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Proceedings of the Chemical Society, Vol. 27, No. 389 |
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Proceedings of the Chemical Society, London,
Volume 27,
Issue 389,
1911,
Page 177-200
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摘要:
[Issued 291611 1 PROCEEDINGS OF TRR CHEMICAL SOCIETY. VOl. 27. No.389. June 14th, 1911. Extra Meeting, Professor PERCYF. FRANK-LAND, LL.D., P.R.S., President, in the Chair. This meeting was held in the Theatre of the Royal Institution, by kind permission of the Managers. inThe PRESIDENT, opening the proceedings, said : We are: gathered together in tliis historic chamber to celebrate what has come to be one of the most impartant festivals in the Calendar c)f the Chemical Society, the delivery of the Paraday Lecture, thc present.ation of the Faraday Medal. The high significance of this meeting is most effectively realised if ~7ecall to mind the names of the illustrious men who have functioned as Faraday lecturers in the past. Dumas, Cannizzaro, Hofmann, Wurtz, Helm- holtz, and Mendel6eff are those who have passed away leaving imperishable memories behind them.Lord Rayleigh, Professor Ostwald, and Professor Emil Fischer, we rejoice to think, still remain great captains of science militant here upon earth. To this distinguished line of Faraday lecturers the Chemical Society has now added another member in the person of Professor Richards, a€ Harvard, the eminent savant whom we are to have the pleasure and privilege of hearing to-night. Professor Richards requires no int,roduction from me; his work, his important contributions to science, especially his determination of atomic weigh& and his experiments on the compressibility Qf the elements, are not only well known in this country, but throughout the cheiiiical world.I have great, pleasure in calling upon Professor R,icha.rds to deliver the Famday lecture. Professor RICHARDSLhen delivered the Faraday Lecture, of which the following account is an abstract: * The fundamental properties of the elementa. The subject of my lecture to-night concerns the methods aiid general results of several extended series of investigations, planned with the hope of adding a little to the foundations of human knowledge by mems of careful experiment. Among all quantities worthy of exact measurement, the proper- ties of the chemical elements are surely some of the most funda-mental, because the elemelits are the vehicles of all the manifold phenomena within the range of our perception.1lic.ight is clearly one of the most significant of thesc properties, In the exact determination of atomic weights each portion of subsbance to be weighed must be free from the suspicion of con-taining unheeded impurities ;othcrwise its weight will mean little. Every substance must be assumed ta be impure, every reaction must be assumed to be incofmplete, every measureineiit must be assumed to contain error, until proof to the contrary can be obtained. That the atomic weights may be connected by precise niathc- matical equations seems highly probable ; but althougli nisiiy interesting attempts have been made to solve the problem, tlic exact nature of such relationships has not yet been cliscovcrctl. It seems to me that the discovery cf the ultimate generalisation is riot likely to occur until WAaiiy atomic weightrj have been determined with the utmost accuracy.Volume also is important.. About twelvc yea1.s ago, 011 applying van der Waals' well-known equation to several gases, it seemed clear to me that the quantity 0 is iiot really a constant quantity, but is subject to change under the iriflucnce of both temperahwe and pressure. But if the quantity 6 (supposed to be dependent upon the space actually occupied by the molecules) is changeable, are not the molecules themselves compressible? If changes in the bulk of molecules are to be inferred even from gases, may not the expansion ancz contraction of solids and liquids afford a much better clue to the relative expansion and contraction of these molecules ? Much evidence has been accumulated pointing toward a positive answer to these questions.* Full Report, Z'rc~i~.,1911, p. 1201. 179 The ordinary conception of a solid has always seemed to me little short of an absurdity. A gas may very properly be imagined with moving particles far apart, but what could give the rigidity of steel to such an unstlable structure? The most reasonable conclusion, from all the evidence taken together, seems to be that, the interstices between atoms in solids and liquids must usually be small, even in proportion to the size of the atoms themselves, if, indeed, there are any interstices at all. The kinetic theory of gases remains unmolested by these considerations, except as they indicate the changeability of b in the equation of van der Waals, but the new views affect seriously the application of this equation to solids and liquids.The compressibilities of thirty-five elements and many simple compounds were studied with sufficient care to leave no doubt as to their relative values. It becamel at once manifest that the forma- ticm of a compound of a compressible element was attended with greater decrease of volume than the formation of a similar compound of a less compressible element, other things being equal. This is jiist what the theory leads us to expect, and is a fact inexplicable by any ot'her hypothesis as yet known to me. Another essential aspect of the theory of compressible atoms is that which concerns cohesion.If the pressure of chemical affinity causes atomic compression, may not the pressure of cohesive afmity also have the same effect ? The affinity which prevents solids and liquid,, from vaporising is generally admitted to produce great internal pressure; must it not tend to compress the molecules into smaller space? Molecules with high cohesive affinity (those of substances hard to volatilise) should be much compressed, and possess small volume, whereas molecules with a slight cohesiv~ affinity should be more bulky. Moreover, those molecules already much compressed by their own self-affinity would naturally be but little affected by additional pressure. Thus, as regards two substances otherwise similar, the less volatile one would be less compressible, denser, and possess greater surface tension.These outcomes of the theory