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SCHUNCR ON THE XX.-On the Colouring Matters of Madder. BY EDWARD Ph.D. F.R.S. F.C.S. SCHUNCK. THEroot of the Rubia tinctorum commonly called madder consti- tutes one of the most valuable dyeing materials employed in the arts. Though probably known to the ancients it is only in modern times that it has come to be extensively used. At the present time there is perhaps no dye-stuff with the exception of indigo employed to so great an extent in imparting various colours to calico and other fabrics as madder ; and a knowledge of its proper- ties and the ‘most advantageous mode of treating it is indispensable to any one engaged in the arts of dyeing and printing. It stands in about the same relation to other dye-stuffs in the eyes of the dyer and calico-printer as iron does to other metals in the eyes of the engineer.The principal advantages which madder presents are the follow- ing:-1. It is capable of producing according to the mordants employed and the method of treatment a great variety of different colours and shades such as black red of different kinds from a dull brownish-red to a bright red and a delicate pink besides the pecu-liar colour of Turkey red also purple of various shades from a dull reddish-purple to a delicate bluish-purple or lilac as well as cho- COLOURING MATTERL) OF MADDER. date of all shades.-2. Its colouring matters have but little affinityfor cotton fibre and a great affinity for mordants so that it is not difficult to secure a good white on the parts of the tissue to which no mordant has been applied.-3.The compounds which its colouring matter or matters yield with mordants possess an unusually stable chmacter so that it is possible without causing much detriment to the colour to expose them to the action of various agents for the purpose of improving or modifying the shade. They are also capable of resisting the action of air and light in a remark- able degree so much so that I am inclined to believe that the fading which we observe in colours produced by madder is caused rather by the mechanical wear and tear of the fabric than by any chemical decomposition of the colours themselves. It is these properties chiefly which have led to the extensive employment of madder in the arts of dyeing and calico printing.The art of employing madder to the greatest advantage had like many other arts attained to a considerable degree of perfection before any attempt mas made to elucidate the principles involved in it. Indeed the art of Turkey-red dyeing affords a striking instance of a very complicated process of manufacture arriving at a state of great perfection without one step in the process being really understood and without the least improvement having been made in it by any one conversant with the principles of chemical science. All processes in which the action of colouring matters are concerned are in fact of so complicated a nature and depend on the action of bodies for thc most part so remote from the ordinary experienceof the chemist that their elucidation could only be attempted when the science had attained a high degree of developernent.The process of fermentation for instance which plays a considerable part in the formation of many colouring matters is one that could not possibly be understood in the early ages of the science of chemistry. All that could be accomplished was to describe the processes actually in use in the arts without any successful attempt at their explanation. C hevrenl whose interesting and important labours on colouring matters are so well known seems not to have occupied himself with any chemical examination of madder. The first discovery of any importance in this branch of chemistry was made by Robiquet and Colin who succeeded in preparing from madder a substance which on being exposed to heat gave a sublimate consisting of beautiful reddish- yellow needles and to which they gave the name of Alizarine.SCHURCH ON THE This substance they found to be very little soluble in water but soluble in alcohol and ether. Its alkaline solutions were of a beautiful violet or purple colour and it gave with earths and metallic oxides lakes of various colours. The method of prepara-tion which they ahpted left it quite uncertain whether alizarine pre-existed in madder or whether it was a product of decomposition of some other body formed by the action of heat. It is only by recent researches that its pre-existence in the ordinary madder of commerce has been established. But finding that all the usual madder colours could be produced by its means and more-over of great brilliancy and purity Robiyuet and Colin were right in attaching to it a considerable degree of importance.The same series of experiments led to the discovery of another colour- ing matter in madder to which these chemists gave the name of Purpurine. This they found to be dishguished from the preced- ing chiefly by being soluble in alum-liquor the solution having a beautiful pink colour. In other respects it did not differ very much from alizarine. It yielded a crystalline sublimate when heated; it was very sparingly soluble in water but more soluble in alcohol and its alkaline solutions were reddish-purple. The red and pink colouring matters of madder obtained by Gaultier de Claubry and Persoz are as Persoz himself con- fesses identical with the alizarine and purpurine of Robiquet and Colin.To the former chemists however clearly belongs the merit of a very important discovery in the chemistry of madder viz. that of the effect produced on madder by strong mineral-acids. They found that when madder was treated with boiling dilute sulphuric acid it was converted into a dark brown powder which could after- wards be completely washed with cold water without any of the colouring matters being removed the latter remaining in the resi- due while many impurities were washed away by the water. The residue was found to yield in dyeing better results in some respects than madder itself the colours being more brilliant and requiring very little after-treatment while the white portions of the fabric remained unsullied.This process has since then been carried out on a large scale the product having obtained the name of Garancine. This was the first instance that had occurred of the labours of the scientific chemist having been applied to the improvement of the art of madder-dyeing. Persoz as well as Robiquet explained the action of the acid on madder by supposing that the saccharine gummy arid extractive matters contained in the root and pre- COLOURINU MATTERS OF MADDER. 201 sumed to be injurious during the process of dyeing mere charred or otherwise decomposed by the acid or afterwards removed during the washing the undecomposed colouring matters being left behind in a state of greater purity.This explanation though it had at the time every appearance of probability was afterwards discovered to be only partially correct the acid having been found to produce other effects in addition to this. Besides these two colouring matters another was discovered in madder by Kuhlmann and called by him Xanthine. It was described by him as a substance resembling extractive matter having a taste between bitter and sweet and a yellow colour being very easily soluble in water and giving rise by the action of strong acids to the formation of a dark green powder. About the year 1835 a memoir was published by Runge con-taining a description of the properties and method of preparation of three distinct colouring matters from madder which he named respectively Madder-red Madder-purple and Madder-orange.There can be no doubt that the two first are identical with the aliza- rine and purpurine of Robiquet. The discovery of madder-orange mas the first indication of the existence of crystallized yellow colour- ing matters in madder. The memoir of Runge which contained also an account of other substances not of any importance as far as the process of dyeing was concerned was for a number of years referred to as an authority on the subject and for along time no facts of any great importance were added to those previously known. This sho& account may serve to give an idea of the state of our knowledge on this subject at the time when I entered on its inves-tigation. My efforts were in the first place directed to the separa- tion as far as possible of all the substances contained in the ordinary madder of commerce from one another their preparation in a state of purity and their mutual action and reaction during the process of dyeing.After much labour I succeeded in obtaining Robiquet’s alizarine in a well crystallized state without having recourse to sublimation. The alizarine thus obtained differed from sublimed alizarine in containing several atoms of water of crystallization which were lost even on heating the crystals to 100OC. Its colour inclined also more to yellow and had less of the reddish tinge seen in sublimed alizarine. Hence it followed that ordinary madder in the state in which it is employed by the dyer does in reality contain ready formed alizarine and that the latter RCHUNCH ON THE is not a product of decomposition formed from some other sub- stance by heat.My experiments regarding the tinctorial power of alizarine which have often been repented since then fully con- firmed those of Robiquet. I found that by means of alizarine I could produce all the usual madder colours and moreover that the colours so produced mere distinguished for their brilliancy and purity being as beautiful as the ordinary madder colours after they have been subjected to a long coiirse of treatment with soap acids &c. for the purpose of rendering them more brilliant. This simple fact like many othera connected with the chemistry of madder has been the subject of much controversy.It has been asserted by D. Kijchlin that alizarine is not strictly speaking a colouring matter but a mixture of a colourless crystallised resin with a red colouring matter and that it owes to the latter its tinctorial power. That this view is entirely erroneous must be obvious to any person possessing any knowledge of chemistry who has occu- pied himself with this subject. Its unvarying properties and the uniformity of its composition prove alizarine to be a pure unmixed substance. That it plays a principal if not the only part in the production of the colours for which madder is employed seems probable from the circumstance that the finer madder colours contain little besides alizarine in combination with the mordants.If for instance a few yards of so-called madder-pink calico be treated with muriatic acid to remove the alumina of the mordant then well washed and treated with caustic alkali a violet-coloixred solution is obtaiuecl from which acids precipitate yellow flocks consisting of almost pure alizarine which may be obtained in long crystalline needles by solution in boiling alcohol and evaporation of the alcoholic solution. This constitutes indeed the easiest method of preparing pure alizarine on a small scale. The colours produced by pure alizarine do not yield to ordinary madder colours in their power of resisting decomposition by alkalies soap &c. they are equally fast as was observed long since by Robiquet and others. I have in fact after a long course of experiments been led to the conclusion that the final result of dyeing with madder and its preparations is simply the combination of alizarine with the various mordants employed and that consequently if an economical method of preparing alizarine on a large scale could be discovered a great gain would result to the arts.The analyses of pure alizarine made by myself and others have led to pretty nearly the same elementary composition. The formula COLOURING MATTEBB OF MADDEB. 203 which I gave to it in the first instance viz. C,,H,O or C,,H,,OS I have never seen any cause to deviate fiom. Indeed all my sub-sequent researches have appeared to me only to confirm it. It is at all events certain that the purer the alizarine the more nearly does its composition approach what it should be according to this formula.By the action of nitric acid alizarine is converted into a colourless beautifully crystallised acid which subsequent investiga- tions have provednot to be new as I at first supposed but identical with phthalic acid one of the many products of decomposition of naphthaline discovered by Laur ent. From this fact conclusions have been drawn regarding the composition of alizarine which I cannot but consider as erroneous. Since chloronaphthalic acid and alizarine both yield phthalic acid by decomposition with nitric acid Strecker has inferred that there must be a similarity in the composition of the two bodies that the formula of alizarine is C,,H606 and that consequently chloronaphthdic acid is simply alizarine with 1At.of hydrogen replaced by chlorine; and he has adduced many ingenious arguments in favour of this view. If this view of the composition of alizarine were correct it would lead to very important conclusions as the possibility of converting a refuse product like naphthaline into one of great value and importance would in that case not be so very remote. The attempts made by Strecker to replace the atom of chlorine in chloronaphthalic acid by hydrogen and thus convert it into alizarine did not succeed. The far easier experiment of converting alizarine into chloronaphthalic acid by the action of chlorine he does not seem to have attempted. In order to complete the presumed analogy between chloronaphthalic acid and alizarhe Str ecker supposes the latter like the former to yield oxalic acid as well as phthalic acid by decomposition with nitric acid.This is however not the case as no trace of oxalic acid is formed from alizarine by oxidising agents. By a process similar to that adopted by Runge for the preparation of his madder-orange I succeeded in obtaining a body crystallising in beautiful golden yellow needles and scales to which I gave the name of Rubiacine. This was the first to be discovered of a series of yellow colouring matters from madder having very similar properties and a similar composition. These colouring matters are all capable of crystallising and though yellow themselves yield red compounds with bases. They do not contribute to the production of fast colours during the process of madder dyeing SCHUNCK ON THE but are on the contrary as my experiments show very injurious to the strength and beauty of those colonrs.The most cha- racteristic property of rubiacine is the facility with which it is converted by the action of persalts of iron into a new acid rubiacic acid which yields definite crystallised compounds with alkalies. By means of these compounds it was possible to determine the composition and formula of the acid with a tolerable degree of certainty; and as the acid was again convertible into rubiacine by the action of sulphuretted hydrogen it followed that the number of equivalents of carbon in both bodies must be the same. This number I found to be 32.In what relation however the compo- sition of rubiacine stood to that of alixarine was at first not all apparent as the link uniting the two bodies had still to be dis- covered. According to the old classification of colouring matters rubiacine would belong to the division called resinous from being insoluble in water but soluble iu alkaline liquids and alcohol and from its power of resisting the action of strong reagents such as nitric and sulphuric acids. It is a remarkable fact that rubiacine is oxidised and converted into rubiacic acid by means of persalts of iron whereas the same change is not produced by nitric acid. It is improbable that this difference is owing to any predis- posing affinity of the peroxide of iron for rubiacic acid though there is no doubt that some combination does take place; for on treating rubiacine with boiling solutions of persalts of iron it dissolves with a dark brownish-red colour and the solution afier being boiled for some time contains rubiacic acid which is precipitated in yellow flocks on the addition of muriatic or nitric acid the solution itself becoming yellow.Two other bodies still more nearly resembling resins yielding red compounds with bases but not themselves capable of crystal- lieing were discovered in madder. These I found to be equally injurious with rubiacine in the process of dyeing. It is only a consideration of the source whence they are derived which lends to these bodies the least interest. For the purpose of completely understanding all the phenomena which take place during the process of madder dyeing I considered it necessary to ascertain what other constituents the root contains besides colouring matters.Several of these such as sugar and pectic acid have for a long time been known as constituents of madder. The latter may under certain circumstances act very injuriously in dyeing. The xanthine of Kuhlmann is a mixed COLOURING MATTERS OF MADDER. substance. It contains a body which by the action of strong acids becomes dark green and yields a green powder. It is this body to which I have given the name of Chlorogenine and which Rochleder calls Rubichloric Acid. It is a speFies of extractive matter. Its watery solution when heated and exposed to the air acquires a brown colour and in this state is capable of imparting a brown tinge to calico whether mordanted or unmordanted.Hence the uniform dirty reddish-brown tint which a piece of calico exhibits both on the printed and unprinted portions after having been dyed with madder ;to remove this tinge is one of the objects of the after treatment with soap and other materials. In the pro- cess of manufacturing garancine this substance is partly decom- posed partly removed by the subsequent washing. Hence may in a great measure the greater purity and brilliancy of gerancine colours as compared with madder colours be explained. There is a point connected with the chemistry of madder dyeing which has puzzled many especially practical persons who have devoted their attention to the subject that is the apparent necessity of having a certain proportion of lime or its carbonate either mixedwith thematerial.or contained in the water of the dye-bath in order to produce colours which shall resist the subsequent action of soap and other agents. It is a fact well known since the time of Hausmann that in order to insure fastness of colour it is necessary either to employ calcareous water OP to add chalk to the dye-bath the effect of so doing being to impoverish the colours,butat the same time to add to their permanency. Hence too madder grown in a calcareous soil is superior to any other and for some colours dyers generally make up for a deficiency of lime in the root by the addition of chalk. Now the experiments of Robiquet as well as my OWD have demonstrated that in dyeing with pure alizarine the least addition of lime is rather injurious than otherwise as it merely weakens the colours without adding to their durability.Hence the beneficial effect of lime can only be accounted for by some action which it exerts on other constituents of the root. Now I found that the addition of rubiaciae or of any of the resinous colouring matters to alizarine during the dyeing produced very prejudical effects. They weakened the colours and rendered them impure and unsightly. The red acquired an orange the purple a reddish hue while the black became brownish and the white parts assumed a yeliowish tinge. These effects dis- appeared however completely as soon as the foreign colouring VOL.XII. P 2CG SCNUNCH ON THE matter was completely saturated with lime the tinctorial power of the alizarine then appearing again with all its orighal intensity while the other colouring matter was rendered innocuous. The same prejudicial effect was produced by adding free pectic acid to the alizarine but disappeared eiitirely on neutralising the pectic acid with lime. The phenomenon seems therefore to resolve itself into a simple case of elective affinity. The resinous colouring matters and other bodies having a stronger affinity for bases than alizarine seize hold of the alumina and other mordants when all are uncombined but when lime is added they combine with it as the stronger base leaving the alizarine at liberty to unite with the mordants.At the same time I do not suppose even if a speci- men of madder contain exactly sufficient lime to unite with the resinous colouring matters pectic acid and other injurious sub- stances existing in it that the distribution of these substances and the alizarine among the bases will be precisely as my theory pre- supposes; for if even in a mixed solution containing various salts of strong mineral acids and bases it still remains a subject of speculation with chemists in what manner the acids and bases are mutually distributed and whether every base is not combinsd with every acid how much less can we expect it to be a settled matter according to what law a certain number of complex organic bodics existing in solution together will distribute themselves among a certain number of bases.In the case just mentioned I believe on the contrary that however large an excess of lime or other base be taken a certain quantity only of the resinous colouring matters &c. will combine with the lime or other base while the remainder will go to the mordants arid can only be separated by after-treatment a small portion of the alizarine at the same time uniting with the lime or other base and a larger portion with the mordants. Indeed this view of the case may be proved to be correct; for if a piece of printed calico be dyed in the usual manner with madder to which chalk has been added the colour is found on examination to contain in combination with the mor-dants not only alizarine but also a small quantity of resinous colouring matter as well as pectic acid and a brown siibstance insoluble in alcohol which I suppose to be a product derived by oxidation from xanthine or chlorogenine.These impurities are subsequently removed by means of soap acids &c. leaving a COM-pound containing only alizarine and a little fatty acid on the fabric. Now the residual madder left after the dyeing is corn- COLOrRTNG MATTERS OF MADDER. pleted though apparently exhausted of colouring matter may be proved to contain alizarine; for if it be treated with acids a quantity of lime magnesia &c. is removed and after being washed it is found to be capable of dyeing anew and a fresh portion of alizarine and other substances may now be extracted by means of caustic alkalies.On this depends the manufacture of so-called garanceux from the waste madder of dye-houses a product which used formerly to be throwir away. When fresh madder is subjected to the action of strong acids for the purpose of manufacturing garancine the following effects take place 1.The sugar xanthine and other injurious substances soluble in water are either mashed away or decomposed by the acid and so removed. 