Numbers of Elements. 20 25 only which are given in the table to two or more significant decimals, as it is possible that the large number of atomic weights in the o'o column may be really due, to some extent, to the fact that, for the less known elements these THE following rather striking experiment was devised by me two or three years ago, and as it does not appear to have been previously described in print, it may prove of interest to others. A vertical glass tube, 2-2 cm. internal diameter, and about 12 dcm. long, is fitted at the lower end with an indiarubber bung carrying a glass tube, which is bent upwards so as to be parallel to and of approximately the same height as the wider tube. A solution of phosporus in olive oil is introduced into the wider tube so as to reach about 6 inches from the top, and steady suction is applied at the mouth of this tube by means of a water pump. Air enters through the narrow tube and a beautiful series of bell-shaped phosphorescent air bubbles rises through the column of oil. Ca, Pb, K, S-4 elements. Ce (half)-05 elements. 03 Mg, Ce (half)—1·5 elements. 0'4 Ba, Cd, Zn, Rb (half)—3'5 elements. 0.5 Cl, Rb (half)-1.5 elements. 0'6 Cu, Sr-2 elements. 0'7 Ni-1 element. 0.8 Cs, Fe-2 elements. o'g A, Br, I, Li, Mn, Ag, Kr-7 elements. From these figures the lower (dotted) curve is obtained. Considering that the atomic weights of thirty-two elements only are known with sufficient accuracy to be used for this second curve, its general form agrees very well with that of the first curve; there is the same wellmarked rise as integral values are approached, and the intermediate maximum is also well-marked, although it coincides with the value o4 instead of with o'5. This fact may, however, well be due to the comparative lack of data. It appears from the above considerations that there is a marked tendency for atomic weights to approximate to values which are multiples of unity, or, to a less degree, of 0.5, when the present unit, that is one-sixteenth of the atom of oxygen, is used; when the older standard, namely, the atom of hydrogen, is used as unit these relations no longer hold good. (We are indebted to the Chemical Society for permission to use the woodcut illustrating this article). Absorption of Ultra-violet Rays by Saturated Fatty Alcohols.-MM. Massol and Faucon.-Methyl and ethyl alcohols are transparent towards the ultra-violet rays for thicknesses up to 10 cm. For propyl alcohol the transparency diminishes slowly with the thickness, while in the case of the higher alcohols the absorption increases with the thickness of the layer of liquid. The transparency diminishes as the number of carbon atoms in the molecule increases. Secondary alcohols are slightly, and tertiary considerably, more transparent than primary alcohols.— Butl. Soc. Chim., xi,-xii., Nos. 20-21. RARE EARTH REACTIONS IN NON-AQUEOUS SOLVENTS.* By O. L. BARNEBEY. 1. INTRODUCTION. VERY little systematic general analytical work has been done in solvents other than water. Only isolated cases are to be noticed in a review of the subject where application of some non-aqueous solvent has facilitated analytical separations. Among these might be mentioned the ether extraction of iron, the ether extraction of uranium, the separation of barium, strontium, and calcium with alcohol, the ether separation of beryllium and aluminium, the pyridine and the amyl alcohol separation of lithium chloride from sodium chloride. Naumann (Ber., xxxii., 999; xxxvii., 3600, 4328, 4609; xlii., 3789) has studied several reactions, notably the action of hydrogen sulphide and ammonia with most of the common members of the second and third analytical groups in ethyl acetate, methyl acetate, pyridine, and acetone, obtaining very interesting results. The solubility tables of Naumann have been found serviceable, but in error in a number of cases. new enlarged solubility list will be published in future papers dealing with the analytical chemistry of nonaqueous solvents. This paper is concerned with the domain of the rare earths, dealing essentially with the general reactions of neodymium, lanthanum, cerium, and the yttrium group with various acids and bases, A The usual solvent employed is acetone, although occasionally another solvent is utilised to obtain specific zolubilities not obtainable in this medium. The acetone was carefully dehydrated over calcium chloride for several months, and distilled when needed, only the product with constant boiling-point being employed. The conditions for each reaction have been kept as nearly anhydrous as possible, although small quantities of water are unavoidably introduced in some instances. In such cases the general effect of added water has been carefully considered. Among the first reactions studied were those with the salts of the halogen acids, and of nitric and sulphuric acids, inasmuch as their corresponding salts are, as a rule, soluble in water. The iodides of neodymium, yttrium, lanthanum, and Cerium are readily soluble in acetone, the bromides moderately soluble, and the chlorides quite insoluble. The nitrates of the earths are soluble, but the sulphates are insoluble in this medium. Hence solutions of the iodides, nitrates, and to a more limited extent the bromides, furnish good solutes for a study of the comparative reactions of the earths in acetone. Journal of the American Chemical Society, xxxiv., No. 9. CHEMICAL NEWS, Jan. 10, 1913 Rare Earth Reactions in Non-aqueous Solvents. The iodide solutions were prepared by solution of the hydroxides in strong hydriodic acid, evaporation, extraction of the free iodine with carbon disulphide, and solution of the resulting iodides in acetone. The bromide solutions were prepared in the same way, omitting, however, the carbon disulphide treatment. The nitrates were dissolved directly in acetone. In certain cases reactions do not take place with the nitrates or bromides, but do with the iodides; or do not with the nitrates, but do with the bromides; hence some of the general reactions have frequently been tried with more than one salt dissolved in acetone. 