摘要:

THE QUARTERLY JOURNAL OF THE CHEMICAL SOCIETY. I.-On Propione the Ketone of Propionic Acid. BY REGINALDI. MORLEY,Eso. The comparatively late discovery of propionic (metacetonic) acid and the great difficulty attending the preparation of this compound have hitherto prevented a detailed study of its products of decomposition interesting though they are as being derived from the first term of the series C,H,O, in which the character of the fatty acids is clearly and definitely pronounced. The elegant method of preparing this acid which we possess since a passage has been opened from the alcohols to the acids containing C,N additional and placed one step Bigher in the system will doubtless greatly assist in filling up the gap still existing in the history of these substances.The following pages contain some remarks respecting a member of the propiouic family which if prepared at all has not hitherto been directly derived from propionic acid ; namely propione the homo- lope of acetone. Almost ten years before Gotklieb* discovered propionic acid Fre'rny,-f in studying the action of hydrate of lime upon sugar starch and gum obtained together with other products an oily liquid the analysis of which led him to the formda C,H,Q ==2vols. of vapour * Ann. Ch. Pharm. LII 121. t Ann. Ch. Phys. [23 LIX 6. VOL 1V.-NO. XIII. B MR. MORLEY ON PROPIONE and for which on account of a certain analogy it exhibited with acetone he adopted the name of metacetone. When Gottlieb found pro- pionic acid the assumption of a close relation of this acid with Fr6my’s metacetone was at once suggested both by a comparison of the formulz C,H,O Met acet one HO C,H,O Propionic acid and by the analogy of the processes giving rise to the formation of the two substances the latter being produced by the action of hydrate of potassa upon cane-sugar.Induced by the relations exhibited by the above formuls Go tt-lieb examined the deportment of metacetone with oxidising agents and found that it readily yielded the acid C,H,O, together with acetic and carbonic acids and that the action of bichromate of potassa and su’phuric acid upon metacetone was actually the better process for preparing the acid to which he accordingly applied the unfortu- nate term metacetonic or metacetic acid only lately replaced by the more appropriate appellation of propionic acid now universally adopted.More recently Chancel,* in his valuable researches into the nature of the ketones generally was led to doubt the accuracy of FrBmy’s analysis performed at a comparatively early period of the development of organic cheniistry. He suggested that Frerny’s metacetone might be the true ketone of propionic acid represented either by C,H,O =2 vols. of vaponr or in the sense of his mode of viewing the substances,* by C1,H,,,0,=4 vols of vapour and he supported this opinion chiefly by Got tlieb’s observation of metacetone being converted by the action of oxidising agents into propionic acetic and carbonic acids as stated above; a deport-ment assimilating this substance to acetone which as is well known by similar treatment yields acetic formic and carbonic acids.If we consider the difficulty attending the purification of substances produced in irregular processes of destructive distillation a difficulty not undervalued by Fr6my himself and to which attention has again been directed by subsequent experiments of Chancel,$ we cannot * Compt. Rend. XX 1882 ; XXI 908. -I-Compare Brazier and Gossleth’s paper upon caproic and anauthylic acids Chem. SOC. Qu. J. 111 210. 2 J. fharm. XTII 471. THE KETONE OF PROPIONIC ACID. but admit that the above suggestion has in itself a certain proba- bility. On the other hand it beconleg again doubtful if we consider the discrepancy between the boiling-point observed (84’ C.) and that assigned to it by theory (100’ C.) a fact to which Messrs.Bra- zier and Gossleth* have firat directed attention. If we compare the widely differing percentages corresponding to both formulae Frdmy’s formula Chancel’s formula. C,H,O . . . . C,H,O Carbon 73-47 . . . . 6976 Hydrogen 10.20 . . . 11.62 Oxysen 16.33 . . . . 18.62 and particularly if we consider that M. C ahours,? whose analytical skill and accuracy are universally appreciated in his late researches on the volatile oils obtained in the distillation of wood has met with a compound possessing exactly the composition and properties of Fr6my’s metacetone. These statements suffice to show that the history of metacetone is still involved in obscurity and that further researches are required in order to show whether Fre‘my’s metacetone is merely a mixture containing propione as one of its constituents or whether it be a definite compound closely allied to but differing in composition from the true propione To assist in clearing up this question Dr Hofmann induced me to try the preparation of propione by a method which was likely to yield this compound in a state of purity namely by subjecting pro-pionate of baryta to the action of heat.The propionic acid used for this purpose was prepared by the process of Frankland and Kolbe,f with the slight modifications pointed out by Messrs. Brazier and Gossleth$ for the preparation of caproic acid. I have only to mention that the decomposition which takes place in the preparation of the cyanide of ethyl by distilling the sulpho- vinate of potassa with cyanide of potassium (the second step in the process) is by no means confined to the production of cyanide of ethyl and sulphate of potassa as vapours having the most intole- rable odour are evolved during the whole operation and the con- densing-tube is lined with a light-yellow amorphous mass evolving the odour of cyanic acid when treated with hydrochloric acid.* Chetn. SOC. Qu. J 111 224. f-Chem. SOC. Qu. J. 111 183. $ Chem SOC. Mem. 111 388. 5 Chem SOC. Qu. J. 111 210. B2 MR. MORCEY ON PROPIONE The propionate of potassa formed by boiling the cyanide of ethyl with an alcoholic solution of potassa was decomposed by sulphuric acid and subjected to distillation when the propioriic acid passed over and collected in the receiver as an oily layer not miscible with a small quantity of water but disappearing upon considerable dilu- tion.The odour of this substance is hardly to be distinguished from acetic acid and with sesquichloride of iron it yields the charac- teristic red colour of the latter. In order to identify the acid a portion was converted into the ammonia-salt and subsequently into the silver-salt ; the latter was white crystalline tolerably soluble in cold and much more SO but with decomposition in boiling water. On analysis 5.06 grains of silver-salt gave 3-03 , , silver-59.88 per cent. The formula Ag . C6H,0 requires 59.66 per cent of silver.The purity of the acid having thus been established the rest was converted into a baryta-salt by saturation with the carbonate and evaporation This salt crystallises very beautifully and justifies the name of propionic acid by its somewhat greasy appearance; when dried in the water-bath it may be easily reduced to powder. When submitted to destructive distillation (which is conveniently performed in Florence flasks placed obliquely upon a wire gauze over a gas-burner) a brown fluid of not unpleasant odour distilled over ; when dehydrated with chloride of calcium and again rectified it came over of a light-yellow colour. Thus purified the fluid began to boil at 80' C. but the boiling-point rapidly rose to 100' C. between which temperatures a very small portion passed over the last drops having distilled before the thermometer reached 108' C.On rectifying the fraction which distilled from 100' C. to 105' C. it began to boil at 98' C. ; at 100' C. a constant boiling-point was observed. Combustion of the product collected at 100' with protoxide of copper and oxidised copper turnings gave the following results I. 3.08grains of substance gave 7-82 , , carbonic acid 3-32 , , water. 11. 2.78 , , substance gave 7.08 , , carbonic acid 2.93 , , water. THE KETONE OF PROPIONIC ACID. These numbers lead to the formula C H 0 =2 vols. of vapour or C,,H,,O,=4 vols. of vapour which require the following values Theory. Mean of experiments. -5 equivs.of Carbon . . 30 = 69.76 69.34 5 ,> , Hydrogen . 5 = 11-62 1 1.83 1 , Oxygen . . 8 = 18.62 93 _.-43 100*00 The body then produced by the distillation of propionate of baryta is the true propione whose formation is analogous to that of acetone as exhibited in the following equation : -Ba C,H,O = C,H,O + Ba CO,. \ 2 Propionate of baryta. Propione. When pure propione is a colourless or pale-yellow liquid of an agreeable odour and lighter than water with which it is not miscible ; the latter property distinguishes this compound essentially from acetone and characterises it in an unequivocal manner as a derivative of a fatty acid. Propione is miscible in all proportions with alcohol and ether. It is very inflammable and burns with a pale-blue flame without deposition of carbon.The boiling-point of this liquid is not less than 16' higher than that observed by Fre'my in metacetone and is particularly inte- resting inasmuch as it exactly corresponds with the temperature assigned by theoretical speculation. Propione being the intermediate term between the ketones of acetic and butyric acids we are natu- rally led to assume that its boiling-point should be equidistant from thoqe of its neighbours in the system j now this is actually the case as seen from the comparison appended. Boiling-points. Acetone . . C,H,O "6: '*} diff. &. Propione . . C,H,O 100 C. Butyrone . . C7H70 144' C. diff. 44. Moreover if we adopt formula representing 4 vols. of vapour the differences of the boiling-points closely approximate to the differences usually observed in bodies whose compositions differ by C,H,* MR.MORLEY ON PROPXONE. Boiling-points. Acetone . . c H 0 560'*I C H -2C,H 44=2x22 Propione . . C,,H,,O fOOo C.( 4 4-Butyrone . C14H1402 144O C. C,H,=2 C,H 44=2 x 22 It now remained only to study the deportment of propione with oxidising agents in order to obtain new data for or against Cham eel's opinion respecting the constitution of the ketones for a full explanation of which I refer to the paper of Messrs. Brazier and Gosslet h. According to this view propione would be and should yield on oxidation propionic and acetic acids. ACTION OF NITRIC ACID ON PROPIONE. Propione when dropped by small portions into fuming nitric acid caused very violent evolution of red fumes; after all action had ceased the liquid was mixed with" an excess of water and distilled.A portion of the distillate neutralised with ammonia and precipitated with nitrate of silver gave a yellowish crystalline salt which was recrystallised from boiling water when a small quantity of silver was found to separate The solution deposited white crystals which on analysis were proved to consist of propionate of silver. 5.31 grains of silver-salt gave 3.19 , , silver=60*07 per cent. Theory requires 59.66 per cent of silver. The action of boiling nitric acid was now tried with precisely similar results. I have repeatedly endeavoured to ascertain the presence of other acids in addition to propionic acid in the dis- tillate of propione with nitric acid such as nitropropionic acid* or acetic acid but I have not succeeded in establishing their presence by experiment.I cannot however positively aErm that no other than propionic acid is formed my experiments being performed perhaps on too small a scale only a limited quantity of substance being at my command. If we assume that the oxidation of propione furnishes propionic * Gmelin (Handbuch V 130) states that Chancel has obtained nitropropionic acid by oxidising metacetone with nitric acid. But on carefully going over the original memoirs of Chancel I find this fact nowhere mentioned ; it seems that nitropro- pionic acid has hitherto been obtained only from butyrale and from butyrone.AN-4LYSIS OF THE WATER OF AN ARTESIAN WELL. acid only the deportment of this substance differs from that both of its lower and higher homologues acetone yielding under the same circumstances acetic formic and carbonic acids while butyrone and caprone are converted into the nitro-acid of the lower series namely into nitropropionic and nitrovaleric acids. If we leave out of consi- deration for the present Chancel’s view regarding the constitution of ketones which evidently requires further elaboration it neverthe-less appears that the fact of propione being reconvertible into pro- pionic acid together with the boiling-point of this substance differing 44’ from those both of its lower and higher homologues are in favour of the assumption at all events of formuh corresponding to 4 vols.of vapour. Among the series of ketones which are becoming more and more complete there is one most interesting teim still wanting the study of which might probably decide the value of Chancel’s view ; this is the ketone of formic acid which according to his theory should be identical with the aldehyde of the formyl-series. I am now engaged in preparing a considerable quantity of formic acid to be devoted to this investigation and hope before long to lay the result of my labours before the Society.

ISSN:1743-6893    

DOI:10.1039/QJ8520400001

出版商:RSC    

年代:1852

数据来源: RSC

摘要:

AN-4LYSIS OF THE WATER OF AN ARTESIAN WELL. 11,-Analysis of the Water of the Artesian Welt Southampton. BYJOSHUA H. ROBSON,EsQ. QUEENWOOD COLLEGE The few analyses of deep well-water which have hitherto been published exhibit a very great difference in the quantity of their solid matter and even the quality of the water appears to be subject to much variation.* Professor Brande is inclined to believe that the quantity of solid matter depends upon the depth to which the borings have been carried in the chalk; he considers that the greater the depth the less will be the solid contents of the water. From these considerations I was induced at the suggestion of Mr. Galloway to submit to analysis the Southampton artesian well- water as from the great depth to which the borings have been carried in this case it was likely to yield some interesting results.* Vide Meesrs. Abel and Rowney’s Memoir on the Composition of Water of the Artesian Wells Quarterly Journal of the Chemical Society Vol. I. ; and Pro-fessor Brande’s Paper on the Well-water of the Royal Mint Vol. 11. of the same Journal. MR. ROBSON ON THE ANALYSIS OF The analysis was conducted in the laboratory attached to this insti- tution. This well is situated on a common about a mile and a half from the town of Southampton and has cost in its construction between 320,000 and .S30,000. The total depth is about 1280 feet; the depth from the surface down to the chalk is about 580 feet and the depth of the borings in the chalk about 700 feet.It yields a mean supply of 125,000 gallons of water per diem which is pumped up by means of two pumps and delivered into a reservoir about an acre in extent. The temperature of the water is 63' F*(31' C.) the temperature of the air being 57' F. (28' C.) at the time of observation. Its specific gravity is 1002-23; its reaction acid. A careful qualitative analysis of the water having pointed out the presence of soda magnesia iron sulphuric silicic carbonic and hydrochloric acids and traces of phos-phoric acid and potash the following numbers were obtained by quantitative analysis. A. Determination of the total amount of fixed ingredients. Amount of water. Fixed residue. Percentage. I. 5669367 grms. 07404grm. -13060 11. 566.9367 , *7365 , -12990 Mean ,13025 B.Determination of suIphiiric acid Amount of sulphate Sulphuric acid Amount of water. of baryta. per cent. I. 5669367 grms. 00564grm. *00340 11. 566.9367 *0561 *00339 ,, > mean $00339 c. Determination of chlorine. Amount of chloride Amount of water. of silver. Chlorine per cent 1. 566.9367 grms. 1.3941 grm. *06083 11. 566.9367 , 1.3525 , *05902 Mean *05992 THE WATER OF THE ARTESIAN WELL SOUTHAMPTON. D. Determination of silicic acid. Amount of silicic Silicic acid Amount of water. acid. per cent. I. 1133.8734 grms. *0135 p. *00119 11. 1133.8734 , 00168 , *00148 Mean 000133 E. a. Determination of the total amount of iron. Amount of peroxide Peroxide of iron Amount of water.of iron. per cent. I.1133*8784grms. 00046grm. -000405 11. 1133.8734 , -0456 , *000490 Mean *OOM47 F. a. Determination of the total amount of lime. Amount of carbonate Amount of water. of lime. Lime per cent. I. 1133*8734grms. *1792 grm. *00885 11. 113308734 , *1790 , ,00882 Mean *00883 G. a. Determination of the total amount of magnesia. Amount of pyrophos-Magnesia Amount of water. phate of magnesia. per cent. I.1133.8734 grms. 01985grm. *00638 11. 113308734 , 01922 ) *00618 Mean *00628 A given quantity of the water was boiled for a considerable time the apparatus in which the operation was performed being so arranged that no evaporation could take place. The precipitate formed was separated by filtration and the amount of iron lime and magnesia present in the precipitate and the lime and magnesia present in the filtration were determined in the usual way.All the iron was pre- cipitated on boiling the water E. b. Determination of iron in the precipitate. Amount of peroxide Peroxide of iron Amount of water. of iron. per cent. 113308734grms. *00460 grm. *000405 Mean of the results *00043per cent corresponding to *00062per cent of carbonate of the protoxide of iron. MR. ROBSON ON THE ANALYSIS OF F. b. Determination of lime in the precipitate. Amount of carbonate Amount of water. of lime. Lime per cent. I. 113393734 grms. 01113grm. *00549 11. 1133.8734 , 01183 , *00583 Mean +00566 c. Determination of lime in the filtrate. Amount of carbonate Amount of water.of lime. Lime per cent. I. 1133.8734 grms. *0724grm. -00353 11. 1133.8734 3 ,0650 , *00321 Mean *00337 G.b. Determination of magnesia in the precipitate. Amount of Magnesia Amount of water. pyrophospate of magnesia. per cent. I. 1133.8734 grms. 00723grm. *00232 11. 113308734 , 00876 , *00281 Mean *00256 c. Determinationof magnesia in the filtrate. Amount of Magnesia Amount of water. pyrophoshate of magnesia. per cent. I. 1133.8734grms *lo88grm. *00350 11. 1133.8734 , *lo68 , *00343 Mean *00346 *00346per cent of magnesia correlsponds to *00212of magnesium. H Determination of the alkalis Amount of Mixed chlorides Amount of water. the mixed chlorides. per cent. I 1133.8734 grms. 1.0650 grms.,09354 11. 1133.8734 , 1.0455 , *09920 Mean 009287 a. Determination of potash. THE WATER OF THE ARTESIAN WELL SOUTHAMPTON. 11 Amount of Chloride of Amount of water. chloride of potassium potassium per cent. and platinum. I. 1133.8734grms. 01205grm. .00324 11. 1133.8734 , *l280 , *0034!4 Mean *00334 000334per cent of chloride of potassium corresponds to *00211of pot ash. b. Determination of chloride of sodium. Amount of Chloride of sodium Amount of water. chloride of sodium. per cent. I 1133.8734grms. 1.02824grms *09068 IT. 1133.8734 , 1.00646 , 008876 Mean *Of3972 .Of3972per cent of chloride of sodium corresponds to 003524of sodium. I. Determination of carbonic acid. The carbonic acid was determined by adding to a known quantity of water a mixture of chloride of calcium and ammonia.2267.7468 grms. of water yielded in this manner 1.4143grms. of precipitate in which the carbonic acid was determined. Amount of Amount of Amount calculated precipitate employed. carbonic acid evolved. whol~~~~ipitate. I. 05488grm. *2144grm. *55252 11. -6429 , *2730 , *60056 Mean 057654 Percentage in the water -02542. K. Determination of phosphoric acid Amount of Amount of water. pyrophosphate of pho~~~~~~t~d magnesia. 3401*6202gms. 00309grm. *000576 L. Determination of organic matter. Amount of Organic matter Amount of water. organic matter. per cent. I. 1133,8734grms. 00790 grm. -00697 11. 1133.8734 , *0803 , *00704 Mean *00700 MR CROOKES ON THE SELENOCYANIDES.From these analytical results the following composition of the water is deduced In 100 litres. Gramrnes. In the imperial gallon. Grains. Carbonate of protoxide of Carbonate of lime . iron . . *620 . 13.740 *434 9.6180 Carbonate of magnesia . . 5.280 3.6960 Phosphate of lime . Sulphate of lime . Chloride of magnesium . . 1.248 . 4.370 . 3.680 -8736 3.0590 2.5760 Sulphate of potash . . 3.910 2.7370 Chloride of sodium . . . 89.720 62*8040 Silica . . 1.330 *9310 Organic matter . . 7.000 49000 130.898 91.6286 The amount of fixed residue obtained by direct experiment was In 100 litres . . . . . 130*250grammes. In the imperial gallon . . 91.175 grains. Having deducted from the percentage of carbonic acid that portion in combination with lime magnesia and iron the percentage of free carbonic acid was found to be 001643.

ISSN:1743-6893    

DOI:10.1039/QJ8520400007

出版商:RSC    

年代:1852

数据来源: RSC

摘要:

MR CROOKES ON THE SELENOCYANIDES. 111.-ORthe Xelenoeyanides. BY WILLIAMCROOKES,EsQ. ASSISTANT IN THE ROYAL COLLEGE OF CHEMISTRY. The remarkable parallelism between sulphur and selenium which has been traced in so many directions left but little doubt respecting the existence in the selenium-series of a class of compounds corre-sponding to the sulphocyanides. In fact Berzelius* mentions that by fusing selenium with ferrocyanide of potassium a salt may be obtained which possesses the general characters of the sulphocyanide of potassium but is less stable than the latter compound. This salt however appears to have hitherto escaped a closer examination. Ber-zelius makes no mention that it has ever been analysed nor have any other selenocyanides been investigated.* Trait6 111 105. MR. CROOHES ON THE SELENOCYANIDES. This circumstance induced me to re-prepare the potassium-salt in order to fix its composition by numbers and to study at the same time several other selenocyanides in order to establish more fully the character of this class of compounds. I begin the account of my experiments with a detailed description of both the preparation and analysis of the potassium-salt which forms the point of departure of the investigation. Selenocyanide of Potassium.-This salt was prepared by fusing 1 part of selenium with 3 parts of dry ferrocyanide of potassium in a small German glass retort. The greenish-black deliquescent mass was quickly broken up and introduced into absolute alcohol. After digesting for a few days the mixture was filtered; the residue con- sisting chiefly of carbide of iron with a little selenide was well washed with absolute alcohol and the filtrate subjected to a stream of dry carbonic acid in order to convert the soluble cyanide of potassium and cyanate of potassa into bicarbonate which is insoluble in absolute alcohol.* After filtration the alcohol was distilled off together with the hydrocyanic and cyanic acids and their products of decomposition ; the residue which contained a small quantity of free selenium was then treated with water and the extract evaporated over sulphuric acid in uacuo.Selenocyanide of potassium forms a mass of needle-shaped crystals much resembling the corresponding sulphocyanide very deliquescent and decomposed by almost any acid with evolution of hydrocyanic acid and precipitation of selenium.It is strongly alkaline to test paper and produces great decrease of temperature when dissolved in water. When heated in a close vessel it fuses without decomposition into a clear liquid below a red-heat solidifying on cooling as a mass of crystalline structure with access of air however it is deconiposed a little above 100°C. The potassium was determined by heating with dilute hydrochloric acid evaporating the filtrate to dryness heating to dull redness and weighing the chloride of potassium produced. The selenium was at first determined by precipitating the solution of the salt with hydro- chloric acid; but as this method did not give the whole of the sele- nium a portion of it escaping in the form of hydroselenic acid I * In order to ascertain whether the decomposition of the cyanide of potassium by carbonic acid was complete I dissolved half a gramme of cyanide containing a little cyanate in absolute alcohol and passed a rapid stream of dry carbonic acid through the solution for about an hour.There was an abundant deposit of bicarbonate of potassa and the filtrate when evaporated to dryness left a very slight residue which entirely disappeared below a red-heat. I MR CROOKES ON THE SELENOCYANIDES. afterwards hsed the potassium-salt with an excess of nitre and esti- mated the selenium as seleniate of baryta. When heated with dilute hydrochloric acid I. 0*3625 grm.of selenocyanide of potassium dried at lOOOC. gave 0.187 , , chloride of potassium and 09198 , , selenium. When fused with nitre 11. 0.4255gm. of salt gave 0.8276 , , seleniate of baryta which correspond to the following percentages I. 11. Potassium . . . 27.00 -Selenium . . 54.62 54-88 These numbers lead to the formula K C N Se2= K Csey as may be seen by the following table Theory. Mean of experiments. r-A-7 1 equiv. of Potassium . . 39.00 27-05 27.00 1 , , Cyanogen . 26.00 18.05 -2 , , Selenium . . 79.14 54.90 54.75 c_____- 1 equiv. of KCsey . . 144.14 100.00 The formation of selenocyanideof potassium in the fusion of ferro-cyanide of potassium with selenium is represented by the following equation K Cfy + 4 Se=2KC2 N Se + Fe C +N.I have examined the residue left in the retort which together with undecomposed ferrocyanide of potassium consists chiefly of carbide of iron retaining only traces of selenium. Berzelius* mentions that the nitrogen evolved during the process is mixed with the vapour of selenide of carbon. The formation of this latter compound must have been evidently due to the action of an excess of selenium upon the residuary carbide of iron both constituents of which may have been converted into selenides at a high temperature. The gas evolyed in my experiments did not contain any biselenide of carbon at least * Traitk 111 105. MR+ CROOKES OX THE SELBNOCYANIDES. I did not succeed in condensing any; nor is it likely that this com-pound could have been formed as from reasons of economy I invaria-bly used a large excess of ferrocyanide of potassium in proportion to the selenium employed.The above equation requires 1*16of ferrocyanide of potassium to 1 part of selenium. As stated above I fused the two substances in the proportion of 3 to 1 Setenoqanide qf Si'Zver.-This salt falls down when selenocyanide of potassium is added to a solution of nitrate of silver. Prepared in ' this manner it resembles chloride of silver in outward appearance. It may be obtained beautifully mystalline however by previously adding an excess of ammonia to the silver-solution; in this way it is precipitated in minute crystals having exactly the appearance of satin. It blackens readily in the light is insoluble in water and almost so in ammonia and cold dilute acids; when boiled in strong acids it is immediately decomposed and unless oxidising acids are employed selenium is precipitated.The silver in this salt was determined by heating with hydrochloric acid containing a few drops of nitric acid and weighing the resulting chloride; the filtrate served to estimate the selenium wbich was pre- cipitated by sulphurous acid and ammonia Treated in this manner I. 0-3172 grm. of silver-salt dried at 100' C. gave 0.2115 , , chloride of silver. 11. 04464 , , silver-salt gave 0.2985 , , chloride of silver and 0.1656 , , selenium corresponding to the following percentages I. 11. Silver . . . 50.18 50-31 Selenium . . -37.09 and leading to the formula Ag C NSe,=Ag Csey.as the following table shows Theory. Mew of experiments. F-1 equiv. of Silver . 108*00 50.016 50.24 1 , , Cyanogen . 26*00 12.8 -,y 2 , Selenium . . 79-14! 37-13 37.09 1 ) , Silver-salt. 213.14 100*00 MRs CROOKES ON THE SELENOCYANIDES. Selenocyanide of Lead.-On adding acetate of lead to a solution of selenocyanide of potassium a lemon-yellow compound is precipitated. It is soluble in boiling water but is slightly decomposed; the filtered solution which is neutral to test paper deposits on cooling beautiful lemon-coloured needles which are insoluble in alcohol. The salt may be exposed without decomposition to a temperature of 100' C. but assumes when moist a slight pink tint.The crystals are extremely light. The lead was determined by heating a portion of the salt in a crucible with strong sulphuric acid which converts it entirely into sulphate. The carbon was determined in the usual manner. I 0.1735 grm. of selenocyanide of lead dried at loo' gave 0.125 , , sulphate of lead 11 0.6235 , , salt burnt with protoxide of copper gave 0.1309 , , carbonic acid. Centesimally I. 11. Lead . . . 49.22 -Carbon . . -5-72 The formula Pb C N Se = Pb Csey requires the following values Theory. Experiment. -1 equiv. of Lead . . . 103.56 49.62 49.22 2 , , Selenium . . 79.14 37.92 _. 2 , , Carbon . . l2*OO 5.75 5.72 1 , , Nitrogen . . 14.00 6.71 -1 , , Lead-salt . . 208-70 100-00 Selenocyanide of Mercury with Protochloride of Mercury.-This beautiful compound is obtained by adding an excess of protochloride of mercury to selenocyanide of potassiurn ;when concentrated solutions are employed the whole immediately solidifies into a felt-like mass of yellowish crystals ; these when washed with cold water are purified by crystallisation from alcohol.The crystals of this double salt are sparingly soluble in cold water rather more so in hot and very soluble in alcohol and dilute hydrochloric acid; it does not seem however to dissolve in the latter without decomposition as the solution deposits selenium after standing for Rome time ; nitric and nitrohydrochloric MR. CROOKES ON THE SELENOCYANIDES. acids dissolve it entirely the liberated selenium being immediately oxidized The crystals are anhydrous and may be heated to 100' C.without decomposition; they are decomposed a little above that tem- perature intumescing in a remarkable manner. The mercury was determined by dissolving the salt in hot dilute hydrochloric acid and precipitating that metal in the filtrate by hydro- sulphuric acid. The chlorine was estimated by dissolving in strong nitric acid and adding nitrate of silver. I also determined the chlorine and selenium in the same portion by fusing a certain quantity with nitre and carbonate of soda precipitating the chlorine with nitrate of silver removing the excess of silver with hydrochloric acid and precipitating the selenic acid by means of chloride of barium. I. 0.259 grm.of salt dried at 100' C. yielded 0.1755 , , protosulphide of mercury. II. 0.4673 , , double salt! yielded 0.3173 , , protosulphide of mercury. 111. 0.5625 , , salt gave 0.2369 , , chloride of silver and 0.477 , , seleniate of baryta. IV. 0.4425 , , salt gave 0.1855 , , chloride of silver. Percent age I. 11. III. Mercury . . 58-81 58.53 c_ Chlorine . . - - 10.38 Selenium . . - - 23.93 These numbers lead to the formula Hg C NSe Hg Cl representing a compound of equal equivalents of selenocyanide of mer- cury and chloride of mercury which requires the following values Theory. Mean of experiments. -2 equiv. of Mercury . . 200*00 58.71 58.47 1 , , Cyanogen . . 26.00 7.64 -2 , , Selenium . . 79.14 23-23 23-93 1 , , Chlorine .. 35-50 10.42 10.38 -7-1 , , Double salt . 340.64 100*00 All my attempts to produce the simple selenocyanide of mercury VOL. 1V.-NO. XIII. C MR. CROOKES ON THE SELENOCYANIDES. have hitherto failed. In repeated operations I did not obtain anything except the double compound. I was curious to ascertain whether sulphocyanide of potassium might exhibit a similar deportment with chloride of mercury. On adding the latter salt in excess to sulphocyanide of potassium I obtained a voluminous precipitate of needle-shaped crystals possessing about the same solubility in water alcohol and dilute hydrochloric acid as the selenocyanide but I was unable to detect a trace of chlorine in them either before or after cry stallisation from alcohol.On analysis the following results were obtained I. 0.3685 grm. of substance gave 0.2693 , , protosulphide of mercury. 11. 0.3877 , , salt gave 0.2831 , , protosulphide of mercury. Percentage I. 11. Mercury . . . . 62-99 62.93. The formula Hg C NS,= Hg Csy. requires the following values -Theory. Mean of experiments. 1 equiv. of Mercury . . . 1 , , Sulphocyanogen. 100-00 63.29 58-00 36-71 - 62.96 - 1 , , Mercury-salt . . 158.00 100*00 These numbers show that the salt under examination was the simple sulphocyanide of mercury which has not hitherto been anal y sed. Hence sulphocyanide and selenocyanide of potassium exhibit a different behaviour with chloride of mercury. Hydroselenocyanic Acid.-By suspending finely divided seleno- cyanide of lead in a warm aqueous solution of the same salt and subjecting it to a rapid stream of hydrosulphuric acid gas hydro- selenocyanic acid is obtained in solution ; the liquid filtered off from the sulphide of lead must be heated to near its boiling-point to expel the excess of hydrosulphuric acid and again filtered from a small quantity of precipitated selenium.Thus prepared it is a very acid liquid easily decomposed by boiling or exposure to the air ; it cannot be concentrated even over siilphuric acid in vacuo without MR. CROOKES ON THE SELENOCYANIDES. decomposition the addition of almost any acid causes an immediate precipitate of selenium hydrocyanic acid remaining in solution. It dissolves iron and zinc with evolution of hydrogen and displaces carbonic acid from the carbonates.All its salts may be formed from it by direct combination. The free acid existing only in solution an analysis became im- possible ;however the composition of the preceding compounds and the analogy of hydrosulphocyanic acid warrant the assumption of the formula H C N Se = H Csey and hence we have the following series Hydroselenocyanic acid . . H Csey. Potassium-salt . . K Csey. Silver-salt . . Ag Csey. Lead-salt . . Pb Csey. Mercury double-salt . . Hg Csey + Hg C1. The following salts I have only examined qualitatively. Selenocyanide of Sodium prepared by neutralising the free acid is alkaline and very soluble; it crystallises in vacuo in small foliated crystals.Selenocyanide of Ammonium prepared in the same manner is deposited in minute needles very similar to those of the potassiuni- salt ;it is extremely deliquescent. Selenocyanide of Barium-This salt was obtained by dissolving carbonate of baryta in the acid and evaporating over sulphuric acid in vacuo. I could not obtain it in any definite crystalline form. Selenocyanide of Strontiutn obtained like the barium-salt ;it crys- tallises in well-defined prisms. Selenocyanide of Calcium obtained in the same manner as the two former crystallises in groups of stellated needles. Selenocyanide of Magnesium dries up into a gummy mass ap-parently devoid of crystalline structure. Selenocyanide of Zinc.-This salt may be obtained either by dis-solving the metal or its oxide in hydroselenocyanic acid; it forms groups of prismatic needles which are not deliquescent.Selenocyanide of Iron.-Owing to the rapid decomposition of the salts of hydroselenocyanic acid when in contact with stronger acids I was unable to obtain any coloration with salts of sesquioxide of iron by double decomposition. I was also unsuccessful in preparing c2 MR. NOAD ON CERTAIN WELL-WATERS it by treating sesquioxide of iron with hydroselenocyanic acid selenium being immediately precipitated. The salt was however once obtained by accident; I was preparing some selenocyanide of potassium by igniting selenium with ferrocyanide of potassium; the result of the fusion was treated with absolute alcohol in a well-closed flask; on filtering off I found the liquid to have a deep blood-red colour which soon disappeared on exposure to the air with deposition of selenium.I have not obtained any colour at other times the iron always rernain- ing behind as a black powder chiefly containing carbide of iron. Selenocyanide of Copper.-When selenocyanide of potassium is added to sulphate of copper a brownish precipitate falls down which is probably the selenocyanide. I was unable to obtain it in a state fit for analysis as it rapidly decomposed even at the common tempe- rature into black selenide of copper with separation of hydroselenic acid. I cannot conclude without acknowledging the great obligation I am under to Professor Hofmann for placing at my disposal so large a quantity of selenium and also for his valuable advice and assistance during the progress of these experiments.