correspond with the facts in a majority of cases thus far studied. Differences of structure and differences of chemical nature sometimes conceal these relations ; the paralielism appears most strikingly among isomeric compounds. In brief, the bulk of evidence' strongly indicates bhat cohesiveness, as well as chemical affinity, exerts pressure in its action, and hence that each plays a part in deter- nining the volumes occupied by molecules. Carried through to its logical conclusion, the idea that atoms are compressible gives one quite a new conception of the molecular 180 nechanics of the universe.The influence of atomic compressibili-ies may be perceived everywhere, and in most cmea each fact seems ,o fit easily and without constraint into its place in the hypothesis. hen apparent exceptions, such as the abnormal bulk of ice, may ie ascribed in it reasonable fashion to superimposed effects. The more closely the actual data are studied, the more plausible ,he hypothesis of compressible atoms appears. Ten years' experi- ?me with its interpretations leads me to feel that the idea is highly mggestive and helpful in stimulating new search after truth and in correlating and codifying diverse facts. By such fruits are hypotheses justified. Chemical energetics being involved in the consideration of these relations, I sought to improve the technique of thermochemistry.The new method of adiabatic calorimetry was devised, and with it interesting results have been obtained. A11 these and other properties of the elements are to be compared with each other quantitatively. Xew evidence is at hand showing that they do not all vary with the same periodicity as the atomic weights increase. The solution of the cosmic riddle is of the greatest importance to humanity, because only through a complete understanding of his own structure and that of his environment can inan obtain control of the necessary conditions of his existence. The outlook is full of hope for the future. In presenting the Faraday Medal to Professor Richards at the conclusion of the lecture, the PRESIDENTsaid : Professor €tichar&,-It is now my pleasant duty, in the name of the Chemical Society, to present you with the Faraday Medal, which bears the effigy of the Master, and which has been struck expressly- for this occasion. It is the highest Iio?noiir which this Society has to confer.In making this presentation I desire to assure you of tile sincere appreciation and the deep regard which your colleagues in this country have for your work, and also of tlie great and enduring importance which we attribute to your scientific discoveries. Professor 'ODLING,in proposing a vote of thanks to the lecturer, said: Mr. President, Ladies and Gentlemen,-Some two or three days ago I was highly gratified by being invited to be present by the President, the distinguished son of a distinguished father, to undertake the duty of proposing a vote of thanks to the lecturer.But this gratification, 1find now, is sadly marred by the sense of my utter incompetence to express in fitting terms our appreciation for the intellectual treat which has been put before us. At the same time there is, perhaps, a certain inferior fitness in this duty being assigned to me in consideration of my connexion with 181 Professor Faraday, as being for a time his successor in this insti- tution, and with the Chemical Society, by which the lectureship has been instituted. At the present time the Bullerian professor- ship is occupied by Sir James Dewar, who is unfortunately not able to be present with us on this occasion, and whose personal exertions have added so much to the reputation of this professor- ship.In the time between his acceptance of the professorship and his assumption of office, the professorship was held by myself and by Dr. Gladstone, and this particularly, therefore, brings us into association with the Royal Institution. With regard to the Chemical Society I am perhaps entitled to speak on its behalf in a double capacity, in that I am at the present time the senior Fellow of the Society, and that the institution of this lectureship was carried out at my personal proposition, and, in some measure, I venture to say, through my personal activity, because, although the proposition met with hearty goodwill, there were some technical difficulties which required to be smoothed over.As the oldest member of the Chemical Society, I may venture to remind you that I was elected in the presidency of Professor Brande, a long time the secretary of the Royal Society and the favourite pupil of Sir Humphry Davy, and the successor of Sir Humphry Davy in his professorship of the Royal Institution, he, himself being subse- quently succeeded by Faraday. On the institution of this lecture- ship we were fortunate in securing Dumas as our first lecturer. It was thereby at once recognised that a very high standard of proficiency had been established for the lecturers who would follow him. That st'andard has been thoroughly well kept up by Professor Richards, to whose admirable and searching address we have liskened with so much interest.For myself I would venture to say that I do not feel at dl shocked by his proposition asto the absolute continuity of matter in the solid and liquid states. On the occasion of ths first Faraday lecture, Dumas enlarged on the absolute unresolvability of what we called the chemical elements, i~sthey were then known. He pointed out that those forms of matter had existed unchanged for millions of years, and suggested that they were likely to remain unchanged for millions of years to come, a suggestion which I would recommend with all deference to Sir William Ramsay. Our present lecturer, Professor Richards, has, we shall all agree, more than attained the high standard which originally set up.I had the pleasure of hearing Professor Richards at Oxford a few days ago, and 1 was much struck by his expression of hopefulness for the future, that there should be no resting places in chemistry, and that the work should go On for ever. If we lo& back to the time of the institution Of the Chemical 152 Society, some seventy years ago, I think we may say there has been no decade in ~hich fundamental points of importance in the way of discovery and interpretation have been lacking, and neither has continuity failed. On the occasion to which I have referred, Professor