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PRECIPITATION OF THE COLOURING MATPER OF SUGAR. 55 March 18 1850. J. T. COOPER,EsQ. V.P. in the Chair. Charles Shearman Esq. John Cameron Esq. and George Ewbanks Esq. were elected Fellows af the Society. The ‘<Quarterly Journal of the Geological Society” was laid on the table as a donation from the Society. The following Papers were read .‘ On the r‘elations between Chemical Composition Boiling Point and Specific Volume,” by Professor Hermann Kopp (to be published in the next number). X.-On the Precipilation of the Colouring Matter of Sugar by a Metallic Oxide. By HENRYWARBURTON, F.R.S. F.G.S. &c. (Ina letter to PROFESSOR GRAHAM). Allow nie to put upon paper what I said to you the other day respecting the experiments I made many years ago (the year of Mr.Howard’s death) with the view of precipitating the colouring matter of brown sugar in combination with a metallic oxide. My assistant was a gentleman related by marriage to Mr. Howard and his operator in all the experiments on sugar-refining and filtering connected with Mr. I-Ioward’s patents. He gave me the information I was in want of as to the strength of the syrups at which it would be requisite to effect the precipitation of the colouring matter in order to render any process of that kind available to the sugar refiner. He prepared for me a small apparatus for filtering the syrups at a boiling heat and pronounced judgment on the results obtained. The metals I used were iron lead zinc and tin. Iron I at once abandoned.Lead I was afraid of; though with the sub-acetate followed by a little sulphuric acid and that followed by a little hydrate of lime I obtained very colourless results. With the sulphate of zinc the results were very good. A solution of this salt was first mixed with the syrups and then hydrate of lime was added equivalent to the sulphuric acid in the salt. One experiment of this kind was made on the great scale at the boiling- house of a firm with whom Mr. Howard was connected in business and was regarded by them as highly promising. However Dr. Wollaston found a trace of zinc in some of the syrups which had been thus treated and I was afraid of zinc also. NR. WARBURTON ON THE The best results of all were obtained with sulphate of tin; and one experiment on the large scale was niade with this salt at the boiling- house of the firm referred to.I am sorry that I cannot lay my hand on my cotemporary meinoranda of the details of all my experiments with this salt ;and you must be content therefore with the outline of tliern which I now give from memory. The salt was prepared by precipitating the copper of blue vitriol with grain tin the latter being finely granulated by crushing it while hot by a wooden pestle; and to prevent the copper from coating the tin as it precipitated clean copper plates wefe immersed in the liquid with the tin. Perhaps the best way would be to make the precipitation in a clean copper vessel. To hasten the precipitation I sometimes added an excess of sulphuric acid; and I kept the vessels cool by immersing them in water.I could not obtain a strong solution of tin in sulphuric acid by the direct action of sulphuric acid on tin a quantity of subsulphate or insoluble oxide in this case was always found. After adding a solution of the sulphate of tin to the syrup a quan- tity of hydrate of lime rather more than equivalent to the sulphuric acid was superadded and then the syrup was boiled by steam and filtered hot in a vessel surrounded by steam. I also used with great success as a precipitant of the sulphuric acid freshly precipitated hydrated oxide of lead. But this was only in experiments on the small scale. Astonishingly perfect results are obtained with the sulphate of tin when you operate with dilute syrups.The difficulty consists in effecting a complete precipitation of the colouring matter in the syrups of the strength usually employed by the refiner. Dr. Wollaston did not find any oxide of tin in the syrups treated with tin. My friend Dr. Wollaston’s relative always advised the final employment of a small quantity of animal charcoal as it gave a jiuidity to strong syrups that could be obtained in no other way. In our small experiments we added a soupqon of animal charcoal after the tin and lime had done their work. As I made these experiments only for my own amusement and to serve Mr. Howard’s family if his relatives or the firm thought fit to persevere in them I left the matter in their hands. But this was the critical period for them when the refiners were just beginning to take out licenses to boil sugar under Nr.Howard’s patents; and their opinion which appeared to me a well-founded one was that any new improvements suggested at that period would tend to PRECIPITATION OF THE COLOURENG MATTER OF SUGAR. 57 unsettle the minds of the refiners and rather deter them from making up their minds to apply at once for a license. I conclude that all the tin employed may be recovered without difficulty from the precipitate which will be a mixture of gypsum and vegetable matter combined with oxide of tin. It would be a saleable article to metallurgists ; so also will the precipitated copper be. I shall be curious to know whether any experiments you may make with the sulphate of tin prove satisfactory. Of course any other soluble salt of tin will answer when the dissolving acid is neutralized by lime or an alkali subject to the condition that the new compound thus found is not soluble in the syrup.

ISSN:1743-6893    

DOI:10.1039/QJ8510300055

出版商:RSC    

年代:1851

数据来源: RSC

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PRECIPITATION OF THE COLOURING MATTER OF SUGAR. 57 XI.-On the Composition of the Ashes of the Cactus. By FREDERICK FIELD,ESQ The great abundance of various species of Cacti upon all the hilIs and mountains of Chili even upon the most barren spots and in the most arid seasons led me to investigate the inorganic constituents of this tribe of plants more especially as in England and most parts of Europe the Cactus is only known in the conservatories of a few individuals. Several branches from a plant more than 16 feet in height were carefully cut from the parent stem and after having been redivided were exposed to the temperature of 212O FaEr. for the space of fourteen days. 185*00grs. lost 157.42 leaving 27.58 solid matter which numbers correspond to Water .. 85.09 Solid matter . . 14.91 1oo*oo 29.80 grs. of this solid matter incinerated with every precaution in a platinum crucible gave 5.00 grs. of ash equal to 16-79per cent. 185.00 grs. of recently cut branches (with the thorns or spines attached) gave on incineration 2.50 grs. of ash corresponding to 1.35 grs per cent. In the following analyses the soluble and insoluble portions were examined separately the proportions for the sake of perspicuity being reduced to percentage numbers. 58 MR. FIELD ON THE Determination of matter soluble in water I. 100 grs. gave . . 57.010 11. 100 ,) , . 57.300 Mean 57.155 The composition of this soluble matter is as follows in 100 parts Sulphuric acid . . 6-232 Chloride of sodium .18.767 Potash . 9.873 Soda . . 35-585 Phosphoric acid . . 2.265 Carbonic acid . 26.0416 913.768 Loss in analysis . . 1.232 100*000 Determination of matter insoluble in water I. 100 grains gave . . 42.842 11. 100 ) ) . 42,620 -Mean 42-730 The composition of this insoluble matter in 100 parts Sand and charcoal . . 2.300 Silicic acid . . 27-830 Carbonic acid Sulphuric acid . . . . . 25.562 1.952 Phosphoric acid . . . 7.806 Phosphate of iron . . 2.338 Lime. . 17925 Magnesia . . 13.162 Oxide of manganese . . 0.558 Loss . . 0.567 100*000 Upon adding the soluble and insoluble portions together and calculating the general composition of the ash we find in every 100 parts ASHES OF THE CACTUS.59 SOLUBLEPORTION Sulphuric acid . . 3.561 Chloride of sodium . . . 10.726 Potash . 5.642 Soda . . . 20.338 Phosphoric acid . . . 1.294 Carbonic acid . . 14.836 INSOLUBLEPORTION Sand and charcoal . 0.982 Silicic acid . * 114391 Sulphuric acid . Phosphoric acid . . 0.834 . 3.325 Carbonic acid . 10.927 Phosphate of iron Lime. . . . . . . 0.999 7.659 Magnesia . . 5.624 Oxide of manganese Loss in analysis . . . 0.238 1*124 100~000 As the carbonic acid is doubtless derived from the decomposition of organic acids and the sand and charcoal may be regarded as accidental and of no value in the analysis they may be deducted we then have the following numbers Sulphuric acid . Chloride of sodium Potash . Soda . . . Phosphoric acid . Silicic acid Phosphate of iron Lime. Magnesia . Oxide of manganese 6.094 14.869 7.832 28.196 6.404 16.486 1*384 10.649 . 7.747 . 0.339 100~000 From this it appears that the cactus belongs to the first class that is to say to that iu which the carbonates of the alkalis and alkaline earths predominate.