2. GENERAL REACTIONS. A. Reactions with Common Acids and Study of the Halides. Hydrochloric acid yields insoluble earth chlorides. The acid may be added either by passing the dry gas into the earth solution or by employing a solution prepared by diluting concentrated aqueous hydrochloric acid with a considerable volume of acetone. Upon addition of hydrochloric acid white precipitates of the earth chlorides appear immediately in the form of an emulsion from which crystallisation proceeds slowly and incompletely. precipitates are soluble in large excess of the reagent. This solvent action is best shown by continuing the passage of gas for some time when complete solution is effected. Dilution with acetone re-precipitates the chlorides. The Yttrium group chlorides are not precipitated by such salts as cupric, stannous, and ferric chlorides in acetone. However, acetone solutions of a number of common chlorides dissolve the solid yttr um group chlorides, which in the absence of chlorides of this character are practically insoluble. Zinc, bismuth, ferric, cupric, antimonous, stannous, cobaltous, and mercuric chloride solutions in acetone dissolve the earth chlorides quite readily. Cadmium, arsenious, and uranyl chlorides act slowly but appreciably. Upon evaporation the copper, cadmium, and cobalt clorides give crystalline products. Mercuric chloride in acetone added to an acetone solution of yttrium group iodides gives no precipitate imme. diately, but in a short time a white precipitate of the chloride forms which becomes heavier as more mercuric chloride is added. With excess of mercuric chloride the precipitate re-dissolves to a clear solution. Addition of yttrium iodide solution again causes a precipitate to form, but, on the other hand, an excess of the iodide also gives a clear solution. If the solution is concentrated mercuric iodide precipitates, but this can be avoided by dilution with acetone, in which it is soluble. To ascertain the molecular proportions existing between HgCl2 and YI, standard solutions of the two were prepared in acetone. By numerous titrations the following ratios were indicated to exist, although the results are only approximate inasmuch as the end-points were rather obscure: 2YI3. HgCl2, 2YI3.3HgCl2, YI3.2HgCl2. The formation of double chlorides indicated above was tried on mixed rare earth chlorides of both the cerium and yttrium groups. Cupric, bismuth, stannous, and ferric chloride solutions in acetone were found to dissolve large quantities of the solid chlorides, although only a very slight amount was soluble in acetone alone. This strengthens the view that double chlorides are formed in solution. On account of the ready solubility of the chlorides in the corresponding solvent it has not been possible to effect a fractionation of the earth by this means. Crystallisation of double bromides was attempted by evaporating solutions of calcium, cadmium, sodium, and bismuth bromides with the rare earth bromides in acetone solution. The products were of syrupy consistency, and not crystalline. Attempts to crystallise double iodides gave similar results. Silver nitrate in acetone gives a complete precipitation of the halogens from acetone halide solutions, although the first few drops of reagent cause no precipitate to form. Volhard's method for the estimation of silver or determi 17 nation of chloride can be carried out in acetone by adding in the above reaction an excess of standard silver nitrate solution in acetone and titrating the excess of silver present with a standard acetone solution of ammonium sulphocyanate, using a ferric salt as indicator. Ferric nitrate crystallised from fuming nitric acid, then dissolved in acetone, can be employed. Thus prepared the ferric solution is only moderately permanent, the iron gradually precipitating. One can prepare a dilute solution of ferric chloride or sulphocyanate and use measured portions for the indicator. Naturally under these conditions a "blank must be subtracted for the volume of silver nitrate necessary to react with the measured volume of indicator. Hydrobromic acid precipitates the bromides from concentrated iodide, but not from the nitrate earth solutions. When sodium iodide in acetone is added to a rare earth bromide acetone solution sodium bromide precipitates, the earth iodide remaining in solution. Hydrofluoric, sulphuric, oxalic, citric, and mucic acids precipitate the earths completely as the corresponding salts when acetone solutions of the acids are added to yttrium, neodymium, cerium, or lanthanum nitrates dissolved in acetone. Tartarie and phosphoric acids precipitate the earths almost completely. The phosphates are soluble in large excess of acid. Malic