摘要:

QU ART E R LY JOURNAL THE C~E~ICAL SOCIETY OF LONDON. LONDON II-CIPPOLYTE BAILLIERE 219 REGENT ST&EEl1' AND 440 BEOADWAY NEW YORK U.E. YAItIS. J. B. BAILLIERE RUE RhUTCELUII~LC MADltID BAILLY I3AILLICRC CALLE DhL PlLINGIPL. 1862. LONDON PRINTED BY HABRIRON AND 8ONS 8T. NABTIN’S LANE W.U. C'ONTENTS THE FOURTEENTH VOLUME. PAGE Contributions to the knowledge of the Laws of Qas-absorption. By T'bos. 8. ........o.....Sims ........................................ .....).... .....f...................*........................ 1 On Sugar in the Urine. By H. Bence Jones M. D.,F.R.S. ................................ 22 Analysis of the Saline Water of Purton near Swindon North Wilts. By Henry M. Noad Ph.D.F.R.S. F.C.S. ..1.........................................................43 On the Composition of Purton Saline Water. By Augustus Voelcker Ph.D ..... 46 On the Basic Carbonates of Copper with some remarks upon the Carbonates of Nickel and Cobalt. By Frederick Field ...................... .................................. 48 Preliminary Note concerning a new Homologue of Benzoic Acid. By Arthur H. Church B.A. ................................................................................................ 52 On some Prodiicts of the Action of Dilute Nitric Acid on some Hydrocarbons of the Renzol Series (Preliminary Notice) By Warren de la Rue Ph.D. F.R.S. etc. and Hugo Muller Ph.D. F.C.S. ..................... ........................... 54 On the Bisulphide of Iodine.By Frederick Guthrie ............................................ 57 ABSTBAOTS :-On Azobenzol and Benzidine. By P. W. Hofmann .............................. GO On the Constitution of Oil of Cajeput. By Maximilian Schmidl ....,,.. 63 On the Basic Carbonates of Copper. By Frederick Field .... ............... 70 Contribiztions to the History of the Phosphorus Bases. By Augustus William Hofmann F.R.S ..................................................................... 73 On the Ice found under the Surface of the Water in Rivers called Ground Ice. By Richard Adie ................................................................................................ 111 On the Putrefaction of Bile and the Analysis and Theory of Gallstones.By Dr. Thudichum .................................................................................................... 114 On some Derivatives from the Olefines. By Frederick Guthrie ........,......,........ 128 On the Amount of Water displaced from the Hydrates of Potash Soda and Baryta by Boracic and Siiicic Acids. By Charles L. Bloxam .................... 143 On some Minerals from Chile. By Prederick Field ........................................... 153 On the Action of Dibromide of Ethylene on Pyridine By John Davidson .... 161 Account of recent Researches on the Application of Xlectricity from different Sourceg to the Explosion of Gunpowder. By F A. Abel F.R.8 ...,,~,l,,,. 135 PAUE On the Composition of a Carbonaceous Substance existing in Grey Cast Irou.By F. Grace Calvert F.R.S. F.C.S. ................................................................ 199 On the Bromide of Carbon. By Arthur E. W. Lennox ....................................... 205 mal Sixbstances presented to them. By Charles Daubeny M.D. F.R.S.,M.R.T.A. Foreign Associate of the Royal Academy of Munich &c. and Professor of Botany Oxford ............................................................................ 209 On Colouring Mattem derived from Coal Tar. By W. H. Perkin Esq. F.C.S. 230 Researches of the Constituents of Gastric Juice. By William Marcet M.D.,F.R.S. ............................................................................................................... 256 On the Power ascribed to the Roots of Plants of rejecting Poisonous or Abnor-On the Peroxides of Potassium and Sodium.By A. Vernon Harcourt Esq.,F.C.S. .................................................................................................................. 267 Some Results of the Analysis of Commercial Coppers. By 3'. A. Abel F,RS.,and Frederick Field F.R.S.E ............................................................................ 290 On the Gencral Distribution of Bismuth in Copper Ninersls. By Frederick Field F.R.S.E. .................................................................................................... 304 Ou. Leucic Acid and some of its Salts. By 5. Louis W.Thudichum M.D. ........ 307 Contributions to the History of the Phosphorus-bases. By Augustus Wrlliam Hofmann F.R.S. ................................................................................................ 816 Proceedings at the Meetings of the Chemical Society ........................................... 347 Index ........................................................................................................................... 361

