of baryta contained in it viz.from 27 to 28 per cent. This baryta-salt is much less soluble in alcohol than oleate of baryta but MESSES. SSOUl%EltO AND SELMl ON A is converted into a tenacious liquid mass at a much lower tempera- ture than the latter and is more soluble in ether. 8. It has been before observed that when human fat is exposed in water to a temperature varying above and below OoC. a liquid fat may be separated from the solid portion; and this liquid fat if lcft to itself till the next winter and again exposed for some time to the same low temperature yields another tolerably large portion of solid fat If this be again separated by pressure and the liquid fat once more left to itself a still further portion of solid fat will separate in the following winter.Now when the solid fat thus separated in the second or third winter is dissolved in hot alcohol filtered when the temperature of the liquid has fallen to 30' C. and then left to cool further a substance separates out vhich after recrystallization from alcohol dissolves readily in a dilute aqueous solution of carbonate of soda at a boiling heat and therefore consists of a fatty acid. It appears then that human fat when left to itself undergoes a gradual deconiposition by which the glycerine is destroyed and the fatty acid separated a kind of decomposition long known to take place in fats which yield easily volatile acids for instance in butter when it becomes rancid.On a new CQnnpOUnd of Mercnry. By Sobrero and Selmi,* When an alcoholic solution of potash is added to a solution of corrosive sublimate in alcohol of the strength of .PO' a yellow preci- pitate is obtained consisting not of protoxide of mercury but of a compound of mercury with carbon hydrogen and oxygen. This precipitate is amorphous and insoluble in water and alcohol; it may be washed to free it from excess of potash and chloride of potassium. In preparing this substance it is best to employ a temperature of about 5OoC. It is stable at ordinary temperatures and sustains without decomposition a temperature not far from 200' C.; when more strongly heated it assumes an orange colour and decomposes suddenly and with violent detonation being completely resolved into gaseous products without residue. That the compound may possess the property of detonating in the manner just described the prepara- tion must be conducted with attention to the circumstances above- mentioned; if the preparation be made at a lower temperature OF an insufficient quantity of potash added the resulting precipitate deto- nates less strongly and leaves a residue of red oxide of mercury. * Compt. Rend. XXSIII 67 ;Ann. Ch. Phwm. LXSX 108. NEW COMPOUND OF MERCURY. \\Then exposed to direct light this body blackens very rapidly. If lieated in a glass tube while still moist it decomposes with less vio- lence and leaves metallic mercury water and acetic acid.This substance dissolves completely in hydrochloric acid even in the cold undergoing decomposition at the same time and yielding a volatile substance which has a pungent irritating and quite peculiar odour and acts upon the throat in a similar manner to hydrocyanic acid. This volatile substance may be obtained mixed with hydro- chloric acid by distilling the mixture. The authors have not yet analyzed this substance; but they observe that on the addition of nitrate of silver there is formed besides the precipitate of chloride of silver a soluble compound which yields very beautiful transparent crystals. Sulphuric acid dissolves this compound of mercury forming crys- talline products.Nitric acid likewise dissolves it and the solution yields with caustic potash an ash-grey precipitate which when treated with hydrochloric acid gives off a volatile substance having the same odour as that produced when the original mercury-compound is acted upon by hydrochloric acid. Acetic acid dissolves the mercury-com- pound almost completely and the solution when evaporated yields a crystalline substance. The new mercury-compound boiled with a solution of sal-ammoniac drives out the ammonia forming at the same time a soluble crystal- lizable body. A crystalline compound is likewise obtained by boiling that substance with a solution of corrosive sublimate. Although the authors have hitherto been unable to obtain any determinate data for the composition of this remarkable compound they are nevertheless able to assert that it consists of mercury carbon hydrogen and oxygen and that the last three elements are not in the proportion required to form alcohol the quantity of hydrogen being much too small ; moreover that the compound acts like a very strong base and combines not only with sulyhuric nitric and acetic acid but likewise with many other acids.In the