|
1. |
Proceedings of the Chemical Society, Vol. 22, No. 303 |
|
Proceedings of the Chemical Society, London,
Volume 22,
Issue 303,
1906,
Page 1-27
Preview
|
PDF (1727KB)
|
|
摘要:
1smed 29/1/06 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 22. No.303. Thursday, January 18th, 1906, at 8.30 p.m. Professor R. MELDOLA,F.R.S., President, in the Chair. Messrs. J. E. Coates, A. Amos, and M. B. Jack were formally admitted Fellows of the Society. The PRESIDENTannounced that the Society had lost a distinguished Fellow in the person OE Professor Hermann Johann Philipp Sprengel, Ph.D., F.R.S., who was elected in December, 1864, and died on January 14th, 1906. It was also stated by the President that the Society was indebted to Sir Henry E. Roscoe, F.R.S., for an important donation to the Library of nearly one hundred alchemical and old chemical works of great interest and value. Certificates were read for the first time in favour of Messrs.: Richard * Victor Briggs, Sirseah Research Station, Mozufferpore P.O., Bengal, India. Llewellyn Thomas Jones, B.Sc., Brenig View, Tregaron. Samuel Parfitt, 33, Partridge Road, Cardiff. Robert Le Rossignol, B.Sc., 2, Caesarea Place, Jersey Arthur William Thorp, 210, Skerborne Road, Yeovil. Henry Edgar Watt, B.Sc., 19, Summerhill Road, Dartford, Kent. Richard Willstatter, Ph.D., Bergstrasse 25, Zurich V. 2 Certificates have been authorised by the Council for presentation for ballot under Bye-Law I (3) in favour of : William Mace, of Hope, Kingston, Jamaica. George Stanley Talbot, Ocean Island, Sydney, N.S.W. Harry Sands Grindley, ID.Sc., State University, Illinois, U.S.A. The Council has ordered the following letter and report to be printed in the Journal and Proceedings of the Society : GOVERNMENTLABORATORY, CLEMENT’SINNPASSAGE, STRAND, W.C.LONDON, 10th Novem6es., 1905.GENTLEMEN, I have the honour to transmit to you the Report of the Inter- national Committee on Atomic Weights, 1906, to which I have appended the signatures of Professors Moissitn and Seubert as desired by them. It will be seen that the Committee, for the reasons stated in the report, are not prepared to advise any immediate alteration in the values for the atomic weights given in their last report. They recommend, however, in conformity with the desires of the great majority of the Larger Committee, that the values in the table for 1906 be given on the basis of O= 16, to the exclusion of those on the basis of H = 1.I am, Gentlemen, Your obedient Servant, T.E. THORPE. The Hon. Secretaries, The Chemical Society, Bwdingtom abuse, London, W. Report of the International Committee on Atomic Weights. During the year 1905 there has been unusual activity in the determination of atomic weights, and some of the work done relates to the most fundamental values. The entire system of atomic weights is thus affected more or less profoundly, and a general revision of the table would seem to be needed within the near future. Neglecting minor investigations, the more important determinations published since our last report are briefly as follows : Cudmzlcm.--Atomic weight determined by Baxter and Hines 3 (J Amer. Chem.Soc., 1905, 27, 222), by analysis of the chloride. Three measurements of the ratio CdCI,: 2AgC1 gave in mean Cd = 118.476. Six measurements of the ratio CdC1, :2Ag gave in mean Cd = 112.462, General mean of both series, 112.469 ; when Ag = 107.93 and C1= 35.473. As additional determinations are promised, based upon a study of cadmium bromide, a change in the atomic weight of cadmium as given in our table may properly be deferred. Ccwbon.--From the ratios published in 1904, relative to the basic acetate and acetylacetonate of glucinum, Parsons (J.Amer. Chem. Xoc., 1905, 27,1204; Zeit. anorg. Chem., 1905, 46, 215) has computed the atomic weight of carbon. The values obtained by treating the two ratios algebraically are G1= 9.112 and C =12.007. As the latter figure is quite independent of all previous determinations it has distinct corroborative significance.Chlorine and Sodium-In a very elaborate investigation upon the atomic weights of chlorine and sodium, Richards and Wells" have shown that the data furnished by Stas are affected by appreciable errors. Ten syntheses of silver chloride gave, in mean, C1= 35-473 when Ag= 107.93. From ten measurements of the ratio Ag :NaCI, and ten of the ratio AgCl :NaCl, with the foregoing values for silver and chlorine, Na =23-008. Stas's values are C1= 35.455 and Na =23.048. The results just cited are ohvionsly indirect, for they depend upon the atomic weight of silver. The experiments published by Dixon and Edgar? are therefore OE peculiar interest, for they involve the interveution of no intermediate quantities between the atomic weights of chlorine and hydrogen.Hydrochloric acid was directly synthesised from weighed amounts of hydrogen and chlorine, and nine concordant determinations gave, in mean, C1= 35.195, & 0.0019, referred to the hydrogen standard. With 0= 16, C1 becomes 35.463, a value nearly midway between that found by Stas and the new figure given by Richards and Wells. Considering the difficulties of the work, the agreement between this and the previous investigations is as close as could be reasonably expected. Gadolinium.-Urbain (Compt. rend., 1905, 140,583), from ten analyses of the octohydrated sulphate, finds Gd = 157.23; when H = 1.007 and S = 32-06.This value is more than a unit higher than that given in the table, and is probably more trustworthy.$ * Published by the Carnegie Institution of Washington, 70 pp., April, 1905. See also J. Amer. Chem. SOL,1905, 27, 459. .1. Chein. News, 1905, 91, 263. Memoir read before the Royal Society. $ See Eberhard, Zeit.anorg. Chem., 1905, 45, 374 ; on the spectroscopic purity of the rare earth oxides studied by Urbain and others. 4 Iodine.-Baxter has continued his research of 1904 upon the atomic weight of iodine, and has published a second memoir upon this subject (J. Amer. Chew. SOC.,1905, 27, 876). First, from eight conversions of silver iodide into bromide, by heating in bromine, he found I=126.985.Two series of measurements, of five experiments in each, of the ratio AgI to AgCl, gave respec- tively 126.982 and 126,984. Eight determinations of the direct ratio between silver and iodine, weighed separately, gave in mean 126.987. Five determinations of the ratio I :AgI gave 126.983, and four of the ratio Ag:AgI gave 126.989. The average of all six series is I= 126.985 ; when Ag = 107.93, C1= 35.473, and Br =79.955. The last of these antecedent values was checked by a direct comparison of AgBr with AgC1, and the mean of six experiments gave Br = 79,953. The value previously found by Baxter was 126.975 for iodine, and the difference is partly due to his use, in the later investigation, of the new figure obtained for chlorine by Richards and Wells.The iodine work, therefore, is confirmatory of the latter. Nitrogen.-R. W. Gray, in a preliminary notice (Proc., 1905, 21, 156), gives the results of his experiments upon nitric oxide. Ten determinations of the density of the gas, corrected by D. Berthelot's formula, give a molecular weight of 30.005, whence N = 14.005. Six analyses of nitric oxide, effected by burning finely-divided nickel in it, gave N = 14.006. The investigation was to be continued farther. Guye, in an interesting lecture before the Chemical Society of Paris,* has given a complete summary of the researches relative to this atomic weight, which have been conducted by him and his associates at Geneva. He also discusses, somewhat fully, all previous determinations of the constant, and concludes, mainly from the physical evidence, that the atomic weight of nitrogen is not far from 14.01, and that the value 14.04, obtained by Stas, is no longer tenable.Goiag still farther, he reverses the ordinary gravimetric ratios from which the accepted atomic weight of nitrogen was derived, and, applying to them the new value for N, he deduces the atomic weight of silver. The latter is thus reduced from 107.93 to below 107.89, ranging even as low as 107.871. For these low values Guye cites much confirmatory evidence, which is not to be lightly dis- regarded. To this point we shall recur later. Potassium.