ISSN:1743-6893    

DOI:10.1039/QJ8520400012

出版商:RSC    

年代:1852

数据来源: RSC

摘要:

MR. NOAD ON CERTAIN WELL-WATERS IV.-On the Composition of certain Well-waters in the neighbourhood of London with some observations on their aclion on lead. BY HENRYM. NOAD,EsQ. LECTURER ON CIZEMISTRY AT ST. GEORGE’S HOSPITAL. The mineral and organic constituents of the waters employed for domestic use in large towns have lately occupied a considerable share of public attention. It has been justly considered.that the purity of this all-important fluid must exert great influence on general health and with equal truth has it been surmised that waters having their origin in the immediate neighbourhood of crowded cities must contain ingredients incompatible with their use as a beverage and for other household purposes. The mineral constituents of spring-waters usually take their charac- er from the geological nature of the localities in which they originate.Speaking generally they contain nothing objectionable ;but should there be a predominance of any particular ingredient or should the IN THE NEIQHBOURHOOD OF LONDON. amount of saline matter be considerable a marked character is given to the water which then receives the general name of ‘‘ mineral.’’ Such waters rarely require the assistance of the chemist to point out their unfitness for domestic use; they are distinguished either by a peculiar taste or smell or colour or hardness and are at once dis- carded. The question whether water for drinking should or should not contain mineral matter is still a vexed one; and as it is one of medi-cine rather than of chemistry it need not be discussed here.General experience would however seem to indicate that a certain amount of saline matter is not objectionable since there are no spring-waters that do not contain some. In this as in many other things taste grows out of habit and the fickleness of water-drinkers is well known. Those accustomed to the continued use of the purer kinds of water recoil almost with disgust from the saliferous springs while the drinkers of the latter object quite as strongly to the purer fluid as being to their palates flat disagreeable and almost nauseous. But whatever may be thought of the mineral constituents there can be but one opinion as to the influence of those organic impregnations so constantly met with in the waters of large towns.These consist for the most part of bodies in a state of progressive change or decom- position; and chemistry teaches us that such substances when brought into contact with other organic substances have a remarkable dispo- sition to communicate to them their own molecular disquietude-to bring about organic decomposition. What diseases then may the continued use of such water engender ? I believe as I shall presently have occasion to show that in addition to its general unfitness for domestic use water containing organic matter is particularly objec- tionable on account of its liability to become contaminated with lead when kept in cisterns of that metal ;and that earthy and alkaline sul- phates and chlorides even when present in considerable quantity do not in such waters act as preservatives Among the constituents of the well-waters of large towns nitric acid has often been alluded to.Mere traces of it have I believe hitherto been found; at least I am not aware that a quantitative determination of it in any of the waters in or about the metropolis has hitherto been published. That it does however occasionally exist in large quantities is shown by the following analysis by Mr. VV. Fisher of a well-water from Highgate one of a series of water-analyses that has for some time been in course of execution by the pupils in the labora- tory of this medical school. Attention was directed to this water 22 MR. NOAD ON CERTAIN WELL-WATERS ,firstly in consequence of its powerful action on the leaden cistern in wbich it was retained and secondly on account of the unusual amount of saline matter which it contained Its hardness has pre- vented its being much used for domestic purposes which may probably be deemed a fortunate circumstance as I have found the metal evidently acted upon after being immersed in a bottle of the water for a few days only.By the subjoined analysis it will I think appear that the remarkable action of this water on lead is referable to the comparatively small quantities of sulphates and chlorides and to the extraordinary amount of nitrates which it contains. The source of the latter is pretty clearly pointed out by the situation of the well which is immediately contiguous to the old churchyard on the very top of Highgate Hill the loose and sandy soil of which must be teeming with organic substances in all stages of decay and which therefore are constantly furnishing ammonia from the oxidation of which the nitric acid is in all probability derived.The putrefaction of animal matters in contact with calcareous soils is well known to produce nitrate of lime ;and it was long ago shown by G lauber that a vault plastered over with a mixture of lime wood ashes and cow- dung soon becanie covered with efflorescent nitre. In the water in question the nitric acid exists in combination with lime and mag-nesia which earths would naturally have occurred in the form of carbonates held in solution by carbonic acid. Not a trace of carbo- nate now exists ;neither does the water contain any appreciable quality of organic matter which has been destroyed by the powerful oxidising operations which are constantly going on in the contiguous soil.I have examined the water from six other wells at various distances from the churchyard but all coming within the range of the Bagshot sand formation in each nitric acid has been detected ;though from the great trouble attending the quantitative estimation of this sub- stance a complete analysis has as yet been made only of the one first referred to. Now though the presence of earthy nitrates does not perhaps communicate any injurious or unwholesome quality to a water-indeed from the entire absence of decomposing organic substances it may be less objectionable as a beverage than the average waters of large cities-it is nevertheless important to bear in mind the powerful action of such waters on lead and the possibility of its becoming the vehicle through which this subtle poison may be introduced into the system.The public indeed cannot be too emphatically warned against the too common practice of allowing uny water intended IN THE NEICHBOUREIOOD OF LONDON. for domestic use to remain stored up in leaden vessels ;for as I shall have to show presently the existence in the water of considerable quantities of both sulphates and chlorides is not always a security against saturnine impregnation. The nitric acid in the Highgate water was estimated by the fol- lowing process. An imperial gallon was concentrated by evaporation to about half a pint which was macerated with excess of recently prepared sulphate of silver and allowed to remain at rest for twenty-four hours.It was then filtered; rendered alkaline by carbonate of soda; again filtered ;and the filtrate concentrated by evaporation and distilled in a large retort with chemically pure sulphuric acid the distillate being collected in a receiver containing strong baryta-water. The distilla- tion was continued till fumes of sulphuric acid began to appear; it was then stopped and the retort allowed to cool ;a quantity of distilled water was then added ;and the distillation resumed and con- tinued as before till fumes of sulphuric acid began to rise. This operation was repeated thrice preliminary experiments having shown that the last portions of nitric acid are only expelled from the sulphuric acid residue by thus urging them forward in an atmosphere of steam.The contents of the receiver containing nitrate of baryta and excess of baryta-water were exposed to the air in a large dish far twenty-four hours-then filtered-and into the clear filtrate a slow stream of carbonic acid gas was passed till the liquor was no longer alkaline to test paper; it was next evaporated to dryness and the residue treated with successive portions of boiling water till the whole of the nitrate of baryta was dissolved out. The clear solution being precipitated with sulphuric acid gave the amount of sulphate of baryta corresponding to that of the nitrate and from which the amount of nitric acid was calculated.From the first experiment made on water taken from the well in June 1850 76.75 grs. BaO. SO = 85-96 BaO. NO = 35.53 grs. NO, were obtained. From the second made on water taken from the well in October there were obtained from 28,000 grs. of the water 33 grs. BaO. SO = 37 grs. BaO. NO = 15.29 grs. NO,. The latter experiment gives 38 grs. of nitric acid in an imperial gallon of the water a quantity rather larger than that obtained in the former experiment in which traces of nitric acid were found in the sul-phuric acid residue even after three additions of water. In the second experiment six additions of water were made in quantities of about four ounces each time-the residue was now found entirely free from nitric acid.24 MR. NOAD ON CERTAIN WELL-WATERS Saline contents in the Imperial pint By direct estimation 1.2057grains consisting of Silica . . 0-1120 grs. SuIphate of potash . . 2.1306 , Sulphate of soda . . f*f894 ,? Chloride of sodium . . 1*2040, Chloride of calcium . . 0.7390 , Nitrate of lime . 5.0150 , Nitrate of magnesia . . 2.1330 ,? 12.5230 The next water to which I shall call the attention of the Society is from a spring at Clapham which was submitted to me €or analysis in the summer of 1848 in consequence of its strong action on lead. I collected the water myself on the spot and on the same occasion was shown the cistern which was then nearly full of water the surface of which was covered with a tbick greasy scum which proved on examination to consist almost entirely of oxide of lead.1 expected to find this water unusually pure ; to my surprise how- ever it contained nearly 78 grains of solid matter per imperial gallon the composition of which was SiTica. . 0.24 Carbonate of lime . 15-09 0 Carbonate of magnesia . 13.97 Sulphate of lime . . 15-32 Sulphate of potassa . 6.79 Sulphate of soda . 10.77 Chloride of sodium . 11-46 Organic matter . 410 77.74 Here then we have an instance of a water containing an abundance of so-called preservative salts,” corroding lead with remarkable energy,* The oxide of lead could be skimmed from the surface of the water in abundance; but on testing the water beneath taking care to avoid filtering by which a very considerable quantity of the metal even * I was shown by the plumber a piece of the bettom of the cistern which in the cuurse of six months had been eaten into holes.IN THE NEIGHBOURHOOD OF LONDON. 25 when in solution niay be removed no signs of lead could be detected To what are we to ascribe this remarkable action? I believe to the presence in the water of an unusually large quantity of organic matter. It was during the summer months that the corrosion of the cistern took place so rapidly. The organic matters would then be undergoing the most active decomposition and car- bonic acid being constantly evolved against the sides and bottom of the cistern would enter into combination with the surface-oxide and so form carbonate of lead.This is by no means the only instance I have met with of water abounding in sulphates and chlorides acting strongly on lead and in every case that I have yet examined organic matter has been present in unusual quantity. It is worthy of remark that no lead could be found in solution; whenever this does occur in any but pure or alkaline water the metal is probably taken up in the form of oxichloride. Carbonate of lead is wholly insoluble even in water highly charged with carbonic acid. I men-tion this because an idea is very generally prevalent that carbonate of lead like the carbonates of lime and magnesia may be rendered soluble by taking up an extra atom of carbonic acid. I have made direct experiments which negative this assumption and it has since been pointed out to me that the same had been previously done by Dr.Taylor. But water though it cannot take up carbonate of lead in solution may by keeping it in mechanical suspension be the means of introducing this dangerous form of saturnine poison into the system. The practice of filtering water preserved in leaden cisterns and intended for domestic use cannot therefore be too warmly recommended. I wish lastly to say a few words on another class of waters which act strongly on lead viz the artesian-well zoaters of the London basin These waters are I believe always alkaline; those which I have examined are remarkably free from organic matter and as there is no deficiency of preservative salts it is to their alkalinity that I am inclined to attribute the corrosive action which they exert on this metal From several analyses of these waters which have lately been made in this laboratory I select two one from the premises of the Lord Chief Baron at Hatton which was examined by Mr.Henry Pollock in consequence of the rapidity with which it corroded the leaden cistern; and the other from the Lunatic Asylum at Colney Hatch which I analyzed at the request of Mr. Roteh the Chairman of the Board of Governors of that institution with the iew of ascertaining its general fitness for the purposes of the asylum before fresh expenses were incurred for conveying it to MR BUCKTON ON THE DEPORTMENT OF different parts of the building.It is worthy of remark that Mr. Pol-lock was able to detect lead in the clear water of the cistern which I had been unable to do in the case of the Clapham water. The analysis of these two artesian waters gave the following results per imperial gallon Hatton. Colney Hatch. Carbonate of lime . 2.120 6,500 Carbonate of magnesia . -880 1*320 Carbonate of soda . . 15.196 7.100 Sulphate of potash . . traces 2.590 Sulphate of soda . . I 10-456 5.770 Sulphate of lime . 1 4.555 Chloride of magnesium . 99 4-260 Chloride of sodium . . 9.288 I9 Protocarbonate of iron . *480 79 Soluble organic matter Phosphate of lime . . . ft traces -470 traces Silica . *050 8670 38.470 33.235 Saline matter by direct estimation . 384 32.97 Of the excellence of both these waters for domestic use the analyses bear ample testimony; but with the example of the Hatton water before me I felt bound to warn the Governors of the Colney Hatch Asylum against the use of lead either for storing the water or for distributing it.I found however on visiting the institution that my warning was not required that metal being almost entirely banished from every part of the building.

ISSN:1743-6893    

DOI:10.1039/QJ8520400020

出版商:RSC    

年代:1852

数据来源: RSC

摘要:

MR BUCKTON ON THE DEPORTMENT OF V.-Observations upola the Deportment of Diplatosamine with Cyanogen. BY G. B. BUCKTON, EsQ.,F.L.S. The peculiar deportment exhibited by aniline toluidine and several other volatile organic bases when exposed to the action of cyanogen rendered it desirable to investigate the behaviour of some of the fixed bases in the same direction. At the request of Dr. Hofmann and with his supervision I have undertaken some experiments on this DXPLATOSAMINE AND CYANOGEN. subject the results of which I beg to communicate to the Chemical Society. The substance on which I have worked is the remarkable alkaloid discovered by Reiset obtained by the action of ammonia upon the green salt of Magiius long known under the name of Reiset’s first platinum-base for which more recently the shorter name of diplato- samine has been proposed.On passing a stream of cyanogen through a moderately concen- trated solution of diplatosamine free from carbonic acid the gas is slowly absorbed and after some time a yellowish-white crystalline substance is deposited which continues to form until the solution changes colour from the partial decomposition of the cyanogen at which point it is desirable to suspend the operation. This substance is soluble to a slight extent in cold but much more readily in boiling water from which it may be recrystallised without difficulty. It then appears as a mass of minute colourless crystals which under the microscope exhibit the form of hexagonal plates and frequently arrange themselves in regular stellar groups.It is how- ever difficult to obtain them without a yellow tinge from traces of decomposed cyanogen which obstinately adhere even after three zrys-tallisations. When heated in the air the substance spontaneously takes fire and smoulders like tinder leaving as sole residue a light sponge of platinum. It freely evolves ammonia when heated in a dry test-tube; but the presence of cyanogen could not be detected by the usual test of potassa proto-sesquioxide of iron and hydrochloric acid. On analysis this substance gave the following numbers I. 0.3465.grm. of substance dried at looo left on ignition 0.2410 , ,,platinum. IF. 0.4005 , , substance gave 0.2780 , , platinum. 111. 0.4588 , , substance when burnt with soda-lime yielded 1*4700 , , ammonio-chloride of platinum equivalent to 0.0922 , , nitrogen.IV. 0.3957 , , substance yielded 1.2775 , ,,ammonio-chloride of platinum equal to 0*0801 , , nitrogen. These numbers correspond to the following percentages I. ’ 11. 111. IV. Platinum . . . 69.55 69.41 -Nitrogen . . . -20.09 20.24 MR. BIJCKTON ON THE DEPORTMENT OF and also to the formula Pt NH Cy as is exhibited in the annexed table Theory. Experimental mean. r--7 7*-7 1 equiv. of Platinum . . . 98.68 69.64 69.48 2 , , Nitrogen . . 28.00 19.78 20.16 3 , , Hydrogen. . . 3.00 2.12 -2 , , Carbon . . . 12.00 8.46 --____I 141.68 100*00 These analyses show that the action of cyanogen upon diplatosa- mine far from being analogous to that on aniline toluidine &c.(which as is well known combine directly with the gas,). gives rise to the same compound which Reiset obtained by saturating the base with hydrocyanic acid and which he considered as the cyanide of his second series viz. as the hydrocyanate of platosamine or as the cyanide of platosammoniurn. Pt H2}N. HCy orF[}N. Cy. I have carefully compared the substance prepared by the action of cyanogen with that obtained by Reiset’s method and find them identical in all respects. It may be mentioned here that a very convenient method of obtaining the compound in considerable quantity consists in adding cyanide of potassium to the chloride of diplatosammonium (the direct product of the action of an excess of ammonia upon protochloride of platinum).By this process the tedious operation of isolating the base is avoided ; the precipitate requires only two or three crystallisa- tions to remove the soluble chloride of potassium. The formation of the cyanide by the action of cyanogen upon a SO-lution of diplatosamine is readily intelligible. The mother-liquor of the crystals was found to contain a con-siderable quantity of carbonate of ammonia and moreover the carbonate of diplatosamine. This compound was identified by con- version into the sulphate and analysis of the latter. It is evident that the first action consists in a decomposition of water the elements of which unite with cyanogen producing hydro- cyanic and cyanic acids; the former giving rise to the crystalline cyanide ammonia and water PtH N 0.HO + HCy=PtH N . Cy+ NH,+2 €30; DXPLATOSAMINE AND CYANOGEN. the latter inducing the transient formation oi cyanate of diplatosa- mine which by assimilation of the elements of water is immediately converted into the carbonate of this alkaloid and carbonate of am- monia. Pt H N 0,Cy 03-4 HO=Pt H N 0 CO +NH 0CO,. As the general deportment of the salt Pt H N Cy seemed to be somewhat anomalous and in many respects different from that of an ordinary cyanide (the usual tests failing altogether to indicate the presence of cyanogen) I have studied the behaviour of this compound with various reagents in order if possible to obtain new data by which to elucidate its constitution.The cyanide in question is soluble in potassa without decomposition. It imitates in this respect the deportment of cyanide of silver. It is also soluble without change in hydrochloric acid although the crystals deposited from the solution assume a somewhat different shape and a yellow colour.* It may be recrystallised without decomposition also from dilute sulphuric acid. Concentrated sulphuric and nitric acids however decompose it ; but the products of these reactions have not been farther examined. The action of nitrate of silver upon the cyanide is very remarkable and appears to throw much light upon the true nature of this substance. When nitrate of silver is added to an aqueous solution of the cya- nogen-compound a copious white and curdy precipitate immediately falls in outward appearance resembling cyanide of silver and like the latter salt soluble in ammonia.On evaporating the solution filtered off from the precipitate at a gentle heat a crop of beautiful crjrstals made their appearance which lost their transparency on carrying the evaporation to dryness. On raising the temperature beyond this point they suddenly took fire and left a residue of pure platinum. In the conception of the substance being cyanide of platosammonium * The substances crystallised from potassa (I.) and from hydrochloric acid (11.) were identified by analysis. I. 0.4065 grm. of substance gave 0,2830 ,) , platinum. 11. 0.4685 , ,? substance gave 0.3250 ? 9t platinum. The experimental and theoretical percentages are- Mean of Theory.Experiment* experiments. 1. 11. Platinum . . . 69.64 69.61 69-37 69.49 MR* BUCKTON ON THE DEPORTMENT OF I was inclined to consider these needles as the nitrate of platosamine when the reactions would have been represented by the equation PtH,N.Cy+AgNo,=Pt H,N.NOG+AgCy. In order to verify this equation the needles were subjected to analysis when the following results were obtained I. 0.5030 grm. of this salt gave 0.2525 , , platinum. 11. 0.3930 , , from another preparation 0,1960 , , platinum. These numbers far from agreeing with the formula of the nitrate of platosamine exhibit on the contrary a close accordance with the theoretical values required by the composition of the nitrate of Reiset’s &st compound as may be seen by the following com- parison Theory.Experiment. r-pA--7 7-7 Pt H3N NO Pt H6 N NO I 11. Platinum . 55-53 50.68 50.19 49.87 As the determination of nitrogen in the nitrate presented some diffi- culties to vary the analysis and furnish a means of corroboration a solution of the cyanide was precipitated with sulphate of silver the filtrate evaporated and the platinum determined in the sulphate thus obtained- 0.4080grm. of substance gave 0.2215 , , platinum. This result perfectly corroborates the inference drawn from the former analysis namely that the action of nitrate of silver upon the cyanide under examination gives rise to the formation of a salt not of platosamine but of diplatosamine (Reiset’s first base).For the sake of comparison I subjoiu. the theoretical percentage of the salt Theory. Experiment. Platinum. . . . . 5461 54-22 The unexpected results obtained in the examination of the soluble compound produced by the action of the silver-salt upon the cyanide compelled me more carefully to investigate the white precipitate which hitherto I had regarded as cyanide of silver. I found at once that this precipitate is by no means cyanide of silver but that it con-tains platinum as one of its constituents. The quantitative analysis of this white compound presented how- DIPLATOSAMTNE AND CYANOGEN. 31 ever some diffticulty from the extreme tenacity with which the cyano- gen holds the combined metals. No constant results could be obtained by fusing with carbonate of soda and potassa ignition with soda lime or the combined action of nitric acid and chlorate of potassa.The analysis however succeeded without dificulty when the salt under examination was dissolved in strong ammonia and immediately pre- cipitated with sulphide of ammonium when pure sulphide of silver is thrown down the whole of the platinum remaining in solution. This solution when evaporated yielded at first beautiful iridescent crystals which subsequently left pure metallic platinnm on ignition. In this manner the following results were obtained I. 0.6019 grm. of substance gave 0.2884 , , sulphide of silver equal to 0.2511 , , metallic silver and 0.2305 , , platinum. 11. 04555* , , substance gave 0.1745 , , platinum.These numbers correspond to the following percentages I. 11. Platinum . . . 38.29 38.30 Silver . . . . 41.71 -and prove that the white precipitate is nothing but platino-cyanide of silver Ag Pt cy, as is exhibited in the following comparison of the experimental results with the values required by theory. Theory. Mean of experiments. r---2 equiv.of Cyanogen . . . 52.00 20.15 -1 , , Platinum . . . . 98.68 38.10 38.29 1 , ,) Silver . . . . . 108-00 41*75 41.71 1 , , Platino-cyanide of } 258-68 silver . . . . 100-00 This conclusion was fully borne out by the deportment of the silver- salt with reagents when compared with that of the platino-cyanide obtained by the usual method. Detailing the analysis of this substance I have mentioned that on treating the ammoniacal solution of the cyanide with hydrosulphuric * The silver was lost.MR BUCKTON ON THE DEPORTMENT OF acid iridescent needles are obtained. These needles are the corre- sponding platino-cyanide of ammonium. A similar result was found when the silver-salt was treated with potassa with which on ebullition it gave a heavy black precipitate containing all the silver and a colourless solution which yielded long needles of a purple hue by reflected and yellow by transmitted light. These crystals change to a deep yellow when heated and then fuse to a mass of carbon and platinum. The aqueous solution of this compound gives first a bright orange precipitate with the nitrate of the siiboxide of mercury which speedily changes to a cobalt-blue on increasing the quantity of the mercury-salt.It need scarcely be mentioned that this deportment in all respects agrees with that of the platino-cyanide of potassium described by Gm elin which moreover was satisfactorily proved by direct comparison of the two salts. The formation of platino-cyanide of silver from the cyanide which forms the subject of the present communication fully explains the simultaneous production of a salt of Reiset’s first base. The reaction is expressed by the following equation 2 Pt H N . Cy + Ag NO6= Pt H6 N . NO6+ Ag. PtCy,. To obtain a quantitative control of the correctness of this equation a weighed portion of the cyanide was decomposed by nitrate of silver.The precipitated salt was carefully dried upon a weighed filter and the quantity obtained compared with the amount required by theory. I. 0-2398grm. of salt produced 0.2275 , , platino-cyanide of silver. 11. 0.5935 , , another specimea gave 0.5425 , , platino-cyanide of silver. The quantity required by theory and obtained by experiment re- duced to 100parts is as follows Theory. Experiment. I. 11. 91-29 90.70 91.40 The facts observed in the study of the crystalline compound which is formed by the action of hydrocyanic acid or cyanogen upon the oxide of diplatosammonium suggests a mode of viewing the constitu- tion of this substance which is different from that hitherto adopted. ’ If with M. Reiset we consider this compound as the cyanide of platosammonium we are forced to admit that this substance owes its origin to a very singular play of affinity inasmuch as the influence of DIPLATOSAMINE WITH CYANOGEN.hydrocyanic acid on the oxide of diplatoeammonium gives rise to the cyanide of platosammonium whilst on the other hand a metallic solution reconverts this compound into a salt of the original base. It appeared much simpler to regard the compound in question as a salt of the base from which it is derived viz. as a platino-cyanide of diplatosannmoniuni which is isomeric with the cyanide of platosammo-aium. 2 Pt H N . Cy=Pt H N,. PtCyz. This formula explains equally well the formation of the substance by the action of hydrocyanic acid upon the oxide of diplatosammo-nium 2PtH6NgO+4HCy=Pt H6N,.PtCy,+2NH,Cy+% HO but the interpretation of its behaviourwith silver-salts becomes infinitely simpler as the whole change is reduced to a case of ordinary double decomposition.ft H6 N,. Pt Cy + Ag NO = Pt H N . NO + Ag Pt Cy,. t-,-J L-y-L L-v-J ----I Platino-cyanideof Nitrate of Nitrate of Platino-c yanide diplatosammonium silver. diplatosammonium. of silver. To test the accuracy of this view experimentally I prepared a quantity of hydroplatino-cyanic acid by treating the mercury-salt with hydrosulphuric acid. On saturating this acid with the oxide of diplatosammonium I obtained at once a colourless crystalline sub- stance which could not be distinguished from the cyanide previously described either by appearance or behaviour with reagents.The same salt may be more conveniently procured by adding platino-cyanide of potassium to the chloride of diplatosannmonium. On recrystallising and drying at looo 0.2084 grm. of substance gave on ignition 0*14?4!6, , platinum in accordance with the formula Pt H N, Pt cy, the calculated and experimental numbers in 100 parts being Theory. Experiment. Platinum . . . 69.64 69.34 On reference to Reiset’s excellent paper upon the platino-bases it doesnot appear that he attempted the construction of the cyanide of platosammonium by directly operating upon a salt of the correspond- VOL. IV.-NO. XIII. I) DR. GLADSTONE ON THE EXPLOSIVE COMPOUND ing base considering doubtless that the substance would prove itself identical with that previously described by him.As a last step it appeared desirable to try the preparation of the true cyanide of platosammonium as it was not improbable that a com- pound might be thus obtained similar in composition but differing in its molecular arrangement and consequently presenting some possible discrepancies in its chemical and physical properties. Accordingly I digested a few grammes of the chloride of platosam-nionium with an excess of cyanide of silver ; the decanted liquid was found to yield on concentration fine and regular needles of a pale-yetlow colour. These crystals proved to be much more soluble in water and ammonia than the platino-cyanide of diplatosammonium from which they also materially differed in their deportment with reagents.0.4695 grm. of substance gave 0,3256 , , platinum which agrees with the formula Pt H,N cy the numerical percentages being Theory. Experiment. Platinum . . 69.64 69.35 Hence it is evident that there are two substances of the same corn-position the one by the mode of formation and behaviour with re& agents proved to be a salt of a platinum-base with a platinum-acid (platino-cyanide of diplatosammonium) the other as far as we can judge from the method of preparation the true cyanide of platosam- monium. The latter substance appears to call for closer attention than I have been able to bestow upon it; but I hope at a future time to have the honour of laying the results of an extended examination before the Chemical Society.

