摘要:

JOURNAL OF THE CHEMICAL SOCIETY. CONTAINING THE PAPERS READ BEFORE THE SOCIETY AND ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN OTHER JOURNALS. Ph.D. E. J. M~LLS, E. ATKINSON D.Sc. F.C.S. HUGO MYJLLER Ph.D. F.R.S. C. L. BLOXAM Ph.D. H. W. PIKE,Ph.D. H. E. ARMSTRONG Ph.D. G. T. ATKINSOW. E. W. PR~VOST Ph.D. E. C. BABER. W. RAMSAY JAMES ROBINSON. BELL. JOHN BOLAS. R. ROUTLEDGE, THOMAS B.Sc. M.D. D.Sc. MORTYN T. L. BRUNTON J. SALTER. CBILDS,B.A. R. SCHENH,Ph.D. CHRISTOPHER M.D. C. SCHORLEMMER D. FERRIER F.R.S. D.Sc. WATSON WALTERFLIGHT SMITH. GILL. THOMAS M.D. C. HAUGHTON STEVENSON B. J. GROSJEAN. W. A. TILDEN,D.Sc. C. E. GROVES. WILLIAMVALENTIN. H. J. HELM. ROBERTWARINGTON. EDWARD WATTS D.Sc. KINCH. JOHN MUIR. C. R. A. WRIGHT,D.Sc. M. M. PATTISON C. H. PIESSE. NEW SERIES Vol. XII. (Entire Series Vol. XXVIIJ LONDON J. VAN VOORST 1 PATERNOSTER ROW. 1874. LONDON HARRISCIS AXD SONS PHIK'IERS IN ORDINARY TO HER MAJEsTY ST MARTIN'S L1NE.

ISSN:0368-1769    

DOI:10.1039/JS87427FP001

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

a II.-O?2 the Action of Bydrogelz on Xilver N,ftrafe. By W. J. RUSSELL, Ph.D. F.R.S. ITis generally acknowledged that hydrogen to a small extent decom- poses silver nitrate and separates from it metallic silver but this decomposition does not appear to have been minutely studied. I noticed some time ago that aftcr a current of hydrogen had passed for a considerable length of time through a wash-bottle containing silver nitrate a very appreciable amount of deposit was produced ; also that this deposit had a metallic appearance and when examined under the microscope appeared entirely crystalline in structure. Other experiments were made on the subject and it was found that when hydrogen was pcssed through a dilute solution of silver nitrate even for a very long time an exceedingly small amount of precipitate was formed and this of a greyish colour and only by the aid of a micro- scope could any tiace of crystalline struct *re be seen ; on the other hand if a saturated solution of the silver nitrate was taken then com-paratively a considerable amount of precipitate was formed that coming down first being somewhat dull and grey whereas that which precipi- tated afterwards was beautifully bright and crystalline.30 pms 10 grams and 2 grams of silver nitrate were dissolved each in 120 C.C. of water and hydrogen passed through the solutions for about a fortnight. There was then found to be a precipitate which weighed 0.365 in the 30 gram solution one weighing 0.1229 in the 10 gram solution andan amount too small to weigh in the 2 gram solution.The precipitate formed in this kind of way has been examined both by igniting and re-weighing it and by converting it into chloride and weighing it as such ; by both methods it gave results showing it to be pure silver. In the above experiments and in some of the following ones the hydrogen was generated by the action of a solution of copper sulphate on granulated or powdered zinc or of a solution of copper sulphate and zinc sulphate on zinc. In this way a very regular current of hydrogen is produced and one tlhat will coktinue for many weeks and at most the addition of a few crystals of the copper sulphate is all the attention it will require. Another mixture which acts very well indeed and gives a remarkably uniform current for a very great length of time is that of zinc and tin both in the state of powder simply put into a small flask of water at drdinary temperature 10 grams of zinc and 5 grams of tin give off' with ciirious regularity 3 C.C.to 4 C.C. of hydro- gen every day. In one case this was continued for 44days and then only stopped on account of the hydrogen not being required and in a more recent experiment tlie action has gone on for six months and the n2 ON THE ACTION OF HYDROGEN ON SILVER NITRATE. evolution of gas appears to be still as regular as when it was first set up. In most of the following experiments when the hydrogen was required only for comparatively short times it was generated from zinc and sul-phuric acid in a Kipp’s apparatus the gas being always very carefully purified and very thoroughly washed with silver nitrate before using it.First in order to make sure that this precipitation was produced by the hydrogen and not by any impurity it might contain the following experiments were made. The hydrogen was washed and then passed through and over an excessive amount of silver nitrate solution ;it first passed through two large Wolffs bottles filled with pumice-stone wetted with silver nitrate and then through some 12 feet of tubing filled with glass also wetted with the silver solution. The hydrogen after this treatment still precipitated the silver as freely as when purified in the ordinary way; further when a series of separate solutions of silver nitrate had hydrogen passed through them the pre- cipitations took place with apparently the same facility in the last solution as in the first.Other experiments were made with zinc which was free entirely from arsenic and lastly hydrogen was obtained from reactions in which zinc took no part in all cases the same preci- pitation of metallic silver took place. To obtain the hydrogen without using zinc magnesium and platinum both in the form of powder were put into a flask of water; at first a very violent action ensues but afterwards a tolerably regular stream of hydrogen comes off. It appears then that hydrogen is capable of precipitating silver from a solution of the nitrate the precipitation occurring much more readily in a saturated than in a dilute solution.Even from a saturated solution the precipitation takes place only after some time and the amount pre- cipitated as compared with that in solution is always very small. When a saturated solution is used hydrogen must be bubbled through it for nearly half an hour before precipitation takes place; if the current be continued a dull greyish substance separates out at first afterwards the precipitate is perfectly crystalline and bright exb ibiting a beaut,iful appearance. If for instance 10 grams of silver nitrate were taken dissolved in about 8 C.C. of water and hydrogen bubbled through the liquid for 18 honr.s only about 0.1308gram of silver would be preci- pitated. At first the amount of silver precipitated is nearly proportional to the time to which it has been exposed to the action of the hydrogen but after the first 48 hours the amount of silver precipitated increases at a slower and slower rate and after a time the amount of silver present will often begin to diminish.This precipitation of silver by hydrogen is independent of the action of light. Two similar solutions both contain- ing 20 grams of silver nitrate were acted on by hydrogen the one in bright light the other in the dark all other circumstances being made as similar as possible; from the solution in the light 0.2630 gram of ON THE ACTION OF HYDROGEX ON SILVER KITRATE. silver were precipitated and from the one in the dark 0.2703 gram. The precipitation is however very much expedited by heat. On passing hydrogen through the silver nitrate solution only for a minate and then heating ih it very visible although not very heavy precipi- tat,ion immediately appears ;it is amorphons and of a brownish colour.With a cold solution the following happens hydrogen may be passed through it for about 25 minutes witlho.;lt producing the slightest alte- ration in appearance. If the solution be then exposed to the air SO that the gas above the liquid diffuses away silver begins to precipitate after a short time and a considerable amount will in this way sepa- rate out. In one experiment 10 grams of silver nitmte were dissolved in 9 C.C. of water and the hydrogen was passed through the solution for 25 minutes. It was then perfectly clear ; it was allowed to stand all night and there was then found to be 0.01 gram of silver precipf- tated ; this weight of silver corresponds to 1.037 C.C.of hydrogen and if hydrogen precipitates silver equivalent for equivalent from the nitrate this bulk of the gas must have been dissolved in the 9 C.C. of liquid when the passage of the hydrogen through it ceased ; this same bulk of water would dissolve only 0.174 C.C. of hydrogen that is ith of the total amount of gas ; the other +ths must therefore have been dis- solved in the liquid owing to the presence of the silver nitrate or some chemical change must take place previous to the precipitation of the silver. A neutral solution of silver nitrate becomes acid as soon as the silver separates out ; and it has always been found that the silver is precipitated in larger crystals and brighter in appearance from acid than from neutral solutions.When examined by the microscope the silver is found sometimes to have an arborescent appearance at others to be a close network of very fine filaments so intertwined that tho whole of the metal cm be lifted out of the'solution in a connected mass and sometimes it is seen to bo in distinct and separate triangular plates of brilliant metal. The silver prepared by this means is as might be expected remark- ably pure ;any gold in the solution would be precipitated with the first portions of silver and the other metals likely to be present would not be separated out by the hydrogen. There is another way in which the hydrogen may be made to act upon the silver solution that is by merely keeping an atmosphere of the gas above the solution instead of bubbling it through.If a saturated solution of the silver nitbrake be put into a tolerably capacious bottle and the bottle be then filled with hydrogen the action will com- mence rather sooner than if the gas was merely bubbled through it and in 18 or 24 hours a somewhat larger amount of silver will be pre- cipitated than by the other process. With regard to the nature of the reaction which takes place is it a ON THE ACTION OF HYDROGEN ON SILVER NITRATE simple replacement of silver by hydrogen and if so why should it not be possible by continuing the action of the hydrogen to continue the pre- cipitation of silver ? and further if hydric nitrate easily dissolves silver how is it that hydrogen can separate the nitrate into the acid and metal ? First it was proved that the hydrogen was abaorbed by silver nitrate and no other gas evolved during the reaction.By taking a tube some 7 inches long and about &ths of an inch in diameter filling it with pure hydrogen and allowing it to stand in a saturated solution of the nitrate it was found that the solution gradually rose in the tube and at last completely filled it. The following method was adopted for estimating the relatJion between the amount of hydrogen absorbed and silver precipitated. A piece of tubing was bent into this form i:-’ and the horizontal end drawn out but not to a very fine point and bent upwards ; down it was poured the silver nitrate ; then the vertical end was placed ina vessel of water and hydrogen passed through the tube until the whole of the air was expelled ;the drawn out end was then sealed up.The water soon begins to rise in the tube a.nd when the experi- ment is over by marking off where the water stands and weighing the amount of silver separated out at least a tolerably accurate approxima- tion may be obtained to the amount of gas absorbed and silver preci- pitated. If an experiment of this kind be carried on for about aweek it will be evident that some secondary reaction has set in; for large yellow crystals will separate out from the solution ; these crystals were proved by analysis to be silver nitrite consequently it is not to be expected that the hydrogen absorbed and silver precipitated will be in simple atomic proportion.The following experiments show the relation which was found to exist between them. 20 grams of silver nitrate in solution were put into the bent tube with the hydrogen; after 23 hours it was found that 33.12 C.C. (corrected) of the gas had been absorbed and that 0.3024 gram of silver had been precipitated :-33.12 C.C. of hydrogen correspond with 0.3205 gram of silver Silver found ...................... 0.3024 ?> -0181 A quantity of hydrogen equivalent to this weight of silver is there-fore unaccounted for. In another and similar experiment 15 grams of silver nitrate were used and left in contact with the hydrogen for 27 hours; in this case 31.25 C.C. of the gas were absorbed:- 37.25 c c.hydrogen correspond with. . 0.3024 gram of silver. Silver found ...................... 0.2857 , -0167 R ON THE ACTION OF HYDROGEN ON SILVER NITRATE. again then the weight of silver found was less than the equivalent of the hydrogen absorbed. If the experiment be continued for tt much longer time there is a still greater disappearance of silver as compared with the hydrogen absorbed and as before mentioned after about four days the nitrite will begin to crystallise out. In an experiment which went on for six months the following results were obtained :-182*3 C.C. of hydrogen were absorbed which are equivalent to 1.758 of silver whereas only 0.2011 gram was found in the liquid. In another experiment 136.9 C.C.of hydrogen were absorbed equivalent to 1,3197 gram of silver and only 0.1277 of silver was found. Another experiment on a larger scale gave a similar result. 20 grams of pure silver nitrate were taken and exposed to the action of hydrogen from June 28th till August 11th ; it was then found to have absorbed llOX*21 C.C. (cor-rected) of hydrogen which corresponds to 10.72 grams of silver whereas in the liquid there was only 0.7079 grm. of metallic silver. In reality the amount of hydrogen absorbed in this and foregoing experiments was greater than above stated for in all cases a small amount of nitric oxide is evolved. It appears then that after a time a secondary reaction certainly sets in some of the silver which has been precipitated re-dissolving and nitrite separating out.That by the action of the hydrogen on the nitrate there is formed a solution capable of dissolving silver is shown by putting some weighed pieces of silver foil into the neutral nitrate solution and exposing it to the hydrogen ; it will be found that the pieces of silver will graduallylose weight. In order to stop this secondary action by neutralising the acid as soon as formed and thus be enabled to ascertain whether as regards the hydro- gen it simply replaced the silver in the nitrate the following experi- ment was made:-A bent tube was taken similar to those before clescribed ; a saturated solution containing 5 grams of silver nitrate was introduced into it and along with it 3 *5gram of silrer oxide ; the tube was filled with hydrogen aad the action allowed to go on for 20 days 105.3 C.C.of hydrogen had then been absorbed 1.0089 gram of silver precipitated and 0.3958 of the oxide had dissolved up :-105.3 C.C. of hydrogen correspond with 1.0184 gram of silver. Silver found . . . ,. . . ,. . . . . . . . . . . . 1.0089 ?7 that is 1part of hydrogen ia equivalent to 10'7 parts of silver. Again the weight of hydric nitrate corresponding with the amount of silver found is 0.5885 and that calculated from the weight of oxide whicth had dissolved is 0-5994. This seems satisfactorily to shorn that the action of the hydrogen on the silver nitrate is to replace the-silver thus precipitating the metal and forming hydric nitrate and that in the former experiments some secondary reaction is afterwards set up which ON THE ACTION OF HYDROGEN ON SILVER NITRATE.causes the solution of the silver and the formation of silver nitrittb. The questioii is then what is the nature of the secondary action ? And how is it that any such action is set cp ? If the hydrogen takes the place of the silver forming hydric nitrate and silver how can it be that on simply continuing the action of hydrogen they recombine ? Dilute solutions of the ordinary nitric acid have little or no action on silver; if an excess of silver be added to this acid the solution will always remain very acid even if very finely divided metal be used ; a 1 per cent. solution of HNO has the power of dissolving only the slightest trace of the metal; further if a dilute solution of hydric nitrate be saturated with silver nit4rate and then exposed to the action of hydrogen the silver is precipitated as it would be from a neutral solution.From a solution containing 7 per cent. of HN03and saturated with 10 grams of the silver nitrate hydrogen precipitated in 18 hours 0,1275 gram of silver very nearly as much as would have been precipitated from a neutral solution. Even in a solu-tion containing as much as 17.5 per cent. of HNO, silver is precipitated oy hydrogen but there is this difference between what takes place with acid and with neutral solutions stop the hydrogen passing through the acid solution and in a few hours all the silver will have disap- peared. With the neutral solutions this does not happen.This is shown very well with asolution coritaining 7 per cent. of acid. Satu-rate it with silver nitrate; then on passing hydrogen through it the silver is precipitated; stop the current of gas for the first three minutes there is no action; then a string of bubbles rise from the precipitated silver and in a very short time the whole of it has dis- appeared. On again passing in hydrogen the silver is precipitated as before and the whole experiment may be repeated over and over again thus dissolving up and precipitating in the same liquid. Thc explanation of the dissolving up of the silver in these acid solutions is appnrently the presence of a trace of nitrous acid. It has long been believed that the great activity of nitric acid towards many metals was owing rather to its containing a small amount of nitrous acid than to the affinities of the acid itself; and with regard to silver thin un- doubtedly is the case and that it holds good even with very dilute solutions of nitric acid the following experiments show.Two similar pieces of silver foil both weighing 0.3 gram were placed in similar tubes each with 5 C.C. of dilute nitric acid containing only 1.6 per cent. of HNO3. Through one of these solutions only two small bubbles of nitrous acid were passed ; both liquids were then corked up and left to stand for 46 hour^ and the amount of silver dissolved was estimated in the solution through which the nitrous acid had passed 0.0262 gram was found; in the other one 0.0093 gram. If stronger acid solutions be used this action of the nitrous acid is still ON THE 2iCTION OF HYDROGEN OX SILVER SITRATE.more marked. Two similar pieces of silver foil weighing about 2 grams each were put as in the above experiment into dilute nitric acid but containing 1'7.5 per cent. of HN03,in place of 1%per cent. Two or three bubbles of nitrous acid were passed through one liquid only ;immediately the silver in this liquid became covered with minute bubbles and after twenty minutes the whole of the silver was dissolved whereas the other piece of foil after exactly the same length of time was hardly a.t all attacked for the liquid on treating it with a chlo-ride gave only a slight cloud of silver chloride. Nitric oxide passecl into the solution gives of course similar results.There is another curious reaction with regard to the dissolving up of the silver in nitric acid. Two similar pieces of silver were placed in diluted nitric acid but still so strong as to dissolve silver that containing 17.F;per cent. of HN03,for instance and hydrogen was made to bubble through one of the tubes with silver solution while through the other the hydrogen streamed without bubbting through the liquid. In one experiment it was found that after an hour the silver in the tube through which the hydrogen did not bubble was entirely dissolved and in the other one the metal was not attacked to an appreciabIe extent by the acid €or the liquid gaye only a faint cloud on adding a chloride the bubbling of the hydrogen through the liquid having therefore protected the silver.This protective action is however in no way peculiar to hydrogen ; air will act in the same manner. The gas sweeps away any nitric oxide and keeps the nitric acid pure. The dissolving up of the silver after it has been precipitated by the hydrogen from silver nitrate may then be satisfactorily explained if there be any reason for the formation of only a trace of nitrous acid. A trace of this oxide of nitrogen is suEcient to start the action of the acid on the silver and once started the action very rnpidiy increases in intensity. The reaction which takes place is probably something of this kind. The nitrous acid attacks the silver form- ing silver nitrite nitric oxide and water the nitric oxide thus formed reducing hydric nitrate and forming more nitrous acid.Thus the action gets quicker and quicker and may be. started by the addition of a lower oxide of nitrogen. The point still remaining to be explained is then how the first trace of nitrous acid is formed. Assume that to be formed and with this cumulative action the rest is easy of explanation; and certainly if as appears to be the case pure hydric nitrate has little or no action on silver at all events when dilute it is not obvious why it should be formed. The dissolving up of the silver seems however to be directly con- nected with the presence of hydrogen; for instance if a volume of pure nitric acid be taken so dilute that it does not act appreciably upon silver and if it be exposed to an atmosphere of hydrogen instead of 10 ON THE ACTION OF HYDROGEN ON SILVER NITRATE.air then more or less action will be found to have taken place. If for instance a solution be taken containing l+p. c. of HN03,and pre- cipitated silver or silver foil be placed in it after they have remained in contact for a long time hardly the faintest cloud of silver chloride can be obtained from the liquid whereas if an exactly similar experi- ment be made but the air above the liquid be driven out by hydrogen and the vessel then closed on examining the liquid it will be found to contain sufficient silver to yield a dense precipitate of chloride. T’wo portions of precipitated silver were taken each weighing 0.157 gram and placed in separate bottles with 10 c.c. of dilute nitric acid con- taining 1.6 p. c. HNOs ; one bottle was filled with hydrogen the other left full of air. After two days the silver in each was again weighed ; in the bottle with the hydrogen 0.0039 gram had dissolved and-in the bottle with air 0*0006. Again if still stronger solutions of nitric acid be used this action is still more obvious. Two pieces of roll silver as similar as possible in every way weighing about 1gram each and exposing a surface of about 2 square inches each were placed in two large bottles and 50 C.C. of dilute nitric acid containing 7 p. c. of HNOs added. Pure air had previously been passed for half an hour through the dilute acid. One bottle was now filled with hydrogen the other left full of air.After two days it was seen that nearly all the silver in the hydrogen bottle was dissolved; and on examining the liquid in each bottle it was found that in the one case there was 0.9438 gram of silver in solution and in the other (where only air had been) there was only sufficient silver to give a faint cloud of silver chloride. To gain some idea how long this absorbingof the hydrogen by silver nitrate would continue and what would be the ultimate products 0.3 gram of nitrate was dissolved in water and put into a bent tube with the hydrogen. The experiment was started in December and stopped in the following March when it appeared that no further ab- sorption of gas was taking place. Supposing that no trace of nitric oxide remained with the unabsorbed hydrogen then 40.94 C.C.of hydrogen had been absorbed 0.0593 gram silver found in the liquid and 0.1234 gram of silver nitrite thus leaving 0.0446 of silver nitrate undecomposed. The amount of hydrogen which had disappeared was capable of precipitating 0.3932 gram of silver ; that is just twice as much as there was in the nitrate used. Direct experiment shows that the silver nitrite is not decomposed by hydrogen ; consequently under the above circumstances the silver nitrate is not a stable salt but indirectly by the action of the hydrogen it passes over into nitrite which is stable. The nitrite as is well known is very slightly soluble in water but it is soluble to a very considerable extent in a solution of uitrate hence in these tubes a considerable amount is always found in ON THE ACTION OF HYDROGEN ON SILVER NITRATE.solution besides what has crystallised out. On passing nitrous acid into a solution of silver nitrate if tho solution be dilute the nitrite separates out at once. But if the solution be a saturated one no separa- tion takes place ; the nitrite formed at first remains dissolved up and from the decomposition which the nitrous acid in greater part under- goes sufficient nitric acid soon accumulates in the solution to decom- pose the nitrite and an abundant evolution of nitric oxide takes place. In the foregoing experiments it has been shown that as the silver dissolves up silver nitrite separates out ; this is indeed an ordinary product of the action of nitric acid on silver when such reaction takes place out of contact with air.For instance take ordinary nitric acid add an excess of silver to it and replace the air above it with carbonic acid and in a short time lai=ge crystals of silver nitrite will separate out ; or if nitric acid with an excess of silver be simply placed in tt bottle and then the stopper put in the nitrite will form very readily. The series of reactions then which appear to take place when hydrogen is left in contact with silver nitrate are first the replacement of silver by hydrogen the silver separating out in a crystalline form ; then after a certain time by the aid of the hydrogen present a trace of nitrous acid is probably formed and this is capable of attacking the precipitated silver and combining with it.At the same time nitric oxide is given off which by acting on more nitric acid forms more nitrous acid thus accelerating the solution of the silver. If much nitric acid be present the silver nitrite naturally passes back again to nitrate and this may again be acted upon by the hydrogen. The silver nitrite on the contrary is unacted on by hydrogen and will therefore be the end-product formed by this reaction. With regard to other metals platinum palladium and gold are corn- pletely precipitated from solution by hydrogen in the metallic state and at ordinary temperatures and pressures. A solution of copper nitrate by long standing in contact with hydrogen becomes appuently from the change of colour converted into nitrite. Mercuric nitrate seemed to be acted on and a basic nitrate thrown down while bismuth nitrate seems not to be at all attacked.

ISSN:0368-1769    

DOI:10.1039/JS8742700003

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

12 ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. Measurement of the Chemical Action of Solar Light. By E. MARCHAND (J. Pharm. Chim. [4] xviii 417421). THE author believes that the method of Bunsen and Roscoe for measuring the chemical intensity of light by its action on chlorine and hydrogen leads to an exaggerated conception of the amount of chemical energy in the solar rays since tho work accomplished in this reaction is far greater than the total heat-force of the rays. He has devised an apparatus in which light acts on a solution of ferric chloride and oxalic acid. The chemical energy of the light is measured by the volume of carbonic anhydride evolved. This he states is strictly pro-portional to the energy expended 1C.C.of carbonic anhydride being equivalent to *0013X6 calometric degree. The rays most effective are those between 3' and G. [With chlorine and hydrogen the maximum effect is between G and H.] From his experiments at Fkcamp under a cloudless sky he has calculated the chemical energy of the sun for various seasons and latitudes. It appears that at the summer solstice the total energy per square meter in the twenty-four hours is for the equator 479 for the twenty-fifth parallel of latitude 657 and for the pole 498 calometric degrees. At the equinox the mean energy is at the forty-first parallel and amounts to 345'. Perfect transparency of the atmosphere is assumed. At Fdcamp the actual chemical energy received is reduced nearly one-half by imperfect transparency.No details are given. R.W. The Fluorescent and Absorption Spectra of the Uranium. Salts. By H. MORTON BOLTON and H. CARRINGTON (Chem. News xxviii 47 113 164). WHILE the present investigation was proceeding a memoir v as pub-lished by Becquerel in which he anticipated the authors hy recording the measurements of the spectra of many uranium salts. The authors therefore while publishing their work as an independent research lay no claim to aoy of the results previously obtained by t,he above-men- tioned physicist. A ray of light after passing through a tank containing a solution of ammonio-cupric sulphate was allowed to fall upon a test-tube or bottle containing a solution of the substance to be examined.The dispersed light was then observed by the spectroscope. Solid substances such its cr~stalsand powders were examined in a similar manner special GENERAL AND PHYSICAL CHEXTSTRT. arrangements being adopted to facilitate observation. The spectra both of fluorescence and absorption of 80 uranium compounds have been carefully measured and mapped the measurements detailed in the present paper being accompanied by drawings representing the appear- ance and position of some of the most characteristic spectra. The character of any one band is as a rule a type of all the bands in the same spectrum but different salts invariably give different spectra the latter being constant as long as the composition of the salt remains unaltered.A permanent change of appearance in the.spectrum was indeed so uniformly concomitant with change in composition that the authors in studying the action of heat upon a salt were enabled to predict by the persistency of the altered spectrum when a new salt of definite composition was obtained. The absorption-spectra of uranium salts (of which there are two kinds one related to the fluorescence and one not) were examined either b; throwing a pura spectrum upon a screen of the substance in question or upon the vertical side of a tank containing a solution. The latter method was considered the more accurate but some excel- lent results were obtained with a prepared screen 5y operating in the following manner :-A pinhole was made in the screen and the position of the latter adjusted in such a manner that the centre of the band fell on the pinhole ; the refrangibility of the light passing through the hole was then measured by a spectroscope placed behind the screen and the exact position of the centre of the band was thus obtained.From the fact that while the absorption-spectra of uranium acetate and of the double acetates vary greatly when examined in the solid but in solution present an identical spectrum the authors conclude that no double acetate can exist in solution in water but that they break up into their constituent salts. A similar coiiclusion was also drawn in the case of other salts such as the double sulphates and oxgchlorides. The effects produced by the application of heat were also studied.It was observed that in all cases it temporarily and in some cases per- manently modified fluorescent action. With many salts it caused a depression of some or all of their absorption-bands an effect which was most strikingly illustrated in the case of the double carbonates. This displacement of the absorption-bands by heat was measured in connection with seven salts and the results were tabulated. The addition of a little ether alcohol glucose sucrose or glycerin greatly reduces the fluorescence of a solution and a very small quari tity of hydrochloric acid destroys it entirely. The remainder of this lengthy memoir does not admit of useficl abstraction. Each uranium compound is examined singly and in detail ; the appearance of its spectrum aiid the best mode of observ- ing it is described; arid the measurements of the position of the bands both of fluorescence and absorption are tabulated.The neces- sary preparation of the pure uranium salts is also fully detailed. J. W. ABSTRACTS OF CHEMICAL PAPERS. Fluorescent Relations of certain Solid Hydrocarbons found in Petroleum Distillates. By HENRY (Phil. Mag. MORTON [.PI xlvi 89-1@2). INa former paper (p. 235 of this volume) the author refers to a hydro- carbon to which he gives the name “thallene.” When a beam of sunlight after passing through a cell containing ammonio-cupric sulphate falls upon solid thallene a fluorescent ligbt is emitted which gives a spectrum having the following characteris- tics:-There is a broad bright space in the orange and yellow then two green spaces separated by more or less brilliant bauds and finally a blue space.This spectrum differs from that of impure an thracene or chrysogen. The absoiaption spectrum of solid thallene differs from that of com-mercial anthracene in showing a double band near G and a third band at a much lower point than that shown by anthracene. When a sunlight spectrum is thrown on a card part of which is covered with filter-paper rubbed over with thallene the extra-violet spectmm as far as and even beyond H which is invisible on the white card appears very distinctly upon the greeii ground of the thalleiie-covered paper. Below F there is no fluorescent action. The spectrum on the thallene is not uniformly bright.The maxima of brightness are shown to correspond exactly with the absorption-bands before noticed. Thallene thus absorbs rays nearly all of which are converted into fluo-rescent not into heat motions. Thallene in solution fluoresces with a blue colour. The change from the green fluorescence of the solid is explained by the fact that all the bands are moved towards the more refrangible end of the spectrum? those bands which occupied the positions 6.8 8.4 and 9.8 (on Bunsen’s millimeter scale) being moved to 7.2 8.9 and 10.7 respectively in the spectrum of a solution in benzene. In an ethereal solution the bands are even more displaced that marked 6.8 in the solid having moved to 7.3. In a turpentine solution this displacement is not so great still less in olive oil less in benzene and least of all in carbon disulphide solution.The absorption-bands exhibit a similar displacement when a sunlight spectrum is thrown on the side of a crystal tank filled with solution of thnllene in benzene ; long trails of light are then seen running through the solution. There is a very faint olive-green trail (a)about E a very bright vivid green (6) at F a bright sky-blue (c) between F and G and a trail of an indigo tint (d) at G running into violet towards H. The light from the trails c and d examined by a hand spectroscope shows an upper blue band at. 10.7 which is wanting in the spectra of (b) this latter trail being placed at 9-9.15. This is in accordance with Stokes’s law. When thallene in solution is exposed to sunlight it loses its lower bnnd in five minutes and its upper double band in thirty minutes.Xxposed in a hot sollition for ten minutes near the focus of a large lens and allowed to cool thnllene deposits crystals of a light greyish- white colour. This substance called “petrollucene ” by the author GENERAL AND PHYSICAL CHEMISTRY. exhibits a spectrum whose bands occur in positions only slightly more elevated than those of an ethereal solution of thallene. M. M. P. M. Onthe Chemical Action of the Galvanic Current and on the Distribution of the Free Electricity on the Surface of the Conductors. By E. EDLUND (Pogg. Ann. cxlix 87-99). THE author develops his hypothesis that the electrical current is essen- tially a movement of the ether.He deduces from it that the power of chemical decomposition is proportional to the intensity of the current and independent of the cross section of the electrolysed liquid. From the property which the ether has in common with gases to propagate pres-sure equally in all directions it can be deduced that the current inten- sity is proportional to the electromotive force and indirectly proportional to the resistance. The following'are the fundamental ideas of the author with regard to the part which the ether plays in electrical phenomena:-From our knowledge of the native of light we conclude that all bodies possess the power of attracting the ether-molecules and condensing them in their interior until the attraction of the body for the external ether is in eqtii- librium witk the repulsioii of the condensed against the external ether- molecules.Under ordinary circumstances the molecules of matter do not exert any influence upon the ether surrounding them. When dif- ferent atoms containing different quantities of ether unite the ether of both is equally distributed over the molecule one of the atoms losing and the other gaining a portion of ether. That atom which now con- tains less ether than in the free state will be attracted by external ether-molecules whilst the other will be repelled. In accordance with this is the phenomenon that whenever two heterogeneous bodies come into contact with each other one of them becomes positively and the other negatively electric. In a weak electrical current traversing an electrolyte we niay have merely a rearrangement of' the ether-molecules.In a row of water-molecules for instance the ether will within the molecules move from the oxygen to the hydrogen atoms and also from one molecule to the next one in the series ; but in a strong current the ether will move with sufficient force to sever the constituents of water and to cause that series of decompositions and recompositions which in Grotthussen's hypothesis is supposed to take place in an electrolyte traversed by an electric current. R. S. Continuation of Thermic Researches on the Condensation of Gases by Solid Bodies; Absorption of Hydrogen by Platinum Black. By P. A. FAVRE (Compt. rend. Ixxvii 649- 656). THEauthor has endeavoured to show that electrolytic hydrogen is an allotropic active modification of that elenient and that in passing into the ordinary form it disengages 4,600 heat-units.He also proves that the absorption of hydrogen by palladium gives rise to a true alloy since ABSTRACTS OF CHEMICAL PAPERS. the heat developed by the combination (9,000units) is the same for the last as for the first portion of hydrogen added. On the other hand the absorption of hydrogen by platinum (and of other gases by charcoal) are merely cases of capillary affinity in which the gas may be supposed to form a layer whose density diminishes with increased distance from the surface of the solid. This is indicated by the fact that the later portions of gas absorbed evolve less heat than the earlier.The com- plete saturation of platinum-black with hydrogen (24 volumes) disen- gages about 20,700 heat-units for one gram of hydrogen absorbed. Now on considering what t.akes place on electrolysiiig dilute sulphuric acid with (1) a. zinc-palladium couple and (2) with one of zinc-platinum it will be seen that in the former case the hydrogen must enter into combination in the active state since it has not been able to pass into the ordinary gaseous condition ;but in the lather the hydrogen liberated in the active state transforms itself immediately into the ordi- nary modification. In spite of the heat absorbed during its passage from the liquid state into the gaseous (which as indicated by the absorption experiments with platinum-black must be considerable) this change evolves 4,600 beat-units.The absorption of active hydro-gen by platinnm-black ought therefore to develop about 25,300 heat-units and this experiment the author proposes to make. These considerations and some former results are brought to bear upon the thermic relations of the formaltion of water. The author regards the elements of water as present in that compound in the uctive state and he points out the complicated nature of the thermic reactions in\-olved in the formation of water for the study of which process bufficient data do not at present exist. M. J. S. An Example of the Quick Diffusion of a Gas into a Heavier Gas underlying it. By M. v. PETTENKOFER (Zeitschrift fur Biologie ix 245-249).ATthe Marienquelle of Marienbad which spring is enclosed by a slight wooden structure and from which gas is continually being given off in quantity estimated as being equal to a layer over its surface of 360 centimeters in an hour the author found in the gas obtained from under the surface of the water 70 per cent. of carbo.1 dioxide ; at a height of 5 centimeters from the surface the air contaiued only 31 per cent. at 25 centimeters 23 per cent. at 100 centimeters 2 per cent. and at 145 centimeters not more than 4 a per cent. of carbon dioxide. E. I(. Specific-gravity Bottle for Liquids Spontaneously Inflam- mable in Contact with Air. By A. TRIBE(Phil. Mag. [4], xlvi 308). THEbottle usually employed for specific-gravity determinations con- sists essentially of a light flask with a perforated stopper.Regnault introduced a solid stopper and made the neck somewhat longer and INORGANIC CHEMISTRY. narrower. The author makes the neck of as even a bore as possible, and divides it into as many equal parts as can conveniently be read. “ When once the water-values have been determined for each division on the neck it is only necessary to fill the bottle so that the surface of the liquid shall fall within the range of the graduations. Another advantage is that the contents can be raised or lowered to the normal temperature and the volume read off without addition or subtraction of liquid.” G. T. A.