-Atomic weight redetermined by Archibald (Tmns.Roy. SOC.Canada, Series 2, 10, section iii, p. 47) through analysis of the chloride.Four measurements of the ratio AgCl :KC1 gave K = 39.139, and four of the ratio Ag :KCl gave 39.140 ; when Ag= 107.93 and C1= 35.455. If C1= 35.473, then K becomes 39.122. * Bull. SOC.Chim., Bug. 5, 1905, with independent pagination. Compare Richards, Proc. Amer. Phil. Xoc., 1904,43,116. 5 XiZicon.-W. Becker and J.Meyer (Zeit.tcnoyg. C‘hem.,1905,43,251 ; 46, 45) have determined the atomic weight of silicon by conversion of the chloride into the oxide. Eight determinations were made, and, in sum, 46.82400 grams of SiC1, gave 16.58236 grams of RiO,. Hence, with C1= 35.45, Si =28.207. With the Richards-Wells value for chlorine, 35.473, Si becomes 28.257. Additional determinations by a different method are promised.This paper is preceded by an essay by Meyer on the calculation of atomic weights (ibid., p. 242), which deserves careful Consideration. Styontiurn.-From four measurements of the ratio 2Ag :SrCl,, Richards (Proc. Amer. Acad., 1905, 40, 603) finds Sr=87-661, when Ag =107.93 and C1= 35.473. This confirms the earlier value derived by Richards from experiments upon strontium bromide. T’eZZurium.-Gallo (Atti Accad. Lincei, 1905, [v], 14, 23 and 104) have determined electrolytically the ratio between silver and tellurium. From twelve experiments, in mean, Te= 127.61, when Ag= 107-93. Incidentally to this work, as a check upon the method employed, four comparisons between silver and copper were made. In mean, Cu =63.58. l’ho~i.urn.-R. J. Meyer and Gumperz (Bey., 1905, 38, S17) have attempted to separate ordinary thorium into fractions of different atomic weight, and have failed to verify the observations of Basker- ville.The fractions obtained by various processes gave atomic weights varying from 232.2 to 232-7, values which are essentially identical with that given in the table. From the foregoing summary of results, it becomes evident t,hat a far-reaching series of changes will soon be needed in our system of atomic weights. A change in chlorine or nitrogen implies many other changes in the table, and if the accepted value for silver should be modified the alterations would be most sweeping. The atomic weights of silver, chlorine, and bromine enter into the calculation of nearly all other atomic weights, and form, so to speak, the platform upon which the entire structure stands.The changes, however, which are suggested at present, are not final. Work is in progress in several laboratories which may confirm or modify many of the accepted values, and until that work is finished, at least so far as the fundamental data are concerned, it is wisest for us to suspend judgment and await developments. Were we to recon- struct the table of atomic weights on the basis of the evidence now before us, we should do it imperfectly, and a new revision would be demanded next year or the year after. Confusion would inevitably follow. Fortunately, the matter is not urgent, for the corrections which now seem desirable are not large, and the existing figures are accurate enough for all ordinary purposes.We therefore recommend 6 that the table for 1905 be continued in use without change during 1906, even although some modifications are theoretically desirable. A year hence we shall be in a better position for a critical adjustment of the data, and no harm can follow from the delay. In accordance with the expressed wish of a majority of the larger committee, we also recommend that the table based upon the oxygen standard be made official. So far as this committee is concerned, the private opinions of its members will be subordinated to the desires of the majority, and the table referred to hydrogen will no longer appear as a part of its report. For the present, a few suggestions may not be unacceptable, which follow from an examination of the lecture by Guye.Rayleigh, Leduc, Guye, Gray, and others, from their studies of nitrogen and its oxides, have accumulated a mass of strong evidence in favour ot a lower value for nitrogen. The data furnished by Stas, on the other hand, point to the higher value which has heretofore been generally adopted. Can we abandon the one in favour of the other, and accept the new figure without reserve 1 On behalf of the new figure for nitrogen, we must admit that the determinations are remarkably concordant, and that they rest upon a direct comparison of the element with oxygen. The Stas values, with their confirmations by other chemists, are also very concordant, but they are indirect. They all rest primarily upon the atomic weights of silver, chlorine, and bromine, and these were connected with oxygen through experiments upon chlorates and bromates.Our whole system of atomic weights, with only a few exceptions, is based to-day upon the analyses of several oxyhalogen salts. Their accuracy is assumed, and all anomalies which appear in det,erminations based upon other lines of research are commonly ascribed to undiscovered errors. The assumption may be sustained, but it is not yet beyond the reach of criticism. Consider, for example, the well-known ratio Ag:AgNO, = 100 : 157.149. If Ag= 107.93, as determined through the analyses of chlorates and bromates, then N = 14,037, or 14.04 as given in our table.If, on the other hand, N=14.009, as given by Guye, Ag becomes 107.881. The difference between the two values for silver evidently represents a difference in our methods of connecting t'he element with oxygen, the latter being taken as the standard. For each method strong arguments are possible, and for each value other corroborative testimony can be cited. Neither procedure is wholly free from objections, and the final conclusion, therefore, is one of uncertainty. We cannot safely reject either line of evidence, nor can we accept one as surely more exact than the other. Concordant values for silver can be derived from either method of discussion, as 7 Guye has shown, and through them the entire system of atomic weights is4 affected.In this condition of affairs, the position of the committee can only be one of conservatism. It is better to retain the table we have until at least some of the doubts which now affect it have been eliminated. It seems to be essential that the foundations of the atomic weight table should be both broadened and strengthened, and that new lines of research connecting the fundamental values with oxygen shall be investigated. Some work of this kind is already promised from the laboratory of Harvard University, to be carried out by Richards and his colleagues, but that need not exclude other activities. It is to be hoped that a number of investigators may take up the consideration of this problem, and that the methods of attack upon it may be multiplied.The careful study of such salts as the sulphates, carhon- ates, and nitrates might perhaps be profitable. Whether the organic salts of silver could be utilised for good atomic weight detarminations is still uncertain. F. W. CLARKE. HENRIMOISSAN. KARL SEUBERT. T. E. THORPE. 8 1906. Internntional Atomic Weights. . 0 16. 0 =16. Aluminium ................. A1 27.1 Neodymium .................. Nd 143.6 Antimony .................... Sb 120.2 Neon ......................... Ne 20 Argon ...................... A 39 *9 Nickel ........................ Ni 58.7 Arsenic ..................... AS 75.0 Nitrogen ..................... N 14.04 Barium ........................ Ba 137'4 Osmium .....................0s 191 Bismuth....................Bi 208-5 Oxygen .......................0 16.00 Boron ...................... B 11 Palladium ..................... Pd 106.5 Bromine .................... Br 79-96 Phosphorns .................. P 31'0 Cadmium ..................... Cd 112.4 Platinum .....................Pt 194'8 Caesiuiii .......................CS 132.9 Potassium ..................... K 39'15 Calcium ........................ Ca 40.1 Praseodymiuin............... Pr 140% Carbon ........................ c 12.00 Radium ....................... Rd 225 Cerium ........................ Ce 140'25 Rhodium ................... Kh 103.0 Chlorine ..................... C1 35'45 Rubidium .................... Rb 85-5 Chromium .................. Cr 52'1 Ruthenium ..................Xu 101.7 Cobalt ........................ Co 59.0 Saniariuni ................. Sin 150'3 Columbium .................. Cb 94 Scandium .................. Sc 44'1 Copper ........................ Cn 63.6 Selenium ................... Se 79'2 Erbium ........................ Er 166 Silicon ......................Si 28-4 Fluorine ..................... F 19 Silver ........................ A: 107.93 Gadolinium ..................Gd 156 Sodium ....................... Xa 23.05 Gallium .................... Ga 70 Strontium .................. Sr 57'6 Germanium .................. G e 72'5 Sulphur .................. S 32.06 GI ucinum ..................... GI 9*1 Tantalum .................... Ta 183 Gold .......................... Au 197.2 Telluriurn ....................Te 127.6 Helium ........................ He 4 Terbium ..................... Tb 160 Hydrogen ..................... H 1*008 204.1 Indium ....................... In 115 Thorium ..................... Th 2325 Iodine ........................I 126.97 Thulium ..................... Tm 171 Iridium ....................... Ir 193.0 Tin ........................... Sn 119.0 Iron ........................... Fe 55.9 Titanium ..................... Ti 48-1 Krypton ..................... Kr 81.8 Tungsten ..................... W 184 Lanthanum .................La 138'9 Uranium .....................U 238.5 Lead ...........................Pb 206.9 Vanadium ..................... V 51'2 8Lithium .................... Li 7-03 Xenon ........................Xe 128 Magnesium ..................Mg 24.36 Ytterbium ................. Yb 173.0 Manganese ..................Mn 55.0 Yttrium .....................Yt 89.0 Mercury ..................... Hg 200.0 Zinc ...........................Zn 65'4 Molybdenum ............... Mo 96 .0 Zirconium ................... Zr 90'6 Of the following papers, those marked * were read : "1. '' The refractive indices of crystallising solutions with especial reference to the passage from the metastable to the labile condition." By Henry Alexander Miers and Florence Isaac. The authors found that the refractive index of a strong solution of sodium nitrate, measured at intervals while the liquid cools, rises to a maximum value and then falls, crystals appearing before the maximum is reached.If the solution is stirred during the process, the fall is very rapid and is accompanied by a profuse shower of crystals. Other solutions (for example, alum, sodium chlorate, sodium thiosulphate, ammonium oxalitte) behave in the same way. There are always two periods of crystallisation : a first, in which a few crystals are growing gradually ; a second, in which many crystals appear spontaneously ; SO that in the latter the increase of index due to cooling is more than compensated by the decrease due to weakening of the solution. The authors regard these as being undoubtedly the metastable and labile states. This view is confirmed by the behaviour of the same solutions enclosed in sealed tubes and shaken continuously ; if the salt is com- pletely dissolved, they cannot be made to crystallise until they have assumed a temperature corresponding to the maximum refractive index.By means of auxiliary experiments, the refractive indices are interpreted as concentrations, and each series of observations is expressed as a curve with concentrations for ordinates and indices for abscissae ; the maximum points of the curve lie on a new curve, the " supersolubility curve " denoting the limit between the metastable and labile conditions; the same curve is given by the temperatures at which different solutions yield crystals when shaken in sealed tubes; it shows the highest temperature at which any given supersaturated solution can crystallise spontaneously.It is necessary in the case of sodium chlorate to employ friction as well as motion, by enclosing some insoluble substance in the tube, in order to make the crystals appear as soon as the supersolubility curve is reached. In the experiments in open vessels, the refractive index is measured by means of a totally teflecting glass prism immersed in the liquid ; the crystals which appear before the labile state is reached are doubt- less introduced with the dust of the air, or are due to evaporation and cooling at the edges and surface of the liquid, which reduces the solution locally to the labile state. 10 DISCUSSION. Dr. TUTTONsaid that it appeared to him that these interesting experi- ments lead to two important results. Firstly, that determinations of the refractive index of highly concentrated solutions afford valuable indications of the limits of the so-called ‘‘ labile ” and ‘‘ metastable ” conditions, and a new means of exploring the region of supersatura-tion.Secondly, that this new method of research may be of value in cases of dimorphism, where one of the forms only is commonly obtained, by throwing some light on the reasons for the predisposition to crystallise in that particular form rather than in the other. Sir WILLIAM asked whether Professor Miers had made any RAXSAY experiments on the condition of water cooled to below 4’ from a high temperature, and produced from melted ice, but not allowed to rise above 4’.Experiments made by Mr. Wilsmore in his laboratory had failed to show any difference in density of different specimens of water thus prepared ; but he understood that Dr. Chichester Bell hiid been successful in detecting different values for 7, the ratio of the specific heats at constant volume and constant pressure, in two such specimens of water; y was determined by an acoustical method. Mr. PICKERINGsaid that the authors should be congratulated on having obtained a method of studying solutions at that critical period of their existence when crystallisation is occurring, and he suggested that it might be of advantage to study pure liquids in the same may. In reply to a question from Prof. Armstrong, Prof. MIERSsaid that the experiments reveal a state of the solution in which a sudden access of spontaneous crystallisation occurs, and this condition is indicated by the term “labile.” He hoped to extend the experiments to water and other pure substances.*2. “The effect of constitution on the rotatory power of optically active nitrogen compounds. Part I.” By Mary Beatrice Thomas and Humphrey Owen Jones. The resolution of a set of optically active nitrogen compounds and the examination of the rotatory power of their salts in dilute aqueous solution have been made in order to find the rotatory power of the ions. This property of the ions is free from many of the disturbing influences such as rnolecular association and nature of solvent, which affect the rotatory power of non-electrolytes, and render comparable results so diacult to obtain with this class of compound.Relations between rotatory power and constitution ought therefore to become more evident in thecase of ions than of complete molecules. 