摘要:

THE QUARTERLY JOURNAL OF THE CHEMICAL SQCIETY OF LONDON. April 2 1849. The President in the Chair. Mr. George Phillips presented to the Society a bottle enclosing a curious film of gun-cotton which had been formed inside the phial by the spontaneous evaporation of the ether from a collodion solution. The following paper was read XV1II.-Analysis of Gold-dust from the Const of California. BY E. T. TESCHEMACHER ESQ. The great interest excited by the recent discovery of large quantities of gold-dust existing in the sand in the district of Cali-fornia has induced me to lay before the Chemical Society the results of some examinations I have lately made with reference to its compo- sition The specimen of gold analysed was received from my brother resident in Boston United States.An analysis of Californian gold has likewise been made by Mr. T. H. Henry and published in the Philosophical Magazine for the present month. I think it desirable that a number of such analyses should be made and registered in order that an opinion may be formed upon the greater or lesser uniformity in composition of the gold from different parts of the same district ;and although I am unacquainted with the exact locality of my specimen still as the more immediate sources from which the two specimens were derived were so different it is not at all likely that the locality in which they were found was the same. My specimen was in the state of flattened grains weighing from a of a grain to 54 grains each ;the grains were roughened on the surface and of a dull brass-yellow colour and were partially en-crusted by many black specks and some brilliant crystals of mag-VOL.11.-NO. VII. 0 194 MR. TESCHEMACHER ON THE GOLD-DUST OF CALIFORNIA. netic iron with a portion of sand embedded in the cavities. The specific gravity of the dust was 16.33. The quantity submitted to analysis was 15 grains. It was first boiled in hydrochloric acid and after well washing was boiled in dilute nitric wid. The hydrochloric acid dissolved the exterior black specks and the crystals of oxide of iron. The solution obtained was precipitated by ammonia nothing having been dissolved but peroxide of iron weighing 0.07 grains. The subsequent treatment with nitric acid was tried in order to ascertain whether any silver would be dissolved out; but no action whatever took place.The separate action of these acids rendered the grains of gold of a brilliant gold colour. The gctld-dust was then acted upon by aqua- regia. The gold was dissolved leaving the silver in the state of an insoluble chloride. The chloride of silver was dissolved in am-monia and having been evaporated from the sand was reprecipitated by nitric acid. It weighed 1.36 grains. The sand weighed 0.10 grains. The solution of gold was evaporated to dryness and hydrochloric acid added to it ; the gold was then precipitated by oxalic acid in excess and after digestion for three days was separated; it weighed 13-45 grains. Sulphuretted hydrogen was passed through the solution after the separation of the gold a small precipitate was produced which I expected to be sulphuret of copper; but upon dissolving it in a small quantity of nitric acid and adding ammonia not the slightest indication of copper appeared ; on further examination it proved to be gold which had escaped precipitation by the oxalic acid; it weighed 0.20 grains.The solution was now evaporated to dryness ; re-dissolved in hydrochloric acid and precipitated by am-monia the precipitate weighed 0*08grains and consisted of peroxide of iron. The composition is therefore as follows 13-55 gold or in 100 parts 90.33 gold 99 1-02silver , 6-80 silver 0.15 oxide of iron J , 1-00oxide of iron 0.10 sand >, , 0.66 sand 14.82 98.89 Deducting the oxide of iron and the sand the alloy would consist of 92 parts of gold 7 , silver 99 parts MR.BENNETT ON THE THAJIES WBTER AT GREENWICH. 1% The gold-dust analysed by Mr. Henry had a spec. grav. of 15-96 and consisted of Gold . . . . . . 88.75 Or deducting the siliceous matter Silver. . . . . . 8.88 Gold . . . 90.01 Copper with a trace of iron 0.85 Silver . . . 9.01 Siliceous matter. . . 1.40 Copper . . 0.86 e___ 99.88 99-88 shewing thus a difference of about two per cent in the silver con- tained in the two specimens of Californian gold. Another portion of the same sample which I examined contained about eight per cent of silver.

ISSN:1743-6893    

DOI:10.1039/QJ8500200193

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

MR. BENNETT ON THE THAJIES WBTER AT GREENWICH. 1% April 16 1849. The President in the Chair. Messrs. J. Bailey and T. M. Creggan were elected Fellows of the Society. The following papers were read XIX-Analysis of the Thames Water at Greenwich. BY EDWARD T. BENNETT. STUDENT IN THE BOYAL COLLEGE OF CHEMISTRY. In pursuing the series of investigations of the water of the Thames at different localities suggested by Dr. Hofmann two of which the one of the water as it is found at Twickenham by G. F. Clark and the other at London Bridge by J. M. Ashley are before the Chemical Society we have at his request and under his direction and assistance undertaken a third analysis for which the water was collected at Greenwich after having been subjected to the influences both of the London drains and of the sea water coming up with the tide.The water was taken from the middle of the river exactly opposite the Hospital just after the turn of the tide on the 1st of January 1849. It was full moon on the 8th instant at 1Oh. 50m. P.M. and was therefore nearly the highest spring tide; but the wind was blowing very strongly direct down the river which had a material effect in keeping back the sea water on that particular day. The following observations were made at the time. Temperature of the water . . 3O C. (3704~ Fahr.) Temperature of the air . 9O C. (48-2OFahr.) 02 196 MR. BENNETT ON THE THAMES WATER AT GREENWICH The reaction of the water was very slightly acid. It had no per-ceptible taste or odour.The specific gravity of the water after everything held in mecha- nical suspension had conipletely subsided was 1.00116. For the qualitative analysis 42 imperial pints equal to 23840 grammes were evaporated to a concentration which yielded a pre- cipitate weighing when dry 5.5025 grammes ; and a filtrate with washings of 364 grammes. The filtrate was of the colour of brown sherry and strongly acid. The precipitate on examination indi- cated the presence of potash soda lime phosphate of alumina iron silicic carbonic sulphuric and hydrochloric acids with organic matter. The only additional ingredient found in the filtrate was magnesia. Bromine and iodine could not be detected. Doubtful traces of nitric acid were observed on highly concentrating a separate quantity of the water.On carcfully evaporating. 500 grammes of the water to dryness and treating with lime ammonia could not be discovered. The quantitative analysis yielded the following results A. Determination of the total amount of fixed constituents. Amount of water employed. Amount of residue Per-centage in obtained. the water. I. 780.975 grms. 0,3055 grm. 0.039 1177 11. 1001-530 , 0.3910 , 0-0390402 111 1000~000 , 0.4180 , 0.0418000 ~~ Mean 0-0399859 B. Determination of sulphuric acid. Water employed. Sulphate of baryta. Per-centage of sulphuric acid. I. 644,465 grms. 0.0923 grm. 0*0048722 11. 749.240 , 0.1008 , 0*0046180 111. 658.270 , 0.0808 , 0.0042089 Mean 0.0045664 C. Determination of hydrochloric acid.Water employed. Chloride of silver. Per-centage of hydrochloric acid. I. 523.010 grms. 0,062 grm. 0*0030158 11. 538.410 , 0.056 , 0.0026735 111. 615.530 , 0,064 , 0.0026673 Mean 0.0027’855 MR. BENNETT ON THE THAMES WATER AT GREENWICH. 197 D. Determination of silicic acid. Water employed. Silicic acid. Per-centage of silicic acid. I. 853.695 grms. 0*0080grm. 0.0012065 11. 1201.495 , 0.0133 , 0.0011069 111. 1200.215 , 0.0131 , 0*0010915 Mean 0.0011349 23. Determination of lime. Water employed. Carbonate of lime. Per-centage of lime. I. 853.695 grms. 0.1905 grm. 0,0124974 11. 1201.495 , 0.2738 , 0.0127624 111. 1200.215 , 0.2733 , 0*0127517 Mean 0.0126705 F. Determination of magnesia. Water employed.Pyrophosphate of Per-centage of magnesia. magnesia. I. 853.695 grms. 0.0278 grm. 0.0011602 11. 1201-495 , 0.0285 , 0.0008647 111. 1200.215 , 0.0290 , 0.0008812 Mean 0.0009687 G. Determination of the alkalies. Water employed. Mixed chlorides. I. 1668.840 grms. 0*1100grm. 11. 2508m450 , 0.1021 , 111. 1000~000 , 0.0580 , a. Estimation of potash. Bichloride of platinum and potassium. Per-centage of potash. I. 0.0988 grms. 0*0011391 11. 0.0978 , 0*0010521 1x1. 0*0508 , 0.0009778 Mean 0*0010563 b. Estimation of soda. Chloride of sodium. Per-centage of soda. I. 0.0798 grm. 0.0025347 11. 00723 , 0.0025372 111. 0.0425 , 0°00225 11 Mean 0.0024410 198 MR. BENNETT ON THE TIZANIES WATER AT GREENWICH. H. Estimation of organic matter.This was not attempted as soluble and insoluble matter in the filtrate and precipitate separately which were obtained by evaporating a large quantity of the water because the proportions thus determined must evidently have depended upon the degree to which the concen- tration had been carried. But for this purpose specific quantities of the water were evaporated to dryness and the whole organic matter was burnt off at the lowest effective temperature with the aid of a current of oxygen. Water employed. Organic matter Per-centage of organic burnt off. matter. I. 1000 grms. 0.0515 grm. 0-00515 11. 1000 , 0.0611 , 0-00611 111. 500 , 0*0310 , 0.00620 Mean 0.00582 I. Determination of carbonic acid. At the time of collecting the water a syphon capable of containing 534 cubic centimetres was filled three times and discharged into each of four Winchester quart bottles containing a mixture of chloride of calcium and ammonia.After complete subsidence the precipitates which had formed in two of the bottles together weighed . . 2.111 grms. From the other two bottles , . 2104 , Total . . . 4215 , The carbonic acid was expelled by means of hydrochloric acid in the usual apparatus. Precipitate employed. Carbonic acid Per-centage in Per-centage in evolved. the precipitate. the water. I. 0.614 gnu. 0.220 grm. 35.830 0-0235407 11. 0,465 , 0.163 , 35.054 0-0230309 111. 0.444 ,> 0.153 , 34.459 0-0226399 Mean . . 0.0230705 The water from four other bottles was treated on the spot with a solution of arsenious acid in hydrochloric acid.The whole of the sediment after standing some time was collected on one filter and carefully examined for sulphide of arsenic but without success ; thus proving the absence of free hydrosulphuric acid. The indications of iron in the form of soluble salts were exceed- ingly slight. An attempt to estimate the phosphate of alumina MR. BENNETT ON THE THAMES WATER AT OKEENWICH. 199 gave 0*0003439per cent; a quantity too minute for the separate determination of the phosphoric acid. Alumina was not found in any other state than that of phosphate. Following the usual arrangement by combining the whole of the acids and bases according to their chemical affinities the in- gredients found in the water assume the subjoined form.In 100 litres In an imperial gallon Grammes. Grains. Sulphate of potash . . . 1.9552 . . . 1.3710 Sulphate of soda . . . . 5.5937 . . . 3.9224 Sulphate of magnesia . . 0.7808 . . . 05475 Chloride of magnesium . . 1.6374 . . . 1.1482 Chloride of calcium . . . 2.3205 . . . 1.6272 Carbonate of lime . . . 20.5353 . . . 14.3997 Silicic acid . . . . . . 1.1349 . . . 0.7958 Phosphate of alumina traces. . . . traces. Iron . . . . .} . . Organic matter . . . . 543200 . . 4.0810 39.7778 . . . 27.8928 Direct determination of fixed constituents . . . . 39.9859 . . . 28.0387 Deducting from the total per-cerrtage of carbonic acid the portion in combination with lime the per-centage of free carbonic acid amounts to 0*014035;corresponding to 71610813 cubic centimetres in 100 litres or to 19.8535 cubic inches in an imperial gallon.The arrangement as above does not exhibit any chloride of sodium in the water which no doubt must exist as such in the Thames at Greenwich especially at high water. In the same manner sulphate of lime is undoubtedly present though not shown in the table. But as the precise form or the proportions in which the individual constituents are distributed in a mixed solution is not known-for experiment proves they may be variously associated in solution according to the degree of concentration-every arrangement must be more or less hypothetical. We have therefore adopted the principle followed in the preceding analyses of combining the strongest acid with the strongest base as affording the best means of comparison The general features of the foregoing analysis exhibit a large increase in the amount of the fixed constituents as compared with the water taken at Twickenham but not as compared with that MR.HERAPATH ON A MEDICINAL WATER from London Bridge. This appears intelligible from a portion of the large amount of organic matter found at London Bridge having disappeared in the further course of the river. The total amount of fixed constituents being however but slightly diminished the rather considerable decrease of organic matter must be supplied by some-thing that the water has taken up. We find this to consist prin- cipally of the alkalies magnesia and carbonate of lime the latter being taken up and held in solution by carbonic acid.In looking for a source of the additional amount of carbonic acid we think it may be found in the decomposition of the various organic matters both soliible and insoluble which are daily carried into the Thames and of which as our analysis shows a portion disappears in the progress of the river from London Bridge to Greenwich; although this diminution may have been partly occasioned by the influx of sea-water. By comparing the different results of the several analyses it becomes evident likewise that the waters of the river are afTected by other local circumstances probably at both these stations. It niay be mentioned that there are several chemical works which pour their refuse into the river both above and below the point where the water which is the subject of the present analysis was taken. I cannot conclude this paper without mentioning that I have been kindly assisted in this analysis by my father and brother so that each determination is the result of at least three separate and independant experiments.