2. The lime magnesia and other bases which would prevent the colouring matter from exerting its full effect are removed and thus after the washing is completed a suitable quantity of lime soda or some base is added in order to combine with and render innocuous the resinous colouring matters as well as the pectic acid which as is well known is capable of taking up a certain quantity of mineral acids forming with them compounds not easily soluble in water.There is another effect produced by the acid in addition to those just named which I shall refer to presently. To the view here taken it may be objected in the first place that the fact of the colours produced by alizarine being more durable and resisting better the action of alkalies &c. than the compounds of the other colouring matters of madder with mordants is inconsistent with the supposition of its having less affinity for bases than the other colouring matters. Secondly that ordinary garancine even when a sufficient quantity of base has been added to it to combine with the impurities which prevent the alizarine from uniting with the mordants does not in practice produce exactly the same effect as madder.Garancine colours are notoriously not as fast as madder colours and hence garancine cannot be made to replace madder completely however great its advantages are in other respects. To the first objection it is certainly difficult to frame a convincing reply. The second will fall to the ground at once when I state that by a very simple process garancine may be so modified as to be capable of affording colours as permanent as those from madder itself-nay even more so. This process which was patented by Mr. Pincoffs and myself several years ago consists simply in subjecting garancine to the action of high pressure steam or in heating it in a closed vessel P2 SCIIUNCH ON THE while slightly moistened to a temperature of 200°C.or there-abouts. What takes place during this process which is accom-panied by a loss of weight amounting to about 10 per cent. I have never been able exactly to ascertain; but I have reason to believe that it consists in the total or partial destruction of one or more of the resinous colouring matters wliich act so prejudicially during the process of madder dyeing. Be this as it may the effect is so great that if a certain quantity of madder be converted first into garancine and then by means of high pressure steam into the new product the latter is found to act more efficiently as far as the depth of permanent colour which it is capable of yielding is concerned than the original material from which it was prepared ; or in other words a larger proportional quantity of madder must be used to produce the same ultimate effect.As this subject is one our knowledge of which is still far from complete I have preferred on this occasion treating it historically rather than systematically stating as concisely as I have been able in what manner and by whom the various facts connected with it have been discovered. In doing so I must not pass over the labours of Dr. bebus who in his interesting memoir on madder has given us the results of his investigation on its colour- ing matters of which he distinguishes two viz. Zizaric and oxylixaric acids which are identical with the alizarine and purpurine of other chemists.There is another part of this subject which far exceeds in its intricacy as well as in the interest attaching to it that portion of which I have just given a short account; indeed much of it still remains involved in obscurity. The researches of modern chemists have made us acquainted with a number of highly complicated processes in which bodies derived from the organic world are concerned. Of these processes perhaps few are so difficult to comprehend both as to their efficieut causes and their results as those in which fermentation plays a part. The process of alcoholic fermentation one of the simplest cases has been the object of study with many eminent chemists without any definite notion of its true nature being arrived at.Various other phenomena of fermentation besides the conversion of sugar into alcohol and carbonic acid have been discovered and investi- gated such as the transformation of saliciiie into saligenine and sugar of amygdaline into oil of bitter almonds &c. That some process of this nature goes on in madder has long been suspected COLOURING MATTERS OF MADDER. from the circumstance that when ground madder is kept for several years it gradually improves in quality until it reaches a certain point after which it again deteriorates. But what body it was that was acted on diiring this process or what was the nature of the process remained quite unknown. Strecker supposes that the change which goes on consists in the conversion of alizariiie into purpurinc ; but this would constitute anything but an improvement in quality since the colours produced by purpurine are in most respects inferior to those of alizarine.Besides this alizarine is a body not easily decomposed unless exposed to the action of very potent agents and any portion of it once formed in the root would probably resist the action of air and moisture for a very long period of time if not entirely. Mr. Higgin states as the result of his experiments on this sub-ject that there exists in madder a peculiar albuminous ferment which by acting on the xanthine gives rise to the formation of colouring matter and that this process takes place to some extent even during the short period of time occupied by dyeing.This statement I subsequeiitly found to be a correct representation of the truth in its main features and I think that to Mr. Higgin is due the first distinct enunciation of it. That the whole of the colouring matter of madder does not exist ready-formed in the article as used by the dyer may be rendered evident by a simple experiment. If madder be extracted with cold water the clear watery extract does not contain any alizarine or other colouring matter since these are almost insoluble in cold water. Nevertheless the extrsct when gradually heated is found capable oi dyeing in the same way as madder itself. If the extract be made tolerably strong it possesses a deep yellow colour and a very bitter taste; but if it be allowed to stand in n warm place for a few hours it gelatinises and the insoluble jelly which is formed is found to possess the whole of the tinctorial power of the liquid while the latter has lost its yellow colour and bitter taste Hence it may be inferred that the substance which imparts to the extract its bitter taste and yellow colour is capable of giving rise to the formation of a certain portion of colouring matter.This simple fact formed the starting point of a fresh series of researches of which I will in its few words as possible state the results. By extracting madder with boiling water the subsequent gelatinisation or coagulation is prevented and the extract retains its yellow colour and bitter taste a proof that the coagulation observed in the cxtract with cold water is R result of some process of fermentcztion which is arrested when the tempera- tureis suAticiently raiscd.When the extract is agitated with a little animal charcoal the latter absorbs the bitter principle and gives it up again to boiling spirits of mine which on evaporation leaves it in an almost perfect state of purity. In this manner I obtained a substance to which I have given the name of' Rubiatz and of which the principal characteristics are these :-It is amor- phous and shining like gum has a deep yellow colour and an intensely bitter taste is easily soluble in water and alcohol. It is not a colouring matter in the practical seme of the word for it gives to mordants in dyeing only the faintest shades of colour. But if its watery solution be mixed with sulphuric acid and boiled it gradually deposits a quantity of insolnble yellow flocks and becomes almost colourless.These flocks after being well washed are found to dye exactly the same colours as alizarine. In fact they contain alizarine. The liquid gives the reactions of sugar. Taking this fact into consideration it becomes possible to give an account of all that takes place in the process of manufacturing garancine. It is evident that during this process the easily soluble rubian becomes converted into the difficultly soluble alizarine that there is in this case in fact an actual formation of colouring matter which is added to that which already exists in the root. A similar change takes place when caustic alkali is used instead of the acid.A solution of rubian on being mixed with caustic potash or soda simply turns red but on being boiled it becomes dark purple and deposits a purple powder which consists chiefly of a compound of alizarine with alkali insoluble in caustic lye. Fermentation also decomposes rubian with great facility; but in order to effect its decomposition it is not indifferent what ferment be taken; a peculiar ferment is essential for the purpose. A solution of rubian may be left for several days in contact with yeast decomposing albumen casein emulsin &c. without showing any sign of change. But if an extract of madder with cold water be mixed with a large excess of alcohol flocks of a dirty rcd colour are precipitated which after being well mashed with alcohol are found to consist chiefly of an azotised principle which exerts a peculiar and powerful decomposing effect on ruhian.If some of this substance be mixed with a watery solution of rubian and the mixture be left to stand at the ordinary temperature the rubian is found after a few hours COLOURINO MATTERS OF MA1)DEIC. to be as completely decomposed as if it had been treated with a strong acid or caustic alkali though no evolution of gas or any of the usual signs of fermentation have been manifested. The solu- tion if tolerably strong gelahinises just as an extract of madder with cold water does under the same circumstances. The jelly when mixed with cold water is found to be almost insoluble. The water acquires only a slight colour but contains sugar in solution while the insoluble portion contains alizarine mixed with the ferment.With a knowledge of this process of decomposition it becomes possible to explain several curious phenomena the true cause of which was previously unknown. It is well known to madder dyers that if the dye-bath be heated up rapidly to the boiling point instead of gradually as is the usual practice preju- dicial effects ensue. It is evident from what I have just said that the sudden heating puts a stop to the action of the ferment as would be the case in any other process of fermentation whereas the gradual heating allows it to exert its full decomposing power on the rubian. Hence too the advautage of mixing together several sorts of madder one containing for instance an excess of rubian in proportion to ferment the other a superabundance of ferment to counterbalance it mill be apparent.The improvement which takes place in the quality of madder after long keeping is pro-bably also an effect of the same cause. Indeed it seems highly probable that the alizarine which undoubtedly exists ready formed in ordinary madder owes its formation to the action of fermenta- tion on rubian; and an experiment which I made with fresh madder roots goes far to prove that this is in fact the case and that surprising as it may seem the fresh root contains no trace of ready-formed colouring matter. The experiment was as follows Some madder roots having been taken out of the ground and cut small without being dried produced the ordinary colours when used for dyeing in the common manner.But on treating the roots after being cut into pieces as quickly as possible with boiling alcohol a yellow extract was obtained which contained rubian but which even after all the alcohol had been driven away was found incapable of imparting to mordants any but the slightest shades of colour ;while the portion of the root left undissolved by the alcohol on being subjected to the same test as the extract imparted to mordants no more colour than the latter. It was evident thercfore that thc alcohol in this case had effected a separation bttweeii the ~0~~~~1’-~’,rc)‘lri~iiiha ?)odp aid tlic agcut SCHUNCK ON THE which under ordinary circumstances is destined to effect its trans-formation into colouring matter.The same relation it is appa- rent subsists between rubian and erythrozym as I have called the ferment of madder as between amygdaline and emulsine. It affords another of the instances of the mutual fitness of things and adaptation of means to an end which we find occurring so often in all departments of nature and which point so unrnistakeably to an intelligence superior to our own. What it may be asked would have been the consequence if there had not been placed in close proximity with the colour-producing body of this plant another substance peculiarly fitted to effect its decomposition ? Why that probably one of the most valuable of our dyeing mate- rials and some of the most beautiful of our dyes would have remained for ages unknown for it may be doubted whether sup- posing this peculiar fermentative substance to have been absent in the root we should ever except by mere chance have discovered the valuable properties of the latter.The property which principally distinguishes erythrozym from other ferments is the power which it possesses of effecting the decomposition of rubian. When allowed to act on a watery solution of cane-sugar the latter yields alcohol carbonic acid and hydrogen. The liquid is found to contain also a minute quantity of succinic acid the formation of which I at one time supposed to be characteristic of this process of decomposition. Pasteur has however since then discovered that this acid is always formed in small quantities during the ordinary fermentation of sugar by yeast.In its composition erythrozym differs from all other known ferments. It contains carbon hydrogen nitrogen and oxygen but the proportion of nitrogen is remarkably small as it hardly exceeds 4 per cent. At first sight the change which rubian undergoes when decom- posed by means either of acids alkalies or ferments would seem to be simple enough. Tt might be supposed to consist simply in a splitting up of its complex molecule into alizarine and sugar and to resemble many analogous processes with which me are acquainted and which result in the formation of sugar and another body the two together having formed originally a conjugate-compound. Nevertheless the process is by no means so simple as might at first be supposed.The products of decomposition formed in these cases never consist of alizarine and sugar only. The part insoluble in cold water contains in all cases besides COLOURINU MATTERS OF MADDER. 213 alizarine two resinous bodies one easily soluble in alcohol which I call Rubiretine the other less solnble in that liquid and to which I have applied the name of Verantine. These bodies though resembling resins in some respects must be classed as colouring matters since their colour secms to be inherent and not a merely accidental property. But in addition to these there is uniformly found accompanying the alizarine a third body belonging as far as general appearance and properties are concerned to the same class of substames as rubiacine.This third body is however in each case quite distinct. When acids have been employed for the decomposition of rubian then this third body is found to have the following properties It is tolerably soluble in boiling water and crystallises in lemon-yellow silky needles ; it is decomposed on being heated but resists the action of nitric and concentrated sulphuric acids; T have called it Rubianine. When alkalies are used instead of acids then rubianine is replaced by Rubiadine which is a body crystallising in beautiful golden-yellow scales insoluble in water but soluble in alcohol and is completely vola- tilised when heated. But when rubian is decomposed by fermen- tation it yields neither of these two but in their place Rubiafine a substance resembling rubiadine in most of its properties but essentially distinguished from it by passing into rubiacic acid when treated with perchloride of iron.This substance is usually accom- panied by another of similar properties of which it is difficult to say whether it must be considered as distinct from the others since I have not succeeded in obtaining it in a state of perfect purity. I call it Rubiagine. Now all these bodies which accom- pany alizarine make their appearance so invariably on the occa- sions which I have named that their occurrence cannot be con- sidered as accidental. Let us see therefore how their simulta- neous formation from rubisn is to be explained. I assume for rubian the formula C,6H,,0,0.Hence it follows that rubian is converted into alizarine simply by the loss of 14 eqs. of water. The forrna- tion of verantine and rubiretine is due to another kind of decom- position. The formulze of these two bodies being respectively C2,H120 and C,,H,,O,, it will be seen that by adding both together we obtain 1 eq. of rubian minus 12 of water. The composition of the class of bodies to which rubianine belongs is rather doubtful. It is probable that the formula of rubianine is C,,H,O,,. If so it is formed from rubian by the separation from the latter of 1 eq. of grape sugar. Rubiafine howcver being 214 SCIIUNCB ON 'I'ITE easily convertible into rubiacic acid must contain 32eqs. of carbon and its formula is therefore probably C,,H,,09 that of rubiadine being the same.In its conversion into these bodics rubian there- fore loses 2 eqs. of sugar since C56H34030+ 3HQ = C,,H,,09 + 8C1,H120,,. It appears from this that rubian undergoes not orre but three different processes of decomposition when acted on by acids alkalies or ferments; that the formation of sugar is con- nected not with that of alizarine but with that of rubianine and its allies and that in fact there is no reason why only one of these processes should not takc place to the exclusion of the others ;why for instance rubian should not be so decomposed as to yield alizarine alone without any of the accompanying bodies which are from this point of view not only a source of loss but also positively prejudicial in practice.I am aware that the view which I take of the composition of rubian and its products is open to some objection. In the case of this as of all other uncrystallisable organic bodies with very high atomic weights doubts will arise in the mind of the chemist as to its right to be considered a pure unmixed substance. It might be supposed for instance that rubian instead of being it pure substance is a mixture containing among other things a conjugate compound of alizarine and sugar a view which has indecd been taken by Rochleder and that the othcr products of decomposition are purely accidental. I may therefore very naturally be called on to adduce if possible further argu-ments in favour of the view I have taken instead of basing it solely on such as are derived from an examination of the composition of these very complex bodies.I will therefore state in few words such as have occurred to me. In the first place then I have found that if the action of the ferment on rubian be retarded by means of antiseptic substances the deconiposi- tion of the latter is not prevented but there is then found no trace of alizarine among the products of decomposition m hich then consist almost entirely of rubiretine and verantine. Now if rubian were a conjugated compound of alizarine and sugar 01' con-tained any such cornpound alizarine must of necessity appear among the products of the fermentation however much this might be re- tarded.-2. If rubian contained the elements of sugar it ought when decomposed with nitric acid to yield odic acid.Such is however not the case when perfectly pure rubian is employed. The only product is phthalic acid so that in this case rubiaii behavcs as if CCLOUKING &I-ITTERS OF MADI>EIi. it contained alizarine only. The same takes place when hypo- chlorite of lime is the decomposing agent.4. It is found that when chlorine is made to act on rubian the phenomena are of a totally different description. By means of chlorine rubian is converted into a yellow crystallised substance almost insoluble in water but soluble in alcohol and almost neutral in its character which I have called Chlororubian. Its formula is C4,H2,C10,, and it is consequently formed from rubian by the elimination of 1 atom of sugar and the replacement of 1 atom of hydrogen by 1 of chlorine.But chlororubian is itself also a glucoside; for by the action of strong acids it splits up into grape sugar which may be obtained from it with its usual crystalline appearance and other properties and into a chlorinated body possessing the properties of a weak acid and which has the cornposition of rubiadine with 1 atom of hydrogen replaced by chlorine hence calledchlororubiadine. Rubian then when decomposed by chlorine behaves exactly as if it mere a glucoside; it yields an atom of sugar and chlororubian the latter of which by decomposition with acids gives another atom of sugar and a substitution product of one of the rubiadine series containing 32atoms of carbon. No products of substitution standing in any relation to alizarine make their appearance as far as my observations extend.* Now if rubian behavcs when decomposed in one particular way as if it contained alizarine only ; when subjected to another kind of decomposition as if rubiretine arid verantine were its sole con- stituents; and when exposed to a third species of action as if it were made up of sugar and one of the rubiadine class of bodies * Among the many anomalies with which this subject abounds the following is deserving of mention.By the long-continued action of chlorine chlororubian is converted into percilloro?-ubian a colourless crystallised substance the formula of which is C,,H,Cl,O,,. Now it is singular that the 9 atoms of chlorine of this body are far more firmly combined with the other constituents than the 1 atom in chloro- rubian ; for the latter by the action of strong caustic alkalies loses the whole of its chlorine which may also be detected by silver salts aftcr treatment wich nitric acid whilst percblororubian is not affected in the least degree either by caustic alkalies or by strong nitric acid.Chloronibian also is capalrle of combining with bases and plays the part of a weak acid whilst perchlororubian though containng 3 more atoms of chlorine is a perfectly neutral substance quite insoluble in caiistic alkalies and not uniting with any base. Lastly chlororubian is a glucoside easily decom- posed by strong acids and yielding sugar as one of its products of decomposition ; whilst perchlororubian is not in the least affected by the strongect acids the atoms which in chlororubian go to form sugar being from some cause or other prevented from doing so after having entered into the composition of perchlororubian.SCHUNCK ON THE I think I am justified in arriving at the conclusion that not one of these different bodies pre-exists in rubian that the molecules of the latter arrange themselves in a different manner according to the decomposing agent employed and that in fact we know nothing whatever of the internal constitution of that body. This is not a question of mcre speculative interest which concerns only the theoretical chemist; it may become one of great prac- tical importance. The quantity of alizarine which a certain quantity of rubian is under ordinary circumstances capable of yielding amounts to between 10 and 20per cent.of the ruibiaii employed; but if my views be correct it mould be possible in theory to obtain nearly 80 per cent. The remaining 60 per cent. appear in the form either of useless or even injurious products. In my opinion a wide field is here opened for further experiment aud research. If our knowledge of the products of decomposition of rubian were confined to the points to wliich I have adverted the matter would be simple enough but a great additional complication has been introduced into it by the fact of the discovery of an acid which is actually a conjugate compound of alizarine and sugar. This discovery we owe to Rochleder who has described the acid under the name of Ruberytliric acid.I have given it the name of Rubianic acid because the composition given by Rochleder is so very different from that to which my experiments have Zed that I cannot help supposing the two acids to be distinct though it is not probable that there should exist two different acids having properties so nearly alike. It is a true acid giving definite crystalline compounds with alkalies a circumstance not observed by Rochleder. It is tolerably soluble in boiling water and crystallises in beautiful silky needles of a lemon-yellow colour. It is decomposed by the same agents which effect the decompo- sition of rubian into alizarine and sugal; no secondary products in this case makirig their appearance.Now nothing could appa- rently be simpler than to attempt to explain the results obtained in my experiments as Rochleder has endeavoured to do by supposing that rubian contains rubianic acid ready formed and that the alizarine observed in the decomposition of the former is due to that of the acid only. Nevertheless I have obtained I believe clear proofs that rubianic acid does not pre-exist either in madder or in rubian. It is formed from the latter by the simul-taneous action of alkalies or other bases and oxygen. Oxygen is COLOURTNQ MATTERS OF MADDER. 