11 Two homologous series, each consisting of five compounds, were chosen for examination ;in one series, three of the hydrogen atoms in the ammonium ion are replaced by the phenyl, methyl, and allyl groups, whilst the fourth atom of hydrogen is replaced successively by the ethyl, n-propyl, isopropyl, isobutyl, and isoamyl groups; in the other series, the phenyl, methyl, and benzyl groups are present with the same five aliphatic groups. The ethyl compound of the latter series has already been described by one of us, and Wedekind has resolved the 11-propyl and isobutyl compounds.The compounds originally resolved by Pope and Peachey, namely, the phenylbenzglmethylal1y~-ammonium salts, fall naturally into both these series. The following are the values of [MI, for the ions at 15' : Phenylmethylallyl series. Ethyl 16", 12-propyl 106O, isopropyl 103O, isobutyl 55O, isoamyl 18", benzyl 167O. Phenylmethylbenzyl series. Ethyl 19*4O, In-propyl 299', isopropyl 39S0, isobutyl 323O, isoamyl 2S7O. In all cases examined, the value of [MI, for the basic ion is diminished slightly with increasing temperature bet ween 10' and 50'. In both series there is a well-marked maximum of rotatory power at the second member of the series, the propyl or isopropyl compound; in the allyl series, the rotatory power of these two com-pounds is almost identical, but in the benzyl series the propyl compound occupies quite a different position.The application of Guye's hypothesis to the case of nitrogen gives an expression for the rotatory power of the compound in terms of the masses of the substituting groups which does not account for the results in an entirely satisfactory manner. In those cases where the active iodide could be recovered its rotatorypower was examined in solution in alcohol and in chloroform. The rotatory power was always greater in chloroform than in alcohol, and the iodides invariably underwent racemisation in chloro- form solution with very different velocities. "3. ''The determination of available plant food in soil by the use of weak acid solvents." By Alfred Daniel Hall and Arthur Amos.The authors have investigated the effect of repeating the at'tack of weak acid solvents on soils of known history derived from the Rothamsted experimental plots. After ihe first extraction, the soil is washed and again extracted with the same solvent, the process being repeated several times. The solvents employed were water charged with carbon dioxide and a 1per cent. solution of citric acid. The first extraction does not remove the whole of the phosphoric 12 acid capable of going into solution in the given solvent, the reaction is a reversible one, and a position of equilibrium is attained between the phosphoric acid in solution and the bases in the soil.With carbon dioxide and water, the position of equilibrium is approximately constant for successive extractions and is characteristic of the manurial history of the soil. With dilute citric acid, the phosphoric acid going into solution falls for the first four or five extractions and then becomes approximately constant. In the case of the Rothamsted soils, which have been continuously manured with superphosphate, the phosphoric acid going into solution decreases logarithmically, indicating that the amount dissolved is proportional to the active mass of a particular compound present in the soil, six-tenths of which become dissolved at each extraction. The total quantity of this compound is equal to the phosphoric acid supplied as manure during the last 50 years, less that which has been removed in the crop.Soils which have received more varied compounds of phosphoric acid as manure do not show the same regular decrement in the amounts passing into solution, indicating the presence in the soil of a number of compounds of phosphoric acid of differing solubility. The investigation lends no support to the theory that all soils establish in the soil water a solution of phosphoric acid of approxi-mately the same composition and independent of the fertilisers the soil receives. DISCUSSION. Dr. DYEXsaid the paper was one of much interest; for whilst in his original examination of these soils he had, by one extraction only with citric acid, found in the surface soil the greater part of the calculated accnmulation of phosphoric acid due t.0 the manuring, the authors had now, by their supplementary extractions with the same reagent, discovered the remainder almost with the accuracy of an accountant’s balance sheet-except in the case of the dunged plots.In three cases, the earlier investigation showed that some of the phosphoric acid had gone down into the lower depths of the subsoil, and, furthermore, the actual quantity of phosphoric acid added in the dung could only be vaguely guessed. It was satisfactory to hear that the authors still considered that for practical analytical purposes one extraction sufficed. Mr. PICKERINGasked whether the influence of the volume of solution used-which would mean a variation in the proportions of citric acid to soil--had been investigated, also whether the effect of pulverisation of the soil had been examined, for he had found that the amount of potash and iron dissolved by citric acid from a soil depended largely on the degree of fineness to which the soil had been reduced.13 In reply, Mr. HALLsaid that in all cases the amount of citric acid solution had been kept constant, 1 litre to 100 grams of the soil. Soil which passed the 3 mm. sieve was used without any grinding, but as there were other reasons for supposing that the soil phosphates were almost wholly found on the outside of the soil particles, grinding should not make much difference to the phosphoric acid results.*4. '(The action of ammonia and amines on diazobenzene picrate." By Oswald Silberrad and Clodfrey Rotter. When diazobenzene picrate is acted on by ammonia gas, it rapidly loses the characteristics of a diazo-salt and forms a dark red product. Two possibilities presented themselves, namely : (1) the formation of ammonium picrate, accompanied by further reactions between the diazo-complex and the excess of ammonia ; (2) an intramolecular trans- formation of the diazo-picrate to trinitrobenzeneazophenol, somewhat analogous to the diazoaminobenzene transformation. The intense red colour of the product appeared to lend some pro- bability to the latter assumption, but an examination of the reaction completely disproved the presence of azo-compounds.The products proved to consist mainly of ammonium picrate, and diphenylamine, aniline, and phenol were also detected. Thus, the course of the reaction is evidently represented by the equations : 2C6H5*N,*O*C6H2(N0,),+ ;3NH3 = (C6H5N2)2NH+ 2NH4*O*C6H,(NO2), (C,H,N,),NH = (C,H,),NH + 2N2;(C6H5N&NH+ H20 = C6H5*NH2+ C6H5*OH+ 2N2. Other compounds occurred in small quantities as the result of secondary reactions. When treated with aniline, diazobenzene picrate gives rise to aniline picrate and aminoazobenzene ; the latter compound evidently resulted from a transformation of diazoaminobenzene ;thus, in this case, the reaction takes place as follows : C6H,*N,*O*C6H,(N02),+ 2C6H,*NH,= C6H5'N2*NHaC,H5+ C,H5*NH,*0*C6H2(N0,)3. DISCUSSION.Dr. MORGANstated that in conjunction with Mr. Wootton he had studied the picrates of diazo-compounds, and especially the stable product derived from p-aminobenzanilide (see p. 23). This compound was precipitated even in strongly acid solution and was, therefore, in all probability a diazonium derivative. They had not detected syn-and anti-isomerism in this series. It would be interesting to know whether the more explosive diazobenzene picrate was a diazo-compound or a diazonium salt. In reply, Dr. SILBEBRADsaid that the comparative stability of 14 diazobenzene picrate was remarkable considering its constitution, but, nevertheless, he regarded it as a true diazonium salt. Under these conditions, it seemed improbable that syn-and anti-derivatives could be prepared, which was in accord with Dr.Morgan's observations op similar compounds. "5. '' The preparation of bistriazobenzene." By Oswald Silberrad and Bertram James Smart. The explosive properties of bistriazobenzene have hitherto pre-cluded the verification of its composition by analysis ; for this reason, a reinvestigation of the compound has been undertaken, and at the same time