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Proceedings of the Chemical Society, Vol. 21, No. 293 |
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Proceedings of the Chemical Society, London,
Volume 21,
Issue 293,
1905,
Page 99-128
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摘要:
Issued 14/4/05 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 21. No.293. Wednesday, March 39th, 1905. Annual General Meeting. Pro-fessor w. A. TILDEN,D.Sc., F.R.S., President, in the Chair. Dr. A. E. H. TUTTONand Mr. A. G. BLOXAMwere appointed Scrutators, and the Ballot was opened for the election of Officers and Council for the ensuing year. The President then presented the Report on the state of the Society during the past twelve months. Mi". W. J. SELLmoved the adoption of the Report; this was seconded, and carried unanimously. REPORTOF THE COUNCIL. THECouncil are glad to be in the position to report that the Society continues to flourish, and that, as measured by the number of papers read, its activity has exceeded that of any previous year.On December 31st, 1903, the number of Fellows was 2,700. During 1904, 128 Fellows were elected, and 5 reinstated, making a gross total of 2,833. The Society has lost 28 Fellows by death; 37 have resigned ; the elections of 4 have become void; 52 have been removed for non-payment of subscriptions, and 1 Fellow has with- 100 drawn. The total number of Fellows, therefore, on December 31st, 1904, was 2,711. The names of the Fellows who have died are : A. H. Allen. W. H. Dodd. J. Mason. F. E. Allhusen. R. E. Doran. D. Munro. J. Barclay. W. Francis. T. A. Pooley. Sir I. L. Bell. A. Gibson. H. St. John. F. B. Benger. C. G. Grenfell. C. J. Sawer. C. Beringer. H. Grimshaw. W. H. Stanger. H. N. Bilimoria.G. Howsam. R. M. W. Swan. W. Chattaway. T. Isherwood. A. W, Williamson. P. L. Dey. J. Jackson. T. H. Dodd. A. Kitchin. The following Fellows have resigned : G. Ansdell. J. Edmunds. C. S. Purcell. J. F. Ballard. T. A. Ellwood. A. Sandford. J. Bardsley. F. A. Gatty. W. Sessions. H. H. Barker. H. Gordon. M. J. Sheridan. G. E. Battle. G. 35. Gregory. W. Taverner. J. Bsynes. H. E. Haddon. G. Trench. J. Bottomley. W. Hampton. H. F. Waller. G. W. Burman. E. C. Ibbotson. A. W. Warrington. W. F. Butcher. A. W. D. Leahy. A. L. White. J. Caley. A. E. McKenzie. H. F. A. Wigley. H. M. Chapman. T. R. Marshall. B. Winstone. T. A. Dickson. W. iMars11,zll. E. Dowzard. C. A. Alitrchell. Among the Fellows removed by death, the Society mourns the loss of Prof.Alexander W. Williamson, who twice filled the ofice of President, and to whose initiative the publication of the Abstracts was largely due. The number of Honorary and Foreign Members at the date of the last Annual General Meeting was 30. Six names were added to the list by the election on May 18th, 1504, of Prof. A. H. Becquerel, Prof. C. A. Lobry de Bruyn, Prof. F. W. Clarke, Madame M. Curie, Prof. C. Liebermann, and Prof. E. W. Morley. The Society has to lament the death of one of the newly elected Members, Prof. C. A. Lobry de Bruyn, on July 234 1904. The number of Honorary and Foreign Members, therefore, is 35. 101 During the year 1904, 215 scientific communications have been made to the Society, 188 of which have already been published in the ?'runs-actions, and abstracts of all have appeared in the Proceedings.The volume of I'ralzsactions for 1904 contains 175 memoirs, occupy- ing 1,761 pages, whilst that for the preceding year contains 142 memoirs, which occupy 1,490 pages. The Journal for 1904 contains also 4,617 abstracts of papers pub-lished mainly in foreign journals, which extend to 1,920 pages, whilst the abstracts for 1903 numbered 3,882 and occupied 1,640 pages. The abstracts for 1904 may be classified as follows : Part I. No. of Pages. Abstracts. Organic Chemistry .......................... 1,072 1,968 Part 11. General and Physical Chemistry ............ 606 Inorganic Chemistry.. ......................... 541 Mineralogical Chemistry ..................... 132 Physiological Chemistry .....................501 Chemistry of Vegetable Physiology and Agriculture .............................. 311 Analytical Chemistry ........................ 55s S4S 2,649 Total in Parts I. and 11. .............. 1,920 4,617 Owing to the great increase in the number of papers abstracted, it has become necessary to add to the editorial st,aff. Dr. C. H. Desch has been appointed Assistant Sub-editor, with the object of taking part in the preparation of abstracts for the press, and of relieving Mr. Greenaway of a portion of the clerical work. Although an award of the Faraday Medal was made in 1895, fifteen years have elapsed since the delivery of the last Faraday Lecture.On April 19th, 1904, the Lecture mas delivered by Professor Ostwald, in the lecture theatre of the Royal Institution, the use of which had been kindly granted by the Managers for the occasion. The subject of the Lecture was ''Elements and Compounds." The Wislicenus Memorial Lecture was delivered by Prof. W. A. Perkin on January 26th of the present year. On the occasion of the celebration of the Jubilee of the Doctorate of 102 Sir Henry E. Roscoe, a Past President of the Society, on April 22nd, 1904, the Council welcomed the opportunity of sending an address of congratulation to him. Proposals have been received from the Chemical, Metallurgical, and Mining Society of South Africa, and from the American Chemical Society, for a reciprocal exchange of Journals for members of each of these Societies and of the Chemical Society at a rate just sufficient to cover the cost of printing, addressing, and postage.After careful consideration, the Council were unable to accede to the proposals, as the effect on the finances of the Society could not be estimated, and a limit could not be set to the number of Societies which might seek the benefit of a similar exchange of Journals. The question of co-operation in the preparation of Abstracts in English has been raised afresh by the American Chemical Society by the appointment of a committee to confer with the Chemical Society on this important subject. The Council have reappointed the Com- mittee which discussed the possibility of co-operation in 1899, and await the proposals of the American Committee with every desire to consider their practicability.Acting on the suggestion made in the Presidential address at the last Annual General Meeting, the Council have arranged for the preparation and publication of a series of Reports on the advance made each year in chemistry. These reports mill be issued early in each year, and it is hoped that they will prove to be of value not only to the Fellows, but to students of chemistry generally. Obituary notices of several deceased Past Presidents have not as yet been published, These notices have now been received and are in type. Among them is included an obituary notice of Sir Edward Frankland, as the Council have been unable to obtain the manuscript of the Memorial Lecture, delivered on October 31st, 1901.A further increase in the use of the Library has to be re-corded, 1,057 books being borrowed during 1904, as against 991 during the previous year. The additions to the Library comprise 119 books, of which 67 were presented, 296 volumes of periodicals, and 52 pamphlets, as against 126 books, 271 volumes of periodicals, and 43 pamphlets last year. An alteration in the wording of Library Rule IV. has been made to enable new books to be borrowed at an oarlier date than formerly. The Society has been the fortunate recipient of the eudiometer used by the late Sir Edward Frankland in the analysis of ethyl in 1849, presented by Professor Frankland ;of a bronze medal of Roger Bacon, presented by Mr.Oscar Guttmann; and of an engraving of Berzelius, presented by Professor Retzius, of Stockholm. A special Committee was appointed last June to revise the Bye- laws, and reported in due course to the Council. The revised Bye-laws were submitted by the Council to the Society for consideration at an Extraordinary General Meeting on February Sth, but failed to secure acceptance, being referred back for further consideration. A memorial, bearing the signatures of nineteen women engaged in chemical work, praying for the admission of women to the Fellowship of the Society, has been under consideration. The Council were advised that “married women are not eligible for election as Fellows of the Society; that it is extremely doubtful whether the Charter admits of the election of unmarried women as Fellows; that it would not be wise to elect even unmarried women without first applying for a supplemental Charter; and that the election of women as Associates would be legal after a modification of the Bye-laws expressly authorising their election.” An alteration in Bye-law 111.extending the privileges of the Associateship to women accordingly formed one of the changes in the Bye-laws recently