217 essential to its formation. In a closed vessel however great the excess of alkali which may be employed at the same time not a trace of it is formed. Its composition which is easily ascertained from that of its potash salt which crystallises in beautiful puce- coloured iieedles is a confirmation of the correctness of this view for as its formula is C,,H,,O,, it will be seen that its formation is due to the elimination from rubian of 4 atoms of carbon and 2 of hydrogeii which must have been removed in the shape of carbonic acid and water.By decomposition it yields as will be evident from the formula 1 atom of alizarine and 2 atoms of grape sugar. Its existence then is no argument against the correctness of the view cvliich I take of the composition of rubian and its derivatives. I do not claim the discovery of this interest- ing and beautiful acid which is due to Rochleder if his substance and mine are identical. I merely claim the discovery of the circumstances on which its formation depends.If as I suppose it does not pre-exist in the root then it will afford the first instance in which the formation of a true glucoside or conjugate compound of sugar from a still more complex body by the action of oxygen has been observed. Before concluding it remains for me to say a few words in regard to purpurine the colouring matter which has by some chemists been supposed to be in addition to alizarine essential to the production of madder colours. The two chief properties whereby according to those chemists who have examined it it is distinguished from alizarine are 1. That it dissolves in alkalies with a cherry-red or bright red colour alizarine giving with alkalies beautiful violet solutions.2. That it is entirely soluble in boiling alum-liquor forming a solution of a beautiful pink colour with a yellow fluorescence whereas alizarine is almost insoluble in the same menstruum. These properties are how- ever not of a sufficiently decided character to entitle it to rank as a distinct substance as they might possibly be produced by an admixture of alizarine with some foreign substance. Having con- vinced myself by numerous experiments that almost all madder colours may be produced by means of alizarine only and that the finer madder colours of the dyer contain little besides alizarine in combination with the mordants I made some attempts to prove that purpurine contains ready-formed alizarine to which its tinctorial power may be supposed to be due.The optical plieno- rnena exhibited by solutions of yurpurine are however so peculiar 218 SCNUNCK ON THE as to lead Professor Stokes who has carcfully examined them to the conclusion that they cannot be produced by any compoiind of alizarine or by a mixture of alizarine with my other substance hitherto obtained from madder. Neverthelcss it is certain that alizarine and purpurine are nearly allied substances since both of them yield pbthalic acid when decomposed by nitric acid a pro- perty which belongs as far as is known to no other substance with the exception of naphthaline. There is one property by which purpurine may be easily distinguished from alizarine viz. that of being decomposed when its solution in caustic alkali is exposed to the air.The bright red colour of the solution when left to stand in an open vessel soon changes to reddish-yellow and at length almost the whole of the colour disappears after which the purpurine can no longer be discovered in the solution. This is probably the cause of the disappearance of purpurine when the method given by me for the preparation of alizarine from madder -and its separation from the impurities with which it is associated is adopted. This method which depends on the employment of caustic alkalies is an imitation of that to which dyers have recourse for the purpose of improving and beautifying ordinary madder colours and it is certain that during this process the purpurine is either decomposed or by some means disappears.The only advantage which purpurine presents over alizarine in dyeing is that it imparts to the alumina-mordant a fiery red tint which in some cases is preferred to the purplish-red colour fioin alizarine. To the iron mordant it communicates a very unsightly reddish-purple colour presenting a disagreeable contrast with the lovely purple from alizarine. In all madder colours which have been subjected to a long course of after-treatment the purpurine is found to have almost entirely disappeared. For the purpose of convenient reference I have subjoined a table containing the formuh properties and principal reactions of the various colouring matters and their products of decomposi-tion mentioned in the preceding pages.Professor Stokes has had the kindness to draw up for the purpose of being appended to this paper the following account of the optical characters of purpurine and alizarine containing the -HYPOCHLO-1 CONCEN-DILUT3 SUL-LIME AND ALUMIN A PEROXIDE OE SALTS OF OTHER PHYSICAL WATER. ALCOHOL. CHLORINE. RITE OF TRATED SUL PHURIC OR MU-NITRIC ACID ALKALIES. RARYTA. AND ITS IKON AKD LEAD. 31ETALLi C FERMENT S. PROPERTIES. HEAT. LIME. ' PHURIC ACIL RIATIC ACID. SALTS. ITS SALTS. --SALTS. -I_-~ ~~ With acetate 0; Alkaline solix Not affected by yeast Amorphoua Begins to be de Very easily so-Not so easilyso Decomposed bj Decomposed Dissolved witl Decomrosed 01 ' Decomposed 01 Gives blood-re With lime an( Removed fron .. .. shining brittle composed at 130' luble in water re-luble in alcohol aE chlorine giving giving phthalatc a blood-red cc boiling giving boiling giving compounds wit baryta water dar€ its watery solu lead watery solu tions reduce salts or.decomposing crt-not deliquescent C. gives 8 subli. moved from the in water; sepa-chlororubian and of lime. lour and decom alizarine mbire phthalic acid. alkalies ; decolr red precipitates tion by excew o tion gives no pre of gold but no1 Bein albumen &c.-Rubian dark yellow and mt.e of alimrine solution by ani-rated by alcohol grape sugar. posed on boilin) tine ve intine posed by exces soluble in purc hydrate of alu cipitatc ; with ba. salts of silver 01 but easily decomposed transparent in and much char. mal charcoal from its combina- the solution witl rubianine id su of caustic alkal.water. mb. sic acetate of lead copper. by erythrozym giving H3,030 tion aith animal alizarine rubiretine,, blackening. gar. giving alizarin( light red precipi- '56 thin layers veq bitter. charcoil. coal. rerantine rubiafine, tate. rubiretine veriu rubiagine and sugar. - tine rubiadin and sugar- Verazitine C28H10010 Crystallises in long transparent dark yellow nee. dles with much Lustre. -Amorphous pul. verulent reddish. brown. At 100" C loses its water of crys tallisation and be. comes opaque at 216" C. begins tc sublime partlydecomposed leav ing much char-coal. Heated in a tube gives little oily sublimate and much char. coal. Soluble in boil ing ale ohol ;solu tion is dark ye1 low and wheI conceEtrated de posits crystals 01 cooling and stand ing.Slightly soluble in boiling water with a yellowcolour. Almost insolu-ble in cold and boiling water. Soluble in boil ing alcohol anc dcposii ,ed agair on cooling as 2 brown powder. Decomposed by Zhlorine and con- verted into a co- lourless sub-stance. .. .. .. .. Dissolved in thf cold with a yellon colour and no1 decomposed or boiling the solu. tion. .. .. .. ~ Dissolved with a brown colour and decomposed on boiling the so-lution with black ening. ~~-.. .. Decomposed bj boiling nitric acid giving phthalieacid. Decomposed by concentrated ni-tric acid on boil-ing not by dilute acid Dissolves in a1 kalies with viole colour ; solution1 in caustic alkalie; do not change co lour in the air that in ammoni loses its ammonia Soluble in alka. lies with a dirt)brownish-red co.lour. Ammoniacal so. lution gives with ohlorides of cal-5um and barium purple precipi-tates. -Ammoniacal so-ution gives pre- :ipitates with ime and baryta ialts. Not more solu- ble in a boilingsolution of alum than in boiling water ;compoundwith alumina not decomposed on boiling with weak caustic lye. -*. .. Peroxide of iron removes it from its solution in caustic potash or -. I. e. With acetate of iead alcoholic 80. lution gives a pur. ple precipitate,which on stand. ing becomes red. With acetate of lead alcoholic so-lution gives dark brown precipitate Ammoniacal so. lution gives pur. ple precipitate5with salts of sil. ver and copper; alcoholic solution becomes of beau-tiful purple with acetate of copper. -_. Amorphous re- sinous brittle opake dark brown. Softens at 100°C then melts then decomposed.Very little soln- ble in cold and boiling water. Easily soluble in cold alcohol. .. .. .. ,. Dissolved with a yell0 wish-brown colour and de-composed on boil-ing the solution with blackening. .. .. Decomposed by boiling nitric acid and con-verted into a yel- low substance littlealcohol. soluble in Soluble in alka lies with a brown- ish-red colour. ~. ~~ Rubiretine c44H24020 Crystallises in bright lemon-yel. low silky needles Heated in a tube gives littlc yellow crystallinf sublimate and much charcoal. Tolerably solu-ble in boiling water crystallises out again on cool-ing. Soluble in alco. hol. Decomposed by :hlorine and con- Jerted into per- :hlororubian. (2) .. .. Dissolved with a yellow colour and decomposed on boiling the so-lution with black.ening. ,. .. Dissolved byboiling concen-trated nitric acid without being de- composed. Dissolved wit,h difficulty by a1 kalies givingblood-red soh tions. Ammoniacal so-.ution gives red 3recipitates with the chlorides of barium and cal-:ium. .. .. - Soluble in per- chloride of iron 3o1u tion but not con.ierted into rnbiacic acid. With acetate of lead,lution alcoholic gives so-no precipitate. -,-~~ *. Dissolved with .. .. Decomposed by boiling nitric ~~ In Boluble in per-With acetate of chloride of iron. The baryta com- pound crystallises More soluble ir Behaves likt .. .. Crystallises in When heated Almost insolu-yellow needles 01 .. .. .. lead alcoholic so-dark yellow rubianine. entirely rolati ble in boiling alcohol than a Rubiadine ru lution gives precipitate.no colour which acid. in dark brownish- in golden-yellow lised giving sii blimate of yellow changes to yel. red needles solu- water. bianine. glittering scales C32H1309 or four-sided ta micatreom shin lowish-brown on ble in water. bles. ing scales. ---_.__ ---boiling. ------~ Crystallises in When heated Slightly soluble Soluble in boil .. .. -. .. Dissolved with .. .. Dissolved bs Soluble in caus Ammoniacal so-R,emoved from Dissolves in per-With acetate of greenish -yellow entirely volati in boiling water. ing alcohol anc a yellow colour; boiling dilute ni-tic alkalies wit1 lution gives with its alcoholic solu- chloride of iron lead alcoholic so-Rubiacrne needles or in ta. bed giving sii crystallises ou' not decomposed tric acid without a purple colour.:hlorides of cal-tion by exceas of with a dark lution gives a tate. red precipi- bles with much blimate of bril on coolling. on boiling the so. being decomposed :ium and barium hydrate of alu-brownish-red co-dark '32 Hllo10 lustre. liant yellow scales lution. red precipitates. mina. lour and con-verted by boiling into rubiacic acid. Lemon -yellow When heated Slightly soluble Slightly solublt .. .. .. .. Dissolved with .. .. Decomposed by The potash sal Watery solution Watery solution Watery solution .. .. Watery solution powder not crys Fives no crystal in boiling water. in boiling dcohol a yellow colour boiling concen. crystallises 01 of the potash salt of the potash salt of the potash salt of the potash salt talline.line sublimate. which becomer trated nitric acid. cooling of itssolu $ves with chlo-gives F3.h gives reddish-gives with nitrate darker but no1 tion in boilin6 ride of ca€cium an orange -eo-brown with per-of silver a yellow but give8 of pre-precipitate not black on boiling water in long t cryst,alline loured precipi-chloride no iron the solution. silky brick -rec )range -coloured tate. changed on boil-Rubiacic Acid needles; the co precipitate with cipitate. ing the liquid ; lour of its waterj :hloride of ba-with sulphate of C32H9017 solution is red rium a yellow copper a red pre- chloride with mer-but changes tc precipitate. cipitate; of per-purple on the ad dition of caustic cury a yellow potash; the sali crystalline preci- is decomposed OK cipitate.heating with 2 slight explosion I------~ Crystallises in When heated Very little solu- Soluble in boil. .. .. Dissolved not .. .. Dissolved by Soluble in caus- .. .. .. .. Dissolves in per-With acetate of With acetate of yellow shining entirely volati ble in boiling Fa- ing alcohol and decomposed on boiling nitricacid tic alkalies with a :hloride of iron ead alcoholic so-:opper alcohoiic ktli dark brown- ution gives a Iolution gives an Rubiafine ieedles and scales lised giving ye1 ter. crystallises out oc boiling the soh-not decomposed. reddish-purple in low crystalline su cooling. tion. :arbonated alka shprple colour :rimson precipi-)range -coloured c32H1309 blimate. lies :olour.with a red md converted by ,ate. pecipitate.)oiling in:o ru-hic acid. Crystallises in When heated Insoluble in boil- Easily soluble .. .. Dissolved with .. .. Dissolved by Soluble in alka- Soluble in lime .. .. Vary little solu- With acetate of With acetate of yellow needle8 yives little crys. ing water. in boiling alcohol a reddish-brown boilingnitricacid lies with a blood- rid baryta water ble in perchloride .ead alcoholic'so- :opper behaves :ollected in grain! talline sublimate not crystallising colour decom-solution on cool-red colour. vith blood -red )f iron. .&on turns dark like rubiafine. Rubiagine md nodules. and much char-on cooling. posed on boiling ing depositing rolour. yellow and after :oal. the solution with yellow shining iome time gives blackening. needles. )range -coloured :ranular precipi-;ates.--I_-Crystallises in When heated Soluble in boil- Soluble in alco- Decomposed Dissolved with Decomposed on Decomposed by Dissolves in Watery solution Watery solut!on Djssolves in per- With acetate oi Alkaline aolu-Decomposed by ery- tion watery red tions reduce mlts ,hyrozym giving ali- lemon -yellow Tives sublimate ing water and hol. dowly by chlo-i dark red colour boiling giving boiling nitric acid :austic alkalies gives with lime gives no precipi-chloride of iron lead tiirns solu. salts of silver not wine and sugar. dky needles. If alizarine and xystallises out rine products of which becomeE slizari and su- with facility. vith cherry -red water a light red tate with acetste with a greenish-of gold but much charcoal. &gainon cooling ; decomposition be- reddish-brown on Zar.:olour which on precipitate ; with of alumina. bro wn colour the without eving watery solution is ing soluble in wa- boiling the soh aoiling changes baryta water a Bo1i:tion contain-any precipitate ; Rubianic Acid bitter and red-ter. tion little sulphn ;o purple aliza-crimson precipi-ing protochloride. with basic acetate C52H29027 lenslitmus paper. rous acid being rine and sugar tate. it gives a copiouE wolved. being formed ; re& precipitate. Kith carbonate of ?otash,gives silky mce-coloured nee- ---iles of potash salt. Crystallises in Wben heated Soluble in boil-I Soluble in boil-Converted by .. .. .. .. Decomposed on Decomposed by Soluble in alka- Watery solution Watery solution Soluble in per- With acetate of Watery solution lrange -coloured :ives a little ng water and ing alzohol crys- chlorine into per- boiling dying boiling nitric Lies with a blood-turn red with gives no precrpi-chloride of iron lead alcoholic so-gives no..preclpi-ieedles slightly ihite crystalline leposited on cool-talliseri out on chlororubian. chlororubiadine wid giving co-red colour; con-lime water ; with tate with acetate with a brawnish-lntion gives m tate with nitrate Chlororuhian jitter on being ublimate and ng in amorphous coolini; ; solution and grape sugar. lourless solution verted by excess baryta water it of alumim. yellow colour be- precipitate ; with of silver. coming after some basic acetate wa- '44H27C1024 hewed. nuch charcoal. nasses does not redden From which ni-of caustic alkali turns red and on time dark brown.litmus paper. trate of silver pre- into oxyrubian boiling deposits tery solution cipitates chloride with loss of its red flakes and be- gives red precjpi- of silver. chlorine. comes colourless. tate. -I_-~ The baryta com-Alcoholic sola-Insoluble in per-lead alcoholic of Crystallises in When heated Insoluble in boil- Soluble in boil- Converted by ,. .. Dissolved with Dissolved by ni- Soluble in caus-pound formed by With acetateso-Alcoholic solu- mall yellow nee- rives acid fumes ng water. ing alcohol and chlorine into a In orange colour tric acid of sp tic fixed alkalies tion gives no pre-chloride of iron. Son gives with cipitate with ace-lution gives no icetate of copper lles and scales. ,nd a little crys- crystal lises out dark yellow vhich becomes gr.1.52 in the with a purplish-double decompo- tate of alumina. alline sublimate again on cooling ; amorphous resin- iark purple on cold; the soliit.ion red colour and in dtion crystallises precipitate even t copious light Chlororubiadine Lnd leaves much solution reddens ous substance in- )oiling the solu- gives no precipi-ammonia and car- from water in long on adding ammo- xown precipitate. c,2H12CQ :harcoal. bliie litmus paper. soluble in water tion. tate with nitrate bonated alkalies red needles ar-nia also. but easily soluble of silver but on with a blood-red ranged in fan-in alcohol. boiling chloride colour. shaped masses. of silver precipi- tates. I-----Crystallises in When slowly Insoluble in boil- Soluble in boil- Dissolved not ..*. Diasolved by ni-Insoluble in al- .. ,. With acetate of :olourless trans-ieated entirely .iigwater. ing alcohol and iecomposed on tric acid of sp. kalies. lead alcoholic so-lution gives no larent flat four- iolatilised giving crystallises out aoiling the solu gr. 1-52 ; not de- precipitate. ided iridescent I sublimate of again on cooling. bion. composed on boil-Perchlororubian ,ablcs. night micaceous ing the soluticn. C,*H,CW 15 icales ; suddenly ieated it is de-lecomposed with ilight explosion. .~ ---------I 0. Crystallises in When heated Slightly soluble Soluble in boil- Dissolved not .. .. Decomposed by Soluble in alka- Ammoniacal so-Soluble in boil-.. With acetate of ;mall orange-co-tarefully it is n boiling water ing water and decomposed on boiling dilute ni- lies with bright lution gives with ing alum -liquor lead alcoholic so-owed or red rolatilised with-Kith a pink co-crystallisen out boiling the solu tric acid more purplish-red co.chlorides of cal- with a pink co-lution gives a Purpurine ieedles. )ut much residue our. on cooling. tion. easily than aliza- lour; solutions in cium and barium lour not sew purple precipi-:iving a subli-rme. caustic fixed al. purple precipi-ratingprecipitated but on cooling tate not changed nate of shining kalies lose theii tates. on standing, icales and nee-colour by the ac. by muriatic acid which dissolves Ilea. tion of oxygen. on boiling with excess of acetate of lead giving a purple solution. C OLOURLN'G ilI-ir4TERG OF IIIADDER. 219 results obtained by him on a renewed examination of their action oil light.Optical Characters of Purpurine and Alizarine. The optical characters of purpurine are distinctive in the very highest degree; those of alizarine are also very distinctive. The characters here referred to consist in the mode of absorption of light by certain solutions of the bodies and occasionally in the powerful fluorescence of a solution. They are specially valuable because their observation is independent of more than a moderate degree of purity of the specimens and requires 110 apparatus beyond a test-tube a slit and a small prism a little instrument which ought to be in the hands of every chemist. Alkaline solution of purpurine.-If purpurine be dissolved in a solution of carbonate of potash or soda (it is easily decomposed by caustic alkalies,) the solution obtained absorbs with greatest energy the green part of the spectrum.In this and similar cases it is necessary to take care either to use a sufficiently small quantity of the substance or else to dilute sufficiently the solu- tion or view it through a sufficiently small thickness; otherwise a broad region of the spectrum is absorbed and the peculiar characters of the substance depending on its mode of absorbing light are not perceived. If the solution be contained in a wedge- shaped vessel the effect of different thicknesses is seen at a glance ; but a test-tube will answer perfectly well if two or three different degrees of dilution be tried in succession.When the light trans- mitted through an alkaline solution of purpurine of suitable FIG. 1.-Solution of purpurine in carbonate of soda or potash or in ahim liquor. FIG. 2.-Solution of purpurine in bisulphide of carbon. FIG. 3.-Solution of purpurine in ether. FIG. 4. -Alkaline solution of nlizarine. strength after being limited by a slit is viewed through a prism two remarliablc dark bands of absorption (Fig. 1) are seen about SCHUNCK ON THE the green part of the spectrum comprising between them a band of green light which though much weakened in comparison with the same part of the unabsorbed spectrum is briglit compared with the two dark bands which latter in a sufficiently strong solution appear perfectly black.The places of the dark bands estimated with reference to the principal fixed lines of the spectrum are given in the figure. Solation in a solution of alum.-This solutioii has the same peculiar mode of absorption and (Fig. 1) mill serve equally well for it. But it has the further property of being eminently fluor- escent which the alkaline solution is not at all. The fluorescent light is yellow but ordinarily appears orange from being seen through the fluid. The difference between the alkaline and alum- liquor solutions as to fluorescence does not depend on the acid reaction of the latter but on the alumina. A solution exhibiting to perfection the peculiar properties of the alum-liquor solution map be obtained by adding to a solution of purpurine in carbonate of soda a solution of alum to which enough tartaric acid to prevent precipitation and then carbonate of soda has previously been added; and in this case the fluorescent solution is obtained at once and in the cold.This forms a very striking reaction in a dark room according to the method described in the Philosophical Tramactions for 1853 p. 385 with the combination solution of nitrate of copper and a red (Cu,O) glass. Some other colourless oxides besides alumina develop in this manner fluorescence though to a less degree. Solution in hisubhide of carbon.-This solution gives the highly characteristic spectrum (Fig. 2) exhibiting four bands of absorption of which the first is narrower than the others and the fourth is very inconspicuous hardly standing out from the general absorp- tion which takes place in that region of the spectrum.The second and third bands are the most conspicuous of the set. Solution in ether. -This gives the characteristic spectrum (Fig.3) exhibiting two bands of absorption. The solution is fluor-escent but not enough so to be perceptible by common observa- tion. The spectra of the solutions of purpurine in other solvents might be mentioned but these are more than sufficient. In an optical point of view purpurine is remarkable for the general similarity of character combined with diversity as to detail which its various solutions exhibit as to their mode of absorbing light COLOURING MATTERS OF MADDER Alkaline solution of alizarine. -The solution of alizarine in caustic or carbonate of potash or soda or in ammonia exhibits on analysis the characteristic spectrum (Fig.4) having a band of absorption in the yellow and another narrower one between the red and the orange. There is a third very inconspicuous band at E almost lost in the general darkening of that part of the spectrum. Other solutions.-The solution of alizarine in ether or in bisul- phide of carbon shows nothing particular. There is a general absorption of the more ref'rangible part of the spectrum but there are none of those remarkable alternations of comparative trans- parency and opacity which characterize purpurine. Alizarine is hardly soluble in alum-liquor; and in the case of the red solution of mixed alizarine and verantine mentioned by Dr.Schunck at page 451 of the Philoso9hical Transactions for 1851 the absence of the remarkable absorption-bands (Fig. 1) and the absence of fluorescence show instantly and independently of each other that it is distinct from purpurine. Optical detection of purpurine and a2izarine.-The characters of these substances are so marked that I do not know any substance with which either of them could be confounded even if we restricted ourselves to any one of the solutions yielding the pecuhax spectra. Not only so but these properties enable us to detect small quantities in the case of purpurine the merest trace of the substance present in the midst of a quantity of impurities. In the case of purpurine a solution of alum is specially convenient for use because the impurities liable to be present do not with this solvent absorb the part of the spectrum in which the bands occur.In this way I was able though operating on only a very minute quantity of the root to detect purpurine in more than twenty species of the family Rubiacete which were examined with this view comprising the genera Rubia Asperula Galium Crucianella and Sherardia The detection of alizarine by means of the characters of its alkaline solution is much less delicate because many of the impurities liable to be present absorb the part of the spectrum in which all but the least refrangible of the absorption- bands occur; and as this band is not that which corresponds to the most intense absorption a larger quantity of the substance must be present in order that the band may be perceived.VOL. XII. Q