the method for its preparation has been somewhat modified. Griess (Ber., 1888, 21, 1559) took the oxamic acid of p-phenylene- diamine as the starting point for the preparation of this compound; in the present work, however, it has been found advantageous to proceed from p-aminoacetanilide. The successive steps of the preparation are seen from the following series of intermediate products : p-aminoacet-anilidc, acetyl-p-aminodiazobenzene perbromide, p-aminotriazobenzene, p-triazodiazobenzene perbromide, bistriazobenzene. AcetyZ-p-unzinodiaxobenxeneperbromide, CH,*CO*NH*CGH,*N2Br3, crystallises in small, yellow plates (m.p. l26O) with decomposition. p-Arninotriaxobenxene, NH,*C,H,*N,, was prepared by tlhe hydrolysis of acetyl-p-aminotriazobenzeue with caustic potash, previously un- successfully attempted by Rupe and von Majewski (Ber., 1900, 33, 3406). Bistriaxobenxene, N,*CGH,*N, (m. p. 83') explodes on heating ; its analysis was, however, successfully carried out under diminished pres- sure, and gave results which agreed with the above formula. DISCUSSION.Dr. FORSTERinquired whether p-bistriazobenzcne has a distinctive odour, because he had noticed that m-and p-nitrophenylazoimides have a faint odour of anise, which is more marked in the case of p-tolyl-azoimide and p-chlorophenylazoimide, whilst in the case of p-methoxy-phenylazoimide the odour is comparable with that of anethole itself, being less sweet and more pungent than the perfume of the last- named substance. Curiously enough, o-nitrophenylazoimide is odourless. In reply, Dr. SILBERRADsaid that he had noticed an anise-like odour, but considered the smell more similar to that of a nitro-compound, and suggested that this might be regarded as an argument 15 0in favour of the formula -N</, for nitro-derivatives analogous to N-N< I I of triazo-compounds.23 *6. (‘aradual decomposition of ethyl diazoacetate.” By Oswald Silberrad and Charles Smart Roy. When ethyl diazoacetate is exposed to light at the ordinary tempera- ture, a gradual evolution of nitrogen occurs, and after the space of several years, thick, colourless, rhombic crystals resembling cane sugar gradually make their appearance. On examination, this compound proved to be the triethyl ester of 4 :5-dihydro-3 :4 :5-pyrazoletricarb-osylic acid. Subsequent work showed that the same compound can readily be pro- duced by warming ethyl diazoacetate with copper dust. In both cases, the reaction is evidently due to the intermediate formation of furnaric or maleic esters. This view is confirmed by the work of Buchner and Witter, who prepared the trimethyl ester by the action of the corresponding ester of fumaric or maleic acid on methyl diazoacetate (Annalen, 1895, 273, 239).*7. “Studies on nitrogen iodide. 111. The action of methyl and benzyl iodides.” By Oswald Silberrad and Bertram James Smart. The ccction, of methyl iodide.-Previous experiments by Stahlschmidt (Pogge.ndor$’s Ann., 1863, 119,421) on the interaction of nitrogen iodide with methyl iodide led him to represent the reaction by the following equation : 2N13+ 6CH31= N(CH3)*15+ NH,I +2CH13. Since the formula here assumed for nitrogen iodide is not in accord with that proved by Clhattaway (Proc., 1899, 17, 20; Amer. Chem. SOC.,1900, 23, 363, &c.), or with the constitution N18:NH,, established by one of the authors (Silberrad, Trans., 1905, 8’7,55 and 66), renewed experiments have been carried out on the above reaction.The formation of tetramethylammonium pentaiodide as observed by Stahlschmidt was confirmed in the present work, and its nature established by its preparation from tetramethylammonium iodide and iodine. Iodoform was not, however, as he believed, a product of the reaction between nitrogen iodide and methyl iodide, but resulted from the alcohol, present in his experiments. In the present work, alcohol was excluded; the nitrogen iodide was prepared from ammonia and iodine chloride and was allowed to react with excess of methyl iodide under water. The products found were tetramethylammonium penta- 16 iodide, ammonium iodide and iodate, and free iodine. The quantities of all these products were determined and the reaction was proved to proceed almost quantitatively according to the following equation : 6N2H3T,+ 24cH31+ 3H,O = 6N(CH,)41, + 5NH,I + 31, + NH,-I03.No compounds corresponding to Stahlschmidt's di-iodomethylamine or butyric acid were produced. Action of benxyl iodide.-This iodide was found to react readily with moist nitrogen iodide. The nature of products, however, depends on the proportion of benzyl iodide taken, bright green or garnet-red crystals being deposited according to the conditions of the experiment. These proved both to be periodides of tribenzylamine. Tribenzylammoniunz pentaiodide, N(C7H7)3H15,which forms bright green crystals melting at 121-122', is sparingly soluble in alcohol, and undergoes a slight decomposition on recrystallisation.Tribenzylammonium di-iodide, N(C7H7),H12,crystallises in garnet- red prisms melting at 115-1 16' ; it dissolves more readily in alcohol than the pentaiodide, and can be more easily obtained in the crystalline condition, The pentaiodide can be readily converted to the red di-iodide by the partial abstraction of its iodine by shaking with potassium iodide solution. Conversely, the di-iodide can be converted into pentaiodide by treatment with alcoholic iodine. Both compounds can also be obtained direct from tribenzylsmine by the addition of the required quantity of iodine to the iodide of the base."8. '( Action of bromine on benzeneazo-o-nitrophenol."By John Theodore Hewitt and Norman Walker. By the action of bromine on 4-benzeneazo-2-nitrophenolin presence of glacial acetic acid and fused sodium acetate, the 6-hydrogen atom is replaced. The constitution of the resulting compound, which when pure melts at 154.5-155", was confirmed by fission with excess of fuming nitric acid. The resulting p-nitrophenyldiazonium nitrate was isolated by conversion into p-nitrobenzeneazo-P-naphthol,whilst 1.5 grams of 2-bromo-4 :6-dinitrophenol, melting before purification at 116' (uncorr.), were obtained instead of bhe theoretical amount of 1.6 grams from 2 grams of the azophenol. Korner gives the melting point of bromodinitrophenol as 3 18O.The following derivatives of benzeneazobroinonit,rophenol have been analysed : sodium and potassium salts, acetyl derivative (m. p. 137"), and benxoyl derivative (m. p. 131'). 4-p-Tohenemo-2-4 pheno2 was prepared in a similar manner from p-tolueneazonitrophenol; 7.7 it melts at 161'. Fuming nitric acid furnishes 2-bromo-4 :6-dinitro-phenol as a product of fission ;its acetyl derivative melts at 124O, the benxoyl derivative at 129'. *9. The condensation of dimethyldihydroresorcin and of chloro-ketodimethyltetrahydrobenzene with primary amines. Part I. Monoamines, ammonia, aniline, and 11-toluidine." By Paul Haas. Dimethyldi hjdroresorcin re-icts with ketonic reagents as a diketone ; in most of its other reactions, however, it behaves as a hydroxyketone In this form, it con-having the formula CMe2<~~~~~~~~>CH.denses with a single molecule of a primary amine by the elimination of water between the hydroxyl group and the amino-hydrogen, giving rise to a secondary amine. This replacement of the hydroxyl group by a basic group -NHR caused the remaining ketonic oxygen to become hydroxylic, as shown by the fact that the new substance gives a colour reaction with ferric chloride and cioes not react with ketonic reagents ; when, however, the basic substituting group is rendered more acid by acetylation, the resulting compound no longer gives any coloration with ferric chloride and condenses with semicarbazide, showing that the oxygen atom has become ketonic.Chloroketodimethyltetrahydrobenzene, unlike djmethyldihydro-resorcin, reacts at once with two molecules of a primary amine, giving rise to the hydrochloride of a mixed secondary and tertiary base CH *C(NHR)>CH. Bases of this type having the formula C1\.le2<ca~-c(. .