proposed by the Council. The third Report of the Joint International Committee on Atomic .Weights, with its revised table of atomic weights, has been issued to the Fellows in the Proceedhgs. Grants amounting in all t.0 2215 have been made during the year from the Research Fund, and $26 16s.6d. has been returned. OF the papers published in the Transactions during 1904, thirty-two were con-tributed by authors to whom grants had been made from the Research Fund. The total income of the Society for the year 1904 was 26,700 5s. 8cZ. and the expenditure $5,982 14s. 6d. ;in 1903, these were 26,S17 19s. 7d. and $5,926 18s. 3d. respectively, so that whilst the income has fallen byE117 13s. lld., the expenditure has risen by 255 16s. 3d. A glance at the balance sheet for 1903, however, shows receipts amounting to 2257 which cannot be regarded truly as income from normal sources ; in 1904 only $5 was so received. Allowing for these items, the income for 1904 shows an increase over that of 1903 of &134 6s.Id. The Treasurer’s chief anxiety is due to the ever-increasing size of the Journal and the corresponding increase in cost. Both exceed those of 1903, the size by about 17 per cent. and the cost by about 10 per cent., the excess due to printing alone in 1904 amounting to 22SO 12s. Id., whilst the total increase in cost reaches the large sum of $365 6s. lld. Part of this is due to the fact that the January number for 1904 con-tained a double set of Abstracts, thus leading to an increase both in Abstractors’ fees and in printing, these two items really representing thirteen months instead of twelve. As pointed out by the President on resigning the Treasurership two years ago, the steady increase in the 104 size and cost of the Jourwal seems to render it inevitable ‘‘ that, in the ‘‘near future, some more stringent regulations both as to the state of “the manuscript and the dimensions of the pzpers will have to be “imposedJJif the Society is to carry on its work of publication efficiently.In addition to the cost of the Journal, there is in the present accounts a sum of $237 68. Od. for the printing of Vol. IV, Part 1 (Authors) of the Collective Index (1893-1902). On the other hand, there has been a saving of $42 14s. 5d. in the cost of the Proceedings. The Library has cost less by the sum of 2,150 13s. 3d., and the general ndmini- strntive expenses, which in 1903 mere abnormally high, owing to special circumstances, have fallen from $1,138 5s.6d. to $893 1s. Od., R saving of 2,245 4s. 5d., notwithstanding the cost of introducing house telephones and also connecting the Society with the Post Office system. The Treasurer reports that the new system of keeping the Society’s accounts has been in full working order for two years and has been found most satisfactory in every way. The Council desire to place on record their appreciation of the valuable services rendered to the Society by Professor Wynne, and an expression of their regret that his removal from London obliges him to relinquish the office of Senior Secretary. By placing him among the Vice-Presidents, it is hoped that the Society may continue to receive the advantage of his experienced co-operation in the work of the Conncil.The TREASURERmade R statement as to the Society’s income and expenditure during the past Session, and proposej R vote of thanks to the Auditors, which was seconded by Dr. L. T. TIIORNE,carried unanimonsly, and acknowledged by Mr. E. GRANTHOOPER. The PRESIDENTthen delivered his address, in which, after recapitu- lating the events connected with the Society which had occurred during the past year, he gave an exposition of his researches on the relation of specific heat to atomic? weight in elements and compounds, the results of which led to the following conclusions. 1. The influence of temperature on the specific heats of many elements and compounds is much greater than was formerly supposed. 2. There appears to be no one condition or set of conditions under which the law of Dulong and Petit is true of all the elements.3. The nearest approach to a constant available for practical purposes is found by taking tho mean specific heats of metals between the freezing and boiling points of water, recognising glucinum, boron, carbon, and silicon as exceptions, together with hydrogen, oxygen, nitrogen, and perhaps chlorine in the solid form. It is possible that the atomic heats of elements in the gaseous state 105 may be equal, direct experiment on the gases having led to the value 2.4 for hydrogen, 2.5 to 2.7 €or oxygen, and 2.6 for carbon (in carbon dioxide). 4. The independence of each atom in an element or compound must be regarded as a fact of the utmost importance from the point of view of theory.That the molecular heat of a compound is the sum of the atomic heats of all the elements present is in harmony with the results of observations on other additive properties, such as specific volume and specific refraction. Such independence suggests the idea that chemical combination results from the mechanical fitting together of atoms, so that R section through a mass would exhibit, if the atoms were visible, a certain tactical arrangement probably corresponding with the closest approximation possible under prevailing conditions, It has yet to be shown that chemical combination results, in aZZ cases, from the existence of electric charges resident on the atoms or in electrons associated with them.The molecules of carbon compounds, especially, may be regarded as being probably formed by the adjust- ment of the constituent atoms to one another in respect to space, and it is noteworthy that the liquid binary compounds of carbon, the hydrides, chlorides, and oxides, are not electrolytes, and no case is known of the electro-deposition of carbon from such compounds in the elemental form. Professor RAPHAELMELDOLAproposed a vote of thanks to the President, coupled with the request that he would allow the Address to be printed in the Transactioias. Professor G. CAREYFOSTER seconded the motion, which was car1 ied by acclamatiou, and acknow- ledged by the President. Professor H. MCLEODproposed a vote of thanks to the Treasurer, Secretaries, Foreign Secretary, and Council for their services during the past year.This mas seconded by Dr. J. A. VOELCKER,and unanimously adopted. Professor W. P. WYNNEresponded. The Scrutators then presented their Report to the President, who declared the following to have been duly elected as Officers and Council for the ensuing year. President ;Raphael Meldola, F.R.S. Vice-Presidents who have fiUed the ofice of President: H. E. Arm-strong, Ph.D., LL.D., F.R.S.; A. Crum Brown, D.Sc., LL.D., F.R.S.; Sir William Crookes, D.Sc., F.R.S. ; Sir James Dewar, MA., LL.D., F.R.S. ;A. Vernon Harcourt, M.A., D.C.L., F.R.S. ;H. Muller, Ph.D., LL.D., F.R.S.; W. Odling, M.A., M.B., F.R.S. ;W. H.Perkin, Ph.D., LL.D., F.R.S. ; J. Emerson Reynolds, Sc.D., M.D., F.R.S. ; Sir 1OG Henry E. Roscoe, LL.D., F.R.S. ; W. J. Russell, Ph.D., F.R.S. ; T. E. Thorpe, C.B., LL.T>., F.R.S.; W. A. Tilden, D.Sc., F.R.S. I'ice-Presidents :Horace T.Brown, LL.D., F.R.S. ; Harold B. Dixon, M.A., F.R.S. ;Wyndham R. Dunstan, M.A., LLD., F.R.S. ; David Howard; A. Smithells, B.Sc., F.R.S.; W. P. Wynne, D.Sc., F.R.S. Secretaries: M. 0. Forster, D.Sc., Ph.D. ; A. W. Crossley, D.Sc., Ph.D. Foreign Secretarp :Sir W. Ramsay, K.C. B., LL.D., F.R.S. Treasurer: Alexander Scott, M.A., D.Sc., F.R.S. Ordinary &!embers of Council: Edward C. C. Baly; Augustus E. Dixon, M.D. ;J. J. Dobbie, MA., D.Sc., F.R.S. ; Bernard Dyer, D.Sc. ; Alfred D. Hall, M.A. ; A. Lapworth, D.Sc. ; J. E. Marsh, M.A. ; E. J. Mills, D.Sc., F.R.S.; G.T. Moody, D.Sc.; W. J. Sell, M.A., F.R.S.; J. M. Thornsou, LL.D., F.R.S.; J. Wade, D.Sc. ANNIVERSARY DINNER. The Anniversary Dinner of the Society took place at the Whitehall Rooms on Wednesday, March 29th, at 7 p.m., when the following Fellows and their guests dined together : Armit, Dr. Attfield, Prof. J., F.R.S. Beadle, Mr. C. Reale, Mr. W. P., K.C. Beilby, Mr. G. Bevan, Mr. E. J., President of the Society of Public Analysts. Bodmer, Mr. R. Borns, Dr. H. Bousfield, Dr. W., Master of the Cloth- workers' Company.Bowley, Mr. J. J. Brown, Dr. H. T., F.R.S., Yice-Preside7it. Browne, Sir J. Crichton-, F.R.S., Treasurer of the Boyal Institution. Callendar, Prof. H. L., F.R. S. Cannon, Mr. M. J. Carpmael, Mr.A. Carr, Mr. S. E.,Assistant Secretary. Chapman, Mr. A. C. Church, Sir W. S., Bart., K.C.B., President of the h'oyal College of Physicians.Conrad, Mr. J. C. Cottrill, Mr. F. Cowley, Mr. G. Crossley, Prof. A. W., Eon. Secretary-elect. Daily Telegraph, The. Dakin, Dr. H. D. Day, Xr. A. B., Master of the Society of Apothecaries. Dickins, Mr. F. V., C.B. Divers, Prof. E., P.R. S., Deputy-President of the Society of Cheinicnt Industru. Dodds, Mr. 5. M. Dnnstan. Prof. W. R.. F.R.S., Vice-Prkident. Dyer, Dr. B. Elliott, Sir T. H., K.C.B., Secretary of the Board of Agricztlture. Fairley, Mr. T. Farmer, Prof. J. B., F.R.S. Fenton, Mr. H. J. H., F.R.S. Formoy, Mr. J. A. Forster, Dr. M. O., Hon. Secretarly.Garwood, Prof.E. J. Gibbons, Mr. W. M. Glazebrook, Dr. R. T., F.R.S., Director of the iVationa1 Physical Laboratory. Gordon, Mr. J. G. Gowland, Prof. W., F.S.A. Greenaway, Mr. A. J., Sub-Edito?.. Groves, Mr. C. E., F.R.S. Guttmann, Mr. 0. Haggarth, Mr. R. N. Haldane, The Rt. Hon. II. B., K.C.,M.P. Hall, MI.S. Harden, Dr. A, 107 Henry, Dr. T. A. Hewitt, Dr. J. T. Heycock, Mr. C. T., F.R.S. Hicks, Dr. If’. &I.,F.R.S., Priitcipal,L~?Liversity CoIley&,SIw& cI tZ . Hill, Mr. C. A. Hills, hlr. J. S. Hodgkinsoii, Prof. W.1:. Holloway, Mr. G. T. Hooper, Mr. E. G. Howard, Mr. 1’. Jacksoii, Mr. 11. Joliiistoii, Mr. J. H. Jones, Dr. II. 0. Page, Mr. F. J. M. Pam, Mr. A. Fenton, Col. A. Y.,R.A., C.B. Yerkin, Dr.