ISSN:1743-6893    

DOI:10.1039/QJ8510300057

出版商:RSC    

年代:1851

数据来源: RSC

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MR. GRAHAM ON DECOMPOSITION XII.-On the application of Liquid Difusion to produce Decom-positions. By THOMAS F.R.S. F.C.S. GRAHAM The experiments to be described in the sequel of this paper were conducted in the same manner as those contained in a late com- munication to the Royal Society.* A set of phials of nearly equal capacity were made use of all cast in the same mould and further adjusted by grinding to a uniform size of aper-ture. The dimensions for a phial (see Fig.) were 3.8 inches in height with a neck 0.5 inch in depth; aperture 1.25 inch in diameter and capacity to base of the neck 2080 grains of water or between 4 and 5 ounces. For each phial a plain glass jar was also provided,4 inches in diameter and 7 inches in depth. The me- ~ thod of observing the diffusion of a salt will be best explained by an example.For my present object it was necessary to observe the spontaneous diffusion into pure water of several salts already dissolved in 100 times their weight of water. The phial was filled with such a solution of sal-ammoniac for instance to the base of the neck or more correctly to a distance of exactly 0.5 inch from the ground surface of the lip. The neck of the phial was then filled up with distilled water a light float being placed on the surface of the solution and care taken to avoid agitation after the phial had been placed within the jar. The latter was then filled up with distilled water so as to cover the open phial to the depth of an inch which required about twenty ounces of water.The saline liquid in the ‘‘solution-phial” is thus allowed to communicate freely with the water of the “water-jar.” The water of the latter forms an atmospliere into which salts spread or diffuse escaping from the solution-phial with different degrees of velocity. The phial and jar together form the “diffusion-cell.” The diffusion is interrupted by placing a small plate of ground glass upon the mouth of the phial and raising the latter out of the jar. The amount of salt diffused or the ‘‘diffusion-product,” is learned by evaporating the water of the jar to dryness or with this and the following chlorides by precipitating with nitrate of silver. The diffusion was always allowed to proceed for a period of exactly seven days unless another time is expressly mentioned.The experiments were conducted in a vault of which the temperature did not vary more than one degree on either side 50° F. * On the Diffusion of Liquids. Read December 21 1849. BY LIQUID DIFFUSION. The one per cent solution of sal-ammoniac in the solution-phial would contain 20.8 grains of salt. Of this quantity of salt 3.49 grs. were found to diffuse out into the water-jar in the time mentioned in one experiment and 3-86 grains in another experiment. The mean of these two diffusion-products is 3.42 grs. which is therefore the quantity of hydrochlorate of ammonia diffused out of the solution phial containing a I per cent solution of that salt in a period of seven days. The diffusion of a 1 per cent solution of chloride of sodium in similar circumstances gave in eight cells the following products 3-02 2.83 2.86 2-68,2.74 2.70 2.80 and 2.94 grs.of which the mean is 2.85 grs. These results for the chlorides of ammonium and sodium approach to the theoretical ratio of 1.4142 to 1.7320 that is of the square root of 2to the square root of 3. Anhydrous chloride of calcium gave 2.01 and 2.04 grs. in two experiments ; mean 2.02 grs. Anhydrous chloride of magnesium gave 2-15and 1-90grs; mean 2.03 grs. These two earthy chlorides appear therefore to be equally diffusible. I may place along with these results the diffusion- products which the alkaline hydrates and a few other salts would have afforded in similar circumstances the latter numbers being deduced from experiments detailed in the paper on the diffysion of liquids already referred to.SALT DIFFUSED FROM A 1 PER CENT SOLUTION IN EQUAL TIMES Hydrate of potash . 4-84! grs. > soda . . 4.03 ), 7 Chloride of ammonium . 3.42 , , , potassium. . 3.42 ,, ... . 2.85 ,, , , sodium . . 2.35 ,, Sulphate of soda. . 2.02 ,, Chloride of calcium . . , , magnesium 2.03 , Sulphate of lime. . . 1.21 , 1.21 ,, , , magnesia . The alkaline hydrates have the highest diffusibility being twice as diffusive as the sulphates of the same bases and four times as diffusive as the sulphates of magnesia and lime. Tkie salts of potash and ammonia of the same acid have an equal diffusibility which is greater than the diffusibility of the corresponding salts of soda.Now it has been shown that when two salts are dissolved together MR. GRAHAM ON DECOMPOSlTION in the solution-phial they diffuse independently each salt maintaining its own rate of diffusion. Hence the possibility of separating salts to a certain extent by diffusion in a manner analogous to the separation of substances of unequal volatility by distillation. Further decompositions may be effected by diffusion such as the decomposition of alum the sulphate of potash being separated from the sulphate of alumina from the higher diffusibility of the former substance. It appeared probable also that in a mixture of several salts the acids and bases would have a tendency to arrange themselves so as to form the most diffusive compounds when an opportunity for diffusion was presented.This would be analogous to the sublimation of carbonate of ammonia when carbonate of lime and hydrochlo- rate of ammonia are heated together. As the order of affinity is often determined in mixed salts by volatility or insolubility according to the canons of Berthollet so it may be regulated and determined in a similar sense by diffusibility. The application which I have particularly in view is the possible decomposition of the sulphates of potash and soda and of the chlorides ofpotassium and sodium by means of lime when the affinity of that base for an acid is aided by the high diffusibility of the hydrate of potash or of soda. 1. A solution was made of 1 part of sulphate of potash in 100 parts of lime-water with which six phials were filled and placed to diffuse in jars containing lime-water instead of water simply for the usual period of seven days.To obtain the salts diffused the fluid of the jars was treated with an excess of bicarbonate of ammonia and evaporated twice to dryness. The filtered liquid contained only sulphate and carbonate of potash without a trace of lime. The r>ro.xlortions of these salts found indicated a diffusion-product from .I.& two phials of Hydrate of potash . 1.08 grs. 23-69 Sulphate of potash . 3.48 , 76.31 c___ 4.56 , 100*00 The diffusion-product of the remaining four cells was similar Hydrate of potash . 2.19 grs. 21.66 Sulphate of potash . 7.94 , 78.34 10.13 , 100.00 More than a fifth part of the diffused salt appears thus to be hydrate of potash and a considerable decomposition of the sulphate of potash has therefore taken place.BY LIQUID DIFFUSION. 2. Sulphate of soda dissolved in lime-water was diffused into lime-water in a precisely similar series of experiments. The diffusion-product obtained in a set of four cells appeared to consist of Hydrate of soda . . 0.90 grs. 11-45 Sulphate of soda. . . 6.87 , 88.55 7-77 , 100~00 Of another set of four cells the diffusion-product was repre-sented by Hydrate of soda . . 093 grs. 13.22 Sulphate of soda. . 6-10 , 86.78 c__ 7.03 , 100*00 The hydrate of soda formed and diffused is very sensible amount- ing on an average to about 12 per cent of the whole diffused salt.It may be remarked that although sulphate of soda may be justly supposed to require a less powerful affinity to decompose it than sulphate of potash still the latter salt appears to yield to the action of the lime to a greater extent than the former in these experiments ; the weight of hydrate of potash diffused being fully double that of the hydrate of soda. The result in question may be confidently referred to the superior diffusibility of the hydrate of potash and establishes beyond doubt the nature of the agency by which the decomposition in both cases is principally if not wholly effected. The low diffusibility of the sulphate of lime (one fourth of that of hydrate of potash) retains a large proportion of that salt behind in the solution-phial where indeed it was deposited in crystals.It is proper to remark that a similar deposition of sulphate of lime took place in lime-water containing so much as 1 per cent of sulphate of potash or sulphate of soda in the course of two or three days in a close vessel quite irrespective of diffusion. One of the solution- phials was found to contain so much as 2.04 grains of hydrate of potash formed in consequence of this deposition of sulphate of lime without any diffusion in the course of seven days. The same decom- position of sulphate of potash with deposition of sulphate of lime was observed by Scheele and afterwards referred by Berthollet to the insolubility of the latter salt which enables the affinity of lime for sulphuric acid to prevail over that of potash for the same acid.MR. GRAHAM ON DECOMPOSITION 3. Similar solutions of 1per cent of chlorides of potassium and sodium in lime-water were diffused into lime-water. Eight cells of chloride of potassium gave 25-51grains of diffused salt containing only 0.04 grain of hydrate of potash. Eight cells of chloride of sodium gave 20-77 grains of diffused salt containing no more than 0.08 grain of hydrate of soda. The decomposition of the alkaline chlorides is so small as to be barely sensible not exceeding in the most favourable case more than &th part of the salt diffused. Lime therefore appears in- capable although aided by diffusion to decompose the chlorides of potassium and sodium to a sensible extent.4. Solutions in lime-water were diffused of 0.25 and 0.5 per cent of the alkaline sulphates not with the view of increasing the product of alkali but for the purpose of observing the diffusion where no deposition of sulphate of lime is possible owing to the dilute con- dition of the solutions. The experiments however come to be more liable to derangement from currents produced by small changes of temperature and other accidental causes of dispersion where the solution in the phial differs so little in density from the water of the jar. One set of four cells containing the quarter per cent solution of sulphate of potassa in lime-water gave 0.321 gr. of hydrate of potash Another similar set gave 0.614 gr. of hydrate of potash.The hydrate of soda diffused from four cells of the quarter per cent solution of sulphate of soda was 0,260gr. The diffusion was always into lime qwat er. The half per cent solution of sulphate of potash in lime-water gave 0 62 gr. hydrate of potash in two cells ; or twice as much alkali as the quarter per cent solution. The diffusion-product was alto-gether 2.60 grs. so that 23.86 per cent of the salt diffused con-sisted of hydrate of potash. No sulphate of lime crystallized or was deposited in the phial or jar in any of these experi-ments so that the decomposition of the sulphate of potash by lime cannot be referred in any degree to the insolubility of sulphate of lime but must be ascribed entirely to the high diffusibility of hydrate of potash.5. Carbonate of lime dissolved in carbonic acid water or a satu- rated solution of bicarbonate of lime was now applied to form a 1 per cent solution of sulphates of potash and soda. These solutions were diffused from the phials into pure water as the liquid atmos- phere of the jars. Decomposition of the alkaline sulphate always took place and without any visible deposit of sulphate of lime but BY LIQUID DIFFUSION. to a less extent than in the preceding experiments with hydrate of lime. The proportion of potash salts diffused in two pairs of cells was 4-86 and 5.84 grs. ; of which 0.26 and 0.30 gr. was carbonate of potash or 5.35 and 6.2 per cent of carbonate of potash. The proportion of soda-salts diffused in two pairs of cells was 3.40 and 3-78 grs, of which 0.26 and 0.29 gr.was carbonate of soda; or 7.65 and 7.67 per cent of carbonate of soda. The excess of carbonate of soda diffused over the carbonate of potash in these experiments is probably accidental. The experiments on the decomposition of an alkaline sulphate by means of carbonate of lime aided by diffusion are chiefly interesting as they illustrate a decomposition which may occur among the salts of the soil and with the formation of an alkaline carbonate from a reaction between carbonate of lime and an alkaline sulphate although the solutions may be too dilute to admit of any separation of sulphate of lime in the solid state. But the decomposition of the chlorides of potassium and sodium is a more important problem than that of the sulphates of potash and soda.The direct diffusion of these chlorides with hydrate of lime appears to be inadequate to produce this effect for no more than a trace of fixed alkali was obtained in the experiments already described. It was further observed that a saturated solution of the chlorides of potassium and sodium in lime-water did not afford the smallest appreciable quantity of alkali by diffusion. Bicarbonate of lime had no greater effect upon the alkaline chlorides. But the conjoint action of lime-water and the sulphate of lime upon these chlorides gave better results. 6. Lime-water and solution of sulphate of lime both saturated solutions were mixed together in equal volumes and the liquid was employed to dissolve 1 per cent of chloride of sodium.The phials charged with this solution were allowed to diffuse into pure water. After separating the hydrate of lime from the water of the jars the latter exhibited only the faintest possible alkaline reaction due to soda. The proportion of alkali was too minute to be appre- ciated by the alkalimetrical method although a quantity so small as 0.01 gr. could be determined. To enable the hydrate and sul- phate of lime to act upon the chloride of sodium it was found necessary first to heat the solution before diffusion. 7. The solution of sulphate of lime with an addition of 2 per cent of chloride of sodium was kept at the boiling point for half an hour No deposition of sulphate of lime occurred then or after the liquid cooled.Two or three days afterwards this solution was VOL. 111.-NO IX. F MR. GRQHAM ON DECOMPOSITION mixed with an equal volume of lime-water and diffused into pure water for the short period of three and a half days. The liquid of the jars was evaporated to dryness as usual with an excess of pure carbonate of ammonia to precipitate the salts of lime. The hydrate of soda diffused in three cells amounted to 0.234gr. and the sulphuric acid to 0.209 gr. Allowing the sulphuric acid to have diffused as sulphate of soda and putting out of consideration the undeeompoaed chloride of sodium which was also diffused we have a diffusion-product of Hydrate of soda . . 0234gr. Sulphate of soda . . 0.371 , 0.605 gr. These quantities are necessarily small from the form of the experi- ment but could easily be increased by enlarging the diffusing surface which is at present limited to the area of the aperture of the solution phial.They are amply sufficient however to establish the fact that the united affinities of hydrate and sulphate of lime are sufficient to decompose chloride of sodium when aided by diffusion of the hydrate of soda formed. Of chloride of potassium we have reason to believe that the decomposition would be more considerable in similar circum- stances. Two phials of the same liquid as in the last experiment were diffused into water for the longer period of seven days and eighteen hours. The whole lime found afterwards in the water-jar and pre- cipitated by the addition of carbonate of ammonia was represented by 1.01 grain of carbonate of lime.The soluble salts filtered from the last amounted to 6-14! grains and contained carbonate of soda equivalent to 0.686 gr. of hydrate of soda and sulphuric acid equiva- lent to 0.373 gr. of sulphate of soda. It is difficult to decide in what form the lime reached the water-jar but this earth was probably diffused out of the solution-phial partly as hydrate of lime partly as sulphate of lime but principally as chloride of calcium. The last two salts would destroy a portion of free alkali in the evapo- ration but the hydrate of soda obtained even after this deduction amounted to 10.52 per cent of the whole salts diffused. With a smaller quantity of chloride of sodium than 2 per cent in the original mixture the alkali although not increased in absolute quantity might no doubt come to form a conside2ably larger proportion of the diffusion-product.The experiments also throw a curious light upon the condition of BY LTQUID DIFFUSTON. mixed salts. It follows from the absence of hydrate of soda in the diffusion product of the first experiments that cold solutions of sulphate of lime and chloride of sodium may be mixed without decomposition or without any sensible formation of sulphate of soda. But on heating this change is induced and it is permanent ;sulphate of soda is formed and continues to exist in the cold solution for it is the decomposition of that salt alone by hydrate of lime which appears to afford the diffused hydrate of soda.More than one con- dition of equilibrium is therefore possible for mixed solutions of sulphate of lime and chloride of sodium. It would be interesting to submit such a mixture to a diffusion experiment after being kept for different periods The effects of time and temperature are so often convertible that we might anticipate a gradual formation of sulphate of soda. If such be the case we have an agency in the soil by which the alkaline carbonates required by plants may be formed from the chlorides of potassium and sodium as well as from the sulphates of potash and soda; for the sulphate of lime generally present will convert those chlorides into sulphates. The mode in which the soil of the earth is moistened by rain is peculiarly favourable to separations by diffusion.The soluble salts of the soil may be supposed to be carried down together to a certain depth by the first portion of rain which falls while they find after- wards an atmosphere of nearly pure water in the moisture which falls last and occupies the surface stratum of the soil Diffusion of the salts upwards into this water with its separations and decompo- sitions must necessarily ensue. The salts of potash and ammonia which are most required for vegetation possess the highest diffusi- bility and will rise first. The pre-eminent diffusibility of the alkaline hydrates may also be called into action in the soil by hydrate of lime particularly as quick-lime is applied for a top-dressing to grass lands.