ISSN:1743-6893    

DOI:10.1039/QJ8520400026

出版商:RSC    

年代:1852

数据来源: RSC

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DR. GLADSTONE ON THE EXPLOSIVE COMPOUND VI.-Onl the Explosive Compound usually de~o~~~~~e~ loda’deof Nitrogen. BY J. H. GLADSTONE,Ph.D. F.C.S. The following experiments were made last summer vith a view to settle the real composition of the so-called iodide of nitrogen.” This substance resulting from the mutual action of iodine and ammonia in U8UA LLY DENOMINATED IODIDE OF NITROGEN. solution has already been the subject of much investigation ; and the study of its reactions by different chemists has led to four different formulze being assigned to it. The extremely explosive character of the substance precludes the idea of analysing it in the usual manner as it would be impossible to place a portion in the scale-pan of a balance with any safety after it had been dried.Indirect modes of analysis by which the relative proportion of its constituent elements is determined appear to be offered by various decompositions which the black powder may be made to undergo. "I.Bineau* alone has studied any of these hitherto and his experiments led him to assign to the so-called iodide of nitrogen the composition NHI,. The quantitative results recorded below will test the truth of this €ormula. The substance employed by me was always prepared by decom- posing an alcoholic solution of iodine by means of ammonia in excess The black powder thus formed was completely washed by suffusion with distilled water and decantation. It was found that during this reaction an amount of iodide of ammonium is formed slightly exceeding half the amount of iodine employed a mere trace of iodic acid is also produced.This fact is opposed to the formula NI assigned to the black powder by Mitscherlich ;for 4 NH3+4 I=NI+3 NH I; in which case the iodide of ammonium obtained would be quite three-fourths of the iodine originally acted upon; but it decides nothing as to whether 1 2 or 8 atoms of hydrogen in the ammonia are substituted by iodine; for 2 I + 2 NH = NH I + NH I (Millon). 4 I + 3 NH = 2 NH I + NHI (Bineau). 6 I + 4 NH = 3 NH I + NI,. The black powder suffers spontaneous decomposition in pure water. Bubbles of gas are slowly given off; iodine is set free; and the solution (which is acid to test paper) contains hydriodic and iodic acids together with ammonia.In an attempt to make use of this decomposition as a means of analysis the iodic acid was found to be to the hydriodic acid in the ratio of 1 atom to 8.44 atoms; but it is not likely that the two acids always maintain the same pro-portion The addition of ammonia to the water in which the black powder is immersed tends to prevent its spontaneous decomposition. * Ann. Ch. Phgs. [3] XV 71. 332 DR. GLADSTONE ON THE EXPLOSTVE COMPOUND Potash on the contrary accelerates it. So do acids in general. A solution of carbonate of potash has much the same action as pure water. Chlorine destroys the black powder but not instantaneously ; bromine water causes its immediate decomposition. Strong nitric acid attacks it violently.Hydrosulphuric acid causes its instant decomposition without the evolution of any gas and with the formation of ammonia and hydriodic acid alone sulphur being in the meantime deposited. This affords a ready method of determining the relative proportion of iodine and nitrogen. Accordingly some of the black powder was diffused through water and a stream of hydrosulphuric acid gas was passed through it until the solution which assumed at first a red tint became colourless and smelt strongly of the gas. It wits then gently heated and filtered; the hydriodic acid was precipitated as silver-salt excess of silver was removed by the addition of a large excess of hydrochloric acid and the resulting chloride of ammonium was estimated in the usual manner.The amount of ammonio-chloride of platinum obtained was 5.83 grs. ;that of iodide of silver 12.53 grs. which is equivalent to Nitrogen . . . . 0.366 grs. Iodine . . . . . 6.75 , If we divide these numbers by the atomic weights of the respective elements we obtain Nitrogen . . . . . 261 Iodine. . . . . . 533 or the proportion of 1 atom of nitrogen to 2.04atoms of iodine. The action of sulphurous acid appeared to offer the means of determining the relative proportion of nitrogen iodine and hydrogen also if that element really be a constituent of the black powder. The transformation of the substance into ammonia and hydriodic acid takes place instantly without the evolution of any gas unless the temperature be suffered to rise considerably when a secondary action is instituted.At the same time a quantity of sulphurous acid is converted into sulphuric acid equivalent of course to the quantity of water decomposed in order to supply the necessary hydrogen. A carefully prepared fresh solution of sulphurous acid was added gradually to some of the black powder diffused through water until the decomposition was complete. The solution thus obtained was divided into two equal portions. The one portion was evapo- USUALLY DENOMINATED IODIDE OP NITROGEN. rated down with excess of hydrochloric acid and the ammonia was converted into platinum-salt ;the other portion was very gently warmed to expel sulphurous acid nitrate of silver was added to precipitate the iodine and subsequently the sulphuric acid was thrown down as baryta-salt.There were obtained 8.65 grs. of ammonia-chloride of platinum ;18.53 grs. of iodide of silver; and 17.57 grs. of sulphate of baryta. This is equivalent to Nitrogen ......0.542grs. Iodide .......9.98 , Sulphuric acid ....6-04 , Dividing these numbers by the atomic weights we obtain Nitrogen .....388 or 1 equiv. Iodine ......788 ,,2.03 , Sulphuric acid ...1520 ,,3.92 , This confirms the preceding result and shows moreover that the black powder contains 1 equivalent of hydrogen; for 1 atom of ammonia 2 atonis of iodine and 4 atoms of sulphuric acid can only arise from 4 atoms of sulphurous acid 4 atoms of water and NHI,. NHI I-4 SO +4 HO =NH +2 HI +4SO,. Serullas* observed that when this black powder is decomposed by dilute hydrochloric acid a red solution is obtained from which the addition of an alkali reprecipitates the explosive compound a portion however being always decomposed into its elements.Millont made the further observation that if the black powder be treated with a saturated solution of hydrochloric acid it dis-appears without the evolixtion of any gas and the resulting solution is neutral to test paper. He believes that the substance is resolved into ammonia and the acids of iodine and concludes from this peculiar reaction that the explosive body must have the composition NH I. It is difficult to see how this conclusion follows from the premises the more natural idea would be that the black powder being ammonia in which a portion of the hydrogen is replaced by iodine combines as such with the hydrochloric acid thereby neutralising it.Yet Serullas has long since recorded various reasons tending to prove that this is not the case :he believed that the solution contained iodic and hydriodic acids along with the hydro- chloric acid; and what confirmed him in this belief was the obser- *Ann. Ch. Phys. XLII 200. t Ann. Ch. Phys. [2] LXIX 83. DB. GLADSTONE ON IODIDE OF NITROGEN. vation that when these two acids of iodine are mixed together and supersaturated with ammonia the explosive compound is obtained especially if hydrochloric acid be present. Now this certainly arises from the two acids when mixed reacting upon one another to produce free iodine; and the explanation of the eminent chemist just mentioned does not account for the fact that when the decom- position of the black powder has been effected by water or other acids than the hydrochloric a solution is obtained from which ammonia does not reprecipitate it.On repeating the experiment I found that the red solution obtained by dissolving the explosive compound in strong hydro- chloric acid contains not a trace of free iodine; it gives no blue colour with starch. When evaporated to dryness in a water-bath it comes out as a solid body of a somewhat yellow colour soluble in water or alcohol and neutral or nearly so to test paper. If potash or baryta-water be added to this solution it re-precipitates the black powder. The addition of nitrate of silver causes a mixed precipitate of chloride and iodide of silver.Sulphurous acid gives rise to a separation of iodine which a larger quantity converts into hydriadic acid. The dried substance when heated per se suffers decompo- sition; it gives off a pungent odour then iodine sublimes and afterwards chloride of ammonium. Ether extracts from the evapo- rated solution that which imparts to it its colour and leaves some chloride of ammonium behind. All these reactions are perfectly explained by considering the solution produced by means of hydro- chloric acid as a mixture of chloride of ammonium and protochloride of iodine. The reaction is as follows NHI,+3 HCl=NH C1+2ICI. And it has been already ascertained by Mitscherlich that the explosive compound is produced when protochloride of iodine is treated with ammonia.The reaction in this case will be 2 IC1+ 3 NH =NHI +2 KH C1. The same cheniist states that terchloride of iodine with ammonia causes the formation of the same black powder. If this be really the case we must suppose that some one of the oxygen-compounds of chlorine is formed at the same time. But an aqueous solution of terchloride of iodine is to say the least of very uncertain consti- tution; and even the liquid resulting from the action of aqua regia upon iodine may contain the protochloride. If iodic acid be dis- solved by strong hydrochloric acid in the cold a yellow solutiofi DH.. HOPMANN’S COMPOUND TESTING JET. is obtained having a chlorous odour; but I find that the addition of ammonia causes no black precipitate in such a solution unless it has been previously heated.In accordance with the practice now adopted in naming those compounds in which two equivalents of hydrogen in ammonia are replaced by two of another body this explosive compound should bear the appellation “Iodimide.” When this paper was read before the Society Dr. Playfair re-marked that some time since he had prepared the same explosive powder by pouring a solution of hypochlorite of lime into a solution of iodide of ammonium He believed they were in the proportion of single equivalents; and as this reaction may be readily explained under the supposition that the compound is NH I it had confirmed in his mind the view propounded by Millon.Upon considering the reaction subsequently I perceived that a compound having Bineau’s formula might equally be obtained from the same salts in the same proportions but that ammonia would appear among the products of decomposition. The reaction might be either CaO C10 + NH,I=NH I +2 Ca C1+4 I30 or 2(Ca0 C10)+2 NH,I=NH I,+2 Ca C1+4 HO+NH Upon repeating the experiment with bleaching powder any alkaline reaction of which had been more than neutralized by acetic acid I found a large quantity of ammonia set free. This reaction then like every other with which I am acquainted indicates the same composition for this explosive powder.

ISSN:1743-6893    

DOI:10.1039/QJ8520400034

出版商:RSC    

年代:1852

数据来源: RSC

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DH.. HOPMANN'S COMPOUND TESTING JET. VII.-Campoz&nd Testing Jet. BY A. W. HOFMABNN, Ph.D. F.C.S. The very extensive and daily increasing application of gas as a source of heat in chemical experiments has suggested to me a small contrivance which is intended to facilitate the operations of the analyst. The ordinary Argand gas-burner which is almost universally employed for heating small vessels such as flasks retorts and test-tubes is not adapted to the purposes of the blow-pipe. In opera-tions with the latter instrument a simple jet of gas is required .j.a DR. HOFMANN'S COMPOUND TESTING JET. issuing from a cylindrical orifice of rather considerable dimensions the necessary amount of gas being adjusted by the stop-cock. This simplest of all gas-flames serves equally well for oxidation and reduc- tion and exhibits the phenomena of colour in the most conspicuous manner.The ordinary method of analysis being a combination of testing in the moist way and by the blow-pipe it is necessary either to use two gas-lamps-the one with the Argand burner the other with the single jet-or to have a gas-stand so arranged as to admit of screw-ing on either the one or the other. Rut as it is inconvenient to multiply the number of gas-lamps especially in a laboratory in which several analytical students are working and as unscrewing hot gas- jets is a most unpleasant operation I have endeavoured to unite the two jets in one stand dispensing at the same time with the necessity of taking the apparatus to pieces.The object in view is accomplished simply by substituting for t,he ordinary stop-cock a three-way cock. The whole arrangement be-comes at once intelligible by a; glance at the wood-cut which represents the burner half-size. A is'the loaded' foot into which the elbow-union-piece B is screwed. One end of this union is connected with a flexi- ble pipe? not shown in the draw- ing; to the other screws the three-way stop-cock C. The plug .V has only one orifice and when turned in a vertical di- rection supplies the Argand-burner through the perforation E. Into the side of the stop- cock is soldered a small pipe F having a bore of about Q of an inch. This is prolonged to the distance of Tb of an inch above the top of the Argand burner where it is brazed to a small support for the blow-pipe not represented in the drawing.Wlien the plug D is turned DR. KOLBE ON THE ORGANIC RADICALS. in a horizontal direction the gas is shut off from both jets but when turned in an inclined position may be made to supply both jets at once or either alternately. By this contrivance either of the jets will be lighted before the other is extinguished. In order that the jet may be likewise used for heating larger apparatus there is a support G on which may be fixed a copper chimney either plain or provided with the wire-gauze for producing the air-flame. The above burner has been made under the superintendence of Mr. J. J. Griffin whose assistance I thankfully acknowledge.

ISSN:1743-6893    

DOI:10.1039/QJ8520400039

出版商:RSC    

年代:1852

数据来源: RSC

摘要:

