摘要:

273 XLlII.-On the Decay of Gutta-percha and Cuoutct'iouc." By Prof. WILLIAM ALLEN MILLER M.D. F.R.S. THEinquiries to which this investigation has given rise have ex- tended over many months and have included a large number of analyses but the results obtained may be stated in a small com- pass as they are very definite. T have examined numerous samples of gutta-percha cables both injured and sound which have been in use for several years and I find in all cases that the deteriorated portions have undergone chemical change and that change consist3 in a process of oxidation. Whatever 1aetard.s or prevents this oxidation retards or prevents the decay of the gutta-percha some of the specimens which I examined being as good as new though they had been manufac- tured and used electrically for years; whilst others in a few months had become brittle rotten and unserviceable.As the general result of these inquiries I find that whenever the gutta- perch has been completely submerged in water no injurious change has occurred sea-water appearing to be eminently adapted to the preservation of the gutta-percha. On the other hand alternate exposure to moisture and dryness particularly if' at the same time the sun's light has access is rapidly destructive of the gutta-percha rendering it brittle friable and resinons in aspect and in chemical properties. A gradual absorption of oxygen takes place and the gutta-percha slowly inrreases in weight becoming at the same time proportionately soluble in alcohol and it1 dilute solutions of the alkalies.In every instance however some por-tion of the gutta remiined unchanged in composition. My experiments have also been extended to the prolonged action of air moisture and light upon india-rubber and here also I find that these agents effect analogous changes though somewhat less rapidly. * A paper on this subject by Nr. S p i 11 e r having recently appeared it bas been thought that the Fellows might be interested in an official report made five years ago to the Joint Committee appointed by the Lords of the Comirlittee of Privy Coiincil for Trade and the Atlantic Telegraph Company to inquire into the Constriiction of Submarine Telegraph Cables-[ ED.] VOL. XVTII. X 274 MILLER ON THE DECAY OF The caoutchouc however instead of becoming brittle is con- verted into a glutinous mass losing its elasticity increasing in weight to a certain extent and becorning partially soluble in alcohol and diluted alkaline liquids These deductions are made from the examination of a number of samples supplied to me partly by Captain Galton and Mr.L. Clark including specimens of coated telegraphic wires suspended in air specimens of submarine cables specimens of wires sunk in the soil under various conditions besides experiments instituted by myself upon the action of various agents upon gutta-percha and they include the results of an extended and well-contrived series of experiments made at the works of the Electric Telegraph Company under the direction of Mr.L. Clark. I will here subjoin an abstract of the principal experimental details and for the convenience of reference will arrange them under the following distinct heads :-1st. Experiments upon pure gutta-percha. 2nd. Experiments upon commercial gutta-percha. 3rd. Experiments upon submerged cahles. 4th. Experiments upon decayed and damaged cables exposed in air and underground under various circumstances. 5th. Experiments upon caoutchouc. 6th. Experiments upon other compounds. 1. Experiments on Pure Gutta. Pure gutta differs in some of its properties from the comrner- cia1 gutta. I found on examining the whitest samples purified by Dr. Cattell that it formed a porous milk-white mass wholly soluble in benzol in ether in bisulphide of carbon arid in the ordinary solvents of gutta-percha.It is a'perfectly pure hydro- carbon probably containing 4&I130. I found it to consist of-Found. C20 HN. Carbon ...... 88-96 or 88-88 Hydrogen. ..... 11.04 11.12 100~00 100~00 When exposed to a temperature of 212" it softens but does not liquefy; it loses a trace of moisture and tbeu gradually absorbs GUTTA-PERCHA AND CAOUTCHOUC. oxygen becoming brown brittle and resinous in appearance. In one specimen the increase in weight amounted to 4.45 per cent. The oxidized portion is insoluble in benzol which when digested on the brown mass dissolves out a quantity of unaltered gutta which had been protected from oxidation by the coating of resin. This resinous mass when thus purified was found to have been produced from the gutta-percha by simple absorption of oxygen the gutta having in one experiment absorbed more than a fourth of its weight of oxygen from the atmosphere.2. Chemical Experiments on Commercial Gutta-percha. The gutta-percha of commerce is not a pure proximate vege- table principle but it consists chiefly of a hydrocarbon which may for brevity be termed pure gutta or simply gutta mixed with a product of its oxidation which is in the form of a soft resin amounting to about 15 per cent. in the best commercial samples. The following is the composition of a piece of ordinary good commercial gutta-percha taken from a piece of new cable supplied to me by Mr. L. Clark :-Pure giitta .......... 79.70 Soft resin ..........15.10 Vegetable fibre.. ...... 2.18 Moisture ............ 2.50 Ash ................ 0.52 100.00 The moisture reported in this analysis is mechanically diffused through the mass of the gntta-percha and seems to have some influence upon its pliability and toughness 100 parts of the commercial sample when dried at 212"till it ceased to lose weight deducting the ashes contaiued- Carbon ............. 84.66 Hydrogen ............ 11-15 Oxygen .............. 4.19 100*00 s2 276 MILLER ON THE DECAY OF GUTTA-PERCHA. This gutta-percha softens and liquefies by a heat of 212". It is soluble with the exception of a few flocculi of fibrous matter in benzol in bisulphide of carbon and. in ether. Alcohol dissolves none of the pure gutta but extracts a portion of the soft resin.This resin is an oxidised compound probably in a transitional condition to a higher stage of oxidation. I found it to con- sist of-Carbon .............. 76.15 Hydrogen ........... 11.16 Oxygen .............. 12-69 100~00 The true gutta was extracted nearly pure from this sample by dissolving it in benzol filtering and adding alcohol when a coagulum of pure gutta was obtained which was found to con-sist of- Carbon .............. 87-22 Hydrogen ............ 12.04 Oxygen .............. 074 The presence of the small quantity of oxygen in this case was due to a little of the resin which still adhered to the precipitated mass of gutta Commercial gutta-percha may be preserved for months and even years with little change either in water or in air provided light be excluded.This I have found from my own experiments and the results which I have myself obtained are confirmed by experiments made by Mr. Clark. The following are some of the most important of these experiments :-SO0 grs. of thin sheet gutta were exposed under various conditions at the end of last October at the Electric Cable Works. The various samples were examined on the 2nd of July of this present year (1860). 1. In netting exposed to sun and rain in open air. 2. In a bottle open to the air and light but excluded from rain. 3. In R bottle open to the air but excluded from light. 4. In fresh water open to air and light.5. In fresh water open to air excluded from light. 6. In fresh water excluded from air and light. 7. In sea water exposed to air and light. 8. Tn sea water excluded from light but exposed to air. 9. In sea water excluding both light and air. The specimens 4 5 6 7 8 and 9 were wholly unaltered with the exception of a slight increase in weight due to the absorption of water which they lost again after exposure to the air for an hour or two. The tenacity and structure of the material did not appear to have undergone the slightest chahge. No 2 which had been folded up and introduced into a bottle the mouth of which was open and inverted had increased in weight from 500 grs. to 524.5 grs, or about 6 per cent.owing to absorption of oxygen from the air. The outer layers of the sheet where exposed to light were brittle and resinous in appearance but the inner portion which had been screened from light by the outer folds was but little altered in texture or appearance. On examining chemically a portion of the most brittle part I found a large portion of it to have lost the composition of gutta and to have become converted into a matter soluble in alcohol 55 per cent. of the mass being in fact transformed into the resin already spoken of. The sample No. 3 which had been kept in the dark had expe- rienced little or no change. It had only increased 2.5 grains in weight or 0.5 per cent.; and when treated with alcohol gave up ‘1.4 per cent. of resinous matter to it.These results agree with those which I made upon gutta-percha which had been exposed to the light of day for the shorter period of two months. This specimen had become quite brittle had in- creased in weight 3.6 per cent. and yielded 21.5 per cent. of resinous matter soluble in alcohol; whilst a piece of the same sheet kept in the dark had undergone no sensible change. Samples of sheet gutta-percha were also subjected in November last to the action of the following liquids and exposed to diffused daylight :-A. Boiled linseed oil. C. Stockholm tar. B. Linseed oil not boiled. D. Coal tar. I when examined on the 4th of August 1860 or at the end of nine months these liquids were found not to have exerted any perceptible solvent action upon the gutta which retained its tex- ture add tenacity in all those portions which had been fairly submerged in the liquid and protected from the light aild atmos- 278 MILLER ON THE DECAY OF GUTTA-PERCllA.pheric air; but in those portions which had projected into the atmospheric air contained in the jar where it was also exposed to the effects of diffused daylight the texture had become rotten and the material more or less brittle and resinous. All the liquids above mentioned are calculated to exclude oxygen from the gutta-percha and thus they are enabled to exert a pre- servative influence upon it without however in any degree soften- ing or dissolving its texture. Hence they are likely to be highly valuable agents in coating the insulating material.3. Experiments on Submarine Cables. I have examined several specimens of cable from different lines which have been submerged for periods of time varying from a few weeks to seven years In no case where the cable has been com- pletely and continuously submerged have I found any sensible deterioration in the quality of the gutta-percha. No. 1. Holghead Irish cable (from Captain Galton) taken up in February 1859 after seven years’ submergence. No. 2 a. b. c. Three specimens from the Dutch line from Orfordness to Schevening (Mr. L. Clark) submerged five years raised in August 1859. This cable was enclosed in a coating of galvanized iron wire and contained a single wire of copper in gutta bound round with hemp and tape soaked in boiled elinseed oil tallow and Stock-holm tar.a. External coatiiig of galvanized wire not damaged by cor- rosion. This sample had been buried on the Dutch coast to a small depth in sand. b. and c. Outer galvanized wire much corroded but the gutta-percha quite sound. The gutta-percha wire had in each of these samples been exposed to the air out of the metallic casing for some months and consequently was drier than the sample a taken from its metallic coating just before it was analysed. No. 3. Cable off Portland (Captain Galton); down for seven months; composed of seven thin copper wires twisted into a strand covered with tar then coated with gutta-percha without any metallic protecting envelope. No. 4. Cable from line bet ween Cnndia and Alexandria (Captain G a1t o u).Construction similar to the last ; it showed superficial MILLER ON THE DECAY OF GUTTA-PEBCIIA. 279 erosions of the gutta-percha after submergence for a few weeks ; but the composition of the gutta was unchanged. No. 5. New gutta-percha covered wire (Mr. L. Clark) ; never used. 'L'he only chemical difference perceptible in these different specimens was in the quantity of water mechanically retained in each. 100 parts of each contained :-2. h . 4. 5. 1. a. 6. c. 3. ----_---Water .. ,. .. 0-84 3.36 1.75 1.49 4.8 0.96 2.50 Ash . . . . . . . . 1-05 .. .. 0'76 3-52 0-75 0.50 4. Experiments upon damaged Cables suspended in Air or placed underground. Of damaged cables I have had various specimens for examina- tion.1 to 6. Six samples described by Mr. Sa wwr d in his evidence before the Committee January 12 1860. 1. Buried in chalky or gravelly soil coated with a white friable crust of altered gutta-percha. This was very brittle and con-tained 35 per cent. of resin ; this resin contained 17 per cent. of oxygen combined with a hydrocarbon of the same composition as pure gutta. 2. Was in soil exposed to leakage of gas-pipes and also was resinous arid brittle but less so than No. 1. 3. Was described as pulpy when raised as if fermenting; taken from ground into which drainage from oak trees or posts occiirrecl. When forwarded to me it was hard and tough the copper wire within was slightly corroded rind adhered to the gutta-percha the channel around the wire lined with a pale brown powder.This powder contained traces of copper. It appears to consist of gutta-percha as it was almost wholly soluble in benzol and was insoluble in alcohol. The material in this case seemed to have undergone comparatively little permanent change although so very different in appearance from ordinary gutta-percha when it was taken up. It fused bclow 212O. It had been painted with some pigment 280 NILLER ON THE DECAY OF CAOUTCHOUC. containing lead and on burning left an ash amounting to 1-87 per cent. 4. Not very brittle taken from iron pipes. 5. Exposed to a dry heat near a baker's oven; coated with red lead. 6. Exposed to a dry heat (exact source not indicated).This was extremely brittle could be powdered without difficulty and was almost converted into a resinous substance. It fused below 212",it left 1.03 per cent. of ash when burnt and appeared to have been coated with some pigment. In all these samples those which were most brittle contained the oxidized resinons body in largest proportion. This resinous substance varied somewhat in the proportion of oxygen which it contained in the different samples but presented the same general properties. It was soluble in cold alcohol and still more largely in boiling alcohol; was insoluble in ether and but sparingly in benzol; diluted alkaline leys dissolved it with facility and the solution coagulated on the addition of an acid in excess. 7 and 8.Samples of gutta-percha covered wire taken from a tunnel in the Stour valley placed in the tunnel in 1850 (Mr. L. Clark). One portion of this A was comparatively little injured; the other B was brittle and rotten. This sample had been coated with some pigment containing lead. It would be useless to cite in detail the various analyses which I have made of these several samples or to give the numbers obtained for the proportion of moisture ash and resin .which they contained or to quote the proportions of carbon hydrogen and oxygen ascertained to exist in the nltercd I;ortion as contrasted with the unchanged portion present in each sample. It may be stated generally that wherever the proportion of resin was greatest the sample of gutta exhibited the greatest degree of brittleness; and this brittlenew was always found to be niost marked in the specimens which had experienced the greatest degree of oxidation ; and further that these changes appeared to occur most rapidly and decidedly ill those points where the gutta- percha was alternately wet aQd dry.5. Experiments on Caoutchouc. The caoutchouc of commerce is like gutta riot a pure vegetable principle and consists of a hydrocarbon of definite Composition MILLER ON THE DECAY OF CAOUTCIIOUC. mixed with a small quantity of resin the amount of which varies in different specimens. The following are the results of my analtlgsis of a sample of pure unmanufactured Para rubber compared with a sample of good sheet masticated or manufactured rubber.Virgin. Masticated. Pure caoiitchouc ........ 96.6 ...... 96.64 Moisture.. .............. 1.3 ...... 0.82 Resin .................. 1.8 ...... 2-06 Ash.. .................. 0.3 ...... 0.48 100.0 100.00 Or deducting moisture and ash its elementary composition gave-Virgin. Masticated. Carbon .............. 85-82 ...... 85.53 Hydrogen,. ............ 11.11 ...... 12.06 Oxygen .............. 3.07 ...... 2-41 -...... -100~00 100~00 Caoutchouc like gutta-percha is as already stated liable to deterioration by exposure to the action of oxygen in the presence of solar light but the gum is less rapidly injured if exposed to their influence in the native state than if it has been previously masticated. When subjected to the action of air excluded from light it does not experience any marlred change even during very lotig periods.It is however important to observe that the masti- cated rubber is much more porous than the unmanufactured caoutchouc. M'hen immersed in water caoutchouc absorbs a much larger quantity of this liqriid than gutta-percha and the masticated much more than the unmanufactured or virgin rubber. I subjoin the results of my exaniination of some samples submitted to experiment by Mr. L. Clark. A.-Virgin Para Hubber Finest Quality. 500 grains of this was exposed in each experiment, in the form of R narrow tape-like strip of rubber which had been stretched while hot and suddenly cooled. It was of a very pale brown colour. The various samples mere submitted to experiment at the 282 MILLER Oh’ THE DECAY OF CAOUTCHOUC.end of October 1859 and were examined nine months afterwards (August 4th 1860). No. 1 which had been exposed in netting in the open air to sun and rain had become blackened and rotten but was neither sticky nor crumbled had increased in weight 34.5 grains or 7 per cent. No. 2 was exposed in the air and light but kept dry in a bottle placed mouth downwards; it had increased in weight 14 grains or 2.8per cent. by absorption of oxygen and had become brown soft and sticky especially in the parts most exposed to light. It gave up 11-81 per cent. of an oxidized soft and viscous resin to alcohol. The annexed analysis will give an idea of the composition of the resin thus formed :-Carbon ..............67-23 Hydrogen ............ 9-54 Oxygen .............. 23-23 The proportion of oxygen differs a little in different samples. No. 3 which was exposed to diffused light in fresh water in an open bottle had become white and opaque from the absorption of moisture arid had increased 86 grains or 17 per cent. but it had experienced no other alteratioii in chemical properties and when dried resumed its origirial characters. No. 4 exposed in sea-water in an open bottle to diffused light liad absorbed 3.6 per cent. of its weight of watcr but was only a little altered in appearance not in chemical composition. B.-Masticated Rubber Sheet Best Quality. A similar series of experiments was made simultaneously upon masticated sheet caoutchouc.No. 1 exposed to sun and rai~i had collected into a sticky mass which had lost its tenacity and elasticity. No. 2 in the inverted liottle exposed to diffused light and air had increased in weiglit 8 grains or 1.6 per cent. and had collected into a lump which was viscous and had lost its elasticity especially in the parts most exposed to the action of light. When treated with alcohol it was found to yield 12.64 per cent. of its weight of MILLER ON THE DECAY OF CAOUTCHOUC. resinous matter to this solvent. These changes were in marked contrast; to NO.3 which was kept in a glass bottle in the dark for the same period but exposed to the air freely. It had increased in weight only 0.6 per cent. did not show any sign of alteration in tenacity or elasticity and yielded to alcohol 2.0 per cent.of resin only. hTo. 4 a sheet of the same rubber immersed in fresh water open to the air and diffused light had increased 87 per cent. by absorption of water that is to say it had nearly doubled its weight. It had become white opaque slimy and sticky when pressed and allowed water to be squeezed out by pressure. It lost weight rapidly by drying when exposed to the air. No. 5 similar to the last but exposed in sea-water. It was slightly opaque and slimy bot had increased only 5 per cent. in wcight by absorption. A secoiid sample in sea-water in a closed bottle emitted a smell of sulpliuretted liydrogeir and had gained 5 6 per cent. in weight by absorption. Its elasticity and tenacity were not impaired.The gradual permeability of masticated caoutchouc to water was further strikingly shown by enclosing a quantity of acetate of potash in bags made of sheet rubber and accurately sealed. They were then immersed iii water arid at the end of nine months the salt in each of the bags was found to have become liquefied by the water which it had absorbed and the bags had in each citse gained in weight several grains. C.-A similar Series of Experiments was made with Sheet Rubber vulcanized. 3. The sheet exposed in the netting to the sun and rain had lost 2 per cent. in weight; it was scarcely less tenacious than at first. 2. A similar sheet in fresh water absorbed 19 per cent. but was not otherwise altered.3. A similar sheet in sea-water was rather more slimy and had only gained 1.6 per cent. in weight. Each of the three substances viz. natural masticated and vul- canized rubber were submitted to the action of the following solvents for nine months :-A. Boiled linseed oil. B. Unboiled linseed oil. C. Stockholm tar. 284 MILLER ON THE DECAY OF GUTTA-PERCHA &c. The virgin mbber had resisted the action of the solvents almost perfectly retaining its toughness excepting in those parts which were above the surface of the liquid and exposed to light. In the tar this rubber had contracted spontaneously but was still strong and elastic. The masticated rubber mas in each instance greatly swollen and gelatinized and indeed in the case of the uriboiled oil was com-pletely dissolved.The vulcanized rubber had also lost its tenacity and had become swollen and gelatinous but retained its form and a certain degree of elasticity. A sample of india-rubber cable (from Captain Galton) which contained six strands of copper wire each coated with rubber then bound rouud with tape and again with rubber had experi- enced a singular change having become where in contact with the wire quite glutinous and sticky. This change however did not progress in the specirnen which I kept for some months in my room but the viscosity on the contrary gradually diminished.* 6. Experiments on other Substances. An insulating mixture composed of gutta-percha shellac and powdered glass or clay known as ‘‘Wray’s Compound ’’ (from Captain Galton) was also submitted to experiment.Heated to 212O it softened but retained its shape. It lost by drying 0.5 per cent. of moisture and when burnt left 22 per cent. of a white ash chiefly silicate of alumina. This compound absorbs water but sparingly. 500 grains left in fresh water for six months increased 7.5 grains in weight or 1.5 per cent. ad a similar increase in weight occurred in another experiment where sea-water was used. Sample of Gutta-Percha Cable (from Captain GaIt on) vukanized by Mackin,tosh’s Putent. The wire was found to be blackened on its surface from the action of the sulphur owing to the formation of sulphide of cop-per and traces of copper were f’ound in the gutta-percha covering. 9 The quantity of viscous matter was too small to admit of satisfactory analysis I ascertained however that no copper was present in the viscous mass and that the wire was not corroded.I could not determine whether grease was present in small quantity as was not iiiilikcly.