ISSN:0368-1769    

DOI:10.1039/JS8742700012

出版商:RSC    

年代:1874

数据来源: RSC

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INORGANIC CHEMISTRY. In o rg ani c C he mi s t r y. The Non-luminous Flame of the Bunsen Burner. By R. BLOCHMANN (Ann. Chem. Pharm. clxvii 295-358). THEprocesses which go on in the interior of the Bunsen flame were studied by aspirating and analysing the gases from various parts of a flame 120 mm. high. In the first series of experiments the gases were taken from the atmosphere surrounding the flame at a distance of 10 mm. Up to a height of 20 mm. no products of combustion had diffused into the air but from 30 mm. to 120 mm. carbon dioxide and water vapour were found in slowly and irregularly increasing quantities. In the second series the gases were drawn from the periphery of the flame at every 10 mm. vertically. The quant'ity of free oxygen pre- sent indicated that from 29.4-48 volumes of air had become mixed with the products of combustion from 100 volumes of gas.After correcting for the carbon dioxide and moisture in the air and coal gas? the following table of the volumetric composition of the gas from the periphery of the flame was calculated :-Height from burner. 10 mm. cop3.30 H20. 14-36 0. 8.29 N. 74.05 =20 cop 4.35 - 3.49 14.95 7-95 73.61 4-29 4.07 14.68 8.31 72.94 3.63 3.95 12.90 8.94 74-21 3.27 3-64! 11-22 10.03 75-11 3-08 3.92 11-02 9.72 75-34! 2.81 4.35 10.82 9.20 75.63 2.49 4.91 10.73 8.92 75-44 2.18 5.38 10.72 8.60 75.30 1.99 5.73 10.81 7.76 75.70 1.89 6-58 10.97 6.61 75.84 1.67 7.18 11.14 6.17 75.51 1-55 The complete combustion of the coal gas would have given 2.27 as the ratio of water to carbon dioxide.It is thus seen that the gas does not burn equably the hydrogen burning chiefly in the lower and the carbon in the upper parts of the flame. This appears to be due to the VOL. XXVII C ABSTRACTS OF CHEMICAL PAPERS. low specific gravity of hydrogen which enables it to diffuse from the dark cone into the zone of combustion more rapidly than the other gases. The relatively large proportion of burnt gases at the very base of the flame when connected with the facts that a space exists between the burner arid the base of thc? flame and that the inner and outer zones of combustion meet at that point seems to indicate t,hat a portion of the gas has time to form with tlie exterior air an explosive mixture which ignites as a whole when its temperature becomes sufficiently high.In the third series the gases were aspirated from the interior of the flame at four points viz. 10 mm. below the orifice of the burner and 25 50 75 mm. above it The point of the inner cone was about 55-60 mm. from the burner. The composition of the mixture from the interior of the burner showed that the gas was at that point only mixed with about 40 per ceiit. of the air required for complete cornbus- tion. Below the point of the inner cone little or no combustion takes place for combustible gases aiid free oxygen are found in presence of one another. Above this point the combustion is almost complete only 6 per cent. of combustible gases being found at 75 mm. These consist of hydrogen carbon monoxide and traces of marsh-gas ;oxygen is entirely absent.The carbon monoxide of which both here and at 50 mm. there is far more than is contained in the original gas is evi-dently formed in the inner zone of combustion. A portion at least of the hydrogen found at 75 mm. must be due to the decomposition of the hydrocarbons since between 25 and 50 mm. it rapidfy disappears while at 75 mm. there is scarcely less than at 50 mm. The additional fact of a decided expansion (independent of temperature) of the gases while passing the point of the inner cone points to some such reaction as'C2H4+ O2=2CO + H4. The author has also repeated and extended Knapp's experiments on the extinction of the luminosity of a gas-flame by the admixture of other gases in place of air.Oxygen nitrogen carbon dioxide and monoxide and hydrogen all produce this effect. When an inert gas is used the space between tlie burner and the basc of the flame is greatly increased; as much as 1.5 mni. was observed. On augmenting the supply of inert gas the flame either opens at one side the opening be- ginning at the bottom and extending upwards to the summit or else the top of the flame vanishes altogether leaving a mere ring with the upper side very irregular. It was noticed that when the luminosity of the gas was destroyed by admixture of nitrogen it could be partially restored by addition of a little air. Attention is also drawn to the opposite effects produced by oxygen according as it is mixed with the gas before combustion or immediately at the point of ignition in which case as is well known it greatly enhances the luminosity.The cause of the luminosity of flames is discussed but without any definite conclusion being arrived at. M. J. S. INORGANIC UHEMISTRY Proportion of Carbonic Acid in Atmospheric Air; Variation at Different Heights. By P. TRUCHOT (Compt. rend. lxxvii 675-678). THEamount of carbon dioxide was determined by passing a known amount of air through a solution of barium hydrate of known strength contained in four Wolfe'a bottles and by subsequent titration. Ten litres of air were found sufficient for a determination. The observa- tions were made at Clermont Ferrand during the months of July and August both on an elevated terrace and on the country.Carbon dioxide Vo1. in per litre. 10,000 air. m.gr. During the day ...... 0 "701 3-53 On the terrace.. ........ { During the night .... 0 -801 4*03 Removed froin Shy.. .............. 0.624 3 -14 .. { Night.. ........... 0.753 3 *78 In the sun.. .. 0 *703 3 *54 country In the shade . . 0 *825 4 *15 Night.. ............ 1-290 ti -49 These figures show that the amount of carbon dioxide is larger during the night than in the daytime and that the amount does not materially vary in tJhe neighbourhood of a town. The sun influences the quantity of carbon dioxide near vegetation. From observations made at different elevations it was found that the quantity of carbon dioxide diminishes considerably as the altitude increases.COz Vol. in Tempe-Pressure.per litre loo>ooo 'pot of Date. observation. Height. rature. at. 0" air at Oo and 760. and 760. m. mm. 26th 28th 1 30th Bug. Clermont Ferrand.. 395 25' 725 0.623 3.13 3873 .... 27th Bug. { Top Of Puy-do) 1446 21' 638 0.405 2-03 D8me ........ 29th Bug. .. Peak of Sancy .... 1884 6' 5'78 0.342 1-72 These results may be explained when we consider that the carbon ioxide is evolved from the surface of the earth and that its specific avity is greater than that of air. W. R. Apparatus for Dissolving Hydrogen Sulphide under Pressure. By J. P. COOKE,Junr. (Chem. News xxviii 64). THEapparatus consists of three bottles A B C; a bottle D four times the size of one of these and a small wash-bottle.A is the generator and is furnished with one exit-tube by which it is con-c2 ABSTRACTS OF CHEMICAL PAPERS. nected with the mash-bottle which acts better if it contains moistened sponge than if the gas simply passes through water. The gas is thence conducted through B and C in the usual manner to D which is fur- nished with three tubes. Two of these extend a short distance below the stopper (which like all the others is of india-rubber) ; one is the inlet and the other is a vent. The third tube reaches to the bottom of the bottle and is placed in connection with a water-head. When the generator is charged and the connections are made the vent of D is opened till the air is driven from the apparatus. The.vent-tube is then connected with a manometer and when the pressure equals that which it is known the water-head will exert.the vent is closed. The water- supply is then turned on cautiously at first] lest water should be forced back into the generator but afterwards at full pressure. The solution of the gas is drawn from B or C by adapting a tube to the inlet in such a way t.hst a syphon is formed. 100 C.C. of such a solution made under a pressure of two atmospheres will precipitate a gram of antimony. To ensure the solution of the sulphate formed in the generator it is advis- able to place the latter near a source of gentle radiant heat. In dis-mounting the apparatus care must be taken to relieve the pressure on the generator cautiously otherwise the hot solution of sulphate will boil over.The expanditure of hydrogen sulphide in a large labora- tory was reduced by this apparatus to five per cent. of its usual amount. B. J. G. Existence and Decomposition by Heat (Dissociation) of Sulphur Tetrachloride. By A. MECHAELIS and 0. SCHIF-FERDECKER (Deut. Chem. Ges. Ber. ri 993-996). BY saturating sulphur sulphochloride (S,Cl,) cooled to -20" with chlorine the author has obtained a light-brown clear liquid which on analysis yields numbecs closely agreeing with those required by the formula SCI,. On being removed from the freezing mixture the liquid boils and evolves chlorine. The following tables show the decomposition of sulphur tetrachloride at various degrees of temperature :-I. Swlphw tetrachloride.Increase Temp. Diff. sc14. SCl> Diff. for 1". -22 100~00 0.00 7 58.05 8-3 15 41.95 58.05 5 13-22 2% 10 27-62 72.38 3 5.66 1.9 7 21.137 78-03 5 10.04 2.0 2 11.93 88.07 + 0.7 2.7 8.87 91.13 3.06 1.1 5.5 6.4 1.1 6.2 943 97.57 INORGANIC CHEMISTRY. II Sulphur dichlomkle. sc12. S&12. Diff. for 10". + 20 93.45 6.55 6.23 30 87-22 12-78 6.41 50 75-41 24.59 5.79 65 66.78 39-22 6-36 85 54-06 45.94 90 26.48 73-52 7.03 100 19.45 80.55 7.10 110 12.35 87-65 6.91 120 3.a 94.56 130 0.00 100.00 5 *44 M. M. P. M. Sulphur Oxytetrachloride. By A. MICHAELIS and 0. SCHIF-FERDECKER (Deut. Chem. Ges. Ber. vi 996-999). WHEN sulphuryl hydroxychloride (CI-S02-0H) is mixed with sulphur tetrachloride and the mixture cooled to -18' and saturated with dry chlorine a white crystalline mass is obtained which after purification has the formula S20sCJ4.This substance is therefore identical with that which Millon obtained by passing moist chlorine into sulphur chloride saturated with chlorine. The authors assign to it the rational formula SC13-0-S02C1. It melts at 57" giving off chlorine and sulphur dioxide. The residue after cooling contains thionyl chloride and pyrosulphuric chloride. 4s203c& s,05c124-5S0C12+ c11 -+ SOZ. =* After long keeping this substance is changed into a yellow liquid which possibly contains the theoretic isomeride SOC13-0-SOC1. M. M. P. M. Solidification of Nitrous Oxide. By T H o M A s W 1 LL S. NITROUS OXIDE was one of those gases which Faradq succeeded in liquefying almost at the beginning of his scientific work in 1823.Dry nitrate of ammonia was enclosed in one end of a bent sealed glass tube and exposed to the action of heat ; the salt was decomposed with some difficulty but eventually the decomposition was complete and the pressure exerted by the first portion of the generated gas proyed sufficient to liquefy the remainder for at the conclusion of the experiment two layers of liquid remained in the tube the lower one proving to be water and the upper one liquid nitrous oxide. The interior pressure as indicated by one of Faraday's mercurial gauges was 50 atmospheres and the temperature 45" F. Thilorier and after- wards Natterer obtained the same result by the direct compression of the gas with a force-pump.Faraday again worked at the subject of the liquefaction and solidifi- cation of gases in 1845 and then succeeded in freezing the liquid nitrous oxide into a mass of transparent crystals by exposing it in a sealed tube to the cold of a bath of solid carbonic acid and ether i?z ABSTRACTS OF CHEMICAL PAPERS. vacuo the pressure in the interior of the tube at the time as indicated by the gauge sinking to less than one atmosphere. Therefrom Faraday concluded that nitrous oxide could not be solidi- fied by the cold produced by its own evaporation unless aided by the external withdrawal of the pressure. This belief was corroborated by his experience; for on opening several tubes containing the liquid a large portion of it was immediately converted into gas but the remainder was only cooled without showing any sign of solidifica- tion.Some experiments made by Natterer with much larger quantities of the liquid (using indeed as much as a quarter of a litre at a time) in which he also failed to obtain the solid by spontaneous evaporation seemed further to confirm this conclusion. It is possible that in the above observation the gauge after cxposure to such high pressures may not have been sufficiently trustworthy to register low ones. The above result is directly opposed to that obtained with carbonic acid. The melting or freezing point of carbonic acid is -7O" or -72" F. and the pressure of its vapour at this point is equal to 5.3 atmospheres ; hence it is seen how readily it can become solid by its own evaporation at a pressure of only one atmosphere.In fact this spontaneous evaporation will cool the solid carbonic acid down to a temperature of about -148" F. or 78" F. below its freezing point and possibly the solid nitrous oxide in the sealed tube at the time when the gauge registered less than one atmosphere was thus cooled below its freezing point. In comparing the behaviour of carbonic acid and nitrous oxide it must however be borne in mind that solid car- bonic acid is exceptional. Faraday himself pointed out the remarkably high tension of its vapour when in the solid state and showed the somewhat paradoxical result that if the boiling point of a liquid be defined (as it usually is) as that point at which the tension of its vapour balances the pressure of the atmosphere then the boiling point of carbonic acid is colder than its freezing point by about 40' F.boiling point = -110" IF.; melting or freezing point = -70" F. Dumas in 1848 actually obtained a rery small quantity of solid nitrous oxide by the evaporation of the liquid but apparently in too small quantities to allow- of any accurate observations being made. Having lately had some facilities afforded me for working with large quantities of liquid nitrous oxide I have endeavoured by a few experiments to obtain it in the solid state by means of the cold arising from its own evaporation and to some extent these experiments have been successful. Solid carbonic acid is produced with great ease when the liquid issues fiom almost any jet into almost any kind of receiving vessel and the use of special apparatus is only to obtain it with the greatest economy in the consumption of gas ; perhaps for this purpose the ordi- nary circular brass box of Thilorier's is the best.To obtain lipid carbonic acid in a vessel freely open to the air is extremely difficult if not absolutely impossible. Nitrous oxide on the other hand can be kept readily in the liquid state in open vessels for a consider-able time without alteration provided the vessel is kept still. For the production of solid nitrous oxide the above-mentioned brass box is of no use the evaporation of the liquid not being sufficiently INORGANIC CHEBlISTRY.promoted. It seemed possible however by the introduction together with the liquid of a strong stream of air to aid this evaporatioii ; and this proved to be the case fbr a very small quantity of the solid was by this means produced. By altering the arrangement and substituting for the brass box a straight glass tube somewhat contracted at its orifice the result obtained was better. Finally an arrangement some- thing like an injector was adopted A very fine steel tube (such tubes as are used in some surgical operations) was directed into the axis of a thin brass cone having a small opening about the eighth of an inch at its apex. On causing a stream of the liquid to issue from the jet' it is retained in the cone f'or a moment and is then forcibly blown out at the apex together with a strong stream of air.The solid is in this way formed in some quantity and may be collected in a dish lined with filter-paper or other suitable vessel. XOdoubt for this result there is a large consumption of gas. The appearance of the solid is more compact than that of the well- known carbonic snow which is probably accounted for by the fact that larger particles of the liquid are frozen this freezing taking place with carbonic acid immediately ihe jet of liquid leaves the tube and while it is yet in the state of fine spray ; but in the case of nitrous oxide only after it has to some extent been collected into larger drops. Unlike solid carbonic acid nitrous oxide will melt and boil if gently warmed before assuming the gaseous condition.Hence if touched with the fingers or placed in contact with the skin it melts and produces a painful blister. The temperature of its freezing or melting point is -120" F. or -99"C. as observed with an alcohol thermometer. The boiling point usually said to be -88" C. is according to my experi- ments -109" F. or -92" C. but I should give more credence to the lower figure. The readings of alcohol thermometers at such low tem- peratures are no doubt, somewhat untrustworthy Those used iu this case have been graduated from actual observations above zero ; but below zero the degrees have simply been placed at equidistant inter- vals. As probably the alcohol gets rather thick and more viscid at this lower point and the contraction consequently less the above figures will still be too high.The proximity of the boiling and freez- ing points caused me to try to freeze the liquid by simply blowing a stream of air through it ; in which I succeeded perfectly. Liquid nitrous oxide is immiscible with water as seen in Faraday's original experiment the tube containing two layers of liquid. An experiment on a larger scale has fully confirmed this fact and it is somewhat curious that a gas comparatively so soluble in water shonld when it becomes a liquid be immiscible with that fluid. Water and nitrous oxide were pumped together into an iron vessel and the vessel afterwards inverted. On opening the cock the whole of the water was expelled before any of the nitrous oxide appeared.An additional quantity of water was placed in the vessel while still in its inverted position and nitrous oxide again pumped in beneath it. On standing for twenty-four hours the cock was again opened with the same result 8s before ;the liquid nitrous oxide having ascended through the heavier water. The specific gravity of the liquid I believe to be 0.9004 ; and from ABSTRACTS OF CHEMICAL PAPERS. some experiments I am inclined to think the liquid is exceedingly compressible but of this I a,m not able to speak with certainty. If the solid be placed upon water it does not appear to come into contact with it no doubt being protected by a film of its own vapour. I hope shortly to be able to continue these experiments in other directions. T.W. Zinco-magnesium Chloride. By G. WARN E R (Chemical News xxviii 186). WHEN magnesium chloride is dissolved to saturation in a hot solution of zinc chloride having a specific gravity of 1.6 a salt having tlhe composition ZnClz.MgCIz.6H20 is deposited on cooling. It forms deliquescent rhombic prisms with truncated summits. The following table shows the amount of water absorbed from the air in a given time by equal weights of various chlorides the amount absorbed by calcium chloride being t’aken as unity :-Calcium chloride ....................... 1.00 79 , crystallised .............. 0.52 Zinc chloride crystallised ................ 1.00 Zinco-barium chloride crystallised. ......... 0.40 Zinco-magnesium chloride crystallised.. ....0.59 Magnesium chloride. ..................... 0.43 T.B. Chemical and Crystallographic Notices on some Salts of Glucinum and the Metals of Cerite. By C. MARIGNAC (Ann. Chim. Phys. [4] xxx 45-69). I. XaZts of GZueiwum.-The author has reinvestigated the double Buo- rides of glucinum with the alkali-metals whose existence had been denied by Klatzo. They are easily obtained by concentrating mixed solutions of the respective fluorides and admit of recrystallisation from water. The potassium salt GF2.2KF generally forms hard mammil- lated crust,s but by cooling a somewhat dilute solution it may be obtained in crystals derived from a right rhomboidal prism. They generally present the form of thin hexagonal plates the basal planes being largely developed.When the solution contains excess of potas-sium fluoride the crystals have the appearance of rectangular prisms owing to the elongation of one of the secondary axes. The salt is soluble in 19 parts of boiling water or in 50 parts at 20’. When heated it decrepitates and melts at a low red heat it contains no water. By concentrating a solution containing a large excess of glucinum fluoride a second salt was obtained of the formula GF2,KF. It forms a hard vitreous mammillated crust from which no deternii- nable crystals could be extracted and it cannot be recrystallised from water. Corresponding salts of gZuci?cum and sodium were prepared. The compound GF2.2NaE’ exists in two forms one derived from a right and the other from an oblique rhomboldal prism.It is soluble in 34 INORGANIC CHEXISTRY. part-s of boiling water or in 68 parts at 18'. After fusion at a red heat it solidifies to a transparent' glass which falls to powder spon-taneously. The compound G;F,.NaF is veyy similar to the potassium salt. The awmonium salt GF,.2NHIF forms prismatic crystals isomorphous with the potassium salt. Numerous measurements of the angles of the preceding salts are given in the paper. The fluosilicate bromate and iodate of glucinum could not be pre- pared in the solid form ; neither could the double chloride of glncinum and mercury announced by Bonsdorff. The salt GK,( S04)2.2H20 pre- sents hard white opaque mammillated crystals the form of which could not be determined. The hex-hydrated sulphate was obtained accidentally.It forms foliated prismatic crystals which are very eBorescent and lose their brilliancy on removal from the mother- liquor. A solution. of glncinum ditliionate gives off sulphur dioxide on concentration and yields crystals of the sulphate. The perchlorate is very deliquescent. Attempts to prepare the double salts of glucinum sulphate with cupric and ferrous sulphates described by Klatzo were unsuccessful the two salts always crystallising separately. The same want of success attended efforts to combine glucinum nitrate with magnesium lanthanum and didymium nitrates and the sulphate with aluminium sulphate or with soda-alum so that the only existing evidence from isomorphism respecting the atomicity of glucinum is derived from the similarity in the forms of phenakite Si02.2G0 and willemite SiO2.22n0.11. On some Salts of Cerium Lautimwn alzd Didymiurn.-The author confirms the observations of Ceudnowicz and Hermann who had con-tradicted his own earlier researches on the crystalline form and amount of hydration of cerous sulphate. By evaporation in a vacuum at ordinary temperatures the salt 3CeS04.8H20 separates in right rhom- bo'idal octahedrons ; but when the. solution is evaporated in the air at 40"-,50" hexagonal prisms are obtained having the composition CeS04,3H20. The latter is absolutely isomorphous with the corre-sponding lanthanum salt. Two similar salts of didymium exist ; the trihydrated is hexagonal but that with 8 equlvalents of water is not isomorphous with the cerium salt.The nitrates of lanthanum and didymium contain 4 molecules of water. They belong to the same crystallographic system but though very similar in appearance cannot apparently be referred to the same primitive form. The a.tnnzonio-Zanth,anum nitrate La,(NK,)z(NOs)io,8H20 and the corresponding didymium salt are perfectly isomorphous. They form oblique rhombo'idal prisms with the basal edges replaced by octohedral planes. The awmojiio-cerous .nitrate (notl analysed) examined by Des Cloizeaux is also isomorphous with the above. The chZoropZatimtes of the three metals 4RCl2.3PtCl4.36H20,are isomorphous aiid very similar. They form square pyramids with basal planes. They are very soluble crystallising only from syrupy solu- tions.They lose half their water at 100". ABSTRACTS OF CHEMICAL PAPERS. Note on the Atomic Weight of Zunthanum.-Four. determinations of the weight of oxide in lanthanum sulphate which had been crystallised a great number of times and was almost perfectly free fi.om didymium, gave numbers leading to the atomic weights 92.52 92.56 92.24 and 92.48. The first two were made by simple ignition the others by pre-cipitation with ammonium oxalate. The author therefore adopts the number 92.5. M. J. S. Action of Sodium Sulphite and of Sulphurous Acid upon Lead Iodide. By A. MICHAELIS and G. KOETHE(Deut. Chem. Ges. Ber. vi 999-1000),. SODIUM SULPHITE and lead iodide form sodium iodide and lead sulphite. Sulphurous acid decomposes lead iodide forming lead sulphite and hydriodic acid.M. M. P. M. Chlorides of Molybdenum. By L. PAUL and B. KEMPE LIECHTI (Deut. Chem. Ges. Ber. vi 991-993). BYthe action of dry chlorine upon metallic molybdenum there is pro-duced the black pentuchloride MoC15. This compound is crystalline ; it can be fused and sublimed without decomposition. At a tempera-ture of about 250" it is reduced by hydrogen to the trichloride MoCI3 which is a reddish-coloured amorphous mass unchanged in the air and insoluble in water. When heated in a stream of carbon dioxide this compound is split up in accordance with the equation i., 2M0C13 = WOCIZ + MoClp. The dichloride which remains behind is a yelIow amorphous sub- stance insoluble in nitric acid but easily soluble in strong hot hydro- chloric acid from which solution a salt crystallises out having the formula Mo2Cl,.3H20.The tetrachloride which is carried over with the carbon dioxide forms a semi-crystalline brown sublimate easily decomposed by moisture. M. M. P. M. Action of Iodine on Chromium Dichloride. By R. W. EME ttSON MCIVOR (Chem. News xxviii 138). THE chromium chlorochroniate the preparation and properties of which are described by Thorpe (Chemn. ATews xx 245) can be formed by heating chromium dichloride with dry iodine. The following reac-tion takes place :-:3Cr02C12+ 41 = CrzOsC12+ 41C1. B. J. G.