course of the experiments made with this substance other mercury-compounds were obtained having more or less relation to it. Thus a substance different from the preceding is obtained by slowly adding a very weak solution of potash to a boiling solution of corro-sive sublimate &c. On dissolving mercury in nitric acid expelling all nitrous products by continued boiling and adding the solution to alcohol of 36O in the same proportion as for the preparation of fulminating silver no immediate action takes place provided the mixture be made at a temperature below 100'; but if the temperature be raised to looo a white crystalline compound is instantly formed and its formatioii continues even when heat is no longer applied.This reaction not- withstanding the rapidity with which it goes on is not attended wlth evolution of gas. The precipitate contains mercuric oxide nitric acid carbon and hydrogen ; when treated with hydrochloric acid it yields a volatile product having the peculiar odour mentioned in a fornier part of this paper.It may be confidently predicted that compounds analogous to tlic above will be obtained by siniilar processes in which amylic or methylic alcohol is used instead of common alcohol and other metals such as silver instead of mercury. On Etliyi~~mereuric Nitrate. By Ch. G;erhardt.* Gerluardt did not succeed in preparing the yellow detonating oxide of mercury by the process described by Sobrero:and Selmi;? he is moreover of opinion that this process is not likely to yield a product sufficiently pure for analysis. On the other hand he readily ob- tained the peculiar salt produced on mixing alcohol with mercuric nitrate. This salt has a very remarkable constitution as will be seen by the following observations. Mercurous nitrate has no action on alcohol.When an lacid solu- tion of that salt is mixed with alcohol of 3G0,and the mixture heated basic mercurous nitrate separates out in white crystals which do not contain organic matter. When alcohol is mixed with a very concentrated solution of mercuric nitrate there is formed in the cold an amorphous white precipitate of basic mercuric nitrate ; if the mercury-salt contains excess of nitric acid no precipitate is formed in the cold. On heating the liquid however a white crystalline Precipitate separates even before the liquid begins to boil and its formation continues without further application of heat. This is the salt obtained by Sobrero and Selmi. When examined by the microscope it exhibits a highly characteristic form consisting of six-pointed stars or hexagonal tables which are shaded in such a manner that similar stars appear within them whose vertices project into the angles of the tables.The salt is insoluble in water and in alcohol. When heated in a small tube it decomposes suddenly and explosively but does not detonate. After drying over sulphuric acid the composition of the salt was found to be as follows Ann. Ch. Pharm. LXSSX 11 1. -t. See the pieceding paper. X. GERHARDT ON ETHYLO-MEKCURIC NITRATE. Calculation. e rim nt. C 24 3.1 2.7 2.9 2.9' 0.4 0.3 0.3 H2 2 0.3 Hg 600 78.3 78.4 N 28 3.3 3.6 014 112 15.0 -766 100.0 These numbers agree with the formula NO5. HgO + NO,. C Hg 0 + 2Aq which formula is conformed by the equation 2 (NO5.3 HgO)+C H O,=the new salt +4HO.That this salt is a mercuric and not a mercurous salt is shown by its property of dissolving completely in hydrochloric acid withont leaving a trace of calomel; it evolves however when thus treated the peculiar odoriferous substance mentioned by Sobrero and Selnii. The solution in hydrochloric acid is precipitated yellow by potash. When a strong solution of potash is poured upon the new salt it turns grey; by boiling with the same solution it turns black without however being completely decomposed. The black substance is always mixed with crystals however long the boiling may be con-tinued. This black substance is not dissolved by hydrochloric acid although but a small quantity of calomel is formed. It follows there- fore that the salt is essentially altered by the action of potash.Ammonia acts upon it in a similar manner. A large quantity of mercurous nitrate is likewise found in tlie alcoholic solution from which the new salt has separated. A mercu-rous salt frequently separates in small needles after the new salt has been removed by decantation. The formation of mercurous salt probably depends upon secondary actions for the mixture of alcohol and corrosive sublimate gives off a strong odour of aldehyde when heated even though the action is not accompanied by any evolution of gas. The new salt is acted upon by sulphuretted hydrogen sulphide of mercury being formed and likewise a body having the characteristic odour of niercaptan. Hence in determining