ISSN:1743-6893    

DOI:10.1039/QJ8510300060

出版商:RSC    

年代:1851

数据来源: RSC

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NOTICES OF PAPERS CONTAINED IN THE FOREIGN JOURNALS. BY HENRYWATTS,B.A. F.C.S. On the presence of Lead Copper and Silver in Sea-Water and on the existence of the latter in Plants and Animals. By MM. Malaguti Durocher and Sarzeaud.* The existence of silver in sea-water was suspected by the authors from the following considerations ;it is extensively diffused in the mineral kingdom it is easiIy converted into chloride by the action of salt-water ;its chloride is soluble in other chlorides especially in chloride of sodium; and its sulphide is readily acted upon by sea- water and converted in to chloride. Further as silver frequently accom- panies galena and that mineral always contains small quantities more or less appreciable of iron zinc and copper it seemed probable that these metals might also be found in sea-water.The authors’ re-searches were limited to the detection of silver lead and copper- the presence of iron being already known and the detection of zinc in very minute quantities being almost impossible for want of a test of sufficient delicacy. As the quantity of the above metals in sea-water is extremely small the utmost care was necessary to ensure that they were not introduced by the reagents employed in the analyses. The silver after precipitation by sulphuretted hydrogen or otherwise was alloyed with lead by fusing the precipitate with litharge and reducing agents as free from silver as they could be obtained and the metallic button thus produced was cupelled to separate the silver-a comparative experiment being made in every instance with the same materials but without the silver-precipitate in order that any error arising from the presence of traces of silver in the reagents might be detected and allowed for.The water used for solution washing Stc. was spring-water containing but a very small quantity of solld matter and ascertained by careful examination to be quite free from silver. This was considered preferable to distilled water inasmuch * Ann. Ch. Phys. [S] XXVIII 129. NOTICES OF FOREIGN PAPERS. as the latter might have taken up traces of silver by being kept in vessels of tinned copper or by contact with the solder at the joints of the tin tubes in the distilling apparatus since copper tin and lead frequently contain minute quantities of silver.Silver in sea-satt.-400 grms. of sea-salt fused with 25 grms. litharge and 1grm. lamp-black yielded a button of lead which left a very small button of silver on the cupel whereas the same quantity of lead extracted from the same litharge left nothing upon the cupel. This preliminary trial was checked by precipitation with sulphuretted hydrogen.-3 kilogrammes of crude-salt (obtained from salt-marshes and not subjected to any purifying process whatever) were dissolved in 24 litres of the spring-water above-mentioned and the solution saturated by sulphuretted hydrogen purified by two washings. The liquid became opalescent but after standing for two months it regained its transparency and deposited a greyish-white precipitate.This deposit was cupelled with 3 grms. of pure lead and a button of silver obtained but not much larger than that produced by the former method from a much smaller quantity of salt. From this it would appear that sulphuretted hydrogen does not precipitate the whole of the silver contained in a solution of sea-salt ; and in fact if such a solution be precipitated as completely as possible by sul- phuretted hydrogen and afterwards evaporated to dryness the residue if treated with lead and cupelled as above will yield a button of silver. Estimation of silver in sea-water.-A considerable quantity of sea- water was taken from off the coast of St. Malo a few leagues from land and preserved during the course of the experiments in a wooden cistern from which it was taken out as occasion required in glass vessels.The presence of silver in this water was first demonstrated by the sulphuretted hydrogen process above described ;but in order to obtain a more exact estimation of the quantity 50 litres of the water were evaporated to dryness and the crude-salt thence obtained weighing 1300 gramrnes was divided into 13 equal portions and each portion fused with 30 grms. of pure litharge and 1 13 grms. of lamp-black. This mixture which was made very intimate by long trituration in a porcelain mortar was gradually heated to dull red- ness in a cixcible and maintained at that temperature for fifteen or twenty minutes; the heat was then gradually raised till the mixture fused and afterwards increased to whiteness as soon as that tem- perature was attained the crucible was withdrawn from the fire.Thirteen operations of this kind yielded 12-4 grrns. of lead and the silver contained in this was found by cupellation (deducting that which was yielded by the lead alone in a test experiinent) to amount to 0.0005 grm. Now as this demi-milligramme of silver was ex-tracted from 50 litres of sea-water it follows that 100 litres-or for simplicity say 100kilogrammes of sea-water-contain 1milligramme ; hence the proportion of salt in sea-water is approximately 1 part in 70 NOTICES 100,000,000 80 that a cubic myriametre of sea-water contains 1000 kilogrammes or a cubic mile (English) contains about 2g1b. avoir- dupois. This estimation must be regarded as a minimum; for all the preceding operations are attended with slight loss.Silver in Fuci.-The well-known faculty which plants possess of condensing within their substance certain of the principles which form the medium in which they grow induced the authors to search for silver in sea-weed with the full expectation that these plants would be found to contain it in larger proportion than the sea-water itself. The species examined were Fucus canalimlatus F. vesiculosus F. serratus F. ceramoydes F. !?aodosus; Ulva cmpressa. These plants were incinerated by burning them on an iron grating supported on four feet resting on plates of porcelain the whole apparatus having never been used for any other operation. The ashes of all these species yielded buttons of silver by cupellation.100 grms. of the ashes of Fucus serratus yielded 0.001 grm. silver ; the same proportion was found in the ashes of Fucus ceramoi'des; the other species yielded buttons too small to be weighed. The proportion of silver contained in the ashes of Fucus serratus and ceramoi'des is From this it is calculated that the fuci are about 26 times 10000* as rich in silver as the water itself. By similar methods the authors have demonstrated the existence of silver in various chemical products in the preparation of which sea- salt is employed e. y, in carbonate of soda and hydrochloric acid. The quantity of silver in carbonate of soda was found to be greater than that in the sea-salt itself. The excess arises from the use of sulphuric acid in the preparation that acid always containing lead and therefore also silver.The wood of various trees e. g. the oak birch beech hornbeam aspen apple and ash grown at a considerable distance from the sea and on laud which had never been manured with salt or sea-weed likewise yielded ashes in which silver was detected. The presence of silver in these plants appears therefore to be connected with the general distribution of silver in the mineral kingdom-a fact pre- viously established by the experiments of two of the authors of this memoir. The blood of an ox was likewise found to contain silver derived oi course from the vegetable substances on which the animal ha$ f cd These experiments are sufficient to show that the occur-rence ot silver in organic substances is by no means uncommon although they cannot safely be regarded as a proof of the constancy of its occurrence.With regard to the question whether the silver in the waters of the ocean has been carried thither by rivers in recent times and derived from the waste of that which is used by man or whether its existence therein is of more ancieut date-the authors observe in the first OF FOREIGN PAPERS. place that supposing the proportion of silver in all parts of the ocean to be the same as that which was found in the particular portion examined the total quantity contained in the ocean would amount to about 2,000,000 tons a quantity which is probably greater than that which has even been extracted from the earth by artificial means.The question however is more completely decided by the examina- tion of marine deposits anterior to the existence of man upon the earth. For this purpose the authors searched for silver in rock-salt occurring in sedimentary strata and deposited from ancient salt lakes or marine basins and likewise in coal. In the rock-salt the presence of silver was demonstrated beyond all doubt; the ashes of the coal likewise yielded a button of silver but the authors consider that the result of the experiment is rendered somewhat doubtful partly by the possible occurrence of iron pyrites in the coal (though the most careful examination failed in detecting any) and partly in consequence of the large quantity of the reagents which it was found necessary to use.The occurrence of silver in the rock- salt is however quite sufficient to show that the presence of that metal in sea-water is of ancient date. Lead and copper in Fuci.-Ten kilogrammes of a mixture of several species of fucus chiefly F. serratus nodoszcs and ceramoiiles gathered on the coast of St. Malo were incinerated and yielded 1.7 kilograrnmes of ashes. These ashes were washed with a large quantity of water to free them from soluble salts especially sulphate of lime which they contain in large quantity. The residue was then digested in hot nitric acid not in excess the liquid left to stand for several days and then mixed with a large quantity of spring-water all these operations being conducted in porcelain basins.After filtration the liquid was introduced into a glass vessel and saturated with sulphuretted hydrogen previously washed ;a very light floc-culent greyish precipitate was soon formed consisting chiefly of sulphate of lime. The whole was then left at rest for several weeks ; the liquid filtered; and when the filter was dry the sulphate of lime was easily removed by a feather. There was then left on the filter 8 very thin film of a brownish colour. As this could not be detached the filter was burnt over a porcelain capsule; the ashes dissolved in nitric acid; the liquid diluted with water and filtered and then strongly acidulated with sulphuric acid. It immediately became turbid and after a few hours a white heavy precipitate settled down which when washed and dried weighed 0.047 grin.From this precipitate a button of lead was easily obtained by the blow-pipe. Now as the quantity of ashes operated upon was 1700 grins. and as 32 parts of lead correspond to 4.7 of sulphate it follows that the l2 ashes contain at least 1,000,000of their weight of lead. The nitric acid the sulphuric acid the filter-paper and the glass used in thc 72 NOTICES experiments were examined for lead with the utmost care and were found to be quite free from it. The experiments were repeated three times and always with the same result. The presence of coppw in the sea-weed was demonstrated by two distinct processes.-l The acid liquid separated by filtration from the sulphate of lead in the operation above described was super-saturated with ammonia and then filtered the clear solution had a blue tint.It was again saturated with acid and a bright iron wire im- mersed in it; the wire soon became coated with metallic copper.- 2. 12’15grms. of sea-weed (undried) were introduced into a large glass vessel previously washed out with aqua-regia and a su%cient quantity of spring-water added to immerse them completely. The liquid was then saturated with chlorine gas previously well washed the vessel closed and the whole left at rest for twenty-four hours. This operation was repeated every day till the fuci were completely bleached and no further action took place. After this the liquid was concentrated by evaporation in a porcelain basin then saturated with ammonia filtered and neutralized with pale acetic acid.The neutral solution treated with a few drops of ferrocyanide of potassium gave the characteristic red-brown colour indicative of the presence of copper. These experiments sufficiently establish the presence of lead and copper in fuci and therefore also in sea-water. The fuci were chosen in preference to other marine plants because having no real roots they do not insert themselves into the rocks but merely rest upon them and must therefore derive all their mineral constituents from the water. In conclusion the authors observe that the presence of silver copper and lead in sea-water though it may appear singular on first consideration will be easily understood if it be remembered that the sulphides of lead and copper are very widely diffused in nature as likewise is the sulphide of silver either alone or associated with other metals.Now salt-water attacks all these sulphides and converts them into chlorides which it dissolves. The waters which circulate through the upper parts of the earth’s crust and which almost always contain chlorides and other salts of the alkalis react in the same manner on these natural sulphides dissolving out small quan- tities of metal which they carry away and transfer to the tissues of plants ;lastly the same waters contribute together with the solid food to introduce these metals into the bodies of animals. OF FOEETGN PAPERS. On a Chromate of Copper and Potash. By A. Knoy.* When bichromate of potash is poured upon recently precipitated hydrated oxide of copper a light brown crystalline compound is formed composed of small hexagonal tables.This salt is insoluble in water. Carbonate of ammonia and caustic ammonia dissolve it producing a deep green solution. This solution if saturated while hot and then left to cool deposits brilliant green prisms having a golden lustre by reflected light; these crystals appear to be the chromate of copper and ammonia described by Malagu t i. The same chromate of copper and potash is obtained by mixing a solution of sulphate of copper with excess of bichroinate of potash arid gradually adding caustic potash. It contains KO. Cr 0 + 3Ca 0. CrO + 3HO. On a native Borate. By 6. L.U1ex.t Beneath the nitre beds of Southern Peru there are found white tuberculous masses which in that country are called Tiza.In size they vary from a hazel-nut to a middling sized potato and have exactly the external appearance of the Aluminite described by Halle; but the fractured surfaces show that the mass is composed of soft white silky fibres interlacing each other; they absorb water rapidly and have a slightly saline taste. Embedded in the tuberculous masses are sometimes found sharp-edged fragmepts of Andesite and of quartzose and argillaceous minerals and invariably large rhombic prisms of Brogniartin. The density of the crystalline fibres is 1.8; their form appears to be that of a hexagonal prism or perhaps a rhombic prism with the acute lateral edges truncated.Their composition is as follows Boracic acid . 