|
1. |
Proceedings of the Chemical Society, Vol. 7, No. 104 |
|
Proceedings of the Chemical Society, London,
Volume 7,
Issue 104,
1891,
Page 171-192
Preview
|
PDF (1449KB)
|
|
摘要:
Issued 31/12/1891. PROCEEDINGS OF TEE CHEMICAL SOCIETY. No.104. Session 189 1-92. December 17th, 1891. Dr. W. H. Pepkin, F.R.S., in the Chair. Messrs. William A. S. Calder, Arthur Colefax, Charles E. Eastick, Henry C. Jenkins and Thomas Neilson were formally admitted Fellows of the Society. Certificates mere read for the first time in favour of Messra. Arthur Adams, Broomfield Place, Smethwick ; Francis V. Darbishire, 59, Elieastrasse, Dresden ; James Hendrick, Laurel Cottage, Water- moor, Circncester ; Henry Hollingshurst, 2, Jentha Road, East Hill, Wandsworth ; Frank William Lucas, &LA.,183, Belle Vile Road, Leeds ; Ernest John Pan-y, B.Sc., Brooklands, Bensham Manor Road, Thornton Heath ; William Pullinger, 27, Queen’s Road, Oldham ; Charles F.Seymour Rothwell, 82, Manson Street, Manchester ; Thomas John Buckler Sandercock, Sidcup College, Sidcup, Kent ; Henry John Spray, 15, Bucharest Road, Wandsworth ; Alfred James Squires, 16, Lower Road, Newark, Notts. Of the following papers those marked * were read :-i5. ‘‘ The ‘gas-volumeter ’ and ‘ gravivolumeter.’ ’’ By G. Lunge (cf. these Proceedings, ante, p. 168). In the Proceedings of this Society (No. 96, April 4,1891), Professor Japp describes an instrument by means of which the observed volume of a single gas gives directly the weight of the gas. This instrument is based on the principle of reducing gases to a, standard Folume by means which are the same as those I first introduced in t,he “gas volumeter,” but Professor Japp prefers to call it by another name “gravivolumeter.” To this I objected in a brief note in the Berichte (24, 1656), and Professor Japp has since replied in the last part of his full paper published in the Transactions of the Society (1891, 59, 894).If it were merely a question of the name of an apparatus, I should not trouble the Society, as I have nothing to add to what I then said in the Berichte, leaving it to others to choose between the names in question. But in his answer to my object’ions Pro-fessor Japp has charged me with making contradictory statements and ignoring “a commonplace of physical measurement ;” this com-pels me to ask the Society to publish my refutation of these charges. In the Berichte (lor. cit.), I stated that the “ gravivolunieter ” is in point of fact absolutely identical with the “ gas volumeter,” but that by modifying the form of the regulator (“ Reductionsrohr ”) which I prefer, Professor Japp has diminished the accuracy of the instru- ment.He remarks: “I fear I must leave Professor Lunge to 3-econcile these two statements.” If he had referred to my original descriptions in the Berichte (dated February 14tfh, 1890) and the Zeitschrift fur angewandte Chemie, (March lst, l890), he would have had no difficulty in doing so. My regulator contains a certain volume of air, which under “standard ” conditions causes the mercury to rise to a fixed point, and by producing this condition simultaneously in the reguIator and the gas-burette, I reduce the gas contained in the latter to standard con- ditions also, thus avoiding in t,he measurement of the gas the necessity for observations of temperature and barometric pressure and all calcu- lations connected therewith.My apparatus has completely realised this object, and Professor Japp has adopted the self-sarne principle and availed himself of the same means for effecting the reduction. It is manifestly indifferent, as far as the principle is concerned, whether the standard volume of air in the regulator is 25 c.c., or 50, or 100, as I have distiuctly stated in a passage possibly overlooked by Professor Jnpp (Ber., 23, 444, line 30). For the sake of obtaining more accurate results, I pi*efei-red in practice to take 100 c.c., and to con- tract the tube below this point, in order to get larger divisions, but I did not confine my apparatus to any such special form.On the con- trary, I showed, even in my first communication, several modificatioiis of the regulator (with cylindrical top, with bulb top, with tap, and with a capillary) ; I also said (Zoc. cit., p. 444, line 24) : “ I quote, of course, these combinat#ions, to be varied at will, merely as exarnpZes how the apparatus may be arranged,” and in t’he Zeitsclirift fiir an-gewandte Chemie, 1890, pages 140 and 144,I remark that any “ nitro-meter ” (nforfioriany “gas-burette”) “may serve the purpose of a regu- Iatod7 Consequently, when he adopted for this purpose an ordinary 50 C.C. gas-burette, Professor Japp did not introduce any nzodification in the principle of my “ gas volumeter,” but merely selected one out of the various forms which would at once occur to any chemist on reading my description, although certainly not that which admits, in my opinioil, of the greatest accuracy in working.1: think this ex- planation will suffice for the reconciliation of my two statements. As already stated, I have objected to a new name being given to an inst,rument identictil with the one invented and named by myself, except that the readings are taken in a new way; but since then I have met with another reason why the name “gravivolumeter” should not be applied to the instrument. That name was bestowed years ago by Houzeau on another instrument of totally different principles and use (Compt. rend., 88,747, and 90, 870), and it would be likely to cause great confusion if designations previously proposed for totally different instruments were applied to new ones.Professor Japy further says : “The acknowledgments of obligation throughout my entire note could hardly have been more profuse.” But he seems to have overlooked the following passage at the end of my first paper in the Berichte in which : ‘LIreserve to myself the further exten- sion of the principle embodied by my gas volumeter, in this and in other directions, as well as the improvement in detail of the instruments shown here only in outline ; but Ishall be grateful for any siiggestions on the part of other scientists,” In the Zeitschrift fiir angewandte Chemie, 1890, 142, more than a year before Professor Japp’s first note, I repeated the above, adding that I intended to employ the name ‘‘ gas volumeter.” Professor Japp admits that I have priority in the principle of reading off volumes of gases directly as weights, as when em-ploying the gas volumeter for the estimation of nitrogen in organic combustions