摘要:

QUARTERLY JOURNAL OF TTTE CHEMICAL SOCIETY XV.-On. the Composition of a Specimen of Atacamite from the province of Copiapo Chihi. BY FREDERICK FIELD. A mineral consisting essentially of chlorine copper and water was originally fouiid in the bed of the river Lipas in the desert of Atacama in Peru and from this circumstance it has been calIed Atacamite. Since its discovery however it has been observed in many other localities; in some silver mines in Peru as well as in the copper districts of Huusco Bajo and Aconcayun in ChiIi in the lavas from Vesuvius and the mines of Schwarzenberg in Saxony. I have recently observed it in large md beautiful masses in the province of Copiapo. The analyses by various chemists of this mineral diffey very much. Proust gives the following as the constitution of a specimen from -Chili :*- Oxide of copper .. . . 76.5935 Hydrochloric acid . . . . 10.638 Water . . . . . I . l2*76? 100~000 and of one from Peru:- Oxide of coppr . . . . 70.5 Hydrochloric acid . . . . . 11.4 Water . . . . . . . 18.1 -100.0 * Ann. CIi. Phys. [2] xxxii. 49. VOL. VII.-NO. XXVI I. 194 MR. F. FIELD ON THE COMPOSITJON OF ATACAMITE. Klaproth finds another specimen to contain- Oxide of copper .....73.0 Hydrochloric acid .. . 10.1 Water ........16.9 100.0 Again Berthier has analysed two specimens of Atacamite from Cobija in Bolivia and gives us the following as his results :-I. 11. Chlorine .......14.9 15.2 Copper .......13.3 13.6 Oxide of copper ....50.0 54.1 Water .......21.8 17.2 loo'o 100.0 Having procured some beautiful specimens from this province while visiting a mine in the vicinity of Copiapo I imagined that a brief sketch of the composition and character of the mineral would not be uninteresting more especially as the analyses hitherto made have been somewhat conflicting owing probably to the difficulty of obtaining specimens of sufficient purity for analysis.The mineral from Copiapo crystallises in right rhornbic prisms as well as hexagonal tables although I have observed them also in beautiful stellated crystals radiating from a centre. They have a deep emerald-green colour are perfectly transparent and very lustrous giving a pale apple-green streak and forming a similar coloured opaque powder when crushed.Hardness about 2.6 ;spec grav. 4.25. Before the blow-pipe the mineral is reduced on charcoal a button of metallic copper remaining ;at the same time the flame is tinged with a deep blue with green edges. The mineral is perfectly soluble in ammonia very slightly so in water. Hydrochloric and nitric acids even when highly dilute dissolve it without effervescence. It was associated im- mediately with brown oxide of iron and carbonate of lime although in the same vein there were blue sulphides of copper antimonial sulphide of copper (Fahlerz) and carbonates of copper both blue and green. Analysis of the mineral gave me the following results :-I. 11;. Chlorine ......14.94 15*01 Copper .......56-46 56.24 Water .......17.79 18*00 DR.J. H. GLADSTONE ON THE ACTION OF SUGAR ON IRON &C. 195 Now supposing (which is probably the case) tbat one equivalent of copper is associated with one of chlorine the remainder being in the state .of oxide the following would be the constitution of the mineral :-I. 11. Chloride of copper ...28.22 28.35 Oxide of copper ....63.99 Water .......17-79 18.00 100*00 9997 which would give very nearly the following formula :-CuC1.3 Cu 0+5 H 0. The composition of the mineral from Cobija analysed by Bert II ier resembles somewhat those froin Copiapo. From Cobija. From Copiapo. Chloride of copper .. 28'2 28.22 Oxideof copper .. . 50.8 53.99 Water .......21.8 17-79 -lOO0O 1oo'oo Chloride of copper ...28.7 28-35 Oxide of copper ....59.1 53.62 Water ........17*2 18.00 100.0 99-91

ISSN:1743-6893    

DOI:10.1039/QJ8550700193

出版商:RSC    

年代:1855

数据来源: RSC

摘要:

DR. J. H. GLADSTONE ON THE ACTION OF SUGAR ON IRON &C. 195 XVL-On the Corrosive Action of Sugar orn Iron and other Metals. By J. H. GLADSTONE, Ph.D. F.R.S. Owners of iron-built ships frequently object to sugar freights alleging that the saccharine juices which exude from thc casks rust the metal deeply. In sugar refineries also it has occasionally hap-pened that portions of machinery made of iron have been wholly dissolved. Starting from these assertions of practical men I have made the following observations. If a piece of iron be partially immersed in a solution of pure cane- sugar and it be set aside in a rather warm place where air has 196 DR. J. H. GLADSTONE ON THE CORROSIVE ACTION OF access to it the metal will soon become deeply corroded about the edge of the liquid; but that portion which is permanently immersed will remain bright for a considerable space of time.The solution then contains protoxide of iron which absorbing oxygen from the atmosphere presently separates as the sesquioside and subsides in the form of a red powder leaving the sugar free to exert its influence again upon the metal. In this manner the action becomes con-tinuous the organic principle acting as a carrier of oxygen; and we can readily understand how a small quantity of sugar may eat into a large sheet of iron. A definite compound seems to be formed by the oxide Qf iron and sugar. It is very soluble in water but insoluble in alcohol. Its solution is of a deep red-brown colour. It has the peculiar astringent flavour usually belonging to iron salts.The addition of ammonia or potash does not cause the precipitation of the metallic oxide ; neither do alkaline carbonates; but a black precipitate is obtained at once on the addition of sulpliide of ammonium and a pale blue colour is produced by the ferrocyanide of potassiim and a deeper blue by the ferridcyanide. Nitric acid causes at once the formation of nitrous fumes after which neutralisation by an alkali produces an abundant precipitate of the sesqnioxide. When boiled with sulphate of copper the red oxide also precipitates. A stream of hydrosulphuric acid passed through the solution throws down the whole of the iron as snlphide and leaves a perfcctly neutral solution containing nothing thrt could be distinguished from the uncombined sugar.This compound then evidently consists of protoxide of iron with sugar but little if at all altered The determination of the proportions in which these substances are combined is attended with difficulty for the substance itself shows not the slightest disposition to crystallise; and the separation of it from uncombined sugar by means of alcohol was not found to be sufficiently practicable. The most likely way to obtain a pure substance appeared to be by allowing the sugar to saturate itself gradually with the metallic oxide. Accordingly some sugar solution which had been left in a warm place with iron for eighteen months and had evaporated to dryness during that time mas examined. When redissolved in water it contained no sugar unless in co:nbination with the metallic oxide ; but it was not identical with the preceding conipound.It mas iiisipid with a slight ferruginous after-taste. The action of different rcagcnts upon it was much the same as upon that first produced; but it was much more stable not being affected by the oxygen of the atmosphere. A stream of hydrosulphuric acid caused oiily a partial decomposition SUGAR ON IRON AND OTHER METALS. setting free a substance which had a decidedly acid reaction to test-paper though *an insipid taste. The acid thus partially separated was capable of dissolving fresh oxide of iron but did not attack the metal itself though immersed in it for some days. A portion of the compound just described was evaporated to dryness in a water-bath weighed incinerated in a platiiiuni crucible with the addition of a few drops of nitric acid to ensure the complete oxidation of the metal and the sesquioxide of iron weighed.Sugar compound takeu . . 6.603 grm Sesquioxide of iron obtained . 1.263 , which is equivalent to 1.136 grm. of protoxide of iron or I7.20per cent. This is almost precisely what ought to be obtained from a com-pound of single equivalents of oxide of iron and sugar :-Calculated. Found. Protoxide of iron . 17.39 17-20 Sugar . . 82.61 82.80 -__I) 100~00 100*00 However this must be taken rathea as an approximative than as an exact expression of its composition. It is indeed not unlikely that the assumption of acid properties was accompanied by a slight oxiLiation of the organic principle.From the analogy of the baryta and lime compounds of sugar in which that substance loses one equivalent of the elements of water in combining with the oxide we should expect the formula of the compound first formed to be c1 KO 010 Fe 0. It is probable that these two are not the only compounds produced by the action of sugar on iron; for although no indications were observed of any soluble compound of the sesquioxide yet the red powder deposited from the solution contained more or less of some organic principle in intimate combination. Since sugar attacks a mass Gf iron so readily it seemed highly probable that it would dissolve the oxide easily; but such was not found to be the case.Some freshly-precipitated protoxide of iron which had been well washed was boiled in a solution of pure sugar and set aside with it for a period of twenty-four hours in an air-tight vessel but not a trace of iron was found in the solution A second experiment was made in which the oxide of iron was presented in a nascent condition to the organic principle ; a solution of pure cane- sugar being mixed with one of sulphate of iron and the whole being 198 DR. J. H. GLADSTONE ON THE CORROSIVE ACTION OF just supersaturated with potash. The precipitated protoxide was separated by filtration; the solution which was at first perfectly clear soon became turbid from the formation of sesquioxide but the amount of iron actually dissolved was extremely small.That the solution of even this trace depended upon the presence of the alkali appears probable from a third experiment where a large excess of potash was added to a similar mixture of sugar and sulphate of iron and a deep red solution was obtained containing a large quantity of the metallic oxide This solution when freely exposed to the air showed very little sign of absorbing oxygen. As a supplement to this experiment some freshly precipitated and washed protoxide of iron was mixed with a quantity of potash in a solution of sugar contained in an air-tight vessel. After the mixture had stood awhile protoxide of iron was found in solution; but it existed in but very small quantity even after the expiration of a month. In order more fully to determine the nature of this action of sugar on iron a piece of that metal was immersed in a solution of pure sugar in a glass tube inverted over mercury in such a way as to exclude the access of air and to retain any gas that might be formed.After the lapse of three months it was found that not a particle of any permanent gas had been formed and the solution remained very nearly as colourless as at first.* It thus appears that the sugar does not attack the iron as an acid does-by causing the replacement of hydrogen by the metal and the consequent evolution of that element in the gaseous form. The presence too of free oxygen appears necessary to the action; and yet it has been seen by previous experiments that it is difficult to get sugar to combine with the oxide itself unless an alkali be present when doubtless a different compound is formed.Experiments were tried with various strengths of the saccharine solution and with brown as well as white sugar; and in every case the iron was attacked. In order to test the effect of salts in con-junction with the sugar pieces of iron were placed in five vessels containing equally strong solutions of cane-sugar to four of which had been added respectively chloride of sodium chloride of am-monium nitrate of potash and sulphate of magnesia. After awhile protoxide of iron was found in all the five solutions and there was about an equal deposit of the sesquioxide in the different cases. The addition of chloride of sodium to a mixture of freshly precipitated * In a similar manner iron vessels are employed without risk in sugar refineries mhcre the vessel is always kept filled with the saccharine solution.SUGAR ON IRON AND OTHER METALS. protoxide of iron and sugar did not cause combination to take place between them. A piece of zinc placed in contact with iron in the sugar solution was found not to prevent the dissolving of that metal but both were attacked. The effect of a solution of sugar upon other metals was tried; but none was found to be affected by it to an extent at all comparable witb iron Cbpper.-Considering the great influence which the presence of sugar exerts in preventing the precipitation of oxide of copper it niight be anticipated that it would exhibit an action on the metal itself analogous to that already described.But it is not so. In an experiment made in the summer time a few weeks’ exposure of pieces of copper to a sugar solution showed a trace of the metal dissolved; but in the winter time an exposure of seven months’ duration merely produced a very faint blueness of the saccharine liquid which was scarcely blackened by the addition of sulphide of ammonium. Lead.-Lead was attacked much more readily. Three days’ ex-posure in warm weather a few weeks in cold weather or a few hours at a boiling temperature produced a solution which was distinctly blackened by a soluble sulphide. Zinc.-This metal was very slowly acted upon. Seventeen days’ exposure in warm weather was found to give a solution containing some oxide of zinc; but about forty hours’ boiling did not cause the solution of a sufficient quantity to be detected by the ordinary reagents.In the experiment where iron and zinc in contact were exposed to the sugar a much larger proportion of the zinc appeared to be dissolved; after the oxidation of the iron by nitric acid and the removal of the oxide by ammonia the alkaline solution gave a copious white precipitate when tested with hydrosulphuric acid. Tin.-Tin was also very slowly attacked. The small quantity at any time found dissolved was in the condition of the binoxide. In an experiment in which the sugar solution was boiled with pieces of this metal for perhaps forty hours no indication of it in the liquid was obtained. Mercury and SiZuw.-These metals were not found to be acted upon by sugar in the slightest degree.