DR. KOLBE ON THE ORGANIC RADICALS. VIII.-Or&the Chemical Constit.ution and Nature of Organic Radicals. BY N. KOLBE,Ph.D. F.C.S. (Conclusion.) Of all the chemical compounds with which we are as yet more intimately acquainted no one is more nearly related to the alcohols represented by the general formula C H(n+z)O, than hydrated oxide of phenyl (phenylic acid) (CI2H,) 0.HO. If the general characters of the alcohols consist in. their property of combining with sulphuric acid to form the so-called etherosulphuric acids ; in the capability possessed by the oxides they contain of simulta-neously eliminating their water of hydration and combining on the one hand with acids to form neutral salt-like compounds (the so-called compound ethers) and exchanging on the other hand their oxygen for chlorine bromine sulphur &c.whereby thus combinations similar to chloride or sulphide of ethyl are pro-duced which may be re-converted into the corresponding alcohols ; and finally if the alcohols are characterised by being converted when heated with the hydrates of the alkalies or other oxidising agents into the conjugate acids of their series,-oxide of phenyl may be said to fulfil these conditions inasmuch as it combines with sul- phuric acid to phenylosulphuric acid HO .SO,+ (C12H5) 0.SO, which exchanges its basic atom of water for other bases analogously to sulphovinic acid thus yielding neutral double salts of oxide of phenyl with a metallic sulphate which on being heated produce again hydrated oxide of phenyl.The analogy is carried out farther by the DR. KOLBE ON THE CHEMICAL property of hydrate of phenyl noticed by Laurent and Gerhardt* in their beautiful researches on the phenides of combining in the nascent state with acids for example with benaoic acid to form a kind of ether corresponding to benzoic ether {C12H5) 0.(cl2H,)-C, 0 (benzoate of oxide of phenyl) (C H6) 0.(CI2 H,)^C, 0 benzoate of oxide of ethyl (C12H6) 0.((4 H,)^C, 0 benzoate of oxide of phenyl which by being heated with hydrate of potassa is split again into its constituents benzoic acid and hydrated oxide of phenyl. The latter substance participates likewise in the peculiarity of the alcohols of yielding the haloid-compounds of the radical corresponding to the oxides if we may consider as such a compound the chloride of phenyl (C12H5) C1 obtained by Gerhardt and Laurentf by the action of pentachloride of phosphorus upon hydrated oxide of phenyl an ether-like substance which is re-converted by boiling with solution of potassa into phenyloxide-potassa (phenylate of potassa) With regard to the property of the alcohols of being converted by means of appropriate oxidising agents into definite acids which contain the same amount of carbon but two equivalents less of hydrogen which are replaced by two equivalents of oxygen the acid which corresponds to hydrated oxide of phenyl :HO.(Cl0 H,)^C, O, is as yet unknown; it can however scarcely be doubted that we shall succeed in obtaining it directly from hydrated oxide of phenyl as soon as proper energies have been directed towards filling up this gap.Hydrated oxide of phenyl exhibits on the other hand very re- markable differences from the alcoholsof the fatty acids. The oxides of the latter are mostly gifted with feebly basic properties and com- bine with acids particularly when they meet with them in the nascent state The oxide of phenyl however which certainly forms similar combinations although with much greater diGculty is evidently possessed of a far greater tendency to perform the part of an acid. Like water and many metallic oxides which comport themselves with strong bases like acids and with acids like bases this substance is capable of entering into combination with both ;forming apparently with the acids neutral compound ethers but only when the acid itself is in the nascent state as is for instance the case in the decomposi- tion of the so-called chloride of benzoyl (dinoxy-chloride of benzoyl) by hydrated oxide of phenyl into benzoate of oxide of phenyl.The hydrated oxide of phenyl combines as is well known with much * Gerhardt et Laurent C. R. 1849,429. f Gerhardt et Laurent C R. 1849,435. CONSTITUTION AND NATURE OF ORGANIC RADICALS. 43 greater readiness with the alkalies directly forming pure s&s from which it is separated unaltered by stronger acids in the form of oily drops. Oxide of ethyl does not however appear to be totally devoid of acid properties. The two well-known crystallised salts ethyl- oxide-potassa and ethyloxide-soda are perfectly analogous ta the phen yloxide-potassa.A second far more characteristic difference between the phenyl- compounds and those of the common ether-radicals consists in the proportionately much greater stability of phenyl exhibited in an unequivocal manner by the remarkable metamorphoses whiuh hy- drated oxide of phenyl undergoes when acted upon by chlorine bromine or nitric acid. It can now be scarcely doubted any longer that chloro-bromo-and nitrophenylic acids still possess the original molecular grouping of phenylic acid that they are true substitution-products oxides of secondary phenyl-radicals containing in the place of two three or even more equivalents of hydrogen an equal number of equivalents of chlorine bromine hyponitric acid &c.We are already acquainted with the combinations of the following secondary radicals derived from phenyl of which it is as yet not determined whether they can also exist as such in the free state Phenyl= C, H Radical of Phenylic acid Chlorophenyl , , Chlorophenassic acid . . C12{ Ff Dichlorophenyl . . C12{ 3 } , , Chlorophenessic acid Trichlorophenyl :( C12{. Pentachlorophenyl ? C, Cl ? , , Chlorophenissic acid , , Chlorophenussic acid Tribromophenyl . C,( f:3 } , , Bromophenissic acid Dinitrophenyl . . C12{ ,,“S,} , , Nitropheqessic acid Nitrophenissic acid . . C12{ 3g&,> Trinitrophenyl ’’ ” (nitropicric acid) , , Nitrodichlorophenissic Nitrodichlorophenyl C, { 3*} acid A strong proof of the correctness of the view that tnchloro- phen ylic dinitrophenylic and trinitrophenylic acids are still possessed of the chemical constitution of phenylic acid and endowed with similar properties appears to me to be furnished on the one hand by the fact that the first of these upon treatment with potassium- 4!4! DR.KOLBE ON THE CHEMICAL amalgam exchanges its chlorine gradually for hydrogen and on the other hand by the observation made by Gcrhardt and Laurent that the two nitrophenylic acids form with benzoic acid combinations quite similar to those of phenylic acid compound ethers in which the dinitrophenylic and trinitrophenylic acids occupy the place of the base (C12{z$o,)O. (CI2HJnC2 0 benzoate of oxide of dinitrophenyl (CI2{ $Po> 0 .(C12HJ-C, 0 benzoate of oxide of trinitrophenyl. Like the ether-radicals of the series C H(,+1) which are homo- logous to hydrogen and which we must consider as produced by the combination of C H with H phenyl may also be considered as a repetition of hydrogen namely as hydrogen which has com-bined with the additional carbohydrogen C, H,. If this assumption is already justified by the analogy just demonstrated of the ptenyl-alcohol with the hydrated oxides of the ether-radicals it receives farther confirmation from the fact that corresponding combinations of phenyl to the remaining manifold terms of the methyl- ethyl- amyl-series &c. may be found with scarcely an exception. This analogy is most strikingly proved by the capa- bility of phenyl of combining like methyl ethyl &c.with 2 equiva-lents of carbon to form a conjugate radical the combinations of which exhibit the greatest similarity with those of acetyl propionyl &c. It is true we have not yet succeeded in converting hydrated oxide of phenyl into the acid HO . (CI2HJ-C, 0 in a similar manner to the conversion of hydrated oxide of methyl into acetylic acid or what is equivalent in obtaining directly from hydrated oxide of phenyl the cyanide of phenyl ((4 H5) Cy (benzonitrile) which yields benzoic acid by treatment with the alkalies or acids ;but we must bear in mind that as yet only one method of the many that may lead to this end has been tried namely the distillation of pbenylosulphate of baryta with cyanide of potassium (Hofmann).* A more favour- able result might perhaps be obtained by an appropriate treatment of chloride of phenyl discovered by Gerhardt aiid Laurent with cyanide of potassium.In making the well-founded assumption that benzoic acid bears to hydrated oxide of phenyle the same relation as acetic acid to hydrated oxide of methyl propionic acid to alcohol and caproic acid * Ann. Ch. Pharm. LXXIV 32. CONSTITUTION AND NATURE OF ORGANIC RADICALS. to hydrated oxide of amyl it must be taken for granted that all these acids are analogous in their constitution ;and hence that benzoic acid likewise contains a conjugated radicalal in which phenyl is the ad- junct of C ;benzoyl= (C,,HJnC2. If we adopt this hypothesis which likewise finds support in the arguments set forth in Vol.LXXV p. 233 of Liebig's Annalen the following formuls will be the most simple expressions of the rational compositiou of the known benzoy 1-compounds. Benzoyl = (C1 H,)"C2. Hydrated oxide of benzoyl HO .(C, H5)-C2 0 Oil of bitter almonds. Hydrosulphate of benzoyl. HS . (C, H5)"C2 S Sulphobenzole (C ah our s*). Hydrochlorate of chloride Chlorobenzole (Cahourst). of benzoyl . . . . . -HC1. (CI2 H5)"C2 C1 Dinoxide of benzoyl . . (C12 H5)IC2 O,? Benzoeoxide (Berzelius:). Benzoylic acid . . . . H0,(Cl,H5) C, 0 Benzoic acid. Dinoxichloride of benzoyl (C12 H5)-C, So-called Chlorobenzoyl. { 2 Dinoxibromide of benzoyl (CI2H5)-C2 , Bromobenzoyl. { 2 Dinoxi-iodide of benzoyl . (C12H5)-C2 { , Iodobenzoyl.Dinoxicyanide of benzoyl . (C12H5)-C2 , Cyanobenzoyl. { 8 { 2 Dinoxisulphide of benzoyl (C12H5)"C2 , Sulphobenzoyl. Dinoxamide of benzoyl . (C12H5)-C2r , Beozamide. { 2% SUBSTITUTION-PRODUCTS OF THE BENZOYL-COMPOUNDS. { Ef Chlorobenzoylic acid . . . HO .(C12 )-C, 0 Dichlorobenzoylic acid . . HO. (C12 { Fi )-C2 0 TrichIorobenzoylic acid . . HO. (C12 { )T2 0 Bromobenzoylic acid . . . HO. (C12 { g )"C2 0 . . . HO . (C12 { g4)-Cz, Nitrobenzoylic acid 0 Nitrobenzoic acid. Dioxamide of nitrobenzoyl . (C12 { $)4 >-c2,{ 2H2 Dinitrobenzoylic acid. . . HO . (Clz { &O4)^C2 0 )-(& 0 Benzimic acid. Amidobenzoylic acid . . . Ho .(Cl2 { 2H2 ~ ~ ~acid.~ ~ m i a In whatever manner we view oil of bitter almonds as the hydrogen-combination of the group C, H 0,,as the second product * Ann.Ch. Pharm. LXX 41. f Ann. Ch. Pharm. LXX 40. $ Berzelius' Lehrbuch der Chemie 5 Aufl. IV 332. DR. KOLBE ON THE CHEMICAL of oxidation of the radical C, H, or as the aldehyde of benzoic acid its very numerous and complicated phenomena of decomposition and particularly the metamorphoses which it undergoes with ammonia present difficulties to each view which it is impossible at present to remove but which will probably vanish upon a repetition of former researches and a careful investigation of the various statements. At present it appears to me that the manifold relations of oil of bitter almonds’ p.articularly to the remaining benzoyl-combinations may be best explained by the view upon which is founded the forniula HO .(C12H5)^C2 0 ; namely that this substance is the hydrate of the lowest oxide of benzoyl analogous to the aldehyde of acetic acid. Its behaviour with chlorine in its conversion into dinoxichloride of benzoyl and hydrochloric acid HO . (C12 HJ-C, 0 + 2 C1= (C12 H5)^C, { i-H C1. certainly differs from that of aldehyde inasmuch as the latter appears not to yield a dinoxichloride of acetyl but to retain its basic atom of water unaltered passing over finally into chlorale ; this greater stability of the atom of water in aldehyde may however be ascribed to the more powerfully acid properties of the latter and its conse- quently greater affinity for the basic atom of water. It must remain undecided whether the compounds described by Cahours the hydrosulphate of benzoyl and the hydrochlorate of chloride of benzoyl possess a rational composition corresponding to the formulz given above ; their properties are still too little known .to enable us to deduce therefrom reasons favourable to any one view.At any rate the above view furnishes a perfectly satisfactory inter- pretation of the genetic relations of these two compounds to the hydrate of the oxide of benzoyl HO (CI2 H,)-C, 0 + P CI = H C1. (CI2 H5)-C2 C1+ P { a3 L-C,---I Hydrate of oxide of benzoyl. Hydroehlorate of chloride of benzoyl. HC1. (C,2H,)nC2 C1+ 2(KS.HS) = HS. (C,,H,)-C, S + 2KC1+2 HS L,-d L-v--.J Hydrochlorate of chloride Hydrosulphate of benzoyl. of benzoyl. The h ydrosulphobenzoyl produced by the direct action of hydro- sulphuric acid upon oil of bitter almonds appears to be identical with the hydrosulphate of benzoyl.The sulphobenzoic acid discovered by Mit scherlich whichisformed under circumstances similar to those of nitrobenxoylic acid classed above among the substitution-products of benzoylic acid (and which CONSTITUTION AND NATURE OF ORGANIC RADICALS. 47 must be viewed as the oxygen-compound of the secondary radical (Cl2{ 304)^C2) is generally considered as analogous to the latter. The analogy of the mode of formation and the rational composition Qf these two acids would be perfect if the composition of the sulpho- benzoic acid did correspond to the formula NO .(C12{ H* so,)^C2 0, and saturated only 1 equiv.of base. It is however bibasic and contains moreover 1 equiv. more of sulphuric acid. I do not doubt however that sulphuric acid effects a perfectly similar meta- morphosis of benzoylic acid to nitric acid with this difference only that the substitutioll-product corresponding to nitrobenzoylic acid HO . (Cl,{ :da)^C, 0, combines with an equivalent of sulphuric acid forming a double acid in which the two constituents (C12{ FdJnC2 0,and SO, retain their original saturating capacities. The composition of sulphobenzoic acid might therefore be expressed by the rational formula 2 HO . {(C12{ Fd?'Tz,0, and its forma- so3 tion by the following equation HO .(C12 H,)-C, O,+ 2 SO,=2 HO (C12 {f)Ja)^C2 0, I -so --J L-Benzoylic acid.Sulphobenzoic acid. Whether sulphurous acid be really capable of replacing 1equiv-of hydrogen as assumed in the above formula cannot be decided apriori but solely by facts. At any rate this assumption does not appear to be bolder than that of the displacement of hydrogen by hyponitric acid. Why should SO not behave in a similar manner to NO,? In the formation of the so-cdled sulphacetic acid we meet with a perfectly similar process of decomposition. Its rational formula 2 HO (C { H 2 )-C2 0,,explains in a no less satisfactory manner 02 i so, its bibasic properties and its relations to acetic acid HO .(C H,)"C, O,+2 SO+ HO . {(C { f/&)nC, 0 so3 L-7-2 L-2 Acetic acid. Sulphacetic acid. DR. KOLBE ON THE CHEMICAL I do not consider it improbable that many of the organic acids the chemical constitution of which is still unknown-such as malic acid tartaric acid &c.-will prove on closer examination to be conjugate acids as suggested some time ago by Dumas and Piria,* and to which circumstance they will be found indebted for their polybasicity.The above considerations lead to the question whether the ether- radicals are not capable of combining with other elements as they do with the adjunct C, to form similar conjugate radicals. f have no hesitation in answering this question affirmatively and think that before all kakodyl must be viewed as a conjugate radical of this description in which 2 equivs. of methyl form the adjunct of 1equiv. of arsenic kakodyl = 2 (C H3)-As.It has already been shown (in Vol. LXXV p. 218 of Liebig’s Annalen) how easily and naturally the formation of oxide of kakodyl is explained by this hypothesis. It may be applied without difficulty to all kakodyl- compounds which have already been treated on this view in the “Handworterbuch der Chemie,” Vol. IV p. 218 ff I will not omit to mention here that the highly interesting mode of formation of chloride of methyl by heating kakodylate of superchloride of kakodyl agrees with none of the views hitherto adopted of the constitution of the kakodyl-compounds better than with the above assumption that methyl is pre-existing in the radical. The group of conjugate radicals discovered by Frankland in which methyl ethyl &c. occur as adjuncts of the metals zinc tin &c.is nearly related to kakodyl. In methyl-zinc methyl-tin ethyl-zinc as in acetyl and kakodyl the powers of affinity of the conjugate members C, As Zn Sn are not only considerably increased by their combination with the adjunct but their boiling- points are also considerably diminished these phenomena are pro- bably in most intimate connection with each other and may possibly arise from the assumption of a large amount of latent heat. A simple comparision of the boiling-points of the two corresponding acids oxalic acid and acetylic acid HO . (C HJ-C, 0, shows that the boiling temperature of the radical C has decreased about 130° by its combination with 1 equiv. of methyl if a conclusion may be drawn from the boiling-points of the combinations as to those of the corresponding radicals C, and (C H3)-C,.In like manner the arsenic combined with 2 equivs. of methyl (in kakodyl) is found to boil already at 170° and methyl-zinc to be a very volatile liquid spontaneously inflammable in the air.-Although attempts to prepare combinations of methyl-zinc and ethyl-zinc have as yet been unsuc- * Ann. Ch. Pharm. XLIV 70. CONSTITUTION AND NATURE OF ORGANIC RADICALS. 49 cesaful still it appears very probable that these bodies must be viewed as radicals partly from their behaviour and partly froni observations made by Frankland,* on the properties of the com- binations of ethyl-tin (stannethyl) which ace exceedingly similar to those of tin. Conjugate radicals similar to those last mentioned in which phenyl exists as the adjunct of metals have not yet been obtained; the former appears however to exist like the other ether-radicals in conjugated combination with sulphur and to form with the latter a radical corresponding to benzoyl (Ci2 H,)"S2 which may be assumed as pre-existing in hyposulphobenzidic acid.Some years ago I described in Liebig's Annalen Vol. LIV p. 145 four acids very closely allied to each other namely chlorocarbohyposulphuric acid chloroforniylohyposulphuric acid chlorelaylohyposulphuric acid and methylohyposulphuric acid of which the three latter may be produced directly from chlorocarbohyposulphuric acid in a manner similar to the re-production of acetic acid from chloracetic acid.I have noticed in the same memoir the interesting relations existing on the one hand between chlorocarbohyyosulphuric acid and chlora- cetic acid and between methyloxalic acid and acetic acid on the other hand and have made the conjecture that they might perhaps possess an analogous chemical constitution. The less doubtful it appeared to me that ~hlo~oca~bohypos~~lphuric, and methylohypo- sulphuric acid (besides the intermediate acids) contain hyposulphuric acid in conjugate combination with various adjuncts the greater was the support that I believed to have obtained for the view that the same adjuncts were contained in chloracetic and acetic acids only in combination with oxalic acid in the place of hyposulphuric acid. As however these views have been modified since then inasmuch as we no longer consider acetic acidas a conjugate oxalic acid but as the oxygen-compound of the conjugate radical (C H,)-C, it appears reasonable to entertain the opinion that those acids considered hitherto as conjugate hyposulphuric acids may be possessed of a rational coniposition corresponding to that of acetic acid.There is in fact nothing to prevent our assuming in methylohyposulphuric acid the existence of the conjugate radical (C H,)-S, and to ascribe to the adjunct the capability of exchanging its hydrogen like acetyl for an equivalent quantity of chlorine which would lead to H the formation of the secondary radicals (C,( cf)nS2 (C { N c1, and (C C13)-S2 of which chloracetylo- chloroformylo- and chloro- * According to a private communication.VOL. IV.-NO. XIII. E DR KOLRE ON THE CHEMICAL carbo-hyposulphuric acid must be considered as the oxygen com-pounds. As according to Muspratt’s experiments the methylo- hyposulphuric acid obtained by the oxidation of sulphocyanide of methyl by nitric acid is identical with that obtained from chloro- carbohyposulphuric acid the same view may also be extended to the homologous compounds formed by the oxidation of the sulpho- cyanides of ethyl and amyl namely ethylohyposulphuric acid and amylohyposulphuric acid. The conjecture made just now that hyposulphobenzidic acid might also possess a similar constitution to which we may also add hyposulphotoluidic and hyposulphonaph- thalic acids does not appear to me to be met by any difiiculties.Their mode of formation alone differs from that of methylo- ethylo- and aniylo-hyposulphuric acids ; as the carbohydrogens of the series C N,,$-21 corresponding to benzole toluole and naphthalole namely hydride of methyl (methylole marsh-gas} hydride of ethyl (ethylole) and hydride of amyl (amylole) are known not to enter into any com- bination with fuming sulphuric acid. The latter appear indeed to possess in general a much greater stability than the former as is shown particularly by the difference in their behaviour with fuming nitric acid; marsh-gas at least obtained by heating a mixture of acetate of soda and hydrate of lime remains perfectly unaltered on treatment with nitric acid even when passed through a mixture of the latter and concentrated sulphuric acid.The following table of corresponding acids the radicals of which consist on the one hand of C, on the other of S, both combined with the same adjuncts may serve for the farther elucidation of the foregoing Formylic acid. Unknown. €30. H-C, 0 HO . H-S, 0 Acetylic acid. M ethyiodithionic acid. (C H,)^S, 0, HO . (C HJ-C, 0 HO Chloromethylodithionic acid Chloracetyiic acid. { chlorelaylohyposulphuricacid). I-€0 (C,{ ;7-c2 0; HO . (C,{ Ef)-S2 O5 (I Dichloracetylic acid Dichloromethylodithionic acid (unknown). ~chlorofor~ylohyposulphuric acid). Trichloracetylic acid Trichlorom~thylodithionicacid (chloracetic acid). (chlorocarbohyposulphuric acid). HO .(C Cl,)-C, 0 HO . (C ClJnS2 0 CONSTITUTION AND NATURE OF ORGANIC RADICALS. Proyionic acid. Ethylodithionic acid Ho * (c~ H5)nc2 ‘3 HO (C H,)”S2 0 Caproic acid. Am ylodithionic acid. €30 WlO H,l)^C2 0 HO (ClO Hl,)^S2t 0 Phenylodithionic acid (hyposulphobenzidic acid). €3.0 (C H,)”S, 0 Kreotylodithionic acid* (sulphobenzoic acid). NO * (CL&T-I7)32 0 Naphthylodithionic acid (hypos~phonaphtha~c acid). HO (C, HT)-S, 05. The fact that acetyl and benzoyl combine in several proportions with oxygen justifies the supposition that the radicals of methylo-dithionic acid (C H,)-S, ethylodithionic acid (C H,)-S2 &c. might perhaps also combine with a smaller amount of oxygen. Sulphomethylosulphuric acid (Muspratt “Annalen der Cheniie,” Vol LXV p.261) the sulphethylosulphuric acid of Lowig and Wcidmann and the sulphamylosulphuric acid of Gerathewohl might be looked upon as lower oxides of these radical’s. The mode of formation of these acids which are obtained by the oxidation of disulphide of methyl hydrosulphate of sulphide of ethyl and hydro- sulphate of sulphide of amyl by nitric acid differs so little from that of the above dithionic acids with 5 equivs. of oxygen (which are obtained from the corresponding sulphocyanides) that one can scarcely imagine how different products can be formed under such equal circumstances. Add to this that their properties and those of their salts differ according to the various statements little or scarcely at all from those of the dithionic acids and finally that nearly all the ana- lytical results obtained with the so-called sulphomethylo- sulphethylo- and sulphamylo-sulphates correspond much better with the cornposi- tion of the methylo- &c.dithionates. The above reasons lead me to believe that the view first entertained by Gerhardt that Lowig’s sulphethylosulphuric acid contains 5 equivs. of oxygen (in the anhy- * The conjugate radicals of this second series of acids deserve particular names as well as those of the first. I have called them dithionic acids and have distinguished their adjuncts by placing their names in front. To the radical homologous to phengl C, H, which is the adjunct in toluplic acid I have given the name kreotyl (derived from kreosote) as I am of the opinion that kreosote is the homologous alcohol corre- sponding to hydrated oxide of phenyl ; hydrated oxide of kreotpl having the rational formula (C14H7) 0 .HO. E2 52 DH. KOLWE ON THE CHEMICAL drous state) may be extended to the corresponding methyl- and amyl- compounds although Muspratt (1. c.) has concluded from his corn- parative investigation of sulphethylosulphuric acid and ethylodithionic acid that they arc different substances (comp. ‘‘ Handworterbuch der Chernie,” Supplement p. 73 ff. and 169 ff).-I will not omit to mention that the heavy oily compound the sulphethylosulphurous acid discovered by Lowig and Weidmann into which hydrosul- phate of sulphide of ethyl is first converted by the action of nitric acid and which is transformed by continued treatment with nitric acid into ethylodithionic acid may be viewed according to its composition as a lower oxide of the radical (C HJ-S, possessing the rational formula ((2 H5)-S2 0,.Although methyl ethyl amyl phenyl &c, are of themselves only repetitions of hydrogen (produced by the combination of additional carbohydrogens)* C H, C H, C, HiO,and C, H with H it is remarkable that they seem notwithstanding to possess the capability of combining with another equivalent of hydrogen to form binary compounds hydrides from which they may be made to pass over to other substances as chlorine hyponitric acid amidogen &c. I have already at an earlier period made the conjecture? that marsh- gas did not possess the simple composition assigned to it by Berze- lius but that it might be the hydride of methyl (C H,) H; it appears to me that this view affords the best interpretation of its formation from acetates CaO .(C H3)-C2 0,+ CaO . HO = (C H3) H + 2 (CaO . GO,) c-“ -J hF-3 Acetate of lime. Hydride df methyl. This view has received a new support from the observation lately made by Frankland that iodide of methyl and zinc in the presence * It would he desirable to follow a more definite rule and principle of nomenclature in naming the different carbohydrogens particularly those that occur frequently side by side as C H, C H, and C H,. This might easily be effected by retaining the termi- nation yl to the names of the radicals formed by the combination of honiologous carbo- hydrogens with H by giving to the homologous carbrbohydrogens and the analogues of C H, C H, &c the nanies of the radicals with addition of the terminating syllable me and by denoting the hydrides of the radicals by the terminating syllable ole in the following manner C H Ethylene.C, H Phenylene. C H Naphthalene. C H Ethyl. C, H Phenyl. C H Naphthpl. C H Ethylole. C, H Phenylole (benzole). t I-Iandworterbnch dar Chemir 111 700. C H Naphthalole (naphthalin). CONSTITUTION AND NATURE OF ORGANIC RADICALS. 53 of water or methyl-zinc and water are decomposed into protoxide of zinc and hydride of methyl. Unfortunately the chemical deportment of this hydride of methyl as also that of the hydrides of ethyl and amyl discovered by Frankland,* has been so little studied that no arguments can be derived therefrom either for or against the above view unless I may perhaps mention here an observation made by Varrentrapp and myself namely that equal volumes of dry marah- gas and chlorine yield by exposure to diffused daylight equal volumes of hydrochloric acid gas and a chlorinated inflammable gas of which we have however as yet left undecided whether it is really chloride of methyl or an isomeric combination.A much fitter means of testing this question is presented by the interesting metamorphoses of benzole which stands in the same relation to benzoic acid and phenyl as hydride of methyl does to acetic acid and methyl. Its behaviour with nitric acid and sul- phuric acid clearly shows that one equivalent of hydrogen exists in it in a different form to the remaining five.The question how it is that benzole in exchanging this one equivalent of hydrogen for NO and passing over into nitrobenzole changes its chemical character altogether while by the substitution of a second equivalent of hydrogen a body is formed (dinitrobenzole) bearing the greatest similarity to nitrobenzole may be easily answered if me consider benzole as the hydrogen-compound of the phenyl-radical as hydride of phenyl=(C1 HJ H whereas the assumption expressed by the old formula C, H6 that all six equivalents of hydrogen are of eqiial value renders no account whatever of the above circumstance. It is evident that on the entrance of the first equivalent of hyponitric acid in the place of the hydrogen that is combined with phenyl there is formed nitrite of phenyl= (C12HJ NO, the phenyl itself remaining unaltered.It is only by the action of a hot mixture of sulphuric and nitric acids that the substitution of NO for hydrogen is extended to the radical the nitro-compound of the secondary radical C, { $o namely nitrite of nitrophenyl (C12{NHd) . NO 4 (dinitrobenzole) being produced which differs evidently not more from nitrite of phenyl than nitraniline does from aniline methylodithionic acid from chloromethylodithionic acid or nitrobenzoic acid from benzoic acid. Of all the reactions of dinitro-benzole its-behaviour with sulphide of ammonium shows most clearly that the two equivalents of NO play a perfectly different part ;for * Ann.Ch. Pharm. LXXI 171 ; and LXXIV 41. *-' DR. KOLBE ON THE CHBMICAL on the conversion of dinitrobenzole into nitraniline the equivalent of hyponitric acid which occupies the place of hydrogen in the radical remains unaltered; the conversion of NO into amidogen is confined to the hyponitric acid existing in the compound externally of the radical atom (C12{ &).N0,+6HS=(C12{ $o) .NH2+4HOfBS Dimtrobenzole. The metamorphosis which benzole undergoes by treatment with sulphuric acid namely the formation of sulphobenzide and sulpho- benzide-sulphuric acid is also in perfect accordance with the above mode of viewing if we consider sulphobenzide as phenylodithionic oxide (C12H5).S, O, and sulphobenzide-sulphuric acid as phenylodithionic acid HO .(C, H,)^S2 0 (corresponding to methylodithionic acid &C.) Attempts to prepare the chloride of the phenyl-radical from the hydride by proper treatment with chlorine have not hitherto been successful.The ultimate success of such experiments can however be doubted the less since chloride of phenyl has been obtained in another way by Laurent and Gerhardt by the action of penta-chloride of phosphorus on hydrated oxide of phenyl. Mitscherlich's chlorobenzide is perhaps a substitution-product of this substance namely the chloride of dichlorophenyl (C12 { :$) C1 and chloro- benzin is possibly a combination of the latter with 3 equivalents of hydrochloric acid C, {Fc)Cl .3H C1.The homologues of benzole namely toluole cumole and cymole as also naphthalin are so nearly allied to that substance that I have no hesitation in ascribing to them a similar constitution and to consider them as composed according to the following rational formule toluole = (C14H7) H ;cumole = (C18€Ill) H ;cymole= (C20H13)H ; naphthalin= (C2 €I7) H. The radical C, H is the only one which we have not had as yet as adjunct of C in a compound corresponding to acetic acid and benzoic acid; on the other hand naphthylodithionic acid (hyposulphonaphthalic acid) HO .(C2 H,)"S, O, in which naphthyl is the adjunct of S, corresponds to methylodithionic acid and phenylodithionic acid (hyposulphobenzoic acid.) The numerous derivatives of naphthalin obtained therefrom by treatment with chlorine bromine nitric acid &c.merit in a high degree the attciition of chemists. There is perhaps no class of CONSTITUTION AND NATURE OF ORGANIC RADICALS. bodies so well adapted to demonstrate in a convincing manner the insufficiency of the assumption of the immutability of organic radicals. All attempts to interpret the modes of formation of these deriva- tives of naphthalin their metamorphoses and relations to each other according to this view may be considered as having totally failed. I shall therefore confine myself to giving an arrange-ment of those formulae which I consider as the most probable expression of their rational composition; they are grounded upon the hypothesis that naphthalin contains the radical C, H (naphthyl) and that the latter admits of the substitutions of its hydrogen by chlorine hyponitric acid &c within a certain limit without under- going a farther change in the molecular grouping of its atoms.Naphthyl = C, H,. Hydride of naphthyl . . . . (C H,) H Naphtalin. Chloride of naphthyl . . . (C H?)C1 Chlonaphthase. Souschlorure de napht alaline Hydrochlorate of chloride of naphthyl (C20 H,) C1. HCl chloride of naphtalin (Berzelius.) Bromide of naphthyl . . . (C H,) Br Bronaphthase. Hydrobromate of bromide of naphthyl (C% H,) Br .HBr Unknown. Nitrite of naphthyl . . . (C H,) NO Nitronaphthalase. Naphthylamine . . * (C H,)NH Naphthalidine. Naphtliylodit~onic oxide . . . (C H,) SO Sulphonaphthalin (Berz.) Naphthylodithionic acid .HO (c Hyposulphonaphthalic acid 20 7) 2 5 (Berz.) SUBSTITUTION-PRODUCTS. Chloride of chloronaphthyl . . . (C { Ef ) C1 Chlonaphthese. Chlorure de naphta- Dihydrochlorate of chloride of chloronaph-(c { €Ifc1. HC1 line &loride of naph-thy1 . . . . . . . thaline (€3 erzelius.) Chloride of dichloronaphthyl . . (C20{ Fi) Cl Chlonaphthise. Dihydrochlorate of chloride of dichloro-Chlorure de chlo- naphthyl . . . . . . ('20 { Ff2) ' HC1 u't pht ase. Chloride of trichloronaphthyl . . . (C20{ tt)C1 Chlonaphtose. Dihydrochlorate of chloride of trichloro-cl. HC1 Chlorure de chlo- naphthyl . . . . . . { Fc) C1 naphtese. Chloride of quintichloronaphthyl . . (C Chlonaphthalase. Chloride of hypachloronaphthyl . . (C C1,) C1 Chlonaphthalise.{ !:) Br Bromide of broponaphthyl . . . (C Bronaphthese. { i:; Br Bromide of dibromonaphthyl . . (C Bronaphthise. DR. KOLBE ON THE CHE3lICAL Bromide of tribromonaphthyl . . . (C,* !;> { Br Hydrobromate of bromide of tribromo-(C { g:3)B2.HBr Bronaphthose. Sousbromure de bra-naphthyl . . . . . . naphtise. H Br HBr Bromure de bro- Dihydrobromate of bromide of tribromo-. (c20 { Br,) naphthyl . . . . . naphtese. Dihydrobromate of bromide of quadribro-. . . . . (C { !:>Br .2 WBr Br:g:st: monaphthyl bra-Souschlorure de Hydrochlorate of bromide of chloronaphthyl (C20{ Ef ) Br * HCl bronaphtase. Chloride of chlorobromonaphthpl . . (CZ0{ zf) C1 Chlorebronaphtise. Br Chloride of chlorodibromonaphthyl .. C1 Chlorebronaphtose. Dihydrobromate of chloride of chlorodibro-cl I.IBr Broniure de chlo- naphthyl . . . . . . naphtese. Chloride of dichlorobromonaphthyl . . C1 Chloribronaphthose. Bromure de chlo- Dihydrobromate of chloride of tribromo- H cl. HBr robronaphtese. monaphthyl . . . . . . (‘20{ Br) Dihydrochlorate of bromide of dichlorobro-Br HCl Chlorure de bro- monaphthyl . . . . . . { 3)Br naphtese. Bromide of trichlorobromonap~~thyl. . (Czo Bromechlonaphtnse. Dihydrochlorate of bromide of trichlorobro-Br. HC1 Chlorure de bro- monaphthyl . . . . . . mechlonaphtise. Nitrite of nitronaphthyl . . . (C ) . NO Nitronaphthalese. { a4 . . . (C { s4 Nitrite of dinitronaphthyl ) . NO Nitronapbthalise. { Ei ) C1 chlorwk. Chloride of dichlorodinitronaphthyl .. (C Binitronaphtaline bi-2 NO { F! chlor6. Chloronaphthylodithionic acid . . HO . (C )“S2 0 Acide sulfonaphtalique acid . HO . (C,{ zi )-S2 0 Acide sulfonaphtalique ~ichloronapt~thylodithionic bichtork. Trichloronaphthylodithionicacid . HO . (c2,)Ff3 )“S, 0 Acide sulfonaphtalique { trichlor& H Quadrichloronaphthylodithionic acid . €10. (c { ,-,i’ )-s, 0 hide sulfonaphtalique qt,adrichlork CONSTITUTION AND NATURE OF ORUANIC RADICALS. 5'1 Acide sulfonaphtalique Bromonaphthylodithionic acid . . HO . (C,{ i; )^S, 0 brom& !:2{ Acide sulfonaphtalique Xtronaphthylodithionic acid . . HO . (C { Z8,)IS2 0 nitr6. Acide sulfonaphtalique bibrom& Dibromonaphtbylodithionic acid . HO .(C )-S2 0 Acide thionaphtalique Thionaphthalic acid* .. 2 HO. [('%I :)&{ 5303 )-'27 '5 (Laure nt.) Napthtinhyposulphuric acid (Berzelius.) The two highly remarkable compounds containing chlorine and oxygen but no nitrogen which Laurent has obtained by the action of nitric acid on the dihydrochlorate of chloride of dichloro-naphthyl (C,o{ 2)Cl . 2HC1 and on chloride of quintichloro-naphthyl (C2 C1 possessing the empirical formula?C, H C1,0, { 3) 5 and C, C1 0, besides the acids obtained from the latter by treat- ment with potassa HO . C, H C1 0 (chloronaphthalic acid) and HO . C, Cl 0,,appear to possess a rational composition corresponding to the salicyl- and anisyl-compounds (see further on) and to belong H to the conjugate radicals (CIS { cf } O,)-'C and (Cis C1 O,)-C,.Since Strec ker? has called attention to the similarity existing between this chloronaphthalic acid and alizarin both with respect to their composition (alizarin = HO . C, H50,)and properties I scarcely consider it too bold an assumption to suppose that the H primary radical of the above hypothetical radical (C18 { cf } O,)-C, namely (CI H O,)-C, exists in alizarin. I propose for it the name alizyl. The following rational forrnulx?appear to me to afford the best interpretation of the mutual relations of the above compounds Alizyl = (C18 H5 OJ-C Dinoxychloride of alizyl . . (CIS H 02)%,,{ 3 Unknown. Alizylic acid . . HO . (CIS H 0,)^C2 0 Alizarin. Dinoxychloride of chloralizyl . (CIS{ F; } 0,)T2 Oxide (La { 0 tose de chloroxknaph-cj t.) * Conjugate acid of thionaphthylodithionic acid and sulphuric acid.f-Handworterbuch der Chemie von Liebig Poggendorff and Wohler IV 598. Art. Madder. DR. KOLBE ON THE CHEMICAL Chloralizylic acid . HO . (C18{ Ef} O,)-C, 0 Chloronaphthalic acid. Dinoxychloride of pentachloralizyl. (C, CI O,)^C, { Ei o%(&de chloroxQnaphta-(L au rent.) Pentachloralizylic acid. HO . (CIS C1 O,)-C, 0 Acide chloroxdnaphtalt5-siqae. (Laurent.) Hofmann in his latest excellent researches on the volatile bases,* has already expressed the opinion that there are probably two corresponding series of organic bases amidogen- and ammonia-bases and that the existence of amidogen-bases in which we assume with Liebig amidogen in combination with a compound radical does not necessarily preclude the existence of ammonia-bases in which we imagine ammonia as pre-existing in combination with a compound body.While thiosinamine thialdine the ureas and many vegetal bases the chemical constitution of which is as yet perfectly un-known may perhaps belong to the latter series Hofmann is cer-tainly right in viewing the volatile bases described by himself and Wurt z as the amidogen-combinations of compound radicals as ana- logues of ammonia of which the one (radical-) equivalent of hydrogen is replaced by a compound radical Ammonia . H .NH Methylamine . (C H5) *NH Phenylamine . . (C12 H,) .NH (Aniline). &C. &c. Another argument might be added to the many proofs already established by Hofrnann in favour of the view that ethylamine aniline &c.are really amidogen-combinations of the radicals C,H5 and C1 H, and have not according to Berzelius’ mode of viewing to be considered as conjugate ammonias (with the adjuncts C H and C, HJ. The important discovery that bromide of ethyl and am- monia are transformed into hydrobromic acid and ethylamine (C HJ Br+H .NH,=(C H5) .NH, I3Br +c7-.-v-3 Bromide of ethyl. Ammonia. Hydrobromate of ethylamine. and that nitrous acid reconverts etbylamine into an oxygen-com-pound of ethyl namely into nitrite of oxide of ethyl appears to me to place the question of the chemical constitiition of ethylamine parallel with the question whether we should consider bromide of ethyl as the bromide of the ethyl-radical or as hydrohromic acid * Ann.Ch. Pharm. LXXIV 125. CONSTITUTION AND NATURE OF ORGANIC RADICALS. combined with C H, viz. as C H,. H Br. It would according to the above facts be perfectly inconsistent to view ethylamine as ammonia conjugated with C H, and as expressed by the rational formula (C H,) .NH, or (C H,) (H .NH,) ;bromide of ethyl on the other hand being assumed as the ethyl-radical combined with bromine. An objection that has been repeatedly raised against the view that organic nitrogenised bases are amidogen-compounds is that amidogen has not the property of forming bases in support of which have been quoted amide of potassium oxamide oxamic acid &c. of which it cannot be doubted that they contain amidogen none of which are however endowed with basic properties.This kind of argument might certainly be classed with the no less paradoxical assertion that hydrochloric acid contains no chlorine because the latter forms neutral or indifferent bodies with potassium carbon &c. The diffe- rence between chloride of potassium chlorobenzoyl (C12H,-C, Ct { c, and hydrochloric acid is not less than that between amide of potassium benzamide ((4 H,)-C,, '2 { NH2 and ammonia. It cannot be doubted that the chemical nature of the amidogen- compounds exactly as with the chlorine-compounds is essentially modified as well by the nature of the body with which aniidogen combines as by the part which it has to play in such combinationsi While in amide of potassium it appears to play the part of a salt- former it is found in oxamide C2 { benzamide acetamide &c.to occupy the place of oxygen. From all these compounds to which may be added the amidogen-acids it may be expelled with facility as ammonia and oxygen may enter into its place. In amidobenxoylic acid HO .C, { EhJnC2,0 (benzimic acid) the amidogen appears to occupy the place of hydrogen as the chlorine does in chloro- H benzoylic acid NO.