and for vapour densities.I had further claimed that I had attained the end of reading off volumes of gas directly as weights, by employing a certain weight of the substance to be aaalysed. To this Professor Japp objects that I do not find absolute weights, but merely percentage weights. Literally this is correct; but, as in almost all cases it is not the absolute but the percentage weights which are required, I fail to see the force of Professor Japp’s objection.I fully acknowledged the “ sinnreiche Idee ” of Professor Japp. which realises one of the “ further extensions ” of my principle foreshadowed in the above-mentioned passage of my first paper ; butl I ventured to submit, firstly, that it was not called for except in a limited number of cases, secondly, that it involved a loss of sccnracy in the reducing operation. Both of these assertions I must main- tain. As for the first, I had already provided for all ordinary cases. In gas analysis proper, the reduction of volumes to weights is only quite exceptionally called for ; in the gas-volumetric analysis of solid 013 liquid substances, the direct estimation of the percentage weight by my method is a distinct advantage over that of the absolute weights as shown above; and for the estimation of nitrogen and vapour densities it is necessary to employ, in lieu of gas-burettes, specially constructed instruments, as described in my former papers.According to my second criticism, Professor Japp’s special form of regulator admits of only ath (perhaps even hth) of the accuracy yielded by the form which I prefer. This he tries to refute by taxing me with ignorance of “ a commouplace of physical measurement,” namely, that there is no advantage in ma,king one of the inter-dependent parts of a determination much more accurate than another ; but he is in error, for he assumes that I generally work with a 50 C.C.gas burette, whilst, as a matter of fact, I prefer, wheyever possible, to work with far greater volumes, for which purpose the gas-burettes, as shown in my various papers, are constructed to hold np to 150 C.C. An uncertainty of lj20th in 100 with the large gas-burette is exactly the same as in my regulator, namely, 1/2000th, as against 1/500th, the probable error with Professor Japp’s regulator, “calculated on the basis of 25 C.C. as the average amount of gas measured.” By means of a small movable straight edge, combined with a spirit level (the description of which I shall shortly publish), I can attain such accuracy in levelling the mercury in both tubes that the above minimum of error is actually realised. Even with 50 C.C.of gas in 1-~the burette, the accuracy is ____ -1 th.This is, I think,50 x 20 1000 sufficient refutation of Professor Japp’s charge of ignoring “a commoii- place of physical measurement.” I will lastly explain a passage in my note in the Be?-ichfewhich Professor Japp seems to have misunderstood, the fault being doubt- less attributable to the extreme conciseness of that note. I there said that by employing a volume of 25 C.C. only, in the regulator, the accuracy of reading is aprio7.i reduced to ith, and, on account of the inconvenient form of the tube, probably even to kth. The ‘‘incoz1- venient form ” is that of a cylinder of equal width throughout as com- pared with that of an instrument bulged out at the top, in which only the bottom part is cylindrical and graduated, and the divisions may therefore be much larger than in the former case.In England, the bottom part need only hold 10 or 15 C.C. ;at Zurich or Munich, 20 C.C. A 50 C.C. burette would have to be made very inconveniently long, if equally large divisions (easily readable to 1/40th) had to be provided, “78. “The composition of cooked vegetables.” By Miss K. J. Williams. The vegetables examined after cooking were :-Artichoke (Jerusa- 175 lem), broad bean, haricot bean, beetroot, cabbage, carrot, cauliflower, celery, cucumber, lettuce, mushroom, onion (Spanish), parsnip, pea (green), potato, radish, salsify, scarlet runner, sea-kale, spinach, tomato, turnip and vegetable marrow.Determinations were made in these of the following :-Water. Carbon and hydrogen. Nitrogen (total) by Dumas method. Nitrogen by soda-lime combustion. Nitrate extracted by dilute alcohol. Ashes. Sulphur. Woody fibre by digestion with dilute sulphuric acid, &c. Cellulose by Schnlze’s potassium chlorate method. Carbohydrate convertible into glucose. Pat. Heat of combustion. The results are given in a series of tables. DISCCXSIOK. Mr. WARIKGTONremarked that the determinations of the heat of combustion were of considerable value, as these were the only data on which, at present, a comparison of the relative values of the different foods could be based ; to w-hichDr. ARXSTROSGobjected that the value of a vegetable food must depend both on the amounts of carbohydrates and albuminoids present and on their character, and therefore it did not seem probable that the determination of the heat of combustion would be of such special value.Mr.WARINGTONthen pointed out that the quantity of albuminoids required for the renova- tion of tissue in the human body mas so small (at most 40 grams per day) that it could hardly fail to be present in an ordinary mixed diet ; unless, therefore, an increase were being made to the nitrogenous tissues, the value of a food practically depended upon the amount of heat which it could generate in the body, a remark which the Chair-man subsequently said his experience of vegetarian diet enabled him to corroborate. Dr. K;IPPTNGasked whether any attempt had been made to deter- mine the effect on their composition of alterations in the mode of cooking vegetable foods.Professoi-RAMSAY,who had given an account of the paper, said in reply that in his opinion more value would attach to the determina-tions of heats of combustion if the digestibility of the foods had also been ascertained. As to the influence of modes of cooking, considerable 176 differences had been noticed by Miss Williams between potato boiled in the skin and without skin, but this was the only case hitherto studied. *79, “Metallic hydrosulphides.” By S. E. Linder and Harold Picton. The authors have investigated the sulphides of copper, mercury, arsenic, antimony, cadmium, zinc, bismuth, silver, indium and gold (cf. these Proceedings, 1890).With the single exception of bismuth, all these metals form hydrosulphides of a more or less complicated charact’er, which, in niost cases, undergo molecular condensation with elimination of