ISSN:1743-6893    

DOI:10.1039/QJ8500200195

出版商:RSC    

年代:1850

数据来源: RSC

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MR. HERAPATH ON A MEDICINAL WATER XX.-Analysis of a Medicinal Water from the Neighbourhood of Bristol. By THOXNTON ESQ. J. HERAPATH At a distance of about fifteen miles from Bristol on the Cherry Rock Farm,* in the parish of Kingswood Gloncestershire there exists a spring or well of water which has been long held in great estimation by the inhabitants of Kingswood and the surrounding districts on account of its highly medicinal qualities. According to the present proprietor Mr. W. A. Long of Wotten-under-Edge (at whose request it was that the following analysis was undertaken) the water was analysed about forty years ago and a pamphlet written upon the subject; but nothing can be now learnt with regard to the name of * This farm is now in the occupation of Mr.T. Alway and is distant about three- quarters of a mile from the town of Wickwar ; half a mile from the Wickwar station ; one mile from the village of Kingswood and three niiles from the Charfield station on the Bristol and Birmingham Railway. FROM THE NEIGHBOURHOOD OF ERISTOL. the analyst or the results of his examination. It appears from the information which has been kindly afforded me by the above-mentioned gentleman that the well from which the water was obtained is from 45 to 50 feet in depth and the water rises to within 24 or 25 feet of the surface; its quantity is never sensibly affected either by a wet or dry season. The surface is a thin mould which rests upon a stratum of stiff clay of about five feet in depth; this clay is stained with iron in several places.This is succeeded by a bed of blue lias stone which contains numerous fossil shells.* There are several thin beds of this stone and in the spaces between them is stiff clay strongly impregnated with salt which can be seen glistening in it as well as tasted. Below this again there is for about 15 feet a dry marly clay which is described as being much mixed with the above-mentioned fossil-shells and round smooth stones like lap-stones. It is from the bottom of this bed that the water rises. Most of the springs in this neighbourhood when sunk to a great depth are generally inclined to be salt and a great deal of the blue lias stone which is plentifully met with here is stained with iron. The temperature of the water when taken differed only by about one degree from that of the surrounding atmosphere.Its specific gravity at 60° Fahr. was 1.00507. It evinced a slightly acid reaction with very delicate test-paper ; this however was most probably caused by the free carbonic acid present in the water as the paper immediately resumed its original colour upon the application of a gentle heat. The water possessed a very marked unpleasant saline taste. It was neither chalybeate nor sulphureous; but the rapid manner in which it under- went decomposition upon keeping showed that it contained a large proportion of organic matter.t A qualitative analysis likewise pointed out the presence of sulphuric carbonic crenic and apocrcnic acids chlorine lime magnesia soda and potash.There were also small qiiantities of phosphoric and nitric acids iodine bromine (?) oxide of iron silica and alumina (9). Quantitative analysis. * Described by the well-diggers as greatly resembling cockle-shells. f-This was still more clearly shown by its behaviour with chloride of gold when tested in the manner recently proposed by M. A. Dupasquier (Journ. de Pharm. et de Chim. XIII. 164 ; also Comptes Rendus Avril 5 1847). Upon adding a few drops of a solution of this salt to two or three hundred grains of the water contained in a small flask and applying heat as soon as the liquid began to boil the brownish-red tint mentioned by that chemist became immediately perceptible. The same effect was produced by exposing the solution to the sun’s light but more slowly.202 MR. HERBPATH ON A MEDICINAL WATER A. Determination of the total amount of saline constituents. Water employed. Weight of fixed residue. Per pint. I. 8794.36250 grs. 56.200 grs. 56.1200 11. 4397.18125 , 28.156 , 56.312 Mean. 56.256 B. An imperial pint (8794.3625 grs.) of the water was boiled for one or two hours in a porcelain vessel until all traces of the carbonic acid were expelled it was then allowed to remain undisturbed for some hours in order to give time for the precipitated carbonates &c. to deposit ; the supernatant fluid having been drawn off by a syphon the precipitate was collected on a filter well washed with water dried at about 300 or 350° F. and weighed; it amounted to 3.85 grains in weight (a).As it was found that a small quantity of the earthy carbonates still obstinately adhered to the sides of the basin it was dissolved off by means of a few drops of dilute hydrochloric acid; the acid solution thus obtained was supersaturated by a little carbonate of ammonia and evaporated to dryness ; the residue having been gently ignited to expel the ammoniacal salts was found to weigh 0.26 gr. This was added to the carbonates previously obtained (a) and both were subjected to analysis. They gave of Carbonic acid . . 1.747 grs Carbonate of lime. 3-978 , = Lime. . . 2.22770 grs. Sulphate of barytes 0-034 , = Sulpburic acid 0.01150 , Silica* . . . . 0.120 , These numbers are equivalent to Carbonate of lime . . 3.96665 Sulphate of lime .. 0.01955 Silica . . 0~12000 4.10620 Besides the above I also detected exceedingly minute traces of oxide of iron alumina magnesia and phosphoric acid; but they were much too small in quantity to be estimated with exactness. C. The filtered water having been intimately mixed with the washings of the filter (a) was carefully divided by means of a * This residue of silica was dark in colour but upon being heated to redness became perfectly white although it did not experience any perceptible diminutioii in weight. This would appear to prove the presence of a little bituminous matter. FROM THE NEIOHBOURROOD OF BRISTOL. 203 graduated tube into four separate portions of equal weight. Of these the first was employed for the estimation of the sulphuric acid and chlorine ;the second for that of the lime and magnesia ;in the third the soda and potash were estimated; and in the last the organic matter.The following quantities were obtained Sulphate of barytes 18.328 grs. = sulphuric acid 6.2124 grs. =24.8496 per pint ; Chloride of silver (fused)* 4.657 grs.= chlorine 1.16425 grs. =4*657 per pint. The second portion gave Carbonate of lime 1.725 gis. =lime 0.9658 grs. =3.8632 grs. per pint Pyrophosphate of magnesia 3.837 grs.=magnesia 1.3704 grs. =5*4816 grs. per pint. The third portion gave Mixed alkaline chlorides 5.125 grs. Yotassio-chloride of platinum 0.086 gr. =chloride of potassium 0.0262 gr. =potash 0.0165 gr. =0.0660 per pint; there were therefore of Chloride of sodium 5.0988 grs.=2-7193 grs.of soda= 10.8772 per pint. The fourth portion was evaporated to dryness at about 300° to 320°F, and the residue was kept at that temperature until its weight remained constant; it was then heated to redness with an excess of anhydrous carbonate of soda and the loss of weight noted; it amounted to 0.826 grs.; consequently the entire weight of the orga- nic matter contained in a pint of water was 3.304 grs.? D. Estimation of the iodine.-The alcoholic solution of the salts contained in a quart of the water was evaporated to dryness the residue re-dissolved in a small quantity of water and the solution precipitated by proto-chloride of palladium ;the iodide of palladium obtained when dried at 212O F, was found to weigh 0.022 gr.= 0.0154 gr. of iodine = 0.0077 gr. per pint = 0.0143 gr. of iodide of silver. F. Estimation of the nitric acid.-The salts which remained after the evaporation of 17588.725 grains of the water were introduced into a small tube-retort where they were treated with * The reduction which subsequent experiment proved it was necessary to make in this on account of the presence of iodide of silver indicated the true quantity of chloride of silver to be 4.6534 grs. =chlorine 1.16335 grs =4.6534 grs. per pint. t For the estimation of the crenic and apocrenic acids see F. MR. HERAPATH ON A MEDICINAL WATER a slight excess of moderately-strong sulphuric acid. The mixture was then heated in a sand-bath and the acid vapours which were given off were conducted into a glass receiver where a large excess of recently precipitated carbonate of silver was held in suspen- sion in a small quantity of distilled water.Great care was taken to suspcnd the operation immediately upon the appearance of the fumes of sulphuric acid. The solution of nitrate of silver &c. which remained in the receiver having been boiled to expel any carbonic acid which might have been present was filtered to separate the excess of carbonate and chloride of silver and precipitated by a little dilute hydrochloric acid ;the chloride of silver thus produced (which of course corresponded to the nitrate of silver present in the solution) was collected on a filter washed &c. and weighed Ag C1 (fused) = 0,038 gr.= nitric acid 0.014 gr. = 0.007 per pint.* G. Estimation of the Organic Acids.-The whole of the salts which remained upon the evaporation of a quart of the water were boiled for a short time with a dilute solution of potash. The solu-tion having been filtered and the excess of alkali supersaturated with acetic acid it was precipitated by acetate of copper &c. in the usual manner. It gave of Aprocrenate of copper? 0.458 gr. = apocrenic acid 0-3538gr. = 0.1769 per pint. Crenate of copper 0.3510 gr. = crenic acid 0.2562 gr. = 0°1281 per pint. If we deduct therefore frorn the entire weight of the organic matter obtained by the preceding experiments = 3.3040 grs. that of the above described organic acids 0.3050gr.(0.1796 + 0.1281) we obtain 2.9990 grs. as the true weight of the extractive or nitro-genous organic matters contained in a pint measure of water G. Estimation of the gaseous carbonic acid.-This was performed in the usual manner by passing the gas which was evolved upon boiling the water through an amnioniacal solution of chloride of calcium. A pint measure of the water gave 4.43grs. of carbonate of lime = 1.94192 grs. of carbonic acid = 4.1242 C.I. at the ordiuary temperature and pressure.$ * For this simple and elegant method of estimating the nitric acid I am in-debted to my father Professor W. Herapath by whom it has been long known and adopted. f-In the above calculations the numbers given by Berzelius for the atomic weights of the two acids have been employed.According to his experiments the combining equivalent of apocrenic acid would appear to be represented by the number 135-6 and that of crenic acid by 108-0.-Poggendorff’s Annalen XXIX 238 et seq. $ 103 C.I. weigh 47262 grs.-Dulong and Berzelius. FROM THE NEIGHBOURHOOD OF BRISTOL. 205 From the analytical results contained in the preceding pages the following composition for this mineral water has been deduced Per pint = 8794.3626 grs. Per gallon = 70357.9 gra. Carb. acid gas at 60° F. 4.1242 C.I.= , 32.9936 C.1. Imperial pint. Imperial gallon. Fixed constituents. Chloride of magnesium . 0.0600 . . 0.4800grs. Chloride of potassium . 0.1048 . . 0.8384 Chloride of sodium . . 7.6030 . . 60.8240 Iodide of sodium .. 0-0090 . 0.0730 Bromide of sodium ? . . traces. . . traces. Sulphate of magnesia . 16.2190 . . 129.7520 Sulphate of soda . . 15.3450 . . 122.7600 Sulphate of lime . . 9.3895 . . 75.1160 Nitrate of lime . 0.0120 . . 0.0960 Apocrenate of magnesia . 0.%030 . . 1.6240 Crenate of magnesia . 0.1450 . . 1.1600 Nitrogenous organic matter 2.9990 . . 239920 Carbonate of lime . . 3.9666 . . 31.7328 Carbonate of magnesia . traces. . traces. Carbonate of protorride of iron traces. . . traces. Phosphate of lime . . traces. . . traces. Alumina? . . traces. . traces. Silica . . 0.1200 . . 0.9600 Bituminous matter ? . . traces. . . traces. 5 6.1759 449.4072 Absolute quantity of saline 450.0480 gredients obtained . May 7 1849. The President in the Chair. The address delivered at the Anniversary Meeting of the Geological Society by Sir Henry de la Beche was presented by the author. The following communication by Mr. Danson was read ;likewise a note on a singular substance resulting from Cloves by Dr. R. Scott of Liver-pool and a note on the composition of the Deep Well Water of the RoyaI Mint by W. T. Brande Esq.*

ISSN:1743-6893    

DOI:10.1039/QJ8500200200

出版商:RSC    

年代:1850

数据来源: RSC

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205 FROM THE NEIGHBOURHOOD OF BRISTOL. XXL-On the Sulphites of Potash Chromium Lithia and Bismuth BY JOSEPH DANSON. STUDENT IN THE LIVERPOOL COLLEGE OF CHEMISTRY. In Dr. Muspratt’st paper on the sulphites the composition of the above-mentioned salts was not ascertained ; I therefore undertook * The publication of this paper has been deferred at the request of the author. t Liebig’s Annalen Band L. 1844 page 259. 206 MR. DANSON ON THE SULPHITES OF POTASH their preparation and analysis with a view of lessening the gaps in this interesting series. Sulphite ofpotash.-This salt was obtained by passing sulphurous acid through an aqueous solution of potash until the liquid smelt strongly of the gas; ether was then added to the solution which was placed in a flask well corked and allowed to stand at rest for three weeks-during this time a white crystalline precipitate was deposited.0.2040 grm. gave 0.2729 grm. sulphate of baryta = 0.0746 sul-phurous acid or 36.56 per cent. 0.1204grm. gave 0*1600grm. sulphate of baryta = 0.0437 sul-phurous acid or 36.29 per cent. Centesimally represented Theory. Found. Mean. w-I. 11. 1 equiv. of Potash . . . 48 53.93 -7 1 , , Sulphurous acid 32 35.95 36.56 36.29 36.42 1 , , Water. . . . 9 10.11 -L 89 99.99 Formula KO SO + aq. I can only account for the excess in the sulphurous acid from the presence of traces of sulphuric acid in the salt. It has been remarked that a sulphife can scarcely be kept for an hour exposed to the air without a portion being converted into suZphate; in this respect the salts of sulphurous acid differ from those of selenious acid which do not oxidize on exposure.* Sukhite of Chromium-This salt is formed by passing sulphurous acid through water holding in suspension freshly precipitated oxide of chromium; when the gas was passed through the menstruum for some time the whole becomes clear forming a dark green liquid.If the solution be now boiled to expel the excess of acid a green powder is deposited having the following composition 2 Cr 0,3 SO,+ 16 aq or 2 (Cr 0 SO,) + HO SO + 15aq. I expected to find the chrotnium salt correspond with the sulphites of alumina and sesquioxide of iron but the analytical results at once destroyed the supposed analogy. The following formulze represent the three compounds Siilphite of alumina .. Al 0 SO,+ 4aq. Sesquisulphite of iron . . . Fe 0 SO,+ 7 aq. Sulphite of chromium ; . 2Cr 0 3SO,=l6 aq. The analysis of the salt yielded the following results 0.1020 grm. gave when heated to redness 0.0408 grm. of the oxide of chromium or 40.00 per cent. * On the salts of selenious acid Quart. Journ. of Chem. Society April 1 1849 page 54. CHROMIUM LITHIA AND BISMUTH. 207 0.1467 grm. gave 0.1280 grm. sulphate of baryta=0.0350 sul-phurous acid or 23.85 per cent. Centesimally represented Theory. Found. 1 equiv. of Oxide of chromium . . 160 40.00 40.00 3 , , Siilphurous acid . . . 96 2400 23.85 16 , , Water . . . . . . 144 36.00 c 400 100*00 When heated in a test tube moisture and sulphurous acid are given off; when the heat is continued for some time a mirror forms on the upper part of the tube disappearing when the heat is increased.SuZphite of Lithia.-If sulphurous acid be passed through water holding in suspension the carbonate of lithia the whole soon dissolves forming a colourless liquid; the salt may be procured either by adding absolute alcohol or by boiling the solution to expel the free acid when white feathery crystals are deposited which on exposiwe to the atmosphere become of a light yellow colour. 0.0563 grm. gave 0.0663 grm. sulphate of baryta = 0*01821sul-phurous acid or 32.14 per cent. Centesimally represented Theory. Found. 1 equiv. of Lithia . . . . . 14 14.00 -Sulphurous acid .. 32 32-00 32.14 I Water . . . . 54 54.00 W 100 100-00 Formula LiO SO + 6 aq. Subhite of Bismuth.-I obtained this salt by agitating freshly precipitated oxide of bismuth with a strong solution of sulphurous acid keeping the mixture in a flask well corked for four days; the precipitate was of a straw colour but became nearly white when dry. Heated in a test tube the salt sublimed giving off no moisture. 0.1810 grm. gave 0.1593 grm. oxide of bismuth or 81.01 per cent. centesimally represented Theory. Found. 1 equiv. of Oxide of bismuth . 237 88.10 88.01 1 , , Sulphurous acid . . 32 11.89 -269 99.99 Formula RiO SO,. The oxide of bismuth obtained by heating the nitrate to redness does not absorb any sulphurous acid. This sulphite in all probability corresponds with the carbonate BiO CO ?