the mercury the organic matter must be first destroyed by boiling the salt with aqua-regia then evaporating to dryness and digesting the residue in water.If this precaution bc neglected the inercury will come out 1 or 2 per cent too much the sulphide collected on the filter being in fact inl- pure. The composition of the new halt leads to the supposition that the detonatiug oxide discovcred by Sobrero and Selmi is an oxide of DlL. HITTORYF ON THE mercuric ethyl that is alcohol in which the hydrogen is replaced by niercury C Hg 0,. Here then we have another instance of tlic striking analogy which exists between the products of the action otb alcohol and of ammonia that is to say between the ethers and thr aniides. We know indeed that the ammoniacal oxide of znercury likewise detonates and forms characteristic salts.On the Allotropy of Selenium. By Dr. Hittorff." Our knowledge of the thermic relations of selenium is due to Ber- eelius whose statements as given in his treatise have been copied without alteration into other compendiums of chemistry; they are as follows "Selenium becomes soft when heated is semi-fluid at loo' and fuses at a temperature a few degrees higher. During cooling it remains soft for a long time and may be drawn out like sealing-wax into threads which appear ruby-red by transmitted light. When solidified it assumes a specular surface exhibits perfect metallic lustre and is altogether not unlike blood-stone. Its fracture is con- choidal and vitreous.When fused selenium is left to cool very slowly its surface becomes uneven granular lead-grey and no longer specular. The fracture is fine-grained dull and exactly re- sembles that of a lump of metallic cobalt. A second fusion followed by rapid cooling destroys this appearance and restores to selenium its original external characters.'2 A fact observed by the author of this memoir places the relation between crystalline and amorphous selenium in its true light and shows that the preceding statements require correction. He finds namely that granular selenium does not fuse till heated to 217" C. and that it then passes at once from the solid to the liquid state without previous softening. VVheii cooled in the ordinary way the fused mass does not return to the solid state at this temperature but remains liquid and passes through all degrees of softness till at a temperature below SO' C.it gradually hardens into amorphous selenium. On plunging the bulb of a thermometer into fused sele- nium heated above 220' C. in a small crucible the temperature was found to fall quite resularly during cooling. There was no stoppage or retardation. The latent heat absorbed during the fusion of crys- talline selenium is therefore not given up under these circumstanccs but remains in the amorphous selenium and is essential to that state. At lower temperatures this condition of the selenium is stable. * Pogg. Ann. LSXYI 214. ALLOTROPY OF SELENIUM. 0I Pieces of fused amorphous selenium which the author has had iii his possession for several years have remained unaltered.The passage to the crystalline state takes place however on exposing the amorphous selenium for a time to a temperature between 80" and 2i7' C. the latent heat being at the same time evolved. In these experiments an oil-bath was used consisting of three concentric copper cylinders. By means of a spirit-lamp of constant level and a stirrer the oil of the inner vessel could easily be main- tained for any length of time at a constant temperature. The amorphous selenium was placed at the lower part of a common test-tube and fused round the bulb of a thermometer. The test- tube being introduced through an opening in the cover into the oil of the bath in ilhich a second thermometer is placed the ther- mometer in the seleiiium soon takes the temperature of the medium but instead of remaining at that temperature quickly rises above it.By the time that it has returned to the temperature of the oil-bath the amorphous selenium on being taken out is found to have as- sumed the granular condition. In amorphous selenium therefore we have a substance which under these circumstances softens when heated then becomes semi-fluid and afterwards returns to the solid state. The conversion into the granular modification takes place most quickly and the thermometer rises most above the temperature of the oil-bath when the latter is between 125'and 180'. With a quantity of selenium weighing about 20 grms. the thermometer usually rose from 40' to 50" above the temperature of the oil.The return to thc Iatter temperature takes place very quickly. A still greater rise of temperature is attained by using instead of the oil-bath an air-bath which conducts away the heat less quickly. A conveizient