摘要:

TIT E QUARTERLY JOIJRNAL OF THE CHEMICAL SOCIETY. VII1.-On the Solid Compound obtained by Distilling Xteclric Acid with Lime. BY THOMAS H. ROWNEY,PE.D. F.C.S. (ASSISTANT IN THE COLLEGE LABORATORY GLA SGOW.) Though the solid compounds obtained by the distillation of mar-garic and stearic acids with lime have been examined by Bussy Redtenbacher and Varrentrap these chemists do not agree in the formulx given by them to these bodies. Bussy,* to the product obtained from margaric acid gave the formula C,,H,,O and to that obtained from stearic acid C6sH670. The first of these compounds he named margarone and the second atearone. Redtenbachert also describes two compounds the first margarone he considers to be C,,H,,O and the second to be margarone combined with a hy-drocarbon and to have the formula C&H&O or C33H330+ CI,H,,.Varrentrapt likewise gives the formula C,,H,,O for margarone. Some time ago having prepared some of the solid compound by distilling stearic acid with lime I made an examination of it in order to ascertain the cause of these different statements; but my results differed considerably from those obtained by Bus sy Redtenbacher * Ann. Ch. Phys. [2] LIII 1833. f-Ann. Ch. Pham. XXXV XXXVI. $. Ibid. vor,. VL-NO XXII. H 98 MR. ROWNEY ON THE SOLID COMPUUND OBTAINED BY and Varrentrap. A reference to their papers on the subject how- ever at once made the cause of these different results apparent. In the following paper I have endeavoured to explain this first detailing my own experiments and then comparing the results ob- tained with those of the previously mentioned chemists.To obtain the compound stearic acid as produced in the stearine manufactory was mixed with half its weight of quicklime in an iron pot; this was put into a deep sand-bath and covered with sand and the distillation carried on rapidly; the distillate whilst hot was quite liquid but it very soon began to deposit crystals and when quite cold an abundant crop of crystals was deposited; these were separated from the oily liquid by filtration. I found the best method of purifying the substance was to melt it by gently heating it and then mix some ether with the liquid obtained; by exposure to cold crystals were deposited; the oily matter retained by the ether was separated from the crystals by filtration.By repeating this process several times all the oily matter was removed ; then by crystallizing two or three times from boiling ether the substance was obtained quite pure. In this state it forms beautiful white crystalline plates soluble in boiling alcohol and very soluble in ether; it fuses at 76' C. but after fusion does not solidify until the temperature falls to 72' C.; the fused substance crystallizes on cooling. When cold it may be reduced to powder by rubbing in a mortar but it becomes highly electrical by friction so much so that it is difficult to collect the powder. When heated in a test-tube with strong sulphuric acid it is decomposed sulphurous acid is given off and a black carbonaceous residue left in the tube.Nitric acid does not act upon it even when boiled with it but it is decomposed when heated with a mixture of strong sulphuric and nitric acids a volatile oily acid being formed. This decomposition I was not able to follow out for want of sub- stance. Other oxidizing agents were tried but with no satisfactory results. The following numbers were obtained by analysis the fused sub- cstance being employed and the combustions made with chromate of lead. I. *2033grm. of substance gave:* *2535 , water. 11. -1770 , substance gave -5355 , carbonic acid. * The carbon of the first and the hydrogen of the second combustion were lost. DISTILLING STESRIC ACID WITH LIME. 111. 01720 grm.substance gave -5165 , carbonic acid and -2115 , water. IV. -2155 , substance gave *6477 , carbonic acid and -2660 , water. These numbers correspond to the following percentages I. 11. 111. IV. Mean. c.. -82.51 81.89 81.97 82.12 H . . 13-85 -13.66 13-72 13.74 0.. --4.14 100~00 The numbers required for margarone C3,H330 are c. . 82.84 H. . 13.80 0. . 3.36 100~00 wnich do not agree very well with those obtained by analysis. The experimental numbers however agree better with the folloR<ng formulae of which I have given the calculated numbers. C2,H,,O* C28H%30* C . . . 82.23 C . . . 82.35 H . . . 13.70 H . . 13-72 0 . . . 4.07 0 . . . -3.93 100~00 100*00 It will be seen that the difference in the quantities of carbon and hydrogen in these formulz is very small indeed and consequently that it is difficult to decide which formula to adopt merely from the analysis of the substance itself; but by obtaining a substitution-product I was led to adopt the formula C,,H,,O or C5&5&.Bussy tried the action of chlorine upon his substance but ob-tained no satisfactory results. With bromine I have met with better success; but iodine even when fused with it has no action upon it. When bromine is added to the fused substance in a small flask it acts upon it immediately hydrobromic acid being given off and a red oily liquid remains at the bottom of the flask ; this solidifies into a crystalline mass when agitated under water; the excess of bromine H2 100 MR.ROWNEY ON THE SOLID COMPOUND OBTAINED BY was separated from it by washing first with dilute ammoniacal water and then with cold alcohol. To obtain the substance pure it was dissolved in cold ether and by allowing the ethereal solution to evaporate spontaneously tufts of feathery crystals were deposited ; the mother-liquor was poured off the crystals were again dissolved in ether and the solution allowed to evaporate. When this process had been repeated three or four times very brilliant crystals were obtained. Under the microscope these were found to consist of square plates collected together into feathery tufts ; when viewed by means of polarized light they exhibit a brilliant display of colours; the original substance on the contrary shows no colours.The fusing-point of the bromine-compound was found to be from 43OC. to 45O c. For analysis the substance was dried in vacuo over sulphuric acid and the combustions were made with chromate of lead. I. *3077grms. of substance gave *674,0 , carbonic acid and -2710 , water. 11. 02836 , substance gave 06235 , carbonic acid and 02490 , water. 11. a2758 , substance burnt with lime gave -1810 , bromide of silver. I. 11. IIr. Mean. e . . 59-77 59.95 59.86 H . . 9-78 9-75 9.76 Br . . -27.93 27-93 On comparing these numbers with the three following formula they will be found to agree best with the formula C28fi70 which is the one I have adopted though this probably is not the true atomic weight of the compound.C . . 59-03 C . . 59-70 C . . 60.33 H . . 9.47 H . . 9-58 H . . 9.70 Br . . 28-56 Br . . 27.85 Br . . 27.18 From these experiments it will be seen that I have obtained results differing from those of previous experimenters on this subject this difference is caused by the atomic weight of carbon having been DISTILLING STEARIC ACID WITH LIME. altered it being lower now than at the time of the previous investi- gations and the formula? of stearic and margaric acids have also been altered. Bussy considered the formula of rnargaric acid to be C35H3404,but this has since been altered to its present formula C34H3404. Redtenbacher from his analyses gives the formula CG,H,,O, for stearic acid; but his numbers when recalculated from the present equivalent of carbon agree with the formula C,4H3404 and the numbers he gives for margaric acid do not agree with the present formula.Bus sy after several experiments considered the compound he obtained by distilling margaric acid with lime to be derived from the anhydrous acid by losing 1 equiv. of carbonic acid; hence the formula given by him C35H3,0,-C0,=C,4H3,0. Redtenbacher and Varrentrap also consider this to be the reaction though the formula given by them differs from BUSSY’S owing to the difference in the formula of the acid; but a comparison of the properties of the substance and the numbers obtained by analysis shows that the compounds examined by them were the same and also that they agree with that examined by myself as will be seen by the following table of the corrected numbers of BUSS~S, Redtenbacher’s and Varrentrap’s along with those obtained by myself and the theore- tical numbers Bus sy.Red t e n bacher. Var rent r ap. T.H.R. Theory C,H,O. C . . 82.20 82.39 82-00 82.12 82.35 H . . 13.51 13-86 13.78 13.74 13.72 0 . . 4.29 3.75 4.22 4.14 3-93 The fusing-point of the substance was found to be-B uss y. Redt e nb ach er. Varr ent rap. T.H.R. 77O c. 77O c. 76’ C. 76’ C. The numbers of the compound obtained by Redtenbacher by distilling stearic acid with lime and to which he gave the formula C~~H~SO, when corrected agree with the formula C33H330 they also agree with other formula? the percentage difference in the carbon and the hydrogen being very small in the different formulae as previously stated.As he only made one analysis of the com-pound and the fusing-point is near that of the first compound it is doubtful whether it really is the true margarone. The compound obtained from stearic acid by Bus sy must also be considered doubtful as the numbers he obtained do not agree with any pro- bable formula. The ex perirncnts of 113 u s sy R e dt e n b ach e r and V ar r e 11t r a p PROFESSOR WAY ON DEPOSITS OF SOLUELE together with my own show that stearic and margaric acids when distilled with lime yield the same products of decomposition. The solid compound is also obtained under the following circumstances By distilling the acids per se; secondly by distilling the lime baryta or potassa-salts of these acids ; and thirdly by distilling the acids with lime or baryta.It will be seen that the decomposition proceeds further in this case than when acids lower in this series are treated in a similar manner. This is probably owing to the high temperature required to distil the compound over. As the name stearone or margarone is not applicable to this com- pound I have given it the provisional name of Stearene until some- thing more definite is known of its constitution. Since this examination has been finished Messrs. Delffs and Overbeck* have described three compounds obtained by distilliiig the lime or baryta-salts of myristic cocinic and laurostearic acids and which they have named myristone cocinone and laurostearone ; but I do not think the fonnulz given by them are quite correct as the numbers given by them will agree with several formuke the hydrogen in all the analyses being far too high for the formulz of those compounds; and it is very probable that the compound described as myristone C,,H,,O, is identical with that described in this paper as stearene C281-1280,.or C5GH5602,the fusing-point of both being nearly the same viz.75" C. myristone 76" C. stearene. This investigation was made in the laboratory of Dr. T. Anderson to whom I am much indebted for advice during its prosecution.