\V. I1 , F.R.S., Pc/,st Presi-ded. Perry, Prof’. J., P.R.S. Philip, Dr. J. C. Ping, Mr. W. Power, Dr. F. r>. Preece, Mr. A, C.E. Press dssocintion, Thc. rye-Smith, Dr. I’. H., P.R.S., Vicc-Chanccl/or of the U’iLivwsity of LO7tdOlb. Jones, Mr. 0. T. Jndd, Prof. J. W., CIS., 1:.It.S., DHOL of dhe Ihyd Collcgc of X~ICIICC‘. Keiiip, hlr. W.J. Iinowlts, 3Ir. J. liohn, Dr. c. A. Larmor, Prof’. J., F.R.S., S’c~i*~/(o-gof the Boynl Socicty. Led1, il1r. s. D , I.S.O. Lewkowitsch, Dr. J. Lockyer, Sir J. Noriiiau, I<.C. I;. ,F.E.S., Uircctor of the Soln~I’hgsics Ob-sercrrtory.Lowry, Dr. ‘l’. AI. I,yinn, Mr. A. IllacE\ian, MY. 1’. nlnson, blr. H. illatthews, Dr. V. E. Meldola, Prof. H., F.H.S., Pi~esi~Eciit-CEECt. Rlesscl, Dr.R. Rlilliiigton, hIr. J. 1’. Mills, Rlr. J. I’. Mohr, Dr. €3. Nonil, Dlr. E. S. Xlondy, Mr. E. P. Moody, Dr. G. T. Moore, llr. J. E:. S. Morgaii, Dr. G. T., Editur. Morniiig Post, l’hc. Morrell, Dr. R. S. Moss, Mr. C. C. 15. Ifuller, Dr. H., F.K.S., PusL Prcaideiif. Newtli, Mr. G. S. Newton, bIr. A. W. ()@vie, MY. F. G., PriitciprZ As~istaitt-,>iccreLary, ~’echnoh~!/(1 rid Hiyho. Edt~dioxin ,Ycieiicc m~riArL, Bond of Educctliuit. Oitoil, Prof. K. J. 1’. Railmy, Sir IV.,1i.C. B., F.It.S., Fo~ciyiisecmtn1’21. Kastah, Nr. W. €1. Rayleigli, Tlic Rt. Hon. Lord, O.M., F.R. S. I~eyiiolcts, I’rof. J. E., F.R.S., Pa::t Prcs i(llZ1lt. Robinson, Mr. 1<.A., Presided of 21re Phnrnzncciiticnl Society.Scott, Dr. A., F.R.S , TTcnsurer. Sell, bIr. W.J., F.R.S. Spielmann, Mr. I?. E. SLmdarcZ, l’he. Stevenson, Mr. H. E. Stevenson, hlr J. Sucnr, Dr. IT. It. LZ. Swinbnnie, Mr. J. Teed, Dr. F. L. :I’homson, Prof’. J. ill., F.B S. ~i~~~I~e,D~.r,. T. Thori)e, Dr. J. F. Thorj)e, Piof. T. E., CAE., F.R.S., Past Prcsidee7~t. Thoqx, Nr. W. H. Tilden, Prof. TV. A, V.P.H.S., Prcsi-do1I. Tilley, Nr. J. IfT. Tilley, ah. V. J. Tims, Yh. Tuuniclitfe, 311..J. F. Tyrer, Mr. T. Voelcker, I)r. J. A. Wade, Dr. J. Watt, Sir George, 0.J. 15. Webb, Sir Aston, R. A. Wranipelnicier, Alr. T. J. Wyniie, Prof. W. I’., F.B.S., Hoit. Secretary cud Vice-Presi~~eiit-clect. Yoiiiig, hlr. A. 108 The following Toasts were proposed :-By THE PRESIDENT.1. His Most Gracious Majesty the King. 2. Her Majesty the Queen Alexandra, their Royal Highnesses the Prince and Princess of Wales, and the otlier Members of the Royal Family. By Sir WILLIAMS. CHURCH,Bart., K.C. E., President of the Royal College of Physiciccns. 3. Prosperity to the Chemical Society, coupled with the name of The Presideitt By Professor RAPHAEL F.R,.S.,MELDOLA, Pyesident- Elect of the Chemical Society. 4. Scientific Institutions, coupled with the names of Professor LARMOR,JOSEPH D.Sc., F.R.S., Secretary of the Koyal Society, and Dr. R. T. GLAZEBROOK,F.R.S., Divector of the National Physical Laboratory. By Sir WILLIAMRAMSAY,K.C.B.,LL.D., F.R.S., Foreign Secretary of the Ciienaical Society.5. The Guests, coupled with t,he names of The Right Honourable R. B. HALDANE,K.C., M.P., and Professor JOHNPERRY, D.Sc., F.R.S. The PRESIDENT,in proposing the toast of ‘‘ His Most Gracious Majesty the King,” said he did not intend to question the loyalty and the good sense of the Fellows of the Chemical Society and their guests by making a speech. The toast was drunk with enthusiasm. The PRESIDENTnext proposed the toast of “Her Majesty the Queen Alexandra, their Royal Highnesses the Prince and Princess of Wales, and the other members of the Royal Family.” No words, he said, were necessary to recommend the toast, but it would be appropriate to say on that occasion that they had all watched with interest the progress of the voyage undertaken by Her Majesty and 109 her Royal daughters, and they trusted that they would return in due time from the sunny seas of the South refreshed and invigorated by the sea breezes.The toast having been duly honoured, SIR WILLIAMS. CHURCH,K.C.B., in proposing the toast of “Prosperity to the Chemical Society,” said he did not know what may have been passing in the President’s mind at the time when he (the speaker) was thought to be a fit person to propose the toast. It may have been that the President’s memory went back to the time when few, excepting those of the medical profession, had any acquaintance with the chemistry of their day, and when few took any interest in the study of the phenomena of nature.When they looked round that assembly there could be no doubt of the position chemistry had taken in these days. That Society was one of the oldest of the Societies in the Kingdom, dealing with different branches of science. It was founded more than sixty years ago- in 1841-and as long ago as 1848 it received its charter. Just consider what had taken place since those days. At that time the Society numbered only 300 members. He did not know the present nurnbers, but what he did know was that the advances made ill Chemical Science and the advantages to the world derived there- from could not possibly be over-estimated. In that advance their Society had played a very large and prominent part. When one considered the extraordinary advance of knowledge which had taken place since 1841-and how the science of chemistry was now connected and inter-connected with all the ordinary necessaries of life, it was remarkable to consider the difference between the position of Chemical Science in this country in 1841 and to-day.Out of their Society--which had for its object the advancement and the distribution of knowledge, and the publication of special researches in its own branch of science--had grown other societies -those which dealt with the application of chemistry to the arts and necessaries of life. The principal societies were the Society of Chemical Industry, the Instit’ute of Chemistry, the Society of Public Analysts, and the Pharmaceutical Society.He did not know whether their Society had any titular god or goddess upon its sigillum or seal, but it must have been a difficult matter to make a choice, because they might have chosen Ceres as illustrating the peace and prosperity which had accrued to the country through the advances of chemistry; or, on the other hand, he feared they could equally have chosen Bellona when they considered how much chemistry had done in the promotion of arms. But neither of these objects had been the aim of their Society. Its true object had been the advancement of knowledge by searching out the forces 110 and secrets of nature. What higher aim could a Society have'! In those few words he gave them the toast of Prosperity to the Chemical Society.The PRESIDENT,in replying, said he hoped they would agree with hiin that it was quite a proper thing to do to invite Sir Wm. Church, President of the Royal College of Physicians, to propose the toast, remembering that if chemistry did not spring entirely out of medicine, at any rate, the two branches of applied science had always been closely associated in tlie past. He was glad Sir William Church reminded them of tlie very important principle that experiment was the most secure basis of progrcss in all natural knowledge, which he thought was not always borne in mind by all his chemical friends. Some of them were ready to invent new hypotheses for explaining everything that occurred day by day, forgetting that every liypothesis, 110 matter how attractive, would Eooner or later be superseded by something more comprehensive, based upon fresh knowledge.They had the honour of entertaining that evening one of the most brilliant exponents of the application of t,liat principle-of course, he need scarcely say he referred to Lord Rayleigh. Experiment was the best foundation-and he was looking to his friend, Sir Wm, Ramsay, to fully agree with him. Dr. Johnson once said that when a man knew lie was going to be hanged in a fortnight, it teiided greatly to concentrate his thoughts. They would, therefore, readily understand his own position during the past fort,niglit. That festival was the occasion of what might be called the apotheosis of tlic retiring President. He should wake up in the morning to find that he was no