(C12{ C14)-C, 0, and it cannot be detected in this compound by the ordinary means any more than the chlorine can in the last-named acid. It is well known that on boiling these substances with solution of potassa neither ammonia is given off on the one hand nor chloride of potassium formed on the other.Can it appear strange after these statements that amidogen should combine and form bases with hydrogen and its analogues methyl phenyl &c.; that it exercises the functions of a base-former in organic DIt. KOLBE ON THE CHEMICAL bases ? The analogy of the different functions which amidogen and chlorine exercise would be perfect if the chlorides of methyl and ethyl in fact all the chlorine-compounds of the homologues and analogues of hydrogen were equally similar in their properties to hydrochloric acid as methylamine ethylamine phenylamine &c. are to ammonia. Methylamine and ammonia which according to Wur t z corre-spond so closely in their chemical behavioixr and even in their physical properties that their compounds can only be distinguished from each other by analysis may be compared in this respect to acetic and formic acids which contain the same radicals as adjuncts and do likewise not differ much more in their properties than those two bases Benzoic acid .HO. (C,H ) C, 0 (C12H ) .NH Aniline. Toluylic acid . HO. (C14H7 )-C, 0 (C14 H ) .NH Toluidine. &C. &C. On a closer examination and comparison of the above compounds it will be seen that what has been said (in Liebig’s Annalen pp. 225 and 233) of the coniparatively subordinate influence exer- cised by the adjuncts of the above acids over the chemical character of the latter may be almost equally applied to the amines of the same carbohydrogens For with whatever carbohydrogen (radical) the arnidogen may be combined,-provided that it is an analogue of hydrogen,-the resulting amines possess the peculiar chemical cha- racter of their prototype ammonia to such a degree that they would be always regarded as imitations of ammonia even if their rational composition were unknown.In the same manner as the member C, occurring in the above acids in combination with different adjuncts gives the principal stamp to the character of the resulting conjugate radicals formyl acetyl &c. and their combinations the correapond- ing amines appear to owe their basic nature almost exclusively to amidogen. Hofmann’s important discovery that several equivalellts of hydrogen in the radical of aniline niay even be replaced by chlorine iodine hyponitric acid &c.and that their products of substitution chloraniline (el$ ) .NH, dichloraniline (C12{ Et).NH, nitra- (‘ONSTITUTION AND NATURE OF ORGANIC RADICALS. niline (Ci2 { E.0) .NH, &c. are still possessed of basic properties proves most indisputably how little in general the basicity of the arnines is dependent upon the nature and composition of their radicals. These facts appear at it cursory glimpse to be favourable to the hypothesis constructed by the adherents to the theory of types that the part which an element plays in organic Composition is not dependent upon its original properties but solely upon the position which it occupies in the combination. Upon closer investigation of the question it will however be found that Hofmann’s investiga-tion of the chlorinated bases contains indeed the refutation of those extreme views.That chemist has shown that the basicity of aniline decreases in an inverse proportion to the number of the equivalents of chlorine and bromine introduced in the place of hydrogen. Brom-aniline is still a tolerably powerful base though weaker than aniline itself dibromaniline likewise still possesses basic properties its salts exhibit however but very slight stability ; tribromaniline finally is no longer basic but is like trichloraniline a perfectly indifferent body. Bromitie has therefore evidently imparted a portion of its original (negative) character to the compound into which it has entered in the place of hydrogen; the fundamental properties of aniline among which its basic nature must unquestionably be reckoned as of the highest importance are more or less modified in consequence of the above process of substitution; they are therefore not exclusively conditional upon the equality of the position of the elements.H ofmann’s latest and highly important discovery that all three equivalents of hydrogen in ammonia may be successively replaced by the so-called ether-radicals without the original basic character of the ammonia being lost is not only of thegreatest interest to the radical theory inasmuch as it appears to nie to place beyond all doubt the existence of compound radicals but promises also to throw quite unexpectedly new light upon the chemical constitution of many organic bases hitherto not properly understood.The re- markable isomerism of toluidine (C14H,) .NH, and methylaniline (C,2 H5). N {CH3} would if we were unacquainted with the mode of formation of the latter be to us equally enigmatical to the hitherto inexplicable isomerism of aniline and pico1ine.-As we have well-founded reasons for viewing aniline as composed according to the rational formula (CI2HJ .NH, we may imagine picoline to be a methylated base analogous to methylamine perhaps DR. KOLBE ON THE CHEMICAL If this assumption be well founded picoline would according to the experience we possess up to the present time only admit of the entrance of one atom of an ether-radical in place of its hydrogen ;this might be easily decided by a simple experiment.Since the one (radical-) equivalent of hydrogen in ammonia is pos- sessed of fiinctions different from those of the two others in amidogen the question arises which of the three equivalents of hydrogen is first replaced by ethyl in the conversion of ammonia into ethylamine (by treatment of the former with bromide of ethyl) ;or in other words -. CH whether the rational formula (C H,) .NH, or H .N { 5} must be assigned to ethylamine. The facility with which arnidogen may be transferred from the radical-hydrogen to other corn binations for instance in the formation of oxamide bcnzaniide &c. evidently imparts the greatest degree of probability to the first formula which is also generally adopted. The formation of aniline from nitrobenzole can scarcely be made to accord with any other formula for aniline than (Cl €i5).NH,.If therefore we should succeed at some future period in producing this base in the same manner as ethyl- amine-perhaps by the action of ammonia on the hitherto unknown bromide of phenyl (C12H5) Br,-which camot be regarded as unlikely or in producing from hydride of ethyl a nitrite of ethyl (C H5) .NO, and from this ethylamine,-the correctness of the view that the first substitution of the one equivalent of hydrogen in ammonia occurs with the radical-hydrogen might be considered as pretty well proved. The extent to which methyl ethyl and the so-called ether-radicals in general are capable of playing the part of hydrogen in organic eoimbinations is most clearly shown by the remarkable combination of iodide of ethyl with triethylamine discovered by Hofmann the hydriodate of ammonia in which all the equivalents of hydrogen are replaced by ethyl (C H5).N 2(C H5) (C H5) I as also by the oxygen-base obtained therefrom (C H5).N 2(C H5),(C H,) 0.HO which represents in the ethyl-series the member that is wanting in the ammonia-series hydrated oxide of ammonium.There can I think exist no more simple or decided proof of the existence of compound radicals than these methylated or ethylated bases. It is a circumstance worthy of notice that met'nylaniline although it contains the elements of C H more than aniline has a boiling- CONSTITUTION AND NATURE OF ORGANIC RADICALS.63 point only 10' C. higher than the latter (192"),while the isomeric toluidine boils at 200O. Again ethylaniline only boils 22O higher than aniline notwithstanding the difference existing between them of 2 (C HJ. Diamylaniline which contains 10 (C H,) more than aniline and should therefore have a boiling-point about 200" higher than the latter boils at a temperature only 100' higher than aniline ; lastly the boiling-point of amylethylaniline (262") which contains 7 (C H,) more than aniline exceeds that of the latter only by 80° instead of 140°,which is therefore likewise only half the ordinary increase. It hence appears as though the entrance of (C H,) into organic combinations effects at times only half the increase in the boiling- point that one is accustomed to expect and as though the form in which the homologising carboh ydrogen is added to the compound had no unimportant influence over this point.The above observa- tions are at least in favour of the view that where this carbo- hydrogen in the form of methyl ethyl &c. replaces the hydrogen exterior of the radical the boiling-ppint of' the combination rises only one half the amount that it does in cases where the carbohydrogen enters into the place of the radical itself. At any rate it appears to me to show in a most decided manner that the regularity of the increase in boiling-points caused by the entrance of certain elements into organic combinations is subject to many encroachments. The conversion of organic amines by the removal of 1 equivalent of hydrogen into compound amides which bear the same relation to the former as the simple amides to ammonia can be explained in a simple manner only by the assumption that this elimination of hydrogen takes place in the radical combined with the amidogen the amidogen itself remaining unaltered ; that therefore there is formed from qniline (C13H5) .NH, anilide of the rational composition (C12HJZNH ;from naphthalidine (C20H,) .NH, a naphthalidide= (C,* HJZNH ;from nitraniline (C12 { H4 ) .NH, a nitranilide = NO4 H (c, { Nb,)zNH,. The question now at once arises how it can be explained that bodies of so similar a composition as aniline and anilide possess such different properties ; that amidogen in combina- tion with the one carbohydrogen C, H should form a base while it forms with the other C, H, a body beariug a much greater resemblance to chlorine and oxygen ? This question may be easily answered if the fact be borne in mind that besides hydrogen itself DR.KOLBE ON THE CHEMICAL only those compound radicals that are homologous or analogous to it are capable of producing bases with amidogen or in general only radicals that can play the part of hydrogen as ethyl phenyl naphthyl &c. among which must also necessarily be included the secondary radicals derived from thcni lor instance chlorophen yl C, { tf} nitrophenyl C, { :b,} &c. The so-called addi- tional carbohydrogens C H, C H, C, €I4,C, H, &c. by the combination of which with 1 equivalent of hydrogen we imagine the above radicals produced and which evidently fulfil functions quite different from the latter must not be confounded or placed in the same rank with them.Incapable themselves of playing the part of hydrogen or indeed of a radical and therefore incapable of forming bases in combination with amidogen but apparently only destined to produce series of analogous combinations these carboh ydrogens only give rise by combination with amidogen to a series of different amides which still possess to a full extent the general characters of the simple amides. Anilide (C, H,)SNH is a true amide the properties of which are not altered to a greater extent by the addition of C, H, than those of formic acid WO . H-C, O, in its conversioii into benzoic acid = HO .(C12 H,)-C, 0, by the assumption of the same additional carbohydrogen in the adjunct of its radical. The following very simple expressions are obtained for the rational composition of the corresponding amides and anilides aniidic and anilidic acids by representing anilide (C12HJTH by And in the same manner as amidogen is represented by Ad. AMIDES ANILIDES. Carbamide . . . . Oxamide . . . . . C2{ % Oxanilide . . . . Benzamide . (C12 H )-C, :%{ Benzanilide . (C,,H )-C { kd Suberamide . (c €3 ):C2{ ?& Suberanilide (C H )zC2{ 2d &C. &C. CONSTITUTION AND NATURE OF ORCQANIC RADICALS. AMIDIC ACIDS. 0 Sulphamic acid . . HO. S { Aa; SO 0 Carbamic acid . . HO. c {Ad; CO Oxamic acid .. HO .C,{ 0 C 0 &C. ANILIC ACIDS. Carbanilic acid . . HO. c {zd; co oxanilic acid . . HO .c2{kd; C 0 &C. It is a remarkable and certainly not purely accidental circum- stance that a portion only of the acids that yield amides form also apidic acids and imides. With the exception of benzimide of which it is more than doubtful whether it may be reckoned among the imides there exist neither amidic acids nor imides of the fatty acids and those nearly related to them such as benzoic acid toluylic acid &c. On examining the series of known amidic and anilidic acids imides and aniles it will be observed that these compounds are formed exclusively from those acids which are capable of existing in the anhydrous state and are at the same time particularly inclined to form acid salts such as sulphuric acid carbonic acid oxalic acid besides the whole series of acids so nearly related to the latter succinic acid suberic acid camphoric acid phtalic acid &c.It must remain undecided whether the peculiarity of these acids of being capable of existing even without their basic atom of water is necessarily in some connection with their capability of forming amidic acids and imides ;we may perhaps expect some further elucidation of this subject as soon as we are better acquainted with the nature of these combinations particularly of the imides. With regard to the chemical constitution of the imides which we do iiot yet understand the interesting observations made by Dumas Malaguti and Leblanc that the amides are converted into cyanogen-compounds by the abstraction of water-acetamide VOL.I%'.-NO. XIII. F 1)H. KOLBE ON THE CHEMICAL { 2H2 (C H3)-C2 into thc cyanide*) of its adjunct cyanide of methyl (C H,)"C N; benzamide (CI2 HJ-C, { O2 into cyanide N*, of phenyl (C12 H,)-C N (benzonitri1e)-appears to afford a new point of view from which to investigate this question. I consider it as not improbable that in the conversion of amidic acids into imides by the elimination of 2 equivalents of water the process by which it is effected is the same as in the formation of cyanide of methyl from acetamide or in other words that the imides consist of I equivalent of the hydrated acid combined with a cyanogen-com-pound.If "we express the rational composition of an amidic acid of which there also exists an amide by the general formula { 2H HO .PIC, ; PSC, 0 (in which P represents the adjunct of 2 the acid) the formula HO. PZC N; PIC, 0 would be the rational expression of the composition of the corresponding imide and the conversion would proceed according to the following eqna- tion Nb2; HO.PZC,{ 0 PLC, 0 = HO .P3 N ;PZC 0,. + 2 HO. 3 c v 3 L v Amidic acid. Imide. This hypothesis by which the acid properties of the imides are likewise accounted for requires that we should assume in the acids yielding imides namely snccinic acid suberic acid phtalic acid camphoric acid &c. 2 equivalents of carbon combined with an adjunct as in the fatty acids.These adjuncts differ however mainly from those in the fatty acids in not consisting of ether-radicals but of the homologising carbohydrogens themselves C H, C H, &c In the same manner therefore as acetic acid butyric acid &c. may be viewed as repetitions of formic acid the former may be considered as repetitions of oxalic acid Oxalic acid HO. C, 0 HO. HT2,03 Formic acid. Succinic acid HO.(C H2)'3, 0 HO.(C H3)"C2 0 Acetic acid. Rdipinic acid HO.(C H4)ZC2,0 HO.(C,H,)-C,,O Propionic acid. Suberic acid. HO.(C H(?):C, 0 H0.(C6H7)T2,03Bntyric acid. &C. &C. * There might possibly exist two isomeric combinations of the empirical composition C W N one of which might be the nitro2e~i-combi1iation of the conjugate radical (C H3)-C, namely (C €13)-C, 3' (cyanogen the carbon of which has the adjuuct methyl) j the other the real cyanide of methyl (C H,)"C N =(C2 H,),Cy.In like manner benzonitrile might perhaps be viewed as (C,? H5)-C2 N differing from the still unknown true cyanide of phenyl {G,2 Hi), Cy. CONSTITUTION AND NrATURF OF ORGANIC RADICALS. fi7 Many chemists who consider the acids analogous to oxalic acid asalso the combinations belonging to this series camphoric acid phtalic acid pyrotartaric acid &c. as bibasic acids double their atomic weight. If‘ this view which is supported by a number of facts should be correct the kind of composition with which we have already become acquainted in speaking of sulphobenzoic and sulph- acetic acids may perhaps furnish us with pkey to the proper under- standing of the chemical constitution of those conjugate oxalic acids.These may be viewed in a similar manner to the above-mentioned as compound acids of oxalic acid and another conjugate oxalic acid in the following manner Oxalic acid ....... HO . C 0 Succinic acid .......2 HO .{(C H c4 04 )zC 0 Pyrotartaric acid ......2HO .{(C2 zr”)CC20, c6 o6 Adipic acid .......2HO .{(C2 os >cC203 c8 H3 23 Pimelic acid .......2 HO .{tC10 HI0 >CC2o3 2 3 Phtalic acid Suberie acid 2 HO .{((312 .......2 HO .{@I2c ....... 2 Hi2)zOd o3H )CC,O 3 Camphoric acid ......2 €10 .{ 2 ,H14)32 O3 3 Hyposulphosuccinic acid . .3 HO . According to the above view the composition of their amidic acids and imides would be expressed by the following rational forniulze Succinamic acid ..HO .(C H )3,{ gh,};C 0 Phtalamic acid ...HO .(CI2H4 )SC,{ $H2 .C2 0 Camphoramic acid ..HO .(C16H14)1C,( $H2} ;C2 0 &€.Succinimide ..HO .(C4 H )zC2 N ;C 0 Phtalirnide ...HO .(C12H >3, N; C 0 Camphoriniide . .HQ .(C, TI,,)zCz N ;C 0 &c. P2 DR. KOLBE ON THE CHEMICAL I do not deny that difficulties are met with in following up this hypo- thesis still farther. Among others it would be necessary to assume in the aniles for instance in succinanile the existence of the very hypo- thetical compound NC(C, H4) combined with (C4 H4)r3C2 and forming a peculiar cyanogen in which the carbon as well as the nitrogen are each joined with an additional carbohydrogen ; thus succin-anile would be = MO .(C H4)zC2NZ(C, H4) C 0,; phtalanile= NO. (C, H4)1C2 N\7(C1,H4) C 0, &c. Such compositions as these do certainly not appear adapted to increase our confidence in the probability of this hypothesis on the constitution of the imides. Nevertheless I consider it not impossible that these difficulties may be removed by future researches. A fresh investigation of this subject which is yet so little exhausted might perhaps lead to no uninteresting results. Among the various hypotheses that may be advanced upon the chemical constitution of anisylic acid and particularly for the expla- nation of the wonderful and manifold correspondence exhibited by anisylic acid and anisole on the one and benzoylic acid and benzole on the other as regards their chemical behaviour none appears to me more simple or probable than the view expressed in the formuh HO (C14 €3 O,)-C, 0 (anisylic acid) and (C14 H 0,) H (anisole); namely that their combinations possess a chemical composition similar to that ascribed to benzoylic acid and benzole and that they are only distinguished from the latter compounds in containing instead of C, H, the complex atom (C14H 0,).Objections may perhaps be raised as to the capability of the group (C14H7 0,)of playing the part of a radical and exercising functions similar to those of the adjunct C, H of benzoyl or the carbohydrogen C1 H in toluole as assumed by this hypothesis. The following comparative table of correspond- ing anisyl- and benzoyl-compounds and the corresponding bodies derived from both will be best adapted to weaken any objections made from a theoretical point of view against the plausibility of the assumption that oxygen can be the constituent of an organic radical Anisyl.Benzoyl. Pl* H7 02)-C 1 (Cl% H,)^C% I Anisglous acid. i Oil of bitter almonds. WO. (C14 H 02)-C, 0 1 I10 . (C12 H5)-c2 0 Anisylic acid. Benzoylic acid. 110 . (CI4 If; O2)-c?,0 HI0 (C, H,)-C, 0 '3 CONSTITUTlON AND NATURE OF ORGANIC RADICALS. Chloranisylic acid. Chlorobenzoylic acid. Nitranisylic acid. Nitrobenzoic acid. Ho ' ('14 {:8,)02)^'2 Dinoxybromideof anisyl. Dinoxybromide of benzoyl ('14 H7 '2)-'2 {gi DinoxychIorideof anisyl. Dinoxychloride of benzoyl.Dinoxamide of anisyl. Dinoxamide of benzoyl. ('14 H? 03)-c2t {&Tb20 Anisole. Benzole. (c14 H Oi?> Sulphanisolide. Sulphobenzide. ('l* H 02) so2 (C12 J35) 802 Sulphanisole-sulphuric acid. Sulphobenzole-sulphuric acid. HO .(C12 H7 0,)-S2 O5 HO a ((42 H,)^S2 0 Nitranisole. Nitrobenzole. (Cl*H7 02) NO4 w12 H5) NO4 Dinitranisole. Dinitrobenzole. ('14 {:6)O2' Anisidine. Aniline. ('14 H7 02) NH2 Nitranisidine. Nitraniline. &C. &C. Independent of the proof which the above comparison appears to me to afford that oxygenated organic radicals are capable of playing the part of ordinary radicals consisting merely of carbon and hydro-gen I think that after the assumption of secondary organic radicals no doubt can exist on this subject.If the existence of hypothetical DR. KOLBE ON THE CHEMICAL radicals is assumed in the nitrophenylic acids containing four eight and even twelve atoms of oxygen we can have no hesitation in ascribing to the complex-atom (C14H 02)the properties of a radical. It is certainly difficult to conceive in what form the two equivalents of oxygen are contained in the adjunct of anisyl and the radical Qf anisole anisidine &c. One might imagine them to play a similar part to the two equivalents of chlorine for instance in dichlo- H robenzoylic acid HO . (C12{ c$)-C2 0, or in dichloraniline fC12 { 8) NH, assuming therefore the grouped atom (Ci4 H70,) to be a secondary radical derived from the primary one (C14 H9)* &~kia substitution of 4 volumes of hydrogen by 2 volumes of oxygen is however in itself rather improbable and unsupported hitherto by any data Maq- chemists consider anisole as a similar and homologous corn-to po~~nc~hydrated oxide of phenyl (phenylic acid) from which indeed it differs only in containing C H more.This view is supported particularly by the fact that anisole is formed from anisylic acid under the same circumstances as hydrated oxide of phenyl is produced from salicylic acid which is homologous to anisylic acid. This fact can however only be considered as a slight proof as all other circumstances are favourable to the assumption that anisole possesses a constitution similar to benzole. Neither anisole nor its derivatives dibromanisole or trinitranisole possess the acid properties of phcnylic acid dibromophenylic acid and trinitrophenylic acid.On the other hand however chrysanisic acid lately discovered by Cahou1*s,* which is formed together with trinitranisole by the action of fuming nitric acid upon anisylic acid and is isomeric with trini- trailisole possesses exactly the properties which one would expect from a homologous combination corresponding to trinitrophenylic acid. r> lhere can be no hesitation in the decision of the question whether chrysanisxc acid or trinitranisole is most nearly related to trinitrophe- nyk acid since the first of the two possesses all and the second ilone of those properties so characteristic of trinitrophenylic acid. are moreover acquainted with a substance isomeric to anisole namely kreosote which appears at the same time to possess the greatest similarity to hydrated oxide of phenyl to which it is at any rate much more closely related in its properties than to anisole SO that it may be assumed with some degree of probability that krcosote and llot anisole is the compound honiologons to hydrated oxide of AIIA.Ch.1’11):. [3j xsl 11 CONSTITUTION AND NATURE OF ORGANIC RADICALS. phenyl sought for. A farther support for this view is furnished by the boiling-points of these bodies Hydrated oxide of phenyl boils at 187' the homologous compound containing C H more should therefore boil as usual 19O higher therefore at 206'. The boiling- point of kreosote approaches the latter number very closely it being 203' while anisole boils at as low a temperature as 152'.A similar regularity in the difference of boiling-points is likewise exhibited by anisole and its homologue phenetole (C ahonrs loc. cit.) obtained by the distillation of salicylate of oxide of ethyl with caustic baryta which has according to Cahours a boiling-point 20' higher than anisole (172O) and differs in its composition by an increase of C H, and but slightly in its cheniical behaviour from the latter substance. Hydrated oxide of phenyl and kreosote are evidently the alcohols of the homologous radicals C12 H and C, H, the former being HO . (C12H,) 0 the latter HO (C14 H,) 0 hence trinitrophe-nylic acid is composed according to the rational formula and chrysanisic acid according to the formula The following are the rational formuls of the isomeric combina- tions in question together with those of the members as yet un-known L--v-J Hydrated oxide of phenyl.Trinitrophenylic acid. L-v-3 Unhnown. L-'v-2 Chrysanisic acid. L-v-3 hnisole. Trinitranisole DR. KOLBE ON THE CHEMICAL L-v-J Unknown. L-v-3 Trinitrophenetole. It can scarcely be considered doubtful that salicylic and salicylous acids cmrespond in their rational composition to anisylic and anisy- lous acids Salicylic acid . . HO . (GI H O,)-C, O3 Salicylous acid . . HO . (C12H O,)-C, 0 Anisylic acid . . . HO . (GI*H7 O,)-C, 0 Anisylous acid . HO . (C14 H O,)-C, 0 and that the hydrogen-combination of the radical (C12 H 0,) isomeric with hydrated oxide of phenyl will likewise be discovered.The difference in the behaviour of salicylic and anisylic acids when heated with baryta is certainly highly deserving of attention; it is how- ever not more strange than many other reactions in which homo- logous combinations so frequently differ from each other. Since H ofmann’s researches on methylaniline diethylamine &c. have taught us that the ether-radicals can replace hydrogen in organic combinations I consider the existence of a compound similar and analogous to anisole having the rational formula (C1213 0,) . (C H3) as not improbable. It is possible that the anisole obtained from salicylate of oxide of methyl may possess such a composition (C H 0).(C12H O,)^C, 0 + 2 BaO = (CI H 0,) . (C 13,) + 2 (BaO CO,) and that as it differs probably but little from the anisole prepared from anisylic acid (C14 H 0,) H these slight differences have been overlooked. If formobenzoic acid may be considered as a double-compound of oil of bitter almonds and formic acid its isomerism with anisylic acid and gaultheric acid may be easily explained by their different rational formuls HO * (C14 H7 O,)^C, 03 Anis ylic acid. ((32 H3) 0 (C12 H O,)^C, 0 Gaultheric acid. HO . H-C, 0,; HO . (C, H,)-C, 0 Formobenzoic acid. rT I he following rational formukc afford likcmisc an explanation of CONSTITUTION AND NATURE OF ORGANIC RADICALS. 73 the isomerism of the four combinations composed according to the empirical formula C, H NO Salicylamide .. . . . (C12 H502)-C2 {2H2 Nitrotoluole . . . . . (Cl4 H7) . NO Benzamic acid . . NO . (C12 { NHHa)^0 Anthranilic acid (car- } HO . C (And; 0 CO%.* banilic acid) . . . By these formuh the chemical character of each individual com- pound is so definitely expressed that a cursory examination thereof is sufficient to enable us to understand for instance why salicyla- mide yields upon being heated with potassa ammonia and not aniline ; why anthranilic acid yields under similar circumstances neither salicylic acid nor ammonia but carbonic acid and aniline; and why benzamidic acid without being identical with anthranilic acid yields the same products HO C{ (Clz i)zNH2}; C0,+2KO=(C,H,).NH,+2(K0.C02) L---Anthranilic acid.HO . (Cl,{ 3H)-C2 0 + 2 KO = (CI2 H5).NH + 2 (KO. CO,) Y Benzamidic acid. I have in the foregoing endeavoured to show by a series of examples how easily the facts which appeared hitherto incompatible with the radical-theory and have been principally employed by the opponents of this theory as arguments against the existence of compound radicals may be made to accord with the above theory as soon as the idea of the immutability of these radicals is set aside and exchanged for the opinion that they are complex atoms in which certain atoms may be substituted by others. I have also endeavoured to establish the view that new secondary radicals are thus produced many of which still possess properties similar to those of the primary ones; that however not all radicals are equally adapted for con- version into secondary radicals (e.y.ethyl being less so than acetyl) ; that indeed one and t’ne same radical according to the manner in which it is combined possesses this property in different degrees (ethyl for instance possesses it to a higher degree in the compound * hiid = (Ck2 IJ4)ZNI12 (anilide). DR KOLBE ON THE CHEMICAL ethers than it does in the simple ones) Lastly I have deemed it necessary to distinguish between two classes of organic radicals the true repetitions (analogues) of hydrogen (the ether-radicals) and the conjugate radicals in which the former exist as adjuncts for instance of C, As Sb Sn &c. Besides these there appears to exist a third class formed by the combination of homologising car- bohydrogens C H, and similar compounds with simple substances for instance with C in the radical of succinic acid with Pt in elayl-platinum &c.and which may therefore be viewed as homo- lopes of these elements. The question still remains to be answered whether and how the assumption of alterable chlorinated radicals can be made to accord with the electro-chemical theory. According to this theory the nature of a chemical combination is dependent on that of its con-stituents arid hence the substitution of the negative chlorine for the positive hydrogen would be impossible. It appears to me necessary before all to examine carefully whether the hydrogen replaceable by chlorine really is the electro-positive constituent of the radicals and whether the chlorine which exercises the functions of hydrogen retains the negative properties generally ascribed to it.In simple inorganic combinations it is in most cases easy to determine which element is the positive and which the negative constituent but in organic compounds it is much more difficult to decide this question.-Berzelius adhered to the rule that the application of what is and will still become known with respect to the mode of combination of the elements in inorganic nature serves as a guide for the proper judgment of their combinations in organic nature by which we may hope to arrive at correct and con- cordant conceptions of the mode of composition of those bodies which are produced under the influence of vital processes as also of those which are produced by the metanioryhoses of these bodies by chemical means.” This principle led to the hypothesis that organic combinations must contain compound radicals exercising therein functions similar to those of simple radicals in inorganic nature and that in such a complex atom playing the part of a simple radical electro-positive properties are predominant as in the latter by which the combination with the negative elements is effected; no farther point of view is however furnished us by this hypothesis from which to arrive at a decision of the question which electro- chemical properties are possessed by the elements composing those groups of atoms as there is no analogy in inorganic chemistry with regard to this point.CONSTITUTION AND NATURE OF ORGANIC RADICALS. We must therefore content ourselves at present with the con- viction that there were in the elements constituting organic radicals electrical oppositions at the time of their combination as required by the electro-chemical theory and must leave it to the future to discover by other means which of those constituents are the positive and which the negative ones. Even in the single and most simple case in which two elements carbon and nitrogen combine directly to form an organic radical it is quite out of our power to determine with any degree of probability to which of the elements cyanogen owes its predominant negative properties and whether the nitrogen or carbon constitutes the positive (with respect to the negative) constituent.The solution of these questions becomes much more difficult with reference to the radicals con-sisting of carbon and hydrogen which are produced under far more complicated circumstances and cannot be formed like cyanogen directly from their elements. In this difficulty the phenomena of substitution afford appropriate means with which at any rate to impart some probability to the conjecture that the hydrogen for instance in acetyl is possessed of electro-chemical capacities differing from that contained in water or hydrochloric acid. We are also justified in doubting that the chlorine entering acetyl or aniline in the place of hydrogen carries with it the powerful electro-negative properties of which it is pos-sessed in its inorganic combinations.It can indeed be no longer doubted that in the simple substances the direction of the powers of affinity peculiar to them in their so-called normal state is altered under certain circumstances and frequently by apparently unim-portant causes and that therefore they assume at times an electro- chemical character differing from that they usually possess. The red amorphous phosphorus produced by heating phosphorus to 240' C. is certainly still the same substance but with respect to its chemical properties it is quite a different body. This element most remarkable next to the alkali-metals for its affinity for oxygen possesses singularly enough after exposure to the requisite heat not a trace of this affinity.The red phosphorus differs so perfectly from the normal phosphorus in its physical properties and in the altered direction of its powers of affinity that if its relations to colourless phosphorus were unknown it would certainly be con-sidered as a new element. These facts appear to me to warrant the assumption that hydrogen may also exist in organic combinations in a state in which it is possessed of properties differin9 from those of the ordinary electro- DR. KOLBE ON THE CHEMICAL positive element. Does not hydrogen exhibit a great difference with regard to its aflinities in the free and the nascent state? In the same manner I consider it not impossible that the chlorine entering into the place of hydrogen in compound radicals assumes by this act of substitution a less negative character than that peculiar to it in its normal state.It would not according to this be the positive hydrogen and the negative chlorine bromine &c. that re-place each other but bodies differing perhaps no more in their electro-chemical properties than oxygen and sulphur. This mode of viewing evidently still exhibits great deficiencies it shows however at any rate that it is not impossible to make the enigmatical phenomena of substitution accord with the radical-theory. “A good theory,” as Hofmann* very aptly remarks (;is more than a temporary expression of the state of science collecting under a general view the facts acquired up to the moment of its birth.It must not like ephemeral hypothesis vanish before the light of suc-ceeding discoveries but expanding with the growth of science it must still correctly represent the known facts though of necessity modified into a more general expression.” Who could doubt that the radical of theory is capable of such an expansion ? If the conception hitherto adopted of the immu- tability of organic radicals be only done away with the explanation of the phenomena of substitution will present no farther difficulties. It would be ridiculous to allow a single fact difficult of expla-nation to induce us to throw aside at once a theory which has served us for so long a period as a trustworthy guide in the difficult field of organic chemistry and has preserved us most securely from the errors of a code of laws like that which has been laid down by Laurent and Gerhardt-unless indeed we had some better theory to substitute for it.The radical-theory has already outlived the theory of metalepsy and the theory of types of which at the present time scarcely mention is made in the researches of French chemists; the nucleus-theory and the ingeneous invention of whole numbers of atoms will likewise disappear as rapidly from the field; for chemistry is indeed something better than a mere arithmetical problem into which Laurent and Gerhardt erideavour to convert it. By founding the hypothesis that replacements of hydrogen by chlorine hyponitric acid &c. occur in compound radicals the question whether oxygen can constitute the component of a radical is likewise answered.It is easy to render to oneself an account of the form in which oxygen exists in the radicals of nitrobenzoic and * Phil. Tians. 1851 I 96. CONSTITUTION AND NATURE OF ORGANIC RADICALS. nitrophenylic acids ; in many other cases as in anisyl salicyl we are as yet unable to do so and must therefore content ourselves for the present with the establishment of the mere fact. Perhaps these are also secondary radicals which we have not as yet been able to trace back to their primary ones. Since Frankland succeeded in isolating from their combinations the ether-radicals ethyl and amyl to which are added the radicals methyl and valyl obtained by the electrolysis of acetic and valeric acids various opinions have been put forward and supported with regard to the nature of these carbohydrogens and of these the view that they are not the true radicals but isomeric modifications of them appears to have become the one most generally entertained.According to Laurent and Gerhardt they possess double the atomic weight ascribed to them by Frankland and myself because the formulz C H, C H, &c. are at variance with their law of whole numbers of atoms. I acknowledge that it is not in my power to follow these chemists in their train of argument. The circum- stance that none of these radicals re-combines directly with oxygen chlorine sulphur &c. to form simple ethers is however more deserv- ing of attention. The importance attached to this circumstance is the greater because other radicals particularly kakodyl enter with such facility into combination with the above-named metalloids ; upon this circumstance endeavours have been made to establish the view that these indifferent carbohydrogens are not the true radicals contained in the ethers.It is a tolerably general but certainly unfounded opinion that the organic radicals in the free state must be gifted with powerful affinities. Many have expected particularly of the ether-radicals that their properties would not be much unlike those of potassium. This prejudice has evidently originated with the great diflicitlties hitherto met with in the isolation of the ether-radicals from their combinations. This is however at present effected in the most simple manner ;and since contrary to expectations methyl ethyl amyl &c.differ much in their combining powers from potassium as well as from kakodyl one is too much inclined to regard their indifferent properties as the most certain proof that they are not the ether-radicals Those who argue thus forget that hydrogen and platinum also belong to the radicals and that these two substatices exhibit just as little tendency to combine directly with oxygen chlorine &c. without the mediatiq infi uenee of another agent. Nothing justifies us in classing the ether-radicals with potassium ; on the other hand it appears to me quite natural to compare them with DR. KOLBE ON THE CHEMICAL hydrogen as a repetition of which they must be regarded.In fact they differ no farther in their properties from the latter than is con- ditional upon their mere complex composition. Hydrogen and methyl both possess under ordinary circumstances no affinity for oxygen iodine sulphur &c. ; when mixed with chlorine in the dark they both remain unaltered combination only ensues under the influence of light. It is however no more strange that chloride of methyl is not formed under these circumstances which the analogy with hydrogen would lead us to expect than that on igniting a mixture of methyl-gas and oxygen no oxide of methyl but water &C. is formed. It is easily conceivable that the stronger affinities of oxygen and chlorine for the constituents of methyl must predo- minate as is the case likewise when kakodyl is brought together with free oxygen or chlorine.The deficiency exhibited by the ether-radicals in strong powers of affinity does not therefore appear to me any reason whatever why they should be excluded from the series of radicals; in that case hydrogen must also not be allowed to stand as a radical. And finally the circumstance that kakodyl zincethyl stibethyl and as may be predicted with tolerable certainty even acetyl the lower oxide of which aldehyde possesses so powerful an affinity for oxygen are much more nearly related to the alkali-metals as regards their powers of combination cannot be regarded as a rule for the ether- radicals as these possess a constitution totally different from the above conjugate radicals.The principal support for the view extensively entertained that methyl ethyl butyl amyl and capryl in the isolated state possess double the atomic weight assigned to them that therefore their com- position should be expressed by the empirical formulae C H (methyl) c,HI0 (ethyl) Cl Hl (butyl) c, H,2 (amyl) c, H, (capry]) is found in the circumstance to which attention was first called by Hofmann that the boiling-points of butyl am$ and capryl differ from each other successively by 40° on account of the difference in their com- position of 2 C H, while if they were composed according to the formulae C H, Cl0 Hll C, H13 their boiling-points would only differ successively 20". This observation appears to me worthy of the greatest attention; I cannot however consider it as decisive.Hofmann himself by the discovery of the methylated- and ethyl- ated aniline-bases has brought to light facts which rob the assump- tion that the boiling temperatures of organic combinations increase 20" for every additional C M of its general validity. As the boiling-points of those aniline-bases increase almost regularly by only CONSTTTUTION AND NATURE OF ORGANIC RADICALS. loo,instead of 20° for every equivalent of C H added to the aniline the difference of C H in the ether-radicals may likewise just as easily effect a difference of 40' in the boiling-point. The question whether these carbohydrogens are the real ether- radicals or merely isomeric combinations appears to me at any rate to be of but little importance with respect to the radical-theory.They may be shown by future researches to be combinations of a different nature without endangering the radical-theory in the slightest degree. In the present state of science however the preference must undeniably be given for its greater simplicity to the assumption of the identity of those carbohydrogens with those of the radicals hypothetically assumed in the ethers

