摘要:

THE QUARTERLY JOURNAL OF THE CHEMICAL SOCIETY. VI1.-On a New Afethod of obtaining Hippuric Acid in considerable quantity without evaporafion of the Urine; and on some of its Products of Decomposition. BY EDWARD RILEY F.C.S. ASSISTANT AT THE MUSEUM OF PRACTICAL GEOLOGY. The preparation of hippuric acid by the methods usually adopted is tedious and involves considerable labour. Many processes have been proposed but all experimenters on this subject have adopted the plan of evaporating the urine to + or Q of its original bulk. H. Schwarz mentions,* in speaking of the preparation of hippuric acid that a urine is rarely obtained which gives hippuric acid simply on the addition of hydrochloric acid without evaporation Lowig also mentions that by the addition of hydrochloric acid to cow’s urine a crystalline precipitate is deposited which the older chemists considered to be benzoic acid.I shall now describe some experiments by which I have been led to a simplification of the method of preparing this acid. Three parts of fresh cow’s urine obtained from the same cow were treated according to Liebig’s process as given in Turner’s ‘‘Elements of Chemistry;” the cow from which it was voided was fed upon brewers’ grains twice in the twenty-four hours and allowed to graze on a neighbouring common. The urine was heated on a water-bath from a half to three-quarters of an hour with an excess of milk of lime during which time distinct traces of ammonia were evolved; it was then filtered from the undissolved lime neutralized * Chem.Gaz. Aug. 1 1845. VOL. V,-NO. XVIII. H MR. EDWARD RILEY with hydrochloric acid left slightly acid and then evaporated to abont + or -+< of its original bulk; the portion that crystallised on cooling mas filtered from the residue and purified by treating it three times with animal charcoal and lime and then crystallising. Thus obtained it was perfectly white and in long acicular needles ; but the quantity did not amount to niore than from 5 to 10 grains. The quantity being small three other pints of urine were treated as above dcseribed except that after filtration the liine was left in excess; the cvaporation was not so rapid as in the former case. From the small solubility of hippuric acid I thought some might be obtained although it was only evaporated to t of its original bulk.Hydrochloric acid was added an immediate precipitate was formed which appeared in exceedingly niinute crystals almost like an amor- phous powder; this was filtered off. Thinking that more might possibly be procured another portion of acid was added a very considerable quantity amounting to five or six times that previously obtained was deposited and removed by filtration. This unexpectecl result induced me to add another portion of acid and as large a quantity was produced as in the second case; this was separated from the liquid which now ceased to give any further precipitate on the addition of an acid. From these circumstances it was obvious that hippuric acid must be more insoluble in a very acid solution in the cold than in a solution slightly acidulated.Hydrochloric acid was added to soine of the urine that had not been used in the previous operation and in a few seconds crystals began to form shooting out in needles from a nucleus ; after it had stood a few minutes the bottom of the flask was completely covered with a crystalline deposit of hippuric acid of considerable thickness. The amount of hippuric acid obtained from the three pints concen- trated by evaporation amounted to about 6 oz. by measure after the liquid had been decanted. These results led to some further experiments on the urine of cows. The urine from several cows wa8 tested at various times and generally gave large quantities of hiD-puric acid on addition of hydrochloric acid.It was found from various experiments that oz. of hydro-chloric acid to a pint of urine gave the best results. Sulphuric acid appeared to separate colouring matter. Sometiines but littlc was to be obtained from the urine at othcr times very coiisiderable quantities were obtained. The urine was tested in the following manner about 3 or 4 oz. of it were poured into a precipitating glass with about 4 to 3 of a draehin of hydrochloric acid. If 110 precipitate appearcd it was vigoronsly ON ,4 NEW METHOD OF OBTAINING HIPPURIC ACID. stirred when hippuric acid would be precipitated in considerable quantity at the bottom of the glass If on the contrary the liquid were not stirred needle crystals would shoot out from a nucleus some adhering to the sides of the glass others falling to the bottom.It was desirable to know the exact quantity of hippuric acid that could be procured 1 pint of urine was taken from a cow 4 oz. by measure of commercial hydrochloric acid added; it was then allowed to stand twelve hours filtered on two filters one exactly counterpoising and encircling the other and dried gradually in the air until it ceased to lose weight. The weight thus obtained was 158.83 grains calculated per cent gives 2.269 , per imp. gal. 1270*64 or 2.9 oz. avoirdupoise. The hippuric acid was only slightly coloured. It was lightly scraped from the filter and the filters were again weighed when the excess was found to be 0.92. This deducted and calculated as before gives 157.78 grains calculated per cent gives 2.252 , per imp.gal. 1262.240or 2.88 oz. avoirdupoise. Thus showing that the little colouring matter on the filter made no appreciable difference in fact some small quantity of hippuric acid was left adhering to it. The method of obtaining and purifying the hippuric acid was as follows the urine was caught from five to seven in the morning from seven cows the urine from each being put into a separate vessel; each urine was tested in the manner before described; that which gave an immediate precipitate on stirring was poured into a large vessel whilst the rest was rejected. It was mixed with com-mercial hydrochloric acid in the proportion of & oz by measure to a pint; this was left until the evening when the hippuric acid was decanted from the supernatant liquor and was afterwards thrown on a square filter; the urine collected during the day was then treated in a similar manner and filtered off the following morning.I have in this way obtained from a gallon as much as would twice fill a small 2 oz. ladle when pressed down tight and sometimes rather more; the hippuric acid wax freed from the excess of urine by twisting it in a piece of linen into a ball and then squeezing it until no more liquid was expressed. When about seven of these measures had been obtained amounting H2 to 13 lb. by weight of the moist hippuric acid all the urine being expressed that was possible by simple pressure it was placed in a large thin milk-pan of a capacity of 24 gallons rain-water added and an excess of lime and about 3 0%.of commercial animal charcoal ; the milk-pan was then placed over an ordinary washing-copper and the water in the latter heatcd to boiling.The mixture was heated until all the hippuric acid was dissolved then kept at the same temperature about half an hour longer filtered through large filters into another similar pan replaced on the copper heated until the temperature did not rise then iieutralized with hydrochloric acid and about 4 to 5 oz. by measure more of the hydrochloric acid added. It was carefully covered and left until the next morning when the liquid was found to be still luke-warm ;but magnificent crystals of the square prismatic form soiiietirries 2 inches in length were foulld adhering to the sides and bottom of the dish; the dish was allowed to cool on the copper which n7as not cool on the evening following that on which it was purified.The crystals were drained and allowed to dry between blotting-paper. The crystals thus obtained had only a slight tinge of colour being sometimes rather more some- times rather less than $ lb. in weight. I have occasionally obtained them nearly white by the first crystallization when the animal charcoal was good. By repeating the above operation on the crys-tals they may be obtained in beautiful snow-white prisms without a tinge of colour. It often happens that the whole of the hippuric acid does not crystallize out that sometimes considerable quantities may be obtained by adding 4 or 5oz.of hydrochloric acid to the mother-liquor ; a small portion of the mother-liquor should always be tested to see whether any more acid may be obtained from it; this sometimes happens in purifjring the acid at one time whilst not at another. The acid prepared in the above manner was submitted to analysis after being twice recrystallized from distilled water to purify it from a trace of lime which it invariably contains; when prepared as above it gave on analysis results agreeing with the established formula C, NH 0,tHO. it is important to know from what food the greatest quantity of hippuric acid is produced. The observations made 011 this subject tend to show that when cows are fed on grass the hippuric acid exists in the urine in the largest quantity.The urine from cattle fed on other food does not give so large a quantity of hippuric acid. I think we may infer (though perhaps not without a doubt) that thc hippuric acid is obtained from thc grasscs in the pastures somc ON A NEW METHOD OF OBTAINING HIPPURTC BCID. 101 of which contain a peculiar substance curnarin thought to be benzoic acid previously to the examination of Dr. Bleibtreu,* which probably may by its passage through the animal organism be trans- formed into hippuric acid the cumarin occurring in the Antho-ranthum odoraturn or spring grass common in our meadows; also in the Melilotus o@canalis or melilot and in the Asperula ado-rata or woodruff. This subject I hope to investigate.Through the kindness of Professor Miller of Cambridge I am enabled to give the form of the crystals of hippuric acid which previously to his examination I thought I had succeeded in obtaining in two different forms ; but he assures me they are similar. Prismatic symbols of the simple forms a 100 b 010 c 001 e 101 u 011 m 110 r 111. The face c is common to the zones e e' vu'; c is common to the zones eb va. The faces a b c r are very small. The angles between iiormals to the faces are bc goo 0' ca 90 0 ab 90 0 v21' 91 35 e e' 81 32 m m' 79 58 e m' 65 11 ue 58 7 v ld 56 42 rV 31 1 rm 36 41 Cleavage c tolerably perfect. Strong acids as is well known decompose the hippuric acid into benzoic acid and glycocol.Dilute nitric acid may be used to purify hippuric acid the nitric acid only destroying the colour-ing matter. I have in this way obtained very good crystals free from colour. Strong hydrochloric acid readily dissolves hippuric acid; and after boiling some time the mass becomes turbid and an oily substance of a dark colour floats on the surface viz. benzoic acid which crystallizes on cooling and may be separated by filtration from the hydrochlorate of glycocol which remains in solution. The benzoic acid thus obtained being submitted to sublimation in * Mern. Chem. SOC. 111 205. DR. STRECKEB’S CONTRIBUTIONS TOWARDS the apparatus described by Mohr gives beautiful crystals of per-fectly white benzoic acid with only a slight odour.I have obtained considerable quantities of benzoic acid by the above method and am convinced that it might be prepared from this source much more economically than from gum benzoin. I have also prepared glycocol from the mother-liquor by the method of Dessaignes. In reference to this substance I may mention that I have not been able to obtain the fiery-red colour mentioned by Mr. Horsford on heating glycocol with a strong solu- tion of potash. Schwarz* makes the same observation. I have prepared glycocol by the action of sulphuric acid on hippuric acid which appears to act as well as hydrochloric acid. The excess of sulphuric acid is removed and the sulphate of glycocol decomposed by precipitated carbonate and a little hydrate of baryta whereby a sweet solution is obtained which crystallizes in apparently different crystals to those prepared by the action of hydrochloric acid on hippuric acid; they all effloresce on exposure to the air. They have not been analyzed.

ISSN:1743-6893    

DOI:10.1039/QJ8530500097

出版商:RSC    

年代:1853

数据来源: RSC

摘要:

DR. STRECKEB’S CONTRIBUTIONS TOWARDS VIK-Contributions tozuards the history of Tunnic Acid. BY DR STRECKER. (FROM A LETTER TO DR. HOFMANN.) The opinions of chemists regarding the transformation of tannic into gallic acid are still divided. Whilst some assume that tannic acid splits into gallic acid carbonic acid and water Mulder has lately asserted that the whole amount of carbon in taniiic acid passes over into gallic acid only water being assimilated so that the two acids would contain the same number of carbon equivalents; and Wetherill has even gone so far as to consider tannic and gallic acids as isomeric. The observation that the distillation of tannic acid even when conducted with the utmost care invariably yields a certain amount of a non-volatile residue whilst according to the old formula it should split exactly into pyrogallic acid carbonic acid and water together with the well-known fact that the action of powerful acids upon tannic acid invariably gives rise to the formation of an ulmin-like body whilst gallic acid is not affected by acids of the same X CIiciii GaL 1850 475 THE HwroXY OF TANNIC ACID.103 concentration suggested to me the idea that tannic acid might contain another compound in addition to gallic acid. On examining the question I have arrived at the curious result that tannic acid when acted upon by acids yields together with gallic acid sugar SO that henceforth tannic acid may be classed with the conjugate sugar-compounds. I have thrown down a solution of pure tannic acid with sulphuric acid; boiled the precipitate of sulphate of tannin with water or very dilute sulphuric acid; neutra- lised the solution with carbonate of lead; and precipitated the gallic acid still dissolved with acetate of lead.The liquid when freed from the excess of acetate of lead by hydrosulphuric acid gave on evapo- ration a syrupy residue possessing all the properties of sugar modified by acids. It reduced an alkaline solution of protoxide of copper although it did not contain a trace of gallic acid (which produces the same effect) and readily fermented on addition of yeast. This latter experiment appears to me conclusive. Accordingly the formula of tannic acid will have to be altered; and although I have not yet been ahle to determine the quantity of sugar which is produced by a known weight of tannic acid I nevertheless even now believe that the coniposition of this substance is represented by the formula '40 18 '26 as will be seen from the subjoined comparison of the numbers found and calculated Theory.Berze lius. Liebi g. M ul der. Streck er. C . . 51.5 61.5 51.5 61*5-52*1 51.4-61.5 H, . . 3.8 3.8 -4.1 3.6-3.9 3.9-3.9 Og6 . . 412.7 ---100.0 Thus the transformation would take place according to the following equation C40H18026t loHo=2 (c14H8012) -k C12H1!201Y As the number of water-equivalents which is assimilated in this change is unusually large the question arises whether tannic acid is a perfect analogue of the other conjugated sugar-compounds ; at all events we have to assume a hydrate of carbon in a state of conjugation. From these experiments it is evident that this conjugate sugar- compound belongs to the principles most universally diffused in vegetable nature and it can scarcely be doubted that the other tannin-like substances will have an analogous composition.

ISSN:1743-6893    

DOI:10.1039/QJ8530500102

出版商:RSC    

年代:1853

数据来源: RSC

摘要:

MR BLOXANI ON THE IX.-On the detection and qualitative separation of Tin,Anti-mony wnd Arsenic; and on the relation existing between these metals and others which are precipitated from their acid solutions by Sukhuretted Hydrogen. BY CHAELESL. BLOXAILI. The difficulty which I experienced some years since in the analysis of the alloy known as Britannia Metal from the want of a certain and ready method of separating tin antimony and arsenic induced me to undertake a close investigation into the reactions of these three metals; and the results of this inquiiy have appeared to me to possess so much interest that I venture to lay them before the Society. There is perhaps no problem in the whole range of qualitative analysis which has engaged so much attention and so repeatedly defied all attempts at solution as the separation of the three metals under consideration; and the reason of this is evidently the great similarity in properties exhibited by two of the metals antimony and arsenic conjoincd with the disposition of the third tin to form an insoluble binoxide which enters into combinations likewise insoluble with the oxides of antimony and arsenic.Before describing the method which I have found the most effective for the separation of these mctals I shall briefly pass in review some of those which have becn already proposed for effecting this object. In doing this however I shall only mention those methods which are applicable in ordinary qualitative analysis omitting those which were designed only for the separation of the metals in particular cases as well as those processcs which require a great expenditure either of time or skill on the part of thc analyst The observation made some years ago by Level,* that the three nietals could not be separated by means of nitric acid perfectly coincides with the result of my own experiments which have shown that small quantities of arsenic arc not dissolved out of a mixture containing tin antimony and arsenic by nitiic acid.The method proposed by Simont for the detection of small quantities of arsenic in the presence of antimony consists in fusing the mixed sulphides of these mctals with nitratc of potash extracting the fused mass with water acidulating the filtered solution with nitric DETECTION OF TIN AXTIMONY AND ARSENIC 105 acid adding nitrate of silver and precipitating the arseniate of silver by the careful addition of ammonia.In order to ascertain whether this niethod could be applied to the separation of the three metals in cases where but a small quantity of arsenic is present I prepared a solution containing 0.0475 grm. antimony 0-0475 , tin and 0*0050 , arsenic (corresponding to 47.5 per cent of antimony 47.5 per cent of tin and 6 per cent of arsenic,) but failed in detecting the arsenic by treating the precipitated sulphides according to the method detailed above. I have found moreover as would be expected that this method is very unsafe even for the detection of larger quantities of arsenic; since it is very difficult to add exactly the amount of am-monia necessary to neutralize the free acid and it is well known that the arseniate of silver is soluble in the slightest excess either of nitric acid or of ammonia.I have also tried to apply to the separation of antimony tin and arsenic the method reconimended by Meyer* for the separation of antimony and arscnic. This method consists in fusing the mixed metals (antimony and arsenic) or their sulphides oxidised by nitric acid with nitrate of soda and extracting the arseniate of soda from the fused mass with water which leaves the antimony in the residue. Since if tin were present it would also be left in the residue I thought it might be practicable to separate thc antimony and tin by treating this residue with tartaric acid.Bisulphide of tin was dried and fused with nitrate of soda; the fused mass was extracted with cold water; the aqueous solution was perfectly free from tin; the residue was washed and boiled with a concentrated solution of tartaric acid the solution filtered mixed with hydrochloric acid and subjected to a current of sulphuretted hydrogen when a yellow precipitate of bisulphide of tin was obtained. Moreover when tersulphide of antimony was treated according to this process the residue left by water could not be entirely dissolved by tartaric acid. These experiments proved that no dependence could be placed upon this method for the separation of antimony and tin. Some experiments have also been tried upon the method recently proposed by Fleitniannf- for the detection of tin antimony and arsenic.* Ann Ch. Pharrn LXVI 236. .i-Ann. Ch. Pharm. Jan. 1851 MR. BLOX-4N ON THE This method consists in testing for arsenic in one portion of the solution by adding excess of potassa and boiling with metallic zinc when if arsenic be present arsenietted hydrogen will be evolved and may be recognised by its property of blackening a solution of nitrate of silver; whilst antimony and tin are detected by treating the other portion of the solution with zinc and hydrochloric acid and kindling the hydrogen which is evolved; the flame of antimonietted hydrogen is known by its depositing upon a porcelain plate a spot of antimony insoluble in solution of hypochlorite of soda whilst the arsenic spot is soluble in this reagent.The tin is then detected by boiling the metals reduced by zinc with hydrochloric acid and testing the solution for protochloride of tin with hydrosulphuric acid. In order to prove this method I employed it in testing a solution containing 0.095 grm. tin and 0.005 , antimony when the metallic stain deposited upon a porcelain dish was not redissolved by solution of chloride of soda (prepared by transmitting a very slow current of chlorine through a dilute solution of carbonate of soda until it was but slightly alkaline). On the other hand when a solution containing 0.095 grm. tin and 0.005 , arsenic was employed the metallic stain was instantly dissolved by solution of chloride of soda.I could not succeed in detecting the antimony by this method in solutions containing respectively 0.099 grm. arsenic and 0-001 , antimony 0.495 grm. arsenic and 0.005 , antimony and 0.095 grin arsenic and 0.005 , antimony since in these three cases the very largc metallic crusts which were deposited upon the porcelain dissolved entirely in solution of chlo-ride of soda. Hence it appears that this method does not enable us to detect even 5 per cent of antimony in a mixture of that metal with arsenic. DETECTlON OF TIN ANTIMONY AND ARSENIC 107 The test for arsenic furnishes results which are far more satis- factory. A solution containing 0.095 grm. tin and 0 005 , arsenic was mixed with a considerable excess of potash and a few fragments of granulated zinc (free from arsenic) introduced ;the flask containing the mixture was then fitted with a perforated cork carrying a short piece of wide glass tube and heated to boiling upon a sand-bath; when a piece of paper spotted with solution of nitrate of silver was held over the extremity of the tube the black arsenide of silver was immediately formed.In another experiment a solution containing 0.495 grm. antimony and 0.495 , tin was treated according to the above method; no black spot was visible upon the paper but when 0.01 grm. arsenic was added to the mix- ture a black spot was at once produced. Other experiments were tried all tending to show that this test is a most valuable one for arsenic in the presence of antimony and will probably be found of great service in judicial investigations espe- cially as it may in all probability be applied equally well to a potash solution of the sulphides of these metals.The objections which seem to me therefore to restrict the appli- cation of Fleitmann’s method have regard chiefly to the test for antimony since it has been shown that small quantities of this metal may escape detection; moreover the solution of chloride of soda cannot be preserved for any length of time and the operation requires a special apparatus which it is well if possible to avoid in qualit at ive analysis. I have attempted to apply qualitatively the last method proposed by Rose* for the quantitative separation of tin antimony and arsenic which consists in fusing the mixed oxides (obtained by treating the metals with nitric acid) with caustic soda digesting the fused mass with water and precipitating the last traces of antimoniate of soda by means of alcohol.Tersulphide of antimony was oxidised with nitric acid dried and fused with a large excess of hydrate of soda in a silver crucible; the fused mass was digested with cold water and set aside for twelve * Herl. Monathel. I’ogg. Ann. LYXIII 582. 108 MR. BLOXiM OY THE hours ; the solution was thcn filtered and mixed with somewhat more than one-third of its volume of strong alcohol and allowed to stand during the night; a considerable quantity of antimoniate of soda was deposited and on filtering this off and testing the clear liquid with hydrochloric and hydrosnlphuric acids scarcely a trace of antimony was detected.When tersulphide of arsenic was treated in exactly the same manner and the aqueous solution of the fused mass was mixed with alcohol and allowed to stand for some hours numerous small crystals were deposited which after washing with alcohol till free from ad- hering arsenic were shown to contain this metal in considerablc quantity ; this circumstance of course would prevent the application of the method in qualitative analysis since it appears that unless attention be paid to the strength and quantity of the spirit as mentioned in Rose7s paper arsenic and antimony might both be found in the precipitate; moreover I may cite as an objection to the qualitative application of this process the rather considerable quantity of substaiice required which is seldom at our disposal in thc examination of this group of oxides.I have also found that a small quantity of arsenic cannot be detected in a mixture of the three inctals by this method of fusion with hydrate of soda. An alloy containing a large quantity of tin together with small’ quantities of antimony and arsenic was oxidised with nitric acid and the residue fused with excess of hydrate of soda; the fused mass was boiled with water in which it almost cntirely dissolved; the solution was acidulated with nitric acid and filtered; the filtrate was carefully tested for arsenic by evaporating to a small bulk mixing with excess of ammonia evaporating to dryness redissolving in water and adding nitrate of silver when no precipitate whatever was obtained; on the other hand the precipitate produced by nitric acid in the aqueous solution of the fused mass was mixed with charcoal and reduced with cyanide of potassium and carbonate of soda in a crucible; the metallic button was found to contain arsenic.Rose’s method is also inapplicable in ordinary qualitative analysis to the separation of antimony and tin because previously to oxidation by nitric acid these must be reduced to the metallic state which cannot be conveniently effected when small quantities are to be examined. The following cxpcrimcnt was rnacte to ascertain whcthcr thc residue obtained by oxirtising the tersulphidc of antiriioriy with nitric DETECTION OF TIN ANTIMOSP AND -\RSENIC.acid ~~oulcl bchavc in thc same way when fused with hydrate of soda as that produced by the oxidation of the metal. Tersulphide of antimony was oxidised with nitric acid dried and fused with a large excess of hydrate of soda; the fused mass was digested with cold water and allowed to stand for twelve hoizrs; the aqueous solution was filtered acidulated with hydrochloric acid and sulphuretted hydrogen passed ; a considerable quantity of orange sulphide of antimony was precipitated. When bisulphide of tin was oxidised with concentrated nitric acid dried fused for a considerable time with a large excess of hydrate of soda and the fused mass digested for twenty-four hours with cold water it slowly dissolved leaving a very slight residue which was filtered off but passed through the filter when I attempted to wash it; a repetition of the experiment gave a similar result ;this would point out a serious difficulty since it would be highly important that the fused mass should form a perfectly clear solution if no antimony were present.An experiment has been tried upon the method of separation re- commended in Galloway’s manual of qualitative analysis. Bisulphide of tin was gradually added to fused nitrate of ammonia and the mixture heated for some time until all nitrate of ammonia had volatilised and finally strongly ignited for some minutes. The ignited residue was boiled with a stroug solution of tartaric acid filtered the solution mixed with hydrochloric acid and sulphuretted hydrogen passed; a decided though it must be confessed not very abundant yellow precipitate was obtained.I had previously ofteu observed the partial solubility of the binoxide of tin in tartaric acid which may deceive us as to the presence of antimony. The method of Levol* for the separation of tin and antimony which consists in boiling the finely-divided metals with hydrochloric acid is inapplicable in ordinary analysis because unless the pre-cautions pointed out by the author of this method be strictly ad- hered to *part of the antimony is dissolved by hydrochloric acid as was originally shown by Elsner,? whose results have been con-firmed by niy own observations. I have also tried some experiments upon the old method of separating tin and antimony by boiling the metals reduced by zinc with nitric acid and separating the mixed oxides thus obtained by means of tartaric acid or bitartrate of potash.Antiriiony which had been precipitated by zinc from a solution of * Ann. Ch. Phys. XIII 125. J. Pr. Chein. XXXV 313. MR. BLOXAM ON THE the terchloride was oxidised by heating with a mixture of concen- trated nitric acid with two volumes of water; the oxide was well washed and boiled with a saturated solution of tartaric acid for some hours; it would not entirely dissolve; the oxide prepared by using more dilute nitric acid dissolved to a somewhat greater extent. Bitartrate of potash was also tried with the same result.Marsh’s method of separating tin and arsenic which consists in the evolution of the latter as arsenietted hydrogen by digesting the acid solution with zinc is not applicable in ordinary analysis ; firstly because of the dificulty of obtaining in every case a solution free from nitric acid; secondly because tin is sometimes an impurity of commercial zinc and thirdly because. antimony interferes with the detection of the arsenic. The process of Fresenius and Babo,* in which the arsenic is reduced by cyanide of potassium and carbonate of soda in a stream of dry carbonic acid is unexceptionable as far as the detection of arsenic is concerned; neither antimony nor tin interferes with this test; I have repeatedly tested pure sulphide of antimony by this method without obtaining any trace of metallic sublimate.Unfor-tunately however so small is the quantity of the mixed sulphides that can be employed in this operation that it is hopeless for an ordinary analysj to attempt the separation of antimony and tin in the residue. After having satisfied myself that no certain and easy method existed of separating antimony tin and arsenic I tried a great number of experiments with the view of discovering such a method; and since in the course of these attempts I have met with some reactions of these metals of which I nowhere find any account I may perhaps be permitted to bring forward a few of them as it appears to me a by no means unimportant branch of analytical science to know what methods will not be competent to effect a particular separation.Tersulphide of antimony was fused with Liebig’s cyanide of potassium with continual stirring; the mass was retained in fusion for some time; while fused it had a deep brown colour but became white on cooling; the mass dissolved entirely in water and the solution gave an orange precipitate on addition of dilute hydrochloric acid; I was astonished that in this experiment no reduction of the antimony had taken place. When bisulphide of tin was treated in a similar manner globules of metal were obtained and acetic acid added to the aqueous so-lution gave a yellow precipitate. * Ann Ch. Pharm. XLIX 287. DETECTION OF TIN ANTIMONY AND ARSENIC. 111 When either bisulphide of tin or tersulphide of antimony was fused with nitrate of soda and the mass extracted with cold water neither metal was found in solution but the residue left by water was in each case partly soluble in tartaric acid.Tersulphide of antimony was added to fused chlorate of potash; the fused mass powdered and boiled with water; much antimony was found in the aqueous solution; but when bisulphide of tin was thus treated no tin whatever was found in the solution; when a mixture of bisulphide of tin with a little tersulphide of antimony was employed all the antimony was left behind in the residue. Tersulphide of antimony was fused with nitrate of potash the mass powdered and digested with cold water ;the solution contained no antimony and the residue was only partly soluble in hydrochloric acid.Bisulphide of tin behaved in a similar manner. When freshly precipitated tersulphide of antimony was oxidised with cold or hot concentrated nitric acid a portion of antimony was found in the solution and the residue was almost entirely dissolved when boiled with solution of tartaric acid. The nitric solution con- tained more antimony when a mixture of one volume of the concen- trated acid with two volumes of water was employed. The tersulphide of antimony dissolved almost entirely in a mixture of the concentrated nitric acid with four volumes of water. On boiling bisulphide of tin with very dilute nitric acid no tin was found in the solution. A solution of terchloride of antimony was boiled with excess of carbonate of lime and filtered; antimony was still found in consi- derable quantity in the solution.When a solution of bichloride of tin was treated in the same manner no tin was found in solution. However when a solution containing a large proportion of tin and a small quantity of antimony was neutraliseil with carbonate of lime and filtered no antimony was found in solution; the same result was obtained on boiling. In the course of my examination into the reactions of antimony and tin I found that when a solution of terchloride of antimony was mixed with an excess of solution of sesquicarbonate of ammonia and boiled the precipitate at first produced was entirely redissolved; whilst on making the same experiment with solution of bichloride of tin no tin whatever was found in the filtered solution.Thinking that this observation might lead me to the separation of these metals I examined the reaction more minutely and invariably 112 AIR. BLOXAM ON THE found that no tin could be detected in solution after boiling with ail excess of sesquicarbonate of ammonia. I discovered however that occasionally this reagent produced in a solution of terchloride of antimony a precipitate which was not perfectly soluble in excess although a large quantity of antimony was invariably found in the solution. Finding that this precipitate was always less after boiling the terchloride of antimony with a little nitric acid I tried whether the treatment of the solution with powerful oxidising agents would ensure the complete solubility of the precipitate.With this view I tried successively chlorine chloride of soda and chlorate of potash in the presence of free hydrochloric and nitric acids but always with the same result namely that although in many cases the precipitate was entirely soluble in excess it depended so much upon the strength of the solution and upon the amount of sesquicarbonate of ammonia added that it would be in vain to attempt or expect the complete solution of the antimony although it was invariably found that the tin was entirely precipitated. I therefore determined to have recourse to a special method for the detection of tin in the Precipitate. After several trials I found that the best special reaction for this metal was that of the hydrochloric solution with protochloride of mercury by which an incredibly small amount of tin may be detected.The precipitate produced by sesquicarbonate of ammonia was fused with cyanide of potassium the fused mass digested with water and the reduced metal boiled with hydrochloric acid ; the filtered hydro-chloric solution was then tested with protochloride of mercury when if a very small quantity of tin was present it gave a very highly crystalline precipitate ; with a larger qumtity a precipitate not visibly crystalline; and when very much tin was present a grey precipitate of metallic mercury. In order to ascertain to what extent the above method was appli- cable to the separation of antimony and tin in the ordinary course of analysis I analysed solutions containing weighed quantities of these metals always proceeding according to the following routine.The solution containiug the two metals was precipitated by sulphn- retted hydrogen; the sulphides washed upon a filter dissolved in yellow sulphide of ammonium reprecipitated by hydrochloric acid with addition of a little hydrosulphuric acid ; the precipitate after washing dissolved in hydrochloric acid with a little nitric acid; the solution mixed with an excess of sesquicarbonate of ammonia boiled for a few minutes filtered; and the filtered solution after concentra- tion tested for antimony by acidulating with hydrochloric acid and passing sulphuretted hydrogen. DETECTJOS OF TIN ANTIMONY AND ARSENIC. 113 The filter with the white precipitate produced by sesquicarbonate of ammonia after washing twice or thrice with this reagent (for when washed with water it passes through the filter) was dried incinerated in a porcelain crucible the ash fused with a little cyanide of potassium and treated as above described in order to detect the tin.By this process I haw succeeded perfectly in detecting the two metals even in eases where they have been mixed in the proportions of 99 to 1 and when only 0.003 grm. or even less of the metal which was in small quantity has been present. In these cases the tin was always present in the forin of bichloride and the antimony either as terchloride or pentachloride. I may mention as an important precaution when testing for traces of tin that the reduced metal should not be boiled for any con- siderable period with hydrochloric acid since I have found that the reaction with protochloride of mercury cannot then be obtained ; whereas it is quite sufficient to raise the acid to the boiling-point when the merest trace of tin may be detected.In the course of these experiments I have also found that the pure canary-yellow colour of the bisulphide of tin may be altered in a very remarkable manner by the presence even of very small quan- tities of antimony; in fact most ordinary solutions of bichloride of tin were found to give a greenish-yellow precipitate from this cause and a very slight admixture of antimony in a solution of tin could be detected in this manner. A solution containing 99.95 parts of tin as bichloride and 00.05 , antimony as terchloride gave with sulphuretted hydrogen a precipitate which had a decided green tinge when compared with pure bisulphide of tin.With a solution of 99.45 tin and 00.55 antimony the precipitate had a distinct green colour; and on increasing the proportion of antimony it became very dark. I thottght at first that thc dark colour might be due to the presence of protochloride of tin but could not detect any in the solution. Having satisfied myself of the accuracy of the above process for the detection of the tin and antimony I next inquired how far the presence of arsenic would interfere n-ith it. I found that when VOL. V.