摘要:

JOURNAL OF THE CHEMICAL SOCIETY. I.-On Pyrophosphotriamic Acid. By J. H. GLADSTONE, Ph.D.,F.R.S. ITwas my intention in conjunction with my assistant and fkiend Mr. J. D. Holmes to follow up our previous papers on some of the amides of phosphoric acid* with a more complete investigation of the whole subject But our paper on the action of ammonia on sulphochloride of phosphorus was scarcely printed when Mr. Holmes was taken seriously ill and his death last mid- summer has deprived the world of a careful experimenter and a good man. I feel his loss the more because he had many thoughts and observations connected with these compounds of phosphorus which he never committed to writing. Oa looking over our note-books I find a tolerably complete history of a remarkable acid amide which with a few additional experiments will form the present communication.If dry ammonia gas be allowed to stream slowly into a flask containing oxychloride of phosphorus kept cool by being immersed in water the liquid is gradually converted into a white solid mass by the absorption of two equivalents of ammonia. If at that point the flask be immersed in water at 100"C. the mass will be found capable of absorbing two more equivalents of ammonia and on the addition of water to the white substance thus produced there results an insoluble amide the subject of the present inquiry. In order to obtain it pure the oxychloride of phosphorus employed must be free from pentachloride but it is not necessaryto attempt to free it from hydrochloric acid.During the latter portion of the * Journal Chem. SOC.,1864 p. 225 and 1865 p. 1. VOL. XIX. B GLADSTONE ON PPROPHOSPHOTRIAMIC ACID. process it is desirable to break up the solid mass from time to time in order that all parts of it may be exposed to the gaseous ammonia; and if this be properly done the contents of the flask will be found to have increased in weight nearly if not quite 44 per cent. The white amorphous powder produced by the action of water must be washed with cold water till the washings give no indica-tion of a chloride and then it is better to finish the washing with a little dilute alcohol. The compound thus obtained is ta,steless but when moistened it reddens blue litmus paper and it effervesces with solutions of alkaline carbonates.When suspended in solutions of metallic salts it usually decomposes them entering into combination with the metal and that in the presence of the liberated acid. These salts so easily formed are all insoluble or very sparingly soluble in water like the acid itself even the salts of the alkalis. Another remarkable circumstance connected with this acid is that it is capable of combining with 1,2,3,or 4 atoms of the base according to the peculiarities of the metal itself or the way in which it is presented. This compound though almost insoluble in water is very slowly attacked by it especially at a high temperature with the produc- tion of pyrophosphodiamic acid. When boiled with dilute hydro-chloric acid it is speedily resolved into phosphoric acid and ammonia pyrophosphodiamic acid being an intermediate product.When heated with strong sulphuric acid it instantly dissolves and this solution also contains yyrophosp hodiamic acid. The following analyses were made of different preparations of the substance dried at 1GO0 C. :-I. 0.3315 grm. boiled with hydrochloric acid and the ammonia determined in the usual manner gave 1.243 grm. of am-monio-chloride of platinum. II. 0.197 grm. gave 0.755 grm. of ammonio-chloride af platinum. 111. 0.197 grm. decomposed in the same way gave 0.247grm. of pyrophoaphate of magnesium. IV. 0.2595 grm. gave 0-987 grm. of ammonio-chloride of platinum V. 0.2445 grm. gave 0.309grm.of pyrophosphate of magnesium.VI. 0*18&5grm. regained from its ammonium salt gave 0.705 grm. of ammonio-ohloride of ~latinum. GLADSTONE ON PYROPHOSPHOTRIAMIC ACID. VII'. 0.225 grm. of substance regained from its combination with copper gave 0.2825 grm. of pyrophosphate of magnesium. VIII. 0.320 grm. burnt with oxide of copper gave 0.114grm. of water. These numbers when reckoned to 100 parts give I. 11. 111. IT. v. TI. VII. VIII. Phospho~s.... -35.02 -35'29 -35-38 -Nitrogen .... 23.64 24.03 -23-85 -23-96 --I-Hydrogen .... -3-93 agreeing very closely with the numbers deduced from the formula P,N,*,C),* Calculated. Mean of Analyses. Phosphorus ........ 62 35.43 35-23 Nitrogen ........ 42 24-00 23-84 Hydrogen ........ 7 4-00 3.93 64 Oxygen ..........-36-57 - 175 100.00 This may be viewed as the third member of the series of amides of pyrophosphoric acid of which the first two have already been described by me ; and it should by analogy be termed pyrophos- pho triamic acid.Ppophosphoric acid .................... P H4Q7 Pyrophosphamic acid .... P2NH@6 or P2(NH2) H3Q6 Pyrophosphodiamic acid .... P2N2H6Q5or P,2(NH2)H,8 Pyrophosphotriamic acid .... P2N3H@4 or P23(NH2)H Q4 The reaction by which this substance is produced by the treat- ment of oxychloride of phosphorus with ammonia and water in succession may be briefly expressed thus :-Z(PC13Q + 4NH3) + 2H20 = P2N3H@4 + 6HC1+ 5NH3 just as in the production of pyrophosphodiamic acid formerly de- scribed-2@?c130 + 2NH3) + 34Q = P2N2H6&& + 6HC1+ 2NH3 bat in both cases there are intermediate products not recognized B2 GLADSTONE ON PYROPHOSPHOTRIAMIC ACID.in the above equations. I reserve the fuller consideration of what takes place when ammonia is passed over oxychloride of phosphorus till a future occasion SALTS. If the rational formula of this acid be that above given it might be expected that only one equivalent of hydrogen would be replaceable by a metal or in other words that pyrophosphotriamic acid would be monobasic just as the -diamic acid is bilasic and the -amic acid is tribasic. The analysis of its salts shows indeed that such monobasic compounds are produced with the alkali- metals and many others but it also shows that most metals are capable of displacing one or more equivalents of that hydrogen which we are apt to consider as more intimately associated with the nitrogen.SrLvER-sALTs.-Moiiometallic.-Tf a solution of nitrate of silver be added to an aqueous solution of pyrophosphotriamic acid it gives a white gelatinous precipitate. But it is not easy to prepare in this way a quantity sufficient for analysis and a portion so pro-duced gave n determination of silver which led to the conclusion that the salt was impure. A better method is to suspend the acid in cold water and add a solution of nitrate of silver when a floccu-lent precipitate subsides and becomes granular. It is white amorphous and insoluble in water ; dilute nitric acid or ammonia will dissolve out a little silver and leave the pure monometallic salt.This salt is decomposed at once by hydrochloric acid ; and this affords a ready means for its analysis as the pyrophosphotriamic acid itself is converted on boiling into phosphoric acid and ammonia which can be determined in the usual way. The following determinations were obtained :-I. 0.259 grm. of silver-salt washed with dilute ammonia gave 0.133 grm. of chloride of silver and 0*208of pyrophos-phate of magnesium. 11. 0.241 grm. similarly washed gave 0.122 grm. of chloride of silver and 0.581 grm. of ammonio-chloride of platinum. 111. 0.298grm. of salt washed with dilute nitric acid gave 0.1515 grm. of chloride of silver and 0.235 grm. of pyro-phosphate of magnesium. IV. 0.285 grm. similarly washed gave 0.145 grm.of chloride of silver and 0.679 grm. of ammonio-chloride of platinum. GLADSTONE ON PYROPHOSPHOTRIAMIC ACID. This agrees closely with what ought to be obtained from a sub-stance having the composition P,N,H6AgQ4. Calculated. I. 11. 111. IV. Phosphorus .. 62 21.98 22-42 -22.01 -Nitrogen . . .. 42 14.89 -15.11 -14.94 Hydrogen .... 6 2.13 I -I -Silver ........ 108 38-30 38.64 38.09 38.26 38.29 Oxygen ... . .. 64 22.70 282 100*00 ~irnetaZZic.-If a feebly ammoniacal solution of nitrate of silver be added to a solution of pyrophosphotriamic acid there precipi- tates a yellowish salt. Or if the monometallic compound just described be treated with such an ammoniacal salt of silver in excess it becomes of a bright yellow colour heavy granular and easily washed by decantation.When dry it forms an orange-yellow powder. Dilute nitric acid or ammonia converts it at once into the white monometallic salt. Acetic acid attacks it but slowly even when strong and at a boiling temperature. It was analysed by decomposition with hydrochloric acid. I. 0.509grm. of the yellow salt gave 0.442grm. of chloride of silver and 0-675grm. of ammonio-chloride of platinum. 11. 0.5745 grm. gave 0-4995grm. of chloride of silver and 0.252 grm. of pyrophosphate of magnesium. 111. 0.286 grm. gave 0.2485 grm. of chloride of silver and 0.3695 grm. of ammonio-chloride of platinum. IV. 0404 grm. gave 0.3515 grm. of chloride of silver and 0.183 grm. of pyrophosphate of magnesium. These numbers agree well with the composition P,N3H,Ag3Q4.Calculated. Found. I. 11. 111. IV. Phosphorus .. 62 12.50 -12.25 -12.65 Nitrogen .... 42 8.47 8.32 -8.10 -Hydrogen .... 4 0.81 --Silver ........ 324 65132 65.34 65.46 65-39 6548 Oxygen 64 12.90 --.. -496 100*00 GLADSTONE ON PYROPHOSPHOTRIAMIC ACID These two silver-salts white and yellow and their ready con-vertibility into one another afford a good test for pyrophospho- triamic acid. BARIUM-SALTS. -MonometaZZic. -This salt was prepared by diffusing the acid through a solution of chloride of barium and carefully neutralising the liberated hydrochloric acid by a few drops of ammonia. It was decomposed byhydrochloric acid the dif-ferent constituents being determined in the usual way.I. 0.429 grm. gave 0.2045 grm. of sulphate of barium and 1.1795 grm. of ammonio-chloride of platinum. 11. 0.3465 grm. gave 0.1665grm. of sulphate or"barium and 0.3145 grm. of pyrophosphate of magnesium. These numbers indicate the formula P2N,H6BaQ,. Calculated. Found. I. 11. Phosphorus .. 62 25-56 -25-34 Nitrogen .... 42 17*31 17*24 -Hydrogen .... 6 2.47 Barium ...... 68.6 28.28 28.06 2827 Oxygen ...... 64 26.38 242.6 100*00 .Dimetallic.-When pyrophosphotriamic acid was suspendedin an excess of an ammooiacal solution of chloride of barium it I combined with twice as much of the metal. The following analyses were made :-I. 0.2335 grm. of salt gave 0.174grm. of sulphate of barium and 0.4895 grm.of ammonio-chloride of platinum. 11. 0.2445 grm. gave 0.1835 grm. of sulphate of barium and 01793 grm. of pyrophosphate of magnesium. These indicate the composition l',N,H,Ba24&. Calculated. Fpund I. 11. Phosphorus .. 62 20-00 -20.48 Nitrogen .... 42 13-54 13-14 -Hydrogen .... 5 1-60 -Barium ...... 137.24 4.23 43-84 4418 -Oxygen ...... 64 20.63 -310.2 GLADSTONE ON PYROPHOSPHOTRIAMIC ACID. LEAD-SALTS. -Lead is capable of entering into combination with pyrophosphotriamic acid in three different proportions. MononaetaZZic.-If the acid be treated with a solution of nitrate of lead the result is a mixture of the compounds of 1 and 2 atoms of the metal. If however the solution be rendered decidedly acid with nitric acid a pure mono-metallic salt may be produced.0.203 grm. of the acid thus treated gave 0.327 grm. of salt which indicates a compound of the formula P,N,H,PbQ4. The exeess of weight being due to the addition of lead and the removal of a corresponding amount of hydrogen gives the follow- ing percentage :-Calculated. Found. Lead . 37-3 per cent. 38.1 per cent. Dimeta&.-To produce this compound the acid was suspended is water and an excess of a strong but slightly acid solution of acetate of lead was added. A dense white granular precipitate was the result. It was analysed in the usual way. 0.354 grm. of salt gave 0*2805grm. of sulphate of lead and 02035 grm. of pyrophosphate of magnesium. This agrees sufkiently with the formula P2N,H,Pb,Q4.Calculated. Found. Phosphorus .. 62 16.32 16.05 Nitrogen .... 42 11.05 -Hydrogen.. .... 5 1.32 -Lead .......... 207 59-47 53.95 Oxygen.. ...... 64 16-84 -380 100*00 This compound is not turned yellow by iodide of potassium except on the addition of hydrochloric acid. TrimetaZZic.-When pyrophosphotriamic acid was warmed with basic acetate of lead it combined with a larger portion of the metal. The following analyses were made :-I. 0.3405grm. of salt gave 0.321 grm. of sulphate of lead and 0-1535of pyrophosphate of magnesium GLADSTONE ON PYROPHOSPHOTRIAMKI ACID. 11. 0.2365 grm. gave 0.175 grm. of sulphide of lead and 0.3165 grm. of ammonio-chloride of platinum. This agrees with the formula P,N,H,Pb,B,. Calculated.Found. I. 11. Phosphorus .. 62 12.85 12.59 -Nitrogen .... 42 8-70 -8.39 Hydrogen ... . 4 0.83 -Lead ...... 310.5 64.35 64.40 64-08 c Oxygen ...... 64 13-27 -482.5 100*00 THALLruM-sALT.-Pyrophosphot~amic acid treated with nitrate of thallium gives a heavy white compound which is easily decomposed by rather strong nitric acid. CoPPER-sALTs.-Both neutral and ammoniacal salts of copper give up their metal to pyrophosphotriamic acid. Monometallic.-The acid when treated with a solution of nitrate of copper to which some drops of nitric acid had been added gave a pale blue compound. Ou analysis this was found to contain rather more copper than a pure monometallic salt should have done ;but it consisted mainly in all probability of such a com-pound.Dimetallic.-0.164 grm. of the acid digested awhile with a solution of acetate of copper gave a greenish salt which when dried at 100' C.,weighed 0.215 grm. These numbers indicate that two equivalents of hydrogen had been replaced by copper though perhaps the conversion had not been complete. The increased weight ought by calculation to have been 0.220. If some of the acid be thrown into a solution of a copper-salt in excess of carbonate of ammonium an effervescence takes place and there results a green powder insoluble in ammonia but from which dilute acids dissolve out the copper. I. 0-236 grm. of this salt gave 0-080 grm. of oxide of copper and 0.646 grm. of ammonio-chloride of platinum. 11. 0-304grm. gave 0*103 grm. of oxide of copper and 0.285 grm.of pyrophosphate of magnesium. This was certainly P,N,H,Cu2Q4. GLADSTONE ON PYROPHOSPHOTRIAMIC ACID. Calculated. Found. I. IT. Phosphorus .... 62 26-25 -26.18 Nitrogen ...... 42 17.78 17.17 -Hydrogen ...... 5 2.12 -Copper ........ 63.2 26.76 27-04 27-03 Oxygen ........ -64 27-09 - -236.2 100*00 ZINC-SALT.-The acid decomposes chloride of zinc forming a white pyrophosphotriamate. CaDMIuM-sALT.-It forms a white compound also when treated with chloride of cadmium. IRo~-sALT.-MonometaZZ~c,-If the acid be digested with a solution of ferrous sulphate a salt of a yellow-drab colour is pro- duced which resists the solvent power of dilute acids. 0.075 grm. of substance increased in this way to 0.089 grm.which points to the formula P,N,H6FeQ4. The salt obtained ought to have weighed 0.086 grm. ; but it probably contained a trace of ferric oxide mixed with the ferrous compound. I have not succeeded in preparing any ferric pyrophosphotriamate though the attempt has been made with ferric chloride acetate and ammonio-citrate. This is the more remarkable as pyrophos- phamic acid and phospboric acid itself show such a readiness to combine with iron in that condition. CoBALT-SALT.-ni~etalzic.-The acid digested with a slightly ammoniacal solution of nitrate of cobalt forms a compound of a beautiful violet colour not decomposed by diliite hydrochloric and but slowly by dilute sulphuric acid. 0.136 grm. gave thus 0-177 grm. of salt which is sufficiently near to the theoretical amount to show that the composition was P,N,H,Co,B,.CJculated. By synthesis. Cobalt .. 25.6 per cent. 24.3 per cent. The same salt seems to be produced when the acid is treated with an ordinary solution of chloride of cobalt but an analytical experiment gave also in this case less than the required percentage of metal. NICKEL-SALT.-A feebly ammoniacal solution of sulphate of nickel gives a bright green pyrophosphotriamate. WADSTONE ON PYROPHOSPHOTRIAMIC ACID-MAN GANEsE-BALT. -Chloride of manganese gives a yellowish salt of this acid. CHROMIUM-SALT.-A green compound may be produced by means of acetate o€ chromium. MAGNEsIUM-SALT.-This was produced by warming the acid with t?n ammoniacal solution of magnesia and washing with water containing a little ammonia and afterwards with pure water.On analysis it appeared to be a mixture of monometallic and dime-Uic salts. ~oTAssIUM-SALT.-~onorneta~~ic.-~pphosphotriamicacid de- composes carbonate of potassium without dissolving. The white almost insoluble salt is readily decomposed by acids. The follow- ing determinations mere made :-I. 0.312 grm. of salt gave 0.356 grm. of potassio-chloride of platinum. 11. 0.329grm. gave 0.3402 grm. of pyrophosphate of mag-nesium. 111. 0.2985 grm. gave 0.3355 grm. of potassio-chloride of platinum. This agrees with the numbers deduced from the formula P,N,H,KB,. Calculated. Found. I. 11. 111. Phosphorus .. 62 29.10 -28.87 -Nitrogen .... 42 19.72 Hydrogen ....6 2.82 Potassium ,.. 39 18.31 Oxygen . . . . . 64 30.05 213 100*00 AMMoNIUM-sALP.-The acid forms a sirnihr sparingly soluble ammonium-compound which cakes together in small white lumps and readily parts with the base when treated with dilute acids in the cold. I. 0-129grm. of salt gave 0.5946 grm. of amrnonio-chloride of platinum. 11. 0.2095 grm gave 0*9805 grm. of ammonio-chloride of platinum. 111. 0%428 grm. eve 0.3995 grm. a€ pyrophosphate of mag-nesium. GLADSTONE ON PTROPHOSPHOTRIAMXC ACID. IV. 0.220 grm. gave 1.014 grm. of ammonioddoride of platinum. This indicates the compound P,N,H6 (N€14)Q4. Calculated. Found. I. 11. 111. IT. Phosphorus .. 62 32-29 32.61 -I-Nitrogen .... 56 29-17 28.90 29-34 -28-90 Hydrogen ....16 5.21 -c -Oxygen ....a . 64 33.33 --192 100*00 MERCuRY-s(BLT.-TetrametalZ~c.-Tt was observed early in the investigation that if pyrophosphotriamic acid be boiled with oxide of mercury the oxide loses its colour and forms a white compound which is insoluble in dilute nitric or hydrochloric acid. This mer- eury-salt may be also prepared by diffusing the acid through a solution of corrosive sublimate but Mr. Holmes seems always to have employed a slightly acid solution of the double chloride of mercury and ammonium. It is a heavy white granular powder which becomes yellowish and eventually dark-coloured when exposed to light. Iodide of potassiuni first turns it scarlet and then dissolves oub the mercury. The following analyses were made :-I.0*4175 grm. of salt gave 0.3405 grm. of dphide of mercury. 11. 0.5405 grm. gave 0-5 grm. of sulphide of mercury. 111. OW6 grm. gave 0*%4 grm. of sulphide of mercury and 0.8305 grm. of ammonio-chloride of platinum. IV. 0.3415 grm. gave 0.277grm. of sulphide of mercuryqand 0*1305grm. of pyrophosphate of magnesium. These numbers require the farmula P,N,H,Hg,B,. Calculated. Found I. 11. 111. IT. Phosphorus . . . 62 10-86 --1Qt67 Nitrogen ...... 42 7.35 -c 7.50 -I Hydrogen. . . . 3 0.53 --Mercury ...... 400 70.05 7'0.31 70.25 69.96 6992 Oxygen.. 64 11.21 --572 i08*00 GIADSTOm OX PraopHoptPEOTRrnC ACID. PLbTrNm-sdLT.-when pyrophosphotriamic acid is treated with a strong aqueous solution of platinic chloride a bulky yellowish compound is fbrmed.This is entirely decomposed wher washed with water in presence of the liberated acid; but it may be safely washed with alcohol and then water has not the same effect upon it. 0*097grm. of the original acid gave 0.207 grm. of this platinum-compound which shows that two equivalents of the metal must have entered into combination displacing no doubt four equivalents of hydrogen; the formula being PONS H,P t”,&. Calcnlated. Found. Platinum.. 63.7 per cent. 54.1 per cent. An attempt to prepare a salt of gold in a similar manner was nnsuccesaf$. The rational formula P,(NH,),HB has been given above for this pyrophosphotriamic acid but the element8 are susceptible of another arrangement which brings them more closely in accord-ance with the formula of pyrophosphoric acid and indicates four equivalents of hydrogen as in a different position to the remain- ing three.Pyrophosphoric acid .. .. P,H443 Pyrophosphotriamic acid .. ’ p,H4(pa)J The following table exhibits at a glance the number of hydro- gen atoms displaced by different metals as far as the salts have been hitherto examined quantitatively :-3 eqs. 4eqe. Ammonium.. ............ I- Potassium .............. Magndum.. ............ Barium ................ Leful.... ................ Copper.. ............... - Iron.. .................. -I- cobslt .....0. ............ Sgver .................. Mercury ................ Platinum.. i.0.0 00 i0 0.