ISSN:1743-6893    

DOI:10.1039/QJ8500200205

出版商:RSC    

年代:1850

数据来源: RSC

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208 NESSRS. MATER AND BRAZIER ON PLATE CJL,QSS. May 21 1849. Wm. ,411en Miller M.D. Vice-president in the Chair. William Glass Esq. was elected a Fellow of the Society. The following papers were read XX1I.-An Analysis of Plate Glass. BY MESSRS.J. E.MAYERAND J. S. BRAZIER STUDENTS IN THE ROYAL COLLEGE OF CHEMISTRY. In going over the analyses of the different varieties of glass which have been recorded we find that but little attention has been paid to the composition of plate glass a material which is almost be- coming a necessary of life. It is moreover remarkable that no analysis of the plate glass manufactured in Great Britain has ever been published. The following pages contain the results obtained from the analysis of three different specimens of plate glass which we undertook at the request of Dr.Hofmann.* These specimens were procured at the three most extensive plate glass manufactories of England. Which are-I. The British Plate Glass Company St. Helens Liverpool. 11. The London Thames Plate Glass Company Bow Creek Blackwall. 111. The London and Manchester Plate Glass Company Sutton St. Helens Liverpool. For the purpose of analysis these specimens of glass were reduced to the most minute state of division which was effected by levigating in the usual nianncr. None of the specimens whilst digesting in water gave any reaction with the most delicate test papers. To determine the extent of their solubility in water from four to five gramnies were digested in that menstruum for about forty-eight hours the clear solution in each case yielded on evaporation but a slight residue too small for determination.* I am indebted for these specimens to the kindness of Mr. Fincham of the British Plate Glass Works.-Dr. A. W. Hofmann. MESSRS. MAYER AND BRAZIER ON PLATE GLASS. 209 The specific gravity of these specimens of glass is as follows British Plate Glass . . 2.319 London Thames Plate Glass. . 2.242 London and Manchester Plate Glass . . 2-408 A qualitative examination showed the presence of silicic acid potash soda sesquioxide of iron alumina lime and in one case traces of manganese. The silicic acid was determined in the usual manner by fusion with pure carbonate of potash. The sesquioxide of iron the alumina and the lime were afterwards precipitated from the hydro- chloric filtrate To determine the alkalies the glasses were decomposed by means of hydrofluoric acid in an apparatus recommended by Brunner,* which consists of a leaden capsula with a flat bottom about six inches in diameter and four inches high in the centre of which is placed a small leaden ring about an inch and a half high which serves as a support for a platinum dish.The leaden capsula has a cover fitting perfectly tight. To set the apparatus in action it is necessary to cover the bottom of the capsula with a layer of pulverized fluorspar about half an inch in thickness and to pour upon it some sulphuric acid sufficient to form a thick paste A weighed portion of the finely powdered glass after being put in the platinum dish is covered with water and placed on the leaden ring.The whole is then kept at a gentle heat either on a sand bath or by means of a spirit-lamp. By a few preliminary experiments we found the action on the glass to be exceedingly slow when covered merely with water ; it was then suggested to us by Dr. Hofmann to try instead of water a strong solution of ammonia; we found that the hydrofluoric acid being much more rapidly absorbed by this latter agent the decom- position was facilitated in a remarkable manner. The first of the two following tables shows the amount of sub-stance employed; the results obtained are exhibited in Table 11. TABLE I. I. 11. 111. British London Thames London & Manchester Plate Glass.Plate Glass. Plate Glass. 1 2 1 2 1 2 grm. grm. grm. grm. gm. grm. Quantity Of glass for} 1.3429 1,1750 1.1579 1.1906 1.0508 1.1095 general analysis . . Quantitv of glass for estimation of alkalies} 1.9400 2.1500 1.4200 1.6800 19200 2'0f00 * Poggeudorfs Annalen XLIV. page 134. VOL. 11.-NO. VI1. P 210 MESSRS. MAYER AND BRAZIER ON PLATE GLASS. TABLE 11. I. 11. 111. British London Thames London 8z Manchester Plate Glass. Plate Glass. Plate Glass. 1 2 1 2 1 2 grm. grm. grm. grm. grm. grm. Silicic acid . . . . 1.0402 0.9180 0.9090 0.9390 0.8200 0.8630 Chloridesof potassium} 0.5700 ,,,6460 .. .. 0,2675 0,5360 and sodium . . . Bichloride of platinum) 0.3100 o.3610 .. .. 0,0925 0.1835 and potassium . Chloride of sodium .0.4735 0.5360 .. .. 0.2390 0.4790 Sesquioxide Of ironand} 0.0127 0.01G 0.0320 0.0495 0.0373 0.0405 alumina . . . . Carbonate of lime . . 0.1266 0,1135 0-1245 0.1305 0,0887 0.0987 Siilphates of potash} .. .. 0-4105 0.4940 .. .. and soda . . . . Sulphate of baryta. . .. .. 0.6645" 0.79601' .. .. The following numbers correspond with the foregoing results 1.-BRITISHPLATE GLASS I. 11. MEAN. 0 Silicic acid . . 77.4592 77.2700 7703646 Potash . 298110 3.2192 3.0151 Soda . 12-9232 13.2028 13.0630 Lime . . 5.2192 5*4096 5.3144 Manganese . . >> >> 99 Sesquioxide of iron . 0.945 7 0.8936 0.9197 Alumina . . trace trace trace 99-3583 99.9952 99.6768 II.-LONDONTHAMES PLATE GLASS. I. 11. MEAN. Silicic acid .. 78.5050 78.8669 78.6859 Potash . . 1.2744 1.4176 1.3460 Soda . . 11.5919 11.6724 11*6322 Lime . 6-0605 6.1 380 6-0992 Manganese . 9J 9) >> Sesquioxide of iron . trace trace trace Alumina . 2.7636 2.5970 2.6803 100*1954 100.69 19 100.4436 * These numbers were obtained iii a11 indirect determination of the alkalies. MESSRS. PVIAYER AND BRAZIER ON PLATE GLASS. 211 III.-LONDONAND MANCHESTER PLATE GLASS. I. 11. MEAN. Silicic acid . . 78.0357 77.7827 77.9092 Potash . 1.7453 1.7062 1-7237 Soda . 12.4373 12,2822 12.3598 Lime . 4.7270 4.9816 4.8543 Manganese . traces traces traces Sesquioxide of iron . >> J> ,I Aliimina . 3.5495 3.6502 3.5998 100*4948 100*4029 100.4488 A table is subjoined containing analyses of several varieties of plate glass in order that the composition of the plate glass in this country may be compared with that manufactured abroad.The Venetian glass was analysed by M. Berthier the Bohemian mirror glass by Yeligot and the French glasses by Dumas.* London London aiid Venetian Bohemian French Plale British Thames Man-Plate Plate Glass. Plate Plate Chester Glass. Glass. No. 1. No. 2. Glass. Glass. Plate Glass. Silicic acid . . . 68.6 67.7 75.9 73.85 77-36 78.68 77.90 Potash . . . . 6.9 21.0 5.50 3.01 1.34 1.72 Soda ... . . 8.1 .. ii.5 12-05 13.06 11.63 12.35 Lime ... . . 11.0 9.9 3.8 5.60 5.31 6.09 4.~5 Magnesia. . . . 2.1 .. .. .. .. .. *. .a Manganese . . . 0.1 .. .. .. .. trace Oxide of iron . . 0.2 .. .... 0.9 1 trace .. Alumina . . . . 1.2 1.4 2.8 3-50 traces 2-68 3.59 98.2 200*0 100.0 100*00 99-65 100.42 100.41 Plate glass is usually considered as a double silicate of lime and soda or of lime and potash. The following atomic expressions repre- sent the different analyses contained in the above table; the amount of potash contained in the English varieties of glass being very trifling this oxide has been neglected altogether in the construction of their formula Venetian plate glass . . 2 KO 3 NaO 5 CaO 22 SiO Bohemian mirror glass . . KO CaO 4 SiO French plate glass No. I . 4 NaO CaO 11SiO French plate glass No. 2 . . KO 3 NaO 2 CaO 14 SiO British plate glass . . 2Na0 CaO 9 SiO London Thames plate glass . 2 NaO CaO 8Si0 London & Manchester plate glass . 2Na0 CaO 9 SiO * Comp. Knapp’s Technology Vol. XI. page 16. Pa

ISSN:1743-6893    

DOI:10.1039/QJ8500200208

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年代:1850

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212 MIL HENRY MEDLOCK ON THE AMYL SERIES XXI1I.-Researches on the AmyFXeries. BY HENRYMEDLOCK, ESQ. 11. AinyEo-urethane.-The original object of my experiments upon the action of chlorocarbonic acid (phosgene gas) on fixsel-oil was the formation and study of a compound corresponding to that obtained by Dumas* in the treatment of chlorocarbonic ether with an aqueous solution of ammonia to which the term urethane has by its discoverer been applied. In a paper recently communicated to this Society,t I detailed the results of some experiments which seemed to point out the existence of a member in the amyl-series homologous to chlorocarbonate of ethyl although the ccmpound in question was of very unstable character; being in the presence of water rapidly decomposed into carbonate of amyl with evolution of carbonic and hydrochloric acids.Repeated observations proved that the compound obtained in this reaction could not be heated without suffering partial decomposition. On treating the crude product which had been heated with ammonia chloride of ammonium mas abundantly formed together with a small quantity of a fatty substance crystallizing with remarkable facility the chief portion however of chlorocarbonate at my disposal had evidently been decomposed under the combined influence of heat and moisture so that the quantity of the crystalline compound obtained was too small to admit of establishing its composition by analysis or for the study of its products of decomposition; aualogy only allowed me to conclude that it was the urethane of the amyl-series.It appeared very probable that by modifying the process in such a manner as to exclude the slightest trace of moisture the chlorocar- bonate of amyl and by subsequent treatment with ammonia the urethane likewise might be obtained. In repeating the experiment perfectly pure fusel-oil was introduced into a glass balloon of 60 litres (about 12gall.) capacity filled with dry phosgene gas ;rapid absorption took place as was evident by the elevation of temperature the liquid at the same time assuming a fine amber cclour. After being in contact for a quarter of an hour air was admitted to replace the absorbed gas a portion of the fluid being immediately transferred to a perfectly dry retort and submitted to distillation.It comuicncd boiling at 120' * Ann. de Chimie et de Phys. T.LIV p. 225. f-Quarterly Jouriial Chcm. SOC. ~o1 p. 538. I MR. HENRY MEDLOCR ON THE ARIYL SERIES. (248O F.) the thermqmeter rapidly rising to 224O (43502~ F.) where it remained tolerably stationary. The fluid distilling over at this temperature and that also which remained in the retort no longer solidified on the addition of ammonia indicating at once that decom- position had taken place. The facility with which my former prepa- rations were decomposed the peculiar odour of the compound and the temperature at which it steadily boiled left no doubt of its being the carbonate of amyl produced by the action of heat upon the chlorocar- bonate ;hence it is evident that the latter compound does not admit of being obtained in a state of absolute purity.The decomposition of the chlorocarbonate into carbonate of amyl carbonic and hydrochloric acids in the presence of water is easily intelligible. In the experiment however which I have described water was excluded with the greatest care. The hydrogen and oxygen therefore necessary for the formation of the hydrochloric and carbonic acids must have been derived from the substance itself. This view is experimentally supported by the large quantity of charred substance which remained in the retort after the distillation. On treating the remaining portion of chlorocarbonate of amyl which had not been heated with an aqueous solution of ammonia the mixture entered almost into a state of ebullition evincing a very powerful reaction.The oily liquid floating upon the surface solidified on cooling to a crystalline mass which was subsequently freed from adhering fusel-oil by pressure between folds of bibulous paper and from chloride of ammonium by washing with distilled water until it no longer affected a salt of silver. The change which takes place in this reaction is represented in the following equation C,oH,,O,C,{~} +2N II,=C,0H,10,C,(~f~2} + N H*Cl L-y-J L--y-.L--J Chlorocarbonateof arnyl. Amylo-urethane. Amylo-urethane as I propose to designate this compound is soluble in alcohol ether and boiling water from which it crystallizes on cooling in beautiful iridescent satiny needles. It is fusible at 60' (140"F.) and distils without alteration at 2.200 (428OF.) the distillate solidifying in the neck of the retort into a fatty crystalline mass.Analysis gave the following results I. 0,4940 grm. of substance burned with protoxide of copper gave 0.9983 , carbonic acid and 0.4418 , water. 11. 0.3540 , substance gave 214 MR. HENRY MEDLOCK ON THE AMYL SEBIES. 0.6050 grm. of bichloride of platinum and chloride of ammo-nium closely coinciding with the formula as will be seen by the following comparison of the theoretical numbers with the experimental results Theory. Experiment. I--12 equivs. of Carbon . . 72 54-96 55.11 13 , Hydrogen . 13 9-92 9-93 4 ,> Oxygen * . 32 2443 -1 equiv. of Nitrogen . 14 10.69 10.70 _I-1 , Amylo-urethane 131 100.00 By distillation with caustic baryta amylo-urethane is decomposed into ammonia and carbonic acid together with an oily product possessing the characteristic odour of fusel-oil and exhibiting a boiling temperature of about 132O (296.6 F.) which is that of pure hydrated oxide of amyl; in this case also the water necessary to accomplish the reaction is furnished by the total destruction of a portion of the substance itself.Sulphuric acid completely dissolves amylo-urethane in the cold producing no action upon it whatever even when allowed to remain in contact for several days on the addition of water it separates again forming a crystalline pellicle on the surface of the fluid; if it be heated it is resolved into sulphamylic acid and ammonia with the evolution of carbonic and sulphurous acids.The analysis of the baryta-salt gave the following results 0.2530 grm. dried in vacuo gave 0.1210 , sulphate of baryta = 0.0712 , barium. Agreeing perfectly with the formula Ba SO, C, Hi SO,+ HO as may be seen by the following comparison Theory. Exyer. I-'-A-10equivs. ofcarbon . . . . 6000 24-52 -12 , Hydrogen. . . . 12-00 4.90 -9 , Oxygen . . . . 72-00 29-43 -2 , Sulphur . . . 32.00 13.09 -1 equiv. of Barium . . . . 68.64 28.06 28.14 1 ecluiv. of Barium-salt . . 244.64 100~00 ME. HENRY MEDLOUK ON THE AMYL SERIES. 215 The opinions held by chemists regarding the constitution of the urethanes are divided ; some assume in these compounds the existence of a peculiar acid-carbamic acid; if this view be adopted the com- pounds in question will accordingly be considered as the carbamates of methyl ethyl and amyl; others regard them as carbonic ethers associated with the elements of carbamide.The beautiful investiga- tion of M. Wurtz appeared to offer a new mode of viewing them. The discovery of methylidine and ethylidine and the remarkable analogy of these bases to aniline render it probable that future re- searches will elicit compounds in the new alkaloidal series analogous to the derivatives of aniline. In fact the compounds corresponding in the methylidine- and ethylidine-series to carbanilide and carbani- lamide have actually been obtained. Now the composition of members in these new alkaloidal series analogous to anthranilic 01 carbanilic acid perfectly coincides with the formulae of the different urethanes.Aniline . %*P N Anthranilic acid . . C,,H7 NO4=CI2H7 N+fLCO Ethylidine . c4 * N Urethane . . C H N04=C4 H N+2CO2 Amylidine (P) ClO HI3 N Amylo-urethane . . C12H, NO4= C10 HI N + 2 Cog It was necessary and Dr. Hofmann particularly directed my attention to these points to test this view by the study of the metamorphoses of the new compound; if the formative elements of the urethanes were actually grouped as those in anthranilic acid amylo-urethane should have yielded with alkalies amylidine and with sulphuric acid sulphamylidic acid ; repeated trials however have proved the results to be as I have above detailed.Hence it appears that this class of compounds are merely isomeric with the true carbamic acids of the new alkaloids which the progress of science will not fail ere long to bring to light. 216 MR. MUSPRATT ON THE CARBONATE OP ALUMINA. June 14 1849. The President in the Chair. Wm. Neild Esq. was elected a Fellow of the Society. The following alteration in the 14th bye-law was proposed by the Council,-cc That no paper shall be read at any meeting of the Society which has not been in the hands of the Secretary for at least one week previously to the day of meeting ; and that no paper once deposited with the Secretary shall be returned to the author.” The following communications were read On the Carbonate of AEumina by SHERIDAN MUSPRATT,PH.D.-Dr.Muspratt analysed the precipitate produced by carbonate of ammonia in a solution of pure alum ; the precipitate was washed until no trace of ammonia remained in the precipitate or filtrate. This precipitate prior to Mr. Phillips’ remarks at the meeting of the British Association at Swansea had been always described as hydrate of alumina Al Ok,HO ; the analysis proves that it is a carbonate. The analytical results are as follows 0.1600 grms. of Substance gave in Will’s apparatus 0.0095 , ),carbonic acid. 0.1450 , , substance yielded 0.0650 , , alumina. Centessimally represented Theory. Experiment. ,-3 equivs. of alumina . . 153 44-86 44.82 2 , , carbonicacid . 44 12-91 12-19 16 , , water . . . 144 42.23 -341 100*00 These results coincide closely with the formula 3 A12 03,2 CO f 16 aq.On the Manufacture of Soda and on the Composition of Salt-cake Black-ash Soda-ash and Soda-waste by FREDERICK and JOSEPH MUSPRATT DANSON, Escs-The authors after describing in this paper the ordinary soda process introduce the following analyses of the different products of the manufacture. SALT CAKE AS ANALYSED BY DR. MUSPRATT. Sulphate of soda. . . . . 95.936 ,) , lime. . . . . 0.572 ,) , magnesia . . . 0-136 Chloride of iron . . . . . 1,357 Sesquioxide of iron . . . . 0.291 Insoluble matter . . . . . 0.400 Water and free acid . . . 1.308 1oo*ooo MESSRS. MWSPRATT AND DANSON ON SODA &C. 217 COMPOSITION OF BLACK-ASH. Calculated on 100 parts without charcoal and sand Carbonate of soda .. 26.233 28*890 , , lime . . 12.913 14.221 Sulphide of calcium . . 23.479 25,857 , , sodium . . 0-363 0.399 Chloride of sodium . . 2.786 3.068 Sulphate of soda . . 0.743 0.819 Iron alumina . Phosphate of lime and :} 5.653 6-226 Magnesia". Caustic lime . . . 8.388 9'237 , soda . Silicate of magnesia Charcoal andsand . . . . . 7.506 1-840 9-197 8.267 2.026 c Water &c. . 0.899 0.990 1oo*ooo 1oo*ooo COMPOSITION OF SODA-ASH. Ordinary Ash for soap Ash for ash. makers. plate glass. Brown. Muspratt. Danson. Carbonate of soda . 71.614 77*085 78.55 Caustic soda . -4.881 4-15 c c Hydrate of soda . 11.231 Sulphate of soda . 104202 5.110 1-70 Sulphite of soda . 1.117 Aluminate of soda .0.923 Sulphide of sodium . 0.630 Carbonate of lime . 0.320 Sesquioxide of iron . 0.324 0.27 Carbonate of potash 0*200 1 , , magnesia -I 0.33 c Cyanide of sodium . Silicate of soda . 1.042 2.400 0'25 Chloride of sodium . 3*051 7.130 5*62 c Sulphide of calcium 0.200 Charcoal and sand . 0.316 0.659 0-48 Water . 0.504 1-061 8-65 1oo*ooo 100-000 1oo*ooo * These constituents of black-ash are not stated in former analyses.-Dr. M. MR. EVANS ON CHROMATE OF COPPER. COMPOSITION OF SODA-WASTE. Calculated for 100 parts without charcoal and sand. 1. 11. I. 11. Fresh. Old.* Fresh. Old. Sulphide of calcium ..30.835 21.905 25.789 36*698 Bisulphide of calcium . 0.520 5.070 5.969 0.618 Carbonate of lime .. 19.681 35.065 4 1-202 23.423 Caustic lime ....10.110 7.409 8.723 12*032 Iron alumina .. Phosphates of lime and -16.216 7.572 8.914 7*398 Magnesia. .... Sulphate oflime ... 3.857 2.147 2'528 4.590 Silicate of magnesia . 1.300 3.080 3.626 1.785 Sulphide of sodium ..2.412 1.226 1.443 2.870 Charcoalandsand ..15.978 15.060 -Water andloss .. . 9.091 1.466 -1.726 10589 1oooooo 1oo*ooo 100-000 100~000 In the above analysis the quantities of carbonate of lime and bisul- phide of calcium differ materially. The oxysulphide of lime decomposes readily giving rise to sulphide and bisulphide of calcium and caustic lime which latter speedily attracts carbonic acid. Very old waste principally consists of sulphate and carbonate of lime. June 18 1849.Col. Ph. Yorke in the Chair. John Shier M.D. LTdI. was elected a Fellow; and M.M. Boussin-gault Chevreul Gay-Lussac L. Gmelin H. Kopp Laurent Mitscherlich Pelouze Regnault H. Rose Thenard and Wohler were elected Foreign Members of the Society. The following papers were read On Chromate of Copper. By H. SUGDEN Student in the Liver-EVANS pooZ CoZZege of Chemistry.-When a salt of copper is precipitated by chromate of potash a yellowish-brown precipitate is produced which becomes reddish-brown when dried. This salt contains a large and variable quantity of chromate of potash. After being washed for four days until no soluble matter passed through the filter the salt was dried and heated to redness and the author was then enabled to extract con- siderable quantities of chromate of potash from it by boiling water.The *This naste was ahout six weeks old ;it \!as hied 011 awater-bath before being analysed. MR. HEISCH ON THE ESTIMATION OF CYANOGEN. 219 composition of the brown salt before being heated and treated with hot water is stated by the author as follows Oxide of copper . . 40-59 Chromic acid . . 54.62 Potash . . 1.65 Water and loss . 3.14 1oo*oo Corresponding to the formula 29 (CuO CrO,) KO CrO + 10 Aq. On the quantitative estimation of Cyanogen in analysis. By CHARLES HEISCH, Ess.-Having occasion to analyse a number of the compounds of cyanogen and mercury I was led to seek a more ready means of estimating the latter body than that usually adopted viz.an ulti- mate analysis. After one or two trials I found the following method give such good results that I thought a communication upon the subject might not be unacceptable to the members of the Chemical Society more especially as it is applicable not only to the analysis of the cyanides of mercury but to that of many of the double cyanides sueh as cobalticyanide of potassium &c. which have hitherto been analysed by combustion. The substance to be analysed is put into a small flask capable of containing from two to three ounces with some pieces of pure zinc and a little water. A cork is fitted to the flask perforated with two holes through one of which a tube-funnel passes to the bottom of the flask and in the other is fixed a tube bent twice at right angles; the other end of this tube is dipped into a solution of nitrate of silver.Sufficient sulphuric acid is now added to cause a brisk evolution of hydrogen when the whole of the cyanogen is converted into hydrocyanic acid and is carried over into the nitrate of silver and there precipitated as cyanide of silver. The heat produced by the action is usually enough to drive over all the hydrocyanic acid formed; but should this not be the case the flask may be heated until no more cyanide of silver precipitates. In dealing with the salts of mercury by this method it is necessary to add to the sulphuric acid enough nitric acid to prevent the action being stopped by the amalgamation of the zinc. In proof of the accuracy of this method I may state that 11-87’grs. of bicyanide of mercury gave 12.554 grs. cyanide of silver by calculation it should have given 12.608 grs.