longer President of the Chemical Society, but one t'liat had been President, and no matter what might happen in years to come, that great source of pride and satisfaction could not be taken from him.Many other changes also came about at the same time, and lie could not help referring again with great regret to the change which deprived them of the help and the association of their friend Professor Wynne, the Seiiior Secretary. The Society owed a great deal to its officers, and especially to the Secretaries, and in welcoming Professor Crossley to fill the vacant post, they might feel confident t'liat the share of the Society's affairs which fell to his lot would not suffer at his hands. The Society had now passed its first youth, having cele-brated its Jubilee fourteen years ago. Of course, as Sir William Church had reminded them, many changes had taken place, not only in the extent of their knowledge but in the fundamental nature of their ideas with regard to all chemical questions since the foundation of the Society.Occasions like that must revive very vividly in the minds of some of the past presidents-several of whom he saw present that evening-the successive changes that had gone on since they held office. In the past year they had lost, in the person of the late Professor Williamson, a past president, one of those great men who had helped to lay the foundations of their science and of whom so few now re-mained. The Chemical Society had grown rapidly, but more particularly during the last ten or twelve years. He had been an officer of the Society for six years, and even in his time the membership had increased, roughly, about 100 per annum.When they entered upon the occupancy of the rooms which were allotted to them by the Government in Burlington House, the members in their ranks did not exceed about one-third of what they were now. That was thirty years ago. But now they were be-ginning to feel like some of those crust8aceans, who periodically found their shells too tight. They wriggled out of it some-how and then grew a new shell better fitted to their enlarged proportions. They were not yet in a position to do that, but certainly the Society began to find its present quarters rather a tight fit.It seemed to him that a few informal gatherings for conversation, sometimes, perhaps, for demonstration and experi-ment, would be of great advantage to them; but he confessed he had never been able to see how it could be accomplished in their present quarters; and he could not help feeling some sentiment of envy toward their friends, the German Chemical Society, who occu- pied the palatial Hofmann-Haus in Berlin. They could hardly hope yet to secure quarters comparable with those. Nevertheless, the idea was fixed in his mind that informal gatherings might be useful in removing misunderstandings that sometimes would exist -notwithstanding the eff ort's of the Council and the Publication Committee-such as arose when authors of papers were not satisfied with the number of pages assigned to their important contributions.Questions of that kind arose, and occasioned now and then little heart-burnings-not very much-but even that little could probably be removed if they had opportunities of meeting together to talk-and to smoke, if they liked-and of getting to understand and to know one another rather better. The Fellows of the Chemical Society could really not be reproached for indulging too freely in conviviality. They dined only once in two years-and he was told that some of them drank beer after the ordinary scientific meetings-which, no doubt, occasionally were con- ducive to thirst.. He was confident that the Society would continue to grow and prosper.It was necessary that it should grow, if they were to continue the development and publication of their splendid JOURNAL.He would say fearlessarythat; their JOURNAL- 112 iE not in bulk, certainly in quality, was equal to any scientific journal in the world-and it did, at the present time, fairly represent British chemistry. Of course, they must all go on reading French and German, but he wished some of their friends on the Continent could be induced to learn to read English-and the only way to compel them to do so was to make the JOURNAL so good that they could not afford to ignore it. All this could only be accomplished by their sticking together, by doing their scientific best, and pouring into the JOURNALall the products of their laboratories and experimental work.PROFESSORRAPHAELMELDOLA,F.R.S., proposed ‘‘ Scientific Institutions.” Looking at the list of institutions represented there that evening, he said, it might be confidently asserted that every one of the subjects represented by those institutions came well within the cognisance of the Fellows of the Chemical Society; and he supposed there was no branch of natural knowledge at the present time into which chemistry had not, in one way or another, inserted itself. They welcomed all co-workers in their domain. There were representatives of institutions other than those that had been mentioned, and lie hoped Sir Thomas Elliott would allow the Roard of Agriculture to be considered a scientific institution.Chemistry had certainly made itself felt in that department. They welcomed Professor Larmor, not only on behalf of the Society which he represented, but in his individual capacity. The great specialisation of science in modern times had taken away a great many of the communications which the Royal Society used to receive. This in no way detracted from the status or the importance of the Royal Society, but it rather spoke in favour of the active development of modern science in various directions. Professor Larmor’s name stood pre-eminent in the great work of chemical science, although with regard to his own work, he (Professor Meldola) was afraid he must confess that he and many of his colleagues were not able to follow the Professor in all his abstruse flights.With regard to Dr. Glazebrook, they all knew that although a comparatively young institution, the National Physical Laboratory had amply justified its foundation. He need hardly remind those present that any institution which helped them to standardise the instruments they used, conferred an inestimable benefit upon their science and upon the work they were undertaking. Moreover, judging from a recent report of the National Physical Laboratory, much work had been done lately which might legitimately be classified as more or less chemical in character, and in welcoming the Director of that Laboratory they could only express their satisfaction that the results which had been achieved had been achieved with compara- 113 tively modest means, when they considered that the Government aid to the National Physical Laboratory was about one-fourth that given to the Reichsanstalt at Berlin, and one-fifth that given to the Bureau of Standards for the United States.In conclusion, he paid a tribute to the work of Sir Norman Lockyer, Lord Rayleigh, and Sir William Ramsay. PROFESSOR LARMOR,JOSEPH in replying, said he was glad to be greeted as an official of the parent Society, which had preserved the closest possible relations with her offspring. He believed that in this country there was a notion that much more could be achieved by the scientific workers here than in any other country in the world. Continental nations gave very extensive subsidies from public money, whereas in England it was considered that scientific men should provide their own means.also responded. He said his Institution DR. R. T. GLAZEBROOK had a large field to cover, and at each point of that field they were brought into close contact with other Societies. They claimed to be a kindred institution because they had the same high aims and employed exactly the same experimental methods as those pursued by the Chemical Society. He was glad to bear witness to the great assistance given them by their chemical friends, and the impossibility of conducting much of that work without that assistance, so cordially and generously given. K.C.B., next proposed (‘The Guests.” HeSIR WILLIAM RAMSAY, said he would not be so invidious as to allude to their guests by name or qualification.These details could all be found in the ‘(Dictionary of National Biography ” or in the more modest (( Who’s Who.” They were delighted to see their friends and guests present, and hoped to see them all again on many similar occasions. The RT. HON.R. B. HALDANE, in responding, said he objected to be divided by a line, as Sir William Ramsay had done, from Pro- fessor Perry. If Professor Perry could, as Sir John Fisher once said, teach the differential calculus to the working classes, he (Mr. Haldane) had ventured to teach equally dubious things to the working classes. He could not call himself a chemist, but he had got a conviction that the problem which lay in front of the British nation