-NO. XVIII. I MR. BLOXAM ON THE arsenic was present the addition of sesquicarbonate of ammonia failed to throw down the whole of the tin ; and in a case where the latter amounted to 5 per cent of the arsenic no precipitate whatever was produced by sesquicarbonate of ammonia ; moreover the presence of arsenic of course interfered with the subsequent detection of the antimony in the filtrate from the binovide of tin.It therefore became necessary to find some method of separating the arsenic from the antimony and tin before taking any steps to separate these metals from each other. Finding that as I have already stated all the tin was precipitated from a solution of the bichloride by carbonate of lime even in presence of chloride of ammonium and that arsenic acid appeared not to be precipitated at all under the same circumstances I attempted to detect by this method 1 part of arsenic as arsenic acid in the presence of 20parts of tin in the form of bichloride but found that the whole of the arsenic was carried down with the binoxide of tin.I also tried to separate them by oxidising the sulphides with nitric acid and fusing the residue with cyanide of potassium at a high temperature but found that arsenic could not be entirely expelled in this way When a mixture of bisulphide of tin and tersulphide of arsenic (containing 1 part of tin to 20 parts of arsenic) was oxidised with nitric acid the residue dried ignited; and boiled with water until the aqueous solution gave no further indication of arsenic this metal could still be detected in the residue.It was found that when the residue obtained by oxidising a mix- ture of bisulphide of tin and tersulphide of arsenic (containing equal weights of these metalsj with nitric acid was fused with hydrate of soda ;the fused mass dissolved in water ;an excess of nitric acid added ; the solution evaporated to dryness ;and the residue boiled with water ; the merest trace of arsenic was found in the solution. This experiment was repeated with the same result. A mixture of bisiilphide of tin and tersulphide of arsenic contain- ing equal weights of these metals was fused with nitrate of potash ; the fused mass dissolved almost entirely in water and the aqueous solution when acidulated with nitric acid and heated gave an abundant precipitate which after thorough washing was found to contain arsenic.Having failed in these attempts to discover a method for the complete separation of arsenic I had rccourse to the extraction of the sulphides of arsenic from a mixture of these with the sulphides of DETECTION OF TIN ANTIMONY AND ARSENIC. tin and antimony by means of' scsquicarboiiate of ammonia a method which has been occasionally employed by other analysts. I found that when pure tersulphide or pentasulphide of antimony was digested either with or without heating in a solution of sesqui- carbonate of ammonia (prepared by agitating the commercial salt with cold water as long as any was dissolved) very small quantities of the sulphides were taken up so small indeed that this degree of solubility did not appear likely to interfere in analysis whilst the two sulphides of arsenic dissolved at once in this reagent.When bisulphide of tin was treated in the same manner none was dissolved even on boiling with sesquicarbonate of ammonia. To ascertain how far the solubility of the sulphides of antimony would affect the result if sesquicarbonate of ammonia were used T precipitated by sulphuretteci hydrogen a solution containing bichloride of tin and terchloride of antimony in the proportions of 99 parts of tin to 1 part of antimony dissolved the precipitated sulphides in yellow sulphide of ammonium reprecipitated by hydro- chloric acid and digested the precipitate with a saturated solution of sesquicarbonate of ammonia.I found that although a little anti- mony was contained in tlie solution the greater part remained in the residue and the same result was obtained in several experiments. The next question to be decided was how far the behaviour of the sulphides of arsenic with sesquicarbonate of ammonia would be modified by the presence of those of antimony and tin. Sulphuretted hydrogen was passed through a solution containing arsenic and antimony in the proportion of 99 :1 (about 0.004 grm. of antimony being present) the arsenic as arsenious acid dissolved in hydrochloric acid and the antimony as terchloride. The precipitate thus obtained was washed and digested in a saturated solution of sesquicarbonate of ammonia with the aid of a gentle heat; a fine orange-yellow residue of tersulphide of antimony was left undis-solved.This experiment was repeated many times with the same result. When the proportion between the two metals was reversed there being about 0.0035 gri. of arsenic present the latter was detected with great ease in the solution of the sulphides in sesquicarbonate of ammonia. A solution containing 0.0475 grm. tin as bichloride and 0.0475 , arsenic as arsenious acid ma9 precipitated hy snlphnrctted Ityclropcn tlw prccipitntc washrd 12 dissolved in yellow sulphidc of aninioniuin reprecipitated by hydro- chloric and hydrosulphuric acids agitated with cold sesquicarbonate of ammonia and filtered; the filtrate contained a considerable quan- tity of bisulphide of tin. In soinc cases where even a rather large amount of bisulphide of tin was mixed with the sulphide of arsenic the precipitate dissolved almost entirely in scsquicarbonate of ammo-nia; and this is ail additional instance of' the stranse alteration in the reactions of tin to which the presence of arsenic 0' rives rise.In order to separate the tin from the arsenic I ultimately resorted to a special method which consisted in deflagrating the mixed sul-pliides (together with the filter if necessary) with nitrate of potash digesting the fused niass with water when part of the tin was left behind in the insoluble residue and acidulating the aqueous solution with nitric acid which on heating precipitated the whole of the tiu. as binoxide. This precipitate together with the residue left on digesting the fused niass with water was washed dried and ignited with the filter; the ash fused with cyanide of potassium; the fused mass digested with water ; and the rcsidud metal looiled with hydro- chloric acid ; the filtered solution was then tested with protochloritlle of mercury for tin.In a solution containing 0.095 grin. arsenic and 0.005 tin the latter metal was very easily clctected in this way. The experiments detailed above led me to the following method for the qualitative detection of tin antimony and arsenic which is ap-plicable to any solution in which these metals exist provided that any arsenic acid is first reduced to the state of arsenious acid. The solution is largely diluted with water acidulated with liydro- chloric acid and sulphuretted hydrogen passed through it to satura- tion; the liquid is allowed to stand for some time in a warm place and the precipitate collected upon a filter; this precipitate is now washed several times with water and dissolved with the aid of heat in yellow sulphide of ammonium ; the solution thus obtained is mixed with an excess of hydrochloric acid and some strong solution of hydro-sulphuric acid ; the reprecipitated sulphides collected on a filter well washed transferred to a test-tube or small flask and digested at about 82' (180' F.) with a saturated solution of sesquicarbonate of ammonia for about half an hour.If the precipitate consisted of one of the sulphides of arsenic it would entirely dissolvc but it must then be rcrncrnbered that the DETECTION OF TIN ANTIMONY AND ARSENIC.117 presence of tin is by no means precluded; it may however be safely inferred that no antimony is present. If there be any residue insoluble in sesquicarbonate of ammonia it may contain bisulphide of tin and pentasulphide of antimony; it must be washed on the filter with sesquicarbonate of ammonia as long as the washings furnish any considerable yellow precipitate when acidulated with hydrochloric acid; it is then dissolved in a mixture of concentrated hydrochloric acid with about one-eighth of its bulk of concentrated nitric acid using as little acid as possible. The solution is then mixed in a beaker with a considerable excess of sesquicarbonate of ammonia and boiled for a few minutes.If no precipitate is produced the absence of tin is certain but if a precipitate is formed it must be collected upon a filter for exami-nation. This precipitate may contain aiitimonic acid and binoxide of tin. It must be washed three or four times with sesquicarbonate of am-monia; dried; incinerated with the filter in a porcelain crucible; a little cyanide of potassium added to the ash ;the mixture fused ; the fused mass boiled with water ; the reduced metal allowed to subside the supernatant liquid poured off; the reduced metal (remaining in the crucible) heated to boiling with concentrated hydrochloric acid ; and the solution diluted with water filtered and tested for tin with protochloride of mercury. The solution filtered from the precipitate produced by sesquicar- bonate of ammonia in the nitro-hydrochloric solution of the sul-phides of antimony and tin will contain under any circumstances a part of the antimony; in order to detect this metal the solution is acidified with hydrochloric acid (when if much antimony be present a precipitate of antimonic acid will be at first produced and after- wards redissolved by an excess of acid) ; a stream of sulphuretted hydrogen is then passed through the solution when the production of an orange precipitate will at once indicate the presence of an-timony.We have now to examine the solution obtained by digesting the original sulphides with sesquicarbonate of ammonia. It has been already shown that this solution may contain both bisulphide of tin and pentasulphide of arsenic ; it is acidulated with hydrochloric acid some hydrosulphuric acid added and the precipitate divided into two equal parts which are thrown upon separate filters and washed till the washings are free from chlorine.One part of the precipitate is dissolved off the filter in warm ammonia thc solution cvq)oratccl to dryness on the water-bath and 118 RiR BLOXAM ON THE the residual pentasulphide of arsenic tested according to the method of Fresenius and Babo (reduced by cyanide of potassium and carbonate of soda in a stream of carbonic acid). The other portion of the precipitate together with the filter is dried and deflagrated with nitrate of potash (the filter being cut into strips and gradually added to the nitre in a state of fusion) ;the fused mass is poured from the porcelain crucible into one of iron and when cool boiled with water; nitric acid is then added till an acid reaction is produced; and the insoluble binoxide of tin collected upon a filter dried and tested for tin by the process described above for the examination of the former precipitate containing tin which in fact might be advantageously examined together with this precipitate.By this process I have successfuly examined solutions containing tin antimony and arsenic in the following proportions the tin being present as bichloride the antimony as terchloride and the arsenic as arsenious acid dissolved in hydrochloric acid. 1 Arsenic. 1 Antimony. Tin. 2.5 2.5 95.0 5 *O 90.0 4 47.5 5.0 47.5 5 47.5 47.5 5*O 6 7 1 5 -0 90.0 1 47.5 5.0 47.5 5.0 In these cases the unit of which the above numbers are multiples was 0.001 grm.These and similar analyses have been often repeated not only by myself but by individuals who had no previous acquaintance with this method and even by beginners in the study of analysis and the result has shown me that with comparatively little care more certain analyses can be made by this method than by any other which has come under my notice. The process seems rather a long one for the object in view; I have made several attempts to shorten it by detecting the arsenic ant1 DETECTION OF TIN ANTIMONY AND ARSENIC tin in one operation but the result when small quantities of the metals were present was not satisfactory.After having framed a method upon which I felt that I could rely for the separation of these three metals I determined to ascertain how far these could be separated from the other metals of this group the members of which form sulphides insoluble in dilute acids. The only method I believe employed in general analysis to effect this object consists in heating the mixed sulphides with sulphide of ammonium containing an excess of sulphur which is known to dissolve the sutphides of tin antimony and arsenic together with traces of sulphide of copper and small quantities of bisulphide of platinum and tersulphide of gold. It was necessary in order to ascertain the efficiency of this method to analyse various mixtures containing known weights of the metals to be separated and I ac-cordingly conducted a series of experiments of this nature some of which I may perhaps cite.In these experiments the method of proceeding was as follows The solution was acidified with hydrochloric acid completely pre- cipitated with sulphuretted hydrogen the precipitate collected on a filter well washed and boiled for two or three minutes with the yellow sulphide of ammonium (prepared by the action of the air upon the hydrosulphate of sulphide of ammonium obtained by satu- rating solution of ammonia with sulphuretted hydrogen). The sul- phide of ammonium solution was filtered off and acidulated with hydrochloric acid a quantity of a strong solution of hydrosulphuric acid was then added and if the precipitated sulphur was in the slightest degree tinged it was examined for antimony tin or arsenic by the method given above.On analysing a solution containing 0.500 grm of lead and 0.005 , of tin a part of the tin was found in the sulphide of ammonium solution showing that the bisulphide of tin was not retained to any consi- derable extent by the sulphide of lead. The tin was also found in the sulphide of ammonium solution when there were present 0.500 grm. bismuth with 0.005 , tin. Also in the analysis of a solution containing 0.100grm. gold and 0.005 , tin. XR. BLOXARI ON THE The tin was likewise distinctly detected in a solution containing 0.500 grm. platinuni and 0.005 , tin.When a solution containing 0-500grm. mercury and 0,005 , tin was analysed in this way no tin was found in the sulphide of am-monium solution in two experiments. When the same quantity of tin was present (0.005 grni.) together with only 0.250grm. mercury the tin was only just recognised in the sulphide of ammonium solution in two experiments. In the examination of a solation containing 0.500 grm. cadmium and 0.005 , tin no tin was found in the sulphide of ammonium solution (in two experiments) but when half the quantity (0.250 grm.) of cadmium was present the tin was just recognised distinctly in two cxperi- ments. In the case of a solution containing 0-01grm. tin and 0.09 , copper no tin was found in the sulphide of ammonium solution but abun- dance in the residue.Even in the presence of only 0.03 grm. copper the whole of the tin was found in the residue. When equal weights (0.01 grm.) of tin and copper were present most of the tin was found in the residue althmgh some was detected in the sulphide of ammonium solution. Very little tin was found in the solution in sulphide of ammonium when 0.03 grm. tin and 0.06 , copper were employed. When 0.030 grm. tin and 0.075 , copper were present (being in the proportion of 1 till 2.5 eoppcr) very little tin was found in the sulphide of ainmoninrii solution DETECTTOX OF TIN ANTIMONY AND ARSENIC. 121 In the case of 0.03 grm. tin and 0.09 , copper a slight trace of tin was found dissolved in the sulphide of am-monium.A scarcely perceptible trace was found in solution when 0.03grm. tin and 0.12 , copper were employed and when the copper was increased to 0.135 grm. (being in the proportion of 1 tin :4*5 copper) no tin was found in the sulphide of ammonium solution. Many of the above experiments were repeated several times with different specimens of sulphide of ammonium. I' also made several attempts to analyse a specimen of gun-metal (containing 90 copper and 10 tin) by dissolviiig in aqua regia preci- pitating the diluted solution with sulphuretted hydrogen and boiling the precipitated sulphides with sulphide of ammonium but could not succeed in detecting the tin in the sulphide of ammonium solution though it was easily found in the residue.It appears then from these experiments that the extraction of bisulphide of tin from a mixture of this sulphide with those of iead bismuth gold platinum mercury and cadmium is sufficiently com- plete for most practical purposes; but that in the case of the two latter sulphides if no tin be found in the sulphide of ammonium solution we can only conclude that the proportion of the tin to either the mercury or cadmium is not greater than that of 2 to 100. In presence of copper however it appears that no safe conclusion as to the absence of tin can be drawn from the circumstance that this metal is not found in the sulphide of ammonium solution of the sulphides. In the analysis of a solution containing 0.005 grm.arsenic and 0.500 , lead the arsenic was detected in the sulphide of ammonium solution. In a case where 0*005grm. arsenic and 0.500 , cadmium were present arsenic was found in the sulphide of ammonium solution. MR. BLOXAM OF THE When 0.005 grm. arsenic was present with 0*500 , mercury a considerable proportion of the arsenic was found in the sulphidc of ammonium solution. In anal ysing a solution containing 0*500 grm. bismuth and 0.005 , arsenic less arsenic than I expected was found in the sulphide of ammonium solution in two experiments. Tn the case of 0.150grm gold and 0.003 , arsenic the latter was distinctly found in the sulphide of ammonium solution though in smaller quantity than was expected. The same was observed with 0.500 grm.platinum and 0-005 , arsenic. No arsenic was found in the sulphide of ammonium solution in the ana!ysis of mixtures containing respectively 1.00 grm. copper with 0.01 , arsenic and 0.90 grm. copper with 0.01 , arsenic. When 0.50 grm. copper was present with 0.01 , arsenic the latter metal wag detected in the sulphide of ammonium solution and was always found when smaller proportions of copper were present. From these experiments I inferred that the detection of arsenic is not influenced to any considerable extent by the presence of any metal of this group except copper but that it is slightly affected by the presence of platinum gold bismuth and lead. If copper be present the absence of arsenic in any greater propor-tion than that of 2 to 100 copper may be inferred if no arsenic is found in the sulphide of ammonium solution.In the analysis of a solution containing DETECTION OF TIN ANTIMONY AND ARSENIC. 123 0.01 grm. antimony and 1.00 , copper the antimony was distinctly found in the sulphide of ammonium solution; and none was found in the residue left by sulphide of ammonium when 0.01 grm. antimony was present with 0.10 , copper. Antimony was also distinctly found in the sulphide of ammonium solution in the following cases 0.005 grm. antimony to 0.5 grm. lead 0.005 , > 0.5 , bismuth 0.005 , J> 0.5 , cadmium 0.005 , Y 0.5 , mercury 0.005 , 2 0.5 , platinum 0.005 , 3 0.1 , gold. The detection of antimony therefore does not appear to be influ- enced to any considerable extent by the presence of any other metal of this group.Since the presence of copper may to a considerable extent prevent the detection of tin and arsenic by the ordinary method it becomes necessary when copper is present to examine for those metals in that portion of the precipitate by sulphuretted hydrogen which is insoluble in sulphide of ammonium. For the detection of arsenic in this portion of the precipitate I have usually resorted to the delicate test of Fresenius and Babo.* The detection of tin however is more difficult; and the following method has yielded me the most certain results. The residue left by sulphide of ammoniunz is collected on a filter well washed and boiled as usual in the analysis of this precipitate with a mixture of concentrated nitric acid with two volumes of water to dissolve those sulphides which are soluble in this reagent; the residue which contains the binoxide of tin is collected on a filter and washed ; the filter together with the precipitate incinerated ; the ash fused with cyanide of potassium; and the fused mass boiled with water.The residuary metal is heated with hydrochloric acid and the solution tested with protochloride of mercury. By this method the tin was easily discovered in the following cases * Aim Ch. uiid Phaxm. XLIX 287. 1. 0.01 grm. tin 0.24 grm. mercury 0.24 grm. lead 0.24 grm. copper and 0.01 grm. cadmium. 2. 0.01 , tin 0.25 grm.mercury 0.25 grm. lead and 0.50 grm. copper. 3. 0.01 , tin and 0.09 grm. copper. 4. 0.01 , tin and 0.05 , copper. 5. 0.01 , tin and 0.03 , copper. In order perfectly to convince myself of the accuracy of this method for the detection of antimony tin and arsenic in the presence of coiisiderable quantities of the other members of this group T have made numerous analyses of solutions in which different proportions of these metals were present and have not as yet met with a case where they escaped detection. Two cases especially have engaged my attention viz. 0.01 grm. antimony 0.50 , copper with 0.10 , tin and 0.24 grm. lead 0.24 , coppm 0.24 , mercury 0.01 , bismuth 0.01 , cadmium 0.01 , antimony 0.24 , arsenic and in the latter I have satisfied myself that no mistake can arise as to the presence of tin from the reactions of the other metals of this group.I have moreover employed this method in analysing various alloys for technical purposes and have never been able to detect any false affirmation or negation of the presence of antimony tin or arsenic. Incidentally to this investigation I often observed that considcr- able quantities of cadmium escaped detection ; on examining into the cause of this disappearance of the cadmium I found that when tin was present a large proportion of cadmium might be left undis- solved when the sulphicles insoluble in sulphide of ammonium were treated with dilute nitric acid (a niixture of 1 volume of ordinary concentrated iiitric acid and 2 volumes of water).In the solution containing 02-4gm. 1i:crcury 0.24 , lead 0*24 , copper and 0.01 , cadmium the cadixiurn was very easily found in the solution of the sulphides in dilute nitric acid. When 0.01 grm. tin however was added to the above solution thc cadmium could not be detected in the nitric solution. I found that the cadmium was always detected when the residue left by nitric acid was incinerated and fused with cyanide of potas- sium in the process for the detection of tin. During the fusion with cyanide of potassium a red-brown sublimate of oxide of cadmium was formed on the lid of the crucible; this sublimate was dissolved in hydrochloric acid and the solution mixed with strong solution of hydrosulphuric acid when a fine yellow precipitate of sulphide of caclniium was obtained.I mention this circumstance with regard to the cadmium because it seems to me probable that the (at present) iinaccountable disappearance of some of the other members of this group of sulphides may hereafter be traced to some similar cause and that analysts will be induced rather to rely upon special tests in a particular search after individlxal metals regarding the general course of analysis merely as affording a systematic method of ascer-taining what substances enter largely into the composition of the matter under examination. I hope to be enabled at some future time to continue this investigation in order either to assure myself of the efficiency of the method which is at present generally followed in the analysis of the precipitate produced in acid solutions by sulphuretted hydrogen or to point out where the cliffculties are to be expected and how they may bc overcome.These experiments were conducted in the laboratories of the Royal College of Chemistry ; and it gives me great pleasure to express my sincere thanks to Professor Hofinann for the kind advice and assistance which I have received froin him during their progress. I subjoin in a tabular form the method which I now adopt for the detection of tin antimony and arsenic in the precipitate pro- duced by sulphuretted hydrogen in a solution previously acidulated with hydrochloric acid.MR. BLOXAM ON THE DETECTION OF TIN $C. The precipitate is well washed and boiled for some minutes with yellow sulphide of ammonium. -----L-----T The solution is acidulated with hydrochloric acid and mixed with some strong hydrosulphuric acid. The precipitated sulphides are washed and digested at a gentle heat with a saturated solu- The residue is collected The solution is exam tion of sesquicbarbonate of ammonia for about on a filter dried and in- ined as usual. half an hour and filtered. cinerated j the ash fused with cyanide of potassium j The residue is washed The solution is acidu- the fused mass boiled with with solution of sesqni-lated with dilute hydro- water; the reduced metal carbonate of ammonia chloric acid a little hy- heated to boiling with till the washings give no drosulphuric acid added concentrated hydrochlo-considerable yellow pre- and the resulting preci- ric acid ;and the solution cipitate with hydrochlo- pitate washed and di- diluted with water fil-ric acid and dissolved vided into two parts.tered and tested with pro- off the filter in hot hy- r-* -T tochloride of mercury. A drochloric acid with a One part is The re-white or grey precipitate little nitric acid. The so-dried and de- mainder of (according to the quan- lution is mixed with ex- flagrated the precipi-tity of tin) indicates the cess ofsesquicarbonate of (with the fil-tate is dis-presence of t in. ammonia and boiled for ter if neces- solved off the two or three minutes sary) with filter in warm nitrate of ammonia; The preci- The solu- potash the the solution ,itate is tion isslight.fused mass evaporated gashed with ly acidulated boiled with to drynesson I little ses-with hydro-water; and awater-bath; picarbonate chlotic acid the aqueous and the resi- 3f ammonia and sulphur- solution aci- due tested lried and etted hydro- dulated with for arsenic incinerated gen passed dilute nitric according to .he ash fused through it. acid. A white the method nith cyanide If the preci- precipitate of Frese-ifpotassium; pitate has a will indicate nius and .he fused pure orange the presence Babo. nass boiled colour the of tin which vith water; presence of may be con- ,he reduced antimony firmed netal allow- may be in-drying ti ?d to Sub-ferred ; but precipitate ride ; the in any other upon a filter ; queous so-case the incinerating ution de-precipitate the latter; :anted ; the should beeol- fusing the netal heated lected on a fil- ashes with :o boiling ter; washed ; cyanide of with concen- boiled with potassium ; irated hydro- concentrated washing the :hloric acid; ammonia; a reduced me-:he solution few bubbles tal ;and boil.Muted with of sulphuret- ing with hy- water and ted hydrogen drochloric tested with passed; and acid. Thehy. protochlo-the solution drochloric ride of mer-filtered. The solution may cury. White filtrate is then be test-or grey pre- acidulated ed with pro. cipitate ; with hydro. tochloride 01 presence of chloric acid mercury. tin. and sulphu- retted hydro- gen passed.Orange pre- cipitate indi- cates anti-mony.