arrangement for the purpose is an ordi-nary drying apparatus consisting of a copper cylinder having two apcrtures in its cover so that a thermometer may be introduced through one of them and the test-tube with the amorphous sele- nium and the second therrnonieter through the other. If now the cylinder be heated with a small spirit flame which raises tghe temperature to about 130' C. the naked thermometer rises at first above that inimei-sed in the selenium. But as soon as the latter has risen to 125* it begins to mount rapidly and soon attains a tempe-rature between 210' and 215'.The process of transformation is slower as the temperature of thc bath is farther below 125'. The rise of temperature is then smaller but continues longer. In the vapour of boiling water the process takes several hours if the quantity be somewhat considerable; at 80° it lasts much longer ; in both these cases the evolution of hcat is im-perceptible. The time required for the transformation depends greatly on the mobi!ity of the particles. If thc amorphous scleniuni '32 1)R. HITTORPB ON THE be not fused but in the state of powder it assumes the crystalline form so rapidly at looo,and even at go' that the immersed ther- mometer rises from 25' to ZOO.At 80° in the vapour of ordinary spirit of wine the rise of temperature is imperceptible even in this case. The greater the fluidity of the amorphous selenium the inore readily does it give up its latent heat. From this cause the trans- formation takes place more slowly at temperatures above 180° because the temperature of the selenium can never rise above 217O the melting point of the crystalline variety. The latter can only be accurately observed by means of the oil-bath. For this purpose the bath is kept at a constant temperature of more than 220° arid the crystalline selenium together with the thermometer immersed in it. The thermometer soon rises to 217' then remains stationary for a long tune between 217' and 218* and finally attains the tem- perature of the oil.The selenium is then found to be melted. On taking a general view of the thermic relations of selenium it is impossible to overlook its strong resemblance to sulphur. It is well known that the latter is obtained in a soft plastic state by heating it above 250° and then cooling it as quickly as possible which is usually effected by pouring it into cold water. It then remains soft for a long time at the lower temperature and returns but slowly to the crystalline state. This transformation however takes place quickly as observed by Regnault,* if the sulphur be exposed to a temperature higher than the boiling-point of water. At the same time an appreciable rise of temperature takes place; the thermometer immersed in the sulphur rises to ill' the tempe- rature of the medium being 98'.The latent heat absorbed by sulphur heated to 2S0° is unable to escape during the short time in which it cools; at a lower tempe- rature it becomes more permanent and requires several days to escape. It may possibly become quite stable at a still lower tem- perature at which the soft surface hardens. In the case of selenium the latent heat takes a still longer time to escape the time occupied in ordinary cooling being in fact insufficient for the purpose. At temperatures below SO" the selenium hardens retaining its latent heat and the condition thus assumed is perfectly stable. Moreover selenium not only retains that latent heat at ordinary temperatures but under favourable circumstances readily absorbs it.It is well known that selenium is obtained in the form of a red powder when it separates from its compounds or solutions at ordinary temperatures. Thus sulphurous acid protochloride of tin zinc and iron throw down red selenium from selenious acid ; and seleniuretted hydrogen water deposits red selcnium on exposure to the air. Both amorphous and crystalline selenium are dissolved by strong oil of vitriol at +. l'ugg Ann. LIlI 266. ALLOTROPY OF SETJENIUX. 40' C. and the green liquid wheii tnixed with water deposits red selenium. This red selenium however is nothing more than amor- phous selenium in a state of minute dirision; for the latter also appears red in thin films by transmitted light and gives a red streak. The red precipitate turns black when it is heated above 50° softening at the same time and agglomerating into a shining vitreous mass.Lastly Count Schaffgotsch found the specific gravity of red sele- nium the same as that of fused amorphous selenium. Thus the density of red selenium was found to be 4.259 and after aggregation 4.264 and that of the glassy modification 4.276-4-2863 while that of granular selenium was 4*796-4805 at ZOO C. Precipitated sele- nium likewise gives out heat when it passes into the granular