was how to develop what he might call the grey matter of the executive 6rain.All the things spoken of that night repre- sented something new in the nation, and not only something new, but something of which they would have to see a great deal more if the nation was to hold its own in these days. Science counted for more than ever it did. The West had had a rude awakening at the hands of the East. The controversies which agitated the minds of politicians were of less importance than the great question of 114 how to make the permanent element in politics more powerful and better than it was. He was not t,alking of Cabinets. They come and go, but to-day they seem to go more rapidly than ever.There was too little science in the present day, although one or two things had been done for which they were very grateful, in connec- tion with the Navy and the Army and the Defence Committee. mat was one link. If they turned to the different departments of the Government there was hardly one which did not require science, if its policy was to be an effective policy. The War Office and the Admiralty were dependent on the higher problems at the command of science. The Department of Public Health-the Local Government Board-was in the same position, and so was the Board of Trade, which brought another kind of science-that science which could only come from a very wide survey from the largest point of view of the dull subject of statistics.Wherever they turned science was needed, and yet there was not sufficient attrac- tion to a man of high attainments to put himself at the disposition of the State. Foreign Governments held out careers far in excess of any rewards and honours which the British Government could afford. Was it impossible to see an era in which the head of the Government could have at his disposition the first intelligence and the best brains which the nation could command? While that might be a dream, it was, he thought, a dream which events were preparing them for seeing realised. If we were to hold our own we must not be behind Berlin, the United States, or the French nation. There was a policy more worthy the consideration of poli- ticians than some policies which were taking up the time of the House of Commons, and this policy had the great advantage that it was a non-party one.He looked forward to the day when some- body would put his back into this business, that somebody would have the power of so impelling the administration of the day that it would be forced to respond to the demand of every class of t'he electorate, and every section of British society. Anybody who wished to attract public confidence could do worse than take up a policy of that kind, and he believed t8he British Treasury would open its hand. Science never st'ands still, and if science .does not stand still, Governments cannot afford to stand still in their use of science. These were speculations which, perhaps, went beyond the moment, but he had a strong feeling that the time was very nearly, if not quite, ripe for them.They would see what was the mind of the nation on this point, and doubtless they would be subjected to the acute disappointment to which all were usually subjected when they formed great expectations. He hoped to see the position of 115 science raised in the next few years, and he looked to the time when brute force would count for little, and knowledge for more. PROFE also responded. s sOR PERRY Thursday, April 6th, 1905. Professor R. MELDOLA,F.R.S., President, in the Chair, It was proposed by Professor ARMSTRONGand seconded- by Di-. LAPWORTHthat the minutes of the previous meeting be taken as read. After some discussion, the President ruled that the course prescribed in Bye-law XI be followed.Illessrs. B. M. Jones, C. E. Fawsitt, A. Angel, and W. H. Ratcliffe were formally admitted Fellows of the Soriety. Cjertificates were read for the first time in favour of Messrs. : Albert Edward Andrews, 37, Oakhurst Grove, East Dulmich, S.E. Francis George Belton, 16, Clarkson Street, Sheffield. Edward S.H. E. Brettell-Vaughan, The Cwm, Aston-on-Cluu, Silop. Thomas Walter Firth Clark, 117, Clerkenwell Road, E.C. Horace Finnemore, 21, Linden Mansions, Highgate, N. John GrifEths, B.Sc., 'l'he Hollies, Upton Park, Chester. James Henry Howgate, B.A. The Avenue, Bakewell, Derbyshire. William Henry Leek, B.A., Elm View, Leigh, Lancashire. Francis Grimshaw Martin, King Henry VIII School, Coventry.Alfred Mortimer, B. A , Trinity Cdlege, Stratford on-Avon. Sydney Dockeray Stennitt, M.Sc., 16, Richmond Terrace, Whit- church, Salop. Edmund Henry Stevens, B.A., Haw House, Rothbury, Nortliumber- land. Harold Blythen Stevens, 225, Oxford Street, W. Francis Henry Wall, 14, Hardman Street, Liverpool. Of the following papers, those marked * were read : 51%".''The kinetics of chemical changes which are reversible. The decomposition of as-dimethylcarbamide." By Charles Edward Fawsitt. This investigation is a continuation of the work already published on carbamide (Zeit. physikal. Chem., 1902, 41, 601) and methyl-carbamide (Tmns., 1904, 86,1581). The theory which mas put for- ward to explain the decomposition of carbamide and methylcarbamide holds good also in the present case.116 There is in every respect a very strong similarity between the decomposition of as-dimethylcarbamide and that of the cases already studied, and there can be no doubt that all the alkylcarbamides decompose in a similar manner. Dimethylcarbamide decomposes on heating with acids into the corresponding ammonium salt and dimethylamine salt, the mechanism of the change corresponding with a reaction of the first order having a velocity about six times as great as that of carbamide. "52. u A new formation of acetylcamphor." By Martin Onslow Forster and Hilda Mary Judd. IThe inzine, C,H1,< CH*cMe:NH, obtained by the action of mag-co nesium methyl iodide on a-cyanocamphor, crystallises from petroleum and melts at 126"; it has [aIu 263.2' in chloroform, and develops an intense blue coloration with alcoholic ferric chloride.It is indifferent towards aqueous alkalis, but is resolved quantitatively by acids into acetylcamphor and ammonia. Magnesium phenyl bromide converts a-cyanocamphor into the corresponding derivative of benzoylcamphor, previously obtained by heating the enolic modification of the diketone with ammonium formate. The compound C,,H,,O, produced when magnesium methyl iodide acts on hydroxymethylenecamphor or its a-benzoyl derivative, is a pleasant-smelling liquid which boils at 228-229" under 764 mm., and has [a], 195.0' in chloroform ;it is indifferent towards phosphorus pentachloride, phenylcarbimide, hydroxylamine, and ammoniacal silver oxide, hut yields camphoric acid with potassium permanganate, which it decolorises immediately.The dibromide, C,,H,,OBr,, melts at 152-153' and has [a], 157.2' in chloroform,. The compound C13H,o0,prepared from hydroxymethylenecamphor and magnesium ethyl iodide, boils at 236-238' under 745 mm., and has [a],,168.2 ; its chemical properties resemble those of the lower homologue. The dibromide, C13H200Br2, melts at 88' and has [a],, 130.5'. "53. bb Preparation and properties of 1 :4 :5-trimethylglyoxaline." By Kooper Albert Dickinson Jowett. In the attempt to prepare substances having a constitution analogous to that of pilocarpine, the following compounds mere isolated and vharacterised.4 :5-Dimethylglyoxaline, C,H,N2, first prepared by Kunne (Bes., 1895, 28, 2039), boils at 165' under 10 mm. pressure and forms a crystalline nitrate (m, p. 180°, not 164Oas stated by Kunne) and a picrate, yellow needles (m. p. 196-197'). 1:4 :5-TrimethyZgZyoxaEine, C,H,,N,, boils at 117' under 20 mm. pressure and crystallises in needles (m. p. 46"); the crystals are soluble in all proportions in water, alcohol, or ether. The nitrate, C,H,,N,,HNO,,H,O, forms long needles (m. p. 46"); the ITLydr?.o-chloride, C,H,,,N,,HCl,H,O, forms needles which lose their water of crystallisation over sulphuric acid or at 110'; the anhydrous salt melts at 199O. The following salts were also prepared: the auri-dloride, yellow needles (m.p. 202') ;platinichloride, yellow crystals (m. p. 224-225") ;picrate, yellow needles (m. p. 218") ; methiodide, long needles (m. p. 158"). 2-Bromo-1 :4 :5-trimethyZgZ~oxali~ae,C6H,N,Br,2H,O, obtained by the bromination of trimethylglyoxaline, crystallises from hot water in long, silky needles (m. p. 49"); the anhydrous base melts at 83O. The following salts were also prepared : hydrobyonaide, cubical crystals (m. p. 208O); mwichloride, yellow needles (m. p. 191.) ; picrate, yellow needles (m. p. 173"). 94. Bromomethyl heptyl ketone." By Hooper Albert Dickinson Jowett, In the course of some experiments made with the view of preparing the glyoxaline from methyl heptyl ketone, this ketone yielded bromo- methyl heptyl ketone by the action of bromine in chloroform solution.By subsequent fractionation of the product, the bromoketone was isolated as a pale straw-coloured liquid boiling at 12P under 15 mm. pressure. 