ISSN:0368-1769    

DOI:10.1039/JS8742700017

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Miner a1o gi c a 1 Chemistry. On the Constitution of Natural Silicates. By K. HAU sH o FE R (Ann. Cheni. Pharm. clxix 131-146). AN attempt to exhibit the constitution of natural silicates by means of graphic formula founded principally on known facts of pseudomorphy. Starting with enstatite SiR"03,corresponding with the neutral carbo- nates which is formulated O-Si=gIR" and regarded as a normal silicate the addition of R"O yields olivin R"I~ISiY~ZRt ;and o-O-R"' 2R"O furnishes R"Io-Si {o-R/f/o which is believed to form part of chondrodite ; whilst the introduction of (SiO,)" gives OZSi-0 1. /R",\ the general formula of petalite. OIS1-0 These formulm represent saturated compounds but they may ob- viously be so arranged as to present free atomicities.Thus SiMg,O~ (olivin) may be qISi=o-Mg-o-* O-MF?-O-X. These elementary groups may therefore combine with basGs witlh Si02 or with one another in various proportions chondrodite for instance consisting of SiRirOa + 2SiRir0,. The existence of silicates SizRfr06 points to the union of several atoms of silicon by means of oxygen. Thus steatite may be formu- lated-X -Si-O-Si-0-Si-O-Si-O-X II 11 I1 !I 00 00 00 00 ii II ii 11 Mg Mg Mg HH the two atomicities marked *being either free to combine with other radicals or else saturating one another. The primary nucleus of the garnet group is Si3(R2)ViR3r'012 repre-senting grossular and allochroite. The removal of 3SiCa03 and 2Ca0 from grossular and the introduction of HzO furnishes epidote which in the anhydrous form consists of two groups of the form of anorthite and one of euclase the latter consisting of the anorthite group, Si2Rr1'2R,"OB +R"0.Abstraction of CaO from anhydrous epidote yields smpolite. Each of these two species is known to form pseudo- morphs after the other. On the assumption that the group -Ca- Ca< -Ca -is isomorphous with -Al= idocrase may be represented as composed 1 -Al= ABSTRACTS OF CHEMICAL PAPERS. of four groups of the primary nucleus Si,AI,Ca,O,,,with one similar group in which 3Ca replaces 2A1 and the pseudomorphy of garnet and scapolite after idocrase becomes intelligible. The conversion of almandine into chlorite consists in the removal of Si2(Fez)”0~ and in- troduction of 4MgHz02 and 2H20.The further action of magnesia and water yields serpentine. Almost all these formulae are given in the graphic form in the paper. M. J. S Researches on Emeralds and Beryls-Part I. On the Colour- ing-matter of the Emerald. By C. GREVILLE WILLIAMS (Proc. Roy. SOC.,xxi 409 ; Phil. Mag. [4],xlvi 314-328). THEcolouring-matter of the emerald has been attributed to iron to chromium and to organic matter. With regard to the last the author shows that both emeralds and beryls contain carbon but he thinks that it is probably present in the form of diamond and has nothing to do with the colour of the emerald for “colourless beryls may contain as much carbon as the richest-tinted emerald.” The colour is really due to the presence of chromic oxide.Accounts are given of the author’s experiments on the effects of fusion upon (i) opaque beryls (ii) emeralds (iii) an artificial mixture of beryl ingredients. Whatever may have been the temperature at which beryls and emeralds were formed the author has convinced himself that rubies were formed at a very high temperature since the peculiar reaction between a;lumina and chromic oxide to which the red colour of the ruby is due takes place only at a heat as high as that of the oxy- hydrogen flame. G. T. A. American Minerals. By A. R. LEEDS(Amer. Jour. Sci. [3] vi 22-26>. I. Hydrated Ufiisilicate approaching Pyrosc1erite.-This mineral occurs in the Bare Hills Maryland between a wall of deweylite on one side and talc on the other.The deweylite graduates into albite and the talc is bounded by serpentine. The mineral has many of the character- istics of pyrosclerite the points in which it differs from that species beingt he following. Hardness =1.5 -2. Specific gravity = 2.558. Colour greyish inclining sometimes to bronze-yellow. Its composition is- SiO% Also,. Fe203. FeO. MgO. Na20+Li20. H20. 35.99 9.52 5.35 1.08 32.94 0.41 14°60=99*89 corresponding with the formula- Z(+(MgO) + + { (A~,0~),(FezO~),))3SiOz.4~~0 which is on the type of pyrosclerite plus one mol. H,O. 11. Pseudomorpk after Pecto1ite.-Occurs in calcite traversing the trap near Bergen Hill New Jersey. In general appearance and specific MINERALOGICAL CHEMISTRY.29 gravity it resembles talc but in hardness (= 2*5),and reaction when heated alone or in a borax-bead it corresponds with sepiolite (meer- schaum) with which it agrees in composition analysis giving Si02 MgO. A1203. FeO. MnO. CaO. HzO. 60.55 26.56 1.02 0-72 0.65 1.41 9*30=100*21 111. Leucaugite from Amity New 1Ybr7; resembles in general ap-pearance the spinel which abounds in the neighbourhood and especi- ally that of Warwick New York but its density and composition are those of leucaugite from which it differs however a little in hardness H being 5.5. Analysis gave- Si02. A1203. Fe203. MgO. CaO. HzO. 50.05 7-16 0.56 14.48 25.63 1.66=99*54 It will be seen that the relative proportion of lime and magnesia is slightly different from the proportion in leucnugite.IV. Alumino-magnesic Silicate accompanying Corzlm,durn.-The corun-dum of Chester Pennsylvania is sometimes bordered by lesleyite con- taining potash and lithia the first constituent diminishing in amount as the lesleyite recedes from the corundum. The new mineral was found accompanying the lesleyite. Analysis-SiO* Al,03. Fe203. FeO. MgO. LizO. NazO. H20. 30.62 21.73 0.42 5.01 29.69 0.11 0.14 12*26==99*98 The oxygen ratio for R,O (including the small per centage of ferric oxide due to superficial oxidation of the ferrous oxide) R,O, SiO and H,O is 4.84 3 4 3.23. The mineral resembles ripidolite in physical properties but its oxygen ratio is not that of ripidolite nor has any specimen of that mineral in this neighbourhood been found by the author to contain a trace of lithium.V. Blonstone Variety of Albite from Delaware Co. Pemwy1vania.-Composition-Si02. AlzOa. Pe203. CaO. MgO. Na20. &O. H20. 67.70 19.98 trace 1.47 0.11 8.86 1.36 0.08=99*56 It has the usual properties of albite. VI. Antholite from Xtar Rock Comord,Delaware Pennsylvania.-Has the usual properties of this amphibole. By the analytical results it will be seen that oae-third of the usual amount of ferrous oxide is replaced by other bases. Composition-Si02. Also3. FeO. MnO. CaO. MgO. E20. Na20. H20. 55.12 0.55 8.20 0.33 0.75 31.18 1.01 1.55 2*21=100*90 VII. ‘Werrheritefrom Van Arsdale’s Quarry Bucks Co. Pennsylvar~ia. -This particular variety of scapolite has usually been classed as an ekebergite hut its composition is nearer that of the least altered varieties of wernerite.Analysis gave- SiOp 47.47 Also,. 27.51 Fe203. trace MgO. 1-20 CaO. 17.59 Na20. 3.05 E20. 1.40 HsO. 1*48==99*70 73. J. G. ABSTRACTS OF CHEMICAL PAPERS. Microsommite. By GI.. TOX RATH(Jahrbuch fur Mineralogie 1873 544). THIS name was gix-en by Scacchi to a mineral which he discovered in the Vesuvian outcasts of the eruption of 1872. He describes it as occurring in very small hexagonal prisms (20 weighing about a milli- gram) resembling nephelin in form but differing from that mineral by an occasional peculiar grouping in tufts and especially by contain- ing chlorine. Vom Rath who received from Scacchi a number of the Vesuvian outcasts of the eruption of the 26th of April 1872 has made a more particular examination of the microsommite contained in them.It occurs in both kinds of blocks ejected from the great crater in the Atrio namely t'he monolithic consisting of single fragments of old porous Somma lavas and the conglomerate consisting of loosely united fragments of lava together with eisystals of augite. Both kinds are usually covered and bound together by a thin crust of new lava. In the monolithic blocks the minerals newly farmed by sublimation- leucite sodalite microsommite augite hornblende iron glance-fill the pores ; in the conglomerates they 611 the interstices between the individual lumps and crystals Microsommite belongs to the hexagonal system its form is pris- matic terminated by the dull end-face.The edges between the prism and the bases are sometimes truncated by the faces of the double six- sided pyramid. The inclination of the pyramidal to the prismatic faces P :(x P is by measurement about 111"50' hence the ratio of the axes is a c (vertical) = 2.88 1,and the calculated values of the angles are P co P = 158' 34' ; P P (lateral) = 43" 40'. The faces of the prism are vertically striated sometimes nearly rounded. The crystals are colourless and transparent about as hard as felspar ; have a sp. gr. of 2.60 (at 15") ; melt with diiliculty before the blowpipe; suffer no loss even on intense ignition. The mineral dissolves in nitric acid with separation of gelatinous silica and the solution gives with silver solution a copious precipitate of silver chloride.Analysis gave-SiO2. A1203. CaO. E20. E%O. C1. SO3. 33.0 29.0 11.2 11.5 8.7 9.1 1.7 = 1042 If we suppose t'hat the chlorine is united with sodium (9.1 C1 .t 5.9 Na the latter being equivalent to 8.0 NazO) the excess of Qhe analysis becomes reduced to 2.2 p. c. and we obtain 0.7 p. c. Na20 in addition to the 5.9 Na. The sodium given by the analysis was weighed as sulphate together with the potassium and estimated by difference after the potassium had been determined as platino-chloride. It is therefore very pro-bable that the estimation of the sodium was rather too high and that the whole of it is really combined in the mineral with chlorine. The oxygen of the silica (= 18.0) and that of the alumina (= 13.5) are nearly in the ratio of 4 3 80 that this portion of the compound = A1,03.2Si02 as in sodalite nosean and hauyne.Microsommite like hauyne contains lime and alkali in isomorphous mixtnre and MINERALOGICAL CHEMISTRY. therefore represents a hemisilicate of aluminium calcium potas- sium &c. united with sodium chloride and a small quantity of calcium sulphate. Its probable formula is- ~~~~} A1203.2Si02+ NaCl + &(Ca0.Si02) which gives by calculation- SiOz. Alz03. CaO. &O. NEL C1. SO3 33.9 28.3 10.5 10.4 6.3 9.8 1.7 = 100.0 Microsommite eonnects the sodalite group with nepheline to which latter the mineral approaches nearly in its crystalline form. In fact the most obtuse of the double hexagonal pyramids known in nephelin agrees nearly with the double pyramid of the newly formed Vesuvian prisms the formation of which must be attributed to the action of volcanic vapours laden with sodium chloride on the leucites (potash alumina) and the augites (lime) of the lava.Here therefore we meet with a new example of the action of sea-water in the formation of minerals by volcanic processes. H. W. Occurrence of Tellurium Minerals in the United States. By Dr. BURKART (Jahrbuch fur Mineralogie 1873 476-495). THEoccurrence of bismuth telluride telluric bismuth or tetradymite Bi,Te, in Virginia and Georgia has long been known. Genth also analysed a sulpho-telluride of bismuth Bi2S3.2Bi2Te3 occurring in North Carolina (Anz.J. of Sci. [el xix 16 ; xlv 317). More recently tellurium minerals have been found in California viz.silver telluride or hessite near Georgetown in Eldorado connty ; bis-muth telluride together with native gold in the Melones and Stanislaus mines in Calaveras Co. and sylvanite or graphic tellurium at the New Melones mines. Giiido Kustel (Mirtirng and ScientiJic Press qf San Francisco 20th May 1865) describes the principal tellurium ore of the Mellones mine as a telluride of siluer and gold of sp. gr. 9 to 9.4 containing 35.40 p. c. Te 40.60 Ag and 24.80 Au = 100*80. In a subsequent communication (Berg. u.. EGttenm. Zeitung 1866 128) Kustel states that he has also found in this mine silver telluride natire tellurium copper-nickel iron pyrites and native gold but no sylvanite or altaite. Tellurium ores from three other localities in Cali- fornia are mentioned by B.Silliman (Academy of Natural Science of Cul$omzia 2nd December 1867). Genth obtained from various persons a somewhat numerous collec- tion of tellurium minerals from the western declivity of the hlifornian range namely petxite hessite altaite native tellurium and three new mi&rals viz. ealaverite melonite aiid montaite. The tellurium ores of the Stanislaus mine occur in micaceous and chloritic slates together with quartz dolomite apatite a uranium ore kitanic iron iron pyrites copper pyrites and small quantities of galena ABSTRACTS OF CHEMICAL PAPERS. blende and native gold. They occur for the most part finely divided and mixed together in snch a manner that it is difficult to separate a quantity of any one of them sufficient for analysis.(a.) Petxite and Hessite.-Auriferous silver telluride or petzite is the most abundant of all the Californiam tellurium ores. The specimens from the Stanislaus and Golden Rule mines were destitute of crystal- line structure exhibited a distinctly concho'idal fracture metallic lustre steel-grey to iron-black colour and iron-black streak ; hardness = 2.51 ;sp. gr.9 to 9.4. They contained 24*80-25-70 p. c. gold 40.60- 42.36 silver and 31.94-34.16 tellurium agreeing with the formula Au2Te.3Ag,Te. They- contained therefore more gold than the pet- zite or sylvanite of Nagyag but need not on that account be regarded as a distinct species inasmuch as gold can replace silver in various proportions.Petzite is also found abundantly in the Red Cloud mine at Gold Hill Boulder county Colorado. Hessite Ag2Te containing little or no gold is found in the Stanis- laus mine but always mixed with other minerals viz. native gold altaite and quartz. (b.) A7taite PbTe occurs in the Stanislaus and Golden Rule mines mixed with hessite and petzite. It is distinguished from the other tel- lurium ores by its tin-white colour inclining to greenish-yellow. Hardness = 3. Two specimens gave the following analytical num- bers (1) after deduction of 1.03 p. C. quartz ; (2) after deduction of 1.96 P.C. :-Pb. Ag. Au. Te. (1.) 60.71 1.17 0.26 37.31 = 99.45 (2.) 47.84 11.30 3.86 37.00 == 100 These numbers show that (1) consisted of 99.25 p.c. altaite and 2.20 hessite ; (2) of 77-42 altaite and 23.11 hessite. (c.) Native TeZZuriurn occurs mixed with the preceding minerals in small greyish-white specks. (d.) MeZomite,-This is a new mineral belonging to the hexagonal system. Genth observed only one microscopic but perfectly formed hexagonal plate the mineral being for the most part indistinctly granular and laminar but exhibiting a very distinct basal cleavage. It has a metallic lustre reddish-white colour and dark grey streak. Heated in a glass tube before the blowpipe it yields a sublimate which melts to colourless drops leaving a grey residue. Heated on charcoal it burns with a bluish flame yielding a small white deposit and a greyish-green residue from which by fusion with sodium car- bonate in the inner flame a grey magnetic powder of metallic nickel is obtained.It dissolves with green colour in nitric acid the solution leaving on evaporation a white crystallhe powder of tellurous acid. Analysis gave- Silver ... 4.08 which requires 2.42 Te and therefore represents 6.50 p.c. Hemite YY JJ Lead .... 072 , 0.45 ,7 ?? 1.17 Altaite Nickel. .. 20.98 , 68.27 )) ,¶ 89.25 ,) Melonite yy Tellurium73-45 , -7) Y? 2.29 , Native L__ tellurium. 99-21 n.14 MINERALOQIOAL CHEMISTRY The nickel contains only sufficient cobalt to give a very light blue colour to a borax bead. The composition of melonite as determined by the analysis agrees approximately with the formula NiTe3 which requires 23.51 p. c. Ni and 76.49 Te.(e.) Cnlavarite AuTez.-This is also a new mineral which Genth found only once in the Stanislaus mine as'sociated with petzite. It is massive non-crystalline soft (hardness = 3) with metallic lustre bronze-yellow colour yellowish-grey streak an4 uneven fracture approaching the conchoidal. Heated on charcoal before the blowpipe it burns with bluish-green colour leaving a gold bead of a bright yellow colour. Nitric acid colours it darker and separates gold. In aqua regia it dissolves with separation of silver chloride. Analysis gave after deduction of 1.45 p. c. quartz- Gold. Silver. Tellurium. I. 40-70 3.52 55-89 = 100*11 11. 40.02 3.08 56.00 = 100 The silver is due to the admixed petzite. Deducting this the analytical numbers for calaverite agree nearly with the formula AuTe3 which re- quires44.7 p.c. gold and 55.83 tellurium. (fa> Nontade BiZO3.TeOa.HzO(or 2HzO).-This mineral formed by oxidation of tetradymite BizTe3 was first observed by Genth during the examination of the tetradymite of Highland in Montana ; subsequently the so-called tetradymite from Davidson Co. North Carolina which was in great part oxidised and gave off chlorine when treated with hydrochloric acid was found to be identical with it. The '* yellow bismuth oxide " from Whitehall in Virginia analysed by Jackson (Am. J. of Xci. [2] x 78) is also regarded by Genth as pro- bably the same mineral. Montanite is not crystallised but exhibits here and there the scaly structure of the original tetradyrnite and is in reality a pseudomorph after the latter on which it forms a coating.It is earthy soft dull to waxy in lustre yellowish to white and opaque. Before the blowpipe it exhibits the reactions of bismuth and of tellurium and gives off water when heated in a tube. Genth's analyses lead to the following results :-I. Oxygen. 11. Oxygen. 111. Oxygen. Ferric oxide .., 0.56 -1.26 -0.32 -Lead oxide.. .... 0.39 -__. -Cupric oxide.. .. -1-04! -1-08 -Bismuth oxide . . 66.78 6.85 68.78 6.29 71.90 7-37 Tellurous oxide, 26.83 7.30 25.45 7.05 23.90 6-51 Water ........ 5.74 -3.47 -2.86 - 100.50 100*00 100.06 The oxygen ratio between the bismuth oxide and the tellurous oxide is nearly 1 1,but it is as yet uncertain whether the composition of the mineral is Biz03.Te03.Hz0or IZi2O3.TeO3.2HZO IT.W. VOL XXVII. u ABSTRACTS OF CHEMICAL PAPERS. The Nickel Ores of Horbach near St. Blasien in the Black Forest. By E. KNOP (Jahrbuch f. Mineralogie 1873,521-529). THESEores are imbedded in the serpentinized gneiss of the locality in irregular nodules accompanied by copper pyrites enclosing here and there granular aggregations of iron glance. They consist of nickeli-ferous magnetic pyrites having a magnetic action a metallic aspect a pinchbeck-brown colour inclining to steel-grey darker than that of true magnetic pyrites and black streak. Hardness between 4 and 5. sp. 9:. = 4.43. Cleavage imperfect in one direction only. Analysis of material carefully freed from the accompanying copper pyrites and iron glance gave as a mean 45-87 p.c. sulphur 41.96 iron and 11.98 nickel agreeing nearly with the formula FeaNiSla which requires 45.9 S. 42.8 Fe. and 11.2 Ni. The ore for which the name h o r b a c hi t e is proposed may accordingly be regarded as an isomor- phous mixture of the trisulphides of iron and nickel- 4Fes3 + XS,. This composition has not hitherto been observed among native sul- phides all those previously known being either bisulphides monosul- phides sulphides of lower degree or compounds of these with bioxides. On the other hand the composition of the Horbach ores does not appear to be quite constant; a specimen of sp. gr. 4.7 having been found to contain 40.03 p. c. sulphur 55.96 iron and 3.86 nickel. The author here enters into a theoretical discussion of the constitu- tion of the several varieties of magnetic pyrites for which we must refer to the original paper.Horbachite subjected to lixiviation in contact with the air becomes oxidised and partly converted into the sulphates of iron and nickel which dissolve out. Knop suggests this method for the extraction of nickel from the Horbach ores instead of the treatment in the dry way hitherto adopted whereby enormous quantities of sulphurous acid are thrown off causing great injury to the neighbouring forests. H. W. Indium in American Blendes. By H. B. CORNWALL (Chem. News xxviii 28 reprinted from the American Chemist). ZINC blendes from West Ossipee and Eaton both in New Hampshire gave distinct spectroscopic indications of indium.In a specimen from Roxbury (Connecticut) the indium could be detected in the raw mineral without dissolving in acid. B. J. G. Meteoric Ikn from Shingle Springs Eldorado County Cali- fornia. By B. SILLIMAN (American Jour. Sci. [3] vi 18-22). THIS mass weighing 85 lbs. was found in 1869 and is believed to be the first discovered in California. Its cross-section was approximately a semicircle. It was very homogeneous in composition two masses of MINERALOGICAL CHEXISTRY. pyrites 3 and 5 mm. in diameter being the only accompanying mineral. For a depth of about 5 mm. from the surface the iron was harder than in any other part. Its density determined an a mass of 750 grams was 1.875 the shavings cut by the planing machine having a density of 8.024.The high density of the mass compared with ordinary meteoric iron is probably due to the large percentage of nickel which is more than twice the average amoLint. A structure resembling the Wid- mannstattian figures was developed by etching but it was visible to the microscope only. The suggestion of Berxelius that the Wid- mannstattian figures are due to the segregation of the nickel alloy in lines of the octohedron in virtue of its comparative insolubility in the etching acid seems unsupported by this result. According to this theory a high percentage of nickel would cause a clearer development than usual. The existence of a hard crust in this case would seem however to indicate that the mass had not endured the intensity and duration of heating of average meteoric iron so that crystalline structure was but feebly developed.The Cape of Good Hope iron (Rammelsberg ~~~?~e~aZc?~e~2~e, 919) has aiso no Widmannstattian figures and it contaius much nickel (15.09 per cent.). It has how- ever much more cobalt (2.56 per cent.) than the Californian iron and but five elements in its composition. The following is the composition of the Californian mass :-Fe 81-48; Ni 17.17 ; Co 0.60 ; Al 0.09 ; Cr 0.02 ; Xg,0.01;Ca 0.16 ;C 0.07 ; Si 0.03 ; P 0.31 ; S 0.01 ; I(,0.03 = 99.913. Clark analysed a meteoric iron from Tennessee which contained Ni 17.10 ; Co 2.04. Smith (Amer. Jozw. Xci. [Z] xix 155) obtained Ni,14%2; Co 0.46 with a mass from the same State. The average amount of nickel in 80 analyses referred to was 7.25 per cent.B. J. G. Product of Oxidation of Meteoric Iron; Comparison with Terrestrial Magnetites. By STANISLAX MEUNIER(Compt. rend. lxxvii 643-6443}. INformer papers the view has been developed that terrestrial rocks may be regarded as thtt crust of a globe the interior of which has a constitution similar to that of meteorites serpentine for instance forming the exterior of deeper lying masses of chantonnite. This view is now extended to magnetite which may be compared with the product of oxidation of a meteoric iron. The want of the structure which in meteoric iron gives rise to Wicimannstadt’s figures is no obstacle to this view since experiments show 6hat oxidation deprives meteoric iron of all trace of this structure.The absence of nickel from magnetite is also no insuperable objection since the author has observed that a sample of meteoric iron which had been treated with aqua regia and then washed and dried became after a time covered with ef33orescent crystals of pure nickel chloride. The tendency of iron to form insoluble peroxide might thus prevent it from being washed away while the nickel might be removed in the soluble form. This fact appears to account also for the almost invariable presence of nickel in serpentine while it is absent from chantonnite the former D2 ABSTRACTS OF CHEMICAL PAPERS. according to the preceding supposition having derived it from the washings of embedded magnetite. It is also noticeable that in reducing serpentine with carbon the iron and nickel combined forming an alloy which approached the composi- tion of meteoric iron.M. J. S. Carbon Dioxide in the Air of the Soil of Munich at Different Depths and at Different Times. By M. V. PETTENROFER (Zeitschrift f. Biologie ix 250-257). THEauthor has continued his determinations of carbon dioxide in the air of the soil (vide Chem.. Xoc. Journal [2] xi 361). The monthly means of carbon dioxide in 1,000 parts of air are as follows:- C02in COsin C02 in COz in air from air from air from air from 18’71. depth of depth of 18’72. depth of depth of 4 meters. 1Q metera. --meters. 4 meters. 1% Norember ...... 6,693 5.4’72 May. ........ 11*813 8 Y75 December ...... 6.048 4.125 June ........18 -718 11.983 18’72. July ........ 26 -110 14 547 .,.. 19 ’724 10 -308 January ........ 5.312 3.864 August February.. ...... 5.369 4.176 Sept>ember..,. 1’7*288 11 -156 March.. ........ 6-552 3.593 October .,,.. 12 ‘338 8 -227 April .......... 2.825 5.641 On comparing these numbers with those previously given it will be seen that the quantity of carbon dioxide is much larger throughout but that the variations at different seasons occur in the same order the minimum occurring in winter and the maximum in summer The mean of carbon dioxide in the air at the depth of 4 meters was 6.73 per 1,000 in 1871 and 11.81 in 1872; there is no apparent reason for this great difference. The numbers obtained by Fleck in similar experiments in the botanical garden of Dresden are given and also show an increase of carbon dioxide from the surface of the soil downwards; but here the amount is much larger being greater at a depth of 2 meters than at Munich at 4 meters and the variations with season are not so regular.E. K. The Warm Springs of Costa Rica. €37 A. V. FRANTZIUS (Jahrbuch f. Mineralogie 1873 496-510). THESEsprings more than 30 in number may be regarded as a. con- tinuation of the remarkable series of warm mineral springs discovered by Humboldt in Venezuela and extending for 150 miles from Cape Paria to Merida. The Costa Rica springs begin indeed 13 degrees of longitude farther west but are situated under nearly the same‘ parallel of longitude vie. 10” N. on a strip of land running for 30 miles from ORGANIC CHEMISTRY.east to west. Most of them occur in narrow mountain gorges on the banks of rivers or are even overflowed by the rivers so that they are visible only in the dry season. Many of them are situated near the border-line between the trachytic lavas of the volcanos (Turialba Irazu Barba Poas and Miravalfes) and the diorite and syenite moun- tain masses of Aguate Candelaria and Dota. Their temperature is higher in proportion as they are situated at a lower level. The highest observed temperature 55.6O R. (= 69.5"C. = 157.1" I?.) was exhi-bited by a spring situated about 800 Paris feet above the sea-level whilst another 4,000 feet above that level had a temperature of only 23.2" R. (=29" C. = 84.2" F.).Only one of these waters has been analysed namely that of Agua- caliente near Cartago an analysis of which was made in 1858 by Count Schaffgotsch. This water has a sp. gr. of 1.0022 and contains in 16 ounces 19.74 grams of anhydrous salts consisting of-&SO4. Na2S04. NaC1. NaaC03. CaC03. MgCO,. SiOz. Loss. 1.15 4.78 7.55 1.11 3-28 0.86 0.47 0.54 = 19.74 The water also contains free carbonic acid amounting to more than 2.35 grains but the quantity was not exactly determined. The water of most of the springs is probably similar in composition to that of Aguacaliente at least so far as regards the predominance of common salt. This is evident from the saline incrustations which form in places where the water stagnates and evaporates quickly during the dry season This circumstance gives a practical importance to t,he springs of Costa Rica inasmuch as cattle have a preference for localities where salt is deposited.They are also used as medicinal baths. The proportion of sodium chloride is however not sufficient to give them the character of true brine-springs. H. W.