ISSN:1743-6893    

DOI:10.1039/QJ8520400041

出版商:RSC    

年代:1852

数据来源: RSC

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PROCEEDINGS AT THE MEETINGS OF THE CHEMICAL SOCIETY. January 20 1851. THOMAS GRAHAM EsQ.,V.P. in the Chair. M. Balard was elected a Foreign Member of the Society. The following presents were announced “The Pharmaceutical Journal for January :” presented by the Editor. The Journal of the Franklin Institute :” presented by the In- stitute. cc Sillimads American Journal of Science and Arts for September 1850:” presented by the Editor. “he Art Union of London Almanac for 1851:” presented by the Publisher. Tbe following papers were read 1. (‘On the Magnetism of the Elementary Bodies and their Binary Compounds :” by Mr. Richard Adie. 2. ‘‘Analysis of the Water of the Artesian Well at Southampton :” by J. Robson Esq, of Queenwood College.3. I‘ On the Selenocyanides:” by William Crookes Esq. of the Royal College of Chemistry. February 3 1851. WILLIAMALLENMILLER,M.D. V.P. in the Chair The following presents were announced “The Pharmaceutical Journal for February :” presented by the Editor. “The Journal of the Franklin Institute for December 1850:” presented by the Institute. PROCEEDINGS OF THE CHEMICAL SOCIETY. ‘‘ The Annual Reports of the Royal Cornwall Polytechnic Society from 1835-1849 :” presented by the Society. “Boerhaaves’ Chemistry 3rd Edition 1753 :” presented by Mr. H. Sugden Evans. The following papers were read 1. “On the Composition of certain Well-waters in the neighbour- hood of London with some observations on their action on lead :” by Henry Noad Esq.Lecturer on Chemistry at St. George’s Hos-pital. 2. ‘‘Observations on the Deportment of Diplatosamine with Cyanogen:” by G B. Buckton Esq. F.L.S. February 17 1851. RICETARD EsQ. President in the Chair. PHILLIPS The following memoirs and journals were presented On the condition of certain Elements at the moment of Chemical Change by Benjamin Collins Brodie Esq.” by the Author. “On the Chemical Constitution of the Rocks of the Coal Forma- tion by Hugh Taylor Esq.” by Dr. Anderson. “On the Optical Properties of a compound of Iodine and CO-deine by William Haidinger Esq.” by Dr. Anderson. ‘‘On a remarkable compound of Iodine and Codeine by Thomas Anderson M.D. F.R.S.E.” by the Author. ‘‘ Sillirnan’s American Journal of Science and Art for January 1851 :” by the Editor.“ The Quarterly Journal of the Geological Society for February 1851 :” by the Society. The following paper was read ‘‘ On the Explosive Compound usually denominated Iodide of Nitrogen by Dr. J. H. Gladstone.” VOL. 1V.-NO. XIII. 82 PROCEEDINGS OF THE CHEMICAL SOCIETY. March 3 1851. RICHARDPHILLIPS, EsQ. President in the Chair. Astley Paston Price Ph. Do and William J. Russell Esq. were elected Fellows of the Society. The following presents were announced ‘EThe Pharmaceutical Journal for March :” by the Editor. cc The Journal of the Franklin Institute for January:” by the Institute. “ Fourth Report on the Analysis of the Ashes of Plants by J Thomas Way and GIW.Ogston Esqrs.” by the Authors. “ Miscellaneous Results from the Laboratory by J. Thomas Way Esq.” by the Author. The following paper was read “ On the Combination of Arsenious Acid and Albumen and re- m’arks on Liebig’s Theory :” by Sheridan Muspratt Ph. D. March 11 1851. RICHARDPHILLIPS, EsQ. President in the Chair. Montague Lyon Phillips Esq. and David Gambre Esq. were 1ected Fellows of the Society. The following presents were announced (‘Experimental Researches in Electricity series 22 -27 by Michael Faraday D.C.L.” by the Author. ‘‘The Literary Gazette for January and February:” by the Editor. “ A Letter to the Right Hon. Sir George Grey Bart. M.P. on Medical Registration and the present condition of the Medical Cor-porations by Emeritus” by the Author. “ Head Juries of the Exhibition of 1851:” by Dr. Lyon Play- fair. A paper was read by Professor Clark on the Chemical Examina- tion of Waters.