ISSN:1743-6893    

DOI:10.1039/QJ8601200198

出版商:RSC    

年代:1860

数据来源: RSC

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2%2 DEBUS ON XXL-On the Polyatomic Alcohols. A Discourse delivered before the Fellows of the Chemical Society of London. BY DR. H. DEBUS,F.C.S. THEpolyatomic alcohols are derived by replacing in n atoms of water n atoms of hydrogen by an n-atomic basic radical con- sisting either oftcarbon and hydrogen or of carbon hydrogen and oxygen.” For glycol which contains the diatomic radical C2H, we haven = 2. 2 At. of water. Glycol. And if we assume glycerine to contain the triatomic radical C3H5 the formula for glycerine will be-::] -O3 3 At. of water. Glycerine. Compounds among the acids the polybasic acids which corre- spond to the polyatomic alcohols have been known for several years. Mr. Graham’s excellent researches on phosphoric acid and the phosphates led him to the conception of his theory of polgbasic acids which was afterwards adopted and further developed by Liebig.Our present mode of viewing these bodies is chiefly founded on the investigations of Gerhardt and Williamson. The doctrine of polyatomic alcohols principally owes its development to the researches of Wurtz and Berthelot undertaken within the last few years. A. Diatomic Alcohols. Glycol,+ the first body of this class was obtained three years ago by Wurtz by placing iodide of ethylene$ in contact with * n is considered to represent a number greater than 1. + Compt. rend. xliii 199; Inst. 1866 277; Ann. Ch. Pharm. c 110. S Faraday (1821),Ann. Phil. xviii 118; Regnadt Ann. Chim Pbys. lix 367. THE POLYATOMIC ALCOHOLS.acetate of silver ; a lively reaction takes place iodide of silver and acetate of glycol being produced Ag W3O C2H30 ] 0 + (C2H4)”12 = (C2H4)..) 0 + 2 AgI C2H30 1 Iodide of ethylene. C2H3O Iodide of Ag silver. 2 At of acetate of Diacetate of glycol. silver. The diatomic radical ethylene replaces the two atoms of silver in two atoms of acetate of silver and thus unites the two mole-cules to form acetate of glycol. Iodide of ethylene stands to diacetate of glycol in the same relation as iodide of ethgle to acetic ether.* (C2H4)”12 C,H,I Iodide of ethylene. Iodide of ethyle. Diacetate of glycol. Acetate of ethyl& If diacetate of glycol be distilled with hydrate of potash at 250° C. acetate of potash and glycol are obtained.Diacetate of-Hydrate of Glycol. Acetate of potash. glycol. potash. The best mode obtaining monacetate of glycol is by Dr. Atkin-son’s process,? which consists in heating an alcoholic solution of one atom of bromide of ethylene with two atoms of acetate of potash enclosed in a soda-water bottle for two days at 100”C. The liquid is separated from the bromide of potassium subjected to distillation and those portions are collected as monacetate of glycol which come over at lS2O C. * (C2H,)”C12and (C2H4)”Br2,contain in equal volumeB of their vapours twice as much chlorine and bromine as C2H,Cl and C2H,Br. 3. Phil. Mag. Dec. 1858 ; Ann. Ch. Pharm. cix 232. Q2 224 DEBUS ON + (C,H4)”Br = C2W) 0 Bromide of ethy-lene. Acetate of potash.Diacetate of glycol. Diacetate of Alcohol. Monacetate of Acetate of ethyle. glycol. glycol. By distilling monacetate of glycol with hydrate of potash glycol can easily be prepared.* In a similar manner the following glycols homologous to ethylo-glycol have been obtained. (c3it”) o, from propy1ene.t (c4$f) 02,from buty1ene.S (c5~;)’’) o, from amy1ene.Q These bodies are syrupy liquids volatile without decomposition and soluble in water and ethylic alcohol Ethylo-glycol boils at 197” C. propylo-glycol at 188” C. and nmylo-glycol at 177” C.. The exceptional property of this class of homologous substances to boil at a lower temperature as they become richer in carbon and hydrogen is very remarkable. Compounds of these glycols have been obtained by the action of the chlorides bromides or iodides of ethylene propylene or amylene on certain potash or silver salts ; also by the action of acids on these glycols ; and by decomposing potassium or sodium-gly col with iodides.Chemical Properties of the GZyco7s. 1. With monatomic acids they form two ethers by the succes- sive replacement of two atoms of hydrogen by monatomic acid radicals. * Ann. Ch. Pharm. ex,317-8. + Compt. rend. xlv 306 ; lnst. 1857 300 ;Ann. Ch. Pharm. cv 202. $ Compt. rend. xlvi 244. 5 Ann. Ch. Pharm. cvi 24. THE POLYATOMIC ALCOHOLS. Glycol. Monacetate of glycol. Diacetate of glycol. a. Compound obtained by replacing in glycol one atom of hydrogen by a monatomic acid radical,* HI (C2H4)") O, Monacetate of glycol.C2H30 Monacetate of glycol is formed not only by the action of bromide of ethylene on acetate of potash but also by heating equivalent quantities of glycol and anhydrous acetic acid at temperatures not exceeding 170° C. b. Compounds obtained by replacing in glycols two atoms of hydrogen by two monatomic acid radicals either of the same or of a different kind.t Diacetate of Diacetate of et hy lo-gly col. propylo-glycol. Diacetate of 0 bu tylo-glycol. Diacetate of C2H3O These four compounds axe formed by the action of the bromides of the radicals C,H, C3H6 C,H, and C5H10,on acetate of silver. Here also may be mentioned sulphocyanide of ethylene.$ Bruning obtained by the action of an alcoholic solution of' potash on iodoform a substance to which he attributes the formula * A tkinaon.Phil. Mag. Dec ,1858. + Wurta. Compt. rend. xlvi 244; xlv 306; xliii 199 Ann. Ch. Pharm. c 112 ; cv 203 ;cvi 25. $ Bug Ann. Oh. Phrtrm xcvi 302; c 229; Chem. Gm. (1856) 416; Phil. Mag. [4] xiii 374. 226 DEBUS ON The same body was prepared by Buttlerow from iodoform and ethylate of sodium but he represents it as diiodide of methylene CH,I,. With acetate of silver it furnished iodide of silver and a liquid which distilled at about 170° C. and vhich Butt lero w con-siders to be diacetate of methylo-glycol. The latter treated with baryta yielded not methylo-glycol but acetate and formiate of baryta. This subject requires further examination.* 2. If glycol and hydrochloric acid be heated together water and chlorhydrine of glycol are f0rmed.t Chlorhydrine of glycol.Chlorhydrine of glycol will probably yield by renewed treat- ment with hydrochloric acid under suitable conditions &chloride of ethykene and water. 0,Cl + HC1 = (C2H,)”C12 + 0 (CH,H,,.,) Propylo-gig col and hydrochloric acid form chlorhydrine of propylo-glycol and water. 0 + HC1 = H Sulphuric acid which is bibasic and like glycol is derived from two atoms of water yields similar derivatives. Sulphuric acid. UIycol * H (SO,)”) ~~ Intermediate compound. Intermediate compolmd. -(s02)TJl2 (C2H4)”,C12 Dichloride of sulphuryle. Dichloride of ethylene. * Ann. Ch Pharm. cxi 242. (August 1859,) + Compt. rend. xlviii 101; Ann.Ch. Pharm. cx 12F. $ Williamson. Chem. SOC.Qu. J.’vii 18O;rProc. R. S. vii,-ll ;Ann. Ch. Pharm. xcii 242. THE POLYATOMIC ALCOHOLS. Hydriodic acid and glycol form according to temperatures either iodide of ethylene or iodhydrine of glycol and water. (C H)”) 0 + 2HI = + 230 H2 + Iodhydrine of glycol. Chlorhydrine of glycol is rapidly decomposed by caustic potash chloride of potassium oxide of ethylene and water being produced. 0,Cl + KHO = KC1 + 0 + (C2H4)”0 EH*)..) Oxide of ethylene. Oxide of ethylene is isomeric with and has the same vapour density as acetic aldehyde. Oxide of ethylene is decomposed with great violence by pentachloride of phosphorus dichloride of ethy-lene and oxychloride of phosphorus being produced.(C2H4)”0 + PC16 = (C,H,)”Cl + PC130 From oxide of ethylene glycol compounds can be regenerated which substances Wurtx could not obtain from aldehyde. Penta- chloride of phosphorus and acetic aldehyde furnish a body which has the composition of dichloride of ethylene but it is only isomeric and not identical with Dutch liquid. Probably oxide of ethylene is the ether of glycol for it stands to this alcohol as anhydrous sulphuric acid does to-A substance which would bear the same relation to glycol as common ether bears to ethylic alcohol might be obtained by the action of dichloride of ethylene on- 228 DEBUS ON 02 + (C,H,)”Cl = Na (C H )” (C:H:)”) O2 g35) 0 The decomposition of chlorhydrine of propylo-glycol with caustic potash yields oxide of propylene; and no doubt similar derivatives will be formed from other glycols.* 3.If a mixture of hydrochloric and acetic acids be made to act on glycol a body is produced which Simpson calls chloracetine of glycol.? c c c Glycol. Acetic acid. Monacetate of glycol. 0 + HC1 = ‘QH3’ ’.) 0,Cl + i) 0 (C2H4) Bfonacetateof glycol. Ohloracetine of glycol. Chloracetine of glycol is a substance intermediate between Dutch liquid and diacetate of glycol. It is isomeric with chlora- cetine of ethylidine which Simpson obtained by treating acetic aldehyde with chloride of acetyle.1 It can be produced by passing a current of hydrochloric acid gas through monacetate of glycol at 100”C. * Compt. rend. xlvii 346; xviii 101; Ann.Ch Pharm. cviii 86 and cx 126 127;Chem. Gaz. vol. xvii 155. 4-Proc R. S. ix 726; x 114. 2 Compt. rend. Nov. 29 1855. THE POLYATOMIC ALCOHOLS. Chloracetine of glycol and butyrate of silver form butyro- acetate of glycol. -. Chloracetine of glycol. Butyroacetate of glycol. If a stream of hydrochloric acid gas be passed through a mixture of eqiiivalent quantities of butyric acid and glycol at looo chlor-butyrine of glycol if formed. 4 Monobutymte of glycol. (C H4)” 0 +c4H701If HC1 = 0,Cl + 0 Chlorbutyrine of glycol. In a similar way chlorbenzoate of glycol has been produced. Iodacetine of glycol is formed by passing a current of hydriodic acid gas through a mixture of equivalent quantities of glacial acetic acid and glycol.This compound cm&o be prepared with great facility by exposing monacetate of glycol to the action of hydriodic acid gas. -Todacetine of glycol. Chloracetine of glycol chlorbutyrine of glycol chlorbenzoate of glycol iodhydrine of glycol iodacetine of glycol as well as chlor-hydrine of glycol are all decomposed by caustic potash into oxide of ethylene water and potash salts. 230 DEBUS ON Chloracetine of glycol. Acetate of potash + (C2H4)”0 + H,O This process furnishes a convenient method of preparing oxide of ethylene as the chloracetine can be obtained easily in large quan- tities. It is worthy of notice that in this reaction no glycol is reproduced; we also observe that bodies which yield oxide of ethylene in this manner with potash are either glycol in which one atom of hydrogen has been replaced by a monatomic acid radical and the elements of peroxide of hydrogen by chlorine or iodine-or glycol in which only HO has been replaced by C1 or I.Chlorhydrine of glycol. Chloracetine of glycol. On account of this decomposition with caustic potash they might be regarded as compounds of oxide of ethylene with hydro- chloric acid chloride of acetyle iodide of acetyle &c. 4. Glycols produce with monatomic acids neutral compounds corresponding to the ethers of monatomic alcohols; with poly- atomic acids acid bodies analogous to sulphovinic acid. If from a polyatomic alcohol one two or three atoms of peroxide of hydrogen be separated the remaining part of the alcohol comports itself like a mono- di- or triatomic radical.(.“.4)tJ] 0 -2Ho = (C2H4)” H Under some conditions glycol comports itself as if derived from one atom of water and its composition may be represented by the formula THE POLYATOMIC ALCOHOLS. If it be mixed with sulphuric acid and heated to 15q0 C. sulphou glycolic acid* is formed which may be considered as sulphuric acid wherein one atom of hydrogen is replaced by the atomic group C,H,O. Glycol. Sulphoglycolic acid. Sulphoglycolic acid appears to be monatomic. The reactions of glycol with hydrogen and diatomic acids may be conveniently expressed by adopting for glycol the formula (C,H,)”. (HO). HO the diatomic radical C,H, is here represented as combined with peroxide of hydrogen which is monatomic.The formulx of several compounds noticed are accordingly ; (C2H4)”(H0) C1 Chlorhydrine of glycol. (C2H4) ”C1 C1 Dichloride of ethylene. (C2H4)”(H0) I Iodhydrine of glycol. (C,W “I I Diiodide of ethylene. (C2H4)”(C2H302) C1 Chloracetine of glycol. (C,H,)”(C,H,O,) I Iodacetine of glycol. (C2H4)”(C4H702) C1 Chlorbutyrine of glycol. (C,HJ”(C,H,O,) C1 Chlorbenzoate of glycol. (SO,)” Sulphoglycolic acid. H The radicals C,H,O, C,H,O and C7H502,have the composition of the peroxides of the acid radicals of Mr. Brodie and these peroxides would be the radicals of the monatomic oxygen-acids if such acids be regarded as hydrogen-acids constructed on the type HCl. The above formulze of glycol and several of its derivatives are only meant to express the composition of these bodies in a more simple manner with regard to certain changes.5. In contact with potassium or sodium etbylo-glycol loses one * Proc. R. S. ix ’725. 232 DEBUS ON or two atoms of hydrogen which are replaced by metal. The following two compounds have been prepared Na 1 Propylo- butylo- and amylo-glycol comport themselves with potassium or sodium very probably in a similar manner. Iodide of ethyl and 0 decompose each other and produce iodide of sodium and bodies which may be respectively considered as glycol wherein one or both atoms of hydrogen are replaced by ethyl. 0 + C,H,I = H 0 + 2(C,H,I) = Na Monethylate of O, in contact with potassium loses hydrogen and a compound is produced which may be consi- dered as glycol wherein one atom of hydrogen has been replaced by ethyl the other by potassium.0 + K = (CH )" 0 + H C2H5 K2 I Iodide of ethyl acts on (C H )I' 0,and produces iodide of potas-Ka C2H5 I aium and diethyl-glycol. 0 f C,H,I = KI + The latter is isomeric with acetal.* * Wur t z. Compt. rend. xlvii 346; Ann Ch. Pharm. cviii 84. THE POLYATOMIC ALCOHOLS. 6. Pentachloride of phosphorus and ethylo-glycol form hydro-chloric acid oxychloride of phosphorus and dichloride of ethylene.* 7. Chloride of zinc abstracts water from ethylo- and propylo- glycol and converts the one into acetic- the other into propylic aldehyde. H (C H )”lo2 -If4 gl 0 = C,H,O Acetic aldehyde.H d6(C H )”) 0 - O Propylic aldehyde. = C3H60 8. In contact with air or oxygen and platinum-black the glycols oxidize with great rapidity. Nitric acid converts ethylo- glycol into glycolic glyoxylic and oxalic acids. From propylo- and amylo-glycol lactic and butylo-lactic acids have been obtained.? C2H602 C3H802 c4H1002 Glycol Propy lo-glycol. Butylo-glycol. CP403 C3H603 C4H803 Glycolic acid. Lactic acid. Butylo-lacticacid. The acids contain two atoms of hydrogen less and one atom of oxygen more than their corresponding glycols. The same relation exists between the fatty acids and their alcohols. If in glycolic acid two atoms of hydrogen be replaced by one atom of oxygen oxalic acid is formed. From lactic and butylo-lactic acids compounds homologous to oxalic acid will probably be obtained.* Comp. rend. xlv 228; Ann. Ch. Pharm. civ 174. 