ISSN:1743-6893    

DOI:10.1039/QJ8540600097

出版商:RSC    

年代:1854

数据来源: RSC

摘要:

PROFESSOR WAY ON DEPOSITS OF SOLUELE 102 1X.-On deposits of soluble or gelatinous Silica in the lower beds of the Chalk formation. BY J. THOMAS WAY F.C.S. CONSULTING CHEMIST TO THE ROYAL AGRICULTURAL SOCIETY OF ENGLAND. The author described the discovery which in conjunction with Mr. J. M. Paine of Farnham he had made of large deposits of silica in the condition in which it is readily soluble in solutions of caustic potash or soda when boiled with these solutions at ordinary temperatures in open vessels. 4 Clicin. Gaz Nov. 1 1852. 01%GELATINOUS SILICA IN THE CHALK FORMATION. 103 The beds containing this silica are geologically situate at the base of the chalk formation between the upper green sand and the gault clay. At Farnham where the beds have been most examined they are very fully developed coming to the surface over a considerable breadth of land and extending to the distance of several miles.Judging from the dip of the strata and from such sections as the quarries in the neighbourhood afford the author believes that the total thickness of the deposit in question cannot be at this spot less than from 80 to 100 feet in thickness. It is not however of uniform character throughout but consists of beds of yellowish light soft rock intercalated with loose and apparently sandy marls. The attention of the author was first drawn to this subject during the examination of a series of specimens representing the strata of the chalk formation which were collected for analysis about three years ago.On examining some of the lower deposits of this series he was struck with the circumstance that though of a yellowish-white colour of small density and having every appearance of being chalk marls (under which name they are indeed generally used in agriculture) they did not in many cases exhibit the smallest effervescence when treated with an acid and contained nierely a trace of lime in any form. The following results were obtained from the analysis of a specimen of this earth. Silica . . 40.30 Peroxide of iron . . 2.26 Alumina . . 3.44 Soluble Lime . -61 in acids Magnesia . . *47 Chloride of sodium . *14 \\Potash . *43 Insoluble Silica . . 41.23 in acids Alumina witi a lit'tle oxide of'iron . 11-12 Traces of lime and magnesia .100*00 The silica C'soluble in acids" is here the total quantity of silica which is soluble in potash after treatment with boiling muriatic acid in the usual way. The quantity of solilble silica directly dissolved out by potash without previous treatment with an acid is in this case 28.70 per cent. The author observed that the existence of these beds was not altogether unknown before Since he had been engaged upon this examination he had found that similar deposits of PROFESSOR WAY ON DEPOSITS OF SOLUBLE soluble silica had been mentioned by Sauvage in the Annales des Mines as occurring in the Epartement des Ardennes in France. Sauvage had found as much as 56 per cent of soluble silica in these deposits; and from their description it was plain that they were the same beds although somewhat differing from the corresponding strata in England.Within the last two years as many as 80 or 100 samples havc been carefully collected by the author and Mr. Paine from the land of the latter at Farnhani and examined in reference to the pro- portion of soluble silica they contain. In all cases the quantity of soluble silica has been determined by boiling the dry and powdered earth in moderately strong solution of caustic potash or soda which dissolves the free silica without as is well known affecting that portion which is combined with alumina as clay or the silica that may exist as sand. The quantity of soluble silica so ascertained has been found to constitute from 5 to 72 per cent of the dry earths.As a rule the deposits which are geologically nearest the gault clay contain the smallest proportion which increases in the beds as they rise towards the green sand. The largest proportion that has been observed hitherto has been abovc stated as 72 per cent. This particular bed is at Farnham of about 10 or 12 feet of thickness and close to the surface of the land on the hill-side. It is very remarkable when dry on account of its extreme lightness by which and by its porosity it is easily recognized. Very many of the beds have bcen found to contain as much as 60 per cent of free solublc silica and 20 or 30 tons have been sent to London affording when ground up an average amount of 64per cent. There is therefore no doubt of the beds in question being available as a source of soluble silica if it should be found desirable so to employ them.The author mentions that although many of the beds contain no carbonate of lime there are others in which both soluble silica and carbonate of lime are associated. These beds are generally of a harder and more cornpact character and are used locally as building-stones. The ‘(firestone,” which is quarried to a considerable extent at Godstone and Reigate in Surrey and used in London to form the backs of fire-places is from the same deposit and of similar conipo- sition. Mr. Way has found the building-stone to contain about 25 per cent of soluble silica with 50 per cent of carbonate of lime and 25 per cent of clay. With the exception of the building and firestone rock which are of considerable hardness the other bcds arc easily reduced to powder ; OR GELATINOUS SILICA IN THE CHALK PORMATIOS.105 indeed when first dug up in the moist state they readily crumble between the fingers. When examined by the microscope the silica is found to be amorphous. With the exception of a few casts of foramin= the deposit is not infusorial. hlr. Way proposes to employ these beds as a source of silicate of lime for agricultural purposes. He finds that the silica can be made to combine with lime with great ease in several ways a mixture of slaked lime with the powdered rock when made into a thin mortar and left for several weeks is found to be entirely converted into silicate of lime The process is hastened by adding 2 or 3 per cent of car-bonate of soda which becoming caustic dissolves the silica forming a soluble silicate which is subsequently decomposed by the lime ;and in this way the soda acting as a carrier between them causes a speedy union bebeen the silica and lime.Another method of producing the silicate of lime is to mix the slaked lime with the powdered rock and sufficient water to bring the mixture to the thickness of gruel and to heat to nearly the boiling- point; the combination is complete in about an hour. In all cases the silica is used in the proportion of 3 equivs. to 1equiv. of lime. A mixture of the rock with chalk when heated to low redness in a reverberatory furnace gives the compound in a very fit condition for agricultural use; but it is necessary that the heat should be carefully regulated otherwise the silicate becomes altogether insoluble in water.The author has found silicate of lime produced in either of the above ways soluble to the extent of about 20 grains in the gallon of distilled water; and as the largest portion of the 20grains so dis-solved is silica he considers this solubility sufficient in relation to the quantity of water passing through plants to supply all the silica required by wheat barley and other plants of the silicious class. He proposes to employ the silicate of lime as a manure for light lands and he anticipates that it will serve to correct the over-luxuriance and tendency to be “laid,” which is so common in well- manured light soils and that it will render the use of guano and other nitrogenous manures more certain and more admissible on such lands.Mr. Way in conclusion suggests a possible connection between the existence of these beds and the production of the chalk itself. He thinks it certain that the deposits of soluble silica can only have been formed from solution and in the absence of heat. Silicate of lime derived hy disintegration from the older rocks inany of which contain it in abondancc and dissolved in water may bc supposed to DR. J. H. GLADSTONE ON be acted upon by carbonic acid derived from the decomposition of animal and vegetable matter or from volcanic sources. The results of such an action would be the production both of carbonate of lime and of soluble silica. The author points out as an interesting fact that we not only find the chalk closely associated with the silica beds but that in the case of the building and firestone before described they are in some cases intimately mixed which could hardly have occurred if the two deposits were not due to some common origin.

ISSN:1743-6893    

DOI:10.1039/QJ8540600102

出版商:RSC    

年代:1854

数据来源: RSC

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DR. J. H. GLADSTONE ON X,-On a Compound Subhate of Potash and Soda BY J. H. GLADSTONE, Ph.D. F.R.S. F.C.S. The saturating power of the common organic acids is a subject to which great attention has been and still is paid. Many acids that were once considered monobasic have had their equivalents doubled or trebled with evident advantage in the cxplanation of their salts. To take one example Tartaric acid formerly viewed as HO C4H20,;,is now represented as 2 HO C,H,O,, and its bibasic character explains at once why if half the quantity of potash neces- sary for its saturation be added to a solution of the acid we obtain riot a mixture of neutral salt and free acid but a sparingly soluble bitartrate; and why we have such an endless variety of double tartrates even one Rochelle salt in which the two alkalies potash and soda are united although they are bases of the same natural family.Chemists have more recently been led to inquire whether some of the inorganic acids usually esteemed monobasic should not be also viewed as bibasic. It has been well remarked that whilst some acids-as for instance-nitric acid always form neutral simple salts others of which sulphuric acid may be taken as a typc exhibit a great tendency to form acid and double salts. In fact every reason which could be urged in favour of the bibasic character of tartaric acid would equally apply to sulphuric acid excepting that we have no compound analogous to Rochelle salt. The argument is perhaps suficiently strong even now; but could a double sulphate of potash and soda be prepared the analogy would be complete; and none I apprehend who are accustomed to double the formula of tartaric acid coidd rcfusc to vicw sulphuric acid also as 2 HO S,06.A COMPOUND SULPHATE OF POTASH AND SODA. 107 It was in the attempt to obtain such a salt that the compound now to be described was discovered. Having occasion to prepare some salt which should show flashes of light on crystallizing I followed the method recommended in Gmelin’s “Handbook of Chemistry,’’ Vol. I p. 207. 2 parts of sulphate of potash and 1 part of chloride of sodium were fused together; the mass removed from the crucible was dissolved in boiling water filtered and suffered to cool. The result was very satisfactory.Small crystals separated each at its formation emitting a luminous flash visible even in shaded daylight. Their appearance struck me as being very uniform yet certainly not that of sulphate of potash; and it occurred to me that they might be a double sulphate of the two alkalies. The crystals were examined by Mr. Crosby of St. Thomas’s Hospital and were found to contain no water but to give a precipitate with antimoniate of potash. They consisted of about 48 per cent of sulphuric acid and 47 per cent of potash; the remaining 5 per cent or thereabouts being soda This was quite inconsistent with the formula KO NaO S,06 ; but it might well contain such a compound mixed with ordinary sulphate of potash. A series of experiments was set on foot in order to obtain if possible pure crystals of this supposed salt.The salts obtained were freed from hygroscopic moisture by heating them ; sulphuric acid was determined in the usual way as baryta-salt and the potash as platinum-salt. Every analysis that was made by me is recorded. Exp. 1. A crop of large crystals was obtained by the process already described. They were very regular in form-six-sided prisms terminating in six-sided pyramids truncated. Salt employed. Sulph. haryta obtained. 38.18 grs. 53.10 grs. 27.61 , 38.65 , Salt employed. Chlor. plat. and pot. obtained. 13.83 grs. 33.32 grs. The acid and base thus determined are in the proportion Sulphuric acid 47-77 and 48.06 per cent Potash . . . 46.58 I Now in order to obtain such numbers as these we must suppose that 6 equivs.of sulphuric acid are combined with 5 of potash and 1 of soda. 108 DR. J. €I. GLADSTONE ON Equivs. Calculated. Average of experiments. Sulphuric acid 6 47.26 47.91 Potash . . . 5 46.57 46.58 Soda . . . 1 6-16 5.34 looooo 100~00 Exp. 2. One part of sulphate of potash was mixed with two parts of crystallized sulphate of soda that is about equivalent proportions ; water was expelled from the mixture by heat and the salts were fused together. The cooled mass was dissolved in hot water which presently afforded crystals similar in appearance to the preceding. They were dried and analyzed. Salt employed. Salt obtained. 38-64grs. 45.60 grs. sulph. of baryta. 14-65 , 35.81 , chlor.plat. pot. These numbers indicate Sulphuric acid 47.96 per cent Potash . . . 47.26 , This salt is evidently identical with the preceding. Exp. 3. One part of sulphate of potash and two parts of crystal-lized sulphate of soda were dissolved together in water by the aid of heat. There separated on cooling small crystals of a perfectly defi- nite appearance six-sided prisms with six-sided pyramids at the ends truncated. They were analyzed as before. Salt employed. Salt obtained. 10.20 grs 14-41grs. sulph. baryta. 8.31 , 19.31 , chlor. plat. pot. Thesc numbers indicate Sulphuric acid 48.49 per cent Potash . . . 44-92 , These results differ but little from those previously obtained. Exp. 4. A mixture of equul parts of sulphate of potash and chlo- ride of sodium fused together and dissolved in hot water afforded crystals which were evidently the same.Exp. 5. Three parts of bisulphate of potash and one part of chlo-ride of sodium were fused together. Hydrochloric acid was given off in large quantity as might be expected; and on dissolving the fuscd mass in hot water and suffcri~igit to cool thcrc scparated A COMPOUND SULPHATE OF POTASH AND SODA. 109 hexagonal crystals apparently identical with those previously exa-mined mixed with another salt in feathery flakes. Exp. 6. The same salts mixed in the same proportions were boiled together for a coiisiderable time in water. The solution yielded the feathery flakes above mentioned along with crystals that appeared to be thin segments of hexagonal prisms but which Dr.Leeson by a minute examination of their angles found to be derived from the octagon of the regular system by the development of two of the opposite planes. They were found to contain soda and no water. On analysis they yielded the following results Salt employed. Salt obtained. 25.09 grs. 35.12 grs. sulph. baryta. 14.17 33-20 ) chlor. plat. pot. )) which indicate Sulphuric acid 48.05 per cent Potash. . . 45.29 , Ax the microscope showed some. small needle-shaped crystals stick- ing to these octagonal ones a portion of the salt was washed several times with a very little cold water and analyzed. Salt employed. Salt obtained. 7.51 grs. 10-37 grs. sulph. baryta 6.00 , 14.22 , chlor.plat. pot. which indicate Sulphuric acid 47.40 Potash. . . 45.83 Another portion of salt was prepared from the same source recrystallized and then washed with a little cold water. The crys- tals were small but of the same form as the first. They were analyzed. Salt employed. Salt obtained. 21.46grs. 29.61grs. sulph. baryta 7.23 , 17.49 , chlor. plat. pot. which indicate Sulphuric acid 47.37 per cent Potash . . . 46-75 , All these results seem to point out a salt similar in composition to all those previously examined. Exp. 7. A saturated solution of carbonate of soda was added to a saturated solution of bisulphate of potash until effervescence ceased. DR. J. €1. GLADSTOXI? ON A crystal or two separated.The solution yielded on evaporation a crop of crystals bearing a general resemblance to the salt formerly obtained. They were dried and analyzed. Salt employed. Salt obtained. 24.42 grs. 33.95 grs. sulph. baryta 12-06 , 27.40 , chlor. plat. pot. which indicate Sulphuric acid 47.73 per cent Potash . . . 43.92 , differing little from previous estimations. Exp. 8. One part of nitrate of potash and two parts of crystallized sulphate of soda dissolved together and evaporated gave crystals of the compound salt mixed with nitre. Exp. 9. In order to see whether the same salt would form in the presence of a large excess of acid 3 ounces of sulphate of potash 6 ounces of crystallized sulphate of soda and nearly 2 fluid ounces of sulphuric acid were boiled together in water and evaporated.The crystals which were small and of the drdinary shape were slightly washed with cold water dried and analyzed. Salt employed. Salt obtained. 27.78 grs. 39.17 grs. sulph. baryta which indicates Sulphuric acid . 48-40 per cent. This scarcely exceeds the previous determinations of sulphuric acid. The salt was evidently the same. Exp. 10. Conversely the effect of an alkaline solution was tried. Two parts of sulphate of potash and one part of hydrate of soda were dissolved together in water. The evaporated solution gave a crop of very minute crystals. They were washed with a little cold water two or three times dried over sulphuric acid and analyzed. Salt employed. Salt obtained. 18.39 grs.25.61 grs sulph. baryta which indicates Sulphuric acid . . 47.81 per cent. Hence the salt was identical with those analyzed before. Exp. 11. Thinking that a large excess of soda might cause the formation of a salt richer in soda 6 parts of that sulphate crystal- lized were dissolved in water with 1part of sulphate of potash and evaporated. Crystals of common sulphate of soda alone separated. A COMPOUND SULPHATE OF POTASH AND SODA. 111 On another occasion when 1 lb. of sulphate of soda had been dissolved along with 4 Ib. of sulphate of potash the solution yielded first six-sided prisms with dihedral summits containing soda ; then large crystals of sulphate of soda; and the mother-liquor from them yielded again a crop of the compound salt.It appears then that all these attempts have failed to produce a sulphate of potash and soda analogous to the double tartrate; but they invariably yielded a compound salt containing a small amount of soda. This has all the appearance of being definite and uniform and seems to consist of sulphuric acid combined with 6 equivs. of base 1 being soda and 5 potash Its formula decides nothing in favour of the bibasic character of sulphuric acid but it does not militate against such a view it may be written 5 KO NaO 3 S,06 though perhaps chemists will generally prefer the expression 5(KO SO,) +KaO SO,. It may be asked why was not the salt subjected to repeated crystallizations before it was analyzed? The reason was that I feared some alteratioii in the salt during such a process; indeed a specimen which had thus been treated was fold to have lost 1 per cent of sulphuric acid showing a considerable decrease in the amount of soda.Salt employed. Salt obtained. 26-11 grs. 35.38grs. sulph. baryta. 25-05 , 34.08 I9 which indicate Sulphuric acid 46.52 and 46.70 per cent. Had the salt been entirely reduced to ordinary sulphate of potash analysis should have given only 45-94per cent. The solubility of this compound salt was found to be very similar to that of sulphate of potash itself 1000 parts of water at 21.2' F. were found capable of dissolving 250 parts; at 55' F. 101 parts ; and at 40°F. 92 parts of the salt. 25 grs. of salt recrystallized during this experiment was found to yield 34.11 grs.of sulphate of baryta indicating 46-90 per cent of sulphuric acid. The crystalline form also is the same as that of sulphate of potash; but the crystals appeared to me more uniform than that salt ordinarily is and having not so great a tendency to become long and branching. iThe compound and the simple salt are both alike anhydrous. Since performing these experiments I have consulted the original paper of Rose in Pogg. MI Ueber die Lichterscheinungen bei 11.iRON LIEBIG OX THIERSCHITE. der Krystallbildung.” I find he has accurately described the crystals which emit light but his quantitative determinations led him to doubt their definite character; I however have always found them uniform in composition in whatever manner they may have been produced. Their production indeed under such various cir- cumstances could not have been anticipated; and they form a remarkable instance of a. certain proportion of the base of a salt being replaced by an analogous oxide without materially affecting its pbysical properties.