Richards enlarged on the fact that, so far from having passed the grand age of chemistry, we were really after all only at the beginning. That is the feeling which must animate all of us.When the Faraday Lectureship was instituted, it was with the two-fold object of doing honour to Faraday, and of enabling the Fellows of the Chemical Society to meet and hear the views of the most eminent men among foreign professors. That Professor Richards possesses the qualification of eminence goes without saying, but that he possesses the qualifications of being a foreigner may be very much doubted. Here we do no& recognise the citizens of the United States, and more particularly the scientific men of the United States, with many of whom it has been my advantage to be associated, as being in any way €oreigners. We are pleased to greet them, and Professor Richards is one of ourselves. At the present moment we have the professors of chemistry at Harvard and Yale on our list of Honorary Fellows, and a number of other illustrious citizens of the United States whom we are proud to consider as being part and parcel of ourselves.Sir WILLIAMTILDEN: Mr. President, Ladies, and Gentlemen,- I rise very willingly to second the resolution which has been laid before the meeting by our senior Fellow. But, as might be expected when you think that Dr. Odling was asked to move the resolution, you will see that he has exhausted the subject. How-ever, I, too, have enjoyed the privilege of being present on a good many occasions when the Fsraday Lectures have been given in this room, and, though, of course, I was very young at the time, I quite distinctly remember the magnificent discourse given by Dumas. I remember also that, i.n his peroration, he seemed to indicate that there was some sort of limit set, either by human capacity or in some other way, to the possibilities of science, but if he had lived, as we have had the advantage of doing, down to the beginning of the twentieth century, he would no doubt have changed that opinion fundamentally.However, Professor Dumas was, at the time of the Faraday lecture, in 1869, almost at the end of his career, and he did not live many years after that. Our Faraday Lecturer to-night has led us to look forward with a hopeful feeling to the development of new ideas in chemistry and physics. He is still a young man, and, as we hope, not half-way through his magnificent career.In seconding the vote of thanks, I should be glad to be allowed to express in your name our most cordial wishes for the continuance of his good health, good spirits, and strength, to carry on those laborious experiments with which we are all familiar on this side of the Atlantic. In listening to his discourse, it was with a feeling of mingled relief and disappoint-ment that I found he was talking about the fundamental properties of the elements without having given us the definition of an element. I gathered with some satisfaction that he was really referring to the old-fashioned elements which were talked of by Dalton and others, and which are referred to in the well-known classification of the elements in the periodic table.For my part, I am afraid I am too old to learn the new sort of chemistry which seems to be coming up, but I do feel very strongly that we are not likely to part with our old friends the Daltonian elements -whether they are preserved or not I do not care-so long as the wonderful development of stereochemistry in the last few years continues to be evolved. It seems to me that the whole of shrew chemistry is the fundamental argument in favour of the stability of atoms in chemical combination. However, this is not the time, nor am I the person, to present these views to you. I should like tr, be allowed to support the proposal which has been laid before you so eloquently and in so interesting a manner by Dr. Odling, that we should return to our cousin from the other side of the Atlantic our most cordial thanks for the brilliant and admirable discourse which he has given us to-night.Professor DIXON: Mr. President, Ladies, and Gentlemen,-On looking back at my late tenure of the office of President, which you, Sir, I think, have defined as two years’ hard labour, I know there is one pleasurable duty which more than made amends for all the routine duties which fell to my lot in that position, and that was the privilega of conveying the invitation of this Society to the Faraday Lecturer of to-night. The Chemical Society looks high, and it expects much. Professor Richards has more than fulfilled those expectations. We have listened to-night to a story that is more entrancing than any fairy tale, because as we followed the flight of the lecturer’s imagination we knew that that flight was surely guided and controlled by a man who had measured and weighed the elements with an accuracy hitherto unknown.Con-cerning the weighing of the elements, our old European ideas of finzlity have been overthrown by Professor Richards and his school, and we are at this moment seeing the fulfilment of the propbecy of Canning when he said, “I look to the new world to redress the balance of the old.” The t3HArRMAN having put the vote to the meeting, it was carried with acclamation. 184 Professor RICHARDS: Mr. President, Ladies, and Gentlemen,- I can hardly find words to express my very deep and heartfelt appreciation, first, of the great honour, the extraordinarily high honour, which the Chemical Society has conferred upon me by inviting me to give this lecture and by awarding me this famous Medal, and, secondly, by the most kind expressions of opinion and of good feeling which I have heard here to-night. I shall treasure this Medal always, as a token of your kindness, and I shall, when-ever I look at it, think of this memorable evening in this memor- able building, where not only the great Faraday, but so many great men, have laboured and lectured.Thursday, June 15th, 1911, at 8.30 p.m., Professor PERCYF. FRANKLAND,LL.D., F.R.S., President, in the Chair. Messrs. William Gidley Emmett, J. T. M. Dunlo?, and A. W. Titherley were formally admitted Fellows of the Society.The PRESIDENTstated that the Council, at their meeting held that afternoon, had sealed an Address of Congratulation to His Majesty King George V. on the occasion of his Coronation, and an Address of Congrakulation to the University of St. Andrews