49.5 49.5 Lime . . 15.7 15.9 Soda . 8.8 8.8 Water . . 26.0 25.8 100.0 100.0 Assuming that the relation of the boracic acid to the soda is the same as in borax these numbers give the formula NaO. 2B0 + 2 CaO. 3 BO + 10 aq. The author is of opinion that this mineral is identical with the Hydro-borocalcite described by Hayes. The brogniartin with which this borate is mixed consists of sulphate of soda and lime NaO. SO + CaO. SO,. * Ann. Ch. Pharm. LXX,52. -f Ibid. LXX 49 74 NOTICES On the Preparation of Hydrobromic and Hydriodlc Acids. By Ch. Mene.* bf. Mene recommends for the preparation of these gases the use of crystallized hypophosphite of lime resulting from the preparation of phosphuretted hydrogen by means of phosphuret of lime or else sulphate of soda in the state in which it is found in commerce.The proportions are as follows Water . 1pt. or Water . 1 pt. Iodine or bromine . 5 , , Iodine or bromine . 3 , Hypophosphite (cryst) 4 , , Sulphite (cryst) . 6 , The hypophosphite of lime is introduced into a flask or a retort together with a small quantity of water and liquid bromine poured in by means of a funnel. The reaction takes place in the cold; but it is indispensable to put into the iieck of the retort or flask a few pieces of cotton or asbestus in order to retain the vapour of bromine which would otherwise be volatilized by the heat evolved. The operation is the same with iodine excepting that it is necessary to apply a gentle heat.The use of crystallized sulphite of soda is more economical because it is a commercial product. The crystals are simply moistened with water then iodine or bromine added and a gentle heat applied. These two processes are not attended with the dangerous explosions to which the old method is liable. On Anisol and PhenetoI. By A. Cah0urs.t In a former memoirJ M. Cahours has shown that when anisic acid or its analogue,- the salicylate of methyl is distilled in contact with an excess of baryta the baryta is transformed into carbonate and a limpid colourless liquid distils over having the compo-sition C, H 0 C, H 0 = 2 CO + C14H 0,. To this liquid Cahours gives the name of Anisoh By the action of fuming nitric acid upon anisol three distinct products are formed according to the proportions used and the rapidity of the action.If the acid is added in small portions at a time and the containing vessel is surrounded with pounded ice to prevent rise of temperature a liquid product is formed which differs from anisol merely by the substitution of 1 eq. hyponitric acid for 1 eq. hydrogen. This compound is called Mononitranisol C, H NO,. It is a limpid amber-coloured liquid heavier than water boiling between 26%’ and 264O C. and having an aromatic oclour somewhat like that of bitter almonds. Caustic potash in * Compt Rend. XXVIII 478. .f. Ann. Ch. Phys. [3] 27 439. Ann. Ch. Phys. [3] 10 327. OF FOREIGN PAPERS.solution has no action upon it; strong sulphuric dissolves it with the aid of a gentle heat; water added to the liquid separates the anisol unaltered. When heated with fuming nitric acid it is converted into binitranisol and subsequently into trinitranisol. When anisol is treated with fuming nitric acid in excess the liquid boiled for a few minutes and then water added a yellow liquid separates which quickly aggregates into an amber-coloured mass easily soluble in boiling alcohol and separating from the solution on cooling in the form of long yellowish needles. This compound is Binitranisol C, H N O,o formed from anisol by the substitution of 2 eq. hyponitric acid for 2 eq. hydrogen.-By treating anisol with a mixture of equal parts of sulphuric acid and fuming nitric acid a third compound is formed in which 3 ey.of hydrogen are replaced by hyponitric acid this is Trinitranisol. When first formed it is a heavy oily liquid but soon aggregates into a hard mass of a clear yellow colour it is perfectly insoluble in water. Action of Hydrosulphate of Ainrnoniu on the preceding Compounds. 1. Anisidine.-C! H N O,.-When an alcoholic solution of hydro-sulphate of ammonia is brought in contact with mononitranisol an energetic reaction takes place sulphur being deposited and a basic sub- stance formed by the substitution of 1 eq NH for 1 eq. NO,. This base is Anisidine. To obtain it in a state of purity the alcoholic solution is evaporated at a gentle heat till it is reduced to a third or a fourth of its original bulk then mixed with a slight excess of hydrochloric acid and filtered after the addition of a small quantity of water in order to separate sulphur.The filtered liquid evaporated at a gentle heat deposits crystals of the hydrochlorate of the new base; and these crystals when distilled with a concentrated solution of potash yield the anisidine in the form of an oily liquid which solidifies in crystals on cooling. Hydrochlorate oJ' anisidine crystallizes in fine colourless needles. When a hot concentrated solution of this salt is mixed with a concentrated solution of bichloride of platinum yellow needles of a double salt are deposited on cooling. Anisidine likewise forms crystalline compounds with oxalic nitric and sul- phuric acid.2. Nitranisidine.-C, H N O,.-Formed by mixing an alcoholic solution of binitranisol with hydrosulphate of ammonia. The solution is then evaporated to a third of its bulk mixed with a slight excess of hydrochloric acid filtered and the filtered solution treated with ammonia. A red crystalline precipitate is then thrown down which is washed with distilled water and dissolved in boiling alcohol. The solution left to cool slowly deposits the base in long needles having the colour of garnet and considerable lustre. It is insoluble in cold water but dissolves with tolerable facility in boiling water and the solution solidifies in a mass on cooliag. Boiling alcohol dissolves it ivith facility. Ether likcwisc dissolves it rcadily especially when 76 NOTICES warmed.The solution if left to spontaneous evaporation deposits the base in long orange-coloured needles. With nitric sulphuric hydrochloric and hydro bromic acid nitranisidine forms salts which crystallize very distinctly. The sulphate when pure is perfectly colourless. The hydrochlorate forms with bichloride of platinum a double salt which crystallizes in orange-brown needles. Nitro-benzanisidide.-C, Hi N 0,. When crystals of nitranisidine are dropt into chloride of benzoyl no action takes place in the cold; but on gradually raising the temperature a brisk action soon com- mences ;hydrochloric acid is given off; and a coixipound is formed analogous to benzamide and benzanilide. The solid mass thus pro- duced is then treated successively with water hydrochloric acid and an alkaline solution to free it from benzoic acid and nitranisidine.It is then washed several times with distilled water and dissolved in a quantity of alcohol just sufficient to take it up at a boiling heat it then separates in a state of purity on cooling. This substance crystallizes in small needles of a blonde colour. It is insoluble in water both hot and cold and scarcely soluble in alcohol at ordinary temperatures. Fuses when gently heated and volatilizes at a higher temperature. Dissolves in strong sulphuric acid when gently heated imparting a deep red-brown colour to the liquid. Nitl.o-cinnanisidid~.-C, H, N 0,.-Obtained in the same manner as the preceding compound by the use of chloride of cin-namyl instead of chloride of benzoyl.Dissolves sparingly in cold alcohol and with tolerable facility in boiling alcohol from which on cooling it separates in small yellowish needles. Similar products are likewise obtained by the action of chloride of cumyl and chloride of anisyl on nitranisidine. 3. Rinitranisidine.-C, H N O,,.-Formed by digesting trini- tranisol at a gentle heat with an alcoholic solution of hydrosulphate of ammonia. Separated by converting into a hydrochlorate and treating the solution with excess of ammonia. It is then gradually deposited in the form of red flakes which after being repeatedly washed with distilled water and then dried either in vacuo or over the water-bath are converted into a powder which exhibits a bright red or a violet-red colour according to the strength of the solution from which it was precipitated; it is quite destitute of crystalline character.Cold water dissolves but a mere trace of this compound; boiling water dissolves it in small quantities. Cold alcohol dissolves but little of it ;boiling alcohol takes it up pretty readily and if slowly cooled deposits it in the form of blackish violet-coloured needles resembling crystals of cinnabar. Slightly soluble in warm ether from which it separates in needles of a very deep violet colour. Fuses at a moderate heat and solidifies on cooling in a radiated crystalline mass having a blackish-violet colour and resembling cinnabar. With hydrochloric nitric and sulphuric acid binitra-nisidine forms salts which are soluble and crystallizable if the acid be OF FOREIGN PAPERS.added in excess; but water decomposes them setting the base at liberty. Fuming nitric acid attacks it strongly at a boiling heat producing a substance of a brownish-yellow colour like resin which dissolves in potash and then assumes a very deep brown colour. Binitranisidine may be considered as anisidine with 2equivalents of hyponitric acid substituted for 2equivalents of hydrogen Cl,H7N3010=C14HsN02+2N04-~HH. Chrysunisic ucid.-Cl4. H N O14.-When anisic or nitranisic acid is treated with fuming nitric acid binitranisol and trinitranisol are formed and likewise an acid product which is soluble in hot alcohol and crystallizes on cooling in the form of rhomboidal scales of a magnificent golden-yello w colour.This compound is chrysunisic acid; it is isomomeric with trinitranisol and therefore a homologue of picric acid (trinitrophenol). It may in fact be regarded as picric acid plus 1 eq. methylene (C2 Hg). '14 H5 N3 Ol4 = 'l2 H3 N3 '14 + '2 H2* U L-+ Chrysanisic acid. -,?T-IJ Methy!ene. Picric acid. This acid is not sensibly soluble in cold water; boiling water dissolves it in small quantities and deposits it in crystals on cooling. Alcohol at ordinary temperatures dissolves but a mere trace of it; boiliug alcohol dissolves it abundantly so that a saturated solution solidifies in a mass on cooling. Ether dissolves it especially when warm and on evaporation deposits it in very brilliant yellow lamina Fuses when carefully heated and on cooling solidifies in a crystalline mass when more strongly heated it gives off a yellow vapour which condenses on the sides of the retort in small very brilliant scales.When boiled with strong nitric acid it is converted into picric acid. By distillation with chloride of lime it yields a large quantity of chloropicrine. When mixed with a quantity of potash just sufficient to saturate it it forms a very soluble salt; an excess of potash decomposes it converting it into a brown substance. Chrysanisute of amtnoniu C, H N 01, crystallizes in small needles. Its solution precipitates a great number of metallic salts- forming with salts of protoxide of copper a yellowish-green gela- tinous precipitate; with salts of sesquioxide of iron light yellow ; with zinc-salts a precipitate similar to the last but lighter ; with pro-tochloride of mercury no immediate precipitate if the solutions are dilute ; yellowish-red flakes if they are concentrated ; with nitrate of lead a copious flocculent precipitate of a fine chrome-yellow colour ; with nitrate of silver a fine yellow flocculent precipitate ; and with nitrate of cobalt a gelatinous precipitate of a yellow colour slightly tinged with green.-Cbysan,isate of silver C, (H Ag) N OI4 is precipitated in fine yellow flakes on mixing solutions of nitrate of silver and chrysanisate of ammonia.78 NOTICES Chrysnnislc ether C, H N 0, is obtained by passing dry hydro- chloric acid gas into a solution of chrysanisic acid in strong alcohol till it is no longer absorbed; then boiling the liquid gently for a short time and adding water.A voluminous precipitate is then produced which must be thrown on a filter and washed with water containing ammonia to remove any chrysanisic acid that niay remain unaltered. It is afterwards washed with pure water and then dis- solved in boiling alcohol which on cooling deposits it in trans- parent scales of a very rich golden-yellow colour. Dissolves in warin ether ;fuses at about looo. &dphanisolide.-c, H S O,.-When vapour of anhydrous sul- phuric acid is passed into anisol artificially cooled the vapour is gradually absorbed and the liquid thickens. If water be then added three products are formed viz anisol unaltered sulphanisolic acid and sulphanisolide which is a solid substance analogous to sulpha- benzide ; it forms delicate needles having a silvery lustre and easily soluble in alcohol and ether.DERIVATIVES OF SALICYLIC ETHER. When chlorine gas is passed in excess through salicylic ether (salicylate of ethyl) heated over a water-bath a solid substance is formed which is soluble in hot alcohol and crystallizes on cooling in beautiful colourless tables. This compound is bichh-ruretfed salicylic ether formed from salicylic ether (Cis H, 0,) by the substitution of 2 eq. chlorine for 2ey. hydrogen its com- position is therefore C, H Ci2 0,. The corresponding bromine compound which forms magnificent crystals is obtained in a similar manner When salicylic ether is acted upon by a mixture of sulphuric and fuming nitric acid a product is obtained which dissolves in boil- ing alcohol and crystallizes on cooling in beautiful white scales with a faint tinge of yellow.This compound is Binitro-salicylic ether formed by the substitution of 2 eq. N 0,for 2 eq hydrogen hence its composition is C, H (N oJ20 = C, H N2 Ol4. Phenetol.-C, H, 02,-Salicylic ether forms definite compounds with caustic alkalies. On distilling the baryta compound the salicylic ether is resolved into 2 eq. carbonic acid and 1 eq. phenetol, which distils over '18 '10 '6 = O2.+ cl6 '2 Phenetol is a colourless very mobile liquid lighter than water ; and having an agreeable aromatic odour; it is insoluble in water but dissolves readily in alcohol and ether.Solution of caustic potash has no effect upon it. Sulphuric acid converts it into a copulated acid. Chlorine and bromine convert it into crystallizable products. BinitrophenetoZ.