ISSN:0368-1769    

DOI:10.1039/JS8651800273

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

285 XLlV.-On the Absorption of Vapours by Charcoal. By JOHNHUNTER, M.A. and SCHEELE PRIESTLEY were aware of the property which charcoal possesses of absorbing different gases. Guy ton &I or-veau in 1782 stated that he had seen a piece of charcoal absorb all the gas contained in a jar and Lo witz recognised the deodo- rising and decolorising powers of charcoal. Count Morozzo was the first who attempted to obtain an accurate measurement of the volume of gas absorbed but his observations are of comparatively little value as he does not mention the nature of the charcoal and appears to have allowed it to come into contact with the air before being introduced into the gas. In 1799 shortly after the experiments of Mor ozzo mere published Messrs.ltouppe and Van Norden made a number of observations on the same sub- ject ; the method adopted by them however was also defective and had the additional disadvantage that the absorptions were determiued over water instead of mercury. In 1812 Th. de Sau ssure communicated to the Geneva Society his celebrated memoir on the absorption of the gases by din'erent bodies and although the subject appears to be deserving of further iovestiga- tion it has scarcely attracted any attention since that time." In 1863 I published in the Philosophical Magazine the results of tt series of experiments on the absorption of gases by different varieties of charcoal. My principal object in commencing this iiiquiry was to obtain greater absorptions than any previously observed by using charcoals formed from very dense and hard woods.The charcoals prepared from logwood and ebony exceed boxwood charcoal in the power of condensing gases within thcir pores the first absorbing 111.3 times its volume of ammonia. On further investigation I found that charcoal made from the shell of the cocoa-nut had by far the greatest absorbing power. It is very dense and brittle the pores are quite invisible and when broken the edges present a semi-metallic lustre. It absorbs scarcely any mercury during cooling increasing only seven per cent. in weight. Having examined the absorption of a large * Some important experiments on the absorption of gases by chwcoal were pub-lished by Dr. R. Angus Smith in 1863 (Proc. Roy. SOC.xii 414).-E~.VOL. xvrII. Y IIUNTER ON THE ABSORPTION OF number of the gases I extended the inquiry to the absorption of aqueous vapour arid the vapours of different liquids principally with a view of ascertaining whether any relation existed between their absorption and chemical composition. The present short paper contains the results of these experiments. The apparatus employed is represented in Fig. 1. %’he liquid to be converted into vapour is contained in a small glass bulb which is iutroduced into the graduated tube C standing in the mercurial bath G. This tube is surrounded by an outer glass vessel B which is connected with a flask A by a beiit tube H. Through an opening in the cover of the outer vessel B a thermo-meter is introduced for the purpose of determining the tempera- ture of the vapour.The graduated tube passes through an opening in the lower part of B and close to it is a pipe for the purpose of conveying the vapour to a small worm surrounded by cold water where it is conderised. FIG.1 Jn performing an experiment a quautity of the liquid requisite to give the required temperature is placed in the flask:’A. The graduated tube C having been carefully dried and filled with warm mercury to avoid any risk of moisture being present is in- verted in the bath and a small glass capsu1e:containiug the liquid whose vapour we wish to absorb is iutroduced into the tube. The flask A is then connected with the outer vessel B and the tube VAPOURS BY CIIARCOAL. leading from the latter to the condenser is attached.On heating the liquid in the flask to its boiling point the vapour passes over fills B and is then condensed. The contents of the little capsule in C enter into ebullition and the vapour occupies a number of divisions which are read off when the temperature of tbe external vapour remains nearly constant. The height of the barometer and difference in level of the mercury in the tube and in the bath are also noted. The oharcoal having been heated to redness out of contact with air is plunged while in a state of incandescence tinder the mercury and then introduced into the tuhe. When the absorption is completed the residual volume is read off. The tube C could be moved up and down so as to adjust the mercury in it to about the same level during the entire experiment.For the purpose of obtaining high temperatures oil of turpentine and fousel oil were introduced into the flask A ;the former gave a tern-peratrire of from 158" to 161"C. and the latter from 127"to 131OC. A remarkable fact connected with the absorption of vapours by charcoal is that it teminates in a much shorter time than in the case of the permanent gases rarely> if ever exceeding an hour. Methylic alcohol is more largely absorbed than the other vapows examined at temperatures of go6 loo' and 127OC. exceed-ing the absorption of ordinary alcohol; yet at 159'C. the order is reversed methylic alcohol being absorbed to the amount of 60.5 vofumes and ordinary alcohol 83.4,by one volume of cocoa-nut charcoal showing that the absorptions do not decrease in the same ratio.In all cases the absorptions became less as the tempei4ature rose and it is interesting to observe the great change in ammonia and carbonic acid which are absorbed respectively at OOC. 171.7 and 67.7 by one volume of cocoa-nut charcoal and at 127"C. only 21.9 and 16.6. In several cases as ether chloro- form the absorption changes slowly as the temperature rises. Glacial acetic acid was used in determining the absorption of acetic acid vapour. In the following tables v represents the number of volumes of the vapour absorbed by one volume of cocoa-nut charcoal at the temperature and pressure at which the experiment is performed. T and T are the initial and final temperatures P and F the pres- sures deduced by subtracting the difference in level from the height of the barometer.These experiments were performed in the laboratory of the Queen's College Belfast. Y2 288 IIUNTER ON THE ABSORPTION OF WATER . V T i P P 49.8 .... 130.0 133.0 .... 554.7 649.2 42.3 .... 121.0 120.0 .... 548'3 541.8 42.8 .... 122.2 121.0 .... 586.3 580.3 385 .... 123.5 126.0 .... 628.0 624.0 45.8 .... 130.0 131.0 .... 695.8 687.8 41.0 .... 127'0 131-0 .... 663.4 650.4 45.8 .... 129'0 132.0 .... 673.1 672.6 44.5 .... 125.0 128.5 .... 684.3 681.1 Mean .. 43.8 .... 127.3 127-7 .... 629.1 623-5 23.4 .... 159.0 159.5 .... 695.7 6942 23-5 .... 159.3 159.5 .... 698'8 697'3 25.5 .... 158.2 159.2 ....687.7 696.2 22.2 .... 159.0 159.0 .... 692.5 698.0 26.8 .... 158.2 159.3 .... 691.2 692'2 21.0 .... 157.5 158.0 .... 688.3 688.3 Mean .. 23.7 .... 158.5 159.1 .... 692.3 694.3 BISULPHIDE OF CARBON. V T T P P 93.4 .... 158.5 159.0 .... 691.8 693'3 90.0 .... 157-0 156.0 .... 0'61.8 668'8 90.8 ... 1579' 159.0 .... 650.4 644.4 88.7 .... 157.2 160'0 .... 641.4 645.8 93.1 .... 155.0 158'0 .... 645 2 645.7 Mean .. 91.2 .... 167.1 158'4 .... 658.1 658% 117.8 117.1 .... .... loo.@ 100*0 100*0 .... 100*0 .... 669.7 6723' 6'71.7 674.2 116'6 .... 100*0 100 0 .... 671.2 6677 Mean .. 117.2 .... 100*0 100-0 .... 671.0 671.2 METHY LIC ALCOHOL. V T T P P 56.7 .... 159.0 159.4 .... 684.2 683.2 60.2 .... 158-5 159.2 .... 689.7 687.2 61.3 ....158.0 159.5 .... 686.0 683.5 63.9 .... 158-0 159.0 .... 681.3 680.5 Mean .. 60.5 .... 158'4 159.2 .... 685.0 683'8 123.3 .... 127.0 131.5 .... 686'0 656.7 127.2 .... 12 6.3 129'0 .... 679.1 660.1 12 3.4 .... 126'1 126.0 .... 678.7 672'0 Mean .. 126.6 .... 126.5 128.8 .... 681.3 662.9 148.9 .... 100.0 100.0 .... 656.2 640.2 146.8 .... 100~0 100*0 .... 660.8 653.8 158'3 .... 100.0 100.0 .... 672.8 661.8 Mean .. 150'7 .... 100*0 lOO*O .... 663-3 651.6 151.2 .... 91.0 91*o .... 716-7 714.2 154.1 .... 91.0 91.0 .... 713.0 714.5 154.9 .... 90'0 90.0 .... 693.2 697.2 Mean .. 153.4 .... 90.6 90'6 .... 70'1.6 $08'6 VAPOLJRS BY CHARCOAL. 289 FOUSEL OIL. V T T P b 31.5 .... 156.5 158.5 .... 663.7 657-2 26.0 .... 159'0 159.8 ....695.6 699% 28.6 .... 159.0 160.0 .... 697.1 704.1 25.1 .... 159.5 160.5 .... 699.2 7004 Mean .. 27.8 .... 158.5 159.7 .... 688-9 690.4 ALCOHOL. V T T P P 87.8 .... 157.5 159.3 .... 662.4 662.4 80.8 .... 157.7 161.5 .... 665.5 659.5 82-0 .... 167.8 160.7 .... 671.8 668'8 84.0 .... 157.0 158.0 .... 661.2 661.7 Mean .. 83.4 .... 157-5 159.9 .... 665.2 663.1 111.8 .... 126.2 129.7 .... 641.1 622.3 111.0 .... 126.0 125.0 .... 691.6 680.8 109.8 .... 126.0 127.0 .... 665-6 653.8 110.8 .... 126.0 1.26.2 .... 660.2 622.3 Mean .. 110.8 .... 126.1 126.9 .... 664.6 644.3 140.0 .... 100'0 100.0 .... 660.3 656.8 137.2 .... 100'0 100.0 .... 649-2 6 47.2 146.2 .... 100.0 100.0 .... 652.0 6 53-0 Mean .. 141.1 .... 100.0 100.0 .... 653.8 652-3 144.7 ....90.0 90.0 .... 700.7 703-7 142.3 .... 90.0 90.0 .... 702.0 706-0 134.8 .... 88.0 88.0 .... 708.5 710.3 Mean 161.8 .. 145.8 .... .... 90.0 89.5 90'0 89.5 .... .... 717-8 707.2 720.8 710.2 BENZOL. V T T P P 63.0 .... 126.8 129.8 .... 661.3 656.3 61.8 .... 129.7 130.8 .... 658.4 619.4 53.7 .... 127'0 130.8 .... 662.6 647% 50.4 .... 126.5 129.8 .... 660.3 659.2 Mean . 58.7 .... 127.7 130.3 .... 660'6 645.6 ETHER. V T T P P 53.8 .... 158.0 160'0 .... 686.2 682.2 54.0 .... 159-0 160.5 .... 686'0 685.0 55.4 .... 157.8 159.0 .... 687'7 683-7 Mean .. 54.3 .... 158.3 159'8 .... 686.6 683.6 70.6 .... 12'7.3 12'7.6 .... 658.0 656.5 67-0 .... 128.5 131.0 .... 667'8 662'3 67.3 .... 126.4 126.2 .... 667'6 663.6 Mean ..68:3 .... 127'4 128.2 .... 6644 660.8 82'8 .... 100.0 100*0 .... 643'4 643.9 80'7 .... 100.0 100~0 .... 654.2 640.2 92.9 .... 100*0 100.0 .... 649.7 644.7 91-6 .... 100'0 100*0 .... 645.3 644.8 Mean .. 87.0 .... 100.0 100'0 .... 648.1 6434 290 CHAPMAN ON CAPEYLIC CHLOROFORM. V 7- i P P 20.5 .... 158.0 159.3 .... 653.8 655.8 22.3 .... 157'5 161.0 .... 649.8 649-8 20.2 .... 157'8 159.0 .... 676.2 685.2 20.2 .... 158.0 159.0 .... 650.3 650-3 Mean .. 20'8 .... 157'8 1595 .... 657.5 660.2 28.0 .... 100°O 100.0 .... 658.3 656.3 32.0 .... 100'0 100.0 .... 641.7 641.a 28.6 .... 100.0 100'0 .... 640'2 644.7 Mean .. 29-6 .... 100'0 100'0 .... 646.7 650.7 ACETIC ACID. v T T P P 82.9 .... 158.0 160.0 .... 692.0 683.0 86.3 ....158.0 159.0 .... 667.1 948.6 80.1 .... 158.7 159-2 .... 688'3 68923 83-1 .... 157.6 159.0 .... 690'2 683-a Mean .. 88.1 .... 158.1 169.3 .... 6844 675.9 dMMONIA. V T i P P 18.6 .... 127.0 129.7 .... 641.3 645.8 21.7 .... 121.0 119-8 .... 671.4 663.9 25-5 .... 129.1 131.0 .... 670.5 658.5 Blean .. 21-9 .... 126.7 126.8 .... 661.0 655.4 CARBONIC ACID. V T T P .P 16.4 .... 125'0 125.0 .... 666.4 670-4 15.7 .... 126.2 128.0 .... 700.7 703.2 Mean 17.7 .. 16.6 .... 127.3 .... 126*2 127.0 .... 126.7 .... 682.1 683-0 687.1 686.9

ISSN:0368-1769    

DOI:10.1039/JS8651800285

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

CHAPMAN ON CAPEYLIC XLV.-On Caprylic and CEnanthylic Alcohols. By ERNEST T. CHAPMAN. BY the distillation of castor-oil with an excess of alkali Rouis obtained a substance which he himself regarded at one time as caprylic at another as cenanthylic alcohol This substance has been the subject of numerous investigations but the results ob-. tained do not coincide Nevertheless all chemists who have AND CENANTHYLIC ALCOHOLS. worked on this subject obtain a compound boiling at about 178O but they differ as to the composition and vapour-density of this compound. In other words a substance having one of the chief characteristics of homogeneity a constant boiling point and obtained from one source by one method is found by different chemists to differ in composition.This unsatisfactory state of affairs it wa8 which in the first instance attracted my attention to the subject and induced me to re-investigate it. And though my investigations have not in any way served to explain this anomaly they have I think placed it beyond doubt that under some circumstances both caprylic and cenanthylic alcohols are present in the distillate and that the sub- stance boiling at 178' is not always amanthylic alcohol. In order to obtain the alcohol the castor-oil was saponified with solution of soda and the soap formed was separated by means of salt and transferred to a metal retort. About a third of its weight of caustic soda was then added and the mixture dried by heating it until the smell of the alcohol was produced; the head of the retort was then fixed on and the distillation proceeded with.The distillate consisted of water and an oily substance; the latter was agitated with a concentrated solution of bisulphite of soda and allowed to stand for 24 hours; the resulting mass was squeezed in a cloth to separate the solid from the liquid portions and the oily part of the latter was removed and dried over caustic potash and then distilled off. The distillate was then fractionally distilled; it began to boil below IOQ" but the greater part came over between 170' and 180° after which the thermo- meter rose steadily and evenly without showing any signs of be-coming stationary up to the boiling point of mercury beyond which temperature I considered it unnecessary to continue the distillation.[N.B.-Those portions which passed over above 250' had no action on potassium even when boiled upon it. Penta-chloride of phosphorus also was without action upon them.] That part of the fluid which distilled between 178-181' was redistilled when by far the greater portion boiled constantly at 179O. Two combustions of the substance were made and gave the following results :-Combustion. Substance. CO2 H,O A 0469 gave 1.267 *5959 13 -502 ) I .357 *63Q1 CHAPMAN ON CAPRY LIC Theory. d Found. B Average. C 73.846 73.67 73-72 73.695 H, 13-846 14-11 24.07 14.090 0 12.309 A determination of the vapour-density of this substance was made. The balloon employed in this as in all other vapour- density determinations throughout this paper was filled with hydrogen.The results were- Temperature of the air .. .. .. 14*5O Barometer .. .. .. .. . . 749 mill. Temp. of bath at moment of sealing .. 209' Increase in weight of globe . . .. 0.8680 Cubic contents of globe . .. .. 283 C.C. Residual gas .-.. .. .. 0 Weight of hydrogen in globe .. .. 0-0238 Weight of vapour in globe .. .. 0.8918 Volume of vapour at 0' and 760 mill. .. 160-2 Therefore sp. gr. 62.0 (H = l) or 4305 (air = 1). Suspecting that there might be some hydrocarbon present with a similar boiling point to that of the alcohol I treated the sub-stance with iodine and phosphorus with the view of obtaining a compound of the alcohol-radical which should have a boiling point considerably &her than the alcohol.On fractionally dis- tilling the product the greater portion of the distillate was found to be a liquid heavier than water boiling at 212"with slight de- composition. This was collected separately and digested at a moderate warmth with caustic potash whereby the alcohol was reproduced but with a slightly higher boiling point viz. 182O. A little of this alcohol was converted into chloride of capryl by treatment with pentachloride of phosphorus the chloride thus formed boiled at 175" the temperature which has ordinarily been stated to be its boiling point. It like the iodide was then con-verted into an alcohol with the same boiling point as that obtained from the iodide. I therefore assumed this substance to be pure at least to be free from hydrocarbons.A combustion of it gave the followiiig results :- 293 Substance. co1 H.70 -5955 .. .. 1.3383 .... ,6283 Theory. Found. C .. 73-84 73.66 H, . . 13.84 14.08 O.... 12.32 This determination it will be seen differs but little from the preceding determinations nothwithstanding the difference of boil-ing point. A determination of the vapour-density of this substance gave the following results :-Temperature of air .. .. .. 14O Barometer . . .. .. .. .. 751 mill. Temperature of bath at sealing .. .. 204' Increase of weight in globe .. .. 0.9846 Cubic contents of globe .. .. .. 315 C.C. Residual gas .. .. .. 0 Weight of hydrogen in globe .. .. W0266 Weight of vapour in globe .... 1,0112 Volume of vapour at 0" and 760 mm. .. 172 Therefore sp. gr. 65.4 (H. = 1) or 4.54 (air = 1). The substance employed in the above experiments was quite free from iodine ;its boiling point was perfectly constant ; its smell differed from that of the crude product and its taste was far less burning. Bromide of capryl was prepared both from the crude alcohol and from the substance purified as above. The two liquids were pcrfectly similar ; but the crude product gave a much smaller pro- portion of the bromide than the purified alcohol that is to say in fractionally distilling the products much more liquid boiling below 190' was obtained from the crude alcohol than from the purified substance. If distilled from an oil-bath the temperature of which was not allowed to exceed 191' it boiled without de-composition.A portion of it was digested with alcoholic ammonia in a sealed tube at R temperature of 100' for twenty-four hours; the tube was opened and the contents distilled with solution of potash ;the clistillate mas mixed with a fresh portion of bromide and again digested at the same temperature. (A much higher Jcohol in which chloride of capryl and as I supposed chloride 294 CHAPMAN ON CAPRYLfC temperature cannot be employed as decomposition is very apt to take place.) The product was evaporated to dryness on the water- bath dissolved in water potash added arid the strong smelling oily liquid which separated was again digested with a fresh portion of bromide.The product was again evaporated on the water- bath then introduced into a retort with a concentrated solution of pot-ash and distilled by passing a current of steam through it. The water having been separated from the base a portion of the latter was dissolved in alcohol acidulated with hydrochloric acid and precipitated with bichloride of platinum. The precipitate formed immediately and seemed to be amorphous. It was filtered off and its percentage of platinum determined. The following figures mere obtained .-Quantity of Substance. Platinum found. Percent age. -4457 .0814 18.2 7 -4985 -0910 18.26 *5167 -0941 18.22 Average percentage 18-25. Theoretical 18*17. An analysis of the base itself was made. Substance. CO2 H20. N. -5445gave 1.6259 and .'7135 and 00216 Theory.Found. C, . . 81.59 81.49 H51.. 14.44 l4*56 N .. 3.97 3-89 100*00 99-89 These numbers can I think leave little doubt that the substance in question is Tri-caprylamine and that therefore the distillate obtained from castor-oil and excess of alkali contains caprylic alcohol. I think I am in a position to show that it also contains cenan th ylic alcohol. That portion of the original alcohol which boiled between 170°-178" was submitted to careful fractional distillation but without obtaining a definite boiling-point. This I supposed was due to the substance in question being a mixture of caprylic and aenan-thylic alcohols and perhaps also of hydrocarbon. To remove the latter the substance was treated with pentachloride of phosphorus and distilled The distillate was agitated with weak AND (ENANTHYLIC ALCOHOLS.of cmanthyl are nearly insoluble and the oily matters which were not dissolved were separated dried on chloride of calcium distilled off and fractionally distilled. They began to boil at 166O about half coming over between 266" and l*iOo. The ther- mometer then rose to 175O at which temperature the remainder distilled. I did not examine the latter portion further but have no doubt that it was chloride of capryl. The part which came over at the lower boiling point was subjected to repeated fractional distillation. The greater portion of it passed over between 168' and 170'. It was then digested with potash and distilled off when it was found to boil at about 1'73'.One combustion of this substance was made. It yielded numbers which would not quite coincide with those of oenanthylic alcohol but were sufficiently near to make it probable that the substance was simply contami- nated with a little caprylic alcohol. Substance. GO; H,O. 4845 gave 1.2948 and -6236 Theory. Found. C .. 72.42 72-88 H16.. 13-79 14-30 0 .. 13.79 lOO*OO This substance was converted into bromide. This bromide is much more easily decomposed than the corresponding capryl compound. It cannot be distilled without liberation of bromine. By treatment similar to that which furnished tri-caprylamine it was made to yield a base possessed of very similar properties and which also gave a precipitate with bichloride of platinum.Two determinations of the percentage of platinum in the platinum-salt gave ;-A. substance taken *4625gave ,0948 of platinum B. , j *5975 ** 20*49p*c* B. equals 20.70ps.I-The amount of substance was not sufficient to make an analysis; 01237 ? average 20.595 per cent. but these determinations taken in conjunction with the analysis of the alcohol seem to me to show that the substance in hand is a mixture of caprylic and oenanthylic alcohols. The percentage of platinum in the tricaprylamine salt would be 18.17 ; in the tri-enanthylamine salt 23.5 CHAPMAN ON CAPRYL'IC During my investigations of capryl compounds I obtained caprylic ether. It was produced by the action of bromide of capr~lon potasso-caprylic-alcohol.The latter substance was ob-tained by acting on caprylic alcohol with potassium. When on adding more of the metal no further action was observed the resulting suhstance was washed by deeantatiori with ether pressed between blotting-gaper and dried in vacuo. Equivalent quanti- ties of this substance and of the bromide were digested together in a sealed tube at 100' for about an hour. The tube was then opened and the fluid contents distilled off. The distillate was found to boil at 53'; only a few drops had a higher boiling poiut and they contained bromine. One combustion of the substance was made. Subst'ance. co2 HjO. -5255 1.5197 *6740 Theory. Found. c 79.34 38-87 H 14.05 14.25 0 6.61 100.00 Metallic zinc decomposes both the iodide aid bromide of capql when they are digested with it.Iodide and bromide of zinc and a hydro-carbon are the products. In order to compare the alcohol obtained from castor-oil with that formed synthetically from petroleums 1 acted on that portion of the Canadian petroleum which distils from 115" to 120° in a manner analogous to that described by Pelouze and Cahours," and like them obtained a compound having the composition of chloride of capryl; from this I formed both the acetate and the alcohol. Of this 1atter substance the following vapour-densities and analyses were made. The substance seemed to me to be in all respects analogous to the caprylic alcohol obtained from castor-oil; it boils at lt33O. * Ann. Ch.l'hys. [ 4 1 I 53. 0' and760atvapourof'Volume 297 Determination A. Temperature of air ............................ 16" Barometer .................................. 745 mm. Temperature of bath at moment of sealing.. ...... 2lSp Coitents of globe ............................ 364 C.C. Weight of hydrogen coutained by globe .......... 0.0303 Residual gas .................................. 0 Increase in weight of globe .................... 1.1336 Weight of vapour which globe contained.. ........ 1.1639 ................ zoo C.C. Therefore sp. gr. 64% (1-7=1) or 4.5 (air = I). Determination B. Temperature of air . . .. .. I. z7a Barometer . . .. .. .. .. 743 mm. Temperature of bath .. .. .. 221" Contents of globe .... .. .. 362 C.C. Weight of hydrogen in globe .. t. 0.0299 Residual gas .. .. .. .. 0. Increase of weight in globe .. .. 1,0978 Weight of vapour in globe .. .. 1.1277 Volume of vapour at 760 and 0' .. .. 195 C.C. Therefore sp. gr. 64.3 (H = 1) or 4465 (air = I). Two combustions of the substance were also made :-Substance. cos HiO. A .. -5642 gave 1.5255 and 7104 R .. -4846 , 1-3113 , 6110 Theory. Found. Average. A B C .. 73.84 73.73 73-79 73.760 HIS.. 13-84 13.99 13-36 13.955 0 . 12-32 100~00 I conclude from the above that the decomposition of the castor- oil soap or ricinolate of potash is not so simple as it is ordinarily reprcseiited to be; that in addition to the alcohols mentioned in GRTESS ON A NEW CLAW OF the above paper many other substances are present ; and finally that I have riot met with any fact which militates against the assumption that the compound C,Hl80 from castor oil is identical with that obtained from petroleum.Since writing the above I have made another distillation of castor oil and alkali (the seventh which I have made) arid for the first time find that almost all the products combine with bisulphite of soda. I merely mention this as showing that the composition of the clistillate is not by any means constant.