ISSN:0368-1769    

DOI:10.1039/JS8742700027

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

ORGANIC CHEMISTRY. Organic Chemistry. Ethene Chlorhydrate. By A. LADENBURG and E. DEMOLE (Deut. Chem. Ges. Ber. vi 1023-1024). BYheating this compound with acetic anhydride in sealed tubes to 110' it is converted into ethene acetochlorhydrate which compound has already been obtained by Simpson and Lourenqo by a different reaction. c. s. New Derivatives of Propyl (continuation see this Journal [2] xi 871). By A. CAROURS (Compt. rend. lxxvii 745-750). Pro23yZ 0xaZate.-When anhydrous propyl alcohol is distilled wit11 dry oxalic acid mixed with one-third of its weight of sulphuric acid a colourless limpid liquid condenses in the receiver. Water separates this into two layers. The upper layer is washed first with sodium ABSTRACTS OF CHEMICAL PAPERS.carbonate solution and then with water and finally dried over calcium chloride. By rectification the product yields a very limpid colourless liquid having an aromatic odour recalling that of ethyl oxalate. Its sp. gr. at 22" = 1.018. It consists of p~qiyloaalate C,0z.(OC3H~)~. It boils at 209"-211". An aqueous solution of ammonia converts it into oxamide. Alcoholic ammonia if not in excess does not,give with it any precipitate of oxamide but on evaporating a crystalline body is obtained consisting of propyZ ommate C2O2(NHz) OC3H,. This sub- stance when heated in a tube melts to a colourless liquid and gives off vapours which condense in the form of slender prisms. P~opylCarboaate.-The action of sodium upon propyl oxalate is analogous to its action upon ethyl oxalate the product being yropyl carhowate CO(OC3H,)2 which is a colourlcss limpid liquid boiling at 156"-160" and having 8 specific gavity of 0.968 at 22".Its odour is somewhat like that of ethyl carbonate. Roiling concentrated potash- solution converts it into propyl alcohol. With an aqueous solution of ammonia or more rapidly with an alcoholic solution it is converted at ordinary temperatures into prop31 uretha'ize which crystallism in prisms. Propyl Xa;ZicyZate.-This compourzd is formed when a mixture of propyl alcohol salicylic acid and oil of vit)riol in the proportion of 2 parts of each of the first two to 1part of the third is submitted to distillation An oily liquid is condensed which is washed with water containing sodium carbonate to free it from a small quantity of sulphurous acid.It is then washed with water dried over calcium chloride and rectified. Propyl salicylate C7H6O2.OC3W7, thus formed is a colourless limpid liquid having a high refractive index. It has an aromatic taste and an odour resembling that of methyl saticylate. Its sp. gr. at 21" = 1.021. It boils at 238"-240. It is slightly soluble in water and freely soluble in alcohol and ether. Like its methyl and ethyl homologues propyl salicylate forms crystalline compounds with alkalies. It behaves also like its homologues when heated with anhy- drous baryta. Chlorine and bromine act energetically on propyl sali- cylate producing well-marked crystalline bodies. Fuming nitric acid added in small portions at a time elevation of temperature being avoided converts it into propyl witrosalicylate or indigotate which is a heavy yellow oil.If the nitric acid is added in excess and the whole is boiled crystals of picric acid are formed. An aqueous solution of ammonia converts prop91 salicylate into salicylamide. Prop$ Phenate.-Propyl iodide is heated for several hours at 100" -110" in a closed vessel with potassium phenate in alcoholic solution. Ou. adding water to the contents of the tubes when the reaction is over an oily liquid is separated which is to be washed first wit11 alkaline and then with pure water and rectified. Propyl phenate C6H,.0C3H, thus produced is a colourless very mobile liquid having the odour of ethyl phenate. Its sp.gr. at 20" = 0.968. It boils at 190"-191". It is attacked by bromine added in excess with the aid of heat colourless crystals being formed. Fuming nitric acid also acts upon it with energy producing at first an indigo and then a reddish-browu colour the liquid then becoming lieavy and oily on addition of water. If the acid is added in excess and heat is applied the oily liquid formed on ORGANIC CHEMISTRY. addition of water is of a yellow colour. Sulphuric acid converts propyl phenate intlo a sulpho-acid. P~opyl;Nitrite.-Wben nitrous acid formed by the action of nit'ric acid on starch is passed into propyl alcohol the whole being kept cool the vaponrs are immediately absorbed. On addition of water an oily liquid separates which after the process of purification employed with the compounds above described yields propyZ nitrite NO.OC,H7.This is a colourless very mobile liquid boiling at 43"-46". It burns with a yellowish flame. Like ethyl nitrite it has the odour of apples. Its sp. gr. at 21 = 0.935. B. J. G. Derivatives of Normal Propylic Alcohol. By H. ROEMER (Deut. Chem. Ges. Ber. vi 1101). TRIPROPYLAKIWE boils at 144Q-1460 and has a less powerful ammo- niacal odour than monopropylamine and is less soluble in water. Phosgene gas acts on propylic just as on ethylic alcohol ; the chZoro-carbonic propyZ-ethei- formed boils at 120"-130" ;when it is treated with water or aqueous ammonia pyopyl carboNate is formed but the best way of preparing this substance is to act on prop91 chlorocarbonate with sodium propylate.Propyl carbonate is a light liquid boiling at 160'-165". Aqueous ammonia acts on propyl chlorocarbonabe forming propyl carbamate ; t#his urethane is verv soluble in ether and alcohol less so in water. ' It melts at 50". " Similarly propyl; yhenyZ-c&rbarnate, { Z5sH5 CO is obtained by the action of aniline ; this compound melt; at 570-59". Attempts to prepare propylised aniline and propyl-sulphocarbimide met with little success. C. R.A. W. On the Sugar of Couch-grass Root and Triticin. By HERMANN MU LLER (Arch. Pharm. [3] ii 500). THEauthor concludes that the root of couch-grass (Friticum repens) contains no dextrose and no cane-sugar as the extracted sugar exhibited no tendency to crystallisation and gave a molecular rotation- [a]y = 54"to the left which was scarcely altered by heating with diluted sulphuric acid the value 53.9" to the 'left being thus obtained.In a former paper the author stated that by treatment with milk of lime a small quantity (0.437 gram) of a dextro-rotatory feebly-sweet tasting substance was isolated and this was then viewed as dextrose ; but he now finds on examination of larger quantities that this body consists of a small quantity of laevulose calcium chloride and calcium malate. Keither is lactic acid a normal constituent i.e. it is not present as such in the root but is formed by fermentative changes in the extract of the root on kecping. ABSTRACTS OF CHEMICAL PAPERS. The sugar present in the root is considered by the author to be solely fruit-sugar as when freed from gummy matters by treatment with lead acetate it gave the rotation- [a-Jy= -79.1" whilst the lzvulose separated by means of calcium hydroxide gave the rotation-[a],= -102.7" pure lzvulose giving -106".The quantity of sugar (estimated by a Fehling's solution 2 C.C. of which represented 0.010 gram of lEvulose) varies from 2.45 to 3.33 per cent. of root dried at loo' probably vary- ing in amount with the growth of the plant its development the time of year &c. &c. Triticin is best extracted from couch-grass roots by the following process. The dried and chopped root is treated with 25-30 per cent. alcohol drained in a displacement apparatus and well washed with water ; the dilute alcoholic extract is precipitated completely by lead acetate and the filtrate treated with sulphuretted hydrogen and con- centrated to a syrup on the water-bath.Several volumes of strong alcohol are then added and the gum washed with alcohol and dissolved in water. This treatment with lead acetate sulphuretted hydrogen alcohol &c. is repeated several times till lead acetate gives no further precipitate. The purified substance is then dissolved in a little water precipitated by strong alcohol and the precipitate decolorised by boiling its solution with freshly ignited well-washed animal charcoal ; the solution is concentrated and dialysed for 5-6 days the water in the water vessel being reneyed daily ; the gum is precipitated by alcohol washed with the same and dried in thin layers on a porcelain basin at 80"-100' and the pulverised residue is rubbed and dried at 100'-110'.A thousand grams of root will thus yield 15-20 of purified triticin tjhe quantity actually present being from 60 to 80 grams. The preparation requires 12 to 14 days. C. R A. W. Silico-acetic Acid. By A. LAD EN B UR G (Deut. Chem. Ges. Ber. vi 1029-1030). THE ethylic ether of this acid is produced together with zinc methyl- ethylate ZnCH3( OC2H,) and other bodies by heating ethyl silicate and zinc methide gradually to 12O0-3OO0 and opening the tubes from time to time for the escape of gases. Ethyl ortho-silico-acetate SiCH3(OC2H5)3,is a liquid boiling at 145O-15lo. It is soluble in alcohol and insoluble in water which however slowly decomposes it.Its specific gravity is 0.9283 at 0". By the actionof hydriodic acid it yields a solid insoluble body the composition of which agrees nearly with that of silico-acetic acid Si(CH,)OzH. It has the greatest resem- blance to silicopropionic acid and when heated takes fire yielding silica carbon dioxide and water. To prepare zinc methidc the author heats zinc-filings with methyl iodide sodium-amalgam (1 per cent. of Na) and a few drops of acetic ORGANIC CHERIISTRY. ether in a flask connected with a reversed condenser to the upper end of which is fitted a descending tube dipping into a column of mer-cury of 40 centimeters. The dry product is then distilled from an oil-bath. In this manner an excellent yield of zinc methide boiling at 47" is obtained.c. s. Ethylcrotonic Acid By W. P E :r n IE F F (Deut. Chem. Ges. Ber. vi 1098). THEorigin of ethylcrotonic acid leaves little doubt that its formula is When fused with potassium hydrate it forms acetic and butyric acids (Frankland and Duppa). From the examination of the calcium and silver salts the author finds that the butyric acid is the norma(; acid and not isobutyric acid. Normal butyric acid appears to give rise to a calcium salt containing a variable amount of water of crystallisation ; thus (CaH70J2Ca + H20,separates from a heated solution in small shining plates ; the salt with 4molecules of water of crystallisation separates from the mother- liquor on standing ; half of the water is lost by exposure to air for two or three days.Besides the two known isomerides ethylcrotonic acid and pyroterebic acid (the latter of which forms acetic and isobutyrio acids by the action of potash-W. C. Williams) four other six-carbon acrylic acids may possibly exist hydrosorbic acid may perhaps be one of these (Fittig and Barringer). C. R. A. W. Relations between the Molecular Rotatory Power of Tartaric Acid and of the Tartrates. By H. LANDOLT (Deut. Chem. Ges. Ber. vi 1073-1078). THEinvestigations of Biot Arndtsen and Krecke have demonstrated that the specific rotatory power of tartaric acid increases with the dilution of the solution and with the temperature ; and moreover that irregularities in dispersion occur when the solution contains more than 10 per cent.of acid. The salts of tartaric acid are now found to be less subject to these irregularities than the free acid. In order to determine the molecular rotatory power of the tartrates solutions of equivalent strength were employed the errors due to dilution being thus eliminated. In the case of the free acid the formula 15.06-0*131 C. gives the specific rotatory power of a solution having any degree of concentration C being the number of grams of acid contained in 100 C.C. The determinations were in all cases made with D light. Many experiments proved that the molecular rotatory power of acid ABSTRACTS OF CHEMICAL PAPERS. tartrates is approximately equal to twice that of tartaric acid while neut’ral tartrates possess nearly three times the rotatory power of the free acid.Small variations in the molecular rotatory power were observed in various salts the rotatory power being found to decrease as the metal contained in the salt is replaced by one having a greater atomic weight. It is also noticeable that the specific rotatoi-y power of a tsrtrate con- taining two metals is the mean of the specific rotatory powers of the tartrates of the metals entering into its composition-K,C,H,O Sp.rot. power. ....... 28.48 Mol. rot. power. 64.42 Na2C4H406.. ...... 30.85 39.85 Mean ............ 29.66 62.13 KNaC4H4o6. . . . 29.67 62.34 The salts (ASO)‘HC~H,~~, (As0)’KCIH4U6 K(C2H,)CaH40 and Ba&(C2H,)C4H406 were found to rotate in accordance with the law already stated but the numbers obtained were not quite so satisfactory as in the previous cases.On the other hand Ma(BoO)’C4HI06 and K(BoO)’C4H406 gave unsatisfactory results owing to the fact that the rotatory power increases largely with the dilution of the solutions. In the case of tartar-emetic this increase is remarkably great a 7.982 per cent. solqtion possessing a molecular rotatory power equal to about 22 times that of tartaric acid. Ethyl tartrate has a molecular rotatory power 2+ times as great as t>hat of tartaric acid and the specific rota- tory power of an alcoholic solution of tartaric acid is rather less than than of an aqueous solution ; but its rotatory power may be increased by heating in a sealed tube or by dilution with water.A solution of tartaric acid in methylic alcohol is inactive but dilution restores the rotatory powers of the acid. The author intends also to test the law of multiple rotatory powers by an examination of the malates and camphorates. T.B. Iron Tartrates and Citrates and their Amrnoniacal Com- pounds. By C. MEHU(J. Pharm. Chim. [4],xviii 85-92). FERROUS tart rate FeC4HP06 was obtained by boiling together equal parts of wire nails (pointesfines de Payis) or fragments of iron wire tartaric acid and water. Under these circumstances hydrogen is evolved and the ferrous tartmte is deposited as a white insoluble crystalline powder which after thorough washing with hot water undergoes no change on exposure to the air. If,however the washing has been imperfect the product gradually acquires a brownish tint on keeping.The acid liquor which has been filtered from the ferrous tartrate becomes yellow on exposure to the air but ebullition with iron decolorises it. Ferrous tartrate does not dissolve to any extent in aqueous tartaric ORGANIC CHEMISTRY. acid citric acid acetic acid or ammonium chloride but dilute mineral acids dissolve it readily and ttbe solutions undergo oxidation on expo-sure to the air. The solution in hydrochloric acid rotdtes the plane of polarisation to the right. Ammo?zio-ferr.ic tartrate 2(C4H606) .Fe2O3.2(NH,) .-Ferrous tartrate dissolves readily in ammonia and the solution absorbs oxygen from the air at the same time acquiring a brown tint. By evaporating this sdution on dishes heated to loo" greenish scales having the composi- tion represented above are obtained.This salt is insoluble in alcohol or ether easily soluble in water non-deliquescent in the air and when dried over vitriol retains 3H20. Ammonio-ferric tartrate prepared by dissolving gelatinous ferric hydrate in acid ammonium tartrate was found to be variabie in composition. Ferroz~s cit?-ate C6H,0,Fe.H,0 was prepared in the same manner as the tartrate citric acid being substituted for tartaric acid. Even when well washed it becomes coloured on drying unless extreme care is taken and on exposure to sunlight it acquires a reddish tint and undergoes partial oxidation. Hot water dissolves a small proportion of ferrous citrate but the salt is not deposited on cooling and the addi- tion of alcohol scarcely renders the solution turbid.Ammonz'o-ferric citrate 2(C6H807),Fe203 2(NH3).-When ferrous citrate is treated with liquid ammonia a solution is formed which becomes rapidly dark on exposure to the air ; and by evaporating this solution on flat dishes heated to lOO" greenish scales having the above composition are obtained. Ammonio-ferric citrate is insoluble in strong alcohol but water dissolves it in all proportions. One part of tlie salt dissolved in two parts of water yields a solution which is not syrupy. W-R Researches on Sorbic Acid. PART11. By E. KACHEL and R. FITTIG (Ann. Chem. Pharm. clxviii 2'76-294). Tetrabromocaproic Acid ; Xorhic Acid I%tmbromide.-T he authors have slightly modified the process formerly given by Fittig and Barringer for the preparation of this compound.Sorbic acid is mixed with about ten times its weight of carbon sulphide and the calculated quantity of bromine then added by degrees. Traces only of hydro-bi-ornic acid are evolved and the liquid remains clear and on standing a day or two deposits large well-formed crystals of the tetrabromide. These crystals are purified by recrystallisation from dilute alcohol. To gain some information as to the nature of the bye-products of which however only small qnantj ties are produced the mother-liquors were evaporated to dryness the residue dissolved in cold solution of sodium carbonate and a concentrated solution of the same salt added. The sodium salt of the tetrabromide which was thus thrown down was filtered off and hydrochloric acid added to the filtrate.A small yellowish precipitate was thus obtained and this distilled with water gave a very small quantity of a volatile organic acid. The wsidue on cooling deposited needles of a compound which was at first believed to be sorbic acid inasmuch as it had the appearance as well as the meltiug point of that body. Analysis however showed that it ABSTRACTS OF CHEXITCAL PAPERS. contained 41.65 per cent. of bromine or very nearly the amount 4l.88 required by the formula of ~nonobrom,osorbic acid C3H,Br02. The quantity of material was insufficient for its further examination. The properties of the tetrabromide have already been described pretty fully.The sodizcrn salt C6HJ3r402Na.2Hz0 forms magnificent silvery scales. It is easily soluble in water and in alcohol but quite insoluble in a concentrahed solution of sodium carbonate. The potassium salt is very soluble and difficult to obtain pure. It is not precipitated by the addition of potassium carbonate to its solution. The ainnzoitiurn salt separates in fine needles from the solution of the tetrabromide in excess of ammonia. The barium salt (CsH,BraOs)LBa.l~HzO, may be formed by mixing barium chloride and the sodium salt. The caZciwn salt (CsH,Br,O,),Ca. 7Hz0 is obtained in a similar manner. It crystallises with great facility in fine large silvery scales. It is much less soluble in cold water than the barium salt and makes its appearance even in somewhat dilute solutions.The zinc salt resembles the barium compound in appearance. Decompositioiz of the Salts by Heat.-When boiled with water the salts undergo decomposition regenerating the tetrabromide which separates in the form of a liquid becoming crystalline. A portion of the salt undergoes complete decomposition and the hydrobromic acid liberated assists the separation of the tetrabromide forming at the same time a corresponding quantity of bromide of sodium. When sodium hydrate or carbonate was added for the purpose of neutralising this hydxobromic acid as it was generated resinous pro- ducts only were obtained. By substituting barium carbonate for the alkaline salt a volatile highly irritating compound was produced which with ammoniacal nitrate of silver gave a reddish precipitate de- positing metallic silver on application of heat.The authors therefore believe this product of decomposition to have been acrolein but for want of material have not been able to examine the re$ction further. The residue contained only a small quantity of brown resinous matter but no organic acid could be detected. Action of Hydrogen on the !l'et.rabromide.-The action of sodium amalgam and water proceeds in two stages. The four atoms of bro-mine are first removed sorbic acid being regenerated and this by the assumption of two atoms of hydrogen is converted into hydrosorbic acid. Caproic acid is not formed. Sorbic Acid Dibrornide (Uibronzohydrosorbic Acid 1.-In the prepara- tion of the tetrabromide it was observed that the first two atoms of bromine are taken up more readily by the sorbic acid than the last.Proceeding in the manner already described but employing two instead of four atoms of bromine the dibromide C6H802Br2,corre-sponding with hydrosorbic acid was obtained. It forms small spark-ling scales meltiiig at 94'-95" ; dissolves easilF in ether alcohol carbon sulphide and hot benzene; is also slightly soluble in hot water. Simultaneously with the crystallised dibromide is formed a quantity of an oily fluid substance which the authors have not yet studied but ORGANIC CHENISTRY. which they consider may possibly be a compound isomeric with the dibromide. Eydrosoybic Acid-In the former paper it was stated that hydro- sorbic acid melted with potassium hydrate gave butyric acid.Further experiments show that acetic acid is formed at the same time. The butyric acid gives a calcium salt which crystallises with one molecule of water and the solution of which deposits nearly the whole of the salt on the application of heat. It is therefore normal butyric acid. Hydrosorbic acid therefore furnishes normal butyric acid and acetic acid when fused with potassium hydrate. The two isomeric com- pounds ethylcrotonic and pyroterebic acids suffer the sgtme deoom-position. Hydrosorbic acid is certainly different from the former but it is possible that it may be identical with pyroterebic acid. The difference in boiling point and specific gravity may arise from incorrect observations.The authors purpose making a careful comparison of the two acids. Some experiments upon the action of fused potash on sorbic acid led to no definite result. W. A. T. Oxpethane-sulphonic Acid and Oxymethane-disulphonic Acid. By MAX HULLER (Dent. Chem. Ges. Ber. vi 10511-1034). AFTERadverting to the attempts of Theilkul and Schwarz to prepare the methylic homologue of isethionic acid the author says that he found aIrnost the theoretical amount of isethionic acid could be obtained when alcohol is saturated with sulphuric anhydride so as to form a liquid which fumes in the air. The product diluted with water and boiled until the ethionic acid is decomposed is first treated with lead carbonate to remove the excess of sulphuric acid and the filtrate after precipitation with hydrosulphuric acid is neutralised with potassium carbonate and evaporated to dryness.The potassium isethionate thus obtained may be rendered absolutely pure by crystallisation from hot alcohol of 80-90 per cent. Methyl alcohol t.reated in a similar manner yields potassium oxymethane-disulphonate but the oxymethane-mono- sulphonate may be readily prepared by slowly adding sulphuric anhy- dride to a mixture of methyl alcohol or rnethylsulphuric acid with it considerable excess of sulphuric acid and subsequently treating the product in the manner above described. Both the free acid and its salts are very stable remaining unchanged even after long boiling with wster or with concentrated acids.The potassium salt forms large rhombic crystals which are t’olerably soluble in water but insoluble in alcohol. The ammonium compound forms small needles and the barium salt small transparent plates. The potassium oxymethane-disulphonate prepared from the product of the action of excess of sulphuric anhydride on methyl alcohol is contaminated with a dark coloured impurity which may be removed by treatment with alcohol of 40 per cent. The residue on being crystal- lised from boiling water yields the pure potassium compound in tufts ABSTRACTS OF CHE?/IICAL PAPERS. of needles. The barium salt obtained by precipitating the potassium compound with barium chloride crystallises in needles. Both the acid and its salts like those of oxymethane-sul phonic acid are very stable and can be boiled with water or concentrated acids without undergoing decomposition.EH3 The author assigns the graphic formula c-0 to methyl--SO2OH sulphuric acid and -OH to oxymethanesulphonic acid ; the CI:20Ef oxymethanedisdphonic acid he believes to be cSzEE its sta- bility being due to the direct union of the sulphur in the sulphur group with the carbon atom. He has also obtained indications of an acid bisulphomethylsulphuric acid -SO,OH corresponding with '-cl-" -SO,OK ethionic acid which he intends to investigate further C. E. G. The Compounds of Chloral with Sulphuric Acid. By J. GRAUOWSKI (Deut. Chem. Ges. Ber. vi 1070-1072). THE compound ~loHg~l~~S3~~6 formed by the action of sulphuric mhy- dride on chloral may likewise be obtained by washing the product of the action of sulphuric acid on chloral with cold water and crystallising the residue from ether the reaction being- SC2HCI,O + 3SO.&& -HZO = C1~HgC115X3016.This compound may with care be crystallised from warm alcohol. It melts at 70° undergoing decomposition at the same time. At 100' chloral distils over leaving a residue of sulphuric acid and chloralide. Tt decomposes by keeping into sulphuric acid and insoluble chloral ; with acetyl chloride it forms a new compound C8H12C112S3017, in small needles which melt at 92". The author has aleo obtained a compound CsH,4C1,2S2015 by the action of fuming sulphuric acid on chloral and likewise a crystalline compound C6H6c1503 melting at 129" by the treatment of dichloracetal with the fuming acid.C. E. G. A Polymeric Modification of Is0butyraldehyde. By G. A. BARBAGLIA (Deut. Chem. Ges. Ber. Ti 1064). TIIE author finds that the action of bromine and iodine on isobutyr-aldehyde produces a polymeride 3( C4HsO) = CI2HxO3,identical with that previously described by him (ibid. v 1052) as formed by the action ORGANIC CHEMISTRY. of chlorine on the aldehyde. It is readily prepared by psssing a current of air charged with bromine vapour through the liquid. The polymeride crystallises in slender needles melts at 60° and is un-changed even by long-continued exposure to a teniperature of 200". It reduces silver salts and is not acted upoii by dry chlorine bromine or iodine.Cyanogen does not cause the polymerisation of the aldehyde. C. E. G. Action of Ammonium Trisulphocarbohate and Sulphocarba- mate on Acetone and Aldehydes. Eiy E. MULDER(Ann. Cfhem. Pharm. clxviii, 228-241). ACETONINE is formed in small quantity only by the action of ammonia upon acetone. The base being unstable it appeared not improbat)le that a better result would be obtained by acting with acetone on a salt of ammonia. With carbonate or oxalate of ammonia t>his is not the case but the experiment is more successfiil when trisulphocarbonate of ammonis is is employed. Trisulphocarbonate of acetonine is then obtained. This body is very unstable even at ordinary temperatures evolving H,S and CS2. By treatment with hydrochloric acid it yields acetonine hydrochloride and with oxalic acid the oxalate.The author represents the constimtion of acetonine by the following formula :-NzxC~(CH,), N-C=( CH3) 2 / NILCIZ(CH,),. By heating trisulphocarbonate of acetonine with ferric chloride the sulphocyanide reaction is obtained. Sulphocarbamate of ammonium NH2.CS.HS.NH3 mixed with acetone yields after some days a beautifully crystallised yellowish body the analysis and reactions of which show that it is acetonine sul- phocarbamate. By the action of carbon bisulphide on aldehyde-ammonia Liebig and R?edtenbacher obtained a body which they considered as a kind of base and named car8oth;aZ&.ae C,Hl0N2S2. The author has prepared the same compound by bringing together aldehyde and sulphocarbamate of ammonia.He therefore considers carbothialdine as diethylidene-ammonium az~@hocnrbamate-LCH.CH3 NH2-C S-S-Ny \CH.C3H. Sulphocarbamate of ammonium and acrolein yield a similar com-pound NH,.CS. SN (C3H& or d~allylide.ne-anzmoizizcm.sulphocarbaw,ate. In like manner valeral and benzoic aldehyde furnish corresponding compoupds. ABSTRACTS OF CHEMICAL PAPERS. The product of the action of carbon oxysulphide on alcoholic ammo- nia is a colourless body probably NH,.CS.HO.NH,. When ammonium sulphide is substituted for ammonia a body, COS(NH4),S is formed which evolves H2S at ordinary temperatures leaving the same compound. This ammonium oxysulphocarbamate bebaveg with benzoic aldehyde like sulphocarbamate the resulting compound being NH2.CS.0N( C~HG)~.Heated witoh alcohol the filtrate deposits a colourless crystalline body which is not hydrobenzamide. Ammonium carbamate gives with benzoic aldehyde a solid mass NH,.CO.ON( C7H6), which after heating with alcohol yields crystals of hydrobenzamide. Acetone acts neither upon ammonium oxyaulphocarbamate nor upon the carbamate. W. A. T. Silver-Urea. By E. MULDER (Deut. Chem. Ges. Ber. vi 1019-1021). BYacting with freshly precipitated silver oxide on an aqueous solution of urea Liebig obtained a compound having the composition 2CH4N20 + 3Ag20. When a solution of silver nitrate and urea is precipitated with caustic soda a gelatinous yellow precipitate is formed having the composition CO(NHAg),.As Liebig did not make an ultimate analysis of his compound but only determined silver and wea it appears very probable that the two bodies are identical indeed they con- tain almost the same per centage of silver. c. s. Action of Ammonia on Bromacetyl-urea. By E. MULDER (Deut. Chem. Ges. Bey. vi 1015-1018). INa previous communication (last POL p. 382) it was shown that this reaction yields digly collamic diuramide together with another body which appears to be triglycollamic triuramide. The latter is always formed in small quantity only and differs from the diuramide by not yielding a platinum double salt and not melting below 230° whereas the diuramide melts at 195"-200". c. s. Derivatives of Uric Acid. By E. MULDER (Deut. Chem.Ges. Ber. 1010-1015). ON dissolving dialuric acid and urea in warm water and tilling with this solution a flask which is then well st?oppered urea dialurate crys- tallises out. It is sparingly soluble in water and forms crystals grouped in stars. It is not oxidised in the air like free dialuric acid its aqueous solution has an acid reaction and gives a fine blue colour by adding ferric chloride and ammonia. The free acid and alloxantin give the same reaction. When a solution of alloxan and urea is evaporated in an exsiccator ORGANIC CHEMISTRY. allzlranic acid C,H,N,O, is obtained foi*ming crystals which are grouped in stars. It is sparingly soluble in cold water more freely in hot water and has a slight acid reaction. It neither gives the reaction of alloxan nor does it yield mycomelic acid with cold ammonia.Its aqueous solution is precipitated by basic lead acetate mercuric nitrate and baryta-water. The lead salt yields on decomposing it with hydrogen sulphide and evaporating the filtrate a crystalline body pos- sessing the properties of alloxanic acid. On adding silver nitrate and a little ammonia silver alluranate C5H,AgN405 crystallises out. Hydriodic acid converts alluranic acid into hydantdin. Its solution in ammonia or dilute alkalis when freshly prepared gives with acids a precipitate of the acid but no longer after standing. It is interesting for the physiologist that alloxan and urea cannot exist together in solution. By adding silver nitrate and a little ammonia to an aqueous solution of alloxan a precipitate consisting apparently of C4AgrsN204 is formed.Hydriodic acid reduces alloxan at the common temperature to allox-antin but at 100" to dialuric acid. c. s. Hornologues of Oxaluric Acid. By W. H. PIEE (Chemical News xxviii 173). WHENone molecule of urea is fused with one molecule of succinic anhydride at a temperature of 120*-130" an oily liquid which solidifies to a crystalline mass is obtained. This was powdered, washed with alcohol and crystallised from water which deposited it in brilliant scales consisting of an acid melting with decomposition at 203"-204" and having the composition C5H1,N204. The new sub- stance is moderately soluble in hot water or acetic mid almost in- soluble in cold water or alcohol and insoluble in ether chloroform or carbon disulphide.Sulphuric acid diesolves it and the addition of water causes its precipitation in an unaltered state. With alkalis or alkaline earths it forms easily soluble salts but the lead salt and tbe silver salt C5HIAgN204 form white crystalline precipitates nearly in- soluble in boiling water. The author proposes to call the new acid 8ucchw-ca&a?nk acid and represents it by the following formula- CH~-CO-NH-CCO-NH~ 1 CH2-40OH. CE,-CO--NE-CS-NH~ Xuccino-sulphocarbamic acid I was pre-CH2-COOH pared and purified like the last-described body sulphurea being snb- stituted for urea and the fusion being conducted at about 150". It forms a yellowish crystalline powder which melts at 210*5°-211" is insoluble in cold water alcohol and ether and dissolves rather less readily than succino-carbamic acid in boiling water or acetic acid; snlphuric acid however dissolves it readily but without alteration VOL.XXVII. E ABSTWCTS OF CHXMICAL PAPERS. The alkaline salts of succino-sulphocarbamic acid are easily soluble but the lead salt and silver salt form white precipitates which blacken when heated. The fusion of citraconic anhydride with urea gave rise to the libe- ration of carbonic anhydride and the formation of citraconamide ; but when citraconic anhydride is fused with sulphurea combination takes CO-NH-CS-XHz, place and citraco-suljphocarba~~c acid C3H/ 'COOH is produced. It melts with decomposition at 222"-223" and yields easily soluble salts with alkalis.Its lead salt and silver salt form white precipitates which like the corresponding salts of succino-sulphocarbamic acid become black on heating. When lactide is heated with urea carbonic anhydride is evolved and B substance which is still under investigation is formed. The same substance is produced when lactide is heated wit'h sulphurea carbon .oxysulphide being evolved in this case. When succinic anhydride it heated with sulphocarbanilide phenyl- sulphocarbimide and aniline are liberated and the latter substance then reacts on the anhydride. The author intends to continue and to extend his researches. T. B. On Ethyl and Diethyl-allylamine. By ALBE RT RXNN E (Ann. Chem. Pharm. clxviii 261-266).has PIPERIDINEbeen proved by Cahours to be a secondary base. Whether it be amylene the two affinities of which are saturated by the bivalent group NH or ethyl-allylnmine or methylcrotonylsmine is open to question. The author has prepared ethyl-allylamine for the purpose of comparison. Allylamine was prepared from ally1 sulphocarbimide by the action of sulphuric acid; it was mixed with ethyl iodide in a tube which was sealed and gently warmed. After the action had ended the con- tents of the tube were distilled with potassium hydrate. Allylamine, ethyl-allylamine and diethyl-a1 lylamine came over. Ethyl-allylamine was separated by fractional distilladion. It came over between 83"-85". It is colourless mixes with water and has a strong ammoniacal smell.It is not identical with piperidine as its boiling point is 22"lower. Its salts also are entirely different. Diethyl- allylamine boils between 100' and 102'. It dissolves in twenty times its bulk of water of 18" and when gently warmed separates out producing a milky turbidity like that exhibited under similar circum- stances by conine. It is isomeric with ethyl-piperidine but has a boiling point 20" lower. W. R. Haloid Derivatives of Toluene. By E. WROBLEVSKY (Ann. Chern. Pharm, clxviii 147-213). MEPERstates that sodium has no action on a mixture of methyl iodide and the author's liquid bromotoluene correspondiug with oxybenzoic ORGANIC CHEMISTRY 51 acid but the author finds that an action takes place a hydrocarbon which is probably isoxylene being formed.Aee&ornetabromo~a,.atol~idine,C&&BP(CE3)NE(CzH30) was ob-tained by gradually adding bromine to acetoparatoluidine in presence of water. When crystajlised from spirit it forms beautiful needle- shaped crystals It melts at 117*5O,and is easily soluble in alcohol but slightly solrrblc in water. Alooholic potash converts it into meta-~romopa~~t~~uid~ne, a colourless liquid,.which solidifies at .+FJ0 boils at 240° has a specific gravity of 1.510 at 20° and is easily soluble in alcohol. The same hse was obtained by brominatim of the corr8- sponding toluidirme. The ?zitrate crystallises from water in lmge yellow leafy plates melting at 182". The hydrochloride is slightly soluble in water from which it separates in large white square prisms melting at 221" with partial decomposition.The acid oxalate C7H6BrNH2 CZH2O4 crystallises in large white needles which are slightly soluble in water. The acid sulphate C,H6BrNH2.H2S04-I-H,O is very soluble in water from which it separates in large roseate needles. When the amido-group of the above base was replaced by hydrogen according to the method of Griess metabromotoZziene boiling at 181"-182" and having a specific gravity of 1.4009 at 21" was obtained. This bromo- toluene does not solidify at -20° and when oxidised yields bromo- benzoic acid identical with that obtained by the action of bromine on benzoic acid. Hence this brornotoluene belongs to the rnet~a series. Metabromotoluene was afso obkained by heating diazometabromotoluene sulphate with water- iMetccbrom op ariodo tduene C6H31pBrWH3.-W hen diazometabromo- toluene prepared by the action of nitrous acid on bminotoluidine nitrate is dissolved in nitric acid and treated with hydriodic acid an oil separates which when purified forms a colourless liquid boiling at 265".It is easily soluble in alcohol and does not solidify at -14". Whennitratedit yields ne'troptr;riodornetabrornotoZu~~, CGLfiNOaIPBiJ"CH3 which separates from alcohol in needles and melts at 118O. When toluidine is digested for 16 hours with an equivalent quantity of glacial acetic acid and afterwards distilled the latter portion of the distillate consists principally of acetorthotoluidine and acetopara-toluidine and by treating the first portion of this with soda again digesting it with acetic acid and repeating these operations acutortho-toluidiy&ewas obtained in the pure state.AcetornetnbromorthoioZuidi?ze C6H3Brm( CH3)NH,(CzH30) was ob-tained by treating the last-named substance with bromine in presence of water. It crystallises in beautiful long needles which melt at 157" dissolve easily in alcohol and with less facility in boiling water. The action of acetyl chloride on metabromotoluidine also yields this sub- stance. Alcoholic potash converts it into metL~bro.morthotol~idine.This latter forms large octohedrons melts at 57" boils at 240" and is easily soluble in alcohol but not readily soluble in water. The hydrochloride crystallises from water in white prismatic crystals having a pearly lustre.Hydrochloric acid separates it from its solution and it sub-E2 ABSTRACTS OF CHEMICAL PAPERS. limes unchanged. The nitrate separates from water in long needles, and melts at 183" at the same time undergoing decomposition. The sulphate (C5H6BrNHz),.HzS0,+ l&H,O is deposited from water in white pearly tablets. When the sulphate of the diazo-derivative of metabromorthotoluidine is heated with alcohol metabromotoluene is obtained. ~etabrornort~iodotoluene, C7H6Brm10,was obtained by treating meta- brornorthodiazotoluene with hydriodic acid. It forms a colourless liquid smelling like bromotoluene and boiling at 260". Its specific gravity is 2.139 at 18O and on treatment with nitric acid it yields witrometnbromorthiodotoluene C,H5NO2Brm1O.This compound is easily soluble in alcohol and forms fine prismatic crystals. When meta- bromorthodiazotolueue sulphate is boiled with water metabromortho-cresol is formed as follows:- C7HsBrNZ.HS04 + HzO = C7Ef6Br(HO)+ Nz + HSSO,. It forms beautiful needles having a golden lustre and is almost in- soluble in water but more easily soluble in alcohol. It melts at 88*5O and its aqueous solution is coloured greeu by iron chloride. Its potas-sium salt C6H3Brm(CH3)(KO)o+ HzO forms shining red scales. Sulplto-Derivatives of Metabromotoluene.