on the Celebration of the Five Hundredth Anniversary of the Foundation of that University. To HIS MOSTGRACIOUS KING GEORGE MAJESTY V. May it please Your Majesty, We, the President, Council, and Fellows of the Chemical Society beg leave tol offer to your Majesty our sincere and most respectful congratulations on the auspicious event of your Coron* tion. We approach you with the more confidence when we remember how much the science of Chemistry and the position of our Society are indebted to the favours of your august House.We ever bear in mind that a Royal Charter was granted to the Chemical Society by Queen Victoria, and that the Royal College of Chemistry, which was so largely instrumental in fostering and developing the study of our science in this country, was founded by your illustrious Grandfather, the late Prince Consort. It is, moreover, with special gratitude that we recall the lively interest which, as recently as 185 two years ago, was taken by your Majesty and Her Majesty Queen Mary in the International Congress of Applied Chemistry, when you extended the Royal welcome to the chemists of all nations assembled in the Capital. We venture $0 hope that not only chemical research, but the pursuit of all useful knowledge, may be promoted and furthered in this realm under your benevolent and gracious patronage, and we beg to assure Your Majesty of our loyal devotion as we do earnestly hope and pray that Your Majesty’s reign may be long, happy, and fruitful.Signed on behalf of the Chemical Society, (Signed) PERCY President.F. FRANKLAND, ,, ALEXANDERSCOTT,Treasurer. ,, ARTHURW. CROSSLEY1. Honorary ,, G. T. MORGAN I Secretaries. ,, HORACE Foreign Secretary. T. BROWN, Dated this the Fifteenth Day of June, One Thousand Nine Hundred and Eleven. To THE UNIVERSITY ST. ANDREWS.OF On t.ho auspicious event of the Celebration of the Five Hundredth Anniyersary of the Foundation of your University, we, on behalf of the Chemical Society, desire to offer you our most sincere and hearty congratulations. We share the world-wide interest which is evoked by the oldest and most picturesque of the Scottish Universities, and we rejoice to think that this ancient seat of knowledge should have so early recognised the claims of natural science as to establish a Chair of Chemistry already one hundred years ago. We congratulate you on your not having allowed the venerable traditions of the past to overshadow the urgent needs of the present, and we cordially admire the munificent and devoted generosity of your friends in raising the worthy buildings, equipped on modern lines, for the study of Chemistry.It is, moreover, with lively satisfaction that we have comet to regard your Chemical School as an active and fertile centre of research, in which have been conducted a large number of valuable investigations, the results of which are embodied in the Transactions of our Society.We trust that the now happily accomplished absorption of the Dundee College by the University may prove of great mutual benefit, and that the blending of the young institution with the old may be a guarantee of continued strength and fertility. In the name of the Council and Fellows of t,he Chemical Society we wish you all prosperity in the future, and we would express the earnest hope th& tho grey Town set by the Northern Sea may never cease to a+ttract and inspire active workers, not only in our own science, but also in other branches of learning.Signed on behalf of the Chemical Society, (Signed)PERCY President.F. FRANKLAND, ,, ALEXANDERSCOTT,Treasurer. ,, ARTHURW. CROSSLEYHonorary ,, G. T. MORGAN \ Secretaries. ,, HORACE Foreign Secretary. T.BROWN, Dated this the Fifteenth Day of June, One Thousand Nine Hundred and Eleven. The PRESIDENTannounced that the Secretary of State had intimated his intention of making Regulations dealing with the smelting of materials containing lead, the manufacture of red or orange lead, and the manufacture of flaked litharge, in accordance with a draft', copies of which may be obtained on application to the Factory Department, Home Office, London. Certificates were read for the first time in favour of Messrs.: Lionel Gowing-Scopes, 3, Estcourt Street', Devizes. George Wishart> B.A., Royal School, Armagh. A ballot for the election of Fellows was held, and the following were declared subsequently duly elected : Ernost Andrew A tkins. Joges Chandra Ghost?, B1.A. Norman Ernest Atkinson. Cyril Herbert Koszelski Gonville. Arthur Owen Blackhurst. Rowland Lewis Goold. George Arthur Bradshaw, M. Sc. Edward Lionel Joseph. Arthur Frederick Clarke. Henry Edmund Linenbroker. Charles Ernest Cooke. Herbert James Ling. Thomas Cowling. Richard William Merriman, M. A. Ganesh Datta, B.A. Ftlix Gabriel Paul. Rudolph Demnth. Leonard Ison Pitt, B.Sc. Benjamin Gallswor thy. William Keighley Walton. Edgar Harold Gardner. Of tho following papers, those marked * were read: “1’74.‘(The alleged complexity of tellurium.” By Augustus George Vernon Efarcourt and Herbert Brereton Baker.It has been asserted by Flint (dmer.J. Sci., 1910, [iv], 30,209) that tellurium can be separated into two fractions by partial precipitation of the tetrachloride by water. Using 200 grams of highly purified telluric acid, the authors have repeated the Rork. After four partial precipitations, Flint obtained a diminution of a whole unit in the atomic weight of tellurium, but the authors find that the atomic weight is not altered. The mean result of five determinations of the atomic weight of the fourth fractionation was 127.54, that of material similarly purified, but without the, fractional precipitation, being 127.53.They conclude that no separation is effected by this method, and that it is probable that Flint’s material was insufficiently purified. DIscusSION. Prof. ERNSTCOHENsaid that he was extremely interested in the facts communicated by Dr. Baker, as they cleared up several doubtful points in some researches on the allotropy of tellurium which had been carried out during the last two years in his (the speaker’s) laboratory. It had been known for a long time that allotropic forms of tellurium existed, but we had been entirely ignorant of the relations between them and of the conditions under which they could be formed. The measurements of Exner, Berthelot, Beljankin, and others in this direction did not agree with each other, but an explanation of this disagreement was found in the fact that the allotropic change of one of these forms was markedly affected by Light, which displaced the equilibrium.Flint’s recent statements introduced difficulties which the authors had now removed, as they had shown that tellurium must still be rega,rded as a single elementary substance. It was thus possible to bring all these phenomena, which appeared so mysterious, under the head of dynamical allotropy. *I 75. The purification and properties of acetic acid.” By William Robert Bousfield and Thomas Martin Lowry. Acetic acid may be purified by distilling from potassium per- manganate, using a still-head to retain acids of higher boiling point, and then freezing to remove the water.The purified acid melts at 16*60°, and has a density of 1.05148 at 18O/4OYand 1.04922 at 2Oo/4O; its maximum conductivity when mixed with water is ~,8=0‘001641,. 