ISSN:1743-6893    

DOI:10.1039/QJ8550700195

出版商:RSC    

年代:1855

数据来源: RSC

摘要:

200 DR. T. H. ROWNEY ON THE ACTION OF AMMONIA ON OILS. XVE-Preliminary Notice on the Action of Ammonia on the Oils and Fats. BYTHOMAS H. ROWNEY,Ph.D. F.C.S. ASSIBTAHT IN TBE COLLEGE WORATORY BLASGOW. Few experiments having been made on the action of ammonia 0x1 the oils and fats I have turned my attention to this subject and in the laboratory of Professor Anderson of Glasgow have submitted several oils and fats to the action of ammonia. As the experiments are likely to occupy some considerable length of time-owing in most cases to the slowness of the action-I have thought it advisable to send a short notice of some compounds already obtained reserving for a future period the full details of my experiments. At present I wish to confine my remarks to the compounds obtained firstly by the action of ammonia on almond and castor oils themselves and secondly to those obtained by the action of ammonia on the same oils after they have been solidified by the action of nitrous acid gas.By the action of ammonia on almond and castor oils crystalline compounds are obtained; that from almond oil I have examined and find it to have the formula C36H, NO, being that of oleamide. The compound from castor oil 89.Bouis has examined and he gives to it the formula C36R, NO, and names it Ricinolarnide.* When nitrous acid gas is passed into almond OF castor oil these oils are converted into solid compounds called Elaidine and Palmine. In the case of elaidine this change is said to be effected without any decom- position taking place elaidic acid having the same formula as oleic acid.But according to the experiments of Playfair a decomposition must take place when castor oil is acted upon by nitrous acid as he gives the formula C, H, O6 to palmic acid which differs from that of ricinoleic acid by C H. To ascertain the correctness of these opinions I have subjected elaidine and palmine to the action of ammonia and have obtained beautiful crystalline compounds from them differing in many respects from oleamide and ricinolamide but having exactly the same formulee as those two aiuides. * This compound I have also obtained but did not examine it M Bouis having wli*eady done so. MR. E-A HADOW ON THE ACTION OF NITRIC ACID ON COTTON. 201 From these results it would appear that castor oil does not undergo any decomposition when acted upon by nitrous acid but that the change must be similar to that which takes place in almond oil when it is subjected to the action of this acid.The formula of palmic acid should therefore be altered to C36 H, 06 palmamide being c36 H3 No4. The following table shows the relations between these acids and amides :-Oleic acid. Ricinoleic acid. '36 H34 '4 '36 H34 O6 Oleamide. Ricinolamide. c36 H35 '36 H35 Elaidic acid. Palinic acid. '36 H34 '4 '36 H34 O6 Elaidamide. Palmamide. C.361335N0!2 '36 H35 I hope in a future communication to bring before the notice of the Society some other compounds which I bave obtained.

ISSN:1743-6893    

DOI:10.1039/QJ8550700200

出版商:RSC    

年代:1855

数据来源: RSC

摘要:

MR. E-A HADOW ON THE ACTION OF NITRIC ACID ON COTTON. 201 XVI[II.-Qn the Subsfitation-Compounds obtained by the Action of Il’itric Acid on Cotton. BY EDWARD ASH HADOW STUDENT IN THE LABORATORY OF KING’S COLLEGE LORDON. Analyses of Gun-cotton have been published by M. Pelouze M. Peligot Dr. Gladstone Mr. Porrett Mr. Ransome and likewise by M. Schonbein; they however exhibit a remarkable want of agreement with each other both in the formulae to which they give rise and in the percentage increase of weight which they would represent the cotton to have obtained on its transformation into gun-cotton. M. Pelouze states that cotton constantly gains from 74 to 76 per cent. giving the formula C, H17O,, SNO, corresponding to an increase of 75 per cent.exactly. M. Peligot’s formula is C, H O, 3NO, according to which the gain must be 94.4 per cent. Mr. Rausonie obtained C, EI Ole ZXO, which represents 20.2 MR. E. A. HADOW ON THE SUBSTITUTION-COMPOUNDS an increase of 65.4. Dr. Gregory states it to be 69.5 which cor-responds with that required by the formula which Dr. Gladstone ascribes to the most explosive gun-cotton C, [:go*) 02-,, while the formula of Yorrett and Teschemacher C, H8 08,4 NO, would double the original weight of the cotton. &I. Schonbein gives merely the percentage of carbon nitrogen hydrogen aud oxygen from which the lowest formula that can be calculated corresponds nearly to C4 H, O, Nlo. In consequence of this disagreement between the formulze giving rise to so marked a difference in the percentage increase of weight deduced from them it was evident that a careful determination of the weight actually acquired by cotton after immersion in acids ought alone to throw much light on the matter by pointing out the formula upon which most reliance was to be placed and from which the composition of the soluble variety might be determined provided that it were indicated by a definite and constant increase of weight.While ascertaining this point I was anxious likewise to discover what strength and what proportions of acids were capable of producing the soluble gun-cotton as well as whether there were more than one such compound; expecting that if such were the case there would always be an increase of weight closely corresponding to two or more numbers from which formulae might be calculated or by which at least the results of analyses might be controlled.In the preparation of these compounds nitric acid was not used alone since a very slight difference in strength produced a great digerence in the result. HO NO gives an insoluble product while HO NO + HO destroys the texture of the cotton ; and having ascer- tained that when sulphuric acid is used no trace of it exists in any of the compounds a mixture of the two was always used the latter acid being advantageous for the purpose of increasing the bulk of the mixture retaining the water abstracted from the cotton and pre- venting the solution of the conipound which takes place to a greater or less extent in nitric acid alone.The mixtures were likewise made in atomic proportions that their formulae might be easily retained in the memory and similar mixtures be prepared from acids of various strengths,-after some trials those which contained 1 equiv of mono-hydrated nitric acid with 2 equivs. of monohydrated sulphuric acid proved to be best and mixtures were made with the acids in this pro- portion with from 1 to 5 additional equivs. of water-the fifth was found to disintegrate the cotton. Thc results obtained from 100 of cotton were as follows :- OBTAINED BY THE ACTION OF NITRIC ACID ON COTTON. 203 HO NO 2(HO SO,) ] HO=277 Insoluble in ether+ ' + alcohol, HO NO Z(H0 SO,) f 2 HO=176 except the last which is HO NO5 ] 3 HO = 1m7 slightly at tacked WO SO,) I-'' 4 HO = 157 ] Very soluble.~(Ho,SO,) 1 HO NO about 2(do,pb,) ] 5 HO = 140 ] Soluble in great measure. The interval between the third and fourth appeared in some degree to correspond to what had been expected; that between the fourth and fifth was doubtful from the loss of the latter and from its appa- rently containing an admixture of unchanged cotton; but on trying fractional additions of water a corresponding intermediate increase of weight was likewise produced in the cotton e. g. both compounds proving perfectly soluble. It was likewise found on repeating these experiments that it was difficult to obtain the same increase of weight unless the mixtures corresponded accurately in composition. The cotton in these experiments was thoroughly dried in a current of dry air at 212' and in consequence of its hygro- scopic properties was weighed in the same tube in which the drying took place.At first the gun-cottons were likewise carefully dried at low temperatures after thorough washing in distilled water ;but the results not being found quite accurate and a gradual loss of weight being observed at temperatures below 212* the desiccation was effected by placing them in vacuo over sulphuric acid for twenty-four hours after which they were found not to sustain the slightest diminution in weight. The acids were also used in large proportion to the quantity of cotton that the water abstracted might have no appreciable effect in diluting the mixture; and as a precaution the immersion was continued for several hours although the full effect appears to be produced in a very short space of time.It was how- ever found that notwithstanding these advantageous conditions for the production of definite compounds very variable increments of weight were acquired by the cotton ranging from about 40 per cent. upwards. Immersion in acids previously warmed was then tried but as the cotton was found to lose weight in proportion to the duration of the 204 MR. E. A. HADOW ON THE SUBSTITUTION4OMPOUNDS immersion owing to a slow solution even at 120' F. nothing could be learnt from the weighing of the compound; in other respects however the result of the experiment with hot acids proved curious and interesting from the fact that Ho' 3 NO which at 60' 2(HO SO,) 1 gave rise to an almost insoluble compound produced at 130' one perfectly soluble in ether +Q alcohol the other acid mixtures con-taining more than 3 equivs.of water produced soiuble compounds both at 60' and 130° but their solutions differed remarkably in one respect ;for all soluble products formed at ordinary temperatures when dissolved in the proportion of 6 grains to the ounce give thick glutinous solutions while all those which are the result of acids at the temperature of 130' give perfectly fluid ones which produce on drying membranes far exceeding the former in strength and tough- ness and much better adapted to photographic or surgical purposes. By far the best mixture for producing collodion-wool is that repre- sented by the formula zzc:)j,) +3&HO which is obtained by mixing 89 parts by weight of nitric acid sp gr.= 1*424,with 104 parts by weight of sulphuric acid sp.gr. =1.833 As-( Sulphuric acid sp. gr. =1.833=Z(HO SO,+ *33HO) =103.9I I. Nitric acid sp. gr. =1*424= HO NO + 2.84 HO = 88.5 H0,N0,+2(H0,S03) +3k110=192*4 These specific gravities are specially referred to from their being those of the acids most frequently met with in commerce. Good collodion- wool is also produced by stronger acids if there be not less water than that required by the formula f$:(&,3) + 3 HO and the temperature is raised to 130'; however the stronger the acids the more liable is the collodion-wool to become partially insoluble after drying.If there be less than three additional equivalents of water the products are equally insoluble whether the acids are employed hot or cold. Finding that the weighing of the product resulting from the action of warm acids could be of no service in proving the existence of definite compounds I tried at Mr. Hardwick's suggestion the effect of reimmersing the cotton in a portion of the same cold acid mix-ture with which it had been previously treated noting at the same time whether any second increase of weight were obtained. The results were highly satisfactory. For the preparation of the highest OBTAINED BY THE ACTION OF NITRIC ACID ON COTTON. 205 compound a mixture was made of 2 volumes of the strongest sul-phuric and 1 vol. of colourless nitric acid sp.gr.= 1 -521. 27.5 grains of cotton after some hours' immersion weighed after washing and drying i.n vacuo 49.88 grains corresponding to a gain of 81-34 per cent. In this case it was hardly expected that a second immersion would cause an increase; by experiment it was found to have sustained a slight loss as it now weighed 4962 showing that the acids have a slight solvent power even at ordinary temperatures. This increase of 81.34 per cent. in weight does not correspond with any of the analyses hitherto published although the greatest care was taken to avoid error on account of the important aid it would afford in deducing a formula for this and other compounds. the first immersion an increase of 58.7 per cent. ; by a second im- mersion it was found to have' increased to 62.9 per cent.thus fulIy answering our expectations. A third immersion brought it to G4 per cent. On account of the great difference observed between the products of +3 HO and the same +4 HO an intermediate mix- ~(Ho,SO,) 1 ture was made. The first immersion gave an increase of 67.3 per cent.; a second immersion 70 per cent.; a third 71.4 per cent. Hence it was concluded that there were at least three compounds of which from 100 of cotton there would be obtained quantities approximating to 164,172 and 182; and it is probable that any acid mixture would produce such a definite compound were it not diluted at the same time by the water it abstracts which when the dilu- tion exceeds a certain point gives rise to a second compound the great mass of the liquid probably having but little influence in con- sequence of the imperfect diffusion arising from the want of perfect fluidity and the adhesion to the fibres of the cotton the washing and thorough drying then enable the original acid mixture to raise the second cornpound to that which would have resulted in the first instance had no dilution taken place.It is evident also that the number of immersions required must vary according as the acid mixture is much within or approaches near to that state of dilution which limits its power of producing a certain compound a given quantity of water having much more effect in one case than in the other. In trying the effect of various reagents on gun-cotton I ascertained that it could be perfectly restored to the original cotton without loss 206 MR.E. A. HADOW ON THE SUBSTITU!l"ION-COMPOUNDS of form by means of hydrosulphuret of potassium KS HS. At Dr. Miller's suggestion this was made use of to effect the analysis of the compounds and to confirm the previous results. An aqueous solution was first tried but found to occasion loss of weight on account of the long boiling required an alcoholic solution was there- fore prepared by thoroughly saturating a strong alcoholic solution of potash with sulphuretted hydrogen by transmitting the gas until it wouId absorb no more aud ceased to give a precipitate in sulphate of magnesia. As however the reduction was found to proceed easily at ordinary temperatures it proved better to effect the change by continuing the immersion for twenty-four hours and thus avoid the risk of decomposition and loss which prolonged boiling occasioned.That the cotton so obtained was free from nitrogen-compounds was proved by strongly heating it with caustic potash and conducting the gases evolved into a solution of litmus very faintly reddened when the colour remained unchanged; by the close correspondence in the quantity obtained from gun-cotton with that originally used or the restoration back to the original weight; and by its possessing all the physical characters of common cotton which differs from all products obtained from it by the action of acids in its depolarising action on light and in its far greater softness and compressibility when wet and also by the action of HO SO,+ HO which dissolves the nitro- compounds producing a solution which is not blackened below 212O while common and reduced cotton are completely carbouised below that temperature.Two combustions of the reduced cotton have been made; one in which the determination of hydrogen failed in consequence of an accident gave in 100 parts 44.4of carbon; another made by Mr. Hardwick gave- Found. Calculated. Carbon . . . 44-86 44.44 =l2 c. Hydrogen . . Oxygen . . . 6.64 48.50 6.17 =10 H. 49.39 =10 0. L____. 100~00 100~00 The other products of the atoms of KS 13s are nitrite of potash (KO NO,) and a little ammonia. No trace of nitrate could be discovered in the solution which was evaporated to dry-ness with excess of acetic acid to expel the nitrous acid.An attempt was made to turn the reaction of KS HS upon gun-cotton to account in effecting the determination of the nitrogen by this OBTAINED BY THE ACTION OF NITRIC ACID ON COTTON. 207 means ; but the results were unsatisfactory in consequence of the co-existence of ammonia and nitrous acid in the liquid. The solution could not be heated to expel the former without risk of loss in the weight of the reduced cotton neither could the ammonia be retained by addition of an acid without escape of NO, from the reaction of sulphuretted hydrogen and nitrous acid on each other. An altogether different mode was therefore adopted which consisted in making a solution of the compound in pure sulphuric acid and after conversion of the oxides of nitrogen into nitric acid by means of some oxidating agent estimating its amount by the method of M.Pelouze depending on its property of converting proto- into perchloride of iron and from the amount of the latter calculating the former. Before performing this the properties of a solution of gun- cotton in sulphuric acid were examined. A portion immersed in cold concentrated sulphuric acid soon dissolves withoui evolution of any gas producing a clear colourless solution ; if this be poured at once into five or six times its bulk of water so that-the temperature does not rise before dilution takes place the clear solution obtained gives no evidence whatever of nitric acid or any oxide of nitrogen even though raised subsequently to the boiling point ;neither does it dis-colour solution of permanganate or chromate of potash.If however the original solution in concentrated acid be diluted with only once or even twice its bulk of water a vio!ent effervescence ensues with abundant evolution of nitrous acid (NO,) or peroxide of nitrogen (NO,) together with carbonic acid. If again the solution in con-centrated acid be heated before dilution carbonic acid is evolved while the oxides of nitrogen are retained provided that the sulphuric acid is in sufficient excess if it be now diluted with water nitric oxide NO, escapes with effervescence. It became necessary there- fore to effect the complete conversion of the nitrogen oxides into nitric acid.After trial of various oxidising agents the object was successfully attained by the use of bichromate of potash which imme- diately peroxidises NO and NO, but is without action on NO, hence it was necessary to use a solution of gun-cotton in pure sulphuric acid made in the cold which was then added to a strong solution of bichromate contained in a retort; the mixture (which immediately acquired a dark green tint from reduction of the chromic acid) was carefully distilled precaution being taken to ensure the entire expulsion of the nitric acid which was then estimated as above stated by Pelouze’s method. The quantity of cotton in a given sample of gun-cotton having been determined by reduction by KS HS and the nitrogen by the above 208 MR.E. A. HADOW ON THE SUBSTITUTION-COMPOUSDS method it is easy to see whether the compound contains any atoms of NO not displacing an equivalent number of atoms of HO. The following results of analysis leave no doubt that it is purely a subati-tution compound :-COMPOUND A.-Prcduced by action of strongest acids and most probably by repeated immersion in any mixture not weaker than Ho $3 HO. Quite insoluble in any mixture of ether 2 (HO SO,) } and alcoho<. but soluble in acetic ether. Highly explosive. I. 27.5 of pure cotton gave by three hours' immersion in strongest acid 49.88 first time; 49.6 second time. 11. 6.85 of this gun-cotton gave by reduction 3.78 of cotton. 111. 6.37 of gun-cotton by reduction gave 3.48of cotton. IV.20.50 of gun-cotton gave NO = 10.84. - By Calculation. By Synthesis. By Analysis. c36 H21 OSO No,* I. 11. 111. Cotton found . 55-13 54.6 55.19 54.54 NO,-H . 0 - 44.07 45*46 .- 99.26 100*00 The composition of cotton being fully determined by the analyses of MM. Mitscherlich Pelouze and Payen to be in the proportion of C12H10010 the preceding analysis would give rise to the formula '36 9 NO }03,=891. H21 100 cotton produced 181934 by calculation 183.3. COMPOUND B.-Produced most probably by any acids of composition intermediate between Ho } + 8 SO and 2 (HO so31 That which was examined was obtained by several immersions in 'OY No } +3+ HO. It is explosive yet perfectly soluble in 2 (HO SO,) ether ++ alcohol ;quite insoluble in acetic acid.I. 27.6 grains of cotton gave by first immersion in the above mixture 46.2 grains ; by the second immersion 47.1; by the third 47.31. 11. By reduction 6.08 grs. of the compound gave 3.50 of cotton. OBTAINED BY TIIE ACTION OF NITRIC ACID ON COTTON. 209 Calcukted. From Synthesis. I. Cotton found 58.34 57.56 57.45 NO,-€I-I . . -(not determined) 42.55 100*00 Formula would be C, Fgo4] 03,=846. 100 of cotton produced 17'1.4 by calculation 174. Co%r POUND C.-Produced by 2 (130 SO,) } +4 HO. Like the prc- ceding this compound is very soluble in ether but differs from it in bciiig likewise perfectly soluble in glacial acetic acid. In this as in the former compounds the cotton fibre is quite uninjured.It is highly combustible rather than explosive and burns with a slow jet of flame when rammed into a tube and ignited. I. 24.1 gm. of cotton weighed after first immersion 38.26; after second immersion 39.26 ; after third immersion 39.53. TI. By reduction 9.94 grs. of the compound gave 6-00of cotton. By Calculation. By Synthesis. By Analysis. Cn6 H23 -I. 11. Cotton found . 60.96 60.36 60.67 N04-H . . -(not determined) 39.33 Formula C, :Go*} O, == 801. 100 cotton produced 164.0 by calculation 164.8. C:!)nwouND D.-The existence composition and identity of this COM-potind with xyloidine are inferred from the following reasons :-1st. There is a compound lower than C since produces by one immersion an increase of only 59 per cent. yet this product is perfectly soluble; if however C wcre the last all products not attaining 64 per cent.in their amount of increase would contain unchanged cotton and would be only partially soluble. VOL. VI1.-NO. XXVLI. P 210 MR. E. A. HADOW ON THE SUDSTITUTIOP3-COMYOUNDS "0 "0, 2nd. The product of the action of 2 (HO SO&1+5 110 ill which the texture of the cotton is more or less destroyed is only partially soluble in ether,-cotton apparently unchanged re- maining behind; it thus appears that the soluble portion is the lovirest compound obtainable by the action of the mixed acids on cotton. 3rd. As the next member in the series its cornposition would be C, fgo4)030,which exactly corresponds with that as-signed to xyloidine; and 100 of cotton should yield 155.5.The soluble portion of these products further corresponds with xyloi- dine in giving an opaque film on drying and in its solubility in glacial acetic acid. Althongh the xyloidine of woody fibre and starch agree in composition they may be d-istinguished by the action of KS €IS which reduces each to its proximate con- stituents when the usual reaction with iodine may be obtiliiid in the one case but not in the other. The modifications procluced by the action of hot acids have not yet been examined; there is in these cases greater difficulty of avoiding loss in washing in conscqnence of their disintegrated state if im- mersed sufficiently long to obtain definite compounds. It is evi- dent however that there are at least two produced respectively by Ho' +3 110,and +4N0 since the former becomes insohiblc 2 (110 SO,)} aftcr drying while the latter remains soluble.All the compounds soluble in ether givc trailsparent films on drying csccpt I). Thc presence of this last-named compouiid is one of thc causes of opacity on the drying of some collodions;the otlier causes are water in the alcohol or ether or the presence of acetic ether. All these coii~pounc~u may be prepared with mixtures containing much larger proportions of sulphuric acid and water ;but these have the disadvantage of rapidly dissolving the compounds if used waim. While endeavoiiring to ascertain the state in whicli nitrogen exists in these compounds I was led to examine the action of caustic potash on the highest cornponiid with which as is di knoun it proclnces a sdation capable of rediicing salts of silver to a mirror-like snrfacc upon the vessel th?t contains them.The decomposition of gun-cotton by 3 solution of potasli t,ilics place slowly at ordinary temperatures but almost instantly on raising it to 7 t?On ; each portion then irriiriersed cause4 a ConSidfYdble extrication of hc:rt hy which the tcniycraturc is soon raised to the hiling point anit ammonia is evolved with effcr- OBTAINED BY THE ACTION OP NITRIC ACID ON COTTON. 211 vescence. In making the solution for examination the temperature was kept at lSO" to avoid the formation of secondary products; at this point the gun-cotton quietly disappears without effervescence producing at last a dark treacly fluid.This was diluted neutralised with acetic acid and precipitated by neutral acetate of lead; the liquid filtered from the precipitate gave a further abundant precipitate with the basic acetate from which it was at first concluded that there were two distinct acids present; this however was afterwards found to arise from the solubility of the lead precipitate in the acetate of potash that had been formed from which solution the basic acetate again precipitates it. The liquid filtered from both prccipitatea contained nitrite and nitrate of potash. The lead precipitates after thorongh washing on a linen filter were diffused through watcr and decomposed by sulphurctted hydrogen during which process effervescence occurred with escape of NO, showing that notwithstanding the washings the precipitates had undergone they still retained a portion of nitrate.The brownish solution obtained was again precipitatcd by acetate of lead washed and decomposed as before when a pale yellcw strongly acid liquid wcis obtained retaining the original rcducing power upon the salts of silver unimpaired and capable of rapidly decomposing carbonatcs with cffervescence. Its power of forming crystalline salts was examined by slowly evaporating a solutiori of the compound on a slip of glass and viewing it under the microscope. The ammonia- salt appearing to be the most promising the liquid was neutralised with ammonia and allowed to evaporate irk vacz~o. After some time little tufts of prismatic crystals formed ; on examination however these were found to be devoid of reducing power and proved to be oxalate of ammonia.That the oxalic acid had not been formed by the subsequent processes was proved by detecting it in the original solu- tion of gun-cotton in cold aqueous potash. The liquid freed from oxalic acid by nitrate of lime was found to possess many of the cha- racters of saccharic acid such as its property of carrying don7n nitrites with its lead-salt and its redwing power on salts of silver which is manifested in both cases on adding to thc respective sohitiom a portion of a solution of nitrate of silver aninionia stxfficient to cause a clear solution and subsequently caustic potash without which in either case no mirror-like deposit will take place even on boiling; in certain proportimis tbc colo~xr of the reduced silver is identical.Like the neutral saceharates the ncntral salts of this acid (which might be termed pyroxilic acid until its idcntity with some other is proved) likewise give precipitates with salts of lime baryta and cadmium. The principal differences between the two acids are that no crystalline MR W. J. RUSSELL ON A acid pyroxalate of potash could be obtained the solution drying ii~ vacuo to a girnimy mass whereas the acid saccharate is very easily crystallised; and that the saccharates of the above-mentioned bases are far more soluble in the heat than in the cold and are visibly crystalline under the microscope; while t!ie pyroxalates of lime and baryta are but slightly soiuble on warniiiig the liquid and that of cadmium does not redissolve at all on the mere application of heat though like the saccharate it is readily soluble in an ~XCCSSof the salt of cadmium.The precipitates are likewise all amorphous with the exception of the lime-salt which has the form of little nodules. I have not bcen able further to examine the properties of this acid or obtain a coiripound with the certabity of its bciiig sufficicntly pure for analysis in conse-quence of the want of crystalline form and the obstinacy with which a portion of colouring matter is retained.