state. In the aggregated form it is the most convenient for this experi- ment; because it can then be easily pounded and dried in uucuo over sulpfiuric acid. If it be then held in the vapour of boiling water the thermometer rises during the transformation 125'-130°.Finely-divided red selenium gives off its water very slowly at ordinary tem- peratures; the author did not succeed in drying it completely. If exposed to the direct rays of the sun it gradually becomes crystalline. To observe the escape of heat it is best to apply a temperature of 80° such as that afforded by the vapour of ordinary spirit of wine; at this temperature the transformation is very rapid. Selenium is not always separated from its compounds in the amor- phous state at ordinary temperatures. The solutions of selenide of potassium and selenide of ammonium when exposed to the air always deposit it in the crystalline form. The crusts which form on their surface are entirely made up of small crystals which appear very distinct and definite under the microscope ; their specific gravity at 15O C.is 4.808.Vitreous and crystalline selenium differ greatly in their electrical conducting power. The former is known to be an insulator. Granular selenium conducts much better and whicb is very remarkable its resistance is considerably diminished by heat. Two small plates of carbon were immersed in melted selenium contained in a crucible and the amorphous mass brought into the crystalline state by exposing it to a temperature of 140' in the drying apparatus. It was then introduced together with a galvanometer having ZOO turns of wire and an astatic needle into the circuit of a single pair of Grove's battery. While the selenium was in the amorphous state no deflection was produced upon the needle under these circumstances; but after the transformation into the crystalline modification a deflection of 17O was produced at ordinary temperatures.On raising the tem- perature the deflection increased still further and at 210' C. it amounts to 80'. If this increase of conducting-power were to con- tinue the selenium when raised to a red heat would conduct as well Mr6EILER ON PIJOSPEIITDR OF TUNGSTEN. as the ordinary metals; but after the absorption of the latent heat at 217' the needle sudderily returns to 20". The allotropic states of sulphur and selenium are brought about by latent heat. The saine cause probably produces similar effects in other bodies although the relations are not so simple as those above considered.The author is of opinion that Schrotter's red phosphorus is formed in a similar manner viz. by the abstraction of latent heat from ordinary phosphorus and that it is really the crystalline modi- fication of the body ordinary colourless phosphorus being the amor- phous variety. It is true that no crystalline structure has been detected in the red phosphorus; but on the other hand it is always obtained either in a state of very minute division or somewhat aggre- gated in crusts conditions not very favourable to the observation of its structure. On Phosphide of Tungsten. By Wohler.* Phosphorus and tungsten combine directly but without emissioix of light and heat when finely-pounded metallic tungsten contained in a glass tube is heated to redness in phosphorus vapour.The result- ing compound is a dull dark grey powder very difficult to oxidize and composed according to the formula W3PB.This forinula requires 18-7 per cent of phosphorus; two experiments gave 28.38 and 18-87. Much more remarkable is the phosphide of tungsten obtained by reducing a mixture of tungstic and phosphoric acids at a very high temperature in a crucible lined with charcoal. In this manner a compound is obtained crystallized in magnificent geodes having exactly the appearance of certain geodes filled with crystals which occur in the mineral kingdom. The production of this beautiful arrangement was not the result of a single accident but was repeated in four different experiments. In every case there was formed a hollow mass of grey coke-like phosphide of tungsten several inches high more than an inch wide corresponding to the dimensions of the crucible and lined internally with the most brilliant crystals many of which though they were very thin prisms attained a length of nearly an inch.They have a steel grey colour and an exceedingly brilliant metallic lustre. They are six-sided prisms apparently iden- tical in form with gypsum. Their spec. grav. is 5.207. They * Ann. Ch. Pharrn. LXXIX 244. W~HLERON PHOSPHTDE o~ TUNGSTEN. aye perfect conductors of the electric current. When treated with zinc and dilute acid they liberate hydrogen gas and when immersed in a solution of a copper-salt they become covered with metallic copper.This phosgbide of tungsten