ISSN:0368-1769    

DOI:10.1039/JS8651800290

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

GRTESS ON A NEW CLAW OF 298 XLVII.-On a New Class of Organic Compounds in which Hydrogen is replaced by Nitrogen. By PETER GRIESS.. THEinteresting substances described in the first part of this paper (p. 268) obtained by the action of nitrous acid upon some of the amido-acids of the phenyl group induced me also to study the action of nitrous acid upon similarly constituted bodies from other groups. 1 have thus obtained a number of remarkable products of which for the present I will describe only those which may be referred to amido-acids belonging to the family of aromatic acids. Here also the reaction takes place in a similar manner to that previously described yet a coiisiderable difference is observed in the fact that the atoms of nitrous acid and amido-acid which act upon each other are not equal in number but that one atom af nitrous acid acts upon two atoms of the amido-acid.Diazodinitrophenol is formed according to the equation- C6H,N,05 + NHO = C,H,N,O + 2H20. Picramic acid. Diazodinitrophenol. On the other hand the action of nitrous acid upon amido- benzoic acid for illstance is expressed by the equation-2C,H7N0 + NHO = C,,H,,N,O +-2H20. Amidobeneoic New compound. acid. ORGANIC COMPOUNIX3 ETC. 299 The compounds which arise according to the last equation possess all the characteristic properties of the bodies described in the first paper. They exhibit moreover many peculiarities which are partly founded on their complicated composition and are par- ticularly manifested by a larger number of products of decomposi- tion.I refrain from treating minutely of these relations at present and content myself with giving first a special description of the preparation and properties of one of these substances. DIAZO-AMIDOBENZOIC Ac~D. This substance is prepared hy passing a current of nitrous acid into a cold saturated alcoholic solution of pure amidobenzoic acid C,II,(H,N)O,. After the gas has been passing for a few moments the wine -red colour disappears and immediately or after a short time the new body separates in the form of an orange-yellow crystalline powder. The heat generated must be moderated by cooling with water. When the quantity of the precipitate no longer increases the operation is discontinued and the new sub-stance collected on a filter in order to separate it from the mother-liquor.Frequent washing with warm alcohol renders it perfectly pure. An aqueous solution of amidobenzoic acid when submitted to the action of nitrous acid also yields the new body. This mode of preparation however is scarcely to be recommended as the resulting product is never so pure or so beautiful as that obtained by the first method. The following process on the other hand is very advantageoils especially when working with small quantities. It is based on the observation that the ethers of nitrous acid exert the same action upon amidobenzoic acid as the free nitrous acid itself. On mixing an alcoholic solution of nitrous ether (which for this purpose may be prepared simply by saturating cold alcohol with nitrous acid) with an alcoholic solution of amidobenzoic acid scarcely any alteration takes place in the cold; but on gently heating tlle mix- ture up to about 30" its colour at once changes from red to yellow whilgt the new body is precipitated in abundance generally in the form of microscopic needles which are rendered perfectly pure by washing with alcohol.Pure nitrite of ethyl as well as nitrite of amyl produce exactly the same results. Analysis of the acid led to the formula The fidlowing equation explains the formation of this substance for which I have proposed the name of Diazo-amidobenzoic Acid. 2C7H7N0 + NHO = C,,H,,N,O + 2H,O. drnidobenzoic New acid. acid. In fact the operation may be conducted in such a manner that the quantity obtained corresponds almost exactly with that required by theory.As a rule however other products arise in variable proportions the formation of which is chiefly due to an excess of nitrous acid. In a subsequent part of this paper I shall again refer to this circumstance. Diazo-amidobenzoic acid is obtained in small crystals of a beautiful orange-yellow colour. They appear as small prisms when seen under the microscope. It is inodorous and tasteless almost insoluble in water alcohol ether ksulphide of carbon and chloroform and consequently cannot well be recrystallised from these solvents. Mineral acids dissolve it readily especially on the application of heat but it cannot be separated from them again without decomposition.When dissolved in a solution of potash or ammonia and then neutralised with an acid the new substance is precipitated all unaltered in the form of a yellow gelatinous mass. It can be dried at 100" without decomposition. At 180" it deflagrates in consequence of a rapid evolution of gas. Although diazo-amidobenzoic acid is a somewhat weal acid it nevertheless completely saturates the strongest alkalis and expels carbouic acid from their carbonates. SALTSOP DIAZO-AMIDOBENZOIC ACID.-Although diazo-ami-dobenzoic acid always combines with two atoms of metal yet it cannot be viewed as a bibasic acid if by that term is understood an acid containing a diatomic radical and capable of forming two series of salts-acid and neutral-as it fulfils neither of these conditions.It assumes more the character of a compound acid. Diazo-amidobenzoate of Potnssium C14H9K2N304. In order to ORGANTC CO%IPOUNDS ETC. obtain this salt a quantity of the acid is introduced into a large excess of a concentrated aqueous solution of carbonate of potas-sium which has been heated up to 80°. On cooling a quantity of extraordivarily small needle-shaped crystals separate they are of a yellowish-white colour and when floating in the mother-liquor give rise to a most vivid fluorescence. Diazo-ainidobenzoate of Ammonium Cl,HB(NH4)%N30,, crystal-lises in microscopic needles which when in aqueous solution are readily decomposed by heat. Diazo-amidobenzoate of Sodium C,,HgNa,N30, resembles the potassium-salt in all respects.Diazo-arnidobenzoate of Barium C14HgBa2N~04, is obtained in the form of a yellowish-white crystalline precipitate on treating the potassium-salt with a sdution' of chloride of barium. In order to purify it for analysis it is well washed with water and dried over sulphuric acid This salt is nearly insoluble in water quite insoluble in alcohol and in ether. When 5eated on platinum-foil it deflagrates. Diazo-amidobenxoate of Magnesium crystallises in yellow needles easily soluble in water. Diazo-amidohenzoateof Xiher C,,HgAg2N,04,falls as a greenish-yellow mass on treating a neutral solution of the acid in ammonia with nitrate of silver. It is purified from the mother-liquor by repeated washing with water.When dried it appears its a yellow powder equally insoluble in water alcohol and ether. It remains unaltered at 100". At a higher temperature it deflagrates with violence thus rendering it impossible to determine the silver by heating. The analysis is however easily performed by dissolving the salt in dilute nitric acid and precipitating the silver with hydrochloric acid. The calcium-salt is a yellowish-white precipitate resembling the barium salt. A solution of the potassium salt gives a yellowish-green pre- cipitate with chloride of mercury and a yellow precipitate with chloride of iron. Diazo-amidobenzoate of copper when dry appears as a green amorphous powder. The zinc salt is yellow amorphous insoluble in water.Diazo-arnidobenzoate of EthyZ C,,Hg (C,H,),N,O,. This com-pound is prepared by passing a stream of nitrous acid through an alcoholic solution of amidobenaoic ether C7H4(H,N) (C,H,)O,. T'OL. XBI I I. x GRTESSI ON A NEW CLASS OF Yellorv crystals soon appear in the solutiori. They rapidly iu- crease and soon cause the whole liquid to solidify. The crystals are collected on a filter and separated from the mother-liquor by washing with cold alcohol. One recry stallisation from boiling alcohol yields this body in magnificent hair-like needles of an almost golden-yellow colour. They are insoluble in water but dissolve readily in alcohol and in ether. They fuse at 144" (uncorr.) but do not resolidify on cooling uritil the lapse of several days.At a higher temperature they are decomposed with evolution of nitrogen. The deportment of the ether towards dilute acids appears to be that of a weak base dissolving in them although with difficulty and being reprecipitated on addition of ammonia. It would however he difficult to obtain definite compounds as it is scarcely possible to prevent the acids from causing a further decomposition. The formation of the ether takes place according to the following equation :-2C,H4(H2N)(C2H5)0 + NHO = C,,H,(C,H,),N,~ + 2H,O. Amidobenzoic ether. New ether. Diazo-amidobenzoate of MethyZ C H (CH,)N,O, is prepared by acting upon an ethereal solution of amidobenzoate of methyl with nitrous acid. The new ether separates in small crystalline globules or in short lance-shaped yellow crystals.It melts at 160" (uncorr.) and on resolidifying exhibits the same peculiarity as the preceding compotind which it also resembles in all other respects. PRODUCTSDECOMPOSITION ACID. OF OF DIAZO-AMIDOBENZOIC Action of the Hatoid Acids upon Diazo-armmidobenzoic Acid.-On treating this acid with strong hydrochloric acid no reaction is observed at the ordinary temperature but on gentle heating an evolution of nitrogen takes place the original acid disappears whilst a crystalline body is produced. It is separated by filtration from the mother-liquor from which a second white crystalline substance is obtained on evaporation. The first body is purified by dissolving in a large quantity of boiling water and decolorising with animal charcoal.On cooling a copious crystallisation of delicate white needles is obtained iv hich arc rendered perfectly pure by a second crystallisation. They are easily soluble in O1:CfANIC CO3fPOUND8 ETC. alcohol and in ether with difficulty in cold more readily in hot water; they are so volatile that they cannot be dried in the water- bath without loss. This substance is a well-defined acid. An analysis gave numbers leading to the formula of chlorobenzoic acid C,H,C10,. Limpricht and Uslar were the first to point out that chlo- robenzoic acid produced by the decomposition of chlorinated chloride of benzoyl with water is not identical with the substance of the same composition obtained by distilling salicylic acid with pentachloride of phosphorus and treating the resulting distillate with water.The latter acid discovered by Chiozza was in a more recent research by Kolbe and Lautem ann,* distinguished as a peculiar acid and called by them chlorosalicylic acid. Both the crystalline form and the melting point (152" uncorr.) of the compound prepared according to my method decided me in declaring it to be identical with the chlorobenzoic acid of Limpricht and Uslar. I have mentioned another product of decomposition which is found dissolved in the hydrochloric mother-liquor from which the chlorobenzoic acid had been separated. This second body is obtained in a state of perfect purity by evaporating the hydro-cliloric acid dissolving the residue in alcohol precipitating with ether and several times recrystallising the precipitate.The sub- stance thus obtained corresponds perfectly in its crystalline form its sweetish-sour taste and its beautifully crystallised platinurn- salt with hydrochlorate of amidobenzoic acid. Its identity was further established by a chlorine determination. The following equation may serve to elucidate this transforma- tion :-CI4Hl1NBO4 + 2HC1= C,H,ClO + C7H5(H,N)O2.HCl+ N,. The quantities of the products of deccmposition obtained cor- respond with this assumption as shown by the following deter- mination of the quantity of the nitrogen evolved. The substance was introduced into a long-necked flask from which the air had been expelled bv a stream of carbonic acid and treated with a sufficient quantity of hydrochloric acid.The gases evolved during ebullition were coilducted into a graduated glass tube filled with * Ann. Ch. Pharm. cxv. 183. 22 GRIESS ON A NEW CLASS OF potassa solution. The gases remaining in the flask were driven into the graduated tube by a fresh current of carbonic acid. After absorption of the carbonic acid the residue was found to be pure nitrogen. 1:06 grm. of substance cried at 100' and decomposed with hydrochloric acid gave 75 C.C. nitrogen at Oo and 760 mm. bar. = 8.9 px. The equation given above requires 9.9 p.cs These facts lend a powerful slipport to the view that diazo-amido- benzoic? acid is a compolind acid of diazobenzoic acid and amido-benzoic acid yiz. :-By taking this formula the decomposition by hydrochloric acid is at once explained.In the first stage of the reaction the original compound is split up iuto its two constituents amidobenzoic acid and diazobenzoic acid and in the second the diazobenzoic acid which possesses but little stability exchanges its two atoms of nitrogen for hydrochloric acid thus forming chlorobenxoic acid. This view of the rational formula of diazo-amidobenzoic acid is still further confirmed by the following experiments :-On heating the dry substance to 180" or 190' in an apparatus similar to that above described a violent reaction suddenly ensues which if much substance has been employed assumes the character of a weak explosion. Torrents of nitrogen are evolved and are col- lected in the graduated tube.The neck of the flask containing the substance becomes filled with a sublimate of white crystals whilst a fused substance remains at the bottom. The gas collected in the graduated tube is pure nitrogen whilst the crystals by their sweetish taste and their deportment with nitrous acid with which they yield the original substance* are at once recognised as ami- dobenzoic acid. The fused substance remaining at the bottom of the flask pos-sesses the character of an acid ; it is insoluble in water but easily soluble in alcohol. I have not analpsed it; the mode of its formation however can leavc scarcely a doubt of its composition * The deportment of an alcoholic solution of amidobenzoic acid with nitrous acid offers a simple method for thc detection of the latter.Even traces of nitrous acid contained in an alcoholic or ethereal liquid may easily be reeogniscd by the formci- tion of diazo amidolJenzoic acid being C7H,0,. The reaction would coiisequently take place thus :-C,,H,,N,O = C7€17N0,+ C,H,O + N,. Diazo-amidoben-Amido-benzoic New acid. zoic acid. acid. The qnantity of nitrogen actually obtained corresponded with that required in the preceding equation. 0.447 grm. substance gave 33.9 C.C. nitrogen at 0" and 760 m.m. bar. = 9-53 p.c. ; theory 9.8 p.c. This experiment shows that the same quantity (viz. 3 of the total amount) of nitrogen which is expelled from diazo-amidobenzoic acid by hydrochloric acid is also set free by the action of heat alone.A totally different result is obtained on attempting to deter-mine the amount of nitrogen by ignition with soda-lime. Here actually only the one equivalent of nitrogen contained in the double acid in the form of amide is converted into ammonia the other two atoms of nitrogen escaping as such. 0.4785 grm. gave 0.3895 grm. platinum-salt corresponding to 4.6 p.c. of' nitrogen. Tlie quantity of nitrogen in the form of amide contained in diazo-amidobenzoic acid is 4.9 p.c. Diazo-amidobenzoic acid must therefore be added to those sub-stances which cannot be analysed with correct results by the method of Will and Vnrrentrapp. Action of Hydriodic acid upon Diazo-arnidobenzoic acid-On heating diazo-amidobenzoic acid with aqueous hydriodic acid the same phenomena are observed as those produced by the action of hydrochloric acid.Two new bodies are formed one of which separates as a reddish-coloured crystalline mass whilst the other is retained in solution by the acid mother-liquor. If t,he first be dissolved in very dilute alcohol and digested with a little animal charcoal the filtered solution c;n cooling deposits a copious crop of white or slightly-reddish crystals which are rendercd fit for analy- sis by a second crystalhatiol;. The new substance appears in the form of delicate platres ex-tremely soluble in alcohol and in ether but difficultly soluble in water. Adtlysis proved thein to be iodobenroic acid C;,H,IO,. The mother-liquor of this acid contains hydriodate of amido-lxnzoic acid mhicli whcn purified forms whitc riccdles of sw:.etisll-sour taste easily soluble in water difficultly soluble ilk alcohol iiisoluhle iii ether.BRIESS ON A NEW CLASS OF The formation of the two products just described is accom- plished in exactly the same manner as that of chlorobenzoic and amidobenzoic acid :-C14H,,N,0 + HI = C7H,I0 + C7H7N0,. It appears thus that the formation of chlorobenzoic and of iodo-benzoic acid is based upon a new and most peculiar mode of sub-stitution the pecnliarity of which consists in the replacement of two atoms of nitrogen by one atom of hydrochloric or hydriodic acid. Doubtless similar results will be obtained with other hydro- gen acids and will thus give rise to many new and interesting com pound s. Not only these acids however but also their ethers decompose the double acid with evolution of nitrogen.I have not had sufficient time at iny disposal to submit the pro-ducts thus obtained to a more minute examination. Action of Chlorine Bromine and lodine upon Diazo-arnidobenxoic Acid. Chlorine bromine and iodine individually act upon diazo-arnidobenzoic acid. The degree of energy with which this action takes place as well as the formation of distinct products is deter- mined not only by the nature of the element but also in an eminent degree by the form in which the element is employed whether in the anhydrous strte or in the presence of water or alcohol. The addition of anhydrous bromine to the double acid gives rise to an explosive decomposition; torrents of nitrogen and liydrobromic acid are evolved whilst the residue is changed to a brownish easily fusible resin.This resin is nearly insoluble in water easily soluble in alcohol and in alkaline liquids; acids reprecipitate it from the latter without alteration. It evidently consists of a mixture of brominated acids from which it is scarcely possible to isolate a definite compound by crystallisation. When the resin is submitted to dry distillation in a retort a brominated derivatiye of benzoic acid sublimes whilst the residue is charred with evolution of hydrobromic acid vapours. Finely divided diazo-amidobenzoic acid suspended in water and submitted to the action of bromine yields products differing in a ORGANIC COMPOUNDS ETC.marlied manner from those produced by the action of anhp-drous bromine. For although the resin above-mentioned is formed in considerable quantity yet chiefly crystallisable acids are produced the scpni*ationof cvliicli however is still attended with clifficul ty. If we bear in mind that in the action of bromine upon water we produce hyrlrobromic acid and oxygen and assuming the simplest case that both these in combination with an excess of bromine act only upon the first constituent of diazo-amidobeneoic acid viz. upon the atomic group C,H,N,O, it is obvious that at least the two following series of acids may be formed :-C,H,BrO C N,Br0 C,H,Br,T) C,€I,B,O,. If we further consider tliat the second constituent of diazo-arnidobenzoic acid is likewise acted upon by bromine the number of substances capable of being produced by this reaction is still further increased.I have endeavoured to obtain some of them by recrystallising the mixture from hot water and alcohol. Bromo-benzoic Acid C7H5Br02 crystallises in beautiful long plates of a pearly lustre difficultly soluble in hot water but readily dissolved by alcohol and ether. Trihromobenxoic acid C7H,Br,0, is obtained in small needle- shaped prismatic crystals which in their deportment with solvents differ but little from the preceding compound. They may be volatilized without decomposition. Chlorine in every respect resembles bromine in its action upon diazo-amidobenzoic acid. The double acid is decomposed with evolution of nitrogen and formation of chlorinated derivatives.The action of iodiiie upon diazo-amidobenzoic acid is less energetic than that of bromine ; dry iodine-vapour does not attack the acid at all. It is on the other hand easily decomposed when suspended in hot water and treated with iodine. The iodine- vapours soon change the original cornpound into a brown nearly insoluble crystalline body and into a second substance which is dissolved by the water ; a considerable evolution of nitrogen takes place at the mine time. The first substance is obtained in R state of purity by dissolving it in very dilute alcohol digeating with animal charcoal and once re-crystallising the product from GRTESS ON A NEW CLASS OF alcohol and ether. It is a well defined acid and appears gene- rally in long narrow nearly colourless plates which by the application of a gentle heat may be sublimed without decom- position.On rapidly heating them they are decomposed with evolution of iodine-vapour. A combustion made of the pure acid gave numbers leading to the formula of iodoxybenzoic acid C,H,IO,. The second product which remains dissolved in the water is obtained by evaporating the solution and recry stallising the residue from boiling water. It is hydriodate of amidobeiizoic acid. The following simple equation elucidates the formation of these two substances :-C14HllN304+ I + H20 = C,H,IO + C,H,N02.HT + N,. Action of Nitric Acid upon Diazo-amidobenzoic Acid.