188 DISCUSSION. Dr. VELEYremarked that those workers who had been engaged in the purification of even the commonest acids could fully appre- ciate the difficulties encountered in preparing acetic acid free from its homologues, so as to obtain trustworthy data for its physical constants, such as electrical conductivity, melting point, and density. The method adopted for destroying the formic acid by oxidation with potassium permanganate appeared to be of especial interest, as doubts had been expressed as to the statements contained in text-books that formic acid can be completely oxidised under these conditions.Dr. WADEsaid that in purifying acetic acid for the preparation of esters he had succeeded in eliminating propionic acid and its immediate homologues by fractional distillation with a small quan- tity of water, with which it was perhaps not generally known that all the lower fatty acids, with the exception of acetic acid, formed volatile azeotropic mixtures. He employed, however, an evaporator still-head, which, as Young had shown (Trans., 1899, 75, 699), was much more efficient than the pear column employed by the authors. He doubted whether the oxidisable impurity observed by the authors was formic acid; it was well known that other oxidisable impurities were often present in commercial acetic acid.Dr. L. F. GUTTMANNstated that in the course of some experi- mental work on mixtures of acetic acid and acetic anhydride he had had occasion to prepare pure acetic acid. On attempting to do so by freezing a large quantity of (( purest ” glacial acetic acid, allowing it to thaw partially, discarding the liquid portions, and repeating this procedure five or six times, he had expected to obtain a glacial acetic acid of a high degree of purity: the analysis of this acid, however, gave over 100 per cent. The normal solutions used were most carefully standardised, yet the result remained the same. Pure acetic acid, giving a value of 100 per cent., was subsequently obtained by fractional distillation of the products; it therefore appeared as if pure commercial acetic acid might contain some acetic anhydride which could not be removed by fractional crystallisation.He wished to know whether the authors had had similar experiences.Dr. TITHERLEYpointed out that the reducing substance supposed to be formic acid might be glyoxylic acid, which was a common impurity in acetic acid, and which would probably pass over in the earlier fractions on distillation. As glyoxylic acid in small quantities mould account for the observations of the authors, he 189 asked if any attempts had been made to prove the presence or absence of this substance. Dr. LOWRY,in reply, said that the acetic acid was distilled in presence of a little water, but the quantity was not sufficient to carry over the higher homologues before the acetic acid asl a minimum boiling mixture.The permanganate method of purification had the advantage that there was no real risk of producing any acetic anhydride; the acid was distilled while still moist, and was subsequently dried by freezing. The oxidisable impurity of low boiling point might contain glyoxylic acid, but the object was to get rid of it, and not to identify or isolate it. *176. The solubility of carbon dioxide in beer.” LL By Alexander Findlay and Bucchok Shen. Previous experiments on the absorption of carbon dioxide by beer (Langer and Schultze, Zeitsch. fiir das ges. Brauwesen, 1879, 2, 369) have been interpreted as showing that beer dissolves more carbon dioxide than the corresponding water-alcohol solution ;and the supposed increase has been attributed to adsorption by the colloids present in beer (Emslander and Freundlich, Zeitsch.physikul. Chem., 1904, 49, 317). These conclusions, however, am not in harmony with experi-ments carried out by Findlay and Creighton (Trans., 1910, 97, 536), and the authors now show that carbon dioxide is, as a matter of fact, less soluble in beer than in the corresponding water-alcohol solution, and that the contrary conclusion reached by Langer and Schultze must be attributed to their having used beer supersaturated with carbon dioxide. *177. “An addition to the Buchner funnel.” By Alfred Charles Glyn Egerton. The apparatus consists sim- ply of a small glass hood, which can be connected to a drying: tube.The glass hood is made of such a diameter that 190 it fits inside a Buchner funnel, the joint being made Fir-tight with a rubber ring situated in a groove round the rim of the hood. It is well to employ a, gentle pressure with the ring of a retort-stand to hold the hod in position? unless working with air under diminished pressure. A precipitate collected in the usual manner on the funnel can bel dried by means of this simple additional apparatus in a very short time. Besides dispensing with the trouble of transferring the precipitate to a desiccator, the apparatus saves much time in the drying. The drying is most rapid when a steady, not too rapid, stream of air is drawn through the apparatus by means of the filter-pump after passing through a large drying tower filled with calcium chloride; further, the hood, which is made of blown glass or, for very rapid drying, of metal, can be warmed with a flame.The precipitate can, if desired, be dried under diminished pressure by affixing a screw clip to the air inlet of the drying bower. Another application of tlhe apparatus is the drying of a precipitate in a non-reactive atmosphere; the gas cm be circulated round and round, if necessary, by means of a blowing arrangement fitted to the filter-pump. This small, ifiexpensive apparatus changes a Buchner funnel into an exceptionally efficient desiccat’or, which dries, not only precipitates collected on the funnel by the usual methods employed therewith, but also cm be used conveniently for drying crucibles, etc., in a current of dry air.