ISSN:1743-6893    

DOI:10.1039/QJ8530500104

出版商:RSC    

年代:1853

数据来源: RSC

摘要:

M. CHARLES GERH$RDT ON ORGANIC ACIDS. X,-Researches on the Constitution of Organic Acids. BY 34. CHARLESGERHARDT. COMMUNICATED BY DR. WI L LI AM S0N. The experiments which I am about to lay before the Society are intended as the Commencement of a series of researches undertaken with a view to find a general expression for the molecular consti- tution of organic acids; or rather to explain the properties of double decomposition belonging to this class of compounds. I endeavoured to connect organic acids numerous and various as they are by a general formula which would be for them what the formula of am-monia is for the organic alkalies; in a word I sought among the compounds of mineral chemistry for a body which is reproduced by simple substitutions of one or other of its elements as ammonia is repoduced from the organic alkalies by substitution of the groups methyl ethyl phenyl &c.by one two or three atoms of hydrogen. This term of comparison this body typical of acids 1 believe I have found. For the understanding of my experiments it is necessary to name this body at once. It is water in the molecule of which I assume one atom of oxygen and two atoms of hydrogen two atoms which may be replaced by simple metals or by complex groups like methyl ethyl &c. The results obtained a short time ago on this subject by Dr. Willianieon in England and by M. Chancel in France art well known. These chemists have indeed proved that alcohol common ether and their homologues represent molecules of water in which the two atoms of hydrogen are partly or wholly replaced by complex groups; so that common alcohol represents water in which half the hydrogen is replaced by the group ethyl (C H,=Et) Et H }07 whilst common ether represents the same molccute of water in which the two atoms of hydrogen are so replaced According to this thcory now almost universally adopted the 128 M.C'HARLES GERIIARDT compound formed by replacing one atom of hydrogen iii alcohol by potassium is to be considered as watcr ill which the two atom of hydrogen are replaced one by ethyl the other by potassium Et K }'* It may be called potassic ethylate that is the potassium-salt of an acid which is nothing else than common alcohol a weak acid evidently for water decomposes its salt into alcohol and caustic potash.In like manner coixmon ether is the ethyl-salt of this ethylic acid. The starting point for my experiments was supplied by this analogy together with the fact that ethylic acid gives rise to a chloride (hy- drochloric ether or chloride of ethyl) when acted upon by pentachloridc of phosphorus; and that according to 34. Cahours' experiments various organic acids such as benzoic nitrobcnzoic cuminic anisic and cinnamic experience an exactly similar change by the influence of the same reagent. As potassic ethylate in reacting on ethylic chloride forms potassic chloride and ethylic ethylate that is common ether (the experiment is well knownj I sought with the chloride of one of the above- mentioned acids and the potassium- or sodium-salt of the same acid to obtain a body corresponding to common ether; in other words I sought to obtain the anhydrous acid as ether itself is nothing but alcohol minus water.With sodic benzoate and benzoic chloride the experiment suc-ceeds perfectly well. The soda-salt should be dried and mixed with an equivalent weight of the cllloride; the mixture is then heated to 130' C. in a sand-bath at which temperature a limpid solution is formed which decomposes with deposition of chloride of sodium when heated a few degrees higher. The action is then complete not a trace of gas is evolved and the fearful smell of the benzoic chloride entirely disappears. The product suspended in cold water and washed with carbonate of soda lcaves a white substance without odour and perfectly colourless which analysis shows to be anhy- drous benzoic acid c,* HI0 03 that is to say benzoic benzoate; for it is to benzoic acid what ether is to alcohol and if benzoic acid is representcd similarly to alcohol as water in which one atom of hydrogen is replaced by thc group benzoyl C H 0=Bz ORGANIC ACIDS.then my new substance is water in which the two atoms are sirnilarly rcplaced E:} Q* The following are the properties of this anhydrous benzoic acid. It is obtained in the form of beautiful oblique prisms which melt at 33OC.; they are volatile without decomposition insoluble in water soluble in alcohol and ether; these solutions are perfectly neutral.When dissolved in hot alcohol the acid is deposited on cooling in the form of an oil which remains a long time without solidifying ;the same thing occurs when the substance is distilled; in which case it sometimes remains liquid for several hours. Cold water has no action upon it; but boiling watcr traiisforms it little by little into common benzoic acid. The same transformation is effected in a few moments by boiling ammonia. Alcohol itself transforms anhydrous benzoic acid in the course of time into benzoic ether; the group benzoyl is then replaced by the group ethyl. Having succeeded so well with the chloride of benzoyl and benzoate of soda I made similar experiments with other chlorides and other salts. I did not of course limit myself to cases of the action of chlorides upon salts of the same acid; but took the chloride of benzoyl and successively salicylate cuminate cinnamate and acetate of potash.Benzoic salicylate cuminate and cinnamate were thus formed. These products are for the most part very fusible solid bodies or oils heavier than water without smell and are rapidly decomposed by the alkalies in a similar manner to benzoic acid with alkalies. Several of them arc not volatile without decomposition ; thus the benzoic salicylate when distilled in a moist state decomposes into salicylic acid and a neutral body fusible at 72' C. which is the true benzoyl,* isomeric with the benzoyl of M. Laurent * There can be no doubt that this substance is identical with the compound discovered by Ettling among the products of distillation of be:izoate of copper which was subse- quently analysed by Dr.Stenhouse who gives the same formula namely c, 13 0,. Stenhouse states that the fusing-point of this substan e is 700 and that it yields benzoate of potassa when heated with solid hydrate of potassa hydrogen being evolved. The compound CM H 03 obtained by E ttling among the products of distillatioil of salicylite of copper and described by him by the name of parasalicyt has the same composition as M. Gerhardt's benzoic benzopl but differs from it in its properties fusing as it does at 127" and being as it appears only slightly acted upon by potassa. Probably this substance stands to benzoic benzoyl in the same relation as salicylous acid to benzoic acid.-A.W. H. VOL. V.-NO. XVIII. K C, H, 0,= BZBz that is to say it is to hydrogen H, what hydrated benzoic acid and anhydrous benzoic acid are to water. Hydrate of potash in a state of fusion converts it into benzoate with evolution of hydrogen. I will limit myself for the moment to this summary announcement of my experiments and propose following them out with all the care which the subject requires. Lf a general conclusion niay now be drawn from these results I would say that they destroy the liind of privilege hitherto enjoyed by a small number of bodies known by the generic name of alcohols of being susceptible of joining other organic bodies. Alcohols and hy- drated acids are evidently bodies of the same kind.Philosophically alcohols acids ethers salts and anhydrous acids may be reduced to the same generic formula-to the formula of miter in mhich 1 or 2 atoms of hydrogen are replaced eithcr by simple metals or by hydro- carburetted groups (methyl ethyl phenyl &c.) or else by oxygenated groups (benzoyl cuminyl acetyl &c.) I have now succceded in preparing anhydrous acetic acid in a state of perfect purity and giving by analysis numbers exactly agreeing with those calculated from its formula. The following is the method of preparing it Acetate of potash is fused so as to expel all water of crystallization and is then mixed in a small retort with about half its weight of bcnzoic chloride. On the application of a gentle heat the reactioii speedily occurs-benzoic acetate being no doubt formed at first.But the reaction does not stop there. A limpid body distils over with a very powerful smell reminding of acetic acid and flowers of ic acebessine.” On rectification this liquid boils constantly at 137O C.; it falls to the bottom in water and does not mix with it at once but only after continued agitation. Hot water dissolves it at once with production of acetic acid. The fol- lowing figures show the result of combustion Analysis. Calculation. Carbon . . 46-87’. 47.05 Hydrogen. . 5-95 5-88 It is therefore C,H603 or rather $$$. O* This anhydrous acetic acid evolves great heat on mixture with dry * A similar view regarding the constitution of acetic acid has been proposed by Professor Williamson,-Ch.Soc. Qu. J.-EDs. MR BRUCE ON CARBONATE OF AMYL aniline; the mixture solidifies entirely on cooling. If an excess of aniline is avoided only one body is produced crystallizing in beau- tiful nacreous plates. This body is shown by analysis to be acet- aniline. It is remarkable that no salt of aniline is formed at the same time. We must therefore consider the action as consisting of a double decomposition between the aniline and the anhydrous acid ; thus forms We must I think consider amides and anilides as ammonia in which more or less hydrogen is replaced. I am now engaged in the inves- tigation of this point. Amidogen-acids would correspond to hydrated oxide of ammo-nium.

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DOI:10.1039/QJ8530500127

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年代:1853

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MR BRUCE ON CARBONATE OF AMYL XI.-Note on the Preparation of Carbonate of Amyl. BY JOHNA. BRUCE OF THE ROYAL COLLEGE OF CHEMISTRY LONDON. Carbonate of arnyl has been lately examined by Mr. Medlock whose experiments have been described to the Chemical Society.* He obtained this compound by a method which had not yet been used for the preparation of carbonic ethers namely by the action of phosgene gas upon fusel-oil and subsequent decomposition of the chlorocar- bonate formed under the influence of heat in the presence of water. The process which originally had furnished the carbonate of the ethyl- series and which consists in distilling the oxalate with potassium has never been applied to the aniyl-series. The reaction of potassium upon the ether-oxalates being still but * Chem.SOC. Qu. J. I 368. K2 AIR. BRUCE ON CARBONATE OF ABIYL. imperfectly understood Dr. Hofmann requested me to repeat the experiment with oxalate of amyl in order to obtain some additional data for a more correct interpretation of the phenomena attending the decomposition. Potassium when coming in contact with perfectly dry oxalate of arnyl is rapidly attacked the liquid becomes warm and a brown mass forms around the metallic globules whilst a colourless infiam- rnable gas is disengaged. The reaction however soon slackens and only commences again on heating the liquid. On distilling the fluid a brown residue was obtained consisting chiefly of carbonate of potash and charcoal while a pale-yellow distillate passed over; this liquid when rectified with a thermometer was found to consist of not less than four different substances.It began to boil at 130' C. (266' F.) at which temperature chiefly fusel-alcohol distilled ; the boiling-point then rapidly rose to about 225' C. (433.4 F.) when it became stationary for a very considerable time indeed until three-fourths of the whole had passed over. The liquid distilling at this temperature was pure carbonate of amyl as proved by the analyses hereafter to be detailed. The mercury then again rose until the temperature was 260' C. (500' F.) when it became once more stationary but only for a short period evidently because a small portion of undecomposed oxalate of amyl which boils at this temperature -was_ still present in the liquid.After this had been evaporated a viscous somewhat dark residue having a very powerful odour remained in the retort. The portion which had been collected between 223' and 226' C. (433.4' and 438.8 F.) was repeatedly redistilled until a liquid of a constant boiling-point at 226' C. (438.8 F.) was obtained which at 15.5' C. (60' F.) had a sp. gr. of 0.9065 When submitted to combustion it gave the following results I. 1.91 grains of substance gave 4.60 , , carbonic acid and 1.95 , water. y IT. 2.05 , , substance gave 4.90 , , carbonic acid and 2.10 , , water. Percentage-composition I. 11. Carbon. . . 65-68 65.12 Hydrogen . 11.30 11.31 MR. H. GERLAND ON SALICYLIC ACID. These numbers agree pretty closely with the formula as may be seen in the following comparison of the theoretical numbers with the results of the experiments Theory.Mean of the Experiments. -11 eqs. Carbon . . 66 65-34! 65.40 11 , Hydrogen . 11 10.89 11.35 3 , Oxygen . . 24 23-77 --c_____ 101 100*00 Carbonate of amyl may be produced by the action of potassium or sodium (the latter metal was indeed employed in most of my experiments) upon oxalate of amyl with great facility and to any extent; its preparation in this reaction is not attended with the same difficulties which we experience in performing the experiment in the ethyl-series. The actual process however which gives rise to its formation remains still doubtful although the preceding experiments have furnished a new element for its correct interpretation namely the observation of a large quantity of arnyl-alcohol being reproduced during the reaction-a reproduction which has escaped notice in the preparation of the carbonic ether par mceltence on account of the solubility of the ethyl-alcohol in water

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DOI:10.1039/QJ8530500131

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年代:1853

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133 MR. H. GERLAND ON SALICYLIC ACID. XIL-New Formation of Salicylic Acid. BY H. GERLAND. FROM A LETTER OF DR. KOLRE TO DR. HOFMANN. Mr. Gerland has been lately engaged in my laboratory with a comparative investigation of the three isomeric acids namely Zinin’s benzamic acid Fritzsche’s anthranilic acid and Chancel’s carbanilic acid induced chiefly by the frequently asserted view of these acids being identical According to certain theoretical views which I have already MB. EI. GERLAND ON SALICYLIC ACID. stated,* I considered myself justified in doubting the identity of benzamic with anthranilic acid it being more probable however that anthranilic acid is identical with carbanilic acid and that it stands in the same relation to carbonic acid as carbamic acid.This assump- tion is based upon the view that benzoic acid is an oxide of the conjugate benzoyl-radical (C12 H,)"C, namely HO (C12H,)-C 0, that nitrobenzoic acid HO (C, NO -CZ 0 contains a secondary (H. ) benzoyl-radical in which NO replaces H; and that the nitro- benzoyl of nitrobenzoic acid is converted by treatment of the latter with sulphide of ammonium into amido-benzoyl of the formula Benzoic acid . . HO (C12 H )T, 0 Nitrobenzoic acid HO (C, {;b,)-C, 0 Benzamic acid (Amido-benzoic acid) Ho ('12{ According to this view benzamic acid would be benzoic acid with 1 equivalent of hydrogen in its radical replaced by 1equivalent of aniidogen while the isomeric anthranilic acid has the chemical constitution of carbamic acid and is only distinguished from the latter by containing anilidogen instead of amidogen.The experiments performed by Mr. Gerland which he will shortly communicate in detail have proved that benzamic and an- thranilic acid are in fact distinct acids and that they not only differ materially in their chemical properties but also yield under similar influences perfectly different (sometimes very interesting) products of decomposition. * Chem SOC. Qu. J. IV 73. '3.z:N)nc2~ MR. H. GERLBND ON SALICYLIC ACID. While anthranilic acid is always deposited from the hot aqueous solution in needles sometimes an inch in length benzamic acid can only be obtained from its hot saturated aqueous solution as an indis- tinctly crystalline mass.The salts of the two acids exhibit much similarity in appearance; those of benzamic acid are however genc- rally speaking much more soluble than the corresponding salts of anthranilic acid. The difference of the two acids is rnost clearly shown in their comportment with potash sulphuric and nitrous acid. Anthranilate of potash when heated with hydrate of potash yields aniline; the benzamate does not yield a trace of this body. While strong sulphuric acid converts anthranilic acid into sulpha- nilic acid with evolution of carbonic acid gas; benzamic acid on the other hand dissolves in it without evolution of gas forming a violet solution. If nitrous acid (prepamd by acting on arsenious acid with nitric acid) is passed through a dilute warm aqueous solution of anthranilic acid till no more nitrogen is evolved it remains clear and yields on evaporation fine long needles of an acid free from nitrogen and possessing the composition and properties of salicylic acid.With salts of sesquioxide of iron it yields the characteristic violet colour produced by salicylic acid under the same circumstances and on dry distillation a considerable quantity of phenol is pro-duced a portion of the acid subliming unchanged. The conversion of anthranilic acid into salicylic acid by means of nitrous acid which you anticipated in your paper* on the action of nitrous acid on the amidogen-bases takes place according to the following equation : -130 t C, H NO,+NO,=HO. C1 €35 O,+ HO $2 lV* u Anthranilic acid.Salicylic acid. A dilute aqueous solution of benzamic acid also undergoes a change when exposed to the action of nitrous acid; not a trace of salicylic acid is however formed. An alcoholic solution of benzamic acid through which nitrous acid is passed becomes red then turbid and deposits a red crystalline body insoluble in water and alcohol but readily dissolved by ammonia and potash which Mr. Gerlaiid is at present examining. If benzarnic acid retains the constitution of benzoic acid (i. e. if it 4 Chctn. SOC. Qti. J. 111 235. MR. ROBERT VI ARINGTON’S is amido-benzoic acid) it is probable that a benzoic acid would be obtained by its decomposition with nitrous acid in which one equiva- lent of hydrogen in the radical is replaced by one equivalent of oxygen namely HO,(C, { :4)-~, 0,. The results of all experiments which have at present been con-ducted in this direction would appear to favour this view.