3. Compt. rend. xlv 306; xliv. 1306; xlvi 1232; Ann. Ch. Pbarm ciii 366; cx 316 ;cvii 197; cv 205 ;Chcm. Gaz. xvii 8; xvi 441 ;xv 341. 234 DEBUS ON C2H403 C3H603 C4H803 Qlycolic acid. Lactic acid. Butylo-lactic acid. C2H204 C3H*O4 C4H604 Oxalic acid. Malonic acid ? Succinic acid ? The composition of these acids and their corresponding glycols may also be expressed by the following formulze. Glycol. Propy lo-glycol. Butylo-glycol. H H 0,; (5.) (C H 0)" 0,; (8.) (C H 0)" H3 H4 "I Glycolic acid. Lactic acid Butylo-lactic acid. H H (3.) (c202)"] 0%; (6.) (C H 0)" H H3 . -Oxalic acid.Mdonic acid ? Succinic acid 1 According to the formulae 2 5 and 8 glycolic- lactic- and butylo-lactic acids ought to be bibasic. Our present experience is very deficient on this point and further experiments are required for its elucidation. If glycol be oxidized by nitric acid glyoxylic acid" is formed together with glycolic and oxalic acids. Glyoxylic acid is an inter- mediate compound between glycolic and oxalic acids just as oil of bitter almonds is intermediate between benzylic alcohol and benzoic acid. C7H80 C2H403 Benzylic alcohol. Glycolic acid. '7"6' C2H203 Oil of bitter almonds. Glyoxylic acid. C7H602 C2H204 Benzoic acid. Oxalic acid. And as oil of bitter almonds and solution of potash decompose each other and produce benzylic alcohol and benzoate of potash so the same alkali with glyoxylic acid forms glycolate and oxalate * On the action of nitric acid on alcohol." Phil.Mag.,Nov. 1856. THE POLYATOMIC ALCOHOLS. of potash; and as oil of bitter almonds oxidiees with great ease and yields benzoic acid so glyoxylic acid takes up oxygen readily and becomes converted into oxalic acid. 2C,H60 + H20 = C,H,O + C7H602 Benzylic alcohol. Benzoic acid. 2C2H203 + H,O = C,H4O3 + C2H204 Ulycolic acid. Oxalic acid. These acids combine with the potash present. C7H60 + 0 = C,H60 Oil of bitter almonds. Benzoic acid. C2H203 + 0 = C2H,04 Qlyoxylic acid. Oxalic acid. A substance between glycol and glycolic acid or glycol and oxalic acid has not yet been obtained from glycol.But from ethylic alcohol by oxidizing it with nitric acid a body of the com- position C,R,O has been obtained. This body combines with bisulphite of ammonia and soda; acts on ammonia like oil of bitter almonds;yields like acetic aldehyde sulphur-compounds with sul-phuretted hydrogen; and is easily oxidized by nitric acid into glyoxylic and oxalic acids two substances which are also produced by the oxidation of glycol; C,H202 seems to be a true aldehyde to glycol and oxalic acid. C2H60 = Glycol. Alcohol. C,H,O = Glyoxal. C,H,O = Oxalic acid. Acetic acid. 236 DEBUS ON H (C2.)’/ 0 + 0 = (C20Y] 0, H H QlyoxaL cflyoxylic acid. (C,.)” 0 + 20 = (C 0J1 0 H ”) €f “I Glyoxal. Oxalic acid.B. Compounds of the aldehydes CnH2,0 and C,H,_,O. a. Acetic aldehyde. Acetic aldehyde is as has already been stated isomeric with oxide of ethylene. From aldehyde a series of bodies can be prepared isomeric with several glycol-compounds and their corn-position is as if they were derived from a diatomic alcohol of the formula With regard to these compounds aldehyde may be represented as the oxide of the diatomic radical C2H4 ethylidine isomeric but not identical with ethylene. 1. Acetic aldehyde and pentabromide of phosphorus form bromide of ethylidine and oxybromide of phosphorus.* (C,H,)”O + PBr,Br = (C,H,)”Br2 + POBr Aldehyde. Bromide of ethylidine. Pentachloride of phosphorus and aldehyde decompose each other in a similar manner.Chloride of ethylidine,? which is isomeric only with chloride of * Wurtz %c Frapolli. Compt. rend. xlvii 418; Ann. Ch. Pharm. cviii 225. .t. Ann. Ch. Pharm. cv 323. 1 IIE POLYATONIC ALCOHOLS ethylene is decomposed by caustic potash into chloride of vinyle and hydrochloric acid the same products of decomposition which are obtained under similar conditions from chloride of ethylene. 2. Hydrochloric acid and aldehyde form water and oxychloride of ethylidhe.* Oxychloride of ethylidine. Oxychloride of ethylidine is decomposed by water into aldehyde and hydrochloric acid it is isomeric with chloretheral. 3. Chloride of acetyle and aldehyde combine and form This body is also produced by the action of chlorine on aldehyde. With solution of potash it fomns aldehyde chloride of potassium and acetate of potash.4. If acetic aldehyde and anhydrous acetic acid be heated in a sealed tube to 18OOC. both unite and form 0 = Acetate of aldehyde$ which boils at 168OC. and is isomeric with diacetate of glycol. Hydrate of potash decomposes this compound acetate of potash and aldehyde being produced. 5. Bromide of ethglidine and $:5) 0 form bromide of sodium and acetal. (C2H,j”Br2 + 22;’s) 0 = 2NaBr + Acetat. * Compt. rend. xlvi 662; Ann. Ch. Pharm. cvi 336. + Cdmpt. rend. xlvii S74; Ann Ch. Phrm cix 156. $ Geuther. Ann. Ch. Pharm. cvi 249 VOL XI1. R 238 DEBUS ON Ethylic alcohol acetic aldehyde and hydrochloric acid produce a liquid which boils at 95°C.and has the formula $H5) 0 + HC1 = ii) 0 + C2H,Cl This compound is decomposed by ethylate of sodium acetal and chloride of sodium being formed. Acetal which is isomeric with diethyl-glycol is also formed by the oxidation of ethylic alcohol. If hydrochloric acid acts on acetal chloride of ethyl occurs amongst the products of decom-position. When chlorine acts on ethylic alcohol the following substances are obtained. C6Hl,C1 0 = Monochlorinatedacetal. C6Hl,C120 = Bichlorinated acetal. C,H,,Cl,O = Trichlorinated acetal. Chloral stands to trichlorinated acetal as aldehyde does to acetal. 6. If a mixture of sulphuric acid water peroxide of manganese and ethylic and methylic alcohols be distilled the following two compounds are obtained.THE POLYATOMIC ALCOHOLS. Acetal wherein one or both atoms of ethyl have been replaced by methyl. The following is a list of those compounds derived from glycol and acetic aldehyde which are isomeric. Aldehyde C2H40 Oxide of ethylene C2H40 Chloride of ethy-(c )/fc12 Chloride of ethy-(c )Icl, lidine 24 lene 24 Chloracetine of Chloracetine of C2H30 et hylidine glycol (C2H4)”! OjC1 Acetate of alde-hyde C2H30 (c2H4)”] C2H30 ‘2 Diacetate ofglycol Acetal 0 Diethylo-glycol b. Valerianic aZdehyde. The aldehyde of valerianic acid has also been combined with acetic and benzoic acids. Acetic acid corn- o2 Benzoic acid pound compound These compounds are respectively decomposed by caustic potash into valerianic aldehyde and acetate and benzoate of potash.* Acetate of vderianic aldehyde is isomeric with diacetate of amylo- glycol.c. Bewoic aldehyde. Pentachloride of phosphorus and oil of bitter almonds form oxychloride of phosphorus and chlorobenzole. (C7H6)”0 + PCl = (C7H6)”C1 + POC13 Oil of bitter almonds. Chlorobenzole. * Guthrie and Kolbe. Ann. Ch. Pharm. cix 298. It2 240 DEBUS OH If chlorobenzole be placed in contact with ::33. 0,chloride of sodium and (E7;?’’\ 0 are produced. c H3 In a similar manner we obtain (g:::] 0 from ethylate of sodium C2H5 acetate of benzole from acetate of silver ‘2 and chlorobenzole and Acetate benzoate and chloride of benzole can be decomposed with caustic potash acetate and benzoate of potash and chloride of potassium together with oil of bitter almonds being respec- tively formed; a corresponding alcohol of the formula CH6) 0, 7 H2 could not be obtained.” With regard to these compounds oil of bitter almonds may be regarded as the oxide of the diatomic radical (C7H,)”.d. Cuminic Aldehyde. Chlorocumole and benzoate of silver yield chloride of silver and benzoate of cumo1e.f * Ann. Ch. Pharm. cii 356 373. -t Ann. Ch. Pharm. cvi 258 ; cix 367. Petersb Acad. Bull. xvii 126. THE POLYATOBlIC ALCOHOLS. Acetate of cumole has also been prepared from acetate of silver and chloride of cumole. Caustic potash decomposes these bodies in a manner analogous to that in which it decomposes the benzole compounds. Meconine and saligenine may perhaps be added to the diatomic alcohols.B er th el ot obtained Stearo-meconine (~$2$Y’’] 0 Cl8H35O Saligenine appears to be the alcohol of salicylous and salicylic acids. Salicylous acid is produced from saligenine by oxidation with chromic acid as aldehyde and acetic acid are from ethylic alcohol. Benzole-alcohol (C7H6)”) 0, derived from chloro- H2 beneole (C7H6)”C1 will be if it at all exist isomeric with saligenine. Saligenine (‘YH6y) 0 332 Saliretine formed by the action of sulphuric acid on saligenine is perhaps the ether of saligenine. Saliretine Salicine may be represented as saligenine wherein one atom of hydrogen has been replaced by C6H 11‘5 (C7H6)” H Salicine c6H11051 ‘2 and populine as saligenine wherein one atom of hydrogen has been replaced by benzoyle C,H50 and another by C6H1,0,.242 DEBUS Oh’ Populine Very little is known of the alcohol of anisic acid C,H,,O,.* C. Triatomic Alcohols. GLYCERINE represents three atoms of water wherein three atoms of hydrogen have been replaced by the triatomic radical (C,H5)”’. H3) C3H5) O,,Glycerine. H3 03 €13 1. This substance combines with monatomic acids with elirnina- tion of water and produces neutral compounds which by resgec- tive treatment with caustic potash or soda hydrochloric and acetic acids and water are decomposed into glycerine and acid. As one two or three atoms of hydrogen can be replaced in glycerine three compounds may be formed from glycerine and the same acid.(C3H5)’’’Io3 II I-,H30) 0 H + O H Glycerine. Acetic acid. Acetine. Glycerine. Acetic acid. Biacetine. + 4-330 Glycerine. Acetic acid. Triacetine. These bodies are obtained by heating mixtures of glycerine and Cannizaro and Bertagnini Cimento i 99; Ann. Ch. Pharm xcviii 188. Liebig and Kopp’s Jahresbericht (1855) 623. THE POLYATOMIC ALCOHOLS. 243 acid in sealed tubes at temperatures varying from 100’ to 300’ C. for several hours. According to temperature pressure and the relative quantity of materials employed one two or three atoms of hydrogen are replaced in glycerine by acid radicals. The pro- duct is treated with slaked lime or carbonate of soda in order to remove the uncombined acid and digested with ether.The compound is left as a residue when the ethereal solution is evaporated. The glycerides as these compounds may be called of the volatile fatty acids are oily liquids; stearine and palmitine are solids ;only few are volatile without decomposition. The following is a list of those compounds which contain a monatomic acid or basic radical that have already been prepared.* MONOGLYCERIDES. (2H5)‘“)-H 0 Glycerine. H 0,Monopdmitine‘ (CHH3 H )”’ 10,Monostearine. ‘18IH35O ‘2H5)”’)H 0,Monobutyrine. (C HH3 H )”’ 10 Monoleine. C,,H330 (2H5)”?-H 0 Monovalerine. (C H H lo3 Benzoycine. )”’ C,H5O DJGLYCERIDES. (C H )”’ H3 10 Diacetine. 0 Dibutyrine. CP3O CP3O * Compt. rend. xxxvii 398; xxxvhi 668 ; Ann. Ch. Pharm. lxxxviii 304 ; xcii 301 305; Chem.SOC. Qu. J. vi 280; vii 222. Chem. Gaz. (1853) 421 ; (1854)340. Jahresbericht (1853)451; (1854) 448; Ann. Ch. Phys [3] xli 216; Proc. R. S.vii 130. 244 DEBUS ON (C H )”’ (C H )’” 1 1 0 Divalerine. ~s~3500 Distearine. C5H@ C5H$0 c,23350 (C H )”’ C2H5 10 Diethyline. H3 C24 Berthelot considers divalerine dipalmitine distearine and dioleine to contain one atom of water more than represented by the above formulse. TRIGLYCERIDES. (C,H5)’/’ ::$#$/ 0 Tripalmitine. C16H310 Tristearine ; identical with ‘3 the stearine of (C,H,) ”’ ‘1c18H330{ 0 Trioleine. SH330 C18H330 0 Tribenzoycine. Some of these compounds as monostearine diethyline distearine tribenzoycine &c.crystallize. Chevreul Pelouze and Gdlis Duffy Heintz and especially Berthelot have furnished important researches on the glycerides. According to the method which the latter chemist employed it seems that some of the compounds obtained by him were not quite pure and the analy- THE POLYATOMIC ALCOHOLS. tical results bear out this supposition. But considering the general chemical comportment of glycerine the formuls given in the above list are most probably a correct representation of the composition of these compounds. 2. The compounds produced by the action of sulphuric tartark arid phosphoric acids on glycerine possess an acid character; corn-bine with bases ; decompose very easily into glycerine and acid by treatment with water ; and may be compared to sulphovinic acid.If the latter be considered as sulphuric acid wherein one atom of hydrogen has been replaced by ethyl then the corresponding compound of glycerine may be represented as sulphuric acid wherein one atom of hydrogen has been replaced by the mona- tomic radical C3H,02 derived from glycerine. The same remark applies equally to tartro- and phospho-glyceric acids. Sulphoglyceric acid" is formed by mixing one part of glycerine with two parts of sulphuric acid. Glycerine. Sulphoglycericacid. Sulphoglyceric acid is monobasic ; the following salts are known :-%:702] Ba 0 Sulphoglycerate of baryta. gb:70210 Sulphoglycerate of lime. Ca :$'"")0 Sulphoglycerate of lead. Pb Tartroglyceric acid is formed by heating equivalent quantities of glycerine and tartaric acid to 150" C.Glycerine. Tartaric acid. Tartroglyceric acid. * Pelouze. (1836.) Ann. Ch. Phys. lxiii 21; Ann. Cb. Pharm. Liebig & W ohler. xix 211. 246 DEBUS ON It appears that only the lime-salt of this acid is known. (C H 0 )” 0 Tartroglgcerate of lime. c: C3H702 1 phosphoric acid 1(PO)IN2H702)0 + (YO) 03=C3H702g 10.. 0 H Qlycerine. Phosphoglyceric acid. Phosphoglyceric acid* is formed by mixing glycerine with solid A compound of this acid is supposed to exist in the yolk of eggs and in the brain; it is dibasic and has furnished the following salts :-0 Phosphoglycerate of baryta. (PO)”’ 0 Phosphoglycerate of lime. Ca (PO)“I 0,Phosphoglycerate of lead.Pb Sebacine being a derivative from glycerine and a bibasic acid has to be mentioned. Glycerine. Sebacic wid. Sebacine. Sebacine is neutral and is decomposed by oxide of lead into glycerine and a lead-salt of sebacic acid. * Compt rend xxi 718; Gobley. J. Pharm. [S] ix 161 ; xi 409 ; xii 5. THE POLYATOMlC ALCOHOLS. Van Bernmelen” obtained succinine benzosuccinine and citro-glycerine by heating glycerine to 220” C. with succinic acid with a mixture of benzoic and succinic acids and with citric acid. These substances are insoluble in water alcohol ether and bisulphide of carbon; their formulze which Van Bem-melen attributes to them are subjoined but no great reliance can be placed on their correctness. (C3HS)/’’ 1 H 0 Succinine.3 If glycerine saturated with hydrochloric acid gas be heated in a sealed tube to looo C. for several hours chlorhydrine and dichlorhydrine are formed.? Glycerine. Monochlorh ydrine. I Glycerine. Dichlorhydrine. Dichlorhydrine and hydrochloric acid at 100’ C. produce epi- chlorhydrine. Dichlorh ydrine. Epichlorh ydrine. When dichlorhydrine changes to epichlorhydrine the radical (C3H5)”’perhaps loses one atom of hydrogen and is converted into the diatomic radical (C,H,)”. In this case the formula of epichlorhydrine mould be (3H4)”) 0,Cl. * Liebig and Kopp’s Jahresber. (1856). 