ISSN:1743-6893    

DOI:10.1039/QJ86214FP001

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

BENCE JONES ON SUGAR IN THE URINE. II.-On Sugar in the Urine. BY N BENCEJONES,M.D. F.R.S. PART1. On the detection of Sugar when added to NeaEthy Urine. THEdetection of small quantities of sugar in water and in a solution containing organic and inorganic substances constitute two questions as different as the detection of small quantities of arsenic or opium when dissolved in pure water or in it compound fluid. Nothing is easier than to determine the presence of small quan- tities of sugar arsenic or opium in distilled water; but when organic matters are also present the difficulty of the analysis becomes sometimes excessive. Very small quantities cannot be detected. The limit that can be found varies with each substance according to the nature and amount of the organic matter present according to the process of separation used and according to the skill of the chemist.In cases of poisoning the separation of the poison from the contents of the stomach or from the substance of the different AMMONIA Fig. X. AMMONIA IN WATER Fig 1X. BENCE JONES ON SUGAR IN THE URINE. organs of the body constitufis the whole diBculty; and this is also true regarding the detection of sugar. Whatever process is used for separating the sugar and the organic matter some diffi- culties will be met with and some limit to the quantity of sugar that can be detected will be found. It is the object of the first part of this paper $0show the diE- culties and limits which exist when Lehmann's process for detect- ing sugar in the urine or the fermentation process or Soleil's Saccharimeter or Br u cke's processes are used.I am much indebted to Drs. Ulrich and Valentine for carrying out my wishes and for making the results as trustworthy as possible. L ehm an n' s Process. In his '(Physiological Chemistry " (Translation p. 285 vol. i} Lehmann says ''If a specimen of urine contain very little sugar it is advisable to extract the solid residue with alcohol to precipi- tate the sugar by the alcoholic solution of potassa to dissolve the ccmpound of sugar and potassa in water and then to apply the sulphate of copper test." Some experiments were first made on the solubility of potass-sugar in alcohol of different strengths.200c.c. of alcohol were made of three different degrees of strength go" 80" 70° and the same amount of grapemigar was added to each The rotation was found by the saccharimeter to be between 8" and 9"; the temperature was 18@. (64' F.) The sugar was precipitated by potassa washed with absolute alcohol and dissolved in water ; and the solutions were neutralised with hydro- chloric acid evaporated decolorised and examined by the saccha- rimeter. The alcohol of 90" then gave 4" of rotation. The alcohol of SO" gave 2" of rotation. The alcohol of 70" gave no rotation. A similar experiment was repeated with an amount of sugar which gave 11"to 12" rotation The alcohol of 90" gave 6"of rotation. The alcohol of 80" gave 44". 1 grn. of pure grape-sugar was dissolved in 50 c.c. in 100c. c. and in 150c. c. of an alcohol between SO" and 90° and potassa dissolved in alcohol of the same strength was added to each solu- tion. In each a precipitate fell but after standing many hours it was scarcely perceptible at the bottom of each glass. 1 grn. of sugar in 300c. c. of alcohol between SO0 and 90° gave a marcely perceptible precipitate with potsss-alcohol BENCE JONES ON SUGAE IN THE URINE On the other hand the whole of the sugar was precipitated when 6 grns. of sugar were dissolved in 200c. c. of methylated alcohol of 99'; and when 3 gms. were dissolved in 150c. c. of alcohol of 98" to 100' treated with potasea arid the sugar-potassa determined by the saccharimeter the whole was regained.These experiments show that the evaporation of the urine must be carried nearly to dryness in order that the residue may be treated with nearly absolute alcohol. It was therefore necessary to determine the effect of the evaporation on the sugar added to the urine. Known quantities of sugar were added to urine before and after evaporation. 1000c. c. of urine were evaporated ; 6 grns. of sagar were then added to the residue which was extracted with alcohol 98' and ultimately 3 grns. of sugar were recovered. 325c. c. of urine treated the same way with 8 grns. of sugar gave 54 gns. A second experiment gave the same result. If to 100c. c. of urine 8 grns. of sugar were added and the evaporation in the water-bakh was carried to dryness; 5 grns. were recovered by extraction with alcohol.A second experiment gave the same result. When the same quantity of sugar was added to 500 c. c. 4gms. were recovered. If to 500 c. c. urine 15 grns. were added between 7 and 8 were recovered after evaporaticn. In 1000c. c. when 8 gms of sugar were added only 2 grns. were recovered When the same quantity was added to 2000 c c. a trace only was detectable. Hence during evaporation of small quantities of urine there is but little decomposition of the sugar that is added; but when large quantities of urine are evaporated in the water-bath much sugar is lost; and Lehmann's process for detecting small quan- tities of sugar in the urine is not sufficiently delicate. On the Fermentation Test. Of all the tests for sugar the most conclusive when it can be obtained is the production of carbonic acid and alcohol by yeast.The following points were examined :-1. Whether equal quan- tities of yeast give off equal quantities of carbonic acid,-that is whether any eiror arises from deducting the quantity of carbonic BENCE JONES ON SUGAR IN THE URINE. acid given off by the yeast itself from the quantity given off by the yeast and sugar together? 2. What is the least quantity of sugar in water and urine that can be detected? 3. What effect urea oxalate of urea and the residue of the urine have on the process of fermentation? 4. What is the delicacy of the test as compared with the saccharimeter and Fehling’s solution ? 1. On the carbonic acid given off by yeast washed once with water :-324.28grns.of yeast gave 1-57carbonic acid=0*42 grns. per cent. 421.50 , 3 >J *= 0.48 JJ In second experiment,- 240.70grns. of yeast gave 0.75 carbonic acid = 0.31per cent. >Y 321.47 , ; 1.00 = 0.31 , 2. What is the least quantity of sugar in water and urine that can be determined? Half a grn. of grape-sugar with 29.99 grns. yeast gave 0.39 grn. carbonic acid. 33.08 grns. yeast without any-sugar being added gave 0-16 grn. carbonic acid. Therefore 29.99 grns. yeast gave 0.14grn. carbonic acid. Hence half a grn. of sugar gave 0*39-0*145grn. carbonic acid = 0.24. Theoretically= 0.24. In a second experiment after the yeast had been well washed to remove every trace of alcohol the following numbers were obtained :-Half a grn.of sugar with 40.58 gms. of yeast gave 0*34carbonic acid. Without sugar 52-27grns. of yeast gave 0.06 :. 4058,give 0046. Hence half a grn. of sugar gave 0*34-0.05=0*29carbonic acid. The residue after fermentation was put into the smallest possible retort and heated to boiling. The first drops that came over were tested for alcohol thus :-To one cubic centimetre of a moderately strong solution of bichromate of potassa two or three drops of concentrated sulphuric acid were added and then a few drops of the liquid supposed to contain alcohol Heat was then gently used and the fluid immediately became green from the alcohol present. ,> BENCE JONES ON SUGAR IN THE URINE. Hence half a grn.of sugar in water gives carbonic acid that can be weighed and alcohol that can be detected. One grn. of sugar was then added to 6 cubic centimetres of urine and this fluid without concentration was fermented and the sugar was detected. But if 1 grn. of sugar was added to 50 c. c. of urine and this evaporated to 5 or 6 c. c. no fermenta- tion occurred on the addition of yeast; neither was any fermenta- tion observed when two or three grains of sugar were added. If 3 gms. of sugar were added to 30 c. c. of urine and this evaporated to 20 c. c, the fluid quickly fermented and the loss of weight was nearly the theoretical quantity. The effect of urea and of oxalate of urea* was then determined The same sugar-solution was fermented without urea and with a small quantity of urea.Without Urea. With Urea. 1st Exp. 2nd Exp. Apparatus with sugar solution and yeast 1493.10 1506.63 1402.60 , without , , , 1340.30 1351-60 1286‘48 Yeast 152.80 155’03 116.12 Apparatus before fermentation . . 1493.10 1606.63 1402.60 after 7 Y9 147’2.26 1485.73 1381-64 Carbonic acid given off . . . . 20.84 20.90 20-96 Hence the presence of the urea did not affect the fermentation. If a concentrated solution of urea was taken and 3 grns. of sugar were added to 6 c. c. of solution no trace of fermentation occurred. When 4 grns. of oxalate of urea were added to 34.6 grns. of sugar in solution fermentation proceeded; but if much oxalate of urea was present fermentation was stopped. 4 grns. of Oxalate of Urea.Much oxalate. Apparatus with oxalate of urea and yeast 1618.90 1416-23 , without ? ,I jj 1400.62 1295.08 Yeast . . . 218.28 121.15 Apparatus before fermentation . 1618.90 1416.23 , after -3 . 1603.76 1415.20 I_-Carbonic acid given off . . . 14.94 1.03 Carbonic acid given off by yeast alone . 1*oo * Experiments were made with oxalate of urea because this substance existed in the fermenting fluid when the urea was chiefly removed by oxalic acid added to the concentrated urine. BENCE JONES ON SUGAR IN THE URINE. Hence with much oxalate the fermentation was almost entirely stopped. On the comparison of the delicacy of the Fermentation-test and with Fehling’s standard solution. A watery solution of grape sugar was prepared which gave a solution of 104°=2*288 grains of sugar in each cubic centimetre.* 15 c.c. of this solution=34.25 grains of sugar were fermented with yeast that had been once washed. A second experiment was made with the same quantities and a third experiment was made to determine the carbonic acid in the yeast :-1st Experiment. 2nd Experiment. 3rd Experiment. Yeast employed . 263.90 270.66 210-15 Carbonic acid given off 18.29 18.70 0.62 Carbonic acid in yeast 0.76 0.78 Carbonic acid in sugar 17.53 17.92 Hence sugar in each C.C. of solution =2*376 grains-2.437 grains 10 c. c. of the same solution were diluted to 160 c.c. and tested by fresh prepared Fehling’s solution. 10 c. c. of Fehling’s solution were reduced by 5.6 c. c.of the diluted sugar solution. Hence 10 c. c. of the solution before dilution contained 21.9 grains sugar and each c. c. contains 2.192 grains sugar. Hence in each cubic centimeter of the solution there were present :-By fermentation 2.371 and 2.437 grs. sugar mean = 2.356 grs. By sacchsrimeter . . 25288 grs. By copper test . * 2.192 grs. On So lei l’s Saccharirneter. Before the saccharimeter can be used the fluid about to be examined must be decolorised. To effect this animal charcoal acetate or subacetate of lead and ammonia or chlorine gas must be used. These substances whilst removing the colour keep back or destroy some of the sugar and it was desirable therefore to determine the loss * This number is obtained by making a solution of sugar which contains .01 gramme of sugar in each cubic centirnetre when examined by Fehling’a solution.This amount of sugar in solution gives seven degrees of rotation BENCE JONES ON SUGAR IN THX URINE. First charcoal :-A colourless solution of sugar which gave 7' of rotation was mixed with animal charcoal boiled for a few minutes and left for a few minutes longer before it was filtered. The charcoal was washed three or four times with hot water. The washings were added to the fluid which first came through and the whole was then found to give the same rotation as at first. A fluid dark brown from the colouring matter of the urine had three grains of sugar added to it and it was then mixed with animal charcoal; after standing some time it was filtered and as it was not colourless it was again treated with animal charcoal and this was repeated a third time.The animal charcoal was many times washed with hot water. The clear fluid Lzltirnately obtained was examined by the saccharimeter and the loss was found to be not more than the frequent filtrations might account for. A colourless solution of sugar in water gave between 9 and 10" of rotation. 75 c. c. of this solution were shaken with a small qnantity of purified and fresh-burnt animal-charcoal the fluid was then filtered and the charcoal was not washed. The solution then gave between 7" and 8' of rotation. 75 c. c. of the same solution with twice the quantity of animal charcoal gave a rotation between 5' and 6". 75 c.c. of the same solution with three times the quantity of animal charcoal gave a rotation of between 4* and 5". One volume and a half of the same sugar-solution .masmixed with one volume of animal charcoal. The clear fluid which passed through the filter was found to have lost half its rotating power. It follows from these experiments that a large excess of animal charcoal retains much sugar and that the more charcoal used the less sugar passes through the filter ;but .all the sugar that is kept back can be washed out with boiling water. It was desirable to know how much charcoal could be used without perceptible loss of sugar. 50 c. c. of a pure solution of sugar gave 27" of rotation. It was mixed with between 55 and 60 grains of charcoal shaken and filtered and then gave 26'.25 c. c. of a nearly colourless diabetic urine were diluted to 55 c.c.; the rotation was then between 15' and 16O. 50 c. c. of the same urine shaken with 60 grs of charcoal gave a colourlcss solution which rotated between 31' and 32". Some experiments were made with wood-charcoal to see its effects on sugar and onthe colouring matter of the urine. The wood-chmcoal was finely powdered but not fresh burnt BENCE JONES ON SUGAR IN THE URINE One volume of pure sugar solution was shaken with half a volume of wood charcoal and left to stand for some time. The solution gave 19" of rotation both before and after treatment. The same charcoal was shaken with urine the fluid which filtered through was nearly as dark coloured as at first.These experiments were repeated with fresh burnt wood charcoal. The solution of sugar was not affected. The colouring matter of the urine was partly removed but the whole of the colour could not thus be taken away. On the action of basic and neutral acetate of lead on solutions of sugar. Dr. E. Robiquet in his instructions for using his diabetometer says that 25 c. c. of diabetic urine are to be mixed with 1 c. c. of extract of lead and 1 c. c. of liquid ammonia. The whole is to be shaken for some minutes to give a deposit. If the clear liquid is not completely decolorised the same quantity of lead and ammonia is again to be added. If the decoloratioii is then com-plete the amount of sugar may be determined by the amount of rotation observed.25 c. c. of sugar-solution were diluted to 50 c. c. with water. Two experiments gave 121"and 22O of rotation. The same quantity of the same solution was mixed with 20 c. c. of neutral acetate of lead and 2 c. c. of ammonia and themhole was diluted to 50 c. c. after filtration the rotation was found to be in the first experiment between 18" and 19O and in the second experiment 18'. 25 c. c. of sugar-solution diluted to 50 c. c. gave between 9O and 10' of rotation. 25 c. c. of same solution with 12 c. c. of acetate of lead and 2 c. c. of liquid ammonia and the whole diluted to 50 c. c. of rotation. 7'gave only By using three times as much solution of lead and ammonia the iotation was only 4' to 5'. On the action of basic acetate of leadalone.50 c. c. of urine were mixed with a solution of sugar which gave 9" ui'rotation; after precipitation by basic acetate of lead it was found to have lost 3"of rotation. A second experiment gave the same result. 9'and 8'urine which gave between A of rotation gave &om 5" to 6' after precipitation. The lead-precipitate was washed with hot water on the filter and boiled with hot water but the sugar could not be removed. BENCE JONES ON SUGAR IN THE URINE. In order to compare the action of basic and neutral acetate of lead on saccharine urine and on solutions of sugar in water alone and in water with common salt and water and phosphate of soda the following experiments were made. A pure sugar-solution gave 10" to 1l0of rotation; when mixed with common salt and precipitated by basic acetate of lead it gave the same rotation; whenmore common salt was used no difference was observed.A solution of sugar which gave 9' of rotation was mixed with solution of common salt and urate of soda and precipitated by basic acetate of lead; the rotation was then found to be between 7" and 8". When the quantity of salt and urate of soda was less the rotation was 8'. A solution of sugar giving between 10"and 1l0 of rotation was mixed with much phosphate of soda and then precipitated by basic acetate of lead it then gave 8Oto 9". A solution of sugar which gave 5O after being mixed with much phosphate of soda and precipitated by basic acetate of lead gave from 3"to 4O of rotation.A solution giving loo to llo,mixed with a little urate of soda and then precipitated by basic acetate of lead gave 10' of rota-tion. When neutral acetate of lead was used instead of basic acetate very different results were obtained. A pure sugar-solution gave 10' to 11" of rotation. When the solution was mixed with common salt phosphate and urate of soda it gave after precipitation 10" to 11" of rotation and the rotation was unchanged when a greater amount of these salts was added before precipitation. 1st. These experiments confirm the fac% that a pure solution of sugar is not precipitated either by basic or by neutral acetate of lead but that sugar is precipitated by neutral acetate of lead and ammonia. 2nd. Basic acetate of lead when added to saccharine urine causes the precipitation of some sugar.The urates and phos- phates in the urine cause this precipitation of sugar and not the chloride of sodium; for when a solution of sugar in water is mixed with chloride of sodium basic acetate of lead causes no precipitation of the sugar. But when urate or phosphate of soda also is present then some sugar is precipitated. 3rd. When neutral acetate of lead is added to solutions of BENCE JONES ON SUGAR IN THE URINE. sugar containing chloride of sodium phosphate and urate of soda no precipitate of sugar occurs. On the action of Chlorine. Into a solution of sugar in water containing 6 grains of sugar to 20 C.C. of water chlorine gas free from hydrochloric acid was passed for half an hour.It was left for twenty-four hours and then hardly any difference of rotation was observed. Into a solution of the same strength chlorine was passed for an hour and a half and it then was left for twenty-four hours; the loss was less than a grain of sugar. 325 c. c. of urine were mixed with 3 grains of sugar and to 20 c. c. The concentrated fluid was heated for twenty minutes with chlorine. It had then a yellowish urine colour which could not be removed by further exposure to chlorine and the subsequent use of animal charcoal did not give a solution which could be examined by the saccharimeter. Pe tt e nk ofe r’ s Test. The fluid in which sugar is suspected is decolorised as far as possible and then mixed with a few drops of a concentrated solution of glychocholic acid in soda or cholalic acid.Three or four drops of concentrated sulphuric acid are then added and the whole gently heated without boiling. If sugar is present a purple colour is seen at the edge of the watch glass this is more evident on it white ground. A standard solution of grape-sugar was made 1 c. c. containing 0.005 sugar and 5 drops of the solution = 1 milligramme and was mixed with cholic acid and concentrated sulphuric acid intense purple blue immediately formed. One drop of this solution = 0.0002 of sugar mixed with cholic and sulpliuric acid gave after a few miputes a slight purple red and ultimately a tinge of blue. 5 drops of diabetic urine containing 7 grs of sugar to the ounce of urine were mixed with cholic acid and a strong sulphnric acid.After it few minutes a slight purple red appeared which ultimately became bluish. One drop of this diabetic urine without decoloration gave a purple red. Cholalic acid was found to have the same reaction as cholic acid. BENCE JONES ON SUGAR IN THE URINE Trommer’s Test. Among the different ways of employing this test that recom- mended by Lehmann was found to be best. By it & per cent. (or 0.24gr. to 1 oz.) of sugar added to the urine was easily detected by deposit of suboxide of copper. 2or 3 c. c. uf urine are mixed with a few drops of potassa and filtered and then an equal quantity of strong potassa is added with about 3 drops of a solution of sulphate of copper; the whole is well shaken and the clear liquid poured off from the hydrated oxide of copper which has not dissolved.If the blue solution when heated (long boiling is quite unnecessary) becomes colourless without depositing suboxide of copper then two drops more of the sulphate of copper should be added and the experiment repeated. A separation of suboxide is often thus obtained provided the boiling has not been continued so long at the first heating as to decompose the sugar. Pure grape-sugar in water gives the well-known red suboxide. In urine the suboxide is bright yellow or dirty yellow. When 0.01 gramme of grape-sugar dissolved in water was precipitated by acetate of lead and ammonia and the precipitate treated with a little oxalic acid solution the sugar solution gave a dirty yellowish reduction with standard copper-solution.A solution of grape-sugar was mixed in different proportions with a solution of chloride of ammonium. The separation of the suboxide of copper was stopped when the solution containing -& of a grain of sugar also contained 1 grain of chloride of ammonium. In some experiments the suboxide of copper was deposited whilst ammonia in quantity was being given off The same series of experiments were made with urea and grape- sugar the urea hindered the separation of the suboxide when a solution containing r4mof a grain of sugar contained also 1 grain of urea. 3r ucke’ s Processes. Professor Brucke has published two processes for detecting small quantities of sugar in urine In the first or alcohol process he advises that the urine should be mixed with four times its hulk of absolute alcohol.An alcoholic solution of potassa is then to be added and the fluid is left for twelve hours to deposit potassa-sugar. The alcohol is then to be poured off and the deposited matter dissolved in water and tested by reduction and other tests. BENCE JONES ON SUGAR IN THE UBINE. According to the experiments described in the early part of this paper when small quantities of sugar exist in solution an alcohol of 80 per cent. will only give from one-third to a scarcely perceptible quantity of the sugar which existed in a solution. If a very small quantity of sugar mas present this percentage of alcohol would therefore fail to detect it.With absolute alcoliol by this process the whole of the sugar is precipitated but if the percentage of alcohol falls below 80 little or no sugar will be obtained. An alcohol of 90 per cent. gives only half the sugar that is present; and hence this method of Professor Briicke is very imperfect and very costly ; even with nnetliylated spirit. In his second process he recommends that the urine should be precipitated with neutral acetate of lead and then with basic acetate of lead and after filtering off the precipitate ammonia should be added; in this last precipitate the chief part of the sugar present will be found. What is the amount of sugar n7hich when added to the urine can be detected by this process? 