ISSN:1743-6893    

DOI:10.1039/QJ8500200212

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年代:1850

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220 MR. FIELD ON COPPER SLAGS. XX1V.-Examination of some Nags from copper smelting fumaces. BY FREDERICK FIELD,ESQ. The phenomena occasioned by the continued action of heat upon mineral substances in connexion with various fluxes such as lime felspar &c. have been carefully studied by several eminent philoso- phers their experiments I believe however have bcen chiefly con- fined to the laboratory and to the products obtained within the confines of the crucible in the assaying furnace. Many hundred analyses of slags resulting from all kinds of fluxes employed by the assayer have been made by M. Bertier and more recently by Mr. Mitchell in order to shew the different states of mineral and flux before and after fusion and their researches have been inva- luable to the assayer and practical smelter throwing considerable light upon the various and oftentimes complicated action resulting at an elevated temperature.The following analyses have been made upon the products of furnaces in which the ingredients were enabled mutually to react upon a more extended scale the fluxes being at the same time not very unlike those employed by the assayer. The experiments described below ill I hope not be entirely destitute of interest phenomena frequently taking place in operations of con-siderable magnitude which cannot be observed in the smaller and humbler experiments in the laboratory furnace. The slags the analyses of which form the subject of the present paper were obtained from the furnaces of the South American and Mexican Company in Chile and the analyses were performed in the laboratory of that establishment.The method of smelting copper carried on at the works of the company is that patented by Mr. Napier. When the mineral was mixed with 20 per cent of its weight of common salt and 15 per cent of lime and the whole kept in a state of fusion for some time the slags on being skimmed presented an uniform mass perfectly limpid and free from metallic particles upon cooling however the mass separated into two distinct portions which could be divided from each other with the greatest facility a slight blow of the hammer being sufficient to cause,them to fly asunder it appeared to me interesting to determine the composition of both portions in as much as they presented very distinct physical appearances the lower stratum having a highly crystalline texture very much resembling certain species of syenitic rock while the upper portion had a fine glassy appearance totally devoid of crystallization.MR. FIELD ON COPPER SLAGS. This latter which we shall distinguish as No. 1 or glassy slag py- sessed a fine dark green colour closely approaching to black having exactly the appearance of the glass from which the common wine bottles are manufactured it presented a highly conchoidal fracture and was immediately decomposed by aqua regia and even by boiling hydrochloric acid. A qualitative analysis shewed the presence of silicic acid alumina oxide of iron lime magnesia manganese chlorine sodium with traces of sulphur.The following is its composition in 100 parts. Silica . . 49.26 Alumina . . . 12-37' Yrotoxide of iron . . 18.60 Lime . 7-84 Magnesia 2.62 Oxide of copper . 0.70 Chloride of sodium . 0.48 Soda . 7.93 Manganese . * *} traces Sulphur . Loss in analysis . 0.20 100*00 The chloride of sodium was estimated from the amount of chlorine obtained by boiling 200 grains of finely pulverized slag for an hour with distilled water and subsequent precipitation with nitrate of silver. As the slag was perfectly decomposable by aqua regia fusion with baryta for the estimation of the soda was unnecessary that alkali being determined by the method proposed by Heintz for the separation of magnesia from the alkalies.The lime alumina iron &c. having been separated by carbonate of ammonia a stream of hydrosulphuric acid was passed through the filtrate previously acidulated in order to precipitate traces of copper ;after boiling with a subsequent addition of ammonia phosphate of ammonia was added to precipitate the magnesia; an addition of acetate of lead removed the excess of phosphoric acid and again the excess of lead was separated by meaps of a mixture of carbonate of ammonia and ammonia; on evapora- tion to dryness and subsequent ignition chloride of sodium remained in the platinum basin from which the amount existing as such in the slag was deducted and the soda estimated from the residue. This slag as before remarked has a clear glassy structure and has not the most distant appearance of containing copper.The 0.70 per cent of black oxide found by analysis is present in combination with silicic acid. In contact with metallic iron the colour is changed from black MR. FIELD ON COPPER SLAGS. to a fine red owing doubtless to the reduction of the protoxide to the suboxide in the following manner. 2 (Cu 0 Si 0,)+ Fe = (Cu 0 Si 0,)+ FeO Si 0,. This phenomenon was always observed when the slag had come in contact with the rabble used by the furnace-man or with the fore-iplate of the furnace The under slag (No. a) which is termed sharp or metallic slag presented a very different appearance from the former it was unde- composable by aqua regia and a long continued fusion with carbonate of soda was necessary for its entire decomposition.A qualitative analysis proved the existence of the same substances as in the former specimen. On ignition to whiteness with carbonate of baryta only very small quantities of alkali were observable. The following is the quantitative analysis of this slag Silica . . 49.60 Alumina . . 14.00 Oxide of iron . . 32.94 Lime . 1*23 Oxide of copper Soda . Magnesia. . . 1.06 0.70 0.11 Chloride of sodium . 0.43 Manganese . . traces. 100.07 It will be observed that the amount of silica is nearly equal in these two analyses; in the former it is 49.26,in the latter 49.00,but all the other ingredients the alumina excepted are in widely different propor- tions. In fact slag No.2 may almost be considered as a silicate of iron and alumina these three bodies alone forming more than 96 per cent of the whole mass. We may imagine that slag No. 1 acted as a bath from which No. 2 had crystallized ;that silica in certain combinations with soda iron lime &c. dissolved a silicate containing an excess of iron and deposited it on cooling in crystalline forms more or less defined; in other words that the metallic slag was held in solution in the glassy slag the latter containing nearly the whole of the soda lime and the more fusible compounds. However small the quantity taken from the furnace the same phenomenon always occurred viz. the complete separation of a crystalline slag from a homogeneous mass resembling black glass.When smaller proportions of salt but the same quantity of lime were employed viz. 10 per cent of the former and 15 per cent of the latter in regard to the mineral of copper no separation of the kfR. FIELD ON COPPER SLAGS. slags took place on skimming but the mass presented a very hfferent aspect to the two former specimens. It was now highly variegated and had a beautiful serpentine appearance very much resembling many specimens of igneous rock I have since seen in this country (Chile) and so hard as to be capable of receiving a beautiful polish. A qualitative analysis gave me the same ingredients as in the two former slags with the addition of sulphur and unburned carbonaceous matter. This slag also had to be decomposed by fusion with carbonate of soda and the alkali it contained was estimated by fusing it with baryta.100 parts gave me Silica 42-20 AIumina . . 10.80 Lime. 6-43 Magnesia . 2.14 Protoxide of iron. 31.00 Oxide of copper . 0-45 Chloride of sodium . 0.34 3.44 Soda. Sulphur . . . 1-43 Escoria . 1.56 Loss in analysis 0.21 On examining some acorias from a furnace some few leagues from Coquimbo I observed on breaking a portion beautiful needle- shaped crystals grouped together in large and distinct cubes in one of the cavities having very much the appearance of those in No. 2 only larger. They were separated with some clifficulty from the mass and in qualitative analysis shewed the existence of lime silica oxides of iron and copper alumina and magnesia.Twenty-four grains were andysed and yielded the following per-centage corn-position Silica . 35.60 Protoxide of iron. . 50.46 Alumina . . 6-85 Lime 4-48 Magnesia . 0.16 Oxide of copper . 2.32 0 Loss. 0.13 MR. MAKINS ON THE EXPANSIONS The large amount of protoxide of iron is here to be observed and from many experiments not yet concluded it appears to me that the other ingredients in the crystals besides the silica and iron are not essential to the crystalline structure of the mass but may be reckoned as foreign substances. I have not as yet however met with any that contained only silicium oxygen and iron. As I am at present constantly engaged in investigations re-garding the nature of the substances placed in the furnace and the condition they present after fusion I trust to be able at some future time to lay before the Society a more detailed accouut of the various silicates obtained.Every different proportion of ingredients every prolongation of temperature causes not only a difference in constitu- tion but an entire change in physical appearance so that perhaps by many careful analyses we may arrive at more satisfactory con-clusions rewarding the formation of natural silicates and other minerals of ?igneous origin