ISSN:1743-6893    

DOI:10.1039/QJ8540600106

出版商:RSC    

年代:1854

数据来源: RSC

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11.iRON 1,ZEBIG OX THIERSCHITE. XI.-Note on Thierschite. BY J. LIEBIG. (FROM A LETTER TO DR. HOFMANN.) Some time ago I received from Dr. F. von Thiersch General Conservator of the scientific collections of Bavaria a fragment of a white marble column from the Parthenon for thc purpose of analyzing the incrustation with which the external surface of the column was covered the chief object of the examination being to decide whether the column had been painted with a colour of a still determinable nature. The incrustation was about & of an inch thick and possessed the hardness of fluor-spar. Under the microscope when illuminated by sun-light it appeared as a lustrous opaline aggregate of warty nuclei exhibiting a concentric structure. When seen by the naked eye it appeared an uneven layer of a dingy-grey colour covering the whole outer surface of the stone.A portion of the detached crust dissolved in acetic acid with effervescence ; the solution contained nothing but lime. The greater portion was insoluble in acetic acid but mas readily dissolved by nitric acid only a trifling residue remaining behind. The nitric solution gave upon addition of ammonia a snow-white precipitate insoluble in ammonia. After addition of acetate of soda it furnished with salts of silver and lead a white precipitate. This deportment pointed towards oxalic acid and indeed a more minute examination soon convinced me that the chief niass of the incrusta- tion which had been taken for a pigment used in painting the column consisted of crystallized oxalate of lime.I treated the precipitate produced by ammonia in the nitric BARON LlEBIG OK TIITERSCHITE. 113 solution with chloridc of copper which converted it into a bluish powder wliilst the liriie was dissolvcd. The copper precipitate dissolved readily in ammonia ; and this solution yielded after the copper hid been tlirown down a beautiful crystallization of oxalate of ainmoiiia which was decomposed without deposition of carbon into carbonic acid and carbonic osidc when heatcd with concentrated sulphuric acid and from which oxalic acid with all its properties was prepared in sufficient quantity for an analysis if such had been considered necessary. Dr. Sendtner Adjunct to the Botauical Gardens in Munich who has a great deal of expcrieiice in researches of this kind was unable to discover any organic structure either in the incrustation itself or in the residue insoluble in nitric acid.I believe therefore I am justified in considering this incrustation which will probably be found upon many lime-stones as a mineral species ;and since Sandall has observed crystallized oxalate of lime bettvecn metastatic calc-spar crystals in Hungary without proposing a mineralogical name for it I have great pleasure in coupling with this mineral the name of the learned man whose labours have so successfully contributed to the elucidation of antiquities and who has given rise to the present observations. The origin of this oxalate of lime can scarccly be doubtful; it is evidently derived from lichens vegetating upon the lime-stone ; it is the residue of a series of generations following each other during centuries until the whole surface of the stone-in consequence of the gradual destruction of former vegetations whose organic matter decayed while the oxalate of lime produced during their vitality remained unaltered-was so completely covered that new germs of lichens no longer found the soil of carbonate of lime necessary for their development.The residue of the incrustation insoluble in nitric acid when heated in a slam tube was slightly charred; it contained traces of a humus-like substance evidently the last residue of the lichens protected by the oxalate of lime from entire destruct ion.

ISSN:1743-6893    

DOI:10.1039/QJ8540600112

出版商:RSC    

年代:1854

数据来源: RSC

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BARON LlEBIG ON TIITERSCHITE. XII.-On Kyanuyenic Acid. BY J. LIEBIG. (FROM A LETTER TO DR. HOFMANN). During some experiments made by Professor Bischoff regarding the amount of uric acid in dog’s urine the latter was very frequently VOL. VI.-NO. XXII. I BARON LIEBJG ON KTANURENIC ACID. examined for uric acid. In no case could a trace of this acid be detected. During these researches the urine deposited sometimes but not very frequently a precipitate which on account of its minute divi- sions was difficult to filter. Ail examination of this deposit has proved that it consists chiefly of a new acid which I propose to call kyanurenic mid in order to remind us of its origin. On dissolving the coloured deposit of dog’s urine in lime-water diluting with water and adding hydrochloric acid to the gently warmed liquid kyanurenic acid separates in delicate colourless needles which on drying become very light and assume a satiny Iustre ; they redden blue litmus-paper.From concentrated solutions the acid is deposited in the form of a powder. When heated in a glass tube the acid fuses to a brown liquid which on further application of heat sublimes a trace of charcoal remaining behind. The subli- mate is white satiny lustrous crystalline; it dissolves in alcohol and differs by this deportment from the original acid. Kyanurenic acid may be readily distinguished from uric acid by its solubility in hydrochloric acid ; the precipitate which is produced in alkaline solutions of the acid upon addition of hydrochloric acid disappears again if an excess be added.It dissolves readily in boiling kydro- chloric acid and in dilute sulphuric and nitric acid; in the latter apparently without decomposition. Its hot saturated solutions solidify upon cooling to a magma of short cxtremely lustrous needles. In cold concentrated sulphuric acid kyanurenic acid dissolves without change ; on gently warming the solution assumes a light-brown colour and now deposits upon addition of water a beautiful lemon- yellow amorphous precipitate which is sometimes mixed with crystals of unchanged acids. Kyanurenic acid readily dissolves in the caustic and upon application of heat also in the carbonated alkalies also in lime- and baryta-water ; when employed in sufficient quantity it perfectly destroys their alkaline reaction Evaporation of these solutions yield well crystallized salts.The lime-salt forms stellar groups of short hard needles ; the baryta-salt feather-like united leaflets exhibiting the lustre of mother-of-pearl both salts are difficultly soluble in water. A solution of the acid in ammonia furnishes upon addition of nitrate of silver a dense white preci- pitate insoluble in hot water. I have abstained from sacrificing to an elementary analysis the small portion of this substance which I had at my disposal inasmuch as the composition of this body which seems to occur but rarely and in small quantities appeared to me less important than the MESSRS. CLARKE AND MEDLOCK ON DEEP WELL-WATER. 115 proof of its existence and the study of those properties by means of which it may be readily recognized again. According to the experi- ments which I have made kyanurenic acid contains no nitrogen or only so small a quantity that the minute portions which I was able to devote to the experiments were insufficient to show its presence.