ISSN:0368-1769    

DOI:10.1039/JS8661900001

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年代:1866

数据来源: RSC

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13 TI.-% the Action of Carbodc Oxide on SodiumethyZ. By J. ALFRED WANKLYN. WHENthe compound containing sodium-ethyl and zinc-ethyl which I have described on a former occasion,* is placed in contact with carbonic oxide it becomes black. The darkening takes place slowly at ordinary temperatures but very quickly almost instan- taneously at temperatures approaching 100"C. The black deposit is not carbonaceous for it dissolves in hydro- chloric acid. It is metallic consisting of metallic zinc and most probably also of metallic sodium. Absorption of the gas and formation of an oily product accompany this deposit of metal. The moat convenient way of exhibiting the oil is to wash out with water the vessel in which the experiment has been performed and then to distil the wash-water.The oil distils over with the first portions of the distillate. In one experiment nearly 2grm. of oil were yielded by 1 grm. of sodium employed in the state of sodium-ethyl. The oil waa dried and rectified. The greater portion boiled at about 105"C. and gave the fol-lowing result on analysis :-I. 02076grm. gave *5218CO and 02800grm. H,O. In another experiment a quantity of oil having about the same boiling point waa obtained. 11. *lo29grm. gave *2597grm.CO, and ,1155grm.H,O. The numbers approximate to those required by a compound containing one atom of carbonic oxide and two atoms of ethyl co('gH5) 2' Celcniated. Found. C5 F 60 69-77 I. 68.55 11. 68.83 HI,0 10 16 - 11.63 18.60- 12.31 19@14 12.47 18-70- 86 100*00 100*00 100*00 Am.Ch. Pharm. (1868) cviii. 67. 14 WANKLYN ON THE ACTION OF CARBONIC OXIDE ETC. These details leave no doubt of the reaction which takes place between carbonic oxide afid the compound containing sodium- ethyl. We have :-(1) Disappearance of carbonic oxide. (2)Precipitation of metal. (3) Formation of an oil of pretty constant boiling-point and commensurate in quantity with tte sodium-ethyl taken and ap- proximating sufficiently in composition to CO(C,H,),. h~termore the wash-water from which the oil distilled over was ljtrongly alkaline. The reacliofi may therefore be repre-sented by the equation :-CO -t 2NaC2H5= Na2 + CO(C,H&. An experiment showed that zinc-ethyl alone is not attacked by carbonic oxide.The precipitation of zinc is obviously a secondary action. Sodium on being set free would instantly attack the zinc-ethyl liberating zinc and forming fresh sodium-ethyl. The oil CO(C,H,), is probably identical with yropione (ethyl- prupionyl). I am at present engaged in preparing a quantity suflEicient to admit of purification and of an examination of its physical properties and reactions. Among the latter I propose to study its oxidation products and to inquire whether it is capable of uniting with hydrogen so as to form a pseudo-amylic alcohol. It may be remarked that it is by no means impossible that on adding water to the black mass containing finely divided metal saturated with the oil CO(C,H,) addition of hydrogen may have taken place and indeed both the boiling point of the oil and the analyses point in this direction. Propione boils at 101"C. Amylene-hydrate boils at 108"C. ; whilst our oil boiled at 105OC. The analytical numbers given by the oil are also intermediate between those required bp pro- pione and amylene-hydrate.

ISSN:0368-1769    

DOI:10.1039/JS8661900013

出版商:RSC    

年代:1866

数据来源: RSC

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15 111.-Note on the Constittdion of Cmhk Oxide. By J. ALFRED WANXLIN. THEgeneral result of modern chemical research has been the addition of a new clause to Dalton’s atomic theory. To the dictum c‘ The elements consist of atoms of different weights and the compounds are simple groupings of these atoms,” we make this modern addition An atom of an element is invariably com-bined with the same number of equivalents. The apparent con- tradictions of the law which occur very frequently are explained by self-saturation more or less complete as the case may be. In the compounds of hydrogen with carbon which but a few years ago seemed to defy all attempts at classification we have an admirable example of the working of the law. We find the utmost diversity in the ratio between the hydrogen and the carbon but the state of condensation of each hydrocarbon always falls out so as to admit of the appropriate amount of self-saturation in every case; and indeed organic chemistry as a whole teaches this doctrine of uniform saturation.Inorganic chemistry on the other hand abounds in examples of failure of the law. Proto- and per-salts of the metals (though these are easily ex-plicable) ammonia and hydrochlorate of ammonia the oxides of nitrogen and oxide of carbon are cited against the law. In presence of these instances chemists take very different views. One class of chemists abandon the greater part of the law and insist only upon the declaration that the atoms of one set of elements combine with an even number of equivalents whilst the atoms of the other set of elements combine with an uneven number of equivalents.These chemists are satisdied with very little predication in any given case and yet have not disposed of all of the adverse cases for the oxides of nitqeh do not fail under even this very limited statement of the law. A second class of chemists take refuge in the possibility of there being two orders of chemical combination the me atomic the other mere apposition. In the hands of these chemists the law is in danger of being reduced to a mere figure of speech. A third class abide by the law in its integrity and look forward to an explanation of the inorganic difficulties. 16 WANKLYN ON THE CONSTITUTION OF CARBONIC OXIDE.I have to offer an explanation of the anomaly which appears in the constitution of oxide of carbon. This compound contains only one atom of carbon in its molecule and yet the one atom of carbon is united with only two equivalents of oxygen. It is unrepresented by either a hydrogen or a chlorine or even a sulphur analogue for methylene chloro-methylene aud proto- sulphide of carbon have not yet been obtained though they have often been sought This circumstance points to the oxygen as the source of the irregularity. Let us put 8 for the atomic weight of oxygen and let the atom of oxygen be capable of saturating two atoms of hydrcgen and the difficulty with regard to carbonic oxide vanishes. 0" = 8. Mmh Gas. Carbonic Oxide Carbonic Acid. 0" 10" This being so the usual oxygen-compounds such as water car-bonic acid the common oxides of the metals will contain oxygen in its second state of condensation'.Now there is no reasou for believing that the commonest state of combination of oxygen or any other polyatomic element is of necessity its simplest state. The compounds of carbon have taught us how very common and stable a complex grouping of an element may be; and too little is known about the various states of condensation of carbon to admit of our attaching much weight to the circumstance that compounds containing only 8 of oxygen in the molecule are as yet unrecognised ;and moreover Rose's quadrantoxides appear to offer examples of the occurrence of this simple oxygen-atom in the uncondensed state.How for example is the quadrantoxide of the monatomic metal silver (containing 4 of oxygen to 108 of silver) to be explained if the atomic weight of oxygen be not 81 I will conclude with suggesting a nomenclature and a notation to express the different states of condensation of a given element taking carbon as the example. The carbon of marsh-gas I pro-pose to call (< one-fold carbon,'' or carbon simplex (symbol C). The carbon of alcohol and acetic acid two-fold carbon or carbon duplex (symbol @) ; the carbon of glycerin three-fold DEBUS ON THE CONSTITUTION ETC. carbon,’’ or carbon triplex (symbol @) &c. ; and carbon multiplex is a general expression for all but carbon simplex. The following are examples of this notation (I have taken oxygen simplex 0”=8):-Alcohol ................ GH,O Methylic Ether. ......... C,H@ Tetrylic Alcohol ........ @H,,O Common Ether.. ........ G!‘,H,,O

ISSN:0368-1769    

DOI:10.1039/JS8661900015

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年代:1866

数据来源: RSC

摘要:

DEBUS ON THE CONSTITUTION ETC. W.-On the Constitution of some Carbon-compounds. By HENRYDEBUS,Pb.D F.R.S. Part I. THEsilver-salt of dibromacetic acid decomposes according to Messrs. Perkin and Duppa,* under the influence of heat and forms argentic bromide and bromogl ycollic acid. The silver-corn- pound of the latter produces under similar conditions argentic bromide and an acid the composition of which is supposed to be represented by the formula C,H,O,. These chemical changes may be represented by the following equations :-C2HBr2Ag02 + H20 = C2H3Br0 + AgBr Bromoglycollic acid. and C2H2BrAg03 + H20 = C2H,04t + AgBr. The conversion of dibromosuccinic acid into tartaric or racemic acid takes place by similar reactions. It appears that Messra.Perkin and Duppa adopted the formula C,H,04 for their new acid without experimental verifica- tion because in many instances organic bodies exchange one atom of chlorine or bromine for the elements HO. I am not aware indeed that the acid or any of its salts have been analysed. It is however well-known that organic bodiesmay also lose their chlorine * Chem. Soc. Qu. J. xii. 5. -f The acid CPH404 may be regarded as standing to the hypothetical glycerin CjHaO& in the same relation as gljceric acid does to common glycerin. VOL. XIX. C DEBUS ON THE CONSTITUTION or bromine according to other modes than the one indicated by the above equations. Ethylenic chloride boiled with an alcoholic solution of potash loses the elements HC1; dibromopyrotartaric acid yields with caustic soda aconic acid sodic bromide and water ; and a simiIar mode of decomposition is exhibited by the bromine- c3mpound of milk-sugar by dichlorhydrin and trichlorhydrin.The silver-salt of bromoglycollic acid might undergo a similar change and furnish the acid C2:,IE203and argentic bromide. The formula C,H203 belongs to glyoxylic acid formed by the action of nitric acid on coamon alcohol. I proposed to myself the following questions :-(1) Which of the two formulz C,H,O and C,H,O belongs to the acid obtained by Messrs. Perkiii and Duppa from dibrom-acetic acid. (2) In case the composition of this acid is represented by C,H,O, is it identical or isomeric with glyoxylic acid ? These questions appeared to me to possess considerable theo- retical interest in consequence of considerations which *ill be described in this paper.I have to thank my friend Mr. Dup pa for the dibromacetic acid employed in the following experiments :-A quantity of dibromacetic acid which boiled at about 225" C. was diluted with water neutralised with calcic carbonate at ordinary temperatures and the lime-salt was precipitated with argentic nitrate. The white crystalline precipitate after previous wabhing with cold water was boiled for some minutes with water. It decomposed easily into argentic bromide and an acid which remained dissolved in the liquid. The argentic bromide was separated by means of a filter and the filtrate neutralised with argentic oxide. The silver-compound thus obtained decomposed at the temperature of boiling water producirig as in the former case argentic bromide and a soluble acid.The clear acid liquid dissolved marble with effervescence and gave after neutralisation and suitable concentration a crop of small prismatic crystals. The latter were placed in hot water in such quantities that a saturated solution was formed and on allowing this aolution to cool the crystals were again obtained in a pure state. These crystals were carefully compared with glyoxylate of lime (prepared from alcohol) and found to agree perfectly with the latter in form solubility and reactions. Their aqueous solution gave a white precipitate with lime-water which precipitate dis- OP SOME CARBON-COMPOUNDS. solved in acetic acid immediately after its formation but lost its solubility in that acid after it had been kept for some time Or after exposure to a temperature of 100"C.The precipitate pro-duced by lime-water in calcic glyoxylate decomposes at 100"into oxalate and calcic glycollate. Zinc acetate and plumbic acetate gave white crystalline precipitates but plumbic nitrate and argentic nitrate failed to produce any change in the aqueous solution. Every reaction was made twice once with the salt from dibromacetic acid and the second time with calcic glyoxylate from alcohol and in each instance both salts behaved exactly in the same manner. The experiments made to determine the solubility of the sub-stance in water gave the following results :-(a) 7.371 grms.soiutim of the salt made from dibromacetic acid gave after evaporation at 100" C 0.053grm. solid residue. (b) 4.97 grms. solution of the lime-salt made from alcohol gave after evaporation at 100" C. 0.0355 grm. residue. The solutions had been prepared at the same time and under precisely the same conditions at a temperature of 18" C. 100 parts of water dissolve therefore of substance (u) 0.719 grm. of substance (b) 0.714 grm. According to these results I believe I am justified in assuming that the acid prepared from dibromacetic acid is identical with glyoxylic acid prepared by the oxidation of common alcohol. The formula of the latter is C211203,and therefore the decompo- sition of the silver-salt of bromo-glycollic acid may be represented thus :-C2H,AgBr03 = C,H,O + AgBr.Qlyoxylicacid. If we consider the compounds which are derived from ethylic bydride by the gradual addition of oxygen to the latter our attention is in the first instance arrested by the fact that each mode of reaction takes place twice. If ethylic hydride is represented by the formula and if I% denotes one atom of hydrogen and one of oxygen both c2 DEBUS ON THE CONSTITUTION of the same chemical value which attaches to them in the ordinary water-type where they are written separately by the side of the radical which stands for a second atom of hydrogen and so com-pletes the molecule then the oxygen-compounds in question may be represented by the following series :-Alcohol Aldehyde = C2{ggH Acetic acid = C2{ z:H Glycollic acid = C2{ Glyoxylic acid I C {gg Oxalic acid = C2{gg The changes of the group C are therefore the following : G (I).Addition of one atom of oxygen; (2). Loss of two atoms of hydrogen; (3). Combination with one atom of oxygen the pro- ducts of the reactions being alcohol aldehyde and acetic acid. The repetition of these processes produces glycollic acid glpoxylic acid and oxalic acid. Instead of allowing these changes to take place in succession we may consider them to take place simiiltaneously; we may add at once two atoms of oxygen to ethylic hydride; and instead of subtracting twice each time two atoms of hydrogen we may at once remove four atoms of this element and finally add two atoms of oxygen to the residue.In this manner we arrive at the following compounds :-HHH Ethylic hydride = C2{ HHH Glycol Glyoxal Oxalic acid = C2{0gc OF SOME CARBON-COMPOUNDS. and herewith the list of the oxygen derivatives of ethylk hydride is complete. It is worthy of notice that the successive steps from ethylic hydride to oxalic acid as represented in the foregoing tables show that the six atoms of hydrogen in the ethplic hydride arrange themselves in two groups each group containing three atoms of the element and undergoing the same transformations. The introduction of oxygen and the removal of hydrogen fo1lows a certain rule which must be dependent on the constitution of ethylic hydride and the nature of oxygen The most simple view of the constitution of ethylic hydride in accordance with the above facts follows from the following considerations.Modern chemistry assumes that chemical reactions take place between molecules ; the determination of the molecular weight of bodies is therefore one of the most important problems of the science. The molecular weight of marsh gas is represented by the formula CH,. Instead as is commonly done of contemplating compound bodies as originating by union of their atoms we adopt the opposite method and consider them to be derived from a series of molecules. A molecule may be looked upon as a system of atoms governed by certain forces which system must be in a state of equilibrium if no external influences produce a disturbing effect.If such a molecule is approached by a second molecule one of the following effects may take place. Either the two molecules simply unite and form one new molecule or as a consequence of action and reaction two or morenew molecules result Examples of the first kind are the formation of chloride of ammonium from hydro-chloric acid and ammonia the double salt of bichloride of platinum aud chloride of potassium the combinations of water waith many salts and other similar cases. The second mode of action may be exemplified by the formation of acetamide and hydrochloric acid from chloride of acetyl and ammonia. If we imagine one atom of hydrogen to be removed from the molecule of marsh-gas it appears as a natural consequence that the equilibrium between the atoms of the molecule must be destroyed and that a resultant of given magnitude and direction must originate.The same process may be conceived with a second molecule of marsh-gas and a similar resultant must be obtained. If now the tworesidues of marsh-gas are placed together so that these two equal re- sultants counteract each other a stable molecule must be obtaiued. This is commonly expressed by saying that u1 atom DEBUS ON THE CONSTITUTION of methyl has replaced an atom of hydrogen in marsh-gas and that this atom of methyl plays the part of an atom of hydrogen. Ethylic hydride would according to the above considerations be composed of the two residues CH and CH of marsh-gas; it would be identical with methyl. Schorlemmer has prepared ethglic chloride from methyl and thus the above view appears to be confirmed.CH,.CH + C1 = CH,.CH,CI + HC1. Ethylic chloride. The compound molecule ethylic hydride (or methyl) which con- sists of the two residues CH and CH can evidently not remain in equilibrium if from one or the other residue an atom of hydrogen is withdrawn just as some forces which are around a given point in equilibrium cannot remain SO if we snppose one of the forces to be removed. If however of these forces two are equal and act in opposite directions both may be removed from the point without; disturbing the equilibrium of the remaining forces. In a similar manner a stable molecule may be derived from ethylic hydride if each of the residues of which it is composed loses one atom of hydrogen.Thus we obtain CH,.CH, or ethylene. The two chemical units which have thus been removed from ethylic hydride in order to obtain ethylene may be added again and therefore we say that ethylene is diatomic. It is not necessary that these two units shoulcl be hydrogen they may be chlorine or bromine forming chloride or bromide of ethylene. CH,.CH + C1 = CH,Cl.CH,Cl. Chloride of ethylene. CH2.CH2 + Br = CH,Br.CH,Br. Bromide of ethylene. Each of the two marsh-gas residues present in ethylene may lose an atom of hydrogen and thus the stable molecule of acetylene results which because four units may be added to it is tetratomic. OF SOXE CARBON-COMPOUNDS. CH,.CH CH.CH Ethylene.Acetylene. CH.CH + Cl = CHCl,.CHCI Acetylene. Chloride of acetylene. The view on which the foregoing considerations are based leads to the conclusion that CH and CH in ethylic hydride CH and CH in ethylene and CH and CH in acetylene are the proximate constituents of the molecules of these bodies. It is apparent that when oxygen is introduced into the molecule of ethylic hydride the hydrogen ought to comport itself as if it were arranged in two groups each consisting of three atoms and each change produced in the molecule ought to take place twice. Three couples ot' bodies are thus produced the members of each couple possessing similar chemical properties. Alcohol CH,.CH,H ; CH,B.COB Glycollic acid Aldehyde CH,.COH ; COH.COH Glyoxylic acid Acetic acid CH,.CO&; C0H.COH Oxalic acid Perkin and Kekul6 have called attention to the alcoholic pro-perties of glycollic acid.I have shown that glyoxylic acid possesses the characteristic properties of an aldehyde and the relation of oxalic to acetic acid is self-evident from the above table. The properties of alcohol aldehyde and acetic acid are dependent on the change which the group Ca3 has undergone; it shows alco- holic properties when it has become CH,$€,-the properties of aldehyde in the state of' COH,-and of acid when it has been transformed into COH; and becanse the gronp CH occurs twice in ethylic hydride therefore two bodies with alcoliolic properties two aldehydes and two acids may be derived from it. If the changes which the two groups CH, CH may undergo in succession in ethylic hytlride take place simultaneously in both residues the following bodies result :-Ethglic hydride ..............CH,.CH Glycol.. .................... CH,.HCH,A Glyoxal .................... COH.COII Oxalic acid.. ................ COH.COB In the former cases the derivatives of the two groups CH, CH 24? DEBUS ON THE) CONSTITUTION were in each substance not the same; in glycollic acid CH,A.COf€; for example one of the residues COH contributes the acid and the other CH,H the alcoholic properties; whereas in the cases mentioned in the last table the derivatives of the two residues CH, CH are in exactly the same condition and therefore we have so to say a double alcohol a double aldehyde and a double acid viz.glycol glyoxal and oxalic acid. From considerations of a similar nature to those hitherto employed it is easy to foresee the probable existence of tbe body CH,lX.COH a substance which would possess the composition of acetic acid but the properties of alcohol and aldehyde and would stand to glycollic acid in the same relation as common alde- hyde to acetic acid. From the point of view here adopted it is also easy to recog- nise why cyanide of methyl and the nitrile of acetic acid must be identical. CH,CH Ethylic hydride. CH,COH Acetic acid CH,.CN Nitrile of acetic acid-cyanide of methyl. With regard to the bodies which may be looked upon as deriva- tives of ethylic hydride and chlorine it is at once seen that there must be at least two isomeric series of chlorinated bodies.Hy-drogen may be replaced in CH, CH atom after atom first in one group CH, and then in the other. Or the substitutions may proceed in both groups at once. The following table represents the two modes of substitution :-Ethylic chloride CH,.CH,Cl 1 CH,.CH,Cl Ethylic chloride CH,.CHCl 2 CH,Cl.CH,Cl Chloride of ethylene CH,.CCl 3 CH,Cl.CHCl CH,Cl.CCl 4 CHC1,.CHCI2 CHCl,.CCl 5 CHCl,.CCl CCld.CC1 6 CCl,.CCl Theory asserts that if all the hydrogen atoms in CH . CH are of the same chemical value the formulz C,H,Cl C,HCI, and C,CI represent only one compound while the formulze C2H,C1, C2H,C1, and C,H2C1, on the other hand represent each two compounds C,HCI, prepared by the action of chlorine on chloride of ethyl seems indeed to be identical with the body OF SOME CARBON-CaMPOUNDS.C2HCl from chloride of ethylene. The chlorinated chloride of ethylene boils at 154",and has a specific gravity of 1.662;the isomeric body from chloride of ethyl was not obtained quite pure and in this impure state was found to boil at 146' and to have the specific gravity 1.644. And inasmuch as they appear to com- port themselves in the same manner with alcoholic potash-solu- tion I think these bodies may be considered to be identical. Hubner* asserts the existence of three bodies of the formula C2H,C1,. Two are the well-known derivatives of chloride of ethyl and chloride of et,hylene and the third was obtained by him from pentachloride of phosphorus and chloride of acetyl.The exist- ence of this third chloride of the formula C,H,Cl is however very doubtful because Hiibner obtained by accident only one drop of it which appeared to boil at 60° and just served for one chlorine determination. Such evidence does not appear to me to be sufficient for the admission of new bodies into the scientific system. The constitution which has been adopted for ethylic hydride and its derivatives in these pages is also confirmed by the syuthesis of acetic acid from cyanide of methyl or from potassium-methyl and carbonic acid. The same theory explains also why the products of the decomposition of chloride of ethylene by caustic potash are identical with those obtained by the action of caustic potash on chloride of ethglidene.The chloride of ethylene may be repre- sented by CH,Cl.CH,Cl the chloride of ethylidene by CH,.CHCI,. The results of their decomposition by caustic potash are water chloride of potassium and chloride of vinyl C,H,Cl. The latter therefore originates by the subtraction of HCl from the organic chlorides. But whether we take HC1 from CH,Cl.CH,Cl or from CH,.CHC12 the result must in both cases be the same viz. CH,.CHCl. We assume that if an organic body loses chemical units such units cannot be taken out of the same carbon group which forms one of the proximate constituents of the body but are supplied by different carbon groups of which the body happens to be composed. If for example ethylic hydride by the removal of two atoms of hydrogen is to be converted into ethylene or the latter into acety- lene each of the residues CH in CH,.CH must lose 1 at. of hydrogen. Thus CH,. CH would become CH,. CH, or CH. CH * Ann. Ch.Pharm. CXE. 330. DEBUS ON THE CONSTITUTION respectively and not CHCH, or C,C!H,. This view is supported by the fact that hitherto the attempts to prepare methylene CH have been unsuccessful and that bodies of the molecular weights CH and CH, are unknown. It also appears worthy of notice that the glycol of the methylic and the glycerin of the ethylic series are still unknown. The experiments of Butlerow and of Simpson,* undertaken with the desire to obtain these bodies are known to chemists. If the glycol of the methyl series existed its formula would be "E:} O, or CH,BA.As soon as we attempt to replace the iodine in CH,T, by && water is eliminated and dimethylenic oxide C,H40 is pro-duced. It would therefore appear as if the group H could not exist twice in combination with 1at. of carbon. If this is the case the failure of the experiments to obtain the glycerin of the ethyl-series is explained. Ethylic hydride contains only two atoms of carbon and therefore the group H can only be introduced twice into the place of hydrogen. Propylic hydride contains 3 atoms of carbon and accordingly in glycerin which may be considered as a derivative of propylic hydride we have 3G ; and as a further confirmation we find the first tetratomic alcohol to contain four atoms of carbon.The following table contains the formuls of the alcohols derived from some of the hydrocarbon-compounds of the series CnH2ni-2 :-Methylic seGes. Ethylic series. Propylic series. Butylic series CH,H C,H,H C,H,H C,H,H C,H4HA C,H,Afi C4H,HB C,H,Hga C,H f-If-Ia We perceive by this table that in no compound does the number of the groups $I exceed those of the carbon-atoms. I believe this rule holds good in all native compounds. Not long ago Cariust described as propyl-pliycite a body which had been prepared from epichlorhydrin and to which he gives the formula c3H4}04. This body would form an excep-*4 * Jahreabericht 1857 461. Ann. Ch. Pharm.cvii. 110 ;cxi. 242 ; cxiv. 204 j cxv 322. .t. Ann. Ch. Pharm. cxxxiv 71 OF SOME CARBON-COMPOUNDS.tion to what appears in the above and many other examples aa a rule. The propyl-phycite is however described M an amorphous Viscous mass and the same properties belong to its derivatives. Even if it were possible to obtain such bodies in a suficiently pure state for analysis it might still be doubted whether the for- mula C3H4] 0 was the correct representation of the composition H* of the propyl-phycite because it may have been in the state in which it was analysed a hydrate. Pseudopropylic alcohol forms hydrates with a definite boiling point. Carius has however prepared by the action of sodium-alcoho-late on dichlorbromhydrin two bodies which he considers to be the ethers of the propyl-phycite H 0 and c3H4 10,.From (C2H5)3 c3*4] (C2H5)4 these bodies we cannot deduce the formula of the corresponding alcohol. Williamson and Kay* obtained from chloroform and sodium- alcoholate a substance which may be regarded as the ether of cH”’}03, methyl- glycerin (C2H5.X and Mr. Rassettt has prepared from chloropicrin oythocarbonate of ethyl ci’)04. The (C2H5)4 corresponding hydrogen-compounds however cannot be obtained from these ethers. Another circumstance deserves attention. Carius could not replace more than two hydrogen-atoms in propyl-phycite by acid radicals. The treatment of dichlorbromhydrin C3H,.fi.C12Br with sodic acetate and acetic acid failed to produce the ether ‘SH4 }04 but gave instead a number of substances which (C2H30)4 must be regarded as the result of a very complicated reaction.From the above it will be seen that our knowledge of the propyl- phycite is still very incomplete and that its formula has not been established on a satisfactory basis. If we consider it as a hydrate of the formula c3H3} 03,H20 the rule which obtains H3 with regard to other artificial and natural alcohols would also apply to the propyl-phycite. The rule which asserts that the atomicity with regard to the Ann. Ch. Pharm. xcii. 346 .i. Chem SOC.J. (2) ii. 198. DEBUS ON THE CONSTITUTION group aof a carbon-compound cannot be greater than the number of carbon-atoms present holds good also for the acids. The methyl-series contains only monoatomic acids for the body COna is unknown. The ethyl-series contains diatomic but no undoubted triatomic acid ; whereas in the propyl-series glyceric acid is certainly triatomic &c.&c. The view adopted in the present paper assumes that all the hydrocarbons of the general formula CnH2n+2consist of as many residues of marsh-gas molecules as there are carbon-atoms in the compound or in other words contain these residues as their proximate constituents. The alcohols aldehydes and acids of these carbon and hydrogen compounds are produced by the substitution of oxygen or 8,or of oxygen and $€ for hydrogen. If we compare the formuh of formic acid acetic acid and oxalic acid Formic acid ............ H.COfi Acetic acid .............. CH,.COfi Oxalic acid .............. CO$€.COB it appears that the basicity of an acid is equal to the number of times the group COB occurs in it.I think this rule applies to all organic acids derived from the hydrocarbons C,H,+,. Thus propionic acid CH,.CH,COH is monobasic ; malonic acid COQ. CH,COB bibasic ;mesoxalic acid COI'I.CO.COfi bibasic ;tartaric acid COH.CHH.CHH.COQ bihasic and tetratomic. The group COH is derived from CH, and therefore a tribasic acid must be derived from a hydrocarbon-compound in which the group CH occurs three times. Propylic hydride is CH,.CH,.CH, and there- fore no tribasic acid can occur in the propylic series. Citric acid is a tribasic acid and its corresponding hydrocarbon is represented by the formula CsHl,. This hydrocarbon could be derived from six molecules of marsh-gas.The first five molecules would produce CH,.CH,.CH,.CH,.CH,. In order to obtain 3CH3 in C6H14,the sixth molecule CH must attach itself not to one of the two CH, but to one of the residues represented by CH,. Thus because the residue and the marsh-gas molecule must each lose one atom of hydrogen we obtain CH,.CH,.CH,.CH CH3 (CH,--and by substitution OF SOME OARBON-COMPOUNDS. 29 COBCH,.CH,.CA { ggg citric acid. Black oxide of manganese oxidises the three groups COB and the residue CH,.CH,.CH takes up one atom of H and forms acetone. Tribasic acids which may be considered as derived from one of the hydrocarbons CnH,,, must contain the residue CH or C amongst their proximate constituents. The rational formula of propylic hydride is CH,.CH,.CH,.or CH,.CH c-v-J If in each of the residues 1at. of hydrogen is replaced CH CH,Cy .CH,Cy by cyanogen we obtain-; and replacing the ni-CHCy trogen of the cyanogen by On we have COB,CH,CH,COft CH,CO$ = carballylic acid .* The corresponding hydrocarbon of carballylic acid would be CH,.CH,.CH.CH,.CH,.CH, or accord-ing to one of the more common expressions The atomicity of an acid or an alcohol depends on the number of times the group ft is contained in it. Tartaric acid contains 6 atoms of oxygen 6 atoms of hydrogen and 4 of carbon which elements according to the chemical properties of tartaric acid must be arranged in the following manner C0fi.CHfi.CHfr. COH; and in an analogous manner succinic acid = CO&.CH,.CH,.COH and malic acid = COH.CH$f.CH,.COfi. Succinic acid may be prepared from butyric acid the latter from butylic alcohol and butylic alcohol from butylic hydride. Thus we have the following series :-CH,.CH,.CH,.CH Butylic hydride CH,.CH,,CH,.CH,a Butylic alcohol CH,.CH,.CH,,COH Butyric acid CH,&CH,,CH,.COB CO&CH,,CH,.COH Succinic acid COH.CH.H.CH,.CO~~ Malic acid CORCHXI.CH.~~~.COQ Tartaric acid * Simpson. Proceedingsof the Roy. SOC.xii. 236. MATTHIESSEN ON THE EXPANSION OF WATER. The manner in which the proximate constituents of butylic hydride become changed in consequence of the gradual introduc- tion of oxygen into its molecule is clearly perceptible in the above table. The question very naturally arises can the second atom of hydrogen in the residues ,..CHQ.CHn .. .be replaced by H and the bodies COH.Cfifi.Cfifi.COf€ = C,H60 and COft.C8€& CHQ.COfi = C,H,O be obtained? According to our present experience it appears that this cannot be done. Tartaric acid is hardly attacked by chlorine and nitric acid removes one of the groups CHH altogether and produces tartronic acid COH.CH$€.COH= C3H40,. Also tartronic acid is not succeeded by an acid wherein two atoms of oxygen have joined the group CH,. The composition of such an acid would be = C0fi.CHH.COfi = C,H40B. The ammonia-salt of mesoxalic acid is = C,(NH,),O,. The relations of this acid to various members of the uric acid series also tend to establish the formula C3H,0S. Therefore we pass from tartronic acid to mesoxalic acid by the addition of 1 at.0. to the group CHH and the sub-traction of H,O. COIJ[.CHIJ[.COIJ[ Tartronic acid coH.co.co~ Mesoxalic acid The latter may be converted into tartronic acid by means of sodium-amalgam. The properties of the group CH, as exhibited in the above examples occur again in many other cases.