ISSN:1743-6893    

DOI:10.1039/QJ8500200220

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

MR. MAKINS ON THE EXPANSIONS XXV.-On the Relative Expansions of Mixtures of Alcohol and Water under the inyuence of a certain rise of Temperature and on a new instrument for taking the Spec@! Gravities of the same. BYG. H. MAKINS,ESQ. About two years since I made some experiments upon an instru- ment described by the AbbB Vidal of Toulon and called by him the ‘I Ebullioscope Alcboin6trique.” The instrument was designed for estimating the proportion of alcohol in mixtures containing it and especially in those wherein specific gravity gave false results in consequence of saccharine or saline bodies being held in solution which so increased the specific gravity as often to disguise even large proportions of alcohol. Before going to the immediate subject of this paper I may just mention the conclusions to which I came with regard to the instru- ment in question.Having been put before Mr. Bate (the maker of Sikes’ hydrometer to the Excise and Customs) as an instrument likely to supersede the hydrometer from the fact of its embracing indications which the hydrometer itself could not shew while at the same time the ordinary indications of the latter were readily obtained by it it became an object to test carefully its effectiveness. I found as most persons will anticipate that the first and greatest objection to the instrument was dependant on the fact of the boiling OF MIXTURES OF ALCOHOL -4ND WATER. 225 point of a liquid being so considerably influenced by the state of the barometer at the time of its examination.For as the latter is high so will the point of ebullition be high in proportion and consequently the specific gravity of the alcohol under examination appear lower than it should do. We examined at the time the difference in the boiling points between the barometer points 29.1 and 30.1 in several specimens of alcohol of different degrees of dilution; as examples froin these I may mention Excise proof in which for the one-inch pressure there was a difference of 1*4O temperature; and in the case of 70 under proof (specific gravity 977*2),we found as much as 1*8O for the inch of difference. A second and great difficulty especially to persons not much accustomed to chemical manipulation as for instance those using Excise instruments consists in the extreme care required to read off the degree indicated by the ebullioscope just at the moment of the boiling of the liquid; for if this be not done precisely at the proper time evaporation of the spirit speedily takes place rendering the specific gravity of the mixture very much higher than it was at the commencement of the examination.The instrument being now constructed under a patent in London has induced the makers to bestow much care upon its construction and consequently to obviate the former evil by an adjustment upon the scale to be regulated by the height of the barometer. During the time I was engaged on this subject Mr. Negretti who had bestowed much care and thought upon the thermometers for the instrument suggested that another instrument might be made in which the sources of error would be less and wherein the simple expansion of the spirit by a certain number of degrees of heat would effect the end of ebullition.From some experiments he shewed me I was induced at once to undertake the examination of the subject with him. I had some hesitation as to whether the incomplete results we have already obtained were worth the attention of the Society for I am not yet able from various causes to communicate the whole of our experiments but am induced to bring forward that part of them relating to the expansion of spirits not containing saccharine matter from the fact of an article having appeared describing an apparatus for the same purpose and detailing some results obtained with it which I do not consider altogether correct ; at least my own con-clusions based on most careful experiments seem to contradict the?.The article I allude to is by Silbermann and appeared in the ‘< Comptes Rendus” for October 23 1848 ; which by the VOL. 11.-NO. VII. Q 226 MR. MAKINS ON THE EXPBNSIOX FIG. 1. way was transcribed into the January number of the “Chemical Gazette.” T( I will now describe the instrument we employed as tx upon inspection it may seem a somewhat complicated one 6C to effect an object which might be brought about in a 4c tube similar to the common thermometer tube; indeed a 3( thermometer bulb and tube on a large scale furnished with 21 1C a stopper below for the admission and adjustment of the P sample of spirit would very well answer the purpose.Our 1C instrument consists of a couple of chambers connected by za a set of tubes (see Fig. 1);from the upper chamber rises a tube and scale the former of as uniform bore as could a0 be procured and to the lower is attached a small stop- cock. The form given to the instrument was adopted in 40 order to afford as large a metallic surface as possible so as to heat a badly-conducting fluid quickly and uniformly 150 and its parts were so shaped and put together that the free exit of any portions of air which might enter with 60 the spirit by the stopcock was ensured. A thermometer was placed in the interior for shewing the temperature 70 more correctly of the enclosed spirit.This last is a point of some importance to the results 80 afforded and I may instance what I have frequently ob- 90 served in taking the specific gravity of alcoholic liquids and 100 similar badly conducting fluids viz. that a thermometer will often indicate a difference of a degree or more in different parts of a thousand grain bottle according to the manner in which the bottle has been filled. In using the instrument our plan was to fill it slowly by gradual depression in a tall vessel containing the specimen for examination. A slight shaking then sufficed to dislodge any air which might have been adherent to the sides of the tubes &c. after which the zero point was carefully 3adjusted by nieans of the stopcock. -This having been = effected the temperature of the whole was brought to 62*F.by means of immersion in a large vessel of water at that temperature. It was then quickly plunged into a second vessel containing water at 92O F. and agitated until the thermometer in the instrument indicated this rise of 30° F. when the expansion was carefully noted. The actual expansions are here of course not observed no allowance being made for that of the instrument itself which is considerable and diminishes by just its amount that of its contents; all that is here ascertained being the relative dilatation of the several specimens of different specific gravity. Attention may here be drawn to the difference in the amount of expansion for the same number of degrees OF MIXTURES OF ALCOHOL AND WATER.increase of temperature when this increase is in different parts of the thermometric scale. And again that this difference increases as the proportion of alcohol in a mixture is diminished In the case of proof spirit for example I found that between 60° and 90° F. an expansion indicated by a rise of 6.48 inches on the scale was ob-tained while between 90° and l2Oo F. it increased to 6.84 inches. The most convenient temperature for operating was between 62O and 92O F. and a number of specimens were first very carefully prepared to agree with the indications of Sikes’ hydrometer or as nearly as possible to these. The spirits were allowed to stand 48 hours after mixing before being subjected to expansion and the laboratory was kept as nearly as possible at 62O F.We commenced with the examination of distilled water (the 100 point of Sikes) the water having been previously boiled so as to expel any air contained in it. The stem and body of the instrument happened to be so proportioned as to give a rise of 1-47 inches for the 30° of difference of temperature; and the time occupied in thoroughly heating the water amounted (generally) to about one minute. As distilled water formed our starting point of comparison we repeated the experiment with it several times with every possible care but uniformly with the same results. The measurements of the expansions of the samples we examined each ascending by lDo of Sikes’ hydrometer are given in the table below Inches.90 under P. gave an increase of 1.72 80 . 2.10 69.9 . . 2.69 60 . 3.30 50.1 . 3.96 39.7 30.1 . . . . . 4.695.32 20 . . 5.78 10.7 . . 6.18 Proof . . 6.48 The experiments upon this last and upon water as also upon the specimen 70° over proof which I shall have to mention were several times repeated but the same amount of expansion was uniformly obtained. Then to pass to over-proof specimens Q2 MR. MAKl NS ON THE EXPANSION 228 FIG. 2. PIG. 3. Alcohol 8p. grav. Proof per cent. at 620. point. -811 = 70 30.2 -I+ -P 70-= 10.7 = 20 = 30.1 = 39 7 = 50.1 972 = 60 977.2 = 70 983.5 = 80 #-10 80 -990.5 = 90 90 -Water -100 OF MIXTURES OF ALCOHOL AND WATER.Inches. 10 over P. rose to . 6-72 20.2 . . . 6-94 30.2 . . . 7.15 40.2 . . 7-43 49.5 . . . 7.72 60.4 . . . 8.03 70 . . 8.13 We stopped our examination at 70° over proof. I have here constructed a scale which for distinctness is divided into two parts. In the 6rst (Fig. a) the assumed expansion of anhydrous alcohol for the 30° of increase of temperature between 62O and 92O is shewn. This space is divided into 100 equal parts each part representing 1 per cent. of alcohol; at the side are placed the expansions of specimens (each descending by loo of Sikes’) from anhydrous alcohol to water. The zero point (Fig. 1) has been omitted in the scales to diminish their length; it should be placed 1.47 inch below the first division and represents the height to which the stem of the instrument was sled in each case previous to expansion.Alcohol of 70° over proof consists of about 6 parts water to 94 of alcohol so that in the construction of the table this expansion of alcohol of 70° over P. has been divided into 94 equal parts each division repre- senting 1 volume of alcohol; to these 94 6 divisions have been added to make up 100 thus completing the range between water and anhydrous alcohol. The second scale (Fig. 3) is similarly divided into 100 parts and opposite these divisions at their proper points as to proportions of alcohol and water are ranged the several proof points examined with their specific gravity at 6Z0 F. On comparing the two tables a gradual increase will be observed in the rate of expansion from some points and a decrease from others; and these amounts of increase and decrease do not in any way correspond to the relative quantities of alcohol and of water in the mixtures but are totally independent of them.Now from Silbermands paper you might be led to a very different conclusion viz. to this that the expansion takes place at a uniform rate of increase corresponding to the increasing proportions of alcohol for he says “If a series of mixtures of alcohol and water be made beginning with water 100 parts alcohol 0; water 99 alcohol 1; water 98 alcohol 2; water 97,alcohol 3 &c.; up to water 0 alcohol 100; and their several points of elevation at the respective tempera- tures of 25O and 50° (cent) be carefully marked on the tube a 230 MR.MAKINS ON THE EXPANSION OF ALCOHOL &c. complete centessimal alcoholometric scale will be produced which will indicate the quantity of alcohol contained in any mixture of alcohol and water by introducing it at 254 and afterwards heating it up to 5OO.” If the measurements I have given are compared it will be found that they are in an increasing ratio up to 40 under proof (which contains about 28 alcohol + 72 water) ; they then decrease somewhat rapidly to 30 over proof. A third change then takes place and they again increase to 60 over proof. And lastly they again decrease very rapidly to 70 over P. ;and possibly to anhydrous alcohol though from the various sources of error in observations on very strong alcohol we did not use it above 70 over proof that is to say of a specific gravity of 0*811at 62O.Now if all this be true and I may state that every possible precaution was observed to ensure the accuracy of the experiments it becomes a question to determine why these expansions do not take place just in the proportion of the dcohol contained in the respective mixtures or in other words why certain regular variations in the rate of expansion take place about certain points in the scale. I believe the answer may be satisfactorily given in a few words; namely that the expansions depend on the existence of certain definite hydrates of alcohol which hydrates are formed somewhere near the proportions at which these changes occur.In conclusion I must repeat that the experiments I have described were undertaken some two years since and having been prevented carrying them fully out at the time I did not intend to bring them before the Society until they had been brought into a much more definite form by repeating them on mixtures containing alcohol in regularly increasing proportions ;but the appearance of the paper I have mentioned compels me to put them incomplete as they are into the form of a notice hoping as I do to work the subject fully out and having done so to bring it again before the Members. I may mention that the instrument we have used (or a more simple modification of it) affords a very ready and accurate means for the determination of the specific gravity of such mixtures and is I believe much more likely to be useful than the common glass hydrometer now so much employed for the purpose.The sensibility may of course be augmented by increasing the proportion of the chamber as compared with the tube always talting care not to have the latter so small as to be influenced to any great extend by capillary action again by using a greater range or higher temperature and lastly by making the chamber of such form and ME. HARDWICK ON THE OIL OF “BASSIA LATIFOLIA.” 231 material as shall yield but little to expansion and consequently exert a lesser influence upon the expansion of the liquid contained in it. Mr. Negretti is now making the instrument in a simple and inexpensive shape for such purposes.