-Diazo-amidobenzoic acid is immediately destroyed by fuming nitric acid with evolution of light.In ordinary concentrated uitric acid it dissolves readily with a reddish colour; on heating however a violent reaction ensues the liquid rapidly frothing up whilst quail- tities of red fumes are evolved. On evaporating the excess of nitric acid on the water-bath a powerfully acid viscid residue is obtained which is frequently interspersed with crystals and is readily taken up by all solvents. It con8ists chiefly of a new cvstallisable acid which may be purified in the following manner. The residue is dissolved in water and the solution treated with an excess of baryta-water hy which a resinous matter is thrown down. After separating the precipitate the solution is freed from the excess of baryta by passing a stream of carbonic acid then filtered and the filtrate is evaporated on the water-bath uutil a crystal-line pellicle appears on the surface.On cooling a quantity of tlie harium-salt formed crystallises out in thick yellow needles. By again evaporating the mother-liquor the rcmaiiider of tlie salt is obtained. After the salt has been purified by several re-crystallisations it is dissolved in water and mixed with a quantity of sulphuric acid just sufficient to precipitate the whole of the baryta. The solu-tion when evaporated yields the new acid in rhombic prisms of a yellow colour which when re-crystallised from alcohol or ether are perfectly pure. An analysis of the substance dried at 100’ gave numbers corresponding to the formula C I13NsO~y ORG-4NIC COMPOUNDS ETC.309 I propose for it the name of trinitrooqthenzoic acid. It is a bibasic acid and its constitution may be expressed by the followiiig formula :-C:,I-I (NO,),a,. It crystallises in well defined rhornbic prisms and is extremely soluble in water as well as in alcohol and ether. The acid when dry is nearly white yet its solution possesses an intense yellow colour and like picric acid imparts that coloiir to animal membranes. It has an intensely bitter taste melts when warmed arid deflagrates at a higher temperature. Sulphide of ammonium reduces it with formation of a new body and separation of sulphur. It combines with bases forming well defined salts iiearly all of which are soluble in water whilst some are beautifully crystal- lised.I have only examined a few of them. T?*initrooccyhenzoate of Bari~m.-6,ffBa,(h’0,),03 is easily soluble in water ; a boiling saturated solution however deposits but few crystals on cooling its solubility in hot and in cold water differing but little. By spontaneous evaporation of the aqueous solution this salt is obtained in thick needle- shaped con-centric crystals of an intense yellow colour. They are all but insoluble in alcohol and ether and extremely explosive. They contain water of crystallisation part of which they lose on beirig dried over sulphuric acid. The ammonium-saltis prepared by saturating the acid with aqueous ammonia; it forms yellow prisms easily soluble in water but diffi- cultly soluble in alcohol ; they resemble picrate of ammonium in many respects.The silver-salt C,HAg,(NO,),O, appears in the form of yellow globular crystals easily soluble in water. Action of Nitrous Acid apon Diazo-umidobcnzoic Acid.-The products which are obtained on submitting the double acid to the decomposing influence of nitrous acid differ according to the presence either of alcohol or of water. Action of Nitrous Acid in the presence of Water.-The double acid when suspended in boiling water and submitted to a current of nitrous acid is completely decomposed with evolution of gas; the resulting red liquid on cooling deposits a reddish crystalline substance. Recrystallisat ion from boiling water with addition of a little animal charcoal yields it in hcautiful narrow plates of -.a ~ightyellow colour. ‘l’liis substance is witrocxybenzoic creid (I,T-I,(NO,)O, already dcscyibecl by G erl a lid. 310 GRIESS ON A KEW CLASS OF Action of Nitrous Acid in presence of AZcohoZ.-On suspending diazo-amidobenzoic acid in alcohol saturated with nitrous acid and passing a current of the same gas through the liquid whilst the whole is kept in ebullition exactly the same phenomena are observed. as those previously enumerated. The double acid is rapidly dissolved with formation of a deep brownish-red solution and simultaneous evolution of nitrogen. On evaporating the alcohol as soon as the double acid has completely disappeared a reddish-brown residue is obtained consisting chiefly of a crystallisable volatile acid.To purify this acid it is sublimed in a retort in order to separate it from the accompanyitlg non-volatile resin. By repeating this operation several times or by recrystallisirig the sublimed acid from boiling water it is obtained in white indistinct needles or plates having the coniposition of benzoic acid. If we neglect the formation of the red resin the formation of the benzoic acid may be illustrated by the following equation :-C1$HI1N&?( + 2CZHGO + NHOj = 2C7H,jOL + 2CaH40 + 2HzO -I-4N. Alcohol. Benzoic Aldehyde. acid. Action of Ammonia upon Diazo-amidobenzoic Acid. Diazo-amidobenzoic acid dissolved in dilute aqueous ammonia is easily decomposed on boiling with evolotion of nitrogen gas. If the dark reddish-brown liquid obtained be evapo-rated on the water-bath and treated with dilute hydrochloric acid a reddish-brown amorphous body is precipitated whilst the mother-liquor contains a second product of decomposition.The red body is purified by dissolving in alcohol precipitating with water and desiccating over sulphuric acid. Tt is a red amorphous powder insoluble in water and ether but easily soluble in alcohol. It possesses the character of an acid dissolving with facility in alkalies from Tvhich it is reprecipitated by acids. A neutral soh- tiori of the acid in ammonia gives brown amorphous precipitates with solutions of' metallic salts. I have not determined its corn-position." The niother-liquor containing the second product of decomposi-tion is evaporated and the chloride of ammonium precipitated by * Relying upon a single combustiou I had set lip for this body the formula CI,HI,,05.I have since found that it contains nitrogen; and I intend to submit it to investigation at some future time. ORBASIC COMPOUNDS E’I’C. 311 dichloride of platinum. The precipitate is filtered off and the filtrate saturated with sulphuretted hydrogen ; the sulphide of platinurn is separated; and the solution evaporated on the water bath. The residue consists of amido-benzoic acid combined with hydrochloric acid. Exactly the same decomposition takes place when diazo-amido- benzoic acid is acted upon by a dilute solution of potash. I have performed the experiment just described in many differ- ent ways.Nothing appears more simple than to suppose that diazo- aniidobeiizoic acid under the influence of alkalies splits up thus Cl4Hl1N3O4-I-H20 = C7H603+ C7H7N02+ N2. There would accordingly exist in diazo-amidobenzoic acid that is in its pre-existing atomic group C,H,N,O, an intermediate body by means of which it might have been easy to step from the amido-acids to the corresponding oxyacida. However all the experiments I have made with this object have failed the result being always amidobenzoic acid and the same red amorphous borly . These facts give a sufficiently clear representation of the chemical deportment and the nature of diazo-smidobenzoic acid. I might have considerably increased the number of products of decomposition as there are matiy other bodies which induce an alteration of diazo-amidobenzoic acid ; but in order not to extend the limits of this investigation too far I have preferred to abstain from communicating further experiments made in this direction.DIAZO-AMIDOAN JSIC ACID. Anisic acid although not standing in the same homologous series with benzoic acid yet exhibits a great auslogy with it in its whole chcmical and physical deportment an analogy which is sustained throughout nearly all the derivatives of both these sub-stances. It mas to be expected that amidoanisic acid under the influence of nitrous acid would be converted into a compound possessing those properties which are so characteristic in diazo-amidobenzoic acid. Experiment has entirely confirmed this supposition.Thct new compound is obtained by exactly the same method as that 312 CJRIESS OK A NEW CLASS O@ employed for the preparation of diazo-amidobenzoic acid. A current of nitrous acid gas is passed into a cold saturated solution of pnre amidoanisic acid or the latter is treated with an ether of nitrous acid. In both cases the substance required separates as a yellowisli green amorphous powder; it is collected on a filter and purified by repeatedly washing with alcohol. It deserves here to be particularly noticed that in order to ensure the success of this experiment it in above all things necessary to operate at a ioiv temperature and carefully to avoid an excess of nitrous acid; as otherwise the desired substarice is not even always formed and if formed is re-dissolved with the greatest facility and con-verted into another product.The latter phase is at once recog- nised by the commencement of an evolution of gas as well as by the appearance of a deep brownish-red colour. It is best not to operate upon large quantities and the operation siicceeds well if the solution of amidoanisic acid is introduced into a number of test-tubes and these severally submitted to the action of nitrous acid. The separate portions may then be mixed and purified as before described. The formation of the new substance takes place tlius :-Amido-anisic acid. New acid. One glance at the mode of formation and at the few properties already known of this substance suffices to stamp it as tlie true analogue of diazo-amidohcnzoic acid.I have called it diuzo-anlido-nnsinic acid and consider its ratioiial composition to hexpressed by the formula,-It presents itself in the form of a yello~ or @reenisli-yello;v amorphous powder and but seldom exhibits traces of cry. etalline form. It is insoluble in water as well as in alcohol and ether. Powerful acids dissolve it though not mitliout decomposition. In aqueous solutions of the nllialies or1 the other hand it dissolves without altcration if tlie temperature be kept bclow thc boilitig point. Weali acicls precipitate from tliese solutioiis the original siiljstance as a ycllow gc3l:ttinous mass. It may be drid at looo jyitilout dwger and is decoml)os;rd OillJ-at ;X coilsidc~iil,i~ higher OEGANIC COMPOTJNDS ETC.313 temperatiire. Heated 011 platinum-foil it defligrates slightly tlie residue then melting and burning qaietly with a smoky flame. Salts of Diazo-amidoartisic acid.-Diaza~amidoanisic acid is a double acid which like its analogue in the benzoic group always combines with tno equivalents of metal. Its salts are partly of great beauty; and whilst possessing but little stability when in aqueous solution will when dry bear a temperature exceeding 160'. Its salts with the alkalies are alone soluble in water the rest forming almost without exception yellow or greenish- yellow precipitates. The potassium-salt C,GH13K,N306 is obtained by dissolving the acid in an excess of carbonate of potassium. If the tempera- ture be maintained below 80° nothing but carbonic acid is evolved ; the solution assumes a yellowish-green colour.On cooling the salt is deposited in golden yellow oval plates ; they are collected on a filter and washed with very dilute alcohol until it runs off nearly colourless. In order to recrystallise this salt ft process which is not always successful it is dissolved in the least possible quantity of water at about 80° from which the greater portion separates on cooling. It is scarcely possible to obtain the remainder of the salt by concentratiiig the mother-liquor as on doing so an evolution of gas soon commences; tlie colour of the solution also changes from yellowish-green to a deep brownish red thus in-dicating the decomposition of the substance.The salt when dried over sulphuric acid has the composition C,6H,3K2~,06.2H20. The water of crystallisation is expelled only at about 169O. The crystals especially when floating in the solution exhibit a vivid scintillation resembling crystallised iodide of lead suspended in water. The salt is easily soluble in warm water; difficultly soluble in a concentrated solution of carbonate of sodium or potassium ; insoluble in alcohol and in ether. From a concen- trated aqueous solution it is precipitated by alcohol as a light yellow powder. It deflagrates at 180'. Its solution in water has no action on vegetal colours. Diazo-amidoccnisate of sodium ClBH,,Na2N,O6 is prepared in exactly the same manner as the potassium-salt which it resembles in all respects.It crystallises in well-defined six-sided plates of a golden-yellow colour and is less soluble in water than the potas- sium compound. When dried over sulphuric acid it still retains 18 molecules of water of crystallisation. nin,-o-niiLi~oanisate of uiimonium forms readily s:oluble golclcn- GKIESS ON A NEW CLA$SB OF yellow pIates. The aqueous solution is rapidly decomposed by ebullition. Magnesium-salt. -Greenish-yellow globular masses of crystals difficultly soluble in water. With the alkaline earths and the metals diazo-amidoanisic acid forms insoluble or nearly insoluble salts which separate as yellowisli-green gelatinous masses. Diazo-umidoanisate of Ethyl C,6H,3(C,H,),N306 is obtained by acting upon an alcoholic edution of amidoanisic ether with nitrous acid.If a moderately concentrated solution has been employed the new ether at once separates in small crystals By separating the mother-liquor and recrystallising the substance from alcohol it is obtained perfectly pure for analysis. Diazo-amidoanisate of ethyl is easily soluble in hot alcohol ;the greater part of it crystallises out on cooling in the form of long narrow plates of a yellowish-red colour. Nther likewise dissolves it but it is insoluble in water. It is not volatile without de- composition. When heated on platinum-foil it fuses and gives off volatile products of decomposition and finally burns with a smoky flame. The new ether possessea the character of a weak base; it dissolves very sparingly in dilute acids and is repre-cipitated by ammonia.Concentrated acids and alkalies decompose it in the same manner as the free acid. Diazo-amidoanisate of Methyl C,6H,,(CB3),N306 is obtained from amidomisate of methyl in exactly the same manner as the ether mentioned before. It forms yellowish-red plates which in nearly all their properties resemble the preceding compound. Products of decomposition of Diazo-amidoanisic Acid. In its deportment with reagents diazo-amidoanisic acid exhibits the same mutability as the correspondiug compound in the benzoic group. 'The resulting products of decorriposition are throughout analogous to those of diazo-amidobenzoic acid. I will here give a short description of a few of them. Decompositioiz with Hydriodic Acid.-On heating the new acid with hydriodic acid lodankic acid C,H,IO, and hydriodate of amicloanisic acid are formed with abundant evolution of nitrogen.The first compound separates as a reddish crystalline mass whilst the ORGANIC COMI'OUPI'DS ETC. latter remains dissolved in an excess of hydriodic acid. Iodanisic acid when perfectly pure appears in the form of exceedingly small needles almost insoliible in alcohol ether and in water. Hydriodate of amidoanisic acid obtained by evaporating the hydriodic mother-liquor is extremely soluble in water easily soluble in alcohol. It crystallises in plates or needles and fre- quently in star-shaped groups. The trausformation of diazo-arnidoanisic acid under the influence of hydriodic acid is repre- sented by the following equation :-It is remarkable that the decomposition of diazo-amidoanisic acid by hydrochloric and hydrobromic acid is totally different from that with hydriodic acid.No traces of chloranisic or brom-misic acids are formed ; the resulting products are arnidoanisic acid and a brownish-red acid insoluble in water which I have not yet thoroughly examined. Exactly the same products arise when a solution of diazo-amido-anisic acid is boiled for some time with an alkali. Chlorine bromine and iodine also act upon diazo-amidoanisic acid; the products which arise I have not yet examined ; neither have I followed up the transformations which the acid undergoes under the influence of sulphuric and nitric acids. Action of Nitrous Acid upon Diazo- amidoanisic Acid in the pre-sence of Alcohol.-When suspended in boiling alcohol and treated with a current of nitrous acid gas the new acid is rapidly decom- posed with evolution of nitrogen.Orr distilling off the alcohol a residue is obtaiued consisting of an acid which when re-crystal- lised in order to separate it from a resinous body with which it is mixed appears in the form of small prisms exhibiting all the pro-perties of ordinary anisic acid. Its formation takes place thus :-C16W15N306 + NHO2 r 2C2H60 = 2CgHy0.4 + 2CiHJO + 2HBO + Nj. Anisic acid. Aldehjde. The experiments just described will suffice to show the intimate relation which exists between diazo-amidoanisic acid aEd diazo- amidobenzoic acid. In fact there are but few bodies to be found which exbibit so great an analogy both in their physical arid GRIESS ON A NEW CLASS OF chemical dcportment.This analogy is carried to a still higher degree in tbc following compounds so that it would be but a repetition of the previous pages to enumerate their properties in detail DIAZO-AMIDOTOLUYLIC ACID. The preparation of this compound from amidotoluylic* acid is identical with that of diazo-amidobenzoic acid. Its formation takes place according to the following equation :-Tt crystallises in yellow microscopic prisms which diffcr from the crystals of diazo-amidobenzoic acid only in their superior size. It is insoluble in water as well as in alcohol and ether; acids dissolve it with decomposition; the alkalis on the other had dissolve it without alteration.When heated on platinum foil it deflagrates and then burns with a smoky flame. It is inodorous and tasteless. I have made only a few qualitative observations on the salts of diazo-amidotoluylic acid. Diazo-amidotoluylate of potassium forms a crystalline mass easily soluble in water. The same may be said of the sodium- and the ammonium-salt. The aqueous solution of the latter especially is easily decomposed on ebnllition. Diazo-amidotoluylate of barium prepared by precipitating the ammonium-salt with chloride of barium is a yellow precipitate insoluble in water and in alcohol. Diazo-amidotoluylate of silver is also a precipitate which on account of its gelatinous nature can be separated only with difficulty from the mother .liquor.* The amidotoluylic acid was prepared from Noad’s toluylic acid. I still con- sider‘this acid obtained by the oxidation of cymene by nitric acid as the true homologue of benzoic acid in spite of the reasons brought forward by Strecker and MijlIor (Ann. Ch. Ph. cxiii. 67) against thisview. For although these chemists relying on observations of the melting point and the form of crystallisation of the toluylic acid discovered by them pronounced it to be the true homologue of benzoic acid jet the deportment of their acid with certain oxidising agents with which it yields oil of bitter almonds is equally against this view. The manifold derivatives of Noad’s toluylic acid which I have prepared and which are scarcely to be dis-tinguished from the corresponding derivatives of benzoic acid will assist in restoring this acid to its original place in the systcm.t-1RO.1NTC COT19PO UNDS E:TC. The transformations of diazo-amidotoluyiic acid under the in-hence of reagents have also only been qualitatively investigated ; they resemble in every way the phenomena described when treat- ing of' diazo-amidobenzoic acid. Nitric acid converts it into a yellow crpstallisable acid easily soluble in water and in alcohol and which is in all probability homologous with trinitro oxybenzoic acid. Nitrous acid converts the new acid when suspended in water into derivatives of oxytoluylic acid whilst when suspended in alcohol it yields an acid which is no doubt identical with toluylic acid.Hydrochloric acid gives rise to the formation of chZorotoZuyZic acid and hydrochlorate of amidotoluylic acid with simultaneous evolution of nitrogen. Hydrobromic and hydriodic acids give rise to perfectly analogous decompositions. The iodotoluylic acid thus obtained crystallises in delicate white plates or needles with difficultly soluble in water easily soluble in alcohol and ether. It greatly resembles iodobenzoic acid. Its formula is C,H,IO,. DIAZO-AMIDOCUMINIC ACID. This acid of all those jwt described is the most difficult to obtain. Its preparation _succeeds best in a test -tube surrounded with ice and containing an alcoholic solution of amidocuminic acid into which a current of uitrous acid is passed great care being taken to avoid an excess of gas.It is best to stop the current as soon as the solution begins to become turbid from separation of crystals. On allowing the liquid to stand for a short time the whole of the new substance formed is deposited. It is collected on a filter and purified by washing with cold a1 cohol. Diazo-amidocuminic acid crystallises in yellow microscopic prisms or plates nearly insoluble in cold alcohol quite insoluble in water. It is the most unstable of all the analogous compouiids just described and is decomposed with evolution of nitrogen on merely boiling with alcohol. It exhibits however all the charac- teristic reactions of the double acids previously described. Diazo-amidocuminate of barium is a yellowish-white amorphous powder.Diazo-amidocuminnte qf silver fdls as a yellaw amorphous T'OL. XVIII. 2A 318 QRIESB ON A NEW CLASS OF ORGANIC COMPOUNDS. mass on treating an ammoniacal solution of the acid with nitrate of silver. APPENDIX. When describing the preparation of the different double acids the necesaity has always been pointed out of maintaining a low temperature and avoiding an excess of nitrous acid. The formation of these diazo-amido acids does not take place at all if a large excess of nitrous acid is brought in contact with a hot alcoholic solution of the amido acids. In this case a per-fectly different reaction ensues; the atomic group NH, which is supposed to exist in the amido-acids is simply replaced by one atom of hydrogen.The other products are water aldehyde and nitrogen as shown in the following equation -C,H,(XHZ)O + NHO + CzHGO = C'sH,O;1 + CBHAO + ZHLO + N2. This decomposition succeeds best in the following manner :-Al- cohol previously saturated with nitrous acid is heated to ebulli- tion and the solution of the amido-acid then added whilst a con- tinuous stream of nitrous acid gas is passed through the mixture. The liquid generally assumes a brownish-red colour whilst a vigorous evolution of nitrogen takes place and continues until every trace of amido-acid is decomposed. As soon as this point is reached the excess of alcohol is distilled off and the resi- dualy acid which is generally of a reddish colour is purified by recrystallisation and sublimation Each of the amido-acids which I have examined up to the present moment may in this manner be converted into an acid identical with that from which the amido-acid may be supposed to have originated by nitration and subsequent rednction.This following formula?will illustrate this transformation :-C*H& Anisic acid. C,H,(N02)0 Nitranisic C,H,(NH# Amidoanisic C,H,O,. Anisic acid. acid. acid. ~7H60 C7HdNOJO2 C;H&NH,)02 c;Y60;. Benzoic acid. Nitrobenzoic Amidobenzoic Benzoic acid. acid. acid. C6]E-I4(NOp)aO C~H~(NO.&&I C~,H,~NOX);(NH~)O C6H4(NO,),O" Dinitrophe-nylic acid. Trinitrophenylicacid. Amidodinitrophe-nylic acid. Dinitrophenylic.acid. * See page 270 of thifi journal.