-When metabrornotoluene is treated with fuming sulphuric acid three sulpho-derivatives are formed and when a solution of their barium salts is evaporated a slightly soluble a-salt is first deposited and on further evaporation two other salts ,@ and y The a-barium salt forms small prismatic crystals.The a-potassium salt forms beautiful prismatic crystals and yields salicylic acid on fusion with potash. Hence the a-acid is meta-brbmotoluene-orthosulphonic acid. The P-barium salt 2[ (C7H6BrmS030)zBa]+ 3&0 forms fine lustrous crystals.-The P-lead salt [C7H6BP( S03)0]zPb + 3H@ separates from water in fine large needles.-The /3-calcium salt 2[ (C7H6BrmSOto)2Ca]+ 5Hz0,forms large rhomboidal leaflets. The $-potassium salt forms large shining leaflets and yields salicylic acid on fusion with potash consequently the p-acid is also a meta-bromotoluene-orthosulphonic acid the two acids having the positions 1 2 3 and 1 3 6 respectively..The y-barium salt 2[(c7H6BP S03)2Ba] + 5Hz0 crystallises in needles and the corresponding potas- sium salt yields on fusion with potash a small quantity of an acid which is not coloured by iron chloride and consequently cannot be salicylic acid but it mag. be either a paraoxybenzoic acid or oxybenzoic acid. p-Barium Nitrometabromotoluene-orthosulphonate 2[(C7HaN0J3rmS030)2Ba]+ 7Hs0 was obtained by nitrating the &barium salt just described. It forxne needle-shaped crystals which are easily soluble in hot water. The lead salt [C7H,Br"N0z.S03]2Pb + 3Hzo,forms prismatic crystals easily soluble in water. The calcium salt 2[ (C7H5Brm(NO2) S030)zCa] + ~EzO,separates from alcohol in large prismatic crystals which are easily soluble in water or alcohol ORGANIC CHEMISTRY.53 Metabromotoluene yields two nitro-derivatives one of which is solid the other liquid. The solid compound a-nitr~metabromotol~~ene cqstallises in prismatic crystals which melt at 55". It boils at 267" and is easily soluble in alcohol. The liquid compound 13-nitrometa-bromotolzcene is a colourless liquid smelling of bitter almond oil and boiling at 269". Its specific gravity is 1.612 at 20". Orthobromotoluene and its Derivatives.-Orthobromotoluene was ob-tained in a pure state by first converting Rosenstiehl's orthotoluidine into the corresponding diazo-derivative of toluene and afterwards con- verting this into the perbromide which when digested with alcohol yields orthobromotoluene in the pure state. It boils at 182" has a specific gravity of 1.401 at 18" and remains fluid at -20".Only resinous products were obtained on oxidising it but with bromine it yields a dibromotoluene boiling at 240". Ort7lobrorrzometato~zcidinewas obtained by converting Beilstein and Kuhlberg's metatoluidine into the aceto-derivatire and treating this aa described in the early part of the present paper. It boils at 240" and its nitrate crystallises in red prismatic crystals. When it is con- verted into the perbromide of the corresponding azo-derivative and heated with alcohol it bromotoluene identical with that last described is formed. Parabromotoluene yields two nitro-derivatives one of which is solid the other liquid. The solid modification a-parabromorthonitro-toluene, melts at 43" and boils at 256"-257".The liquid form P-parabromo-metanitro-toluene,remains fluid at -20° boils at 255"to 256" and has a specific gravity of 1.631 at 18". Reduction with tin and hydrochloric acid yielded the corresponding bases. a-parnbromortho-tolzcid~nesoli-difies at -2" and the P-parabronwmeta-tohidineform prismatic crystals melting at 67". The nitrate of the former crystallises in beautiful crystals having a pearly lustre while that of the latter forms prismatic crystals. Parametadibromo-toluene '1 3 4 was obtained by brominating solid toluidine and digesting the perbromide of the diazo-derivative obtained from this with alcohol. It has a specific gravity of 1.812 at No,boils at 238"-239" and remains fluid at -20°. Nitric acid transforms it into a nitro-dibromotoluene which melts at 86"-87" and separates from dilute alcohol in fine needles.Reduction by tin and hydrochloric acid transforms this compound into a dibromotoluidine which melts at 95" and does not unite with acids. Fittig's dibrorno-toluene probably has the positions 1 2 4 and the author did not succeed in obtaining its nitro-derivative in the pure state. Ortlzometa-dibroniotolzcene C6H3.BrmBro.CH3, 1 2 5,? was obtained by bromi- nating metahromotoluene. It boils at 236" has a specific gravity of 1.8127 at 19" and it remains liquid at -20". Its nitro-derivative corresponds with that last described but its amido-derivative melts at 83" and does not combine with acids This dibromotoluene was also obtained by digesting the perbromide of the diazo-derivative of metabromorthotoluidine with alcohol.OrthometadibromotoZue?ae 1 2 3 ? was obtained either by decomposing the perbromide of the diazo-derivative of orthobrornometatoluidine with alcohol or by brominating orthotoluidine and treating the dibromotoluidine ABSTRACTS OF CHEMICAL PAPERS. with alcoliol and nitrous acid. 'It crystallises in long needles melts at 42*5" and boils at 239". Its dro-derivative is easily soluble in alcohol from which it separates in fine needles melting at 59". The dibromotoluidine C7H5BPBFNH2,referred to above as being formed by the bromination of orthotoluidine forms fine pearly needles easily soluble in alcohol and melting at 50". eta-metadibromotoluene 1 3 :5 was obtained from dibromo-paratoluidine by substituting H for NH,.It separates from alcohol in long needles which melt at 60" and boil at 241". Its nitro-derivative is easily soluble in alcohol from which it separates in prismatic crystals melting at 1%". When the sulphate of the azo-compound derived from this nitro-dibromotoluene is heated with water no cresol is formed but dibromotofuene 1 3 5 is repro-duced; when however hydriodic acid is used in place of water d~bro~~~odotoZuene, C7H5Br2mIP,is formed. This compound crystallises in long needles which melt at 86" and boil at 270'. The ortho-ortho-dibromotoluene 1 2 6 WM obtained by converting metatoluidine into a dibromo-derivative and replacing its NH by H. It boils at 246" has a specific gravity of 1.812 and doefi not solidify at -20".Its ?zitro-derivative separabs from benzene in beautiful prismatic crystals which melt at 79". Aeeto-dibromotoluuidine C7H5Br&H(C2H,0), was obtained by adding bromine to acetometabromotoluidine in pre- sence of water. It crystallises from water in fine flat needles melting at 154". Alcoholic potash converts it into a-dibromotoluidine which forms pearly crystals melting at 92.5". It does not combine with acids and plcoholic nitrous acid converts it into the last described dibromo toluene Zeta -metaparatr~bro?n,otol~en~, P 3 4 5. The solid met% dibromoparatoluidine was first converted into the corresponding diazo-derivative and this was afterwards converted into the perbro- mide which on digestion with alcohol yielded the above-mentioned tribromotoluene.It forms a colourless liquid which boils at 260" and remains fluid at -20". OrtPco-ortho~tr?'bro~~~~oZ~e~. -When an acid solution of metatoluidine hydrochloride is brominated a tribromotoluidine C7Ha3r02BrXNH2m is obtained. It is slightly soluble in alcohol from which it crystallises in needles melting at 97". When this base is decomposed by alcoholic nitrous acid the above tribromotoluene is formed It separates from benzene in long silky needles is slightly soluble in alcohol melts at 70" and boils at 290". Its nitroderivative €orms leafy crystals slightly soluble in alcohol easily soluble in benzene and melting at 215". Aceto~netachZorotoluidiire CsH[3(;lm.CH3.NHp(C2H,0),was obtained by passing chlorine into acttoparatoluidine in presence of water and crystallising the Product from water.It forms fine large leafy crystals which melt at 99 ,and dissolve easily in alcohol but sparingly in water Alcoholic potash converts itl into a chlorotoluidine C7H6ClmCH3NH2p. This compound boils at 222" and has at specific gravity of 1.151 at 20". The in'trate separates from water in large shining yelIowish prisms which melt at 189" ; 100 parts of water dissolve 2.593 parts of it at 19". The kydroch2oride is slightly soluble in water from which it separates in large white quad1 angular prisms having a pearly lustre and subliming above 210". The acid omdate C,H6C1.NH,.C2H201,is ORGANIC CHEMISTRY. slightly soluble in water and it crystallises in large needles.The acid sulphate C7H&1.NH,.HzSOa dissolves readily in water and crystallises in large needles. This chlorotoluidine was also obt'ained by the action of chlorine on a solution of a toluidine salt. Metachlorotolzcene C6&Clm. CHS was obtained by replacing the NH2 of the last-described base by H. It boils at 156" and yields metachlorobenzoic on oxidation. Isomeric deriuatiives of Parachloroto1zcene.-The products of the nitrs- tion of parachlorotoluene were separated by fractionation into two isomerides. a-chloronitrotokuenzs boils at 243O has a specific gravity of 1.307 at 18" and remains fluid at -18". l.3-chloronitrotoluene boils at 253" has a specific gravity of 1.3259 at 18" and remains fluid at -13". These chloronitrotoluenes were converted into sulpho-acids and the barium salts were prepared.The a-salt (C7H5CINO2SO3)2Ba +4H20 is slightly soluble in water and crystallises in fine needles while the @salt is very soluble in water. Liquid a-chlorotoluidine was ob-tained by the reduction of a-chloronitrotoluene. It forms a colourless liquid which boils at 238" has a specific gravity of 1.1855 at 20" and remains fluid at -20". Its hjdTochEoride CTH6C1.NH2HC1 +H20 forms prismatic crystals easily soluble in water and subliming like sal-ammoniac. The nitrate forms white prismatic crystals melting with decomposition at 179". 100 parts of water dissolve 2.853 parts of it at 17. Solid p-chlorotoluidine was obtained by the reduction of p-chloronitrotoluene. This substance forms large white tables having a pearly lustre.It melts at 83" boils at 241" and dissolves easily in alcohol but with difficulty in water. The hydrochZorid6 forms pearly elongated leaflets which sublime like sal-ammoniac and are more soluble in water than the corresponding salt of the liquid a-cblorotolui- dine. The nitrate forms large white pearly tables melting with decomposition at 165". 100 parts of water at 17" dissolve 5.014 parts. Isomeric Metlzylclilorophenetob from the above Chloroto1uidines.-The mixture of chloronitrotoluenes obtained by nitrating paracblorotoluene was amidised and the isomeric chlorotoluidines were separated by crystallising their hydrochlorides (the @-salt being as stated above more soluble than the a-salt). Each base was then converted into the sulphate of its diazo-derivative and on heating these with alcohol no chlorotoluenes were obtained but isomeric methylchlorophenetols a-methyZchloroy,henetol forms an aromatic liquid almost insoluble in water but easily soluble in alcohol.It boils at 210"-220" and has a specific gravity of 1.127 at 19.5. ~-~nethylchlorophsnetol bas an odour like that af its isomeride boils at 210°-220" and has a specific gravity of 1.131at 18'. By heating the sulphates of the azo-derivatives just referred to with hydriodic acid two isomeric iodochlorotoluenes are obtained. C7H6C1N2,HS0,+HI =H&Oa +N2+CTE&1I. a-chlo-riodotohene is a colourless liquid smelling like iodotoluene boiling at 242" and having a specific gravity of 1.716 at 17" It is easily soluble in alcohol insoluble in water and it does not solidify at -14".P-clzloriodotoluene boils at 240" has a specific gravity of 1.770 at 19*5" aud it solidifies at +10". ABE3TRACTS OF CHEMIUAL PAPEXS. Nitro-d~chZorotoZzcenewas obtained by nitrating the dichlorotoluene produced by the action of chlorine on toluene in the presence of iodine. It is a colourless liquid which boils with partial decomposition at 274" solidifies when cooled to -14" and possesses a specific gravity of 1.455 at 17". Alcohol or ether dissolves it readily and it possesses an odonr resembling that of bitter almond oil. Its reduction results in the formation of a dicldorotolzcidine which crystallised from dilute alcohol in leafy crystals melting at 88" and boiling at 259".Acids do not combine with it. As dichlorotoluene yields only one amido-derivative it follows that in the preparation of parachlorotoluene no isomeride is formed. I',B. Bromotolnenes. By H. HGBNEE and J. POST (Ann. Chem. Pharm. clxix 1-69). THISelaborate paper eontains fhe results of a research which the authors in conjunction of some of their pupils carried out with the object of examining the derivatives of the two isomeric bromotoluenes which are formed simultaneously by the direct action of bromine on toluene. Some of the results have already been published separately (see this Journal ix 120,1055 ; x 696 1005 1094; xi 886). (1.) ParabromotoZzceize.-This compound was obtained in a perfectly pure state by repeated crystallisation fkom alcohol and pressing the crystals between paper.It forms splendid colourless crystals melting at 28"-29" solidifying again at 28" and boiling at 185.2". By oxida-tion it yields parabromobenzoic acid melting at 245". When it is dissolved in fuming sulphuric acid either at a temperature not exceed- ing 80" or at 160°-180" it yields two monosulphonic acids which may be separated by recrystallising the barium salts ; that of the a-acid being much more soluble than the B-compound. a-Series. a~Purabromotolzcene-su223horticacid CJ3,Br(CH3) SO,H is a very soluble orystalline laminated mass. a [C6H3Br(CH3)SOJ2Ba + 7HzO forms colourless well-defined long and compact rhombic needles. a [C6H3Br(CH3)S03]2Pb+ 3H20 is obtained from a concentrated solution in loug needles which when re-crystallised from a dilute solu- tion are converted into small light yellow compact rhombic plates.u [C16H3Br(CH3)S03],Sr + 7H20 crystallises in hard four-sided pyramids. u C6H3Br(CH~)SO2.NH2 was obtained by treating the impure chlo- ride of the acid with solid ammonium carbonafie and then adding con- enhated ammonia. It dissolves sparingly in cold water freely in alcohol ether and hot water and crystallises in long soft silky needles melting at 151"-152". a C6HzBr(N01)(CH,)SO,H was produced by adding the anhydrous barium salt to warm fuming nitric acid ; it crystallises in small pale- yellow deliquescent needlw arid forms very soluble salts. u [CGHzBr(N02)(CH,)SOs]J%i t HzO separates by slow evapora- ORGANIC CHEMISTRY.57 tion in thin yellow needles and from a concentrated solution in crys-tals resembling sal-ammoniac. a [C6H2Br(N02)(CH,) SO,],Pb + 2+H20 forms colourless .glisten- ing octohedrons; sometimes it was obtained in needles which also contain water but are more soluble in alcohol than the octohedrons. a [C6&Br(No2) (GH,) SO3lzSr + $H20 crystallises in thin fan- shaped needles. a C6HzBr(N02) (CH3)S03Na forms long and very thin needles. a ParaZtromoszc~hobenzoicacid was prepared by boiling barium a-pa.rabromotoluene-sulphonate with a ohromic acid solution. On con-centrating the solution C6H3Br(CO2H) S03K + K20crystallises out in thin needles. a C3H3Br{ gg Ba + iH,O crystallises in thin glistening plates ; a C6H3Br{ iz } Ca and ac C6H,Br { :g } Pb + 2H20 form small needles.0 Series. P-ParabromotolzLenesulrphonic acid is readily soluble in water and alcohol sparingly in ether and forms a crystalline laminated mass. It is not converted into an isomeric modification by heating it to 210". p [C6H3Br(CH3)S03]zBa+ E20crystallises when a dilute solution is slowly evaporated in hard compact plates and from a concentrated solution in very thin and brilliant plates. If it be mixed with one of the isomeric salts or with the calcium salt it separates from a concen-trated solution as a white powder. 13 [C6H3Br(CR,)s03]2Pb + 3H20 crystallises in silky stellar needles. p [C6H3Br(CH3)S03]2Ca+ 4H20 is a very soluble salt and forms either thin long rhombic needles or compact plates.p C6H3Br(CH,) SO,Na + H20crystallises in thin transparent four-sided prisms. 0 [C6H3Br(CH3)S03]21Mg+ 8$H20(?)forms softy silky tufts and p [C6H3Br(C1E-f3)SO,],Sr + H20thin plates. 0 [C6]EI,Br( CH3)S0,]2Cu + 7H20 crjstallises in large pale-blue plates. p C6H3Br(CH3)S02C1 was obtained by the action of phosphorus pentachloride on the acid or its sodium salt. It crystallises from chlo- roform in plates melting at about 35" and possessing a peculiar smell. 0 C6H3Br(CH,) SOz.NH3crystallises from water in long slender glistening needles melting at 166"-167'. /3 ~6HzBr(N02>(CH3)SOzH is formed by adding dry p parabromo-tolueuesulphonic acid to warm fuming nitric acid. It crystallises from ether in deliquescent scales possessing a very bitter taste.P [C6H2Br(N02) (CH,) SOal2Ba 3-2H2O crystallises in warty needles. ,d [C6H2Br(NO2) (CH,)SO,],Pb + 3H~oseparat6s from a solution in ether-alcohol in thin colourless needles. [C6H2Br(N0,)(CH,) so3]2cu + 6H20 forms microscopic four-sided green prisms. 58 ABSTRACTS OF CHEMICAL PAPERS /3 C6H2Br(N02)(CH3)S0,A.g is a precipitate consisting of glistening scales. /3 [C6H,Br(NO2) (CH3)S03],Sr + 7HzO dissolves freely in water and alcohol and forms small yellow needles. The sodium salt is very soluble and could not be obtained in distinct crystals p Parabromos.u~hobenxoicacid C6H3Br( so3H) COzH. Wheu p-parabi-omotoluene-sulphonic acid is boiled with the chromic acid mix. ture a large portion is completely destroyed while another is slowly oxidised to the corresponding benzoic acid which forms a deliquescent mass and yields very soluble salts.The barium and calcium salts consist of microscopic plates. j3 Ortl~otol~.2ce~zeesz~l~hoolzic acid is obtained by the action of water and sodium-amalgam on the /? brorno-acid. Its salts are all very soluble. p [C6Hd(CH)SOs]J?b + 4H20crystallises in needles. (3 [CBH4(CH3)S03]zBa+ HZO ahd ,G C,H*(CH3)SO3K + H,O form monoclinic plates and the anhydrous sodium salt forms needles. The chloride of this acid is an oily liquid and the amide which is freely soluble in water alcohol and ether crystallises in monoclinic prisms melting at 152"-153*. ,i3 z'olyl sulphydrate C6H4( CH3) SH was prepared by treating the chlo- ride of the brominated acid with tin and hydrochloric acid and acting on the bromotolyl sulphydrate thus formed with sodium-amalgam and alcohol.It forms soft glistening plates and is insoluble in water j3 [C,Hd(CH3) S],Pb is a bright brick-red precipitate which readily absorbs oxygen and becomes white. (2.) 0rtkobromotoluerze.-To obtain a pure compound the liquid portion which was separated from the solid bromotoluens was cooled down to -2O" and zt few pieces of calcium chloride were added 011 which soon some solid bromotoluene was deposited. The liquid was %lien twice cooled down to -21" when a few more cr stals separated out. After being further purified by fractional distisation nnt,il it distilled at 183*2",it was boiled for ten hours with a mixture of manga-nese dioxide sulphurjc acid and glacial acetic acid and the sgme operation repeated twice.Thus all the para-compound which W~S still present was oxidised to parabromobenzoic acid while a large por- tion of orthotoluene was completely destroyed and not oxidised to an acid resembling in that respect other similar ortho-compounds. To remove every trace of parabromobenzoic acid the liquid was first sub-nlitted to fractional distillation and then left in contact with pieces of sodiurn. PLlre orthobromotoluene is a very refractive liquid possessing aromatic odour and boiling at 181°-1820. When heated gently with Nordhausen sulphuric acid it yields ody one sulphonic acid forming salts which are tolerably soluble crystallise well and lose their water of crystallisation only above looo,and in most cases none over sulphuric acid.[C6H3Rr(CH,) So3l2Ba+ 2H20 forms rhomboydal plates ; the stron-tium salt is a very similar body. [C6H3Br(CH,)SO3],Ca + 2HZ0crystallises very slowly from a con-centrated solution in compact rhombic six-sided plates. ORGANIC CHEMISTRY. [C,H,Br( CH3)S03]2P1-,+ 2H20 separates fi*om a wry concentrated solution in very thin small plates and from a dilute in tufts of needle-shaped plates. C6H,Br( CH,) SOBNa + &H20 forms well-defined brilliant rhomboidal plates. C6H3Br(CH,)S0,K. + $H20crystallises in plates or in short fhick white needles. The copper salt. is very soluble and crystallises in very thin and light- coloured plates while the zinc salt forms small glistenirig plates and the magnesium salt small scales.C6~,Br(CH3)S02Clwas prepared by freating the dry sodium salt with phosphorus pentachloride. It foyms a ci-ystalline mass consisting of needle-shaped crystals and possessing a pungent smell. It crystd-lises from ether in large plates melting at 52'-53". It is but slowly acted upon by caustic soda or boiling water and dissolves sparingly in concentrated sulphuric acid and without change in fuming nitric acid. At 250" it begins to boil and at 260" it is decomposed into charcoal sulphur dioxide and C6H3BrCl( CH,). When heated with water to 200" for several days ih is reconverted into orthobromotoluene-sulpho-nic acid no isomeric modification being formed. C,K,Br( CH,) S02.NH2is sparingly soluble in cold water more freely in boiling water and very readily in alcohol and ether ; it crystallises in long glistening needles melting at 133O-134" and boiling with decomposition at about 290".Ortkobromotolyl sulphydyate C6H3Br(CH,)SH,is formed by boiling the chloride with tin and hydrochloric acid. It is a refractive limpid liquid having a peculiar smell and boiling with decomposition but volatilising with steam. The 1-ead salt is a bright yellow precipitate. On heating the sulphydrate with dilute nitric acid or acting on the sodiiim salt with alcoholic iodine the disulphide (C6H3Br(CH3)S)2 is formed crystallising from alcohol in small needles and from a mixture of xylene and alcohol in long needles melting at 56"-58". Ort7Lob1'0112012ity0tolue.i.les.li~hoiiic acid is a deliquescent mass readily soluble in alcohol and ether.The free acid as well as its salts has a very bitter taste. The following four salts crystallise from water in microscopic but well defined crjbtals :-[C6H2Br(NC),)(CH,)sO312Ba+ 2H20 [C,H2Br(N0,) (CH,) SOd]Pb + 2H20 [C6H2Br(N02)((33,)S03J2Ca [C6H&r(N02) (CH,) SO,]K. C6H2Br(N02)S03Na+ HzO crystallises in tufts of long needles and is less soluble in water than the preceding salts.. Orf7~obromosu~hoben%o~c cr cicl C,H,Br( SOyH)C02H was prepared by oxidising the barium salt of the corresponding toluenesulphonic acid with chromic acid solution. C,II,Br(CC),H)sO,K 3. $E120crystallises from water in thin plates resembling naphthalene. ABSTRACTS OF CHEMICAL PAPERS.C6H3Br{ gg:} Ba + 2Hz0 separates on adding alcohol to the con- centrated solution in tufts of glistening and very thin needles. C6H3Br{~~~} Pb + 2H20 forms small white glistening needles ; the calcium salt is very soluble and forms long silky needles. Metatoluenesulphonic acid was obtained by the action of sodium amalgam on a solution of barium orthobromotoluene sulphonate. [C6H4(CH3)S03]oBa+ 2Hz0 is very soluble in water and alcohol and forms a crystalline powder. [c6H4( CH,) S03JzPbf 2Hz0ciytallises from a concentrated aqueous solution in thin plates grouped in rosettes and from absolute alcohol in long needles. [C6H4(CH3)S03],Cais very soluble in water. On heating a con-centrated alcoholic solution the salt separates in small glistening plates which redissolve on cooling.C6H4(CH3)S03Na+ iHzOis very soluble in water and crystallises from absolute alcohol in large shining plates. C6&( CH,) So3K + iHzO is a similar compound crystallking from alcohol in plates resembling naphthalene. Metatohenesulphonic chloride C,H,( CH,) SOaCl is a limpid pale- yellow liquid having a penetrating smell. It does not solidify at -lo" and is not decomposed by water even at 130'. Ammonia con- verts it into C6H4(CH3)SO2.N&,crystallising from water at 40" in large plates and at 20" in thin needles melting at 90"-91". Metatolyl sulphydrate c6H4(CH3)SH,is formed by acting with th and hydrochloric acid on the chloride. It is a heavyrefractive liquid having a powerful smell and attacking the skin.Boiling dilute nitric acid converts it into the disulphide (C6H4(CH3)S)2, an oily liquid boil- ing at about 150". Crystallised bromotoluene being a para-compound can yield only two sulphonic acids and both have been here described. ' Of these the @-compound formed by replacing the bromine with hydrogen and treating the resultbg toluene with sulphuric acid is converted by fusion with potash into salicylic acid. The two sulphonic acids derived from the solid bromotoluene have therefore the following constitution :-Br The liquid bromotoluene is most probably an ortho-compound because bromine acts on the aromatic hydrocarbons in a similar waz ORGANIC CHEMISTRY. to that of sulphuric acid and nitric acid which latter always produce simultaneously a para-compound and an ortho-compound.By re-placing the bromine in the sulphonic acid with hydrogen metatoluene- sulphonic acid is produced and therefore the constitution of ortho-bromotoluene-sulphonic acid is expressed by one of the two following formulse :-In the last part of the paper Huebner discusses therelations existing between the composition of salts and their water of crystallisation and points out that all the acids derived from orthobromotoluene form with the dyad metals salts most of which contain two molecules of water, whilst those of the alkali-metals contain generally half a molecnle. The conclusion consists of a discussion on molecular compounds and quantivalence. . c. s. Action of Potash on the Monochlorophenol boiling at 218O By A.FAUST (Deut. Chem. Ges. Ber. vi 1022-1023). THISreaction according to Petersen and Baehr-Predari yields hydro- quinone. This the author cannot confirm ; he obtained only resorcin and consequently this monochlorophenol as well as paraphenolsulphonic acid and the non-volatile nitrophenol belong to the 1 4series. c. s. Researches on the Isomeric Cresols and their Occurrence in Coal-tar. By M. S. SOUTHWORTH (Ann. Chem. Pharm. clxviii 267-276). FROXthe ease with which thymol is converted by oxidation into a quinone it was thought probable that the cresol which is obtained from that body by removal of propylene would under similar treatment furnish the unknown toluquinone. Experiment however did not con- firm this idea.But although toluquinone has not been obtained certain substit;ution-derivatives of it are known. Borgmann has prepared tri- chloro-toluquinone by acting with hydrochloric acid and potassium chlorate upon the cresol from coal-tar. This cresoi however is un-doubtedly a mixture of at least two isomeric compounds and the expe- riments of Borgmann give no clue as to which of the three cresols is the parent of this trichlorinated derivative. The author’s experiments were undertaken partly in order to clear up this point and partly to gain further knowledge of the chemical constitution and properties of these bodies. MetacresoZ.-This is the cresol from thymol. By treating it with hydrochloric acid and potassium chlorate the author obtained dichloro- ABSTRACTS OF CHENICN; PAPERS.tolumetaquinone but by protracted action of the reagents he did not succeed in getting a body containing a larger proportion of chlorine. This compound crystallises fmm alcohol in yellow transparent tables which become brown on exposure to liglst It is slightly soluble in water but dissolves in alcohol and ether. It may be sublimed but at the same time undergoes partial decomposition. Solution of sulphurous acid converts it very readily into the corresponding hydroquinone CsHC12.CHs(OH) a colourless body which when crystallised from water retaius water of crystallisation pfoloably 2K20.It melts between 167" and 169" and may be sublimed without decomposition. By treat-ment with acetyl chloyide it furnishes an acetyl derivative which crys- tallises from alcohol in small clustering needles melting between 12'2" and 124".Dichlorotolumetaquinone acted upon by sodium amalgam did not yield toluhydroquinone. Paracresol.-This componnd subjected to the action of hydrochloric acid and potassium chlorate gave dark-coloured uncrystallisable pro- ducts from which no definite result could be obtained and which in the opinion of the author contain no chlorinated quinone. Orthowesol.-A fraction boiling at about 190" was employed. This undoubtedly contained a little paracresol but as just stated the para- modification furnishes no quinone and therefore any body of that nature produced must be an ortho-derivative. Treatment with hydrochloric acid and potassium chlorate resulted in this case in the formation of st.yellow body crystallising in shining transparent lamina which proved to be a mixture of di- and trichIoro- toluorthoquinone. Borgmann obtained precisely the same result in operating upon the cresol from coal-tar. When this mixture of chloroqixinone was reduced by sulphurous acid a mixture of the corresponding di- and tiichlorohy droquinones was formed and by distillation with water their separation was effected without difliculty the former being easily volatilised in vapour of water the latter remaining in the residue. Dichlorotoluorthohydroquinone C6HC1,.CH3.(OH), melts at 119"-121" sublimes easily and crystallises from hot water in feathery needles. Trichlorotoluorthohydroquinone crystallises from the solution left after distillation in long needle-shaped crystals.It melts at 211"-212". This was the melting point found by Borpann for his trichlo- rotoiuhydroquinone obtained from coal-tar cresol which also agrees with this compound in the rest of its properties. It would therefore appear that the two compounds are identical and hence that orthocresol is a constituent of the cresol from coal-tar. W. A. T. Pentabromoresorcin and Pentabromorcin. By C. LIEB E RMAN N and A. DITTLER (Ann. Chem. Pharm. clxix 252-269). A CONSIDERABLE portion of this paper is occupied with a detailed account of experiments on bromoresorcin the results of which have been already published (Deut. Chem.Ges.Ber.,v 1100,and this Journal [2] xi p. 502) ORBAXE CHEXISTRY.63 stating in addition that all their attempts to convert the tribromoreaor- quinone into tribromoresorcin or pentabromoresorcin have been unsuc- cessful. Pentabromorcin nndergoes a decomposition similar to that of the resorcin compound both when treated with a solution of silver nitrate and when snbrnitted to the action of heat; in the latter case however the reaction is more difficult of control than with thexsorcin derivative the molecule of bromine liberated attacking the tribromor- ciquinone. This new substance crystallises from chloroform in minute needles of a bright yellow colour. Pentachlororesorcin,. when heated sublimes unclianged. C. E. G. Synthesis of Anthracone and Dimethylanthracene. By W. A.VAN UORP(Ann. Chem. Pharm. clxix 207-5220). WHEX xylyl chloride prepared by the method of Lauth and Grirnaux (Atziz. Chem.Pharm.,cxlv 115) is heated to 210" with twice its voliime of water for twelve hours a thick oily liquid of aromatic odour is obtained. This when submitted to fractional distillation may be separated into a yellow volatile oil and ~~~et~~lan~~rae~~ze which passes over as a semisolid mass towards the close of the operation ; the proportion of the latter is but small and considerable loss is experienced in purifying it from the repeated pressings sublimations in a current of carbonic anhydride and crystallisations from glacial acetic acid necessary for that purpose. It forms large glistening scales very similar to anthracene in appearance which melt about 200'.By oxidation with chromic anhydride in a glacial acetic acid solution it forms two quinones one of which is yetidily soluble in glacial acetic acid melts at 153",and sublimes in thin scales ; the other is soluble wit,h difficulty in the acid and sublimes at a high temperature in yellow needles ; these quinones do not yield compounds analogous to alizarin. The oil previously mentioned gives more dimethylanthracene by re-peated fractional distillation but could not itself be obtained in t.he pure state ; it is probably however xylyl-zylene as when passed through a red-hot tube filled with pumice it splits up into dimethylanthracene and hydrogen in the same manner t.hat the hydrocarbon benzylbenzene Cl,Hl, obtained by the action of water on benzyl chloride yields anthracene.Dibl.onzodimetlzyZaiithl.ncene isprepared by adding a solution CI6Hl2Br2 of bromine in carbon sulphide to one of dimethylanthracene in the same solvent; on evaporation a yellow crystalline mass is left which is easily soluble in benzol ether and absolute alcohol. It is best recrys- trtllised from glacial acetic acid when it forms yellow needles melting at 154'. These are decomposed by red-hot lime with formation of dimethylanthracene. The second and third sections of this paper "The Action of Water at 64 dRSTRACTS OF CHEMICAL PAPERS. 200"on B;enzyl Chloride," and "The Behavionr of Benzyltoluene at a Red-heat," have been already noticed (last volume p. 500). The author concludes by observing that the formula of anthracene CsH4-CH 11 ,is inadmissible as it cannot be derived from benzyltoluene CJ%-CH C6&-CHz-C,H*-CH3 by the elimination of H4; the formula 1 C6H4/cH\C8H(',is however compatible with that of benzyltoluene 'CH' just given namely c6&<g2\c6a6 The methods employed for the synthesis of anthracene and dimethylanthracene point out the way by which the higher homologues of anthracene may possibly be obtained.C. E. G. Chlorination and Iodination of' Anthracene. By T. BOLAS (Chemical News xxviii 167). WHENanthracene was digested for some days with antimony pent% chloride a current of chlorine being at the same time passed into the mixture the greater part of the anthracene was carbonised but on subjecting the product to distillation it was found to yield a crystalline mblimate.A portion of this sublimate dissolved in hot benzene from which it separated in crystalline crusts which melted at 236* 247" and 252' after one two and three crystallisations. That portion of the sublimate which was insoluble in benzene yielded on sublimation beautiful needles which melted above 330° and contained an amount of chlorine nearly corresponding with that required by the formula C&LH4. It is however probable that this substance is either derived from some impurity in the anthracene employed or from a hydrocarbon formed by the polymerisation of anthracene and that the true hexa- chloranthracene is to be found in the portion soluble in benzene. When anthmcene is fused with iodine hydriodic acid is evolved even if the temperature does not rise above 155" and the greater part of the anthraceue is carbonised but a small portion of matter soluble in benzene or acetic acid is produced.When a solution of iodine in phenol is boiled with anthracene hydriodic acid is evolved. By moderating the violence of the above reactions and assisting the action of iodine with an oxidising agent the author hopes to obtain more definite results. T.B. The Aotion of Pyromellitic Acid on cc-Naphthol. By J. GRABOWSKI (Deut. Chem. Ges. Ber. vi 1065-1069). OF the numerous compounds which may be produced by the action of pyromellitic acid on a-naphthol the most important from its analogy with the phthalic acid and carbonic acid compounds is yyromelZitei7a-tetrGa-naphtholanhydride C6H,(COOH)r + BC,oH,OH 7-6HzO = C,H3,O6.ORUANIC CHEMISTRY. 65 This is formed when one molecule of pyromellitic acid is heated with four molecules of a-naphthol in an oil-bath to 300". The product after being exhausted with boiling acetone and purified by fractional crystallisation from phenol yields microscopic crystals which have the composition C,H,Os + C6H,0H[,and lose their phenol when heated to 260". Frorn the mother-liquors the compounds a-and 6-pyornellitein-tetra-a-nap htholhemianhy dride are obtained the first 2C50H2807, C6H50H in thin plates the second in very slender needles they lose their phenol when dried at 260" and are reduced to C50H2807.In the acetone solution the compound .I-pyromellitein-tet,.a-a-~~(~p htholhemianhydride is found.It melts at 265" and when dried at 150" has the composition C50H2807.On heating one molecule of pyromellitic.acid with three of a-naphthol to 250" as long as water escapes and removing the excess of naphthol by distillation in a current of aqueous vapour a brownish- black mass is left This when purified by repeated solution in potash precipitation by acid and solution in ether forms a brown powder tri-a-napktho~2/ro~~~~Zl~t~i~ acid which has the composition C40H2408 and is readily soluble in alcohol ether and acetone. It dissolves in alkalis with a deep green colour. T?.i-a-na~litholiiei?,ianh2/dro~~?.o?nellitAic acid C4,H2,07,is produced together with the last mentioned compound when a mixture of one molecule of pyromellitic acid and three of a-naphthol is heated to 280"-300".It is a yellowish brown powder soluble with difficulty in cold alcohol or ether. It yields a fine blue solution with alkalis. C. E. G. Carvol and Carvacrol By A. KEKULEI and E. FLEISCHER (Deut. Chem. Ges. Ber. vi 1087). CARTTOL is obtainable from oil of carraway (Carurw carvi) by fractional distillation and boils at 224.5"to 225". It can however be more readily obtained pure by converting it into the crystalline sulphuretted hydro- gen compound discovered by Varrentrapp and decomposing this by potash care being taken to allow the alcoholic potash to act for a short time only and at the ordinary temperature. On treating it with crystallised orthophosphoric acid much heat is evolved and the carvol becomes converted into its isomeride carvacrol (which as shown in a former paper is identical with campho-cresol or oxycymene derived from cymene-sulphonic acid j.So great indeed is the heat evolved during this intramolecular interchange (wzolecu-Zare Umlageru?zg) that the action becomes explosive unless the carvol is diluted with carvene. For this purpose the crude oil of carraway can be used; 5 parts of acid to 50 of carvol suffice. The result- ing carvacrol is obtained pure by solution in potash precipitation by an acid and distillation. It boils at 232"-232.5" (236.5" to 237" when the whole mercury column is in the vapour). Phosphorus trisulphide converts carvacrol almost wholly into cymene.The pentasulphide also forms thiocymene. The same results are obtained with carvol only little or no cymene is thus obtained with the pentasulphide. Both cymenes give on oxidation ordinary toluic acid (melting point 1~5"--176") and terephthalic acid. The thiocy- YOL. XXVIT. F ABSTRACTS OF CHEMlCAL PAPERS. mene in each case appears to be identical with that from camphor giving the same characteristic metallic compounds the crystalline mercury salt melting at 108~5"-109"in each case. Hence oxycymene (carvacrol) is isomeric with thymol these two bodies representing the only two theoretically possible modifications of hydroxylated cymene (this hydrocarbon being 1:4 propyl methyl-benzene). Just as thymol gives propylene and y-cresol when treated wikh phosphoric anhydride so carvacrol yields propylene (yielding a bromide which distils perfect,ly at 142")and a cresol not yet investigated.Similarly thymol gives thymotic acid melting at 120",on treatment vith sodium and carbon dioxide. Carvacrol gives by the same process camacrolic crcid melting at 133"-134". Both acids are indicated by t.he formula C6H2 gz {L and give (like salicylic acid and all acids prepared synthetically by Kolbe's reactiou) a blue coloration with ferric chloride. The action of oxidising agents on cayvol 'and carvamol has not as yet given any definite results excepting the production of oxalic acid. When car- vacrol is fused with caustic potash two acids are produced resembling those obtained by acting in the same way on the sulphotoluic acid corresponding with thiocymene.Possibly these are oxytoluic and oxyterephthalic acids. Phosphorus pentachloride acts on carvacrol as on all phenols a chlorocymene being formed together with a solid crystalline tertiary phosphoro-cymene ether volalile with partial decomposition. The chlorocymene boiled at 214' and gave by oxidation monochlorot oluic acid melting at l84"-186". Researches on these and tlie corresponding bromo-derivatives are contemplated SO as to throw light on the positions of the hydroxyl group in the two isomerides thymol and carvacrol respectively. The sulpho-acid of carvacrol is solid and crystalline and gives crystalline salts when oxidised by manganese dioxide or potassium dichromate and dilute sulphuric acid.Considerable quantities oE thymo;l are produced idslzticnl with that obtaiwed f~o~n tlzynol melting at 46" giving a hydroyuinone melting at 139"-140° and so on. The identity of the quinone thus obtained from each of the two isomerides necessarily follows from the ascription of the formula?