602. t Ann. Chim. et de Phys. (3.) xli. 216; Ann. Ch. Phann. xcii 302 ;Ixxxvii; 311; Liebig Jahresbericht. (1854) 449; (1853) 455 248 DEBUS ON Chlorhydrine boils at 227”C.dichlorhydrine at 178’ C. and epichlorhydrine at about 120” C. Chlorhydrine and clichlorhy- drine regenerate glycerine by treatment with oxide of lead or pot ash. 4 On heating glycerine saturated with hydriodic acid to 100”C. for forty hours iodhydrine is generated.* 2(($3H5)”’l J 0,) + HI = C~H,,IO + ~H,O Iodhydrine. Iodhydrine is not volatile without decomposition ; when treated with potash it yields iodide of potassium a substance resembling glycerine and a body C6H1003,which is probably the ether of glycerine. 0 Oxide of glyceryle Glycerine (2H5)”’) 3 5. The chlorides of phosphorus and glycerine produce the same substances which are obtained by acting with hydrochloric acid on glycerine ; monochlorhydrine dichlorhydrine and epichlorhy- drine as well as small quantities of trichlorhydrine and epidi-chlorhydrine are formed.The last two substances are formed abundantly by the action of PCI on dich1orhydrine.t (23H5Y’’1 0 + PCI = (22H5)’’’) 0,Cl + HCl + PC1,O Monochlorhydrine. (‘,H3”’) 0 + PC1,O = (C,H,)”’,Cl + PH,O H3 Trichlorhydrine. Dichlorhydrhe. Epichlorhy drine. (C,H,)”’C1 -HC1 = (C3H3” C1 Trichlorhydrine. Epidichlorhydrine. * Compt. rend xxxix 748 ; Ann. Ch. Phys. (3) xliii 279; Ann. Ch. Pharm. xcii 311 ; Jahresbericht von Liebig & Kopp (1854) 453. ?. Ann. Ch. Phys. (3) lii 433; Jahresbcricht von Liebig (18571 477. TIIF POLYATOMIC ALCOIIOLS. Trichlorhydrine boils at about 155’ C. and epidichlorhydrine at about 120’ C.; both if heated to 100”C.with moist oxide of silver regenerate glycerine. 6. The derivatives from glycerine and the bromides of phosphorus are very numerous ; monobromhydrine dibromhydrine tribrom- hydrine epibromhydrine hemibrornhydrine acroleine and two compounds C,,H27Br07 and C6H9Br2P,have been obtained in a tolerably pure state.* Glycerine and terbrornide of phosphorus act upon each other as follows :-RJ onobromhydrine Monobromhydriue. Dibromhydrine. The distillation of dibromhydrine with pentabrornide of phos-phorus yields tribromhydrine and a compound C,H,Br,O. (2H5)’”)+ PBr = (C,H,)”’,Br, O,Br + HBr + PBr,O Dibromhydrine. Tribromhvdrine. Epibromhydrine is obtained in large quantities by the action of liquid bromide of phosphorus on glycerine.Dibromhydrine. Epibromhj drine. Along with monobromhydrine dibromhydrine and epibrom- hydrine Berthelot and Luca obtained three substances the formuh of which according to these chemists are C6H$h!o2 C6H,Br2P and C,,H,,BrO,. * Ann Ch. Phys. (3) xlviii 304; Ann. Ch. Pharm. ci 68; Jahresbericht. von Liebig & Kopp (1856) 599. 250 DEBUS ON Glycerine Hemibromhydrine. HBr -11H,O = C,,H,7Br0 Glycerine. The two formulze C,H,BrO and C,,H,7Br07 seem to be not well established and the substances which they represent require further investigation. C,H,Br,P will be considered with the nitrogen derivatives of glycerine. The formation of acroleine by the action of PBr on glycerine is easily understood C,H,O -2H20 = C,H,O Acroleinc.The water which separates from the glycerine unites perhaps with the phosphorous acid produced at the same time. Monobromhydrine dibromhydrine epibrornhydrine and hemi- bromhydrine by treatment with potash and tribromhydrine and C,H,Br,O by treatment with moist oxide of silver regenerate glycerine. Dibromhydrine is the chief product obtained by the action of PBr on glycerine. Epibromhydrine boils at 138”C.; dibromhydrine at 219” C.; hemibromhydrine below 200° C.; tribromhydrine at about 180” C. ;and monobromhydrine in vacuo at about 180”C. These five substances are neutral liquids. Tribromhydrine (C,H,)”’Br, brominated bromide of propylene (C,H,Br)”,Br, and terbromide of allyle obtained by the action of bromine on iodide of allyle are isomeric but not identical; only the first and last are able to furnish glycerine.7. The action of iodide of phosphorus on glycerineis represented by the following equation.* (C3H5)”’1 H 0 + PI = (C3H5)’,1 + PH,U + I Y Glycerine. Iodide of allyle. Phosphorous acid. The teratomic radical glyceryle (C,H,) ’”,changes in this reaction and becomes converted into the monatomic radical allyle. Besides iodide of allyle some propylene C,H6 is formed in consequence of a secondary reaction. * Ann. Ch. Php. (3) xliii 257; Ann. Ch. Pharm. xcii 306; Jaliresbericht (1854) 451. TIIE POLYATOMIC ALCOHOLS. 8. Compounds derived from glycerine with more than one acid chloride or bromide have next to be considered.* Dibrom-hydrine and pentachloride of phophorus produce hydrochloric acid oxychloride of phosphorus and chlorhydrodibromhy drine.O,Br + PC130 + HCl (2H5)’’’1+ PCl = (C,H,)’”,Cl,Br2 Dibromhydrine. Chlorhy drodibromhy drine. From dichlorhydrine and pentabrornide of phosphorus bromhy- drodichlorhydrine is obtained. (2H5)’N{ O,Cl + PBr = (C3H5)”’,Br,C1 + PBr30 + HBr Dichlorhy drine. Bromhydrodichlorh ydrine. Chlorhydrodibromhydrine and bromhydrodichlorhydrine are neutral liquids which regenerate glycerine by treatment with moist oxide of silver. Instead of chlorine or bromine the atomic group (C,H,O)’O derived from acetic acid may be introduced into these substances. Chloride of acetyle and glycerine form acetochlorhydrine acetodichlorhydrine and water.+ C,H,O,Cl = + Chloride of acetyle. Glycerine. Ace tochlorhy drine. Acetochlorhydrine. Acetodichlorhy drine. Acetochlorhydrine and acetodichlorhydrine are neutral liquids volatile without decomposition. The action of chloride of acetyle on a mixture of glycerine and acetic acid produces diacetochlorhydrine. * Ann. Ch. Phys. (3) lii 433; Liehig’s Jahreahericht (1857) 416. 252 DEBUS ON Glycerine. Chloride of acetyle. Acetic acid. 02,C1 + 2H20 Diacetochlorhydrine. If a mixture of equivalent quantities of chloride and bromide of acetyle be allowed to act on glycerine acetochlorhydrobrom- hydrine is formed. (c3H5)”’1 0 $-C,H,O,Cl + C,H,O,Br H3 Glycerine in contact with hydrochloric acid and benzoic acid produces benzochlorh ydrine.02C1 + 2H20 Benzochlorhydrine. Diacetochlorhydrine and acetochlorhydrobromhydrineare new tral liquids volatile without decomposition. The majority of the compounds enumerated under 3 5 6 and 8 may be considered to be formed according to the subjoined equation where n is equal to 1 2,or 3 A stands for one atom of mon-atomic acid and B denotes the compound formed. The formation of trichlorhydrine may be taken as m example. (Y5)’’’! 0 + 3 HC1 -3 H20 = (C,H,)’”,Cl THE POLYATOMIC ALCOHOLS. Nevertheless there are some compounds which are not formed in accordance with this equation as exemplified in epidichlor-h ydrine. ($3H5)’’’) 0 + 2 HC1 -3 H,O = (C,H,)%12 E pidichlorbydrine. Epidichlorhydrine is able nevertheless if treated with moist oxide of silver to regenerate glycerine.In most cases if hydrochloric acid or the chlorides or bromides of phosphorus act on glycerine the elements of peroxide of hydrogen separate from the latter and for HO one atom of chlorine or bromine enters the compound ;but if oxygen acids such as acetic acid act on glycerine the latter exchanges HO for the peroxides of the acid radi‘cals discovered by Mr. Brodie. Monochlorhydrine. Dichlorhydrine. (C3H5)”’1 J 0 -3H0 + 3C1 = (C,H5)’”C13 H3 Trichlorhydrine. Acetine. The formula of glycerine may therefore be htten (C3H5)’” HO . HO . HO and expressions for its derivatives obtained by substituting for HO either bromine chlorine or one of the peroxides of the acid radicals.This mode of representation has been adopted in the following list which contains the compounds mentioned under 3 5 6 and 8. But I wish it to be understood that I do not mean to say that peroxide of hydrogen preexists in glycerine but merely that in certain reactions the elements HO are exchanged for chlorine bromine or compound bodies. VOL. XII. 42 254 (C3H5)”’(HO) (HO) (C,H,)”’(HO) (HO) (C3H,)”’(HO) (HO) (C,H,)”( HO) C1 (C,H,)”’(HO) Br (C3H,)’” c1 C1 (C3H5)”’ Br Br (C3H5)” Br c1 (C,H,)” C1 Br (c3H5)l”(H0) (C2H302) (C3H5)”’(C,H30,)(C,H,02) (C3H~)”’(C2H302)c1 (C3H5)”’(C2H302) Br DEBUS OW (HO) Glycerine. C1 Monochlorhy drine. Br Monobromhy drine. c1 Dichlorhydrine. Br Dibrom hydrine.c1 Trichlorhydrine. Br Tribrornh ydrine. c1 Bromhydrodichlorhydrine. Br Chlorhydrodibromhydrine. c1 Acetochlorh y drine. c1 Diacetochlorh ydrine. c1 Acetodichlorhydrine. c1 Acetochlorhg drobromh ydrine. (C3H,)”‘(C,H502)(HO) c1 Benzochlorhydrine. The following compounds cannot be derived in this manner from glycerine because their formation does not take place accord- ing to the equation mentioned on page 252. (C3H5)”’)E; = (C3H,)” C1 = C,H ,lo3 C6H9Br0 C3H7Br30 (C3H,)”) (go)’Epichlorhydrine (C,H4)’’I gi Epidichlorhydrine. Iodhydrine. Hemibromhydrine. Compound of dibromhydrine and { hydrobromic acid ? 9. Glycerine and hydrate of potash form with evolution of hydrogen formiate and acetate of potash.* ---_-Glycerine -4cetate of potash.Formiate of potash. + 4H + H,O Dumas and Stsas Ann Ch. Phys. lxdii 148; Ann. Ch Pharm. xxxiv 129. THE POLYATOMIC ALCOHOLS. 10. A mixture of anhydrous phosphoric acid and glycerine on being subjected to distillation yields acroleine. H, C3HdI03 -2H2O = C,H,O Glycerinr Acroleine. 11. Monochlorhydrine acts on ammonia* and forms the hydro- chlorate of a base which Berthelot calls glyceramine. C3H,02,C1 + N {::I. Monochlorhydrine. (H Hydrochlorate of glyceramine. According to Berthelot if a stream of ammonia gas be passed through a solution of dibromhydrine in anhydrous alcohol bromide of glyceramine is formed The production of the latter from ammonia and dibromhydrine is intelligible only when we assume that one atom of water takes part in the reaction.C,H,O,Br + H,O + 2NH = N + HBr + NH,Br Dibromhydrine.' Hydrobromate of glyceramine. Tribromide of allylet acts easily on ammonia and forms a base called dibromally1amine.S C,H,,Br + NH = C,H,Br + NH,Br Tribromide of allylc. and- 2((B 'aH .>''Br) + 3NH = N H Dibromallylamine. In this instance two atoms of the monobrominated radical allyle replace two atoms of hydrogen in ammonia and form the base in question. The presence of another atom of hydrogen in * Ann. Ch. Pharm. ci 76. t Ann. Ch. Pharm. civ 247. 5 Phil. Mag. [4] xvi 267 ;Ann. Ch. Pharm. cix 362. s2 256 DEBUB OW the latter replaceable by other radicals was proved by treating dibromallylamine with iodide of ethyl ; ethyldibromallylamine was thus obtained.By treating glycerine with liquid bromide of phosphorus Bert helot obtained a substance* of the composition C6H9Br2P. If in this formula the phosphorus be replaced by nitrogen we have the formula of dibromallylamine. It is probable that these two substances have a similar constitution and are related to each other as triethylamine is to triethylphosphine. 12. Nitric acid oxidizes glycerine with great ease the result of the reaction being an acid called glyceric acid.? C3H,0 + 0 = C,H604 + H20 Glycerine. Glyceric acid. Glyceric acid is formed from glycerine in a manner analogous to that of acetic acid from alcohol or glycolic acid from glycol; two atoms of the hydrogen of the alcohol being replaced by one of oxygen.The acid which stands to glyceric acid in the same relation as oxalic does to glycolic acid or malonicz to lactic acid appears to be the tartronic acid of Dessaignes.§ C,H*O3 C3%03 C3H6O4 Glycolic acid. Lactic acid. C,H,O4 C3H404 -Oxalic acid. Malonic acid. Tartronic acid. Although the formation of tartronic a4 from glyceric acid ias not yet been experimentally established other properties point out the existence of an intimate connexion between these two substances. The oxidation of propylo-glycol yields according to the condi-tions of the experiment lactic OP glycolic acid.11 * Ann. Ch. Pharm. ci 73. t Phil. Mag. Narch 1858; Ann. Ch. Pharm. cvi 81. $ Ann. Ch. Pharm. cvii 251.5 Compt. rend. xxxiv 731 ; Ann. Ch Pharm. lxxxii 362 j Ixxxix 339 ;Jahres-bericht (1852) 475. II Ann. Ch.l’harm. cv 204-5. THE POLYATOMIC ALCOHOLS. Lactic acid. (8,H$’’)-0 + 50 = C,H,O~ + co + ~H,O Cllycolic acid. Glyceric acid may be converted into lactic acid,* and tartronic into glycolic acid. The transformations of glyceric and tartronic acids and their composition support the view therefore that they are connected in the same manner as oxalic and glycolic acids. According to our knowledge of several salts of glyceric acid this substance appears to be monatomic. But if we consider its deri-vation from glycerine the view of M. Wurtz,? who considers glyceric acid to be triatomic is very probably correct. (23H30)”1 0 Glyceric acid.This point however requires further investigation. Thus by a variety of reactions me recognize glycerine to be derived from three atoms of water and to contain three atoms of hydrogen replaceable by other radicals and the triatomic radical (C,H,). Accordingly me obtain from glycerine and a monatomic acid at least three compounds corresponding to the ethers of common alcohol and with hydrochloric acid at least three chlorides the formation of which takes place in a manner analogous to that of chloride of ethyl from 2H51 0 or of chloride of potassium from ]0. The same reaction which occurs once in these two instances repeats itself in the case of glycerine three successive times. The great number of compounds which can be prepared in this way by changing the acids may be considerably augmented by employing two or three different acids at the same time as illustrated by the following examples.(C3H5)”’ (HO) (HO) (HO) Glycerine. (C3H5)”’(HO) (C2H3O2} C1 Acetochlorhydrine (C,H5)”‘ Br (C2H302) C1 Acetochlorhydrobromhydrine. * Ann. Phm. cis 227; Phil. Mag. December 1858. 3. Soei6tC Chimique de Paris (13 Mai 1859) 38. 258 THANN AND WANKLYN ON THE ACTION OF But the triatomic radical C3€I, by a modification in its consti- tution connects the glycerine series with other interesting com- pounds. Under the influence of iodide of phosphorus iodide of allyle is formed from glycerine in which the radical C,H is monatomic. From iodide of allyle allylic alcohol and its deriva- tives can be prepared as well as glycerine be regenerated.Acro-leine the aldehyde of allylic alcohol may also be produced by the direct action of phosphoric acid on glycerine. Iodide of allyle hydrochloric acid and mercury generate propylene ;and the dibro- mide of the latter enables us to prepare propylo-glycol and its derivatives including lactic acid If sulphuric acid which has been allowed to absorb propylene be distilled with water propylic alcohol is obtained and the preparation of the numerous bodies of the propylic series becomes practicable. Thus we find propylic alcohol propylo-gl ycol allylic alcohol and glycerine and their respective derivatives intimately connected. (C,H,) monatomic in. . 9H5)’ 10 Allylic alcohol. (C,H,)”’ triatomic in .. H3 Glycerine. (C,H,)”’,H . . = (C3H6)”,diatomic in (C3HJ’ .H I0 J (C,H,)’”,HH . = (C3H,)’ monatomic in Propylo-glycol. . (yv’) 0 Propylic alcohol.