-YR) may also be prepared by condensing the mono-sub3tituted derivatives, obtained by the action of dimethyldihydroresorcin on the amine, with a second molecule of the same amine in the presence of zinc chloride. 10. '' Silicon researches. Part X. Silicon thiocy anate." By J. Emerson Reynolds. The author found that silicon thiocyanate, Si(SCN),, is best pre- pared by prolonged digestion of pure lead thiocyanate in a benzene solution of silicon tetrachloride. An excess of the lead salt must be used, as the latter exchanges but one of its two thiocyanogen groups for chlorine, forming the yellow, crystalline compound PbCl(SCN), silicon thiocyanate remaining in solution. The latter compound is obtained in fine white crystals, when most of the benzene is removed by distil- lation; but if any moisture is present the crystals become yellow owing to decomposition.This method of preparing the thiocyanate 18 gives a much better product than Miquel's (Ann. Cl~im.Phys., 1877, [v]. 11,343), in which the materials are heated to about 400°, as in this investigator's process charring results, and an impure substance is obtained. The pure thiocyanate melts at 143.8' (corr.) and boils at 314.2' (corr.), distilling without decomposition.The chief interest attaches to the constitution of the compound, as the somewhat analogous phosphorus ''trithiocyanate )' has been shown by A. E. Dixon (Trans., 1901, '79, 541) to exhibit "a form of tautotnerism,)) in some cases acting as P(NCS), and in others as P(SCN),. The author has compared silicon thiocyanate with the phenylamide, Si(NH*C6HJ4, described in Part V of this series of papers, and has examined several interactions of the thiocyanate with aniline and other substances, and concludes from the results that it is correctly repre- sented by the expression Si(SCN),. 11. '' Halogen derivatives of substituted oxamides." By Frederick Daniel Chattaway and William Henry Lewis. The action of the halogens on substituted oxamides has been little studied, and the description given of the substances formed is not very satisfactory, as the crude products obtained were not subjected to any process of purification. The action of chlorine on oxanilide has been studied and a number of substituted oxanilides has been prepared in a simpler way in order to compare them with the foregoing products The usual product of the chlorination of oxanilide is a mixture of s-di-p-chlorophenyloxamide and of its s-dichloroamino-derivative. When aniline or a substituted aniline is heated with ethyl oxalate, a symmetrical disubstituted oxamide on the ethyl ester of a substituted oxamic acid is formed according as the aniline or the ethyl oxalate is in excess. The symmetrical chlorophenyloxamides, which are almost insoluble in ordinary solvents, crystallisb well from nitrobenzene, in which on heating they readily dissolve.The following compounds were described : s-di-p-chlorophenyl-oxodichloroanzide, colourless rhombs (m. p. 169') ; ethyl p-chloro-phenyloxanaate, colourless plates (m. p. 155') ;p-chlorophenyloxamide, colourless needles (m. p. 24 1') ;s-di-p-chlorophenyloxamide,colourless, thin plates (m. p. 288') ; ethyl 2 : 4-dichlorophenyloxainate, colourless, hair-like prisms (m. p. 119') ; 2 :4-dichloro~herLyloxarn~de)colourless, hair-like crystals (m. p. 234') ; s-di-2 :4-dichZorophenyloxamide,colour-less, slender prisms (m. p. 276") ; s-dirnethyloxodichloroamide, colourless, slender prisms (m.p. 37") ;s-diethyloxodicldoroanzicle, pale yellow, viscid 19 liquid which decomposes on heating ; s-dimethgloxodibromoamide,pale yellow, flattened prisms (m. p. 95') ; s-diethyloxodibromoamide, pale yellow plates (m. p. 82"). 12. L6 Menthyl benzenesulphonate and menthyl naphthalene-/3-sulphonate." By Thomas Stewart Patterson and John Frew. Menthyl benzenesulphonate and menthyl naphthalene-P-sulphonate have been prepared by khe pyridine method. The former crystallises from alcohol in silky needles melting at SOo, the latter separates from alcohol in solid, opaque crystals melting at 114-114*5". The corn- pounds themselves decompose on continued heating at or above the rneltiug point, so that their rotations have been determined in ethyl alcohol, benzene, and nitrobenzene.The chief points of interest are as follows : (1) there is considerable variation of rotation with change of solvent. (2) The values of [MI, for the /3-naphthalene compound are consistently lower than for the benzenesulphonate in a given solvent. (3) The solvents, however, do not exert proportionate influences on the rotations of the two compounds. (4) Menthyl benzenesulphonate has a lower molecular rotation than menthyl benzoate by about 56", and menthyl naphthalene-P-sulphonate a lower rotation than rnenthyl P-nnphthoate by about 113". (5) As regards the influence of tempera-ture change on the rotations of these compounds in solution, it was found that the greater the rotation produced by a solvent the more rapid was its diminution with rise of temperature.The molecular rotations in dilute solution seem to tend at higher temperatures t,owards a common value of about -170". 13. "Some reactions and new compounds of fluorine." By Edmund Brydges Rudhall Prideaux. The fluorine was prepared by the electrolysis of anhydrous hydrogen fluoride contained in a copper vessel (Moissan, " Le Fluor et ses Compos6s "). In every case when the gas was analysed it was found to contain oxygen, and special experiments proved that this oxygen was produced at the anode even after the current had passed for a considerable time. Liquid fluorine has no solvenc or chemical action on iodine. The colourless iodine fluoride was analysed by a volumetric method, and four concordant percentages of iodine confirmed the formula IF, established by Moissan (Compt.rend., 1902,135,563) from the results of gravimetric analysis. Bromine fluoride was prepared for the first time ;analyses carried out by a gravimetric method led to the formula BrF,. Liquid fluorine has neither solvent nor chemical action on solid bromine. Gaseous fluorides of selenium and tellurium were prepared by the direct combination of the elements in the cold. The formulz of these gases were proved to be SeF, and TeF, by determinations of their densities. Analysis of TeF, also showed it to have this formda. These gases are colourless and easily condensable by moderate cold or pressure to white, crystalline solids and colourless liquids respectively. Tellurium hexafluoride has an unpleasant odour and decomposes water slowly at 15’ ;selenium hexafluoride does not decompose water at 15”.The vapour pressure curve of SF, was determined for comparison with those of SeF, and TeF,. The three curves resemble one another closely. In the case of SF, and SeF,, the melting points lie above the temperatures at which the vapour over the solid attains a pressure of 760 mm., whilst in the case of TeF, the melting point lies just below the boiling point. The critical temperatures of the liquefied gases rise in the order SF,, SeF,, TeF!‘,. The molecular volumes at temperatures equally removed from the melting points were found to be very nearly the same. The refractivities of the three compound gases bear no simple additive relation to those of their constituent elements.The refractivities minus a constant are directly proportional to the densities of the gases. 14. “Contributions to the chemistry of the rare earths. Part I.” By Mario Esposito. The methods advocated for the separation of cerium, lanthanum, and “ old didymium ” have been examined comparatively with the following results. Preparation of the Material.