0.1256 gave 0.2228 CO, and 0,0928 H,O. C =48.4 ; H = 8.2. 0.312 ,, 0.2652 AgBr. Br= 36.2. C,H170Br requires C = 48% ; H =7.7;I3r = 36.2 per cent. The liquid has the characteristic odour of the ketone and acts very quickly on the eyes, causing a copious flow of tears. Attempts to condense the bromoketone with potassium phthalimide were unsuccessful. *55. Ld Limonene nitrosocyanides and their derivatives." By Frederick Peacock Leach. It has been previously shown (Tmns., 1904, 85, 931) that limonene P-nitrosochloride gives rise to a crystalline nitrosocyanide (m.p. 90-91"). The investigation has been continued with the result that both the a-and P-nitrosochlorides of limonene have been found to yield the same isomeric nitrosocyanides, the reaction between the potassium 118 cyanide and the nitrosochlorides being carried out at 25 -30'. The nitrosocyanides are unimolecular and optically active and, therefore, analogous to the limonene nitrolaniiiies discovered by Wallach (Annulen, 1889, 252, 113). The a-nitrosocyanide crystallises in prisms (m. p. 90-9 lo),whilst the P-compound crystallises in fine, woolly needles (m. p. 140-141"). These isomerides are to be regarded as having the cis-and trccns-con- figurations, because on hydrolysis, both, by loss of carbon dioxide from their respective acids, give rise to the normal oxime of dihydrocarvone.From the d-and I-a-nitrosocyanides were also obtained the benzoyl derivatives (.thin plates, m. 1). 10So), methyl and ethyl ethers as viscid oils, and the hydrochloride crystallking from alcohol in thin leaves (m. p. 56"). The d-and I-benzoyl derivatives of the P-nitrosocyanide each crys- tallise from dilute alcohol in long, silky needles (m. p. 121'). The d-and I-a-amides each gave a methyl ether as R viscid oil, a benzoyl derivative (m. p. 152'), and R hydrochloride (in. p. 100-lolo). The cl-and Z-a-acids each gave ammonium and silver salts, the former being finely crystalhe ant1 the latter amorphous. The d-met hyl ester melts at 65'. Rncenzic compoztnds,-a-Nitrosocyanide separates in prisins from petroleum (m. p.Sl'), it's benzoyl derivative melts at 96'. The P-nitrosocyanide forms fine needles (m. p. 159-1 60") and its benzoyl derivative crystallises in needles melting at 9s". *56. 6L The action of carbon monoxide on ammonia." ByHerbert Jackson and Dudley Northall-Laurie. The authors have studied the behaviour of these gases when heated together in the presence of platinum, or when subjected to electric sparks or high frequency discharges. They find that the main reaction is the formation of ammonium cynnate, which, under the conditions of the experiment, rapidly changes to carbamide. Hydro-gen is produced, and some of this interacts to give water, which in its turn brings about the formation of ammonium carbonate.The amount of ammonium cyanide formed is small. Other products are obtained by prolonging the experiment, but only in quantities which are small cmzpared with the yield of the main product, csrbamide. I)ISCUSSION. Professor E. J. MILLSsaid the a,uthors' experiments reminded him of some of his own carried out EL number of years ago. He then found that, by passing a current of mixed carbonic oxide and ammonia gas 119 over strongly heated caustic potash in presence of carbon, cyanide was formed in large quantity. In fact, a potassium salt containing more than 70 per cent. of cyanide was readily produced. The carbon, of course, precluded the formation of any cyanate. “57. “The action of acetylene on aqueous and hydrochloric acid solutions of mercuric chloride.” By John Samuel Strafford Brame.Bilz and Mumm (Be?..,1905, 37, 4417) and Hofmann (Ber.,1904, 37,4459) show that the white precipitate obtained when acetylene is passed into aqueous mercuric chloride is trichloromercuriacetaldehyde, *C(HgCI),*CHO. The author obtained results three years ago which agree closely with those of the above and other observers, but atten- tion is now called to the considerable differences between the deter- inined 2nd calculated values, the analytical results for mercury being very low, whilst those for chlorine are too high. From the reactions, however, the foregoing constitution seems to be the most reasonable one. Berge and Reychler(Bu2l. Soc. chim, 1897, 17,218) state that acetgl- ene has no action on dilute hydrochloric acid solutions of mercuric chloride, but the author obtained a fine crystalline substance, which was afterwards found to havo been described by Biginelli (Ann.$’arm. Chiaz., 1898, 16), who ascribed to it the constitution Cl*HC:CH*HgClfrom estimations of mercury and chlorine only, This conclusion has been confirmed by complete analysis and the compound is further described.Biginolli states that when boiled with water the above compound yields CH,:CH*HgCl,but the author fails to obtain such a result. It is shown that the product is really trichloromercuriacetaldehyde, but a certain amount of mercurous chloride is also present, this being ascribed to the reducing action of the aldehyde liberated on the mercuric chloride.Biginelli’s statement that C,H,*HgC12 gives with alkalis an acetyl- ide, (C,H,),HgO, cannot be confirmed, but evidence from analyses and properties shows the substance to be identical with the acetylide SC,Hg,H,O described by Travers and Plimpton (Trans., 1894,65,264). Attempts are being made to prepare the anhydrous acetylide. The first action of acetylene with mercuric chloride appears, there- fore, to be one of simple combination, the additive product being then decomposed by water with the production of aldehyde and C(HgCl),*CHO. 120 58. "The basic properties of oxygen at low temperatures. Additive compounds of the halogens with organic substances containing oxygen." By Douglas McIntosh. Crystalline compounds of chlorine with methyl and ethyl alcohols have been obtained at low temperatures (-SO"), the formula of the former being probably CH,OCI, whilst the latter has the composition C,H,OCl; their melting points are -96' and -88' respectively.Compounds of a similar type were isolated containing bromine, the methyl alcohol derivative, CH,OBr, being a red, crystalline sub- stance melting at -53". Uethyl ether, although not yielding a solid product with chlorine at -95O, furnished a bromine compound, C2H,jOBr,melting at -68". Ethyl ether yielded C'4H,oOCl, (m. p. -51') and C4HloOBr2(rn. p. -400). Acetone combined with chlorine to form C,H,0Cl2 (m. p. -53"), whilst with bromine it gave rise to C3H,0Br2 (m. p. -12'). Ethyl acetate yielded the additive products CH,*CO,Et,Cl, (m.p. -64") and CH,-CO2Et,Br3 (m. p. -39'). Acetaldehyde and acetic acid also seem capable of combining additively with chlorine and bromine at low temperatures. 59. "Note on the interaction of metallic cyanides and organic halides." By Nevi1 Vincent Sidgwick. It is possible to explain the formation of both nitriles and isocyanides in this reaction by means of the same additive compound, and that of themost probable type, in which the addition has been to the bivalent carbon only. Such a compound, like an unsymmetrical oxime, could exist in two stereoisomeric forms, It*!?*' and R*R'l, where M=K,N*M M*N Ag, &c., and R =alkyl or acyl. The first of these would easily lose MI to give a nitrile, in accordance with Nef's view, but the second could not, as the metal and the halogen are t'oo far apart, and it would there- fore undergo the Beckmann reaction. This change brings these sub- stituents nearer together, so that now they combine and become eliminated, leaving an isocyanide : R.