acid gives almost complete precipitation upon standing. Formic, lactic, maleic, and succinic acids give incomplete precipitation of the four earths studied. Lactic acid precipitates the earths completely from the iodide solutions. cinnamic, or stearic acids do not precipitate the correHydrosulphuric, propionic, benzoic, salicylic, hippuric, sponding salts of yttrium, neodymium, lanthanum, and and stearates are but very slightly soluble in acetone. cerium. However, the cinnamates, benzoates, hippurates, Stearic acid gives partial precipitation of the earths from the iodide solutions. Of the above list of reactions those of formic and lactic acids (see tartaric acid fractionation later) merit especial description, inasmuch as they show evidences of being good reagents for separation purposes. Formic acid diluted with acetone and added to a cerium solution gives a small amount of a white precipitate instantly. On standing this precipitate gradually becomes heavier. Lanthanum precipitates in a like manner. Neodymium yields no precipitate at first with a moderate amount of formic acid, but upon standing a pink precipitate appears. A large excess of formic acid throws down a precipitate at once. No precipitate is obtained using any concentration of acid with the nitrates of the yttrium group in acetone even after allowing to stand for forty-eight hours. The precipitates of cerium, lanthanum, and formic acid could be used as a rapid means of fractionation neodymium are slowly soluble in water. Undoubtedly of the mixed earths. The Lactic acid yields white gelatinous lactates with the nitrates of the yttrium earths. The precipitation is almost complete. The lactates are very soluble in water, and very soluble in dilute ammonia. Stronger ammonia (sp. gr. o'9) dissolves the lactates, forming two immiscible layers both containing yttrium. Warming re precipitates the earths from the ammoniacal solutions. When lactic acid in acetone is added to a moderately strong solution of cerium nitrate no precipitate appears. Dilution and prolonged standing cause the lactates to settle out. solubility of the cerium precipitate in water and its deportment with ammonia resemble yttrium. Neodymium precipitates like cerium. Lanthanum is more difficult to throw down with lactic acid, the precipitate forming much more slowly than with cerium or neodymium. The yttrium group precipitates so readily and the others so slowly that without doubt lactic acid can be applied as a rapid fractionation agent for the concentration of this group away from the others. B. Reactions with Bases. The reaction of a number of organic bases were tried in acetone with the earth nitrates, but they gave no precipitates or general appearance of reaction. Among these were aniline, ethylaniline, acetamide, naphthylamine, diphenylamine, phthalamide, pyridine, quinoline, and urea. Benzylamine gives partial precipitation. Phenylhydrazine added to a concentrated nitrate solution of the earths gives two immiscible layers, the lower layer containing practically all of the earths. The lower layer is slightly pink and is miscible with acetone, hence is not obtained in dilute solutions. Ammonia Reactions. When anhydrous NH3 is passed into an acetone solution of yttrium nitrate, lanthanum nitrate, cerium nitrate, or neodymium nitrate, a heavy white precipitate forms which contains varying amounts of earths, nitric acid, ammonia, and acetone, the first and last named being the highest in percentage composition. These precipitates are difficult to handle, inasmuch as in many cases when desiccation is utilised to free the precipitates from the acetone held in loose combination, decomposition occurs, yielding a dark coloured mass which contains considerably more nitrogen than corresponds to the nitric acid and ammonia content. The nitrates are not well adapted for the study of this reaction, due to the difficulty of keeping the conditions sufficiently anhydrous. Naturally if water is present in appreciable amounts the hydroxides are formed in part at least. Decompositton due to oxidation is another factor with the nitrates. Some of the compounds obtained were semi-explosive when heated, hence the oxide value could not be obtained by direct ignition. This reaction is being further investigated. Reactions with the Alkaloids. Acetone is a good solvent for the alkaloids. When a number of the alkaloids are dissolved in acetone and the acetone solution added to an acetone earth solution. compounds are formed which contain the earth nitrate and the alkaloids, hence they appear to be a new type of alkaloidal compounds. The quinine compounds of cerium, lanthanum, neodymium, and yttrium are precipitated by the addition of an excess of acetone solution of quinine to the acetone earth solution as white amorphous bodies (the nitrates were employed). The precipitates in the case of yttrium, lanthanum, and neodymium are soluble in the earth nitrates. The cerium compound is precipitated with the first drop of alkaloidal solution, hence is not soluble in excess of earth nitrate. All are soluble in water. Solutions of lanthanum, cerium, neodymium, and yttrium earth nitrates in acetone were treated separately with acetone solutions of quinine, and the precipitates handled like those with brucine. The acetone is very difficult to remove from the quinine. The com. pounds 4LaONO3.C20H24N2O2, 4NdONO3.C20H24N2O2, 4YtONO3.C20H24Ñ2O2, and 