ISSN:1743-6893    

DOI:10.1039/QJ8540600113

出版商:RSC    

年代:1854

数据来源: RSC

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MESSRS. CLARKE AND MEDLOCK ON DEEP WELL-WATER. 115 XIIL-Analysis of the Waters from the Deep Wells of Westbourne Park and Russell Square and the Artesian Well of the Hanzoell Lunatic Asylum. BY CHARLESHARWOOD CLARKE,EsQ. B.A. F.S.A. AND HENRYMIDLOCK,EsQ. F.C.S. The deep well of Westbourne Park is situated a short distance to the north of Westbourne Grove. It was sunk several years since by J. W. Treeby Esq. for the purpose of supplying the houses on his private estate. The surface of the ground in the neighbourhood is 735 feet above the Ordnance datum line. The depth of the well is 230 feet and the water rises to within 120 feet of the surface. It is sunk through various strata of sand and clay and a bore-pipe carried to a depth of 15 feet into the chalk.The supply of water is derived from two strata the chalk and the sand immediately above it. The samples for analysis were collected in December 1852 the one (A)being taken from the well and the other (B)from the bore-pipe which leads into the chalk. Both specimens were bright and colour- less and possessed an agreeably refreshing but slightly saline taste. At the time the water was collected the bore-pipe had been closed and the sample (A)was considered as being derived exclusively from the sand strata immediately above the chalk. The quantitative analysis yielded the following results A. Determination of the total quantity of fixed constituents. Water employed. Residue obtained (dried at 1200 C. =24S0 F.) Percentage. 44520 grs. 36.3744 grs.0.081703 B. Determination of organic matter. Water employed. Organic matter expelled at Percentage. a dull red heat. 44520 grs. 0.4573 gr. 0.001027 r2 MESSRS. C. FI. CLARKE .4ND 11. MEDLOCIL OK C. Determination of silicic acid. Rater employed. Silicic acid obtained. Percent age. 44520 grs. 0*4152gr. 0.000932 D. Determination of iron alumina and phosphates. Water employed. Precipitate obtained. Percentage. 44520 grs. 0.2185gr. 0~000490 E. Determination of lime. Water employed. Carbonate of lime obtained. Percentage of lime. 44520 grs. 2.2246 grs. 0.002798 F. Determination of magnesia. Water employed. Pyrophosphate of magnesia obtained. Percentage of magnesia. 44520 grs. 1.7817 grs. 0.001451 G. Determination of c hlorine.Water employed. Chloride of silver obtained. Percentage of chlorine. 70000 grs. 43.4695 grs. 0.015351 H. Determination of sulphuric acid. Water employed. Sulphate of baryta Percentage of sulphulic obtained. acid (SO,). 70000 grs. 39.0852 grs. 0.019170 1. Determination of alkalies. Water employed. Mixed chlorides obtained. 70000 grs. 46.4693 grs. a. Determination of potassium. Water employed. Bichloride of platinum and Percentage of chloride of potassium potassium. obtained. 70000grs. 55.0502 grs. 0.012559 6. Determination of sodium. Water employed. Chloride of sodium obtained. Percentage of sodium. 70000 grs. 29.6747 grs. 0.016667 J. Determination of carbonic acid In order to obtain a perfectly fresh sample of the water for the determination of the carbonic acid the well was pumped nearly to dryness and the water collected as it issued rapidly from the strata of sand.A bottle containing ammonia and solution of chloride of calcium and capable of holding in addition 70000 grs. of water was TIIE WELLS OF WESTBOURNE PARK RUSSELL SQ. AND HANWELL. 117 filled and the precipitated carbonate of lime subsequently determined. Water employed. Precipitate of carbonate of Percentage of lime obtained. carbonic acid. 70000 grs. 390909 grs. 0.024572 containing 17.2004grs. of carbonic acid. The second sample of water (B) was taken from the bore-pipe which passes to a depth of 15 feet into the chalk and was supposed to be derived exclusively from the chalk strata below the sand.The following results were obtained by quantitative analysis. A. Determination of the total quantity of the fixed constituents. Water employed. Residue obtained (dried at Percentage. 1200 C. =248' F.) 44520 grs. 36.0498grs. 0.080973 B. Determination of organic matter. Water employed. Organic matter expelled Percentage. at a dull red heat. 44520 grs. 0.6683gr. 0.001500 C. Determination of silicic acid. Water employed. Silicic acid obtained. Percentage. 44520 grs. 0.3003gr. 0.000673 D. Determination of iron alumina and phosphates. Water employed. Precipitate obtained. Percentage 44520 grs. 0.3973gr. 0*000892 E. Determination of lime. Water employed. Carbonate of lime obtained. Percentage of lime. 44520 grs.2.1364grs. 0.002710 F. Determination of magnesia. Water employed. Pyrophosphate of magnesia Percentage of obtained. magnesia. 44520 grs. 1.4630grs. 0*001191 G. Determination of chlorine. Water employed. Chloride of silver obtained. Percentage of chlorine. 44520grs. 265804 grs. 0.014755 H. Determination of sulphuric acid. Water employed. Sulptiate of barytn obtained. Percentage of sulphuric acid (SO,). 44520 grs. 23.9932grs. 0*018502 118 MESSRS. C. H. CLARKE AND €I. RIEDLOCK ON I. Determination of alkalies. Water employed. Mixed chlorides obtained. 44520 grs. 28.9.235 grs. a. Determiuation of potassium. Water employed. Bichloride of platinum and chloride Percentage of of potassium obtained. potassium. 44520 grs.37.3976 grs. 0.013415 6. Determination of sodium. Water employed. Chloride of sodium Pcrcentage of obtained. sodium. 44520 grs. 17.5143 grs. 0.015467 J. Determination of carbonic acid. The water was taken direct from the bore-pipe and introduced immediately into the bottle containing ammonia and chloride of calcium. Water employed. Precipitate of carbo-Percentage of nate of lime obtained. carbonic acid. 70000 grs. 38,8218 grs. 0.024402 containing 17.0816 grs. of carbonic acid. The deep well in Russell Square is situated on the north side of the square. The surface of the ground is 82 feet above the Ordnance datum line. The well is sunk through the sand and a bore-pipe carried to a depth of 100 feet into the chalk. The total depth of the well is 230 feet and the water rises to within 130 feet of the surface differing in height only by a few inches from the level of the water in the well at Westbourne Park.The sample for analysis was collected in December 1852 and gave the following results A. Determination of the total quantity of fixed constituents. Water employed. Residue obtained (dried Percentage. at 120° C =248O F.) 44520 grs. 30.3701 grs. 0.068213 B. Determination of organic matter. Water employed. Organic matter expelled Percentage. at a dull red Beat. 44520 grs. 0.5005 gr. 0.00 1098 C. Determination of silicic acid. Water employed. Silicic acid obtained. Percentage. 44520 grs. 0-5112gr. 0.001148 THE WELLS OF WESTBOURNE PARK RUSSELL SQ,.AND HANWELL. 119 B. Determination of iron alumina and phosphates. Water employed. Precipitate obtained. 44520 grs. 0.1694 gr. E. Determination of lime. Water employed. Carbonate of lime obtained. 44520 grs. 143220 grs. F.Determination of magnesia. Water employed. Pyrophosphate of magnesia obtained. 44520 grs. 0.5852 gr. G. Determination of chlorine. Water employed. Chloride of silver obtained. 44520 grs. 20.0015 grs. H. Determination of sulphuric acid. Water employed. Sulphate of barpta obtained. 44520 grs. 19.7274 grs. I. Determination of alkalies. Water employed. Mixed chlorides obtained. 44520 grs. 26.2831 grs. u. Determination of potassium. Water employed. Bichloride of platinulu and chloride of potassium obtained.44520 grs. 20.7468 grs. b. Determination of sodium. Water employed. Chloride of sodium obtained. 44520 grs. 19.9537 grs. J. Determination of carbonic acid. Water employed. Carbonate of lime obtained. 50640 grs. 26.9546 grs. containing Percentage. 0.000380 Percentage of lime. 0.001801 Percentage of magnesia. 0.000472 Percentage of chlorine. 0-011106 Percentage of sulphuric acid (SO,). 0.0152 13 Percentage of potassium. 0.007458 Percentage of sodium. 0.017620 Percentage of carbonic acid. 0.023420 11%600grs. of carbonic acid The artesian well at Hanwell is sunk near to and supplies the Asylum. The depth of the well is 236 feet and the water rises to a height of 36 feet above the surface the level of the ground being 74.5 feet above the Ordnance datum line.The sample submitted to analysis was collected in February last and gave thc following results 120 ~SSICS.c. H. CLARKE AYI) n. AIEDLOCK ox A. Determination of the total quantity of fixed constituents. Water employed. Resitliie obtained Percentage. (dried at 120W='L4S0 I".) 44520 grs. 30.4350 grs. 0.0685 14 B. Determination of organic matter. Water employed. Organic matter expelled rat Percentage. a dull red heat. 44620 grs. 1.1473 grs. 0.002719 C. Determination of silicic acid Water employed. Silicic acid obtained. Percent age. 44520 grs. 0.1155 gr. 0.000259 D. Determination of iron alumina and phosphates Water employed. Precipitate obtained.Percentage. 44520 grs. 0.2046gr. 0.000459 B. Determination of lime Water employed. Carbonate of hie obtained. Percen tagc of lime. 44520 grs. 3.2725 grs. 0.00411 F. Determination of magnesia Water employed. Pyrophosphate of magnesia Percentage of obtained. magnesia. 44520 grs. 3-9270 grs. 0.003196 G.Determination of chlorine Water employed. Chloride of silver obtained. Percentage of chlorine. 44520 grs. 15.4693 gis. 0.008588 H. Determination of sulphuric acid Water employed. Sulphate of haryta Percentage of sulphuric obtained. acid (SO,). 44520 grs. 19,7967 grs. 0.015266 I. Determination of alkalies Water employed. Mixed chlorides obtained. 44520 grs. 22.2607 grs. a. Determination of potassium Water employed.Bichloride of platinum and Percentage of chloride of potassium potassium. obtained. 44520 grs. 35.8204 grs. 0.012845 b. Determination of sodium Water employed. Chloride of sodium obtained. Percentage of sodium. 44520 grs. 11.3328 grs. 0.008666 J. Determination of carbonic acid THE \YELLS OF WESTI30URNE PARK RUSSELL SQ. AND HANWELL. 121 Water employed. Carbonate of lime obtained. Percentage of carbonic acid. 50640 grs. 33.6767 grs. 0*029605 containing 14.8177 grs. of carbonic acid. From the above analyses we have deduced the following results In Table 1 the constituents as found by analysis are given separately and in Table 11 the acids and bases are associated in the usual manner TABLEI. Westbourne water.Russell -Square Hanwell C:lk. water. water. Lime . . . . . 1.9588 1.8972 1.2611 2.8813 Magnesia . . . . 1-0159 0.8341 0.3307 2.2376 Potassium . . . . 8.7918 9.3909 5.2096 8.9919 Sodium . . . . 11.6670 10.8271 12.3342 6.0665 Iron alumina and phosphates 0.3430 0.6247 0 2663 0.3217 Sulphuric acid (SO,) . . 13.4195 12.9514 10.6491 10.6961 Chlorine . . . . 10.74G1 10.3287 7-7746 6.0121 Carbonic acid . . . 17.2004 17.0816 16.3941 20.4824 Silicic acid . . . . 0.6529 0.4712 0*8037 0.1817 Organic matter . . . 0.7191 1.0502 0.7690 1,8033 TABLE11. ~~ Westbourne water. Russell Square Hanweu water. water. ~~ ~~ ~ ~ ~ Carbonate oflime . . . . . 3.4978 3.3878 2.25 19 5.1451 , magnesia . . . . 2.1223 1.7425 0.6908 4.6746 Chloride of sodium .. . . . 17.7083 17'0205 12.8116 9.9072 Sulphate of soda . . . . . 9.4181 2.5980 9.7261 3.0642 Carbonate of soda . . . . . Sulphate of potassa . . . . . 19.1220 21.0949 11.6213 20.0590 Silicic acid . . . . . . . 0.6529 0.4712 0.8037 0.1817 Iron alumina and phosphates . . . 0.3430 0,6247 0.2663 0.32 17 Organic matter ..... 0.7191 1.0502 0.7690 1.8033 -Total . . . . . . 57.0895 I 56.3851 48.3588 47.7548 Solid residue obtained on evaporation . 57.1927 56.6812 47.7511 47.9600 Free carbonic acid (grains in a gallon) . . 11.0060 12-7174 Free carbonic acid (in cubic inches at 44O F.) 22.0120 25.4348 Degree of hardness Clark's before boiling 40.3 120.1 scale . . . . f after boiling 00.9 1O.4 MR. IV. FERGUSON ON A striking feature in the foregoing analyses is the almost complete identity of the water froiii the sand and that from the chalk in the well at Westbourne Park.This circumstance proves that the so-called chalk-water supply to the deep wells of London is not entirely con- fined to that stratum. The great similarity between the Westbourne and Russell Square waters and the levels at which they stand in the wells being the same show that both wells are supplied by the same water- stratum. These waters also agree very closely in composition with the water of Trafalgar Square.* On comparing the analysis of the Hanwell water with those of the deep well-waters of London the difference between them is comparatively trifling showing an evident connection between them notwithstanding the great difference of level at which the Ilanwell water stands as compared with the wells of London.This would seem to indicate the existence of a basin to thc west of London the water in which stands at a much higher level than the water under London and from the overflowing of which the deep wells of the me- tropolis derive a considerable portion of their supply. We are indebted for this suggestion to Mr. Henry Marten who examined the dis- trict for the West London Water Works Company. The analyses hitherto made of the deep well-waters of London and the neighbourhood are not sufficiently numerous to admit of any definite conclusion being drawn as to the probable sources of the water supply. We have been induced however to communicate the results of our analyses to the Society as an additional contribution to a know- ledge of the deep well-waters of London.