ISSN:0368-1769    

DOI:10.1039/JS8651800298

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

319 XLVI1.-On Nitro-Compounds (Part 11). With Remarks on! Isomerism. By EDMUND J. MILLS D.Sc. F.C.S. THEexperiments recorded in the preceding part* resulted in a classification of nitro-componnds according to their products of reduction and in a contribution to the solution of the problem of the isomerism of the two nitranilines. The present part is chiefly devoted to the consideration of the two nitrobenzoic acids and some general remarks are appended on the subject of isomerism itself. (1) Nitrobenzoic Acid. By the name a@ha-nitrobenzoic acid I designate the solid pro- duct of the action of absolute nitric on ordinary benzoic acid. This is at present the only trustworthy process for obtaining it. The preparation is somewhat tedious thorough nitration being effected only after eighteen hours boiling of the mixture and nitric acid being repeatedly added to replace that which is lost by evaporation.After cooling and addition of water nitroben- zoic acid separates out ; it may be purified by continued washing with the precipitant. The term beta-nitrobenzoic acid may be applied to that variety which was obtained by treating crude toluol with nitric acid by Fischert (who named it “paranitxobenzoic acid ”) and Wilbrand and Beilsteint (who distinguished it as nitrodracylic acid ”) and in all probability much earlier by Abel.5 P-Nitrobenzoic acid has been examined with considerable detail by several chemists who have formed from it illarge number of derivatives similar to but nut identical with those derived from the sister compound.My object was to ascertain if possible the source of this difference. In preparing the second acid Wilbrand and Beilstein’s method was followed precisely with the excep- tion of the final crystallisation from alcohol which was found unnecessary. The fact that dinitrotoluol accompanies this body in large quantity is a very remarkable circumstance. The mem- 8 Journ. Chem. SOC. [21 ii. 153. f Ann. Ch. Pham. cxxvii 137. 2 Ann. Ch. Pharm. cxxviii 257. 5 Ann. Ch.Pharm. lxiii 313. 2a2 3fILLS ON NITRO-COMPOUNDS. bers of the aromatic marsh-gas series in fact cannot be advancer1 to higher stages of nitration than the first without inducing a complicated reaction. P-Nitrobenzoic acid differs in a most marked manner from the a-modification.The latter is said to dissolve in 400 parts of water* at 10' C. ; the former according to two determinations of my own in 2,630 parts at 14'. The powder of the less soluble acid is highly electric. The formation of this substance may be approximately expressed by the following equation- 6C;HS + 17HNO3 = 5CjHG(N0,)2 + /3CjHj(NOJO; + 15H20+ 3N204 which was arrived at by weighing the first two of the specified prorlticts correction being made for the solubility of the latter in the necessary washings. Found. Theory. 7-\ Dini tro toluol 23.8821 grm. 84.84 5 mol. 84.49 9 P-Nitrobenzoic acid 49670 , 15.15 1 mol. 15.51 28.1491 100-00 1oo*oo Combustions and determinations of fusion-point were made both of the two nitrobenzoic acids and the dinitrotolnol the results yielding very closely the well established nrimbers cf recent observers.The action of hydriodic acid on the two nitranilines having borne fruit in some addition to our knowledge of the more inti- mate nature of those bases very naturally suggested its extension to the two iiitrobenzoic acids which are immediately related to them. Experiment showed that boiling hydriodic acid of tnode-rate strength produces the corresponding aim i dohenzoic hydrio- dates with liberation of iodine. These salts may be obtained in tolerable purity by evaporating the liquid containing the products of tlir reaction to dryness heating the residue to 1OO"as long as iodine continnes to escape dissolving in water filtering and crystallising.A small quantity of a brown substance removed in this process is probably clue to the oxidisiiig influence of free iodine. * I find the acid to dissolve in 352.5 parts of water at 13' C. Higher numbers given by other authors probably refer lo a subBtance obtained with the aid of sul-phuric acid and having a higher fusion-point than normal nitrohenzoic acid (128"). MILLS ON NlTltO-COMl’OUh’DS. The a-hydriodate dissolves easily in cold cthcr alcoliul or hot water crystallisiug readily from these solvents. It is a com- paratively stable body. The P-hydriodate dissolves less readily and is soon coloured by exposure to air especially if the temperature be raised. Neither of these bodies produces a.coloured reaction with argentic nitrate. The following iodine determinations were made :-(a)0.5740 grm. substance dried at looo gave 0.5145 grin. argentic iodide. (p) 0.4323 grin. substame dried at looo gave 0.4218 grm. argentic iodide a. Found. P. Theory. C‘iH (HSN)Oz.HI. Iodine 48-44 47.27 417.93 Hence the nitrobenzoic acids belong to the class of “anlido-gens.” In order to institute a comparison between the temperatures of attack of these substances by hydriodic acid the same method was employed to which I have already alluded in Part I of these researches. I may be permitted to add here a brief description of the apparatus which the accompanying figure will help to explain. A beaker A more than two-thirds filled I\ ith oil of vitriol is adjusted on a ring-stand in the ordinary manner ;its edge supports a thick cork through the centre of which a hole is bored to admit the tube u in which the reaction is to be performed.This tube contailis a smaller om (the ‘‘weighing-tube,” in B which the given substance is weighed) not shown in the figure which is kept vertical by small beaks or outward pro-cesses from its edge. An 322 MILLS ON NITRO-COMPOUNDS. inclined position would interfere with the result. The tube a is furnished at its orifice with a cork having two apertures-one central to admit a thermometer and one lateral to permit the escape of air and vapours. The thermometer is always brought to the same position previous to an experiment by reference to the stem of the ring-stand and any other convenient line preferably vertical in the vicinity.The tube R is placed at a suitable dis- tance for observing the gradual obscuration due to the free iodine of the band of light occupying the proximate part of the cylindrical bulb of the thermometer It is merely furnished at b with an upright glass thread to aid the eye in returning to the Same position and on its upper part with a spirit level. It admits of motion both vertically and horizontally. Both it and the ring-stand should he left unmoved throughout a series of observations. The operator's back is towards the light and the experiments must be perfoi*med in the shadow of a partially opaque screen to avoid the direct illumination of the beaker A.The bath of oil of vitriol in A has its surface on a level with that of the liquid in a. It should be heated uniformly and with tolerable rapidity. The "attack-point " is the temperature at which the cylindrical por- tion of the bulb of the thermometer ceases to be visible. The results thus procured show a remarkable difference between the nitrobenzoic acids-a difference greater even than that which obtains in like manner between the two nitranilines. The num-bers are given in a table accompanying the present paper,* and curves are drawn to facilitate an immediate comparison. The necessary details of the apparatus for which alone these results are here taken to hold good are as follow Oil of vitriol in the bath ... . 250 C.C. Internal diameter of a .. .. 13.62 m.m. Diameter of thermometer .. . . 3.80 , Thickness of weighing tube .. .. 0.37 , Hence width of obscured annulus .. 4-54 , Volume of hydriodic acid employed .. 5-00 C.C. Weight of substance taken . . . . 0.20grm. Rate of heating .. .. .. 1' in 11 seconds. (2) Action of Nitric on Benzoic Acid. The experiments of Wilbrand and Beilstein already alluded to have shown that 6-nitrobenzoic acid may be successively * See opposite page. MILLS ON NITRO-COMPOUNDS. 323 transformed by known reactions into 6-amidobenzoic p-azo-amidobenzoic and benzoic acid. It was left an open question by those chemists whether the substance last produced was absolutely identical with ordinary benzoic acid or different from it.The resemblance is indeed most remarkable. It has been already pointed out that in fusion-point solubility in water and form of the calcium-salt* there is no practical distinction between these bodies. I may add that their ethylic ethers are precisely alike in odour a point on which frequent stress is laid in distinguishing isomeric substances. In order to decide this point if possible I submitted both ordinary benzoic acid and that derived from &nitro-benzoic to the action of nitric acid in the manner already de- scribed at the commencement of this paper. The liquid finally obtained was not precipitated with water but evaporated to dryness at 100'. When the free nitric acid had completely vola- tilised and the product had been allowed to cool a gummy mass presented itself in which crystals speedily made their appearance.The whole was transferred to a quantity of filter-paper and heated to 100' for a few hours. White crystals mere then found on the upper surface of the paper while a very easily fusible substance had soaked down to its interior. The crystals are readily purified by means of alcohol in which as well as in ether they rapidly dissolve in the cold; in boiling water they dissolve but sparingly; CURVESILLUSTRATING THE ATTACK OF ALPHA-NITROBENZOIC AND BETA-NITROBENZOIU ACID. 1.691 1.674 0-," 1.655 4 ?1 .rl 8 + 1.574 3 1.547 x" "0 1.512 $ 1,491 z$ 1.465 1-452 1 *439 JC Wil brand and Beilstein loc. cit. MILL$ ON NITRO-GO31POUNDS in water at 15' scarcely at all.With caustic potash there is first a violet and then a red coloration ; but not solution unless the liquid has been weak. These remarks with the exception of the reaction just mentioned (which belongs to the derivative from the source S),apply equally to both bodies. The fusion-point of the nitro-compound (from ? P-Senzoic acid) was 201"*9(cor.) ;. its composition that of dinitrobenzoic acid. 0.2655 grm. substance dried at 100° gave 0.3802 grm. carbonic dioxide and 0.0569 grm. water. Found. Theory. Carbon 39-05 39.62 Hydrogen 2.38 1 *89 The readily fusible body occurring with this is extracted from the paper by ether the solution filtered evaporated to dryness and the residue heated to 100" till constant.Thus prepared it probably contains a small quantity of the preceding compound with which it agrees closely in its reactions; it is however more soluble in alcohol or ether. It melts at 88' (cor.) and scarcely solidifies on cooling. 0.37635 grm. substance dried over oil of vitriol gave 0.6044 grrn. carbonic dioxide and 0.1035 grm. water. Theory. Found. C7H4(N02)aOP CTH (NO;)02 Carbon 43.79 39.62 50.30 Hydrogen 3.06 1.89 2-99 This product therefore is intermediate in composition between mono-nitrobenzoic and dinitrobenzoic acid but decidedly approaches the latter. The white crystals obtained from common benzoic acid as mentioned above melt at 137'05 (COI.) ; after re-crystallisation from dilute nitric acid washing and drying the fusion-point is 136'03 (tor.)-a very slight alteration.They dissolve in 422.2 parts of water at 13"; and constitute I believe a definite com-pound. 0.3391 grm. substance dried at IOO" gave 0,6225.grm. car-bonic dioxide and 0.1006 grm. water. Theory. Found CrHj(NO2)02 Carbon 50.07 50.30 HJ-hg:.r% 3-29 2-99 MILLS ON NITRO-COMPOUNDS. Hence these crystals have the composition of mononitrobenzoic acid but are not physically identical with it. I have not yet ex- amined the more fusible body which accompanies them and which appears to have hitherto escaped the notice of' chemists. The following experiments have a very important bearing on those just described :-(3) Simultaiieous Action of Sulpphuric uizd iYitiic Acid on Ordiiiary Henzoic Acid.When benzoic acid is heated to 100"in a closed vessel with sulpburic and nitric acids and the liquid cooled and mixed with water a white crystalline precipitate falls the yellow mother- liquid retaining in solution at least one other product. The nature of the result varies according to the time of digestion and the quantity and strength of the mixed acids. (1) The precipitcLte.-IIt is immaterial whether benzoic or a-nitrobenxoic acid bas been used as the starting point. In either case the product continues for some time to exhibit the composi- tion of mononitrobenxoic acid with an increased fusion-point and (it cannot be doubted) a decreased solubility. This fusion-pint is always higher than I28",provided the first stage of nitration has been reached.One precipitate of this kind coincided remarkably with the white crystals last described in the preceding section. The sub- stance fused at 136O.4 (cor.). 0.3225 grm. substance dried at loo" gave 0.5956 grm. carbonic dioxide and 0.0933 grm. water. Theory. Found. C7H,(N02)02 Carbon 50.37 5w30 Hydrogen 3.21 2.99 If the action be continued beyond six hours especially if abso- lute nitric acid be used the nitration advances a stage further and dinitrobenzoic acid is obtained. This appears to be a deFtnite product and has already been studied by Voit ,* Neither his results nor my own however agree with those of Cahour s ; the time of preparation is not short nor is the fusion-point of the * Ann.Ch. l'harm. xcix 100. MILLS ON NITRO-COJIPOUNDS. acid a low one. On the contrary it melts at 206'07 (cor.) I may add also the following numbers :-0.4196 gym. substance dried at looo gave 0.6190 carbonic dioxide and 04821 grm. water. Found. Theory. Carbon 40.23 39.62 Hydrogen 2.18 1.89 (2) The mother-liquid.-This is filtered from the precipitate and the sulphuric acid it contains exactly removed by means of barytic hydrate nitrate or carbonate. The residual solution is evaporated to dryness ultimately at 100'. The cooled crystalline mass which is invariably coloured yields it perfectly colourless product on extraction with carbonic disulphide. This body may be either mononitrobenzoic acid or a mixture of that compound with small quantities of dinitrobenzoic acid.The nitrobenzoic acid obtained in this way hsed first at 127O.5 (cor.) ; after cooling to solidification it melted at 122O.4 (cop.). Another preparation melted at 122"*3(cor.). It gives a red colouration with caustic potash. 0.3508 grm. substance dried at loo" gave 0.6393 grm. car-bonic dioxide and 0*1080grm. water. Found. Theory. Carbon 49-70 50.30 Hydrogen 3-42 2.99 As an instance of the mixed result I may adduce the following numbers :-0.2812grm. substance dried at loo",gave 0.4921grm. carbonic dioxide and 0.525 grm. water. Found. Carbon 47*73 Hydrogen 3-26 (4) Simultaneous Action of Sulphuric and Nitric Acid on &Nitro-benzoic Acid. When the above named acids are heated together to a tempera- ture of about 115O for several hours cooled and cautiously stirred with a moderate quantity of water a precipitate falls after some MILLS ON NITRO-COMPOUNDS.time. The yellow mother-liquid yields a second product on ap-propriate treatment. If the temperature of digestion be only 1004 only @-nitrobenzoic acid (with unchanged fusion-poia t) separates on the addition of water. (1) The precipitate.-This has tlie composition of dinitrobenzoic acid. It dissolves very readily in cold alcohol or ether and to a considerable extent in hot water. The solution is acid to litmus. With caustic potash it gives a beautiful red colouration. The fusion-point of one preparation was 161O.9 (cor.) ; after keeping several months during which it was once heated on the water- bath for a few hours the fusion-point was found to be 184O.3 (cor.) Another preparation gave the number 166O.5 (tor.)$ 0-2870grm.substance dried at loo" gave 0.4207grm. carbonic dioxide and 0.0618 grm. water. Pound. Theory. Carbori 39.98 39.62 Hydrogen 2.39 1.89 (2) The mother-liquid.-This was treated precisely as that men- tioned in the preceding section. The product however having been found to be impure from calcium-salt was mixed with a little water and primary potassic oxalate dried and extracted with ether. The latter solvent on evaporation left the body in a pure state and almost free from colour. The substance melts at 153'-1 (cor.) to a clear liquid; dissolves with remarkable ease in cold alcohol or ether but only slightly in water and gives with potash or ammonia a beautiful deep red colouration.Rapidly heated alone it explodes. After fusion it solidifies with extreme reluc- tance. 0.2920grm. substance dried over oil of vitriol gave 0.4256 grm. carbonic dioxide and 0.0697 water. Theory. Pound. C7H,(NOJ201 Carbon 39.75 3962 Hydrogen 2.65 1.89 This appears to be the only product remaining in the mother- liquid. Under tlie circumstances in which I examined it it probably contained a small amount of the "precipitate." MILLS 05 NITKO-COMPOUNDS. (5). Geizernl Observations. The remarkable difference between the temperatiires at which a-nitrobenzoic and B-nitrobenzoic acid are attacked by hydriodic acid points clearly to a difference between the nitryl radicals they contain.This it will be remembered was the conclusion arrived at in the case of the two nitranilines and it may doubtless be extended to many other isomeric nitro-compounds. Whether the nitryl of a-nitrobenzoic acid is or is not identical with that of a-nitraniline is still an open question. The experiments described in sections (2) (3) and (4) throw considerable light on the point they were intended to decide. It appears from (2)-though from equal weights of the bodies not having been taken the results are not absolutely precise-that benzoic acid prepared from gum benzoin is uitrated only with difficulty whereas that obtained from P-nitrobenzoic acid is nitrated with remarkable ease. Under the circumstances meu- tioned a mono-nitrocomponnd is obtained from the former a di-nitrocompound from the latter.Now if the resistance to nitra-tion which ordinary benzoic acid manifests could be sharply overcome it is clear that we ought to obtain P-nitrobenzoic acids from it. This condition is satisfied by the employrnent of a mis-ture of sulphuric and absolute nitric acid; a substance is pro- duced having the composition of di-nitrobenzoic acid and melting at 206’-7. But benzoic acid derived from 6-nitrobenzoic acid yields to nitric acid alone di-nitrobenzoic acid melting at 20io-9. This is as close an approximation as can be fairly expected. A further proof of the strong resistance which common benzoic acid presents to nitration is found in the contents of the mother- liquids obtained after digesting with sulpliuric and nitric acid and precipitating with water.That from a-nitrobenzoic acid contains altered a-nitrobenzoic acid ;ihat from ,@-nitrobenzoic acid con-tains di-nitrobenzoic acid. On the whole therefore I consider that there are two species of benzoic acid. Gregory* long since observed the occurrence of two potassic benzoates. I intend to examine these interesting bodies still further persuaded that they are the true sources of all the phenylic isomers. * Ann. Ch I’ha.rm. lxxxvii 125. 31ILLS ON PJ1‘1’RO-COMPOli N 1)s. (6). Kemurks on Tsornc?&m. The great problem of isomerism still pressing for solution has hitherto been treated almost solely in accordance with atomic views.The statical theorists who have adopted these and who snppose all bodies constituted of atoms fixed in space hold that isomeric substances are produced by a variation of the position of some radical or radicals in the same molecule The attempts to express this in formulze and the invention-of a corresponding phraseology are matters almost too familiar to require special notice. OD the other hand the principle of atomic motion-so largely accepted in physics so little in chemistry-does not seem to have ever been considered available for speculations in this direction. There have been however partial indications of the attainment of a theory having no reference to corpuscular notions. Thus Graham* long since enunciated a peculiar doctrine of chemical action and bestowed the names “zincous ” and “chlo-rous” on the two opposite functions of one and the same element at the instant of disturbance.Brodie,? also claimed for sub- stances at the moment of chemical change a two-fold aspect or “polar” antithesis. Kekul61 and others pointed out that in certain bodies containing replaceable hydrogen one-half of this exhibits a different property from that shown by the other half; ‘I and they employed the terms alcoholic ” and “saline ” to ex-press the difference. Now these distinctions in function con-sidered as belonging to certain relative weights of known radicals have no necessary connection with the doctrine of atoms though frequently associated with it in ordinary scientific language. Let us consider a special case of the phenomenon we are dis- cussing.a-Nitrobenzoic acid is produced by the action of nitric upon benzoic acid from gum benzoin ;P-nitrobenzoic acid results from the more complicated reaction between nitric acid and toluol where oxidation as well as nitration takes place. Omitting for the present the oxidation observed in preparing the latter isomer it is obvious that the difference in character whereby we distin-guish two kinds of nitryl is conferred during the formation of the Substances containiug them. The nitryl of the nitric acid is of * Elemmts (1842) p. 204. 9 Phil. Trans. 1850 p. 762. Lehrhuch. vol. i. p. 180. MILLS ON NITRO-COMPOUNDB. one nature; and this nature becomes altered in one or both cases of its transference.If therefore we would account for the alteration we must do so by exploring further the reaction itself in other words it is a question of force. That the functional change in nitryl does not depend wholly by any means on the composition of the residues with which it is associated is clear from what we know of the nitranilines and nitrobenzoic acids. That it does not arise from what is termed the ‘‘satureability ” of these residues is equally obvious. That-nitryl influences and is influenced by the nature of what is com- bined with it is no doubt true to a certain extent; but if the properties of the nitranilines be compared in detail with those of the nitrobeneoic acids it will become evident that the change alluded to has a logical claim to be considered a distinct pheno- menon.The numerous and remarkable oppositions furnished by isomer- ism whether exhibited with respect to solubility polarisation fusion-point basicity or the like appear to present us ouly with the following principle of co-ordination,-that we may induce a permanent change in the properties of radicals by virtue of certain reactions. The formation of isomeric bodies indeed probably depends on precisely the same laws as that of bodies having differences of composition. The substitution of a radical with certain functions for one with certain other functions but the same composition differs only in this last respect from the exchange of a radical for one completely distinct ;and without reference to isomerism it is easy to see that mere composition has a very subordinate bearing on the properties of a substance.When we reflect that of the radicals R r (having the same composition) we may have n R and m r simiiltaneously in a com- pound where n + m is a constant quantity but where n and m may vary the most complicated cases have a basis of classifica-tion. Thus if the somewhat formidable array of the turpentines owe its number to the opposite natures which hydrogen is un-doubtedly capable of assuming,* we should have here n i-rn = 16; and we might of course anticipate more isomers in this group than we are at present acquainted with. Again with regard to * For an instance of this see especially Hofmann on Ilydra obenzol Proc. Roy. SOC.xii 578.SIMPBON ON THE SYNTHESIS OF TEIBASIC ACIDS. 331 the hydric tartrates of which there are three well-established species. If we conceive their isomerism to be also due to the functional difference of hydrogen ‘md that here we at once account for their number and can deduce from the small percentage value of the hydrogen concerned that whatever difference there is must be very small. These however are merely hypotheses on two special cases; but I may remark with respect to the latter that there is no evidence whatever to justify the common statement that ‘‘ inactive ” hydric tartrate is a com- pound of the two fc active ” species if it be meant that the last two have respectively half the molecular weight of the first. The general formula of an isomeric group may be written as follows :--A a &c.being the two opposite forms respectively of the ulti-. mate component radicals ; the italics represenbing their number and being constant in SUM for each of them. The real problem of isomerism appears to be as follows:-Under what conditions of action does chemical force induce a per-manent alteration in one or more functions of radicals? This I conceive to be the problem of every-day chemistry itself which is occupied for the most part with the production of permanently different bodies.