*I M-E.1 = G + MI.M*N -+ R*N RON If this is the case, we must suppose that an alkyl iodideand potass- ium cyanide, or an acyl halide and silver cyanide (which yield nitriles), 121 give the $6 syn-haloid ” form, and an alkyl iodide and silver cyanide the <‘anti-haloid.” It may also be pointed out that neither of the formulae of hydro-cyanic acid can be that of a strong acid, because if it were the alkali salts would be derived from that form, and would not be, as they are, highly hydrolysed in solution.60. “The chemical dynamics of the reactions between sodium thiosulphate and organic halogen compounds. Part 11. Halogen substituted acetates.” By Arthur Slator. Many of the halogen substituted acetates interact, more readily with sodium thiosulphate than the corresponding methyl haloids. The reactions with ethyl iodoacetate and methyl, ethyl, and sodium bromo- and chloro-acetates have been investigated and shown in all cases to be bimolecular reactions. The esters are considerably more reactive than the sodium salts. The temperature quotient of the reactions with the esters was found to be in all five cases approximately 2.S; with the sodium salts, an appreciably smaller value was obtained. The reaction between ethyl bromoacetate and potassium, ammonium, barium, stron- tium, sodium silver, lead and sodium lead thiosulphates have been measured, and from the results obtained it is probable that the reaction is primarily connected with the S,O,” ion, and that the undissociated or partially dissociated salts are relatively inactive.The velocity of reaction is proportional to the concentration of the S,O,” ion, and the measurements may therefore be used to estimate such concentrations. The dissociation constant of lead thiosulphate measured in this way was found to have the value I1Pb“)[S,O,”]i[PbS,O,l= 1.5 x 61. ‘‘The tautomerism of acetg1 thiocg anate.” By Augustus Edward Dixon and John Hawthorne. When acetyl thiocyanate is brought into contact with aniline at temperatures ranging from -12’ to about 120’, in presence of an inert solvent, such as benzene, interaction occurs spontaneously, with development of much heat, the chemical changes running concurrently on two distinct lines : (1) a change by double decomposition, in which the sulphur appears wholly in the form of thiocyanic acid, as shown by the equation Ac-SCN + ZPhNH, =Ac-NHPh +PhNH,,HSCN ; (2) an additive process in which the sulphur plays a thiocarbimidic part, thus: Ac*NCS +PhNH, =AcNH*CS*NHPh. At 87’, one-half of the total weight of product consists of acetanilide together with aniline thiocyanate, the remainder being acetylphenylthiocarbamide ; at lower temperatures, the proportion of thiocyanate and anilide rises, 122 and for temperatures below 30" reaches 90 per cent.and upwards of the total, whilst at temperatures above 87" the proportions are reversed, the yield of thiocarbamide increasing, with a corresponding decrease in the amount of the other two products, until in the neigh- bourhood of 120' the sum of the latter diminishes to some 2 or 3 per cent. Although the thiocarbimidic character of a cetyl thiocyanate, as measured by its power to yield the additive compound, acetylphenyl- thiocarbamide, increases regularly with the temperature of interaction, it would seem that this power is not acquired through ordinary isomeric change. For in all cases Litherto observed, the transforma- tion by heat of a thiocyanate into a thiocarbimide is non-reversible, the latter representing the stable and permanent form, whereas here the percentage of acetylphenylthiocarbamide resulting at any given temperature is not afiected by previous heating of the thiocyanate, but is determined solely by its teinperatnre at the moment of iuteraction.These phenomena come neither under the head of tautomerism proper, which is conditioned through the intramolecular migration of a hydrogen atom, nor into the category of migration of whole atomic groups: in point of elasticity, they present some resemblance to dissociation changes, but until further inquiry has been made the authors prefer not to advance definite views as to their nature and causation. 62, ''A method of determining the specific gravity of soluble salts by displacement in their own mother liquor, and its application in the,case of the alkali halides." By John Young Buchanan.The method presents obvious difficulties of manipulation, but as it furnishes at one and the same time the specific gravity of the salt and that of its mother liquor, both being determined at the temperature of equilibrium, it may be sometinies advisable to encounter these diffi- culties. This method has been applied in the case of the chlorides, bromides, and iodides of potassium, rubidium, and ctesium, and the follow-ing are the values obtained for the specific gravity D of each of these salts at the temperature Y', referred to that of distilled water at the same temperature as unity.Salt, MR. KCl. IiBr. KI. RLC1. RbRr. RbI. CsC1. CsRr. CsI. Teinp. T. 23.4" 23'4" 24.3" 22.9" 23'0" 24-3" 23.1" 21'4" 22.8" Sp. gr. D. 1.951 2.679 3.043 2.706 3'210 3.425 3'983 4.455 4.505 123 63. (( The combination of mercaptans with unsaturated ketonic compounds." By Siegfried Ruhemann. The author has continued his research (Buns., 1905, 87,17) on the union of mercaptans with olefinic ketonic compounds effected under the influence of bases, since on using hydrogen chloride as catalytic agen Posner frequently obtained mixtures, owing to the fact that mercaptans, besides combining additively at. the ethylene linking, partly condensed with the ketonic group. Besides the compounds which previously had been described as being formed from mercaptans and mono-olefinic IIketones, C:C*CO-, other substances have been prepared by the union of benzylideneacetophenone and ethyl benzylidenebenzoylacetnte.Cinnamylideneacetophenone, the di-olefinic ketone of the type IC:CH*CH:CH*CO-, as shown before (Zoc. cit.), takes up 1 mol. only of 1 either phenyl mercaptan or isoamyl mercaptan, instead of 2 mols., as stated by Posner (Bey., 1904, 37, 509). This investigator has since acknowledged the error. The behaviour of cinnamylideneacetone is analogous ; this substance unites with 1 mol. of phenyl mercaptan to yield the compound C,H,*CH:CH*CH(S*CGH,)*CH,*CO*CH,(m. p. 53-54'), whilst according to Posner's statement an oil is thus formed, which on oxidation is transformed into a disulphone.In harmony with tho author's result is the fact that cinnamylidene- benzylideneacetone, CGHs*CH: CH*CH: CH*CO*CH: CH'C,H,, unites with 1 mol. of either isoamyl mercaptan or phenyl mercaptan, but 2 mols. of mercaptan may also be added to the tri-olefinic ketone, yet the separation of the compound from the additive product with 1 mol. of the mercaptan which is formed at the same time has not been effected. Moreover, the acetylenic ketone, methoxybenzoylpheiiylacetylene, CGH,.~:iC*CO*C,HI*O.CH,,unites with 1 mol. of phenyl mercaptan to form C,H,*C(S*CGH,):CH*CO*C,H,*O*CH, (m.p. 121--122O), which is yellow as compared with the additive substances of mercaptans with olefinic ketones, which are almost all colourless.The olefinic cyclic ketones, benzylidenephenylinethylpyrazolone, N-C-CH,C6H5*N<C0. &: CH.C,H, , and benzylidenephenylazlactone, unite with phenyl mercaptan, but, whilst the pyrazolone derivative forms an additive product (m. p. 140') with 1 mol. of the mercaptan, 124 the azlactone takes up 2 mols. of phenyl mercaptan to yield a compound (in. p. 156-157’) which probably has the formula c6H,*cH,(s*C6H,)*c(co*s*C,H,)*NH*co*c6H5. 64. “The existence of a carbide of magnesium.” By J. Trengove Nance. The residue left after burning magnesium in carbon dioxide, if shaken with water or dilute hydrochloric acid, gives a smell resembling that of geraniums. This smell is always obtained when magnesiuni is heated with carbon, or in air containing carbon dioxide, and the residue treated as above. It is due to the presence of a hydrocarbon formed by the action of water on the residue, for it is driven off by heat, can be concentrated in a distillate, and if the gas is passed through a red hot tube together with air, carbon dioxide is formed.The prcseiice of acetylene from a carbide of magnesium being sus- pected, a mixture of magnesium powder and powclered wood charcoal was gently ignited. The yellowish residue was treated with dilute hydrochloric acid, and the gas, mainly hydrogen, which was vigorously evolved, gave the following indications of the presence of acetylene. It burnt with a faintly luminous, two-zoned flame, and when passed through ammoniacal cuprous chloride it produced a brownish-red precipitate.With ammoniacal cupric solutions, decolorised by hydroxyl- amine, a brilliant crimson precipitate was obtained (compare Ilosvay von Nagy Ilosva, Ber., 1899, 32, 2697 ; Abstr., 1900, ii, 52). These precipitates dissolved, wholly or partially, in dilute hydrochloric acid, with evolution of acetylene, copper passing into solution. By analogy, the carbide formed should be ISTgC,, but it was not obtained in a sufficiently pure condition for a quantitative analysis. It does not seem to interact as vigorously with water as the calcium cornpound. 