ISSN:1743-6893    

DOI:10.1039/QJ8500200224

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

ME. HARDWICK ON THE OIL OF “BASSIA LATIFOLIA.” 231 XXVL-On some new Acids contained in the Oil of the “Bassja LatijXa.” BYT. F. HARDWICK, EsQ.,Student in King’s College London. COMMUNICATED BY DR. MILLER. The rapid advances that have been made of late in that depart- ment of Organic Chemistry which embraces more particularly the constitution of the vegetable oils and fats are too well known to need remark; it has been shown that not only does each of these bodies with few exceptions contain a distinct and peculiar acid but that these different fatty acids are nearly allied in chemical constitution ; speaking generally they may be represented by the formula CH + 0,. The object in undertaking the present investigation was to deter- mine the composition of one of these vegetable oils the produce of ‘‘Bassia Latifolia ;” from the results obtained it appears that an acid exists in this substance which has not hitherto been found elsewhere; this acid to which it is proposed to apply the name of “Bassic acid” may be isolated with comparative facility.I am much indebted to Professor Royle for procuring me a spe-cimen of the Oil of Bassia in considerable quantity. The following particulars with regard to the tree from which it is obtained are gathered from his excellent u Illustrations of Himalayan Botany.” The Bassia Latifolia belongs to an important genus of plants which are found along the central range of the Himalayan mountains and in the northern and southern provinces of India. The most common species of this genus are the Bassia Latifolia and Longifolia or Illupei tree both of which are extremely valuable in an economical point of view ;not only is their wood in much request as timber but they yield parts useful in medicine and their fleshy berry-like flowers are eaten by the natives.Those of the Bassia Latifolia moreover are subjected to fermentation and a powerful and cheap spirit is distilled from them. The Oil is procured from the 232 XR. HARDWICK ON SOME NEW ACIDS seeds by expression and is much used as a substitute for cocoa-nut oil in cooking and for making soap. The Bassia Butyracea of the Almora Hills is a species less commonly met with; it is characterized by furnishing a concrete oil of a white colour and very delicate flavour; it is probably analogous to the shea or butter tree of Mungo Park which is described by him as closely resembling the Bassia Latifolia.PROPERTIES OF THE or^ OF BASSIA.” Bassia oil is of a yellow colour but is gradually bleached on exposure to light; it possesses a faint though not disagreeable odour and has somewhat the consistence and appearance generally of ordinary butter; its specific gravity is 0.958O; on the application of heat it begins to soften about 75O Fahr. and at 80° to 85O is almost entirely liquid. Alcohol sp. gr. 0.840 hardly affects this oil; anhydrous alcohol dissolves it sparingly but deposits the whole or the greater part on cooling; it is abundantly soluble in ether both hot and cold and is eaponified by potash or soda without difliculty.With regard to its chemical constitution it may be briefly stated that it contains a liquid acid the oleic in considerable quantity and also two solid fatty acids of different melting points which form the subject of the present paper. On distillation it yields an abundance of acroleine and by the action of oxide of lead a substance may be procured from it which has all the properties of glycerin. PREPARATlON OF ‘I BASSIC ACID.” In the preparation of this acid the oil was saponified by a weak solution of caustic soda and the soap separated by common salt once or more in order to whiten it it was then re-dissolved in water and decomposed by hydrochloric or tartaric acid. I found the latter of these the most efficacious it separates the acid in a much shorter time and does not render it yellow which hydro- chloric acid is apt to do.The mixed fatty acids as thus ob- tained were found to have a fusing point of about 112O Fahr. (445OC);the fatty mass was next submitted to pressure in order to separate as much of the oleic acid as could in that way be squeezed out sild the w1id portion afterwards crystallized six or eight times from alcohol to attain the same object more com-pletely. When the melting point has risen as high as 135O (57.2OC) it becomes quite constant and as I found moreover that it was not in any way altered by t,he use of coal-naphtha pyroligneous IN THE OIL OF “BASSIA LATIFOLIA.” spirit or rectified oil of terpentine I was at first induced to suppose it to be a pure substance; this however is not the case.If the mixed acids as obtained by crystallization from alcohol of a melting point 135* be repeatedly crystallized from ether the melting point rises rapidly at fist afterwards more slowly until at length it becomes fixed at 159O (7005~ C) and is not affected by any further treatment. I found that in this process two pounds of the oil yielded about eight ounces of mixed acids free from oleic acid and rather more than half an ounce of the Bassic acid in a state of purity. Bassic acid as thus obtained is a very white crystalline substance perfectly tasteless and inodorous it does not feel greasy and is easily pulverized ;its solution in alcohol reddens litmus. By analysis with chromate of lead it yielded the following numbers.I. 6.37 grains gave 17.76 CO and 7.34 HO 11. 3.61 , 10.09 CO , 4.2HO. which give in 100 parts I. IT. Carbon . . 76-04 76.22 Hydrogen . 12.8 12.92 Oxygen . . 11-16 10.86 100~00 100*00 These analyses agree with the formula Ca6H360,. Atomic weight. Theoretical per-centage. ‘36 . 216 76.06 H36 36 12-78 32 11.26 04 -284 100~00 DISTILLATION OF BASSIC ACID. Bassic acid is volatile without change if the heat be carefully regulated I found the best way to effect the distillation was to im-merse the retort in a bath of fusible metal or what answers as well of tin and lead in the proportions to form plumber’s solder ;the acid then distils over perfectly white and so little decomposition takes place that the melting point is lowered no more than one or two degrees.If instead of the metal bath the heat of a common lamp MR. HARDWICK ON SOME NEW ACIDS be used although the distillation appears to proceed as before without interruption yet on examination the product will be found to consist almost entirely of liquid carbo-hydrogens with hardly a trace of acid; to complete the purification the distillate is to be crystallized a few times from alcohol until the melting point rises to 159' and afterwards its solution in ether allowed to evaporate spontaneously; by this means the acid is deposited in beautiful rhombic plates which are perfectly clear and transparent and on one occasion were as much as inch in the side.The melting point of these crystals is exactly the same as that of the acid itself with which the numbers they yield on analysis show them to be identical. 3.54 grains gave 9.8 CO and 4-04HO which correspond to Carbon . . 75-71 Centismally. 76-06 Theoretical. Hydrogen Oxygen . . . 12.71 11-58 12.78 11-26 100~00 looooo BASSIATE OF POTASH. This salt may be formed by boiling the acid with a solution of carbonate of potash and evaporating to dryness on digesting the residue in strong alcohol the Bassiate of potash dissolves leaving behind the excess of carbonate and may be procured pure by distilling off the spirit ;-it is a white powder having a soapy feel and does not deliquesce on exposure to air ;with water it forms a gelatinous mass but dissolves perfectly both in alcohol and ether ;it crystallizes out on cooling in innumerable small needles which cross each other in every direction and when pressed and dried have a glistening aspect; this crystallization is by far the most perfect from an ethereal solution and in using the Bassiate of potash as a means of preparing the corresponding silver and baryta salts by which the formula and atomic weight of the acid are to be determined it is well to take advantage of it and ensure the purity of the salt; in this way traces of fatty matter are removed which still adhere to the acid and which although not sufEkient in quantity to affect its melting point or the numbers it yields on analysis may yet interfere with the determination of metallic silver or of baryta; that this impurity does exist is shown by the acid itself as well as by the potash salt prepared from it giving a somewhat milky solution with alcohol whilst the distilled acid or the crystallized salt are both perfectly IN THE OIL OF ‘‘BASSIA LATIFOLIA.” and entirely soluble.Perfectly pure ether should not be used as the salt is almost insoluble in this but ether containing alcohol ill such proportion as to have a specific gravity of about 0.745 ; the rectified ether of the pharmacopoeia answers very well. BASSIATE OF SODA. This is prepared in a similar way to the last mentioned salt ; it is white and hard having altogether the appearance of a soap; it is scarcely at all affected by cold water and difficultly soluble in warm ; alcohol takes it up freely ; it does not however crystallize on cooling but forms a gelatinous mass.BASSIATE OF SILVER. Bassiate of silver may be prepared by decomposing an alcoholic solution of pure crystallized Bassiate of potash by nitrate of silver ; it falls as a curdy mass which requires very careful washing with distilled water in order to free it entirely from all traces of the pre- cipitant. When dry it is a very loose and bulky powder exhibiting no appearance of crystalline structure and slowly darkening in colour on exposure to light. By analysis the following results were obtained I. 6-14 grains gave 12.32 CO and 5.06 HO 11. 7-03 , 14.11 CO , 5.7 HO 111. 6-61 , 13-33 CO , 5.41 HO which give in 100parts I.11. 111. eB Carbon 54.72 54.74 55.00 Hydrogen . . 9.16 9.01 9.09 Oxygen and Silver . 36.12 36.25 35.91 100~00 100~00 100*00 I. 9.47 grains when ignited left 2.61 silver 11. 12.47 9 3-45 , these correspond in 100 parts to I. 11. Silver . . . . 27-56 27.67 and lead to the formula Ago CS6H, 0 Atomic weight. Calculated C36 . 216 55-24! H35 . 35 8-95 . 32 8.19 04 . -108 27.62 *g 391 100~00 236 MR. HARDWICK ON SOME NEW ACIDS BASSIATE OF BARYTAe This salt is precipitated on dropping a solution of chloride of barium into an alcoholic solution of Bassiate of potash; it is very white not so bulky as the silver salt and has a glistening semi- crystalline appearance; it is insoluble both in alcohol and ether.It gave on analysis the following quantities I. 6.17 grains gave 13-80CO and 5-43HO 11. 5-1 ,I 11-42? CO and 4.66 HO which yield on 100parts. I. 11. 9 Carbon . . 61.00 61.07 Hydrogen . . 9-78 10.02 Oxygen and baryta . 29.22 28.91 100~00 100~00 I. 10.55 grains left on ignition 3.00BaO CO 11. 16.24 4.65 BaO CO, 99 giving as the per-centage of baryta-I. I1 22-07 22-21. for the baryta salt of bassic acid requires BaO Atomic weight. Calculated. . . 216 . . 61.36 35 9-94 03-24 . 6-83 BaO . 77 . . 21-87 -352 100~00 BASSIATE OF LEAD. Like the lead salts of the fatty acids generally this salt is a light white powder insoluble in water alcohol and ether; it is pro-cured by decomposing Bassiate of potash with acetate of lead.CHLORO-BASSIC ACID. If a constant stream of dried chlorine gas be passed through a portion of Bassic acid kept by a water-bath at a temperature of 2124 an interesting series of changes takes place; the acid first becomes very liquid and almost as limpid as water then after remaining in this state for a short time slowly and by degrees 237 IN THE OIL OF “BASSIA LATIFOLIA.” it thickens until it gets viscid like gum and at length is entirely converted into a slightly yellow resinous looking body which on cooling solidiiies and is easily pulverizable ;it is quite transparent and has a well marked vitreous fracture. The action of the gas is slow and must be continued for two or three weeks until the vapour of hydrochloric acid gas is no longer perceptible and a piece of moistened litmus paper is bleached by the excess of chlorine.By analysis it yielded the following numbers I. 7.2 grains gave 9-12CO and 2-84 HO 11. 6-90 , 8.75 CO , 2.74 HO on 100 parts I. 11. Carbon 34-56 34.19 Hydrogen 4.38 4-36 Chlorine and oxygen 61.06 61-45 1oo*oo 100*00 By igniting the acid with lime dissolving the product in nitric acid and precipitating with nitrate of silver 7.7 grains gave 17.84 Ag C1. equivalent to Chlorine 57-16 per cent. These analyses agree with the formula Atomic weight. Theoretical per-centage. %6 216 39.06 26 410 {3 360 56.78 0 32 -5.06 -634 100*00 It appears therefore that a substitution of a certain number of equivalents of chlorine for an equal number of hydrogen has taken place the general frame-work of the formula remaining unaltered and this view is further supported by an examination into the properties of the newly-formed substance.Not only is it acid to test paper but it forms insoluble salts with lead baryta &c, either of which may be formed by dissolving the acid in alcohol and dropping in a solution of acetate of lead or of chloride of barium; 80 again if a small portion of the powdered acid be digested in a cold solution of carbonate of potash it ie quickly saponified forming a 238 MR. HARDWICK ON SOME NEW ACIDS white flocculent soap almost insoluble in cold water but easily dissolved by alcohol; I quite failed however in every attempt at crystallizing this Chloro-bassiate of potash it seems perfectly amorphous as indeed is the acid itself The following is a list of the compounda of bassic acid that I have hitherto examined.Bassic acid '4H36 '36 Bassiate of potash , soda , silver '36 H35 '4 *g 77 baryta '35c36 O4 Ba , lead Chloro-bassic acid The analyses of these are quite conclusive as to the formula of the acid and prove it beyond a doubt to be a member of that series before alluded to as characterized by containing (CH) + 04 it stands immediately above Margaric acid which until recently was the highest known. Myristic acid . ' C,,H,,O4 ** Palmitic acid . ' C32H3204 Margaric , .c34 H3404 Bassic , . ' '36 H36°4 *** *** Cerotic acid &c. . ' c,*H54 0 Volatility without change is an important character of this series and one not found in any fatty acid that does not belong to it; it has been shown that Bassic acid is not only volatile but may by careful distillation be procured in a purer and more perfectly crys- talline form than by any other method. It would be interesting to find whether or not the glycerin compound of this acid could by any means be separated from the original fat. I have not as yet succeeded in effecting this but its actual presence may be easily demonstrated by boiling out a portion of the oil with alcohol for a considerable time in order to remove the liquid oleine as far as may be on cooling crystals will be found scattered about here and there in globular masses; they are harder and more white than the surrounding fat and have a higher melting point.IN THE OIL OF (‘BASSIA LATIFOLIA.” 239 BASSIA ACID OF LOWER MELTING POINT. I now proceed to give in detail the course pursued with regard to that portion of the mixed acids melting at 135O from which the Bassic acid had been in a measure separated. The treatment with ether was continued as before but with this important variation from the original arrangement that the different crops of crystals as they were successively formed were rejected and the solution retained; the object being to remove by degrees the whole of the Bassic acid in virtue of its inferior degree of solubility.When the melting point of the acid which crystallizes out becomes fixed it is evident that nothing further will be gained by continuing the process and therefore what remains of the ethereal solution may be evaporated in order to procure the acid it contains in a solid form. The melting point of this compound ranges between 129O and 131O (54O-55’ C.) but is easily affected by the action of caustic alkalies and also of alcohol; this indicates the presence of small quantities of fatty matter and oleic acid both of which being extremely soluble in ether wotild of necessity be left in the last mother liquor. I found that the only way to remove these impurities effectually was to submit the whole to distillation which as before must be con- ducted in a metal bath in order to equalize the distribution of heat ; the distillate when freed from liquid carbo-hydrogens by alcohol has a fusing point of 132O to 134* and is the desired acid in as pure a state as I have been able to procure it.With regard to the properties of this substance it is not SO per-ceptibly crystalline in its structure as Bassic acid but more homo- geneous and wax-like; if a drop of its solution in alcohol be allowed to evaporate or a small portion of the acid itself be melted over the surface of a glass plate so as to form a thin film it presents on solidifying the curious appearance of a series of concentric rings which may not unaptly be compared with a section of bone under the microscope. These characteristic rings are observed both before and after distillation and also in the mixed acids of 135O melting point but disappear in the Bassic acid as it approaches to a state of purity; an ethereal solution of this acid on spontaneous evapo- ration deposits it in warty and granular masses which melt as before between 132O and 134O.With the various metallic oxides it forms salts all of which may be formed in a similar manner to the corresponding compounds of Bassic acid; the salt of potash is soluble both in alcohol and ether and crystallizes from the latter solvent in tufts of needles much resembling the crystallized Bassiate MR. HA4RDWICK ON SOME NEW ACIDS of potash ; these needle-like crystals when decomposed by tartaric acid yield a product melting as before at 132O to 134O; the baryta and lead salts are both quite insoluble.By analysis the following numbers were obtained I. 4.4grains gave 12-01CO and 5.01 HO 11. 4-69grains gave 12-83CO and 5-44HO or in 100 parts I. 11. Carbon 74.44 74-61 Hydrogen Oxygen 12-65 12.91 .- 12.65 12.74 100~00 100~00 The silver salt prepared by the action of nitrate of ailver on the crystallized potash salt yielded as follows I. 5.99grains gave 11.81 CO and 4.72 HO 11. 5-96 grains gave 11.7 CO and 4.69 HO in 100 parts 1. 11. Carbon 53.77 53.54 Hydrogen 8-75 8-74 Oxygen and silver 37-48 37-72 100*00 100*00 By ignition I. 10.11 grains gave 2.94 metallic silver 11. 1444grains gave 4-23metallic silver centesimally represented I.TI. Silver 29.08 29-29 These analyses correspond somewhat with the formula for Palmitic acid C, H 0, which requires in 100parts Carbon . 75.00 Hydrogen . . 12.50 Oxygen . . 12-50 100.00 The silver salt of the same acid requires IN THE OIL OF ~‘BASSIALATIFOLIA.” Carbon . . 52-89 Hydrogen . 8.54 Oxygen . 8.87 Silver . . 29-70 100~00 Both the melting point of the acid itself however and its pro-perties in general quite disprove the idea of its identity with Palmitic acid. The most probable view of the case seems to me that the true formula of the acid is C, H, 0, intermediate in the series between hlyristic and Palmitic acids and that a portion of Bassic acid is still present as an impurity the variation occasionally observed in the melting point strengthens this assumption but after a careful study of the various salts formed by this acid I have been as yet unable to effect any further purification or sepa-ration of Basaic acid than that above detailed.

ISSN:1743-6893    

DOI:10.1039/QJ8500200231

出版商:RSC    

年代:1850

数据来源: RSC

摘要:

IN THE OIL OF ~‘BASSIA LATIFOLIA.” XXVI1.-Researches on Strychnine. By E. C. NICHOLSON and F. A. ABEL. SENIOR ASSISTANTS AT THE ROYAL COLLEGE OF CHEMISTRY. I.-ON THE COMPOSITION OF STRYCHNINE AND OF ITS SAJA% In his researches on the aniline series Dr. Hofmann communi- cated some experiments upon the action of iodine on aniline,* which terminated in the formation of iodaniline a substitution-product possessing like chloraniline and bromaniline the basic character of the original atom. Incidentally to this investigation Dr. Hofrnann recalls the experiments upon the action of iodine on various natural alkaloids which had been formerly undertaken and had led to very different results. It was upon this ground that he invited us to subject the results of former enquiries to a new examination.Various chemists have examined the behaviour of iodine with organic alkaloids. Pelletier-i- obtained by the action of this element on strychnine brucine cinchonine quinine morphine and codeine a series of substances the study of which led him to the conclusion that they were compounds of the original bases with one or two equivalents of iodine corresponding to the compounds of ammonia * Mem. Chem. SOC.London,Vol. III. p. 269. I-Liebig’s Annalen Vol. XXII. p. 113. VOL. 11.-NO. VII. R 242 MESSRS. BBEL AND NICHOLSON'S with that element. His results with reference to brucine aid strych- nine at least have been subsequently confirmed by Regnault.* A similar class of compounds has been produced by Bouchardat,Jy who studied the action of iodine upon the salts of strychnine.He considered these substances to be the hydriodates combined with more or less iodine analogous to the iodinated iodides of potassium and ammonium. Among the various compounds elicited in these several investiga- tions those of strychnine appeared to be the most definite. This circumstance as well as the facility with which both strychnine and its salts may be obtained in a state of perfect purity induced us to select this body for our experiments. We succeeded without difficulty in preparing the iodinated com- pounds described by Pelletier ; on submitting however several of these substances to analysis the quantities of carbon and hydrogen found were invariably below the theoretical numbers of the formulze calculated from the generally adoptcd composition of strychnine.Convinced by the constancy of our results obtained with a variety of preparations of the definite nature of the compounds we were com- pelled to seek for the cause of the deficiency in the composition of strychnine itself. This substance has been analysed successfully by Liebig Regnault and Gerhardt whose numbers calculated according to the new equiv- alents carbon and hydrogen are appended in the following table together with the formulz deduced by these chemists from their results. I Liebig. Regnault. Gerhardt. c HI N O,$ I c, I%, N,b 0,s c, H N2 0411 c, H "2 047 r-_-_-L--_l-7 r-_-h-7r-A-7 Theory. Experiment. Theory. Theory Experiment.Theory Exyt. I I. 11. 111. Carbon . . 76.92 75.62 75.86 75.66 74.69 74-96 74.63 75.86 7554 Hydrogen . 6.83 6-68 6-60 6.74 6.8b 6 69 6-89 6.89 6.99 Nitrogen . 6.00 5.70 6-04 8.21 8.43 8.46 -8.06 8.10 Oxygen. . 10.25 -11.50 9.39 --9.19 -I 100 00 i -I 100.00 100~00l --100~00 -* Liebig's Annalen Vol. XXIX 58. + Comptes rendus T. IX.475. 2 Liebig's Annalen V. XXVI. p. 17. 5 Idem.V. XXVI.p. 58. 11 Idem. V. XXVI. p. 18. Trait6 de Chimie organique par M. Liebig traduit par M. Gerhardt vol. 11. p. 664. Recherches sur la Classification Chimique des substances organiques par M. Gerhardt page 49. RESEARCHES ON STRYCHNINE Besides the above other forniulz have been quoted at different periods. Liebig,* from a determination of platinum in the double salt of bichloride of platinum and strychnine has corrected Regnault’s formula to c44 H, N 04.Subsequently Regnault in a letter to Liebig? has proposed the formula ‘42 H22 N%‘4 finding it agree better with the equivalent obtained from Liebig’s platinum-determination and with his own analysis of the hydrio- date than the above corrected formula. Gerhardt in his trans- lation of Liebig’s Organic Chemistry has likewise made several statements respecting the composition of this alkaloid. After having declared himself in favour of the formula referred to in Regnault’s letter to Liebig$ he finally adopts the expression quoted in the above tablet. The difficulty of arriving at any conclusion as to the correct formula of strychnine from such contradictory statements induced us to repeat the analysis of this body.A simple determination of the elements appeared to be of little assistance in the construction of the formula if we consider that the different expressions above quoted with the exception of Liebig’s first are principally based upon analyses exhibiting no greater discrepancies than about four tenths of a per-cent in the carbon and hydrogen. Hence it became necessary to control the results by an extensive examination of the salts of this base and also by a careful study of its products of decomposition. In this paper it is our intention to detail the analysis of strychnine and a number of its compounds reserving for a future communication a description of the products of’ substitution and decomposition.The strychnine employed in our experiments obtained from the laboratory of Mr. E. Merck of Darmst,adt was crystallized in beautiful four-sided prisms requiring but one recrystallization from dilute spirits to render it absolutely pure. Analysis of strychnine.-The combustion of strychnine in the ordinary manner did not present any difficulties; in fact we found contrary to the statements of many chemists that this base and its salts burn with the greatest facility. * Liebig’s Annalen Vol. XXVI. 57. t Idem. Vol. XXIX. 58. $ Gerhardt’s tratislation of Liebig’s Trait6 de Chimie organiqiie Vol. 11. p. 558. 5 Idem. Vol. 11 p. 664. R2 244 MESSRS ABEL AND NICHOLSON’S I. 0.2947 grm. of substance burnt with oxide of copper gave 0.8143 , , carbonic acid and 0.1817 , , water.11. 0.3179 , , substance gave 0.8783 , , carbonic acid and 0.1935 , , water. 111. 0.4145 , , substance gave 0.2462 , , water. IV. 0.4038 , , substance burnt with chromate of lead and chlorate of potash yielded 1.1172 , , carbonic acid and 0.2420 , , water. V. 0.6015 , , substance burnt with soda-lime gave 0.3615 , , platinum. VI. 0.6043 , , substance gave 46. C.C. of moist nitrogen Bar. 759mm*4y, Therm. 18O C. Per-centage composition I. 11. 111. IV. v. VI. Carbon . . . 75.35 75-34! -75.45 -Hydrogen . . 6-85 6-76 6.59 6-65 -I Nitrogen . . --8.52 8.81 These numbers agree better with the formula than any other proposed as the following comparison with the theoretical niimbers will show Theory.Mean of expt. -42 equivs. of Carbon . . 252 75.44 75.38 22 , , Hydrogen 22 6.58 6-71 2 , , Nitrogen . 28 8.38 8.66 -4 >, ,> Oxygen . -32 9.60 1 , , Strychnine . . 334 100~00 In order to prove the accuracy of the above determinations and for the control of the formula derived therefrom we submitted the double compound of strychnine with bichloride of platinum tercbloride of gold and protochloride of palladium to a careful analysis with reference to their metallic elemelits. The mean of these analyses which we shall hereafter give in detail lead to an RESEARCHES ON STRYCHNINE. expression closely corresponding with the equivalent of strychnine when represented by the above formula Equivalent deduced from the mean of ten determinations of platinum .. 337.1 Equivalent deduced from the mean of three determinations of gold . 331.6 Equivalent deduced from the mean of two determinations of palladium . . 338.0 Mean . 335.5 Theoretical equivalent 33$0 SALTS OF STRYCHNINE. The characters of many of the compounds of strychnine are enume- rated in most chemical manuals. Of these we shall merely give the analytical results confining ourselves to a description of such salts only as have not previously been fully examined. Hydrochlorate of Strychnine.-This salt is formed by dissolving strychnine in hydrochloric acid. Two crystallizations from water render it perfectly pure. It is neutral to test paper.I. 0.2701 grm of substance gave 0.6704 , , carbonic acid and 0.1614 , , water. 11. 0.3351 , , substance gave 0,8349 , , carbonic acid and 0*1881 , , water. 111. 0.5912 , , substance gave 0*2280 , , chloride of silver. IT. 0.1733 , , substance gave 0.0671 , , chloride of silver. V. 0.6060 , , substance exposed in an air-bath to a temperature of 1200 lost 0.0445 , , water. VI. 0.3985 , , exposed to the same temperature lost 0.0280 , , water. which numbers correspond to the following per-centage composition I. 11. IIr. IV. V. VI. Carbon. . 67.69 67.95 - - - - HydrogenChlorine . . 6.63 - 6.23 I -9.54 9.57 - - - Water . 7 - - 7 7.33 7.02 246 MESSM. ABEL AND NICHOLSON'S leading to the formula c42 H92 N O4 cl for the salt dried at loo0C.and for the crystallized salt C, H, N2 O, H C1 + 3 aq. as may be seen by the following comparison to which we annex the results obtained by Regnault* and Gerhardt.? A. & N. Theory. Mean. Regnault. Gerhardt. 42 of Carbon . 23 , Hydrogen . 23.00 6.20 6.43 6.75 6.94 2 , Nitrogen. . 28.00 7.56 -- . 32.00 8.65 --4 > Oxygen J 1 , , Chlorine. . 35.50 9.58 9.55 9.81 -99 9) Hydrochlorate .>370.50 100.00 of strychnine . I 3 , , Water . . 27.00 6.79 7-17 -1 equiv. of crystallized salt 397.50 Gerhardt has also determined the amount of water in this salt and finds that it contains two atoms which are only expelled on exposing the salt to a temperature of 160' C. Contrary to this statement we have found this salt as well as the hydriodate hydro- bmnate srilphates and phosphates to lose the whole of their water of crystallization on exposure over sulphuric acid in vacuo.Hydrobromate of strychnine produced by dissolving strychnine in hydrobromic acid and crystallizing from water I. 0.2288 grm. of substance gave 0.5104 , , carbonic acid and 0.1154 , , water. 11. 0.6248 , , substance yielded 0.2802 , , bromide of silver. In 100 parts I. 11. Carbon . . . . 63.83 -Hydrogen . . . 5.60 -Bromine . . . -18.69 * Liebig's Annalen V. 26 P. 30. f-Recherches sur la Classification Chimique etc. par R.I. Gerhardt p. 51. RESEARCHES 0N ST&YC11N INE . leading to the formula as is seen by the following comparison Theory.Expt. -42 equiv of Carbon . . . . . . . 252.00 60.97 60.83 23 , , Hydrogen . . . . . . 23.00 5.56 5.60 2 , , Nitrogen . . . . . 28-00 6.78 -4 , , Oxygen . . . . . . 3200 7-76 -1 , , Bromine . . . . . . 78.26 18.93 18.69 1 , , Hydrobromate of strychnine 413.26 100.00 Hydriodate of strychnine is prepared in a similar manner to the hydrochlorate. This is one of the most insoluble salts of strychnine. In purifying it the excess of hydriodic acid should be rapidly removed by washing otherwise when the salt is exposed to the air products of decomposition are formed which we shall notice in our future communication. I. 0.3269 grm. of substance gave 0.6546 , , carbonic acid and 0-1482 , , water. 11. 0-3294 , , substance gave 0.6595 , , carbonic acid and 0.1489 , , water.111. 0,4736 , , substance gave 0.2396 , , iodide of silver. IV. 0.3576 , , substance gave 0*1808 , , iodide of silver. Per-centages obtained I. 11. 111. IV. Carbon . 54*61 54.60 -Hydrogen . . 5.03 5.02 -Iodine . . . -27.00 27-24! agreeing with the formula c, H, N 0.4 H 1 as is shown by the following comparison (together with Regnault’s analysis of this salt) MESSBS. ABEL AND NICHOLSON’S -Theory. A. & N. mean. Regnault. 42 equivs. of Carbon . 252.00 54.62 54.60 55.08 23 , , Hydrogen . 23.00 4.98 5.02 -2 , , Nitrogen . 28.00 6.07 -4 , , Oxygeii . 32-00 6.95 -1 , , Iodine . . 126.36 27.38 27-12 26.12 Hydrosu@hocyanafe of strychnine.-This salt has recently been described in a memoir by Dollfus* who at the instigation of Professor Will availed himself of the insolubility of sulphocyanide of silver for the determination of the equivalents of several organic bases; we have likewise investigated this salt.Our analyses made with two different specimens slightly differ from the results obtained by Dollfus ; the equivalent derived from our determinations of the hydrosulphocyanic acid nearly coincides with the calculated number. Strychnine being very difficultly soluble in water a direct determi- nation was made of it in this salt; by precipitating with ammonia collecting on a tared filter washing and drying at looo C. a tolerably accurate result was obtained. We availed ourselves of this method in the analysis of several other salts of strychnine.Analysis of the hydrosulphocyanate I. 0.3704grm. of substance gave 0.9090 , , carbonic acid and 0.1975 , water. 11. 0.2398 , , substance gave 0.1013 , , sulphocyanide of silver. 111. 0.5377‘ , , substance gave 0.2260 , , sulphocyanide of silver. 0.4563 , , strychnine. In 100 parts I. 11. 111. Carbon . . . . . . 66.93 -Hydrogen . . . . . 5.92 -L Hydrosulphocyanic acid -15-90 14.93 Strychnine . . . . I -84.86 * Liebig’s Annalen Vol. LXV. p. 212. RESEARCHES ON STRYCHNINE. 249 Corresponding to the formula c, H, N 04 H CY 8 as may be seen by the follow in^ comparison which is accompanied by the numbers obtained by Dollfus Theory. A. &N. Dollfus.44 equivs. of Carbon .. .264 67.17 66.93 67.70 23 ....Hydrogen ... 23 5.85 5-92 6.39 3 ....Nitrogen. ... 42 10.68 -7 I 4 ....Oxygen .... 32 8.15 2 .., Sulphur .... 32 8.15 -Theory. A. &N. Dollfus. 1equiv of Strychnine ....334 84-98 84-86 -1 ,,,,Hydrosulphocyanic acid 59 15.02 14-96 14.45 -c___ 393 100*00 99.92 The equivalent of strychnine derived from the above analyses is as follows I. 11. Equivalent deduced from the determination of }334.3 hydrosulphocyanic acid ...... 336.1 Mean .............. 335.7 Theoretical equivalent ........ 334.0 Neutral subhate ofstrychnine.-This salt is prepared by saturating dilute sulphuric acid with finely powdered strychnine it crystallizes in large four-sided prisms which are neutral to test-paper.I. 0.2905 grm. of substance gave 0.6996 , , carbonic acid and 0.1615 ,,,,water. 11. 0.3889 ,,,,substance gave 0.1184 ,,,,sulphate of baryta. Per-centage obtained I. 11. Carbon .......65.68 - Hydrogen ....... 6-17 - Hydrate of sulphuric acid .. -12.79 250 MESSRS. ABEL AND NICHOLSON’S These numbers correspond to the formula c4 H2 N 04 €3 804 as is seen by the following comparison to which we append Regnault’s* analysis of this salt Theory. A. & N. Regnault. 42 equiv. of Carbon. . . . . 252 65.80 65.68 65.34 23 , , Hydrogen . . . 23 6.01 6.17 6-10 . . 28 7.31 -2 , , Nitrogen . 8 , , Oxygen . . . . 64 16.71 -1 , , Sulphur . . . . 16 4.17 -1 , , Neutral sulphate of strychnine . . Theory.Experiment. +-1 equiv. of Strychnine . . . . 334 87.22 -1 , , Hydrated sulphuric acid 49 12.78 12.79 383 100.00 Acid sulphate of strychnine is formed by adding diluted sulphuric acid to the preceding salt ; it crystallizes in long thin needles and is very acid to test-paper. The analyses were made with material from two different preparations I. 0.3589 grm. of sulphate yielded 0,7729 , , carbonic acid and 0.1885 , , water. 11. 0.3071 , , substance gave 0.1642 , , sulphate of baryta. In 100 parts I. 11. Carbon . . . . . . . 58.73 -Hydrogen . . . . . . 5-83 -Hydrate of sulphuric acid . . -22-46 The following comparison shows this salt to correspond to the formula c, H, N 04 H so, H so4 * Liehig’s Annalcn Vol.xxvl. p. 33. -\ 251 RESEARCHES ON STRYCHNINE. Theory. Expt. 42equivs. of Carbon . .. 252 58.33 58.73 24 ....Hydrogen ...... 24 5.56 5.83 2 ....Nitrogen ....... 28 6.48 12 ....Oxygen ....... 96 22-22 2 ....Sulphur ....... 22 7.41 1 equiv. of Acid sulphate of strychnine .432 100.00 Theory. Experiment. F 1 equiv. of Strychnine ....334 77.30 I 2equivs. of Hydrated sulphuric acid 98 22.70 22.46 432 100.00 The small excess of carbon and hydrogen and the deficiency of sulphuric acid in the above analyses arises from the presence of a little neutral sulphate in the substance employed for the determi- nations it being exceedingly difficult to separate this salt completely from the acid sulphate. Nitrate of strychnine.-On gently heating finely powdered strych- nine in nitric acid diluted until it is but feebly acid to the taste the base is dissolved ;the solution while cooling deposits beautiful colourless needles of nitrate of strychnine.If the nitric acid be employed too concentrated the solution assumes a yellow colour immediately on the application of heat and the compound produced is no longer a salt of strychnine but the nitrate of a base containing the elements of hyponitric acid in place of hydrogen which we shall more minutely describe hereafter. The existence of an acid nitrate of strychnine is mentioned in ‘‘Liebig’s Trait6 de Chimie Organique,” we have not been able to prepare this compound; it is very probable that the formation of the nitro-base just mentioned has given rise to the assumption of an acid nitrate.0.3168 grm. of this salt gave on combustion 0.7365 ,,, carbonic acid and 0.1668 ,,,,water in 100 parts Carbon .........63-40 Hydrogen ........ 5-85 corresponding to the formula c*,H, N 04 H NO, 252 MESSRS. ABEL AND NICHOLSON'S as may be seen from the following comparison annexed to which we give an analysis of this salt by Regnault* Theory. A. & N RegnauIt. -"-42 equivs. of Carbon. . . . . 252 63-47 63.40 63.10 23 , , Hydrogen . . . . 23 3.79 5-85 5-89 3 , , Nitrogen . . . . 42 10.38 -10 , , Oxygen. . . . . 