ISSN:0368-1769    

DOI:10.1039/JS8651800319

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

SIMPBON ON THE SYNTHESIS OF TEIBASIC ACIDS. 331 XLVIIL-On the Synthesis of Tribasic Acids. By MAXWELL M.D. F.R.S. SIMPSON INa paper which appeared some time ago in the ‘I Transactions of the Royal Society,”* I showed that the cyanides of the diatomic radicals (at least those which form glycols) when treated with potash yield bibasic acids which contain respectively four equiva- lents of carbon more than the parent radicals. Analogy would * Philosophical Transactions for 1861 p. 61. 332 SIMPSON ON THE SYNTHESIS OF TRIBASIC ACIDS. lead us to infer that tbe cyanides of the triatomic radicals would suffer a corresponding decomposition when treated with the same reagent and yield tribasic acids containing respectively six equi- valents of carbon more than the original radicals Thus as we obtain in this way from the cyanide of ethylene (to take a par- ticular case) a bibasic acid of tho composition C,H60 (auccinic acid) so from the tercyanide of allyl (C6H5Cy,) if the analogy holds good we ought to get a tribasic acid having the composition %H,Ol2 :-C,H,Cy2 +2(;}O2) + 4H0 = 8 4 4 0 + 2NH, c! E’I The following experiments were performed with the view of testing the correctness of the above inference :-The first step towards the solution of this problem is of course the preparatian of the hitherto unknown body tercyanide of allyl.This body I succeeded in obtaining by exposing to the temperature of a water-bath for about 20 hours a mixture of 1 equivalent of terbromide of allyl 3 equivalents of pure cyanide of potassium and a quantity of alcohol equal to three times the weight of the cyanide contained in a large glass balloon with a reversed L iebig’s condenser attached to it.At the expiration of this time Ifound that all the cyanide of potassium had been converted into bromide and that the alcohol which now contained impure ter- cyanide of alIyl in solution no longer gave a precipitate with water. The reaction which takes place is expressed by the follow- ing equation :-C6H,Br + 3KCy = C6H5Cy + 3KBr. As soon as the alcohol became cold it was separated from the bromide of potassium by filtration and distilled. The residue thus obtained was then digested with cold water and filtered by which means it was disembarrassed of a large quantity of tarry matter which remained on the filter.Having in this way prepared the tercyanide of allyl the next step is to submit it to the action of caustic potash. Accordingly the filtrate was treated with a strong solution of that alkali and SIMPSION ON THE YYNTHESlS OF TE!BhSIC ACIDS. 333 exposed to heat so long as ammonia continued to be evolved. The product which now contained an organic acid combined with the potash was evaporated considerably and treated cautiously in a capacious basin with nitric acid in excess. This liberates the organic acid and at the same time partially destroys the im- purities with which it is contaminated. The excess of nitric acid was then removed by evaporation at as low a temperature as pos- sible and the dry residue treated with strong alcohol which dis- solved the organic acid but not the nitre which accompanied it.The acid obtained on filtering and distilling off the alcohol was finally rendered quite pure by subjecting it in a glass globe with a long neck to the action of boiling undiluted nitric acid as long as red fumes continued to be evolvcd The residue left after the evaporation of the nitric acid now crystallised readily from water. The crystals dried at 100' Cent. gave numbers 011 analysis which establish the formula C,,H,O,, as will be seeu from the following table :-Theory. TLp'Zz? I. 11. 11:. C, .. 72 40-91 40.63 41-24 41.34 H8 .. 8 4.54 4.66 4.82 4*47* O, .. 96 54-55 --176 100.00 The reaction which generates this body is explained by the equation given at the commencement of this paper.This acid orms colourless crystals which are very soluble in water and alcohol and sparingly soluble in ether. They have an agreeable acid taste. The free acid gives with acetate of lead an abun-dant precipitate soluble in strong acetic acid. The neutralised acid forms with perchloride of iron a reddish brown precipitate from which the acid can be partially removed by solution of ammonia. Neither chloride of barium nor chloride of calcium affects the neutralised acid. An abundant precipitate however * The specimen of acid used in the last two analyses was prepared in a somewhat differenh manner. The divergence took place at the point in the above process where the mixture of free acid and nitre is digested with alcohol.The acid obtained on evaporating the alcohol instead of being boiled with nitric acid was converted into the silver-salt which mas afterwards decomposed by sulphuretted hydrogen. It wa0 twice clystallised from watw before analysis. VOL XT'III. 213 334 SIMPSON ON TBE SYNTHFSTS OF TRTBASIC ACIDS. rnalics its appearance on the addition of alcohol to the mixed soh- tions. It is a very stable body not heiiig decomposed by boiling concentrated nitric acid These reactions resemble those of SUC-cinic acid. It is however readily distinguished from that acid by its behaviour on exposure to heat. Thus it melts when exposed to the temperature of about 158' Cent. and when subjected to a higher temperature suffers decomposition.The following reaction is perhaps characteristic. The solution of the acid when boiled with freshly precipit,ated oxide of mercury and filtered yields on evaporation beautiful white crystals which have a lustre equal to that of metallic silver. The following is a description of the crystalline form of this acid for which I am indebted to Professor Miller of Cambridge :-* PRISMATIC. -Simple forms 100 102 110,210 211. AngleB between normals to the faces :-102 100 102 .. .. 66" 26' 102 102 ..,. 47 a 100 110 ..,. 46 0 e. 102 110 I 110 .. 88 0 100 210 .... 27 22 100 211 .,.. 37 41 110 211 .... 32 23 210 211 .... 26 59 Cleavage 100 very perfect and easily obtained This body has been named by Kekul6-f carballylic acid.I cannot however accept this riame without a slight modification of it as recent researches have proved that it rightfully belongs to crotonic acid.$ I propose therefore in order to avoid confusion to call it tri-carballylic acid. I regret to say I have not succeeded in obtaining the tercyanide of ally1 in a fit state for analysis. On evaporating a portion of the alcohol in the midst of which the terbromide of allyle and cFanide of potassium had reacted a black mass was obtained which I partially purified by solution in ether. On evaporating JE Professor Miller informs me that these numbers must be looked upon as roiigh approximations only the crystals he operated upon not having been quite perfect. t Lehrbuch der Organischen Chemie.ii 187. A preliminary,notice of this acid has already appeared in the Proceedings of the Royal Society. :Annalen der Chemie und Pharmacie. Band cxxxi 58. SIMPSON ON THE SYNTHESIS OF TRIBASIC ACIDS. 335 the ether a brown liquid was left which was very soluble in water. This when gently heated with sodium gave cyanide of sodium. When treated with potash it yielded an organic acid and ammo- niacal gas. With muriatic acid it gave an organic acid also no doubt the same and muriate of ammonia. These three reactions coupled with the composition of the acid formed in the second furnish almost conclusive evidence of the generation of tercyanide of allyle by the above process. I have prepared and analysed several of the salts and ethers of tri-carballylic acid of which I will now give an account.12 5O6/'/I Di-carballylic Ether. 06.-This body is readily pre- (C,H,), pared by conducting a stream of dry hydrochloric acid gas into a hot solution of the acid in absolute alcohol; 8,s soon as the reaction is complete the alcohol is distilled off and the residue washed with a solution o€ carbonate of soda and then with pure water. On submitting the oil thus obtained to distillation I found that almost the entire liquid passed over between 295" and 305' Cent. My analyses of this liquid establish the formula given above as will be seen from the fdlowing table :-- Theory. Experiment. per cent. / I. A 11. T C, .. 144 55.38 54-59 54-86 H, .. 20 7.69 7.83 7.43" O, . . 96 36.93 260 100.00 This ether is a colonrless liquid slightly soluble in water and having an acrid taste.It boils at about 300"Cent. Heated with solid potash it suffers decomposition alcohol being formed and the acid regenerated. T?*i muriatic -carballylic Amy lic Ether. %$€ffJ-O,.-Dry acid gas was conducted into a mixture of one part by weight of tri-carballylic acid and two parts of pure amylic alcohol maintained at the temperature of boiling water. The acid gradually dissolved during the passage of the gas. As soon There was a dight loss of water in this analysis. 2B2 336 snrPsoN ON THE SYNTHESIS OF TRTBASTC ACIDS. as it had entirely disappeared the stream of gas was interrupted and the liquid was heated in a retort to 220' Cent.It was then partially purified by solution in absolute alcohol and in ether. The numbers I obtained on analysing this liquid confirm the formula 1 have given being as near the required numhers as could be expected from a liquid not purified by distillation. Theory. per cent.' Experiment. C, H3* .. . . 252 38 65-28 9.84 63-51 9-96 O, .. 96 24.88 386 100mOO This ether is a thick oily liquid heavier than water and having a very acrid taste. Its boiling point is beyond the range of the mercurial thermometer. I could not observe any symptoms of ebullition at 310' Cent. It bore this high temperature without suffering any apparent decomposition. On heating it in a retort with solid potash a liquid distilled over which I recognised to be amylic alcohol by its boiling point and other properties.The acid of the ether remained in the retort united with the potash. one part by weight of tricarballylic acid and two parts of pure glycerin was maintained in a sealed tube for several hours at the temperature of ZOO0 Cent. The tube was then opened and a slight excess of a solution of caustic baryta added to its contents. The excess was afterwards precipitated by car-bonic acid and the filtered liquor evaporated to dryness on a water-bath. The residue was then treated with absolute alcoho1 to remove the uncombined glycerin and finally dissolved in water and precipitated by alcohol. By these means a light buff'-coloured precipitate mas obtained which would not crystallise. Its com-position is I have no doubt truly expressed by the formula given above although my analyses do not correspond very weli with it.The following are the numbers I obtained :- SIMPSON ON THE SYNTHESIS OF TRIBASIC ACIDS. ,737 Theory. Experiment. yr-A * per cent. fl I. 11. . 108.0 28.05 28.81 -c18 H12 .. 12.0 3-12 3.82 L -OI6 .. 128.0 33.25 -Ba . . 153.2 35.58 -34.01 The acid in the above salt is bibasic; its composition is repre-sented by the formula :-Its formation is explained by the following equation :-Soda-salts of Tri-carballylic Acid. -The soda-salts of this acid are very soluble in water and difficult to crystallise. I believe that three salts may be formed containing respectively one two and three equivalents of sodium.One equivalent of the acid I found required for complete neutralisation exactly three equivalents of pure recently-ignited carbonate of soda. I could not obtain this salt in a fit state for analysis I formed the salt with two equivalents of sodium by adding one equivalent of the acid to two other equivalents which had been previously neutralised and cvaporating the mixture on a water-bath till crystals were formed. These were pressed between folds of blotting-paper and recrpstallised. Their coraposition is very pro-bably represented by the formula :-Dried at 100° Cent. they gave 18.95per cent. of sodiiim instead of 18.7' per cent. The salt containing one equivalent of sodium would not crys- tal 1ise. Tri-curballylate of Lime Ca, C12H50Q" 0 + 4HO.-This salt is readily formed by adding a slight esccss of hydratc of lime 338 SIMPSON ON THE SYNTHESIS OF TRIBASIC ACIDS.to a solution of tri-carballylic acid and afterwards removing this excess by means of carbonic acid. On evaporating the filtered liquor a white amorphous powder separates which is the salt in question. It is very soluble in dilute acids and sparingly soluble in water. It has the composition represented by the above formula. Dried at 100" Cent. it yielded 23.83 per cent. of calcium instead of 23.30. Tri-curballylateof Copper. 12 c:136'")06.-When sulphslte of copper is added to a hot solution of tri-carballylate of soda a beautiful bluish-green powder precipitates which is the salt in question. It is insoluble in water but soluble in dilute acids.Its composition accords with the formula I have given. I obtained from the salt dried at 100' Cent. 34:04 per cent. of metallic copper instead of 35.45. fii-carbdyhteof Lead. O,.-This salt is obtained l2 Pb3O 7 by precipitating tri-carballylate of soda with an excess of acetate of lead. It is a perfectly white powder insoluble in water but soluble in dilute acids. The formula I have given correctly repre- sents the composition. Dried at 100' Cent. it yielded 63.87.per cent. of metallic lead instead of 64.23. Tri-curballylate of Siher. 12 5 6"'I> 06.-When nitrate of A& silver is added to a solution of tri-carballylic acid previously neutralised by ammonia a white precipitate falls which is the salt in question.This was very carefully washed with distilled water dried in the water-oven and analysed. The results I ob-tained establish the above formula as will be scen from the follow-ing table :-Theory. Experiment per cent. I. 11. . . 72 14.49 14-96 -. . 5 1-01 1.20 -O, . . 96 19-31 -L Ag .. 324 65.19 64.05 497 100~00 -This salt is slightly soluble in water and freely soluble in dilute nitric acid and in ammonia. SIMPSON ON THE SYNTHESIS OF TRIBASIC ACIDS. 339 That tri-carballylic acid is tribasic is I think fully established by the manner in R-hich it has been formed and the composition of the salts and ethers I have just described. Forinulated according to the water and carbonic acid types it is thus written :-The manner of its formation inclines me to prefer the latter for-mula although it is more cumbrous.Moreover it brings out more clearly the relationship that exists between bi- and tribasic acids :-Succinic acid. ‘hi-carballylicacid. (bibasic). (tribasic). This acid is I believe at present the sole representative of its class. It will not however long remain so as the process by which it has been obtained will I have no doubt prove to be of general application. Tri-carballylic acid bears the sitme relation to citric acid that succinic bears to malic acid C,2H80 Tri-carballylic acid. C,H608 Succinic acid. C1,H80, Citric acid. C6H,010 hlalic acid. That this relationship exists not only on paper but also in the nature of the bodies themselves we can hardly doubt when we call to mind that the acid in question has recently been generated from aconitic acid,” one of the products of the decomposition of citric acid by heat and that acetone another of these products is closely allied to the radical from which tri-carballylic acid is derived.Impressed with these considerations I have endeavoured to transform this acid into citric acid. The resolution of this problem I have attempted in a great many ways but hitherto withodt success. For instance 1 have endeavocreC to form the bromine compound of tri-carballylic acid in the hope that it would yield * Ann. Cii.tPharm. cxxxii. 61. NEWLAXW ON AN A3lMONIACAL DEPOSIT the desired acid when subjected to the action of hydrated oxide oE silver according to the following equation :-C,,II,Ur O, -!-AgO.HO = C,2T3,0,4 + AgBs.My experiments in this direction were however cut short by my inability to form the brominated acid. I am at present engaged in endeavouriiig to solve the inverse problem namely the direct transformation of citric into tri-carballylic acid.

ISSN:0368-1769    

DOI:10.1039/JS8651800331

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

NEWLAiWS ON AN AMMONIACAL DEPOSIT XLIX.-Om a?$Amnaoniacal Deposit formed in the process of Drying Blood. By JOHNA. R. NEWLANDS, F.C.S. SOMEmonths since when visiting the premises of Mr. Richard Tons blood drier of Bow Common Lane London my attention was arrested by the occurrence of a nearly white crystalline deposit adhering to the roof of a shed in which the process of boiling and drying blood mas carried on This deposit was prin-cipally found in the further end of thc shed where the gases generated in the process found their way into the external atmo- sphere. It was present in no great quantity being partly attached to the wooden rafters but chiefly adhering to the sides of an iron pipe through which steam 'vp as occasionally passed. Some portions of the deposit formed small stalactites due probably to the water produced by a slight escape of steam having dissolved the crystalline matter and the resulting solution having evaporated whilst in the act of slowly trickling down.The portion of the deposit immediately adjoining the iron pipe was as might be expected mixed up with a layer of peroxide of iron and the entire mass just as it came off on the application of a gentle pressure gave on analysis the following results :-Per cent. Moisture .. .* .. .. 0.44 Insoluble silicious matter .. . . 0.32 Peroxide of iron .. .. . . 1-21 Sulphate of calcium .. . . 0.84 Sulphate of ammonium .. . . 96-93! Chloride of ammonium .. . . 0.07 -I-09%2 FORMED IN THE PROCESS OF DRYING BLOOD.341 The small quantities of silica and sulphate of calcium mere no doubt due to the dust from the roof which was covered with pantiles resting upon wooden beams some of which appeared to have been whitewashed. The peroxide of iron as already ob- served came from the pipe to which the deposit was attached. The white portion of the crystalline matter analysed separately was found to consist of nearly pure sulphate of ammonium. One word in conclusion as to the origin of this deposit. The blood is first raised to the boiling point by the introduction of steam; it is then submitted to the action of a press and finally dried over hot iron plates. During these operations there is a small amount of ammonia evolved and also traces of sulphuretterl hydrogen and the presence of these gases in conjunction with the oxygen of the air and the steam given off would appear to be quite sufficient to account for the formation of sulphate of ammo-nium. Whether such formation is preceded by that of sulphuric or sulphnrous acids or of the sulphide or sulphite of ammonium I do not for the present undertake to decide.