ISSN:1743-6893    

DOI:10.1039/QJ8540600115

出版商:RSC    

年代:1854

数据来源: RSC

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MR. IV. FERGUSON ON XIV.-On the increase in Weight of Molasses casks occasionally arising from Absorption BY WILLIAM EsQ. F.C.S. FERGUSON In September 1851 attention was attracted to an unusual increase of weight in a shipment of molasses which occurred in the London Docks; it was some time before the cause could be discovered and t,he steps taken to ascertain it ended in the perfect assurance that it * Quart. Journ. Ch. SOC. I 97. Till3 INCRESSE IK WEIGHT OF MOLASSES CASKS. 123 was due to absorption. The great extent to which the action had taken place and the large amount of property in our dock warehouses which is thus proved to be occasionally affected by it lead me to be- lieve that a detailed account of this extraordinary instance may prove acceptable to the Society.For the following particulars I ani in- debted to Mr. Muggeridge of the London Docks in whose care the molasses were stored and by whom the progress of the action was watched. In August 1849 a quantity of molasses were housed for the first time in a damp cellar where they lay until September 1851 when the increase of weight was observed. In order to ascertain its amount the whole of the casks of the importation were re-weighed when it was found that every cask which had not lost a portion of its contents by breakage had gained considerably in weight. The casks were coopered and made tight and in February 1852 were again weighed when (where breakage had riot occurred) a further increase was found to have taken place.The total weight of the shipment was 1270 cwt. It was stored in 110 casks containing from 11 to 12 cwt. each. The increase on different casks varied considerably reachin 0. in some cases 38 Ibs. or about 3 per cent of the contents. The total observed increase was 23i cwt. or about 1.83 per cent. This does not represent the total real increase for it would appear that in some casks the absorbed water had just been sufficient to cover the loss from breakage but not tell as increase; and there does not seem to have been one cask which had not suffered more or less loss. The real increase of weight due to absorption must have been much greater than that shown by the weighings. Important as this result was to the merchant it was greatly exceeded by one that was after- wards observed and which was as follows.A quantity of molasses imported in large tanks were in July 1849 racked into 347 puncheons weighing about 12 cwt. each the total weight being 4160 cwt.; they were stowed in a lofty cellar where they remained till September 1852 when they were re-weighed for delivery. At various times some of the casks were found with heads bulging out from internal pressure although none of them were full when housed and it was necessary to draw off a portion to prevent them from bursting. When the bung was started the molasses rushed out with great force ascending several feet to the roof of the cellar. On re-weighing the increase was as before found to be different in different casks. On 52 there was a loss from breakage 248 had gained from 1 lb.to 30 lbs. each 67 from 30 lbs. to 40 lbs. and 20 MR. W. FERGUSON ON MOLASSES CBSICS. from 401bs. to 51 lbs. each. The total increase of weight on the shipment was 56 cwt. If we take the casks on which this incrcasc took place laying aside the 52 on which there was loss the excess of absorbed water over the leakage was about 1.6 per cent; in some of the casks it had reached as high a percentage as 4325. A third case was also observed in December 1848. 500 puncheons were filled from tanks in which they had been imported and stored in the same cellar till July 1852 when some of them were re-weighed with the same various results as to increase 5 puncheons gave the following results No.1 weight 11 3 13 lbs. gained 23 Ibs. This was the largest increase of weight though on a large number of casks it reached nearly to the same percentage. In No. 5 the excess of water absorbed over any leakage that may have occurred is 5 per cent. The bungs were at this time started and the casks which had been stored not quite full were found full to overflowing. One cask which had lost 14 Ibs. and another 9 llus. were also full We know that these casks had not been overdrawn. Now to effect a loss of 14Ibs. 4 gallons of treacle must have been replaced by water not taking into account the quantity which was required to fill the cask completely. In the case of No. 5 where the increase of weight was 68 Ibs. the quantity of water absorbed must have been very great for after supplying the loss due to leakage (ar?d all casks leak more or less) 6.8 gallons of water entered through the pores of the wood during a period of 34 years. These puncheons in which this maximum effect took place had been American meal- casks made of Quebec timber which is much more porous than the mood of which West India puncheons are usually made. The specific gravity of the freshly-imported molasses of the last lot was 1.394 and when taken in July 1852 was 1.375.