sulphuretted hydrogen when submitted to the action of acids. Taking copper as a type, on treatment with sulphuretted hydrogen, copper hydrate forms a solation of the hydrosulphide 7CuS,H2S. Acetic acid, in presence of excess of sulphuretted hydrc- gen, promotes molecular condensation, a product being formed which has approximately the composition 9CuS,H2S; while acetic acid, in absence of sulphuretted hydrogen, promotes the formation of a product approximately represented by the formula 22CuS,HZS. Chlorbydric acid produces still further condensation.Mercuric sulphide forms products approximately represented by the formuh 31HgS,H2S; 62HgS,H2S. The latter forniula represents the precipi- tate formed in presence of acid, and is a remarkably stable substance. Zinc sulphide solution obtained from the hydrate contains about 14 per cent. excess of sulphur as sulphuretted hydrogen ; in presence of acetic acid, a product represented approximately by the formula 12ZnS,H2Sis formed. The authors regard their results as evidence tending to support the conclusions that the metallic sulphides are in niost cases polymerides of very high molecular weight. “80. “ The physical constitution of some sulphide solutions.” ByHarold Picton. The author has specially examined the solutions of mercuric, anti- monious and arsenious sulphides.In each case the whole of the dissolved sulphide is found to be present in the form of very finely divided particles. Arsenious sulphide is found capable of existing iu “solution ” in three distinct types of sub-division. The following examples illustrate the main characteristics of sulphide “ solu-tions ” :-Mercuric su1phide.-Particles are visible under the microscope (1000 diameters) ; is not diffusible even in absence of a membrane. Arsenious sulphide (a).-Particles are just visible. 177 Antimonious su1phide.-Particles are not visible and it is not diffusible, but particles are detected by their power of scattering light, the scattered light being polarised.Arsenious sulphide @).-Not diffusible ;the particles scatter and polarise light. Arsenious sulphide (y).-Diffusible in the absence of a membrane ; particles are shown to exist by optical behaviour. The solutions examined exhibit, a series passing from those in which the particles of the solid are visible to those in which the particles simulate the phenomena of liquid diffusion, and, although not visible to the eye, are detected by their power of scattering light. *81. " Solution and pseudo-solution. Part I." By Harold Picton and S. E. Linder. The authors advance what they regard as a good prim4 facie case for the belief that there is a, continuous series of grades of solution passing without break from suspension to crystallisable solution.They hold that in the lowest grades of solution a certain loose attrac- tion exists between the particles and the molecules of the solvent. This conclusion they support with experimental evidence gathered from their own work and from other sources. They regard the very finely divided particles in the lower grades of solution (colloid solu-tion) as large molecular aggregates retaining many of their molecular properties. They consider that in passing up through the different grades of solution, these aggregates on the whole become smaller and the forces by which they are held in solution become more definitely those of chemical attraction. They describe a new property, which seems to hold for a large range of solutions, extending from suspen- sion to crystallisable solution.This property consists in the repulsion of the dissolved substance, as n whole, from one of the electrodes of a battery immersed in the solution. Thus, in the case of colloidal arsenic sulp hide, the sulphide aggregates are repelled from the nega- tive electrode. They are also repelled, but much less strongly, fi7oni the positive electrode. In the case of the crystallisable colouring matter Magdala red in absolute alcohol, an exactly similar phe-nomenon is observed, but the repulsion is this time from the positive electrode, and there is no perceptible repulsion from the negative electrode at all. The property is of much interest in itself, but also as exhibit'ing similarities between the different grades of solution.DISC CSSIOX. 3fr. PAGEsuggested that observations on the nature of solutions, such as those described by the authors, might with great facility be carried out in capillary tubes under the microscope. 178 Mr. WALENNsaid that in working with electro-coppering solutions containing resin in suspension he had had occasion to notice a clear-ing of the liquid at the anode, such as had been referred to. Professor RAMSAYsaid that the problem of Brownian motion, or pedesis, had engaged his attention since 1878, when he published a paper in the Pyoceedings of tlie Geological Society bearing on the settling of mud in salt water. The problem attacked by Messrs. Linder and Picton was one in which he thought pedesis played an all- important part, as the small particles, the existence of which had been proved by their power of polarising light', were in exceedingly rapid motion.Messrs. Linder and Picton had shown that there is r'~ regular transition from visible particles to particles or molecules such as those of oxyhaemoglobin. It must, therefore, be concluded that such exceedingly small particles are also in rapid motion; and the smaller the particle, the more rapid the motion. Pedesis had not received, as yet, any satisfactory explanation ; the only fact which appeared to throw any light on its nature was that the addition of ft salt to the solvent, rendering it an electrolyte, hindered pedesis, and finally caused coagulation and settling.The discovery of the true nature of pedesis would in all probability be the key to the problem of the nature of solution. Mr. WARINGTONpointed out that the coagulation of clay by salts had been studied by Schloesing (Chimie AgricoZe, p. 62; Freiny's Encydope'die, tome x) and W. Skey (Chern. News). Mr. HERBERT said that the phenomena discovered by the JACKSOS authors were similar to those observed in trhe case of the liquids pro-duced during the washing of many precipitates, Fuch, for instance, as lead hydrate or silver nitroprusside, which refuse to settle completely as soon as the liquid in which they are difhsed becomes approximately pure water, or which show a tendency to come through the paper when washed on a filter. Such precipitates can be made to furnish turbid liquids in which the particles are so fine that they will not settle for many months, although, as is well known, the addition of a, drop or two of a saline solution, e.g., sodium acetate or potassium nitrate, will cause rapid deposition of the solid.These opalescent liquids give the results described and shown by the authors when examined at right angles to a narrow beam of strong light. He had found in the case of lead hydraie that the microscope revealed moving particles with an average diameter of 1/3.5,000 of an inch. Some, in the case of silver nitroprusside, were less than the 1/100,000 of an inch. The limit of separation with lenses and nators giving the greatest possible angle for water immersion (viz., 1.33 numerical aperture is :- 179 For X 5269 ..........128,225 lines to the inch. ,, X 4861 .......... 