145 c.c. of fresh morning urine were treated with acetate of lead basic acetate of lead and then ammonia. 5 c. c. of a standard solution of sugar containing 0.025 gramme ;= + of a grain nearly of sugar was added before precipitation. The solution was almost free from colouring matter after precipitation by basic acetate of lead and quite free when precipitated by ammonia. On adding 20 drops of a standard solution of copper to the potass solution of the subacetate of lead no red suboxide of copper formed but a dirty suboxide of copper fell. The solution of the ammonia precipitate in oxalic acid gave only a trace of red oxide but plenty of dirty coloured suboxide. In the cold after 24 homs the same reduction occurred. 200 c.c. of fresh morning urine were treated as in the last experi- ment but only 0.012gramme = 6 of a grain of sugar was added.The oxalic acid solution of the ammonia precipitate gave with 10 drops of copper solution a slight reduction a dirty yellowish pre- cipitate was obtained on boiling. The potash solution of the sub-acetate of lead precipitate destroyed the blue colour of the sulphate of copper solution but gave no precipitate. 200 c. c. of fresh mid-day urine n-ere ireated as before 0.05 gramme = 9of a grain of sugar was added. The three precipitates mere examined as well as the solution filtered from the ammonia precipitate . 1. The acetate of lead precipitate gave no reduction. VOL. XIV. n BENUE JONES OX SUGAR IN THE URINE. 2. The basic acetate of lead precipitate was dissolved in potasszp.and gave no reduction; the blue colour of the copper solution disappeared however. 3. The precipitate with ammonia was treated with solution of oxalic acid and on the addition of 4 c. c. of standard-copper soln- tion a good reduction was obtained of a yellowish colour. 4. The clear liquid from the ammonia precipitate gave no reac- tion of sugar. 200 c. c. of fresh urine were treated as before; only a01 gramme = + of grain of sugar was added. The oxalic acid solution con-tained as usual the whole of the sugar. 2 e. c. of copper solution gave a dirty yellowish precipitate. When the same quantity of grape-sugar was added to distilled water and treated in the same way the oxalic-acid solution tested by the standard copper solution gave the same dirty-yellow pre- cipitate.To 700 c. c. of urine a known quantity of solution of grape-sugar giving 12' of rotation of the saccharimeter was added. The urine was treated as before. The ammonia precipitate decomposed by oxalic acid contained sufficient sugar when diluted to the known quantity to give a rotation of 8'. Instead of decom-posing the ammonia precipitate by oxalic acid sulphuretted hydrogen was used and if requisite this was twice repeated; the filtrate is then almost colourless even when 5000 c. c. of urine have been used for an experiment. To 1300 c. c. of urine a known quantity of a solution of grape sugar was added giving 13' of rotation. In the ammoniacal precipitate enough sugar was found to give between 7' and 8" of rotation.To 1137 c. c. of urine a known quantity of sugar solution was added giving 11' to 12' of rotation in the ammoniacal precipitate; enough sugar was found to give with the same quantity of water 8' to goof rotation. This experiment when repeated gave in the ammoniacal precipitate 8' of rotation. Hence by Brucke's lead process when + + 6 3of a grain of grape-sugar are added to about 200 c. c. of urine decided evidence of sugar was found in the ammonia precipitate. And by the quan- titative experiments it appears that about two-thirds of all the sugar added can be recovered by this process. The results of these experiments on the detection of sugar when added to the urine may be thus summed up RENCE JONES ON SUGAX IN THE UIZiNE.1. Lehmann’s process for detecting sugar in the urine cannot be employed when small quantities of sugar arc present in large quantities of urine ; by evaporation and decoloration all the sugar is lost. 2. The process of fermentation is stopped by the residue of the urine by much urea and by oxalate of urea still more decidedly. Half a grain of sugar in water can be detected by the alcohol prod uced artd may be determined approximatively by the carbonic acid given off; but in concentrated urine much larger quantities will be entirely overlooked. 3. In decolorising the urine €or use in the saccharirneter sugar is always lost; animal charcoal retains sugar in proportion to the amount of charcoal used. When the urine is decolorised by basic acetate of lead and ammonia two-thirds of the sugar may be lost.4. Pettenkofer’s test for sugar is the most delicate test known; $ of a milligramme in distilled wzter can be detected by it and a little colouring matter of the urine does not hinder the reaction. If much colouring matter is present it must be removed. 5. Trommer’s test is capable of discovering :T per cent. of sugar in the urine but when very small quantities of sugar are in solution with hydrochlorate of ammonia or urea the reduction of the oxide of copper is not perceived; TAT of a grain of sugar with 1 grain of hydrochlorate of ammonia in water gives no reduction; and ___-of a grain of sugar with 1 grain of urea stopped reduction. I o 6. Brucke’s processes.In the alcohol process if 80 pcr cent. alcohol is used only 1or less of the sugar is obtained and even by 90 per cent. alcohol one-half is lost. The necessity for so much absolute alcohol as will give with the urine a mixture of 90 per cent. makes the process nearly useless. By Brucke’s lead process the best results have been obtained; + of a grain of sugar in 200c. c. of urine could be detected and 8 of all the sugar added was recovered. Moreover when sulphuretted hydrogen is used to decompose the ammonia precipitate the sugar is obtained in a state fit for fermentation and free from colour so that the saccharimeter can be employed. PART 2.-On the detection of sugar naturally present in healthy urine. The presence or absence of‘ sugar in healthy urine is not only of great interest in relation to the true comprehension of the nature of diabetes but it is also of importance in respect to 02 BENCE JONES ON SUGAR IN THE VRINE.our kiiowledge of the chemical chmges which occur in the body in health. If sugar exists in the urine in health as Briick e maintains then diabetes must be considered as an exaggeration of a healthy state and not as a distinct and peculiar condition of the system; and it will be necessary to admit that in health and in diabetes the same chemical changes take place in the system but that the greater amount of change in the one case constitutes health and the lesser amount in the other case is called diabetes. Professor Brucke deserves all credit for the accuracy of his observations and for the clearness of his statements; and thoiigh I failed by the alcohol process to satisfy myself of the truth of the results which he obtained by that method yet by his lead process I have fdy convinced myself after a lengthemd investigation which only the perseverance of Dr.Ulrich could have carried out that there is sugar in healthy urine; and that in addition to the proofs of its presence mentioned by Professor Brucke it may be detected and measured by the saccharimeter; and that by fer- mentation alcohol in recognisable quantity may be obtained. On the detection of sugar in healthy urine by Briicrle’s alcohol process. 140 c. c and 20Qc. c. of fresh urine were mixed with four times their bulk of alcohol sp.gr. 808 (or 95 per cent.) a solution of potasss in the same strength of alcohol was added and the fluid mas left for twelve hours to allov the potass-sugar to deposit itself. The liquid was then poured off; the deposited matter ~vas dissolved in water and tested by Trommer’s test Biittger’s test and a solution of potassa alone. No conclusive result was obtained. Three other experiments were then made with 1,000 c. c. of urine and alcohol of the same strength. The copper test gave a decided reduction ; the potassa alone hardly deepened in colour. The bismuth test was not conclusive; on testing the deposit from the alcohol for uric acid it was found to be present in considerable quantity. In the Medico-Chirurgical Transactions vol.26 p. 215 (1848) I have shown that uric acid reduces the oxide of copper in Trommer’s test. Hence the reduction obtained in these three experiments mas rio proof of sugar being present and I determined to try whether by using large quantities of urine sufficient sugar BENCE JONES OX SUGAR IN THE UlCINE. could be prwipitated to admit ofthe determiiiation of its presence and amount by the saccharimeter. 3,000 c. c. of urine (about 5 pints) were added to 12,200 c. c. of alcohol (Lbove 21 pints). This quantity was divided into three portions; potassa dissolved in alcohol was added to each portion before it was set aside to deposit the sugar-potassa. The precipi- tate was dissolvcd in water neutralised M ith oxdic acid filtered through animal charcoal and concentrated on a water-bath to about one ounce (30 c.c.). The clear fluid was examined by the saccharimeter but no trace of rotaticn could be observed. In ariothcr experiment 1,000 c. c. of fresh urine were mixed with 4,000 c. c. of alcohol and treated in the same way; but no trace of rotation was observed. Another series of three portions of 1,000 C.C. of urine each was mixed with 12,000 C.C. of alcohol sp. gr. 808. The smallest quantity of water was used for dissolving the potassn sugar ; a very small quantity of animal charcoal was used for decolorising the solution which vas examined hy the saccharimeter; but no rotation could be seen. Failing thus to detect sugar by the saccharimeter I used Pettenkoffer’s test on fresh portions of urine.260 c. c. were mixed with alcohol and treated with potassa. A very small quantity of cholalic and of cholic acids was dissolved in concentrated sulphuric acid arid some of the fluid thought to contain sugar was added but no purple tint in either case was produced. The test failed to find sugar though the same solutions detected 2 milligrammes of sugar (-03of a grain) dissolved in 10 drops of water and one drop of diabetic urine containing *05 grain of sugar gave ii fine purple colour. As it was possible that by using alarger quantity of urine some trace of sugar might be found 3,000 c. c. of urine were precipitated by alcohol. The deposit was dissolved in a very small quantity of water and decolorized by animal charcoal but no decided evidence of sugar was Qbtained.At the time when these experiments were made with the alcohol process I did not know how little sugar was precipitated by potassa from 80 per cent. alcohol. As this process failed the lead process wits tried. On the detection of sugar i?z healthy urine by Briicke’s lead process. 200 c. c. of healthy morning uriile passed by A were treated BENCE JONES ON SUGAR IN THE URINE. with lead and ammonia; the basic acetate of lead precipitate was dissolved in a small quantity of potassa and the solution was tested with Fe hling's standard-copper solution ; no reduction was obtained but the blue colour of the copper solution disappeared and the liquid became of a light amber colour but not a trace of suboxide of copper was seen.The ammonia precipitate was treated in the cold with oxalic acid and the filtrate was examined for sugar by the copper solution but no reduction occurred ZOO c. c. of mid-day urine (A) mere treated exactly in the same way and with exactly the same results. 500 c. c. of healthy urine (A) treated in tlTe same way with oxalic acid gave no decided evidence of sugar by reduction or by Pett enkoffer's test. This experiment repeated with another quantity of urine gave the same result. When in another experi- ment the ammoniacal precipitate was decomposed by sulphu- retted hydrogen decided evidence of reduction was obtained. 1,000 c. c. of same urine (A) treated with oxalic acid instead of sulphuretted hydrogen gave a reduction which was not sufficiently distinct.When this expcriment was repeated and sulphuretted hydrogen employed a distinct reduction of the oxide of copper took place and Pettenkofer's test also showed that sugar was there. This last experiment was three times repeated and reduc- tion always occurred. 1,000 c. c. of the urine of another healthy man (B) was treated in the same way by lead and sulphuretted hydrogen; the clear filtrate was evaporated and it reduced the copper solution readily. 2,000 c. c. of the urine (A) gave LZ very plentiful reduction. The experiment was repeated; the filtrate from the sulphide of lead was evaporated to dryness and extracted with absolute alcohol ; potassa-alcohol was then added ; and a deposit formed on standing which gave a good reduction.It was requisite to prove that the reduction was caused by sugar. For this purpose larger quantities of urine were treated in the same way and the ammonia precipitate was tested for sugar by the saccharimeter and by fermentation. 5,000 c. c. of urine (A) were examined ; the filtrate from the sul- phide of lead was evaporated iri vacuo ;and the residue dissolved in a little water was decolorised by a little animal charcoal; half the solution examined by the saccharinieter gave 4' of rotation Iu two other experiments with different quantities of the urine (A) Zo and 3" degrees of rotation were observed. BENCE JONES ON SUGAR IN THE URINE. 5,000 c. c. of urine (B) treated in the same way gave 5" of rotation.1,100 c. c. of the urine of a third person (C) treated in the same way gave lgo of rotation; and by the reduction-test sugar was easily found. In two experiments with 10,000 c. c. of urine (A) treated with oxalic acid the decoloration could not be made so as to allow of the use of the saccharimeter; but the reduction-test and Pettenkofer's test gave full evidence of sugar. Hence in those different healthy persons and in six different experiments the rotation showed that sugar waspresent in the urine. On the wmount of rotation obserced in healthy urine. Two more experiments were made with the urine of (A) and (B) to determine the greatest amount of rotation in health. 5,000 c. c. of the urine (A) were treated as before with sul- phuretted hydrogen.The whole of the fluid was used in the saccahrirneter and the rotation was between 7" and 8". 5,000 c. c. of the urine (B) when all the fluid way used gave from 10"to 11' of rotation. On the proof of the presence of sugar in healthy urine by f ermentation. 10,000c. c. (10 litres) of the urine (A) were treated with sulphm retted' hydrogen. The filtrate was evaporated and half was fermented in two portions. 1st Portion. 2nd Portion. Yeast employed . 31.22 grs. 29.30 grs. Total carbonic acid given off 0.80 gr. 0.86 gr. Carbonic acid from yeast . 0.43gr. 0.41 gr. Carbonic acid from sugar . 0.37 gr. 0.45 gr. Hence total carbonic acid from sugar = 0.82 gr. = 1.68 gr. sugar; so that the total quantity thus obtained from 10 litres was 3.36 grs.sugar. 14,000 c. c. of urine (A) after the filtrate from the sulphide of lead was evaporated to dryness had the sugar precipitated from BENCE JONES ON SUGAR IN TBE 'C'RINE. absolute alcohol by potassa. The precipitate was dissolved in water neutralised by hydrochloric acid and evapurated ; the residue extracted by strong alcohol ; the alcoholic solution again evaporated to dryness; and the residue again dissolved in water mixed with yeast which had been well mashed and kept at a temperature between 125" and 30' C. (77' and 86') F. in half an hour it began to ferment. Yeast employed in sugar-solution . 34-12 grs. Carbonic acid given off . . 1.8 gr. Yeast without sugar-solution . 109.6 grs. Carbonic acid given off .. . 0.3 gr. Therefore carbonic acid in 34.2grs of yeast may be neglected. Tlie yeast aiom mixed with water and distilled gave a scarcely perceptible trace of reduction when the distillate was added to a solution of chromic acid whereas the other yeast-mixture dis- tilled gave a fluid which showed plentiful reduction proving that alcohol was preseilt after fermentation. The total carbonic acid given off = 1.8 gr.; this corresponds to 3-7 grs. sugar obtained from 14 litres of healthy urine. An undetermined quantity of the different fluids which had been used in the experiments with the saccharimeter was evapo- rated ; the residue extracted with strong alcohol ; the alcoholic solution evaporated ; the residue again redissolved in strong alcohol; and the solution mas evaporated to dryness dissolved in water and mixed with slightly washed yeast.Yeast used . * 44% grs. Carbonic acid . . 2.4grs. Yeast without sugar-solution 100.3 grs. ;carbonic acid 0.7 gr. Hence 44.6 yeast give 0.3 gr. carbonic acid. Hence carbonic acid from sugar = 2.4grs. -0.3 r= 2.1 grs. = 4.3 grs. sugar. The fluid distilled from yeast alone reduced chromic acid; the fluid which was distilled froin the other apparatus reduced the chromic acid much more decidedly. On the determination of the amount of sugar present in heulthy urine. Although the saccharimeter and fermentation afford the most BENCE JONES ON BUQAR IN THE URINE. satisfactory proof of the presence of sugar yet the quantitative determination by either of these methods is not so accurate or so useful as by means of Fehling’s standard-copper solution; because the processes for decolorising and for separating the sugar from the urine cause a great loss which does not occur when the amount of sugar is determined by a standard solution because then it smaller quantity of urine will give conclusive results.1,000c. c. (1litre) of urine (A) was treated as before; the filtrate from the sulphide of lead was evaporated on a water-Ijath decolorised with a little animal charcoal and then tested by Fehling’s solution. The volume of fluid was 29 c c.; of this 15 c. c. were required to reduce 10c. c. of Fehling’s solution. Hence the 29 c. c. contained 0.09 gramme sugar = 1.4 grain as by the process one-third of the sugar present is lost.The litre contained about 2.2 grs. of sugar. In another litre (A) the volume of fluid was 18 c. c.; of this 12 c. c. reduced 10 c. c. of Fehling’s solution. Hence 18 c. c. contained 0.07 gramme sugar = 1-08 gr. Adding one-third to this we find that the litre contained about 1.5 grains. In another litre (A) the volume of fluid was 18 c. c.; of this 13 c. c. reduced 10 c. c. of Fehling’s solution. Hence the 18 c. c. contain 0.06 gramme sugar = 0924 gr. One-third added = 1.38 gr. to litre iirine. In another litre (A) the volume of fluid was 18 c. c.; of this 11c. c. reduced 10c. c. of Fehling’s solution. Hence the 18c. c. contain 0.08 gramme sugar = 1.23 gr. One-third added = 1.8gr. sugar to litre urine.A litre of urine (B) was treated in the same way. The volume of fluid was 18 c. c.; of this 7 c. c. reduced 10 c. c. of Fehling‘s solution. Hence the 18c. c. contain 0.13 gramme sugar = 2.0 grs. One third added c 3.3 grs. sugar to litre urine. In another litre (B) the volume of fluid was 26.6 c. c.; of this 12.6 c. c. reduced 10 c. c. of standard solution. Hence the 26.6 contain 6.7 gramme sugar = 1.5 gr. One-third added = 2.3 grs. sugar to litre urine. By the saccharimeter also evidence of rotation was obtained. Hence 1st Exp. 2nd Exp. 3rd Exp. 4th Exp. 1litre (A) urine contained 2.2 grs. 1.54 1.38 1% gr. sugar. 1 litre (B) urine contained 3.0 grs. 2.3grs. sugar. From these experiments on healthy urine it follows :- BENCE JONE8 ON SUGAR IN THE URINE.1. That by the alcoholic process when 140 c. c. to 3,000c. c. of urine were employed no result was obtained by the reduction test by Pettenkofer's test or by the saccharirneter chiefly because the percentage of alcohol was not great enough. 2. That by the lead process most conclusive results were obtained qualitatively and quantitatively by the reduction test by fermentation and by the saccharimeter. By the reduction test qualitatively 200 c. c. of urine gave no evidence; 500 c. c. failed and 500 c. c. gave proof of sugar; 1,000 c. c. gave very evident sugar; 3,000 c. c. gave much more proof. By this test quantitatively 1,000 c. c of one man gave 2-2,1.5,1*4 and 1% grs. of sugar. The same quantity OC urine in another man gave 3.0 and 2.3grs.of sugar in one litre. By the saccharirneter quantitatively 5,000 c. c. of urine partly used gave 2O 3O and 4" of rotation. In another man 5Owere observed. In a third man a smaller quantity of urine gave 1' to zvof rotation. By this test quantitatively 5,000 c. c. of one man all used gave 7" to 8" of rotation. The same quantity from another man gave 30"to 11". By fermentation qualitatively an unknown quantity fermented gave distinct evidence of alcohol and 2.1 grs. of carbonic acid. Quantitatively 10,000 c. c. of urine were used and ultimately 1.64 gr. of carbonic acid was obtained. 14,000 c. c. of the same urine gave most positive proof of alcohol and 1.8 gsr. of carbonic acid. These experiments therefore fully confirm Professor Briick e's statement that sugar exists in healthy urine.By obtaining alcohol from the fermented fluid and by never failing to find rotation when the saccharimeter was used provided sufficient urine had been taken for the experiments I have added to the evidence given in his original paper.