ISSN:1743-6893    

DOI:10.1039/QJ8540600122

出版商:RSC    

年代:1854

数据来源: RSC

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MIL HENRY Irow ON SOME NEW BASIC PRODUCTS. I25 XV.-On some New Basic Products obtained by the Decomposition oJf Vegetable Alkaloids. BY HENRYHow EsQ. F.C,S. ASSISTANT TO EROFESSOR ANDERSON OF GLASGOW. In the following pages I purpose submitting to the notice of the Society the results of some experiments so far as I have proceeded with them on the action of the halogen-compounds of the alcohol radicals on bases of vegetable origin. The beautiful researches of Hofmann on the behaviour of artificial liquid bases and of ammonia under these circumstances led him to remark that a similar course of investigation in regard to basic substances generally would no doubt tend to throw much light on the nature of these bodics. On com- paring the formulz of some of the vegetable alkaloids with which I was best acquainted their relations to each other were such that I was curious to bring to light the result of experimenting upon some of these substances in the direction mentioned.The established formula for niorphia which was first given as the correct interpretation of the analysis of the pure alkaloid by Laurent,* and which I have confirmed by experiments of my own is C34H19NO6. It will be seen by a comparison of this formula with that of codeine as established beyond a doubt by Professor Anderson,? C36H21N061 that these alkaloids differ from each other exactly by C,H,. Now reasoning from analogy if these bases follow the same laws of decomposition as their volatile congeners I should by the action of iodide (e.9.) of methyl upon morphia obtain either codeine or a base having the same centesimal composition according to the reaction expressed in the equation It was with this idea that I commenced the folIowing series of experiments ; and although the reaction represented above was not that which 1 studied first-for iodide of ethyl was ready to my hand-the results which I obtained with this compound though not such as to render me sanguine as to the actual conversion of the one * Ann.Ch. Phys. [3] XIX. f-Trans. Roy. SOC. Edinb. XX I 57. MR. HENRY HOW ON alkaloid into the other-a problein which has engaged the attention of chemists of great name*-were sufficiently marked in character to urge me to prosecute the inquiry with what success will be seen in the sequel.If in the succeeding pages the numbers given in one or two instances fall somewhat below the standard of accurate analytical proof I trust that to those acquainted with the nature of the materials employed the mention of their costly character will be sufficient excuse for a want of repetition of experiments where a great ileal would not have been gained by the same; believing that sufficient evidence is furnished as to the composition at least of the substances produced. 1 beg here to offer my most sincere thanks to Professor Anderson in whose laboratory attached to the University of Glasgow my experiments were performed for the opportunity of conducting this inquiry. In detailing the investigation I have preferred to narrate the individual reactions &c.in the order in which they were examined. ACTION OF IODIDE OF ETHYL UPON MORPHIA. Morphia in a state of fine powder was introduced into a com-bustion-tube strongly sealed at one end a little iodide of ethyl added and then absolute alcohol in quantity judged to be sufficient to dissolve the alkaloid. I found about 25 grains niight be con-veniently employed in a tube of small bulk ; and alcohol occupying about three times the space of the alkaloid was found sufficient a very small quantity of iodide of ethyl being required. When the substances were all introduced the tube was carefully sealed before the blow-pipe and upon its cooling the whole was immersed in boiling water. Coniylete solution took place when a small quantity of morphia was employed but not so when morc was used; action commenced very speedily as was obvious from the nature of the solid product in the tube which had not the appearance of morphia.The boiling was continued some hours when coinplete solution had not taken place at first in order that any morphia which had at first remained undissolved might in its turn be acted upon as the alcohol became free as it were by deposition of the new product. When the action had continued about six hours or so the tube was allowed to cool and then opened; the alcohol containing the excess of iodide of ethyl nearly colourless and quite limpid was poured off from the white crystalline solid product which was then washed with a little * Ann.Ch. Pharm. XXVI 60. NEW BASIC PRODUCTS FROM VEGETABLE A4LKALOTDS. 127 alcohol and dried. It was found to dissolve readily in hot water; accordingly the whole was treated in this manner in case of any morphia remaining unattacked from which it being insoluble or very difficultly soluble in this menstruum the product would by this means be purified. However complete solution took place ; and the fluid deposited on cooling a substance in fine white needles; these were collected dried and analyzed a preliminary experiiiient having shown that they contained much iodine. In the following analysis the iodine was determined by direct pre- cipitation of an aqueous solution by nitrate of silver; the coinbustion made with chromate of lead ;5.155 grs.dried at 21P gave 9.725 , carbonic acid and 2.665 , water. 4.470 , gave 2.365 , iodide of silver. Experiment. Calculated. Carbon. . 51.45 51-71 C, 228 Hydrogen . 5*74 5.44 H, 2% Nitrogen . 3.17 N 14 Oxygen . 10-87 0 48 Iodine . . 28.59 28.81 I 127.1 100~00 4441a I A comparison of the experimental numbers with the calculation appended will show that we have here a substance which may be termed the hydriodate of cthylomorphia and whose constitution niay be represented by the formula an atom of hydrogen of the original alkaloid being replaced by an atom of ethyl in the production of the new base according to the equation The above salt is the only product of this decomposition and the entire morphia is transformed into it in the air-dry state as crystallized from water it contains an equivalent of water which it loses at 212O... -- Mlt. HENRY €1017;’ ON 9.805 grs. air-dry lost in the water-bath CO.195 , water. The percentage calculated from this result is 1.98 and 1.98 is that corresponding with the formula C3SH2YN06, HI+aq. Hydriodate of ethylornorphia is difficultly soluble in absolute alcohol more easily so in rectified spirit readily dissolved by Lot water from which it is deposited on cooling in brilliant colourless crystals which magnifying power shows to be flattened prisms it is not altered in the air. Neither potash nor ammonia yielded a precipitate with an aqueous solution of this salt ; but before attempting to isolate the base which this fact pointed out would have to be sought in another way I attempted to control the above formula by an analysis of a platinum- salt,but was unsuccessful.A saturated aqueous solution of hydriodate of ethylomorphia was converted into hydrochlorate by the successive eniployment of nitrate of silver and hydrochloric acid and to the clear aqueous solutioii so obtained bichloridc of platinum was added ; no precipitate was formed a mixture of strong alcohol and ether was added to a small quantity of this solution and it and the remaining aqueous fluid were allowed to stand during a night; in the morning the former fluid had deposited beautiful tufts of brilliant yellow needles which though small were seen when magnified to be well- defined groups of prismatic crystals while at the bottom of the larger aqueous liquid was an arnorphuus yellow sediment ; this was collected and burned in the usual way but the resulting percentage of platinum was 2.5 too high to correspond with the theory.I look upon this as an effect of decomposition; and in this respect the new base seems to bear a close analogy with its parent alkaloid which I have found very prone to change in contact with an excess of bichloride of platinum. In order to obtain the base a quantity of the crystallized hydriodate was dissolved in water gently heated and oxide of silver gradually added till it was in excess. The fluid remained colourless so long as hydriodate was present but instantly a decided excess of oxide of silver prevailed dark streaks appeared and upon filtration a highly caustic liquid was obtained of a red-brown colour ; this deposited no crystals upon cooling or upon concentration and when the whole was evaporated to complete dryness at 21a0,a semi-transparent solid very dark-coloured residue was obtained.This residue was found to be difficultly soluble in strong alcohol XEW BASIC PRODUCTS FRORl VEGETABLE ALKALOIDS. 129 (90 per cent) and a boiling solution deposited a substance amorphous to the naked eye but revealing under the microscope distinct crystal- line structure; it was scarcely altered in appearance by exposure to the air ; but upon adding hydrochloric acid to a portion so exposed it was observed to dissolve with slight but distinct effervescence to a yellow fluid which gave a heavy ycllow precipitate with chloride of platinum.It was rcadily and completely soluble in cold water to a red-brown fluid which exhibited the following behaviour with various re-agents with bichromate of potash a fine heavy yellow precipitate soluble in hydrochloric acid ; the acid solution became speedily green upon heating from reduction of the chromic acid;-with sulphate of copper a green with acetate of lead a white and in excess with nitrate of silver a black precipitate. The latter precipitate upon the fluid in which it had been formed being heated gave a slight metallic mirror and was found to be not completely soluble in ammonia showing that the base had been oxidized at the expense of the oxide of silver.When it was added to an aqueous solution of sesquichloride of iron the latter assumed a green colour darkening to an almost black fluid with a larger quantity of the alkaline solution and it was then found to give a blue precipitate with ferridcyanide of potassium from which fact it is plain that in this instance also the base had undergone oxidation ammonia was evolved ou heating solution of chloride of ammonium with the alkaline fluid. Consideration of the foregoing reactions did not permit me to hope for a succcessful analysis of the alkaline residue as the-pure ethylomorphia; however I made the attempt 4.040grs. dried at 212O gave 10.130 , carbonic acid and 2.505 , water. The percentages calculated from these numbers I place in juxta-position with the required values for the base Experiment.Calculated for ethylomorphia. ,-Carbon. . 68.38 72-84 C3* 228 Hydrogen 6.88 7.34 Hzs 23 Nitrogen . 4.47 N 14 Oxygen . 15.35 0 48 -100~00 313 and the conclusion I draw from the comparison is that the ethylo- morphia I subjected to analysis had already undergone partial oxi- VOL. V1.-NO. XXIT. K MR. HENRY EOW ON datioii from contact with oxide of silver. I cannot at present add anything to this imperfect history for my material was exhausted in the experiments described but sufficient is shown I think to make future inquiry of interest. It is obvious the base is extremely prone to decomposition by oxidizing agents; in this character it also re- sembles its parent morphia but it shows the tendency in a more marked degree.I did not attempt to continue the ethylation in this case a trial of the kind being made with the methyl-product to be next described. ACTION OF IODIDE OF METHYL UPON MORPHIA. Morphia was submitted to the action of iodide of methyl under precisely the same circumstances as have been described with reference to iodide of ethyl; after about half an hour’s boiling the change appeared complete a heavy white crystalline powder occupying a larger space than the original alkaloid being formed. The fluid remained almost colourless and drained away readily from the new product when the tube was opened. The product was found to dissolve readily in hot water showing that complete change had taken place.As the water cooled a deposit was quickly formed in fine brilliant square prismatic colourless needles of high refractive power. A portion was analyzed in the same manner as the former product 4.455 grs. dried at 212O gave 8.245 , carbonic acid and 2.152 , water 4.335 , give 2.380 , iodide of silver. Experiment. Calculated. 7-. 50.47 50.57 c36 216 Carbon . Hydrogen . 5.36 5.15 H, 22 Nitrogen . 3.27 N 14 Oxygen . 11.26 O6 48 Iodine . 29-66 29.75 I 127.1 -100~00 427.1 These results point to a decomposition precisely analogous as was to be anticipated to the one with iodide of ethyl; the hydriodate of methylomorphia being formed according to the equation NEW BASIC PRODUCTS FROM VEGETABLE ALKALOIDS.131 The salt in the crystallized state contans 2 equivs. of water which it loses at 212O. 9.630 grs. lost on drying in the water-bath 0.400 , water. The percentage calculated from this number is 4.15 ; and 4-06is that which corresponds to the formula C,,H,lNO + 2 HO. This is precisely the formula found for the hydriodate of codeine as dried at 212O by Professor Anderson;* so that the air-dry hy- driodate of methylomorphia is identical in composition with the corresponding salt of codeine as dried at 212O; the salts however are only isomeric for nothing could be more unlike the fine crys- talline alkaloid codeine than the alkaline substance obtained by the action of oxide of silver upon the hydriodate of the new base.In short it resembles in every particular the corresponding ethyl-com- pound in appearance and reactions so closely that to describe them would be to repeat what has been said of that substance. I did not attempt an'analysis of this base but having obtained some in the dry state proceeded to try the further action of iodide of methyl upon it. With this view the base was separated by the action of oxide of silver of which an excess wa8 attempted to be avoided on the hy- driodate and subsequent evaporation of the caustic aqueous fluid which was coloured reddish-yellow to dryness at 212O; in this state it presented an appearance as beforesaid exactly similar to that of ethylomorphia produced by the same means namely that of a dark- brown semi-transparent amorphous mass.Its reactions were iden- tically those of the former base. The methylomorphia so obtained had most probably commenced to undergo partial oxidation but as this was unavoidable the whole was powdered and placed in contact with iodide of methyl and alcohol. Action commenced even in the cold; for on shaking together the contents of the vessel the fluid became filled with a light-brown flocky substance which upon trial gave a precipitate with nitrate of silver showing the presence of hydriodic acid. To ensure reaction the tube containing the mixture was sealed and subsequently placed in water at 212O ; upon this a resinous substance was immediately formed at the bottom of the tube and the supernatant liquid became quite clear the flocky matter disappearing.The heating was continued about half an hour and no further change taking place in appearance the tube was allowed * Trans. Roy. SOC. Edinb. XX. K2 MR. HENRY HO\V ON to cool ; a very slight deposit appeared adlicring to the sides of the tube of rather a resinous nature. The tube was opened and the clear fluid poured from the resin; water was added to it no change produced; the aqueous fluid was then distilled to separate the excess of iodide of methyl and subsequently evaporated at 21.20; the residue left was a black amorphous mass which was found to dissolve only partially in water to a very dark fluid while a considerable portion remained in the form of a black powder; this proved to be insoluble in every menstruum with the exception of strong nitric acid which gave a reddish- yellow solution nitrous acid being evolved.The watery fluid contained a hydriodate of a base; the quantity being very small I attempted to obtain some idea of the change effected by converting it into a platinum-salt carefully avoiding an excess of platinum-solution. I obtained a yellow curdy salt but in very small quantity and on determining the percentage of platinum with the utmost care I obtained 21.141per cent which is far above that required by the platinum salt of even morphia itself The resinous deposit which was described as adhering to the sides of the tube appears to be identical with the substance contained in the alcoholic fluid; at least it furnished a solution in hot water which upon evaporation at 212O,left a residue agreeing in its charac- ters and qualitative reactions precisely with that left by drying up the spirituous liquid; its quantity was too small to admit of quantitative experiments.I do not venture to draw any definite conclusions from these facts with regard to the continued action of iodide of methyl upon methylo- morphia but that a decomposition of a more complicated nature than the simple assumption of another equivalent of ethyl takes place is I think obvious. It will be shown presently that this con-clusion seems to be warranted by a deportment of a similar nature observed in reference to a basic product derived from codeine. Further experiment however must decide the nature of these changes.REACTION BETWEEN MORPHIA AND CHLORIDE OF AMYL. Morphia was placed in contact with chloride of amyl under circum- stances precisely similar to those which have been mentioned with regard to iodide of ethyl and methyl. No change took place after three days; for upon opening the tribe the alkaloid was found unaltered. Knowing the reactions of this member of the alcohol series to be somewhat sluggish I repeated the experiment expecting a longer exposure to heat might be requisite to effect a decomposition. NEW BASIC PRODUCTS FROM VEGETABLE ALKALOIDS. 