ISSN:1743-6893    

DOI:10.1039/QJ8520400080

出版商:RSC    

年代:1852

数据来源: RSC

摘要:

NOTICES OF PAPERS CONTAINED IN THE ‘‘ Philosophical Translations” and Foreign Journals. BY HENRYVI.T~~~~, B.A. F.C.S. On the Dimsion ef Liquids.* By Professor Graham F.R.S. F.C.S. The experiments described in the author’s former paper on this subject furnished strong grounds for believing that isomorphous salts possess a similar diffusibility. All the salts of potash and ammonia which were compared appeared to be equi-diffusive; so also were the salts of certain rnagnesian bases. A single preliminary observation on the nitrates of lead and barpta however opposed the general conclu- sion and demanded further inquiry. It is scarcely necessary to say that any new means of recognising the existence of the isomorphous relation between different substances must prove highly valuable.Let us inquire therefore how far liquid diffusion is available for that purpose. The salts were still diffused froin weak solutions that is from solu- tions containing from 1. to 8 per cent of salt; but now a measure of the solution equal to 100 grs. of water was made to contain 1 grain of the salt to form what is called the 1 per cent solution instead of 1 grain of salt being added to 100 grs. of water as before without reference to the condensation which generally occurs. The quantities 1 2 4 and 8 per cent thus indicate the parts of salt present in a constant volume of liquid,-as 10 20 40 and 80 grs. of the salt in 1000 water grain-measures of the solution. The same phials for the solution and jars for the external water-atmosphere continued to be used and the nianipulations were similar.It is believed however that the temperature of the liquids was maintained more uniform in the new experiments than the old partly by the better regulation of the temperature of the apartment and partly by placing the jars close together upon a table with upright ledges and covering the whole * Philosophical Transactions 1850 p. 805. G2 PROFESSOB GRAHAM ON THE over with sheets of paper during the continuance of an experiment. The mass of fluid in 80 or 100 jars which were employed at once and placed together made the small oscillations of temperature which might still occur slow and less injurious. The investigation is also extended to sever$ new substances such as hydrocyanic acid acetic acid sulphurous acid alcohol ammonia and salts of organic bases without reference to isomorphous relations.It is very necessary to have data which are minute and accurate respecting the diffusion of a considerable variety of substances. This it is the object of the present investigation to endeavour to supply leaving speculative deductions in general respecting the nature and laws of liquid diffusion for a future occasion. The density of all the solutions was observed at a constant tempera- ture namely 60' Fahr. 1. Hydrochloric acid-The period of diffusion arbitrarily chosen for this acid was five days. The di5sate or quantity of acid diffused was determined by precipitating the liquid of the external reservoirs with nitrate of silver and weighing the chloride of silver formed.In the 1and 2 per cent solutions the liquids of two jars were generally mixed and precipitated together. The number of cells diffused at once unless otherwise specified was always eight cells of the 1 and 2 per cent solutions and four cells of the 4 and 8 per cent solutions. In this abstract the means only of these experiments are given. The diffusates at the same temperature were found to be as follow Diffusion in five days at 51' Fahr.; two cells. Grs. Ratio. From 1per cent solution . . 7.41 0.97 From 2 per cent solution . . . 15.04 2.00 From 4 per cent solution . . . 30.72 4-08 From 8 per cent solution . . . 67-68 9.00 The 2 per cent solution is taken as the standard of comparison for the ratios instead of the 1 per cent solution from the greater accu- racy with which the diffusion of the former can be observed.The increasing diffusibility with the larger proportions of acid here observed is unusual at least in the degree exhibited by the 8 per cent solution. Other substances as will be immediately observed of nitric acid appear to lose proportionally in diffusibility as their solutions are concentrated. Hydrochloric acid belongs to the most diffusive class of substances known; it appears to exceed hydrate of potash at 53'05 as 7.56 to 6.12,or as 100 to 80.9*. * Phil. Trans. 1850 39. DIFFUSION OF LIQUIDS. The rapidity with which hydrochloric acid diffuses and the facility with which that substance may be estimated induced the author to examine the progression with which its diffusion takes place with increasing times in a minute manner.The 2 per cent solution was diffused for times increasing by six hours from twelve hours or 0.5 day to 4-75 days six cells being diffused for every period. Instead of determining the acid diffused separately in each jar or pair of jars the contents of the six jars of each experiment were mixed together and a definite proportion of the liquid precipitated by nitrate of silver and the chloride of silver weighed so as to obtain at once the mean result. Another observation for 5.75 days is added although made at a sen-sibly higher temperature. DIFFUSION OF HYDROCHLORIC ACID 2 PER CENT SOLUTION; ONE CELL.Time. Temperature. Diffusate in grains. Differences. days. 0-5 5i.75 0.909 0.75 53.75 1.312 *403 1 53.75 1 766 *454 1-25 53.75 2.353 *587 1.5 53-75 2.596 -243 I*75 53.58 3.178 -582 2 53.58 3.410 *232 2.25 53.42 3.967 *557 2.5 53.58 4.339 *372 2-75 53.50 4.618 0279 3 53-50 4.969 *351 3-25 53.50 5.304 -335 3.5 54-85 5.857 *553 3.75 54.85 6.254 -397 4 54.85 6.407 *153 4*25 54.85 6.795 -388 4.5 54.71 7.034 *239 4.75 5471 7.473 *339 5-75 5 6-46 8.363 The differences are evidently affected by accidental errors of obser- vation. The diffusion in 3.5 days is also increased by a rise of tempera-1' more than ofture in that and the following experiments. The diffmion always increases with the time but less rapidly according to a gradually diminishing progression.Hydriodic acid.-Time of diffusion five days as for hydrochloric acid. The acid diffused was estimated from the weight of iodide of silver which it gave when precipitated by nitrate of silver. PROFESSOR GRAHAM ON THE Diffusion from 2 per cent solutions at 51' Fahr. Hydrochloric acid . . 15.04 100 Hydriodic acid . . . 15-11 100.46 These experiments indicate a similarity of diffusion between the two isomorp hous substances h y droch lor1 c and h y driodic acids. Hydrobromic acid.-Time of diffusion five days. The diffusate was estimated from the bromide of silver. Diffusate from 2per cent solutions at 59O.7 Fahr. Hydrochloric acid . . 16.55 100 Hydrobromic acid .. . 16-58 100-18 Hydrobromic acid appears therefore to coincide in diffusibility with hydrochloric acid at this temperature. It mq be remarked that these three acids hydrochloric hydrobomic and hydriodic do not exhibit the same correspondence in another physical property namely the densities of their aqueous solutions containing the same proportion of acid. The densities of 2 per cent solutions of hydrochloric and hydriodic acids appear to be respectively 1*0104and 1.0143 at 6O0 Fahr. and that of hydrobromic acid is an intermediate number. The same acids are also known to differ considerably in the boil- ing-points of solutions containing the same proportion of acid. A considerable diversity of physical properties appears here to be compatible with equal diffusibility in substances which are isomor- phous.Bromine.--Pure water readily dissolves more than 1 per cent of this substance. The solution prepared however contained only 0.864 per cent of bromine as was ascertained by treating it with sulphurous acid and afterwards precipitating by nitrate of silver. Its density was 1.0070. It was evident from the slow appearance of the brown colour in the exterior cell that bromine diffuses less rapidly than hydro- bromic acid. The diffusion-time of bromine was made ten days or double the time of hydrobrornic acid. Two cells contained together a diffusate of 5.80 QFS. of bromine ; another two cells a diffusate of 5.88 grs. ;mean 5.84 grs. at 60'01 Fahr.; or 6.76 grs.for a 1 per cent solution. Doubling the last result we have 13.52 grs. for a 2 per cent solution which is still considerably under the diffusate of hydrobromic acid (16.58 grs.) in half the time. 3. Hydrocyanic acid-Time of diffusion five days. The acid diffused was estimated from the cyanide of silver which it gave with nitrate of silver. Hydrocyanic acid 1.766 per cent made up to a density of 1.0142 with sulphate of potash. Diffused at 64O.2 in six cells 11.40 11.86 11.80 ; niean 11.68 grs. for two cells. Calculated for 2 per cent 13.23 grs. at 64@*2in two cells or about 13.10 grs. at 62O.8 DIFFUSION OF LTQUICS. assuming this acid to be affected in the same way by temperature as hydrochloric acid. Hydrocyanic acid here appears less diffusive than hydrochloric acid at the same temperature 62O*8,as 13.10 to 16.40 or as 79.6 to 100 and not to belong therefore to the same class of diffusive sub- stances.4. Nitric acid.-Time of diffusion five days. The quantity of this acid diffused was always determined with great exactness by neutraliza- tion by means of a normal solution of carbonate of soda. The diffusion of the different proportions of this acid at one tem- perature is as follows Diffusion of nitrate of water in five days at 51O.2 ;two cells. Grs. Ratio. From 1per cent solution . . 6-99 0.95 From 2 per cent solution . . . 14.74 2 From 4 per cent solution . . . 28-76 3-90 From 8 per cent solution . 57-92 7.86 The usual approach to equality of diffusion between chlorides and nitrates is observable in hydrochloric and nitric acids at least in the f and 2 per cent solutions.Diffusion from 1 per cent solution at 53O.5. Hydrochloricacid . . . . 7.56 100 Nitrate of water . . . 7.28 96.3 Diffusion from 2 per cent solution. Hydrochloric acid at 51' . 15.04 100 Nitrate of water at 51'-2 . 14-74! 98.0 The 2 per cent solutions of both acids were also diffused at higher temperatures. Diffusion from 2 per cent solution. Hydrochloric acid at 62O.8 . 16.46 100 Nitrate of water at 63O.2 . . 16.76 101.8 Here the diffusibility of the two acids is as nearly as possible equal. Diffusion from 4 per cent solution. Hydrochloric acid at 51' . 30.72 100 Nitrate of water at 51°*2 . 28.76 93.7 Diffusion from 8 per cent solution.Hydrochloric acid at 51' . . 67.68 100 Nitrate of water at 51O.2 . 57.92 85.3 The Pride divergence between these two acids in the 8 per cent PROFESSOR GRAHAM ON THE solution is produced by the remarkably increased diffusion of hydro-chloric acid in that high proportion. 5. Sulphuric acid.-That time of diffusion arbitrarily chosen for this acid was ten days. The diffusate of this acid wits determined in the same manner as that of nitric acid. The diffusion of the different proportions of sulphuric acid is as follows :-Diffusion of sulphate of water in ten days at 49O.7; two cells. Grs. Ratio. From 1 per cent solution . . . 8.69 1.03 From 2 per cent solution . . . 16.91 2 From 4 per cent solution .. . 33.89 401 Froni.8 per cent solution . . . 68-96 8.16 The diffusibility of different strengths of this acid appears to be pretty uniform but with a slight tendency to increase in the higher proportions like hydrochloric acid. Sulphuric acid is inferior in velocity of diffusion to hydro- chloric acid but still appears to possess considerably more than half the diffusibility of the latter. 6. Chromic acid.-Time of diffusion ten days. The diffusates from four cells of the 2 per cent solution were mixed together and the quantity of chromic acid diffused for two cells reduced by means of hydrochloric acid and alcohol and weighed as oxide of chro-mium. 1.762 per cent of anhydrous chromic acid density 1*01404 dif-fused at 67'-3 gave 19.78grs.of chromic acid in two cells. Calculated for 2 per cent 22-43grs. of chromic acid in two cells at 67O.3. The diffusion of sulphuric acid at 63'05 was 19.73 grs. which would give about 21 grs. of that acid at 67O.3. 7. Acetic acid.-Time of diffusion ten days. This acid cannot be determined accurately by the acidimetiical method owiag to the ace- tates of potash and soda being essentially alkaline to test paper like the carbonates of the same bases although neutral in composition. The weight of carbonate of baryta dissolved by the acid was had re- course to. Diffusion of acetate of water in ten days at 48O.8 ; two ce11s. Grs. Ratio. From 2 per cent solution . . . 11.31 2 From 4 per cent solution . . . 22.02 3.83 From 8 per cent solution .. . 41.80 7.26 The diffusibility diminishes with the larger proportions of acid. This acid appears to be considerably less diffusive than sulphuric acid. I was led to over-estimate the diffusion of acetic acid in a prcliminary DIFFUSION OF L?QVIDS. observation of my former paper by trusting to the acidimetrical method of determination. Hydrochloric acid appears to diffuse about two and a half times more rapidly than acetate of water at the same temperature. 8. Subhurous acid.-The time of diffusion chosen for this acid was ten days for comparison with sulphuric acid. The usual number of eight cells of the 1 and 2 per cent solutions were Wused and four cells of the 4 and 8 per cent solutions The whole diffusates of each proportion were then mixed together and the proportional quantity of liquid representing two cells in the 1 and 2 per cent solutions and 1 cell in the 4 and 8 was converted into sulphuric acid by a slight excess of bromine and determined from the sulphate of baryta.Diffusion of sulphurous acid in ten days at 68O.1; two cells. Grs. Ratio. From 1 per cent solution . . . 8.09 0.954 From 2 per cent solution . . . 16.96 2 From 4 per cent solution . . . 33.00 3.821 From 8 per cent solution . . . 66.38 7.827 This substance appears to be less diffusive than sulphuric acid at the same temperature; the diffusion of sulphurous acid at 68O.1 con-siderably resembles that of sulphuric acid at 49O.7. 9. Ammonia.-The time of diffusion chosen was 4.041 days or that of hydrate of potash with chloride of sodium at seven days.The whole difisates of each proportion were mixed together and the quan- tity of ammonia diffused for two cells determined by an alkalimetrical experiment which was always repeated twice. It was necessary for diffusion to have the ammoniacal solution made denser than water which was effected by the addition of common salt. Diffusion in 404 days at 63q4; two cells. Grs. Ratio. From 1 per cent solution . . . 4-93 1*Of29 From 2 per cent solution . . . 9.59 2 From 4 per cent solution . . . 19-72 4-117 From 8 per cent solution . . . 41.22 8.605 Ammonia appears to have a diffusibility approaching to that of hydrate of potash. It appears somewhat less diffusive than hydro- cyanic acid at the same temperature in the proportion of 12 to 13 nearly ;or to possess about three-fourths of the diffusibility of hydro-chloric acid.10. AkohoE.-Tinze of diffusion ten days. The quantity of alcohol diffused was determined by careful distillation. PROFESSOR GRAHAM ON THE Diffusion in ten days at 48O.7; two cells. From 2 per cent solution . . . . . . . 8.62 From 4 per cent solution . . . . . . . 16.12 From 8 per cent solution . . . 35.50 It would be unsafe to draw any conclusion as to the proportionality of the diffusion of alcohol to the strength of the solution from these experiments. Alcohol does not appear to belong to the same class of diffusive substances as acetic acid which might be expected from their simi- larity of composition but possesses a considerably lower diffusibility.Diffusion from 2 per cent solutions in ten days. Acetate of water at 48O.8 . . 11.51 100 Alcohol at 48O.7 . . . . . 8.62 74.9 The diffusion of alcohol approaches to one-half of that of sulphate of water at nearly the same temperature. Alcohol may be substituted for water to dissolve certain salts and also as an atmosphere into which these salts may diffuse. From experiments which have been commenced on this subject it appears that the diffusion of hydrate of potash iodide of potassium chloride of calcium and others is about four times slower in alcohol of density 0.840 than in water. The salts likewise often exhibit the same relations in their diffusibility in alcohol as in water with some singular exceptions such as chloride of mercury.11. Nitrate of baryta.-Time of diffusion 11-43days.* The salt diffused was precipitated by sulphuric acid and calculated from the weight of the sulphate of baryta formed. Diffusion in 11.43 days at 64'01 ; two cells. Grs. Ratio. From 1per cent solution . . . 7.72 1.026 From 2 per cent solution . . . 15.04 2 From 4 per cent solution . . . 29.60 3.936 From 8 per cent solution . . . 54 50 7.247 12. Nitrate of strontia.-Time of diffusion 11-43days. Of anhy-drous nitrate of strontia 0.82 per cent; density 1.0063. Diffused at 51O.5 in eight cells 5-59 5.62 5.44 5.69; mean 5.59 grs. for two cells ; calculated for 1 per cent 6.79 grs. at 51O-5 for two cells. The diffusion of nitrate of strontia almost coincides with that of the isomorphous nitrate of baryta at the same temperature.* This time is to that of sulphate of magnesia (16*166 days) as the square root of 8 is to the square of 16; but does not appear to expiess the true relation between these salts. DIFFUSION OF LIQUIDS. Diffusion from 1 per cent solutions at 51O.5 in 11.43 days. Nitrate of baryta . . . . . 6.73 100 Nitrate of strontia . . . . . 6.79 100.89 13. Nitrate of lime.-Time of diffusion 11.43 days. The diffusate was evaporated to dryness with an excess of sulphuric acid and the nitrate of lime which is always supposed anhydrous was esti- mated from the sulphate of lime produced. Diffusion in 11.43 days at 64'01 ;two cells. Grs. Ratio. From 1 per cent solution .. . 7.66 1.021 From 2 per cent solution . . . 15.01 2 From 4 per cent solution . . 29.04 3.372 From 8 per cent solution . . . 55.10 7.334 The results throughout for this salt are almost identical with those of nitrate of baryta although these two salts differ greatly in solubility and in one being a hydrated and the other an anhy- drous salt. 14. Acetate of lead.-Diffused for 16.166 days j the time chosen formerly for sulphate of magnesia with seven days for chloride of sodium. The solution contained 0.965 per cent of anhydrous salt with the density 1.0080. As this solution of acetate of lead was found to be precipitated by pure water about 2 per cent of strong acetic acid was introduced into the solution and the same acid was added in a less proportion to the water jars.The salt of lead diffused was afterwards determined by means of sulphuric acid Dif-fused in eight cells at 53'01 7.45 7.29 7.46 and 8.07 grs.; mean 7.56; or 7.84 for 1 per cent in two cells. 15. Acetate of baryk-Diffused for 16.166 days. The solution contained 0977 per cent of anhydrous salt with the density 1.0073. The same addition of acetic acid was made to it as to the preceding acetate of lead in order that the circumstances of diffusion might be similar for both salts. The salt diffused was estimated also in the form of sixlphate. Diffusion of 1 per cent solutions in 16.166 days; two cells. Acetate of baryta at 53O.5 . . 7-50 100 Acetate of lead at 53O.1 . . . 7.84 104*53 Here of two isomorphous salts that of greatest atomic weight sensibly exceeds the other in diffusibility.16. Chloride rf barium.-Time of diffusion 11.43 days. The diffused salt was weighed as sulphate of baryta. PROFESSOR GRAHAM ON THE Diffusion in 8.57 days at 63O; two cells. Grs. Ratio. From 1per cent solution . . . 6.32 1*047 From 2 per cent solution . . . 12.07 From 4per cent solution . . . 23.96 3-970 From 8 per cent solution . . . 45.92 7.608 17. Chloride of strontium.-The diffused salt was weighed as sulphate of strontia. Diffusion in 8-57days at 63'; two cells. Grs. Ratio. From 1 per cent solution . . . 6.09 1*045 From 2 per cent solution . . . 11.66 2 From 4per cent solution . . . 23.56 4.041 From 8 per cent solution .. 44~46 7.626 The series of ratios in the preceding table will be found on com- parison to correspond closely with the ratios of chloride of barium. It may be useful to compare farther the amounts diffused from similar solutions of these two isomorphous compounds. Diffusion in 8-57days at 63' ; two cells. Chloride of barium 1 per cent . 6-32 100 Chloride of strontium 1 per cent 6.09 96.36 Chloride of barium 2 per cent . 12.07 100 Chloride of strontium 2 per cent 11.66 96-90 Chloride of barium 4 per cent . 23.96 100 Chloride of strontium 4per cent 23.56 99.16 45.92 100 Chloride of barium 8 per cent Chloride of strontium 8 per cent 4446 96.83 The near coincidence of the 4 per cent solutions probably arises from an accidental error of observation in the chloride of barium for the latter departs here from the progression of its ratios.We appear then to have a small but constant difference of about 34 per cent in the diffusion of these two isomorphous salts the chloride of barium which possesses the highest atomic weight having the advantage. The diffusion of the 1 per cent solution of the same salts for the longer period of 11.43 days gives 7.50 for chloride of barium at 50O-9 and 7'052 for chloride of strontium at 51° or nearly the same temperature. For the first time we have in the barytic salts a divergence between chlorides and nitrates for the nitrates of the same bases have a number about 6.8 only at the same temperature. I am led however to believe that this discrepancy becomes much DIFFUSION OF LIQUIDS.9s less at low temperatures by experiments which are at present in progress. 18. Chloride ofcalciuum.-Time of diffusion 11.43 days. The salt diffused was weighed as sulphate of lime Diffusion in 11.43 days at 63O.8; two cells. Grs. Ratio. From 1 per cent solution . . . 7.92 1.032 From 2 per cent solution . . . 15.35 2 From 4 per cent solution . . . 30.78 4.010 From 8 per cent solution . . . 61.56 8.021 We may now observe how far the diffusion of the chloride of calcium is analogous to that of nitrate of lime. At the inferior tem- peratures the results for the 1 per cent solution of these two salts were as follow Chloride of calcium at 50'9 . . 6.51 100 Nitrate of lime at 51O.5 . . . 6.54 100.46 While at the higher temperatures namely 63'48 for the chloride of calcium and 64'*1 for the nitrate of lime the results for the different proportions of salt are Chloride of calcium 1 per cent .. 7.92 100 Nitrate of lime 1 per cent . . . 7.66 96.72 Chloride of calcium 2 per cent . . 15.35 100 Nitrate of lime 2 per cent . . . 15.01 97.79 Chloride of calcium 4 per cent . . 30.78 100 Nitrate of lime 4 per cent . . . 29.04 9435 Chloride of calcium 8 per cent . 61-56 100 Nitrate of lime 8 per cent . . . 55.10 89.5 1 The correspondence between the 1 and 2 per cent solutions of chloride and nitrate is sufficiently close but in the 4 and 8 per cent the salts diverge as happens also with hydrochloric and nitric acids themselves The nitrate in both falls off while the chloride sustains throughout the high diffusibility of the lower proportions.19. Chloride of manganese.-Time of diffusion 11.43 days. The salt diffused was estimated by means of nitrate of silver. The 1 per cent solution of density 1*0085,gave at SO0& in eight cells 6-67 6.26 6.79 and 6.81 grs.; mean 6-63for two cells. 20. Nitrate of magnesia.-Time of diffusion 11-43 days. The salt diffused was estimated as sulphate. The 1 per cent solution of density 1.0073 gave at 50°*8 in eight cells 6.29 6-39 6.52 and 6.76 grs. ;mean 6.49 for two cells. 21. Nitrate of copper.-Time of diffusion 11.43 days. The salt diffused was estimated from the oxide of copper obtained by ignition. PROFESSOR GRAHAM ON THE The 1 per cent solution of density 1.0075 in eight cells at 5O0.S gave 6.52 6-36 6.18 and 6.70 grs.; mean 6.44 for two cells. Comparing the preceding salts with chloride of calcium diffused at the same temperature 50'43 we have the following results Chloride of calcium . . . . 6.52 100 Chloride of manganese . . . 6.63 101.15 Nitrate of magnesia . . . . 6.49 99-69 Nitrate of copper . . . 6.44 98.92 This group of salts belonging to the same isomorphous family of bases the magriesian again corresponds closely in diffusibility. The following additional magnesian chlorides were diffused all 1 per cent solutions either in six or in eight cells. The salt diffused was estimated by means of nitrate of silver. The results referred to chloride of calcium at nearly the same temperature 50O.8 are as follow Chloride of calcium .. . 6.51 100 Chloride of zinc . . . . . 6.29 96.61 Chloride of magnesium . . . 6.17 94.77 Chloride of copper . . . . 6.06 93.08 These salts present a greater latitude in their diffusibility if belonging to the same class than is usual. 22. Protochloride of iron.-A solution of this salt of 1.023 per cent was diffused at 53O.5 a somewhat higher temperature than the corresponding chlorides. It gave 6.45 6.48 6.48 and 6.28 grs. in two cells; mean 6.44 or 6*30 for 1 per cent in two cells. This salt appears therefore to belong to the last group. 23. Sespuichloride of iron.-A full series of observations was made upon the diffusion of the different proportions of this salt from 1 to 8 per cent but in all of them decomposition was determined by the diffusion with turbidity also in the solution-phial except in the 8 per cent solution.The mean diffusion from the 1 per cent solution in 11-43 days at 63O.3 was 4-13grs. of sesquichloride of iron with 1.28 gr of free hydrochloric acid in two cells. This result indicates that one-half nearly of the sesquichloride of iron is decomposed in the diffusion. The mean diffusion from the 8 per cent solution at 63O.3 was 55.88grs. of sesquichloride of iron with 6.66 grs. of free hydro- chloric acid in two cells. It appears from this experiment that perchloride of iron approaches the chloride of calcium in diffusibility. That the proto- and persalts of the niagnesian metals should have a similar rate of diffusion is not unlikely from other analogies which they exhibit.24. Subhate of magnesia.-The time chosen for the diffusion of this salt namely 16.166 days is a multiple by 2 of the time of DIFFUSION OF LIQUIDS. sulphate of potash and by 4 of the time of hydrate of potash. The diffusate was evaporated to dryness and weighed. Diffusion in 16.16 days at 65O.4; two cells. Grs. Ratio. From 1 per cent solution . . . From 2 per cent solution . . From 4 per cent solution . . . From 8 per cent solution . . . From 8 per cent solution at 62O.8 . From I6 per cent solution at 62'08 From 24 per cent solution at 62'08 7.31 12.79 23-46 42-82 42.66 75.06 102*04 l*lM 2 3.671 6.701 1 1.759 2.340 25. Su&hate of zinc.-Time of diffusion 16.166 days.The dif- fused salt was evaporated to dryness and weighed. Diffusion in 16-16 days at 65O.4; two cells. Grs. Ratio. From 1 per cent solution . . . 6.67 1.091 From 2 per cent solution . . . 12-22 2 From 4 per cent solution . . 23.12 3.784 From 8 per cent solution . . . 42.26 6.916 From 8 per cent solution at 62O.8 . 39.62 1 From 16 per cent solution at 62'3 74.40 1.878 From 24 per cent solution at 62O.8 101.42 2.560 It will be remarked that the diffusion of these two isornorphous salts sulphate of magnesia and sulphate of zinc differs so much in the 1 per cent solution as 7.31 to 6.67 that is as 100 to 91-25;or 8.75 per cent. This I have no doubt however is an accidental error the disturbances from changes of temperature and other causes of dispersion being in direct proportion to the duration of the experi- ment and therefore much increased with these long times; while the 1 per cent solution also appears to be generally the proportion most exposed to such errors.The sulphate of zinc appears to be the truest throughout in its diffusion of these two salts. The approach to equality becomes close in the 4 per cent and larger proportions of salt particularly with the unusually high proportions of 16 and 24 per cent which were observed in these salts. The diffusion of both salts falls off remarkably in the higher proportions. The result of the comparison of these two magnesian sulphates is no doubt favour-able to the similarity of diffusion of isomorphous salts. 26. Sdphate of alumina.-The time of diffusion chosen was 16.166 days or the same as that for sulphate of magnesia.The usual number of eight cells of the 1 and 2 per cent solutions were diffused and four cells of the 4 and 8 per cent solutions. The whole diffusates of each proportion were then mixed together and the quan- PROFESSOR GRAKAM ON THE tities of alumina and sulpburic acid diffused for two cells deter- mined separately. Diffusion in 16.166 days at 65O.4; two cells. Grs. Ratio. From 1 per cent solution . . . 5-48 1.074 From 2 per cent solution . . . 10.21 2 From 4 per cent solution . . . 19.28 3.780 From 8 per cent solution . . 33-52 6%72 The diffusion of sulphate of alumina it will be observed is very sensibly less than that of sulphate of zinc at the same temperature.27. Nitrate ofsilver.-Time of diffusion seveu days. The quan- tity of salt diffused was ascertained by precipitation with hydro- chloric acid and weighing the chloride of silver formed. Diffusion for seven days at 63'04; two cells. Grs. Ratio. From 2 per cent solution . . . 13.61 2 From 4 per cent solution . . . 26-34 3.87 From 8 per cent solution . . 51-88 7.62 28. Nitrate of soda.-Time of diffusion seven days. The quan- tity of salt diffused was ascertained by evaporation to dryness. Diffusion in seven days at 63'04; two cells. Grs. Ratio. From solution of 2 per cent . . 12.35 2 From solution of 4 per cent 23.56 3.82 From solution of 8 per cent . . 47.74 7.72 The ratios of the last column of the preceding Table are sensibly the same as those already obtained for nitrate of silver.But the diffusibilityof nitrate of soda appears to be increased less rapidly by temperature than nitrate of silver. Hence the diffusibility of these two salts appears more similar at low than high temperatures. Diffusion from 2 per cent solutions in seven days at 53O. Nitrate of silver . . . . 11.24 100 Nitrate of soda . . . . 10.81 96.17 Diffusion from 2 per cent solutions in seven days at 63O.4. Nitrate of silver . . . . 13.61 100 Nitrate of soda . . . . 12.35 90-74 29. Chloride of sodium-Time of diffusion seven days. The salt diffused was treated with nitrate of silver and the chloride of silver weighed. DIPFUSION OF LIQUlDS.97 Diffusion in seven days at 63O.J; two cells. Grs. Ratio. From 1per cent solution . . . 6.32 1-023 From 2 per cent solution . . . 12.37 2 From 4 per cent solution . . . 2496 4.036 From 8 per cent solutiorr . . . 48.44 7.832 These numbers resemble closely those obtained in the diffusion of chloride of barium during the longer period of 8.57 days. The chloride of sodium and nitrate of soda will be seen to exhibit the usual approach to parallelism between the chloride and nitrate of the same metal by the following comparison I)iffusioii of both at 63O.4. Chloride of sodium 2 per cent . . 12.37 100 Nitrate of soda 2 per cent . . . . 12.35 99.83 Chloride of sodium 4 per cent . . 24.96 100 Nitrate of soda 4 per cent . . . . 23.58 94.48 /I Chloride of sodium 8 per cent .48.44 100 Nitrate of soda 8 per cent . . . . 47.74 98-55 As usual the chloride is slightly more rapid in its diffusion tliaii the nitrate. 30. Chloride of potassium.-Time of diffusion 5.71 days. The salt diffused was treated with nitrate of silver and the chloride of silver weighed. Diffusion in 5.71 days at 62'; two cells. Grs. Ratio. From 1 per cent solution . . . 6.69 1*005 From 2 per cent solution . . . 13.32 2 From 4 per cent solution . . . 25-94 3.895 From 8 per cent solution . . . 53.64 8.054 The ratios are in remarkably close accordance with the proportions of salt diffused. The times 5.7'1 and seven days chosen for the chlorides of potas-sium and sodium it will be observed are as the square rootsof 2 and 3.A certain deviation from this ratio of the times of equal diffusion appears on comparing the experimental results obtained at present for these salts. Diffusion of chloride of potassium in 5.71 days at 62O and of chloride of sodium in 7 days at 63O.4. Chloride of potassium 1 per cent . . 6.69 100 Chloride of sodium 1 per cent . . . 6.33 94.47 Chloride of potassium 2 per cent . . 13.32 100 VOL. 1V.-NO. XIII. fi YltOPESSOR GRAHAM ON THE Chloride of sodium 2 per cent . . . 12.37 92.86 Chloride of potassium 4 per cent . . 25.94 100 Chloride of sodium 4 per cent . . . 24.96 96.23 Chloride of potassium 8 per cent . . 53.64 100 Chloride of sodium 8 per cent . . 48.44 90.30 The difference would be about 1 per cent greater if the diffusion of both salts were reduced to the same temperature.The chloride of potassium deviates of course from the nitrate of soda in a similar manner. But chloride of potassium corresponds more closely with nitrate of silver than with chloride of sodium and nitrate of soda at the temperature of the experiments. Diffusion of chloride of potassium for 5.71 days at 62O and of nitrate of silver for 7 days at 63O.4. Chloride of potassium 2 per cent . . 13.32 100 Nitrate of silver 2 per cent . . . . 13.61 102-18 Chloride of potassiixm 4 per cent . . 25.94 100 Nitrate of silver 4 per cent . . . . 26.34 10154 Chloride of potassiuni 8 per cent . . 53.64 100 Nitrate of silver 8 per cent . . . . 51-88 96.71 The coincidence in rate would appear even closer in the 2 and 4 per cent solutions if the diffusion of the nitrate of silver was dimi- nished about 1 per cent on account of its higher temperature.It might thus be supposed that the nitrate of silver followed the sodium rate more accurately than the nitrate of soda and chloride of sodium themselves do. A series of observations were made upon the diffusion of the 1per cent solution of chloride of potassium at a nearly constant tem- perature of 56* but for different times varying from five days to eight days and eighteen hours to discover the progression which proved to be pretty similar to that of the 2 per cent solution of hydrochloric acid. Six cells were diffused for each period of which the mean result is given the times advance by ten hours.Diffusion of 1 per cent solution; two cells. Time. Temperature. Diffusion in two cells. Differences. 5 days 55O.71 5.89 5 days 10 hours 55 90 6.25 0-36 5 days 20 hours 55 .79 6-55 0.30 6 days 6 hours 55 *79 6.71 0-16 6 days 16 hours 55 -90 6.95 0.24 7 days 2 hours 55 -9 7.48 0.53 7 dajs 12 hours 55 9 7.58 0.10 7 days 22 hours 56 03 8.08 0.50 8 days 8 hours 56 *28 8.34 0.26 8 days 18 hours 56 -15 8.60 0.26 DIFFUSION OF LIQUIDS. When the quantities of chloride of potassium are placed beside the same quantities of hydrochloric acid in the former table it is found that the times of diffusion of the salt and acid exhibit an approxi- mately constant ratio. The squares of these times of equal diffusion are as 1 to 2.04 for the shortest period of the chloride of potassium, and as 1 to 2.10 for the longest period but one.The variation in the differences towards the middle of the table is too great to be explained except I fear by some error of observation although no ordinary precaution was neglected in the execution of this laborious series of experiments. 31. Iodides and bromides of potassium and sodium. Iodide ofpotassi?cm.-Time of diffusion 5-716 days. The dlffu- sate was estimated by means of nitrate of silver. (1). Iodide of potassium 1.977 per cent; density 1*0146. Dif-fused at 53O.5 in eight cells 11*4~5,11~506,10~94!! and 11.062grs. ; mean 11.24 for two cells and 11-36for 2 per cent. Comparing this salt with the isornorphous chloride of potassium we have Diffusion of 2 per cent solutions in 5.716 days Chloride of potassium at 55O .. 11.48 100 Iodide of potassium at 53'5 . . 11.36 99.65 The diffusion of the iodide would slightly exceed that of the chlo- ride instead of falling below it as in the table if the temperatures were made equal. (2). Again iodide of potassium 1971 per cent ; observed density 1*01486. Diffused at 59O.8 in eight cells and the mean diffusate of the whole cells determined it gave 12.33 grs. of iodide of potassium for two cells; or 12.51 grs. for a 2 per cent solution. Bromide of potassium-Time of diffusion and mode of estimating diffusate as above. The solution contained 1.975 per cent of salt and had a density of 1.014850. Diffused at 59O.8 in eight cells it gave a mean diffusate of 12.30grs.for two cells ; or 12.46 grs for 2 per cent. For comparison a solution of chloride of potassium containing exactly 2 per cent of salt and having the density 1.0133,was diffusedl in the same circumstances of time and temperature as the two preceding salts. The mean diffusate of eight cells was 12.24grs. for two cells. Hence the following result of the diffusion of three isomorphous salts PROFESSOR GltAHAM ON THE Difl'usion of 2 per cent solutions in 5.7'16 days at 59O.8. Grs. Ratio. Chloride of potassiiim . . 12.24 100 Bromide of potassium . . . 12-46 101-80 Iodide of potassium . . . . 12.51 102.21 Mean . . . . 12.40 Iodide of sodium-Time of diffusion seven days temperature 59O.8.A solution of 2.011 per cent and density 1.01618 diffused in eight cells gave a mean diffusate of 12-34grs for two cells; that is, 12-18grs. for 2 per cent solution. Bromide oj' sodium.-Time of diffusion and tcniperature as above. A solution of 2.146 per cent of density 1.01726 diffused in eight cells gave a mean diffusate of 12-80grs. ; that is 11.93 grs. for 2 per cent. A comparative experiment was made with a solution of chloride of sodium containing 1.917 per cent of salt and of density 1,01376 in eight cells at 60° The diffusates for four pairs of cells were 11.65 11.75 11.63 and 11-47grs. ; mean 11-63grs. which gives by pro- portion 12-14grs. for a 2 per cent solution. As the present salt differs only OO.2 Fahr. in diffusion-temperature from the ti170 pre-ceding salts which is inadequate to produce an assignable difference of diffusion the three salts may be supposed to be diffused at the same temperature without sensible error.Diffusion of 2 per cent solutions for seven days. Grs. Ratio. Chloride of eodiuni at GOO . . 12*14 100 Bromide of sodium at 59O.8 . 11.93 98-27 Iodide of scdium at 5','*8 . . 12.78 100.33 Mean . . . . 12.08 In both these isomorphous groups of salts of potassium and sodium there is certainly a near approach to equality of diffusion. The times for the salts of the two bases being in the empirical proportion of the square roots of 2 and 3 the mean diffusates also approach pretty closely; namely 12.40grs. for the salts of potas-sium and 12.08grs.for the salts of sodium which are as 100 to 97-42 Here the members of each group are certainly very similar to each other in density and probably other physical properties which was not the case with the equidiffusive group containing the hydrogen acids of the same salt-radicals. 32. Cliloride of amr~~onium.-Time of diffusion 5.716 days. The salt diffused was estimated by means of nitrate of silver. Solution 0.988 per cent; density 1.0036. Diffused at 53O in DIFFUSION OF LIQUIDS. eight cellc 6.09 6-07 5.67 5.87; mean 5.92grs. and 5-99 for 1 per cent in two cells. This is somewhat more than 5.68 one-half of the diffusate of the 2 per cent solution of iodide of potassium at nearly the same temperature. The diffusion however of the small proportions of salts of ammonium such as the 1 per cent solution is apt to be given in excess from their low density.33. Dichloride of copper.-Time of diffiision seven days or that of chloride of sodium. The salt diffused was obtained by evaporation to dryness in an air-bath after treating the liquid with an excess of chlorine in the form of chloride from which the dichloride was calculated. It was an object of interest to discover whether the dichloride of copper (Chiz Cl) which should be isornorphous with the chloride of sodium may separate from the protochloride of copper and other magnesian salts and assume the high diffusibility of the salts of alkaline metals. But the salt in question is entirely insoluble in water. A solution however was obtained by dissolving an equivalent qiian- tity of the red suboxide of copper recently precipitated in hyclro-chloric acid of density 1.033 so as to give one grain of dichloride in every hundred water-grain measures of the solution.This acid solution did not precipitate by dilution with water. The salt was diffused into pure water at a mean temperature of 53O.2. 1. Dichloride of copper diffused 6.66 6-57 7.01 and 6.48 grs. ; mean 6.68 grs. in two cells. Chloride of sodium at 53O.4 nearly the same temperature gave 5.90grs. in thc same time. Reducing the result to the temperature of 51' by an approximative correction we should have 6.48 grs. of dichloride of copper for that tempera- ture at which chloride of calcium gave 6-51grs. in 11.43 days and protochloride of copper (Crx Cl) 6.06 grs.at nearly the same tempe- rature also in 11.43 days. So far as we can judge from an experiment at a single temperature it would appear that the diffusion of dichloiide of copper is more rapid than that of the chloride (CuCl) in a proportion which sup- poses the former compound to possess half the "sulution-density" of the latter the times of equal diffusion 7 and 11.43 days being when squared as 1 to 2. With the view of discovering whether the large proportion of hydrochloric acid amounting to 7 per cent present in the preceding solution of dichloride of copper modified the diffusion of the salt a portion of the same acid solution was treated with chlorine-gas to convert the copper-salt into chloride and diffused into water after the excess of chlorine was removed by agitation of the solution with air.The proportion of salt present was thus increased in weight from I ,to 1.36 per cent. The time of difl'usion was 11.43 days and the temperature 53'. 2. Chloride of copper diffused from a 1-36 per cent solution of the 102 PROFESSOR GRAHAM ON THE salt in hydrochioric acid 5-83 5.66 and 5.30 grs in two cells; mean 5.60 grs. The corresponding diffusion from a 1 per cent solution may be supposed to be less than 5*6grs. in the proportion of 1.36 to 1 without any great error. The results thus become chloride of copper diffused 3.98 3-85 and 3-58grs. ; mean 3.80 grs. in two cells. It hence appears that the diffusion of chloride of copper is much diminished by the presence of a great excess of hydrochloric acid in the same solution.Different causes suggest themselves for this result such as the possibility of a combination existing of chloride of copper with chloride of hydrogen in the acid solution; or the influence which must be admitted of the more soluble substance in a mixture of two similar substances in repressing the diffusion of the less soluble. The present result however is entirely opposed to the idea that the high diffusibility of the dichloride of copper observed before is due to the hydrochloride acid present. 3. The diffusion of chloride of sodium also appears to be repressed by contact with a large excess of hydrochloric acid. One per cent of chloride of sodium raised the density of dilute hydrochloric acid from 1.035 to 1.0408.Diffused into pure water for seven days at 52"*9 in eight cells the diffusates of chloride of sodium were 3.80 3.87 4-00and 3.86 grs. ; mean 3.88 for two cells. The diffusion of chlo- ride of sodium is thus reduced in a corresponding measure with that of chloride of copper by association with seven times its weight of hydrochloric acid. These results are interesting in a very different point of view I have always watched for the appearance of some absorbent or imbibing power on the part of the acids more analogous to an endosmotic attraction for water as usually conceived. If such an attraction existed it would complicate the phenomena of diffusion for the volume of water absorbed by the acid would displace and project a portion of the latter into the reservoir the phial not being extensible.The high diffusibility of hydrochloric and nitric acids would be thus explained. Rut by such a mechanical displacement the chloride of sodium would be thrown out in the preceding experiment as well as the hydrochloric acid which is not the case. 4.Even in hydrochloric acid of density 1.184 (25 per cent) the diffusion of 1 per cent of chloride of sodium for seven days at 56O.6 was found to amount to 4.7 grs. only in two cells and is less than from a solution in pure water. 5 In comparing the influence of nitric acid with that of hydro- chloric acid upon the diffusion of chloride of sodium it was found that in a 7 per cent solution of nitric acid the chloride of sodium (1 per cent) was entirely decomposed in the diffusive process at 5fiO.6 and gave hydrochloric acid in the full diffusive equivalent of that acid together with nitrate of soda.DIFFUSION OF LIQUIDS. 34. Bicarbonate of potash.-Time of diffusion 8.083 days or double that of hydrate of potash. The water of the jars was partially charged with carbonic acid gas to prevent the decomposition of this and the other bicarbonates in the act of diffusion. The whole diffusates of each proportion were mixed together and the quantity of bicarbonate of potash diffused for two cells converted into the chloride of potassium evaporated to dryness and weighed. Diffusion in 8.08 days at 68'02; two cells. Grs. Ratio From 1 per cent solution .. . 7-23 1.029 From 2 per cent solution . . . 14.05 2 From 4 per cent solution . . . 26.72 3.806 From 8 per cent solution . . . 52 01 7.408 35. Bicarbonate of ammonia.-Time of diffusion 8,083 days. The whole diffusates of each proportion were mixed together and the quantity of bicarbonate of ammonia diffused for two cells deter- mined by an alkalimetrical experiment which was always repeated twice. Diffusion in 8.08 days at 68'02 ; two cells. Grs Ratio. From 1 per cent solution . . . 6 91 1.013 From 2 per cent solution . . . 13.65 2 From 4 per cent solution . . . 27.00 3-959 From 8 per cent solution . . . 50.10 7.346 The amount and progression of the diffusion of this salt correspond well for all the proportions diffused with the preceding isomorphous bicarbonate of potash.36. Bicarbonate of soda.-Time of diffusion 9.875 days. The whole diffusates of each proportion were mixed together and the quantity of bicarbonate of soda diffused for two cells converted into chloride of sodium evaporated to diyness and weighed. Diffusion in 9-87 days at 68O.1 ; two cells. Grs. Ratio. From 1 per cent solution . . . 7*31 1-059 From 2 per cent solution . . . 13-81 2 From 4 per cent solution . . . 26.70 3.869 From 8 per cent solution . . . 52.38 7.590 A remarkable approach to equality in the diffusion of the bicarbo- nates of potash and soda in the times chosen is observed equally in all the proportions of salt from 1 to 8 per cent. The results for the three bicarbonates may be stated as follow PROFESSOR GRAHAM ON THE the diffusate of the 2 per cent solution of bicarbonate of potash being made equal to 200,as a standard of comparison.Diffusion of bicarbonates of potash and ammonia in 8.08 days at 68O.2,and of bicarbonate of soda in 94375 days at 68O.1 Bicarbonate Bicarbonate Bicarbonate of potash. of ammonia. of soda. From 1per cent solution . 102.9 98.3 104.0 From 2 per cent solution . 2OO*O 19413 1116.4 From 4 per cent solution . 380.6 384-3 380.0 From 3 per cent solution . 740.8 712.6 74t3.3 Or making the diffusate from each proportion of the bicarbonate of potash equal to 100 Bicarbonate Bicarbonate Bicarbonate of potash. of ammonia. of soda. From 1 per cent solution From 2 per cent solution From 4 per cent solution From 8 per cent solution .. . . 100 100 100 100 95.53 97.15 100.97 96.19 101.07 98.20 99 84 101.03 The bicarbonate of ammonia is slightly lower in general than the bicarbonate of potash possibly from a small loss of the former salt by evaporation in the different operations. The times chosen for these two bicarbonates is to that of the bicarbonate of soda as the square root of 2 to the square root of 3 and the remarkable agreement observed in the diffusion of these salts gives support therefore to that relation. In alluding to this relation however it is proper to add that the carbonates of potash and soda deviate from it in a sensible degree and the hydrates of potash and soda very conside- rably. If the relation therefore has a real foundation it must be masked in the salts last named by differences existing between them in certain properties the discovery and investigation of which is of the last importance for the theory of liquid diffusion.37. Hydrochlorate of morphine.-Time of diffusion 11.43 days. The crystallised salt was assumed to be of the cornposition C,,H,,N06. HCl+ 6H0 with the equivalent 3745. The quantity diffused was determined from the chlorine which was precipitated as chloride of silver in an acid solution. Hydrochlorate of morphine 1.88 per cent of the salt supposed anhydrous diffused at 64O.1 in six cells 11.03 10.72 11.01 ; mean 10.92grs. of the anhydrous salt for two cells. Calculated for 2 per cent 11.60 gre. at 64O.1 for two cells.38. Hydroeldorate of strychnine.