138,989 ,, 7 ,, X 4000.. ........ 168,907 .. In the case of particles separated from one another by considerable intervals, these limits will be exceeded, as the dark diffraction outlines will give an apparent measurement of the particles distinctly greater than they really are ;but it is quite clear that it is impossible to call a liquid homogeneous because the microscope fails to shorn stru ct nre. All that can be said is that the particles in water, if not Fisible with lenses of the greatest possible angle for water, are probably not much greater than the 1/180,000of an inch in diameter. Of course, it must be understood that.changes ill the limits will be observed when t,he refractive index of the particles differs very greatly from that of the fluid in which they are diffused, as is the case with in water. It seems probable, therefore, that the phenomena observed in the cases of As,S,, and others which were mentioned, differ only in degree, and not in kind, from those in the cases cjf Sb,S, and similay bodies, and from the opalescent liquids obtained in washing many precipitates. V.2. “ The change proceeding in an acidified solution of sodium thiosulphate when the products are retained within the system.” ByA. Colefax, B.A., Ph.D. Experiments were carried out in the fo3Iowing manner :-A certain volume of a solution of sodium thiosulphate, acidified vc-ith an equiva- lent quantity of acid, was enclosed in a small glass bulb from which the air had been displaced by carbon dioxide; several such bulbs were filled and placed in a bath at a fixed temperature, and at certain definite times after acidification the contents of a bulb was titrated by means of an iodine sclution. The initial tityation of the acidified sodium thiosulphate at the moment of acidification being known, the extent of chemical change is given by the iodine titration.The sulphurous acid resulting from the decomposition of thiosulphuric acid possesses a titration in terms of iodine the double of that of the undecornposed thiosulphuric acid. The possible sources of error are considered under the heads “ Oxidation of sulphurous acid,” “ Titra-tion complications ” and ‘‘Incomplete saline decompo~it~ion.” A.further check is afforded by the determination of bhe acidity of the solution after khe iodine titration is made. For a solution of sulphur-ous acid, there is a constant ratio between the iodiue titration and the acidity of the solution after the iodine titration has been made. This value was determined for the particular iodine and ammonia 180 solutions, by means of a pure solution of sulphurous acid. Hence, whether or not the whole of the increase in iodine titration in the acidified solution of sodium thiosulphate is due to sulphurous acid can be ascertained by a determination of the two values, iodine titration and acidity developed after titration with iodine.The author concludes that the change proceeding in an acidified solution of sodium thiosulphate when t8Ee products, viz., sulphur on^ acid and sulphur, are retained in the system, is a reversible one: a. limit being reached a certain time from the time of acidification. The value of this limit is affected by (1) state of concentration, (2) ratio of the niass of acid relative to the sodium thiosulphate, (3) the nature of the acidifying acid, (4) the temperature. Sulph-III’OUS acid cannot prevent the decomposition of thiosulphuric acid. The presence of both products of the change in the system seems essential for the attainment of a limit value ; for sulphurous acid, when initially present in the system at the time of acidification, has but a small effect upon the Yalues expressing the extent of chemical change.A higher temperature favours the interaction of sulphurous acid and hydrogen or sodium thiosulphate, a secondary change which proceeds at lower temperatures with extreme slowness. Spring’s statement that sodium trithionate is formed by the inter- acticn of iodine, sodium sulphite and sodium thiosulphate seems to be wrong; the author finds that in adding to a solution of iodine a mixed solution of sodium thiosulphate and sulphite no sodium tri- thionate is produced ; the sodium sulphite is completely oxidised to sodium sulphate. *83. ‘‘The action of sulphurous acid on flowers of sulphur.” By A. Colefax, B.A., Ph.D. Debns’s statement that sulphurous acid has practically no action on sdphur is not confirmed.Sulphurous acid acts on flowers of sulphur at the ordinary temperature of the air, and produces thiosnlphuric acid and a polythionic acid, probably trithionic acid. No penta-thionic acid was found. According to Fliickiger (Ja7wesbericht, 1863, 149), sulphurous acid gave, by its action on flowers of sulphur, thiosulphuric acid. The presence of a polythionic acid is proved by a comparison of the iodine titrations and the acidity titrations before and after the addition of iodine requisite for the iodine titration. It is thus shown that there is present a, considerable quantity of an acid having no iodine titration, and which is not merely oxidised sulph- urous acid.Qualitative tests point to the presence of thiosulphuric acid, or trithionic acid, or a mixture of the two. Not even in the dark is sulphurous acid without action on sulphur. A higher tempe- 181 ra,ture (say 80-90" C.) favours the action of sulphurous acid on sulphur ;water has no action on flowers of sulphur, either at ordinaqr temperatures or at this higher temperature. 