133 Accordingly a tube was sealed as before and the contents were kept boiling constantly for about fourteen days. In about four or five days a crystalline substance began to be formed and upon opening the tube at the fortnight's end the solid deposit which had gradually collected was found to be a.hydrochlorate; the alcoholic fluid was poured away and the salt washed and dried; it was soluble in hot water and the colourless solution gave upon gentle evaporation a crystalline substance in the form of opaque tufts of four-sided prisms (magnified) ; when dried and subjected to analysis the crystals gave these results 3.060 grs. dried at 212O gave I* { 1.340 , chloride of silver. , dried at 21eo gave 11. { 4'290 1.895 , chloride of silver. Experiment. Calculated. 7-Carbon . . 63-45 C, 204 Hydrogen . 6.22 H, 20 Nitrogen . 4.35 N 14 Oxygen . . 14.94 48 Chlorine . . 10.83 10.92 11.04 35.5 gf looooo 321-5 which upon a comparison with the calculation and the formula adjoined which is that of morphia will show that we have not in this case a decomposition analogous with the preceding ones ; the hydro- chlorate here formed is indeed the salt of morphia; its appearance and characters are identical with the latter ; and the addition of ammonia to its aqueous solution yields a crystalline precipitate which has all the properties of pure morphia as ascertained by various tests.The reaction thus occurring may be explained as taking place between the chloride of amyl and the elements of water of which morphia as crystallized from alcohol (the state in which it was employed) retains 2 equivs. when dried in the air ; indeed they are not completely expelled except at a temperature considerably above 212' F.So far as I remember I used absolute alcohol; and the chloride of amyl had been I was told distilled from lime at all events when tested with nitrate of silver it gave only slight indi- cations of chlorine in a state precipitable by this reagent; the equa- tion represcnting this change then appears to be -* 134 Mlt. HENRY HOW ON I am not aware if the chloride of amyl has been found to undergo this transformation simply in presence of water ;possibly it may under the circumstances of my experiment ;if not the action of the morphia in this respect seems to be analogous to that of potassa &c. in producing the alcohols from their corresponding halogen compounds. I propose subjecting artificially dried morphia to the action of anhydrous chloride of amyl to ascertain if the compound of this series corresponding to the ethyl and methyl products cannot be so obtained.I now proceed to give the result of some experiments upon a vegetable alkaloid closely allied in origin with the former vie. codeine. ACTION OF IODIDE OF ETHYL UPON CODEINE. About 25 grains of finely-powdered codeine were placed in a com- bustion-tube about 2 feet long sealed at one end; iodide of ethyl was poured upon it in sinall quantity and absolute alcohol added in such proportion as was judged sufficient to dissolve the alkaloid ; the tube was sealed. On cooling of the tube its contents were shaken together and a perfectly clear homogeneous fluid was ob-tained the whole was placed in boiling water.In about two hours the contents of the vessel became nearly solid from the presence of a white crystalline substance. This was considered to indicate the completion of the action. Upon the appearance of the crystalline product the tube was allowed to cool. When it was cut open the fluid was suffered to drain off from the solid which was then scraped out placed upon a filter washed with a little alcohol and finally dried between folds of paper. The substance then presented the appearance of a highly crystalline white mass; it was found to dissolve completely on being covered with a small quantity of cold water. On filtering the fluid from a little dust a tendency to crystallization was observed this was overcome by the addition of some drops of warm water and the clear liquid was placed in the vacuum of an air-pump and left for a night.In the morning although the apparent decrease in the bulk of liquid was but small a considerable crystalline deposit was formed which under magnifying power was seen to be made up of tufts of fine silky white needles ; it was freed from the mother- liquor and then collected and dried. An esperiment on the sinall scale showed that the enbstance contained niuch iodinc ; accordingly NEW BASIC PRODUCTS FROX VEGETABLE ALKALOIDS. 135 it was submitted to analysis. The iodine in the following analysis was determined by direct precipitation of an aqueous solution by nitrate of silver ; the combustion made of course with chromate of lead 5.025 grs.dried at 212* gave 9.690 , carbonic acid and 2.658 , water. 4.453 , gave 2.300 , iodide of silver. Experiment. CaIculated. Carbon . . 52.59 52-73 C, 240 Hydrogen . 5-87 5.71 H, 26 Nitrogen . 3.07 N 14 Oxygen 10.57 0 48 Iodine . . 27-91 27-92 J 127.1 100~00 455-1 These results clearly show that we have here a substance whose rational formula as an hydriodate of a new base may be represented thus C~H,5N0fj derived from codeine according to the following equation by the substitution of an atom of ethyl for an atom of hydrogen; it may be called hydriodate of ethylocodeine C,6H,,N064-C,H,I = C,H,,NO, HI = c, { :f$ } NO6 HI. 45 I immediately attempted to obtain the base by decomposition of the salt by ammonia and potash but no precipitate was obtained even in very concentrated solutions or on the addition of alcohol and ether.However when the potass-fluid was boiled it became muddy and on cooling an oily substance was deposited which presented an appearance somewhat similar to eodeine; but upon dissolving it in boiling water it failed to take the crystalline character of this alkaloid under similar circumstances for the water gave no deposit at all on cooling and it was only by evaporation that the same oily matter again made its appearance. I am inclined to think this not the ethylocodeine but a product of decomposition. I next attempted to isolate the base by acting on the hydriodate with oxide of silver which was added in successive small quantities to a warm aqueous solution of the salt till it was obviously in excess; a highly alkaline MR.HENEY HOW OK fluid was obtained of which a small portion was evaporated to dryiiesv at 21Y ;a semi-transparent dark-coloured residue reniained which effervesced with hydrochloric acid and dissolved to a yellow fluid which gave with bichloride of platinum a yellow precipitate at first ainorphous but becoming highly crystalline on standing ; this character as will be seen presently belongs to the platinum-salt of ethylocodeine obtained by double decomposition and T conclude that the new basic substance is uncrystalline highly soluble in water and capable of absorbing carbonic acid from the air. The nature of my materials compelled me to extreme economy and I contented myself with this single attempt at obtaining the base itself in a dry state; its characters not being inviting for analysis any more than those of the corresponding morphia-compound I preserved the residue of that which I had prepared for an experiment to be described hereafter controlling the former analysis of the hydrioda te by a platinum determination in the double salt of the ethylocodeine and chloride of platinum.The mother-liquor which had deposited the hydriodate submitted to analysis was allowed to stand in the air; it became after some time again nearly filled with tufts of delicate xieedles which gradually assumed a new crystalline form the whole being transformed into well-defined brilliant rhombic crystals of high refractive power.A portion of these was dissolved in water and solution of nitrate of silver added; from the fluid filtered from the iodide of silver hydrochloric acid separated the excess of silver and to the liquid again filtered was added bichloride of platinum ; an amorphous precipitate immediately appeared of a pale yellow colour but it speedily became crystallinc and on allowing the fluids to remain at rest a salt was obtaincd in very fine and well-defined though sniall rhornbic crystals of a rich yellow colour ; of this salt 5.910 grs. gave {1 *060 , platinum. The percentage calculated from this result is 17.93 which falls somewhat below that required by the formula of an anhydrous salt of ethylocodeine which is 18.51 ; but as the salt was so finely crystal- lized and I could perceive no obvious sot~rcc of error 1 an1 inclincct to think that this base like its parent codeine retains an equivalent of water in this form of combination.The percentage of platinurn corresponding to thc formula q(,H2pO6,ILCI I'tCI 4-110 is I~CI'C:contIastLd with t hc rcssult of expcriiuwt NEW BASIC PRODUCTS FROM VEGETABLE ALKALOIDS. 137 Theory. Experiment. 18.20 17-93 and is I think sufficient to prove together with the foregoing analysis the true composition of the base in question. When this salt is boiled in water it becomes at first resinous then dissolves; it appears to have suffered decomposition a substance being deposited on cooling of the fluid in rounded transparent granules rather than oblique rhombic crystals.ACTION OF IODIDE OF ETHYL ON ETHYLOCODEINE. I mentioned that I attempted to isolate ethylocodeine by decom- position of its hydriodate by oxide of silver. A caustic fluid was obtained which upon evaporation in vacuo left an amorphous semi- transparent residue. I concluded from the experiment then mentioned with regard to a platinum-salt obtained from a similar trial on the small scale in which the caustic fluid was evaporated to dryness at 212O,that the base so obtained was the true ethylocodeiiie.* It was now my object to try by the further action of iodide of ethyl whether the ethylation was complete or if another atom of hydrogen could be taken away and replaced by ethyl.With this view the residue obtained by evaporation of the alkaline fluid in vucuo was dissolved in absolute alcohol iodide of ethyl added and the whole sealed up in a tube which was exposed to the temperature of boiling water ; no crystalline deposit appearing the action was contiuued for about twenty-four hours; at the end of this time the fluid became rather dark coloured and a resinous black-looking deposit was formed. The tube was opened the fluid poured from the deposit into a small flask and the chief part of the iodide of ethyl distilled off; water was added to the remaining fluid which was then placed on the water-bath and allowed to remain some hours; at the end of this time all smell of iodide of ethyl ceased and a black substance deposited in small quantity the fluid was filtered from this and upon the addition of nitrate of silver a considerable precipitate of iodide was formed; the excess of silver was removed by hydrochloric acid and bichloride of platinum was added to the filtered fluid ; an amorphous yellow precipitate was formed which upon standing became partially converted into a substance which under the microscope appeared not crystalline but had the form of rounded grains ; this was collected and analyzed.Thc resulting percentage of platiiiuiii obtairid was 22.20 wliiuh ib cotisiderably ahvc that of * Possiblj it liad tin ?c;.goncslight oxidcition. 138 MR. HENRY HOW ON codeine itself. This and the appearance of the resinous substance- which I may mention dissolves almost completely in boiling hydro- chloric acid and is again thrown down by potash-seem to point to decomposition of quite another character than the one sought.I am unable at present to elucidate this question but it seems worthy of investigation. It is perhaps proper to state here that in the first experiment I made upon the action of iodide of ethyl upon codeine the action was continued some hours after the first deposit had been observed and that in this case also a resinous deposit was formed the fluid was highly coloured and the crystalline product was not nearly so well-defined in its characters. It was for this reason that the actionin the experiment the product of which gave the results stated was stopped as soon as the large quantity of crystalline deposit appeared.I have satisfied myself that codeine is rapidly acted upon by iodide of methyl ; no doubt the resulting decomposition is similar in nature to that effected by iodide of ethyl. The preceding experiments are not complete enough or in some respects sufficiently decided in their results to permit of any very definite conclusions being drawn as to the exact nature of the alka- loids to which they relate; so much however has been shown I think as to call for some attempt at deduction. The nature of the alkaline substances produced by the action of oxide of silver upon what I have termed the hydriodates of ethylo-and methylo-morphia and codeine would seem to ally them more closely to what Hofmann has called oxides of tetra-bases than to any other bodies.In the slight but distinct tendency they exhibit to absorb carbonic acid they are certainly removed from any close analogy with the alkaloids from which they are derived; although in the single analysis I have given of one of these substances the so-called ethylo-morphia the evident oxidation it had undergone prevents any support being afforded to this assumption on the one hand so likewise on the other it does deprive it of any pretensions to correctness. The only conclusion I can venture to draw from the facts obtained as to the continued action of the iodides of methyl and ethyl upon these substances is that some change is effected which causes the formation of a basic body having a lower atomic weight than the original compound and the production of the resinous matters seems also to point to a breaking up of the primary molecule ; but of course the expcriments from which this is inferred are too incoinplete to warrant any more decided opinion as to the precise NEW BASIC PRODUCTS PROM VEGETABLE A.LKALOII)S.139 nature of the decomposition. It would follow necessarily from the foregoing view of the constitution of the ethyl and methyl new basic compounds isolated from their salts that if the alkaloids from which they are derived were placed in their appropriate class according to the provisional nomenclature of Hof mann they would come under the designation of nitrile bases; and in the decompositions in which morphia and codeine have been seen to be transformed they would have had attached to them the elements of iodide of ethyl for instance as expressed thus the new salts becoming rather analogous to iodide of ammonium than to hydriodates of natural alkaloids.Experiments made in the same direction with others of the vege- table bases would doubtless prove of considerable interest ; since notwithstanding both those to which I have given my attention appear to belong to the same class a8 was perhaps to be expected from their being so closely allied in origin it is extremely probable that alkaloids contained in plants of a different natural family will be found to possess different constitutions ; I hope to examine a few. I would venture to make one other remark before concluding this paper.The fact that by the action of iodide of methyl upon morphia a salt i8 produced only isomeric and in no way identical with hydriodate of codeine the base of the new salt differing so widely in character from the latter alkaloid does not appear to me to afford great stimulus to any hopes of forming the natural alkaloids by this means; since if we fail in the case of two natural products of the very same plant it seems far less probable to bring about such a result as the production of a base identical with a natural formation from a substance with which it has no relation beyond a certain difference in their relative proportions of carbon and hy- drogen. In conclusion I append a list of the salts I have examined con- sidered as iodides in their dry and crystallized states Iodide of methylomorphia dried at 212O C36H22N06,I ,> Jt ,) crystallized C,,H2,NOv I + 2 HO , , ethylomorphia dried at 21-2O C38H24NOoI 9 > 1 crystallized C38H24N0, I + HO , , ethylocodeine is anhydrous C,H,,NO, T Platinum-salt of , dried at 212O C40H26NO6 C1 PtCl + HO.