“178.“The action of ammoniaand aminesonfl-phenyl-l:3-benzoxazine-4-one.” By Arthur Walsh Titherley and Ernest Chislett Hughes. 2-Phenyl -1 : 3 -benzoxazine-4-one (I) readily combines with ammonia, giving bright orange needles of salicylbenzamidine (II), and primary amines, giving yellow derivatives (111) of similar constitution : These amidine derivatives give colourless hydrochlorides possessing the cyclic constitution : CO-TH C6H4<O-C Ph*NHR,HCl’ 191 passing through the cyclic compound I into N-benzoylsalicylamide in presence of water. The free cyclic bases, which are intermediate compounds in the synthesis of the amidines I1 and 111, are too unstable to exist in the free state.Salicylbenzamidine (11) may also be spthesised from phenyl sitlicylate and benzamidine, and o-hydroxytriphenylcyanidine also results as a secondary product. 2-Phenyl-1 :3-benzoxazine-4-one combines with secondary amines, giving mixtures of labile isomeric cyclic and open-chain cimpounds of the type PV and V: -+ (IV.) Colourless. (V.) Yellow. With dimethylamine no proper separation could be effected, but with diethylamine the colourless compound (IV) was isolated. With diphenylamine a bright yellow compound (V) was obtaine’d, which, owing to steric influences, does not possess normal phenolic proper- ties. It is probable that in all the yellow open-chain derivatives the molecule is bordering on ring-f,ormation, and the colour is attributed to the distarbmce of residual affinity thus created.Replacement of the hydrogen atom of the, phenolic hydroxyl group by methyl in salicylbenzarnidine leads to a, colourless compound, the velocity of hydrolysis of which is normal as compared with similar amidines, whilst that of salicylbenzamidine and its derivatives is abnormally high owing to ring-formation. *179. ‘(Synthesis of 4 :6-dimethoxy-2-/3-methglaminoethylbenz-aldehyde.” By Arthur Henry Salway. 4 :6-Dimethoxy-2-~-methylaminoethylbenzaldehydehas been syn-thesised from P-5-hydroxy-3-methoxyphenylethylamine(Trans., 1910,97,2413) according to a series of reactions similar to those employed by the author in the synthesis of cotarnine (Trans., 1910, 97, 1208).The stages involved in this process are represented by the following scheme : HO’\CH,*CH,*CO,H -+ MeOA CH,-CH2*C02HII I1 --+ \/ \/-OMe OMe &5-Hydroxy-3-methoxy-0-3 :B-Dimethoxyphenyl-pheu ylpropionic acid. propionic acid. 192 NH CO C,H,-+M~O/\CH,-CH,*CO-NH,I1 \/OMe OXe 8-3 :5-Dimethoxyphenyl-Phanylacetyl-8-3 :5-dimethoxy-propionamide. phenylethj lamide. IMeOf)CH2-$! H, -+ MeO(\,CH,---FH2 -+\p(C,H,P \/C;H(C,H,)*N*CH, OMe OMe 6 :8-Dimethoxy-1-benzyl-3:4-di-6 :8-Dimethoxy-2-methyl-1-benzyl-hydroisoquinoline. 1 :2 :3 :4-tetrahydroisoquinoline. MeO/bH,*CH,*NH*CH,I\/ICHO OMe 4 :6-Dimethoxy-2-/3-methylamino-ethylbenzaldehyde. closely re-4:6-Dimethoxy -2 -/3 -methyZaminoethylbena~~e?z.yde sembles cotarnine in it’s physiological action on the isolated uterus. On the other hand, it is considerably less toxic than the latter compound. DISCUSSION.Dr. TITHERLEYinquired whether the author had instituted any experiments to determine which of the alternative tautomeric (open-chain or cyclic) f ormulz represented the constitution of cotarnine and allied derivatives. 180. Cupriglycollates.” By Spencer Umfreville Pickering. That the cupri-compounds formed by the action of alkalis on copper salts contain their copper in the form of CuO or CuOH, and not as metal displacing hydrogen atoms, has been shown by determinations of the molecular weights of six such compounds (Trum., 1911, 99, 169): more conclusive evidence has now been obtained by finding that in potassium cupriglycollate the ratio of Cu:E is 1 :1, in accordance with the formuIa CH,0(CuOH)*C02E, and not 1:2, as it would have to be if the metal displaced hydrogen : (C~O)2C~(C02K)2.Trom a sdufion of copper glycollate mlxea wi6h excess 01 potassium hydroxide, alcohol precipitates a mauve-coloured, strongly alkaline, crystalline substance, which agrees in composi-tion and properties with the y-cupri-salts (containing the cuprite group) suggested as existing jn such solutions. The corresponding salts of sodium and rubidium (-probabky, also, of barium) have 193 been obtained, but not those of lithium, wsium, or calcium, On heating, they seem, in some cases, to be transformed into compounds in which an atom of copper displaces two atoms of hydrogen in alcoholic hydroxyl groups. 4‘181.Polymorphic phthalylhydrazides.” By Frederick Daniel Chattaway and Donald Frederick Sandy s Wunsch. Some years ago it was observed that phthalylphenylhydrazide, when crystallised from any ordinary solvent, separates almost invariably in two modifications different both in crystalline form and in colour. Each modification could be obtained free from the other by altering t.ha temperature at which crystallisation took place. While this work mas in progress, Dunlap (J. Smer. Chem. Soc., 1905, 27, 1091) published an account of similar observations, and it was consequently discontinued.The authors have recently again investigated the subject to ascertain if this property o€ crystallising in two forms is common to all phthalylhydrazides. So far, only one other instance has been found among the simple phthalyl derivatives studied, but it seems certain that this is due to the exact conditions necessary for the appearance of the second modification not having been realised, many other observations on related compounds, which will be communicated later, leading to the conclusion that it should be possible to obtain every phthalyl and substituted phthalyl hydrazide in two forms. A large number of phthalylhydrazides were described. These compounds are very easily obtained by heating together phthalic anhydride and the corresponding hydrazine ; the reaction which occurs may be formulated thus: The crystals separating at the higher temperature are bright yellow or orange, those into which they pass when the temperature is lowered being almost colourless.In every case where only one modification has been observed, it is the one having the deep orange colour. 