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DOI:10.1039/QJ8530500133

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年代:1853

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MR. ROBERT VI ARINGTON’S XII1.-Chemical Memoranda. BY ROBERT WARINGTON. In laying the present short notices before the Chemical Society I do it with the impression that the example may be useful as a means of registering a great number of very interesting and sometimes important facts and observations which taken in their isolated state would not afford sufficient matter for their being’arranged in the form of a paper and therefore are generally laid aside and frequently altogether lost to science; whereas if they were collected and arrauged as a series of memoranda they would serve to occupy profit- ably a few pages of our Transactions with useful practical obser- vations and give rise at the meetings of the Society to much valuable discussion. Under this impression thwefore I have made bold to endeavour to pioneer the way in a path which I hope to see followed by many of our working members.The first memorandum Ishall submit to your attention is On a curiousform of Crystallization of Iodide of Potassium. In the preparation of this salt on the large scale crystals are at times obtained presenting a very curious appearance namely that of a cubic needle or prism of considerable length and of varying diameter and apparently formed by the superposition of cube uport cube. The specimens to which I would more particularly direct your attention Rere procured some years since and have become much injured and fractured ; but sufficient of thein remains to demonstrate fully the following details of measurement.Two only of these cryscals were selected for this purpose; but I may mention that many similar ones were obtained at the same time as these. The first specimen had a total length of 4-40inches which was composed of the following divisions CHEMICAL MEMORANDA. At its point of attachment to the general mass of salt its diameter was & of an inch which continued for +$ of an inch ;it then 85 decreased to Ts5 >> ?, JJ 40 11 , , ,J 3 4 0 , >J 73 40_-33 > ,J 1J ,? -4% PJ ?J 7) 40l6 , where the crystal terminated. =4-40 inches. The second specimen was found to give the following measure- incnts Its entire length was 22x of an inch and the diameter of the cubic needle at its junction with the rest of the crop was & of an inch which continued for -:+ of' an inch; it then 95 I9 decreased to & 3 JJ ,> _I 4 -40 , 48 , ,> 4 0 3 J 9 40 ,> -Total length .. . g-=Z-& inches. It will be evident therefore that these crystals exhibit certain distinct and strongly marked intervals of decrease in their stages of progression ; and this decrease in the diameter of the cube is sudden and abrupt forming at that point sharp and well-defined angles and not passing gradually from one dimension into the other as it elongates. It will be noticed also in looking over the measurements that a perfectly symmetrical cubic arrangement is maintained throughout their whole extent and that the intervals of length corre- spond exactly to a niultiple of the diameters of the cubes.These crystals are most frequently obtained when the solutions from which they are deposited are rather alkaline. MEMORANDUM II. On a method of detecting qualitatively small quantities of Oxide OJ Copper kn solution. This operation depends upon the solubility of the ferrocyanide of copper in an excess of a solution of ammonia and its deposition with its well-marked characteristic appearances as the ammonia evaporates. Thus supposing a frequently occurring case where the oxide of copper in very small quantity is in solution with oxide of iron and that these rnetslls havc beibn brought to their highest state of MR. ROBERT WA~~INGTOX’S oxidation; ammonia is next added in excess and then a few drops of a solution of the fcrrocyanide of potassium and thc whole thrown upon a filter.As the aminonia cscapes from the filtrate by standing and free exposure to the air the red ferrocyanide of copper will be deposited and if the cxperirncnt be madc in a shallow white porcelain dish the result will be very distinct and characteristic and on carefully decanting the fluid mill be found on the white surface. In many cases the process of filtration may be dispensed with alto- gether as the suspended peroxide of iron does not in the lcast iuterfere with the deposition of the ferrocyanide of copper from the solution. I have found this test give unerring indications in cases where no trace of blue colour could be distinguished in the amiiioniacal so-lutiod and where no precipitation could be procured by hydrosulphuric acid gas or the action of a voltaic circuit When organic colouring matter is present this form of test is also very useful as in vinegars &c.and it mas in a case of this kind which came under my notice some years since that I was induced to put it more fully into practice. A party was seeking to recover comFensation for the destruction of some valuable meadow- lands from the action it was affirmed of the waste waters from some copper mines. These meadows owed their luxuriance and consequent value to a periodic inundation by the water from the granite moors of that part of Cornmall. Several copper mines had however been opened on these high lands; and from the scarcity of water it was retained at the mines for some time being used over and over again for stamping and dressing the ores until it became as a natural consequence highly charged with iiietallic impurities.In this state it was at certain intervals of time discharged in large quantities down the valley overflowing the banks of the stream and causing the destruction coniplained of. The great object in a chemical point of view was to trace the cause of the injury into the substance of the injured herbage the dead grass; and this I found could be readily and satisfactorily accomplished by means of the test no117 indicated. Our late respected President Mr. Phillips to whom I mentioned this mode of testing some years since introduced it iiito his trans- lation of the London l’harmacopeia.139 CHEMICAL MEMOltANDA. MEMORANDUM 111. Some additional observations on the Green Teas of commerce. Since the publication of my last communication on this subject read before the Society on May 19th 1851 a series of microscopical and chemical examinations have been published* which have induced me to institute some additional experiments the results of which may not be without interest to some of the members of the Society particularly as they tend to remove a curious anomaly that has lately arisen. In the series of examinations alluded to it is stated that several of the specimens of green tea submitted to investigation were coloured with indigo mixed with porcelain clay; and this is followed by an examination of some of the colouring materials themselves used at Canton for this purpose and which had been obtained from the museum at Kew Gardens.As I had stated? that up to that period no sample in which indigo had been employed as an artificial colouring agent for green teas had come under my notice I felt it incunibent on me to investigate the matter. For this purpose I applied to Sir W. Hooker on the subject and he allowed me in the handsomest manner to take from the cases in the museum small portions of the materials for examination and also favoured me with the loan of the manuscript JoQrnal of Mr. Berthold Seeman by whom the specimens had been collected while at Canton as Naturalist of H.M. ship Herald,' then on a survey in that quarter of the globe.As these documents have been since published and as the subject opens some interesting particulars I have taken the liberty of appending his account in his own words.$ Mr. Seenian here dis- * The Lancet August 9th 1851. -f-Qu. J. Chem. SOC. IV p. 156. $ Hooker's Journal of Botany and Kew Garden Miscellany No. 37 for Jan. 1852 ''In the 'Manual of Scientific Inquiry' you ask whether in the northern provinces of China indigo or any other vegetable dye is used in colouring green tea? Whether different processes of dyeing are pursued in the north from those of the south I cannot say but it is certain that around Canton whence great quantities are annually exported the green tea is dyed with Prussian blue turmeric and gypsum all reduced into fine powder.The process is well described by Sir J. F. Davis (' The Chinese,' III 244) who however falls into the strange mistake of supposing the whole proceeding of colonring to be an adulteration and leaves his readers to infer that it is only occasionally done in order to meet the emergency of the demand ; while it is now very well known that all the green tea of Canton has assumed that colour by artificial dyeing. I had heaid so iiiuch abont tea copper-plates pickinq of the leaves tolling them up with the fingeis boiling them in hot uatcr &c that I became aii\ioiis to sce with my own eyes MR ROBEXT WARINQTON’S tinctly states that around Canton the green tea is dyed with Przcssian blue turmeric and gypsum ;that in the manufacture he inspected the dyes above mentioned were added; and he gives their proportions.That there was no concealment or mysterious pro-ceeding ;that one of the great merchants conducted him over his own and also another manufactory and that everything was conducted openly and exhibited with great civility. And yet strange to say &ir,Seeman appears to have been deceived notwithstanding all this ; for on submitting these materials to the action of chemical tests there could be no doubt that they consisted of indigo of a very inferior quality and leaving a very large proportion of inorganic matter by calcination and of porcelain clay. It is also curious that the very case selected by Mr. Seeman to illustrate the processes is the con- version by means of this facing or glaze of a low quality of black tea (Bohea Saushung) valued at about 4d.to 6d. the pound into high quality green teas valued at from 1s. to is. 6d. the pound; but although Mr. Seemau. does not allow this to be an adulteration yet surely he cannot deny that it is a fraud. Another very good method which I have lately employed of removing the colouring matter from the surface of green teas for the purpose of microscopical investigation and one attended with very little trouble is to take a piece of cream-coloured wove paper or the process of manufacture of which the various books had given me such a confused idea. One of the great merchants coiiducted me not only to his own but also to another establishment where the preparation of the different sorts was going forward.There was no concealment or mysterious proceeding everything was conducted openly and exhibited with the greatest chility; indeed from all I saw in the country I am almost inclined to conclude that either the Chinese have greatly altered or their wish to conceal and mystify everything of which so much has been said never existed. ‘‘ The tea is brought to Canton unprepared. After its arrival it is first subjected to cleaning. Women and children are employed to pick out the pieces of twigs seeds and other impurities with which it happens to be intermixed. The only sorts which may be called natural are those gathered at different seasons ; the rest are prepared by artificial means. ‘4 Without entering into a description of all these prccesses it may suffice to take one as an example.A quantity of Botiea Saushung m-as thrown into a spherical iron pan kept hot by means of a fire beneath. These leaves were constantly stirred about until they became thoroughly heated when the dyes above mentioned were added viz. to about twenty pounds of tea one spoonful of gypsum one of turmeric and two or e’en three of Prussian blue. The leaves instantly changed into a bluish-green and having been stirred for a few minutes were taken out. They of course had shrivelled and assumed different shapes from the heat. The different kinds were produced by sifting. The small longish leaves fell through the first seive and formed Young Hyson while those which had a roundish granular shape fell through last and constituted Choo-cha or Gunpowder.” CHEMICAL MEMORANDA.paper free from blue colouring material and having breathed on its surface or rendered it slightly danip to pour the sample of tea uuder examination from the containing paper or vessel upon it. On then removing it back again a quantity of the facing powder will be found adhering to the surface of the paper; and on placing it under the microscope it will be found studded with the colouring materials used and the blue particles can be subjected to the action of chemical tests with the greatest ease by placing a minute drop of the reagent on the granules with the end of a small stirring rod or slip of glass and noting the effect. MERlORANDUM IV. A modijcation of the ordinary process of sublimation in u straight tube.In examining the blue colouring material used for green tea taken from the Kew Museum so as to demonstrate its being indigo I was led to try a modified arrangement in the ordinary method of using the straight tube for sublimation. It consists simply in introducing the material to be examined into a small capillary tube of such an external dimension that it can be easily passed into the interior of another tube which should be of hard white glass. By this means the substance can be placed over whatever part of the external tube the operator may desire at the same time avoiding any risk of soiling the part of the external tube on which the sublimate is to be condensed and with the power of withdrawing the material at any time for the removal of condensed moisture or only matter as also of shifting its position during the operation.The experiment being completed the internal tube is withdrawn and both the fixed residue and the volatile constituents can be readily submitted to chemical agents or put by for future investigation. I have since employed this arrangement in various other cases as in the detection of arsenic and corrosive sublimate in cases of poisoning with complete success.