ISSN:1743-6893    

DOI:10.1039/QJ8550700201

出版商:RSC    

年代:1855

数据来源: RSC

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212 MR W. J. RUSSELL ON A X1X.-On a Xew Method qf Estimating Sdphur. BY ?VILT,IAMJ. ftuss~zr,,F.C.S. The methods at prescnt in use for thc estimation of snlphur especially when it is contained in organic compounds are well known to be very imperfect. The following rcsearcli was therefore undertaken at the suggestion of Professor Bunsen before commencing a more extended one on some compounds containing this element. The principle of the method consists in oviclating the sulphur by means of oxide of mercury the mercurial vapour given off effcctually pre- venting any explosion. From thc analyses which have been made in order to test the accuracy of the method it will be seen that it is inferior in this respect to none of the processes of organic analysis.The method is also easy of performance and applicable to all sub-stances containing sulphur. The analyses are made in the i'ollowing manner :-An ordinary piece of combustion-tube is closed at one end; for most inorganic substances and such as are easily burnt it need not be mop than thii*teeii or fmrtccn inches in length. From two to three grnis. of purc oxide of rncrcnry are first introduced into the tube and then a mixture of cqtid weights of ciirbonatc of soda and oxiclc of inercury. If the substance to be analysecl is a solid the process of introduction 2nd mixing is c-iactly siniilar to that followed NEW METHOD OF ESTIiGATIXG SULPHLTR. in an ordinary organic analysis. The method to be used when the substance is a volatile liquid will be described when speaking of the analysis of bisulphide of carbon.A cork with a small bent tube which is made to dip into water is inserted into the end of the combustion-tube to enable the operator to regulate the stream of oxygen and condense the mercurial vapours. Before commencing the heating the screen must be placed just in front of that part of the tube containing the substance to be analysed. Coals are then applied so that some two inches of the tube immediately before the screen is strongly heated and should be kept so during the whole analysis At the same time another part nearer the front of the tube is also heated but not so strongly; there are thus alternate portions of the tube in which no decomposition of the oxide of mercury is taking place.In the case of a volatile liquid being andysed this is of great importance for if the whole of the front of tlie tube were heated at once the oxide of mercury would be entirely decomposed long before the substance could be properly burnt ;but by this means not more of the tube need be heated at one time than is necessary to keep up a continuous and regular stream of oxygen. The screen should b-e removed as soon as that part of the tube inmediately in front of it has attained a bright red heat; and in the case of a non-volatile substance the heating may be carried on rapidly so that the whole combustion does not take above ten or fifteen minutes. Simultaneously with the heating of the part of the tube containing the substance to be analysed coals are applied at those places which were at first left unheated and last of all the tube being now at a bright red heat the oxide of mercury first intro- duced is decomposed.The gas given off during the combustion as it bubbles through the water may from time to time be tested by means of a splinter of wood which has been ignited in order to be sure that there is always a considerable excess of oxygen. When the oxide at the end of the tube has entirely disappeared the whole is allowed to cool and the contents of the tube afterwards emptied out into a beaker glass and dissolved up in water. It will generally be found that a little oxide of mercury in some part of the tube has escaped decomposition ;in case none should be present it is well to add a little or what is still better a few drops of chloride of mercury ; for it often happens that a trace of sulphide of sodium is formed which would be decomposed on acidulating the solution and thus cause a loss of sulphur.Hydrochloric acid is now added to the solution in the beaker and the tube well washed out with it. If sulyhide of mercury be prcseiit the solutioii is warmed and tlic clear liquid run through a filter; to MR. W. J. RUSSELL ON A what remains in the beaker glass some more hydrochloric acid is added and a small crystal of chlorate of potash; and the whole again slightly warmed. If the filter appears to have any trace of' sulphide of mercury upon it it should also be put into the solution. By this means every trace of sulphide will in a very few minutes be found to be entirely oxidised.The solutiou is then filtered and the sulphuric acid precipitated in the ordinary may by chloride of barium. The carbonate of soda in general use is well known to contain sulphuric acid and other oxides of sulphur ;and from these it is almost impossible to render it entirely free. The following method was therefore adopted :-The carbonate of soda after being made entirely anhydrous and finely powdered is mixed with an equal weight of oxide of mercury and the two very thoroughly incorporated together so as to obtain a substance of perfectly uniform composition. Some thirty or forty grms. of the mixture are now weighed out and heated in a combustion-tube and the amount of sulphuric acid which it gives carefully estimated.This correction for the excess of sulphur is then applied to all the analyses made with this mixture. The following are some of the results which have been obtained by this process and will show how universally it may be applied and what accurate results it gives. In the first instance pure crystallised sulphur was taken. Quantity used 0.121. Sulphate of baryta obtained 0*8827 corresponding to 0.121 sulphur With sulphocyanide of potassium the following result was ob-tained :-Quantity taken 0*5608. Sulphate of baryta obtained 1.3414. Calculation. Experiment. Cyanogen . . . . . 26*804 -Potassium . . . . . 40.206 -Sulphur . . . . . . 32.989 32.80 In order now to test the method in a still severer manner bisulphide of carbon was next taken which from the very volatile nature of the compound and the large amount of sulphur which it contains is undoubtedly a difficult substance to analyse.The combustion-tube to be used for bodies of this nature should be of considerable length. To prevent loss by evaporation the following plan was adopted. One end of the bulb to contain the liquid is as usual drawn out into a long and thin tube; the other after being sealed up is again heated and NEW METHOD OF ESTIMATING SULPHUR while soft pressed upon a flat surface so as to make the end of that form. The bulb is filled and weighed in the ordinary manner but introduced into the combustion-tube unbroken. Before commencing the heating a thin glass rod is introduced into the combustion-tube and pushed so far up it as just to come in contact with the flattened end of the bulb.The screen is now put into its place a little in front of the liquid and the heating commenced. The coals must be applied at three different places; namely near to the open end of the tube imuiediately in front of the screen and at a part between the two. As before stated the part near to the screen is heated most strongly for it is well to have oLie portion of the tube more free froni mercurial vapours than the rest. As soon as the mercury has beguii to voIatilise from this part the glass rod is pushed against the end of the bulb thus breaking the fine extremity of it against the closed cnd of the combustion-tube.The rod is then withdrawn and the cork with a bent tube may be fitted in. The iron screen should now also be removed and a small paper one placed across the combustion- furnaec a little beyond where the bulb is so that the hot coal which is applied to drive the bisulphide of carbon out of the bulb may not immediately evaporate it. As soon as the heat from the coals which should never be more than three or four inches from the broken end of the bulb has made that part of the tube hot the paper screen is removed. Tf the coals be farther off than this a little of the bisulphide of carbon is apt to take fire inside the tube as it is volatilised owing to there not being a sufficient quantity of mercurial vapour in that part and thus cause a too rapid evolution of gas. The fire is gradually advanced to the end and at the same time more and more of the front part of the tube brought to a state of redness. The following are the analyses of bisulphide of carbon made according to this method :-FIRST EXPERIMENT. Quantity taken 0.157. Sulphate of baryta obtained 0.9645. SECOND EXPERIMENT. Quantity taken 0.156. Sulphate of baryta obtained 09569. Calculation. 1st Expt. 2nd Expt. Carbon . . . . 75.79 -Sulphur . . . . 84.21 84.26 84.13

ISSN:1743-6893    

DOI:10.1039/QJ8550700212

出版商:RSC    

年代:1855

数据来源: RSC

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Mit. It. ltAIL'1'ON ON XX.-On some New Compounds of Phosphorous dcid. By ROBEHTRAILTON,F.C.S. STUDENT IN THE LABORATORY OF UNIVEXSITP COLLEGE. According to Wurtz's vicw of the constitution of the phospliites they are all bibasic. The crystallisecl hydrate of phosphorous acid contains three atoms ol water two of which are basic and may bc replaced by two atoms of a metallic oxide; but the third he says is inseparably bound up with the acid and is essential to its existence as an acid. Phosphorous acid may indeed be regarded as phos- phoric acid in which one atom of oxygen is replaced by hydrogen. According to this view the formula of the crystallised hydrate will be 2H0,PHO, and the general formula of a phosphite 2M0 PHO,. The experiments forming the subject of the present papcr 'cvcrc made with the view of proving that the hydrogen which Wurtz con- siders essential to the existence of a phosphite may be replaced by ethyl amyl &c A quantity of ethylate of soda was prepared by acting upon per- fectly absolute alcohol with sodium and evaporating to dryness at a temperature of about 120' C.A retort was used of about thrcc times the capacity required for the bulk of ethylate of soda produced. The retort containing the dry ethylate of soda was connected with an apparatus for upward distillation and a funnel which admits of being closely corked was secured in the tubulure. On the opposite page is a sketch of the apparatus used; but of course any other arrauge- ment which will cause the condensed vapour to return into the retort will answer the purpose.For every three atoms of sodium used one atom of terchloride of phosphorus was weighed out and mixed with five times its bulk of pure ether. This mixture was introduced into the retort by the funnel a fcw drops at a time the retort during the wholc of the process beins heated up to the boiling point of ether by a water-bath. The intro- duction of the mixture of ether and terchloride of phosphorus occupies a considerable time and must be conducted with caution as the action on each successive introduction is somewhat violent. After all the terchloride of phosphorus had been introduced the hcat was con-tinued until the vapour evolved no longer reddcned blue litmus paper. The ether was then distilled ogby the water-bath the retort trans- f(wed to an oil-bath and tlic oil gradually hcatcd up to 200' C.at S(fME NEW COMPOUNDS OP PHOSPHOROUS ACID. The end of the tnbc dips into nicwury. which point it was steadily maintained until the whole of thc ~ICW product was eliminated. When the operation is carefully conducted very nearly the theo- retical quantity requircd by the formula is obtained. The reaction is easily explained by the following cquation :-3 (NaO C,H,O) +PCl,= 3 C,R,O PO i-3 Na C1. The crude product is distilled in a current of hydrogen as it is found to oxidise if distilled in air and that portion which comes over at 188' C. is collected and redistilled. Towards the end of each redistillation when only a very minute quantity of the substancc is left in the retort a frothing occurs the thermometer falls phos-phuretted hydrogen is given off and if the retort be opened at this juncture the gas inflames spontaneously with a violent explosion.I may here mention a remarkable fact regarding the boiling point of this body. In air it is comtant at 191O C. ; in hydrogen at 188' C. 218 MR. R. RATLTON ON Phosphite of ethyl is a neutral somewhat oily substance possessing a peculiarly offensive odour. It is soluble in water alcohol and ether and burns with a bluish-white flame; its sp. gr. is 1.075 at 60' F. The carbon and hydrogen were estimated by the ordinary method ; the phosphorous acid as follows :-Weighed quantities of the liquid were introduced into stoppered bottles and concentrated nitric acid added.The bottles were left loosely stoppered in a tolerably warm situation for several days ; they were then gently heated until nitrous fumes were no longer evolved. The contents of each bottle were then transferred into separate beakers and the phosphoric acid precipitated as phospliate of magnesia and ammonia which was ignited. The analysis furnished the following results :-0-2405 grm. yielded 0.3786 grm. of carbonic acid I I , 0.11320 , water. 0.5115 , , 0.8047 , carbonic acid ,> >> , 0,4155 , water. 0.4513 , , 0,3020 , 2MgO PO,. 0*4110 , , 0.27140 , >? The percentages are- Cdculuted. Found. /---Q-12C . 72 43.11 42.91 42.89 15H . 15 8.98 8.87 9.03 30 .24 14*37 15.16 14.66 YO,. -56 33.54 33.06 33.42 L___-167 100-00 3 OO*OO 100.00 The vapour-density was ascertained by two experiments ~011-clucted according to the method described by me in the Society's Journal for October 1853 ; and it will be seen that they agree with the calculated density 1 =5*800 Experimental densities { 2 = 5.877 Calculated = 4 volumes 5.763 Tribasic Phosphite of AmyL-This body was prepared from arnylate of soda in a precisely similar manner to that described for the preparation of tlie cthyl-conipound and the analysis was con- ductctl by thc mile process. SOME NEW COMPOUNDS OF PHOSPHOROUS ACID. 219 The production of this body may be explained by the following equation :-3 (NaO CloHllO) +PC1,=3 C,,H,,O PO + 3 Na C1.Its analysis furnished the following results :-0.2477 grm. gave 0.5571 grm. of carbonic acid , 0.2521 , water. ?J ,? 0.31'72 , , 0.7123 , carbonic acid , , 0.3300 , water. 2MgO PO, ,? I.2763 , , 04855 , 14200 , ,) 0.5405 , > The percentages will be as follows :-Calculated. Found. /-.61.3430C. . 180 61.43 61-24 33H . 33 11.26 11.31 11-55 30 . 24 8.20 8-56 8.40 PO . 56- 19.11 1.8.79 18.81 293 100.00 100~00 1 oo*oo Phosphite of amyl is an oily neutral body possessing a still more ofknsive odour than the ethylcompound and is more easily decom- posed by heat. It boils in hydrogen at 236' C. is insoluble in water but soluble in alcohol and in ether. Phosphite of ethyl appears to form two classes of salts accordins to the amount of metallic base presented to it.Thus by acting upon it by one and two atoms of hydrate of baryta respectively in a manner which will be described further on we obtain first a salt in which one atom of ethyl is replaced by one atom of barium,-a reaction which the following equation will explain :-3 C,H,O PO + BaO HO = BaO 2C4H,0 PO + C41-1602. The formation of the second salt may be thus explained :-3 C4H,0 PO + 2 (BaO 130) = 2 BaO C,H,O PO + 2C,H60,. I may here remark that I could not succeed in replacing the third atom of ethyl by barium. BaO 2C,H,O PO,.-This salt is formed when to one atom of baryta dissolved in hot water one atom of phosphite of ethyl is added and the whole gently heated for a few minutes. Alcohol is given off the liquid becomcs neutral and if carefully evaporated in a water- bath deposits the salt as a confused crystalline mass.This salt is extremely soluble in water soluble in dilute alcohol but ouly slightly MR. It. RAILTON ON so in absolute alcohol. The baryta salt was recrystallised the crystals dried between folds of blotting-paper and then under an exhausted receiver over sulphuric acid until it ceased to lose weight. It W~H then transferred to an oil-bath and heated up to 108' C. which teniperature does not decompose it. It is very deliquescent and consequently the analysis shows a somewhat greater increase of hydrogen and deficiency of carbon than might be otherwise expected. 0.8320 grm. yielded 0.6910 grm. of carbonic acid , 0.3710 , water.Y> fJ 1,6195 , , 1.3505 , carbonic acid 9 1) It 0.7455 , water. 1.1065 , , 0*6285 ,) BaO so, , 0*6070 , 2Mg0 PO,. 1) 1.Y 1.1301 , , 0.6380 , BaO SO, YY J9 , 0.6190 , 2Mg0,PO,. Ik'roxn which results the following percentages were deduced :-Calculatect. Found. -SC . . 48-00 23.22 22.65 22.74 1011 . . 10.00 4.84 4.95 5-11 20 . . 16-00 7-74 7.98 8-00 BaO . 76.66 37.09 37.32 37.09 PO . 56.00 27.11 27-10 27.06 206.64 100~00 100~00 100*00 The combustion in the first experiment was made with oxide of copper; in the second with chromate of lead. The baryta and phoaphoroas acid were estimated from the same salt. The salt was dissolved in water and the baryta precipitated with pure sulphuric acid. The filtrate froin the sulphate of baryta was then carefully evaporated to a small bulk and the phosphorous acid oxidised by means of concentrated nitric acid then Precipitated as the phosphate of magnesia and ammonia which was well washed dried and ignited.The potash salt was obtained from the baryta salt by double de- composition with sulphate of potash. It crystallises with difficulty in thin plates radiating from the centre; is soluble in alcohol but not in ether and is deliquescent. The soda salt was obtained in a pirriilar manner and has similar properties. I did not succeed in crystallising it. The nickel zinc iron and magnesia salts were also fornied by cloublc dcconilmitioii with thcir sulphatcs Noiic of them crystallise . SONE NEW COMPOUNDS OF PHOSPHOROUS ACID.221 they are extremely soluble in water but appear to be insoluble iu alcohol. In attempting the formation of the copper salt the copper was reduced even on evaporating ii2 vucuo. 2 BaO C,H,O BO,.-When two atoms of baryta are dissolved in hot water and one atom of phosphite of ethyl added to it and the whole gently heated alcohol is given off and this salt is procluced. It does not crystallise nor do any of the salts prepared from it by double decomposition with the various sulphates. It was dried at 108' C. and gave the following results :-0.7025 grm. yielded 0.2495 grm. of carbonic acid > 9 , 0.1805 , water. 1.82CO , , 1*7%10 , BaO SO, I >> , 0.8372 , 2MgO,PO,. 1.1600 , , 1.0950 , BaO SO, , J7 ,) 05335 , 2MgO PO,.The percentages are ns follows :-Calculated. Founcl. 4c . * . 24.00 9\75 9.69 5 H . . . 5.00 2-03 2.06 0 . . . 8.00 3-35 3.40 2BaO . . 153.28 62.23 62.13 PO . . 56.00 22.74 22.72 -246.28 100.00 100~00 When imre than two atoms of baryta are mixed with one atom of phosphite of ethyl the excess of baryta is gradually deposited on evaporation as carbonate or if the evaporation takes place in uacuo as hydrate. This salt may be evaporated in a water-bath without decomposing but on boiling it is readily deconipoged into alcohol which is given off and diphosphite of baryta which is deposited in shining scales. Analysis of the deposited salt :-1.5510 grm. yielded 1.5905 grm. of BaQ SO, >3 >7 , 0.7720 , 2 MgO.PO,.0.9605 f , 0.9850 , BaO SO, >? 2) , 0.4780 , zni4g0 PO,. From these analyses the formula of this salt will be 2 1x0 2 BaO YO,; or on Wurtz's view NO 2BaO,PHQ,; as will be seen by coriiparing the percentages. Mlt. R. RAILTON ON NITROGLYCERTNE AND Cakmltited. Pound. 2 €10 . . 18-00 7.92 -\ I 99 8.04 2BaO . . 153.28 67-44 67-42 67.38 PO . . 56-00 - 2 4-64 24-59 24-58 -.__ s__- 227.28 1 oo*oo 100.00 100~00 The aiialysis of this salt was conducted in a similar manner to the others except that it was dissolved in dilute hydrochloric acid.