ISSN:1743-6893    

DOI:10.1039/QJ8621400022

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年代:1862

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43 111.-Analysis of the Saline Water of Purton near Swindon North Wilts. BY HENRY PhD. F.R.S. and (2.8. M. NOAD THEwater rises in a field on the Oxford Clay which reaches from the bottom of the hill on which the village of Purton is built to the river Thames at Cricklade a distance of about three miles the spring being about midway between both. The soil of Purton rests on the limestone The field in which the spring rises has long been known in the neighhourhood as ‘ISalt’s Hole.” The medicinal properties of the water are held in high esteem by the inhabitants of Purton and the proprietor has recently erected a pump-room round the well from which about 120 gallons of the water can be pumped up daily. The water which was analysed at the request of Dr.Kinneir of Purton was collected by myself in the month of January in the present year. As pumped up from the well it was quite clear and remained so after long standing. While the pump was in action a faint but decided smell of sulphuretted hydrogen was perceptible but the water itself while still had no such odour. The temperature of the water was nearly the same as that of the air Specific gravity at 60°F. = 19056. Free carbonic acid 50 cubic inches per imperial gallon the water being slowly pumped up from the well. The analysis was performed in thee usual manner the iodine which could be distinctly recognised in one pint of the water being estimated as protiodide of palladium. In the arrangement of the results of analysis the strongest acid is assumed to be combined with the strongest base ; and the lime and magnesia thrown down as carbonates by boiling are considered its existing in the water as carbonates held in solution by carbonic acid.Direct results of analysis calculated to 1 imperial pint. BASES. Experiment. Lime. Magnesia. A1kaline Chlorides. Potassium. Chloride of Sodium. Chloride of --__I--- I... .. . .. 6.422 4143 18.90 1-179 17’721 11. .. .. .. .. 6.257 4,783 19-33 1‘020 18.310 Mean ,. .. 6.340 4.765 19.10 1.009 18.016 ANA1,YSIS OF THE ACIDS (or etemelats replacing them). Carbonic Acid RS Experi-ment. SulphuricAcid. *lo-fine. Iodine with traces of Bromine. Carbonic Acid free and combined. Carbonate of Lime and Carbonate Car-bonic Acid,free.Phos-phoricAcid. APO:crenic Acid. nesia. of Mag- - I,. .. 11,. .. 2-38 2-36 >? I ” I ” Mean 2.37 3.133 - VER~FICATIONLIME. FOR Lime precipitated Lime left in solution Experiment. boi% g. boiling. ---____. I. .......... 2.828 11. .......... 2.857 .--Mean ........ 2-842 VERIFICATION MAGNESIA. FOR Mawwsia Mawesia Total Total Experiment. preciphtcd by leR in --.-*----boiling. solution. I .......... 0.11 1 4-735 4.845 4.748 I1 .......... 0.15 4.785 4.945 4.783 Mean ........ 0.1 3 4.755 4.890 4.765 BALlNE WATER OF PURTON BY DK. KOAD. RESIDUELEFT ON EVAPORATION. Experiment. Mineral Residue. Organic Residue. Total Residue. --I_- -I_- I ............ 51.02 0.114 51-114 I1 ............ 51.21 o*no 51,320 --___.---- Mean ..........51-11 0.112 51-217 Solid Contents of an imperial pint as determined by analysis. Carbonate of lime . . 5.0760 Carbonate of magnesia . . 0.2630 Lime (not as carbonate) . . 3.2200 Magnesia (not as carbonate) . . 4.7580 Potash . . 0.6930 Soda . . 9*5460 Chlorine . 2*8100 Sulphuric acid . . 23*9000 Silica . . 0*2800 Phosphoric acid . . 0.0310 Bromine . traces Iodine . . 0.0094 Crenic acid . . traces Ayocrenic acid . . 0.1120 50.6989 Residue left on Evaporation . . lil*Zl70 Saline Constituents in one lmperial Gallon. Carbonate of lime . . 40.608 Carbonate of magnesia . . 2.104 Sulphate of potash . . . 10.264 Sulphate of soda . . 174.904 Sulphate of lime . . 62.560 Sulphate of magnesia . . 76.592 Chloride of magnesium . . 30*000 46 VOELCKER ON THE COMPOSITION Iodide of sodium . . 0*088 Silica . . Z0080 Phosphoric acid . . 0.248 Crenic acid . . traces Apocrenic acid . . 0,896 Bromine . . traces 400.344