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DOI:10.1039/QJ8530500136

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年代:1853

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142 PUIR. M. W. JOHNSON ON THE ACTION OF AMMONIA XIV.-On the Action of Ammonia upon BinoxyszcI~~hocarhonateof Amyl. BY MATTHEWW. JOHNSON ASSISTANT IN THE LABORATORY OF ST. BARTHOLOMEW’S HOSPITAL. Chemists are acquainted with the singular compound which M. Desains obtained by the action of iodine upon xanthate of potash and described under the somewhat lengthy name of binoxy- sulphocarbonate of ethyl. They likewise recollect the experiments of M. Debus who submitted this compound to the action of am- monia in order to obtain if possible a more definite view regarding its constitution which is still open to discussion. These experiments led to the discovery of a new substance which M. Debus terms xanthamide and which is formed in this reaction together with xanthate of ammonia.The corresponding term in the amyl-series being still unknown Dr. Hofniann suggested to me the preparation and study of this substance while at the Royal College of Chemistry in the laboratory of which Institution the experiments about to be described were carried out In preparing binoxysulphocarbonate of amyl D esains’ process slightly modified was successfully employed. To hydrate of potash crushed to a coarse powder in a mortar fusel-oil and excess of anhy-drous bisulphide of carbon are added and the mixture triturated until a soft yellow niass results. A small quantity of a red oily liquid is generally found disseminated through it. Amyfoxanthate of potash thus prepared is placed in a flask with bisulphide of carbon sufficient in quantity to convert it into a very thin paste.Iodine is then introduced which is immediately deco- lorized with evolution of heat. On agitation a grey mixture is formed consisting of roundish granules of iodide of potassium and a yellow mobile liquid. The whole thrown on a filter and washed with bisulphide of carbon yields a filtrate which on distilling off the bisulphide of carbon leaves the ~inoxysulphocarbonate of amyl a yellow oily liquid which is thus prepared in considerable quantity with the greatest ease and sufficiently pure. This compound was treated with ammonia in order to obtain the substance corresponding to &I. Debus’s xanthamide. The plan which first suggested itself was to pass dry ainmoniacal gas through an alcoholic solution of the substmce and to separate the amide from the ammoniacal salt simultaneously generated by evaporating UPON UI~OXYSULPHOC-~1~UONATE OF ABIYL.143 to dryness and exhausting by means of ether a mode of separation quite successful with regard to xanthamide. This method however failed from the fact that the new compound produced in this re- action which I shall designate by the term Xa~~~a~~Z~~~~~e, is only slightly more soluble in ether than the accompanying ammonia-salt which as proved by subsequent analysis was amyloxanthate .of am-monia. The process finally adopted was to digest the binoxysulpho- carbonate of amyl with a concentrated aqueous solution of ammonia at a slightly elevated temperature In the course of a few minutes the mixture becomes turbid sulphur is deposited and a yellow liquid through which oily particles are seen suspended floats above.Four or five hours suffice to accomplish the reaction. When 1 part by bulk of binoxysulphocarbonate of arnyl is treated with 3 parts of ammonia a semi-solid mass results. This mass diluted with vc-ater and thrown upon a moistened filter affords a clear yellow filtrate mixed with a few oily globules which however on refiltration are completely separated. The oily liquid retained by the filter is now to be well washed with water which dissolves the amyloxanthate of am-monia leaving behind the xanthamylamide with the sulphur. This miwture which has completely separated from amyloxanthate of arn-monia is freed as much as possible from water and passed through a dry filter which retains the sulphur.A transparent pale-yellow oily liquid is now obtained which for the purpose of desiccation is placed in vacuo over sulphuric acid for some time and finally a current of dry carbonic acid gas is passed through the liquid a gentle heat being at the same time applied. The xantham ylamide thus prepared was analysed The numbers obtained were however 0111 y approximative because the substance could not be freed entirely from impurities the method of pre-paring not excluding small quantities of fuse1 oil and even water purification by distillation being impossible because the com-pound is decomposed under the influence of heat. The substance was analysed in the ordinary manner with chromate of lead a binoxide of lead tube being used between the chloride of calcium tube and the potash bulbs to retain any sulphurous acid.The sulphur was determined by ignition in a combustion tube with a mixture of carbonate of soda nitrate of potash and chlorate of potash. The following results were obtained 1. 0.1920 grm. of substance yielded 0,3460 , ,,carbonic acid 0*1781 , ,,water. 144 MR. M. W. JOHNSON OK THE ACTTON OF AMMONIA 11. 0.2290 grm. of substance gave 0.4150 , , carbonic acid 0.2025 , , water. 111. 0.2520 , , substance gave 0.3889 , , sulphate of baryta. IV. 0.2825 , , substance gave 0.4259 , , sulphate of baryta. These numbers lead to the following percentages I. 11. 111. IV. Carbon .49.11 49.38 - - Hydrogen 10.27 9-82 c_ - Sulphur. - - 21.15 20.67 The formula c,,HI NO2 s2 constructed from analogy requires the following values Theory. Mean of Experiments. & 12 eqs. Carbon . . 72 . 48.98 49.24 13 , Hydrogen 13 . 8.85 10.04 I_ 1 , Nitrogen . 14 . 9.52 2 , Oxygen . . 16 . 10.88 -2 , Sulphur. . 32 . 21.77 20.91 147 1oo*oo All my attempts to distil this compound without at the same timc decomposing it failed. When the temperature rose to 184' C. the liquid boiled oily drops distilled over and a strong smell of amyl-mercaptan was noticed. The distillate dissolved in alcohol gave a copious white precipitate with protochloride of mercury. The dark- grey residue in the retort boiled with water and filtered afforded a liquid which evaporated to a small bulk and stirred rapidly depo- sited when cold an adherent granular fawn-coloured precipitate of cyaniiric acid.A small quantity dried and heated in a tube emitted the peculiar suffocating vapour of cyanic acid. This change is represented by the following equation 3 (C12HI NO2 S,) =3 (Clo HI1 S HS) + H C6 N 06 L-?--"-J L-y-J L-y-J Xantham ylamide. Amyl-mercaptan. Hydr Cyanuric acid. When heat is applied to a quantity of the arnide on platinum foil it emits copious white fumes and bizms with a luminous yellow flame UPON BI XOX~JLPII OCARBONATE OF A31 YL. Xanthaniylamide is insoluble in water but very soluble in alcohol and ether. It is neutral to test-paper. It is decomposed when boiled with hydrate of baryta; an oily liquid having the odour of fusel-oil distils over ; ammonia is disengaged at the same time ; and the barytic mixture yields with hydrochloric acid and sesquichloride of iron a deep red liquid indicating the presence of a sulphocyanide.C, HI3NO S + BaO. HO = C, H120 i-Ba . C NS +2 NO LFVP-J L-Y-) Xanthaniylamide. Fusel-oil. The same reaction takes place with potash. Su&huric acid in the cold dissolves it but on dilution the mixture becomes turbid from separation of oily particles. When heat is applied sulphurous acid is evolved and carbonization ensues. Fuming nitric acid acts violently upon it with copious evolution of red fumes; the resulting solution is rendered turbid by dilution and oily globules rise to the top.Concentrated hydrochloric acid does not appear to act upon it even on boiling. Chlorine-water however immediately attacks it giving rise to a volatile oily liquid; sulphur is at the same time deposited. Iodine merely dissolves in xanthamylamide in the cold forming a red liquid which however on the application of heat is quickly decolorised and a colourless oil soluble in alcohol separates. Bromine is immediately decolorised by xanthamylamide a white solid mass resulting which furnishes with alcohol a milky liquid ; water now eliminates a colourless oil. Alcoholic solutions of acetate of lead chloride of copper and nitrate of silver are not precipitated by an alcoholic solution of xanthamylamide. An aqueous solution of bichloride of platinurn however furnishes a copious yellow precipitate having a faint peculiar odour and slightly soluble in alcohol which deposits on evaporation a yellow crystalline compound.The mother-liquid from these crystals quickly becomes brown and on evaporation leaves an amorphous brown residue copious funies of hydrochloric acid being evolved at the same time. When an alcoholic solution of bichloride of platinum is employed instead of an aqueous one perfect solution of the substance results and on evaporation a red crystalline com- pound is deposited. From the filtrate a definite substance can no longer be obtained. Neither potash nor hydrochloric acid appears to affect this platinum-compound. Xanthamylamide forms a perfectly definite compound with proto-chloride of nzercury.When a drop or two of an alcoholic solution of this salt is added to an alcoholic solution of the amide merely a faint turbidness OCCII~S; oil iiicrcasing the proportion of the formcr VOL. V,-NO. XVIII. L 146 MR. M. W. JOHNSON ON THE ACTION OF AMMONIA however until it is present in considerable excess a copious white precipitate falls consisting of minute feathery crystals of the mer- cury-compound; and this when washed with cold alcohol in which it is scarcely soluble and dissolved in a large quantity of boiling alcohol deposits the substance on cooling in a pure state. The pure compound thus obtained was analysed. The carbon was deter- mined by combustion with chromate of lead the binoxide of lead tube being employed in Experiment 111.; in the same experiment the mercury was determined together with the carbon and hydrogen. The mercury was estimated in the other two experiments by decorn- posing the substance with a mixture of quick-lime and dry carbonate of soda in a current of carbonic acid and collecting the mercury in a receptacle formed of the anterior part of the combustion tube. In Experiment V. this operation was combined with the German process for the determination of nitrogen. I. 0.3865 grm. of mercury-compound dried in vacuo gave 0.1565 , , carbonic acid and 0,0675 , , water. 11. 0.4132 , , mercury-compound gave 0*1615 , , carbonic acid and 0°0820 , , water. 111. 0.3898 , , mercury-compound gave 0,1448 , , carbonic acid 0.0720 , , water and 0.2250 , , mercury.IV. 0.3645 , , mercury-compound dried in a water-bath afforded 0.7970 , , mercury. V. 0.7150 , , mercury-compound yielded 0.4160 , , mercury and 1, 0*1700 , bichloride of platinum and ammonium. From these numbers the following percentages are deduced I. Ir. 111. IV. V. Carbon . . 11.02 10.65 10.13 -Hydrogen 1-94 2*2o 2.05 -7 Nitrogen . . --1.48 Mercury . -57-72 58-40 58.18 The simplest atomic expression of these percentages is the for- mula C, Hi NO 8 + 4Hg C1 which require the following values UPON BINOXYSULPHOCARBONATE OF AMYL. 147 -Theory. Mean of Experiments. 1.2 eqs. Carbon . . 72.00 10.45 10.60 13 , Hydrogen . 13.00 1.89 2.06 1 , Nitrogen .14-00 2.03 1-48 2 , Oxygen . 16-00 2.32 - 2 , Sulphur 32.00 4.64 _. 4 , Mercury. 400.28 58.07 58.06 4 , Chlorine . 142.00 20.60 - - 689128 1OO*OO This mercury-compound is insoluble in water ; it gradually decorn- poses however if kept for a considerable period in contact with it an odour of fusel-oil becoming perceptible. It is but slightly soluble in either cold alcohol or ether ; its solubility however is increased on boiling. Cold concentrated sulphuric acid causes an immediate evolution of hydrochloric acid and elevation of temperature at-tended with blackening. Nitric acid acts with energy upon it Cold hydrochloric acid has no effect upon it; but on boiling a portion of the chloride of mercury is dissolved out and another mercury-compound formed containing a smaller amount of the chloride than the original compound; it is a white soft solid sub- stance adhering with great tenacity to the sides of the vessels and when heated melts into a white opaque oil.On boiling the mercury-compound with potash a black precipi- tate is obtained and an odour of fusel-oil becomes perceptible. Concentrated ammonia in the cold immediately decomposes it with formation of black protosulphide of mercury. Baryta likewise decomposes it on boiling with evolution of an aromatic volatile compound protosulphide of mercury remaining behind. An attempt was made to prepare a quantity of pure xanthamyl-amide by decomposing the mercury-compound with hydrosulphuric acid but it proved a failure-an oily liq-aid being obtained which obstinately retained the hydrochloric acid generated in the reaction ; no indication of crystallization was observed.The compound sepa- rated is however doubtless xanthamylarnide. The analysis of the oily product produced by the action of ammonia upon binoxysulphocarbonate of amyl its products of decomposition and the examination of the mercury-compound which I have just now described establish beyond any doubt the existence in the amyl- series of a substance homologous with the xanthamide of the ethyl- L2 148 MR. M. w. JOHNSON ON THE ACTION OF AMMONIA series. The formation of this body is represented by the followil1g equation 2(Clo Hll 2CS 0)+2 H N =C12 H, NO S + L-7-2 L-y-2 Binoxysulphoearbonate Xantham ylamide.of arn31. Amyloxanthate of ammonia. It now remains only to prove by direct experiment that the salt produced together with xanthamylamide is actually amyloxanthate of ammonia. This salt crystallises from an alcoholic or ethereal solution in long colourless prisms which when cautiously heated between two watch-glasses give a beautifully crystallised sublimate. It is gradually decomposed by water ; a cold aqueous solution how-ever niay be obtained which will deposit prismatic crystals on evapo- ration in vacuo; but the presence of a large quantity of water invariably gives rise to an oily liquid-a product of decomposition. When evaporated in the water-bath the salt volatilises with the vapour of water. Exposure to air decomposcs this salt even when dry one of thc products of decomposition being invariably sulpho- cyanide of ammonium.The yellow oil which separates at the same time on being washed with water and dissolved in alcohol does not afford a crystalline compound with bichloride of platinum which suffices to distinguish this substance from xanthamylamide. An attempt to purify the salt by gently heating it in a current of dry air with a view to sublimation proved fruitless; it rapidly decomposed ; white fumes appeared which condensed to colourless and yellow globules ; the yellow colour of the salt deepened in tint ; when suddenly brisk chemical action was set up in the mass attended by copious effervescence and the whole changed at once into a turbid yellow fluid a strong evolution of sulphide of ammonium vapour accompanying the reaction.On dissolving the mass in water a solution containing sulphoeyanide of amnioniuiii was obtained on which drops of fusel-oil floated. Caustic potash added to an aqueous solution of the salt under examination causes the evolution of ainnionia even in the cold and copiously when heated. Hydrochloric acid separates from it a volatile oily acid of a suffocating odour and insoluble in water. Nitrate of silver gives a yellow curdy precipitate; acetate of lead an adhesive yellow semi-solid salt which gradually decomposes and beconies brown. Thcsc observations are sufficient to charactcrize UPOK UISOXYSULPHOCARBONATE OF AILIYL amyloxanthate of ammonia in an unmistakable manner ; nevertheless I thought it desirable to fix by a number the formation of this salt in the decomposition which binoxysulphocarbonate of amyl suffers under the influence of ammonia; and as amyloxanthate of ammonia could not be obtained sufficiently pure for direct estimation I se-lected the lead-salt for analysis.To prepare this compound a con- centrated aqueous solution of the ammonia-salt was mixed with a large quantity of alcohol and added to an alcoholic solution of acetate of lead until a precipitate began to appear; alcohol in excess then afforded a clear solution which on spontaneous evaporation deposited delicate shining .plates of amyloxanthate of lead which were washed with alcohol dried and submitted to analysis 0.2790 grm. of the lead-compound gave 0.1565 , , sulphate of lead corresponding to 38032per cent of lead.Amyloxanthate of lead Pb. C, H, . ZCS 0 requires 38.85per cent of lead. On dissolving amyloxanthate of potasb prepared by the ordinary process in alcohol and adding an alcoholic solution of acetate of lead a salt was obtained having all the properties of the above compound. Incidentally to the preceding investigation a few experi- ments were made with the acid separated by sulphuretted hydrogen from the amyloxanthate of lead. This salt freshly made was quickly washed with cold water suspended in alcohol and treated with hydro- sulphuric acid gas; and the colourless liquid separated by the filter from the sulphide of lead was warmed until the free sulphuretted hy- drogen was dissipated.It then possessed an acid reaction which chloride of barium showed was not owing to sulphuric acid as it gave no precipitate. It gave a yellowish-white crystalline precipitate however with an alcoholic solution of acetate of lead and potash gave rise to the crystalline potash-salt. Evaporation left a liquid highly acid to test-pa.per and farther evaporation caused the evolution of white suffocating fumes. According to a statement of M. Chancel,* the distillation of a mixture of xanthate of potash and sulpbomethylate of potash gives * Comptes Rendus April 21st 1851. 150 MR. Bf. W. JOHNSON ON THE ACTION OF ABLMONIA &C. rise to a compound which he terms sulphocarbonate of ethyl and methyl and which under the influence of ammonia is converted into semi-sulphurettcd urethane or xanthaniide and methyl-mercaptan This statement induced me to institute a few experiments with a view to procure xantharnyltlmide by analogous means.For this purpose I prepared the sulphocarbonatc of amyl and ethyl by distilling a mixture of aniyloxanthate of potash and sulphovinate of potash (I(.C,,H,1.2CS20) + (C,II,.K.2SO,)=(~:0~:l ::$)+2K SO,. Amyloxanthate of potash. Sulphovinate of Sulphocarbonate of potash. amyl and ethyl. The distillate which consisted of a yellow aromatic liquid floating above a colourless one was digested for several days with concen- trated ammonia. A yellow-coloured mixture resulted which emitted the odour of amyl-mercaptan. I was however unable to obtain positive proof of the formation of xanthamylamide.I was more fortunate with regard to the analogous sulphocarbonate of methyl and amyl. This compound when heated with dry ammoniacal gas and digested with it for several months gave rise to a substance which possessed all the properties of xanthamylamide ; the quantity obtained however was too small to admit of an analysis. The formation of xanthamylamide in this reaction is represented by the equation 2CS O+ H N=C, H, NO S,+ C H S. HS. L-v-J L-,-3 Sulphocarbonate of methyl and amyl. Xanthamylarnide. I cannot conclude without publicly acknowledging the kind advice and assistance of Dr. H o frn ann during the prosecution of this in- vestigation.

ISSN:1743-6893    

DOI:10.1039/QJ8530500142

出版商:RSC    

年代:1853

数据来源: RSC

摘要:

DE. G. WILSON ON THE DETECTION OF FLIJORINF,. 151 XV.-On a New Processfor the Detection of Fluorine when uccompanied by Silica. BY GEORGEWILSON,1II.D. Having had occasion recently to examine several substances con- taining a small amount of fluorine along with a large amount of silica I have put in practice two processes one of which is so easily managed and has yielded such excellent results that I bring it before the attention of the members of the Chemical Society. The substances which I had to examine were the ashes of straw hay coal and charcoal ; and likewise granite basalt greenstone and clinkstone in the majority of which fluorine has not hitherto been detected nor indeed sought for owing doubtless to the practical difficulties which attend the detection of fluorine when acconipanied by much silica.The chief difficulty in such inquiries arises from the necessity of carrying on the analysis in vessels of platinurn which makes it impossible to subject large quantities of material to investi- gation. The following process meets this difficulty as it requires only the ordinary glass and porcelain vessels of the laboratory and may be prosecuted with any amount of material. It is founded upon the very familiar fact that when a fluoride combined or mixed with silica is heated with oil of vitriol the fluorine and silicon are evolved in combination as the well-known fluoride of silicon (SiF,) ; and it is applicable to all silicated fluorides which yield this gas. It is further applicable to compounds containing mere traces of fluorides but free from silica which are brought within the compass of the process by the deliberate addition of silica to them SO as to admit of their being heated in large quantity with oil of vitriol in glass vessels.In either case the fluoride of silicon set free is conveyed by a bent tube from a flask or retort into water. The resulting solution containing some gelatinous silica is supersaturated with ammonia and evaporated to dryness during which process the fluoride of silicon and ammonium (2SiF +3 NH F) is resolved into silica which is rendered insoluble and fluoride of ammonium which is dissolved by digesting water on the evaporated residue. The solution of the ammonio-fluoride is then evaporated to dryness and heated with oil of vitriol in a platinum crucible covered by a piece of waxed glass having lines traced through it so as to permit the hydrofluoric acid evolved to etch the glass.I have tried this process 15% DR. G. WILSON ON THE DETECTION QE PLUOHINL. with Peterhead and Sberdeen granite with basalt from Art'hiir'b Scat greenstone from Corstorphine Hill and clinkstone from Black-ford Hill-all threc in the neighbourhood of Edinburgh. I have also tried it with the ashes of barley-straw of hay of coal and of charcoal; and in addition with a fossil bone containing much car- bonate of lime and with a deposit from the boiler of an ocean steamer. To the bone and to the boiler deposit pounded glass was first added. I lay before the Society some of the specimens obtained in this way.They are not selected successful ones but represent the earliest trials. Where the rocks under exaniination have been weathered or the substances (such as plant-ashes) have contained salts of volatile acids (for example chlorides and carbonates) I have treated them first with oil of vitriol in the cold so as to evolve hydrochloric acid and carbonic acid. On afterwards raising the liquid to the boiling-point in a flask with a bent tube a gas was given off if fluorine were present which deposited gelatinous silica when passed through water and produced with it a solution which gave a gelatinous precipitate with potash. The whole of the fluoride of silicon is given off as soon as the oil of vitriol has reached its boiling-point. I am at present engaged in applying this process to a variety of substances and in ascertaining its applicability to the quantitative determination of fluorine. I forbear in the meanwhile to enlarge upon the interesting geological mineralogical and physio- logical results which may be expected to flow from the discovery of fluorine in trap rocks and the recognition of its comparative abun- dance in plants.