ISSN:0368-1769    

DOI:10.1039/JS8651800340

出版商:RSC    

年代:1865

数据来源: RSC

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PROCEEDINGS AT THE MEETINGS OF THE CHEMICAL SOCIETY 1865. January 19th. Dr. Miller F.R.S. Vice-president in the Chair. Alfred Noble Esq. Bristol; J. Carter Bell Manchester were elected Fellows. The following papers were read :-“On the Artificial Formation of Pyridine:” by Mr. W. H. Perkin. “ Laboratory Memoranda :” by Mr. R. Warington jun. Note on Chemical Nomenclature and Notation :’,by Mr. G. C. Foster. February 2nd. Professor Williamson F.R.S. President in the Chair. Charles Eastcourt Esq. Manchester ; Arthur Vacher Esq. 29 Parliament Street; Francis Walker Esq. Sidney College Cambridge ; John Reid Esq. Trinity College Cam- bridge; Thomas Y.Blunt B.A. Shremsbury; Robert H. 31. Bosanquet Esq. Oxford ; Nathaniel Bradley Esq. Prescot Lancashire ; Richard Percival Esq.University Glasgow ; Arthur Smith Esq. Loughborough-road Brixton j Thomas Heath c ot e Win d h a m Esq. were elected Fellows. PROCEEDINGS OF THE CHEMICAL SOCIETY. 343 Dr. Hofmann delivered a discourse On Lecture Illustra- tions.” Februmy 16th. Professor Williams on F.R.S. President in the Chair. The following papers were read :-‘I On a New Reaction for the Production of Anhydrides and Ethers:” by John Broughton B. Sc. ‘‘ On the Oxidation of India-Rubber :” by Mr. J. Spiller. ‘‘Note on the Action of Chloropicrin and Chloroform on Ace- tate of Potash :” by Mr. Henry Bassett. I‘ On a Dense Brine Spring from Nova Scotia :” by Prof. How D.C.L. March 2nd. Professor Williamson F.R.S.President in the Chair. The following papers mere read :-‘I On the Action of Silicate and Carbonate of Soda upon Cotton Fibres:” by F. Crace Calvert Ph.D. F.R.S. “On a Crptallised Hydrate of Phenic Acid :” by F. Crace Calvert Ph.D. F.R.S. I‘ On some Hydrated Cupric Oxychlorides from Cornwall :” by Prof. A. H. Church !MA. March 16th. Professor Willi amson F.R.S. President in the Chair. William Johnson Ph.D. Newcastle-on-Tyne ; George Jones Esq. 106 Leadenhall-street were elected Fellows. The following papers were read :-(I On Vapour-densities :” by Prof. Wanklyn. “On the Action of Chlorine on Arsenious Acid :” by Professor Bloxam. 344 PROCEEDINGS OF TIIE CliEMICAL SOCIETY. Anniversary Meeting March 30th 1865. Dr. Williamson President in the Chair.The following report was read by the President :-Gentlemen In accordance with the established practice in our Society it is my duty to report to you on the occasion of this Anniversary Meeting when we come together for the purpose of electing Officers and Council for the ensuing year the general outline of the progress of the Society during the past year as well as its present position. This is indeed a most agreeable task as the steady improvement in the condition of the Society which haa been going on for several years past has continued to manifest itself during the year just expired. Our members have now increased to 453,besides 38 foreign members and 6 associates and the meeting room in which we assemble is being gradually out-grown by the Society.The Council has taken means to insure a more speedy trans- mission of our Journal to the foreign members of tlie Society and the more frequent publication of the numbers enables us to give earlier publicity than formerly to the gapers which are read at our meetings. There have been thirtg-two papers read at our meetings during the year besides five discussions iricludiiig theoretical and practical subjects of great variety and rnaiiy of them of great interest. We have to deplore the death of four of our members viz. Dr. R. D. Thoinson Dr. Normandy Mr. J. 13. Neilson and Dr. Pugh. Robert Dundas Thornson was the second soil of the Rev. James Thornson D.D. minister of Eccles Bermickshire in the manse of which parish he was born on the 21st September 1810.After spending some time at tlie grammar school of Dronse he went to Edinburgh wliere he subsequently began the study of medicine. He aftcrwards continued his studies at Glasgow where he acquired a fondness for the study of chemistry from the instruction of his uncle Dr. Thomas Thornson. He graduated at Glasgow iii 1831 and after a PROCEEDING8 OF TBE CHEMICAL SOCTETY. 345 voyage to India and China in one of the East India Company’s ships he settled in London as a physician and lectured on chemistry in the Blenheim-street School of Medicine whilst engaged in publishing the (c Records of Science.’’ From London Dr. Thomson returned for some time to Glasgow where he as-sisted his aged uncle in discharging the duties of the Chair of Chemistry.On the death of his uncle Dr. Thomson was ap-pointed lecturer on chemistry at St. Thomas’s Hospital. He also discharged the duties of Medical Officer of Health for the parish of Marylebone an office for which his chemical medical and local knowledge admirably adapted him. There is reason to believe that important improvements in the sanitary state of the parish mere brought about through his zealous and enlightened exertions. For about two years his health showed symptoms of decline and he died on the 13th of August 1864. Dr Thomson was the author of a work entitled “School Chemistry,” and also of the cc Cyvclopzedia of Chemistry,” and his papers on subjects belonging to kindred sciences me said to have been very valuable.Among the chemical questions which he specially investigated may be mentioned the composition of food and of various waters the adulterations in drugs the chemistry of digestion and of cholera. He was also an enthusiastic meteorologist and at the time of his death was President of the Meteorological Society. He was elected a Fellow of t5e Royal Society of Edinburgh in 1858 and of the Royal Society in 1864. He was also a Fellow of the Chemical Society and of several other learned bodies. Dr. Normandy mas by birth a Frenchman. He studied che- mistry under Leopold Gmelin and was the author of several books on general and analytical chemistry. He patented and brought into use an apparatus for distilling water and subse-quently purifying it so as to render it fit for drink.The purifica- tion is effected by filtration through animal charcoal with access of air. The introduction of this apparatus has been productive of great benefit to seafarers. Mr. J. B. Neilson was born at Shettlestown near Glasgow in 1792. His active and powerful mind mas maiiily directed to manufactures and we owe to him the introduction of one of the most important improvements in the smeltiiig of iron by the use 346 PHOCEEDIKGS OF THE CIIEMICBL SOCIETY. of the hot blast. The value of the invention is so well known and SO greatly appreciated that the mere mention of it; is sufficieiit to recall to the mind how great a benefactor Mr. Neilson has been to his own and other countries.Dr. Evan Pugh President of the Agricultural College Penn- sylvania North America died on the 29th of April 1864 at the early age of 36. His father a farmer in Chester County Pennsylvania died when he was very young leaving his mother and four children in limited. circumstances. He was adopted by some relatives and from his childhood showed marlred superiority and intellectual ability ; but his friends mere unable to afford him any better educa- tion than that which was obtainable in the common village school and at the age of fourteen he was apprenticed to a blacksmith. This was quite opposed to his inclinations and a severe trial to him ;nevertheless it is said that he faithfully performed his duties while yet devoting every leisure moment to books and study even often working mathematical problems on the doors and walls of the ymith-shop.At the age of nineteen he gained a reluctant consent to abandon this uncongenial occupation and his next year was spent in a manual-labour seminary in Whitestown New York. Here he took a high place in the classes and made great advances in knowledge supporting himself meantime by his trade and earning enough to make a tour to Niagara and elsewhere. Having inherited a small farm he then returned to his native place and established a boarding-school for bops which was highly successful and rcrnunerative. Two years afterwards he sold his farm and with this money and the proceeds of his school was able to carry out his great design of visitiiig Europe.He spent between three and four years in the Universities of Leipsic Gottingen Heidelberg and Paris a diligent and suc-cessful student of natural and mathematical science. At Gottin- gen he honourably sustained the examinations for the degree of Doctor of Philosophy. From the outset his mind had been attracted towards agricul- tural science and his studies gradually turned more and more in that direction. Relying upon the interest taken in such subjects by Mr. Lawes and Dr. Gilbert in December 1836 whilst at Paris Dr. Pugh addressed a letter to the latter with n proposi-tion to undertake in the Rothnmsted Laboratory a new investi- PROCEEDINGS OF TIIE CTTEMICAL SOCIETY. 347 gation of the question then much discussed of the assimilation of free nitrogen by plants.MY.Lawes gladly assented to the pro-posal and arrangements mere entered into which led to Dr. Pugh’s devoting more than two years to the investigation of this and kindred subjects in conjunction with Mr. Lawes and Dr. Gilbert. The results of the inquiry mere communicated to the Royal Society and were published in the Philosophical Transactions Vol. 151 Part 2 in a paper entitled “On the Sources of the Nitrogen of Vegetation with spccial reference to the quastion whether plants assimilate free or uncombined Nitrogen.” Whilst at the Rothamsted Laboratory the course of the in-vestigation in which he was engaged requiring an accurate and easy method for the determination of small quantities of nitric acid Dr. Pugh perfected a method which has been found very useful by many chemists and an account of which is published in the Quarterly Journal of the Chemical Society of London vol.xii p. 35. In the autumn of 1859 Dr. Pugh returned to America lo assume the Presidency and Professorship of Chemistry of the Agricultural College of Pennsylvania which had been offered to him. He prosecuted his new duties with great energy and ability and for rather more than five years laboured unremittingly in the face of many difficulties to establish the newly-formed and struggling institution on a secure basis-a result he was just beginning to see redised when he was suddenly cut off by brain fever after a few days’ illness and within three months of his marriage. The American journals speak of his death as a great loss not only to the institution over which he presided but to the cause of scientific education in common with agriculture throughout America.Besides those mentioned above Dr. P 11 gh’s published con-tributions to Science were principally the following :-“ Hamatinsalpetersaure identisch mit Pikraminsaure Journal ,furprakt. Chemie lxv 362. “Miscellaneous Chemical Aiialyses lnaugural Dissertation Got tin gen 1856.” List of Papers read at the Meetings of the Chemical Society from March 30 1864 to March 30 1865 :-1. cc On Oxyaniline :” by Dr. Schm i d t. 348 PROCEEDINQS OF THE CREXICAL SOCIETY. 2. “011the Tetrabasic or Ortho-carbonate of Ethyl :” by Henry Bassett . 3. “ Ou the Hexyl Group :” by Prof Wanklyn and Dr.Erlen- meyer. 4 “On an AlkaloYd obtained from the seeds of Ricinus com-munis :” by R. V. Tu son. 5. “On the action of Hydrobromic acid and of Hydriodic acid upon Polyatomic acids and on the behaviour of lodo-siibsti-tution-compounds towards Hydriodic acid :” by Professor Kekule’. 6. “On the constitution of Wood-spirit :” by Mr. William Dancer. 7. “On the Chlorophosphide of Nitrogen and on two new Acids related thereto :” by Dr. J. H. Gladstone and Mr. Holmes. 8. cc On a new method of Gas-analysis 2’ by Drs. Williams on and Russell. 9. rc On the Classification of the Elements according to their Atomic Weights :” by Prof. Williamson. 10. “On the identity of Methyl and Hydride of Ethyl:” by Mr.C. Schorlemmer. 11. On the action of Baryta upon Suberic and Azelaic acids :” by Mr. R. T. Dale. 12. ‘c On the isolation of the Electronegative radicle Valeryl :” by Prof. Wanklyn. 13. I‘ On the existence of Nitrogen in Steel :” by Messrs. Stuart and Baber. 14. On the concentration of Nickel in Lead :” by Mr. Baker. 15. (‘On the blue colour of Forest Marble :’’ by Prof C hu r c11. I‘ 16. On the effect of ignition on Garnets &c. :” By Prof. Church. 17. “On the Brine of Salted Meat :” by Dr. Marcet. 18. ci On the nature of Compound Ethers :” by Prof. Wankl yn. 19. cCNote on the Distribution of Albumen through Muscular Tissues:” by Dr.Marcet. 20. I‘ 011 the action of Sulph-hydrate of Potassium upon Acetic Ether:” by Prof. Wanklyn. 21. “On the Density of certain Minerals:” by Prof. A. H. Church. 22. On the action of Ammonia on Siilpho-chloride of Phospho- rus :” by Dr. J. IS. Gladstone and Mr. J. D. Holmes. PROCEEDTNGS OF THE CNEUMTCAL SOCIETY. 349 23. “On the Artificial Formation of Pyridine :” by Mi-.W. H. Perkin. 24 cc Laboratory Memoranda :’ By Mr. Robert 1Varing t on jun. 26. “On a new re-action for the production of Anhydrides and Ethers :” by John Broughton B. Sc 26. “On the Oxidation of India Rubber :” by Mr. J. Spiller. 27. “Note on the action of Chloropicrin and Cliloroform on Acetate of Potash:” by Mr.Henry Bassett. 28. (‘On a Dense Brine from Saltsprings Nova Scotia:” by Prof. Horn D.C.L. 22. ((On the action of Silicate and Carbonate of Soda upor Cotton Fibre :” by Dr. Crace Calvert. 30. ‘I On the Crystallised Hydrate of Phenic Acid :” by Dr. Crace Calvert. 31. I‘ On some Hydrated Cupric Oxychlorides from Cornwall .” by Prof. A. H. Church. List; of Discourses delivered at the Meetings of the Chemical Society between Narch 30th 1864 and March 30 1865. 1 lC On the Organic Peroxides theoretically considered :” by Sir Benjamin Brodie. 2. ‘‘On the Detection and Discrimination of Organic Bodies by means of their Optical Properties :” by Prof. G. G. Stokes. 3. On the Philosophy of Engliah Agriculture:” by John Thomas Way Esq.4. c‘ On Chemical Nomenclature and Notatiolz :” by Prof. Williamson. 5. ci On Lecture Illustrations ?’by Dr. Hofmann. The Trmsurer presented the Balance-sheet of the Society duly signed by the Auditors. THE TREASUREQ isACCOUNT wrrii THE CHEMICAL SOCIETY. CRS. P z€ 8. CL 1864-5. s b. d. s 9. ct. Po Balance on hand ................................................... 629 14 I1 Journal. By Editor’s Salary to 25th March 1565 ............... 95 0 0 , Yearly Dividend on 2900 3 pcr cent. Consols lcse , Printing Journal ....................................... ‘277 12 0 Income-tax ...................................................... 26 6 6 , Distributing Journal ....................................28 11 ‘6 , Sale of Journals ................................................... 52 2 0 , Reporting Proceedings .............................. 770 , Sundry Receipts froinUarch 25th,1864 to Bkch 25th 413 10 6 1865 as below :-Proceedings , Annual Subscription to Royal Society for theii a 8. d. of ltoyal Proceedings sent to the Pellows of the Admission Fees ........................... 80 0 0 Society. Chemical Society ....................................... 50 0 0 Life Compositions ....................... 150 0 0 --50 0 0 Resident Members’ Subscriptions pre- Library. , Librarian’s Salary to 25th March 1865 ............ 25 0 0 Oious to 1864 .......................... 12 0 0 , Books and Nagazines .................................... 466 110 Non-resident Members’ Subscriptions , Subscription to Cavendish Society ..................previous to 1864 ........................ 7 0 0 , Boolibinding ................................................ 5 I3 10 Resident Members’ Subscriptions for 36 0 4 1864 ...................................... 82 0 0 :ollector an( , Collector’s Commission ................................. 39 14 0 Non-resident Members’ Subscriptions Clcrk. , Clerk ......................................................... 300 for 1864 ................................... 17 0 @ -42 14 0 Resident Members’ Subscriptions for GeneraJ , New Reccigt and Account Books .................. 419 8 1865 ...................................... 362 0 0 Printiug , Circulars and Notices .................................410 0 Non-resident Members’ Subscriptions Stationery , Postage Envelopes ....................................... 10 10 5 for 1865.................................... 81 0 &C. , Stanips ...................................................... 112 7 -0 794 0 0 , Mr. Watts Stationery and Postage ............... 200 23 I2 8 House , Royal Society Share of Tea Expenses ............ 14 19 5 Expenses. , T. €In 1 year‘s Salary to 25th March 1865 ...... 20 0 0 , , Petty Expenses as per Book ............... 3 1 7 , , Gas account .................................... 2 4 3 , , Repairs .......................................... 2 9 9 , Refreshments Dr. Hofmann’s Lecture ............ 2 0 0 , W. Page Cleaning .......................................1 1 0 , Gate Porter ................................................ 2 2 0 -47 18 0 Furniture. , Power of Attorney ....................................... 116 ASSETS. % s. d 1864. Purchase of $100 3 per Cent. Consols ............ 69 17 6 192 Ba?ance at Xassrs. Coutts .................................... 792 8 11 March 4. , Balanceat Messrs Coutts ............................. __-u I1 Consols f1000 3 per cent reduced at 891 (rat8 25th March 1865) ........................................ 892 10 0 1502 3 6 1503 3 3 Subscriptions due :-Resident Members 230 ExEmined and found correct ALFEED SMEE, Non-Resident Membem 61 DANIEL I-LANBUBY $291 valued at ... 206 0 0 London Xarch 25rd 1865. 1889 18 I1 Linbilities None. A11 claims against the Society up to 25th Xarch 18G5 have been discharged WARREN DE LA IIUE.PROCEEDINGS OF THE CIIEJIICXL SOCIETY. The following Fellows mere elected Officers and Council for the ensuing year :-President.-?V. A. Miller M.D. F.R.S. Vice-Presidents who have filled the Ofice of President.-W. T. Brande F.R.S. Sir B. C. Brodie Bart. F.R.S. C. G. B. Daubeny M.D. F.R.S. Thomas Graham D.C.L. F.R.S. A. W. Hofmann LL.D. F.R.S. Lyon Playfair C.B.,F.R.S. A. W. Williamson I?B.D. F.R.S. Col I?. Yorke F.R.S. Vice-Presidents.-Wal ter Crum F.R.S. Warren Do la Rue Ph.D. F.R.S. John Stenhouse LLD. F.R.S. Robert Warington F.R.S. Secretaries.-JY illiam Odling M.B. F.R.S. A. Vcrnon Hzrcourt M.A. Foreign Secretary.-E. Frankland Pii.D. F.R.S.Treasurer.-T h eop h i 1u s Ite d woa d Yh.D. Council.-F. A. Abzl F.R.S. @. B. Buckton F.R.S. Dugald Campbell Esq. H. Debus Pli.D. F,E.S. B. 5’. Duppa Esq. G. Cary Foster Esq. E. A. Hodson Xsq. J. B. Lawes F.R.S. Hugo RIiiller l’h.D. W. J. Itussell Bh.D. Maxwell Simpsoil M.R. F.R.S. C. Greville Williams F.R.S. Tt mas resolved that Lstm IV. relstiug to the withc1ratvir;g and removal of Fellows arid Associates be expunged aud the following bye-lam be substituted for it :-‘c No Fellow shall be at libcrty to \~itl~draw fro= the Society until he shall have paid his arrears arid given to om of the Secretaries a written notice of his intention to resign. ‘‘All Fellows who shall bc in atrrew of‘ their anuual snbscription for more than two years such subscri,ntion having been applied for shall reccivz notice frcm tl:c Ccuccil tl:nt unless the same be paid witliin three months their nan:es are litlble to be removed from the list cf Fellows.” Any proposition to remove a Fellow or Associats frorn the Society must be made by the Courrcil.It shall be read at one ordinary meeting of the Society acd i2t an ordinary meeting next ensuing the proposition did1 be Mloted for and if three-fourths of the Fellows voting didi vote far the xmov:J of slid1 Pellow or Associate he shall b.: rcmoi-cd fmru the Sxicty accordingly. Thc hkt ~1~;111 not be valid uidess twelve or moTe persoils vote. 2c2 352 PROCEEDINGS OF’TITE CITEMTCAL SOCIETY. The thanks of the Society were voted to the President Officers Council and Auditors for their services during t.he past year.April 6th 1865. Dr. Miller F.R.S. President in the Chair. Robert Barton Esq. Bushey Park Teddington; C. H. Berger Esq. Lower Clapton; Wm. Chrispin Esq. Darlington Durham; Alexander W. Gillmore Esq. Southfield Wands- worth ; Arthur S. Hobson Esy. 3 Upper Heathfield Terrace Turnham Green ; Wm. Judd Esq. Christchurch Hants ; Michael Foster M.D. Huntingdon; George B. Robertson Esq. Cathcsrt Hill Upper Holloaay were elected Fellows. The following papers were read :-“On a new Bromine Derivative of Camphor,” by Mr. W. H. Perkin. “Note on a deposit of Sulphate of Ammonia prodnced in the process of drying Blood,” by Mr. J. A. R. Newlands. Prof. Wanklyn made a verbal communication on Tindal and Crofts researches on the Ethers.April 20th 1865. Dr. Millei; F.R.S. President in the Chair. Arthur C. Bow dler Esq. Oxford Road Mancheater ; W. E. Heath fi el d Esq, Princes Square Finsbury were elected Fellows. Prof Blox am read some IC Laboratory Memoranda.” May 4th 1865. M. Holzmann Ph. D. Marlborough House; Joseph Sugden jun. Esq. Halifax; J. N. Kirkham Esq. Gilston Road West Brompton ; were elected Fellows. The following papers were read :-lC On Phosphide OC Magnesium,” by Mr T.P. Blunt. PROCEEDINGS OP THE CHEMICAL SOCIETY. 353 (‘On the Periodides of some Organic Bases,” by Mr W. A. Tilden. May 18th 1865. Dr. Miller F.R.S. President in the Chair. Thomas Fairley Esq. Medical School Leeds; Edward Swann Esq.Lmboratory Crewe; Alfred Upwood Eeq. 148 Goswell Street mere elected Fellows. The following paper was read :-‘<On the Specific Refractive Energies of Elements and their Compounds,” by Dr. Gladstone. June Znd 1865. Prof. Williamson P.R.S. Vice-President in the Chair. Dr. Miller delivered a discourse I‘ On some points in the Analyses of Potable Waters.” June 15th 1865. Dr. Miller F.R.S. President iu the Chair. G. B. Sweet ing Esq. King’s Lynn Norfolk was elected a Fellow. The following papers were read :-(‘On the Transformation of the Lactic into the Acrylic Series of Acids,” by Mcssrs. Frankland and Duppa. “On the Action of Nascent Hydrogen on Azodinaphthyldia-mine,” by Mr. W. H. Perkin. November 2nd 1865. Dr.Miller F.R.S. President in the Chair. James ParkinsQn Xsq. Royal School of Mines ; Fredcricli Row e Esq. Colchester ; were elected Fellows. 354 PROCEEDlNGY OF THE CLZEJITCAL S‘SCIETY. The follcming papers were read :-(c On some New Cornish Mincrsls,” by Prcf. A. 13. Church M.A. On the Caprylic and (Enanthylic Alcoliiols,” bjr Mr Er 11 es t Chapman. “On thc Absorption of Vapours by Charcoal,” by Mr. John Hunter M.A. -November 16th 1865 Extraordinary Gemd Meeting. Dr. Miller F.R.S*jPresident in the Chair. Resolved that authority he given to the Council to dispose of the Society’s Chemical Specimens in such manner as they may see fit. Wm. Marriott Esq. Huddersfidd; CEi,ze Ain-ucy Esq. 40 Aldersgate Street were elected FeIloiw.The following papcr was read :-“On Nitro-Compouds,” Part II ; by Edrnuiid J. Mills D.Sc. A- December 7th 1865. Warren De La Rue F.R.S. Vice President in the Chair. John Hunter Bsq. M.A. Fouritain Villa Belfast; Theodore Maxwell Esq. University College London; FIT. J. Barnes Bwkhurst Hill Essex; W. E. Rickerdike Esq. Dalton Squnre Lancaster j Richard Fitzhugh Esq. Nottingham ; Alfred Gardiner Brown Esq. Trinity-square Soutliwark ; W. B. ‘Ititchie Esq. Belfast were elected Fellows. The following papers were read :-(‘On Pyrophosphodiamic Acid,” by Dr. G1adstone. “On Phenyl-y??osi)E-roric hcirl,,” by Dr. H u go 31ulle r. December Zlst 1865. Dr. Miller F.R.S. President in thc Chair. John Percy M.D. F.R.S. ptoyal School of Mincs; Ernest T.Chapman Esq.; George V. Portrnan Esq.; Charles N. I311is Esq. Bow Common-lane ; Thomas Ward Esq. Bolton Lancashire were elected Fellows. %’hefollowing paper was read :-“On thc Material to be Employed for the Constructioa of Mural Standards of Length,” by Mr. Ya t e s. Donatioils to the Library in the yea2 1865. <‘ A Dictionary of Chemistry and the Allied Branches of other Sciences;” by Henry Watts Farts XXII1.-XXXTL ; fromMessrs. Longmau and Co. ‘‘ Modern Chemistry :’I by Dr. A. W. Hofm ann fl’.C.zllthe fiUthQT. “A Course of Practical Cheinistry adapted to the Use c.f Medical Students” 2nd Edition by TViliiarn Qdling from the Author. c‘ Inorganic Chemistry for Science Classes :’’ hy Fesrnside Hudson from the Author.Fresenius’ “Chemical Analysis,” 4th Edition edited by J. Lloyd Bullockand Arthur Vacher fron Arthur Vacher Esq. “Report on the Air of Mines :” by R. Angus Smith fr=m the Antlior. (( The Use of Alcohol as a Test for the Purity of Croton Oil :’ by R. Warington from the Author. (L Lecture on Perfumcs Flower-Farming and the Methods of Obtaining the Odours of Plants” (delivered before the Royal Agricultural Society) by Seytimus Piesse from the Author, (‘Celestial Chemistry and the Physical Constitution of the Stars and Nebulze;” by Thomas W. Burr from the Author. On Tasmanite :” 103 A. H. Church. Researches on’certain EtIiylphosyhates :” by A. H. Church from the Author 356 PIiOCEEDINGS OF THE CHE3lXCXL SOCIETY cc The Food of Man in Relation to his Useful Work :” by Lyon Playfair from the Author ‘‘ Third Report of the Commission appointed to inquire into the best mode of Distributing the Sewage of Towns and applying it to Beneficial and Profitable Use :” from J.B. Lawes Esq. cr Essay on the Trees and Shrubs of the Ancients :” by C. B. Daubeny from the Author. cc Inferepces and Suggestions in Cosmical and Geological Philo- sophy :” by E. N. Braylep from the Author. On Radiation :” by Dr. Tyndail from the Author. “The Phenomena of Kadiation :” by George Warington from the Author. uAddress to the Members of the Devoiishire Association of Science Literature and Art :” delivered at Tiverton June %th 1865 by C. B. Daubeny from the Author. “Artificial Lactation :” by C.M. Wetherill from the Author. ‘I On the Application of Physiological Tests for certain Organic Poisons and especially Digitaline :” by C. €1. Fogge and Thomas Stevenson from the Authors. ‘(On Some Compounds and Derivatives of Glyoxylic Acid by H. Debus from the Author. ‘(A Letter to the Provost of Oriel on University Extension :” by C. B. Daubeny from the Author. ‘CStatistics of the Foreign and Domestic Economy of the United States” (1864) communicated by the Secretary of the Treasury from the Smithsonian Jrrstitution. Results of Meteorological Observations under the direction of the United States Patent Ofice and of the Smithsonian Institu-tion from 1854to 1859 inclusive from the Smithsonian Institution. ‘< Rapport general sur les Travaux du Conseil d’Hygi2ne publique et de Salubritd dn De’partement de la Seine” (1849-1558 et 1859-1861) rcdige’par Adolplie Trebuchet from the Author.4c.Matkriaux pour servir B l’histoire des me’taux dc la Cerite et du Gadolinite :” par M. Delafontaine from the Author. Recherches sur la composition des Molybdates alcaliris :” par M. Delafontaine from the Author. Nouveaux Phknom2nes des Corps Crystallis& :” par Louis Lavi zz ari from the Author. (‘Lavori eseguiti nel Laboratorio di Chemica del Real Istituto di Firenze :” da E. Bechi from the Author PEOCEEDIKGS OF THE CICEUICAL SOCIETY. 357 ‘‘ 1Suffioni boraciferi di Travaie :” da E. B echi €ram tlie Author. “Libros del Saber de hstronomia del Ri Don Alfoiiso dc Castilla compilados anotados y comentados por Don Manuel Rico y Sinobras.” Tomo iii from the Royal Academy of Sciences of Madrid I‘ Beschreibendes und theoretisches Handbuch der Clicmie :” voii Wi 1Z i a m 0d 1i n g Deutsclie vorn Verfassw autorisirte Bearbeitung von Alp ho n s 0pp en h eim from the Translator.‘‘I-Iamatologische Studieii :” voii Dr. A. S c h m i d t from the Author. ‘I Lehrbuch dcr Organischen Cheniie :” voii H e r m a n 11 K ol b e Bd. ii. Lieferungen 1-9 from the Author. Periodicals :-“Philosophical Transactions,” 1862 part I1; 1863 parts I and 11; 1864 parts i and I1 from the Royal Society. “List of Officers and Fellows of the Royal Society for the year 1864:” from the Royal Society.“Transactions of the Royal Society of Edinburgh,” vol. XXIII part 3 ; and vol. XXII part 1. “Proceedings of the same ;” Szssions 1863-64 and 1864-65 from the Society. cc Memoirs of the Royal Astronomical Society,” vol. XXIII. Monthly notices of the same from the Society. Quarterly Journal of the Geological Society,” for 1865 from the Society. ‘‘Quarterly Journal of Science,” for 1865 from the Editor. “Proceedings of the Royal Institution of Great Rritain,” vol. Y. “List of Members Officers and Professors of tlie same,” for 1865 from the Royal Institution. “The Mining and Smelting XTagazilze,” for 1865 from the Editor. “Calendar of the Science and Art Department of the Corn-mittee of Council on Education” (two copies) from the Department.(‘Journal of the Photographic Society;’ for 1865 from tlic Society. “Pharmaceutical Journal and Transactions,” for 1865 from the Editor. “Procccdings of the British Pharmaceutical Ccn-iercnce,” 1864 and 1855 from Dr. Atfield. “ hnnal Report of the Lceds Philosophical and Literary Society” (1863-64.) from the Society. “Thirty-second %port of the Royal Cornmall Polytechnic Society ” (1864) from the Society. “Proceedings of thc Literary and Philosophical Society of Liverpool ’’ (1863-44) from the Society. “Journal of thc Society O€Arts,” 1865 from the Society. ‘(Chemical News ” for 1865 from the Editor. (‘The Reader ” for 1865 from the Editor. ‘(American Journal of Science and Art,” froin the November 1864 to September 1865 from the Editors.Chemical Contributions to the American Jdurnal of Science and Art in the year 1864” by M. Carey Lea from the Author. ct Journal of the Franklin Institute,” from November 1864 to October 1865 from the Institute. ‘‘Proceedings G€ the American Philosophical Society ’’ (1865) from the Society. (‘Catalogue of the Librayy of the American Philosophical Society :” from the Society cc Transactisns of the Albany Institute,” vol. IV from the Institute. “Tran~actio~s of the Socicty fop the Promotion of Useful Arts in the State of New York,” vol. IV part 2 from the Socicty. ‘I Proceedings of the Academy of Natural Sciences at Philadcl-phia ’’ (1864) from the Academy. “ Smithsonian Contributions to Knowlcdge,” vol.XIV. “Ann~alReport of the Board of Regents of the Srnithsonian Institution ” (1865) from the Smithsonian Institution. 6‘ Export of the Commissioner of Patents (United States) for the years 5860 1861 1862 and Introductory heport for 18G3:” from the Cornmiu ’ csioner. Journal of the Argentine Pharmaceutical Society ” (1 G63) from the Scciety. Les blondes,” Tome VI Nos. 16-18 from the Abb6 Moigno. CQS~~S,J’ 2me Sbrie Tomes I et Tome 11 Livraisons 1-34 froin the Editor. (6 Bulletill de IyAca4@mkI!c3 Scimces de St. P6tersbourg,” Ta;fic 1:’ Peuillcs 9-35 ; ‘7t;;::e TI,Fcdlcs 1-32; Tome JTIIy Fc.uil!cs 1-36; T~mc ?TITI Feuilles 1-36 from thc Academy. “Bulletin dc l’Acnd6rnic rople dc Belgique,” 1864 1865 “Annuaire de 1’AcadGmie rogale de Eelgique :” from the Academy.‘I Memorie ~~eli’~4ccadernia dellc Scieme dell’lstituto di Bologna,” Serie 2 Tomo 111; Fasciculi 1-4; Torno IV Fasciculo I from the Academy. “Rendiconti delle Sessioni dell’Accademia delle Scienze dell’ Xstituto di Bologna” (1863-64) from the Academy. “Memorias de la Real Academia de Ciencias de Madrid,” Tomo PI from the Academy. “ Resumen de les Actas de l’hademia de Ciencias de Madrid” (2362-63) from the Academy. “Denkschriften der Kaiseriichen Akadetnie der Wissenschaften in Wien (Math-phys. Classc),” Band XXIlI . “ Sitzungsberichte dei-selbeii,” 1853 Abth. II Heft 3 ; 1864 Abth. I Hefte 1-5 ; Abth. 11 Eefte 1-5 ; and 1865 Heft 1 from the Imperial Academy of Sciences at Vienua.“ Sitzungsberichte der Koniglich-Baeyrischcn Akadeinie dcr Wissenschaften in Muixhen,” 1864 Band II Hefte 2 3 1855 Ha. I Hefte 1-4 ; Bd. 11 Hefte 1 2 from the Royal Bavarian Acadciny of Sciences. ‘I Jahrbuch der K. M. geologischen Reichsanstalt zu T’Vien,” Hd. XIV Hefte 1-4 (Januar-September 1864); Bd. XV Hefte 1,2 from the Institute. I‘ Zeitchrift fur Chernie und Phxrmmie,” herausgegeben von E.Erlenmeyer Bd. VII Hefte 19-23.-Neue Folge heraus- pgeben von A. Hubner Bd. I Hefte 1-13 from the Editors. ‘<Verhandlungen der Naturforschenden Gesellschaft ili Basel,” Abth. IV Hefte 1 from the Society. cr Ofversigt af Kongl. Vetcnskaps Akademiens Fiirhandlingar,” 1563 from the Royal Academy of Sciences at Stockholm.“Oversigt over det Kongelige danslce Videnskabernes Selslrabs Forhandlinger og dets Mcdlemmers Arbeeten ’’ (1864) from tile Rojal Dniiish Academy of Scicnccs