182. c1 Decomposition of hydrazides and hydrazones by heat.’’ By Frederick Daniel Chattaway, Charles Linaeus Cumming, and Bernard Howell Wilsdon. In continuation of an investigation into the action of heat on hydrazines, the reactions which take place when various hydrazides and hydrazones are heated have been studied. 194 When the phthalylhydrazides are heated, vigorous reaction, accompanied by the evolution of heat, sets in at a definite tem-perature, nitrogen and ammonia are liberated, and a phthalanil is produced ; for example : In the case of hydrazones two main reactions take place, resulting in the formation of an unsaturated hydrocarbon, nitrogen, and a saturated hydrocarbon ;thus, for example : 2C6H,*CH:N*NH*C6H5 +N2+2C6Hs,=C6H5*CH:(;aH*C6H5 or in the formation of an aldehydeanilide, nitrogen, and ammonia, thus : 3C6~,*CH:N*NH*c6H, +N, +NH,,=SC,H5*CH:N*C6H5 a somewhat larger amount of the hydrazone, as a rule, undergoing the latter decomposition.It seems highly probable that the secalled fl phthalylphenylhydrazide, melting at 210°, is really impure phthalanil produced fro= the ordinary or a-phthalylphenyl-hydrazide by the abovedescribed decomposition.183. ''Some reactions of gum kino." By John Lionel Simonsen. The author described some experiments on the constituents of the gum of Pterocarpus Marsuphm. 184. cc Electromotive forces in alcohol. Part I. Concentration cells with electrodes reversible to chlorine ions." By Arthur Lapworth and James Riddick Partington. Fairly satisfactory results may be obtained with such cells, containing alcoholic hydrogen chloride, with electrodes of silver or mercury, and with silver chloride and mercurous chloride, respectively, as depolarisers. The transport number of chloridion is found to be about 0.37, as contrasted with 0.16 in aqueous hydrochloric acid. It was shown that t'his is due to the hydrogen ion, as the transport numbers for the ions of most salts hitherto examined do not appear to be greatly afFected by such a change of solvent.185. Some oxidation products of the hydroxybenzoic acids. Part 111." By Arthur George Perkin. The substance C,,H,O,,, now termed caeruleoellagic acid, previ-ously obtained by heating ellagic or flavellagic acid with sulphuric acid (Proc., 1906, 22,114), can also be prepared by the action of 195 arsenic acid on the sulphuric acid solutions of these compounds. The acetyl derivative C,,O,,(C,H,O), melts at 33@-332O, and is in reality colourless, and the b enzoyl compound Cl,01,,(C7H,0), forms needles melting at 343-345O. By distillation with zinc dust, caeruleoellagic acid gives fluorene, and with boiling potassium hydroxide solution a substance ClzHloOs, which crystallises in prismatic needles, arid is evident41y ail octahydroxydiphenyl, the ncetyl derivative of which, C,,H,O,(C,H,O},, forms colourless needles, melting at 177-178O.Caeruleoellagic acid, to which the constitution : -co-0-HO/\---/\OH HO.\/lO--COl \/OHOH OH is assigned, dyes mordanted fabrics similarly to flavellagic aid, bufi scjmewhat more strongly. 186. The triazo-group. Part XIX. Nitrosoazides of dipentene, d-limonene, and Z-limonene." By Martin Onslow Forster and PF8&*7L!r Na3?u,9 Pas GP*MPrPa. Dipentene nitrosoazide, Cl,H15( :N OH)*N,, prepared from either the nitrosochloride or the nitrosate by the action of sodium azide in aqueous alcohol, crystallises from methyl alcohol in colourleas plates, melting at 72-73O ; alcoholic potash eliminates hydrazoic acid, producing i-carvoxime.i-TriuzoclihydrocaruoTze, C10H150N3, arising from the foregoing nitrosazide (its oxime) by the action of hot aqueous oxalic acid, is a colouriess liquid, having a pleasant odour of peppermint; it boils at 81°/0.4 mm., and has D 1.0409/20°. The semicarbuzone melts at 132-133O. d-Lirnonene nitrosouzide, CloEI,,(:N0H)*N3, whether prepared from the a-or the 8-nitrosochloride, melts at 52-53O, has [aID6.5O, and is converted into Z-carvoxime by the action of alcoholic potash. d-Triasodihydrocaruone, C10H1,0K3, produce4 when the nitroso-azide is heated with aqueous oxalic acid, boils at 93O/0*46 mm., has D 1.0457/20", and [~],88.49~; the semicurbazone melts at 2200.l-limonene mitrosoazide, Clo€I15(:NOH)-N,, melting at 52--53O, and having [a]=-3O, gives d-carvoxime with alcoholic potash. l-Triazodihydrocaruone, C,,Hl5OhT3, obtained by hydrolysis with oxalic acid, boils at 93-94O/0.48 mm., has D 1'0472/20°, and [alD -92'5O; the semicarbazone melts at 220O. 196 187. “The relation of the velocity of chlorination of aromatic compounds to constitution. Part I. Chlorination of anilides.” By Kennedy Joseph Previt6 Orton and Harold King. The speed of chlorination (f ormation of monochloro-derivatives) of a number of acylanilides has been measured in glacial acetic acid solution. It was shown that the rate of the reaction varies enormously with the character of the substituent in the benzene nucleus. The nature of the acyl groups has a comparatively subsidiary effect. Naphthalides are chlorinated at a far greater rate than the anilides.188. ‘‘Chlorination of acylanilides. Effect of the constitution of the acyl group on the proportion of the ortho- and para-derivatives.” By Harold King and Kennedy Joseph Previt6 Orton. The proportion of 0-and p-chloro-derivatives produced in the chlorination of form-, propion-, stear-, and benz-anilide has been estimated. Comparison with acetanilide (Jones and Orton, Trans., 1909, 95,1056) shows that tlre largest proportion of the o-chloro- derivative is Iormed in this case. Acetanilide yields 45, propion-anilide 26, steasanilide 12, benzanilide 11, and formanilide 3 per cent.of the o-chloro-derivative. 189. “The influence of the alternating factor in certain series on the molecular volumes at the melting point.” By Gervsise Le Bas. An examination of the molecular volumes of the paraffins at the melting point shows that the volume differences for CH, alternate in value exactly as do the melting point,s in several homologous series. By finding the number of H equivalents in each compound (since C=4H), that is, W, and dividing this into the volume at the melting point, V, the ratio VjW gives the volume of Ii in each compound. The molecular volumes of the normal paraffins at various tem-peratures can be calculated by means of interpolation formulae with two constants. 