ISSN:1743-6893    

DOI:10.1039/QJ8601200222

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

258 THANN AND WANKLYN ON THE ACTlON OF XXTI.-Action of Metals upon Iodide of Ethylene C4€1412. By CARLVONTHANand J. A. WANKLYN. WHENzinc acts upon iodide of ethyl it combines both with the iodine and with the ethyl producing iodidc of zinc and zinc-ethyl. METALS UPON IODIDE OF ETHYLENE In like manner it seemed possible that zinc would act upon iodide of ethylene in such a manner as to give iodide of zinc and a compound of zinc with the biatomic radical ethylene thus :-(C,H,)"I + Zn = (C,H,)"Zn + Zn,I We have tried the experiment using ether to dissolve the iodide of ethylene and obtained a negative answer as regards the production of a compound of the biatomic ethylene with zinc. Our research was conducted as follows :-The iodide of ethylene was prepared by passing olefiant gas over iodine gently warmed with hot water.The product was freed from excess of iodine by means of a solution of caustic potash washedand dried by pressure between folds of bibulous paper; afterwards it was exposed for a short time in vacuo over sulyhuric acid. The ether was dried by standing over solid caustic potash. The zinc mas pretty pure and finely granulated. A few grammes of this iodide of ethylene were introduced into a glass tube along with zinc and ether and hermetically sealed therein before the blowpipe. The tube so prepared was kept at ordinary temperatures and in the dark. Large quantities of a combustible gas were gradually evolved This gas was allowed to escape from time to time by opening the tube; and some of it was collected over water transferred to the mercurial trough and aiialysed when it proved to be perfectly pure olefiant gas as the following particu- lars of rhe analysis show :-Volume Pressure in Metres.I---I-I I Tempe-rature Centi-grade Volume at 1 metre and 0°C. Volume of gas taken . . . . . . . . 83 *5 0 -1483 1'7.8" 11 *61 After the addition of oxygcn .. .. 46'7'6 0 5272 17.7" 231 5 After the explosion . . . . . . . 440.8 0 5022 11.5" 208 '1 After the absorption of carbonic acid . . 409-8 0 -4860 20.9" 185 0 Found Calculated for C4H4 Volume taken . . 11-61 1106% Contraction . . . 23-40 23.24 Carbonic acid . 23.10 23-24 Oxygen consumed 34.89 34.86 260 THANN AND WANKLYN ON THE ACTION OF That the gas was not a mixture having the same percentage composition and condensation as ethylene was proved by its complete absorption by fuming sulphuric acid.The residue in the production tube consisted apparently of nothing beyond iodide of zinc dissolved in ether. Some of the contents were withdrawn and treated with water with which they did not effervesce ; the rest were distilled directly fkom the produc- tion tube a cork and bent tube having been previously adapted thereto. This distillation i~ascommenced in the water bath and finished over the naked flame. No product containing zinc dis- tilled over. No compound of ethylene and zinc seems there- fore to be formed by this process and the reaction which actually takes place may be thus written :-(C4H4)”IQ+ Zn = C[H4 + Zn,I With other metals we have obtained similar results.Sodium with ethereal solution of iodide of ethylene evolves gas rapidly at ordinary temperatures. This gas was evidently ethylene as it was soluble in fuming sulphuric acid after it had been free from ether vapour by washing with water. The iodide of sodium which formed simultaneously with the gas was coloured blue. A blue coloration of iodide of sodium had been previously remarked by one of us when iodide of ethyl ether and sodium are brought together. Mercury also evolves gas when placed in an ethereal solution of iodide of ethylene. In that case the evolution takes place slowly; but ultimately an immense quantity of gas is given off even when the experiment is conducted at ordinary temperatures and with exclusion of light.At the same time iodide of mercury makes its appearance and gradually assumes the red modification. No signs of any combination between ethylene and mercury were observable. We have also extended our experiments to chloride of ethylene (C4H4)”C12 (Dutch liquid). This liquid mixed with-dry ether is not acted upon by zinc either at ordinary temperatures or in the water bath. By sodium however it is attacked when gently warmed even though the heating falls considerably short of 100OC. Olefiant gas and blue chloride of sodium are the products. The gas was collected over water and subsequently treated with strong sulphuric acid by which it was perfectly absorbed proving tha entire absence of frce hydrogen.NETBLS UPON IODIDE OF ETHYLENE. The reactions established in this paper are of interest in relation to the theory of biatomic radicals and may be regarded as cases in which the biatomic radical ethylene is isolated. Just as under certain conditions iodide of ethyl yields ethyl when acted upon by zinc so does iodide of ethylene yield ethylene when treated with that metal. The parallelism bet ween the following equations is obvious :-~(c,H,I) + Zn = z~,I,+ 3:s-j-45 (C4H,)”I + Zn = Zn,T -k C,”H4 It is our intention to seek for metallic combinations of the biatomic radical ethylene by the employment of other methods than the one mentioned in this paper.

ISSN:1743-6893    

DOI:10.1039/QJ8601200258

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

NETBLS UPON IODIDE OF ETHYLENE. XXIU-Researches on the Atomic Weight of Graphite. BY B. C. BRODIE, F.R.S. PROFESSOB OF CHEMISTRY IN THE UNIVERSITY OF OXFORD AND PRESIDENT OF THE OHEMICAL SOCIETY. [For the numbers of the analyses given in this communication and for other details see the author’s paper on the Atomic Weight of Graphite in the current number of the Philosophical Transactions.] THEfollowing research was undertaken with the hope of throwing light upon a very obscure problem the nature of the allotropic conditions of the elemental bodies. My object was to ascertain whether this difference of condition was to be regarded as apurely physical or as a chemical difference of matter. If it were a chemical difference then different allotropic forms must exhibit different chemical reactions and it was to be anticipated as not improbable that these different forms might even enter into com- bination with different combining weights.No fact of this nature has yet been ascertained; but among the physical properties of the allotropic forms of the elements there mas one which mill hereafter be referred to by which this result was indicated. In the great majority of cases the allotropic conditions of an element are 262 BRODIE ON so easily convertible and have so little permanence that we could hardly hope to discover any chemical difference between them even if such exists. Certain instances however may be found of more permanent forms; of which the most remarkable is that of the forms of carbon.The forms of carbon are identified by the fact that by combustion in oxygen they can all be converted into one and the same substance carbonic acid ;but this transforma- tion requires great heat; and within a very considerable range of temperature the forms of carbon are unaffected by those causes which in other cases determine the transition of the allotropic forms of an element into its one most permanent state. therefore:examined with care the chemical reactions of carbon. Some account of that remarkable substance which afforded the material of this iuquiry may not be without interest The term graFhite has been applied indiscriminately to several varieties of native carbon which have but little in common. Among these however two may be especially distinguished by their superior brilliaucy and by their mstallic streak.The one of these varieties possesses a distinct lamellar structure and the lustre of a metal; in appearance it resembles molybdenum ; the other is amorphous and appears as a powder of a silver-grey colour. The lamellar graphite is imported into this country chiefly from Ceylon where it is found in large masses associated with quartz. It exists also in many other localities; at Travancore and in Spain and in small quantities is frequently discovered associated with volcanic minerals. The amorphous graphite is now chiefly procured from Germany ; I believe from Passau in Bavaria. Formerly mines of it existed at Borrowdale in Cumberland but these are nearly exhausted.It is of much less frequent occurrence than the other kind. In the following investigation the term graphite is limited to these two varieties. The lamellar graphite is also formed artificially during the process of iron smelting when it is dissolved by and combines with the iron. On dissolving cast iron in an acid a residue is left of from 3 to 4 per cent. of graphite. I know of but one example of the artificial formation of amorphous graphite; the carbon which is deposited on the electrode during the passage of the electric light is in this condition. This carbon is soft amorphous and has the streak of a fine black-lead pencil. This change is doubtless effected by the intense heat the extremities of both poles being in the same condition.Of thc other varieties of THE ATOMIC WEIGHT OF GEUPHITE. native carbon which have been vaguely termed graphite at least two exist in large deposits. A deposit of carbon is found in New Brunswick very similar in appearance to anthracite coal. In Greenland also there is a large deposit of carbon which is in its properties intermediate between this and the true graphite. Several applications have been made of graphite in the useful arts. Mixed with clay it is employed in the manufacture of the crucibles used in gold refining. It is also extensively used for the glazing of certain varieties of gunpowder specially that employed for blasting. The graphite is finely ground and the gunpowder rolled with it in iron cylinders. It is also used for the protection of iron from rust and mixed with grease for the lubrication of machinery.Its most important application is for the manufacture of pencils. For this purpose it is consolidated by pressure into blocks fiom which the pencil is afterwards cut or it is mixed with an aggregating material made into a paste and moulded into the required form. The ingenious process of the late Mr. Brockedon for the compression of black lead for pencils is well known. The first experiment in which I succeeded in eliciting a differ- ence in the chemical reactions of the different forms of carbon was in the action upon them of a mixture of concentrated nitric and sulphuric acids. When finely-divided carbon in the form of lamp-black or charcoal from the decomposition of sugar is heated with a mixture of 1of nitric and 4 of sulphuric acids the carbon is rapidly oxidized and a black substance is formed soluble in the concentrated acid but precipitated on the addition of water.This substance is insoluble in acids and saline solutions but is soluble in pure water and in alkalies. It is accompanied with other pro- ducts which render its purification difficult. When the graphite of Ceylon is treated in a similar manner the result is very different; the graphite becomes of a beautiful purple colour and falls to pieces in the flnid. The substance after the acid has been washed from it by water has much the appearance of the graphite itself but is darker in colour. It was found on analysis to contain the elements of sulphuric acid combined with oxygen with hydrogen and with a large amcjunt of carbon.Iwy efforts to procure this substance of a constant composition have been unavailing ;it is insoluble in all reagents ;it may be boiled with a strong solution of potash without separation of sulphuric acid and with slight if any alteration of weight. When heated it 264 BRODIE ON undergoes a remarkable change; gases are given off in the interior of the substance which swells up in a singular manner and is reduced to the minutest state of division. The residue consists of carbon which has the appearance and the structure of the lamellar graphite. This decomposition may be compared in its appearance with that which the chromate of ammonia undergoes by the action of heat.The experiment may be applied to the disintegration and purification of graphite for purposes of the arts with which Fiew the process has been patented. Its details are as follows One pound of powdered graphite is mixed with 4 pounds of concen- trated sulphuric acid with this is mixed 1 ounce of powdered chlorate of potash. The mixture is heated until chlorous fumes cease to be evolved; the residue is thrown into water washed out dried and ignited. The ignited substance is washed in water in which it floats while the impurities fall to the bottom. It is then dried. By this process graphite may be obtained in a state of chemical purity. These experiments established a point of considerable import- ance the existence of a peculiar compound of carbon in the form of graphite.Its discovery led me to turn my attention to tlie oxidation of graphite. I found that graphite heated with a mixture of nitric acid and chlorate of potash increased in weight and that the substance formed was on the application of heat disintegrated with evolution of gas. The disintegrated substance differed but little in appearance from the original graphite. I found however that when the substance formed by the treatment of graphite with the oxidizing mixture was washed free from the salts produced in the reaction dried at looo and again oxidized it gradually underwent a change in appearance until after the fourth and fifth repetition of the process the whole of the graphite was converted into a substance of a light yellow colour consisting of minute transparent and brilliant plates Analysis further showed that this change was attended with a gradual alteration of the constitution of the substance but that finally a time arrived when further treatments with the oxidizing mixture produced.no further change. It is remarkable that this change cannot be produced by one prolonged treatment; before the oxidation can proceed the original conditions must be restored. The details of this process are as follows :-A portion of graphite THE ATOMIC WEIGHT bF GRAPHITE. is intimately mixed with three times its weight of chlorate of potash and the mixture placed in a retort. A sufficient quantity of the strongest fuming nitric acid is added to render the whole fluid.The retort is placed in a water-bath and kept for three or four days at a temperature of 60"C. until yellow vapours cease to be evolved. The substance is then thrown into a large quantity of water and washed by decantation nearly free from acid and salts. It is then dried in a water-bath and the oxidizing opera- tion repeated with the same proportion of nitric acid and of chlorate of potash until no further change is observed; this is usually after the fourth time of oxidation. The substance is ultimately dried first in vacuo and then at 100". A modification of the process which may be advantageously adopted consists in placing the substance with the oxidizing mixture in flasks exposed to sunlight. TJnder these circumstances the change takes place more rapidly and without the application of heat.The analysis of this substance when the necessary correction is made for the residual ash gave the following numbers the mean of nine concordant determinations. Carbon . . 61-04 Hydrogen . . 1-85 Oxygen . . 37.11 1oo*oo These numbers correspond with the formula C,,H,O (C = 12) which requires CII ' . 132 61.11 H4 ' . 4 1.85 06 ' . 80 - 37.04- 216 1oo*oo The crystals of this substance were ascertained by Professor Miller of Cambridge to belong either to the prismatic or the oblique system. It is insoluble in water containing acids or salts but is very slightly soluble in pure water. It combines with alkalies and the crystals have an acid reaction Agitated with dilute ammonia it is converted into a transparent jelly but the substance is not dissolved.On the addition of acids it is separated unaltered from this combination as a gelatinous mass 266 BRODIE OK r-sembling silica. Treated with clcoxidizing agents it is readily decomposed. When a solution of sulphide of ammonium or of potassium is poured upon the dry substance a crackling sound is heard and a body is ultimately formed possessing the metallic lustre and general appearance of graphite itself. Changes similar in appearance take place on boiling the Substance with an acid solution of protochloride of copper and of protochloride of tin. The crystals on the application of heat are decomposed with ignition; gases are evolved and a black residue is left of a body resembling in appearance finely.divided carbon. I propose for this substance the name Graphic acid. I have in vain attempted to procure the product of the decom- position by heat of the graphic acid until it occurred to me to effect the decomposition in a fluid medium by which the particles of the substance were separated &om one another and elevation of temperature precluded. The fluid which I selected for the experiment was the mixture of hydrocarbons of high boiling points from the Itangoon naphtha. When graphic acid is heated in this fluid to a temperature of about 270° water is given off and a brisk evolution ensues of carbonic acid the hydrocarbon at the same time becoming of a deep red colour.The residual substance resembles graphite and gave as the mean of several analyses the following numbers Carbon . . 80.13 Hydrogen . . 0.58 Oxygen . . . 19-29 100*00 which correspond with the formula C,,H,O,. c22 * . 264 80.00 H . 2 0.60 04 ' . 64- 19.40 330 100~00 When this substance is heatedin a current of nitrogen to a temperature of 250° il further change ensues; water is given off THE ATOXIC WEIGHT OF GRAPHITE. accompanied by a small quantity of carbonic oxide. An analysis of the resulting substance gave the following numbers Carbon . . . 81-8Q Hydrogen . . 0.44 Oxygen . . 17.76 100-00 which corresponds with the formula CG6H4Olwhich requires C66 792 81.48 H4 ' * 4 0.41 01 176 - 18.11 7- 972 100~00 This substance would be derived from the preceding by the elimination of 1 atom of water from 3 atoms of the original substance.On a greater elevation of temperature carbonic acid carbonic oxide and water are again evolved but the body may be exposed to a red heat for several hours in a current of nitrogen and only undergo a very partial decomposition the residual substance still containing a considerable portion both of hydrogen and oxygen. Buff and TVGhler have recently discovered a remarkable series of compounds derived from the graphitoidal form of silicon,* among which is a compound of silicon hydrogen and oxygen of the formula Si,H405. The general properties of this substance correspond very closely with those of the graphite compound as separated from its combinations by an acid.It is described as a white and voluminous body which floats upon water in which it is very slightly soluble. We may therefore reasonably infer that the graphite-compound is the same term in the system of carbon as the silicon-compound in the system of silicon. When we pro-ceed to state this analogy in the formula of the substance we are led to very remarkable conclusions. The total weight of graphite which in the compound is combined with 4atoms of hydrogen and 5 of oxygen is 132. If we assume that this weight is like the corresponding weight 84 of silicon to be divided into 4 parts we arrive at the number 33 as the atomic * Ann Ch. Pbarm vol civ. p. 94. 268 BRODIE ON THE ATOMIC WEIQHT OF GRAPHITE.weight of graphite. Representing this weight by the lettcrs Gr. the formulae of the substances CllH405,C2,H904 and Cs6H4Ol1 become Gr,H,0,,Gr,H20 and Gr, H,O 1. There is a property of graphite by which these formulae may be tested. According to the law of Dulong and Petit the specific heats of the elemental bodies vary inversely with their atomic weights. The elements are divided into two classes the one in which the product of the specific heat into the atomic weight is approximately 393 the other in which this product is approximately 6%. This law expresses the only common physical property by which these weights are characterized. The specific heat of carbon however presents a remarkable exception to it.It differs in the different allotropic forms of carbon. The specific heat of native graphite as determined by Regnault is 0.20187. Now 6 x 0*201=1.206and 12x 0.201=2*412,which are not within the limits of error. But if we assume the atomic weight of graphite as 33 we have for the products of the specific heat into the atomic weight the number 6.6 which is according to the law this product being the same as the product of the specific heats into the atomic weights of the elements phosphorus antimony arsenic bismuth and iodine. The relation also which exists bttween the atomic weights of boron silicon and zircon and that form of carbon for which a place may be claimed as a distinct element graphon is precisely the kind of numerical relation which is found to exist between the weights of analogous elements.We have Boron . . 11 Silicon . . 21 Graphon . 33 zircon . . 66 These considerations lead to the remarkable inference that carbon in the form of graphite functions as a distinct element that it forms a distinct system of combinations into which it enters with a distinct atomic weight the weight 33. Analogy would lead us to a similar conclusion with regard to the elements boron and silicon. How far this inference is to be extended to the allotropic forms of other elements experiment alone can decide.