84. "The a-and &modifications of chlorobenzene hexachloride." By F. E. Matthews, Ph.L). By the action of chlorine on chlorobenzene in presence of a dilute solution of sodinm hydroxide, the author obtains a mixture of a-and P-chlorobenzene hexachloride, together with oily products which have not been ini-estigated (cf. these Proceedings, 1890). The solid portion can be separated from the oily substances only with difficulty by pressure between filter-paper and washing with light petroleum.The a-and $-compounds are separated by means of steam distillation, the p-compound being much less readily volatile, and subsequent recrystallisation from alcohol, benzene or light petroleum. a-C,H&l, is a colourless, crystalline substance closely resembling a-benzene hexachloride in its properties ; it melts at about 146", and can be sublimed if carefully heated, but if heated too strongly, 01-on warming with an alcoholic solution of potassium hydroxide, it is quantitatively resolred into 1 :3 :4 : 5-tetrachlorobenzene and hydrogen chloride ; on boiling an alcoholic solution with zinc-dust, chlorobenzene is obtained. P-C,Ht,C1, is only obtained in small quantity : it is more stable than the a-compound and melts at about 260" ; it is decomposed on heating either alone or with alcoholic potash, yieldirg the same tetrachloro- benzene as the a-substance.Meunier's method of separat,ing a-from p-@,H&l, by means of an alcoholic solution of potassium cyanide has been investigated, and has been found to depcnd on the conversion of the a-C,H,C& into 1:2 :4-CsH3Cl3, the cyanide playing the part of a weaK alkali. 1 :3 : 4 :5-CGH2C1, has been investigated, with the result that the author is of opinion that the melting point, 50-51", assigned by Beilstein and Kurbatow, is correct, and that, Otto and Ladenburg and Jungfleisch, who all give tlie melting point considerably lower, were dealing with impure material.The nitro-derivative, C6HCla(N02) (1:3 :4:5: S), was prepared and found to melt at 23"(B. and K. 21-22O). The action of bromine on benzene in the presence of alkali has also been studied, and is found to yield C,H,Br, the product being the mme whether gaseons or liquid bromine was used. On mixing monochlorobenzene with bromine under water and. allowing the mixture to stand for about a week, a considerable amount of pure chlorobromobenzene was obtained. The author calls atkention to a paper by Sachse (Ber., 23,1363), in which Sachse shows that there are two positions of stability of the hexamethylene ring. According to Snchse’s hypothesis, there should be two substances of the formula C,H&1, capable of existence, but three substances of the formula C6H5C17,of which the two cc-modifications would probably have very similar properties. 85.“ The sulphochlorides of the isomeric dibromonaphthalenes. (I.)” By Henry E. Armstrong and E. C. Rossiter. Many statements are on record with reference to the dibromonaph- thalenes which are difficult to reconcile ; the preparation of character-istic derivatives which could be made use of in distinguishing the various modifications is therefore of importance, and the more they are studied the more is this found to be the case ; indeed, more thaii usual difficulty attends their investigation, as little or no reliance can be placed either on appearance or melting point, a slight impurity sufficing to produce most misleading changes in these ; moreover, the separation of isomerides is made very difficult by their tendency to crystallise together, forming mixtures which simulate pure substances in a most remarkable manner.Unfortunately, also, at the high tem- peratures requisite to effect the hydrolysis of many of their sulphonic acids, slight decomposition takes place, in consequence of which an impure product is obtained. Eight of the 10 possible dibromonaphthalenes have been prepared, only the 1: 1’-aa-and the 2 : 3-P,&modifications being unknown. Five of the modifications are referred to in the present notice, viz. :-1: 4-Dibronionaphthalene, prepared by brominating naphthalene. 1: 4‘-Dibromonaph thalene, prepared from Guareschi’s brornonitro- naphthalene by reducing, diszotising &c.1: 3-Dibrornonaphthalene, prepared by Meldola’s method. 1:2’-Dibromoaaphthalene, prepai*ed by brominating p-bromonaph- thnlene. 1: 3’-Dibrornonaphthalene, prepared by the action of PBr6on the bromosulpho-acid obtained from the Dahl modification OP p-naph-thylaminesulphonic acid. These dibromonaphthalenes are readily snlphonated by lzeatiq with twice their weight of H,S04 (so-called 100 per cent. acid) on the water-bath until dissolution is complete ; on adding potassium carb- onate in slight excess to the moderately dilute solution of the sulpho- acid, the potassium sulphonate separates almost entirely from the liquid, and, after recrystallisation, is converted into sulphochloride. 183 The properties of the sulphochlorides are summarised in the follow- ing table:- Yields only one sulphonic acid.S02C1, prismatic needles j m. p. 120". M. p. 82-83". Br Yields only one sulphonic acid. SO,CI, prismatic needles ; m. p. 1759n.'l\/\/Br M. p. 130" Br Yields two sulphonic acids. a-SO,Cl, prisms or hi hlcrystals ; m. p. 157vrefractive stumpy: . P-SO2C1, prismatic needles or long flexible plates j m. p. 128O. Br Only one sulphonic acid isolated as yet.S02C1, prismatic needles which, like the cor- responding dichloro -derivative, become opaque on keeping j m. p. 113'. /\/\ Only one sulphonic acid isolated as yet.SO,CI, massive prisms ; rn.p. 145'.(J,)Br M. p. (?) 57". It was stated by Armstrong and Wynne, in 1886 (these Proceed- ings, p. 233), that when 1:3'-naphthalenedisulphonic acid is treated with bromine, it affords a dibromo-6-monosulphonic acid isomeric with that prepared by Jolin from naphthalene-/3-sulphonicacid ; this con- clusion mas based on the production from the acid by hydrolysis of a dibromonaphthalene of much lower melting point than the 1:4-modi-fication, and altogether different from it in appearance: it is now found that the product of hydrolysis in question was impure 1:4-di-bromonaphthalene, and it follows, therefore, that the acid from which it was derived is identical with Jolin's. It is to be noted that whereas the dibromonaphthalenes all hare higher melting points than the corresponding dichloror,aphthalenes, no such relation obtains between the sulphochlorides of corresponding dichloro- and dibromo-naphthalene.184 86. “ The action of alcohols on sulphonic chlorides as a means of producing ethereal salts of sulphonic acids.” By Henry E. Arm-sbrong and E. C. Rossiter. It is customary to prepare ethereal salts of sulphonic acicls by the interaction of the silver salt and the bromide or iodide of a carbinol radicle. The authors find that several, but by no means all, of the dibromonaphthalenesulphochloridesmay