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DOI:10.1039/QJ8621400043

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年代:1862

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VOELCKER ON THE COMPOSITION IV.-On the Composition of Purton Saline Water. BY AUGUSTUS PH. D. VOELCKER (PROPENOR OF CHEMISTRY IN THE ROYAL AGRICULTUBAL COLLEGE CIRENCESTER. ) NOTICING that Dr. Noad intends reading on the 17th December 1860 a paper on the analysis of Purton saline water I beg like- wise to communicate an analysis of that water which I made for the proprietor in October 1859. The following are the direct results of the analysis. An imperial gallon contains :-Grains. Organic matter and water of combination (being loss obtained on heating residue dried at 320'F) .... 8.750 Lime .. .. .. .. . 34.536 Magnesia .. .. .. .. .. 25.736 Oxides of iron and alumina with traces of phosporic acid .. .. .. .. .. -280 Potash .. .. .... .. 20.707 Soda .. .. .. .. .. 49.006 Chloride of sodium .. .. .. .. 34.297 Sulphuric acid .. .. .. .. 165.074 Soluble silica .. .. I. .. 1.280 Iodine .. .. .. .. * 0.056 Bromine .. .. .. .. .4 *080 Carbonic acid .. .I. .. .. 33.090 Sulphuretted hydrogen .. .. .. traces Specific gravity of water .. .. *. 1.0045 OF PURTON SALINE WATER These constituents arranged into compounds give the following results :-Grains per imp. gal. Organic matter and water of combination (loss on drying residue at 320OF) .. .. . . 8.750 Sulphate of soda .. .. .. 112.239 1. Sulphate of magnesia .. .. .. 77.208 Bromide of magnesium .. .. .. *092 Iodide of sodium .. .. .* .. *066 Chloride of sodium .. .. .. .. 34.297 Sulphate of lime .... .. .. 83.873 Sulphate of potash . . * .. .. .. 1.916 Carbonate of potash . . .. .. .. 28.880 Oxides of iron and alumina with traces of phosphoric acid .. .. .. .. .. 0280 Silica .. .. .. .. .. 1*280 Solid residue dried at 320°F per imperial gallon 348.881 Free carbonic acid .* .. .. 23.820 Dr. Noad has communicated his results to me. They differ materially from mine. But the fact that the water analysed by Dr. Noad contains a great deal more solid matter than the water analysed by me shows sufficiently that we examined two different specimens of Purton water. I have determined at various times the amount of residue which is left on evaporation and find great differences in the total amount of total saline matters. Probably the cornposition of the saline residue varies at different seasons and the water like other saline waters obtained only in limited quantities is not always of the same composition.With respect to the arrangement of the direct results of the analysis into compounds I beg to observe that I have purposely united carbonic acid with potash and not with lime In his arrangement of results Dr. Noad does not give any alkaline carbonates. The Purton water which I examined however con- tains alkaline carbonates for it exhibits a strong alkaline reaction to litmus payer even before evaporation. It is of course impossible to say what proportions of the carboDic acid and sulphuric acid are united with lime and the alkalies and 1 have deviated from the ordinary mode of uniting acids and bases together because the Purton water in its natural condition really contains alkaline carbonates.

ISSN:1743-6893    

DOI:10.1039/QJ8621400046

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年代:1862

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48 V.-On the Basic Carbonates of Copper with some Remarks upon the Curbonates of Xickel and Cobalt. BY FREDERICK FIELD. IN a paper upon this subject lately published in the cr Chemical News," and in Abstract at page 70 of this volume the singular effect of a strong solution of carbonate of soda upon malachite was mentioned together with the action of boiling water irpozi the same mineral. In both instances it speedily becomes black being converted into the black oxide with brisk evolution of carbonic acid. When the blue carbonate of copper (azurite) 3Cu0.2C02.H0is subjected to similar treatment exactly the same phenomenon occurs the whole of the carbonic acid being expelled the action of pure water facilitating thc decomposition far more readily than the solution of carbonate of soda.In a memoir upou the carboirates of copper Rose * iiiforms us that the green carbonate formed on adding a salt of copper to carbonate of soda is converted into the oxide by long digestion with boiling water but no blue compound is obtained. Artificial malachite may however be formed from azurite by heating the latter for some little time in a rather concentrated solution of bicarbonate of soda. A bright blue liquid is produced which after lengthened ebulli- tion deposits a green powder containing exactly the amount of oxide of copper which is found in malachite; it is this pre- cipitate which has a similar composition to that which is produced by boiling a solution of malachite in carbonate of soda does not part with its water under a temperature of 380"F and is evidently formed by the elimination of 1 atom of carbonic acid from 2 atoms of azurite one atom of water at the same time taking the place of the carbonic acid- 2 (3CuO.2C0,. HO) -CO,+ H0=3 (2CuO. CO,. HO) Deville f-mentions that when a salt of copper is gradually added to a strong solution of carbonate of soda nearly the whole of the alkali is precipitated with the copper in brilliant crystals of the double carbonate. In all my experiments warm solutions n-ere employed in which case no douhle compound was formed but a highly basic carbonate and subsequently black oxide were alone produced. "Pogg. Ann. lxxxiv 461 ;Ann. Ch. Pharm. txxx 236. +Ann. Ch. Phys. [3] xxxiii 75 FIELD ON THE BASIC CARBONATES OF COPPER.Carbonate of Cobalt. The various carbonates of cobalt have bcen intimately studied by Rose,* who remarks that the com-position of these compounds depends very much upon the con- centration of the solutions and upon the temperature employed during the precipitation. When sulphate of cobalt is mixed with carbonate of soda a precipitate is formed having the formula 2(CoO. GO,) +3(CoO. HO) +Aq. either from concentrated or from weak solutions and it is only when dilute solutions are decomposed at the boiling point that a precipitate is obtained which approximates to COO.CO +2(CoO. HO) Aq. The same chemist further informs us that when sulphate of cobalt is treated with an excess of bicarbonate of potashin the cold there is formed with brisk evolution of carbonic acid a voluminous precipitate which by long standing is transformed into a mass of tolerably distinct crystals having for their composition KO.CO +COO.CO +9HO. The rather curious phenomena exhibited by the addition of dilute copper-salts to a strong solution of carbonate of soda the latter in great excess led me to investigate the reaction induced upon the salts of cobalt under similar circumstances. When dilute nitrate of cobalt is added to bicarbonate of soda no precipitate occurs until a considerable quantity has been introduced. The solution has a beautiful violet colour and can be brought to ebullition and even maintained at a boiling temperature for some time without undergoing complete decomposition.The precipitate which forms after a further addition of the cobalt-salt has a pure pink colour which scarcely changes its tint even when the liquid in which it is suspended is boiled for several hours. This com-pound appears to hold carbonate soda with remarkable tenacity ; indeed it seems impossible to free it from the latter by any amount of ordinary washing. When the filtrate no longer shows signs of alkaliiiity to test-paper the precipitate removeJ from the filter and heated with a fresh portion of distilled water still yields an alkaline solution On filtering off the carbonate of soda and heating with water as just described the pink colour quickly vanishes and it becomes brown. When nitrate of cobalt is added to an excess of carbonate of soda carefully freed from all excess of carbonic acid the precipitate is not pink but blue maintains its coloirr with some persistency as long RS the super- natant liquid is strongly alkaline and is quite as difficult to free * Pogg.Ann. lxxxiv. 548. Ann. Cli. Pharm Ixxx. 237. T-OL. ZTY. E FIELD ON THE BASIC CARBONATES OF COPPER. from adhering soda as thc other compound. Cobalt it appears differs somewhat from copper when acted upon by either the carbonate or the bicarbonate of soda. When a salt of copper it may be remembered is added to a strong hot solution of the former immediate decomposition takes place carbonic acid is evolved and a highly basic carbonate formed which is ultimately converted into the black oxide. When the bicarbonate is employed a green precipitate of hydrated bicarbonate is obtained.In order to see if oxide of cobalt altogether free from carbonic acid can be procured by long-continued boiling in distilled water solutions of the nitrate of that metal and carbonate of soda mere mixed neither being in great excess. The peach-coloured compound was well washed and suspended in a pint of water which was brought to ebullition arid maintained at that temperature for about ten hours water being added from time to time to compen- sate for the loss resulting from evaporation. The precipitate soon changed colour becoming brown and ultimately black. After filtration it was dried at 212' Fah. and analysed yielding 12.34 of carbonic acid and 78.51 black oxide of cobalt (Co,O,) upon intense ignition The carbonate of cobalt as it originally existed was composed of 2(CoO.CO,) COO. HO) +Aq. and by the action of water at 212* parted with a portion of its carbonic acid and became partially converted into the sesquioxide. A compound containing 12.21 carboiiic acid which upon igni-tion would yield 7'8.41 of the protoperoxide of cobalt would haye the following formula :-2 (COO.GO,) 3 (COO HO)+ Aq + Co203 HO. Found. Calculated. (20,-12.34 CO 12.12 Co,O 78.51 Co 0 78-41 That this compound is a mixture of ordinary carbonate of cobalt with the hydrated sesquioxide arises from the action of dilute hydrochloric acid. When this acid diluted with three or four times its bulk of water is added to the carbonate the latter is almost instantaneously dissolved with brisk disengagement of carbonic acid.Upoii the sesquioxidc however it produces little effect. When cold and comparatively weak the liquid becomes only slightly tinged after being in contact with it many hours. Exactly the same phenomena ocour in the compound just mentioned. On the additioii of dilute hydrochloric acid the whole of the FIELD ON THE BABIC CAltBONATES 03’ COPPER. carbonate is immediately dissolved a black powder remaiuing untouched. When warm and concentrated acid is added to this it is gradually decomposed solution is effected and chlorine is evolved. When nitrate of cobalt is added to a solution of bicar- bonate of soda containing a small quantity of the hypochlorite of that alkali an intense and beautiful green colour is produced aiid no elimination of carbonic zcid results.So strong is the colouring power of this body that 0.2 of a grain of nitrate of cobalt will colour eight ounces of solution a clear bright green as dark as a tolerably concentrated solution of chloride of copper. Large quantities of oxide of cobalt can be dissolved in this way and the liquid if not too strong may be boiled for some time without undergoing decomposition. When however the nitrate of cobalt is rather concentrated and heat is applied a brisk evolution of carbonic acid takes place and sesquioxide is precipitated which adhering in a scaly mass to the sides of the glass and being removed by agitation floats about the liquid in brilliant iridescent plates appearing at first sight to be beautifully and highly crystalline.Cobalt cannot he separated from iron or manganese by this method although every degree of concentration and tem-perature has been tried. When the solutim is not sufficiently warm a small quantity of iron is dissolved when on the other hand considerable heat is applied a small quantity of cobalt remains with the precipitate. Carbonates of Nickel. Nickel-salts exhibit generally speaking the same reactions as those of cobalt in excess of carbonate of soda. I have tried in vain to procure oxide of nickel perfectly free from carbonic acid by boiling the carbonate in water although the resulting compound was very highly basic. No peroxide however is formed as in the case of cobalt. The carbonates of nickel when precipitated in very strong solutions of the alkaline carbonates appear to hold the latter with as great tenacity as the cobalt-compound.