ISSN:0368-1769    

DOI:10.1039/JS8661900017

出版商:RSC    

年代:1866

数据来源: RSC

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MATTHIESSEN ON THE EXPANSION OF WATER. V.-On the Expansion of Water. [Abstract from a paper read before the Royal Society December 21,1865.1 ON re-determining the co-efficient9 of expansion of water they were found not to agree with Kopp’s and as his are results gene- rally used by chemists it may not be here out of place to give the new values. MATTHIESSEN ON TEE EXPANSION OF WATER. It was found that the expansion of water betweeu 4' and 100" the formula by32Oand 4'may conveniently be expressed between Vt = 1 -0'0000025300 (t -4) + 0*0000083890 (t -4)2 -0~000000011~3 (t -4)'s and between 32O and 100' by Vt = 0'999695 + 0.00000547248 -0~000000011260~~ The values calculated from these formulae for the volume OCCU-pied by water at different temperatures are given in Table I.from degree to degree together with the differences for each degree. TABLEI. -~~ ~ Volume Differ-To Volume Differ-Volume Differ-of water me per To. of water :nee per ,-,.' of waterTO. at To. 1". 13 me per 1". C. C. at To. at 'La. I-1.000355 69 1*022050 4 1~000000 -000006 37 1*006616 363 70 1-022648 -000598 5 1-000006 6 1~000028 22 38 1.006979 372 71 1.023252 604 7 1-000066 38 39 1*007351 379 72 1.023861 609 531 40 1*007730 388 73 1-024477 616 8 1'000119 9 1.000188 69' 41 1 008118 396 74 1*025099 622 10 1'000271 83 42 1*008514 404 75 1,025727 628 634 43 1*008918 413 76 1-026361 11 I -000369 110' 44 1,009331 420' 77 1*027000 639 12 1.000479 13 1-000604 12.5 45 1-009751 428 78 1*027646 646 14 1.000742 138 46 1.010179 1351 79 1-028296 650 657 15 1*000892 1501 47 1.010614 445 ao 1-028953 662 16 1.001054 1621 48 1:011{*59 4511 81 1*029615 668 17 1.001227 1731 49 1 *011510 459 a2 1.030283 673 18 1*001412 1858 50 1.011969 466 83 1.030956 19 1'001608 1961 51 1-012435 474 84 1,031634 6 78 20 1.001814 206 52 1.012909 482 85 1-032318 684 689 21 1*002029 215 53 1-013391 488 86 1*033007 694 22 1 002254 225 54 1-013879 4971 87 1-033701 699 23 1*002488 234 55 1*014376 503' a8 1*034400 704 24 1-002731 2431 56 1*014879 5111 89 1-035104 709 25 1.002982 2511 57 1-015390 5171 90 1.035813 714 26 1-003241 259 53 1-015907 525 91 1.036527 718 27 1-003507 2661 59 1 -016432 532' 92 1.037245 724 28 1.003780 273 60 1-016964 538 93 1 037969 728 29 1,004059 279' 61 1*017502 516 94 1.0386C7 30 1 -004345 286 62 1 -018047 552 95 1-039429 732 737 31 1-004635 290 63 1*018599 559 96 1.040166 32 1 004931 296 64 1.019158 566 97 1-040907 741 746 33 1-005249 318 65 1.019724 572 98 1-041653 34 1-0055'78 329 66 1.020296 578 99 1*042404 751 35 1.0059 I6 338 67 1-020874 585 100 1*043159 756 36 1-006261 345 68 1-021459 591 MATTHIESBEN ON THE EXPANSION OF WATER.The values obtained by different observers for the volumeR occupied by water at different temperatures the volume at 4O being taken equal to 1 are given in Table 11. TABLE11. Hagen.$ Matthiessen. T. Kopp.* Despretz.1. Pierre.$ --8 1 ~000000 1 ~000000 1 *oooooo 1 ~000000 1~000000 10 1 *000247 1.000268 1-000271 1 -000269 1-000271 15 20 30 1 -000818 1.001690 1 -004187 1 *000875 1.001790 1 *004330 1.000850 1 *001717 1.004195 1 *000849 1.001721 1 -004250 1 000892 1-001814 1:004345 40 50 60 1.007654 1.011890 1.016715 1,007730 1.012050 1 *016980 1 *007636 1.011939 1 *017243 1 *00’77ll 1 -011994 I*017001 1 ‘007730 1 *011969 1 -016964 70 1-022371 1 -022550 1 -023064 1 -022675 1-022648 80 90 100 1.028707 1,035524 1.043114 1 -028850 1 -035660 1.043150 1 029486 1.036121 1.043777 1.028932 1 *035715 1*042969 1 -028953 1*035813 1 -043169 It wilI be seen from the foregoing table that Kopp’s values are lower than the others; and bearing in mind that the co-efficient of expansion of mercury namely 0.000178,when deduced by means of these falls below that obtained by Regnault namely 0*0001815,but when deduced from my own namely 0*0001812 agrees closely with Regnault’s we are led toconclude that Kopp’s values must be somewhat incorrect.* Pogg. Ann. xcii. 42. .t. Ann. Ch. Phys. lxx 1. $ Ann. Ch. Phye. [3] xiii 325. Calculated by Frankenhoim Pogg. Ann. xcvi. 461. 0 Abhandlungen d. k. Acad. der Wissensch. zu Berlin 1866.