ISSN:1743-6893    

DOI:10.1039/QJ8601200261

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

XXIV.-On the Combination of Carbonic Oxide with Potassium. BY B. C. BRODIE, F.R.S. PROFESSOR OF CHEXISTRY IN THE UNIVERITY OF OXFORD AND PRESIDENT OF THE CHEMICAL SOOCIETP. ITis now some years since Lie b ig made the curious observation that carbonic oxide is absorbed by and combines with potassium. This distinguished chemist did not make any exact experiment on the amount of this absorption and simply put forward a conjecture upon the subject founded upon the inadequate data in his posses- sion. From that time to the present the reaction has not been further investigated. It appeared to me that viewed in connection with recent experiments this question assumed a new interest and that it was probable that the reaction mas of a much simpler character than Liebig had surmised.In the more close examina- tion of this experiment I have discovered some remarkable points in it which have not hitherto been observed. The carbonic oxide used in the follwing experiments was pre- pared by the process of Fownes the decomposition of ferro-cyanide of potassium by concentrated sulphuric acid ;the gas was carefully dried and purified any traces of oxygen from air accidentally present being separated by the passage of the gas through a Lie big's apparatus containing pyrogallate gf potash. The potassium also was as far as possible freed from adhering impurities by filtration through wash-leather immediately before the experiment. This purification of the potassium so that it shall present aperfectly clean surface to the action of the gas is an essential condition of success.The potassium was rapidly wiped from naphtha by blotting paper and introduced into a bulb tube or when large quantities were operated on into a Florence flask which had previously been filled with carbonic oxide and weighed. The vessel containing the potassium was heated in an air bath in such a manner that the progress of the experiment could be observed. A gage-tube dipping into mercury was attached to the apparatus which was rendered air tight. The absorption corn- mences considerably under 100°C. and at about 8OoC.a change in the potassium is indicated by the appearance of the most beautifill arborescence the potassium shooting out into crystals resembling VOT,. XIT. rr 270 BRODIE ON THE COMBINATION OF frosted silver in appearance and at the same time spreading itself over the surface of the glass.This change continues until the whole of the potassium has become similar in appearance and con- verted into these crystals of a dead grey colour. The metallic appearance which the crystals at first present is most probably due to the spreading out of the metal over the surface. During this change the gauge-tube indicates a slow and moderate absorption the mercury standing at the level of about half an inch in the tube while the passage of the gas is regulated with extreme slowness. If pressure is put on the gas so as to accelerate its passage it bubbles through the apparatus. The formation of this substance is the first stage in the action.On its completion a further change is indicated by the formation of dark spots on the surface of the crystals which when their formation has once commenced spread over the surface with great rapidity the carbonic oxide being simultaneously absorbed. This absorption is as rapid as the absorption of carbonic acid by potash and if the gas be not allowed sufficiently free access to the substance the mercury will indicate in the page tube a pressure of from 20 to 30 inches. It is attended with great evolution of heat. This absorption takes place with the greatest rapidity at comparatively low temperatures. With the aim of preserving the substance in this stage I have frequently allowed the temperature to fall before the formation of the dark spots indicated the further alteration.At a certain stage however in the cooling when the temperature has perhaps fallen as low as 40°C. the second action almost invariablycommences nor have my efforts to procure this body in a pure condition by means of other devices been more successful. The final product of the experiment is of a dark red colour and retains the crystalline form of the body from which it is produced. During the progress of the experiment spots of blue and green appear on the substance indicating the partial formation of other bodies. The constitution of the substance is determined by the following experiments :-Increase in weight Increase in weight Potassium taken. on 100 parts. 64.0 grms. 4.57 grrns.71*4 5.461 , 3.967 , 72.4 0.674 , 0.475 , 70.48 4.858 , 3.469 , 71.4 5.6886 , 4.086 , 7143 4.669 , 3.362 , 72.07 CARBONIC OXIDE WITH POTASSIUM. In these six experiments which I have selected at random from a larger number giving equally concordant results the mean increase in weight on 100 parts of the substance is 71-59parts and 100 parts of the sustance formed axe thus constituted. Potassium . . . 58.27 Carbonic oxide . . 41.73 100*00 On the assumption that one atom of potassium weighing 39.2 absorbs 1 atom of carbonic oxide weighing 28 100 parts of potassium would absorb 71.2parts of carbonic oxide and the con- stitution of the substance formed would be- KO * . . 39.2 58.33 co * 28.0- 41.67- 67.2 100~00 The experiments of Berthelot have shewn that carbonic oxide combines with hydrate of potash to form formiate of potash formic acid that is in which one atom of hydrogen is replaced by one of potassium Now the result of this experiment the body COK (or rather C202K2) has the constitution of the radicle of formic acid C202H2,in which the whole of the hydrogen is replaced by potassium.It is not improbable that the intermediate substance may be the body COH, or the hydride of formyle in which a similar replacement is effected. Experiments which I have made with the view of replacing the potassium in this substance by organic groups have been without result. Neither iodide of ethyl nor even chloride of benzoyl act upon it There is every reason to believe that it consists of two bodies anhydrous potash and rhodizonate of potash.Brought in contact with water it decomposes with terrific violence and even the dry substance under circumstances which are not well ascertained occasionally explodes. It may be preserved under naphtha. When pure and anhydrous alcohol is poured upon it a great elevation of temperature ensues but the decomposition is far lcss violent than with water. &hen this experiment however must be made with the greatest caution. No gm is given off but a 272 RRODIE ON TIIE C'oMHINATION &C. portion of ethylate of potarli remains in solution and thc rhodizonate appears as a red insoluble powder. I endeavoured to ascertain the nature of this decomposition. Alcohol mas repeatedly digested with and poured off from the residue; arid the potash was precipitated from it by carbonic acid and determined as sulphate.Two experiments gave the following results .-I. 100 parts of potassium absorbed 72.4 parts of carbonic oxide and 38.4parts of potassium were extracted by the alcohol. 11 100 parts of potassium absorbed 71.8 parts of carbonic oxide and 41.77 parts of potassiuni were extracted by the alcohol. We may assume therefore that of 5 parts of the potassium taken 2 are extracted by the alcohol and 3 remLtin in the residue as rhodizonate which would give for its constitution C,,08K6 I do not pretend that the constitution of the rhodizonate can be thus determined with certainty but its formula has never yet been ascertained by any adequate and reliable experiments.Such cfforts as I haire made to ascertain it have been defeated by the extreme facility with which it is oxidized with formation of cro-conate. Rhodizonate of potash if perfectly pure dissolves in dilute acetic acid with a palc pink colour and the solution gives with acetate of baryta a brilliant rcd precipitate ; but this precipitate alters in colour during the process of washing and the solution of the potash-salt speedily becomes alkaline and yellow from the formation of croconate. I have never seen the oxalate of potash which others have observed in the decompositions of this class of bodies; and I may observe that this decomposition with the formation of croconate of potash and hydrate of potash can readily be accounted for on the hypothesis I have given simply by the action of air and moisture.

ISSN:1743-6893    

DOI:10.1039/QJ8601200269

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

INDEX. A. Acid antimonic and Acid arsenic action of hydrochloric acid upon sulphide of mercury in presence of 159. -bibromacetir 1. -boraoic its action upon alkaline car- bonates 177,180 182. -its action upon the carbonates of baryta and strontia 188 189 190. -its action upon carbonate of lithia 181 187. -its action upon carbonate of potassti 178 184 -its action upon carbonate of soda 179 181 186. -its action upon the chlorides 164. -its action upon iodides and bro- mides 165. its action upon nitrates and carbonates 165. its action upon sulphates 161. -on the action of upon the car- bonates of the alkalies and alkaline earths by C. L. Bloxam 177. -on the action of upon the salts of the more volatile acids at high tem- peratures by Norman Tate 160.-bromacetic on the action of bro-mine on by w. H. Perkin and B. F. Duppa 1. -graphic 266. -hydrochloric action of on some native combinations of oxide of mer-cury with oxide of antimony 29. -and ammonia on the absorp- tion of in water by H. E. Roscoe and W. Dittmar 128. -on the action of upon sulphide of mercury in the presence of certain other substances by F. Field 158. -lactic on the constitution of by H. Kolbe 15. -conversion of into propionic acid by C. Ulrich 23. -lizaric 208. -nitric on a new method for the quantitativeestimation of by E. Pugh, 35. -oxylizaric 208. VOL. XII. Acid parasorbic 46. -propionic conversion of lactic acid into by C. Ulric h 23. -ruberythric 216.-rubiacic 204. -rubianic 216. -rubichloric 205. -sor'ic 46. -titanic by E. Riley 13. Acids diamidic 105. -diamine-amidic 104. -monamidic tertiary 100. -monamidic quartary 103. -new volatile organic of the mountain ashberry by A. W. Hofmann 43. Alizarine and purpurine optical characters of 219. Alcohols diatomic 222. -polyatomic by H. Debus 222. -triatomic 212. Alkalies and alkaline earths on the action of boracic acid upon their carbonates by C. L. Bloxam 177. Alkaline carbonates action of boracic acid upon the at 212' F. 177. -action of boracic acid upon at a bright red heat 182. action of boracic acid upon at a dull red heat 180. Amides 62. Ammonia and its derivatives by A. W. Hofmann 62.-action of upon bisulphochloride of amylene 119. -and hydrochloric acid on the sbsorp- tion of in water by H. E. Roscoe and W. Dittmar 128. -relation between the amount of ab-sorbed in water at O"C and the pres- sure under which the absorption occurs 147. -relation between the amount of ab-sorbed in water under the ordinary atmospheric pressure and the ternpe- rature at which the absorption occurs 150. -acid derivatives of constructed upon the water-type 94. Ammonium bibromacetate of 4. Amylene action of ammonia upon bid- pbochloride of 139. 2E 394 INDEX. Amylene action of chloride of sulphur upon 114. -action of the chlorides of sulphur upon ethylene and 112. -bichlorosulphide of 115. Antimony on the separation of mercury from 32.-oxide of on some native combina- tions of oxide of mercury with by F. Field 27. Arsenic and copper sulphide of 9. -and sulphur on some minerals con- taining by F. Field $. Arsides metal 92. B. Balance sheet of the Chemical Society 176. Barium sorbate of 41. Bar r a t J am e s analysis of the water of Holywell North Wales 52. Baryta and strontia action of boracic acid upon the carbonates of 188. Bibromacetate of ammonium 4. -of ethyl 6. -of lead 4. -of mercury 4. -of potassium 4. -of silver 4. Bisulphamylene oxide of 122. -hydrated oxide of 121. Bloxam Charles L. on the action of boracic acid upon the carbonates of the alkalies and alkaline earths 177. Brodie B.C. on the combination of carbonic oxide with potassium 269. -researches on the atomic weight of graphite 261. Bromides and iodides action of boracic acid upon 165. Bromine on the action of on bromacetic acid by W. H. Perkin and B. F. Duppa 1. * c. Calcium sorbate of 48. Carbonates of the alkalies and alkaline earths on the action of boracic acid upon the by C. L. Bloxam li7. -and nitrates action of boracic acid upon 163. Carbonic oxide on the combination of with potassium by B. C. Brodie 269. Chemical Society anniversary meeting of the 166. -balance sheet 176. -proceedings at the meetings of 290. Chloride of sorbyl 52. Chlorides action of boracic acid upon the 164. Chlorine action of bisulphide of on ethylene 113.Chlorogenine 205. Chlororubian and chlororubiadine 215. Copper and arsenic sulphide of 9. -protochloride of action of hydro. chloric acid upon sulphide of mercury in presence of 159. D. Debus H..on the polyatomic alcohols 222. Diamides organo-metallic 91. -primary 78. -secondary 80. -tertiary 83. Diglpcerides 213. ' D:ttmar IT.,and H. E. Roscoe on the absorption of hydrochloric acid and ammonia in water 128. Duppa and Perkin on the action of bromine on broomaretic acid 1. E. Electrical incandescences on the decom- position of gaseous compounds by by A. W. Hofniann 273 Erythrozym 212. Ethylene action of metals upon iodide of by Carl Von Thann and J. A. Wanklyn 2%. -action of bisulphide of chlorine on 113.-action of chloride of sulphur upon 116. -and amylene action of the chlorides of sulphur upon 112. Ethylidine 236. F. Field F. on the action of hydrochloric acid upon sulphide of mercury in the presence of certain other substances 158. on some minerals containing arsenic and sulphur from Chili 8. --on some native1combinations of oxide of mercury with oxide of anti-mony 27. Food discourse on the composition of the animd portion of our and on its rela- tions to bread by J. H. Gilbert 54. INDEX. 395 6. L. Garanceux 207. Garancine 200 207. Gas hydrochloric acid relation between the amount of absorbed in water at OOC arid the pressure under which the absorption occurs 129. -hydrochloric acid relation between the amount of absorbed in water under the ordinary atmospheric pressure and the temperature at u hich the absorption occurs 136.Gaseous compounds decomposition of by electrical incandescences by A. W. Hofmann 253. Gilbert J. H. discourses on the com- position of the animal portion of our food and on its relations to bread 54. Glycols chemical properties of 224. Graphite researches on the atomic weight of by B. C. Brodie 261. Graphon 268. G re gory Pro fes so r (of Edinburgh) obituary notice of 172. Guayacanite 10. Guthrie F. on some devistives from the olefines 109. Herapath Thornton John obituary notice of 171. Hofmann A. W. new volatile organic acids of the mountain ash beiry 43.-on ammonia and its derivatives 62. -on the decomposition of gaseous compounds by elect1 ical incandescences 273. Hydrochlorate of ninaphtylamine 154. I. Iodides and bromides action of boracic acid upon 165. Iron sesquichloloride of action of hydro- chloric acid upon sulphide of mercury in presence of 159. K. K o 1be on the constitution of lactic acid 15. Kynaston J. W. analysis of the water of a spring at Billingborough Lincoln- shire 57. Lead bibromacetate of 4. Lithia action of boracic acid upon car- bonate of 181 187. Madder on the colouring matters of by E. Schunk 198. Madder-red madder-purple and madder- orange 201 Manganese peroxide of action of hydro- chloric acid npon sulphide of mercury in presence of 160.Nercury bibromacetate of 4. -on the separation of from antimony 32. -oxide of on some native combina- tions of with oxide of antimony by F. Field 27. -sulphide of on the action of hydro- chloric acid upon in the presence of' certain other substances by F. Field 158. Metalamides-organo 89. -secondary 90. tertiary 90. -primary 88. -tertiary 89. Metal-phosphides metal-arsides and metal-stibides 92. MetaIs action of upon iodide of ethylene by Carl von Than and J. A. Wanltlyn 2%. Monamides primary 63. _I_ secondary 66. -tertiary 71. Monoglycerides 243. Mountain ash beri y new volatile organic acids of by A. W. Hofmann 43. Sinaphtylamine 153. -hydrochlorate of 154. -platinum-salt of 155.-sulphate of 154. a Nitrates and carbonates action of boracic acid upon 165. Nitrous substitution on bases produced by by C. S. Wood 152. Obituary notice of Professor Gregory 172. -Thornton J. Herapatb 171. 396 INDEX. Obituary notice of Hugh Lee Pattinson 169. Olefines on some derivatives from the by F. Guthrie 109. Organo-metalamides 90. P. Pattinson Hugh Lee obituary notice of 169. Paviin note on by G,G. Stokes 126. Perchlororubian 215. Perkin and Duppa on the action of bromine on bromacetic acid 1. Phenyl-sorbamide (sorbanilide) 51. Phosphides 87. -metal 92. Potassa action of boracic acid upon car-bonate of at a bright red heat 184. Potassium bihromacetate of 4. -on the combination of carbonic oxide with by B.C. Brodie 269. Pugh E. on a new method for the quantitative estimation of nitric acid 35. Purpurine 200. -and alizarine optical characters of 239. R. Riley E. on titanic acid 13. Roscoe H. E. and W. Dittmar on the absorption of hydrochloiic acid and ammonia in water 128. Rubiacine 203. Rubiadine rubidfine and rubiagine 213. Rubian 210. Rubianine 213. Rubiretine 213. Schunk E. on the colouring matters of madder 198. Silver hibromacetate of 4. -tartrate of 47. Soda carbonate of action of boracic acid on at 212O 179. -action of boracic acid upon the car- bonate of at a bright red heat 186. -carbonate of action of boracic acid upon at a dull red heat 181. Sorbsmide 50. Sorbate of barium 47.-of calcium 48. -of silver 47. Sorbic ether 50. Sorbyl chloride of 50. Stibides metal- 92. Stokes G. G. note on paviin 126. -on the optical characters of pur-purine and alizarine 219. Strontia and baryta action of boracic acid upon the carbonates of 188 190. Sulphate of ninaphtylamine 154. Sulphates action of boracic acid upon 161. Sulphide of copper and arsenic. 9. Sulphur action of chloride of upon amylene 114. -action of chloride of upon ethylene 116. -action of the chlorides of upon ethylene and amylene 112. -and arsenic on some minerals con- taining by I?. Field 8. T. Tate Norman on the action of boracic acid upon the salts of the more volatile acids at high temperatures 160. Triamides 86.-organo-metal 91. Triglpcerides 244. Trimetalarsides 93. Trimetalphosphides 92. Trimetalstihides 93. u. Ulrich conversion of lactic acid into propionic acid 23 v. Verantine 213. Von Than Carl and J. A. Wanklyn action of metals upon iodide of ethylene 258 w. Wanklyn J. A. and Carl Von Than action of metals upon iodide of ethylene 258. Water on the absorption of hydrochloric acid and ammonia in by H. E. Roscoe and W.Dittmar 128. -analysis of the of a spring at Bil- lingborough Lincolnshire by J. W. Kynaston 57. -of Holywell North Wales analysed by James Barratt 52. Water-type acid derivatives of ammonia constructed upon the 94. Wood C. S. on bases produced by nitrous substitution 152. x. Xanthine 201.

ISSN:1743-6893    

DOI:10.1039/QJ8601200393

出版商:RSC    

年代:1860

数据来源: RSC