-C16 H N O,,.-Formed by the action of fuming nitric acid at a boiling heat on phenetol. Crystallizes in yellow needles much like those of binitranisol of which this compound is the homologue. OF FOREIGN PAPERS. Nitr0phenitidine.-C, Hlp N O,.-Formed by passing sulphu- retted hydrogen and ammoniacal gas through an alcoholic solution of binitrophenetol. Crystallizes in brown needles. This compouhd is a base analogous to nitranisine and forms crystallizable com- pounds with sulphuric nitric and hydrochloric acid. The other homologues of the anisol series M.Cahours has not yet formed but there can be no doubt of their existence. The following table contains all the derivatives of salicylate of methyl and salicylate of ethyl described by M. Cahours in this and in former memoirs the bodies of the second group differing from the first only by the additior If C2 H2. FIRST GROUP. SECOND GROUP. c) H O6 Salicylate of methyl. C, H 0,.C H2 Salicylic ether. Monochloruretted Monochlor. sa-'I6{ O6{ salicylate ofmethyl clG{ 06Dc'2H2( licylic ether. 3 } 3} Bichloruretted sali- Bichlor. sali-'16{ 3 } { cylate of methyl. clG{ c"16 } 06'c2H2{ cylic ether. Fi } Monobromuretted Monobrom. sa-? Fi } salicylate of methyl c16{ 06*c2H2{ licylic ether. { '16{ Bibromuretted sali- Bihroniuretted :,%{ } O6{ cylateof methyl.O,.C,H,[ salicyl. ether. '16{ Mononitro -sa- $d4 } 06*c2H2{ licylic ether. '16{ Binitro-salicylate of methyl. '6' '2 Hf{ Binitro-salicyl. ether. 0,.C2 H -2 CO2 = (34)2] H (a4),} O6{ '16{ '16{ C, a C,4{ a4} 02{ Nitranisol. C14{ ;A4 } 0,.C2 H C14H802 * %HZPhenetol. Nitrophenetol. CI4{ } 0 { Binitranisol. C, { 0,{ Trinitranisol. C, H N 0 Anisidine. C14 H N 0,. C H Phenetidine. Nitropheniti-{NO,} :$4{C, H2{ dine. C1 { (adl2} NO,{ Binitranisidhe. Binitrophene-On the Characteristic Properties of the two Acids which compose Racemic Acid. By M. L. Pasteur.* Pasteur has shown that racemic or paratartaric acid is a corn-pound of two acids one of which turns the plane of polarization of luminous rays to the right the other to the left hence called Dextro-racemic acid and Levo-rucemic acid.These two acids enter into racemic acid in equal quantities; and their crystalline forms which are identical in all their individual parts are symme-* Ann. Ch. Phys. [3] XXVIII 56. Nitranisidine. '14{ :64 '2 * 80 NOTICES tricaZ* yolyhedrims iiicapable of coinciding by superposition. The corresponding salts of these acids likewise exhibit the most striking analogies in their physical and chemical properties; the only diffe- rence between them consisting in the opposite directions in which they turn the plane of polarization of luminous rays and in the sym-metry of their crystalline forms. Dextroraeemic acid is identical with tartaric acid.Racewate of Soda and Ammonia.-This is the salt by which the separation of the two acids is effected. When equal weights of racemic acid are saturated the one with soda and the other with ammonia and the neutral solutions mixed the liquid by cooling or by spontanews evaporation deposits a double salt in remarkably fine crystals which if the liquid be left to itself for three or four days often attain the length of several centimetres. These crystals are rectangular prisms having their lateral edges replaced by planes ; and the intersection of ti00 only of these planes with the terminal faces of the prism are replaced by facets; hence the crystals are hemihedral. Further on minutely examining these crystals one by one it is found that they may be divided into two groups the crystals in the one having the hemihedral facets symmetrically situated to those in the other.The crystals of one of these groups turn the plane of polarization to the right; those of the other to the left. In other respects the crystals of the two groups are absolutely identical. It is impossible to obtain a complete separation of the two kinds of crystals by merely picking them out; but after separating them in this way as well as possible and drying them on bibulous paper to remove the adhering mother-liquid complete purification may be effected by dissolving the crystals of the dextroracemate and levoracemate in separate portions of water and crystallizing again.-That these crystals are really of different kinds and that neither of them taken alone con- tains racemic acid may be shown by dissolving one of them in water and treating the solution with a lime-salt.If the solution be some- what dilute no precipitate will be formed at first ; but after a while brilliant isolated crystals will be formed consisting of right rhombic prisms passing into the octohedral form at the angles of the base ; in short the lime-salt is precipitated with all the characters of tartrate of lime. The solutions of both kinds of crystals behave in the same manner. But if instead of taking separate crystals two crystals belonging to different groups be dissolved together the precipitate with the lime-salt even in very dilute solutions will form imrne- diately or after a few seconds in the state of an amorphous powder or of small thin lamin= either isolated or arranged in stellated groups according to the slowness of the precipitation,-in short presenting all the characters of racemate of lime.-Eacemic acid is * The term symmetrical must be understood throughout this Paper in the strict technical sense in which it is used in geometry. OP FOREIGN P;\f-'ERS. not however a mere mixture of dextroracemic and levoracemic acid; every crystal of racemic acid however small gives with a salt of lime the distinguishing character of racemate of lime. In fact the two acids cannot exist together in a solution without combining and forming racemic acid. The same is the case with all the salts of these acids excepting the double racemate of soda and ammonia already described and the double racemate of soda and potash which is isomorphous with it.Dextroracemic and Leuoracemic Acids.-Dextroracemic acid is prepared by mixing a solution of dextroraceniate of soda and ammonia with nitrate of lead and treating the precipitate with sulphuric acid. The acid then separates and may be obtained in crystals the crys- tallization being facilitated by the presence of a slight excess of sulphuric acid. By slow evaporation large clear crystals of great beauty are obtained. These crystals are oblique rectangular prisms with hernihedral modifications. The crystalline form is absolutely iden- tical with that of tartaric acid obtained from ordinary cream of tartar ; the acid has likewise the same composition density and solubility and in short is nothing but tartaric acid.It is convenient how- ever to retain the name of Dextrorucewic acid when we wish to refer to the acid as one of the constituents of racemic acid or to con-trast its propertics with those of levoracemic acid. The preparation of levoracemic acid is precisely similar to that of the dextroracemic ; it has likewise the same composition density and solubility. The crystalline forms of the two acids however are not si~rcilarbut symmetrical,-so that although their faces are pre- cisely the same in form number and magnitude they cannot be made to coincide by superposition. Moreover tartaric or dextro-racemic acid turns the plane of polarization of a luminous ray to the right; levoracemic acid turns it by exactly the same quantity to the left.For these reasons levoracemic acid might also be called Leuotartaiic acid. The crystals of both these acids are strongly pym-electric ;each crystal when heated or cooled becoming charged with opposite electricities at its two ends; but in either case the hrection of the positive and negative poles in a crystal of dextroracemic acid is precisely opposite to that which obtains in a crystal of levoracemic acid. Levoracemates and Dextroracernates.-The relations of form rotatory power and chemical properties already noticed in the dex- troracemic and levoracemic acids are likewise found to the fullest extent in salts of these acids. All the chemical properties of the tartrates or dextroracemates are reproduced even in the minutest details in the corresponding levoracemates.To each tartrate there corresponds a levoracemate differing from the former in nothing but in the position of the hemihedral facets and the direction of the VOL. 111.-NO IX. G 82 NOTICES rotatory power. With regard to the angles of the faces the absolute value of the rotatory power the specific gravity chemical compo- sition solubility optical properties of double refraction &c. the corresponding salts of the two groups are absolutely identical. Racemic acid and Racemates.-It is well known that this acid was originally produced by an accidental alteration of tartaric acid in the manufactory of M.Kestner at Thann. Its production on that occasion appears to have been due either to some particular and unobserved circumstance in the process of fabrication or to some discase in the grapes from which it was formed; at all events it has never been produced again notwithstanding all the attempts which M.Kestner has made for t,hat purpose. Its production is evidently due to some molecular alteration in tartaric or dextroracemic acid by which a portion of that substance is converted into levoracemic acid Now as Biot has shewn that the rotatory action of tartaric acid on polarized light is diminished by reduction of temperature it seemed possible that by the action of intense cold the direction of the rotatory power might be reversed and thus the transformation into levoracemic acid effected.M. I’asteur has tried the experiment but without any satisfactory result. For the present then the direct formation of racemic acid from tartaric is an unsolved pro- blem ;but this much is certain that when equal weights of dextro-racemic and levo-racernic acids are dissolved in water and the solu- tion left to crystallize ; the crystals obtained are perfectly homohedral and present all the characters of raceniic acid.-M. Pasteur has also carefully examined the crystalline forms of several salts of racemic acid,-particularly the neutral and acid racemates of soda and the racemate of antimony and potash-and finds them all perfectly homohedral. On the Separation of some of the Acids of the Series (C H)n 0,.By Justus Liebig. For detecting small quantities of butyric or valerianic acid in a mixture of the two acids and for separating one of them in a pure state fit for analysis the following method may be advantageously pursued. A portion of the acid mixture is first saturated with potash or soda the remainder is then added to the neutral solution and the whole distilled. One of two results will then follow 1. If the valerianic acid is present in quantity more than sufficient to saturate the whole of the alkali the residue in the retort will con-tain no butyric acid but onlypure valerianic acid. 2. When the quantity of the valerianic acid is less a proportional quantity of butyric acid remains behind in the retort together with the whole of the valerianic acid; but the distillate is then free from the latter and consists ofpure butyric acid.OF FOREIGN PAPERS. The quantity of the acid mixture to be neutralized with the alkali must be regulated by the supposed quaiitity of valerianic acid present. For instance if the proportion is calculated at 10 per cent of the mixture must be neutralized ;and in a solution of valerianic acid containing 10 per cent of butyric acid which it is required to separate -+$ of the acid mixture must be neutralized. It is at once evident that by a single distillation one of the acids will always be obtained pure. Thus either the distillate will con- sist of pure lizctyric acid and the residue in the retort of a mixture of valerianic and butyric acids ; or the distillate will contain both valerianic and butyric acid and the residue will consist of pure valwianic acid.By repeating this process of partial saturation and distillation either with the mixed residues or the mixed distillates as the case may be a fresh portion of one or the other acid may again be obtained pure till at last a complete separation is effected such as can scarcely be accomplished by ordinary distillation. Since butyric and valerianic acids have different boiling points it may be supposed that the soda inasmuch as it combines with one only of the acids and that the least volatile-in this case the valerianic- will arrest the volatility of the latter at the temperature at which the former boils ; and in a mixture of the two acids if the valerianic acid is rendered permanent at the boiling point of the butyric it is evident that the butyric acid may be distilled off in the pure state.A mixture of valerianic acid with acetic acid or of butyric acid with acetic acid behaves under these circumstances in a totally different manner. Thus if a mixture of this kind is partially neu-tralized with potash and then distilled the acid which passes over consists not of acetic acid as might be expected but of the two other acids although the boiling point of the acetic acid is upwards of 50° C. lower than the boiling point of butyric acid and upwards of 709 lower than that of valerianic acid. This effect is due to the formation of an acid acetate which does not appear to be decom- posible by either of the other acids.Valerianic acid added to a solution of neutral acetate of potash dissolves immediately and in considerable quantity ; but with acid acetate of potash the valerianic acid remains swimming in oily drops on the surface and does not appear to be more soluble therein than in pure water. On distilling a solution of neutral acetate of potash to which valerianic acid has been added in excess valeriaiiic acid passes over and the residue in the retort contains acid acetate together with valerianate of potash. But if valerianic acid is added to acid acetate of potash and the mixture distilled valerianic acid passes over and the acid salt remains behind free from valerianic acid. Butyric acid behaves in a precisely similar manner to valerianic acid.G2 84 NOTICES Hence when a mixture of butlyric or valerianic acid with acetic acid is partially saturated with potash and distilled either the whole of the acetic acid remains behind in the form of' an acid salt together with butyric acid the distillate in this case being pure and free from acetic acid ; or acetic acid alone remains in the retort and the distil- late still contains a portion of acetic acid which may be separated from the butyric or valerianic acid by repeating the process. On the Derivatives of Xanthic Acid. By H,Debus.