ISSN:0368-1769    

DOI:10.1039/JS8661900030

出版商:RSC    

年代:1866

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33 VI.-Contributions to our Knowledge of the Chemical Action of Sunlight upon Sensitive Photographic Papers. By CHARLESR. WRIGHT, B.Sc. (Student in the Laboratory of Owens College Manchester) In a paper published in the journal of the Chemical Society (Series 11. vol. iii. p. 183) by Mr. A. McDougall a method of measuring the relative sensitiveness to light of photographic papers is described and the results detailed of a series of measure-ments giving the relative sensitiveness of papers salted with solu- tions of different strengths of sodium- chloride potassium-chloride ammonium-chloride and potassium-bromide and afterwards floated upon a strong silver-nitrate bath of constant composition. From these experiments it appears that the sensitiveness of a pho-tographic paper depends solely on the quantity of the halogen contained in the sa2ting solution and that it is not influenced by the metal with which the halogen is combined; for if the results of his experiments on papers salted in solutions of chlorides of varring strengths be graphically represented with percentages of chlorine as ordinates and relative sensitivenesses as abscissze the three curves obtained with solutions of sodium- potassium- and ammonium- chlorides will be found to coincide within the limits of experimental error.This conclusion is also borne out by the fact that papers prepared with solutions of potassium- sodium- ammonium- and bmiurn-chlorides in such a manner that equal quantities of chlorine were contained in each were all found to possess an equal degree of sensitiveness whilst the same was also found to be true for the corresponding bromides.It next becomes of interest to examine the relative sensitive- nesses of papers salted with different halogens; to compare for instance the sensitiveness of a paper salted with a solution con- taining 1per cent. of potassium-chloride with that of one salted with a solution containing an equivalent quantity of bromine or with one in which half the chlorine is replaced by its equivalent of bromine or iodine. The following investigation was undertaken VOL. XIX. D 34 WBIQHT ON THE CHEMIOAL ACTION OF SUNLIGHT at Dr. Roscoe’s suggestion for the purpose of examining these questions. The method described in the above-mentioned paper may be shortly explained thus Let us suppose that papers A B C &c.whose relative sensitivenesses are to be determined are exposed in the disc-photometer for known relative times t, t, t, &c. the points identical in shade with A B C &c. after exposure being read off on a pendulum-strip of standard paper (or on a fixed calibrated strip) ; let the readings be a b c &c. be millimetres and let the times corresponding to these readings (that is the relative times that standard paper would take to assume the tints gained by the papers A B C &c.) be called T, T2 T, &c. Hence the ratio of the time taken by paper A to assume its particular tint to that required by standard paper to assume the same tint is t T or 1 ?! ;and similarly the ratio of the time taken by paper B to t1 assume its peculiar tint to that required by standard paper to assume this same tint is 1 t-; T and so on for the others-that is, t!2 T the sensitiveness of A compared with standard paper is 2,and t that of B compared with standard paper is hence if the t,’ T2 4 similarly sensitiveness of A be taken as unity that of B is -; t!2*I the sensitiveness of C and the others with respect to A are obtained.It hence follows that when pieces of the same paper are exposed at once in the disc-photometer for the times respectively T T T, t, tz t, . . .. and read off as before the fractions 2 -2 -. 6 tl t2’ t, must be equal as each fraction represents the sensitiveness of the paper experimented on with respect to standard paper.It was however found on exposing papers prepared with different halogens in the photometer that the values thus obtained were by no means constant when the value of the t’s varied whilst if the values of the t’s remained the same constant values were obtained. Thus for instance when chlor-iodide and chloro-brom-iodide papers were exposed together the ratio of the t’s being 1.00 to 0.40; the following agreeing values were obtained for the sensi- tiveness of the latter paper as compared with that of the former. UPON SENBITIYE PHOTOGPAPHIC PBPEM. EXP.1.-2*16 EXP.5.2'32 EXP. 9.-2.46 2.-2*17 , 6.-2.36 , 10.-2.53 , 3.-2.29 , 7.-2.38 , 11.-2*62 , 4.-2.31 , 8.-2.40 Mean 2.36.When however the ratio of the fs was 1.00to 0.63 the mean of five similarly agreeing determinations gave the value 1*65. It hence follows that for one or other of these two papers (or per- haps for both) the values of the fractions -T,J 5 5. . . . are not 4 ta' t3 constant which may be expressed by saying that the value of -Tn tn is for this paper not constant. Similarly on comparing bromide and brom-iodide papers the mean of twenty experiments gave the following numbers :-Ratio of sensitivenew of brom-iodide paper Ratio of the t's. to that of bromide. 1.00 to 2.552 0.297 to 1.00 , 1.867 0.393 ,j , 1.678 0.411 , , 0.720 0.706 ,) , 0.704 0-792 , Before pursuing this point any further it became necessary to ascertain (1)that the disc-photometer fulfils its functions and (2) that the phenomena of photochemical induction do not interfere with %he accuracy of' the results.(1.) In order to test the correct working of the photometer papers salted with potassium-chlor-iodide chloro-brom-iodide and chloro-bromide respectively were insolated (a) in the disc photometer and (6) by direct exposure for as nearly as possible the same relative times in both cases. The following numbers were obtained as the relative sensitiveness of these three papers as the mean of twelve experiments :-Disc photometer. Direct exposure. Chlor-iodide . . . . 1.00 1-00 Chloro-brom-iodide 2.30 2.32 Chloro-bromide . . 3.09 2.99 D2 36 WBIQHT ON THE CHEMICAL ACITION OF ElUNLIGHT Also papers soaked in solutions of sodium-chloride containing respectively 0.5 1-0 2.0 and 4.0 per cent.of that salt were similarly insolated giving the following numbers as the mean of eleven experiments :-Disc photometer. Direct exposure. 0.5 per cent. 0.781 0.821 1-0 , 1*000 1*ooo 2.0 1.787 1 788 jj 4.0 , 3,018 2.986 Further normal paper (that soaked in a 3 per cent. sodium- chloride solution) was insolated in the photometer and the values TT ofthe fractions 4' t &c. were found to be sensibly uniform whether the insolation were performed in bright siinlight or diffused daylight ; precisely similar results were obtained with 4 per cent. potassium-chloride paper. (2.)For the purpose of testing the influence of photochemical induction papers salted in potassium-chloride bromide and brom- iodide solutions were severally exposed to the action of direct sun- light for a known time; and at the same time portions of the same papers were exposed under a small disc (of which one-sixth of the area was cut away in the form of sectors) for six times that interval so that in the two cases the absolute time of exposure was identical but in the latter case the exposure was interrupted hy a succession of dark phases; hence the effect of photochemical induction if appreciable would be rendered manifest by the greater darkening of the paper in the second case.On rending off the various insolated papers on a pendulum-strip the following ratios were obtained for the tints assumed .-Chloride paper.Mean of 8 experiments. By direct exposure.. ...... 0.991 By disc photometer ...... 1.000 Bromide paper. Mean of 8 experiments. By direct exposure.. ...... 0.989 By disc photometer ...... 1-000 Brom-iodide paper. Mean of 6 experiments. By direct exposure.. ..... 0.917 By disc photometer ...... 1*000 UPON LYENSITIVE PHOTOQRAPHIC PAPEBI. The differences here observed are not greater in amount than can easily be accounted for by the action of the stray day-which must inevitably get under the small revolving disc; in mn-firmation of this it was observed that brom-iodide pap with which the greatest difference was thus obtained was considembiy blackened by exposure to light of so feeble an intensity & to have no appreciable action on either the corresponding chloride ~f bm mide paper.It is hence manifest that the differences in the relative mm-tivenesses of papers observed above are neither due to chemical induction nor to any abnormal action in tbe &m photometer and it therefore appears that they must hare bees caused by the differences in the ratios of the t’s; and hence we must conclude that papers prepared with different halogm do rrof all darken at the same relative rates. This conclusion may be ex-pressed as follows :-If standard paper be exposed to a constant source of light it assumes a definite series of tints in the relative times 1 2 3,4 . . . . ; if however bromide paper be expoaed W this same source of light the relative times in which it 8138uuIQ# the same series of tints are not 1 2 3 4 ... ,but arein-aQIPd other proportion; and the same is (probably) true for all paw prepared with other halogens. Before proceeding to determine what this proportion is for d paper it becomes necessary to examine whether this proportioic,$r the same for a paper salted with a strong solution of any he as for one salted with a weak solution of the same halogen. Fo? this purpose papers salted in a 10 per cent. sodium-chloride wb tion were exposed in the disc-photometer and read off on a 6 brated strip hence the ratios of the t’s are known from tb positions of the papers in the photometer whilst the ratios of h T’s are obtained from the calibration table of the strip. !& following numbers were obtained as the mean of four agr-determinations :-(The column headed t represents the t’s all reduced to tb greatest of them as unity; that headed T denotes the %?8 similarly reduced ; the column headed R represents the r~th crf the numbers in the t column to the corresponding ones in the T column; while that headed Diff.denotes the + or -dig-of these ratios from their mean.) WRIGIFIT ON TEE CHBMXUAL ACTION OF 8DlqLIOHT t. T. R. Diff. 1*000 1*000 1*000 -0.06 0742 *781 1-05 -0.01 0590 *588 1*oo -0.06 *490 *534 1-08 + 0-02 -420 *477 1.13 + 0.07 *392 *427 1.09 + 0.03 In a precisely similar manner the following numbers were ob- tained with 0.5 per cent. sodium-chloride paper as the mean of four agreeing experiments :-t.T. R. Diff. 1*ooo 1*000 1OOO -0.04 -742 .787 1006 + 0.02 -590 0611 1.03 -0.01 *490 527 1.07 + 0.03 -420 445 1.06 + 0-02 -392 -409 1005 + 0.01 Hence it appears that with these chloride solutions which present great differences in their strengths the numbers in the t column do not differ appreciably from the corresponding ones in the T column hence it follows that the relative rafes of darkening of the 10 per cent. 3 per cent. and 0-5 per cent. sodium-chloride papers are within the limits of experimental error identical. If denote the values of the ratios of the numbers in the t (+-) column to the corresponding ones in the T column this may be expressed by saying that the value of the fraction (5) (which Mr. McDougall’s experiments have shown not to be a function of the metal with which the halogen of the salting solution is com-bined) is a function of neither the strength of the salting solution finorof the time of expobure in the case of chloride papers A similar set of experiments performed with bromide solutions yielded the following numbers as the mean of nine experiments :- UPON IIBNBITIVE PHOTOQRAPHIC PAPERS (A) 6.386 per cent.potassium-bromide paper. t. T. R. Diff. 1-000 1.000 1-00 -0.51 -742 *920 1.24 -0.27 -590 0858 1*45 -0.06 -490 -838 1.71 + 0-20 773 1-84 + 0.33 ,420 *392 0721 1.84 + 0-33 (B)0.25per cent. potassium-bromide paper. t. T. R. Diff. 1*ooo 1*ooo 1*oo -0.56 -742 0935 1.25 -0.31. 0590 0871 1*47 -0.09 *490 -843 1.72 + 0.16 0420 -813 1.93 +0.37 0392 * 782 2.00 + 0.44 From these numbers it appears that with bromide papers the value of the fraction ( +),(1) is afunction of the time of ex-posure and (2) is not a function of the strength of the salting solu-tion,-since the numbers in the column of ratios are within experi- mental error limits identical both with the strong and with the weak solutions.It is therefore clear that if the relative sensitivenesses of papers are to be compared some particular tint must be taken as a standard of reference. If we know the relation between the relative times taken by papers prepared with chlorine as halogen and those by the papers experimented on to gain a certain definite series of tints and also the relative sensitivenesses of these papers with respect to any one of these tints we can then calculate their relative sensitivenesses with respect to any other of these tints.In order to determine the relative times taken by papers pre- pared with various halogens to gain the same definite series of tints papers salted in the undermentioned solutions were insolated in the disc-photometer and read off on a carefully calibrated strip :-Potassium Bromide containing 6.386 per cent. of KBr. ,) Brorn-iodide 4.452 per cent. of KI and 3.193 of KBr. and 3.193 of KBr. )) Chloro-bromide )> 2*000per cent. of KCl 40 WRIGHT ON THE CHEMIUAL ACTION OF lgUNLIUHT Potassium-Chlor-iodide containing 2.000 per cent. of KCl and 4.452of KI. 2.128of KBr. and 2.969 of KI., Chloro-brom-iodide , 1.333 percent. of KC1 All the above solutions contain precisely as much potassium as exists in a solution containing 4 per cent. of potassium-chloride. The mixed solutions (brom-iodide &c.) contain equal quantities of potassium combined with different halogens. In order to verify beyond doubt the results thus obtained the same papers were exposed in the pendulum photometer and read off as before; whilst as a third check the same papers were directly exposed to sunlight for known times and read off. In order to estimate the amount of accuracy attainable by these latter methods 4 per cent. potassium-chloride papers were thus insolated and read off giving the following numbers :-(The same symbols t T R and Diff.are used as the headings of the columns and with the same meanings as in the previous experiments.) (A) Insolated in the pendulum photometer; mean of three agreeing experiments. t. T. R. Diff. 1*ooo 1.000 1*ooo -0*002 *8?6 0871 -995 -0.007 -765 0764 *999 -0.003 -655 0657 1*003 +0*001 541 -548 1.012 + 0*010 -414 04'16 1*005 + 0.003 (B) Insolated by direct exposure ; mean of four agreeing ex-periments. t. T. R. Diff. 0 1*000 1.000 1*000 -0.004 0857 0842 *982 -0.022 0800 *810 1.012 + OW8 0750 0742 *989 -0.015 -714 .757 1*060 + 0.056 -600 *606 1*009 + 0.005 0571 *584 1*023 + 0.019 0500 0501 1*O02 -o'ooz *429 -435 1.014 + 0*010 -400 0380 *950 -0.054 UPON SENSITIVE PHOTOCBAPHIC PAPERS. The smallness of the diiTerences thus obtained shows that fair results may be anticipated by each method.The following are the numbers obtained with bromide paper :-1. By the disc-photometer (mean of five experiments). 2. By the pendulum-photometer (mean of four experiments). 3. By direct exposure (mean of eight experiments). (1) By the disc-photometer :- (2) By the pendulum-photometer :- t. T. R. 1*000 1*000 1*000 *742 *920 1.240 *590 *858 1.455 *490 *838 P711 -420 *773 1.840 -392 0721 1.839 t. T. R. 1*000 l*OOo 1*000 0876 0961 1-097 765 0921 1.204 *655 -890 1-359 0541 -839 1.551 0414 -786 1.904 (3)By direct exposure :- 1*ooot. T. 1*000 R. 1-000 *750 -907 1*208 *667 -828 1.242 600 0894 1-489 -500 *713 1425 ,400 740 1*850 *333 -677 2.031 *250 0486 I -94.3 -2W -541 2.704 The following values are obtained for the mean bromide mrvc by graphical interpolation the numbers in the column t being represented as abscissz and those in the column.T as ordi- nates :- 42 WBIGST ON T3E CHEMICAL ACTION OF BUNLIGHT MEANBROMIDE CURVE. t. T. R 1*OOO 1*000 1.000 *950 0988 1Q40 *goo -975 1-084 2350 *960 1 129 *so0 945 1.181 -750 0930 1.240 700 0910 1.300 0650 *890 1.369 0600 *860 1.433 0550 *830 1.509 *500 0790 1.580 -450 740 1.644 0400 -685 1.713 -350 -625 1986 -300 0565 1.887 *250 -500 2*000 -200 *430 2.150 These numbers signify that if two pieces of any paper prepared with chlorine as halogen gain certain tints on exposure to sun-light for the relative times 1*000and 0.790,two pieces of any paper prepared with bromine as halogen would gain the same tints on exposure to the same light in the relative times 1*000 and 0.500;and so on.The following table gives the values for the mean brom-iodide curve obtained in a precisely similar way from four experiments with the disc-photometer four with the pendulum photometer and four by direct exposure :-MEANBROM-IODIDE CURVE. t. T. R. 1*000 1*ooo 1*000 -900 *980 1.089 *800 *960 1-200 -700 *930 1.367 .600 *goo 1500 -500 -850 1.700 *400 *780 1-950 0300 0700 2.333 -200 0600 3.000 UPON 8ENgITIVE PSOTOGIRAPHIO PAPEM.a It appears from these numbers that if the sensitivenesses of a chloride and a brom-iodide paper be compared the number ex- pressing the sensitiveness of the latter with respect to the former will be three times as great with respect to a tint gained by the chloride paper in a time 0.6,as that with respect to a tint gained by the chloride paper in a time 1.0 for that obtained in the first instance will be 0.60' x x (where x denotes the absolute ratioof 0.200 1-000 ~. the t to the T) ;and that in the second instance -1.000 The mean of four experiments with the disc-photometer gave the following numbers for chloro-bromide paper. MEANCHLORO-BROMIDE CTJEVE. t. T. R. 1*ooo 1*000 1*Ooo *900 0970 1.078 =800 0930 1.162 700 *880 1.257 *600 0820 1.367 -500 .730 1*460 *400 *610 1.525 *300 *480 1.600 The mean of four experiments with the disc photometer gave the following numbers for chlor-iodide paper :-MEAN CHLOR-IODIDE CURVE.t. T. R. 1*000 1*om 1*ooo -900 0980 1-089 *800 0950 1.178 TOO -910 1 *300 0600 *850 1 *417 GOO -770 1.540 *m *675 1*688 -300 *560 1-867 -200 420 2.100 The mean of four experiments with the disc-photometer gave the following numbers for chloro-brom-iodide paper :- 44 WRIGHT ON THE CHEMICAL ACTION OF SUNLIGHT MEANCHLOR-BROM-IODIDE CURVE. 8. 1*ooo T. 1.000 R. 1*ooo *goo ‘980 1*089 *800 *960 1*200 700 930 1.329 -600 ,900 1.500 $00 0860 1.720 0400 *800 2.000 0300 0730 2.433 *200 0640 3.200 The annexed illustration shows the curves thus obtained for these five papers the corresponding chloride line being represented by the straight diagonal line :-The values of these five curves may be all represented at once by the following table which gives the relative times that any of the above papers take to assume (when exposed to a constant source of light) the series of tints assumed by chloride paperin the times 1*000,0.975 0.950 &c.:- UPON SENSXTIVE PHOTOQBAPHIC PAPERS. Chloride. Bromide. Brom-iodide. Chloro-bromide Chlor-iodide. Chloro-brom-iodide. ~~ 1*ooo 1.000 1.000 1*000 1*000 1*ooo *975 *875 #810 -910 0875 -790 -950 -800 735 0840 800 0700 *925 *730 *660 -780 *735 *620 *goo,850 *800 -670 *585 *515 0580 -500 ~420 730 .650 0580 0680 -600 -535 -560 0470 -390 0750 *455 -350 -525 -480 0320 700 0410 290 *475 .425 0265 0650 *360 *240 *430 -375 -220 *600 -320 0200 390 *335 -650 *280 *355 -295 0500 -240 -320 0260 0450 *200 990 -230 *400 -200 These curves were obtained by the use of salting-solutions eqili- valent to a 4per cent.potassium-chloride solution; but it having been previously shown that the rates of darkening of all chloride and bromide payers are respectively identical whatever be the strengths of the salting solutions this may be assumed to be true for all the others hence the above numbers represent the relative rates of darkening of any papers prepared with these five halogens. If the numbers for chloride paper be represented generally by Tc,aud those for bromide papers by Tb,the connection between Toa.id Tbis approximately given by the formula- By the aid of this table the relative sensitivenesses of any of the above papers with respect to any given tint can be calculated when their relative sensitivenesses with respect to any other are known.For example let it be required to compare the relative sensitive- nesses of 4 per cent. chloride and the equivalent chlor-iodide chloro-bromide bromide and brom-iodide papers with respect to the tint taken as the normal in photometric observations (viz. that gained by 3 per cent. sodium-chloride paper on exposure for one second to light of the unit of intensity). As the mean of five ex- periments it was found that on exposure for the relative times 1-000 0.742,and 0.562,chloride chlor-iodide and bromide papers assumed a WRI6tHT QX TBH OHEHIOAL AUTION OF SfRJLIGHT tints which standard paper would have assumed (on exposure to light of the unit of intensity) in the times 0°509,0-682 and 0.905 seconds.Let x,y and x respectively represent the relative times in which the three papers would assume the normal tint then their relative sensitiveness with respect to this tint are respectively 2 2 1 and !; or 1-000,Y- and -. Thus-xy’ 2 z (1J x 1*000 1.000 0*509 1.000 -or 3 = -1.965. O4509 (2.) From the table the relative times in which chlor-iodide paper would gain tints assumed by chloride papers in the relative times 1.000 and 0.682 are 1.000 and 0,407.Hence y 0742 1.000 :0407 0.742 -or y = -1.822. 0.407 (3.) From the table the relative times in which bromide paper would gain tints assumed by chloride paper in the relative times 1*000and 0.906 are 1-000and 0-685. Hence z :0-562 1.000 0.685 0.562 -or z = -0.820. 0.685 5 1.965 P965 Hence -and-X are respectively -and -?/ 2 1.822 0*820’ or 1.078 and 2.396. That is the relative sensitivenesses of 4 per cent. chloride paper and its equivalent chlor-iodide and bromide papers with respect to the normal tint are 1.000 1-078 and 2.396 respectively. Again as the mean of 12 experiments it was found that chlor- iodide and chloro-bromide papers on exposure for the relative times 1*000and 0-431,gain tints which normal paper would (on expo- sure to light o€ the unit of intensity) gain in the times 0.483 and 0.628 seconds.Calculating as before the relative sensitivenesses of these two 1 and lm papers are found to be 4wo ’ or 1.078 and 4022. Again the mean of 10 experiments gave the following numbers for bromide and brom-iodide papers :- UPON SENBITIVE PBOTOBWHIU PAPERS Bromide. Brom. iodide. Bromide. BrOm-iodide. Bmm. Bromide. iodide Relative times of exposureTimee in which standard loO0O 1.867 1.000 1'678 1*000 2.652 paper would aesume the tints gained by the papers exposed.. ............ Relative sensitivenesses.. 2*396 4.624 0.943 2.396 0'648 4'002 0'732 2.396 0-553 2'612 Bromide. Brom-iodide. Mean relative senaitivenesses 2.396 4060 Hence the relative sensitivenesses of the above 5 papers With respect to the normal tint are-Chloride ..............loO0O Chlor-iodide ............ 1.078 Chloro.bromide .......... 4.022 Bromide .............. 2.396 Brom-iodide ............ 4.060 In a similar way their relative sensitivenesses with respect to any other tint may be calculated. It having been observed during these experiments that the same result was obtained whether the papers were exposed to the full noonday sun to the evening sun or in the shade it became inte- resting to observe what effects were produced upon each paper by variations in the intensity of the light acting upon them the time of exposure being constant. In order to observe this- (1.) A b~ass plate perforated with small circular holes the diame- ters of which were accurately measured by a micrometer was fitted light-tight into the wall of a dark room so that the sun could shine perpendicularly upon the plate.A sheet of prepared paper to receive the images of the sun formed by the small holes was placed at such a distance from the plate that the angle sub-tended by the largest hole from the paper was less than the appa- rent diameter of the sun; all the images were thus kept of the same size hence the intensity of light under each image was proportional to the square of the diameter of the hole forming that image. (2.) The prepared papers were exposed at the bottom of vertical cylinders coated internally with black paper and covered over with metal caps having round holes of varying sizes drilled in them; these holes varied in diameter between 77.5 and 25 millimetres the cylinders being 5 decirnetres high and 1deci- 48 WRIGHT ON TEE CHEXIOAL ACTION OF SUNLIGHT metre in diameter.By this means only diffused light from the zenith was employed the intensities of the light being as before proportional to the squares of the diameters of the holes. As a check on the accuracy of the results obtainable by these two methods 4 per cent. potassium-chloride paper was thus exposed with the following result,. (The column A represents the relative intensities of the acting light; the column T the relative times in which standard paper on exposure to a constant source of light would gain the tints assumed by the papers experimented on the largest being taken as unity; the column R gives the ratios of the numbers in the A column to the corresponding ones in the T column ;and the column Diff gives the differences of the numbers in the R column from their mean.In accordance with the law of Professors Bunsen and Roscoe the numbers in the column R should be sensibly constant provided that no serious imperfection exists in the working of the apparatus employed.) 4 per cent. potassium-chloride paper exposed uuder the perforated plate :-MEANOF Two EXPERIMENTS. A. T. R. Diff. l*ooO 1*000 1*oo -0.07 701 *777 1.11 + 0.04 0663 *757 1.14 + 0.07 -653 -719 1-10 -t 0.03 *520 *496 -96 -0.11 -394 -399 1.01 -0.04 *299 *344 1.15 + 0.08 4 per cent. potassium-chloride paper exposed in the cylinders :-MEANOF FOUREXPERIMENTS.A. T. R. Diff. 1-000 1*000 1*oo -0.01 -719 *734 1-02 + 0.01 *595 0625 1-05 + 0.04 -444 0418 -94 -0.07 428 -443 1*03 + 0.02 -326 *330 1*01 4-0.00 The numbers in the columns of differences being in no case large tolerably accurate results may be anticipated by either method. C'PON SENSITIVE PHOTOGRAPHIC PAPERS. OAexposing bromide paper (equivalent to 4 per cent. potassium- chloride) the following results were obtained as the mean of five experiments with the perforated plate and of three with the cylinders. Experiments with the cylinders and bromide paper :-A. F. R. 1-000 l5O0O 1~000 -595 -881 1.4479 -326 0521 1.601 0145 *331 2-289 Experiments with the perforated plate and bromide paper :-A.T. R. 1*ooo l*C)OO 1000 *945 '093 1*051 -932 0992 1.065 759 0928 1.223 0741 0918 1*238 -701 *936 1.307 -663 *912 1.37'1 -653 0904 1 *384 *575 *842 1.$64 *5R2 *859 1.527 *520 -809 1.557 *426 -749 2-759 *394 0691 7.752 *299 ,569 1-902 *258 ,590 2.286 *I91 -390 2.041 *134 -377 2.814 On graphical representation the numbers in the columns A being represented as abscissae and those in the columns T as ordinates these results are found to coincide giving d mean curve identical with that derived from the experiments with the disc-photometer (p. 42); in other words bromide papers on exposure to a constant source of light for times t, t, t3. . . . gain certain tints ; and on exposure for the same time to lights of intensities A A A .. . . the same tints are gained then t A = t -4 = t3 A = . . . . . . = constant. That is the law enunciated by Profs. Bunsen and Roscoe for VOL. XIX. E 50 WRIGHT ON THE CHEMICAL ACTION OF SUNLIGHT standard chloride paper is also true for bromide papers ;viz. that the same tint is gained by exposing the papers for a time 1 to an intensity 10 as is gained on exposure for a time 10 to an intensity 1 or for a time 2 to an intensity 5; and so on. Hence if a pendulum strip be made with bromide paper and the same paper be exposed to varying intensities of light and the tints thus produced be read off on the bromide pendulum strip it should be found that the numbers from the strip calibratiou-table are to one another in the same prqortion as the numbers indicating the intensities of light.On trying the experiment however it was found impossible to read off on the bromide strip owing to the slight difference in tint between the two ends. On exposure of brom-iodide paper in the same ways the follow- ing numbers were obtained as the mean of six experiments by the aid of the perforated plate (direct sunlight) andof four by means of the cylinders (diffused light). Brom-iodide paper with direct sunlight :-A. I‘. R. 1*000 1*ooo 2.000 786 *914 1.163 0551 *843 1.530 O521 -824 1.581 0513 0823 1-604 409 *737 1-805 0310 *741 2.390 235 *610 2.707 0106 ,468 4.437 *060 -349 5.825 Brom-iodide paper with diffused daylight :-A.T. R. 1*000 1-000 1*ooo *719 *894 1 *244 0428 -765 1.787 0234 -644 2.751 .lo4 -406 3.899 As with the bromide paper these numbers are found on graphical representation to yield a mean curve identical with that derived from the previous experiments loith the disc-photometer qc. (that ie Bunsen and Roscoe’e law is likewise true for this paper). UPON SENSITIVE PHOTOGRAPHIC PAPERS. On endeavouring to read off brom-iodide papers exposed to varying interisities of light on a brom-iodide pendulum strip it was found impossible to get any trustworthy results owing to the slight difference in tint between the two ends of the strip. The following numbers were derived from the mean- of four ex- periments with chloro-bromide paper with diffused light from the zenith (cylinders) :-A.T. R. 1.000 1.000 1.000 *719 0837 1.164 *596 *844 1.4416 428 ‘601 1.404 -326 471 1-414 *I45 -357 2460 These numbers also on graphical representation g’ive a curve identical with that derived from the disc-phot onzeter experiments. On reading off papers exposed to varying intensities of light (in the cylinders) on a chloro-bromide pendulum strip the following numbers were obtained as the mean of four experiments. (The numbers in the column P are the relative times in which chloro- bromide paper would on exposure to light of uniform intensity gain the tints assumed by the papers esperimented on the columns A R and Diff. have the same meanings as hitherto.) A.P. R. D3. 1-000 1.000 1-00 -0.08 -719 702 *98 -0.10 595 *658 1.10 $-0.02 -428 *450 105 -0.03 *326 *A10 1.26 $-0.18 Considering the great difficulty of reading off correctly on a chloro-bromide pendulum strip which exhibits much less grada- tion of tint than a chloride one the differences are sufficiently small to show that Bunsen and Roscoe’s law is obeyed by this paper. On exposing chloriodide papers to diffused light of varying intensities (cylinders) the following numbers were obtained as the mean of four experiments :- 52 WRIGET ON THE CHEMICAL ACTION OF SUNLIGHT A. T. R. 1-090 1.000 1-900 *718 -924 1.286 -428 *719 1.680 :234 *463 1.979 *lo4 *314 3.019 These numbers also on graphical representation are found to yield a mean curve identicnl with that derived from the disc-photometer experiments .Chlor-iodide papers exposed to varying intensities of light (cylinders) arid read off on a chlor-iodide pendulum strip yielded the following numbers as the mean of three experiments. (The column Q iridicates the relative times in which chlor-iodide papers would assume the tints gained by those experimented on on exposure to n constant source of light.) A. Q. R. DiK 1*000 1*000 1-00 -0-00 *719 0636 938 -0.12 -595 -579 '97 -0.03 0428 *425 *99 -0.01 -326 -882 1.17 + 0.17 As the chloriodide pendulum strip shows much less gradation in tint than the chloride strip thesenumbers show that Bunsen and Roscoe's law is obeyedby this paper. By exposing chloro-brom-iodide pape*r to diffused light of vary-ing intensities the following numbers were obtained as the mean of four experiments :-A.T. R. 1-000 1.000 1-000 *718 *921 1-280 -428 *a37 1.955 -234 *716 3-061 *lo4 *494 4-74.9 On graphical representation these numbers are found to give a mean curve identical with that derived from the disc-photometer experiments. On endeavouring to read off chloro-brom-iodide papers exposed to varying intensities of light on a chloro-brom-iodide pendulum strip no good results were obtainable from the slight differences in tint between the two ends of the strip. UPON SENSITIVE PHOTOGRAPHIC PAPERS Since all the above papers obey Bunsen and Roscoe's law the table given on p. 45 also denotes the relative intensities of light to which pieces of any papers prepared with the above halogens must be exposed for the same time in order to gain the same series Of tints.The results obtained by the foregoing experiments together with those previously obtained by Mr. McDougall may be briefly summed up thus :-(1.) Papers prepared with solutions of different alkaline chlorides darken to the same extents in the same relatiwe times no matter with what alkaline metal the chlorine be combined and no matter what be the constant percentage of chlorine in the salting folution. (2.) The same holds true for papers prepared with bromide solutions (and hence probably for all the others). (3.) Photo-chemical induction does not exist to any appreciable extent with chloride bromide .and brom-iodide papers (and hence probably with none of the others).(4.) The relative times for which pieces of any one of the above papers must be exposed to light of a constant intensity in order to gain a definite series of tints vary with each paper. (5.) The relative intensities of light to which pieces of any one of the above papers must be exposed for a constant time in order to gain a definite series of tints vary with each paper. (6.) The relative times for which pieces of' any one of the above papers must be exposed to light of a coilstarit intensity in order to gain a definite series of tints are in the same ratio to one another as are the relative intensities of light to which the same pieces must be exposed for a constant time in order to gain the same series of tints.(7.) The relative times for which pieces of any one of the above papem must be exposed to a constant source of light in order to gain a given series of tints or the relative intensities of light to which they must be exposed for a constant time to gain the same series of tints are given by the table on p. 45. (8.) By the aid of this table the relative sensitivenesses of any of the above papers with respect to any particular tint can be cal-culated when their relative sensitivenesses with respect to some one given tint are known. In conclusion I beg to tender sincere thanks to Professor Roscoe for the valuable advice and assistance which he has given me in carrying out the above investigation.