be converted into the ethereal Palt by boiling with ordinary dehydrated alcohol ; the 1: 4-sulpho-chloride especially is remarkable for the readiness and completeness with which it undergoes this change, but a small proportion being hydrolysed and converted into sulphonic acid.The 1 : 4’-sulpho-chloride under similar conditions is entirely hydrolysed ; its behavion~ thus affords a st’rikingcontrast to that of the 1 : 4-compound, espe- cially as both are P-sulphonic derivatives. The 1 : 2’-sulphochloricle, which is an a-sulphonic derivakive, also yields ethereal salts when boiled with alcohols, although in relatively small amount ; this is a further proof that the formation of ethereal salts is not a function of the p-sulphonic radicle. The peculiar behavionr of the 1: 4-sulphochloride is of interest in connection witah Heller’s observation (these Proceedings, 1889, 221) th3t 1:4-dibromo-, dichloro- and chlorobi~omo-naph thalenes behave in a peculiar manner on treatment with S03HC1,being converted into sulphones, whereas isomeric compounds yield sulphonic acids as chief product.It is proposed to study the behnviour of a number of typical sulpho-chlorides towards alcohols and sodium derivatives of alcohols. *87. “The action of bromine on u-and p-bromonaphthalene.” ByHenry E. Armstrong and E. C. Rossiter. It is well known that when naphthalene is submitted to the action of two molecular proportions of bromine, a product is obtained from which a considerable amount of 1: 4-dibromonaphthalene may be separated without difficulty by crystallising from alcohol, leaving as major product a substance melting at 6%-70” ; numerous unsuccessful attempts have been made to determine the nature of this product, and although Magatti and also Guareschi have separated a small quantity of 1: 4’-dibromonaphthalene from it, down to the present time its constitution has remained a mystery.As p-dibrornonaphthalene is formed in small quantity on brom- inating naphthalene, the action OP bromine on this compound was first studied ; it is found to afford 1 : 2’-dibromonaphthalene almost as sole product. To determine the nature of the product of low melting point from naphthalene and two molecular proportions of bromine, it was sulph- onated, and attempts were made to effect a separation by recrystal- lising the potassium salt of the resulting acid ; as these were unsuc- cessful, sulphochloride was prepared : by crystallising this from benzene and from acetic acid, a considerable fraction of the product was ultimately recognised as the sulphochloride of 1 : 4-dibromo-naphthalene.The residual sulphochloride melted at 107-110" ; numerous attempts were made to purify this by crystallisation without success; it was hydrolysed at 260-270", but the product had a low melt- ing point and could not be identified ;but on boiling it with alcohol, a considerable amount of the ethylic salt of 1:4-dibromonaphthalene-sulphonic acid was obtained. It was, therefore, evident that on brominating naphthalene much more 1:4-dibromonaphthalene is formed than is commonly supposed. Fresh attempts were then made to resolve the crude product melting at about, 70" into its con-stituents by means of solvents.Eventually, on fractionally extracting it with light petroleum, it was found that the first separations from fhe last extracts melted at 115-125" : and on crystallising this product from alcohol, it melted at 129-130", and was identified as 1:4'-dibromonaphthalene. A small quantity of 1:4-dibromonaphthalene was obtained from the first extractions by petroleum ; the rest of the product melted at 68-70'. On crystallising this latter from alcohol, a further separa- tion of 1 : 4-dibromonnphthalene was obtained, but the residue still melted at 68-70". However, by alternately crystallising this Iast producl, fi-om petroleum and alcohol, it was gradually split up into 1 : 4-and 1: 4'-dibromonaphthalenee, the melting point of the residue aiwitp remaining con stant at 68-70". From these results it is concluded that the substance melting at 68-70" is a mixture of 1: 4-and 1 : 4'-naphthalene, and from the weights obtained of these it is concluded that the 1 : 4-dibrorno-naphthalene constitutes about four-fifths and the 1 :4'- one-fifth of the mixture.No 1 : 3-dibromonaphthalene was Gbtained. As a mixture of 1: 4-and 1: 3-dichloronaphthalenes is obtained by the action of chlorine on naphthalene, the production of the 1 : 4-and 1: 4'-compounds by the action of bromine would seem to be an indication of a great difference between the action of chlorine and bromine on naphthalene ; but such is not the case. The formation of the dichloronaphthalenes is preceded by that of a comparatively stable tetrachloride, but no such compound is produced by the action of bromine ; pyobably a highly unstable dibromide is first formed, which is at once resolved into hydrogen bromide and bromonaphthalene, and the latter is then further acted on.Experiments, of which an account will be given later on, show that when chloronaphthalene is chlorinated results are obtained very similar to those obtained on brominating bromo- naphthalene. *88. “The action of bromine on a mixture of ortho- and paranitro- a-acenaphthslide.” By Henry E. Armstrong and E. C. Rossiter. Meldola, in 1885 (Trans., pp. 497-518), described two series of compounds derived, one from brominated a-acenaphthalide, the other from nitrated acenaphthalide ; the former was converted by nitration into nitrobromacenaphthalide, from which the amido-group was eliminated, and the resulting nitrobromonaphthalene was reduced, 5 bromonaphthylamine being thus obtained, which-judging from pre- vious observations-must necessarily be the compound of the formula Nitrated acenaphthalide was known to be a, mixture of the ortho- and para-derivatives ;by brominating the mixture Meldola obtained a single product which he supposed to be derived from the paru-con- stituent, and, therefore, he regarded the bromonaphthylamine obtained by eliminating the amido-group and then reducing as the isomeride /V\Br of that prepared from bromacenaphthalide, viz., as 1 1 1 .