ISSN:1743-6893    

DOI:10.1039/QJ8621400048

出版商:RSC    

年代:1862

数据来源: RSC

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5.2 VI. -Preliminztry Note concernirJg a new Homolope of Benzoic Acid. BY ARTHURH. CHURCH,B.A. ATTEMPTS have been made to effect the oxidation of beuxol by means of an oxidizing mixture consisting of bicliromate of potassium and sulphuric acid; it has been found however that the hydrocarbon remained matt acked. Not so however with the other members of the same series toluol and cumol yielding benzoic acid and cymol an acid of totally different properties and constitution. I have succeeded in producing from benzol an apparently new oxygenated body presenting all the properties one might expect to find in a homologue of benzoic acid containing CH less than that substance. This supposition is strengthened by the result of ail experiment in which nitrobenzol was made to yield an acid body appreiitly standing in the same relation to the first-mentioned new acid as nitrobenzol to benzol.The following was the plan pursued in the preparation of the nem acids Pure benzol was dissolved in a slight excess of Nord-hausen sulphuric acid and the mixture heated for some time to 100°C. Itwas then diluted with about its bulk of water and transferred to a retort. Small fragments of bichromate of potassium were added gradually to the liquid the temperature of which was slowly raised. The acid was found partly floating on and partly dissolved in the aqueous distillate. Great care must be taken lest the oxidation proceed too actively and the product be lost. The acid is a white fusible and crystalline solid dis- tinguished €rom Collinic acid to which the same formula has been assigned by its far greater solubility in hot water.The analytical results indicate the formula- C6H402*for the acid; and C6H,M0 for the salts. The fact that benzol is reproduced in large quantity from sulphobenzolate of ammonium C6H,. NH,. SO, when that salt is submitted to dry distillation suggested the probability that the * C = 12; 0 =16; f3 = 32;H = 1. CHURCH ON A NEW HOMOLOGUE OF RENZOiC ACID. 53 acid itself when acted on by an oxidizing agent might yield the products which we should expect to obtain by the oxidation of the original benzol. When sulphotoluolic and sulphocumolic acids are similarly treated benzoic acid is the corresponding product with sulpho- cymolic acid a white powder apparently identical with the insolinic acid of Hofrnann is obtained.Nitrobenzol is attacked with the utmost difficulty by the chromic acid mixture. By long boiling it is however at length converted iiito a white acid which crystallizes from boiling water in large nacreous plates. Analysis has led to the formula- C,H,(N0,)02 for the acid ;an? C,H,(NO,)MO for the salts. Nitrotoluol and nitrocumol are oxidized with considerable ease under similar conditions yielding nitrobenzoic acid in abundance. This is the caw also with nitrosulphotoluolic acid C,HGNO,. €3’. SO, the acid sulpliite of nitrotoluenyl. The acid from nitrobenzol was obtained in June last but MM. CloGz and Mignet announce in the “Corriptcx Rendus” of January Zlst 1861 that they haw obtaieed a new acid from nitrobenzol by oxidizing it with permanganate of potassium or with a mixture of bichromate of potassium and nitric acid. To their acid they assign the espression C,H (NO,)O, But it is not easy to see how such a body can be derived from the oxidation of nitrobenzol which contains only C,. Indeed the authors are by no means certain of the purity of the nitrobenzol which they employed and they even go so far as to suggest that the acid which they describe may have owed its origin to some foreign body with which the commercial nitrobenzol on which they operated may have been contaminated.

ISSN:1743-6893    

DOI:10.1039/QJ8621400052

出版商:RSC    

年代:1862

数据来源: RSC

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VII.-Un some products of the Action of Dilute iVitric Acid on some Hydrocarbons of the Benzol Series. (PRELIMINARY NOTICE.) BY WARREN DELARUE,PH.D. F.R.S. ETC. AND HUGOMULLER, PH.D. F.C.S. Sonm years ago whilst investigating the nature of Burmese naphtha and examining the products of the action of nitric acid on the hydrocarbons obtained therefrom our attention was directed to similar experiments made many years ago by Laurent who discovered amongst the products of the action of nitric acid on coal-tar naphtha and the naphtha obtained by distilling bituminous schist a new acid called ampelic acid of the interesting composi- tion C,W603,* being isomeric with salicylic acid. As we failed to find nmpelic acid amongst the products resulting from the actioii of nitric acid on Burmese naphtha we repeated Laurent’s experiments with coal-tar naphtha but with no better result ; we could detect no substance corresponding with his description of ampelic acid.These experiments with coal-tar naphtha in con- sequence of their giving a negative result with regard to ampelic acid occupied our attention for some time as we were desirous of making out the somewhat complex nature of the products resulting from the long-continued action of nitric acid on this particular class of hydrocarbons. The coal-tar naphtha used consisted principally of toluol xylol and pseudocumol. Reserving for a further communication the details of our investigation we will. simply state at present that we finally succeeded in obtaining four different acids of the aromatic series The interest attaching to some of them may justify the bringing of QU~results in an incomplete form under the notice of the Society and we are the more induced to take this step because we believe that other chemists are directing their attention to similar products.The preparation and separation of the sub-stances under consideration is attended with the expenditure of a DELI RUE AND MULLER ON HYDROCARBONS ETC. 55 considerable time and the completion of our researches may COB-sequently be somewhat delayed. For our experiments we distilled in a capacious retort purified coal-tar naphtha with about 15 times its volume of dilute nitric acid (containing 1 volume of commercial acid to 3 volumes of water).The action of the acid is very slow; but after several days the hydrocarbons are changed into a heavy liquid which gradually becomes converted into a yellowish-white flocculent substance partly suspended in the acid and partly dissolved in it. When no further change is perceptible the retort i5 allowed to cool. The resulting yellowish-white substance is separated by filtration from the acid mother-liquor and treated with a large quantity of boiling water which dissolves the greater part and leaves some semi-liquid nitro-compounds and a few other sub- stances undissolved. On cooling the aqueous solution deposits the white substance it had held in solution. For the purpose of separating the adhering uitro-compounds and nitro-acids the white substance is dissolved in ammonia mixed mith sulphide of animonium and boiled until the nitro-compounds are converted into amidogen- compounds.To the resulting deep-red solution are then added a few drops of hydrochloric acid which causes a brown precipitate of the amidogen-compounds separable by filtration. The filtrate is then completely precipitated by a further addition of hydrochloric acid and the precipitate consisting of several acids is then filtered of€ and treated agair mith a large quantity of boiling water which leaves undissolved an insolulde acid. The substance deposited on cooling is filtered off and dried. After having been previously fused it is introduced into a small retort and then submitted to careful distillation.At first there distils over a colouTless liquid which very soon solidifies like palmitic acid in the neck of the retort. After a certain time a new substance makes its appcarmce and crystallizes in large acicular crystals in the bulb of the retort just above the boiling liquid. The distillation is stopped at this poiut; and after cooling the first-named substance in the neck of the retort is removcd bp gently warming it. On subsequently continuing the ciistillation very little passes into the neck of the retort the residue becoming gradually black and solid whilst the upper part of tlle bulb becomes filled with magnificent crystals. Vrihen the forma- tion of the latter ceases the operation is discontinued. l’he palmitic-acid-like distillate is a mixture of tMo acids anit for tl,e DE LARUE 4ND MULLER ON ITPT)ROCABBONS ETC.purpose of separating them it is powdered and brought into contact with purified Burmese naphtha boiling at about 90" C. (probably hydruret of capryl C,H,,). The hydrocarbon extracts one part of the distillate leaving the other undissolved. After the hydro- carbon has been filtered it is distilled whereon a liquid residue remains in the retort and gradually solidifies to a beautiful crystalline mass. This crystalline substance is an acid possessing the general properties of benzoic acid. A combustion made with material not quite free from the second acid (which we succeeded at last in separating completely with Burmese naptha which me had not employed in our first experiment) gave numbers (C6H,0,) approaching very nearly those of the next lower homologue of benzoic acid.This new acid fuses at about 60' C. but occasionally remains liquid even at the ordinary temperature especially when not quite pure. It is heavier than water and mixes in all pro- portions with alcohol; it is only slightly soluble in cold water but more so in boiliiig water. From n sSttarated hot solution it separates whilst the solution is cooling as a heavy oil which some- times solidifies immediately but at other times only after a certain interval. This ;icid is slightly volatile even at ordinary tern- peratures for it covers itself with beautiful crystallizations. It possesses a very acrid taste. When boiled with water it volatilizes to a considerable extent.It call be distilled per se without decomposition and forms well-crystallized salts with the alkalies. From this description it will be perceived that this acid bears a great similarity to an acid which was described only a few months since by Frohde who obtained it in small quantities amongst the products of oxidation of glue and albuminous substances arid called it accordingly CoZ/idi?zic wid. The diEerence which still exists may be cleared up by ftirthcr investigation i for Frijh d e had not material enough for combustion nor mas his acid quite free from benzoic acid. Although thc quantity of this acid formed from the hydrocarbons is not great we have no doubt that this source will furnish the material for a complete investigation of this highly interesting acid.The acid which is left undissolved by the Burmese naphtha (hydruret of capryl) has the composition of benzoic acid but it ditfcrs in some points from the true benzoic acid wanting its great power of crystallization. It seems not unlikely that this acid is identical with swtyZic acid the isomer of benzoic acid quite recently describzd by Kolbe and Lautemann (C,H,O,). GUTHRIE ON THE BZSULPHIDE OF IODINE. The before-named crystalline sublimate which deposits in the bulb of the retort is an acid which differs considerably from any of the known acids In its chemical properties it resembles closely terephthalic acid but it differs from this acid in its capability of forming large and distinct crystals when it is sublimed.The crystals when obtained by sublimation form arborescent masses of large prismatic crystals. The quaiitity of the acid obtained was too small to ascertain its- chemical nature more fully. Lastly the insoluble acid which remains undissolved when the precipitate is obtained by tlze addition of hydrochloric acid to thc ammoniacal solution of the crude acids after treatment by sulphide of ammonium is principally terephthalic acid (C,K60,). The terephthalic acid is dried and converted into terephthalic chloride which when heated with methylic alcohol furnishes terephthalate of methyl which can be readily purified by re-crystallization from alcohol and thus when decomposed offers a ready means of procuring terephthalic acid in a pure state.

ISSN:1743-6893    

DOI:10.1039/QJ8621400054

出版商:RSC    

年代:1862

数据来源: RSC

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GUTHRIE ON THE BZSULPHIDE OF IODINE. VIIT.-On the Bisukhide of Iodine. BY FREDERICK GUTHRIE. AN examination of the action of certain compound halogens on some of the olefines has led me to consider incidentally the preparation of some of the compound halogens in the pure state. Of compound halogens while the constitution of none is more invariable and definite than that of the bisiilphide of chlorine,- the bisulphide of iodine can scarcely be said to have been prepared notwithstanding the strong analogy between chlorine and iodine. That iodine combines with sulphur is well known; that such combination is attended by the liberation of heat is equally well established; and since homogeneous mixtures of the two may be prepared in all proportions it is clear that a substance having the percentage composition of the bisulphide of iodine may be formed.Bodies so formed have little or no title to the name of chemical compounds. If we remember on the one hand the fact which I have abun-VOL. XIV. F GUTHRIE ON THE BISULPHIDE OF IODINE. dantly proved on former occasions that an equivalent of bisulphide of chlorine functions as two equivalents of chlorine or as some chemists would express it that the rnoleciile of bisulphide of chlorine is biatomic; and if we further remember that at least two equivalents of chlorine or of zinc are required to recompose iodide of ethyl according to the equations- (l)*C,H,I + 2C1 = C,H,Cl + IC1 (2) C,H,I + 2Zn = C,H,Zn + ZnI we must be prepared to anticipate the analogous re-action- (3) C4H51 + S,Cl = C4H,Cl + S,I This the more because in the case of certain compounds such as NaSn we find-(4) C,H,I + NrtSn = C,H5Sn + NaI.The method I employ for the preparation of the bisulphide of iodine is in fact based upon the validity of equation (3). Recornpositions quite akin to (3) are suffered by the iodides of methyl and of amyl; whence we may assert the general equation-(5) C,H,+,I + S,C1 = C,H,+,Cl + 3,I. For obvious reasons the ethyl-compound is preferred The reciprocal action of iodide of ethyl and bisulphide of chlorine is perhaps as interesting in its manner as in its result. The two liquids may be mixed in all proportions without a greater change in colour than is due to the dilution of the coloured sulphide by the colourless iodide ;neither is heat liberated nor other immediate token given of chemical change taking place.The change appears to be complete in about twelve hours. If the vessel be ogen to the air the chloride of Gthyl evaporates as it is formed leaving the bisulphide of iodine in magnificent crystals contami- nated however by the products of the action of the moisture of the air upon the bisulphide of chlorine. For this reason the process is best conducted in a hermetically sealed tube. The CO-reagents are used in the proportions shown by the equation-& very slight excess of the iodide being added. * Equation (1)expresses only the initial recomposition-the ultimate prahcts are HCl,ICl and chlorine substitution-products of C,H,Cl.GUTHRIE ON THE BISULPI-IIDE OF IODINE. On opening a tube so charged which has been left over night and applying the heat of the hand the chloride of ethyl escapes. A gentle heat suffices to expel the residual iodide of ethyl-where-upon the bisulphide of iodine is left in the form of' fine tabular crystals of the lustre of iodine and in a state of absolute purity. Although the exact composition of the substance may be fairly deduced from its synthesis it was submitted to analysis in the following way 0.3270 grm. was heated in a combustion-tube with nitrate of potash and carbonate of soda whereby the iodine and sulphur were converted respectively into iodide and sulphate of potassium. They were then estimated in the usual way Calculated. Found. S .2O*J3 20.28 I 7'9.87 7'9.81 100*00 100.09 Though in this note this curious re-action is considered as a means of preparing the compound halogen S,I it is perhaps of equal interest as offering a method for preparing an organic chlo-ride from its iodide ;-a problem hitherto difficult and cumbrous in solution albeit its inverse is often easy and of frequent occurrence.