ISSN:0368-1769    

DOI:10.1039/JS8661900033

出版商:RSC    

年代:1866

数据来源: RSC

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KOLBE'S PItOGNOSIS OF NEW VIL-Prognosis of new Alcohols and Aldehydes. By Professor H. KOLBE,in Leipzig. IN my several publications on Organic Chemistry I have re-peatedly directed attention to the probable existence of a class of compounds related to the ordinary alcohols and aldehydes in the same manner as diarnines and triamines are related to mona-mines. In a former memoir on the Secondary Alcohols,* I placed am-monia and carbin,? ethylamine and ethylcarbin in parallels thus :-H7 H'I "1"3 H H H c4E5}" c43} [C,] and endeavoured to demonstrate from the known exivtence of secondary and tertiary ammonias the possibility of the existence of secondary and tertiary alcohols several of which are now actually known. A similar parallel drawn in a different direction opens out a new field of chemical research.For just as diamines 2re produced by the substitution of diatomic radicals for hydrogen in ammonia so may it be regarded as probable or,I should rather say predicted with certainty that dicarbinols will he produced under similar circumstances from carhinols as indicated by the following con- stitutional formulze :-c43} H [NJ H Ethylamine. Ethyl-carbinol. Ethy lene-diamine. Ethylene-dicarbinol. Jt Ann.Ch. Pharm. cxxxii 102. .t. For reacona developed in the memoir Bbove referred to I have proposed to designate methyl as "carbin," metliylic alcohol as "carbinol," ethylic alcohol aa '' methyl-carbinol,"which names are used in the present communication. ALCOHOLS AND ALDEHYDES.Further the replacement of the two pairs of typic bydrogen-atoms in ethylene-dicarbinol by diatomic or monatomic radicals will give rise to the formation of secondary and tertiary dicar- binols e.g. :-Ethylene-diethyl-dicarbinol ....... . [%] 0,. 2H0 (C4H4)” Ethylene-diethyl-dimethyl-dicarbinol(C4€&J2} [21 0 .2HO P2HA Ordinary alcohols are converted into aldehydes by substitution of oxygen for one of their typical hydrogen-atoms; and in like manner eth ylene-dicarbinol may be expected to yield an aldehyde by oxidation and elimination of a pair of its typical kydrogen- atoms ; thus :-J Propyl-alcohol. Propg1-aldehyde. (c42)’}0,.2H0 H c2 Ethylene-dicarbinol. Corresponding aldehyde. The acid corresponding to ethylene-dicarbinol and its aldehyde and resulting from the latter by oxidation of the last pair of hydrogen-atoms is succinic acid (C4H4)”r2O.I 0,.2HO. c20, These considerations lead to the further conclusion that other dibasic acids as well as succinic acid mill have tbeir correspond- ing aldehydes and alcohols. Those of malic tartaric and phthaiic acid will be symbolically represented as follows :-Succinic acid. Succinic aldehyde. Succinic alcohol. Mdic acid. lldsdic aldehyde. Malic alcohol. 56 KOLBE’S PROGNOSIS OF NEW ALCOHOLS ANDALDEHYDES. Tartaric acid. Tartaric aldehyde. Tartaric alcohol. Phthalic acid. Phthalic aldehyde. Phthalic alcohol. Malic alcohol is merely isomeric not identical with diethylenic alcohol. Evidently also there must exist tricarbinols with their alde- hydes corresponding to the tribasic acids.The composition of’ the aldehyde and alcohol of aconitic acid are represented by the formula+-Aconitic acid. Aconhic aldehyde. Aconitic alcohol. It may be predicted that the aldehydes and probably also the alcohols,-of the tribasic acids will exhibit acid properties. Hofmann has shown that one of the two nitrogen-atoms in a dianiine may be replaced by phosphorus; and in like manner it is highly probable that in the dicarbinols a double atom of carbon may be replaced by another tetra. equivalent element for example by silicium (SiJ perhaps also by the tetratomic sulphur of sul-phurous acid whereby new alcohols with mixed radicals will be produced ; thus-(C4HI)N HP H1 2H0 H2 ] [z]02.2H0 (c4H4y} 02.2HO (GHS” } [‘(I 02.H2 HL H2 Ethylene-dicarbinol. Ethylene-silici-dicarbinol. Ethylene-sulphi-dicarbinol. Lastly if succinic acid has an aldehyde and an alcohol belong- ing to it we may expect also that the analogously constituted propio-sulphiiric acid and similar polybasic acids with mixed radicals will have their corresponding aldehydes and alcohols as represented by the following constitutional formulae :-Propio-sulphuricacid. Corresponding aldehyde. Corresponding alcohol. GRIESS ON ORGANIC COMPOUNDS ETC. I am at present engaged in endeavouring to obtain the alcohols and aldehydes of polyLasic acids from the acids themselves and hope soon to be able to communicate positive results.

ISSN:0368-1769    

DOI:10.1039/JS8661900054

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

GRIESS ON ORGANIC COMPOUNDS ETC. VIII.-On a new Class of Organic Compounds in which Hydrogen is replaced by Nitrogen. By PETERGRIESS. 111. THE researches published in my two preceding papers on the substitution of nitrogen for hydrogen in organic compounds were confined exclusively to bodies belonging to the acid type. The idea naturally presented itself of also submitting organic bases to the action of nitrous acid. I have chosen for this purpose those which are closely related to the amido-acids of the aromatic series. I have thus obtained new nitrogen-compounds presenting in their composition and deportment a well characterised series parallel to the diazowids. In order to prepare this body aniline [(amidobenzol = C,,H5 (NH,)] is Zissolved in from six to ten times its volume of ordinary spirit; and a slow stream of nitrous acid is passed into this solution which mmt always be kept cool until the whole of the aniline has disappeared.This point is reached as soon as the oily residue obtained by evaporating a small quantity af the solution on a watch-glass solidifies to a semi-crystalline mass. The solidification however occasionally and especially in the summer takes place after some time only. In that case the completion of the process is easily recogiiised by testing whether the oily residue remains insoluble in dilute acetic acid. If this is the case the current of nitrous acid must immediately be stopped because an excess of the acid mould convert the required snbstance into other new products.The alcoholic solution which is of a brownish-red colour now contains even if the operation has been conducted with the greatest care besides diazo-amidobcnzol a GRIESS ON A NEW CLASS OF more or less considerable quantity of other products which are all generated by the action of nitrous acid upon aniline. They con- sist of phenylic acid benzol a new body to which I have given the name of nitrate of diazobenzol nitrate and nitrite of aniline and perhaps also some unchanged aniline. In order to get rid of these bodies the whole of the brown alcoholic solution is poured into a large quantity of water from which the greater part of the diazo-amidobenzol immediately separates as a brown oily liquid which soon solidifies to a crystalline mass whilst a smaller quantity is deposited from the water on standing for some time in the form of yellow crystals.The crystalline precipitate together with the yellow crystals is separated by filtration from the mother-liquor which contains nearly all the bye-products. The crude diazo-amidobenzol remaining on the filter is first pressed between bibulous paper in order to get rid of the last traces of the mother-liquor then washed several times with cold alcohol and lastly twice or three times recrystallised from boiling spirit whereby it is obtained in golden yellow plates of perfect purity. On analysis it gave numbers agreeing with the formula :-The formation of diazo-amidobenzol is represented by the following equation :-2C,H,N + N1.0 = CI2Hl1N3+ 2H,O.Aniline. Diazo-amidobenzol. Properties.-Diazo-arnidobenzol crystallises in golden yellow lustrous plates rarely in needles. It is insoluble in water rather easily soluble in hot insoluble in cold alcohol. It is miscible with ether in every proportion. It melts at 9l0 forming a reddish-brown oil which resolidifies to a crystalline mass at about 50'. At a higher temperature it is decomposed with rapid evolution of gas. If a larger quantity is heated up to 200" a violent explosion is the result. Diazo-amidobenzol is inod~rous and tasteless. Weak acids are not capable of dissolving it whilst powerful acids decompose it at once with evolution of nitrogen. From this deportment it is evident that the well-defined basic properties of' the aniline have been considerably modified by the replacement of its hydrogen by nitrogen.Diazo-amidobenzol is in fact no longer capable of forming with acids ORGANIC COMPOUNDS ETC. any saline compounds whatever and only in its deportment with dichloride of platinum with which it forms a doiible compound does its show that its basic character has not entirely dis- appeared. Platinum-salt of Diazo-amidobenxol.-C12H,,N,.HCl. PtCl,. This salt is easily obtained by treating an alcoholic solution ( f diazo-amidobenzol with dichloride of platinum and hydrochloric acid when it immediately separates in small reddish needles or prisms. They are thrown on a filter in order to get rid of the mother-liquor and are rendered perfectly pure by thorough washing with alcohol.They are very unstable and are gradually decomposed in a moist atmosphere apparently with formation of phenylic acid. They deflagrate at a high temperature; the platinum cannot therefore be determined by simple ignition. Diazo-amidobenzol and Nitrate of Silver.-On mixing the alcoholic solutions of the two substances a bulky greenish-yellow precipitate is at once obtained which on drying shrinks together very much and is very apt to blacken. Its composition is repre- sented by the formula OF DECOMPOSITION -Dew PRODUCTS OF DIAZO-AMIDOBENZOL. composition by hydrochloric acid. When diazo-amidobenzol is warmed with concentrated hydrochloric acid which has been covered with a layer of ether two atoms of water are assimilated and take the place of two atoms of nitrogen the substance at the same time splitting up as shown in the following equation :-C,,H,,N -k H,O -j-HC1 = C,H,O + C,H,N.HCl + N,.Diazo-amidobenzol. Phenylic Hydrochlorate acid. of aniline. The hydrochlorate of aniline is found in the aqueous hydro- chloric acid whilst the phenylic acid is taken up by the ether. I have not analysed either the phenylic acid or the aniline the presence of both bodies having been sufficiently established by their well-known properties. I have however quantitatively determined the amount of nitrogen evolved during the reaction. I obtained 13.67 p. c. of nitrogen. The preceding equation requires 14.21 p.c. It is highly probable that diazo-a,midobenzol under the influence of anhydrous hydrochloric acid would be decomposed thus :- QRIESS ON A NEW CLASS OF C12H,,N -I-H2C1 = c6115cl + C,H,N,HCl + N2.Diazo-amidobenzol. Chlorobenzol. This decomposition would then be quite analogous to that of diazo-amidobenzoic acid by hydrochloric acid. Action of Bromine upon Diazo-amidobenzo1.-When a moderately concentrated ethereal solution of diazo-amidobenzol is treated with an ethereal solution of bromine it will be observed that every addition of the bromine causes a fresh precipitate of small white plates. As soon as the addition of bromine no longer produces a precipitate the white crystals must be rapidly separated from the mother-liquor by filtration and washed with ether until they are perfectly white.The analysis of this substance which I shall communicate in my next paper has proved it to be a compound ol hydrobromic acid with a new body which 1 have called diazo-benzol. The formula of this hydrobromate is-On evaporating the ethereal mother-liquor from which that com-pound has separated white needles begin to crystallise out possessing all the properties of tribromaniline. The transforma- tion of diazo-amidobenzol with bromine may be expressed by the following equation :-C12HllN3+ 6Br = C6H,N2.HBr + C6H,Br3N + 2HBr. Hydrobromate of Tribrorraniline. diazo-benzol. Action of Nitrous Acid.-If diazo-amidobenzol be dissolved in a mixture of strong alcohol and ether and then treated with nitrous acid white crystals of nitric diazo-amidobenzol make their appear- ance; they are formed according to the following equation :-CI2Hl,N + NHO + 2NH03 = f2(C6H4N,.HN03) + 2H20.Nitrate of diazo-benzol. I shall describe this reaction more minutely in a future paper. In his researches on the substitution-products of aniline Dr. H ofm an n observed that the basic character of aniline is weakened in proportion to the amount of hydrogen replaced by bromine chlorine or hyponitric acid so that for instance tribromaniline ORGANIC CONIPOUNDS ETC. 61 becomes a perfectly indifferent body. The feebly basic properties of diazo-amidobenzol have proved that nitrogen also exerts an acidifying influence upon aniline and even in a higher degree than chlorine Gr bromine. The task presented itself of ascertain-ing whether this phenomenon would also occur with brornanilinc nitraniline &c.and whether the action of nitrous acid upon dibrom- and tribrom-aniline might not even give rise to bodies of a decidedly acid character. In what degree this view has been confirmed by my researches I shall communicate hereafter. I will first of all make a few remarks upon chlorinated and brominated aliiline themselves. AND CHLORINE ON BROMINE SUBSTITUTION-PRODUCTS OF A.NILINE. According to the researches of Ar ppe,* the nitraniline which he Gbtained by the decomposition of pyrotartronitranilide by potash is not identical with that prepared by Muspratt and Hofmann by the reduction of dinitrobenzol with sulphide of ammonium. In order to distinguish the two compounds Arppe has given to his own the nane a-nitraniline whilst that of Muspratt and Hof-mann he has called p-nitraniline.The chlorinated and broniiriated anilines were as is well known originally prepared by H ofm an n from the corresponding chlorinated and brominated substitution-products of isatin. Millsf- has recently described a method for the prepara-tion of these bodies which is preferable to that of Hofmann. It consists in converting acetanilide into brom- or chlor-acetanilide and then distilling these compounds with caustic potassa. Mills has left it undecided whether the substituted anilines thus pre-pared are identical with those of Hofmann or whether they are isomeric like the two nitranilines just mentionecl. The solution of this question was of the more interest to me as the fact of the nitrogen bodies to be obtaiued from the brorn- or chlor-anilines being eventually isomeric or identical could have been decided beforehand.I have therefore carefully compared the properties of Mills’s brom- and chlor-aniline with the corn-pounds prepared according to Hofm ann’s method. I found such a perfect coincidence in the properties of the free bases as Js Ann. Ch. Phsrm. xciii. 357. I. Proceedings of the Royal Society. GRlESS ON A NEW CLASS OF well as of their salts that I have no hesitation in pronouncing them to be identical. Bromaniline accordirig to Hofmann melts at 50' C. 1have on the contrary found that the melting point of brornaniline purified by several recrystallisations is 57' C.Neither could I confirm the observation made by Mills that the bromaniline prepared according to his method has a greater tendency to crystallise in needles. When in a state of purity I have always obtained it crystallised in the form oi octahedrons. The same advantages offered in the preparation of brom- and chlor-aniline according to RIills's method hold good as I have found when preparing dibrom- and dichlor-aniline in a similar manner. In order for this purpose to convert the acetanilide into dibromacetanilide it is suspended in water and treated with bromine until the ~hhole of tlie acetanilide has been converted into a reddish resinous mass. The crude dibromacetanilide thus formed may at once without separating the water be submitted to distillation with potash when the dibromaniline distils over in oily drops which soon solidify to white needles.It may be purified from any tribromaniline with which it is mixed by dis- solving in warm moderately concentrated hydrochloric acid in which the latter substance is insoluble. If traces of bromaniline are present the hydrochloric acid solution is evaporated to dryness and then treated with water. By this treatment the hydrochlorate of bromaniline suffers no alteration whilst the dibromaniline loses its hydrochloric acid and becomes insoluble in water and may therefore be completely purified from bromaniline by washing with water. Recrystallisation from dilute alcohol furnishes the dibromaniline in needles or long plates.Although its preparation and properties scarcely leave a doubt of its identity with the compound prepared according to H ofmann' s method I have yet determined the melting point of each of them and have found them to coincide at 79.5" C.* The hydrochlorate a!so of the dibromaniline prepared by me crystallised in the same shape resembling palm-branches a3 described by H ofm ann. Analysis gave numbers agreeing with the formula :-C6H,Br2N.HC1. * Hofmann states the melting point of dibromaniline to lie between 50" and 60"C. ORGANIC COXPOCNDS ETC. The feebly basic properties which dibromaniline possesses are still manifest in its deportment with dichloride.of platinum A concentrated hydrochloric acid solution mixed with dichlo-ride of platinum yields a double salt crystallising in beautiful yellow prisms.This compound is very unstable and is decomposed even by hot water with separation of dibromaniline. Its formula 1s :-C6H,Br2N.HCl.PtCl,. To prepare dichloraniline through the agency of acetanilide the latter is dissolved in hot water and treated with an excess of chlorine until the crystalline mass which was first deposited has become quite soft. This crude dichloraniline is separated from the mother-liquor and distilled with potash. The distillate must be purified in the same manner as the dibromaniline nichloraniline crystallises like the corresponding bromine-com- pound in white needles which are nearly insoluble iu water but are readily taken up by alcohol or ether.A substance which H ofm an a supposed to be dichloraniline was prepared by him from chlorinated isatin. He obtained it together with chlorani- line in such minute quantity that he was unable to give a definite description of its properties still less to determine its composition by an analysis. I have on this account treated the dichloraniline prepared by me with dichloride of platinum and have submitted the resulting double salt to analysis. Numbers were obtained corresponding with the formula- This platinum-salt crystallises in yellow prisms which are also readily decomposed by water with separatiou of the base. The preparation of this compound is much more easily accom- plished than that of diazo-amidobenzol. On treating au alcoholic solution of bromaniline with nitrous acid the diazo-arnidobromo- benzol separates after a short time in the form of yellow needles.They need only be once recryatallised from warm alcohol iu order to render them perfectly pure for analysis. GRIESS ON A NEW CLASS OF Diazo- amid ob romoben zol cry stallises in yellow ish-red lustrous plates or needles which are insoluble in water difficultly soluble in alcohol but very soluble in ether Diazo-aniidobrornobenzol melts at 145' C. In its deportment it exhibits the closest analogy to diazo-amidobenzol its resemblance to that body being even greater than that existing between bromaniline and aniline. I have prepared this compound from bromaniline obtained not only according to Hofm ann's method from bromisatin but also from that made from bromacetanilide as proposed by Mills.No difference could be detected between the diazo-amidobrom- benzols obtained from the bromanilines prepared according to the two different methods. Platinum-salt of Diazo-amidobromobenzol.-On mixing an alco-holic solution of diazo-amidobrombenzol with dichloride of plati-num this salt separates in the form of pale-yellow hair-like crystals which are nearly insoluble in water alcohol and ether. On the application of heat they deflagrate leaving a woolly mass of platinum and carbon. Diazo-arnidochlorobenzo1.-C H,C12N3. It is obtained from chloraniline and forms yellow needles or plates greatly resembling the preceding compound. I have only determined their melting point; it lies at 124.5' C.{C6H3(NOJ a-Diazo-amidonitrobenzol,C,,H,(N Oz)rN = C6H4W2) N2 1 The preparation of this body is also extremely simple. (NHd Alpha-nitraniline is dissolved in a moderate quantity of cold alcohol arid on passing nitrous acid into the solution the new compound separates after a short time as a yellow crystalline mass. When separated from the mother-liquor and washed with cold alcohol it is perfectly pure for analysis. The a-diazo-amido- nitrobenzol is precipitated as I have stated as a yellow crystalline mass in which no distinct form of crystallisation can be recog- nised. Generally it corisists of an agglomeration of granular or mossy microscopic particles. Even by recrystallisation from alcohol it is seldom obtained in a decided form; only once have I succeeded in obtaining yellow needle-shaped crystals whose planes exhibited a beautiful violet lustre.a-diRzo-flmiclonitrobenzol is iusoluble in water very difficultly soluble even in boiling alcohol ORGANIC COMPOUNDS ETC. and ether. It melts at 224.5"C. to a reddish-brown oil. The higher temperature it deflagrates diffusing at the same time an aromatic odour. It is an almost perfectly indifferent substance. I could not even succeed in preparing a compound with dichloride of platinum ; nitrate of silver however still gives even in very dilute alcoholic solutions a yellowish-green amorphous pre- cipitate. C6H3(N02)N2 6-Diazo-amidonitro benzd-C6H4((N0'2)(NH!2) When P-nitraniline is submitted to the action of nitrous acid almost exactly the same phenomena are observed as those which occur in the preparation of the preceding compound.The crystals which have been deposited but which in this case exhibit a per-fectly distinct form are easily purified in the same manner. The P-diazo-amidonitrohenzol differs only in a few points from the a compound. It is equally insoluble in water and appears also to be as difficultly soluble in alcohol and ether. The two substances also seem to agree in their deportment with reagents as far as could be decided by preliminary experiments. On the other hand the melting point of 6-diazo-amidonitrobenzolis 195.5' C. consequently 29' lorrer than that of a-diazo-amidonitro-benzol. The a compound crystallises as a rule in granular or moss-like shapes whilst the P-diazo-amidonitrobenzol separates already during its preparation in small though generally well- defined ruby or reddish-yellow prisms nhich by recrystallisation from alcohol or ether may be obtained of a cousiderable size.Diazo-amidgdibromobenzol.-C12H,Br4N3= C6H,Br,N {C6H3Br'2(NH'2)1 On passing a current of nitrous acid gas into a very dilute alcoholic solution of dibromaniline the diazo-amidodibromobenzol is ohtained as a bulky light-yellow precipitate. Repeated mashing with alcohol renders it perfectly pure. Diazo-amidodibromobenzol has R great tendency to crystallise in different forms. Prom alcohol and ether in which it is very difficultly soluble eyen at the boiling temperature it crystallises in fine golden-yellow interlaced needles which melt at 167'5' C.but defl7grate at a higher temperature. On allowing an alcoholic VOL. XIX. F GRIZSS ON A NEW cuss OF &ion to evaporate spontaneously yellowish-brown granules are ,requently obtained which show a golden- yellow fracture and a radiating crystalline structure. On several occasions and under conditions not accurately determined a-diazo-amidodi-bromobenzol prepared from not absolutely pure dibromaniline crystallised froin ether in extraordinarily beautiful yellow or ruby well-defined prisms. As this form differing in such a characteristic manner from the yellow needles appertained to the dihromaniline obtained from dibromisatin I should have been inclined in spite of what I had previously stated in regard to dibromaniline to seek the cause of this difference in the dibro- maniline prepared by the different methods.I soon however convinced myself that the beautiful red crystals are converted on further re-crystallisation from ether into the same golden-yellow hair-like needles. Diaxo-amialodichlorobenzo7 C ,H ,C14N = {$$$$!$ H3} is also prepared from dichloraniline and crystallises also in hair- like needles which are however distinguished from the bromine compound by their light sulphur-yellow colour. It is insoluble in water and very difficultly soluble in boiling alcohol and ether. It melts at 126*5OC. In their deportment with reagents diazo-amidodibromobenzol and diazo-amidodichlorohenzolexhibit the greatest analogy to the nitrogen-substituted aniline-derivatives already described whilst under the same conditions they yield corresponding products of decompssition.They also form precipitates with nitrate of silver. Their basic character however has completely disappeared ; they no longer give platinum-salts ; in fact they possess more the character of an acid than that of a base as they dissolve with ease in alcoholic potash forming a reddish-brown solution from which the original substance is precipitated in a perfectly unaltered state on the addition of an acid. It is how- ever not possible to prepare salts of a definite composition. Aqueous potash has no action upon these bodies. From what has been stated it is obvious that the acidifying in- fluence exerted by nitrogen when taking the place of hydrogen in aniline is repeated in an equal degree with the substitution-products of that body.OBBANIC COMPOUNDS ETC. G7 If aniline and its bromine hyponitric acid and other derivatives be arranged in the order of their basic properties there may be placed opposite to every individnal of this series a diazo double compound the basic properties of which differ from the basic properties of the corresponding aniline body by the acidifying value of one atom of nitrogen. If the diazo-amidodibromobenzol correspondingto dibromaniline already exhibited distinct acid properties it was to be expected that a body of a perfectly acid character would be obtained by the action of nitrous acid upon tribromaniline.I have instituted many experiments in order to obtain such a body but without success. Nitrous acid has not under any circumstances the slightest action upon tribromaniline. Although it was to be expected that the researches conducted with the aniline group described in the preceding pages would when repeated with bases of analogous composition lead to cor-responding results I have not omitted to prove this analogy by experiment. DIAZO=AMIDOTOLUOL.-~ {:;:;$fHJ-) 14H15N3- In order to prepare this body toluidine (amidotoluol) is dis-solved in a small quantity of strong alcohol and the solution is mixed with two or three times its volume of ether. After passing nitrous acid for a short time the originally nearly colourless solu-tion assumes a yellow colour.A drop of the solution is now taken out and evaporated on a watch-glass ; if it leaves a residue of yellow needles the operation is stopped and the mixture of alcohol and ether is allowed to evaporate spontaneously. Yellow needle-shaped crystals are deposited which must be washed with alcohol and then recrystallised from alcohol and ether. When dried over sulphuric acid and submitted to analysis they gave numbers leading to the formula Diazo-amidotoluol crystallises in yellow or reddish-yellow needles or prisms possessing a powerful lustre and corresponding in their solubility as well as in every other relation with diazo-amido-benzol. Platinum-salt of Diazo-umidotoluol,C14H~,N,.2HC1.2~tC1,.It CIBfEBS ON A NEW OLA€?43 OF is obtained in yellow glittering plates resembling iodide of lead on mixing an alcoholic solution of diazo-amidotoluol with dicblo- ride of platinum. It deflagrates at Q high temperature. DIAZO-AMIDONITRANZSOL. This body falls in small yellow crystals on pamirig nitrous acid into a dilute alcoholic solution of nitmnisidine* [amidonitraniad = C,H,(NO,) (NH,)O]. It forms microscopic yellow ueedles in- soluble in water difficultly soluble in hot ahohol and ether. When dry they are rendered highly electric by friction. They melt on the application of heat to a reddish-brown oil and defla- grate on raising the temperature. Diazo-amidonitranisol under the influence of reagents appears to undergo changes similar to those of its representatives in the aniline group.On referring once more to the most characteristic points of the nitrogen substitution-products of the hydrocarbons of the aromatic series .it will be observed that not only in their formation but also in their properties and decompositions they correspond in every relation with the peculiarities of that series of acids of which the best studied individual is diazo-amidobenzoic acid. !Phis is but natural as dl the transformations which benzoic acid and its homologues undergo under the influence of substitution processes are also effected in the hydrocarbons which in com-bination with CO form the corresponding aromatic acids. In the same measure as benzoic acid on distillation with baryta yields carbonic acid and benzol or as amidobenzoic acid splits up into carbonic acid and amidobenzol so doubtless would diazo-amidobenzol be obtained from diazo-amidobenzoic acid under similar conditions if the instability of this compound did not pre-cl ude ever j possibility of its formation under such circumstances.C7HfiOa -CO = C6H6 Benzoic acid. Ben 01. Diazo-amidobenzoic acid. * The nitraniddine was obta'ned from dinitfaaid which w prepwedarding to Cahour's method from nitranisic acid. ORGANIC COMPOUNDS ETC. The following compounds stand in the same relation :-Diazo-amidotoluylicacid. Diazo-amidotoluol. Diazo-amidonitranisic acid. Diazo-amidonit ranisol. In a preliminary note on these bodies I referred them to the type H2..) N,.This was done at a time when I knew but little of their H2 products of decomposition. If after the observations communi- cated in this paper diazo-amidobenzol for instance were still to be considered as a diamine having the formula GN?,/ Na on r-:1 endeavouring to explain the phenomena of its decompositions the same inconsistencies would become apparent as when supposing diazo-amidobenzoic acid to be constituted according to the rational -formula [ (C H,0)”HN”’J~iW2~ Hal ‘2.