65, ‘(Isomeric salts of the type NR,R,H3. A correction. Iso-meric forms of d-bromo-and d-chloro-camphorsulphonicacids.” By Frederic Stanley Kipping.The further study of the isomeric a-and p-salts, which the author obtained by combining ordinary d-bromo- and d-chloro-cam-phorsulphoiiic acids with dl-and with optically active bases, such as hydrindamine (Trans., 1900, ’7’7, 861 ; 1903, 83, 873), benzylhydhd-amine (Kipping and Hall, Trcms., 1901, 79,430), methylhydrindamine (Tattersall and Kipping, Trans., 1903, 83, 918), and E-menthylamine (Tutin and Kipping, l’rum., 1904, 85, 65), has brought to light the fact that the isomerism of these compounds is not determined by a/ 125 difference in the arrangement in space of the groups united with the quinquevalent nitrogen atom, such as is represented by the syiri bols I IX-N-H and H-N-X, but to the existence of cis-and trans-forms A /\of d-bromo- and d-chloro-camphorsulphonic acids, containing the I I groups X-C-H and H-C-X, and now distinguished as the a-or 1 I normal and p-or iso-acids.The isomeric 3cids are stable in neutral solutions of their sslts in the free state and in presence of mineral acids, even at 100' ;in presence of a free base, however, such as caustic potash, baryta (sodium carbon- ate), hydrindamine, &c., the salts of the normal acid are transformed to a small extent into those of the iso-form, whereas the latter are almost entirely converted into salts of the norinal acid, equilibrium being attained apparently when at least 90-95 per cent. of the COM- pound exists in the normal form. During this change, the two modi- fications doubtless become identical, both passing through one and the same unstable enolic form.All the salts of ordinary d-bromocamphorsulplionic acid which have hittierto been described by the author and by others, excepting those obtained from d-and I-hydrindamine and then separated from the p-forms, are probably mixtures of the two isomerides; the only salts of the iso-acids which are yet known are those previously described as PI-hydrindamine d-bromocamphorsulphonateand the P-moclifications of d-and I-hydrindamine chlorocamphorsulphonates. The molecular rotation of iso-d-bromocsmphorsdphonic acid is approximately [MIL, + 177", that of the corresponding chloro acid being about [MI, +233O, so that in one case the normal, in the other the iso-acid has much the higher value.No new facts have yet been obtained as to the cause of the forma- tion of the isomeric salts of cis-r-camphanic ncicl, but in view of tho above-mentioned results it would seem that the explanation previously suggested is not the true one. 66. '' Isomerism of a-bromo-and a-chloro-camphor." By Frederic Stanley Kipping. The fact that the sulphonic acids derived from a-bromo- and a-chloro- camphor may be transformed into isomerides by the action of bases rendered it extremely probable that the simple halogen derivatives themselves would give rise to isomerides under similar conditions : the following experiments show this to be the case. Poiue ordimiry a bromocamphor, dissolvecl in 96 per cent.. alcohol, gave [alp+ 135'; on adding a very small quantity of sodium ethoxicle 126 to the solution, the specific rotation fell to [a];+ 122O, a value which did not change appreciably during 24 hours or on acidifying the solution with acetic acid.Ordinary bromocamphor, therefore, is partially converted into the iso-form, which has a lower specific rotation, and in the alkaline solution a condition of equilibrium between the isomerides is rapidly attained. Judging from the behaviour of bromocamphorsulphonic acid, this iso-a-bromocamphor should be stable in acid solution. Accordingly some ordinary bromocamphor was treated in alcoholic solution with sodium ethoxids and the solution almost immediately acidified ; on evaporating, crystals of ordinary bromocamphor were first deposited ; these were separated from the mother liquor and treated again with sodium ethoxide and acid successively, these operations being repeated several times.The combined mother liquors gave on evaporation an oily deposit which mas distilled in steam, and then fractionally crystallised from light petroleum : the first deposits consisted of ordinary brorno- camphor, but the later fractions crystallised slowly in camphor-like masses. The specific rotation of this product, which no doubt still contained ordinary bromocamphor, mas [.ID + 38.5” in 96 per cent. alcohol; when, however, a trace of sodium ethoxide was added to the alcoholic solution, the specific rotation increased rapidly and attained a constant value approximately the same as that of the solution of ordinary bromocamphor to which sodium ethoxide had been added.When, moreover, t,he camphor-like mass was dissolved in a little alcohol and a few drops of caustic soda added, a large quantity of ordinary bromocaniphor separated in crystals. These experiments seem to establish the existence of normal and iso-forms of a-bromocamphor, and they explain the use of the caustic potash or caustic soda wbich is added in isolating ordinary bromo- camphor from the crude product of the bromination of camphor : this crude product, as shown by Marsh (Trans., 1890, 5’7,828), doubtless consists of a mixture of the two isomerides, possibly together with unchanged camphor, but the isolation of the pure iso-form would most likely be rz very hard task, which, as Marsh himself suggests, he probably did not accomplish.Similar experiments to the above indicate that ordinary a-chlorocamphor is also capable of existence in a stable iso-form, and the matter is beiog farther investigated. 67. ‘‘ I-Phenylethylamine.” By Frederic Stanl e Kipping and Albert Edward Hunter.’’ In number 3 of the current Bes-ichte (38,801) there appearsapaper by Marckwald and Meth, ‘‘ Uber Amidbildung zwischen optisch-gctiven Siiuren und Basen und die optisch-activen a-Amidoethyl- 127 benzolen,” containing certain statements respecting some work of ours to which we take exception (Tram., 1903, 83, 1147). Firstly, ‘‘Ihnen gelang wohl die Reindarstellung des Snlzes der I-Base, aber die gewonnene Menge reichte zur Isolirung der reinen B4se nicht aus” ; also “K.& H. haben aus Mange1 an &laterial das Drehungs- vermogen des von ihnen gcwonnenen I-Phenyliithylrtmin nur in wassrig alkoholischer Losung bestimmt.” Neither statement is correct; we did not prepare the anhydrous base or determine its specific rotation merely because we were solely engaged in studying its salts. The statement ‘‘ Demaach haben Kipping and Hunter anniihernd reines E-Phenylathylamin in Handen gehabt ” suggests that our base contained some of the d-isomeride; this was not the case, and the specific rotation ( -3.7’) of the hydrochloride prepared by us was in fact slightly higher than that (-3.5’) of Marckwald and Meth’s preparation, although the difference is within the limits of experi-mental error.The fact thnt the benzoyl derivative of the I-base melts at the same temperature as that of the dl-base, when both are crystallised from alcohol, and the fact that the specific rotation of the I-benzoyl derivative is extremely small according to Marckwald and Meth (only + 0.3’ in alcoholic solution) led us to state that the base ‘<seems ” to undergo racemisation during the preparation of its benzoyl derivative ; our statement that “ mixtures of the three compounds also melte3 at 120’ ” (Eoc. cit., p. 1148) is doubtless correct, as the mixtures consisted of approximately equal quantities of the d-, I-and dE-benzoyl derivatives, and we omitted to examine the behaviour of a mixture of the I-and db-compounds only.68. “The influence of the hydroxyl and alkoxyl groups on the velocity of saponification. Part I.” By Alexander Findlay and William Ernest Stephen Turner. The following values of the saponification constant in aqueous solution have been determined (at 25’) : Ester. k. Ester. k. Ethyl phenylacetate 12.4 Ethyl phenylmethoxyacetate 23.3 Methyl mandelate 157 Ethyl phenylethoxyacetate 15.7 Ethyl mandelate 66 Ethyl phenylpropoxyacetate (13.3) Propyl mandelats 55 The value for ethyl phenylpropoxyacetate was calculated from the values obtained in alcoholic solution. The numbers in the foregoing table show at once the greatly 128 accelerating influence which the hydroxyl group exercises on the velocity of saponification, the constant being increased to about five times (for example, ethyl phenylacetate and ethyl mandelate).The increase in the affinity constants of the corresponding acids is about eight times. On replacing the hydrogen of the hydroxyl by an alkyl group, the velocity of saponification is diminished, and the diminu- tion increases regularly with the mass of the alkyl group. The velocity of saponification was also studied in aqueous alcoholic solution, the strength of which was 30 aud 60 per cent. by weight. The values obtained were of course diminished by the addition of alcohol ;they are contained in the following tahle : In 30 per cent In 60 per cent. alcohol. alcohol. Ester. k.It. Ethyl phenylacetate ............... 8.6 (61 Methyl mandelate ..................(109) (84) Ethyl mandelate ..................... 49.4 29.1 Propyl rnandelate .................. 39.5 22.7 Ethyl phenylmethoxyacetate ...... 15.2 (8) Ethyl phenylethoxyacetate ..... 10.2 (6)Ethyl phenylpropoxyacetate ...... -(5) The numbers enclosed in brackets are only approximate, as in the case of the esters to which they apply there was a great decrease in the value of the ;‘constant ” with the time. At the next Ordinary Meeting, on Wednesday, April 19th, 1905, at 5.30 p.m., the following paper will be communicated : ‘‘Complex nitrites of bismuth.” By W. C. Ball. ‘‘C-Phenyl-s-triazole.” By G. Young. R. CLAY AXD SONS, LTD., URKAD ST. HILL, E.C., AND BUh’GAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9052100099
出版商:RSC
年代:1905
数据来源: RSC
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