ISSN:1743-6893    

DOI:10.1039/QJ8550700216

出版商:RSC    

年代:1855

数据来源: RSC

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Mlt. R. RAILTON ON NITROGLYCERTNE AND XX3.-On iiitroglyceriue and the Products of its jr)ecmzposit.ion by Potash. By ROBERTRAILTON,F.C.S. Sobero discovered nitroglycerine some time ago but did iiot de-termine its composition,-probably from the fact of its being a highly explosive substance. There is however no danger to be appreheiided from its analysis if sufficient care be taken. The compound from which the following results were obtained was thus prepared. Equal volumes of concentrated nitric and sulphuric acids were mixed and cooled by immersing the flask which contained them in ice-cold water. Syrupy glycerine was then introduced into the flask a few drops at a time the mixture being well shaken and cooled eacli time. After some time the product floated on the top as an oily substance; it was then poured into cold distilled watcr and repeatedly washed in that menstruum by decantation it was afterwards frced as much as possible from water by blotting-paper and an attempt was made to dry it more completely under the bcll- jar of the air-pump but without success as it was rapidly decom- posed on exhausting the jar.From this circumstance the hydrogen could not be estimated but the relative amounts of carbon and nitrogen were satisfactorily deter- mined by Liebig’s process. About a gramme of the conipound was mixed with as much oxide of copper as half filled a combustion-tube thirty-six inches in length. About eight inches of the remainder of the tube was filled with oxide of copper and the tube theii wholly filled with rediiced copper.Tbe tube was then enveloped in copper foil the combustion proceedcd with and the mixed gases collected in graduated tubcs ovci-rriercury. THE PRODUCTS OF ITS DECOMPOSTTION BY POTASB. 223 The first portion of the gases was allowed to escape; four tubes were then filled and the following are the results in the order in which they were collected :-Number of tubes . . . I. 11. 111. TV. Volumes of mixed gases . 101 91.5 99 97 Ditto absorbed by KO . 69 61.0 65 64 I-I_ Ditto remaining gas . . . 32 30.5 34 38 There being slight discrepancies in these results I obtained tubes more finely divided when a second experinient gave- Number of tubes . . I. 11. In. IV. V. VolumesofmixedcS'ases.178 194 193 173 194 Ditto absorbed by potash 117 128 127 115 1.29 Ditto residual nitrogeii . 61 66 65 58 65 Now as the composition of glyceririe is well known and as the volt-une of nitrogen is proved by these experiments ti! be half that of the GO absorbed by potash wc may safely assume the following to be the change which the glycerine undergoes :-Nitroglycerine is heavier than water in which it is brit slightly soluble; it is soluble in alcohol and in ether. When boilccl for sornc time with an aqueous solution of catktic potash it is dccomposed nitrate of potash and glycerine heing formed. A solution of caustic potash in water was made of nearly the same specific gravity as the nitro-glycerine. The potash solution and thc nitroglycerine were introduced into a flask and boiled for several hours ; at the end the liquid became completely homogeneous when it was carefully neutralised with pure sulphuric acid.The siilphate of potash was crystallised out and on further evaporation the nitrats of potash was deposited. This salt was purified by repeated re-crystallisations and afterwards analysed. The nitrate of potash was dried until it ceased to lose weight and wa$ thcn converted into sulphate of' potash. arm. Wcigbt of the salt used . . 0.979 Ditto -KO SO forimd . -0*8$1 Calculated percentage of KO in KO NO,= 46.54 Found in the above-namcd salt . . =46*41 224 MR. G. KAY ON I may add that the salt obtained by the decomposition of nitro-glycerine exhibited all the reactions of nitrate of potash.For the purpose of obtaining the glycerine the solution from which the nitrate of potash had becu crystallised was evaporated to a syrupy consistence and treated with absolute alcohol. The solut,ion of sly-eerine in alcohol thus obtained was evaporated in a water-bath and the residue treated with ether in which the nitroglycerine had there been any undecomposed mould have been dissolvecl. The ether was removed without having dissolved anything and a portion of the residue heated with bisulphate of potash when thc pungent odour of acrolein was evolved. The decomposition of nitroglycerine by means of hydrate of potash may be represented by the equation Nitrobenzole was boilcd with concentrated solution of caustic potash for several hours ;the resulting solution evaporated nearly to dryness water added and again evaporated the lattcr process being repeated as long as any odoiir was pcrceived. The so?ution was then examined for nitric acid and distinct evidence of its presence was obtained.