* Dessainst has shown that when iodine acts upon xanthate of potash the potassium is removed in the form of iodide and a com-pound formed containing C H S 0,; thus C H K S 0 + I = K I + C H5 S 0,.This product has been further examined by Debus; he however finds that it can be more conveniently formed from xanthate of lead. This salt is obtained by dissolving potash in common alcohol ;adding to the solution a quantity of bisulphide of carbon and hydrated oxide of lead cprresponding to the quantity of potash used; and leaviug the mixture at rest for 6 or 8 hours. At the end of that time part of the oxide of lead is found to be transformed into sulphide mixed with crystals of xanthate of lead while another portion is dissolved by the potash. The black precipitate is separated by filtration and water added to the filtered liquid till a milkiness is produced. After a while the liquid becomes clear and deposits xanthate of lead in long silky crystals containinf; C H 0 '3 Pb 0.This salt is diffused through alcohol and iodine added in small portions at a time till the liquid acquires a permanent brown colour. The iodide of lead is separated by filtration the liquid diluted with its own volume of water and then left at rest for some hours at a temperature of la0C. The compound above-mentioned C H S O, is then deposited in small colourless prisms. This substance is regarded by De b us as BiGxysu&hocarbonaie of ethyl C H S 0 = C H 0 C {3 This substance is very soluble in absolute alcohol and in ether ; its solution gives no precipitate with acetate of lead and with several other metallic solutions. When it is boiled with nitrate of silver a precipitate of sulphur is formed.Chloride of mercury produces with it a white precipitate which blackens at 40°C.; and bichloride of platinum gives after a while a brown pulverulent precipitate. When dry ammoniacal gas is passed into an alcoholic solution of bioxysulphocarbonate of ethyl the liquid gradually becomes turbid * Ann. Ch. Pharm. LXXII 1. f-Ann. Ch. Phys. [S] XX 496. OF FOREIGN PAPERS. and deposits long needles of sulphur. If the filtered liquid be then evaporated in vacuo a saline residue is obtained containing a mixture of xanthate of ammonia and a new substance to which Debus gives the name of Xanthogenamide. These substances are separated by digestion in ether which dissolves the latter only. The xanthogenamide remains after the evaporation of the ether in the form of a yellow oil which ultimately solidifies in a crystalline mass.It is purified by solution in a small quantity of alcohol from which it crystallizes on evaporation in splendid rhomboidal prisms often of considerable size. These crystals fuse at about 30'; they are slightly soluble in water but dissolve in all proportions in alcohol and ether. The solution is neutral and gives DO precipitate with nitrate of silver acetate of lead sulphate of copper or baryta-salts ;but it precipitates bichloride of platinum and corrosive sublimate. The oxides of mercury silver and lead and likewise carbonate of silver decompose this substance producing a sulphide of the metal and a substance which attacks the eyes powerfully and has an odour like that of acrolein.Concentrated sulphuric acid readily dissolves xanthogenamide ; water precipitates it again without alteration. Nitric acid attacks it strongly forming a peculiar acid. Potash and baryta-water at a boiling heat resolve it into alcohol and hydro- sulphocpanic acid. Ammonia at 1509C. produces carbonic acid hydrosulphocyanic acid and a numbey of fetid ppoducts. The composition of xanthogenarnide is C,H,O S,N. In its formation 2 eq. bioxysulphocarbonate of ethyl and 2 eq. ammonia are resolved into1 eq. xanthate of ammonia 2 eq. sulphur and1 eq. xanthogenamide When an alcoholic solution of xanthogenamide is mixed with bichloride of platinum a yellow crystalline precipitate separates, after a few minutes and the filtered liquid continues for some days to deposit crystalline scales.By analysis these crystals gave the following results Calculated. Found. r--7 7-A- 1 Carbon. Eq. . 12 72 1401 13.97 1. 13.39 11. -111. Hydrogen . 14 Oxygen. . 4 Sulphur. . 4 Nitrogen . 2 Platinum . 2 Chlorine . 3 14 2.72 32 6.2464 12.46 28 5*45 197.4 38.43106.2 20.69 2.69 -38.0419.08 -I 2.72 13.35 38.2623.30 -c -37% -I 513.6 100*00 86 NOTICES Hence may be deduced the formula Pt CI, c H 0;c,{;I+ Yt c1 c €3 0; c {i}. The mother-liquid separated from these precipitates is very dark-coloured and when evaporated gives off' vapours of hydro-chloric acid and yields a brown oil which gradually volatilizes together with the water and alcohol vapours; there then remains a brown substance possessing the properties of sulphide of platinum together with a white crystalline body which was recognized as sal-ammoniac.The above-mentioned platinum compound is insoluble in alcohol ether and water. Strong sulphuric acid has no action upon it in the cold and but a slight action when heated. Potash nitric acid and hydrochloric acid produce no alteration in it; bnt qua regia dissolves it with facility At 120°C. it begins to decompose evolving a fdd oil. Potash and baryta transform xanthogenamide into alcohol and a sulphocyanide of the metal the reaction consists in simple decom- position. c6 117 02 s2 3 = c 11 02 $-c2 H Ns2. When xaiithogenainide is submitted to dry distillation mercaptan and vapours of cyanic acid are given off'.If the distillation is performed at 152O C. the residue contains pure cyanuric acid C H7 02 S N = C €16 $2 +-C H NO,. The distillate smells powerfully of mercaptan and cyanic acid ; becomes gradually darker in colour by exposure to light is insoluble in water but miscible in all proportions with alcohol and ether. When it was rectified several times after drying over chloridc of calciuIIi the boiling point did not become fixed but gradually rose from SO0 to 230°C. The portions which first went over were colourless; the last had a strong yellow colour. Both portions had a very feeble alkaline reaction and when dissolved in alcohol gave scanty white precipitates with silver copper and lead salts ;but with corrosive sublimate a copious bulky precipitate which when left for some time in contact with the mother-liquid was converted into crystalline lamin=.By analysis it was found to be a compound of mercaptide and chloride of mercury Ae S . Hg S +-Hg C1. As a check on the preceding results the cyanuric acid produced by the distillation of the xanthogenamide was mixed in the state of a hot dilute solution with nitrate of silver and dilute ammonia was added as long as a precipitate continued to form. The salt thus obtained evolved ammonia when heated and acquired a violet colour. Potash in the cold had no action upon it. Analysis gave the follow- ing results OF FOREIGN PAPERS. -87 Calculated. Found. 7- Eq. 1. 11. Carbon . . 6 36 7.85 7.6 7.4 HydrogenOxygen .. . . 1 7 1 56 0.21 12.27 0.3 - 0.3 _I Nitrogen. Silver . . . . 3 3 42 324- 9.10 70-57 8.98 70.25 -70.41 -___I 459 100~00 Hence the salt is a tricyanurate of silver with 1 eq. water 3 Ag 0. C N3 0 + HO. Liebig and Wohler found in the same salt dried at 300° C. Liebig. Wiihler. Carbon . 8.13 7.82 ' 8.4 Hydrogen. 0.13 0.18 0.12 Silver . . 70.00 71.10 70.52 On Caffeine. By Fr. Roch1eder.r When chlorine gas is passed into a thick magma of crystals of caffeine the liquid becomes heated and a solution is obtained contain- ing four substances hydrochloric acid the hydrochlorate of an alkaloid a weak acid and a very volatile product which could not be procured in sufficient quantity or sufficiently pure for analysis. On heating the solution in the water-bath the excess of chloride is driven off together with the hydrochloric acid and the volatile product which is remarkable for its offensive odour; it irritates the eyes and produces an intolerable pain in the head.As soon as the liquid is evaporated to a third of its original bulk it begins to deposit crystals the quantity of which gradually increases. When the crystals no longer appear to form the liquid is left to cool and the crystals are taken out. They are then washed with cold water in which they are nearly insoluble and then exhausted in boiling absolute alcohol which does not dissolve them at all. They may also be recrystallized from boiling water. They are colourless and transparent contain no water that can be driven off at looo redden litmus slightly and at the same time acquire a slight rose-colour by the action of the ammonia contained in the blue litmus-paper.With baryta potash and soda this substance forms compounds of a dark violet colour. When a solution of either of these bases is brought in contact with the above crystals the latter immediately assume a violet colour while the liquid remains colourless. This eolouring is but transient if the base is in excess but tolerably per- sistent in the case of an excess of acid. * Ann. Ch. Pharm. LXXI 1. 88 NOTICES To this acid ltochleder gives thc name of ainalic acid (from apahos weak) to denote its feebly acid nature and likewise the slight affinity by which its elcments are held together and the consequent facility with which it is decomposed.Ammoniacal vapours impart to amalic acid a red colour faint at first but gradually changing to deep violet. The resulting compound dissolves in water forming a solution of the colour of murexide. This solution however does not yield crystals of murexide; but Roc h le d e r has succeeded in obtaining a crystalline substance from it the description and analysis of which will be given in a future memoir. With ferrous salts and ainxnonia amalic acid forms an indieo-coloured solution. Amalic acid fuses when heated becoming first yellow then red afterwards brown and volatilizes leaving scarcely a trace of carbon but giving off ammonia and forming an oil and a crystallized compound. The solution of amalic acid placed upon the skin produces red stains having a disagreeable odour like those produced by alloxan.It reduces silver salts throwing down black fiakes of metallic silver just as alloxantine does When boiled with nitrate of silver and nitric acid it is decomposed without the formation of even a trace of chloride of silver ;hence amalic acid contains no chlorine. When heated with nitric acid it evolves red vapours and is converted into a new ciystalline body. The composition of amalic acid is C, H N O, as appears from the following analysis Calculation. Experiment. Carbon .. 12Eq. 72 r-7 42.10 41.83 r 42.04 A- 42.04 -7 Hydrogen Nitrogen Oxygen . 7 . 2 . 8 7 28 64 4.09 16-37 37.44 4.35 4-17 4.27 -16.63 16.30 -37.16 37.39 4.18 - -__I_ 171 10000 100*00 100*00 When the mother-liquid decanted from the crystals of amah acid is evaporated to a fourth of its original volume to expel the greater part of the hydrochloric acid it solidifies on cooling in a thick crystalline mass which may be separated from the adhering liquid by pressure between linen and afterwards crystallized from boiling water or alcohol.In this manner a crystalline mass is obtained greasy to the touch and consisting of large laminated crystals. The solution of this substance gives with chloride of platinum a copious yellow precipitate and with nitrate of silver an abundant precipitate of chloride of silver. The crystals consist of the hydrochlorate of a new base. To analyze this base Rochleder converted it into a platinum salt by mixing the mother-liquid above-mentioned with bichloride of platinum collecting the yellow precipitate on a filter and dissolving it in boiling water :the solution on cooling yielded OF FOREIGN PAPERS.very brilliant yellow granular crystals of the double salt. This salt was found by analysis to contain _. Carbon . 4.87 4.86 -Hydrogen . 2-49 2-49 2.42 -Platinum. . 41-42? 41.43 41.61 41.06 agreeing with the formula C H N. C1 H + Pt C1 ; whence the formula of the new base is C H N. To this base Rochleder* gave the name Formyline. Subsequently however on repeating the analysis he found the per centage of carbon to be 5.2 and of hydrogen 2.62. These numbers agree better with the formula C H N.which is that of Methamyline discovered by Wurtz. RIoreover the properties of the so-called formyline are identical with those of methamyline ; whence Rochleder concludes that methamy- line is one of the products of the action of chlorine on caffeine. The composition of caffeine may be thus expressed Cyanogen. Methamyline. By the action of chlorine in presence of water the cyanogen is decomposed; the methamyline is obtained in the form of a hydro-chlorate; and the group C, H N 0 takes up 2 eq. oxygen and 2 eq. water and forms amalic acid C, H N 0 + 2 0 + 2 HO = C, H N 0,. That cyanogen is really contained in caffeine is shown according to Rochleder by its behaviour with alkalis. Caffeine treated with strong potash-ley or soda-lime yields cyanide of potassium or sodium whereas quinine cinchonine morphia and piperine when sirnilarly treated yield not a trace of cyanogen.The volatile tear-exciting substance above-mentioned is considered by Rochleder to be produced by the action of chlorine on the cyanogen of the caffeine at the moment when the cyanogen is separated from the other elements of that substance. M. Gerhardt,? however remarks that it is highly improbable that cyanogea should be actually set free by the action of chlorine on a liquid containing a cyanide or indeed on any cyanogen compound whatever accordingly he is of opinion that the volatile substance just mentioned is chloride of cyanogen. Ac-cording to this view the action of chlorine on caffeine will be repre- sented as follows C16 H, N 0 + 3 C1+ 4 HO = C H N + C, II,N 0, + C N.C1+ 2 C1 H. If the action of the chlorine be continued further a product is obtained from the amalic acid closely resembling cholesterine. This is the substance which Stenhouse obtained by the action of nitric * Ann. Ch. Pharm LXXIII 56. t. Compt. Rend. des Trav. en Chim. Jawvier,1850 25. 90 NOTICES acid on caffeine or theine and to which he gave the name Nitrotheine. This name however is inadmissible inasmuch as the substance in question contains no nitrogen and is formed by the action of chlorine as well as by nitric acid. R o chl e der calls it Cholestrophane. It contains carbon 42.15 hydrogen 4*28 nitrogen 19.56 and is expressed by the formula C, H N 0,.When boiled with potash it evolves a volatile alkali probably methamyline and forms carbonate and oxalate of potash. On the Compounds of Cyanuric and Cyanic Acid with the Oxides of Ethyl Methyl and Amyl and on the products resulting therefrom viz. :Acetyl- and Metacetyl-Urea and Methylamine Ethylamine and Valeramine. By Adolph Wurtz.* 1 Cyanurates of ethy2 and methyl.