ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 18. Session 1885-86. -February Mth, 1886. Dr. Hugo Miiller, F.R.S., President, in the Chair. The certificate of Mr. Charles Kilpatrick, Dearnley, near Rochdale, Lancashire, was read for the first time. The following changes in the Council, proposed by the Council, were announced :-As Vice-presidents : Prof. Dewar, F.R.S., and Mr. David Howard, vice Dr. Schunck, Y.R.S., and Mr. W. Weldon, F.R.S. (deceased). As Members of Council : Messrs. J. A. R. Newlands, S. U. Picker-ing, Prof. Ramsay and Dr. Stevenson, vice Dr. E. Atkinson, Prof. G. (3. Foster, F.R.S., Mi?. Ludwig Mond and Mr. C. O’Sullivan, F.R.S. Prof. Wyndham Dunstan, Dr. Percy Frankland and Mr. Makins were appointed by the Meeting to audit the Society’s accounts.The following papers were read :-14. “ The Constitution of Undecylenic Acid as indicated by its Magnetic Rotation; and on the Magnetic Rotation, &c., of Mono- and Di-allylacetic Acids and Ethylic Diallylmalonate.” By W. H. Perkin, Ph.D., F.R.S. When investigating the magnetic rotation of compounds (Trans., 1884, 421) undecylenic acid was amongst those selected for examina-tion as examples of the series of unsaturated monobasic acids having the formula CnH2n-l*C00H. The numbers obtained, however, were lower than was expected, and did not appear to be consistent with those given by other members of this series, and were therefore kept 154 back for the purpose of further investigating the apparent discre-pancy.Both the acid and its ethylic salt were examined. The acid, purified by rapid distillation under reduced pressure (b. p. 230-235" at 130 mm.), gave a molecular rotation of 12.547. The ethylic salt boiled at 263.5-265-5" (corr.), and gave a molecular rotation 14.530. Comparing these numbers with those of the corresponding saturated compounds, we get- Difference due to unsaturated character. Undecylenic acid. ....... 12'547} + 0.897 Undecylic ,, ........ 11.650 Ethylic undecylenate .... 14*'530}+ 0.890 ,, undecylate ...... 15.640 On reference to the table given in the author's former paper (Trans., 1884, 561), it will be seen that these differences are much lower than those (1.112) obtained for ethylic a-crotonate and oleate, but very nearly equal to those (0.914) found in the case of allyl substitution- products.As these numbers were obtained before the author became aware of the influence of the magnetic field on the optical parts of the polari- meter, it was deemed advisable fo re-examine the ethylic salt. The molecular rotation then obtained was 14.543, thus making the dif- ference due to saturation 0.903, or almost identically that previously found with unsaturated compounds containing the allyl-group. As this appeared to indicate that undecylenic acid is an allyl compound, it was determined to examine allylacetic acid for the purpose of comparison. This was prepared by heating allylmalonic acid as long as carbonic anhydride was evolved and fractioning the residue.It boiled at 185-188" (corr,), and gave a molecular rotation of 6.426. From this we get almost the same difference as with the undecylenic compounds :-Allylacetic acid ........ 6.426 Valeric ,, ........ 5.508 Difference ...... 0.918 It is thus seen that undecylenic acid and its ethylic salt possess magnetic rotations which are peculiar to mono-ally1 derivatives of the fatty acids. The next question is as to the positip of the allyl-group, as it is probable that the magnetic rotation would be the same whether it were, for example, an allyl-hexyl-acetic acid or an allyl-octylic acid : C,H5*CH(CsH,,)*COOH or C3H5*C7Bl4*COOH.But Krafft has shown that when oxidised with nitric acid it yields normal sebacic acid, and there can therefore be scarcely a doubt that unde- cylenic acid is allyloctylic acid, CH, :CH*CH,(CH,),*COOH.Whilst working on this subject it was thought interesting to pre- pare and examine diallylacetic acid. This was made from diallyl- malonic acid, and boiled at 227-227.5" (corr.). It gave a molecular rotation of 10.344. The molecular rotation calculated for octylic acid is 8.577. There is thus a difference of 1.767 for the influence of the two allyl-groups. Deducting 0.903 for the first allyl-group, we get 0.864 for the second--a result consistent with previous results (see former paper), which showed that the influence decreases with succes- sive displacements. The redetermination of the molecular rotation of ethyl diallyl- malonate in a freshly-prepared specimen gave 15.025, or a number differing by only 0.027 from that (14.998) given in the former paper.15. "Reactions supposed to yield Nitroxyl or Nitryl Chloride." By W. Collingwood Williams, B.Sc. Direct union of chlorine and nitrogen peroxide does not take place either at a red heat or at 150" C., nor does the action of chloranhy-drides (such as phosphorus oxychloride or sulphuryl chloride) on nitric acid or nitrates yield nitryl chloride. When chlorine and nitric peroxide are passed through a red-hot tube the product is a mixture of nitric peroxide and nitrosyl chlo- ride containing chlorine in solution, while oxygen gas is liberated. This result is due to the dissociation of NOz into NO + O2at a red heat.When the tube is heated to 150" C. only, no appreciable change occurs, the product being a solution of chlorine in the peroxide, and an exactly similar product is yielded by all the other methods examined. 