\/\/NH2 From the bromonaphthylamines from the two sources, Meldola pre- pared dibromonaphthylamines, from which he then prepared dibromo- naphthalenes, obtaining in this way a modification melting at 74“ from each source.Some time after the appearance of his paper (cf-these Proceedings, 1886, 172), he was led to modify his views of the constitution of the compounds he had obtained in consequence of the discovery by Stallard that the bromophthalic acid which Meldola pre- pared by oxidising one of his dibromonaphthylamines was derived from an a-and not from a 8-bromonephthalene ; Meldola, therefore, suggested that the one amine was the compound NH, : Rr : Me = 2 :4 : l’,and the other the compound NH2 : Br : Me = 1:3 : 3’ or 1: 3 : 2’. Wishing to prepare the 1: 1’-dibromonaphthalene, the authors proceeeded to repeat Meldola’s work, as the argument which he made use of appeared to be a sound one, and there was, therefore, reason to think that the dibromonaphthalene which he had obtained starthg from brominated acenaphthalide was the 1:1'-modification ; that obtained from the other source the authors were inclined to expect would prove to be the 1: 2'-modification, which is known to melt at 74".On preparing the two bromonaphthalenes in accordance with Meldola's directions, products were obtained, however, which both melted at 82-83', the identity of which with 1:4-dibromonaphthal-ene was placed beyond doubt by conversion into the sulphochloride melting at 118-120" and the ethylic sulphonate melting at 156-157'.The production of 1:4-dibromonaphthalene from the bromonaphthyl- nmine prepared from nitrated parabromacenaph thalide is easily undeistood, thus-Br /\/\NH2 /\/\NH2 LO + By2 = I I 1 -I-HBr. \/\/Br Br Its production from a bromonaphthylamine of the formula liowever, is clearly impossible ; but it was conceivable that a hetero- iiucleal derivative is formed 011 brominating paranitracenaphthalide, VLZ. :-111this case, the bromonaphthylamine obtained on eliminating the NHAc group and reducing should be convertible into 1 :1'-dibromo-naphthalene ;according to Meldola, it yields 1 :3-dibromonaphthalene, but he was led to form this conclusion only by the appearance and melting point of the product.The authors have prepared the di- bromonnphthalene in question, and have proved it to be the 1:%corn-pound, as stated by Meldola, by converting it into the two sulpho- chlorides melting at 127"and 157" characteristic of this modification ; and by completely reducing the bromonaphthylamine in question they have obtained p-naphthylamine. There appears to be but one explanation possible of these results, viz., that when a mixture of ortho- and para-nitracenaphthalidesis brominated, the ortbo-compound-not the para-, as Meldola supposed -is alone attacked, and that consequently the same nitrobronionaph- thalene is obtained on displacing the acetamido-group in nitrated parabromo-a-acenaphthalide,and in the product of the action of bromine on a mixture of the ortho- and para-nitro-derivatives of a-acenaphthalide.Meldola, although struck with the remarkable similarity of the two series of compounds which he prepared, was led to notice certain differences : thus he obtained bromonaphthylamines melting, the one at 71*5",the other at 62"; but the authors find that-both products .melt at 72";and that the dibromonaphthylamines prepared from them melt at the same temperature, viz., 106". Messrs. Miers and Pope have examined a number of the pairs of products, and report that corresponding compounds are not only identical in form but also in optical properties, and as no case is on record of different substances being alike both morphologically and optically, there can be no doubt of the correctness of the explanation 110~advanced.%9. " Camphrone, a product of the action of dehydrating agents 011 camphor." By Henry E. Armstrong and F. S. Kipping. The action of concentrated sulphuric acid on camphor appears to have been first examined by Chautard ; it was subsequently studied by Fittig, Schwanert, and Kachler, all of whom agree in stating that under suitable conditions an oily product, having a strong peppermint odonr, is formed, isomeric with acetophorone, C,H,,O, which conse-quently has figured in chemical literature under t'he name camphorone. The various statements regarding the properties of this substance, however, are by no means confirmatory, Fittig stating that it boils at 204-205" and that it has a relative density of 0.939 at 12",whereas Schwanert gives 230-235" as its boiling point and 0.9614 at 20" as the relative density.Armstrong and Miller noticed the presence of a substance haviiig properties similar to those of the product obtained by means of sulph-uric acid among the products of the action of zinc chloride on ca,m-phor; but attempts which they made to isolate a definite substance from their crude product were unsuccessful, It appeared probable that, with the aid of the improved methods of treating ketonic compounds now known, it would be possible to sepa- rate the characteristic constituent from the crude oil, and this has proved to be the case. On treating the fraction boiling at 238-242" of the oil pyepared by means either of sulphuric acid or of zinc chloride with phenylhydr- Bzine, a mixture of a crystalline hydrazone with dark-coloured, oils products is obtained ; the purified hydrazone crysfallises in yellowish 189 plates and melts at about 108".By boiling it in alcoholic solutioxi with ferric chloride and muriatic acid, an oil is obtained which yields a hydrazone identical with that from which it was prepared ; on dis- tilling this oil, the thermometer rapidly rises to 245", the greater part of the liquid passing over at 245-247". On treatment with hydr- oxylnmine, the oil is converted into a hydroxime which crystallises in long prisms melting at 85-86", of which the acetyl derivatrive melts st 69-70". The determination of the composition of these compounds presents coiisiderable difficulty ; malyses of the oil gave the following results :-Carbon, per cent...,.. 80.84 80.88 Hydrogen ,, . . . ... 