-Cyanurate of ethyl is obtained by distilling alkaline cyanurate of potash with sulphovinate of potash over an oil-bath. The product condenses in the neck of the retort and in the receiver in the form of a crystalline mass; it may be purified by repeated solution in alcohol from which it separates on cooling in very brilliant prismatic crystals. Cyanuric ether fuses at 85" C. forming a colourless liquid which is heavier than water.Boils at 276q distilling over completely and without the least de- composition. Vapour-density = 7.4 by experiment 7.37 (4 vol.) bp calculation. Formula C N 0,.3 C H 0. Sparingly soluble in water but easily dissolved by alcohol and common ether. This compound is likewise formed together with cyanate of ether (which boils at 60° C.) on distilling cyanate of potash with the sulphovinate. The two ethers inay be easily sepa- rated by distillation; and the cyanuric ether which remains in the retort forms after purification even finer and more regular crystals * than those obtained by the first described process. Cyanurate of methyl.-Obtained by distilling cyanurate or cyanate of potash with sulphomethylate of potash.When purified by repeated crystallization from alcohol it forms small colourless prismatic crystals which fuse at 140' C. and volatilize at 295'. Vapour-density = 5.98 by experiment 5-94 (4 vol.) by calculation. Formula C N 0,. 3 C H 0. The composition of these ethers verifies Liebig's statement that cyanuric acid is terbasic. Cyanate of ethyl.-Obtained by distilling cyanate of potash with the sulphovinate ;separated by distillation as above described from the cyanurate formed at the same time. When purified by repeated distillation over chloride of calcium it forms a light highly refrac- tive liquid of extremely penetrating odour and exciting a copious flow of tears. Lighter than water Vapour-density = 2.4 (4 vol.). * Ann.Ch. Pharm. LXXI 326 ; Compt. Rend. XXVI 368 ; XXVII 241 (1848) ; XXVIII 322 and 323 ;XIX 169 I86 and 203 (1849). OF FOREIQN PAPERS. Formula c6 H NO = c NO. c H 0. When cyanic ether is mixed with liquid ammonia it dissolves with evolution of heat ; and on evaporation beautiful prismatic crystals are obtained consisting of c6 H N O, thst is to say cyanic ether pZus ammonia. They fuse easily and dissolve with facility in water and alcohol. In contact with water cyanic ether gives off carbonic acid and forms a crystalline mass containing C, H, N 0 2 (C H NO,) + 2 HO = 2 CO + C, Hi N 0,. Cyannte of methyl is prepared and purified by methods precisely similar to those just described for cyanic ether. It is a volatile liquid which with ammonia forms a crystalline compound = C H6 N O, and in contact with water is resolved into carbonic acid and a crys- talline compound isomeric with the ammonia-compound of cyanate of ethyl.2 (6= H NO,) + 2 HO = 2 CO + c6 H N 0,. The compounds thus formed are to a certain degree analogous in composition to urea. For urea with 1 eq. methylene C H, or its ele- ments gives C H N O, which is the body corresponding to urea in the acetic acid series. This is the substance formed by the action of ammonia on cyanate of methyl. Further if to this formula we again add the elements of methylene C N we obtain C6 H N 0 the urea of the metacetyl series. This compound may be formed in either of the two ways mentioned above. By treating cyanic ether with water we obtain the analope of urea in the valerianic acid series.Two other bodies of this series might be formed from cyanate of amyl. The compound formed by the union of cyanic ether with ammonia and that which is produced by the action of water on cyanate of methyl are not however identical but merely isomeric. The former appears to be analogous to urea; while the latter appears rather to belong to the class of Amethanes that is to say compounds of ethers with amidogen. The formula C H N 0 may be decomposed in two ways; viz. C NO. C H 0. NH or C NO. C H 0. C H (NH,). The first of these formuh is that of urea with 1eq. water replaced by 1eq. ether; the second is that of a compound of cyanate of methyl with methylamine (vide infra) . Similarly the compound Cl0 H, N 0 may be regarded as cyanate of ethyl with ethylamine.C, H, N 0 = C NO. C H 0. C H (NH,). Urea = C H N 0 = C NO. HO. NH Cyanate of methyl-oxide and ammonia = C NO. C H 0. NH I-v-Acetyl-urea. Cyanate of ethyl-oxide and ammonia = C NO. C H 0.NH Metacetyl-urea. 92 NOTICES Methyl-cyamethane = C H NO + C H (NH,) Ethyl-cyamethane = C €I NO + C H (NH,). ETHYLAMINE AND METHYLAMINE. Formation.-The ammonia-compounds form a sort of connecting link between organic and inorganic compounds. Indeed ammonia would no doubt be regarded as an organic base and the simplest and strongest of the whole class were it not that it contains no carbon. Possibly however this difference may not be of so much importance as it has hitherto been thought ;for Wurtz has succeeded in form-ing organic compounds from this alkali by adding to it the elements of methylene C H, or etherine C H, without depriving it of its strong basic properties or even of its smell.If to the elements of ammonia NH, there be added the elements of 1 eq. C H, there is formed a compound C H N which may be called Methyl-ammonia MetWy Eamide or Methylarnine. On adding to the elements of ammonia the elements of 1 eq. C H, there results the compound C H N which may be called Ethyl-ammonia, Eth,ylamide or Ethylamine. The compounds C H5 N and C H N may be regarded either as methyl-ether C H 0 and common ether C H 0 in whi:h 1eq. oxygen is replaced by 1 eq. amidogen NH, or as ammonia in which 1 eq.hydrogen is replaced by methyl C H, or ethyl C H,. The relations between these bodies and ammonia may be exhibited as follows H N Ammonia. NH H Hydramide. C H N Methyl-ammonia. NH, C H Methylamide. C H N Ethyl-ammonia. NH, C H Ethylamide. These bases may be formed in three ways 1. By the action of potash on the Cyanic ethers. 2. By the action of potash on the Cyanuric efhers. 3. By the action of potash on the Ureas. These reactions may be exhibited as follows C NO. HO + 2 (KO. HO) = 2 (GO,. KO) + H3 N -+ Cyanie acid. Ammonia. C NO. C H 0 + 2 (KO. HO) =2 ((30,. KO) + C2 H N -w Cyanate of methyl. Methylamine. Cyanate bf ethyl. Ethylamine. If all these formu18 be multiplied by 3 they will exhibit the formation of these compounds from the cyanuric ethers.From the ureas they are formed as follows OF FOREIGN F4PERP. C H4 N 0 t 2 (KO.HO) = 2 (GO,. KO) + H N + H N \+ Urea. C H N2 0 + 2 (KO. HO) = 2 (CO,. KO) + H N+ C H N Acetyl-urea. Met ace$-urea. Methylamine.-When cyanurate of methyl is boiled with excess of caustic potash and the evolved vapours are passed through a condensing tube into water a highly caustic liquid is obtained which smells strongly of ammonia but does not contain a trace of that alkali; it is an aqueous solution of methylamine. On saturating this solution with hydrochloric acid and evaporating to dryness a residue is obtained which dissolves readily in warm absolute alcohol. On cooling the hydrochlorate of methylamine crystallizes out in splendid lamin= which are iridescent as long as they remain in the liquid and assume a mother-of-pearl aspect when dry.From the hydrochlorat,e the base may be obtained in the free state by a process exactly similar to that adopted for the preparation of am-monia viz. by heating the dry salt with quick lime in a flask provided with a gas-delivery tube. The methylamine is then evolved in the gaseous form and may be collected over mercury. Methylamine is gaseous at ordinary temperatures; at Oo C. it con-denses to a very mobile liquid. Specific gravity of the gas 1.13 by experiment 1.075 by calculation. Water at lZO,absorbs 1040 times its volume of gaseous methylamine a larger quantity than of any other known gas; at 25O the volume absorbed is 950 times that of the water.The gas resembles ammonia in the following respects. It is rapidly absorbed by charcoal ; turns reddened litmus paper blue; forms dense white fumes with hydrochloric acid; absorbs an equal volume of hydrochloric acid gas and half its volume of carbonic acid It is distinguished from ammonia by taking fire when brought in contact with the flame of a candle and burning with a yellowish flame. It is decomposed when heated with potassium cyanide of potas-sium being formed and hydrogen set free. This furnishes a good method of analysis. The solution has the strong smell of the gas itself; its taste is caustic and burning. Iodine introduced into this solution is con-verted into a garnet-coloured powder and the liquid which scarcely becomes coloured holds in solution hydriodate of methylamine, I H.C H N. The redinsoluble substance is the compound analo- gous to iodide of nitrqen. The salts of magnesia alumina manganese iron bismuth uranium 94 NOTICES tin lead and mercury are precipitated by methylamine just as by ammonia. Zinc-salts give a white precipitate soluble in a large excess of the alkali.-Copper-salts are precipitated bluish-white ; an excess of methylamine dissolves the precipitate forming a deep blue solution. Cadmium cobalt and nickel salts give precipitates not soluble in excess.-Nitrate of silver is completely precipitated by methylamine the precipitated oxide being easily soluble in excess. Chloride of silver is also dissolved by aqueous methylamine.The solution when left to spontaneous evaporation deposits a black powder analogous to fulminating silver but not exploding either by heat or by percussion.-Chloride of gold gives a brownish-yellow precipitate easily soluble and forming an orange-yellow solution.- Chloride of platinurn gives a yellow crystalline precipitate composed of C1 H. C H N. Pt Cl,. Rydrochlorate of Methylamine gave by analysis the following numbers agreeing with the formula C1 H. C N,N. Eq. Calculated. Experiment. Carbon . .a 12 I-- 17.7 17.4 Chlorine . Hydrogen . .1 .6 35.5 6 52.5 8.8 52.2 8.7 Nitrogen . .1 14 - 21.0 21*7 67.5 100.0 100.0 Chloroplatiiaate of Methylamine which crystallizes in beautiful golden-yellow scales was also analysed and gave carbon 5.3,hydro-gen 2.8 chlorine 444 platinum 41.4 (nitrogen not determined) agreeing with the formula C1 H.C H N. Pt C1,. EthyZamine.-The hydrochlorate of this base is prepared and puri- fied by processes precisely similar to those described for methylamine ; and the base itself is likewise obtained by dry distillation of the hydrochlorate with quick-lime. But as ethylamine is easily con- densed and is liquid at ordinary temperatures the gas-delivery tube is made to pass into a receiver surrounded with a freezing mixture. Light very mobile and perfectly transparent liquid. Begins to boil at 18O C. If poured upon the hand it volatilizes immediately producing a sensation of intense cold. It diffuses a highly penetrat- ing ammoniacal odour.Its causticity may be compared with that of potash. Blues reddened litmus-paper strongly. Forms dense white fumes with hydrochloric acid Each drop of the acid poured into it produces a hissing noise. Caustic potash or baryta may be left in contact with the base at ordinary temperatures without producing any change. In contact with a burning body ethylamine takes fire and burns with a bluish flame. Ethylamine is miscible with water in all proportions and the solu- OF FOREIGN PAPERS. tion possesses exactly the same properties as that of methylamine excepting that it dissolves hydrated oxide of copper less readily and does not precipitate bichloride of platinum. When a solution of ethylamine is mixed with oxalic ether the mixture soon becomes turbid alcohol being formed and delicate crystals being deposited which consist of a compound bearing the same relation to oxamide that methylamine bears to ammonia.This compound is EthyFoxumide C H N 0,. The composition of anhydrous ethylamine is expressed by the forinula C H N as appears from the following analysis Eq* Calculated. Experiment. r--7-7 Carbon . -4 24 53-3 53.4 Hydrogen . *7 7 15.5 15.9 I Nitrogen . .4 14 31.2 30.9 31.3 -45 100.0 100*2 Hydrochtorate of Ethylamine crystallizes in laminz ; fuses at looo and solidifies in a crystalline mass on cooling; its composition is C1 H. C; H N. Eq. Calculated. *Experiment. Carbon . .4 r-24 7 29.4 28.9 29.4 Hydrogen . Nitrogen . Chlorine . .8 .I .l 8 14 35.5- 9.8 17.2 43.6 9.917.5 43.7 9.9-CI 81.5 loo'o lOO*O ChZoropZutinate of EkhyZamine.-Golden-yellow scales soluble in The analysis of this salt gave in 100 parts carbon 9.5, water.hydrogen 3.2,chlorine 42.4and 42 platinum 39.2 and 39 agreeing with the formula C1 H. C H N. Pt Cl,. Valerumine C, HI N.-Formed from ammonia by the addition of C, Hl0 or by the substitution of 1 eq. of amyl C, Hll for 1 eq. of hydrogen. Cyanate of amyl prepared by distilling cyanate of potash with sulphamylate of potash yields this base when decomposed by caustic potash C NO. C, H, 0 + 2 (KO. HO) = 2 (GO KO) + C, H, N \-Cyanate of amyl. -The valeramine distils over and may be condensed in a receiver con- taining water. The alkaline solution neutralized with hydrochloric acid yields the hydrochlorate; and this when purified dried and distilled with caustic lime yields anhydrous valeramine.Valeramine is liquid at ordinary temperatures has a burning 96 NOTICES OF rORElGN PAPERS. bitter taste and a stroiig ammoniacal odour. It is soluble in water. The solution precipitates copper-salts and an excess redissolves the preci- pitate forming a deep blue solution less readily however thaii ethylamine methylamine or ammonia. With nitrate of silver it gives a brownish precipitate soluble in excess. Valeraniine dissolves chloride of silver but less easily than ammonia. Hydrochtolrate of Valeramine C1 H C, fI, N crystallizes in scales unctuous to the touch and soluble in water and alcohol.Carbon . Eq. . 10 60 48.5 Calculated. r-7 48.2 Expenment. Hydrogen Chlorine Nitrogen . . 14 *I.1 14 35.5 14 - 11.3 28.7 11.5 11.4 28.3 - 123 100.0 C~~oro~ta~~na€~ of VaZeramine.-Golden- yellow scales soluble in water. Analysis gave 32.4 platinum 36 chlorine 20.4 carbon 4.8 hydrogen agreeing with the formula C1 H. C, H, N. Pt Cl,. Dr. Hofmann* has lately shown that €zoo and even all three of the hydrogen-atoms in ammonia may be replaced by organic radicals ethyl methyl &e. and has thus obtained new volatile compounds resembling ammonia and possessing very strong basic properties. The following table exhibits the composition of these bases C H = Ae = Ethyl C, H, = Ayl = Amy1 C1 €1 = Pyl = Phenyl ''IN Aniline H Ae Ethylo-phenamine PYl Ae The first of these series contains bodies previously known viz.aniline and Wur t z's ethylamine ;these are Amidogen-bases. The second and third series which may be called Imidogen-bases and Nitrile-bases are new. * Ann. Ch. Pharm. LXXIII 91. ('1