ISSN:0368-1769    

DOI:10.1039/JS8651800342

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

INDEX. A. Abel F. d.,on the compounds of cop- per mid phosphorus 2 $9. Acetate of pheiiyl its formation by the action of bisulphide of carbon on n mixture of acetate of lead and phcnylic alcoliol 24. -of potash note on the action of cliloropicrin and chloroforin 011 by Henry Bassctt 31. Acetic anhydride its formation by the action of bisulphide of carbon on wetate of lead or silver 22. Acetic series of acids the relation of the acrylic series to 152. Acid acetic absorption of its vapour by charcoal 290. -alpha-nitrobenzoic 313. -amidoanisic 312. -amidobenzoic 34. -anisic formation of by the action of nitrous acid on diazo-amidoanisic acid 315, -bcnzoic action of nitric acid on 323. -formLttion of by the action of nitrous acid on diazo-amidobenzoic acid,-310.siinultmeous actioii of sul-phuric and nitric acids on 325. -beta-niorobenzoic 323 326. -bromobenzoic 307. Acid diazo-amidobenzoic action of nitrous acid on in presence of alcohol 310. -products of decompositior of 302. -salts of 300. -diazo-amidocumiiiic 317. -diazo-amidotoluylic 316. -ethyl-crotonic action of potassium-hyclrate on 138. -formation of 134. I_ glycollic formation of from gly-osylic acid 202. -glyoxglic action of zinc on 201. I_ -on some compounds and dcri-vatives of by H. D c bu s 193. I_-compmnd of with bisulphite of soda 193. -hydriodic its action on diazo-amidobenzoic acid 199. -its action on glyoxylates 199. -Iiydrochloric inetliod of demon-strating the composition of 157.-iodanisic 314. -iodobenzoic 306. -iodoxybenzoic 308. -meconic microscopic characters of -methacrylic act,ion of potassium-hydrate on 143. -formation and properties of 142. -methyl-crotonic action of potas--carballylic 334. sium-hydrate on 141. chlorobenzoic 306. -formation and properties of, -c!ilorotoluylic 317. -diazo-amidoanisic 311. -products of decompition of -304. Salt8 Of 313.-diazo-amidobenzoic 299. -action of ammonia on 310. -action of chlorine bromine and iodine upon 306. --haloid acids on 302. _.--hydriodic acid on 308. --nitric acid on 308. --nitrous mid on in pre-Bence of water 309. 139. -nitiic its action on dinzo-amido- benzoic acid 308. -benzoic acid 322.I_ -nitrobenzoic 319. -nitrous its action on diazo-amido- benzoic acid 309. -nitric aimultaneous action of &nd of sulphuric acid on benzoic acid 323. I_-on t3-nitrobenzoic acid 3%. -oxalic formation of fro= glyoxylic wid 202. -picrrtmic formation of diszo-dini-trophenol from 269. 362 INDEX. Acid sulphuric simultaneous action of and of nitric acid on benzoic acid 325. -on /3-nitrobenzoic acid 3%. -tliiophosphaniic 5. -thiophosphodiamic 2. -tribromobenzoic 307. -tricsrballylic formation of 332. salts of 337. -trinitrobcnzoic 309. Acids of the acrylic aeries names alld fornmtion of 155. -rescamhcs on. No. 1,Trans-formation of the lactic into the ncrqlic series of acids by E. Frankland and C.P.Duppa 133. -halol'd action of upon diazo-aniiclo-bcnzaic acid 302. -on th epthzsi3 of tribasic by 3faxwell Simpson 331. Acrylic form of acids extension of the benzoic series 154. -series relations of the artificial to the natural acids of tl:e 147. -of acids their relaiions to tho acetic series 152. c_- their relations to the lactic series 151. Alco!iol-vqour absoyption ~f, bj char-cod 283. hlco!iolq ojl cnprylic and cmnnthylic by E. T. Uhapman 290. Aldehyde it 5 formation from diazo-zniidobenzoia acid 319. AlLalies examination of iaso:u'alc sub-stances for 229. Alkaline salts solu5ility cf magimia in 23. Allyl-tercyanide prepmation of 332. Allylic series of acids coastiiutioz of 154. American petroleum on thc most volatile constituents of by E.X~iiaIJs,54.Amidobeczoic hydriodstcs ct and p, 321. Ai:nizoiiia its action on Bld]dlo< hlori2e of phosphorus by J. a.Bladstcnc f13aJ. D. NOilllCs 1. -I-its setioii on dittzo-amido5cnzoic acid 210. -determination of in waters 125. -method of demonstrating tlie com- position of 167. -gas dGsorption of by cliarcoal 290. AKCT oniasd cor-il3ouisds of glyoxjlatcfi, 196. -deposit on an formed in tlie pro-CCSP of drying blood by J.A. R. N e w-lande 328. A ~un~oniuni, diazo-nmidosnisxtcof 313. -diazo-nmidobcnzoate of $01. -c!iazo-:midotoluylrtte of 316. A~3 71ic ct11civ tricnrbally1ic 3:35. Analysis of potablc waters on some points in the by W. A. Xlillci., 117.-cpnlifati-vc notes upon thc gcneral routine of for mctals by C. L. Bloxam 97. -of substances insolublc in wake? and in acids by @. L. Bloxam 235. Anhydrides and ethcrs on a ncw 1'2-action for the production of by J. Broughton 21. Anuirersarv mceting of the Clmnical Sxicty (3Iarch 30 186.5))344. drsenatc hydrated plum5o-cupric (bay!-donite) from Cornwall 265. Arsenious acid on tlie action of cliloriiic on by C. L. Bloxani 62. Atacamite 80. -grmp notes on a Cornish inir;c:.d of the by A. 1%.Church 21%. Azodinapl:tlij.ldiamine 011 tho actior of nssccrit hj CIrc:.cn 011 by W. li. Ycr-kin 173. B. B;~lsncc-shcctof the C1icmic:sl Bxicty (?865),350. Bayiuni di~~zo-ar:iit?ut,~~~zO:LtC, 301. -dhzo-amldocuiii illat c 317.-diazo-amidotolq lcte o€ 316. -glScei.itric~rr5~ily!3tc cf 3%. Bases on the periovides of sonic of thc organic by W. A. Tilclen 93. Bassett H. note on thc action of chloropicrin and chloroform on ace-tate of potash 31. Bayldonite (hydrated plunibo-cupric arsennte) from Cornwall 265. Senzoic series extmsion of the acrylic form of acids to the 154. Benzol-vapour absorption of 5y clizr-cod 285. ~ia~dphidt: of carb0n formstion c.f acetic anliydride by its action o!i acetate oi lcad or silmr 22. -foolmation of acetzte ~f phei:.; 1 by its action an n mixture of phcnylic alcohol aid nretatc of lcnd 2 1. -ih action on varioud salts 26. --riaphthyldixnine 178. -'oapour abfiorption of by charcw! 288. Bisulphitc of lime CO~~OLLE~ of rvith glyoxylate ~f lime 191..-of soda compo-c:d of with ~'1-oxylic acid 193. Blood cn an nwmonixnl deposil fomicd in the prcczss of drying by J. A. l-7cvltLnde 210. INDES. 363 Bloxam C. L. on the action of chlo-rine upon amenious acid 62. -oil the action of hydrosulphato of miinonis upan freshly precipitated sulphide of copper 94. -notes on tho general routine of qualitative analysis for mchls 97. -on the qualitative analysis of sub-stances insoluble in water arid in azids 226. Blue colouring matter of indigo cstlma-tion of 217. Blunt T. P. on phosphido of magnc-&in,106. Eoi!iijg points of isomeric ethers of thc forniula CnH2!,02 note on the by J. A. Wanklyn 30. Eotallackite 215.BradyH. B. and H. Deane on micro-scopid research in relation to phar- mscy 34. Erine 011 a desse from Sdtsprkgs Nova Scotia by Prof. How 46. Rrochantite 85. C rouic-samphor 92. 13ronzcs arialyscs of some fourid in Great Britain by A. H. Church 216. Broughton J. on a new reaction for tlie production of anhydrides and CthCYS 21. Zrown Dr. A. Crum on the theory of isonieric compounds 230. B ruwii J. T. Table for the calculation of Llimct nitrogen determinations 2iO. But) l-hyiiride in Amerhn petroleum GO. C. Cablcs (gutt-a-pedm) ,experiments upon damaged suspencled in air or p!xd undorgound 279. -submarine experiments on 278. Cadmiuin thiophosphamate of 6. -thiop'3osphodiainste of 4. CsTeine periodide of 100.Cn;tcium-alluminic phosphate hydrated from Comwall 263. -diazo-nmidobenzoate of 301. Calve~t,F. C. on the action of sili-a and crtrbonste of soda on cotton fibre 70. -on a crystsllisod hydrsste of phcnylk :i!diol 66. Cmxphor on a iiew bromine-derivallrc cf by '3.H. Perkin 92. Caoutchouc on the dccay of by W. A. RIiller 280. Capyl broinide of 293. Czprylic and ccnanthyiic alcohoh 011 by E. T. Chapman 290. hbon formation of acetis anhydride by the action of bisulphiclc of on ncetntes 22. -formation of acetate of phony1 by thc action of bisulphide of on a mix- ture of acetate of lcad and phenylic olcohol 24. -action of bisulphido of on varions salts 26. Carbonate and siliczte of aoda action of on cotton fibre by F.C. Calvert 70. Carbonic acid vapour absorption of by charcoal 290. Castor oil alcohols 290. Cerous phosphate hydrated from Corn-wall 259. Chapmen,. E. T. on caprylic aiid ananthyhc alcohols 290. Charcoal on the absorption of vapoms by by John Hunter 335. Chemical combination its idlnence on specific refractive energy 113. Chemical Society balance shcet of the (1865) 350. -donations to the libi-ary of the (1865) 335. -procecdings at the meetings of the (1865),34. Chlorine on tlie action of on axsenions acid by C. L. Bloxom 62. Chloropicrin and chlorofwm note on t!ie action of on acetate of potash: by Henry Bassett 31. Chloropropionate ethylic forantion of from ethyiic lactate 144. Chloroform-vaporir absorption of by chzrcoal 290.Ch rir ch A. H. analysesof some bponzes fwnd in Great Britaiii 215. -notes on a Cornish minxd of tho at-acamite group 228. -on a feiric hy&-"3.t.efrom Corn-wdl 214. -on oms hy&*cstoJ capric ox~~hb- rides from Cornwall 77. -on some 11yilr~t:dcup& 0x9-sulphates from Co?n3a 83. -chemical researches OJ ec);ac ncw md raro Cornish miner& 253. Codeine microscoped chcracters of 36. Colonr of a water mode of observing the 118. Copzer xction of hydros:ilphat,e of ax-monk on sulphidt of 94. -and piio;phoxw on tho coni-~o~III':; oE by F. A. Abol 2?9. -dl~~~o-~2ni~o50iizontj of 291 c1 . I_ Lnl~l~!lospha;i:ntpof 3. Cupric oxychlorides and oxpsulpliatcs from Cornwall on some 'Iiydratett by A.LI. Church 77 83. D. Deane H. and H. B. Brady on micro- scopical research in relation to phar-macy 34.. Debus II. on some compouncls and deii;.atives of glyoxylic acid 193. Diazo-ainidoanisates 313. -aniidobenzoates 301. -amidotoluates 316. dinitruphenol 268 298. I_ nitrochlorophenol 271. -nitrophenol 2'70. ' Dictlioualate cthylic action of trichlo-rick of phosphorus on 135. Dinicthoxalate ethylic action of tri-cliloride of phosphorus on 141. Dinitrotoluol formation of 320. Donatiom to the Library of the Chemical Socicty (1865) 365. Duppa 13. F. am1 E. Frankland rcscarches on acids of thc acrylic series.-No. 1. Transfornotion of the lactic into the acrylic series of ncicls 133. E.Ethers and aiiliydridcs on a new re-action for the production of by J. Brougliton 21. -isomeric of the formula CnI12,102; note on their boiling points by J. A. Wanklyn 30. -tricarballylic 33 5. Ether rapour its absorption by charcoal 289. Etliomethoxalate,ethylic action of trielilo-ride of phosphorus on ethylic 139. Etliyl-caffeine periodide of 102. -crotonate cuprie 137. -ethylic 134. -of lead 137. -. 0f silver 136. -diazo-amidoanisate 314. -diazo-benzoate 301. -hydride in American petroleum 56. Etlijlic cliloropropiona te formation of 144. -dicthoxalate action of trichloride of phosphorus on 133. -dimethoxalate 141. -ethomethoxalatc 139. -ethyl-crotonate formation and pro-perties of 134. -lactate action of trichloride of phosphorus on 145.Ethylic leucate 133. -methacrylate forinntion nnd pro-pcrtics of 143. -methylcrotonate 139. Evaporation of waters and incineration of the reeidue 119. F. Feiric hydrate notes on a from Corn-mall by A. H. Church 21L Ferricyanide of potassium its action on ferric salts 27. Forest marble of Cirencestei; manganese in 207. Fcusel-oil rapour absorption of by charcoal 289. Frankland 3'. and 13. F. Duppa, mscarchcs on acids of the acrylic series.-ATo. 1. Transformation of the lactic into the acrylic series of acids 133. G. Gaseous coiistituents of waters eutixs- tion of 124. Gladstone J. II. on the specific re- fractive energy of elements and their compounds 108. Gladstone J.H. and J. D. Holmes on the action of ainmonia on snlplio- cliloride of phosphorus 1 Glyccri-tricarbullylate of baryta 336. Glyoxylate of lead and ammonia 198. -lime and aninionia 196. -with bisulphite of lime 194. -lactate of lime 195 -silver and ammonia 198. Gljoxylates action of hydriodic acid on 198. --sulphuretted hydrogen on 199. -animoniacal compounds of 197. Griess I?. on a new series of bodies in which nitrogen is substituted for hy-drogen 268 298. Gutta-percha on the decay of by TV. A. Millcr 2'73. Gutta pui-e experiments on 274. M. Hardness of waters det,erminatioii of 119. Hexphosphide of copper 250. Hofmann A. W. on lecture illustram tions 156. INDEX. 365 Eolrnes J. D. and J. H.Gladstone on the action of ammonia on sulpho-chloride of phosphorus 1. How Prof. on a dense brine from Salt- springs Nova Scotia 46. Hunter John on the absorption of vapours by charcoal 285. Hydrated calcium-aluminic phosphate from cornwall 263. -ceroua phosphate from Cornwall 259. -plumbo-cupric arsenate (bayldonite) from Cornwall 265. Hydride of butyl in American petroleum 60. Hydrides of ethyl and propyl in Ameri- can petroleum 56. Hydrochloric acid mode of demonstra-ting the composition of 157. Hydrogen on the action of nascent on azodinaphthyldiamine by W. H. Perkin 1’73. Hydrosulphate of ammonia its action on freshly precipitated sulphide of copper 94. I. Incineration of the fixed residue of waters 119.India-rubber on the oxidation of by J. Spiller 4A. (See also p. 280.) Indigotin or blue colouring matter of indigo on the estimation of by C1. Ullgren 21’7. Insoluble substances examination of for alkalies 229. Iodostrychnine periodide of 105. Isomeric compounds on the theory of by Dr. A. Crum Brown 230. -ethers of the formula of C,H2,02 note on the boiling points of by J.A. Wanklyn 30. Isomerism remarks on by E. J. Mills 329. K. Kelloway rock manganese in 207. L. Lactate ethylic action of terchloride of phosphorus on 144. -of lime compound of with glyoxy- late of lime 195. Lactic series of acida relations of the acrylic to 151. -transformation of into the acrylic series 133. Langitr 87. YOT,.X\-III. Lead on the action of light on sulphide of and its bearing on the preservation of paintings in picture galleries by D. 5. Price 245. -estimation of in waters 129. -ethylcrotonate 13’7. -glyoxylate of and ammonia 198. -thiophosphamate of 6. -tricarballylate of 338. Lecture illustrations on by A. W.Ho f-mann 156. Leucrtte action of tercliloride of phos-phorus on ethylic 133. Lias and oolite on the presence of mau-ganesein by R. Warington jun. 206. Library of the Chemical Society dona- tions to the (1865) . Light on the action of on sulpliide of lead 245. Lime glyoxylate of and ammonia 196. -glyoxylate of with bisulphite of lime 194. -lactate of lime 195. Liquor Opii sedativus microscopical cha-racters of 39.Lyellite 83. M. McDougall A. on a mode of mea-suring the relative sensitiveness of pho-tographic papers 183. Magnesia solubility of in alkaline salt+ 27. Magnesium diazo-amidoanisate of 314. -diazo-amidobenzoate of 301. -on phosphide of by T. P. Blunt 106. Manganese on the presence of in oolite and lias 206. Marsh gas method of demonstrating the composition of 171. Meconate of morphine microscopical ap- pearance of 36. Meconin microscopical appearance of 37. Meetings of the Chemical Society pro- ceedings at the (1865) 342. Metals notes upon the general routine of qualitative analysis for by C. L. Bloxam 97. Methacrylates 142. Methyl-alcohol vapour absorption of by charcoal 288. Metliyl-caffeine iodide and periodide of 103.Methyl-crotonates 140. Methyl cliazo-aniidoanisate of 314. -diazo-amiciobenzoate of 302. Microempicnl PPS~RP~JI in relation ts 2 11 INDEX. pharmacy by H. Deane ttnd H. B. Brady 34. Miller W. A. observations on some points in the analysis of potable waters 117. -on the decay of gutta-percha and caoutchouc 173. Mills E. 3. on nitro-compounds (Part 11),with remarks on isomerism 319. Minerals on some new and rare Cornish by A. H. Church 255. Mixture and solution :their influence on the specific refractive energy of ele-ments and their compounds 108. Morphine microscopical appearance of its meconate and sulphate 36. N. Naphthalene on the formation of pyri-dine from by W.H. Perkin 9. Naphthene-diamine 181. Naphthylamine formation of from azo-dinttphthyldiamine 181. Naphthyldiamine 175. --its behaviour with oxidisling agents 178. -hydrochlorate of 1’76. 7nitrate of 178. -oxalate of 178. -sulphate of 177. Narceine microscopi2al characters of 36. Narcotine microscopical characters of 37. Neilson J. B. obituary notice of 345. Newlands J. A. R. on an ammoniacal deposit formed in the process of drying blood 340. Nitrites estimation of in waters 127. Nitro-compounds on by E. J. Mills 319. Nitrogen on a new series of bodies in which it is substituted for hydrogen by P. Griess 268 298. Nitrogen determinations table for the calculation of 210. Normandy Dr.,obituarynotice 0f,345.0. Obituary notice of J. B. Neilson 345. -Dr. Normandy 345. -Dr. E. Pugh 346. -Dr. R. D. Thomson 344. Odour of waters mode of observing 118. CEnanthylic and caprylic alcohols on by E. T. Chapman 290. Oolite and lim on the presence of .man- ganese In by R. Warington junr. 206. Opium microscopical characters of its various preparations 38. Organic bases on the periodides of some of the by W. A. Tilden 99. Organic matter determination of in waters by incineration 119. -by potmsic permanganate, 120. Oxidationofindia-rubber:by J. Spiller, 44. (See also p. 280.) Oxychlorides and oxysulghates on some bydi-atec! from Cornwall by A. H. Church 77 83. P Paintings on the action of light on sul-phide of lead and its bearing on the preservation of in picture galleries by D.‘ 8.Price 245. Papaverine microscopical characters of 37. Periodides of some of the organic bases on the by W. A. Tilden 99. Pcrkin W. H. on a new bromine de- viative of camphor 92. -on the action of nascent hydrogen on azodinapthyldiamine 173. -note on the formation of pyridine from naphthalene 9. Permanganate potassic use of for esti- mating organic matters in waters 120. Petroleum Canadian caprylic alcohol from 296. -on the most volatile constituents of American by E. Ronalds 54. Pharmacy on microscopical research in relation to by H. De me and H. B. Brady 34. Phenylic alcohol on a crystallised hy- drate of by F. C. Calrert 66. Phosphate calcium-aluminic from Corn- wall 263.-hydrated cerous from Cornwall 259. Phosphide of magnesium on by T. P. Blunt 106. Phosphorus the action of ammonia on sulphochloride of by J. H. Glad-stone and J. I). Holmes 1. -on t,he compounds of copper and by F. A. Abel 249. -terchloride of its action on ethylic diethoxalate 133. -dimethoxalate 141. -ethomethoxalate 139. -lactate 145. -leucate 133. Photographic papers on a mode of mea-suring the relative sensitiveness of by A. McDougall 183. INDEX. 367 Platinopyridine bihydrochlorate of 180. Plumbo-cupric arsenate (bayldonite) from Cornwall 265. Potable waters on some points in the analysis of by W. A. Miller 117. Potash note on the action of chloropicrin and chloroform on the acetate of hy H.Bassett 21. Potassium diazo-amidoanisate of 313. -diazo-amidobenzoate o& 301. -diazo-amidotoluylate of 316. Potassium-hydrate its action on ethyl-crotonic acid 138. -methacrylic acid 143. -methyl-crotonic acid 141. Price D. S. on the action of light on sulphide of lead and its beaying on the preservation of paintings in picture galleries 245. Proceedings at the meetings of the Chemical Society (1866) 342. Propyl-hydride in American petroleum 56. Pugh Dr. E. obituary notice of 346. Pyridine on the formation of from naphthalene by W. H. Perkin 9. -formation of from azodinapthyldia- mine 180. Q* Qualitative analysis notes on t,he general routine of for metals by C.L. Bloxam 9'7. -of substances insoluble in water and in acids by C. L. Bloxam 226. R. Refractive energy of elements and their compounds on the specific by J. H. Gladstone 108. Report of the President and Council -Treasurer . Ronalds E. on the most volatile con- stituents of American petroleum 54 S. Saline constituents of waters estimation of 129. Saltaprings Nova Bcotia on D dense brine from by Prof. How 46. Sediment determination of amount of in waters 118. Silicate and carbonate of soda action of on cotton fibre by F. C. Calrei-t 70. Silver diazo-anlidobenzoate of 301. -diazo-amidotoluylate of 316. -gllroxplate of and ammonia 198. Silver tricarballylste of 338. I_ ethyl-crotonate 136. Simpson Maxwell on the synthesis of tribasic acids 331.Soda-bisulphite compound of with gly- oxylic acid 193. Soda-salts of tricarballylic acid 337. Sodium diazo-amidoanisate of 313. -diazo-amidobenzoate of 301. -diazo-amidotoluylate of 316. -solution and mixture their in-Buence on the specific refractive energy of elements and their compounds 110. Specific refractive energy of elements and their compounds by J. H. Glad-stone 108. Spiller J. on the oxidation of india- rubber 34. Spr e n ge1 H.,researches on the vacuum 9. Sulphide of copper action of hydrosul-phate of ammonia on 94. Sulphide of lead on the action of light on and its bearing on the preservation of paintings in picture galleries by D. 8. Price 245. Sulphochloride of phosphorus the action of ammonia on by J.H. Gladstone and 5. D. Holmes 1. Sulphuretted hydrogen its action on glyoxylates 199. Synthesis of tribasic acids on the by Maxwell Simpson 331. T. Taste of waters observation of 118. Temperature its influence on the specific refractive energy of elements and their compounds 109. Terchloride of phosphorus its action on ethylic diethoxalate 133. -dimethoxalate 141. -ethomethoxalate 139. -lactate 145. -leucate 133. Tercyanide of allyl preparation of 332 Thebaine microscopical characters of 37. Thiophosphamate of cadium 6. -lead 6. Thiophosphodiamate of cadmium 4. -copper 3. _I zinc 4. Thomson R. D. obituary notice of 344. Tilde n W. A. on the periodides of some of the organic bases 99.Tribasic acids on the synthesis of by Sfaswell Simpson 331. 368 INDEX. Tricaprylamine 294. points of isomeric ethers of the formula Tricarballylic ethers 335. CnH21102 30. Wanklyn J. A. on vapour densit,ies 89. U Warington R. jun.,laboratory memo- randa Ullgren Cl. on the estimation of in-I. The action of ferricyanide of digotin or the blue colouring matter potassium on ferric salts 27. of indigo 217. 11. The solubility of magnesia in alkaline salts 27. -on the presence of manganese in V. oolite and lias 206. Water method of demonstrating the Vacuum researches 00 the by H. composition of 164. Sprengel 9. Waters on some points in the analysis Vapour-densities on by J. A. Wank-of potable by W.A. Miller 117. lyn 89. Water-vapour absorption of by charcod Vapours on the absorption of by char-290. coal by John Hunter 285. Z. W. Zinc it0 action on glyoxylic acid 201. Wanklyn J. A. note on the boiling -thiophosphodiamate of,4.

ISSN:0368-1769    

DOI:10.1039/JS8651800361

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

368 INDEX. ERRATA. Page. Line. 127 1 dele “ten.” 127 9 from bottom for 0.00237 read 0000237. 293 The last line should be transferred to the top of page 295.

ISSN:0368-1769    

DOI:10.1039/JS8651800368

出版商:RSC    

年代:1865

数据来源: RSC