ISSN:1743-6893    

DOI:10.1039/QJ8550700222

出版商:RSC    

年代:1855

数据来源: RSC

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224 MR. G. KAY ON XXII.-On Some New Derivatiem of Chloroform. By GEORGEKAY STUDENT IB TEE LABOTZATORP OF VXTTERSITT COLLEGE. Every process of double decompositioii may be viewed in two different ways. Thus when hydrochloric acid Cl H acts on hydrate of potash H Q,* we may sap cither that the hydrogen of the one changes places with potassium of the other or the chlorine of the one with peroxide of hydrogen €38,In the other. This idca is strikingly illustrated by the following experiments in which by the actioiz of Ae 1 at. chloroform GHCI, on 3 at. ethylate of soda lCTa43 the chlorine of the former is replaced by peroxide of ethyl 4& H Q the pro-ducts being 3 at. chloride of sodium and 1 at. of a new body having the empirical f~rii~ula 3 GPi:Q €+ HI6Qj.-i-GHC1 =3NaCl+ .G7RI6@,. * H=l; 8=12; 8x16; B=32. SOME NEW DERWATTVES OF CHLOROFORM. This product may be equally well conceived to be a body in which the basic hydrogen of 3 at. alcohol is replaced by the tribasic radical of chloroform and according to the older theories of the capacity of saturation of salts would contain a tribasic modification of formic acid; for it bears the same relation to formic ether that a so-called tribasic phosphate bears to a monobasic phosphate.-The following is the mode of preparation :-Two ounces of sodium were dissolved in absolute alcohol in a tubulated retort and the excess of alcohol distilled off as much as possible by means of an oil-bath; pure chloroform was then added gradually to the dry mass in the proportioii of 1 equivalent to 3equivalents of the sodium used at first the action was very violent and the retort required to be kept cool to prevent loss by evapora- tion ; the liquid was then distilled from the chloride of sodium which was formed and subjected to a series of fractional distillations.It finally resolved itself into three portions the first of which was small and came over between 50" and 76' C. but chiefly between 50' and 60"; the second which was in considerable quantity and obtained between 78' and 79O was nearly pure alcohol; the last portion boiled constantly at 145' to 146",and amounted to about one-sixth of the whole liquid. The lower portion of the distillate obtained between 50" and 76' had the odour of common ether ;a part of it was treated with sodium and water added when a slight turbidity was produced but no appearance of an oily stratum; it was tested for formic acid and chlorine both of which were found to be present.As the above process yielded only a small product other than alcohol the following modification was adopted :-As much sodium as possible was dissolved in a limited quantity of alcohol; chloroforni was then added care being taken to keep the liquid alkaline and to ensure the decomposition of the chloroform; after which more sodium was added and the process repeated several times until the precipitate formed became bulky. The liquid was then distilled off and again treated with sodium and chloroform as before and separated from the precipitate.This process was con- tinued until 2 ouiices of sodium had been used; the resulting liquid was distilled fractionally when it divided into three portions re- spectively similar in quantity and in boiling points to those afforded by the first experiment. Thesubstance which boilsat 7 4.5' to 146"is acolourless,limpid liquid slightly soluble in water and having a peculiar aromatic odour ; it VOL. VI1.-NO. XXVII. Q 226 MR. Q. KAY ON burns readily with a blue flame and little smoke; its specific gravity is 0.89644,and at -18' C. it still remained liquid. The following analyses were made of this body :-I. 0.1859grm. gave 0.3855 CO and 0.1716 water 11. 0.2404 , 0.4979 , , 0.2283 , These results yield the following percentages :-I.11. Mean. C 56.55 56.48 56.51 H 1025 10.55 10.40 C 33.20 3.2097 33.08 The following is the mean of the experiments placed in juxtaposi- tion with the theoretical values which correspond to the formula G7H1 :-Experiment. Theory. Difference. G 56.51 56-75 -0.24 H 10.40 10-81 -0.41 8 33.08 32-44 + 0.64 The specific gravity of the vapour of the substance was taken and the following data and results obtained :-Weight of globe filled with air barometer 30.1 inches temperature 13.6' C. . . 14.0612 grm. Sealed the globe at 219.5' C. bar. 30.1 in. Weight of globe and condensed vapour barometer 30.17 inches tem perature 109OC. . . . . . . . . . 14.2945 , Capacity of globe in cubic inches . . . 5-77 , Residual air at 12%' C.barometer 30.17 inches . . . . . . . . . 0.08 cub. in. The above data give 5.217 as the specific gravity of the vapour. Assuming that the compound has the formula .S,H,&& the theo- retical specific gravity of its vapour condensed into two volumes would be 5.124; thus-Experimental density . . . 5.217 Theoretical , . . . 5.124 Difference . . . 0-093 As the methods above described yielded this body in small quantity only it was thought that the same substance might be more readily and economically procured by making use of hydrate of potash instead of SOME NEW DERIVATIVES OF CHLOROPOSM. sodium ; but it was necessary in the first place to ascertain what would be the action of caustic potash on the compound.For this purpose a small portion was dissolved in alcohol solid hydrate of potash added and the liquid distilled upwards for two or three hours and then distilled off; the residue was dissolved in water exactly neutralised by hydrochloric acid filtered to remove the tur- bidity and then a few drops of chlorideof mercury added. In a little time and after the application of heat a very slight precipitate was formed having the appearance of subchloride of mercury; it was also blackened by ammonia. Sesquichloride of iron was also added to a portion of the neutral liquid when a red colour rather darker than that of the sesquichloride itself appeared. As the indication of the presence of formic acid was only just perceptible it appears that the action of potash on the compound produces that acid in very small quantity only.Twelve ounces of solid potash and eighteen ounces of powdered quicklime were now added to rather more than three pints of absolute alcohol and theliquid distilled upwards for five or six hours; chloroform was then added gradually in the proportion of one equivalent to three of the potash used the upward distillation being still continued for two or three hours; the liquid was then distilled off by the heat of an oil-bath and submitted to a series of fractional distillations. As in the former experiments the lowest distillate had the odour of common ether. By this method a small distillate was obtained which boiled coii- stantly at 144.5' to 145' C. and was equal in bulk to about one-sixth of the chloroform used; its properties were precisely the same as those of the compound already described.Although this method yielded only a comparatively small quantity of the substance it was much more productive and expeditioiis than the one previously adopted; it was therefore repeated several times the alcohol which was separated each time by the fractiona1 distillations being used for dissolving the potash in the next opera- tion. Ultimately a considerable quantity of the compound was obtained which enabled me to determine the boiling point more exactly that point was now found to be constantly at 146O C. :-The following analysis was made of this compound:- 0.2597 grz. gave 0.5410 carbonic acid and 0.2536water. These numbers correspond to the following percentages opposite to which are placed the percentages in the compound 67H16Q3- 228 MR.0,KAY ON Bxperiment. w46% Difference. G 56.79 56.75 + 0.041 H 10.82 10.81 + 0.01 8 32.39 32.44 -0.05 When pentachloride of phosphorus was added to a small portion of the compound a very dense liquid was formed having the appear- ance and odour of chloroform. One equivalent of dry hydrochloric acid was passed into 17 grms. of the compound; the gas was wholly absorbed a considerable amount of heat being evolved and the liquid assuming a brownish eolour The liquid which still remained neutral after the absorption of the gas was distilled fractionally and finally collected in three portions. The first was about one-sixth of the whole and came over between 20° and 50' C.; the second about one-third was obtained between 50' and 68O; and the last also about a third part passed over between 68' and looo The smallness of these distillates pre- cluded any further attempts to obtain a fixed boiling point. Two equivalents of dry hydrochloric acid were next passed into 29% grms. of the compound ; a large proportion of the gas was absorbed but towards the close a portion passed through the liquid. After this treatment the liquid fumed and was highly acid; it was distilled upwards for some time by which a portion of the free hydrochloric acid was expelled and then distilled fractionally. Ultimately feur distillates were obtained; about one-third of which came over between 56' and 60° one-fourth between 60' and 70' ; one-sixth between 70° and SO"; and one-fourth between 80' and 88'.As in the previous experiment the numerous distillations had so much reduced the bulk of the liquid that it became inipossible to arrive at a constant boiling point. To the lowest of the above distillates about an equal bulk of water was added the substance ffoated on the surface and seemed to be only slightly soluble in the water. It was then mixed with carbonate of soda in sufficient quantity to iieutralise the free acid which yet re-mained and the liquid pipetted from the water distilled upwards for a considerable time over fused chloride of calciuni and then distilled off; it was now found to boil constantly at 55.5 C. The distillate which had been obtained between SOo and 70° after being treated in the same manner also yielded a liquid which boiled at 56OC.These two products besides agreeing in their boiling points had each the odour of formic ether. The following analysis was made of the product which boiled at 55*5Oc.:- SOME NEW DERIVATIVES OF CHLOROFORM. 0.1815 grm. gave of CO, 0.2920,and of water 0.1413 grm. These numbers furnish the following percentages:- C=43*85 H= 8.65 Subjoined are given the calculated percentages in formic ether and in formic ether plus an equivalent of water :-Formic ether. Formic ether + an eq. of water. C 48.64 c 43.37 H 8-10 H 8-43 The vapour-density of this body was also taken by Gay-Lussac's method; the mean of three observations gave the density as 2.439 the specific gravity of the vapour of formic ether is 2.5.From the above results I am led to conclude that the liquid which boiled at 55-5' was merely formic ether mixed with a small amount of water the complete separation of which was difficult in conse-quence of the small quantity of the liquid operated upon. Action of Sulphuric Acid on the compound 4&H,,Q3. To 28.7 grms. of the compound two equivalents of mono-hydrated sulphuric acid were added. The acid sank to the bottom and did not appear to act upon the liquid; but on a slight application of heat the action commenced the mixture becoming dark-coloured ; after the whole of the acid had been slowly added with constant agita- tion of the liquid the mixture was cooled and then added a few drops at a time to about its own bulk of water in which was kept sus- pended by continual shaking rather more than a sufficient quantity of baryta to neutralise the acid employed; a few pieces of ice were also placed in the water ;and the flask in which the operation was per- formed was immersed in a frigorific mixture.After the whole of the acid mixture had been added to the baryta the liquid was found to be alkaline. It was then filtered from the precipitate which was gelatinous and distilled. When about five-sixths had passed over that which remained in the retort began to froth very much and was turbid; the distillation was therefore stopped and the residue on cooling formed a solid crystalline mass which was dissolved in water.The solution was very turbid and was not rendered clear even by repeated filtration. The liquid was then transferred to a flask about an equal bulk of absolute alcohol poured upon its surface and then left at rest for several days. The distillate was next saturated with carbonate of potash when a stratum of liquid rose to the surface; this liquid was pipetted off treated several times with carbonate of potash and then distilled ; 230 MR. (3. GAY ON it boiled constantly at 8OoC. and was found to be common alcohof. The lower stratum was then distilled ;the crystals of carbonate of potash being removed from the retort as often as their accumulation became troublesome ;when the carbonate had been wholly removed the liquid boiled at 100°C.and was merely water. The turbid liquid to which alcohol had been added was found after standing several days to have deposited a quantity of crystals which were hexagonal prisms; they were insoluble in alcohol but very soluble in water ;when dried and analysed they proved to be formiate of baryta. The liquid in which these crystals had formed was again filtered but it still remained turbid; a portion was evaporated and the residue dried at a low temperature until it ceased to lose weight a quantity weighing 0.561 grm. when ignited fur- nished 0.3116 grm. of sulphate of baryta which corresponds to 55-54 per cent. Sulphovinate of baryta with two atoms of vater contains 55.11 per cent. of sulphate of baryta. The gelatinous precipitate first mentioned was now washed with a large quantity of hot water the washings evaporated down to a small bulk and allowed to stand’for two days when a slight crop of crystals was deposited; these crystals were insoluble in alcohol but readily dissolved by water arid were of the same form as those pre- viously mentioned as consisting of forniiate of baryta.A consider-able quantity of alcohol was now passed through the washed precipi- tate reduced in bulk by evaporation on the sand-bath and then left to evaporate at the ordinary temperature; no crystals were formed and when dry a very slight quantity of an amorphous substance remained. From these experiments it appears that the action of sulphuric acid on the compound G7H,,Q3gives rise to sulphovinic acid formic acid and alcohol; no other product was observed.A portion of the dried substance which was believed to be sulpho- vinate of baryta was distilled with dilute sulphuric acid when alcohol and water only passed over. An attempt was also made to replace two of the equivalents of chlorine in chloroform by peroxide of ethyl. For this purpose four ounces of sodium were converted into ethylate of soda the excess of alcohol distilled off and the dry ethylate powdered quickly in a warm mortar. It was then added in small portions at a time to an excess of chloroform in a tubulated retort.+ The action was very brisk * It was necessa:*yto add the ethylate in powder for when in fragments it assumed il dark brown colour and the action of chloroform uponi t was dmost imperceptible.SOME NEW DERIVATIVES OF CHLOROFORM. much heat being evolved rendering it necessary to cool the liquid after each addition of ethylate. In this mariner one-half of the ethylate was added and then the liquid was distilled off and redis- tilled from a retort fitted with a thermometer ; the portion obtained between 60' and 70° being chiefly chloroform was treated as before with the remaining ethylate care being still taken to keep the chloroform in excess. The liquid product of these operations consisting of about half a pint was now subjected to a series of fractional distillations when it resolved itself into chloroform alcohol and a small quantity of liquid having the same boiling point and properties as the compound €+H16Q3 which had been already obtained.Whilst engaged on these distillations I observed that one portion which had come over between SO' and 82' when repeatedly distilled gradually lowered its highest point from 82' to 79-3' this circum- stance leads me.to suspect that some other compound having its boiling point near to that of alcohol had in the first instance been formed but was afterwards decomposed by the frequent distillations. The following attempt was made to obtain a compound homologous with the .61Hl,8j by acting upon chloroform by amylate instead of ethylate of soda :-Two ounces of sodium were dissolved in pure amylic alcohol the excess of fusel oil distilled off as far as possible from the amylate of soda ; chloroform then added gradually to the dry amylate in the pro- portion of one equivalent to three of the sodium used; and the liquid distilled from the chloride of sodium by the heat of an oil-batb and submitted to fractional distillation.A large proportion was found to be fusel oil ;the remainder was an oily-looking liquid which boiled only at a very high temperature (between 260' and290' C.) An attempt was made to purify this liquid but in each distillation a considerable quantity was decomposed even in an atmosphere of dry hydrogen a dark-coloured resinous matter remaining in the retort. In conse-quence of this decomposition and of the small quantity of the liquid available it became impossible to obtain a constant boiling point ; the repeated distillations seemed to show that a fixed point existed some-where between 280' and 300' C.