ISSN:1743-6893    

DOI:10.1039/QJ8530500151

出版商:RSC    

年代:1853

数据来源: RSC

摘要:

PROCEEDINGS AT THE MEETINGS OF THE CHEMICAL SOCIETY. Anniversary Meeting March 30 135 2. PROFESSOR D AU B E N Y President in the Chair. Thefollowing Annual Report was read by the President. Gentlemen The Twelfth Anniversary of this Society which we are to-day assembled to celebrate opens under circumstances peculiarly aus-picious suggesting to us matter for congratulation as to the past and for encouragement with respect to the future. Our body has already by the number of its members by the value of its contributions to science and by the increasing interest testified in its proceedings vindicated to itself a full claim to the place which under the presidentship of Mr. Brande it had acquired amongst the chartered scientific societies of the metropolis ; and is now moreover I am happy to add established in a locality more worthy of its high position and capable of affording those accommodations for the reception of its members and for the display of its library and of its collections of which it has long felt the want.The advantages of the present abode need not indeed be particu- larized in addressing members upon the recollections of most of whom the deficiencies of our former locality must be vividly impressed; nor could they have been secured at a more fortunate moment than the present when they enabled us to accommodate that large assemblage of chemical products n hich were so liberally contributed by various individuals at the close of the Great Exhibition of last year. In coiiscqucncc of these donations may indeed flatter ourselves tm PROCEEDINGS OF THE CE-IEMICAL SOCIETY.that the Chemical Society will hereafter be resorted to not only as the spot where the newest discoveries in this department of science may be expected to be announced and the most authentic information on the existing state of our knowledge on such subjects obtained; but also as the depository of all that is curious and important amongst the natural or artificial productions which may from time to time be elaborated through the instrumentality of chemical processes And when we recollect how difficult and hov toilsome even in expert hands the preparation of many of these compounds is found to be how little there is to induce the mere manufacturing chemist to exercise his skill upon them and how unprofitable it would be for the most assiduous cultivator of the science to obtain by his own unassisted labours any considerable number of the mnltifarious combinations which art is capable of bringing about between the elements of matter the utility of such a depbt for the reception of such presents as we are now attempting to form cannot perhaps be too highly appre- ciated.Each of the substances indeed stored up within our cases may be regarded as a standard with which to compare any new body lighted upon in the progress of chemical investigation and thus as not only aiding directly in the advancement of science but also in the preve,ntion of much unnecessary labour by pointing out what has already been ascertained in each department of inquiry.I may therefore take upon myself to congratulate the Society most warmly on the progress that has been made towards the formation of a Chemical Rilluseurn and to point out as one of the incidental benefits flowing from the Great Exhibition of last year that it has been the means of affording such ample contributions to that treasury of scientific products which it is our pride to possess. I should indeed have deemed the acquisition of a place in which these advantages might be secured as a worthy object upon which to expend a portion of our reserved funds had the general interests of science alone been consulted in this appropriation of them ; but there was also reason to hope that every addition to our means of imparting knowledge would be followed by a greater disposition on the part of the public to avail itself of them ; and hence that these increased facilities would be followed by a proportionate augmenta- tion in the number of our members.And although the influence of these changes will be more felt hereafter yet I am happy to report that already the increase which has taken place in our members is such as to show that this anticipated result has to a certain extent been realised. PROCEEDINGS OF THE CHEMICAL SOCIETY. It appears from the Secretary’s Report that there have been elected since the last Anniversary Meeting 24 members whilst the deaths and resignations together amount only to 8; showing an increase over last year of 16 from which number however might perhaps be deducted 2 who have suffered the time to expire within which the payment of the entrance-fee should have been made and whose election is consequently void.According to this calculation the actual number of Fellows will be 2413; whereas at the last Anniversary Meeting it was only 229 showing that the steady though slow increase in our number which had been remarked on former anniversaries still continues. STATEMENT OF THE NUMBER OF FELLOWS OF THE CHEMICAL SOCIETY AT THE PRESENT TIME AND AT THE CORRESPONDING PERIOD OF LAST YEAR. Present number of Fellows . . 245 Elected since last Anniversary Meeting . 24 Dcaths and resignations since last Anniversary Meeting . 8 Increase since last Anniversary Meeting .-16 Number of Fellows at period of last Anniversary Meeting 229 T. REDWOOD Secretary. March 22 1852. The three Fellows whom we have lost by death since our last Anniversary are Mr. Richard Phillips Mr. William West and Mr. Henry Beaufoy. The first of these gentlemen had vacated the office in this Society in which I had the honour to succeed him only a short time when he was seized by an attack of bronchitis which quickly terminated an useful and busy life mainly dedicated to the investigation of physical truth. Mr. Richard Phillips and his elder brother William who died several years ago were the sons of a printer in George Yard Lom-bard Street a member of the Society of Friends. The elder brother was distinguished as a crystallographer and as a mineralogist in which capacities as well as by his compilations in geology he aidcd matcriatly thc early progress of that science.The PROCEEDINGS OF THE CHEI1lICAL SOCIETY. younger educated as a druggist under the late Mr. William Allen of Plough Court became at least equally distinguished for his acquire- ments in Chemistry. His reputation indeed in this line secured to him at an early age the honour of a place in the Royal Society and caused him also to be elected as an honorary member of the Medico-Chirurgical Society thus bringing him into intimate connexion on the one hand with the chemical philosophers and on the other with the physiologists and physicians of the age. He might indeed be regarded during the latter part of his life as a connecting link between the chemists of the last generation and of the present having been the contemporary of Davy and Wollaston no less than of Faraday and Graham; and in his death we have lost one of the last of that distinguished band of philosophers who before chemical science had so enlarged its boundaries as to include within its domain and to comprehend within the operation of its laws the products of animal and of vegetable life occupied them- selves almost exclusively in the investigation of the combinations of which mineral bodies are susceptible.Mr Phillips’ labours in this latter department were characterized by great neatness and precision ;so that they may indeed be appealed to at the present time as models of skilful and exact research.To him we are indebted for the first correct analyses of the Bath waters in the course of which investigation he discovered the cause of the apparent uncertainty in the indications afforded by the common tests for iron caused by the variations that occur in their effects according as carbonate of lime is present or not. This was followed by an examination of other celebrated mineral springs and by that of several rare minerals one of which relates to his discovery of phosphoric acid combined with uranium,* a fact which had escaped the searching eyes of Berzelius who was thus as much outdone in the above particular by the subject of this notice as Davy had been by him when he detected the presence of phosphoric acid in Wavellite which the great English chemist had overlooked.By this and other of his contributions to science Mr. Phillips so raised his reputation that he was pronounced by Dr. Thomas Thorn- son in his Chemistry the first of modern analytical chemists. It was however in the pharmaceutical branch of the subject that his services were most conspicuous as might be expected from one of his acuteness after a training in the above-mentioned establish- * Annals of Philosophy foi 1823. PROCEEDINGS OF THE CHEMICAL SOCIETY. mcnt in Plough Court of which the chemical reputation ranked justly so high. Indeed the perfect familiarity he possessed with the processes in use enabled him to detect the errors into which the framers of our London Pharmacopoeia had fallen ; whilst the keenness of his reviews gave currency to his censures of which even those who smarted under their severity could scarcely help acknowledging the justice.Accordingly at a subsequent period he was especially con- sulted on the drawing up of two of the editions of the London Pharmacopmia by the College of Physicians itself whose previous labours in that department he had so severely criticised and thus led the way to many of the much needed corrections in the processes since introduced. Indeed during the latter part of his life he was appealed to as perhaps the highest living authority in this branch of chemistry; and his translation of the London Pharmacopoeia the last edition of which he was engaged at the time of his death in superintending was looked upon as the best book of reference on all chemical ques- tions involved in the preparation of medicines.Froin the year 1821 Mr. Phillips conducted the Annals of Philosophy ; and when that periodical was incorporated with the London Edinburgh and Dublin Philosophical Magazine his services were secured as one of its editors a post he held till his death. For this office he was well qualified from the frankness and friendliness of his character no less than from his acuteness of intellect which enabled him to subject the scientific communications which came befcwe him to that rigid scrutiny which the promulgator of every new view and original fact must be prepared to encounter before either the one or the other receives the stamp of public recog- nition and can be admitted as a part of the common patrimony of science.Mi*. Phillips was successively Lecturer on Chemistry at the Lon- don Hospital ; at the Government Military College at Sandhnrst ; at Mr. Grainger’s School of Medicine in Southwark; and at St. Tho- mas’s Hospital. In 1839 he was appointed Curator of the Muscuni of Practical Geology now in Jermyn Street an office which he continued to hold till the date of its formal opening under the auspices of H.W.H. Prince Albert in July last on the very day before which he breathed his last at the age of seventy-two after a short illness. Although I was not myself fortunate enough to be frequently thrown into his society I had seen enough of him to be persuaded of PROCEEDINGS OF THE CHEMICAL SOCIETY.the truth of the character given of him by his intimates who describe him as not less remarkable for his ready powel. of repartee and keen sense of the ridiculous than for the quickness of observation range of knowledge and precision of intellect by which he was publicly distinguished. Mr. William West was born at Wandsworth in the year 1793 of parents both of whom were members of the Society of Friends. In the year 1816 he established himself as a druggist at Leeds where he became quickly distinguished by his exemplary diligence and unremitting attention to the scientific as well as to the comniercial part of his business. His spare moments were mostly occupied in the study of the most recent discoveries in chemistry in analytical researches and in the preparation of the various papers which he contributed to different scientific societies.Of these no less than twenty-three may be enumerated which were read before the Leeds Philosophical and Literary Society; and these were not only of a kind connected with his own professional pursuits but also related to various other depart- ments of science and literature. He took an active and prominent part in the foundation of the above-named society of which he became successively the Honorary Secretary the Vice-president and the President. He also interested himself warmly in the Leeds Mechanics’ Insti- tute and was Vice-President of the Geological and Polytechnic Society of the West Riding of Yorkshire to which he contributed various papers.On the 1st of March 1842 he was elected an Associate of the Institute of Civil Engineers and was awarded the Telford Medal on the 9th of December 1846 for a paper “On Water for Locomotive Engines.” He was also elected a Fellow of the Royal Society on the 19th of February 1846. Mr. West was Chemical Lecturer to the Leeds School of Medicine from the year 1831 to 1846 when ill-health compelled him to resign this post as from the same cause he soon after did the commercial part of his business though still continuing to be engaged in analyses and in scientific investigations of a judicial kind in which his authority was much esteemed up to the period of his decease which took place on the 10th of September of last year.My own acquaintance with Mr. West dates as far back as the period when he formed with myself one of that little band of pro- moters or cultivators of science who obedient to the summons of Sir David Brewster assembled at York in the year 1831 and PROCEEDINGS OF THE CHEMICAL SOCIETY. whilst there in spite of the smallness of our numbers (which however besides the illustrious philosopher who first projected the Meeting included the names of Dalton of Murchison of Forbes and of Sowerby) had the boldness to organise the scheme of that great scientific association which next year obtained its full develop- ment at Oxford and has since been welcomed in almost every large city of the British dominions.The last time I saw Xlr. West was at the meeting of this same body which took place last year at Ipswich when he exerted himself to persuade the General Committee to fix upon his native town for their place of meeting in the year 1854 although with a conscious- ness of declining health which the event has shown to have been but too well founded he declared his persuasion that he should not be alive at the time to welcome us himself. The late Mr. Henry Beaufoy of South Lambeth passed his time in such complete seclusion from the routine of society that there are very few particulars to relate respecting him. He was educated for many years under Dr. Goodenough at Ealing School which well accounted for his classical attainments and the literary predilections he preserved throughout life.When how- ever on the death of his elder uncle it was considered necessary by the family that he should become a mercantile man Henry Beaufoy under the guidance of Mr. Nicholson of Soh0 Square gave his attention to practical chemistry which eventually enabled liini to conduct with success a large manufactory by causing him to appreciate and adopt some modern improvements in science of great value to his trade. Deeply grateful as he was to that Providence which had bestowed on himself and all his father’s children so many blessings he con- sidered it an act of duty to prove his gratitude while living by appropriating a large portion of his income to charitable purposes. Of the extent of these acts of munificence the following statement may convey a brief although a very inadequate representation.To the City of London School alone he appears to have been a benefactor to the amount of X10,OOO. Then he had established four scholar- ships for four students at Cambridge and had instituted various prizes for the best essays and for other purposes. Amongst the rest was &1,000to encourage the study of Shakspeare the interest to be given away to the most deserving candidate upon the anniversary of the poet’s birthday which chanced to coincide with his own. Mr. Henry Beaufoy was the eldest son of Colonel March PROCEEDINGS OF THE CHEMICAL SOCIETY. Beau foy well known for his elaborate nautical and hydraulic cxpe- riments the results of some of which the subject of this notice published in a handsome quarto volume.The entire impression of this work comprising I believe no less than fifteen hundred copies he with his accustomed liberality distributed gratuitously amongst scientific men and societies thus performing at once a public service and an act of filial duty. He was born on the 22nd of April 1786 died on the 12th of July 1851 and lies buried in Norwood Cernetcry in the same grave with his wife as a monument to whom he had erected at his own expense at Lambeth a very handsome building for a ragged school which he established and endowed most liberally. The Papers that have been read at our Meetings since the last Anniversary are by no means inferior either in number or in interest to those of preceding years.I shall not pretend however to do more than just to present to you a list of their titles which are as follows Papers read at the Meetings of the Chemical Society,from April 7t4 1851 to March lfjth 1852,inclusive. “On the Composition of the Water of the Dee and the Don at Aberdeen with an investigation into the action of Dee-water on lead pipes and cisterns.” By John Smith M.D. Fordyce Lecturer on Agriculture and Assistant in the Chemical Laboratory of Marischal College. On a peculiar property of Ether and some Essential Oils.” By Rr. C. F. Sch6nbein. c‘ On the Analysis of the Sediment deposited from the River Nile in Lower Egypt.” By Matthew Tlr. Johnson. “Notice of a Specimen of Chlorobromide of Silver from Chili.” By Colonel Philip Yorke.“On the Tests for Nitrates and a New Test for Nitrites.” By David S. Price Ph. D. “ On a New Test for Iodides.” By the same. rc‘‘Analysis of Milk.” Observations on the Teas of Commerce.” By John Ellis Roberts. By Robert Waring- ton. ‘‘On the Composition and Properties of the Carbonates of Lead constituting the White Lead of Commerce.’.’ By J. A. Phillips. ‘‘On the Equivalent of Phosphorus.” By Professor Schrotter. 161 PROCEEDINGS OF THE CHEMICAL SOCIETY. “Note on a case of Leakage in a Leaden Water-cistern.” By J. H. Gilbert Ph. D. “On Dibenzoylimicle a new derivative of Oil of Bitter Almonds.” By Joshua H. Robson. “On Chromic Acid and Sesquioxide of Manganese.” By J. Adam Fairie.‘’ On the Chromate of Ammonia.” By the same. “On Etlierification.” By Professor Williamson. “On the Valuation and Composition of Protochloride of Tin.” By Professor Penny. “On the Chemical Examination of the Metals and Alloys known to the Ancients.” By 5. Arthur Phillips. “Observations on the Phenomena of Animal Phosphorescence.” By Thornton J. Herapath. Analysis of a Mineral containing Gold from the province of Coquimbo Chili.” By F. Field. “Description of Lapis Lazuli found in large quantities in the Cordilleras of the Andes.” By the same. ‘‘ On the Spontaneous Decomposition of Gun-cotton and its con- geners.” By J. H. Gladstone Ph. D. ‘‘ On the Action of Arsenious Acid on Albumen.” By John B. Edwards. “On the Action of Ammonia on Sebacic Ether.” By T.H. Rowney. cc Analysis of the Water supplied by the Bristol Water-works Company.” By Thornton J. Herapath. I‘ On a quick approximative method of estimating minute quan- tities of Iron by means of a Colorimeter.” By the same. On the Decomposition of Citrate of Lime in contact with putrify- ing Curd.” By Henry How. On a new method of obtaining Hippuric Acid in considerable quantity without evaporating the urine and on some of its products of decomposition.” By Edward Riley. ‘‘On Populin.” By M. Rafaelle Piria. cc On the variation in the qlative proportion of Potash and Soda present in certain samples of Barley grown in plots of ground arti- ficially impregnated with one or other of these alkalies.” By Pro-fessor Daub eny F.R.S.