-Time of diffusion 11*43 days. The crystallised salt was assumed to be of the composition C,,H,,N,O . H C1+ 3H0 with the equivalent 397.5. Hydrochlo- DIFFUSION OF LIQUIDS. rate of strychnine 2per cent density 1.0065 diffused at 64O.1 in six cclls 11-54 11.62 11.31 ; mean 11.49 grs. for two cells. The quantgies refer to anhydrous salt and were estimated from the chlorine as with hvdrochlorate of momhine. .I I These two analogous salts appear to approach very closely in diffusibility. Diffusion from 2 per cent solutions at 64O.l ; two cells. Hydrochlorate of niorphine . . 11.60 100 Hydrochlorate of strychnine . . 11.49 99.05 For a similar period of 11.43 days but at a lower temperature 53O.4 the 1 per cent solution of hydrochlorate of morphine gave a mean result of 5.49 grs.from two cells and the hydrochlorate of strychnine 5.77 grs. from two cells. But the weights of chlo-ride of silver from which these numbers are deduced were too small to admit of much precision. The diffiision of these salts of organic bases in 11.43 days is exceeded by the diffusion of chloride of ammonium or potassium in 5-71 days or half the former time. The vegeto-alkalies appear thus to be divided from ammonia and potash. The new observations of the present paper are favourable to the existence of a relation amounting to close similarity or equality in diffusibility between certain classes of substances. The chlorides and nitrates of the same metal generally exhibit this correspondence as in the chloride of calciurn and nitrate of lime the chloride of sodium and nitrate of soda and also in hydrochloric and nitric acids.Isomorphous salts exhibit the same relation as has been observed in the chlorides bromides and iodides of potassium sodium and hydrogen in various salts of baryta strontia and lead in numerous magnesian salts in the salts of silver soda and probably those of suboxide of copper and in several additional salts of potash and ammonia. Corresponding salts of two of the vegeto-alkalies are also found to be equidiffusive. Before discussing the relations between the different groups of equidiffusive substances which are thus formed it will be necessary to examine their diffusion at widely different temperatures a siibject attended with considerable difficulty.DR. WI1,LIAMSON ON THE 106 Theory of Etheriflcation. By A. W. Williamson Ph.D.* When sulphuric acid is brought in contact with alcohol under certain circumstances a new arrangement is effected in the elements of the alcohol which divide into two groups forming ether and water. Now it is well known that the process by which this change is effected may be represented in two ways the difference of which consists in their respectively selecting for starting-point a different view of the constitution of alcohol. According to the one view an atom of alcohol weighs 23 and is made up of C2 HG0; so that to form ether two atoms of it are needed one of which takes C9 H4 from the other setting free the water with which these elements were combined ;whereas according to the other view alcohol weighs $6 and contains ether and water.These are not the only points of difference which are urged ; but they are the most real and tangible and their consideration is sufficient for our present purpose. If by any direct fact we could decide which of these two expressions is the correct one the ground would be clear for an examination of the process of etherification itself. The following experiments were made with the view of obtaining new alcohols by substituting carburetted hydrogen for hydrogen in a known alcohol. With this view an expedient was adopted which may render valuable services on similar occasions. It consisted in replacing the hydrogen first by potassium and acting upon the compound thus formed by the chloride or iodide of the carburetted ' hydrogen which was to be iutroduced in the place of that hydrogen.The process was first tried with common alcohol which after careful purification was saturated with potassium and as soon as the action had ceased mixed with a portion of iodide of ethyl equivalent to the potassium used. Iodide of potassium was readily formed on the application of a gentle heat and the desired substitution was effected; but contrary to expectation the compound thus formed bad none of the properties of an alcohol-it was nothing else than common ether C* HIO 0. Now this result at once appeared to be inconsistent with the higher formula of alcohol; for if that body contained twice as many atoms of oxygen as are in ether the product ought clearly to have contained twice as much oxygen as ether does.The alternative was evident; for having obtained ether by substituting C2 H5 for H in alcohol the relative composition of the two bodies is represented by expressing that ,fact in our formula. Thus alcohol is C2H5 o, H Phil. Mag. [3] XSXVII 350. THEORY 01” ETHERIFICATXON. and the potassium compound is C2 0; and by acting upon this by iodide of ethyl we have Of course the proportion between the two bodies is the only point here considered and the same reasoning would be applicable to any multiple of the formuh assumed. Some chemists may perhaps prefer doubling them in order to avoid the use of atoms of hydrogen potassium &c.; but the author has not felt himself justified in doing so because that would involve doubling the usual formula for water ; for as will be presently shown water is formed in etherifiea- tion by replacing the carburetted hydrogen of alcohol by hydrogen which of course obliges us to assume the same unity of oxygen in both.Alcohol is therefore water in which half the hydrogen is replaced by carburetted hydrogen and ether is water in which both atoms of hydrogen are replaced by carburetted hydrogen thus go C2 H5 o C2 H5 H C2 H5 This formation of ether might however be explained after a fashion by the other theory-by supposing the potassium cdmpound to contain ether and potash which separate during the action of the iodide of ethyl; SO that half the ether obtained would have been contained in that compound and the other half formed by double decomposition between potash and iodide of ethyl thus ’* K2 0 + C4 Hl0 I2= 2 IK -+ 2 (C4 HI0 0).But although the insuficiency of this explanation becomes evident on a little reflection a further and more tangible method of arriving at a conclusion was devised. It consisted in acting upon the potassium compound by iodide of methyl in which case if that compound were ether and potash the resulting mixture should consist of ether and oxide of methyl; whereas in the contrary case a body of the composition C3 Hs 0 should be formed. Now this substance was actually obtained and neither ether nor oxide of methyl.In this experiment the two theories cross one another and must lead to different results; for it is evident that in the first-mentioned decomposition by which ether was formed the only difficulty in explaining the process decisively consisted in our inability to prove that the carburetted. hydrogen introduced instead of the hydrogen did not have in the- product an atom of oxygen to itself but that on the contrary it was coupled with the carburetted hydrogen already contained in the alcohol-the two in combination with One DR. WILLIAMSON ON THE atom of oxygen. It is clear that if alcohol contains ether and water and the carburetted hydrogen in the first experiment formed a second atom of ether by taking the place of the hydrogen of this water the process being the same in the second experiment we should then have obtained two ethers; whereas if the formation of ether from alcohol be effected by synthesis a new carburetted hydrogen being added to the one already contained in the alcohol we ought to obtain the new intermediate ether which was really produced.The boiling-point of this remarkable body is a little above 10' C. ; it has a very peculiar smell distinctly different froin that of common ether; and like that body it is only slightly soluble in water. It is not acted upon by the alkali-metals at the common atmospheric temperature. By acting upon the potassium-alcohol in like manner by iodide of amyl a similar substitution was cffected of the elements of that carburetted hydrogen in the place of the hydrogen of alcohol and an ether obtained which boiled at 111' C.arid had the composition C7 HI6 0. There is some reason to believe that this body is the same which Balard obtained by decomposition of chloride of amyl by an alcoholic solution of hydrated potash and which that dis- tinguished chemist took for oxide of amyl. From the perfect analogy of properties between the known terms of the alcoholic series it was to be expected that similar substitu- tions might be effected in the others; and this expectation has been verified by experiment. Of course the formuk of the other alcohols must be reduced to half fbr the same rcasons as that of common alcohol. Methylic alcohol is therefore expressed by the formula H3 0 as common alcohol is C2 g50; and in the same manner H amylic alcohol is c5 0 and the same of the higher ones.In conformity to this fact we must be able to obtain the same interme- diate ethers by replacing hydrogen in these alcohols (methylic and amylic) by the carburetted hydrogen of iodide of ethyl as by the inverse process described above. This has been verified in the case of the three-carbon ether which may be obtained indifferently by replacing one-fourth of the hydrogen of methylic alcohol by C2H5 or by replacing one-sixth of the hydrogen of common,alcohol by CH3. C2 H5 Its rational formula is therefore C H3 O. By acting upon the compound z30 by iodide of amyl a third C H3 ethereal compound was obtained of which the formula is c5Hll 0.This is evidently the only one of' the three new ethers which con-taining an even number of carbon atoais might he conceived to have TH EORY OF ETH ERI FIC.ATION. been formed from one alcohol; but when treated with monobasic acids as the hydrochloric it cannot be expected to act in the same manner as its homogeneous isomeric the ether c3 C3 H7 0 of the three-C3 H7 o. carbon alcohol The next thing to be done is to explain theprocess of etherification by the action of sulphuric acid (SO4 H2) upon alcohol; and in order to accomplish that we must show the connexion between those substances and the reagents used in the above-described experiments. With this view we have merely to add to the above facts the acknowledged analogy of the simple and compound radicals in their compounds.It niiist first be shown how a substance analogous to the iodide of ethyl is formed and then how by double decomposition with alcohol it produces ether. This is very easy; for sulphovinic acid is strictly analogous to iodide of ethyl plus iodide of hydrogen which we should obtain by replacing SO* in its formula by an equivalent of iodine ; and in order to represent the formation of this sulphovinic acid which is well known to precede that of ether the simplest mode is at the same tirile the one most free from hy-pothesis; it consists in stating the fact that sulphuric acid and alcohol are transformed into suhhovinic acid and water. bv half the hydrogen of the former changing places with the carbu&ted hy-drogen of the latter ; thus Now from this point it is clear that the process is the same as in the decompositions above described ; for by this sulphovinic acid coming in contact with an atom of alcohol it reacts exactly in the same manner as the iodide did forming of course sulphuric acid and ether so4 so4 C2 H5 --c2 H5 * C2H5 0 c2 135 0 The sulphuric acid thus reproduced comes again in contact with alcohol forming sulphovinic acid which re-acts as before ; and so the process goes on continuously as found in practice.We thus see that the formation of ether from alcohol is neither a process of simple separation nor one of mere synthesis; but that it consists in the substitution of one molecule for another and is effected by double decomposition between two compounds.This 110 DH. WILLIAMSON ON THE view of the matter is therefore consistent with the contact theory inasmuch as it acknowledges the circumstance of contact as a necessary condition of the reaction of the inolecules upon one another. By reducing the formula of the alcohols to one atom of oxygen it also retains the equality of volumes which the contact theory insists upon between the vapours of these bodies and their ethers so that ether truly contains the elements of olefiant gas in addition to those of alcohol in one atom. But on the other hand it attaches equal importance to all the essential facts of the chemical theory and rests the explanation of the process as much upon them as upon those of the contact theory; for one-sixth of the hydrogen in alcohol truly exhibits different reactions from the remaining five and must there- fore be contained in that compound in a different manner from them; and the alternate formation and decomposition of sulphovinic acid is in this as well as in the chemical theory the key to explaining the process of etherification.Innovations in science frequently gain ground only by displacing the conceptions which preceded them and which served more or less directly as their foundation ; but if the view here presented be con- sidered a step in our understanding of the subject the author begs leave to disclaim for it the title of innovation; for the conclusion here deduced consists in showing the compatibility of views which have hitherto been considered contrary ; and the best possible justification of the eminent philosophers who have advocated either one of the two conteiiding theories is thus afforded by reconciling their argu- ments with those of their equally illustrious oppo,ients.Let us now direct our attention to the transfer of homologous molecules in alternately opposite directions which as we have endeavoiired to show is the cause of the continuous action of sulphuric acid in this remarkable process. It may naturally be asked why do hydrogen and carburetted hydrogen thus continu- ously change places? It cannot be from any such Circumstance as superior affinity of one molecule over another for one moment sees reversed with a new molecule ' the transfer effected during the preceding one.Now in reflecting upon this remarkable fact it strikes the mind at once that the facility of interchange must be greater the more close the analogy between the molecules exchanged ; that if hydrogcbn and amyl can replace one another in a compound hydrogen and ethyl which are more nearly allied in composition and properties must be able to replace one another more easily in the same compound; and that the facility of interchange of hydrogen and methyl which are still more siniilar will be still greater. But if this be true must not the exchange of one molecule for another of identical propertics be the most easily effected of all ? Surely it must if there be any difference at all ;and if so the law of analogy forbids our imagining the fact to be peculiar to hydrogen among THEORY OF ETHERIFICATION.substanees resembling it in other respects. We are thus forced to admit that in an aggregate of molecules of any compound there is an exchange constantly going on between the elements which are contained in it. For instance a drop of hydrochloric acid being supposed to be made up of a great number of molecules of the composition C1 H tbe proposition at which we have just arrived would lead us to believe that each atom of hydrogen does not remain quietly in juxtaposition with the atom of' chlorine with which it first united but on the contrary is constantly changing places with other atoms of hydrogen or what is the same thing changing chlorine.Of course this change is not directly sensible to us because one atom of hydrochloric acid is like anothcr; but suppose we mix with the hydrochloric acid some sulphate of copper (of which the component atoms are undergoing a similar change of place) the basylous elements hydrogen and copper do not limit their change of place to the circle of the atoms with which they were at first combined,- the hydrogen does not rnerely move from one atom of chlorine to another but in its turn also replaces an atom of copper forming chloride of copper and sulphurie acid. Thus it is that at any moment of time in which we examine the mixture the bases are divided between the acids ; and in certain cases where the difference of properties of the analogous molecules is very great it is found that the stronger acid and stronger base remain almost entirely together leaving the weaker ones combined.This is well known in the case of a mixture of sulphuric acid and borax and is a confirrnation of our fundamental assumption that the greater the difference of pro- perties the more difficult is the alternate interchange of one molecule for another. But suppose now that instead of sulphate of copper we mixed sulphate of silver with our hydrochloric acid in aqueous solution and that a similar division of the bases between the acids established itself in the first moment forrriing four compounds SO4H2 SO*A@ ClH C1 Ag ;it is clear that this last-mentioned compound being insoluble in water must on its forination separate out and remove from the circle of decompositions which solubility established.BUt of course the three compounds remaining in solution continue the exchange of their component parts and give rise successively to new portions of chloride of silver until as much of that compound is precipitated as the liquid contained equivalents of its component parts a very small quantity remaining in solution and in the circle of decompositions. Such is the general process of chemical decomposition. Of course a compound is removed as effectually from the circle of decompo-sitions by assuming the gaseous form under the circumstances of the experiment or even by being a liquid insoluble in the men-struum. This explanation coincides in its second part with that 112 DR.ANDERSON ON THE CONSTITUl’ION OF which was proposed many years ago by Berthollet; but not making use of the atomic hypothesis upon which the preceding explanation is based that eminent philosopher went no farther back than the division of the acids between the bases on the mixture of salts a fact here deduced from the motion of atoms. It is well known that the general fact upon which Berthollet founded his view is denied by some eminent chemists of the present day; but the instances which they adduce are perhaps only apparent exceptions to the lam and will on further examination be found to afford additional con- firmation of the truth of the great Savoysien’s conception as already shown in the case of boracic and sulphuric acids.In using the atomic theory chemists have added to it of late years an unsafe and perhaps unwarrantable hypothesis namely that the atoms are in a state of rest. This hypothesis the author of the present paper discards and reasons upon the broader basis of atomic motion. On the Constitution of Codeine and its Products of Decompodtion. By T. Anderson M.D.* The composition of codeine has been variously stated by different chemists. According to Regnault the formula of anhydrous codeine is C, H, NO, and that of the crystallised base C, K, NO +2 HO. Gerhardt however objects to this formula because the numbers of equivalents of carbon and oxygen are uneven and the SUM of the equivalents of hydrogen and nitrogen is likewise indivisible by two.From his own analysis Gerhardt deduces the formula c, H, NO, and this formula is fully confirmed by the recent researches of Dr. Anderson. The codeine with which the author’s experiments were made was prepared as usual from the mother-liquor from which morphia had been precipitated by ammonia. This liquid was evaporated to crys-tallisation and the crystals pressed to separate the hy drochlorate of ammonia which is more soluble than the hydrochlorate of codeine these operations being repeated till the greater part of the sal-ammo- niac was got rid of. The crystals of hydrochlorate of codeine were then dissolved in boiling water and the solution treated with caustic potash whereby the codeine was precipitated as an oil which after- wards concreted into a solid mass and was partly deposited in crystals as the solution cooled.Another crop of crystals may be obtained by evaporating the solution and the mother-liquor when concentrated to a small bulk becomes * Transactions of the Royal Society of Edinburgh. CODEINE AND ITS PRODUCTS OF DECOMPOSITION. 113 filled on cooling with long silky needles of morphia which had been retained in solution by the excess of potash. The crystals of codeine are purified by solution in hydrochloric acid boiling with animal charcoal and reprecipitation by potash ;and the resulting precipitate is finally dissolved in hydrous ether free from alcohol to separate any morphia that may adhere to it Anhydrous ether dissolves codeine much lees easily; the solution when evaporated yields smalf crystals of anhydrous codeine.Codeine crystallised from water or hydrous ether forms crystals belonging to the right prismatic system and containing 2 equivalents of water which are given off at 212'. Codeine is an extremely powerful base rapidly restoring the blue colour of reddened litmus and precipitating the oxides of lead copper iron cobalt nickel &c. from their solutions. It is precipitated by potash from its salts and is generally stated to be insoluble in that al- kali; but this is true only of very highly concentrated solutions as a considerable quantity of strong potash may be added to a saturated solution of codeine in water without producing precipitation and even when a very large amount of potash is added acertain quantity of the base is still retained in solution.Codeine is soluble in ammonia but not more so than in water; 100 parts of a moderately strong solu- tion of ammonia at 60' dissolve 1-40parts of codeine ;and according to Robiquet 100parts of water at 59' dissolve 1.26 parts. Codeine is precipitated from all its solutions by ammonia; it does not how- ever fall immediately but is slowly deposited in small transparent cry st als. SALTS OF CODEINE. HydrochZorate.-C, H, NO .HCI. Obtained by saturating hot hydrochloric acid with pure codeine. A concentrated solution becomes nearly solid on cooling; but a more dilute solution yields radiated groups of short needles which under the microscope are found to be four-sided prisms with dihedral summits.The crystals are soluble in 20 parts of water at GO' and in less than their weight of boiling water. The salt dried in the air retains 4 equivs. of water ; one which goes off at 212' and the other three at 250'; the salt at the same time losing acid and aquiring an alkaline reaction. The salt is also sometimes deposited from its solution in anhydrous crystals. Hydriodate of Codeine.-C, H, NO,. HI. Obtained by dissolving codeine in hot hydriodic acid and leaving the solution to cool where-upon it is deposited in long slender needles which fill the whole liquid if it has been sufficiently corrcentrated. Soluble in 60 parts of cold water ;more soluble in boiling water. The crystals contain 2 atoms of water. Xulphate of Codeine.-C,G H, NO,.HO . SO,. Crystallises in radiated groups of long needles or by spontaneous evaporation in flattened four-sided prisms. Dissolves in 30 parts of cold water ; very VOL. 1V.-NO. XIIT. 1 DR. ANDERSON ON THE CONSTITUTEON OF soluble in hot water. Neutral to test paper when pure; but very apt to retain a small quantity of acid which can only be got rid of by repeated crystallisation. The crystaflised salt contains 5 equivalents of water which are given off at 212'; the formula of the crystallised salt is C, H, NO ,HO .SO +5 Aq. Nitrate of Codeine.-C,B HZlNO .HO .NO, Formed by slowly adding nitric acid of specihc gravity 1.060 to powdered codeine an excess of acid being carefully avoided.. Easily soluble in boiling water from which it is deposited in small prismatic crystals on cool- ing.When heated OD platinum it melts and on cooling concretes into a brown resinous mass; at a higher temperature it is rapidly decomposed leaving a bulky coal difficult of incineration. Phosphate of Codeine.-C, M, NO,. HO .2 HO PO,. When tri- basic phosphoric acid is saturated with powdered codeine and the solution mixed with strong spirit this salt is obtained in small scales or short thick prisms which are readily soluble in water. They con- tain 3 equivalents of water of crystallisation which are given off at 212O. Oxalate of Codeine.-C, H, NO .HO .C 0,. Deposited on cooling its hot saturated solution in short prisms or sometimes in scales. Soluble in 30 times its weight of water at 60' and about half its weight at 212'.The crystals heated to 212' gave off 3 equiv-alents of water. At 250' the salt turns brown andat a higher tem- perature is entirely decomposed. Hydrosulphocyanate of Codeine.-C, HzlNO .HC NS,. De-posited in beautiful radiated needles on mixing the solutions of hydrochlorate of codeine and sulphocyanide of potassium. The crystals contain 1 equivalent of water which they give off at 212'. Chloride of Platinum and Codeine,-A moderately concentrated solution of hydrochlorate of codeine mixed with bichloride of platinum deposits a pale-yellow pulverulent precipitate ; a more dilute solution yields no immediate precipitate but after a time deposits minute tufts of silky needles The salt is soluble in water and on cooling is deposited partly in grains partly as a powder ; not however without partial decomposition.By ebullition with excess of chloride of pla- tinum it is completely decomposed. To obtain it pure it niust be precipitated in the cold and without excess of chloride of platinum. The formula of the crystallised salt is C H, NO,. HC1+ PtCl,+ 4HO. At 212' it gives off 3 equivalents of water and the remainder is expelled at 250' the salt at the same time turning brown and being partially decomposed. Codeine forms many other crystallisable salts none of which how- ever have been completely examined. The chromate forms fine yellow needles. With solution of corrosive sublimate codeine forms a white precipitate soluble in boiling water and alcohol and deposited in stellate groups of crystals on cooling.With chloride of palladium CODEINE AND ITS PRODUCTS OF DECOMPOSITION. 115 a yellow precipitate is obtained which is decomposed on boiling and yields metallic palladium The tartrate and hydrocyanate of codeine are uncrystallisable. PRODUCTS OF DECOMPOSITION OF CODEINE. Actionof Sukhuric Acid.-Am orp h ous Codein e.-When codeine is dissolved in moderately strong sulphuric acid the mixture digested for a while on the sand-bath and then treated with carbonate of soda a grey precipitate is obtained consisting of codeine in ail amorphous state. The precipitate must be collected on a filter washed with water dissolved in alcohol and precipitated from the solution by water. It then forms a grey powder with more or less of a green shade insoluble in water readily soluble in alcohol and precipitated by ether from the alcoholic solution.Fuses at 212' to a black resinous mass Readily soluble in acids forming salts which are amorphous and dry up by evaporation into brown resins. Analysis shows it to be identical in composition with codeine in its ordinary state. The action of sulphuric acid upon codeine is indeed analogous to that which it produces upon quinine but the resulting amorphous codeine is not so stable a substance as quinoidine. Moreover the action does not stop at tbe point at which amorphous codeine is pro-duced; for if it be continued a deep-green substance is formed con- taining sulphur and analogous to the sulphomorphide described by Arppe and the corresponding sulphonarcotide of Lauren t and Ge rh ard t.Action of NitricAcid.-Nitrococteine-C,G H, NO,NO, When strong nitric acid is poured upon codeine and heat applied violent action takes place nitrous fumes are abundantly evolved and the solution acquires a red colour. If the fluid be evaporated over the water-bath a yellow resinous acid is left soluble with a red colour in ammonia and potash; but when dilute acid is used a nitro-base is obtained having the composition above given. The best mode of preparing it is to add finely powdered codeine to nitric acid of specific gravity 1*060,kept at a moderate heat in a flask small portions of'the liquid being taken out every now and then and tested with ammonia till the precipitate formed on neutralising the acid no longer increases in quantity.The liquid is then to be saturated with ammonia and stirred rapidly whereupon it will become filled with a bulky precipi- tate of nitrocodeine. The action is very rapid and great care must be taken not to let it go too far otherwise the resinous substance above-mentioned will be produced its formation being indicated by the escape of red fumes; it is best to stop the action before the whole of the codeine is decomposed; but even then it is impossible to avoid the formation of a small quantity of the resinous substance its I2 DR. ANDERSON ON THE CONSTITUTION OF' presence being indicated by the dark colour which the liquid assumeJs on the addition of ammonia The precipitate formed by ammonia is in the form of minute silvery plates with a very slight shade of yellow.It is purified by solution in hydrochloric acid boiling with animal charcoal and reprecipitating with ammonia and subsequently crys- tallised from a solution in alcohol or in a mixture of alcohol and ether. Nitrocodeine crystallised from alcohol is deposited in the form of slender silky needles which have a pale fawn colour and on drying mat together into a silky mass. From alcohol and ether it is obtained by spontaneous evaporation in small yellowish crystals which under the microscope are seen to consist of four-sided prisms terminated by dihedral summits. Nitrocodeine is sparingly soluble in boiling water from which it is deposited in minute crystals on cooling.It dissolves abundantly in boiling alcohol but sparingly in ether. It is soluble in acids forming salts which are neutral to test paper and yield the base in the forin of a crystalline powder on the addition of potash or ammonia. When heated carefully it melts into a yellow liquid which concretes on cooling into a highly crystalline mass. At a higher temperature it decomposes suddenly without flame leaving a bulky charcoal. Cryatallised nitrocodeine is anhydrous. Hpdrochlorate of Nitrocodeine is obtained by dissolving nitroco- deine in hydrochloric acid and evaporating the solution whereupon the salt is left in the form of a resinous mass which cannot be made to crystallise. Subhate of Nitrocodeine C, H, (NO,) NO,. HO .SO, forms radiated groups of short-pointed needles neutral to test-paper and very soluble in boiling water. Oxalate of Nitrocodeine crystalliaes in short prisms of a fine yellow colour readily soluble in water. Platinochloride of Nitrocodeine C, H, (NO,) NO,. HC1+ PtCl +4 HO is precipitated from the solution of the hydrochlorate in the form of a yellow powder insoluble in water and alcohol. By treating an alcoholic solution of nitrocodeine with hydrosulphate of ammonia a new base is obtained which from its analogy with other compounds similarly prepared is probably composed of c36 H, N O, and may be called Axocodeirae ;it has not yet how-ever been completely examined on account of the great difficulty of preparing and purifying it. Action of Bromine on Code~ne.-Bromocodeine-C, H, &NO,.When bromine-water is added in small successive portions to finely powdered codeine the base is rapidly dissolved the solution losing its colour of bromine and acquiring a peculiar and characteristic red shade. After a certain quantity of bromine has been added small crystals make their appearance which are hydrobromate of codeine;but these CODEINE AND ITS PRODUCTS OF DECOMPOSITION. 117 ye only observed if the bromine-water has been thoroughly saturated and are deposited in a small quantity only the remainder being retainedin solution. When the whole of the codeine has been dis- solved ammonia is added and bromocodeine is immediately thrown down as a silvery-white powder; in this state it contains a small quantity of unchanged codeine.It is collected on a filter washed several times with cold water and redissolved in hydrochloric acid from which it is precipitated by ammonia and finally crystallised from boiling spirit. Bromocodeine is scarcely soluble in cold water ;but by boiling a somewhat larger quantity is taken up and deposited again on cooling in minute prisms terminated by dihedral summits. It is readily soluble in alcohol particularly on boiling and is best cryetallised from spirit diluted with its own bulk of water. The crystals are always very small but brilliantly white. It is soluble in ether. When heated it melts into a colourless liquid which is destroyed at a temperature somewhat above its melting-point. It dissolves in cold sdphuric acid and the solution becomes dark- coloured when heated.It is attacked by nitric acid but much less rapidly than codeine itself. Bromocodeine forms two hydrates the first containing one and the second two equivalents of water. Hydrochlorate of bromocodeine forms radiated needles closely re- sembling those of hydrochlorate of codeine The hydro-bromate is sparingly soluble in cold water readily soluble in boiling water and is deposited from the solution in small prismatic crystals. It contains two equivalents of water which are not expelled at 212'. Tribromocodeine.-C, Hg8Br NO,. By continuing the addition of bromine-water beyond the point at which bromocodeine is formed a further action takes places and a bright-yellow precipitate makes its appearance which at first re-dissolves in the liquid but after a time becomes permanent and goes on gradually increasing till a very large quantity of bromine has been added when at length a point is reached at which no further precipitate is produced.If the solution be left till next day however bromine again causes a precipitate; and if it be added as long as anything falls and the solution be again left standing another precipitate is produced identical in all respects with that before obtained ;and this may be repeated day after day for a very considerable time. The yellow precipitate thus obtained is the hydrobromate of tribromocodeine. It is collected on a filter and washed with water in which it is very sparingly soluble. When this salt is dissolved in dilute hydrochloric acid and ammonia added the tribromocodeine is immediately precipitated as a flocculent powder which must be washed with water andpurified by solution in alcohol and precipitation by water.Tribrornocodeine as thus obtained is a bulky white precipitate perfectly amorphous and when dry more or less grey in its colour. It is insoluble in water and ether but readily soluble in alcohol. DR. ANDERSON ON THE CONSTITUTION OF Hydrochloric acid dissolves it sparingly in the cold but more readily on boiling; in this process however it appears to undergo a partial decomposition as a small quantity is always left insoluble. Heated on platinum-foil it becomes brown and is entirely decomposed at its melting-point leaving a coal difficult of incineration.In such cases as have been hitherto examined the substitution of three equivalents of bromine in a base has entireIy destroyed its basic properties; but tribromocodeine is a base though a very feeble one. Its salts are all sparingly soluble in water and amorphous. The hydro-chlorate is obtained by dissolving the base in hot dilute hydrochloric acid and is deposited on cooling as an amorphous powder. The hydrobromate is the substance deposited during the preparation of the base. It is a bright-yellow powder perfectly amorphous and very sparingly soluble in cold water; on boiling however a larger quan- tity is taken up and is again deposited on cooling. Its composition appears to be 2 (C36H, Br NO,) +H Br.The platinochloride is a brownish-yellow powder soluble in water and alcohol. The action of bromine on codeine does not terminate with the production of the base just described but the author has not pursued the investigation any further. There must also exist a dibromoco-deine C, H19Br NO, but it has not yet been actually obtained. Action of Chlorine on ~ode~ne.-Ch~orocodeine-~, H, C1NO,. The action of chlorine on codeine is more complex than that of bromine. When chlorine gas is passed into an aqueous solution of codeine or chlorine-water added to it theliquid turns brown becoming continually deeper in colour and on the addition of ammonia yields an amor- phous resinous base. As there were no means of determining when the action was complete the product was not further examined.A definite compound analogous to bromocodeine was however obtained by dissolving codeine in excess of dilute hydrochloric acid at about 150' or 160' Fahr. adding finely pounded chlorate of potash-agitating the liquid-continually testing with ammonia and adopting precautions similar to those required in the preparation of nitro- codeine and finally precipitating by ammonia. The reaction is as f0hWS 3 (C36H21NOs.HCl)+3 HCl+KO. ClO,=KC1+6 HO +3 (C36H, C1 NO,. HC1.) The chlorocodeine is precipitated in the form of a silvery crystalline powder closely resembling brornocodeine. It has generally a yellow- ish colour and retains a small portion of codeine from which it is purified by dissolving in hydrochloric acid boiling with animal charcoal and reprecipitating with ammonia.It is finally obtained in crystals from its solution in boiling spirit. Chlorocodeine is sparingly soluble in boiling water and the solution CODEINE AND ITS PRODUCTS OF DECOMPOSITION. 119 on cooling deposits minute crystals exactly similar to and isomor- phous with those of bromocodeine. It is readily soluble in strong alcohol especially with the aid of heat and sparingly soluble in ether. It dissolves in sdphuric acid in the cold without change but the solution is charred by heating. Nitric acid dissolves it and the solu- tion is decomposed by boiling but not by any means so readily as codeine. Red fumes are evolved together with a peculiar and exces- sively pungent vapour.The salts of chlorocodeine are exactly similar to those of bromo- codeine. The hydrochlorate crystallises in groups of needles readily soluble in water. The su&hnte c3 H, c1NO,. H[o SO,+ 4Aq is deposited from its hot solution in radiated groups of short prisms which dissolve abundantly in boiling water and alcohol. Theplatinochloride is obtained in the usual way in the form of a pale-yellow precipitate scarcely soluble in water. Action of Cyanogenon ~odeine.-~icyan~codeine-~~, Nzl No6. 2 C N.-When cyanogen is passed into a solution of codeine in the smallest possible quantity of alcohol the gas is rapidly absorbed the liquid acquiring first a yellow and by continued action a brown colour. If the solution be then left to itself for some time the smell of cyanogen disappears and is replaced by that of hydrocyanic acid and crystals are gradually deposited.If the cyanogen be passed through the solu- tion in a slow continuous current the deposit of crystals is very abundant. These are collected on a filter and washed with a small quantity of alcohol; and the filtrate on being again exposed to the action of cyanogen yields an additional qnantity of crystals but not so pure as the former. The product is purified by solution with the aid of heat in a mixture of alcohol and ether from which it is depo- sited in crystals which are colourlese or slightly yellow. Obtained in this way however they are apt to retain a small quantity of codeine and it is therefore advantageous to pass cyanogen into the mixture to be used for their solution by which means the last traces of codeine are converted into the new compound.Dicyanocodeine is soluble in boiling absolute alcohol or a mixture of alcohol and ether and is deposited on cooling in anhydrous thin six-sided plates having a brilliant lustre. It is difficultly soluble in water but is dissolved on the addition ot alcohol. Nothing however is deposited from the solution on standing and by evaporation it is decomposed and crystals of codeine are left behind. With hydro- chloric acid it is converted into a crystalline salt but decomposition take place immediately; for on the addition of potash to the liquid ammonia escapes and if it be left for twenty-four hours hydrocyanic acid is evolved. With sulphuric and oxalic acid dicyanocodeine likewise forms sparingly soluble compounds which decompose rapidly with evolution of ammonia and hydrocyanic acid.The instability of these compounds prevented their further examination. DR. ANDERSON ON THE CONSTITUTION OF Dicyanocodeine belongs to the same class of compounds as cyaniw line but differs from that substance in containing two equivalents of cyanogen. ACTION OF ALKALXS ON CODEINE. Codeine when treated at moderate temperatures with potash yields more than one volatile base according to the circumstances under which the experiment is made. Similar results are obtained by the use of hydrate of potash or of potash-lime or soda-lime prepared in the usual way. The method employed in the experiment was to mix codeine with four or five times its weight of potash-lime or soda-lime and introduce the mixture into a retort with a tubulated receiver having a doubly bent tube attached to its tubulature the end of which passed into a small flask containing hydrochloric acid in order to retain any of the very volatile base which might not be condensed in the receiver.The retort was introduced into an oil-bath and kept at a uniform temperature of 250' Fahr. As soon as this temperature is reached a slight peculiar odoiir is observed which soon becomes more powerful and a small quantity of water retaining the bases in solu- tion collects in the receiver. The decomposition at 250" however is excessively slow and even after many days bases are evolved ap- parently in undiminished quantity ; but the mixture was maintained steadily at this point in hopes of obtaining the product free from ammonia which the preliminary trials had shown to be produced at higher temperatures; but even with this low heat it was evolved always in appreciable and in some experiments even in considerable quantity.The temperature was therefore gradually raised to about 350° when a larger quantity of base was obtained; and after the heat had been sustained for some time small crystals made their appear- ance which deposited themselves in a line round the retort just above the level of the oil in the bath but soon rose into and collected in the neck of the retort. These crystals resemble beazoic acid in their external appearance and are at first perfectly colourless but soon acquire a brownish shade by exposure to light and air.They are a base and rapidly restore the colour of reddened litmus. They are sparingly soluble in water but readily in acids and give a precipitate with bichloride of platinum. The quantity of this substance obtained was excessively minute ; and though considerable quantities of codeine were operated upon all that was obtained served only to make the few qualitative experiments now detailed. The watery fluid which collected in the receiver possessed a pungent and peculiar smell ;it restored the colour of reddened litmus with great rapidity and gave 'abundant fumes with hydrochloric acid. On the addition of solid potash R highly volatile and pungent oily base CODEINE AND ITS PRODUCTS OF DECOMPOSITION.121 collected as a layer on the surface of the fluid and at the same time a gaseous base escaped along with ammonia. From the small quantity of these substances obtained it was impossible to obtain any of them in a pure state Their constitution was therefore deter-mined by the analysis of their platinum-salts which can be separated from one another thouFh not without difficulty. In order to prepare these salts the basic fluid was saturated with hydrochloric acid and evaporated to dryness in the water-bath when it left behind a beauti- fully crystalline mass highly soluble in water and deliquescent in moist air. This was dissolved in absolute alcohol to separate ammonia and the filtered solution mixed with an alcoholic solution of bichloride of platinum when the platinum-salts were immediately thrown down as a pale-yellow powder very sparingly soluble in absolute alcohol but readily dissolved on the addition of water.The separation of the two bases is best effected by heating the washed pre- cipitate with boiling absolute alcohol and adding water in small quantities until the whole is dissolved. The crystals which deposit on cooling consist of one of the salts in a state of purity if the process has been properly managed or at all events only require a repetition of the process to make them absolutely pure. The salt thus obtained is scarcely soluble in absolute alcohol or ether but is readily soluble in water and dilute spirit and is thrown down from the latter solution by ether in the form of fine yellow scales.Its analysis gave results agreeing with the formula C H N .H C1. Pt C1,. The base is conse-quently the methylamine of Wurtz with whose description of that substance and its platinum-salt it perfectly agrees. The preparation of the platinum-salt of theother base was attended with much greater difficulty; and it could not be obtained quite free from methylamine. In order to obtain it the fluid which had depo- sited the methylamine-salt must be evaporated to a small bulk the salt which separated filtered off and ether added to the mother-liquor. Immediately a precipitate is obtained generally in the form of minute yellow needles but sometimes in scales. It is sparingly soluble in alcohol and ether and highly soluble in water from which it crystal-lises in long needles and with such facility that a few drops evaporated on a watch-glass leave the salt they contain in the form of five or six needles crossing the whole space occupied by the solution.The quantity of this salt was too small to admit of carrying its purification by recrystallisation as far as was to be desired and consequently a small quantity of methylamine remained in those subjected to analysis. The results of the analysis approach most closely to the formula C,H,N. HC1. Pt Cl,; consequently that of the base itself C,H,N. The base then obviously belongs to the same series as methylamine and forms the term of the series corresponding to metacetonic acid and in accordance with the system of nomenclature adopted by Wurtz it VOL.IV.-NO. XIII. K 122 DR ANDERSON ON THE CONSTITUTION OF CODEINE. receives the name of metacetamine. No examination was made of the salts of this base as it was not obtained in sufficient quantity but the author takes the opportunity of stating that before obtaining it from codeine he bad ascertained its existence among the products of destruc-tive distillation of animal substances.* The residue in the retort after these bases have been evolved is dark-cinnamon-brown and slightly coherent ; it dissolves in water with a dark-brown almost black colour and gives with acids a floccu- lent brown precipitate of a humus-like substance and perfectly amor- phous which was not examined.It still contains nitrogen ; and by exposure to a heat gradually raised to low redness it gives an additional quantity of volatile bases among which ammonia becomes more and more abundant as the temperature rises. A non-basic oil also makes its appearance but only in very small quantity. Wertheimf- has lately examined the action of soda-lime on certain organic bases He has obtained metacetamine from narcotine and methylamine from morphia ; and considering these substances to be directly eliminated from the bases he expects to obtain the residual atoms in the form of a definite compound. Dr. Anderson enter- tained a similar idea with regard to codeine until he detected the formation of two different bases which seemed to him rather to indicate that these substances appear as the result of a true destructive distillation; and that possibly by varying the circumstances of the experiment other bases may be obtained.The author has also observed another remarkable decomposition of codeine by which volatile bases are obtained. The formation by the action of nitric acid of a resinous acid has already been mentioned. This acid which is insoluble in water dissolves readily in dilute potash with a red colour; and the solution on boiling evolves a volatile base in great abundance. The further examination of the circumstances under which this change takes place is reserved for a future commu- nication. Dr. Anderson has likewise examined the action of iodine on codeine which yields a magnificent crystalline compound presenting the phenomena of pleochroism in a remarkable manner.* The author has likewise conyinced himself that the petinine described by him two years since as existing in bone-oil is represented by the formula C HI,N and not by C3H, N which he then gave for it. He has also ascertained the existence of ethylamine 2nd methylamine in bone-oil. $-Ann. Ch Phartn. LXXIII 208.

ISSN:1743-6893    

DOI:10.1039/QJ8520400083

出版商:RSC    

年代:1852

数据来源: RSC