ISSN:0368-1769    

DOI:10.1039/JS8661900057

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

ORGANIC COMPOUNDS ETC. IX.-Action of Heat on Ferric Hydrate in presence of Water. By EDWARD DAVIES,F.C.S. Liverpool. HAVINCI noticed the occurrence of shilling particles apparently crystalline in precipitated ferric oxide which had been boiled for a considerable time I made the following experiments with a view to ascertain if the oxide could be obtained in the anhydrous state by boiling with water. Being aware that M. P6an de St. Gilles has investigated the properties of the oxide thus altered I con-fined myself to the determination of the amount of water. In the memoir above cited the oxide is spoken of as being a hydrate; it appears however that it is for the most part anhydrous. In the following experiments the ferric hydrate was prepared from ferric VOL.XIX. 0 DAVIES ON THE ACTION OF HEAT chloride. This was made by twice crystallising the ferrous chloride passing clilorine through a dilute solution and removing excess of chlorine by heating gently for some time. The water mas determined by careful ignition the absence of chlorine being proved by mixing a portion of the oxide with pure carbonate of sodium moisteuing with distilled water drying and gently igniting. The mass was boiled with water and on testing tbe solution only a very faint trace of chlorine was in any case detected. 1. Some solution of ferric chloride was Precipitated by am-monia the precipitate thoroughly washed with boiling water and then boiled with distilled water for 112 hours loss by evapo- ration being prevented by a coxidensing apparatus.The oxide became dense and lost its gelatinous appearance. It was again washed and dried at 100" C. On ignition-17.85 grains lost 1.03 grain or 5.7'7 % *Fe,0,H20 contains 10*11%. 2. The solution was precipitated as before and then boiled 100 hours without filtering from the chloride of ammonium thoroughly washed and dried at 100" C. 13.805 grain lost 056grain or 4.05 %. 3. On using hydrate of potassium in slight excess and treating as in No. 2,not filtering and boiling for 100 hours the dehydra- tion was not so complete contrary to expectation as the oxide in the former cases contained traces not to be estimated of ammonia. 25-77 grains lost 1.69 grains or 6.55 %. 4. Fearing that the loss might take place during the drying a portion of washed oxide was dried at 100"C.for at least an equal time being finely pulverised when dry and finally heated until it no longer lost weight after several hours' interval.15-64grains lost 1-43grains or 9-14.% being slightly below one equivalent. 5. Boilirig the oxide for long periods being inconvenient on * Fe = 56. ON FERRIC HPDBATE IN PRESENCE OF WATER. account of the bumping which occurs when the oxide has under- gone the physical change I resolved to try the effect of gently heating for a very prolonged period. The oxide was precipitated in thecold by ammonia washed with cold water and heated for 1004 hours at a temperature varying from 50-60' C. with frequent agitation. In a few days it became dense and brick-red in colour.It was washed with water at 50" C. and dried at the same temperature. 20-50 grains lost %4 grain or 4.09 %. 6. As the oxide in No. 5 contained a trace of ammonia hydrate of sodium was substituted as a precipitant the oxide was washed as before heated at 50-60" C. for 2,000 hours. The flask was closed and heated in an oil-bath. 38.46 grains lost 1-75 grains or 4-55 %. 19-20 *90grain or 4-68 %. It thus appears to be impossible to drive off all the water 4 to 5 per cent. adhering with extraordinary tenacity. The oxide thus prepared is brick-red very dense having a specific gravity of 4.545 that of red hematite being 4.7. It dissolves very slowly in nitric acid more readily in hydrochloric acid. Under the microscope the dried oxide presents angular masses translucent when very thin.Hoping to remove the unchanged hydrate with nitric acid 24.18 grains of oxide prepared as in No. 6 were heated to 5G0 @. for one hour with 2 oz of dilute nitric acid (1 part acid to 3 parts water). 4.77 grains dissolved and the residue was washed until no longer acid and dried at 50" C. 18.48 grains lost -65 or 3.517 %. These experiments show that the immense beds of haematite found in our own and other countries do not demand the suppc- sition of great heat to account for their anhydrous state. Probably much lower temperatures than that employed in the foregoing experiments acting in presence of water for a long period would bring about the same change. The various statements respecting the amount of water in ferric hydrate are thus explained that amount depending on the length of time during which the hydrate was exposed to the action of water and a more or leas elevated temperature.(32 BROWN ON VAPOUR-DENSITY DETERMINATIONS. Chromic and aluminic hydrates were also operated upon by precipitating them with ammonia washing and boiIing for 100 hours. No action appeared to take place ahminic hydrate retaining 3 eqs. of water and chromic hydrate 5 eqs. The hydrates retained their gelatinous condition.