ISSN:1743-6893    

DOI:10.1039/QJ8550700224

出版商:RSC    

年代:1855

数据来源: RSC

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MR. J. FAIRLTE ON THE XXLII.-Oa the Constitution of Commercial Creosotefrom CoaEtar. By JAMESFAIRLIE STUDENT IN THE LABORATORY OP UNIVERSITY COLLEGE. The chemical history of the compound to which Reichenbach ‘I assigns the name Creosote” remains as yet very imperfect. Reichenbach,* Ettliug,? and Gorup BesanezJ have successively examined the substance as found among the products of the dry dis- tillation of wood Et tling obtained the following results :-I. 11. Mean. C 75.72 74.5 3 75-12 H 7.80 7.87 7-84! 0 16.48 17.60 17.04 whence he assigns to creosote the formula Cl8TI9O2 which requires 77.06 C 8.26 H and 18-680. He does not however give the boiling point of the liquid which he analysed. Devilleg assigns to creosote the formula C,,H,O, which requires 77.77 C 7.41 H and 14.81 0 this agrees better with the analytical results particularly in the hydrogen but is yet far from satisfactory.Again St adeler(1 remarks onEttling’s paper that his results present a much closer agreement with the percentages for the formula Cl2H,O2 which are 75.79 C 7.37 H and 16.84 0. He conceived commercial creosote to be nothing but impure hydrate of phenyl of which the formula is undoubtedly C,,H6O?. More recently this substance has been investigated by Gorup Besanez’y who assigns to it the formula C,,Hl6O4. He obtained the following results :-I. 11. 111. m. F. VI. VII. VIII. C 75.32 75.72 75-54 74-76 75.82 75.02 74.78 74-68 H 7.84 7.94 7.85 7.95 7.95 7.95 7.95 7.84 O 16*S4 16.34 16.61 17.29 16.30 17.03 17.24 17-44 C 75%0 76.47 These give a mean of H 7-91.His formula requires 0 l6%9 0 15.19 * Pogg. Ann. xxxi. 497 ; Ann. Ch. Pharm. vi. 202. f-Ann. Ch. Phaixn. vi. 209. 1; Ibid. May 1853j Pharmaceutical Journal Hiii. 289. 5 Ann. Ch. Phys. [3] xii. 228. \\ Ann. Ch. Pliarm. Ixxvii. 25. (n Ibid May 1853j Pharmaceutical Journal xii. 388. CONSTITUTION OF COMMERCIAL CREOSOTE FROM COAL-TAR. 233 The substance analysed by Gorup Besanez was evidently impure its boiling point ranging from 398" F. to 407' (203.3 to 208.3 C.) The following experiments in conjunction with those of Nr. Scrugham,* show that commercial creosote is mainly a mixture of two homologous bodies,viz. Hydrate of Phenylor CarbolicAcid= G6g50 €&H6Q and Hydrate of Cresyl =G7 g7@=.6,H8@.-f The temperature at which the first specimen examined distilled varied from 160" C.at the commencement to 2lh' towards the close of the distillation a considerable quantity of water passed over with the first portions. During the first distillation of the crude liquid the thermometer was somewhat steady at about 184' C. (the boiling- point of hydrate of phenyl),and again though somewhat less at 203' C. (the boiling point assigned to creosote) ;about two-thirds passed over below 200' C. From this portion a considerable quantity of pure hydrate of phenyl may be obtained by fractional distillation. The boiling point of a second specimen examined varied from 190" to 224' C. ; this contained much less of hydrate of phenyl and water The liquid distilling between 200' and 224" was submitted to frequent fractional distillations and ultimately an eighth of the whole quantity first taken was obtained which distilled at 203"C.Although on redistilling the boiling point of this portion did not vary by SO much as two degrees yet when it was repeatedly distilled considerable variation occurred. I had occasion to observe during the fractional distillation of the whole quantity boiling above 200" C. that there was a uniform tendency of the boiling points to become lower on each successive distillation ;nor could the distillation be effected in any case without partial decomposition a small black residue always remain- ing in the retort; and the different fractions although always colourless when first collected invariably assumed a slight yellowish tint after keeping a few days in closely stoppered bottles.Moisture was also constantly observed in the neck of the retort on redistilling portions which had come over repeatedly at above 200" C. Three analyses of this somewhat impure product gave per-centages for carbon not greatly differing from that required by the forniula C7H80,but the hydrogen was always in excess. It was conceived that the substance analysed was creosote but that * Page 237 of this volume. d' In the remainder of this paper,. the double atomic wcights of carbon oxygen and sulphur are used ; viz. 8=12,8=16,8 =32. MR. J. FAIRLIE ON THE this body must be extremely unstable and susceptible of being by oxidation reduced to hydrate of phenyl.A portion of the liquid which was found to boil repeatedly at 200' C. in an atmosphere of dry hydrogen was submitted to upward distillation for some time in an atmosphere of dry oxygen. Under these circumstances the liquid rapidly blackened and finally became slightly viscid. Not more than two-thirds of the quantity taken could be recovered by subsequent distillation a black tarry mass remaining in the retort. The boiling point of the quantity so obtained extended through a considerable range of temperature a large proportion having much the same boiling point as the original liquid; another portion had a lower boiling point and seemed to be a mixture of creosote with the hydrate of phenyl. When the liquid obtained in the purest state by ordinary distil- lation is distilled in an atmosphere of dry hydrogen by far the larger portion passes over at ZOO' C.a very small quantity only distilling at a somewhat lower point this larger portion when repeatedly redistilled in hydrogen is found to boil constantly at that tempera- ture (ZOO' C.) It must be observed that the atmosphere in which a liquid is diu- tilled appears considerably to affect its boiling point in this case the change from common air to hydrogen produces a fall of not less than three degrees. The boiling-point of hydrate of phenyl does not change in any number of distillations being constant at 184O C in common air. Nevertheless this body boils with equal steadiness at 182' C.in an atmosphere of dry hydrogen. The liquid boiling very constantly in hydrogen at 200' C.was burnt with oxideof copper I. 0.41 26 grm of the liquid gave 1.1710 grm. of carbonic acid Yt Y > 0.2988 , water 9, 11. 0.2754 , 0.7845 , carbonic acid 3 33 99 0.1785 , water. The percentages deduced from these agree much more nearly with the formula C,,H802 than with any other which has been proposed for creosote. Calculation. Experiment. I. 11. e,=84 = 77-71 77.40 77.69 H,= 8 = 7.41 8.05 7'20 Q =16 = 14432 -14.55 15.11 108 100*00 100~00 100~00 CONSTITUTION OF COMMERCIAL CREOSOTE FROM COAL-TAR. 235 I may remark that the substance analysed agrees in its general properties with the body described by Reichenbach viz.it is very soluble in ether alcohol and acetic acid but very slightly soluble in ammonia; it is colourless of great dispersive power and is neutral to test-paper; with sesquichloride of iron it gives a faint violet colour. Its specific gravity as obtained in its purest form by ordinary distil- lation was 1.044 at 60" F. Reichenbach gives 1.037 and Gorup Besanez 1.0461 to 1-049. Upon the comparatively impure substance first obtained by ordinary fractional distillation I tried the action of various reagents with a view more particularly to determine its constitution through the products of its decomposition. The results which I obtained are not so satisfactory as could be desired; nevertheless a brief description of them may not be without interest.Pentachloride of phosphorus acts very strongly upon creosote with a very abundant evolution of hydrochloric acid gas; after a while however it is necessary to assist the action by heat. The penta- chloride was added to the creosote until no more was dissolved ;the mixture was then distilled upwards until hydrochloric acid gas was no longer evolved and then distilled in the ordinary way; upon redistillation it began to boil at 2%O0 C. The distillation was con-tinued with a thermometer in the retort till the temperature reached 300' C. when a considerable black residue remained in the retort; a portion of this was finally forced over at a temperature apparently higher than the boiling point of mercury these last portions of the distillate showed some disposition to crystallise.Phosphoric acid was qualitatively ascertained to be present in it in a state of combination. I believe the distillate to be a mixture of the chloride and phosphate of the radical "Cresyl," C,H,. I was unable to obtain either of these compounds in a state of purity although the liquid was dis-tilled a great number of times; but it may be observed that the greater portion of the lowest fractions were collected between 180°-1900 C. between which the boiling point of the chloride pro-bably lies. When the supposed chloride of cresyl was mixed with ethylate of soda and the mixture distilled upwards for some time chloride of sodium was formed in considerable quantity ;when no more appeared to be formed the liquid was distilled off.On addition of water to this distillate a light ethereal liquid of an extremely fragrant odour rose to the surface and this when redistilled boiled pretty 236 MR. J. FAIRLIE ON COMMERCIAL CREOSOTE FROM COAL-TAR. constantly at 197' C. Its composition should be G9H12Q thus-The results of its analysis were not satisfactory although sufficiently near to induce the belief that it was formed the liquid obtained was evidently not quite pure. When equal bulks of creosote and an aqueous solution of potash of specific gravity 1.25 are mixed and allowed to remain at rest for twenty-four hours a crystalline compound is formed presenting the appearance of small pearly scales which float on the surface of the liquid ; the quantity formed however is very inconsiderable.This salt (which has been previously noticed) is extremely unstable ; when collected on a porous tile and placed over sulphuric acid it gradually decomposes and becomes black. It appears to be the Cresylate of potash. The action of fuming nitric acid upon creosote is extremely energetic; it may however be controlled by adding the nitric acid in small quantities at a time the vessel containing the creosote being surrounded by ice. During the action the colour of the liquid gradually changes to a deep red. After the addition of about an equal volume of strong nitric acid it was observed that the liquid had separated into two layers the upper of a deep red colour the lower black and tarry. The upper portion when removed and neutralised with caustic potash solidified into a distinctly crystalline mass sparingly soluble in cold but readily in hot water; 01815grm.of this salt (which I was not able to obtain perfectly pure) gave -0575 grm. of sulphate of potash = 17.08 per cent. of potash the probable H4(zQ2)3 formula of this salt viz. 42 Q requires 16.75. There is no doubt whatever that the acid of this salt is homologue of nitro-phenisic acid and is formed by the replacement of three atoms of hydrogen by 3 (NO,) just as three atoms of hydrogen are similarly replaced in hydrate of phenyl. An attempt was made to obtain an acid which should contain only one or two equivalents of NO,. For this purpose the creosote was previously dissolved in absolute alcohol to which nitrate of urea had been added and acted upon by dilute nitric acid the action in this case was moderate but no definite result was obtained.When equal bulks of sulphuric acid and creosote were carefully mixed the rise of temperature was considerable and the liquid assumed a light red colour. After allowing the mixture to stand for twenty-four MR. H. SCRUGRAM ON SOME NEW COMPOUNDS OF PI-IENYL. 237 hours it was neutralised by hydrate of baryta the excess of baryta thrown down by carbonic acid gas and the liquid filtered and con- centrated by evaporation. The aqueous solution when evaporated to dryness yields the salt in a white granular mass; 07925 grm. of this salt gave *3555 grm. sulphate of baryta=29*4'7 per cent. of H baryta.The formula for sulpho-cresylate of baryta d+ (daa)Qj$$Q3 requires 29.97 per cent. Chlorine gas is largely absorbed by creosote the liquid assuming a bright red colour ; after the action of chloiine has been continued for some time hydrochloric acid fumes are given off. On distilling this liquid after previous washing with carbonate of soda its boiling point was found to vary from 210' C. to 244' C. The first portions of the distillate were colourless the last of a faint violet colour; towards the end of the distillation hydrochloric acid was given off in con- siderable quantity the product being evidently decomposed.