ISSN:1743-6893    

DOI:10.1039/QJ8621400057

出版商:RSC    

年代:1862

数据来源: RSC

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60 On AzobenzoI and Benzidine. ]By P.W. Hofmann. [From the Proceedings of the Royal Society for June 1860.1 AMONG the numerous compounds into which benzol when sub- mitted to reagents is converted axobenxol and its derivatives have as yet received but limited attention. Althmgh more than twentg- five years have elapsed since this interesting body was discovered by Mitscherlich both its formation and its constitution remain still doubtful. Mitscherlich* who discovered azobenzol in 1834 when sub- mitting nitrobenzol to the action of an alcoholic solution of potassa represented this compound by the formula C6H5N t but left the reaction which gives rise to the formation of azobenzol unexplained. In 1845 this body was reprepared by Hofmarin and Musprattt who observed among the collateral products of the reaction aniline and oxalic acid.They represent the formation of azobenzol by the equation ftc6H,No2+ C2H60=C,H,N + C6H,N + C2H,0 +H@ Nitrobenzol. Alcohol. Azobenzol. Phenylamine. Oxalic acid. adding at the same time that they are far from considering this equation as more than the representation of one phase of the trans- formation of nitrobenzol since several other rather indefinite com- pounds are formed simultaneously. At about the same period Zinin made the interesting observation that azobenzol is capable of fixing hydrogen and of being thereby converted into a well-defined base benzidine which he represented by the formula CGH~N. Considering the physical characters both of azobenzol and of benzidine especially the high boiling-points of these substances and the ratio of hydrogen and nitrogen in the latter compound * Pogg.Ann xxxii. p. 224. .t. H=l 0=16 C==12 &c. 2 Mem. of the Chem. Soc POI. iii. p. 113. DR. P. w. HOFNANN ON AZOBENZOL AND BENZIDINE. 61 the sum of the number of equivalents of these two elements not being divisible by 2 many chemists were inclined to double the forrnuh of both bodies and to represent them by the folloving expressions :-Azobenzol . . . . . . c1PI ON, Benzidine . . . . . c12H1 2N2 This view received the first experimental confirmation in the for- mation of the nitro-derivatives of azobenzol which were examined in 1849 by Gerhardt and Laurent. The formation of Nitrazobenzol.. . . C,,H,N,O,= C,,[H,(NO,) J N,, Dinitrazobenzol .b C12H8N404=C,,[H,(NO,),] N, and of several derivatives of these bodies having established the C,,-formula of azobenzol but little doubt could be entertained re- garding the formula of benzidine which is as readily obtained from azobenzol by reducing agents as it may be reconverted into azobenzol by nitric acid*. The molecular valuz of benzidine being thus almost exclusively fixed by the determination of the formula of the compound from which it originates it was of some interest to obtain additional experimental evidence for the molecular weight of azobenzol. With this view I have determined the yapour-density of azoben- zol. This body boiling at a rather high ternperatnre I have availed myself of the method of displacement lately proposed by Professor Hofmann.Experiment proved the density of the azoben- zol-vapour to be 94 referred to hydrogen as unity or 6-50referred to air. The theoretical vapour-density of azobenzol assuming that one molecule of this compound furnishes like the rest of well-examined substances 2 vols. of vapourt is 182-91 referred to 2 hydrogen and 603.2referred to air. This determination of the vapour-density then plainly confirms the higher molecular weights proposed for azobenzol and for benzi-dine. When determining the vapour-density of azobenzol I had occa- sion to observe that probably in consequence of a typographical error the boiling-point of this compound is misstated in all the manuals which I could consult and even in the original memoirs of Mitscherlich himself.The boiling-point is stated to be 193' C. whilst it is in reality 293' C. Benzidiue when expressed by the forniula presents itself as a well-defined diacid diamine. The molecular construction of the diatomic base remained to be decided. * N oble Journal of the Chem SOC.vol. viii p. 293. +H,O = 2 vols. 62 DB. P. w. HOFMANN ON AZOBENZOL AND BENZIDINE. I have endeavoured to solve this problem by the process of ethylation as yet the simplest and the best guide in determining questions of this kind. Benzidine in the presence of alcohol is rapidly attacked by iodide of ethyl. After two hours' digestion at 100"C. in sealed tubes the reaction is complete. The solution on evaporation yields B crystalline iodide Cl6H22N212= C12I312(C2HJ2w29 from which ammonia separates a solid crystalline base very similar to benzidine.This compound which fuses at 65' C. and resolidi- fies at 60' C. is diethylbenzidine c16H20N2 = c12H10 (C2H5)2N29 which forms well-crystallizable salts with the acids and yields with dichloride of platinum a difficulty soluble crystalline platinum- salt containing c,6H22N2c12, 2PtC12. When diethylbenzidine is treated again with iodide of ethyl the phenomena previously observed are repeated. The iodide C20H30V2= ~12Hl&2HJP212 is formed which when decomposed by ammonia yields tetrethyl-benzidine C20H28N2= C12H8(C2H5)4N2* Tetrethylbenzidine resembles the diethylated and the non-ethylated base.It fuses at 85O C. resolidifj7ing at 80' C. produces with the acids crystalline compounds and furnishes with dicliloride of plati-num a platinum-salt of the formula C,oH30N2C12,2PtC12. The further action of iodide of ethyl upon tetrethylbenzidine is extremely slow. After 12 hours' digestion at 100' C. only a very minute quantity of the base had been transformed into an iodide. Iodide of methyl on the other hand acts with great energy. An hour's digestion is sufficient to procluce the final diammoniurn-compound. The iodide C,2H,4N2T2 = 12H8(c2H5) 4(' H3) 2N212 is very difficultly soluble in absolute alcohol but dissolves with facility in boiliug water from which it is deposited on cooling in long beautiful needles. The solution of this iodide is no longer precipitated by ammonia but yields with oxide of silver a power- fully alkaline solution exhibiting all thc characters of the com-pletely substiiuted ammonium- and dismmonium-bases discovered by Professor Hofmann.The solution of this dimethyl-tetrethyl- ated base which contains C,,H,6N20 = '12138 ('2 H5)4 (c'-3[,) zN2I 02 H2 MAXINILIAN SCHMIDL ON OIL OJ!’ CAJEPUT is not further acted upon by either iodide of ethyl or methyl. With acids it forms a series of salts which are remarkable for the beauty with which they crystallize. The platinum-salt is almost in- soluble in water but soluble with difficulty in concentrated boiling hydrochloric acid crystallizing from this solution on cooling in beautiful needles.This salt contains C,,H,,N2C1, 2PtC1,. The above experiments appear to establish the molecular construc- tion of benzidiae in a satisfactory manner. This hase is obviously a primary diamir,e in which the molecular group C1,Hs whatever its nature may be functions as a diatomic radical. A glance at the subjoined Table exhibits the construction of benzidine and of the several compounds which I have described. Diamines. Bemidine. .. . .. Diethylated ben- (‘nH&’’ (C2H5)2 N!2n 5 zidine ...... 03212 Tetrethylated benzidine .. . . iodides of Diammoniums. Primary ..... c(C12%)” H N2j ‘‘I,, Secondary . f(C,,H,)” H (C2H5),’N2]’’12, Tertiary .. . .. L(C12H8)” H (C2H5)4NJ”12, Quartary.. ... t(’ I 2 8)” ( IrT 12 ‘2 H5) 4N21 ’’‘2’ The experiments described in this note were performed in Pro-... fessor Hofmann’s laboratory.