- CH3 IC /\CH CH 1 IfCH CH and I I1CH C.OH \/c I I C3& C3H7 to the two isomerides and it also follows that the 1:3 position cannot OROAXIC CI3EMIrjTRP. be that occupied by the hydroxyls in a hydroquinoiie or the oxygen in quinone (the 1:4 position of the hydrocarbon radicals in cymene being granted Le. toluic and terephthalic acids being taken as 1:4 benzene derivatives). A quinone must therefore be either a 1:2 or a 3 :4 derivative and the latter alternative is excluded if it be assumed as is usual that resorcin is a 1 4 derivative.Attempts to convert thpd iuto its isorneride carvamol or vim vemd are contemplated. These may probably be realised by means of carvol which have not impossibly an intermediate formula analogous to that of ethylene oxide. C R. A. W. Note by Abstractor.-It would be of great interest to determine the “heat of combustion ” of the three isomerides carvol carvacrol and thymol. The evolution of heat during the transformation of carvol into its isomeride of higher boiling point carvacrol would indicate that the heat of combustion of the latker is less than that of the former just as the heat of combustion of hesperidene boiling at 178” is pro- bably less than that of the terpene of nutmeg-oil boiling at 163” (this Journal [el xi 694).Favre and Silbermann have shown that acids of the acetic series develop less heat on combustion than their respective isomerides of the conipound-ether series these latter boiling at 70” to 90” lower than the former; also that the higher members of the olefine family (possessing higher boiling points) have smaller heah of combustion than the lower members of that family so that it is not impossibly a general rule that of a series of isomedes that o”iLe has the 11ighest boiling poiizt which has the leust heat of combustion Ls. which possesses the least of what is often called “potential energy,” but which may perhaps be more conveniently termed intriiuic chemical etwrgy; or in other words the formation of an isomel-ide of higher boiling point from its constituent elements is attended with the evolu- tion of more heat during combination i.e.there is greater “affinity ” between its constituent elements than is the case with an isomeride of lower boiling point. As pointed out (7oc. &A),* this result is not the same as that which might be expected from Thornsen’s recent investigations nor is it in accordance with the relative degrees of stability of the dibromides of certain terpenes when heated. On the other hand Favre and Silber- mann’s experiments lead to the conclusion that in the case of certain terpenes the higher the boiling point the greater the heat of combus-tion.From the abstractor’s results however together with the recent ones of Riban it appears probable that the substances examined by Fane and Silbermann were not pure terpenes but contained cyineue. C. It. A. W. * In the paper referred to (this Journal 1873 p. 694) by an unfortunate erratum the sense is wholly inverted. On line 7 for “ a result q&e in harmoily with Julius Thomsen’s results,” read “ 8 result lzot quite in harmony with Julius Thomsen’s results.” ABSTRACTS OF CHEMICAL PAPERS. New Method of Forming Orthotoluic Acid. By RUDOLPH FITTIG RAMSAY and W~LLIAM (Ann. Chem. Pharm. clxviii 202-253). THATsalicylic acid belongs to the " ortho " group has been indirectly proved by V. Meyer ; for the ordinary bromo- and sulpho-benzoic acids may be resolved on the one hand into oxybenzoic acid and on the other into isophthalic acid.As all attempts to derive phthalic acid from salicylic acid were fruitless the indirect proof furnished by Meyer has been questioned. It was with the view of confirming the indirect proof of &$eyer and of connecting salicylic and phthalic acids directly with each other that the authors undertook their investi- gation. By the action of sulphuric acid on toluene two different toluene- sulphonic acids were formed ; one which exists in larger quantity is undoubtedly " para-;" the other has been termed by Anna Wolkow metatoluene sulphonic acid. This so-called meta-acid when treated with fused potassium hydrate has been converted first into a cresol and finally into salicylic acid.Could it be converted into a toluic acid and oxidised the position of the lateral groups in salicylic acid would be determined. The two acids were separated as much as possible by crystallisation of their potassium salts from water. The more soluble of these pre- sumably ortho was distilled with potassium cyanide and the cyano- toluene produced was oxidised to toluic acid. As a mixture of two salts was employed two toluic acids were obtained. These were sepa- rated by crystallisation of their calcium salts from alcohol of 0.83 sp. gr. after most of the para-salt had been removed by crystallisation from water in which it is less soluble than the ortho-salt. The calcium orthotoluate crystallises from alcohol in feathery tufts.The acid melts at 102". A nitrotoluic acid melting at 143"was formed by treatment witb concentrated nitric acid. The sole products of oxida-tion of orthotoluic acid were carbonic anhydride and water. Before how- ever concluding that metatoluic acid was not present it was necessary to oxidke the residue ; if it were there isophthalic acid would be found as one of the products of oxidation. But no trace of this acid was actually found terephthalic acid alone separating out on oxidation with potassium dichromate and sulphuric acid. As the three toluic acids correspond with the three phthalic acids these results aEord direct proof that the lateral groups in Ralicylic acid occupy the relative positions 1 2. Nifroparatoluic acid was also prepared.It melts at 188"-189" and is deposited from alcohol in monoclinic crystals. The barium salt crystallises with four molecules of water. It appears to be pecu- liar to ortho-compounds or at least to many of them that they can be distilled with water vapour. Salicylic and phthalic acids and ortho- nitrophenol are all volatile whereas the corresponding metn- and para-compounds cannot be distilled. This may prove a convenient means of separating ortho- from meta-compounds. W. R. ORGANIC CHEXISTRY. 69 Metatoluic Acid. By CARLBOTTINGER RAMSAY and WILLIAM (Ann. Chem. Pharm. clxviii 253-261). THEdescriptions of metatoluic acid by Ahrens Tawildarow Wurtz and von Richter differ widely from each other. Could COZ be with- drawn from uvitic acid a toluic acid would be obtained the position of whose lateral chains would admit of no doubt for uvitic acid is derived from mesitylene.Bottinger heated calcium uvitate mixed with half its weight of calcium hydrate for 8-10 hours in a bath of molten lead whereby a toluic acid was obtained which after sublimation fused between 109"-110" and confirmed the observations of von Richter. The barium salt after drying in the air was found to crystallise with !7+ molecules of water. On oxidatioii it yielded isophthalic acid almost quantitatively. Ramsay treated xylene with bromine to form bromoxylene and oxidised it with potassium dichromate and sulphuric acid. The greatest difficulty was experienced in decomposing the insoluble chromium compound which resulted but by repeated alternate boiling with hydrochloric acid and potassium carbonate the salt was decom-posed.The mixture of acids was separated as far as possible by crystallisation of the calcium salt. The less soluble of these salts which crystallised in long needles gave an acid fusing between 205" and 207". It was treated with sodium-amalgam to remove the bromine and the residue was acidified and distilled with water-vapour. From the metatoluic acid which came over the calcium and barium salts were made ;the former resembles calcium benzoate very closely in appearance and crystallises with three molecules of water ;the latter crystallises in small glittering scales and contains two molecules of water. The acid from these salts fused at 9lo-92O corresponding with the observations of Ahrens.It was found however that on crystallisation from alcohol a mixture of well formed monoclinic crystals and warty clusters was deposited which could easily be separated mechanically. The former melted at 106" the latter at 176" showing that a mixture of meta- and para-toluic acids had been the means of leading Ahrens to false con- clusions as to the melting point of metatoluic aoid. W. R. Benzylated and Di-benzylated Acetic Acid. By LYDIASESEMANN (Deut. Chern. Ges. Rer. vi 1086). WHEN the product of the action of sodium on acetic ether was treated with benzyl chloride in an oil-bath for sevei-al hours at 200" and water a,dded to the product a red-brown oil separated which by fractional distillaf,ion yielded unaltered benzyl chloride a liquid boiling at 200" -300" and a heavy viscid oil boiling above 300".The middle portion boiled for the most part at 240"-260" and gave ttn oily precipitate becoming crystalline on standing after saponification with potash and addition of hydrochloric acid. After recrystallisation this substance melted at 47" boiled at about 280" and had the composition C9HI0O2 giving a barium salt C,H,Sa60~. Hence this substance was beiixyhtcc;! acetic acid formed by the reaction- 70 ABSTRACTS OF CHEM[CAL PAPERS. C€I-I,.Na CH,.C,H, + C7H7.Cl= NaCl + I I CO.0.CPHS CO.O.C,H,. Rydrocinnamic acid (benaylacetic acid) has this formula and boils at 2180" ; its melting point being 47". The viscid oil above mentioned when treated with potash and then with hydrochloric acid gave a bulky white precipitate which cohered together and became resinous ; this was distilled in a current of carbon dioxide mid crystallised from ligroin ; white prisms were thus obtained insoluble in water but readily soluble in alcohol and ether and melting at 85O.011 analysis these were found to have the com-position C16H1602, the barium and silver salts being respect'ively Cl6HI5BahO2, and Cl6Hl5AgOZ. Hence this body was dibewzylated acetic acid formed by the reaction- CHKa2 CH (C7&), I + 2C7H7Cl= 2NaC1 + I GO.0.C2H GO.0.C2H3. Further researches on the derivatives of this substance are in pro-gress. C. R. A. W. Bromo-Cmphocarbonic Acid. By J DE SANTOS E f3rLt.a (Deut.Chem. Ges. Ber. vi 1092). CAMPHOCARBONIC acid is obtained together with the comparatively un-stable borneol-carbonic acid by acting with carbon dioxide on the mixture of the sodium derivatives of camphor and borneol obtained by acting with sodium on camphor ; it can be extracted by ether from its aqueous solutions and separates from the solutions of its salts on addition of hydrochloric acid either at once or on standing according to the concentration of the liquor. It melts at 118°-1190. Bromine acts on camphocarbonic acid .energetically evolving hydrobromic acid and forming nzonobrcrmocamphocarbo~2~cacid CloHl4Br0.CO.0H.; rise of temperature during the action must be avoided otherwise carbon dioxide is aalso evolved. The acid is readily sduble in alcohol and ether and but little soluble in water ; it melts at 109"-110" being partially decomposed into bromocamphor and carbon dioxide at 65' ; on boiling its alcoholic solution the same result ensues the bromocamphor produoed melting at 76'.Its salts also are easily decomposed; the barium and silver salts have respectively the formule (CllHl4BrO3),Ba and C11EIilBr03.Ag. C. R.A. W. Terebic and Pyroterebic Acids. By W. CAR, L E T ON WIL I I AM s (Deut. Chem. Ges. Ber. vi 1094). 200 GRAMS of turpentine oil purified by repeated distillation are oxidised by 800 grams of nibric acid sp. gr. 1-25 the mixture being heated to 80" ;when the reaction has ceased the whole is heated for 24 hours on ORGANIC CHEMISTRY the water-bath nitric acid of sp.gr. 1.4being added from time to time until the resinous matter first formed disappears on further oxidation ; no terephthalic acid was found in the products. After evaporation the liquor deposits on standing crystals of terebic acid and of acid ammo- nium oxalate. The terebic acid thus obtained melted at 175" (Caillot found 168" as the melting point). The author confirms Swanberg and Eckmann's results viz. that terebic acid forms two classes of salts tsrebutes C1H9M04,and the so-called din-terebates C,HloM20,; the silver salts of these formulm are anhydrons the barium salts being (C7H9O4),Ba + 2H20 and C7H,,Ba05 + 5H20 the former being non-crystalline; a silver salt C7HgAgOl.C7H,20,was also obtained which lost no water at 110".By dry distillation terebic acid forms pyroferebic acid carbon dioxide being evolved ; almost the calculated yield is obtained. The pure acid boils at 210"; the silver salt CGHyAgOz,and the readily soluble crystallisable barium salt (CGH902),Ba+ 5Hz0have been obtained. Bromine unites with pyroterebic acid forming a dibronzocaproic acid C6Hl0BrZO2, which is reduced again to pyroterebic acid by sodium-amal- gam. Attempts to form caproic acid by the action of sodium amalgam on pyroterebic acid gave no result but strong hydriodic acid formed a vola-tile acid possessing the odour Gf caprio acid and giving a silver sdt containing the same percentage of silver (fouud 48736 ; calculated 48.43). On fusion with caustic potash pyroterebic acid forms acetic and butyric acids (Chautard).The author him verified this statement and shows moreover from the properties of the calcium and silver buty- rates obtained that isobictyric acid is produced and not the ordinary butyric acid. Dilute nitric acid dso yields isobutyrio acid together with oxalic acid. From this the following formula is attributed to pyroterebic acid :-CH3 )CH-CH=CH-CH-CO-OH. CH3 whence the formula CH3 \CH-C-CH-CO.OH CR3' II I CH OH (sic) for terebic acid would appear the most probable were it not alto- gether without analogy. CH [Query yCH-C-CH-CO.OH ? 1 CE3' II I CO OH Nothing but acetic acid has been obtained by the action of oxidisillg agents on terebic acid ; nitric and chromic acids have no action on it nor has oxide of silver ;melting caustic potash gives hydrogen and an ABSTRACTS OF CHEMICAL PAPERS.acetate whilst hydrogenising agents have no action on it. Phosphorus pentachloride is reduced to the trichloride substitution of hydrogen by chlorine taking place ; chloroterebic acid C7H,C10a,is t.hus formed melting at 189*5"-190" and giving salts analogous to the terebates and diaterebates ;sodium amalgam reconverts it into terebic acid. C R.A. W. Podocarpic Acid. By A. C. OUDEMANS, Jun. (Deut. Chem. Ges. Ber. vi 1122-li24). A RESINOUSexcrescence which was found on a Javanese tree Podocnrpus cupresfiina was found to consist of a resinous acid which separates fiom dilute alcohol in rhonibic crystals or when water is added to the alcoholic solution in small white needles.It is insoluble in water almost insoluble in benzene chloroform or carbon sulphide but easily soluble in ether alcohol or strong acebic acid. It melts at 187"-188° and is decomposed at about 320". Its specific rotatory power is /* 136" at 1'7') and its analysis led to the formula c,;H&. The author considers podocarpic acid to be monobasic and to yield salts formed on the following types :-I. C17H21Mf03. 11. Ci,H2oM'203 111. C17H21M03 + ClpH2203. The sodium sakt C17H2,Na03 + H20,forms slender needles soluble in about three parts of watw. The copper salt C17H20Cu03, was obtained by adding a solution of the sodium salt to copper sulphate. Ammonia dissolves podocarpic acid and tbe solution deposits a very soluble salt which is considered by the author to belong to the first class ;but on standing the solution deposits slightly soluble crystals of an acid salt which gradually loses its ammonia on exposure to the air podocarpic acid being left behind.Mononitropodoca,yic acid and diizitropodocmyic acid were obtained by warming podocarpic acid with dilute nitric acid. The former is a yellow crystalline substance slightly soluble in alcohol. Its salts are red or yellow and have a metallic reflex. The salts containing 2M are easy to prepare but those containing M are difficult to obtain. The barizcm salt C17Hl,?3a(N02)03+ 7Hz0,has a beautiful dark-red colour and metallic lustre. The dinitro-derivative is moderately soluble in alcohol and forms crystals which resemble those of potassium femocyanide but appear to belong to the rhombic system.The barium salt C17H1,Ba(N0z)203+ 4H20 forms reddish brown plates which polarise light. The following derivatives of podocarpic acid have been obtained and will shortly be described in the Annalen der Chemie I'.€3. ORGANIC CHEMISTRY. The Constitution of Podocarpic Acid. By A. C. OUUEXIANS Jun. (Deut. Chem. Ges. Ber. vi 1125-1128). BYdistilling the calcium salt of podocarpic acid a tar was obtained which when distilled with water yielded paracresol and a hydrocarbon having the composition C9Tll*; this the author calls carpene. The portion which did not volatilise with water was distilled im vacuo when it yielded hydrocarpot C16H200,a yellowish viscid aromatic liquid boiling at 220"-230" in a vacuum; and methanthrol C15Hi20,a solid sub- stance melting at about 122°C.This substance is probably a secondary product as when hydrocarpol is digested at t'he ordinary pressure carpene paracresol methanthrol and probably marsh- gas are formed. Carpene C9Hl4,resembles the terpenes and becomes resinified on exposure to the air the product having the composition C18H,0,. Carpene boils at 155"-157" has an odour recalling that of turpentine and that of storax and yields a bromo-derivative C9Hz5Br. The author considers that the formula OH c6HZ {:gH GH15 expresses the constitution of podocarpic acid. When podocarpic acid is heated with zinc-dust a hydrocarbon, Ci5HI2,is produced which the author calls metlzanthrene.It is a fluor-escent body melting at 117" and boiling above 360". It combines with picric acid and yields a quinone on treatment with chromic acid. Further details will be published in the Annaten der Chernie. T. B. Ortholuidinesulphonic Acid. By H. LI M P R I cH T (Deut. Chem. Ges. Ber. vi 1008-1010). WREN pseudotoluidine is heated with fuming sulphuric acid it yields two isomeric sulphonic acids C7HsN(S0,H). OrtlLotoZuidineszcl-phonic acid is sparingly soluble in cold water and crystallises in yellowish oblique rhombic plates or prisms containing one molecule of water C,&N( S0,K) -f-&H,O ; it forms silky crystals and dissolves readily in water. C7H,N(S03Na) + H,O forms feathery crystals. [C,H,N( SO,)],Ba + 3H,O crystallises in six-sided prisms which are freely soluble.2[C7H,N( SO,)]Pb + I&H,O (?) forms compact six- sided prisms. C7H8N( S0,Ag) is sparingly soluble and crystallises ixi small white plates. By fusing the acid with potash it yields pseudo- toluidine and on adding bromine to the aqueous solutiop tribromo-toluidine is precipitated and dibro??zotol~idi?2eSu~77L0~z;2.iC acid remains in solution. Tribromotoluidine crystallises in long white needles melting at 112O while the same compound prepared by the direct action of bromine on pseudotoluidine was found to melt at 105°-106". The dibrominated sulphonic acid is readily soluble in hot water and alcohol and crystallises in long whit'c needles with one molecule of water. [C,H,Br,N( SO3)IzBa + 4H2O crystallises in long white needles.ABSTRACTS OF CHE';\IICAL PAPERS. [C7H6Br2H(SO,)],Pb + 3H20forms prisms and does not freely dis-solve. The silver salt is a precipitate consisting of needles and darkens when boiled with water. On suspending the acid in strong alcohol cooled to 0" and passing nitrous acid into the liquid the diazo-compound C7H,N2S03,is obtained as a white explosive powder which readily dissolves iu water. By heating it with absolute alcohol under pressure a tolueneszdphonic acd is formed which on evaporation is obtained in form of a syrup ; its ehloricZe does not crystallise but the ninide forms prisms melting at 148". By acting with hydrobromic acid on the diazo-compound it is converted into b~omotol?cen estslphonic acid which does not! crystallise.[C7H6Br(SO,) J2Ba+ 3H,O forms white warty crystals. The chloride is a syrupy liquid amd the cctuide forms microscopic crystals melting at 156"-15 7". Cresolsulpho~zicacid was produced by heating the diazo-compound with water ; it forms vcry deliquescent crystals. [C7H70(SO3)IIBa+ 2$H20 is readily soluble and forms tnfts of needles. [C)7H70(SO3)],Pb+ 2$H,O is a similar body. These sul- phonic acids are isomeric with those already known. The second pseudotoluidine-sulphonic acid is very soluble and forms indistinct crystals. c. s. Action of Sodium-amalgam on Acetophenone. By A. EMM E E-LING and c. ENGLER (Deut. Chem. Ges. Ber. vi 1005-1006). BYacting with sodium-amalgam on a solution of acetophenone in dilute alcohol secondary phenylethyl alcohol is formed together with the cor- responding pinacone.The alcohol CsH,.CR(OH)CH, is a colourless very refractive liquid boiling at 202*-203" and having a very dis- agreeable smell. The pinacone (C,H,.COH. CHS)O has already been described by the authors,' who then believed it to be the secondary alcohol. It crystallises from dilute alcohol in long pointed crystals and from secondary phenylethyl alcohol in short quadratic prisms. c. s. Propiophenone. By T. I). BARRY (Deut. Chem. Ges. Ber. vi 1006-1008). Yropiopheno.ne (ethyl-phenyl ketone) was prepared by distilling a mixture of calcium benzoate and propionete as a yellowish very refrac-tive liquid boiling at 208"-210" ; it does not combine with the acid sulphites of the alkali-metals.By adding it in small portions to well-cooled fuming nitric acid it is converted into a solid mononitro-compound C6H4(N02) C0.CzH5,crystallising from absolute alcohol in small but well-defined prisms melting at 100". A syrupy modification of this compound is obtained by using nitric acid which has been gently heated AiiZido27ro~iophcnone,CsH,(NH,) C0.CH3,is formed by acting wit,h tin and hydrochloric acid on a solution of the solid nitro- compound in absolute alcohol; it is a syrupy liquid smelling like strawberries and forming a crystalline hydrochloride which yields with platinic chloric the crystalline compound [C,H4(NH2)C0.C2H3,HCl]2. PtCI,. ORGANIC CHEJIISTRY. Recolzdtzry Plientjl-propyZ dZcol/,ol C6H5.CH(OH)C,H,,is produced together with its pinacone by adding sodium-amalgam to a solution of the ketone in dilute aicohol it is a liquid boiling at 210"-211 with partial decomposition.c. s. Propyl-phenyl Ketone. By E. SCHMIDT and E. FIEBERG (Deut. Chem. Ges. Ber. vi 498). KETONE, PROPYL-PBENYL C6H5] CO is obtjainable by the distillation of C3H7 an intimate mixture of benzoate and butpate of calcium ; the crude pro- duct contains also benzene butyrone benzophenone and other substances of high boiling point. By fractional distillation a slightly yellow fluid of pleasant aromatic odour and blxrning taste is obtained boiling at 220"-222" and having the specific gravity 0.990 at 15"; at -20' it is still fluid. A regular increase in boiling point is thus noticeable in ketones of the aromatic family ; thus-Methyl-phenyl ketone boils at 199" Ethyl-phenyl ketone , 210" Propyl-phenyl ketone , 220"-222" whence the difference for CH appears to be about 11".Alkaline bisulphites do not combine with propyl-phenyl ketone ; on oxidation with sulphuric acid and potassium dichrornate it yields benzoic and propionic acids with small quantities of acetic acid and carbon dioxide ; sodium amalgam converts it into the corresponding pinacone-CGH.+2H-C3H7 0 I 0 CGH+.2H-C,H,,* which crystallises from alcohol or better from acetone in needles melting at 64" ; simultaneously with this product pseudobutyl phenyl alcohol is formed (phenyl-propyl-carbinol CH C3H7? C. R. A. W.). { 2 Bromine acts on propyl-phenyl ketone giving a combination-product which yields hydrogen bromide on distillation and another product not yet fully investigated.C. R,. A. W. C(C6HB) (C3H;) (OH) a Que1.y ? I C(CGHj) (CSH;) (OH).-C. K.A. W. ABSTRACTS OF CHEMICAL PAPERS. Coerulignone and its Derivatives. By C. LIEB E R 3% A x N (Ann. Chem. Pharm. clxix 221-251). THIS memoir is principally a summary of the papers already published by the author on this subject (see last volume pp. 70 and 1033) con-taining however some additional particulars. Coerulignone is readily changed by reducing agents into hydro-coerulignone yielding a colourless solution with zinc-dust and alkalis or with sodium-amalgam and with tin and hydrochloric acid a white powder ; with zinc-dust at a red heat an oily hydrocarbon is produced wliich solidifies partly on standing.The author prefers hydrochloric acid and ziuc-dust for preparing large quantities of hydrocoerulignone The latter is slightly soluble in ether and almost insoluble in carbon bisulphide ; when heated it yields a distillate which crystallises but at t,he same time the greater part of the substance becomes carbonised. When coerulignone is dissolved in warm concentrated potash-solution a yellow potassium-salt insoluble in the alkaline solution is deposited in a short time ; this decomposed by hydrochloric acid yields a preci- pitate consisting chiefly of hydrocoerulignone. The author also describes two compounds intermediate between coerulignone and hexoxydiphenyl formed by the action of sulphuric acid on coerulignone or hydrocoerulignone ; the former when treated with concentrated sulphuric acid becomes warm and the blue colour at first produced passes into brown.The product washed with cold water and crystallised from spirit in which it is very soluble forms yellow needles ; these dissolve in concentrated sulphuric acid with a brownish red colour and their aqueous and alcoholic solutions give a deep brownish red with ferric chloride. This compound is very difficult to purify ; its composition is represented by the formula C15Hld06, or coerulignone in which one atoni of methyl is replaced by hydrogen ; (0CH3)3 the acetyl-derivative has the formula C,,H { (OC&&O),' By the 'On-tinued action of sulphuric acid on the new compound and also on coerulignone or hydrocoerdignone especially when aided by a gentle heat, the mixture acquires an intense magenta colour ; on adding a large quantity of water a red precipitate IS obtained which speedily becomes brown.It is an amorphous orange-coloured powder having the composition CI1HI2Os or coerulignone in which 2 at. methyl are replaced by hydrogen. These compounds howet-er have not yet been converted into hexoxydiphenyl. C. E. G. Anilidacetonitril. By C. E li G I E R (Deut. Chem. Ges. Ber. vi 1003-1005). THJS compound is readily formed by the action of aniline on mono-chloracetonitril which was prepared by distilling chloracetamide with phosphorus pentoxide and rectifying the product twice over the same substance.Monochloracetonitril boils at 126"-12 7" not however without decomposition as Bisschopixick has stated some hydrochlorje acid being always formed. On heating it with an ethereal solutioil of ORGANIC CHENISTRY. aniline in sealed tubes to 80°-900 and evaporating the ether impure anilacetonitril is left behind as a brown syrup. It is freed from aniline by shaking the ethereal solution with dilute acetic acid evaporating the ether and dissolving the residue in strong hydrochloric acid. By adding sodium carbonate to the solution first a brown resin is preci-pitated and then the base which is again treated with acetic acid &c Anilidacetonitril NC.CK,NH( C6H5),is a thick yellow liquid wliich is decomposed by heat ; it is insoluble in water and dilute acids but dissolves in alcohol ether and concentrated acids.The hydrochloride is a white crystalline mass which is decomposed by water; the sulphate nitrate and oxalate do not crystallise. On heating the base with potsash ammonia is given off and a compound is formed crystal- lising in fine needles and consisting probably of phenylglycocine. c. s. Dinitrosulphocarbanilide. By A. B rtG c KN E R (Deut. Chem. Ges. Ber. vi 1103). WHEN paranitranihe is digested for a long time with the corresponding amount of carbon disulphide sulphuretted hydrogen is evolved and YHCH NO dinitrosulphocarbanilide CS { ~H:C-,R~NO~ is formed. This com-pound crystallises in needles melting at 160"-161° soluble in alcohol and ether almost insoluble in water.The corresponding mononitro-compound pears to result when phenyl-sulphocarbimide and nitran iline act on one another but is difficult to obtain in a suBciently pure state for ana- lysis. C. R. A. W. Oxethenaniline. By E. D EM o LE (Deut. Chem. Ges. Ber. vi. 1024-1026). Tim compound which Ladenburg obtained by heating oxethenepara- midobenzoic acid is also produced by the direct combination of ethene oxide and aniline taking place slowly at the commoii temperature and more quickly at 50". Oxethenaniline N C6H5 ,is a colourless some- { :€&.OH what viscid liquid which dissolves sparingly in water alcohol and ether freely in chloroform. Its aqueous solution is coloured green by bleaching powder.It boils at 280° and has at 0" the sp. gr. 1-11. Its salts are very soluble and deliquescent. [NH( C6H5) (C,H*.OH)ClH] + PtCl forms reddish brown granular crystals which are soluble in absolute alcohol and insoluble in ether Waber decomposes it platinum separating out and a green solution being formed. c. s. ABSTRACTS OF CHEMICAL PAPERS. A New Base from Nitrobenzanilide. By H. H~~BPITER and G. RETSCHY (Deut. Chem. Ges. Ber. vi 1128). THIScommunication refers to a base having the composition Cl3Hl0N2 and already alluded to by the authors (Deut. t%e???. Ges. Ber. vi 798 ; Chem. SOC. J.,xxvi 1147). The double tin-salt obtained by the action of tin and hydrochloric acid on monobenxolated diamido-benzene forms small almost colourless needles ; and by treating this salt with hydro- sulphuric acid the 7cydrocI~Zoride,C1,HlJV2,HCl is obtained in colour-less needles.It must he crys tsllised from dilute hydrochloric acid otherwise it becomes basic on recrystallisation. The free base obtained by adding ammonia to a solution of one of its salts forms colourless needles almost insoluble in water slightly soluble in benzene or chlo-roform and easily soluble in alcohol. It melts above 240". The plntimm suM (C,,Hl,N,),(HCI),PtC1, forms yellow needles. The O,, nitrate C1,HE0N2,HN forms colourless needles. The sdpphate (C,3H,oN2),H2S04, forms tufts of colourless needles. The nitration of the base has been effected. T. B. Nitro-and Amido-benzylarnlde. By J. STRA KO sc H (Deut.Chem Ges. Ber. vi 1056-1063). THEauthor obtains the nitrobenzyl chloride employed in the preparation of these compounds by gradually adding benzyl chloride to fuming nitric acid cooled to -15" until the mixture has a dark brown colour ; it is then poured into cold water and the precipitate after being washed and pressed is crystaflised from alcohol. The attempt to pre- pare nitrobenzylnmine by the action of alcoholic ammonia on this sub- stance wa8 unsuccessfd but more favourable results were obtained by the substitution of aqueous ammonia ; the brown mass resulting from their action on one a3other at 100" is in great part soluble in hydro- chloric acid yielding the hydrochloride of th; seco&h-y nitrobe?axyldmi,m, g:zggjgz> NIH.HC1. It crystallises in lustrous yellow prisms which melt at 'LI2" and are difficultly soluble in water alcohol and hot hydrochloric acid.With platinic cbloridc it forms a double salt (C14H13N304HCI).LPt~l~, crystallising in pale yellow needles almost insoluble in alcohol and in hot water. The free base obtained by pre- cipitating the hydrochloride with soda crystallises from alcohol in large shining plates of a yellow colour. These melt at !No,and are soluble in hot alcohol but insoluble in water and in ether. It seems to be capable of being distilled without decomposition. After the secondary nitrobeiizylamine has crystallised out from the solution obtained by treating the original product with hydrochloric acid a small quantity of an isomeric base may be precipitated from the mother-liquors by soda.Its hydrochloride crystallises in-white nodules which melt at about 1'73" and are moderately soluble in alcohol hot water and hot hydrochloric acid. The free base likewise crystallises in yellow nodules which arc insoluble in water. The portion of the original producc insoluble in hydrochloric acid ORGANIC CIIEXISTR'17. C,H,NO 1CH2\ consists of tertiary mitrobemyZarnine C,H,NO 1CHI,-N and may be C,H,NO,) CH2/ purified by crystallising it first from nitrobenzene and subsequently from glacial acetic acid. It forms white lustrous needles which melt at 163" and are insoluble in water or in ether and only very slightly soluble in hot alcohol. It is also formed by digesting secondary nitro- benzylamine with an alcoholic solution of nitrobenzyl chloride at 100" for about four hours.As the action of aminonia on benzyl chloride yields all three amines it was to be expected that the primary nitrobenzylamine would be found along with the other bases. This however was not the case neither could it be procured from the secondary nitrobenzylamine by treating it with hydrochloric acid at a high temperature. Se'econcJaq a~)z~~~)~en~la??z~~e is produced when the corresponding nitrobenzylamine is reduced by tin and hydrochloric acid. The hydro- CGHANH ]CH?\ chloride C,H,NH,) CH, NH,3HCI obtained by decomposing the tin double salt with sulphuretted hydrogen crystallises in white lustrous scales which are insoluble in alcohol and ether easily soluble in water less so in hydrochloric acid.The platinum double salt, 1c7H6NE2)2} N.3HCl.PtC14 crystallises in large reddish yellow needles easily soluble in hot water but insoluble in alcohol. The free base precipitated from an aqueous sollition of the hydrochloride by soda ci*ystdlises in glistening needles or plates which melt at 106" and are soluble in hot water alcohol and ether. It may be distilled without! decomposition and becomes colourecl by exposure to the air. The sulphate and nitrate form easily soluble needles. C,H,NI-I,] CH,\ Tertiary amz'dobenxylmti?~e,C,,H,$T = C6H,NH2] CH,-\N. The pro-C,H,NH ) CH,/ longed action of tin and hydrochloric acid on tertiary nitrobeiizylamine cause the tertiary amido-compound at first formed to split up into secondary amidobeuzylamine and toluidine ; but if the action of the reducing agent be continued only until the nitrobenzylainirie has dissolved and the tin be at once precipitated by snlphuretted hydrogen a solution is obtained from which soda precipitates the white crystai-line tertiary rt;widobeneylamine.It forms brill :ant octohedrons ~hich melt at 136",and are insoluble in water but readily soluble in hot alco- hol or ether ; it distils unchaiiged. The hydrochloride crystallises in yellow needles which are exceedingly soluble in water hydrochloric acid and alcohol. The platinum-compound is an amorphous yellow compound. The author was unable to obtain primary amidobenzylamine either by treating nitrobenzyl chloride with ammonia and aiumouium sulphide or by the nitration of acetobeiizylarnide ; but by the action of nitro-benzyl chloride on excess of aniline he succeeded in preparing nitro- benzylphenylamine.The product of the reaction when treated wit11 ftydrochloric acid solidifies to a crystalline pulp from which the aniline hydrochloride is removed by means of warm dilate hy drochluric wid ABSTRACTS OF CHEMICAL PAPERS. leaving the hydrochloride of the new base. Nitrobenyl.plLen~Za~~ai?~e hydrochloride CsH4N02)CH2-NEH,HC1 crptallises from hot con-ccntrated hydrochloric acid in white shining scales which are soluble in absolute alcohol but are decomposed by water into hydrochloric acid and the free base The platinum compound forms brown shining scales which are soluble in water and in hydrochloric acid.The free base crystallises in golden-yellow needles which melt at 68" and are soluble in hot alcohol ether and benzol but insoluble in water. Amidobenxy~phelnylnmi~ze.-This base cannot be prepared by re-duction of the nitro-compound with tin and hydrochloric acid the reaction proceeding much further ;but by digesting nitrobenzylplienyl- amine with ammonium sulphide at 100"for a short time distilling off the excess of sulphide and repeatedly crystaflising the product from con- centrated hydrochloric acid arnidobenzylphenylamine hydrochloride C,H4NH2) CH -NHC,H 2HC1 may be obtained in brilliant needles which are easily soluble in alcohol and in water less so in hydrochloric acid. The platinum salt is dark yellow and anzorphous.The free base is precipitated by soda from n solution of the hydrochloride in glistening scales which melt at 88" and are readily soluble in ether alcohol and benzene. c. E. G. The Oxidation-Products of Caryophyllin. By E. MYL I u s (Deut,. Chem. Ges. Ber. vi 1053-1056). THEauthor finds that the properties of pure caryophyllin are those usually assigned to it except that it is completely insoluble in alkaline solutions. Moreover he proposes to double the original formula making it C20H3202, as the temperature at which it sublimes 285" is much higher than that at which its isomeride camphor ClOH,,O,distils namely 285"-250". On adding caryophyllin in suflticient quantity to fuming nitric acid it dissolves with evolution of heat and after a short time the mixture solidifies to a pulp of microscopic white needles.When it is purified, first by solution in ammonia and reprecipitation by an acid and then by repeated precipitation of its alcoholic solution by water a new acid is obtained in ari amorphous condition. Cnryophyllic acid C20H3206, dis-solves in water with difficulty readily in alcohol ether and glacial acetic acid from all of which it separates in an amorphous state. It may however be crystallised from fuming nitric acid. ,Sod.C:.um caryoyhyllate CzoH,,~a~~6.-Caryophyllic acid decomposes sodium carbonate and on evaporating the solution to dryness and extracting with alcohol an amorphous sodium-compound of the new acid is obtained. Xilver caryophyllate CzoH3oAg2O6, is obtained as a yellow amorphous powder on precipitating a solution of the sodium salt with silver nitrate PHYSIOLOGICAL CHEMISTRY.Barium caryophyZtate C20H30Ba06+ 1$H20,is a yellowish precipi- tate insoluble in alcohol diHLicultly soluble in water. The author concludes by observing that although caryophyllin differs in its physical properties from camphor yet there is a certain resemblance since both substances yield acids by oxidation with nitric acid. C. E. G. The Composition of Cascarillin. By C. and E. MYLIIJS (Deut. Chem. Ges. Ber. vi 1051). CAscArtnxA bark contains a crystallisable bitter matter named by its discoverer (Duval) cascarillin. Tuson in his account of ricinine a base obtained from Ricinus comwzunis says that it is very similar to casca- rillin.The authors deny this for in the first place cascarillin contains no nitrogen ; in the second ricinine is a well characterised base while cascarillin is a neutral body and behaves itself indifferently both to acids and bases. The empirical formula of cascarillin is C6H,02. A rational formula has not yet been found. Bromine acts energetically on cascarillin but the resinous product of the reaction was not obtained pure. A nitro-product gave unsatisfactory numbers on analysis. On boiling cascarillin with dilute acids no splitting up takes place it is therefore not a glucoside. G.T. A. The Constitution of Saffranin. By S. E. PHTLLIPS (Chemical News xxviii 30).