ISSN:1743-6893    

DOI:10.1039/QJ8550700232

出版商:RSC    

年代:1855

数据来源: RSC

摘要:

MR. H. SCRUGRAM ON SOME NEW COMPOUNDS OF PI-IENYL. 237 XXIV.-On some New Compounds of Phenyl. By HENRYSCRUGHAM STUDENT IN THE LABORA.TORYOF UNIVERSITY COLLEGE. Hydrated oxide of phenyl or carbolic acid was obtained in con-siderable quantities from commercial coal-tar creosote. About three quarts of creosote were distilled and all that came over between 184' C. and 202' collected; that which came over below 184' contained a large quantity of water ;on a second distilla- tion the distillate was separated into two portions from 184' to 196' and from 196' to 202' the greatest portion coming over below 197' ; on 8 third distillation the distillate was collected at every four degrees and afterwards at every two degrees. By repeated distillations the boiling point gradually lowered about one third of the whole being collected between 184' and 188'.In distilling the portion collected from 184' to 186' crystals were observed at the end of the tube of the retort and in the receiver. Some of these crystals were introduced into the bottles containing the portions collected at different boiling points and a considerable quantity was formed in those portions collected at and below 188' but none in those portions which were collected above 188'. By this method of introducing crystals already formed into the portions col- MR. H. SCRUGHAM ON lected between 186 and 188' the number of distillations required in isolating this body from creosote was considerably abridged. In the bottles where the crystals were formed there was a consider- able quantity of liquid not crystallized; this was poured off re-distilled and more crystals obtained from it.These were needle-shaped and had a silky lustre and when separated from the mother liquor distilled at 184O and condensed in the neck of the retort into a solid mass of hydrated oxide of phenyl having the specific gravity of 1.0627 and by analysis gave G6H .Q*=Ga H5g. H Chloride of PhenyL-To prepare chloride of phenyl said to have been obtained by Laurent and Gerhardt by the action of penta- chloride of phosphorus on carbolic acid two atoms of the pentachlo- ride were added in small portions to five of carbolic acid. The action was at first very energetic a considerable amount of heat was developed aiid hydrochloric acid evolved ; but after adding fresh portions of the pentachloride the action ceased and it became neces- sary to heat the mixture.When the whole of the yentachloride was dissolved the mixture was distilled upwards and when it had nearly ceased to give off hydrochloric acid the distillate was collected. Very little came over below ZOOOC. but at 210' it began to distil freely and at 240' ebullition ceased and the temperature rose rapidly to 260'; about one-tenth of the whole came over below 240'. The mixture in the retort then began to. thicken and the colour became dark brown; at this point the process was discontinued. The &s-tillate thus obtained was limpid and colourless and possessed the characteristic odoixr of oxychloride of phosphorus ;on treating it with hot water and afterwards with a dilute solution of potash an oily substance collected at the bottom of the vessel and remained un-changed after three or four washings with hot water.On drying and distilling this substance a small portion came over about 110'; the temperature then rose rapidly to 136'; and about two-thirds of the whole quantity came over between 140' and 146O. On submitting this to fractiofial distillation the boiling point appeared to be about 138' ; but the quantity was small. To a few drops of this substance strong nitric acid was added in order to decompose and test it for phosphorus. Very little action took place in the cold; but on heating the nitric acid was decom-posed and nitrous fumes given off; but the substance did not blacken.On boiling this mixture with sulphuric acid no change appeared to be produced; but on adding water a yellow oily matter JC. H=l; f\=16; 3=12. SOME NEW COMPOUNDS OF PHENYL. was precipitated which solidified on cooling. The liquid portion tested with chloride of ammonium ammonia and sulphate of magnesia gave no evidence of the presence of phosphoric acid. To another portion of the distillate nitric acid was added the mixture evaporated down to a small bulk and carbonate of soda added; the whole was evaporated to dryness and ignited ; the residue dissolved in water and tested as above for phosphoric acid; but no precipitate was obtained molgbdate of ammonia likewise gave no precipitate. The experiment of producing chloride of phenyl by the action of pentachloride of phosphorus on carbolic acid was repeated.An excess of the pentachloride was added and the mixture distilled up- wards as before but only a very small distillate was obtained consist- ing chiefly of oxychloride of phosphorus; the residue in the retort became very thick and black. The experiment was then repeated as in the first instance and about the same proportion of colourless liquid obtained; this was purified as before and after subjecting it together with the former to a series of fractional distillations a fixed boiling point was obtained at 136' C. This substance was tested for chlorine by burning a few drops in a glass tube with dry lime; the lime was washed out with water and a little nitric acid the solution filtered and nitrate of silver added when a very decided precipitate was formed indicating the presence of chlorine.A small portion of phenylate of soda was prepared and a few drops of the distillate which boiled at 136' added to it; the mixture heated strongly ; a little water added the liquid filtered and the filtrate treated with nitrate of silver when a precipitate was formed which proved to be chloride of silver. This liquid boiling at 136' C is the chloride qf phenyl; it is a colourless mobile liquid having a fragrant odour. It is soluble in alcohol and ether ; insoluble in ammonia ; partially soluble in cold but easily dissolved in hot potash. The results obtained by the analysis of this body were not very satisfactory owing it is presumed to the presence of hydrate of phenyl.The mean of two combustions with chromate of lead gave per cent. -c. . 66.58 H. . 4-93. 0.3873 grms. of the substance burnt in lime gave 0*5081 , chloride of silver corresponding to 30.83 per cent. of chlorine. 240 MR. H. SCRUGHAM ON 642 . . 72.0 Theory. 64.00 Experiment. 66.58 5". . . 5.0 4.45 4.93 c1 . . 35.5 31.55 30.83 - G6H5C1 112.5 100.00 102.34 Tribasic Phosphate of Phenyl(€&H,), PQ,.-The thick oily sub- stance which remained in the retort after the separation of the chloride of phenyl and appeared to be non-volatile was treated with a strong solution of potash which was afterwards removed by repeated washings with water; it was then dried under the receiver of the air-pump and distilled.A small portion having a brownish colour came over at 200" C. and crystallised in the neck of the retort having all the appearance of hydrate of phenyl. The temperature gradually rose until it became necessary to remove the thermometer after which the liquid began to distil apparently without further decomposition; the distillate was a clear oily sub- stance having a yellow tinge like that of uranium glass ; towards the close of the operation the distillate became darker and a charred mass was left in the retort. On a second distillation of this substance a small portion came over slightly coloured; but the greater part was colourless when first distilled and after standing some time acquired a yellow tinge by transmitted light; a small portion obtained towards the close of the distillation was of a light yellow colour and a charred substance was again left in the retort.The presence of phosphoric acid in this liquid was demonstrated by mixing a few drops of the purest portion with ethylate of soda ; evaporating the mixture to dryness; igniting the residue; adding the charred mass by small portions to fused nitrate of potash ; dissolving the product in water ; ueutralising with hydrochloric acid ;and testing for phosphoric acid in the ordinary way with ammonia and a magnesia salt. Phosphate of phenyl boils at a temperature considerably above the range of mercurial thermometers. It is inodorous soluble in alcohol and ether but insoluble in potash except by boiling.It sinks in a cold solution of potash but rises to the surface on the application of heat and again falls to the bottom on cooling; showing that it expands by heat in a remarkable degree. It also possesses the peculiar property of epipolic diffusion ;by ordinary day-light the epipolic rays which have a fine violet tint are visible at some distance below the surface; the flame of sulphur does not produce this effect more strongly than the light of the sun. SOME NEW COMPOUNDS OF PHENYL. Some difficulty was found in burning this body on account of the high temperature required to volatilise it. The phosphoric acid was determined by adding a weighed portion of the substance to a strong solution of potash the mixture was evaporated to dryness in a silver crucible and nitrate of potash added to perfect the oxidation; this fused mass was dissolved with distilled water boiled and filtered the filtrate acidulated with hydrochloric acid and again boiled to expel all the carbonic acid.Ammonia and sul- phate of magnesia were then added and the double phosphate collected on a filter washed with ammoniacal water dried ignited and weighed as pyrophosphate of magnesia. The following were the results of analysis,--I. 0.3026grm. gave 0.1396water 0.7256 carbonic acid. 11. 0.3388 , , 0.757.2 , 0.8256 >? Hence in 100 parts :-Experiment. Theory. ,----\-I. 11. 111. Mean. 18.6 . . 216.0 66*.11 65.40 65.92 - 65.92 15H . . 15.0 4-59 5.12 5.13 - 5.13 P .. 31.7 9.71 - - 8.90 8-90 40 . . 64.0 19-59 - - - 20.05 (C HJ3 PO 326.7 100*00 1 oo*oo 111. 0.8713 grm. gave 0.2794 , pyrophosphate of magnesia corresponding to 20.24per cent. of phosphoric acid or 8.90 of phosphorus. Acetate of Phenyl G2H3 @ 0.-Acetate of potash dissolved in 426 115 absolute alcohol was acted upon by phosphate of phenyl. No action took place in the cold but after distilling upwards for some time the acetate was decomposed and when the alcohol was distilled off the temperature rose rapidly. The distillate which came over from 180' C. to 220' was distilled fractionally and a fixed boiling point obtained at 190'. This conipoutid is presumed to be the acetate of phenyl; it is a colourless mobile liquid having a peculiar aromatic O~QU~ ; it is slightly soluble in water and dissolves with decomposition in hot water.The following results obtained by the analysis of this body show that it was not obtained in a state of purity. I. 0.3390 grm. gave 0.2012 grm. water 09003 grm. carbonic acid. 11. 0.2279 ,) , 0.1359 , , 0.6078 I) >I VOL. VI1.-NO. XXVIl. R Hence in 100 parts-Experiment. Theory. w-. I. 11. 111. 8G . .96 70.58 72-42 72.7'3 72.57 8EI . . 8 5-88 6.59 6-62 6.60 2Q . .32 23-54 20.99 2Q65 20.83 c2IIsQ 0 136 10o*oo 1oo*oo 100~00 100*00 Ph Nitrophosphate of Phenyl. -Phosphate of phenyl dissolves in fuming nitric acid with evolution of heat; on boiling the solution nitrous fumes were given off and apparently a combination effected.h portion of the compound when cold boiled with hydrate of potash yielded a yellow crystalline body on cooling. On adding cold water to the remaining portion of the compound formed by the action of nitric acid on phosphate of phenyl a yellow oily substance was thrown down which solidified on the application of heat ;this body is probably the rdrophosphafe OJ' phenyl and forms with potash a beautiful crystallinc salt which has not yet been fully examined. Cyanide of Phenyl is obtained by the action of cyanide of potassium on the phosphate. It is decomposed by boiling with evolution of ammonia. Oxide of Phenyl.-A mixture of chloride of phenyl and phenylate of soda was heated with the view of obtaining the oxide of phenyl ;the mixture swelled up and blackened but no distillate was obtained.Nitric acid was added to a portion of the substance and the solution treated with nitrate of silver; a white precipitate was obtained showing that chloride of sodium had been formed ;hence it is probable that oxide of phenyl was separated. Hydruret of Phe?zyZ.--Four ounces of carbolic acid were intro- duced into a retort together with an equivalent of terchloride of phosphorus. The action in the cold was very moderate but on applying heat a brisk action took place. The mixture was distilled lipwards for some time and afterwards the distillate collected a blackened substance was left in the retort. The distillate was then distilled fractionally a portion coming over between 80" and 90" C.the temperature gradually rising to 220° and a black residue being again left in the retort. The first portion was redistilled and nearly the whole came over about 80" C. This body was a colourless limpid liquid which floated on water and had the odour of iienzin or hydruret of' phenyl. On redistilling the other portions very little came ove~ below 18S0 and it appeared to consist chiefly of hydrate of phenyl. SOME NEW COMPOUNDS OF PHENYL. Iodide of PhenyL-To a solution of 6 oz. of iodine in chloroform hydrate of phenyl and phosphorus were added in the proportions of three equivalents of the hydrate and one of phosphorus to five of iodide the phosphorus being introduced in very small pieces and just sufficient heat applied to keep the mixture boiling; it was distilled upwards for about two hours during which time a reddish crystalline substance formed in the neck of the retort.After distilling off the chloroform there remained in the retort a thick viscid mass apparently containing an excess of iodine to this more hydrate of phenyl and phosphorus were added and the mixture distilled to dryness ;a con-siderable quantity of blackened matter remained in the retort. The chloroform distillate which was coloured with iodine mas redistilled all that came over above SO" C. being kept separate and added to the first distillate; the whole was then distilled fractionally. It began to boil at 120"C. :the last portion coming over at 220," and the largest portion froni 190" to 200'; but the whole was highly coloured by free iodine.Sulphide of ammonium was added which quickly removed the colour and it was observed that those portions collected above 160°C. fell to the bottom being heavier than the sulphide of ammonium while those portions having a lower boiling point floated on the surface. A few drops of that which came over about 190" were added to ethylate of soda ; the mixture evaporated to dryness and ignited ; the charred matter added to fused nitrate of potash ; and a portion of the mixture when cold was dissolved in distilled water filtered and the filtrate acidulated with nitric acid; on addition of starch- paste the characteristic blue colour gave evidence of the presence of iodine ;but the small quantity thus indicated showed that the iodide of phenyl is very difficult to obtain.To six and a half ounces of carbolic acid fourteen ounces of iodine and three-fourths of an ounce of phosphorus were added at intervals as the combination was effected care being taken to keep the iodine in excess; hydriodic acid was evolved in large quantities. The pro- cess was continued for about six hours the neck of the retort being elevated and the hydriodic acid vapour received in ammonia. When no more gas was given off the mixture was distilled and a large quantity of black residue was left in the retort. This experiment was repeated a second time and the distillate submitted to fractional dis- tillation; it appeared to separate into two bodies the one boiling below 200° and the other between 250' and 264" C.On adding hydrate of potash to those portions which came over below 250° about three-fourths of the whole dissolved. The portion insoluble in CHEMTCAL NOTES potash was washed with distilled water dried and distilled ; the greater part of it came over above 250O. After repeated distillations of those portions wbich canie over above 250°?a fixed boiling point was obtained at. 260' C. it few drops of this liquid were tested and found to contain iodine. The body thus obtained is presumed to be the Iodide qf Phenyl; it is colonrless when first obtained but acquires a brownish colour after standing some time. I regret tbat I hare not been able to analyse it.

ISSN:1743-6893    

DOI:10.1039/QJ8550700237

出版商:RSC    

年代:1855

数据来源: RSC