16. "The Condition of Silicon in Cast Iron." By A. E. Jordan and Thomas Turner. The authors have endeavoured to ascertain whether crystrtllised silicon can be separated from cast iron. They refer to the work of Wohler, Richter, and others, who believed that they had obtained crystals of silicon, and also to the experiments of Snelus, Morton and Tilden, who were unable to separate silicon from cast iron in this form. 1. Several irons,. including a specimen of pig containing 9.8 per cent. silicon, were submitted to magnetic examination.Though both gmphite and slag could be separated by means of the magnet, it mas not found possible to separate silicon in this manner. 2. The residue left after prolonged boiling with dilute hydrochloric acid was then studied. After drying, the graphite was burned off in n muffle, and the remainder examined for silicon. In no instance was silicon found ; but in the case of a pig with 10.3 per cent. silicon, black scales were obtained of very difficultly decomposable iron silicide. These scales appear to closely resemble in properties the so-called graphitic silicon of some other observers. In the residue before roasting the authors found a quantity of substance resembling Wiihler’s “leucone,” the “ silicon formanhydride ” of Friedel and Ladenbnrg.3. Lastly, graphitic matter from iron was examined. For the two specimens used they are indebted to Dr. Percy. The first was graphite from Dowlais, which had previously been examined by Dr. Percy, who suggested that it might contain crystallised silicon (“ Iron and Steel,” p. 145). It was found to be nearly pure carbon, and to be almost entirely free from silicon in any form. A specimen of kish, from Clarence Works, Middlesbro’, was also examined, but in this case too no crystallised silicon was found. The authors conclude that silicon is present in cast iron in the form of silicide, being probably a solidified solution in the excess of iron. DISCUSSION. The PRESIDENTremarked that khe results now brought forward pointed to the importance of direct synthetic experiments with silicon and iron as a means of ascertaining whether graphitic silicon can separate from iron under any conditions.Since it had been shown that the supposed crystalline modifications of boron were compounds with aluminium and carbon (Hampe, AnnuZen, 1876, 183,75), even the existence of a graphitic silicon appeared doubtful. Mr. TURNERsaid, that although he had not been able to make such experiments, he had examined irons containing up to 10 per cent. of silicon, and had always found the silicoii to be present in the one form. SIRFREDERICKABELdesired to express his concurrence in the con- clusions arrived at by the authors, that there appeared to be no grounds for considering fhat silicon might exist in cast iron in the graphitic or crystalline form, or that, this eloment might occur in two different conditions in cast iron, as carbon did.The results of very numerous experiments and the careful examination of many graphitic residues obtained from cast iron, had long since led him to these con- clusions, but he hesitated referring to his own special experience of many years back in connection with the chemistry of cast iron, after the remarks which Professor Unwin was reported to have made on the occasion of Mr. Turner’s last paper as to the condition of the chemist’s knowledge of cast iron 30 odd years ago. He had been as much surprised as amused to learn that at about the date when certain questions relating to a supply of iron to Woolwich arose, to which Professor Unwin had referred, the methods of‘ determining carbon were faulty, and no distinction was drawn between graphitic and combined carbon.It was true that the analytical results given in the Woolwich Report, “ Cast Iron Experiments, 1858,” included statements of the proportions of graphite only in the partial analyses of samples then carried out for a special object; but in an Official Report, published two years previously by the War Office, the results of amalyses of a number of specimens of cast iron used in the manufactnre of ordnance included the items of “total carbon ” and “carbon as graphite.” In a paper contained in the Quarterly Journal of this Society for 1857, the proportions of combined carborz and of graphite existing in specimens of cast iron of foreign manufacture were also given by Sir Frederick.As regards the methods of analysis practised in those days, and which had been for some time previously taught at the School of Mines and elsewhere, they were in all essential respects similar to and as trustworthy as those now in use. He had learned with surprise that the eminent engineer who had made those criticisms on the work of 30 years ago, had thought it sufficient for his purpose to refer only to the work of one who certainly was never accepted ’by chemists an an authority on iron analysis. As regards the matter of the Nova Scotia iron to which Professor Unwin had referred, and which was dealt with in 1858, not 1853, it was right he should state that, a quantity of iron called Nova Scotian, supplied for gun-manufacture, was rejected, not “because the Chemical Department refused to sanction its use on the ground that it contained too much silicon,” but because, instead of being a grey iron somewhat siliceous but otherwise of high quality, having the characters of charcoal-iron--as was the case with