ISSN:1743-6893    

DOI:10.1039/QJ8510300068

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年代:1851

数据来源: RSC

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INDEX. A. Abel on the bichromate of ammonia and some of its double salts 199. Acetyl-urea 90 91 98. Acid alizaric 249. -amalic 88. -arsenious action of on albumen 14. -aspartic formation of from bima- late of ammonia 187. -azophosphoric 143. tabular view of the properties of and of phosphoric and dentazo-phosphoric 365. -bisulphamylic identity of with hyposulphamylic acid 158. -bisulphethylic identity of with hy- posulphethylic acid 18. -bisulphimethylic identity of with hyposulphamethylic acid 18. -butyric formation of succinic acid by oxidation of 186. -caproic contributions towards the history of 210. -decomposition of under the influence of the galvanic current 222. -chloronaphthalic 250. -chrysanisic 77.-chromic on the bichromate of am- monia and some of its double salts 199. -cuminic on the passage of through the animal system 181. -dentazophosphoric 354. ___. dextroracemic 81. -hydrobromic preparation of 74. -hydriodic preparation of 74. -hydrocyanic compound of bichlo-ride of titanium with 178. Acid hyposulphethylic identity of with bisulphethylic acid 18. preparation of 20. -hyposulphamethylic identity of with bisulphimethylic acid 18. preparation of 22. -hyposulphamylic identity of with bisulphamylic acid 158. -Ievoracemic 81. _I__ metacetic method of obtaining in large quantities 190. -nitrous on the behaviour of ani- line and the alcohol-bases with 231. _I_ enanthylic contributions towards the history of 210.decomposition of under the influence of the galvanic current 224. -pelargonic researches on 240. -racemic 79 82. -succinic formation of by oxidation of buiyric acid 186. -tartaric 80 81. -valeric action of heat upon 121. -xanthic derivatives of 84. Acids on the separation of some of the acids of the series (C H) 0,,82. -volatile of the series (C H)n 0 physiological action of 18 1. Albumen action of arsenious acid on 14. Alcohols observations on the constitu- tion of the alcohols and ethers 45. Alcohol-bases on the behaviour of aniline and the alcohol-bases with nitrous acid 231. Alcohol-radicals observations on the constitution of and on the formation of ethyl by B. C. Brodie 405. -remarks upon the formulz of by -4.W. Hofmann 124. INDEX. Alkaline carbonates use of for prevent- ing incrustation in steam-boilers 13. Alkalo$s artificial thenitrogenated prin- ciples of vegetables considered as the sources of 309. -from beans 305 313 314. -fern (Pterisapuilina) 315. flax (Linum usitatissimum) 312. -guano 314. -horse-flesh 314. _.-lycopodium 3 15. peat 313. -wheat (Triticum hybernum) 312. -wood 313. -artificial obtained by putrefaction 314. by the acid of sulphuric acid 314. -relation of bases derived from ani- line and ammonia with other groups of 303. Alloy natural of silver and copper from Chili 29. Amidogen-bases 96. Amidogen-compounds of tungsten 171. Amido-nitride of tungsten 172.Ammonia action of bromide of ethyl on 299. -action of on chloroplatinate of am-monium 176. -azophosphate of 152. -dentazophosphate of 360. -on the bichromate of 199. chrysanisate of 7 7. -double compounds of bichromate of with protochloride of mercury 202. -formation of aspartic acid from bi- malate of 187. -relation of bases derived from ani- line and ammonia with other groups of alkaloids 303. Ammonia-meter description of an 206. Ammonio-azophosphate of iron 152. Amyl analysis and vapour-density of 33. -action of bromide of on aniline 297. amylaniline 298. ethylaniline 299. -boiling-point of 34. -bisulphide of 158. -caproate of 213. -cyanate of 95. -iodide of 32. -isolation of 32. Amyl-alcohol physiological action of 180.Amyl hydruret of 34 41. Amylaniline 298. -action of bromide of et!yl on 299. Am yle t h ylanilitie 299. Amylethylophenylamine 299. Amylophenamine 96. Am ylophenylamine 297. Anderson experiments on gases gene- rated in a sewer 13. -use of alkaline carbonates for pre-venting incrustation in steam-boilers 13. Aniline on the behaviour of aniline and the alcohol-bases with nitrous acid 231. - 96. -action of bromide of amyl on 297. -action of bromide of ethyl on 284. -action of bromide and iodide of methyl on 295. -action of phenyl-alcohol on 283. -relation of bases derived from aniline and ammonia with other groups of alkaloids 303. Animal system passage of cuminic acid through the 181.Animal and vegetable kingdoms obser- vations on the adjustment between the 52. Anisidine 75. Anisol 74. Anniversary Meeting March 30 1850 97. Aromatic liquid obtained by decom- posing chlorophosphuret of nitrogen with alcohol 362. Ashes of the cactus composition of the 57. Azophosphate of iron 143. -with ammonia 146. -lead 149. -mercury 149. -potash 151. -silver 148. -alumina 147. -ammonia 152. c- baryta 149. -copper 147. Azophosphates composition of 153. B. Baryta action of heat on caproate of 215. _.-azophosphate of 149. -dentazophosphate of 360. -hyposulpham ylate of 159. 460 INDEX. Bases relation of bases derived from aniline and ammonia with other groups of alkaloids 303.-researches regarding the molecular constitution of the volatile organic 279. -separation of by diffusion 266. -synoptic view of basic compounds derived from ammonia 308. Beans alkaloids obtained from 309 313 314. Bichloride of titanium compound of with hydrocyanic acid 17'. Bichloruretted salicylic ether 78. Bichromate of ammonia double com-pounds of with protochloride of mer-cury 202. Bimalate of ammonia formation of as- partic acid from 187. Binitranisidine 76. Binitranisol 74. Binitrophenetol 78. Binitrosalicylic ether 78. Bisulphide of amyl preparation of 158. -preparation of the acid from 159. Boilers use of alkaline carbonates for pre- venting incrustation in steam-boilers 13. Boiling-points relation between chemi- cal composition boiling-points aiid specific volumes 104.Borate on a native 73. Boron nitride of 167. Brazier contributions towards the his- tory of caproic and cenanthylic acids 210. B rodie observations on the constitution of the alcohol-radicals and on the formation of ethyl 405. Bromaniline action of bromide of ethyl on 292. Bromide of amyl action of on amylani- line 298. -a ction of on aniline 291. -a ction of on ethylaniline 299. -ethyl action of on amylaniline, 299. action of on aniline 284. -action of on ethylaniline 287. -methyl action of on aniline 295. c. Cactus composition of the ashes of t.he 57. Caffeinc 87. Cahours on anisol and phenetol 74. -on the composition of mesitilole 17.-researches on pelargonic acid 240. -on the volatile oils obtained in the distillation of wood Calvert on the preparation of certain chlorates and particularly of chlorate of potash 105. Caproate of amyl 213. _.-baryta action of heat on 215. Caprone action of nitric acid on 220. -composition of 2 17. -preparation of 215. Caproyl composition of 226. Cast-iron heat developed by friction of 320. Cement description of for stopping the cavities of teeth by T. J. Herapath, 367. Cetacea creatine a constituent of the flesh of the 229. Chemical Composition relation between and hoiling-points and specific vo-lumes 104. Chemico-legal investigations mode of precipitating all the metals contained in a liquid by one operation in 162.Chloraniline action of bromide of ethyl on 290. ChIorate of potash preparation of 106. Chloride of cyanogen and titanium lf?. -action of on toluidine 151. Chlorine action of upon an equal volume of methyl . -_. action of 2 vols. of upon 1 vol. of methyl . Chlorophosphuret of nitrogen and its products of decomposition by J. H. Gladstone 135,353. -aromatic liquid obtained by the decomposition of under the influence of alcohol 362. -composition of 139. -properties of 138. Chloroplatinate of ammonium action of ammonia on 176. -ethylamine 95. -methylamine 94. Cholestrophane 90. Chromate of copper and potash 73. Chrysanisate of ammonia 77. -silver 77. Chrysanisic ether 78. Colouring matter on the red colouring matters of madder 243.-of sugar precipitation of by a me-tallic oxide 55. Coppcr azopl~osphatc of 147. INDEX. 461 Copper on a chromate of copper and potash 73. -in fuci 71. -natnral alloy of silver and from Chili 29. Crawhall W. obituary notice of 97. Creatine a constituent of the flesh of the cetacea 229. Cyanate of amyl 95. -ethyl 90. -methyl 91. Cyanogen action of chloride of upon toluidine 151 -chloride of and titaiiium 177. Cpanogen-compound of titanium 177. Cyanurate of ethyl 90. -methyl 90. D. Danson on the identity of bisulpha-mylic and hyposulphamglic acid 155. Debus on the derivatives of xanthic acid 84. Dentazophosphate of ammonia 360. -of haryta 359.-of silver 361. Dessaignes on the formation of aspartic acid from bimalate of ammo-nia 187. -on the formation of succinic acid by the oxidation of butyric acid 186. Dextroracemates and levoracemates 81. Diamylaniline 298. Diamylophenyiamine 298. Diethp lamine 300. Diethylammonia 300. Diet hylaniline 288. -hydrobomate of 288. -action of bromide of ethyl on 289. Diethylophenylamine 288. Diffusion of liquids 257. -chloride of sodium 259. -various salts and other substances 260. -ammoniated salts of copper 264. -mixed salts 265. -salts of potash and ammonia 271. -hydrate of potash 276. -salts of soda 277. Diffusion application of liquid diffusion to produce decomposition 60. -of one salt into the solution of another salt 269.c- decomposition of salts by 268. -separation of bases by 266. Distillation of wood on the volatile oils obtained in the 183. Durocher Malaguti and Sarzeaud on the presence of lead copper and silver in sea-water and on the exist- ence of the latter in plants and animals 68. E. Eddoes analysis of the ashes of the 190. Edwards on the action of arsenious acid on albumen 14. Ether observations on the constitution of the alcohols and ethers 45. -chrysanisic 78. -salicylic derivatives of 78. -bichloruretted salicylic 78. -binitrosalicylic 7 8. Etherification observations on by Prof. Graham 24 Ethyl action of bromide of on ammonia 299. -amylaniline 299. I_ aniline 284. -bromaniline 292.-chloraniline 290. -diethylaniline 289. -ethylaniline 287. -ethylochloraniline 291. -nitraniline 293. -I action of solar light on the iodide of 322. -bioxysulphocarborate of 84. -cyanate of 90. -cyanurate of 90. -observations on the formation of by B. C. Brodie 405. -preparation of bisulphide of 19. Ethjlaniine 96 299. -chloroplatinate of 95. -formation of 92. -preparation and propel ties of 94. -_I hydrochlorate of 95. Ethylammonia 299. Ethylamylophenamine 96. Eth>lanrline 285. -action of bromide of amyl on 299. -action of bromide of ethyl on 287. -action of iodide of methyl on 296. -hydrobromate of 286. -platinum-salt o? 286. Ethyl-cyarnethane 92. Ethylobromaniline 292. Ethylochloraniline 291.Eth ylonitraniline 202. 462 INDEX. Ethylonitrophenylaniine 292. Ethylophenamine 96. Ethylophenylamine 285. Ethyl-oxamide 95. P. Feculencies sugar- analysis of by T. J. Herapath 367. Fern alkaloids obtained from 315. Fibrine of muscular flesh 188. Field on the composition of the ashes of the cactus 57. -on a natural alloy of silver and copper from Chili 29. >lax,alkaloids obtained from 312. Flesh on the fibrine of muscular 118. Formyline identical with methylamine 89. Frankland researches on the organic radicals Part 11 amyl 30. -researches on the organic radicals Part 111 on the action of solar light upon iodide of ethyl. Friction heat developed by of water 319. -_. mercury 320.-cast-iron 320. Fuci lead and copper in 70. P silver in 70. G. Gaultier de Claubry on a mode of precipitating all the metals contained in a liquid by one operation (in chemico-legal investigations) 162. Gerhardt and Laurent on the action of ammonia on chloroplatinate of am-monium 176. Gladstone on chlorophosphuret of nitrogen and its products of de-composition 135 353. -action of sulphur on the pentachlo- ride of phosphorus 5. Graham on the application of liquid diffusion to produce decomposition 60. -on the diffusion of liquids 257. I_ observations on etherification 24. Griffin descriptign of an ammonia- meter 206. Gossle th and Brazier contributions towards the history of caproic and cenanthylic acids 210.Guano alkaloids obtained from 314. N. Heat developed by friction of water 319. mercury 320. cast-iron 320. -on the mechanical equivalent of 316. Herapath T. J. analysis of the ashes of the Spanish potato and of the eddoes 193. -analysis of sugar-feculencies 367. -on a cement for stopping the cavi- ties of teeth 367. Hofmann on amidogen- imidogen- and nitrile-bases 96. -note on the action of heat upon valeric acid with some remarks on the formuls of the alcohol-radicals 121. -on the passage of criminic acid through the animal system 181. I-researches on the volatile organic bases No. VIII. on the behaviour of aniline and the alcohol-bases with ni- trous acid 231. -researches regarding the molecular constitution of the volatile organic bases 279.Horse-flesh alkaloids obtained from 314. Hydrobromate of diethylaniline 288. -ethylaniline 286. Hydrocarbon on propylene a new hydro- carbon of the series C H, 111. Hydrochlorate of ethylamine 95. -methylamine 91. Hydrosulphate of ammonia action of on mononitranisol binitranisol and trini- tranisol 75. Hydrurets probable existence of the hpdrurets of organic radicals in coal- gas 42. Hyposulphamylate of baryta 159. I. Imidogen-bases 96. Iodide of ethyl action of solar light upon 322. -methyl action of on aniline 295. -on ethylaniline 296. Iron cast heat developed by friction of 320. -ammonio-azophosphate of 361. _I azophosphate of 143. INDEX.463 J. J oule on the mechanical equivalent of heat 316. Km Keller F. method of obtainingmetacetic acid in large quantities 190. Knop on a chromate of copper and potash 73. K ol be on the chemical constitution and nature of the organic radicals 369. Kopp on the relations between chemical composition boiling-points and specific volumes 104. IJ. Laurent and Gerhardt on the action of ammonia on chloroplatinate of am- monium 176. Lead azophosphate 149. -in fuci 70. Liebig on the fibrine of muscular flesh 188. -on the separation of some of the acids of the series (C H) 0,,82. Light on the action of solar upon iodide of ethyl 322. Lime on potasso-gypsite a double sul- phate of potash and by J. A.Phil-lips 348. Liquids diffusion of 257. Liquid diffusion application of to pro- duce decomposition 60. Lowel H. on the supersaturation of saline solutions 164. Lycopodium alkaloids obtained from 305. M. Madder on the red colouring matters of 243. Malaguti Durocher and Sarzeaud on the presence of lead copper and silver in sea-water and on the exist- ence of the latter in plants and ani- mals 68. M Bn e on the preparation of hydrobromic and hydriodic acids 74. Mercury heat developed by friction of 320. -azopliosphate of 149. Mercury double compounds of bichro-inate of ammonia with protochloride of 220. Mesitilole 185. -composition and vapour-density of 17. Metacetyl-urea 91 93. Methyl cyanate of 91.-cyanurate of 90. -action of chlorine upon an equal volume of. -action of 2 vols. of chlorine upon 1vol. of. -action of bromide of on aniline 295. -action of iodide of on aniline 295. ethylaniline 296. Methyl-alcohol physiological action of 180. Methylamine formation of 92. -obtained from caffeine 89. -chloroplatinate of 94. -hydrochlorate of 94. Methylaniline 295. Methylethylaniline 296. Methylethyloph~nylamine,296. Methyl-cyamethane 92. Methylophenylamine 295. Metals on a mode of precipitating all the metals contained in a liquid by one operation (in chemico-legal in- vestigations) 162. Metoluidine preparation and analysis of 155. -and bichloride of platinum 157. Miitchell analysis of deep well-water from Messrs.Holt’s brewery Rat- cliffe 1. Mononitranisol 74. Mononitroxylol 184. Moody Col, obituary notice of 98. Muscular flesh on the fibrine of 188. Muspratt on the identity of bisulph- ethylic with hyposulphethylic acid and of bisulphimethylic with hypo-sulphamethylic acid 18. 1FI. Nitraniline action of bromide of ethyl on 293. Nitranisidiioe 75. Nitride of boron 167. Nitrile-bases 96. Nitrobenzanisidide 76. Nitrocinnanisidide 76. Nitrogen chlorophosphuret of 135,353. Nitrogenated principles of vegetables considered as the sources of artificial alkaloids 309. 464 INDEX. Nitrophenitidine 79. Nitrotoluidine 184. 0. Obituary notice of W. Crawhall Esq. 98. -Colonel Moody 98. Oils volatile obtained in the distillation of wood 183.Organic bases researches on the volatile No. VIII. on the behaviour of ani- line and the alcohol-bases with nitrous acid 231. -researches regarding the molecular constitution of the volatile 279. -researches on the Part &I. amyl, 30. -radicals researches on the by E. Frankland Part III. on the action of solar light upon iodide of ethyl 322. -radicals on the chemical consti-tution and nature of by H. Kolbe 369. Oxyamido-nitride of tuiigsten 174. P. Past eur on-the characteristic properties of the two acids which compose racemic acid 79. Peat alkaloids obtained from 313. Pelargyl chloride of 241. Pelargone 242. Phenamine 96. Phenetole 78. Phenyl-alcohol action of on aniline 283.Phillips J. A. on potasso-gypsite a double sulphate of potash and lime 348. Phosphorus sulphoperchloride of 6,ll. Physiological action of analogously con- stituted chemical compounds 179. Platinum-salt of ethylaniline 286. Po,ash azophosphate of 151. -chlorate preparation of 106. -on a chromate of copper and 73. Potasso-gypsite a double stllphate of potash and lime by J. A. Phillips, 348. Potato analysis of the ashes of the Spanish 193. Price on creatine as a constituent of the flesh of the cetacea 229. PropyIene a new hydrocarbon of the series C EI, 111. -bromine-compound of 115. -chlorine-compound of I 19. -preparation of 115. Purpurine 255. Putrefaction alkaloids obtained by 314. Qm Quinine action of certain reagents upon 191.R. Racemates 82. Racemate of soda and ammonia 80. Radicals alcohol- remarks upon the for- mula of by A. W. Hofmann 124. r--observations on the constitu- tion of the and on the formation of ethyl by B. C. Urodie 405. -researches on the organic by E. Frankland Part 11 amyl 30. -researches on the organic by E. Frankland Part 111. on the action of solar light upon iodide of ethyl 322. -_. on the chemical constitution and nature of the organic- by H. Kolbe 369. Reynolds J. W. on propylene a new hydrocarbon of the series C H, 111. Report Annual of the Council 97. -Treasurer’s 103. Richmond on the bichromate of am-monia and some of its double salts. Rochleder on caffeine 87.8. Salicylic ether derivatives of 78. Salts decomposition of by diffusion 268. Salt silver in sea- 69. Sarzeaud Malaguti and Durocher on the presence of lead copper and silver in sea-water and on the exist- ence of the latter in plants and ani- mals 68. Scanlan experiments on gases gene- rated in a sewer 13. Schlossberger on the physiological action of analogously constituted che- mical compounds 179. Sewer experiments on gases generated in a sewer 13. Silver azophosphate of 148. -chrysanisate of 77. -in fuci 70. -in land-plants and in animals 70 1N DES. Siher in sea-salt 69. -in sea-water 69. -natural alloy of and copper from Chili 29. -tricyanurate of 87. Solutions saline on the supersaturation of 164.Stenhouse on the nitrogenated prin- ciples of vegetables as the sources of artificial alkaloids 309. Strecker on the red colouring matters of madder 243. Sugar precipitation of the colouring matter of by a metallic oxide 55. _D fcculencies analysis of by T. J. Herapath 367. Sulphate on potaasa-gypsite a double of potash and lime by J. Phillips, 348. Sulphanisolide 78. Sulphate on potasso-gypsite a double sulphate of potash and lime. Sulphur action of on the pentachloride of phosphorus 5. T. Teeth description of cement for stopping the cavities of by T. J. Herapath 367. Titanium chloride of cyanogen and 177’. -compound of bichloride of with hydrocyanic acid 178. -on the cyanogen compounds of 177.Toluidine action of chloride of cyanogen on 154. -preparation of 154. Toluol 184. Tricthylamine 96 301. Trinitranisol 74. Tungsten amido-nitride of 172. -on the arnidogen-compounds of 171. -oxyamido-nitride of 174. U. Ulex on a native borate 73. v. Valeramine chloroplatinate of 96. -_. formation and preparation of 95. Valeramine hydrochlorate of 96. Valerene 41. Vegetables nitrogenated principles of considered as the sources of artificial alkaloids 309. Vogel Dr. Jun. on the action of cer- tain reagents upon quinine 191. Volatile oils obtained in the distillation of wdod 183. Volumes specific relation betweeen che- mical composition and boiling-points and 104. W. Warburton on the precipitation of the colouring matter of sugar by a metallic oxide 55.Warington notice of observations on the adjustment between the animal and vegetable kingdoms by which the vital functions of both are perma- nentiy maintained 52. Water analysis of deep well- from Messrs. Holt’s Brewery Ratcliffe by J. Mitchell 1. -heat developed by friction of 319. -on the presence of lead copper and silver in sea-water 68. Wheat alkaloids obtained from 312. Wilson action of chloride of cyanogen upon toluidine 154. W ohler on the amidogen-compounds of tungsten 171. -on the cyanogen-compounds of ti-tanium 177. -on the nitride of boron 167. Wood alkaloids ohtained from 313. -volatile oils obtanied in the as-tillation of 183. Wurtz on the compounds of cyanuric and cyanic acid with the oxides of ethyl methyl and amyl and on the products resulting therefrom viz.acetyl- and metacetyl-urea and me- thyiamhe ethylyamine and valera- mine 90. X. Xanthogenamide 85. Xylidine 184. Xylol or xylene 184. END OF VOL. 111. \OL. 111.-NO. XII. I1 H LONDON I’tintcd 111 ScliuIze and Co. 13 Poland Stimt.

ISSN:1743-6893    

DOI:10.1039/QJ8510300458

出版商:RSC    

年代:1851

数据来源: RSC