ISSN:0368-1769    

DOI:10.1039/JS8742700037

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年代:1874

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PHYSIOLOGICAL CHEMISTRY. fhy si010gi c a1 Chemistry. Investigation of Hmsn Bile. By 0.JACOBSEN (Deut. Chem. Ges. Ber. vi 1026-1029). OUR knowledge of human bile is still incomplete owin to the difliculty of obtaining fresh bile in sufficient quantity. The file used for this investigation was obtained from an abscess of a strong healthy man It formed a clear dark yellowish-green and perfectly neutral liquid having at 17.5" the sp. gr. 1*0105-1.0107 and containing 2.24-2.28 per cent. of solid matter. Neither dextrose nor urea could be found in it but bilirubin and biliverdin were present. The ash con-sisted of :- In 100 pte of ash. In 100 pts. of dry bile. KC1 ............ 3-69 1.2% NaCl............ 65.16 24.508 Na2C03.......... 11.11 4.180 Na3POa..........15.90 5.984 Ca3(PO&. ....... 4.44 1.6 7'2 100.00 37.620 VOL. XXVII G ABSTRACTS OF CHEMICAL PAPERS. It contained also small quantities of iron silica magnesia and a trace of copper which is found only in that portion of the bile which is insoluble in alcohol. The portion of dry bile which dissolves in ether contained:- Cholesterin ........................ 2.49 Fats and a little sodium oleate ........ 0.44 Lecithin (calculated from the amount of phosphorus). ..................... 0.21 -3.14 per cent. In the alcoholic solution were found :-Sodium glycocholate ................ 44.8 Sodium palmitate and stearate ........ 6.4 -51.2 10 per cent. is insoluble in ether and alcohol. Neither sulpbates nor the least trace of taurocholic acid could be found which however were present in varying quantities in the biles of persons who had died of various diseases; in one case even 14.2 per cent.of sodium tauroclrolate was present in the dry bile. It appears that the proportion of the two cholic acids varies also in a similar way in the biles of animals. Thus in several cases the author found that taurocholic acid preponderated in the bile of the ox. Choline appears also to be a normal constituent of human bile for on boiling it either when fresh or purified with barytai water trime- thylamine is always formed. c. s. Nuclein. By J. W. M~LLER (Pfliiger’s Archiv. f. Physiologie viii 190-194). ANexperimental critique on Miescher’s researches (Chem.Soc. J. [21 ix 742). The author concludes (1) that nuclein is a mixture of sub-stances ; (2) that it is a mixture of conjugate compounds of phosphoric acid with albuminous or albuminoid bodies ; (3) that it is not settled that nuclei is confined to the nuclei of cells. T.S. The Chemical Reactionof the Central Organs of the Nervous System. By R. Gs cH L E I D E N (Pfluger’s Archiv. f. Physiologie, viii 171-180). THISinvestigation was undertaken in order to test the statements of Haidenhain and Liebreich that the grey matter of the brain is acid in its reaction whilst the conducting fibres as well as the peripheral nerves have a neutral or feebly alkaline reaction. Plates of white clay or gypsum imbued wit,h litmus were employed in the author’s experiments and various animals were operated on The brains of seventy animals-horses dogs cats &.-were tested immediately after removal from the skull and found to have the grey PRPSIOLOOICAL CHEMISTRY.83 matter acid and the white matter neutral or slightly alkaline. In one instance only-in an oedematous brain- was the grey matter alkaline in reaction to litmus. The acid reaction of the grey substance is not a post-mortem phenomenon. The grey matter of the spinal cord was also found to be acid and the white substance neutral or feebly alkaline. These reactions correspond with the histological character of the grey and white subst'ances respectively. The grey matter owes its acidity to the presence of ganglion cells ; and these wherever found in quantity hare an acid reaction.It is impossible however to ascer-tain the reaction of these microscopic cells individually. If the grey and white substances be kept apart after death they re- tain their respective reactions of acidity and neutrality or alkalinity. Gschleiden thinks that the acid reaction of the grey substance is due to the presence of free lactic acid. T. S. Influence of the Addition of Fat to the Food on its Digesti-bility. By V. Ho F M E I sT E R (Landw. Versuchs- Stationen xvi 347-383). FOR these experiments two pairs of l& year old South Down wethers were selected each pair being considered as a single average animal. Each pair received daily 1340 grams of meadow hay and 670 grams of elovcr hay besides common salt and olive oil mixed with the food in the quantities indicated in tbe following table which shows the per- centage of the constituents of the food digested during the different periods of the experiments :-Pair A.Period. Food. A~ ~~~~$ ~ Fat. Fibre. ~h($;:&. ~-I. 13 days . . Hay and 10 grams salt 54 -7 53 *1 4'7 *9 57 -1 54 '0 11. 13 days . , 30 grams oil and 54.5 45 *1 62 '3 51 *1 57.p -! grams salt } 111.17 days. { , 45 grams oil and } 56 *5 51.4 68.6 52 *8 58.3 grams salt , 60 grams oil and IT.17 days . { grams salt } 58 *1 57 -4 77 -1. 55 *1 57 -1 TT. 14 days . , 60 grams oil and 57 -0 53 -1 79 *5 55 *7 53.1 2o grams salt } ABSTRACTS OF CHEiMCAL PAPERS. Pair B. Period. Food. Carbo-hydrates.Hay and 10 grains salt 57 -3 53 -9 62 -0 53 -9 59 -6 11.13days . , 30 grams oil,^ and 62.1 58.2 72 -15 59 -4 63 *5 I' 7 gr~mssalt } 111.17 days. { , 45 grams oil and 60.0 56 *O '71*6 5'7 *6 60 *75 grams salt } , 60 grams oil and 63.0 61.9 74.9 .56% 65 -2 IT.17 daye . grams salt } V. 14 days . , 60 grams oil and 57.1 52 *7 75.9 57 *6 55.4 2o grams salt } The clover used was harvested in August 1867 and then contained 17-12 per cent. of albumino'ids but at the commencement of these ex- periments in-March 1870 they had declined to 16.03 per cent. The digestibility of clover also decreases by keeping as shown by previous experiments of the author in which the digestibility of the constituents fell from the time of cutting in six months as follows :-Organic matter Albumino'ids Fibre Carbohydrates per cent.per cent. per cent. per cent. September 1866 .. 66.8 68.4 51.2 73.4 *'February 1867. .. 58.7 65.0 46.2 63.1 After allowing that 56 per cent. of the albumino'ids 58 of the fibre and 64 of the carbohydrates of the meadow hay were digested the cal- culated percentage digestibility of the clover hay in Period I on the average of both pairs of animals was organic matter 52.0 nlbunii-nojids 50.7 fibre 50.4 and carbohydrate 40.7 showing that its diges- tibility was much impaired by keeping owing both to chemical change and to loss of the most tender parts by powdering. G. Kuhn (Lmzdwirth. Verswchs-Stat.,xii 371) and Stohman (Zeitschg-. jiir Biologic vi,.pt. 2 27) have shown that the addition of fat does not increase the digesti- bility of meadow hay therefore the increased digestibility shown in these experiments must be due to the clover.Allowing the same digest)ion as before to the meadow hay the digestion of the clover with 60 grams of oil Period IV which was rather the most favourable experiment was organic matter 61.2 per cent. albuminoids 63.7 fibre 31.7 and carbohydrates 55.0 per cent. These numbers show a con-siderable increase on those for Period I and with the exception of that for carbohydrates agree well with the average percentage digestibility of clover in Wolff's experiments viz. organic matter 60.26 alburninoids 61.65 fibre 51.5 and carbohydrates 65.3. Unfortunately no direct experiments were made with this clover.The live weight of the animals altered but slightly during the experiments. The author con- cludes that the addition of 3 lb. of oil to 18-20 lb. organic matter in the food per 1,000 Ib. live weight of animal increases the digestibility of the organic matter of clover hay especially of the albumino'ids and PHYSIOLOBICAL CHEMISTRY. soluble carbohydrates raising them in the case of old clover hay to nearly their original standard. The oil added was digested in a high degree. The addition of 5 grams of salt per head to the food did not materially alter the digestibility but 10 grams per head slightly decreased it. E. K. Digestibility of the Fat of Hay. By E. SCHULZE (Landw. Versuchs- Stationen xvi 329-33.5). Trm author gives a list of the results of different experimentms on the digestibility of the fat of hay showing that the digestibility differs much in different hays and also in the same hay in different experi- ments ; with sheep it ranges from 8.5 to 60 per cent.The percentage of the ether extract soluble in cold alcohol from different samples of hay does not vary to any great extent being about 70 in the experi- ments of both Khig and Schulxe. This would indicnte that a part of the fat soluble in cold alcohol and also of the insoluble portion is digested though as shown by Konig’s analyses of the fat in the excre- ments those substances which contain least carbon are in both cases most easily digested. It is also probable that the difference in the progress of digestion in different experiments has more influence on the ether extract than on the other constituents of the food No satisfactory results on the assimilation of the fat can be expected except by direct experiments.E. I(. Further Researches on Abiogenesis. B;y D. H u I z I B G A (Pfliiger’s Archiv. f. Physiologie viii 180-189). THISpaper is in continuation of a previous memoir in the same Journal (vii 549). The author finds that the differences he had observed in the facility with which bacteria are developed in solutions of anhydrous and hydrated glucose respectively depend upon the pre- sence or absenceof another body intermediate between starch and glucose. This body forms an opalescent solution with water and is turned of a violet colour by iodine.Huizinga is of opinion that the only datum for determining the life of bacteria (Bacteria termo at least) is the propagation of the organism. T.S. Further Observations on the Temperature at which Bacteria Vibriones and their supposed Germs are killed when exposed to heat in a moist state and on the causes of Putrefaction and Fermentation. By H. C. BASTIAN (Proc. Roy. SOC.,xxi 3%-339). Experiments on the Development of Bacteria in Organic Infusions. By C. C. PUDE (Proc. Roy. and E. RAYLANKESTER SOC.,xxi 349-358).