“On the Cornhounds of Cotton with the Alkalies.” By J. H. Gladstone Ph. D. ‘‘On the Occurrence of Capric and Caprylic Acids in some Fousel Oils.” By T. H. Rowney. VOL. v.--wo. XVIII. M 162 PROCEEDINGS OF THE CHEMICAL SOCIETY. c‘ On Dr. Keller’s supposed formation of Metacetonic Acid from Flour and Leather,” By R. W. Forster. ‘‘ On the detection of Alum in Flour with remarks on the prepa- ration of Distilled Water and pure Potash.” By J. H. Pepper. ‘I Contributions towards the history of Tannic Acid.” By Dr. Strecker. Besides these Memoirs formally communicated to the Society we have had at various times laid before us interesting notices of researches now in progress in foreign countries; as for instance of the new process for determining urea invented by Baron Liebig which promises when fully worked out to facilitate greatly the observations which the physician and the physiologist are equally interested in making respecting the changes that occur in this important ingredient of the urinary secretion.And now Gentlemen little more remains except for me to express my warmest thanks to the Members of the Council generally and to the Secretaries in particular for the kind manner in which they have relieved me from the more onerous part of my duties by the constant attention bestowed by them on the business of the Society rendered this year more than ever laborious by the arrangements consequent upon the change of our rooms. Without their advice and co-opera- tion indeed it would have been impossible for me living as I do at a distance from the metropolis to have accepted the honourable post you have in so flattering a manner assigned to me however desirous I might be to discharge its duties so far as my time and abilities permitted.Indeed I have more reasons than one to apologize to you for my deficiencies and shortcomings especially when I compare myself to the distinguished men who have preceded me in this office. Not only have I felt myself less able efficiently to discharge its duties by reason of my residing so much farther from my post than any of the former presidents but divided as my time has long been between two complicated and rapidly advancing sciences I am neces- sarily the less competent to grapple with many of those intricate questions in chemical philosophy upo~ which I might be expected to offer an opinion.Perhaps indeed paradoxical as it may sound the wide range of subjects which Chemistry herself embraces or to which she is able to lend a helping hand may be regarded as the very circumstance which has most contributed to reconcile me to undertaking other duties in conjunction with those which devolve upon me as Professor of Chemistry in the University to which I belong. The changes PROCEEDINGS OF THE CHEMICAL SOCIETY. for example brought about by nature or induced by art in the growing vegetable cannot but be influenced by those laws which are common to matter whether inert or living and thus are brought to a certain extent at least under the domain of Chemical Philosophy.Hence Vegetable Physiology (and Rural Economy also so far as that art is directed by scientific principles) appears less alien to the pursuits of a chemist than it would be to those of a man of science who was devoted to any kind of natural philosophy more limited in its range of subjects. And I may add this infinite variety in the nature of the researches which our science includes within its juris- diction affords in my opinion the most convincing argument that can be offered on behalf of the necessity for the existence of a society like ours exclusively dedicated to its promotion. Formerly indeed the attempt to draw off from the Philosophical Transactions any portion of that class of contributions upon which so much of their credit has ever rested might have been viewed with some jealousy by the Royal the common parent of all those societies which have subsequently started up.But such a feeling cannot reasonably be entertained at the present moment when chemistry has so enlarged its boundaries as to embrace within its compass the kingdoms of living as well as of inanimate nature. For without here pronouncing upon the difficult and much debated question as to the extent to which vital functions are influenced by chemical laws it may be sufficient to establish the Justice of my remark if we recollect that an infinite variety of curious and important chemical products omes its origin to vital processes in so far as the latter by bringing together the particles of matter under conditions not imitable by art do in fact supply us with a number of new principles to work upon in addition to those furnished by the mineral kingdom ;elements indeed inas- much as they are the roots of new combinations although themselves compounds as being made up of bodies regarded by us as simple.Under such circiimstances it must be apparent to every one that the Royal Society could never have taken cognizance of the whole of that vast range of subjects which modern chemistry embraces and that many papers of great promise and of much practical utility would have been lost to the world but for the existence of such a society as our own. Moreover the experience of the last ten ycars has completely established the position that at no period in the history of the Royal Society have more important Chemical Papers appeared in its Transactions and at none has the number of Com-munications to it in the same department been so numcrous as they M2 PROCEEDINGS OF THE CHEMICAL SOCIETY.have been since the Chemical Society has been established. I need only allude to the memoirs of Graham of Hofmann and of Brodie in proofof the formerpart of this assertion,namely as to the value of the Chemical Papers which have been recently supplied to the Philosophical Transactions by members of the Chemical Society. With respect to the second part of my statement I may remark that the average of papers on chemical subjects not including elec- tricity contained in the Philosophical Transactions during the ten years preceding the foundation of the Chemical Society was only about 3 in two years or 16 in ten years; that during the first four years of our existence namely from 1842 to 1846 inclusive the number of papers was 12 or 23 yearly; whilst during the last quinquennial period they have risen to 20 or to 5 on the average each year.* Yet although there is good ground for believing that the establish- ment of this Society so far from damaging the interests of' the Royal has rather tended to advance them serving as it has as a feeder to that great original trunk of scientific information; and although it is true that the spirit of the age no less than the extension of the fields of research in each department calls impera- tively for a multiplication of scientific institutions throughout the country it affords at the same time no argument against their juxta- position Indeed any arrangement which should effect this object with respect to the chartered scientific institutions of the capital would have much to recommend it not only on the ground of economy and convenience inasmuch as one set of accounts might then do the work of several societies and one meeting-house serve the purpose perhaps of the whole number so brought together; but also in materially promoting the object which each of us has in * This may be seen by the following table.1831 2 Papers. 1842 3 Papers. 1832 0 , 1843 2 , 1833 2 , 1844 2 , 1834 2 , 1845 5 , 1835 0 , 1846 1 , 13 Papers.1836 1 , 1847 1 , 1837 2 , 1848 4 , 1838 1 , 1849 4 , 1839 1 , 1850 9 , 1840 5 , 1851 5 , 23 , 1841 0 , --Total . . 16 Total . . 36 PROCEEDINGS OF THE CHEMICAL SOClETY. common by facilitating the intercourse between men engaged in different departments of inquiry and by removing some of the obstacles that impede their mutual co-operation ;thus rendering the same service to the metropolis which the British Association for the Advancement of Science professes to do with reference to the provinces. Whilst therefore I congratulate you as indeed I have already done on the additional conveniences afforded by our present suite of apartments over our last I would still more heartily hail the day which should see all the principal chartered societies of the metro- polis under a common roof pursuing their separate labours indeed independently but at the same time deriving mutual support and assistance from their contiguity ;exercising no paramount juris- diction but moving forwards in harmony and concert as becomes the federal members of the great republic of science.The audited Statement of the Treasurer’s Account was submitted to the Society as follows A4UDITEDREPORT OF THE TREASURER. Dr. ROBERT PORRETT (TREASURER) IN ACCOUNT WITH THE CHEMICAL SOCIETY OF LONDON. 1_ 1851. 8. 5. d. d. S. d March 31 To Balance from last Account . . . . . . . 263 Y 0 By payment to Mr. Abel for Translations . . . . . 9 2 6 18ft2., Ditto to Mr. Watts One Year’s Salary as Editor of (‘Jour- March 30 , Subscriptions %221 2s.and Compositions 630,since received 25I 2 0 nal” . . . . . . . . . . . 50 0 0 , Donation to Library Fund . . . . . . . 10 0 0 , Ditto to Mr. Medlock One Year’s Salary to 31st Dec. last . %5 0 0 9 If , I , Admission Fees from 22 new Members . 44 2 0 , Ditto to ditto for Petty Cash . . . . . . 8 3 8 , Two Years’ Dividends to 5th Jan. last on L400,3p. c ‘Con , Ditto to Mr. Redwood for ditto . . . . . . 6 1 9 I 11 sols minus Property Tax . . . . . . 23 6 0 , Ditto to H. Bailli&re for Publishing Journals . . . 128 13 0 , Proceeds of Sale of &loo 3 p. c. Consols minus Brokerage . 98 5 0 , Ditto to ditto for Periodicats to 30th June last . . 7 11 0 I It , One Year’s Rent in advance to Jan.1853 from the Meteoro. , Ditto to Williams and Norgate for Foreign Books . . 6 0 6 JI It logical Society for use of Rooms , Ditto to John Chapman. for One Year’s Hent of Apartments . . . 4 14 10 142 Strand to Michaelmas last E55 j and for Tea and J Proceeds of Sale of ‘‘ MemoirsIv9 by Mr. Taylor .... 20 0 0 *I I Coffee a8 . . . . . . . . . 63 0 0 , Ditto for a Turkey Carpet for Council-room . . 11 7 0 , Ditto to R. Ireland for Book-cases and Mahogany Seats . 52 3 0 , Ditto to Thos. Ames for Thirteen Mahogany Chairs . . 22 15 0 , Ditto to Thos. Holland for a Mahogany Glass Case . . 21 0 0 , Ditto to S. Gale for Gas-fittings Diagram-board &c. . . 22 0 0 , Ditto to J. Crandal for Bookbinding . . . . 7 8 10 , Ditto to T.Treloar.for Cocoa-nut Matting . . . . 2 11 9 , Ditto to Buns1 & Co. for Floorcloth . . . . 11 10 0 , Ditto to Mr. Rickers for Books . . . . . 22 2 0 , Ditto to W. S. Burton for Coffee-machine and Teaspoons . 3 Q 0 , Ditto for Bottles and expenses in removing Specimens from *.*.(I the Great Exhibition . 5 18 0 , Ditto to Thos. Riddle for Chairs &c. . . . . . 15 18 0 , Ditto to S.Kirkman for tea coffee &c. including $4.9~.for Attendance and Table to 31st Dec. last . . . . 7 14 2 , Ditto to Cavendish Society for Subscription 1852 . . . 1 1 0 Ditto for Envelopes and Postage-stamps for Treasurer . . 0 2 6 , Ditto for Power of Attorney to receive Dividends . . . 1 1 ti , Ditto to John Gifford for Engraved Brass Plate . . 1 5 0 , Ditto to C.Button for 246 Stoppered Bottles . . . 9 14 0 , Ditto to Yo01 & Son for Coals and Wood . . . 1 10 (; , Ditto to Schulze & Co. for Printing Circulars . . . Ditto to Directors of Polytechnic Institution for Rent to 25td 0 19 ti inst. . . . . . . .... 60 0 0 , Ditto to ditto for Tables and Furniture . . . . 15 18 0 .. Ditto to R. Tavlor for 15 Nos. of “Philosouhical illarazine” 1 15 0 ;; Ditto to ditto >or Printing Catalogues &c. -. . . 10 0 0 , Ditto to Collector for Poundage including l4s.for Stamps Prc. 10 I9 6 --, Balance carried to his Debit in next Account . . . . 91 12 -2 714 18 10 London March 30 1852 d 714 IS 10 R. PORRETT Treasurer. Examined and found correct J. DENHAMSMITH JOHN WAY, TEOMAS 167 PROCEEDINGS OF THE CHEMICAL SOCIETY.Mr. J. J. Griffin and Dr. Price having been appointed Scrutators the Meeting proceeded to the Election of Council and Officers for the ensuing year; and the following gentlemen were declared to have been duly elected PRESIDENT. Charles G. B. Daubeny M.D. F.R.S. F.G.S. F.L.S. VICE-PRESIDENTS. William Allen Miller M.D. F.R.S. Robert Warington Bsq. Lyon Playfair C.B. Ph.D. FRS. Colonel Philip Yorke P.R.S. TREASURER Robert Porrett F.R.S. F.S.A. SECRETARIES. Benjamin Collins Brodie F.R.S. Theophilus Redwood Ph.D. FOREIGN SECRETARY. A W. Hofmann Ph.D. F.RS. OTHER MEMBERS OF THE COUNCIL. Thomas Anderson M.D. Edin-H. Bence Jones MJl. F.R.S. burgh. J. P. Joule F.R.S. John Blyth M.D. Cork.G. D Longstaff M.D. Dugald Campbell Esq. J. Arthur Phillips Esq. Warren De la Rue Ph.D. F.R.S. A. W. Williamson Yh.D. J. H Gladstone Yh.D. George Wilson M.D. F.R.S. Thomas Graham F.R.S. It was moved by Dr Warren De la Rue seconded by Dr. Lyon Playfair and Resolved That it is desirable to alter the By-laws of the Society in so far as they relate to the number of Vice-presidents; so that those Fellows of the Society who have served the oftice of President shall be annually proposed for election as Vice-presidents in addition to the Vice-Presidents elected under the present Bylaws ;and that such alteration be made as follows PROCEEDINGS OF THE CHEMICAL SOCIETY. At page 11 of the printed Charter and By-laws of the Society in the second paragraph and sixth line from the top the words “four Vice- Presidents” to be changed to c‘ four or more Vice-Presidents.” At page 15 in By-law VII the last line of this By-law being the fourteenth line from the top of the page to be expunged and the following words to be substituted :-‘‘ Fellows who have JilZed the ofice of President at any time since the formation of the Society shall be proposed by the Council for election as Vice-presidents ;and this proposition shall be renewed every year excepting when any such are again elected to the Presidency.There shall be four other Vice-presidents who have not Jilled the oflce of President and every year one of these shall retire from octjice.” The thanks of the Society were voted to the President Officers and other Members of Council for their services during the past year.April 5 1852. COLONELPHILIPYORKE,Vice-president in the Chair. The following donations were announced ‘‘The Pharmaceutical Journal for April :” from the Editor. “The Literary Gazette for March 20th and 27th and April 3rd :” from the Publishers. The following gentlemen were duly elected Fellows of the Society The Rev. W. Thomson >LA. Queen’s College Oxford. Robert Keates Esq. 35 Carter Street Walworth. Samuel Gale Esq. 17 Bloomsbury Square. A paper was read ‘‘ On the Detection and Qualitative Separation of Tin Antimony and Arsenic ; and on the relation existing between these metals and others which are precipitated from their acid solutions by sulphuretted hydrogen,” by Charles L.Bloxam. PROCEEDINGS OF THE CHEMICAL SOCIETY. April 19 1852. PROFESSOR President in the Chair. DAUBENY The following donations were announced “Transactions of the Royal Scottish Society,” Vol. 111 Part 5 from the Society. Specimens of Caprylic Alcohol from Dr Williamson. Anhydrous Benzoic Acid from M. Gerhardt. The following papers were read 1. “Researches on the Constitution of Organic Acids:” by M. Charles Gerhardt ; communicated by DP.Williamson 2. “Note on the Prepai*ation of Carbonate of Amyl :” by John A. Bruce. 3. (‘New Formation of Salicylic Acid :” by H. Gerland. (From a Letter of Dr. Kolbe to Dr. Hofmann.) May 3 1852. ROBERTWARINGTON, EsQ. Vice-president in the Chair.John William Perkins Esq. Union Wharf Narrow Street Limehouse and William Wilson Esq. 9 Maida Hill were duly elected Fellows of the Society. The following papers were read 1. ‘‘On the Preparation of Anhydrous Acetic Acid :” by M. Charles Gerh ardt 2. CCChemical Memoranda :” by Robert Warington. 3. (‘On the Action of Ammonia upon Binoxysulphocarbonate of 4. ‘‘On a New Process for the Detection of Fluorine when accom- Amyl :” by Matthew W. Johnson. panied with Silica :” by George Wilson M.D. PROCEEDINGS OF THE CHEMlCAL SOCIETY. May 17 1852. DAUB PROFESSOR ENY President in the Chair. Captain James Whit more 63 Park Street Grosvenor Square was duly elected a Fellow of the Society. A paper was read ‘I On a New Test for Strychnine :” by J.H Pepper The Author suggests the use of a solution of red prussiate of potash in oil of vitriol as a test for strychnine this substance deve- loping in the solution a violet-blue colour when added in the dry state or dissolved in ether. An aqueous solution cannot be used as the presence of water alone produces a blue colour. A verbal communication was made to the Society by Dr. Glad-stone ‘‘ On the Atomic Weights of some of the Elements.” June 7 1852. COLONEL PHILIPYORHE,Vice-president in the Chair. The following donations were announced fc Specimens of Crystallized Lead :” from H. L. Pattison Esq. “Two Specimens of Essential Oil of Bitter Almonds :” from George Whipple Esq. ‘<The American Journal of Science and Arts for May 1852:” from the Editors.lCThe Journal of the Franklin Institute for February March and April :” from the Institute. “The Pharmaceutical Journal for June :” from the Editor. “ The Literary Gazette for May 22nd and 29th and June 5th :” from the Publishers. A Pamphlet on Cotton Flax &c. and their Bleaching ; and on the Oxides and Nitrates of Lead; and Reports on the Examination PROCEEDINGS OF THE CHEMICAL SOCIETY. of the Supply of Water to the Town of Preston:” from F. Crace Calvert Esq. A resolution of the Council was read recoinmending to the Society that the names of thirteen Fellows whose subscriptions are more than four years in arrears he removed from the list of Fellows in accordance with the By-laws of the Society.The following communications were read 1. “A note from Mr. Pepper relating to a paper read at the preceding Meeting on a New Test for Strychnine.” 2. “A note on the Existence of Strontia in the Well-Waters of Bristol :” by William and Thornton J. Herapath. 3. “On the Analysis of Chrome Ores:” by F. Crace Calvert. 4. ‘‘On certain Isomeric Transformations of Fats :” by Patrick Duffy. 5. ‘‘On the Qualitative Separation of Arsenic Tin and Antimony :” by George F. Ansell. June 21 1852. PROFESSOR President in the Chair DAUBENY Alfred Smee Esq. was admitted a Fellow. The following donations were announced r‘ Specimens of Chloride of Platosammonium Chloride of Diplatos-ammonium Chloride of Diplatosammonium and Copper Chloride of Diplatosarnmonium and Lead Bichromate of Diplatosamine Salt .of Magnus Salt of Gros:” from G.B. Buckton Esq. “The Quarterly Journal of the Geological Society for May 1852 :” from the Society. lfThe Nineteenth Annual Report of the Royal Cornwall Poly- technic Society ?’from the Society. “The Literary Gazette for June 12th and 19th :” from the Pub-lishers. PROCEEDINQS OF THE CHEMICAL SOCIETY. The following papers were read 1. “Observations upon a New Series of Double Chlorides con-taining Diplatosarnmonium :” by G.B. Buckton F.L.S. 2. “ On the Action of Iodine on Phosphorus :” by B. C. Brodie F.R.S. 3. ‘(On the Acid Oxalates of the Earths :” by Edward Clapton. 4. ‘‘Researches on the Anhydrous Organic Acids :” by Charles Gerhardt

ISSN:1743-6893    

DOI:10.1039/QJ8530500153

出版商:RSC    

年代:1853

数据来源: RSC