6-13 8.14 numbers which agree satisfactorily with the formula C,,H,,O. But in IILI~CPOUSanalyses of the hydroxime, the carbon was found to vary from 72-4 to 72.8 per cent. ; hydrogen from 7% to 8.0 per cent. ; and nitrogen from 8.6 to 8.9 per cent. : these values do riot agree with those required by a compound of the formula C,,H12N(OH) except the nitrogen values (C = 73.6, H = '7.27,N = 8.6). The acetjl derivative of the hydroxime gave similar resnlts. The liydrazone was found to contain 12 to 12.2 per cent. of nitrogen, the calculated value for C,,H,,N,HPh being 11.8. Evidently it is neces-sary to make R more complete study of the compound to place its composition beyond doubt, especially as the formula C,,H,,O is a very remarkable one.On oxidising the oil with nitric acid, it yields an acid which crystal- lises well. Obviously the substance is one of considerable interest, and its further investigation is likely to throw light on the still open question as to the structure of camphor. As the yield even of the crude product is small, and the preparation of the pure siibstance is a matter of considerable difficulty, it a,ppears desirable to make this preliminary announcement, now that workers are becoming so numerous in this field. *90. Metaxylenesulphonic acids (Il)." By G. T.Moody, D.Sc. In a previous communication (Proceedivgs, 1888, p.77), the author has described the preparation of 1 : 2 : 3-metaxylenesulphonic acid, and has called attention to the fact tJhat only the 1 : 3 :4-acid is formed 011 direct sulplionation of the pure hydrocarbon. Attempts to prepare the symmetrical 1:3 :S-sulphonic acid have not yet met 190 with success, the sulphonation of 1 : 3 : 4-acetnietaxylid failing to give the required substit-ution. Acetmetaxylid (1:3 :4)is readily sulphonnted when heated for some time Ht 140"with 14 times its weight of 20 per cent. anhydrosulphiu-ic acid, and on boiling the solution after the addition of water, mets- xylidinesulphonic acid [Me2 : NH, :S0,H = 1 : 3 : 4 : 6) is obtained. It crystallises from water, in wliicb it is only very sparingly soluble, in well-formed, slender needles, insoluble in alcoliol and other common solvents ; it does not change at 290", anti when heated to a higher temperature, decomposes without having previously melted.The sndiurn salt, C6H,Me,NH2SO3Nn,H2O, is exceedingly soluble in water and crystallises in flat plates. On diazotising the acid and subsequently boiling the solid product with dehydrated methylateci spirit, ethoxymetaxylenesulphonic aclid [Me, : OEt : SO,€€ = 1 : 3 : 4 : 61 was obtained. The sodium salt of the acid crystallises in long, slender needles mliich effloresce when exposed to the air ; the sulphochloride crjstallises from light petroleuiii in beautiful orthorhombic plates, melting at 56' ; the sal phonamide separates from dilute alcohol in small, white scales or flat needles which melt at 169--170".When the diazo-product is boiled with with b~oinliyclric acid, tlic coryespondiiig hromoxylenesulphonic acid [Me, : Er : SO,H = 1 : 3 : 4 : 61 is formed. It crystallises in long, slender needles, am1 does riot melt at 2TO", but at a considerably higher temperature, melts with decomposition. The sodium salt agrees with the description give11 by Weinberg (Ber., 11, 1062), who obtained it on broniination of a dilute aqueous solution of barium 1 : 3 : 4-metaxylenesulphonate ; but the sulphochloi.ide obtained by the autboi', which crystallises in splendid, oblique prisms, melts at 2" higher (62 -6:3'), whilst the salphonamide melts at 5" lower (189*) than found b-j Weinberg.The melting point of the eulphonamide agrees with that given by Sa~tig (,41zr1nle?i, 230,33.j), who prepared it by snlphonating metnxylicline, arid subsequently replacing amidogen by bromine. It thus appears that both xylidine and a( etxylid give the same ncid on sulpbonation, and that the displacement of hydrogen in the amido-group by acetyl does not lead to any change in the position takeii up by the snlphonic, group. "91. " The action of prop-jlene bromide on the sodium derivatives of ethylic acetoacetate arid ethylic benssoylacctate." By W. H. Perkin, ?Juii., Ph.D., F.R.S., and James Stenhouse. The product from etltylic acetate is a rnixt~weof ethylic acetyl- niethyltriniethylenec~rboxylate ar,d ethylic metlli~ldiacetyIaclipate.The former is found to yield a well-crystallised hydroxime (m. p. 153-155") ; when boiled with water, it is gradually converted into acetoisobutyl alcohol. Etbylic methyldiacetylndipate is decomposed on distillation into an oil whichis a mixture of at least two compounds, as, when hydrolysed, it yields dimethyldihydropentenedicarboxylic acid, together with dimethyldibydropentene methyl ketone. Ethylic benzoylniethyZtrimethyleneca1-boxylate and several of its derivatives are also described in the paper. 92. ''Derivatives of tetramethylme." By W. H. Perkin, Jun., Ph.D., F.R.S., and W. Sinclair, B.Sc. By the action of bromine in presence of phosphorus on tetramethyl-enecarboxylic acid, the authors have obtained an almost quantitative yield of the monobromo-derivative. They desciibe its methylic salt, and the corresponding hydroxy-, acetoxy- and ethoxy-acids.By acting on the chloride of the acid with zinc methyl and ethyl, they have prepared tetramethylene methyl and ethyl ketones, of which they also describe the reduction products. ADDITIONS TO THE LIBRARY. 11. By Purchase. A Theoretical and Practical Treatise on the Manufacture of Sulph-uric Acid and Alkali, by G. Lunge. 2nd Edition. Vol. I. London 1891. Chemisch-technische Analyse herausgegelen, von J. Post. Zweite Auflage. Band I. 1888-89. Band 11. 1890-91. Braunschweig. Die optische Anomalien der Krystalle, von R. Rrauns. Leipzig 1891. Analyse der Fette und Wachsarten, ron R. Benedikt.2te Auflage Berlin 1891. Die Pflanzeualkaloide und ihre chemische Konstitution, von A. Pictet. Berlin 1891. Le Tabac, par A. LabalBtrier. Paris 1891. Tabellarische Uebersicht der kiinstlichen organischen Farbstoffk, von G. Schultz und P. Julius. Berlin 1891. Anleitung zui-Untersuchung der fur die Zuckerindustrie in Betrachi komnienden Rohmaterialien, Producte, Nebenproducte und Hiilfs-sulsstanzen, voii R.Friihling und J. Schultz. 4te Anfl. Braunschweig 1891. I92 Jahresbericht uber die Fortschritte in der Lellre von den Gahrungs- Organismen, von A. Koch. Erster Jahrgang 1890. Braunschweig 1891. Elektro-lhletallurgie : die Gewinnung der Metalle unter Verinit- telung des electrischen Stromes, von W. Borchers. Braunschweig 1891. Die galvmische Metallp1ai;tirung und Galvanoplastik, von We Pfan hauser.Wien 1890.. kusfuhrliches Handbuch der Photographie. 2te Auilage. Band I. Heft 3 ;Die Photographie bei kiinstlichem. Licht, von J. X.Eder. Halle a.S., 1891. LIBRARY NOTICE. It has been resolved by trhe Council that in future all new books shall be retained in the Libraryfor two months before they are allowed to circulate. At the next meeting, on January 2ist, the following papers will be read :-“The estimation of oxygen in watep.” By Mr. &I.A. Adams. “ A pure fermentation of mannitol and dulcitol.” By Professor P. 4’. Frankland and W. Frew. “ The luminosity of coal-gas flames.” By Professor. V. B. Lewic. HAllltISON AND SONS,PRINTERS IN ORDINARY TO l€UR NAJESTY, ST. AlAltTIN’S LARE.
ISSN:0369-8718
DOI:10.1039/PL8910700171
出版商:RSC
年代:1891
数据来源: RSC
|
|