197 I.-Table of Constants.ConqJou?td. 3r.w. iv. M.P. dT. Noiiane, CyH20 ...........* 128 56 -51.0" 0.7330 (0") Decaiie, C,,H,, .,........., 142 62 -32.0 0.7454 (0") Untiecane, C,,HC4......... 166 68 -26.5 0.7557 (0") Dodecane, Cl2HPB......... 170 74 -12-0 0.7730 (ni. p.) Triclecaaiie, C,,H2s ......... 184 80 -6.2 0.7755 (in. p.) II.-Constituiive Efects in the T'oEumes of Compounds at thp Melting Points. ill. T. A between A between V/It' lr/ 1V Compound. W. 111. p. A. odd No.'s. even No.'s. (odd). (even). CgH,o ...... 56 165.67 "957 -C,,H, ... 62 184.54 116.9,j 35.i -2.976 C,,H,, ... 68 201.4 35.4 2.9@ -C,,H,, ... 74 219.9 18'51 35.9 -2.972 17-41 C,,H,B ... 80 237.3 35.5 2-966 -ClJH3,, ...86 255.4 Is*'\ 35.9 -2.970 17.8)C,6H,, ... 92 2732 35.8 2'970 -:;::I-C',,H,4 ... 9s 291.2 53.8 -2.971 C,,H,, ... 101 309-0 2.971 Study of the data shows that: ( I) The even members of the series show augmented values of V/JV, and the odd members depressed values. This is in accord with the fact that the melting-point curves are different, the one for the odd members falling below that for the even members. (2) The values of VjTV for the even members diminish to a constant value, 2.970, rmd those for the odd members increase to the sane constant value. Thus, agaiii, there is correspondence between the melting-point and volume curves in that the double curves gradually approach each other as the series is ascended. The conclusion is drawn that for both the volumes and the melting points the alternating factor always exerts a depressing effect on the compound with an odd number of carbon atoms, and a*rielevating one on the compound with an even number of carbon atoms.The alternating factor consequently siniilarly affects both physical properties. 190. The elimination of bromine from phenyl p-methoxystyryl ketone dibromide." By Forsyth James Wilson and Alfred Archibald Boon. Tho authors find that when phenyl p-methoxystyryl ketone dibromide is treated with propyl alcohol, isobutyl alcahol, benzyl alcohol, or acetic acid, one of the products is pheny7 bromo-p-mP thorylstyryl X:eton4, 'MeO*C,H,*CBr:CH.COP h or MeO-C,;H, * CT3:CJ HI.* CX) 1'h , which melts at 93-94'.When the dibroniide is heated with isopropyl alcohol, tert.-butyl alcohol, acetone, or benzoin, the ketone 'is regenerated. rc191. Some new inorganic saltas'' By Thomas Vipond Barker." In continuation of previous work on the regular growths on each other of isomorphous crystals, the author has completed the investigation of the series of alkaline periodates by the inclusion of the lithium salt, which proves to be entirely different from the compound described (but not analysed) by Itamrnelsberg, so that it seems probable that4 his compound was an impure specimen of sodium periodate. A further contribution to the list of isomorphous substances has been made by the preparation of two new doubIe chrornstes of the general formula R,B!tg(CrO,),,GH,O, in which R =Rb or Cs ;these two salts prove to be strictly isomorphous with the corresponding ammonium salt prepared some sixty years ago by Miirnianii, and with the better known series of double sulphates ADDITIONS TO THE LIBRARY.Trinum Chgmicum oder Drey Chymisclie Tractiitlein. I. Fr. Vincentii ICoft'sky . . . Schaner und ausfuhrlicher Bericht von der ersten Tinctur-Wurzzel des Steins der Weiacn, etc. (pp. 1-21 only). Strassburg 1699. (Beference.) Prom Dr. A. Harden, P.R.S. Trinum Chymicum secundum odor Drey Andere Chgniischo Tractiitlein. I. Heinrici Khunrath . . . Philosophische Erkliirung von und uber dem gehoimen iiusserlicheu sichtbaren Gludt ixnd Flammen-Feur der uhralten Magorum oder Weysen urid anderer wahren Philosopheu.II. Eiri fbrtreffliches Judicium uucl Hericht eines erfahrnen Cabalisten, iiber die vier Figuren desv grossen Amphitheatri D. Henrici Khunrathi. 111. Vori dor Tiuctur Antimonii und Oleo Stibii von Theophrnsto Prtrscelso Auch einem * This paper was comriiunicated at the RIeetiiig 011 Juue 1st. 199 hnhang zu der Materi dienlichen Sachen Ton Basilio Valelotino beschrieben. pp. [viii] + 174 (misprint for 184). Strasburg 1700. (Refeyence. From Dr. A. Harden, F.R.S. Valentinus, Basilius. His last Will ancl Testament . . . , wherein he . . . declareth the wayes he wrought to obtain the Philosophers Stone, etc. London 1657-56. (9 parts, each having separate title-page. Wanting first title-page, and pp. 21 to 23 of a “Treatise concerning Microcosme.”) (Refirewe.) From Dr.A. Harden, F.R.S. I I. By Pzcl-chnse. Nikaido, Y. Beet-suga.r making and its chemical control. pp. xii + 35 t. ill. Easton, Pa. 19011. (Recd. 14/6/11.) Pusa Agricultaral Research Institute and College. Report 19tr9-10. pp. 69. Calcubta 1910. Schrauth, IVcdther, uucl Schoeller, IVaZter. I; ber dio T)esinfelitions-kraft komplexer orgnnischer ~1iecksilberver.bindungen. I. At o-mntischer Quecksilbercarbonsauren. (From the Zeitsch. Iiyg. Infect., 1910, 66.) Stoddart, Fyerberick W(dZis. Nitrification ancl the absorption theory. An account of the principles of the modern sewage filter. pp. 24. Rristol 191 1. Thunberg, Tor.stm. Studien iiber die Beein flussung des Gasaus-tausched des iiberlebenden Froschmuskels durch verwhiedene Stoffe.IV-IX. (Prom the Skud Arch. Phpiol., 1910, 24.) Untwsuchungen uber autoxydable dubstnnzen und autoxy-dable Systerne von physiologischem Intercsse. I. and 11, (From the Skccnd. Amhiv. Physiol., 1‘310, 24.) Widmark, E~ikM. Z’. Uutersuchuugen uber die chemischen Bedinguugen fur das Beibehalten der iiorrnalen Struktur der Zellen. I. and 11. (From the Skand. drchiv. Yhysiol., 1910, 23, 24.) THE LIBRARY. The Library will be closed for Stocktaking from Monday, August 14th, until Saturday, August 26th, 1911, inclusive. Fellows are particularly requested to return all Library Books in their possession not later than Wednesday, August 9th. LIST OF FELLOWS, 1911. The List of Fellows for 1911 is now in active preparation, and changes of address received after July 31st cannot bo included in it. In order that the new List may be as completc as possible, those Fellows whose degrees and Christian names do not appear in full are requested to communicate them to the Assistant Secretary. RICHARD CLAY AND SONS, LIMITED, BREAD ST. HILL, E.C., AXD HUNQAI’, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9112700177
出版商:RSC
年代:1911
数据来源: RSC
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