ISSN:0368-1769    

DOI:10.1039/JS8661900069

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

BROWN ON VAPOUR-DENSITY DETERMINATIONS. X.-Tables for the Calculation of Vapour-densityDeterminations. By JAJ. T.BROWN. IFunder the head of vapours we include gases there are several tables which may he used for lessening the labour of calculating a vapour-density. There is one by Gerhardt * giving approxi- mately the values of the expression 760 (1 + 0-00367 T)for every integral value of T frorri 0 to 30. There is another by Bunsen t indicating the vaIues of I + 0-00366T and log. (1 + 0.00366 'T') €or every T = 0.1 from -2 to + 40. mere is also a table calculated by Mr. Greville Williams giving the values of the 1 formula 1+ 0-00367 T for every T = 1 from 0 to 150; and lastly Gerhardtt gives the values of log. (1 + 0-00367 T) for every integral value of T from 0 to 299.But 1 found that by substituting the weight of a cubic centirnetre of air for that of a cubic centimetre of nitrogen in the formula with which I headed a table for the calculation of direct nitrogen determinations I obtained an expression which occurs three times in the formula €or the determination of a vapour-density according to the method of Dumas. For in this formula which is generally written-P' -P + p -p' D= 1+ k (T-t))-v'] 1 H 1 + 0.00367 'I"r60 but which written without any abbreviation and modified becomes * Gerhardt Trait6 de Chimie Organique rol 1 page 50. t Bunsen's Gasomtry translated by Roscoe page 268. Cerhardt vol 1 page 115. BROWN ON VAPOUR-DENSITY DETERMINATIONS. 0*0012932 From we see the repetition of the expression 760(1 + 0-0036Z T)' this expression I have calculated a table of its values for every T = 0.5 from -20 to + 50 and for every T = 1 from 51 to 350.I have also added a column of differences for calculating the fractional values of the expression. In order to find the weight in grarnmes of a given volume of air at any pressure and tempe- rature up to 350' C, multiply the number in the table headed 0*0012932 '760 (1 + 0.00367 T.) corresponding to the temperature by the volume expressed in cubic centimetres and also by the pressure expressed in millimetres. 0.00367 -(T -t)] for 1-k 0.00367T In substituting ['I -t 1+0.00367 t 1 +0*00367t' I have made no actual alteration as the two expressions are equal; but as I have given a table indicating the values of the quantity 0.00367 for every t = 0.5 from -20 to + 50 the 1 + 0.00367 t expression is reduced to the simple form of 1 + k (T -t).In calculating by this table it is only necessary to use it to the fifth decimal place unless the value of v is very large. In calculating the table for correcting for the expansion of the glass viz. that headed 1 + k (T -t) I have adopted the values of k as given by Regnault * taking the average value of t at 30. Gerhardt gives a table for the same purpose headed log. [l + k (T -t)] for every T -t = 10 from 100 to 290 and takes the value of k at 0.000027. The three following examples win illustrate more fully the use of the tables. Ex. 1.-To find the weight of 90 C.C.of air at a temperature of 15" C. and at a pressure of 746 mm. 0~00000161279x 90 x 746 = 0.108282 gramme. Ex.2.-To find the density of a vapour from the following data (Dumas). * Regnault's Elements of Clwmirtry translated by Betton vol 2 page 420. -/-Gerhardt vol 1 page 117. BROWN ON VAPOUR-DENSITY DETERMINATIONS. T = 350' C. T -t = 335 t = 15" c. P' = 28.3920 grammes. P = 28.2093 , v = 90 c. c. v = 0.5 C. C. K = 746 mm. 28.3920 -28.2093 + (0~0000016127x 90 x 746) -(0~000001612x 0.5 x 746) D= [90(1'0104) -0*6(1 + 0*00347x 335)] x 0.000000'744S x 746 28.3920 -28 2093 + 0'1082 -0.0006 0.2903 -=-0.0499 = 5'51 0.0499 Ex. &-To find the density of a vapour from the following data (Gay-Lussac)-D= 0*0012932 + '760 (1 + 0.00367 T) Ht P = 0.1069.v = 43 c. c. H = 761 mm.; H' = 680.5. Diff. of level = 80.5 mm. T = 96. - T 0'0012932 ~___ t 60(1 -!-0.00367T) Diff. -20 0*00000183636 -19.5 0-00000183273 -19 0*00000182912 -18.5 0~00000182552 -18 0~00000182193 -17.5 0~00000181836 0*00,500181480 -17 16.5 0-00000181125 -16 0~00000180772 -15.5 0'0C000180421 -15 0.00000180070 -14.5 0-0000 0179'121 -14 0~00000179374 -13.5 0~00000179027 -13 0-00000178682 -12.5 0'000001 78339 -12 0*00000177996 -11.5 0*00000177655 363 -20 36 1 -19.5 360 -19 359 -18.5 357 -18 356 -17.5 355 -17 353 -16.5 351 -16 351 -195 349 -15 347 -14.5 347 -14 345 -13.5 343 -13 343 -12.5 341 -12 330 -11.5 0.00367 1 + 0.00367t Diff.0*00396071 783 0*00395288 779 0+00304509 777 0'00333732 774 0 00392958 770 0.00392 188 768 0'00391.120 764 0.00390656 762 0.00389694 758 0-00389136 756 0'00388380 753 0.00387627 750 0'00386577 747 0*00386730 744 0'00355386 741 0'00384645 '138 0'00383907 736 0.00353171 '732 BROWN ON VAPOUR-DENSITY DETERMINATIOXS. T --. -11 -10.5 -10 -9-5 -8.5 -a -7.5 -P -6-5 -6 -5.5 -5 -4.5 -4 -3.5 -3 -2.5 -1.5 -1 -0-5 0 4-0-5 1 1-5 2 2-5 3 3-5 4 4.5 5 8-5 6 6.5 7 7-5 8 8-5 9 9.5 10 10.5 It 11.5 12 12.5 13 13.5 14 145 15 3.5'5 16 16.5 0'0012932 760(l i 0 003671 O.OO000177316 0~00000176977 0'00000176640 0-000001 76304 0*00000175970 0-00000175636 O*OOOOO175304 0*00000 17497 4 0*00000174644 0~00000174316 0-00000173989 0'000001 73663 0.00000173338 0-00000173015 O*OOOOOl72693 @00000172372 0-00000172052 0'00000171733 0~00000171416 0'00000 171099 0*00000170784 0-00000170470 0-000CO 170157 Oa00000169846 0*00000169535 0*00000169226 0'00000168918 0-00000168610 0.00000168304 0-00000167999 C.00000 167696 0*00000167393 0-000001 67091 0~00000166791 0-00000166491 0*00000166193 0.00000165896 0~0000016 5599 0*00000165304 OOG000165010 0~00000164717 0'000001 64425 0'00000164134 V00000163844 0'00000163555 0.0000016 3 267 0~00000162980 0*00000162694 0'00000162409 0'00000162125 0'000001 61E42 0'00000 161560 0-00000161279 0-00000160999 0~00000160320 0~00000160442 0-00367 DiK DifX t 1 't 0~0036'ii 339 -11 040382439 730 337 -10'5 0-00381709 727 336 0-00380ga2 725 334 -10 9.5 0*00380257 721 334 -9 0.00379536 719 332 -8-5 0-00378817 716 330 -8 0'00378101 714 330 -7-5 0-00377387 711 328 -7 0.00376676 708 327 -6-5 0-00375968 '105 '326 -6 0.00375263 703 325 -5.5 o'OC374560 700 323 -5 0-00373ri60 698 322 -4-5 0 003'73162 695 321 -4 0.00372467 692 320 -3.5 090371775 690 319 -3 0-00371085 687 317 -2.5 0-00370398 685 317 -2 0*00369713 682 315 -1.5 0.00369031 680 314 -1 0-00368351 677 313 -0.5 0.00367674 674 311 0 0-003ci7000 673 311 + 0.5 0.00366327 669 309 1 0-00365658 668 308 1.5 O.GO3 649 9 0 665 308 2 0.00364325 662 306 2.5 0.00363663 660 305 3 0.00363003 658 303 3-5 0-00362345 655 303 4 0.0036 16 90 653 302 4.5 0'00361037 651 300 5 0'00360386 648 300 5.5 0-00359738 646 298 6 0-00359092 643 297 6 *5 0-00358449 642 297 7 0'00357807 639 2!)5 7-5 0'00357168 636 29 4 8 0.00356532 685 293 8.5 0.00355897 632 292 9 0.00355265 630 291 9-5 0.003 54 63 5 628 290 10 0'00354007 625 289 10-5 6.00353382 623 288 11 0.00352759 621 28; 11.5 0.0G35213 8 619 286 12 0.003515 19 617 285 12.5 0.00350902 615 284 13 0.003 50287 0 12 ' 283 13.5 0.00349675 610 282 14 0.00349065 605 281 14-5 0-003&3456 606 280 15 0.00347850 604 279 15.5 0.00347246 601 278 16 0.003466 45 600 277 16.6 0 00346045 598 BROWN ON VAPOUR-DENSITY DETERMINATIONS.-~ T 17 17.5 18 18.5 19 19.5 20 20.5 21 21.5 22 22-5 23 23'5 24 24.6 25 25.5 26 26-5 27 27.5 28 28.5 29 295 30 30.5 31 31.5 32 32-5 33 33'5 34 34.5 35 35'5 36 36*5 37 37-5 38 38'5 89 39'5 49 40.5 41 41.5 42 42.5 43 43-5 44 44'5 0'0012932 760(1 + 0.00367T; 0 00000160165 0-OCOOO159889 0~00000159613 0.00000159339 0~00000159066 0~00000158793 0-00000158522 0~00000158251 0.00000 157982 0*00000157713 0.00000 157445 0-00000157178 0-0000 0186912 0~00000156647 0*00000156383 0~00000156120 0.00000155857 0-00000155596 0-000001 55 3 35 0-00000155075 0*00000154817 0-00000154559 0*00000154301 0*00000154045 0*00000153790 0*00000153535 O*OOOC0153281 0.00000 153028 0*00000152776 040000152525 0~00000152274 0-00000152025 0*00000151776 0-00000 I51 528 0~00000151281 0'00000151034 0*00000150789 0~00000150544 0'000001 50300 0~0000016005~ 0~00000l49814 0.00 00I) 149572 o.oooao I 49332 0 00000149091 0 -00000 14 88 52 0-0000014561 4 0*00000148876 0-00000118139 0.00nooi 47 902 0-00000147667 0'000001 47 432 0*000001 47 198 0.00000146965 9-00000146732 0-0000014 6500 0.00000146269 Diff.t 0-0036 7 1+ 0.00367t DiE - ~~ 276 17 0.00345447 596 276 17.5 0.00344851 593 274 18 0-30344258 592 273 18.5 0.00343666 589 273 19 0.00343077 588 271 19-5 0.00342489 585 271 20 0*00341904 584. 269 20-5 0-00341320 581 269 21 0-00340739 580 268 21.5 0.00340259 577 267 22 0.00339582 677 266 22.5 0.00339C0.5 573 26 5 23 0*09338432 571 264 23.5 0 00337861 570 263 24 0-00837291 56a 263 261 24?5 25 0'0033(i'123 0'00336 157 566 564 26 I 25.5 0.00335593 562 260 26 OrOO335031 560 258 26.5 0-00334471 559 258 27 0'00333912 556 258 275 0'00333356 555 256 28 0-00332801 553 256 28.5 0.00332248 551 255 29 0'00331697 549 254 29.5 0'00331 148 648 253 30 O.OO33O6 00 545 252 30.5 OW330055 544 251 31 0'00329511 542 251 31-5 0*0@328969 540 249 32 0'0 03284 2 9 539 249 32-5 0-00327890 536 248 33 0.00327354 535 24 7 33.5 090326819 533 2 4'7 34 0.00326286 532 245 34.5 0'00325754 530 245 35 0-00325224 538 244 35.5 0'00334696 526 243 36 0'00384170 524 243 365 0-00323646 523 542 37 oawm23 622 240 37'5 0'00322601 519 241 38 0'00322082 518 239 38.5 0 00321564 516 238 39 0'00321048 515 238 39-5 0 00320533 513 287 40 0'00320020 511 237 40.5 0'00319509 509 235 41 0'00319000 508 235 41.5 0'00318492 507 234 42 0-00317985 505 233 42.5 0'003 17480 503 233 43 0.00310977 501 232 43.5 0.00316476 500 231 44 0-003159% 499 230 44.5 0'0031 5477 497 BROWN ON VAPOUR-DENSITY DETERMINATIONS.T 0-0012032 760(1 + 0.00367T) Diff. t 0.0 0 3 67 1 + 0.00367t -__- 45 0*00000146 039 230 45 0-00314980 45.5 0-0000014 5809 229 45.5 0-00314485 46 0*00000145880 228 46 0'00313991 46.5 0-00000145352 227 46.5 0.00313499 47 0-00000145125 227 47 0.00313009 47.5 0*00000144898 226 47.5 0-003125 19 48 0'00000144672 2 25 48 0*00312032 48'5 0'0000 014 4447 225 48 5 0-00311546 49 0*00000144222 2 24 49 0*00311061 49.5 0'00000143998 223 49.5 0-00310578 50 0~00000143775 60 0.0 0310097 ~-(YO012932 0.0012932 T 'SO(1 + 0+00367T) D8. T T60(1 + 0.00367T) 51 C =00000143330 442 88 0-00000128619 52 0.00000142888 48 9 89 0-00000128263 53 0*00000142449 436 90 0~00000127909 54 0~00000142013 434 91 O*OOOOO127557 55 0.000001415 79 431 92 0'00000 127207 56 0'00000141148 428 93 0*00000126859 57 0*00000140720 426 94 0~00000126513 58 0.00000140294 423 95 0*00000126169 59 0-00003139871 421 96 0.00000125826 60 0~00000139450 418 97 0*00000125486 61 0.00000139032 416 98 0~00000125147 62 0'000001 386 16 413 99 0.0000012 481 0 63 000000138203 410 100 0*00000124475 64 0.OO 000 13 77 93 4 09 101 0-00000124 142 65 0'0000013 7384 406 102 0*O0000I238 10 66 0.00000136978 403 103 0-00000123480 67 0*00000136575 401 104 O*OOOOO123152 68 0*00000136174 399 105 0-00000122826 69 040000135775 396 106 0~G0000122502 70 0~00000136379 395 107 0'000001221'79 71 0'00000134984 391 108 0*00000121858 72 0'00000134593 390 109 0'00000 121 538 73 0*00000134203 387 110 0~00000121220 '74 0*00000133816 385 111 0*00000120904 '75 O*OOOOO133431 383 112 0~00000120590 76 0*00000133048 381 113 0*00000120277 77 0'0 000013 26 67 3i9 114 0~000GOllY966 78 0~00000132288 S76 115 0~00000119656 '79 0~00000131912 374 116 0'00000119348 80 0~00000131538 3'12 117 0~00000119042 81 0~00000131166 3'70 118 0*00000118737 82 0'00000130796 368 119 000000118434 83 OOOUO0130428 366 120 O*OOOOO118 132 84 0~00000130062 364 121 0'00000 11'1832 85 0.00000129698 362 122 0-000001 17633 86 0 00000129336 360 123 0~00000117236 87 0~00000128976 357 124 O'OUOC0116940 DiR.495 494 49 2 490 490 487 486 485 483 481 Diff. 356 354 352 350 348 346 344 343 340 339 337 335 333 332 330 328 326 324 323 321 320 318 316 314 313 311 310 308 306 305 303 302 300 299 297 296 294 BROWN ON VAPOUR-DENSITY DETERMINATIONS.T 0.0012932 %0(1 -f-0.00367T) I)iE - 125 0.00000116646 293 126 0-00300116353 291 127 0'00000116062 290 128 0'000001 157;s 288 129 0~03000115484 287 130 0~00000115197 286 131 0-000001149 11 284 132 0'000001 14627 283 133 0'00000114344 281 134 0'000001 14063 280 135 0'000001 13783 278 135 0'00000 113 50 5 278 137 0'0000011 3227 275 138 0'0000011 2952 275 130 0'00000112677 273 140 0.00000112404 272 141 0'000001121 32 270 142 0'00000111862 270 143 0'00000111592 268 144 0 00000111324 266 145 0'0000 01110 5 8 266 146 0'00000 1 1 07 92 264 147 0'000001 10528 263 148 0'00000110265 261 149 0'00000110004 26 1 150 0'00000109743 259 151 0'00000109484 258 152 0'00000109226 256 153 0'0 0000108970 256 154 0'00000108714 254 155 0'00000108460 253 156 0*00000108207 252 157 0~00000107955 251 158 0~00000107704 250 159 0'00000107454 248 160 0~00000107206 247 161 0'00000106959 247 162 0'000001 06712 245 163 0*00000106467 244 164 0'00000106223 242 165 0'00000105981 242 166 0~00000105739 240 167 0'00000105499 240 168 0'00000105259 239 169 0'00000105020 237 170 0'00000104783 236 171 0'00000 104547 236 172 0'0000010431 1 234 173 0~00000104077 233 174 0-00000103844 232 1'75 0'00000103612 231 176 000000103381 230 177 0-00000103151 229 178 0-00000102922 228 179 0.00 0001026 94 227 T 0.0012932 760(1 + 0.00367T) Diff._I- 180 0~0000U102467 226 181 0~00000102241 225 182 0~00000102016 224 183 0.00000 10179 2 223 184 0~00000101569 222 185 0~00000101347 221 186 0-00000101126 220 I87 0~00000100906 219 188 0~00000100687 218 189 0~00000100469 217 190 0*00000100252 217 191 0~00000100035 215 192 000000099820 215 193 0.0 0000099605 213 194 0*00000099392 213 195 0~00000099179 211 196 0*00000098968 211 197 0.0000009S757 210 198 0.00000098547 209 199 0-00000098388 208 200 0~00000098130 207 201 0.00000097923 207 202 0*00000097716 205 203 0*00000097511 205 204 0*00000097306 204 205 0~00000097102 203 206 0-00000096 8 9 9 202 207 0-00000096 6 97 201 208 0-00000096496 201 209 0-00000096295 199 210 0*00000096096 199 211 0~00000095897 198 212 0.00000095699 197 213 0-00000095502 196 214 0-00000095306 196 215 000000095110 194 216 0~00000091916 194 217 0*00000094722 193 218 0*00000094529 193 219 0-000Q0094336 191 220 0~00000094145 191 221 0*00000093954 190 222 0.00000093764 190 223 0'00000093574 188 224 0*00000093386 188 225 0'00000093198 187 2 26 0'00000093011 186 227 0*00000092825 185 228 0*00000092640 185 229 0*00000092455 184 230 0~00000092271 183 231 0-000000920 8 8 183 332 0-00000091905 182 233 0*00000091723 181 234 0~00000091542 180 BROWN ON VAPOUK-DEKSITY DE'l'EGMINL4TIONS.II T 0.0012932 jO(1 + 0-OO367T) DifE T 0.0012932 60(1 + 0.00367T) DiE - ~~ 235 0~00000091362 180 290 0*00000082428 146 236 0~00000091182 179 291 0.00000082282 146 237 0~00000091003 178 292 0~00000082136 145 238 0'00000090825 178 293 0'00000081991 145 239 0~00000090647 176 294 o-ooooooai846 144 240 0~00000090471 177 295 0'00000081702 144 241 0-00000 0 9029.4 175 296 0~00000081558 143 24 2 0~00000090119 175 297 0~00000081415 143 243 0'00000089944 1'74 298 0~00000081272 142 244 0~00000089770 174 299 0.00000081130 141 245 0*00000089596 1'72 300 0~00000080989 142 246 0*00000089424 173 301 0*00000080847 140 247 0'00000089251 171 302 0~00000080707 141 248 0*00000089080 171 303 0~00000080566 139 249 0*00000088909 170 304 0~00000080427 140 250 0*00000088'739 170 305 0.O 000008 0287 138 251 0*00000088569 169 306 0~00000080149 139 252 0'00000088400 168 307 0 ~00000080010 138 253 0~00000088232 167 308 0*00000079872 137 254 0~00000088065 167 309 0*00000079735 137 255 0.00000087898 167 310 000000079598 136 256 0~00000087731 165 311 0.0000007946 2 136 257 0~00000087566 165 312 0*00000079326 136 258 0-00000087401 165 313 0~00000079190 135 259 0~00000087236 164 314 0-00000059055 134 260 0'00000087052 163 315 0~00000078921 134 261 0'0 000 0 OS6 909 162 316 0-00000078787 134 262 0~00000086747 162 317 0~00000078653 133 263 0*00000086585 162 318 0*00000078520 133 264 0*00000086423 161 319 0-00000078387 132 265 0'000 000862 6 2 160 320 0*00000078255 132 266 0'00000086102 159 321 0~000000~8123 132 267 0~00000085943 159 322 0-0000007i99 1 131 268 0*00000085784 159 323 0~00000077860 130 269 @00000085635 158 324 0*00000077730 130 270 0~00000085467 157 325 0~00000077600 130 271 0'00000085310 157 326 0~00000077170 129 272 0-00000085153 156 327 0~00000077311 129 273 0*00000084997 155 328 0*00000077212 128 274 0*00000084842 155 329 0~000000'77084 128 275 0~00000084687 155 330 0*00000076956 128 276 0-00000084532 153 331 0.00000076828 127 277 0'00000084379 154 332 0~00000076~01 127 278 0*00000084225 152 333 0~00000076574 126 279 0.0000008~0~3 153 334 0*00000076448 126 280 0'00000083920 151 335 0.00000076322 125 281 0-00000083769 151 336 0*00000076197 125 282 0-00000083618 151 337 0*00000076072 125 283 0*00000083467 150 338 0*00000075947 124 284 O~OOOOOOS3317 149 339 0*00000075823 124 285 0.0 0000083168 149 340 0*00000075699 123 286 0~00000083019 149 341 0-00000075576 123 287 0~00000082870 148 342 0.00000075453 123 288 0~00000082722 147 313 0~00000075330 122 280 0~00000082575 147 344 0-00000075208 122 80 LAWES AND GILBXRT ON THE COMPOSITION VALUE 0.0012932 1 1 0*0012932 76O(l + 0.00367T)’ 1760(1 + 0.003671’) g:: 347 I 0~00000075086 0*000000’74965 I :ii .3;; I 0*000000’14723 1 0-000000’74603 120 0*00000074844 121 350 0-00000074483 - 7 T-t 1+k (T-t) T-t 1+:k (T-t) r-t 1+k (T-t) ll-1 1+ k (T -t) - -.35 1*00096 115 1-00326 195 1-00581 275 1*00841 40 1~00110 120 1-00340 200 1*00596 280 1-00866 45 1.00124 125 1*00355 205 1.00610 285 1.00892 50 1*00138 130 1.00369 210 1.00625 290 1-00907 55 1-00151 135 1.00392 215 1-00640 295 1-00923 60 1.00165 140 1*00407 220 1.00655 300 1*00939 65 1.00179 145 1*00421 225 1*006’70 305 1-00954 70 1*00193 150 1.00436 230 1.00685 310 1*00970 75 1.00207 155 1*00451 235 1-00719 315 1.00985 80 1.00220 160 1.00465 240 1-00’734 320 1*01001 85 1.00241 165 1.00480 245 1*00’749 325 1~0101’7 90 1 -00255 170 1*00494 250 1*00765 330 1.01032 95 1*00269 175 1-00509 255 1.00’180 335 1-01048 100 1.00284 180 1*00523 260 1-00795 340 1-01064 105 1*00298 185 1-00551 265 1.00810 345 1*01079 110 - 1-00312 190 1*00566 270 - 1*00826 350- 1*01095

ISSN:0368-1769    

DOI:10.1039/JS8661900072

出版商:RSC    

年代:1866

数据来源: RSC