-Rather more than balf a kilogram of finely-powdered Swedish cerite was mixed into a paste with water, and 375 grams of concentrated sulphuric acid were gradually added. Considerable evolution of heat took place and the mass swelled up somewhat. The excess of acid was then removed by heat, and the cold white or grey mass was thrown in small portions into 5 litres of ice-cold water.The silica was removed by filtration and a current of hydrogen sulphide was passed through the solution to precipitate any arsenic, molybdeuum, bismuth, copper, or lead which might be present. To the filtrate, oxalic acid was added, which precipitated all the ceria, lanthana, and ‘‘didymia ” along with lime and traces of the yttrium group which are present in cerite (Brauner, Trans., 1883, 43,278). The oxalates were thoroughly washed and dried. Xethods of Separation.-( 1) The first method tried was that origin- 21 ally proposed by Watts (Quart. Journ. Chern. Xoc., 1850, 2, 131). Some of the reddish-brown oxide prepared by igniting the foregoing oxalates was boiled for several hours with a strong ammonium chloride solution until no more dissolved.The reddish-brown, insoluble ceria was washed with ammonium chloride solution and dissolved by boiling with alcohol and strong hydrochloric acid. The solution showed strong ‘( didymium ” absorption bands, and probably also contained lan- thanum. (2) Brauner’s basic nitrate method (Trans., 1883,43,278;1885,47, 879) gave fairly good results, but some of the cerium remains in solution. (3) Popp’s method (Annalen, 1864, 131, 360), which consists either in boiling a neutral solution of the chlorides with sodium acetate and sodium hypochlorite or in passing a current of chlorine through a solution mixed with sodium acetate, gives good results on a small scale, but is inconvenient with larger quantities.(4) Although the same objection applies to Mosander’s method with caustic potash and chlorine (Poggendorf’s Ann., 1843, 60, 297), very pure ceria can thus be obtained. (5) For ordinary purposes, however, the process devised by H. Debray (Compt. rend., 1883, 96, 928), slightly modified as follows, seems to give rapid and satisfactory results. The dried oxalates were boiled with strong nitric acid until campletely decomposed, the solution was evaporated to dryness, the last part of the process being conducted on a sand-bath, and the anhydrous nitrates mixed with twice their weight of sodium nitrate were fused in a porcelain dish until no more nitrous fumes were evolved.The cold mass was detached from the dish, coarsely powdered, and digested in warm water acidified with nitric acid. The insoluble, pale yellow ceric oxide was collected and washed with ammonium nitrate solution, as recommended by Schiit8zenberger(Comnpt. rend., 1895, 120, 663). If pure water is used, the finely-divided ceric oxide will pass through the filter. The filtrate was again evaporated to dryness and fused so as to eliminate the remainder of the cerium. The lanthanum and “didymium” were subsequently separated by fractional crystallisation of the oxalates from strong nitric acid solution, as will be described in a future communication. (6) Very pure ceria can be obtained by the following method, which depends on the use of chromic acid.The solution of nitrates was pre-cipitated with caustic soda, and the hydroxides were washed several times by decantation with boiling water. A warm aqueous solution of chromic acid was then added and the whole left for several daye. A heavy, yellowish-white precipitate remained, which, on ignition at a gentle heat, yielded cerium sesquioxide as an almost white powder 22 without the slightest tinge of red or yellow. When thus obtained, the oxide dissolved readily in boiling hydrochloric acid, and the solu- tion, even when viewed through a considerable thickness, did not show a trace of absorption bands. This last method will be further studied. A chromic-acid method was formerly devised by Pattinson and Clarke (Chem. News,1867, 16,259), but the process is entirely different from the foregoing, and has the disadvantage of giving a ceric oxide which is absolutely insoluble in acids.15. '' A synthesis of aldehydes by Grignards reaction." By Gordon Wickham Monier-Williams. Gattermann and Maffezzoli (Bey., 1903, 36,4152) showed that aldehydes could be obtained by the action of organo-magnesium compounds on ethyl formate :aH*CO*0*C2H5+IMgX =C,H,*O*MgI+ X'CHO, and various other investigators have carried out analogous syntheses with derivatives of ethyl formate, for example, bromoform, iodoform, ethyl orthoformat.e, disubstituted formamides, and isonitriles. The author has shown that ethoxymethyleneaniline, C,H,*N:CH *O*C,H,, reacts readily with organo-magnesium compounds to give the anhydro-compound of aniline with the aldehyde in question, from which the latter is easily obtained.The yields are in many cases far better than those given by the older methods. Ethoxy-methyleneaniline was prepared by the action of ethyl iodide on the silver derivative of formanilide, C,H,N:CH*OAg (Comstock and Kleeberg, Amer. Chem. J.,1890, 12, 497), and was allowed to react in absolute ethereal solution at 35O on organo-magnesium compounds. Benzaldehyde, o-tolualdehyde, U-aod P-naphthaldehydes were obtained from the respective bromo-compounds with yields of 46, 54, 48, and 36 per cent. respectively. Some derivatives of P-naphthnldehyde were prepared and analysed, notably P-naphthylacrylic acid, C,,H,*CH:CH*CO,H, and dinitro-P-naphthaldehyde, CloH5(N0,),*CH0.The method was then applied to the synthesis of a new aldehyde, p-thiophenetyl- aldehyde, C,H,8*C6H,*CH0. p-Nitrothiophenetole (Blanksma, Rec. trav. chim., 1901, 20, 403) on reduction gave p-thiophenetidine, C,H,S*C,H,'NH,, a slightly yellow liquid boiling at 280'. Its acetyl derivative is thio-phenacetine, which, however, does not exert the physiological action of phenacetine. The base was successively converted into the iodo- compound, C,H,S*C,H,T, a slightly yellow oil boiling at 146'/11 mm., and the aldehyde, C2H,*S*C6H,*CH0,boiling at 245O. Several 23 derivatives of the latter were prepared, of which the azine is very characteristic. The oxidation of the aldehyde with alkaline perman- ganate gave rise to a sulphonecarboxylic acid, C,H,*SO;C,H,*CO,H.16. “The action of ultra-violet light on moist and dry carbon dioxide.” By Samuel Chadwick, John Edwin Ramsbottom, and David Leonard Chapman. By the action of ultra-violet light on dry carbon dioxide, the authors have succeeded in partially decomposing carbon dioxide in to carbon monoxide and oxygen. The circumstances of the experiment rendered it impossible to decide what percentage of the oxygen was present in the form of ozone. If the carbon dioxide is moist there is no decom- position. The peculiar influence of water vapour is believed to be due to the action which it exerts on the vibrations of the electrons of the atoms of which the molecules of carbon monoxide, carbon dioxide, and oxygen are composed.The facts, discovered by Chapman and Burgess, concerning the induction period of a mixture of chlorine and hydrogen are regarded as confirming this view. 17. (( A contribution to the study of stable diazo-compounds. Preliminary note. ” By Qilbert Thomas Morgan and William Ord Wootton. p-Aminobenzanilide, which has been shown to give on diazotisation a stable diazo-carbonate and a corresponding nitrite (Trans.,1905, 87, 938), also furnishes a diazonium picrate, C,H,*CO*NH*C,H,*N~*O*C~H~~NO~)~, which is precipitated even in the presence of hydrochloric acid. This substance, which is insoluble in water and crystallises from warm alcohol in rosettes of yellow needles decomposing at 132”, does not explode on percussion. When dissolved in aqueous caustic soda and added to alkaline /3-naphthol, it yields a precipitate of benzoyl-p-aminobenzene-azo-/3-naphthol.Mercury acetamide has been found to yield sparingly soluble, stable additive compounds when added to the aqueous solution of a diazonium salt, and a series of these substances is under investiga- tion. The compound with benzenediazonium chloride gave, on analysis, N =12.46, whereas C,H,*N,Cl,Hg(NH*CO*CH~)~requires N =12.26 per cent. Similar stable mercury acetamide derivatives have been obtained from the substituted anilines and their homologues. 