ISSN:1743-6893    

DOI:10.1039/QJ8540600125

出版商:RSC    

年代:1854

数据来源: RSC

摘要:

140 PROFESSOR ETTLING ON SUI.PHANTI3lONIATE OF COPPER & ZINC. XV1.-Note on Sulphantimoniate of Copper and Zinc. BY PROFESSOR ETTLING. (FROM A LETTER TO DR. HOFMANN.) In the January Number of the Quarterly Journal of Chemistry for 1852 p. 332 Mr. Field communicated the analysis of a new mineral which according to the statements of Mr. Domeyko occurs in large quantity in the Pit Altar near Coquimbo together with zinc- blende iron-pyrites and fahl-ore and differs from the latter especi- ally from the zinc-fahl-ore which is closely allied to it by its greenish- grey colour by giving a much lighter red streak and by its softness. On recalculating the results obtained by Mr. Field who has omitted to translate his data into a formula I find that antimony and arsenic in this ore are not present in the form of tersulphides as in fahl-ore but in the form of pentasulphides as in Enargite and Xanthocon a fact which may serve to explain the difference between the properties of this ore and zinc-fahl-ore.Mr. Field's analysis led to the following results Sb. As. S. cu Zn. Pe Ag. Total. 20.28 3.91 30.35 36.72 7.26 1.23 0.07 99.82 If the amount of sulphur be calculated which is required to convert copper zinc iron and silver into sulphides we find 13.525 per cent leaving 16-825per cent for the antimony and arsenic. Calculated as tersulphides these two metals would require 10.048 per cent of sulphur leaving an excess of 6.77 per cent. Calculated on the other hand as pentasulphides antimony and arsenic require 16.753 per cent leaving only the slight excess of 0.072per cent. Hence it can- not be doubted that the new mineral is actually a sui'phantimoniate and sulpharseniate of copper and zinc. Since the sulphur of the basic sulphides stands to that of the acid sulphides=13.525 16*753=4 :5 the formula of the mineral may be written 4 (Cu S Zn S Fe S Ag S)+Sb S, As S or approximately 2(4Cu S Sb S,) +4 (Zn S Fe S Ag S) + (Sb S, As S,). Enargite as is well known is 3 Cu S As S, and occurs at Moro-cocha in Yeru.

ISSN:1743-6893    

DOI:10.1039/QJ8540600140

出版商:RSC    

年代:1854

数据来源: RSC

摘要:

PROCEEDINGS AT THE MEETINGS OF THE CHEMICAL SOCIETY. ANNIVERSARY MEETING March 30 1853. DAUB PROFESSOR E N Y President in the Chair. The Report of tb.e Council and the audited Account of the Trea-surer were read (vid. p. 147). The following gentlemen were duly elected as Council and Officers for the ensuing year PRESIDENT. Colonel Philip Yorke F.R.S. VICE-PRESIDENTS WHO HAVE FILLED THE OFFICE OF PRESIDENT. W. T. Brande M.D. Charles G. B. Daubeny M.D. F.R.S. Thomas Graham F.R.S. VICE-PRESIDENTS. H. Bence Jones M.D. F.R.S. Lyon Playfair C.B. Ph.D. F.R.S. G. D. Longstaff M.D. Robert Warington Esq. SECRETARIES. Benjamin Collins Brodie F.R.S. Theophilus Redwood Ph.D. FOREIGN SECRETARY. A. W. Hofmann Ph.D. F.R.S. TREASURER.Robert Porrett F.R.S. PROCEEDINGS OF THE CHEMICAL SOCIETY. OTHER MEMBERS OF THE COUNCIL. Thomas Anderson M.D.,F.R.S. Dr. Miller. John Blyth M.D. Capt. J. W. Reynolds. Dugald Campbell Esq. Thomas Taylor Esq. Warren de la Rue Ph.D. F.R.S. J. Arthur Phillips Esq. J. H. Gladstone Ph.D. George Wilson M.D. F.R.S. William Herapath Esq. A. W. Williamson 1’h.D. The thanks of the Society were voted to the President Vice-President and Council for their services during the past year. ApriI 4 1853. COLONEL PHILIPYORKE,President in the Chair. The following donations were announced “Report on the Bad Quality of Chemical Products and Drugs used by Calico Printers,” by F. Grace Calvert from the Author. “The Journal of the Society of Arts for March:” from the Society.‘‘The Literary Gazette for March 19th :” from the Publishers. “The Pharmaceutical Journal for April :” from the Editor. A paper was read “On some Compounds of Urea and on a New Method for the Determination of Chloride of Sodium and of Urea in Urine,” by Baron Liebig. April 18 1853. COLONELPHILIPYORKE, President in the Chair. Stevenson Macadam Esq. of Edinburgh was admitted a Fellow of the Society. The following donations were announced ‘‘The Journal of the Society of Arts for April the 8th and 15th :” from the Society. “ The Literary Gazette for April 9th and 16th :” from the Publishers. PROCEEDINGS OF THE CHEMICAL SOCIETY. The Journal of the Franklin Institute for February and March 1853 :” from the Institute.John A. Mease Esq. of the Lake Chemical Works South Shields was elected a Fellow of the Society. The following papers were read “On the general distribution of iodine and bromine :” by Ste- venson Macadam. “On the solid compound obtained by distilling stearic acid with lime :” by Thos. H. Rowney Ph.D. May 2 1853. COLONELPHILIP President in the Chair. YORKE The following donations were announced ‘‘The Literary Gazette,” 3 Numbers from the Publishers. “The Journal of the Society of Arts,” 2 Numbers from the Society. “The Pharmaceutical Journal,” for May from the Editor. Becquerel M. ‘‘Trait6 Experimental de l’Electricit6 et du Magn6- tisme et de leurs Rapports avec les Phenomhes naturels,” Tomes VII 8v0 Paris 1834-40.Bergman “Physical and Chemical Essays,” by Edmund Cullen M.D. 8v0 London Vol. 111,1788-91. Berzelius J. J. “Trait6 de Chimie,” traduit par A. J. L. Jour-dan Tomes VIII 8v0 1829-33. Chaptal M. J. A. “Elements of Chemistry,” translated from the French Vol. 111 8vo.,London 1800. Cramer John Andrew M.D. “Elements of the Art of Assaying Metals,” in 2 Parts ~vo.,London 1741. Fritschius John Christian The Principles of Pyrotechnical Metallurgy and Metallick Essaying,” 12mo. Gellert C. C. Metallurgic Chemistry,” ~vo.,London 1776. Girt ann er Christoph ‘‘Anfangsgrunde der Antiphlogistichen Chemie,” ~vo.,Berlin 1795. PROCEEIITNGS OF THE CIIISIITCAL SOCIETY. Glauber John Rudolph “ A description of New Philosophical Furnaces or a New Art of Distilling also a description of the Tinc- ture of Gold or the true Aurum Potabile,” 12ino.London 1651. Greu Dr. Friedrich A1 brecht Carl ‘‘ Grundriss der Chcmie,” Erster Theil ~vo.,Halle 1796. - “ Systernatisches Handbuch der gesammten Chemie,” ~vo.,Band 11 Erster Theil 1795. “ Pyritologia or a History of the Pyrites,” translated from the German by J. H. Henckel 1757 ~vo.,London. Henry Wm . M.D. F.R.S. ‘‘ Elements of Experimental Chemis- try,” Vol. 11 ~vo.,London 1826. Klaproth Martin Henry I( Analytical Essays towards the Pro-moting the Knowledge of Mineral Substances,” 8170. London 1801. Lagrange J. B. Bouillon (‘Rlanual of a Course of Chemistry,” Vol. 11 ~vo.,London 1800. “Metals Mines and Minerals-h Collection of scarce and valuable Treatises upon.” In four Parts 12mo.London 1738. Webster John ‘IMetallographa; or an History of Metals,” ~vo. London 1671. Packe C hr. “ 153 Chemical Aphorisms,” 32mo. London 1688. Sandivogius Michael (‘A New Light of Alchemy taken out of the Fountain of Nature and Manual of Experience,” to which is added “A Treatise on Sulphur,” “ Nine Books on the Nature of Things,” also “A Chemical Dictionary explaining hard places and words met withal in the writings of Paracelsus and other obscure authors.” Valentine Basil “Chariot of Antimony,’’ with Annotations of Theodore Kirkringius M.D. 12mo. London,l678. From Henry James Brooke Esq. of Clapham Rise. A communication was made “ On Deposits of Soluble or Gelatinous Silica in the Lower Beds of the Chalk Formation :” by John Thomas Way.PRUCEEDISGS OF TIIE CIIEJIICAL SOCTETY. May 16 1853. PROFESSOR GRAHAM,Vice-President in thc Chair. The following donations were announced “The Quarterly Journal of the Geological Society :” from the Geological Society. “The Literary Gazette,” 3 numbers from the Publishers. “The Journal of the Society of Arts,” 2 numbers from the Society of Arts. The following papers were read 1. ‘‘On a Compound Sulphatc of Potash and Soda :” by J. 11. Gladstone Ph.D. 2. “ Note on Thierschite :” by J. Licbig. 3. ‘‘ On Kyanurenic Acid :” by J. Liebig. June 6 1853. PROFESSOR GRAHAM,Vice-president in thc Chair. The following donations were annoiznccd ‘I Bulletin de la Classe Physico-mathdmatique de l’Acad6mic 1111-pdriale des Sciences de St.Petersbourg,” Tom. IX and X from thc Academy. “The American Journal of Science and Arts,” for May 1853 from the Editors. ‘I On the Relations between the Atomic Weights of Analogous Elements :” by G. H. Gladstone Ph.D. from the Author. ‘‘Literary Gazette,” 3 numbers from the Publishers. The following papers were read 1. “Analysis of the Waters from the Deep Well of the Wcst- bourne Water-works at Westbourne Grove of the Well in Russell Square and the Artesian Well at thc Hanwell Asylum :” by Charles Harwood Clarke M.A. P.S.A, and Henry Medlock F.C.S. VOL. v1.-NO. XXII. L PROCEEDTNGS OF THE CHEMICAL SOCIETY. 2.“On the Increase in Weight of Molasscs Casks occasionally arising from Absorption :” by William Ferguson.3. (‘On some New Basic Products obtained by the decomposition. of Vegetable Alkaloids :” by Henry How. June 20 1853. COLONELP HI LI P YORKE President in the Chair. Andrew Tomlin Esq. of Valparaiso was elected a Fellow of this Society. The following communications were made 1. “On the Conditioning of Silk:” by P. J. Chabot M.A. 2.‘‘On a New Method of Estimating the Strength of Chloride of Lime:” by Dr. Astley P. Price. 3. “On a Gas-furnace for Organic Analysis :” by Dr. Hofmann.

ISSN:1743-6893    

DOI:10.1039/QJ8540600141

出版商:RSC    

年代:1854

数据来源: RSC