undergoes no change when heated to the melting-point of manganese. It likewise remains nearly unaltered when heated to redness in the air. Heated on charcoal in a stream of oxygen gas it burns with great splendour; and fornis a deep blue sublimate on the charcoal. It likewise burns with an equally dazzling lustre on fused chlorate of potash. It is not attacked by any acid not even by aqua-regia. The proportion of phosphorus in this compound was found by three experiments to be 7.87 8.70 and 8-78. The formula W*P requires 8 per cent. For the preparation of this very beautiful substance crude phos- phoric acid containing lime and fused in an earthen crucible was generally used; it was mixed in coarse powder with the tungstic acid and generally in the proportion of 2 equivs.YO5:1 W03=Y*7. Thc quantity of' tungstic acid used in each experiment was between 20 and 30 grrus. The mixture was exposed in the charcoal crucible to a heat sufficient to keep nickel in a state of perfect fusion. In this manner the largest and finest crystals were obtained but the sur-rounding crust of phosphide of tungsten was intimately mixed with fused particles of slag which could not be removed by any solvent. A less beautiful product was obtained by the use of pure phosphoric acid; but in this case also the remarkable foimation of the hollow geode-space and the crystallization on its sides were exhibited. The formation of these crystals which project freely and often perfectly isolated into the hollow probably takes place in the liquid phosphoric acid which at first remains undecomposed in the interior of the mass and afterwards being gradually reduced to the state of phosphorus volatilizes leaving the space hollow and intersected with the crystals previously formed.On the Composition of Wolfram. By J. Persoz." When crude tungstic acid in the state in which it is obtained from wolfram is fused with five or six times its weight of nitre at a gradually increasing temperature three distinct salts are obtained possessing different characters and derived from essentially differeBt acids. * Compt. Rend. XXXIV 135. PERSOZ 0s TH 1I COMPOSITIOS OF WOLFRAM. If the heat be raised only a little above the melting-point of the nitre part only of the crude tungstic acid is attacked ; and on treat- ing the product with hot water we obtain a solutim of a salt A and an insoluble residue 2.The residue x,treated with a large excess of nitric acid at a tempe-rature a little below that at which the nitre decomposes becomes very fluid but not transparent. On treating the product with boil- ing water the excess of nitre is dissolved together with a large quan-tity of another salt B and there remains an insoluble salt C which passes through the filter as soon as the wash-water becomes pure. The solution A when left to itself first deposits free nitre if any of that substance be present and afterwards aggloiiierates into a mass of crystals composed of nitre and water together with a very small quantity of a salt belonging to the tungstic group.Boiling water decomposes these crystals dissolving the nitre and leaving a flocculent residue which when digested and frequently washed with hydrochloric acid is converted iiito a mealy powder very soluble in water but insoluble in those acids which have a great attraction for water. The solution when evaporated to dryness leaves a yellowish-white residue which if unaccompanied by foreign matter redissolves completely in water forming a solution possessing strongly acid characters. This solution is not precipitated by nitrate of silver; zinc reduces it forming the blue oxide. When treated with acids which have a strong attraction for water it loses its water of hydra- tion and reproduces the mealy powder above mentioned.When evaporated in vacuo it leaves a yellow crystalline mass which if the acid is very pure is composed of regular octohedrons. Salt 23.-This salt is composed of excess ofnitre mixed with tung- state of potash properly so called. Insoluble salt C.-When this salt is heated to redness with caustic potash and the fused mass digested in water a residue of oxide of iron is obtained together with a solution which when treated with a slight excess of nitric acid forms on boiling a milk-white pulverulent precipitate which is likewise an acid distinct from either of the preceding. This acid and all its salts exhibit the peculiar pro- perty of passing through the filter when washed with pure water. It resembles ordinary tungstic acid in most of its properties; but differs from it by certain very decided characters; for example it changes from white to yellow when heated and recovers its original colour on cooling.In other characters it seems to bear some resem- blance to niobic acid.