18. Triarylsulphonium bases.” By Samuel Smiles and Robert Le Rossignol. Quite recently Kehrmann and Duttenhofer have published a paper (Bey., 1905,38,4297)dealing with mono- and di-arylsulphonium bases, and, although their work does not clash with that of these investigators, the authors considered it desirable to communicate the following preliminary note to the Society.It has been found that triarylsulphonium bases can be prepared in three ways. (1) By the action of thionyl chloride on a phenol or phenolic ether in presence of aluminium chloride. (2) By the action of a sulphinic acid on a phenolic ether in presence of concentrated sulphuric acid. (3) By the condensation of an aromatic sulphoxide with phenols or their ethers. It can be shown that sulphoxides are formed during the first and second reactions, and hence the third reaction may be regarded as the final stdge of the first two.The condensation between sulphoxide and phenol takes place with acid condensing agents, and it is the authors’ view that the sulphoxide, being basic in character, first forms a salt Ar2S(S0,H)*OH,which then reacts with the phenol, losing hydroxyl and forming the sulphonium salt, thus : Ar2S(S0,H)*OH+C,H,*OH = Ar2S*C,H,(OH)*S0,H+H,O. This reaction seems to be reversible and a slight. excess of phenol must be present to render the conversion of sulphoxide to sulptionium salt complete. At present only the hydroxy -and ethoxy-derivat’ives have been examined, but the authors hope to extend the investigation to amide and other compounds. 19. “An improved apparatus for the continuous extraction of liquids with ether.” By Richard Sisson Bowman.The apparatus here described differs essentially from those due to Hagemann (Bey., 1893, 26, 1975), Pellizza (Chem. Centr., 1904, 1, 851), and Mameli (Zoc. cit., 1905, 2, 106). In the latter, hot ether vapour is blown through the liquid to be extracted, whilst in the former the extraction is effected by passing cool liquid ether through the solution. Violent bubbling is thus avoided, together with the consequent risk of carrying over mechanically into the ether flask some of the liquid to be extracted. The apparatus comprises a simple system of tubes, a condenser, and two ordinary flasks, preferably round bottomed, 25 The liquid to be extracted is placed in the flask A in sufficient quantity to very nearly fill the flask to the bottom of the neck. This flask may frequently be replaced with advantage by a wide test-tube.From one-eighth to one-fifth of this volume of ether, with which the substance is to be extracted, is placed in the flask B, which is heated on a water-bath or electric heater. The ether passing as vapour up tube C is condensed in the condenser and falls back and collects in the inner tube, D. A column presently accumulates in D long enough to force its way through the liquid in A, and there is then a constant succession of small drops of ether ascending in A, collecting on the surface of the liquid, and finally overflowing at P and return- ing to the flask B. On completion of the process of extraction, the neck of the flask will be filled with ether.There will also be a column of ether in tube B, reaching a few centimetres above tube P,and hence the neck of the flask may be emptied by opening the stopcock E and allow- ing the ether to run off into some vessel. If necessary, the flask may now be replaced by a similar one containing a fresh portion of the liquid to be extracted and the pro- cess resumed. Among other advantages claimed for this apparatus are that whereas the other forms involve either ex- pert glass blowing or innumerable cork and india-rubber joints, it is simple in construction and may easily be made by anyone moderately skilled in the use of the blowpipe. It is very easy to keep clean and convenient to charge, since t'he vessels which contain the liquid to be extracted and the extracting liquid are ordinary flasks.A large quantity of liquid, moreover, may be rapidly and completely extracted with the use of zt very small quantity of ether. 26 Benzene, ligroin, or any other suitable solvent may be used with equal ease, provided it is immiscible with water and of lower specific gravity than the liquid which it is to be used to extract. ADDITIONS TO THE LlBRARY. I. Donations. Aschan, Ossian. Chemie der alicyklischen Verbindungen. pp. xlv + 1163. Braunschweig 1905. (Recd. 7/12/05.) From the Publishers. Carnegie, Douglas. Law and theory in chemistry. pp. 222. London 1894. (Recd. 21/12/05,) From Professor R. Meldola. Richmond, H.Droop. The laboratory book of dairy analysis. pp. viii + 90. ill. London 1905. (Recd. 20/11/05.) From the Author. C.Thresh, JO?~ The examination of waters and water supplies. pp. xvif460. ill. London 1904. (Red 18/12/05.) From the Author. Walker, A. Jamieson, and Mott, Owen E. An introduction to volumetric analysis. pp. x+ 64. London 1905. (Mecd. 20/12/05.) From the Publishers. 11. By Purchase. Abney, Sir William de Wiveleslie. Instruction in photography. 11th edition. pp. 676. ill. London 1905. (Recd. 18/12/05.) Borel, Pierre. Bibliotheca chimica seu catalogus librorum philoso- phicorum hermeticorum in quo quatuor millia circiter, authorum chimicorum, vel de transmutatione metallorum, re minerali, et arcanis, tam manuscriptorum, quam in lucem editorum, cum eorum editioni bus, usque ad annum 1653 continentur. pp.xii+276. Paris 1654. (Recd. 19112/05.) Boyle, Eon. Robert. New experiments and observations touching cold, or an experimental history of cold, begun. To which are added sn examen of antiperistasis, and an examen of Mr. Hobs’s doctrine tbout cold. #Whereuntois annexed an account of freezing, brought in to the Royal Society, by the learned Dr. C. Merret, a Fellow of it. pp. lviii +845+54. ill. London 1665. (Recd. 18/11/05.) Chemisch-technische Untersuchungsmethoden. Edited by Georg Lunge. Vol. 111. pp. xxvii + 1305 +xliv. ill. Berlin 1905. (Recd. 18/12/05.) Church, Arthur Herbert. Precious stones considered in their 27 scientific and artistic relations. pp.x + 135. ill. London 1905. (Recd. 28/12/05.) Doelter, C. Physikalisch-chemische Mineralogie. pp. xi + 272. ill. Leipzig 1905. (Recd. 21/12/05.) Eder, Josef Maria. Geschichte der Photographie. pp. xvi +484. ill. Halle a. S. 1905. (Recd. 18/12/05.) Heddle, M. Porster. The mineralogy of Scotland. Edited by J.G. Goodchild. 2 vols. pp. lviii + 148, viii + 247. ill. Edinburgh 1901. (Recd. 20/12/05.) Kayser, Edmond. Microbiologie agricole. pp. xii + 440. ill. Paris [1905]. (Recd. 20/12/05.) At the next Ordinary Meeting, on Thursday, .February lst, 1906, at 8.30 p.m., the following papers will be communicated : ‘‘ Hydroxylamine-ap-disulphonates(structural isomerides of hydr-oximinosulphates or hydroxylamine-PP-disulphonates).” By Tamemasa Haga.(‘Studies in t.he camphane series. Part XXI. Benzenediazo-$-semicarbazinocamphor and its derivatives,” By M. 0. Forster. ‘I The relation between absorption spectra and chemical constitution. Part I. The chemical reactivity of the carbonyl group.” By A. W. Stewart andE. C. C. Baly. “The relation between absorption spectra and chemical constitutioii. Part 11. The quinones and a-diketones.” By E. C. C. Baly and A. W. Stewart. ‘‘The relation between absorption spectra and chemical constitution. Part 111. The nitranilines and the nitrophenols.” By E. C. C. Baly and A. W. Stewart. “The action of light on benzylidenephenylhydrazine.” By F. D. Chat taway. “ The union of chlorine and hydrogen.” By I). L. Chapman and C. H. Burgess.‘‘Note on the molecular weight of adrenaline.’’ By G. Barger and A. J. Ewins. “The critical temperature and value of ML-of some carbon0 compounds.” By J. Campbell Brown. R. CLAY AND SONS, LTD., BREAD ST. HILL, E.C., AND BUNGAY, SUFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9062200001
出版商:RSC
年代:1906
数据来源: RSC
|
|