the sample of Nova Scotia iron which led to the purchase of a supply, it consisted in large proportion of white and light mottled iron, some of which con- tained as much as from 1 to 2 per cent. of phosphorus.Certain experiments were made on the effect of melting selected samples of this supply high in silicon, with the result that the strength of the metal was increased without a very niaterial alteration in the propor- tion of silicon ; but these results had no bearing upon tlie fitness of even this metal to resist powder-strains, nor upoii the question whether the supply should not be rejected.The matter having been submitted to arbitration, Mr. Fairbairn, as umpire, decreed in favour of‘ the rejection. In conclusion he ventured to assure Professor Unwin that, by reference to the literature of that time, he would find 158 that chemists were by no means far behind their brethren of the present day in regard to their knowledge of methods of analysis and properties of cast iron. 17. " Certain Aromatic Cyanates and Carbamates.'$ By H. Lloyd Snape, B.Sc.The author finds that on heating phenyl cyanate with pyridine it is converted into diphenyZ dicyanate, CuH1,N20,. He has prepared a number of dicyanates by the action of carbonyl chloride on diamines, and has studied their behaviour with alcohols, as in his previous work on phenyl cyanate (Chem. Xoc. T?-ans., 1885, 770). Diphenylene diisocyanate, CO N*CsHa-C6H4*NCO, was obtained from benzidine hydrochloride and phosgene ; on .treatment with alcohol it is con-verted into dipheny1ene diuqsethane, C0OEt.NH*C6Ha.C,H,*NH*C0OEti, which may also be prepared horn benzidine and ethylic chloroformate ; the corresponding phenylated urethane is obtained by the interaction of phenol and diphenylene diisouyanate. Metatoluylene diamine and phosgene react to form metatoluylene diisocyanate, which is converted by phenol into the carbamate, Me*C6H3(NH-COOPh),. No cyanatme was formed on heating orthotoluylenediamine with phosgene ; bot(h this diamine and orthopheiiylenediamine, however, react with ethylic chloroformate to form urethanes.On heating phenyl hydrazine at 220-230" in an atmosphere of carbonyl chloride, a solid compound of phenyl cyanate with hydrogen chloride was formed. 18. " The Oil obtained from Lime-leaves." By Francis Watts. The fragrant yellow oil of the lime-tree (Citrus Zimetta) obtained by distilling the leaves and young shoots in a current of steam, contains a citrene, C1,,H16, boiling at 178-179", and methylnonyl ketone ; it appears also to contain "terpinol." On distillation about one-half boils above 280" and has the appearance of colophene.ADDlTIONS TO THE LIBRARY. I. Donations. Anleitung zur qualitativen chemischen Anal yse, von C. R. Frese-iiins. Funfzehnte neu bearbeitete und verbesserte Auflage. Brann-schweig, 1885 : from the Aut,li?or. A Practical Introduction to Chemistry; by W. A. Shenstone, London, 1886 : from the Author. Spectrum Analysis; six Lectures delivered in 1868 before the Society of Apothecaries of London; by Sir H. E. Roscoe. Fourth Kdition, revised and enlarged by the author and by A. Schuster. London, 1885 : from the Author. Annales de Chimie, Tomes LV-LX ; Paris, 1805-6 : from Dr. J. H. Russell, F.R.S. Transactions of the South African Philosophical Society.Vol. 111, Part 2, 1883-5. Cape Town, 1885 : from the Society. Fourth Annual Report of the Board of Control of New York Experimental Station, for the year 1885. Rtochester, U.S., 1886 : from the Board. Titles of papers of interest to chemists recently read before Societies in the United Kingdom:- “The Injurious Effect of a Blue Heat on Steel and Iron.” ByC. E. Stromeyer. Institution of Civil Engineers, January 29th. “ Proteid Substances in Latex.” By J. R. Green, B.A., B.Sc. “On Intravascular Clotting.” By L. C. Wooldridge, M.B., D.Sc. “ Observations on the Radiation of Light and Heat from Bright and Black Incandescent Surfaces.’’ By Mortimer Evans, M.I.C.E. Royal Society of London, Jan. 14th, Feb. 4th and 18th. 1. ‘‘ Chemical Affinity and Solution.” By W.Durham. 2. ‘‘ On the probable Heats of Formation of Zinc-Copper Alloys,” By A. P. Laurie. 3. “On the Mean Free Paths in a Mixture of Two Systems of Spheres.” By Professor Tait. Royal Society of Edinburgh, February 15th. At the next meeting, on March 4th, there will be a ballot for the election of Fellows, and the following papers will be read :-“The Influence of Tempe~ature on the Heat of Chemical Corn- bination.” By s. U. Pickering.‘‘ The Action of Heat on the Salts of Tetrethylphosphonium.” By N. Collie. ‘‘ A New Method for the Preparation of Tin Tetrethyl.” By N. Collie and Professor Letts. 160 SALE OF THE “ ABSTRACTS OF PROCEEDINGS.” The Council having resolved to place the “Abstracts of Proceed-ings ” on sale at a price of 7s. 6d. per annum, intending subscribers and Fellows who desire to purchase extra copies are requested to apply without delay to Mr. Van Voorst, Paternoster Row, London, E.C. NOTICE TO SUTHORS OF PAPERS. To facilitate the preparation of these “ Abstracts of Proceedings,” all authors are requested to furnish abstracts of their communications, and to send their papers so that they may be in the hands of the Secretaries, if possible, on bhe Monday before the day of meeting. ERRATUM. Page 102, line 18 from top, for ‘‘ 9318” read “ 9138.’ HARRISON AND SONS, PRINTERS IN ORDlNARY TO HER MAJESTY ST. MARTIN’S LANE.