ISSN:1743-6893    

DOI:10.1039/QJ8621400060

出版商:RSC    

年代:1862

数据来源: RSC

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MAXINILIAN SCHMIDL ON OIL OJ!’ CAJEPUT Q)pl the Consfiifaatbn of 8il of Cajepuf. By EZaximilian Schmidl. (From the Transactions of the Royal Society of Edinburgh Vol. XXII., Part TI. p. 360.) OIL OF CAJEPUT is prepared in the East Indies by distilling the leaves of Melaleuca Lewcodendron with water. * It was formerly used to a great extent as an external and even as an internal medi- cine; but has now become more or less obsolete and is seldom NAXINIILIAN SCHMlDL ON THE met with in a pure or unchanged state except in the hands of wholesale druggists. As introduced into Europe it possesses a light green colour resembling that of a dilute solution of chloride of chromium which is caused by a resinous colouring matter dis- solved in it in very small quantity.The colour of the crude oil is also partly due to copper the presence of which may be accounted for either by the use of a copper head in the distilling apparatus of the Indians or by inten- tional adulteration resorted to for preserving the green colour of the oil which otherwise changes gradually by oxidation to a red-dish-brown the oil then becoming unsaleable for medicinal pur- poses. That the oil possesses a green colour of its own is proved by the fact that the cdour remains after the complete removal of the copper by sulphuretted hydrogen. Oil of cajeput consists mainly of the bihydrate of a hydrocarbon (cajputene) isomeric with oil of turpentine. Its specific gravity is 0.926 at 10"C. On submitting it to fractional distillation bihydrate of cajputene which constitutes about two-thirds of the crude oil passes over between 175' and 178"C.; smaller fractions perhaps products of decomposition are obtained from 178"to 240" C.and from 240"to 250" and at 250" only a small residue is left con-sisting of carbonaceous and resinous matter mixed with metallic copper. On treating this residue with ether a green solution is obtained which when evaporated leaves a green resiu soluble in the portion which boils between 175" arid 178" C. and capable of restoring its original colour. CAJPUTENE;, C,,HzG,is obtained together with two isomeric hydro- carbons (isocajputene and paracajputene) by cohobating bihydrate of cajputene with anhydrous phosphoric acid for half an hour and then distilling off the liquid whereupon cajputene passes over at 160"-16~"C.isocajputene at 176"-178"; and paracajputene at 310"-3 16". -Cajputene is perfectly colourless and has a very pleasant odour resembling that of hyacinths. Sp. gr.=0*850 at 15" C. Vapour-density by experiment 4.717 ;by calculation supposing the mole-cule to occupy 4 volumes of vapour it is 4,712. Cajputene is permanent in the air. It is not affected by iodine at ordinary temperatures but at a higher temperature hydrogen is evolved and a black liquid is formed. Bromiize acts quickly on it producing a dark viscid oil. With gaseous hydrochloric acid it forms a beautiful violet liquid but no crystalline compound even at-'10" C. A mixture of' ordinary nitric and sukhuric acids act upon it with violence forming a yellow brittle resin.Cajputene is insoluble in atcohol but dissolves in ether and in oil of turpentine. Isocajputene C,oH,6.-Obtained (1.) as above. (2.) By dis.. CONSTITUTION OF THE OIL OF CBJEPUT tilling the bihydrate of cajputene with oil of vitriol. It is an oil boiling between 176' and 178" C. Its odour is less agreeable than that of cajputene and becomes more pungent and aromatic by exposure to the air the oil at the same time acquiring a yellow colour. Sp. gr. =0.857 at 16"C. Vapour-density of (1)=4%2 ; ot (2) =4.52. Iodine bromine gaseous h~dro~hloric acid and a mixture of nitric and sulphuric acids act upon isocajputene in the same manner as on cajputene. With oil of vitriol and with diZute sul- phuric hydrochloric or nitric acids (neither of which acts upon cajputene) it forms dark viscid liquids.Isocajputene is insoluble in water and in aZcoho2 but mixes in all proportions with ether and with oil of turpentine. Paracaj putene C,,TI,,.-Obtained as above mentioned by dis-tilling bihydrate of cajputene with anhydrous phosphoric acid ;and passes over between 310"and 316"C. It is very viscous has alemon-yellow colour and in certain directions exhibits deep-blue fluores- cence. Vapour-density by experiment 7.96;by calculation (4vd.) =9-424. The difference between the experimental and calculated vapour- densities i3 probably due to decomposition taking place at the high temperature required for the determination. Paracaj putene oxidises rapidly in contact with the air acquiriq a red colour and resinous consistence.A mixture of nitric and suhhuric acids does not act so violently on it as on cajputene and isocajpritene. With hydrochloric acid gas it forms a dark viscid liquid which does not yield crystals even at-10" C. It is inso-luble in water alcohol and oil of tarpentine; soluble in ether. HYDRATES CAJPUTENE.-~.Mono-hydrate C2,HI6.HO.-OF Obtained by the action of oil of vitriol on oil of cajeput. When the crude oil is raised to the boiling point in a deep open vessel and oil of vitriol continuously dropped into it violent ebullition takes place accompanied after a while by a peculiar crackling sound. As soon as this is observed the flame must be lowered and the acid very cautiously added till the liquid suddenly assumes a dark colour extending in an instant from the surface throughout the whole depth.The vessel must then be immediately removed from the fire otherwise further decomposition will take place attended with evolution of s ulphurous acid. The upper oily liquid is separated from the acid on which it floats then well washed and distilled and the portion which passes over from the 170"to 175" is collected and rectified. It is an oily liquid having a vapour-density of 5.19 to 5.27; by calculation (4 vol.) =5-024. This vapour-density is anomalous inasmuch as the molecule C,,H1,O which occupies four volumes of vapour contains but 1 atom of oxygen. Probably the true formula of the body is MAXIMILIAN SCHNIDL ON THE C4-,H3402= C40H32+ H,O, this molecule splitting up at high temperatures into C401232 and H,O, each of which occupies four volumes of vapour and consequently the two together occupy 8 volumes.* b.Bihydra te C,,Hl,0,=CY,,H16~2H0.-Th~s is the chief con- stituent of oil of cqjeput and passes over in the fractional distilla- tion between 175" and 178" C. After rectification it is a colourless oil which boils constantly at 175" has a specific gravity of 0903 at 17" and vapour-density = 5.43j the calculated vapour- density (4 vol.) is 5-35. When exposed to the air for a considerable time in the moist state it changes to a reddish liquid which ultimately exhibits a rather strong acid reaction with litmus. Iodine dissolves in the oil and under certain circumstances forms crystalline compounds (p.69). Bromine acts quickly upon it and forms crystalline compounds under similar circumstances. Chloriae gas passed into the oil raises the temperature but does not appear to act upon+ it further ; but nascent chlorine (evolved by passing hydrochloric acid gas into the oil mixed with dilute nitric acid) converts it into bicliloride of cajputene CzoH16C12. Anhydrous phosphoric acid heated with the bihydrate takes away the whole of its water converting it into cajputene isocajputene and para- cajputene (p. 64). Chtoride of zinc likewise dehydrates it but less completely. Strong su&huric acid acts but very slowly on the oil at low temperatures; but if the temperature be allowed to rise sul-phurous acid is given off and the oil blackens and ultimately suffers complete decomposition.If the action be checked at a certain point a sulpho-acid is formed which yields a soluble baryta-salt. Strorig sulphuric acid dropped illto the oil at the boiling heat in the manner described at page 65 takes away half the water forming mono-hydrate of caj putene. DiZuute suZplhuric acid on the contrary causes the bihydrate to take up 4 At. more water converting it into C,,H16+ 6EO. Fuming su@huric acid converts the bihydrate into a thick brown liquid which boils above 360". Fuming nitric acid rapidly oxidises the oil even at ordinary temperatures forming large quantity of oxalic acid. Ordiiiary nitric acid produces the same effect at the boiling heat but at ordinary temperatures it over acts very slowly converting the oil into a red liquid.Distilled permanganate or bichmmate of potassium in presence of sulphuric acid it forms a thick resinous liquid. It does not appear to be altered by digestion with peroxide of lead. In contact with aqueous potash or when dropped into melting potash it forms a soluble salt the acid of which is precipitated as a resin by hydrochloric * See "Observations on Anomalous Vapoiir-densities," by Dr. Hofmann; (Pro. ceedings of the Royal Society vol. x pp. 224 596); also Gnzelin's Handbook, English Edition xiii 487. CONSTITUTION OF THE OIL OF CAJEPUT. 6'7 or sulphuric acid. Heated with sodium it forms a crystalline mass soluble in water and alcohoI and consisting of soda and an organic substance which is separated by strong acids in the form of a fragrant resin.When the vapour of the bihydrate is passed over red hot soda-lime a yellow oil distils over having a peculiar odour quite different from that of the bihydrate and at the same time the soda-lime becomes blackened by deposited charcoal and when treated with acids gives oft' a large quantity of carbonic acid. The yellow oil thus formed yielded by distillation a fraction boiling between 180"and 185"C. which gave in two analyses 79-76 and 80.03 p. c. C 12920 and 12.07 H agreeing nearly with the formula C26H24026 which requires 79-59 p. c. C 1244 H and 7-97 0. Bihydrate of cajputene dissolves in all proportions in alcohol ether and oil of turpentine.c. Hex hydrate C?oH2?06 =~20~16,6~0.-~~~oduced by the action of dilute sulphuric acid on the bihydrate or on crudeoilof caje- put. Two parts of dilute sulphuric acid are added to 1part of the crude oil; and the mixture is well shaken €or several days till the watery layer acquires a yellowish colour and then left to itself for about ten days whereupon it deposits crystalline tufts of the hex- hydrate adliering to the sides of the vessel. The crystals melt at 120"C. and solidify again at 85'. On sub-mitting them to dry distillation an oily liquid passes over and condenses again in the colder parts of the apparatus apparently as the unaltered hexydrate. The crystals dissolve sparingly in cold easily in boiling alcohol. Crystals having the same composition were deposited from a secon-dary fraction of crude cajeput-oil which distilled at 216"-2230" C.and was left for a very long time moist and exposed to the air. The crude oil mised with nitric acid andalcohol changes in the course of seven or eight months into a black heavy liquid in which crps- tals are suspended perhaps consisting of the hexhydrate. The same compound appears likewise to be formed in beautiful long prisms when the crystalline inass produced by passing hydrochloric acid gas into rectified oil of cajeput is thrown into water or alcohol. OF CAJPUTENE. CHLORIDE C,,H,GC1,.-Produced by the action of nascent chlorine on the bihydrate. When the portion of cajeput oil distilling between 175" and 178"C. is mixed with very dilute uitric acid and hydrochloric acid gas is passed into the liquid a violent action takes place in a few minutes yellow and red fumes of chlorine and nitrous gas being evolved and if the passage of the gas be continued chloride of cajputene ultimately sinks to the bottom as a limpid brown oil which may be freed from adhering nitric and nitrous acid by distillation over strong potash-ley.It has a fragrant odour and may be kept for any length of time MBXIMILIAN SCHblIDL ON THE without alteration but is decomposed by distillation. Boiled with nitrate of silver it detonates in a peculiar manner and forms chloride of silver. Crystals %-ere once obtained by keeping the oil at a low tempera- ture but not in suffcient quantity for analysis.MONOHYDROCHLORATE C,oH,6,HC1.-Obtained OF CAJPUTENE. by distilling the bihydrochlorate and collecting apart the fraction which boils at 160". A product having the same composition is obtained by treating the bihydrochlorate for several days with aqueous or alcoholic potash ; but its odour is different from that of the product obtained by simple distillation of the hydrochlorate and resembles that of pelargonic ether. OF CAJPUTENE. BIHYDBOCHLOBATE C2,H,,,2HC1.-Obtained by passing hydrochloric acid gas through rectified cajeput-oil mixed with a third of its volume of alcohol or strong aqueous hydro- chloric acid. Crystallihes from alcohol in beautiful radiating tufts. Melts at 55" C. and solidifies again at 30". It has no taste or smell.By dry distillation it gives off hydrochloric gas at 60" and splits into several fractions one of which is the monohydrochlorate. It is also deprived of half its chlorine by heating with aqueous or alcoholic potash. It dissolves sparingly in cold easily in boiling alcohol or ether. When hydrochloric acid gas is passed through rectified oil of cajeput kept at a low temperature a violet liquid is formed which in 10 or 15 minutes solidifies in a crystalline mass. This crystal- line compound is extremely deliquescent liquefying rapidly even when pressed between blotting paper cooled to -25" C. ;the result- ing liquid rapidly gives off fumes of hydrochloric acid and is com- pletely decomposed by distillation. If the crystalline mass imme- diately after its formation be thrown into water or alcohol beautiful long prisms are formed after a few days apparently consisting of hexhydrate of cajputene.BROMIDE CAJPUTENE. OF C20H16Br4.-Obtained by the action of bromine on oil of cajeput. When dry bromine is dropped into the rectified oil a very brisk action takes place and the sides of the vessel become covered with yellow needles which however soon disappear; but if the addition of the bromide be continued till the reaction almost ceases a dark thick viscous oil is formed which after several weeks deposits a granular substance. By boiling the mixture with alcohol the granular substance is extracted ; a heavy oil is left behind; and the alcoholic solution on cooling deposits bromide of cajputene as a soft crystalline substance having a fatty lustre and much resembling cholesterin.Bromide of cajputene melts at'60" C and solidifies again at 32". CONSTITUTION OF TI-IE OIL OF CAJEPUT. By dry distillation it yields a liquid which crystallises again in the cooler parts of the retort. It is not altered by boiling with aqueous potash. It dissolves in ether and in boiling alcohol. Rectified oil of cajeput shaken up with bromine-water forms a red resin from which a solid substance separates in small white prisms extremely deliquescent and rapidly decomposing. Another crystallised bromine-compound (probably a hydro-bromate analogous to the hydriodate) is formed in the same manner as that compound. HYDRIODATECAJPUTENE.-a.Anhydrous C20~16,HI.-Ob-OF tained by adding a solution of phosphorus in bisulphide of carbon to a solution of iodine and oil of cajeput in the same liquid.Brisk action then takes place the vessel becoming very hot; red oxide of phosphorus is precipitated ; the oily liquid becomes reddish ; and gives off vapours probably containing phosphurretted hydrogen and if left to itself for 10 or 12 days deposits crystals of the hydriodate. The reaction probably takes place as represented by the equation 3C2oHl~+ 3PI + 6H0 = 3C20H,71+ PH + PO + PO The crystals of the hydriodate are deposited in cells like those of beehives and possess a black metallic lustre. They are soluble in alcohol and in ether and are very stable not being altered even by boiling with potash.b. Hydrated C2,H1,10 = C20H16HI+ HO. or Hydriodate of Monohydrate of Cajputene. C,oH,70,HI.-When iodine is added in small quantities to cajeput oil crude or rectified at ordinary tem- peratures no visible action takes place (if external heat be applied the action goes too far and nothing but a viscous mass is produced which does not crystallise) ;but on stirring rather constantly the Rction is assisted partly by the heat resulting from the friction of the glass rod partly by the mechanical distribution of the iodine md the temperature of the liquid soon rises from 10"to 40"C. The addition of iodine must then be discontinued asd the vessel immersed in cold water. A black crystalline compound then separates after a short time ;and on separating this substance from the oily liquid by filtration pressing it between blotting paper and when it is nearly dry dissolving it in alcohol or ether a solution is obtained from which the hydrated hydriodate crystallises in prisms having a fine yellow-green colour and metallic lustre.They are very deliquescent and melt at 80"C. into a liquid which does not recrystallise in the cold. Potash-ley liquefies the compound abstracting part of the iodine and with the aid of heat abstracts the whole. It is insoluble in water and is not decomposed thereby; very soluble in alcohol and ether.

ISSN:1743-6893    

DOI:10.1039/QJ8621400063

出版商:RSC    

年代:1862

数据来源: RSC