ISSN:0368-1769    

DOI:10.1039/JS8742700081

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年代:1874

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ABSTRACTS OF CKEMtCAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Influence of Coal Gas on the Growth of Trees. By SP~TH (Landw. Versuchs-Stationen xvi 336-341). and NEYER THE experiments in the Berlin botanical garden (Chem. Xoc. JOWIL. [2] xi 647) on this subject have been continued and the previous results confirmed. .It is also shown that the same quantity of gas applied during the winter has a much less injurious effect than when applied during the period of growth. It was found that when 0.0185 cubic meter (6 cubic feet) of gas were passed daily during the spring into a plot of 14.19 square meters (153 square feet) by 0.785 meter (2* feet) deep on which 17 trees were growing 6 of the trees were dead at the end of seven weeks and after 11 weeks only two were living and these in a sickly state.Lime and elm trees appear to resist the injurious action longest. E. R. Beech Leaves. 137 J. A. WANKLYN (Chemical News xxviii 186). BEECH leaves yield a fragrant decoction and 100 parts of the dry leaves give 20.8 parts of extract which when burned yields 2.4 parts of ash and it was found that this ash contains a notable proportion of man- ganese. The author points out the importance of studying the ashes of leaves as it is by no means improbable that new elements may be thus discovered. T. €3. Tea. By J. A. WAHKLYN (Chemical News xxviii 186). ATTENTION is cdled to the fact that Zoller found 4.38 per cent. of ferric oxide in the ash of genuine tea and in treating of the adultera- tion of tea with iron filings or other preparations of iron it is necessary to bear this in mind.Zoller also found that genuine tea yielded 5.63 per cent. of ash and the analysis of seven samples of airdried com-mercial tea confirmed this result the average amouut of ash being 5.75 per cent. The determination of the total asb soluble ash and insoluble ash of tea will often afford satisfactory evidence of adulteration either with spent tea or with foreign leaves. Two grams are sdcient for the deter- mination. The results of the examination of various leaves are em- bodied in the following table :- VEGETABLE PHYSIOLOGY AND AGRICULTURE. Percentages of Ash in the dried leaves. Total. - Soluble. 1 Insoluble. Common tea.. ..........5 -92 3 -55 2 '37 Paraguay tea ........... Beech ................. 6 -28 4-52 4 *22 2-00 2 -06 2 -52 Bramble ............... 4*53 1*84 2 -69 Raspberry.. ............ Hawthorn.. ............ 'I734 8.05 1'72 3 -78 6 -12 4-27 Willow ................ 9-34 4-16 5 -18 Plum.. ................ 9 -90 5-66 4 *24 Elder.. ................ 10-67 3*19 'I-48 Gooseberry ............ 13.50 ? .83 5 -67 T. B. Micrographic and Chemical Researches on the Textile Fibres of certain Bromeliaceae. By M. SCHLESINGER (J. Phaiw. Chim. [4] xviii 161-167). THEfibres of Billbergia Leopoldi are simple and regular in form ; their walls are parallel and everywhere of the same thickness. A cavity, which is nearly always less than half the diameter of the cellule is always present.The diameter of the fibres is small varying from 6 to 13 millimeters and their length is considerable so that they are specially suitable for fine tissues. When acted upon by freshly prepared ilmmoniacal oxide of copper the fibres undergo a curious change. Some of them smell out and turn round their own axis forming ring- lets and knots ; others puff out in an undulatory manner and under the prolonged influence of the reagent lose all their cellular membranes while their internal membranes are decomposed. The external mem- brane alone remains as a bluish tube. A dilute alcoholic solution of iodine followed by a drop of very dilute sulphuric acid gives to the fibres a reddish-yellow tint ; nitric acid colours them yellow and con- centrated sulphuric acid slightly decomposes them.A solution of caustic soda readily isolates the fibres. In ~~a~~ocl~ordion tinetorum the fibres have a maximum diameter of about 14 millimeters and the length of the cellules is very small varying from 2 to 6 millimeters. The ends of the cellules are rather blunt rarely pointed. As the fibres have not very thick walls the cavity is large and sometimes occupies half the diameter of the cellule. This however is irregular and gives to all the fibre an irregular form. Ammoniacal oxide of copper causes a great swelling of the fibre without however changing its form ; concentrated sulphuric acid dis- solves it completely ; nitric acid colours it yellow and a solution of caustic soda causes the walls to swell so that the cavity is reduced to a fine line and sometimes disappears altogether.J. B. ABSTRACTS OF CHEMICAL PAPERS. Analysis of the Brazil Chestnut the Fruit of Bertholettia, excdsa. By B. CORENWINDER (J. Pharm. Chim. [4] xviii, 14-18). THE following results were obtained and the author compares them with those previonsly found by him in an analysis of the arachido kernel or ea.rth nut (Arachis Iypogma) :-Kernel of Kernel of Brazil chestnut. earth-nut. Water .......................... 8.00 6.76 Oil.. ............................ 65.60 51.75 Nitrogenous substances. ........... 15.31 21-90 Organic matter not nitrogenous .... 7.39 17.66 ......... 1.35 Phosphoric acid -Lime potash silica &c.. ... 2-36) 3-70 !:::} 2.03 100*00 100*00 The percentage of nitrogen in the kernel of the Brazil chestnut is 2.45.The author sugests that the Brazilian chestnut might be more ex- tensively used in Europe. Although its oil soon hecomes rancid and unfit for human consumption it might be utilized in the manufacture of soap &c. and the pressed cake if not available as food for cattle would be a valuable manure. J. B. Analysis of some Cinchona Barks Grownin Jamaica. By J. E. DE VRIJ(Pharm. J. Trans. [3] iv 121-123). THESE barks were examined by the aid of the chemical processes pub- lished by the author supplemented by the use of the yolariscope according to the method also devised by him. He now introduces the following modification of his process. To the solution of the part insoluble in ether a solution of sodium iodide is added and after separating the hydriodide of quinidine-if that alkaloid be present-a solution of bitartrate of sodium is poured into the filtered liquid which precipitates the bitartrate of cinclionidine.The author also points out that it is a mistake to regai-d that portion of the alkaloyds soluble in et#her as consisting wholly of quinine. The following table gives the quantity of quinine contained in 3.00 parts of the different barks examined :-Pure Crystallised quinine. sulphate. Cinchona succirubra (Cold Spring) . . 1.958 == 2.50 C. calisaya.. ...................... 1.265 = 1.612 C. pahudiana.. .................... 0.964 = 1.229 C. officinalis ...................... 0.46 0.586 C.succirubra.. .................... 0.463 0.59 C. micrantha.. ...............:.... ? - Several of these barks contained a riew crystallisablc lavogyrate alkaloid. W. A. T VEGETABLE PHYSIOLOGY AKD AGRICULTURE. Analysis of some Barks of Cinchona Officinalis and its Varieties Cultivated at Ootacarnund. By J. E. DE VRIJ (Pharm. J. Trans. [3] iv lt;l-l84). 100 parts of bark dried at 200" C. contain :-kgstallised kninovic Mixed ?Ye sulphate .lkaloXds pinine. If quinine. acid. Var. angzcstzlfolia grown at Doda- betta elevation ..............} Ditto ditto ............ Seedling of C. o&inalis grown at elevation of 6,200 feet ........ } Similar variety tooNo. 3 .......... Renewed bark of C. o$icinalis; 18 months old ; 7,800 feet........ } Same renewed bark ; 15 moiiths old. Same; 28 months old ............ Dodabetta original C. oflvinalis branch-bark ................1 Same ; small branch-bark.. ......... Same stem-bark mossed.. ........ Same ; uiimossed ................. Large-leared seedling of c. ofiei-nalis; eleration 8,200 feet .... } Dodabetta C. oficilzalis; feet; exposed place .......... 874001 Same sheltered .................. Neddiwattum C. qficinalis ; posed position ; 5,800 feet.. .."lt-} Dodabetta C o$icinaZis ;manured .. The same unmltnured ............ 10 -130 8 -000 lo -199 0 -920 11 -960 9 -100 11 -600 0*761 6 *050 2 *286 2 -914 0 -188 10'670 3 ,707 4 925 0.250 4'630 2 '470 3 *I36 1 -050 8 -140 10 *ooo 4 *530 2 *917 5 *775 3 -718 iot deter-mined.1.612 3 *115 1 "760 2.243 0*400 0 *984 not determined. 0 '227 '7 *285 4 981 6.095 0-822 4 -785 2.600 3 *314 0*400 2.860 none. - 0 -345 8 920 2 '33!5 2 *989 0 -170 8 -424 5 *340 6 * SO? 0.684 5 -726 1.410 1-79? 0 -620 11 *660 8.366 6 -950 3 "750 8 *860 4,780 0,950 0 -758 The rcsults of the analysis of number 14 lead to the conclusion that it cannot be a variety of Clinchona oflcinalis. According to Mr. J. E. Howard it is probably Cinchona erythrawta. W. A. T. Javanese Cinchona Barks. By J. JOBST (Deut. Chem. Ges. Ber. vi 1129-1133). THISpaper contains a comprehensive account of the marks prices and alkalo'idal contents of a number of samples of cinchona bark from Java which were imported at Amsterdam in May 1873.The results of the examinations show that some samples of C&zchona calisuya are very rich in quinine samples marked D and E yielding 3.20 and 7.62 per cent. of quinine sulphate. Other samples of C. calisnya and samples of 0.harskm-liana yielded somewhat less satisfactory results while C. cdoptera yielded Qnly 0.99 per cent. of quinine sulphate. T,B. ABSTRACTS OF CHEMICAL PAPERS. Persian Opium. By P. CARLES (J.Pharm. Chirn. [4],xvii 427-429). A NEW opium bearing this name is now found in commerce. It occurs in conical cakes weighing about 440 grams; its odour is similar to that of green coffee but when heated resembles chocolate. It mixes more easily with water than Smyrna opium and yields 53 per cent.of extract. When the extract has been concentrated it becomes on cooling nearly solid from the separation of crystals of narcotine. Analysed by Fordos’ method the opium yielded morphine 8.4 per cent. and narcotine 3.6 per cent. When only half the ammonia required by this method is added almost the whole of the narcotine crystallises by itself the morphine remaining in solution. By the fermentation test the presence of sugar was established. This opium differs a good deal from the Persian opium described by Guibourt. R. W. The Ash of Diseased Potatoes. By A. S. WILSON (Chem. News xxviii 91). THEpotatoes examined were ‘‘Regents,” grown in the wet season of 1872 and very much diseased. The adhering soil was carefully re- moved from the cavities with a knife.The (fresh ?) sample gave 1-07‘ per cent. of ash which had the following composition :-K. Ha. Mg. Cn. Fe20,. P205. SO3. C02. C1. SiOP 0. 44-61 ‘25 2.36 1.12 *53 14.48 5.57 15.80 1.31 2.89 11*22=100*10 The author compares his results wit’h those of EIannay (p. 930 of this volume) and concludes that potash and sulphuric acid are in- creased to some extent and lime and magnesia diminished in diseased potatoes.* R. W. Notes on Guano. By E. CHEVREUL. 1. (Glompt. rend. Ixxvi 1376-7382).-0ccurrenee of avic acid in guano (see p. 1052 of last volume). 2. (COW@.remi. lxxvi 1500-1508) .-A sample of compact guano of crystalline aspect sent by Messrs. Dreyfus to the Central Society of Agriculture of France evolved carbon dioxide when treated with water (1 gram yielding about 10 c.c.) leaving in solution ammonium car- bonate and a crystallisable subst,ance containing avic acid whilst brown flocks separated which consisted of calcium phosphate and organic matter.A transparent crystalline mass discovered in a specimen of guano, proved to consist of nearly pure ammonium phosphate. Attention is drawn to the necessity of a proximate analysis in com-paring the value of different kinds of manure and also to the very advantageous characters which guano possesses as a fertilising agent * These conclusions will scarcely be substantiated if the results of Hannay and Wilson for diseased potatoes are compared with the mean composition of sound potatoes given by E. Wolff. ’ It seems very improbable that the entrance of a fungus should alter the ash constituents of the tuber unless time and moisture allow diffu-sion from without to take place.That a lack of ash constituents is not the predispos- ing cause of disease is shown by numerous field experiments.-R. W. ANALYTICAL GHEXISTRY. owing more particularly to the above-meo tioned property of yielding ammonium Carbonate and free carbonic acid by the action of water. The author considers that avic acid might serve as a certificate of the genuineneris of a reputed guano. 3. (Compt. remd. lxxvii 1!55--157) .-On examining the various ammonium carbonates to ascertain which of them conferred upon guano the property of evolving carbon dioxide on contact with water tlie author found that the bicarbonate whether prepared by saturating liquid ammonia with carbon dioxide or by exposing the sesquicarbonato to the air exhibited this reaction.4 5 6. (Cow@. rerzd. lxxvii 453 569 SUl).-The chief facts of interest in these three notes are :-That the crystallisable material dissolved from guano by cold water consists mainly of ammonium oxalate mixed with yellow red and brown organic colouring matters ; that the residue left after complete extraction of guano with cold water yields avic acid to hot alcohol although the residue originally possessed no smell of the acid ; that prolonged washing does not remove the whole of the ammonium carbonate from the insoluble residue of guano ; that the bones of birds found in guano have entirely lost their cohesion being reduced by trituration with water to orange flocks the water at the same time becoming acid and dissolving some calcium phosphate ; that one of the samples of guano yielded a salt containing calcium ammonium potassium and oxalic acid soluble in a little water but decomposed by a larger quantity with precipitation of calcium oxalate.From a review of his investigations the author concludes that these crystalline substances have been formed by a slow action in the absence of any notable proportion of water. MI. J. S.

ISSN:0368-1769    

DOI:10.1039/JS8742700086

出版商:RSC    

年代:1874

数据来源: RSC

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ANALYTICAL GHEXISTRY. Analytical Chemistry. Examination of the Methods of Water-analysis. By F. TIEMANN (continuation. Deut. Chem. Ges. Ber. vi 1034-1051). THEmethods examined by the author are those which depend on:- i. The conversion of the nitric acid into ammonia in an alkaline solution (F. Schulze Chwp. Centr. 1861 657 833.-Wolf ibid. 1862 379.-Harcourt Chem. Xoc. J. xv 385.-Siewert Ann. Chern. Pharm. 293). ii. The reduction of the acid to nitric oxide and the reconversion of this into acid (Schlosing Awn,. Chim. Ph.ys. [3],. xl 479.-Reichardt Landw. Verszlchs-St. ix 14 150). iii. The reduction of the acid to nitric oxide and the volumetric estimation of the latter (Crum Amz. Chenz. Pharm. lxii 233.-Frank- land and Armstrong (Ihern. Xoc. J.,xx 67.-F.Schulze Zeitschr. anal. Chem. 1870 401). iv. The oxidation of indigo-solution by the acid (Marx Zeitschr. anal. Chem. 1868 412.-Trommsdorf ibid. 171.-Goppelsroder ibid. 1.V-n Bemmelen ibid. 1872 136.-Yinkener Rose’s Analyt. Chem. Sechste Aufl. ii 830 831.-Fischer J. pr. Chem. 1873 57). The method of Schulze in a modified form (of which description is ABSTRACTS OF CHEMICAL PAPERS. given) is preferred by the author to all others. The methods of Reichhardt and Trommsdorf are also strongly recommended ; the latter is a very useful one for approximate determinations. G. T. A. Estimation of Magnesium Manganese and Cobalt. By W. GIBBS(Chem. News xxviii 51). IFthe author’s method be followed of precipitating ammonio-magnesium- phosphate from a boiling solution microcosmic salt is a better precipitant than sodium phosphate and ammonium chloride.The results are accu- rate to 0.2 per cent. of the magnesium present if ammonium chloride be added before precipitation and ammonia after the liquid has cooled. Microcosmic salt gives good results also with manganese. Wohler’s method of separating cobalt from other metals consists in converting it into potassium cobalticyanide and precipitating the solu- tion of this latter with mercurous nitrate. This precipitation is best effected at the boiling heat with addition of mercuric oxide to remove a’ny nitric acid that might be present. The precipitate after wash- ing with hot water containing mercurous nitrate is then treated as Wohler directs.B. J. G. Reduction of Soluble Phosphate in Superphosphate. By C. U. SHEPARD, Jiinr. (Chem News xxviii 51-54; reprinted from the American Chemist). THE author brings together the results and theories on reduced phos- phate which have already appeared in the last volume of this Journal. He then shows their bearing on the value of superphosphate made from South Carolina phosphate. Fresenius’s ammonium citrate soh-tion dissolves & to -& of the phosphoric acid in South Carolina phosphate. It should be noted however that these experiments were made upon exceedingly fine dust. He gives no experiment with the phosphate as it is used in making superphosphate. Nor does he appear to have tried whether repented treatments of the same portion of sub-stance with ammonium citrate always dissolved the same quantity of phosphoric acid (see this Jourrial [23 ix SO).Some superphosphates made from the above phosphate the soluble and insoluble phosphates in which were determined soon after manufacture were again analysed after the lapse of a year the reduced phosphate being then also deter- mined. The amount of this last was always greater than the loss of soluble phosphate which appears to give support to the theory that the alteration of tribasic phosphate is one cause of reduction,. It must be noticed however t>hat no attempt was apparently made to dissolve anything by ammonium citrate in the so-called “ fresh ” sample. Moreover the excess of reduced phosphoric acid over the loss of soluble phosphoric acid is not really so great sometinies by one-half as it appears in the author‘s tables to be.The loss of soluble phosphoric acid is greater than is there stated since the loss of water by keeping the superphosphate must be taken into consideration. The paper con- cludes with a dewription of other changes which take place in super- phosphate when it is kept for some time. B. J. G. ANALYTICAL CHEMISTRY. Modification of Forbes’s r/lethod of Estimating Titanic A&. By W. BETTEL (Chem. News xxviii 93). THEfinely-powdered substance is fused with twelve times its weight of pure acid potassium sulphate. It is then digestedin cold water (about 300 C.C. to a gram of titanic iron ore) ; a~nd the solution filtered from silica is diluted with nine times its volume of water and treated with aqueous sulphurous acid till all the iron is reduced.It is then boiled for several hours the evaporating water being replaced. Titanic acid is thus srecisitated as a white sowder. which is washed with water containiig a tittle sulphuric acid and ignited as usual. B J. G. Separation of Chromium and Uranium. By W. GIBBS(Chem. News xxviii 63). WHENthe chromium esists in the mixture as chromate together with relatively small quantities of chlorides or sulphates and in the absence of any acid such as phosphoric which forms a mercury salt not easily volatilised the chromium is precipitated by Berzelius’s method with mercurous nitrate. This latter should be free from nitrite otherwise a reduction of the chromic acid will take place ; this was erroneously attributed in a former paper (Amer.Joacr. Xci. [Z) xxxix 5Y) to the cmployment of hot solutions. The precipitation is best effected at a boiling heat and the precipitate washed with a hot dilute solution of the nitrate. Precipitation with barium acetate with addition of alcohol also gives good results. Lead acetate gives a precipitate which passes through the paper. When chlorides or sufphates are present in large quantities the solution may be boiled with soda. The sodium uranate is filtered off washed with water containing soda redissolved in hydro- chloric acid and the uranium determined as usual. The chromium. in the filtrate can be precipitated by ammonia after reduotiou for which purpose an alkaline nitrite is preferable to alcohol since the time occupied in Foiling off the latter is saved.When the chromium is not present as chromate in the substance to be aualysed it is converted into sodium chromate by boiling with a slight excess of soda and then adding bromine-water. The small quantity of chromium which in this process is precipitated with the sodium uranate formed in the reaction is separated as described at the beginning of the paper. B. J. G. Direct Estimation of the Constituents of Carbon Compounds by One Combustion. By A. MITSCHERLICH (Deut. Chem. Gcu. Bey. vi,1000-1002). THEcompound is mixed with mercuric oxide and placed in a com-bustion-tube open at both ends. Before beginning the combustion a stream of pure nitrogen is passed through the tube.The carbon dioxide and water are weighed as usual the last traces being driven out in a stream of nitrogen. If nitrogen is present in the compound nitric oxide is formed which is retained in a weighed apparatus containing ABSTRACTS OF UHEMlCAL PAPERS. chromic acid and stannous chloride placed between the water and carbon dioxide absorption bulbs. By weighing the mercury after com- bustion the amount of oxygen used for the oxidation of the carbon and hydrogen is determined and by deducting this amount from that of the total oxygen and hydrogen contained in the carbon dioxide and water respectively the amount of oxygen in the compound is estimated. The mercury is weighed after subliming it into a small weighed tube ; if the compound contained chlorine bromine or iodine this subliniate must be dissolved and the halogen present estimated.Sulphur or phosphorus forms sulphuric or phosphoric acid. In such cases caustic potash is added after combustion to the residue in the tube and the resulting sulphate or phosphate of potassium analysed by the usual methods. M. M. P. 31. Presence of Cyanogen in Bromine. By J. L. PKIPSON (Chem. News xxviii 51). INthe manufacture of iodine a little cyanogen iodide is often produced. It would appear that an analogous bromine compound is formed in preparing commercial bromine since several samples of the latter even when warranted pure gave indications of cyanogen the amount of which was approximately estimated as follows.Iron filings equal in weight to the bromine employed were mixed with five times their weight of water and added slowly to the bromine with stirring. The liquid was rapidly filtered and in a few days it deposited the whole of its cyanogen asferricyanide of iron. This reactiou might be employed in testing with pure bromine for cyanogen in steel. B. J. G. Estimation of Hydrocyanic Acid in Bitter Almond Water By A. KOSTER (Arch. Pharm. [3],ii 510). THE author estimates the quantity of hydrocyanic acid in the pharma- ceutical preparation by Liebig’s method i.e. by the use of a standard solution of silver nitrate so prepared that if the almond water is of the pharmacopeia strength equal volumes of the water to be examined and of the standard silver must be used; if the standard water is too strong the amount of ordinary water that must be added to it to dilute it down to the right strength is thus found by inspection The Phay-macopEia Germanicn prescribes that 1000 parts of bitter almond water should contain 1of hydrocyanic acid ; hence the silver solution must contain 3.148 grams of silver nitrate AgN03 per litre ths titration method corresponding with the equation 2HCy + 2KH0 + AgNO3 = 2Hz0 + RNO3 + KCy.AgCy and the termination of the reaction being known by the production of a precipitate permanent on agitation; this is rendered much more evident if a little sodium chloride solution be used as indicator.C. R. A. W. TECHNICAL CHEMISTRY. The Separation of the Mixed Alkaloids from Cinchona Barks.By J. E. DE VSIJ (Pharm. J. Trans. [3] iv 241). TWENTY grams of powdered and sifted bark dried at looo are mixed with a milk of lime made of 5 grams of dry slaked lime and 50 grams of water. This mixture is slowly dried and then boiled with the strongest possible spirit used in successive portions of 200 c.c. 100 c.c. and 100 C.C. respectively. The liquid is filtered slightly acidulated with wettk sulphuric acid and the precipitated calcium sul- phate allowed to subside. The greater part of the liquid can then be poured off the rest fileered through a small filter and the alcohol recovered by distillation. The residual liquid with washings of the apparatus is poured into a capsule and heated on a water-bath till all the spirit is expelled then filtered from the mixture of quinovic acid and fatty substances which are deposited.The filtrate reduced to a small volume by evaporation is then whilie stiZZ warm precipitated by a slight excess of caustic soda. When the precipitated alkaloYd melts as is sometimes the case it must be powdered after cooling before col- lecting the precipitate on a filter. After washing with the smallest possible quantity of water the precipitate is drained on blotting-paper then detached from the filter dried and weighed. The amount of quinovic acid may be ascertained in the meantime by Creating the mixture of quinovio acid and fatty substances with a weak solution of caustic soda by which a great part of this mixture is dis- solved.If to this turbid solution a slight excess of chloride of calcium is added only the quinovate of calcium remains in solution and on filtering and acidulating with hydrochloric acid the quinovic acid is precipitated as a,bulky jelly. As the amount of,quinovic acid is generally very small its quantity can rarely be ascertained with accuracy unless the amount of bark be not under 40 grams. The author usually makes two determinations of the alkaloids on two portions of bark of 20 grams each ; these he unites for the estimation of the quinovic acid. W. A. T.

ISSN:0368-1769    

DOI:10.1039/JS8742700091

出版商:RSC    

年代:1874

数据来源: RSC

摘要:

TECHNICAL CHEMISTRY. Technical Chemistry. Sodium Sulphite as a means of Removing Chlorine after Bleaching. By TIIEODOR (Ding]. polyt. J. ccix, SCHUCHARDT 154). WHEN sodium hyposulphite (thiosulphate) is used a thin film of fine!; -divided sulphur is left in the pores of the straw paper &c. which have been bleached ; this on exposure to the air becomes oxidised to sul-phuric acid which destroys the fabric by rendering it brittle. This inconvenience is avoided by the use of sodium sulphite which both yields more sulphurous acid and does not deposit sulphur. W. R. ABSTRACTS OF CHEMICAL PAPERS. Preparation of Magnesium Carbonate from Dolomite. (Dingl. polyt. J. ccjx 467.) THE process is based on the fact tha,t magnesium bicarbonate is more easily soluble in water than the corresponding calcium salt The dolomite is fiiiely ground and placed in a horizontal rotating cylinder into which carbonic anhydride obtained from calcium carbonate and hydrochloric acid is forced at a pressure of 5 or 6 atmospheres.The solution of magnesium bicarbonate is allowed to flow into a vertical cylinder into which steam is passed. The magnesium carbonate is allowed to subside and cut into squares in which form it is brought into the market. W. R. Scott’s Selenitic Mortar. By F. SCROTT (Din$. polyt. J. ccix 30-4s). IFquick-lime be slaked in water containing calcium sulphate in solu-tion the process is attended with phenomena quite different from those which are exhibited if pure water be used.The slaking is then delayed proceeds more slowly and gives a product which if mixed with a certain amount of sand forms an excellent hydraulic mortar. 2 per cent. or less of gypsum is sufficient to produce this change in the lime as to its mode of action on slaking and its properties thereafter. The same results are obtained whether burnt or unburnt gypsum is used and to the same extent. The condition of the gypsum is immaterial. For a good hjdrnulic moStar those limes are chosen which slake most slowly and upon the slaking of these the gypsum exerts the most influence as regards the delay of the phenomenon exerting but little delaying influence iipon those which immediately fall to pieces in water. The addition of the gypsurn then tends to induce the lime to harden after slaking and this hardening follows completely after addition of 1$parts by weight of gypsum to 100 parts of lime and the harden- ing tendency is not increased by further addition of the gypsum.On hardening there is a perceptible rise of temperature. The retardation of the slaking in presence of gypsum is ascribed to the fact that the lime by exertion of surface attraction becomes covered with the gypsum as with a varnish and its pores being thus filled up the delay of the hydration naturally follows. The peculiarity of certain limes which require a considerable lapse of time to disintegrate in contact with water is ascribed to the presence of certain foreign substances which produce the same retarding effect that is noticed when gypsum is present.w. s. Portland Cement from Dolomitic Limestone. By I?. ERDMENGER (Dingl. polyt. J. ccix 286-295). THEauthor concludes from his experiments that cement made from dolomitic limestone hardens under water more quickly than ordinary TECHNICAL CHEMISTRY. 97 hydraulic cement. The specific gravity of this cement when carefully prepared is not less than that of the usual Portland cement. In calcu- lating the proportion of alumina to be added the free lime alone is taken into account. The magnesia must not be regarded as equivalent to lime otherwise a product results which does not harden quickly or resist the action of water to a sufficient extent. NI. M. P. M. The Iron Ore of Bidasoa; its Treatment by Calcination and ROBRIG Lixiviation.By ERNST and ROBT.HAAS(Chem. News xxviii 220-222). SOME experiments have lately been conducted on behalf of an English company working certaiu iron mines in Spain with the view of ascer-taining whether it were ppssible in any way to remove sulphur from %he ore previous to the operation of smelting. The experiments have been fairly successful. The ores which consist principally of ‘‘ spathic carbonate ” and “brown ore,” and contain from -03 to 1.5 per cent. of sulphur were submitted to calcination and the oxidised sulphur sub- sequently removed by lixiviating or in some cases boiling the ore with water. To ascertain the limit to which the sulphur might be removed by suitable calcination and methodical lixiviation an artificially mixed ore was prepared containing 2.5 per cent.of sulphur in the form of ferric sulphide.analyses :- The results obtained are Raw ore. shown by the accompanying Calcined. Lixiviated. Iron.. ............ 43.26 51-55 53.99 Manganese ........ Sulphur .......... 2.07 2.53 2.59 0.75 2.65 0.13 An examination of the wash-water showed that it contained no iron but that sulphates of aluminium manganese calcium and magnesium had passsed into solution. J. W. Contamination of Water by Copper Pipes. By E. REICHARDT (Arch. Pharm. [3] ii 513). THEauthor points out that most waters take up more or less metal from iron and lead pipes and that copper is not in any way a better material. Water which when freshly laid on in 1859 through copper pipes contained 7.2 parts of copper in a million contained 0.8 of copper per million in 1872.Even this latter water gave a perceptibly green metallic soap. Although the quantity has diminished during the thir- teen years yet at the end of that time a most objectionable amount of copper was still taken up. C. R. A. W. The Use of Tartaric Acid in Solutions of Magnesia. By E. LEGER (Pharm. J. Trans. [3] iv 29). SINCE the introduction of citrate of magnesia into therapeutics several VOL. XXTT. H ABSTRACTS OF CHEMlCAL PAPERS. attempts more or less successful have been made to replace the citric acid in consequence of its relatively high price. When ordinary tartaric acid is used the solution at first limpid quickly becomes turbid and deposits the greater part of the salt formed.In seeking to overcome this difficulty the author has tried the various modifications of tartaric acid which are formed under the influence of heat and he finds that metatartaric acid prepared by heating tartaric acid to 170" answers perfectly. The solution of magnesium metatartrate which must be prepared with cold water will keep for seyeral weeks without alteration and as a purgative is more energetic and constant than the citrate. W. A. T. Answer to Coupier's Remarks on the Preparation of Fuchsine without Arsenic Acid. By A. BRijNrNG (Deut. Chem. Ges. Ber. vi 1072). THEauthor states that Coupier's method of preparing aniline colours without the employment of arsenic acid is-not in use in any manufactory owing to the great cost and the bad quality of the product and con- siders the circumstance that he can prepare fuchsine of good quality as cheaply as by the arsenic acid process a sufficient indication that his method is essentially different from that of Coupier.C E. G. Sausages Colotxred by Aniline. By E. REICHARDT (Arch. Pharm. [3] 3 574). THEuse of fuchsine to give to inferior soluble materials the tint which ought to be due only to the colouring matters of blood is of very fre- quent occurrence. Sausage meat thus tinted may be distinguished by digesting the finely divided substance with alcohol or ether whereby aniline colours are dissolved giving the usual tinted solutions. Blood colouring matters on the contrary7 are not thus dissolved.By con-trasting the quantity of normal soda-solution required to bleach the colouring matter extracted from a given weight of sausage with that requisite for a dilute fuchsine solution of known shength an approxi- mate notion of the amount of aniline colour present can be obtained. Thus the author estimated that one sample contained 0.005 gram fuchsine per kilogram of meat. Apart from the unknown biit probably ixijurious physiological action of the fuchsine itself when habitually thus consumed the practice of tintling sausages in this way is to be condemned as it enables much adulteration with inferior and paler silbstances to be carried on and it is always liable to introduce arsenic into the sjstem a result to be objected to even though the quantity actually present in a kilogram of meat may be SO small as not to be readily detected.C. R A. W. TECHNICAL CHEMISTRY. A Method of Preparing the Fur of Rabbits and Hares for the Manufacture of Felt without the use of Mercury. By HIr,r.AEItET. Note by TON DELPECH (J. Pharm. Chirn. [4] xvii 453; Dingl. polyt. J. ccix 230-234). THEfur used for the manufacture of felt is soaked in a solution of mercurous nitrate in nitric acid which alters the structure of the indi- vidual hairs changing the form of the cells diminishing their size and rendering them transparent. Hillaeret has found that thisis due to the action of the nitrous acid evolved by the mercurous nitrate. The action of mercury is hurtful to the workmen employed as their hands are frequently immersed in the solution and they breathe mercurial vapours when the fur is drying.Instead of mercury a saccharine substance such as molasses may be used together with nitric acid. The latter is reduced to nitrous acid and produces the desired change. Greater difficulty is experienced in washing the felt but this is counterbalanced by the absence of danger to the workman. w. R. Cadmium Sulphide in a Pasty Condition. (Dingl. pol$ J. ccix 315.)-Sulphide of cadmium finds a technical application in com-municating a yellow colour to soap. It may be obtained rubbed up with oil in which form it may be more easily diffused through the eoap. W. R. A Red Ink which Resists the Action of most Chemicals. (ibid. 316.)-This ink is a solution of carmine in soluble glass and must be kept in a bottle with a well oiled cork.W. R. Safranin. (ibid.,316.)-Crude commercial safranine may be puri-fied by treatment with alcohol and presents the appearance of a greenish powder with metallic lustre. It can be used for dyeing without a mop- dant and when a small portion is treated alternately with concentrated sulphuric acid and water numerous brilliant colours are produced. W. R. Spontaneous Ignition of Hay. (ibid.,ix 318.)-H. Ranke ob- served an interesting case of the above. A haystack 23 feet in length 23 in breadth and 16 in height emitted zt smell of burning. On removing the hay from the top at a depth of 5 feet in the middle of the stack sparks were noticed which burst into flame.The flame was rapidly extinguished with water. The interior of the stack was carbonised and the carbonaceous residue on heating to 300" in an oil-bath ignitsd spontaneously on exposure to the air. W. R. Gum Arabic of Strong Adhesive Power (Vegetable Glue). (ibid. 320.)-It is a well-known fact that gum arabic will not cause ABSTRACTS OF CHEMICAL PAPERS. blotting-papw to adhere. This may be remedied by adding to 250 grams of the concentrated solution 2 grams of aluminium sul-phate. Alum answers also but not so well. W. R. Testing for Carbonic Acid in Magnesia and Zinc Oxide. By H. CALMBERG; (Dingl. polyt. J. ccix 154).--Care must be taken that all air be expelled by rubbing up the oxides with water in a mortar and warming gently before adding an acid.W. R. Dialysed Iron Oxide as a Mordant in Dyeing. (ibid. ccix 465.)-Ferric oxide is used as a mordant in dyeing. The large amount of acid necessary for its solution acts injuriously on the fabric especially on silk ;this excess of acid may be removed by dialysing the acid solution of ferric chloride. W. R. New Process in the Preparation of Anthracene. (ibid. 466.) -The yield of anthacene from heavy oil may be increased from 10 to 15 per cent. by the use of stirrers in the retorts from which it is distilled. W. R. A Reddish-Brown Paint for Wood. (ibid.,466.)-The wood is first washed with a solution of 1 lb. cupric sulphate in 4 litres of water and then with 3 lb. potassium ferrocyanide dissolved in 4 litres of water.The resulting brown cupric ferrocyanide withstands the weather and is not attacked by insects. It may be covered if desired with a coat of linseed oil 'varnish. w. a. Porosity of Porcelain. (ibid, 468.) -Salvetat has noticed that if unglazed porcelain be allowed to lie in a solution of colouring matter the interior becomes impregnated with the colour while the outsside remains white. By transmitted light however the colour may be made apparent. This property may be employed in ornamenting their porcelain vessels. W. R. The Purification and Utilisation of Sewage. By R. B. GRANTHAM (Chemical News xxviii 163). The Sewage of Manufacturing Towns. By W. T.MCGOWEN (Chemical News xxviii 184).

ISSN:0368-1769    

DOI:10.1039/JS8742700095

出版商:RSC    

年代:1874

数据来源: RSC