80 20.16 -1 equiv. of Nitrate of strychnine 397 100.00 Chroinute of strychnine is formed as a yellowish-brown precipitate when a solution of neutraI chromate of potash is added to hydro-chlorate of strychnine.The precipitate freed from the mother-liquor is soluble in boiling water; on cooling the solution deposits the salt in beautiful lemon-yellow needles which are difficultly soluble in water and alcohol neutral to test-paper and may be dried at looo C. (212O F.). A bichromate also exists ; we have not however subniitted it to analysis 0.3037 grm. of chromate gave 0.0613 , , sesquioxide of chromium. corresponding to Hydrate of chromic acid 15-34per cent which by comparison with the theoretical numbers will lead to the formula c, H, N 04 H Cr 0 Theory. Expt. * 1 equiv. of Strychnine . . 334.00 84.53 I 1 , , Hydrateofchromicacid 61.15 15.47 15.a 1 equiv.of Chromate of strychnine 395.15 100.00 Neutral oxalute of strychnine.-This salt is produced by neutra- lizing oxalic acid with strychnine it is neutral to test-paper 0.4731 grm. of substance gave by the method above described 0.4162 , , strychnine 0.0624 , , carbonate of lime. equal in 100 parts to Strychnine . . 87.98 Hydrate of oxalic acid 11-86 * Liehig's Annalen Vol. XXVI. p. 35. RESEARCHES ON STRYCHNINE. leading to the formula '42 '4,N2 '4 as a comparison with the theoretical numbers shows ; - H22 '2 Theory. Experiment. 1 equiv. of Strychnine . . 334 88.13 87.98 1 , , Hydrate of oxalic acid . -45 -11-86 11-87 1 equiv. of neutraloxalate of strychnine 379 100.00 Acid oxalate of strychnine.-An excess of oxalic acid added to the preceding salt yields this substance which is possessed of an acid reaction 0.2610 grrn.of substance gave 0.2054 , , strychnine and 0.0604 , , of carbonate of lime. affording on 100 parts Strychnine. . . 78-69 Hydrate of oxalic acid . 20.82 The following comparison proves the correct formula for this salt to be O4,HC2 O4 HC O4 - '42 H22 N2 Theory. Experiment 1 equiv. of Strychnine . . 334 78.77 78.69 2 equivs. of Hydrate of oxalic acid . 90 21.23 20.82 1 equiv. of acid oxalate of strychnine 424 100*00 Acid tartrate of strychnine.-On dissolving strychnine in excess of tartaric acid this compound is formed crystallizing in needles which are acid to test-paper. I. 0.4225 grm. of substance gave 0.2904 , , strychnine or 68-73per cent.11. 02222 , , substance gave 0.1527 , , strychnine or 68-74!per cent. these numbers lead to the formula c42 H2,N 04 H '* H4 012 which will be found on comparison to correspond sufficiently with the theoretical per-centage 254 MESSRS. ABEL AND NICHOLSON’S Theory Mean. * 1 equiv. of Strychnine . . 334 69.00 68.735 1 , , Hydrate of tartaric acid 150 31.00 -1equiv. of acid tartrate of strychnine 484 100.00 Neutral tartrate of strychnine is formed by dissolving strychnine in a solution of the above salt. It is neutral to test-paper. 0.4416 grm. of substance yielded 0.3695 , , strychnine or 81*40per cent. leading to the formula 2 (C42 H, N2 04) H c H4 01 as is seen by the following comparison Theory.Esperiment . +-2 equivs. of Strychnine . . 668 81.66 81.40 1equiv. of Hydrate of tartaric acid 150 18-34 -1 equiv. neutral tartrate of strychnine 818 100.00 We endeavoured to form a compound of potash strychnine and tartaric acid by boiling strychnine in an aqueous solution of acid tartrate of potash we found however that no double salt was formed but that the results were neutral tartrate of potash and acid tartrate of strychnine as may be seen by the following equation 2 (K H T)+ C, H2 N 0,= K, T-t (H C, H22N 0,) H,T. The numbers mentioned under 11. at the acid tartrate of Strychnine refer to a salt procured in this manner. Hydrochlorate Gf strychnine and bichloride of platinum.-This compound is produced by the addition of bichloride of platinum to a solution of strychnine in hydrochloric acid as a yellowish-white precipitate nearly insoluble in water and ether and difficultly soluble in boiling dilute spirit from which solution it crystallizes in beautiful plates similar in appearance to mosaic gold.This compound is soluble in concentrated nitric acid giving rise to a new platinum salt which we shall hereafter refer to. The following determiiiations were all made with material from different prepara- tions and dried at loooC. (212OF.) at which temperature this compound retains no water. I. 0%350 grrn of substance gave 0.4874 , , carbonic acid and 0.1157 , , water. RESEARC EIES ON STRYCHNINE. 255 11. 0.4204 grm. of substance gave 0.7205 , > carbonic acid and 0.1660 , ,)water.111. 0.7252 , , substance gave 0.1312 , , platinum. IV. 0.6854 , , substance gave 0.1244 , , platinum. V. 0.6053 , , substance gave 0.1100 , , platinum. VI. 0.4918 , , substance gave 0 0897 , , platinum. VII. 0.5084 , , substance gave 0.0918 , , platinum. VIII. 0.7479 , , substance gave 0.1365 , , platinum. IX. 0.3122 , , substance gave 0.0567 , , platinum. X. 0.3146 , , substance gave 0.0573 , , platinum. XI. 0,4432 , , substance gave 0.0809 , , platinum. XII. 1.1571 , , substance gave 0.2109 , , platinum. Per-centage composition. I. 11. 111. IV. v. VI. VII. VIII. IX. x. XI. XII. C. 46-64 46-72 -----I H. 4-51 4.22 ----Pt. -18.09 18.15 18.16 18.23 18.05 18-22 18.16 18.21 18.25 18.18 leading to the formula C, H, N 0 HCI PtCl as may be seen from the following comparison with the theoretical numbers to which we append the analyses of Liebig* and Gerhardt :t Theory.A* 8~*' Mean Gerhardt. -* -7 Mean. Liebtg. 42 equivs. of Carbon. . 252.00 46.65 46.69 -23 , , Hydrogen . 23.00 4.26 4.44 -I 2 , , Nitrogen . 28.00 5.18 -Y9 4 ,> Oxygen. . 32.00 5.93 --3 , , Chlorine . 106.50 19.72 -7 -1 equiv. , Platinum 98.68 18.26 18.16 17.84 17-85 1 equiv. of ,hydrochlorate of strychnine and bi- 540.18 100*00 chloride of platinum } --* Liebig's Annalen v. 26 p. 57. + Classification Chimique des Substances Organiques par 11. Gerhardt p. 51. 256 MESSRS. ABEL AND NICHOLSON’S Liebig’s beautiful method of determining the equivalents of organic bases from the double compounds of the hydrochlorates with bichloride of platinum is the most precise and elegant mode that could possibly have been imagined.The analysis nevertheless if not conducted with sufficient care may give rise to an erroneous expression. When only two or three hundred milligrammes of substance are at the experimentor’s command an error of 1 or 2 milligrammes in the weight of the metal will give rise to a difference of from four to six tenths of a per-cent which must materially affect the formula for the substance. In three determinations made by Liebig we perceive a difference of four tenths of a per-cent; in two cases he obtained 17.7 and in the third 18.1 per cent.; the latter determination agrees exactly with the average of our ten deter- minations which oscillate between 18.05 and 18.2. Gerhardt’s deter- mination of the platinum is more concordant with Liebig’s lower ones. Hydrochlorate of strychnine and terchloride of gold.-& adding terchloride of gold to a solution of hydrochlorate of strychnine a voluminous bright yellow precipitate of the double salt is formed; it is purified by washing rapidly with cold water and crystallizing from alcohol. When boiled with water this compound undergoes decomposition metallic gold separating. The compound is deposited from an alcoholic solution in light orange-coloured crystals which may be dried at looowithout decomposition. I. 0.3102 grm. of substance gave on combustion 0.4246 , , carbonic acid and 0.0995 , , water.IT. 03756 , , substance gave 0.1095 , , gold. 111. 0.1516 , , substance gave 0.0441 , , gold. IV. 0.4334 , , substance gave 0,1266 , , gold. n 100 parts I. 11. 111. IV. Carbon . . . 37.33 -I -Hydrogen . . 3.55 --Gold . . . . -29-15 29.09 29.21 corresponding to the formula as the following comparison will show RESEARCHES ON STRYCHNINE. -Theory. Experiment. 42equivs. ofcarbon . . . . 252*00 37.41 37.33 23 , , Hydrogen . . . 23.00 3.42 3.42 2 , , Nitrogen . . . . 28.00 4-15 -4 , , Oxygen . . . . 32.00 4.75 -I 4 , , Chlorine . . . . 142.00 21.08 1equiv. of Gold . . . . . 196.66 29.19 29.15 >) >J Hydrochlorate Of 673.66 100~000 strychnine and ter-chloride of gold Hydrochlorate of strychnine and protochloride of palladium is precipitated as a brown flocculent mass when protochloride of palladium is added to a solution of strychnine in hydrochloric acid.It is soluble in water and alcohol from boiling solutions of which it crystallizes on their cooling in dark brown needles. It may be dried at loooC. (212O F.) without decomposition and affords metallic palladium when exposed to a high temperature. I. 0.4437 grm. of substance gave 0.0512 , , palladium. 11. 0.3121 , , substance gave 0.0358 , , palladium. Per-centage obtained 1. 11. Palladium . . . 11.50 11.47 agreeing with the formula C, H, N 0 HC1 PdC1. as is shown by the following comparison Mean of Theory. Expt.-42 equivs. of Carbon . . . . . 252.00 54.87 7 23 , , Hydrogen . . . . 23-00 5.01 -2 , , Nitrogen . . . . . 28.00 6.08 -4 , , Oxygen . . . . . 32.00 7.00 -2 , , Chlorine . . . . . 71.00 15.45 -1equiv. of Palladium . . . . 63.27 11.59 11-50 1 , , Hydrochlorate of strych-459.27 loo~oo nine and protochloride of palladium Strychine and protochloride of mercury.-If a solution of strych-nine in dilute alcohol be added to an excess of protochloride of VOL. 11.-NO. V1I. 8 MESSRS. ABEL AND NICHOLSON’S mercury a white crystalline precipitate is immediately formed which is insoluble in water alcohol and ether it may therefore be easily purified by washing. This compound as well as the following was burnt with chromate of lead in a combustion-tube provided with an elongated bulb as described by one of us in the analysis of the double compound of caffeine and protochloride of mercury,* carbonic acid water and mercury being determined in one combus-tion.I. 0.4815 grm. of substance gave 0.7330 ) , carbonic acid 0.1636 , ,) water and 0.1595 ,) ) mercury. 11. 0.4360 ,) .) substance gave 02070 ) , chloride of silver or 0.0512 , ,) chlorine. in 100 parts 1. 11. Carbon . . . 41.52 -Hydrogen . 3.77 -Mercury . . . 33.12 -Chlorine . . . -11.74 The following comparison of these results with the theoretical numbers shows this compound to have the formula, -c,2 H, N 0492HgCl Theory. Expt. 42 equivs. of Carbon . . . . 252.00 41-64 41.52 22 , , Hydrogen . .. . . 22.00 3-63 3-77 I 2 , , Nitrogen . . . . 28.00 4.63 4 , , Oxygen . . . . . 32.00 !jd29 -2 , , Chlorine . . . . . 71.00 11-78 11-74 ,j 2 , Mercury . . . . . 200.14 33.08 33-12 1 equiv. of Strychnine and proto- 605.14 loo~ooo chloride of mercury The substance therefore is analogous in composition to the aniline and leucoline compounds described by Professor Hofmann. It is soluble in dilute acids. Su&haie of strychnine and protochloride of mercury.-The solution of the above compound in sulphuric acid yields a substance which is * Mem. Chem. SOC.London Vol. III. p. 321. RESEARCHES ON STRYCHNINE. 259 indistinctly crystalline but of perfectly definite nature consisting of the original body combined with one equivalent of sulphuric acid its formula being C, H, N 0 H SO, 2 Hg C1 as the following determination shows when compared with the theoretical numbers 0.2535 grm.of substance gave 0.0439 , , sulphate of baryta corresponding to 7.27 per cent of hydrate of sulphuric acid. Theory. Expt. -1equiv of Strychnine . . . . . . 334.00 51.09 -I , , Hydrate of sulphuric acid . 49.00 7.49 7.27 2equivs. of Chlorine . . . . . . 11.00 10.85 -2 , , Mercury . . . . . . . 200.14 30.57 -1 equiv. of Sulphate of strychnine and 654.14 loo~oo protochloride of mercury Hydrochlorate of strychnine and protochloride of mercury is pre-pared by dissolving the above compound in hydrochloric acid or by adding a solution of protochloride of mercury to hydrochlorate of strychnine.It is difficultly soluble in water but easily so in spirit crystallizing from boiling solutions on cooling. I. 0.4968 grm. of substance gave 0.7175 , , carbonic acid 0.1735 , , water and 0,1559 , , mercury. 11. 0.2990 , , substance gave 0.2007 , , chloride of silver or 0.0496 , , chlorine. In 100 parts 1. 11. Carbon . . . . 89.38 -Hydrogen . . . . 3.88 -Mercury . . . . 31.38 -Chlorine . . . . -16.59 leading to the formula C, H, N O, H C1 2 Hg C1 as is seen by the following comparison MESSRS. ABEL AND NICHOLSON’S -Theory. Expt. 42equivs. of Carbon .......252.00 39.27 39.38 23 ,,,,Hydrogen ...... 23-00 3.58 3.88 2 ,,,,Nitrogen ...... 28.00 436 -4 ,,,,Oxygen ....... 32-00 4.98 - 3 ,,,,Chlorine ......106.50 16.61 16.59 2 ,,,,Mercury ......200.14 31-20 31.38 1 equiv. of Hydrochlorate of strychnine and protochloride of mercury The solutions of the two latter compounds give with ammonia a white precipitate. It appeared not improbable that under these circumstances a new basic atom containing both strychnine and protochloride of mercury was thrown down. To ascertain this a platinum-salt of the above precipitate was prepared and submitted to analysis. This salt gave 18.1 per cent. of platinum proving that the precipitate wa8 nothing but strychnine. The mercury in this instance was not precipitated as chloro-amidide of mercury but held in solution as the double compound of chloride of ammonium and protochloride of mercury Hg C1 N H CI. Strychnine and cyanide of mercury.-This substance is produced in the same manner as the cornpound of strychnine with proto- chloride of mercury; it is more soluble in water and alcohol than the latter and crys&lizes in well defined small prisms.It is inso- luble in ether and may be dried at 100° C. (212*F.)without decom- position. 0.4098 grm. of substance gave 0.7055 ,,,,carbonic acid 0.1395 ,,,,water and 0.1400 .,,,mercury. In 100 parts Carbon . .46.96 Hydrogen . . 3.78 Mercury . .34-16 The following comparison shows this compound to have the formula c, H, N 0,,2 EIg cy RESEARCHES ON STRYCHNINE. 261 Theory. Experiment. f-A-y 46equivs. of Carbon . . 276.00 47.08 46.96 22 , , Hydrogen . 22-00 3.75 3.78 -4 , , Nitrogen .. 56-00 9.59 7 4 ?? 9) Oxygen . 32.00 5*46 2 , , Mercury . . 200.14 34.12 34-16 1 equiv. of Strychnine and} 586.14 loo~oo Cyanide of Mercury Hydrochlorate of strychnine and cyanide of naercury.-Brandes* has described a compound produced by mixing solutions of hydro-chlorate of strychnine and cyanide of mercury the analysis of which Zed to the formula C H, N 0 HCl 4 Hg Cy. We prepared a compound of this nature according to the method described by the above chemist and submitted it to analysis. 0-4356grm. of substance gave 0-8390 , , carbonic acid and 0*0881 , , mercury. In 100 parts Carbon . . 52.53 Mercury . . 20*20 These numbers agree with the formula c H22 N 0 HC1 Hg cy as expressive of the composition of this salt as may be seen by com-parison with the theoretical numbers Theory.Experiment. Fy Mequivs. of Carbon . . 264.00 53-16 52.53 23 , , Hydrogen ' . 23.00 4.63 -3 , , Nitrogen . . 4400 8.46 . 32-00 6.45 -4 9 ,> Oxygen 1 equiv. , Chlorine. . 35.50 7.15 -1 , , Mercury. . . 100.07 20.15 20.20 1 equiv. of Hydrochlorate of Strychnine and Cyanide 496.57 100.00 Mercury * Liebig's Annalen,v. 66 p. 268. RESEARCHES ON STRYCHNINE. It is probable froni this that strychnine combines in various pro- portions with cyanide of mercury. Besides the above compounds of strychnine we have also examined its combinations with phosphoric and arsenic acids which have furnished us peculiar results especially the compound with meta- phosphoric acid; we shall give a detailed dcscription of these com- pounds in a separate paper.Strychnine likewise forms difficultly soluble compounds with protochloride of platinum protiodide and subnitrate of mercury we have not submitted these salts to quantitative examination. The following is a table of the compounds of strychnine analysed by us with their formulae annexed. Strychnine . C42H,N204 Hydrochlorate of strychnine . . C42 H N2 04,HC1 Hydrobromate , , . C H N20, HBr Hydriodate , , * c42 HZ N2 O4 HJ Hydrosulphocyanate , c42 N 04 HCy st Neutral sulphate , , . C H N 0,.HSO Acid sulphate , , . C H N2 04,HSO, HSO Nitrate 9 '7 . C42 H N2O, HNO, Chromate 9 9 . C42 H N2 04,HCr 0 Neutral oxalate , , . C42 €1 Nm 04 HC2 0 Acid oxalate , , .C H Ni O, HC 0,.HC, 0 Neutral tartrate , , -2 (C42 Ha N 04). H2 Cs €14 01 Acid tartrate , , * c42 HZ NI O4 H2 c8 H4 '12 Hydrochlorate of strychnine and bichlo- .}c HC1 Pt cl, ride of platinum . 22 2 4' Hydrochlorate of strychnine and terchlo- *}c,2 22 2 4, ride of gold . HCl AuCI Hydrochlorate of strychnine and proto- .>c HZ N2 o, HCl Pd c1 chloride of palladium . Strychnine and protochloride of mercury. C H N 04 2Hg C1 Sulphate of strychnine and protochloride *} c42 HSo, 2Hg c1 of mercury . 22 2 4 Hydrochlorate of strychnine and proto- *}c 42 0 HC1 2Hgc1 22 2 4' chloride of mercury . Strychnine and cyanide of mercury . C, HaN2O, 2Hg Cy Hydrochlorate of strychnine and cyanide N 0 HCl H~ cY of mercury .c422224' The formula for strychnine arrived at by all these analyses is the same as that last proposed by Regnault which has subsequently been translated by Gerhardt into the expression c44 H24N2 04 the formula of late most generally adopted. The analyses made by Regnault of the hydriodate sulphate and nitrate all closely cor-respond with C4 H, N 04,as may be seen by referring to the analytical details. His determinations of carbon and hydrogen in the base itself are lower however than this formula will admit. '4 H22 N2 '42 ON THE ISOLATION OF THE ORGANIC RADICALS. 263 In conclusion it may be mentioned that the study of a series of products of substitution and decomposition with which we have become acquainted in the course of these experiments fully confirm the analyses of strychnine and its salts so that we have no hesitation in adopting the formula c H, N 0 as the true expression for this base.

ISSN:1743-6893    

DOI:10.1039/QJ8500200241

出版商:RSC    

年代:1850

数据来源: RSC