4CeONO3.C20H24 N2O2 were indicated to exist. Cinchonidine is sparingly soluble in acetone, hence ethyl alcohol was used as the solvent. An excess of reagent precipitates yttrium, lanthanum, and neodymium slowly. Warming hastens reaction and precipitates cerium immediately. The precipitates obtained with the first three are soluble in excess of earth nitrates, but not so with cerium. All are white compounds, soluble in water. Cocaine dissolved in acetone yields with the earth solutions white precipitates soluble in water. Sanguinarine is readily soluble in acetone and yields yellow compounds, forming readily with lanthanum, more slowly with cerium and neodymium, and still more slowly with yttrium. The compounds are soluble in water. The precipitates have a tendency to turn red on standing. Chelery thrine is readily soluble in acetone and gives yellow precipitates with the earths, with lanthanum quickly, with cerium not so rapidly, with neodymium more slowly and with yttrium still more slowly. The precipitates are soluble in water. Piperidine is readily soluble in acetone. It gives white precipitates with the earths, which are almost completely insoluble in acetone but are soluble in water. Hyoscyamine is soluble in acetone. With the earths in excess no precipitate is formed, but with alkaloid in excess white precipitates are obtained. All are soluble in water. Brucine is readily soluble in acetone. With lanthanum, cerium, and neodymium precipitation ensues immediately with the first drop of alkaloid added and gradually becomes heavier, although complete precipitation does not occur for several days with an Yttrium excess of alkaloid. requires an excess of alkaloid to start precipitation. The products are all white, except that of neodymium, which has a pink tinge. All are soluble in water. Weak acetone solutions of the nitrates of lanthanum, cerium, neodymium, and the yttrium group were treated with an excess of brucine dissolved in acetone. The pre cipitates were filtered and washed with acetone by suction, then dried in vacuo over potassium hydroxide for several days. The precipitates retained a large amount of acetone which could be satisfactorily removed only by prolonged desiccation under diminished pressure. Upon analysis the following ratios were found to obtain: La(NO3)3 C23H26N2O4. 2Nd(NO3)3.C23H26N2O4, Yt(NO3)3.C23H26N2O4, and Ce(NO3)3.C23H26N2O4. alkaloid may be functioned as indicated or as basic earth alkaloidal nitrates. The Morphine in acetone gives a white precipitate with the earths, requiring an excess of reagent in case of yttrium, lanthanum, and neodymium, while with cerium the pre cipitate forms immediately with the first drop of alkaloid solution. The first three compounds are soluble in excess of earth nitrate. All are soluble in water. Coniine is miscible with acetone in all proportions. Coniine gives a white precipitate with yttrium nitrate, requiring a larger excess of alkaloid than with the other three earths studied. When added to the earth solution in quantity just sufficient to give a permanent precipitate, the precipitate is soluble in water. When added in larger amounts so that the alkaloid is in excess the precipitate is not soluble in water. Neither precipitate is soluble in alcohol. This deportment indicates the formation of at least two compounds. With lanthanum the reaction is similar except that the precipitate forms with less excess of alkaloid. With cerium the reaction is also similar to that of lanthanum, but does not show the water-soluble compound to such a marked degree. With neodymium the reaction is analogous to that of lanthanum. Strychnine is almost insoluble in acetone, hence a solution in ethyl alcohol was employed. With all four cf the earths white precipitates are slowly formed. They are all soluble in water. Leucine dissolved in warm ethyl alcohol (in which it is only slightly soluble) yields white precipitates soluble in water. Cinchonine, narcotine, and piperine give no precipitates with the four earths studied. (To be continued) Rotatory Power of Camphor Dissolved in Carbon Tetrachloride.-A. Faucon. The rotatory power of camphor dissolved in carbon tetrachloride is independent of the time which has elapsed between solution and the observation. It increases with the concentration and also with the temperature. The variation of the rotatory power under the influence of the temperature depends upon the concentration; thus an increase of 1° increases the angular deviation by a larger amount in the case of concentrated solutions than in that of dilute solutions, and the augmentation is greater at about 12° than at 40°.—Bull. Soc. Chim. de France, xi.-xii., Nos. 20-21. PROCEEDINGS OF SOCIETIES. CHEMICAL SOCIETY. Ordinary Meeting, December 5th, 1912. Dr. M. O. FORSTER, F.R.S., Vice-Presi ent, in the Chair. CAPTAIN G. I. DAvys was formally admitted a Fellow of the Society. The CHAIRMAN announced that the Council had decided : I. That in order to obtain a more equal division of abstracts, those of Physiological Chemistry and the Chemistry of Vegetable Physiology and Agriculture shall, in future, be included in Part I. of the Abstracts, instead of in Part II. 2. That persons requiring expanded Abstracts or translations of papers published in other Journals should apply to the Editor. Ten shillings per printed page (about 500 words) will be charged, and payment should be made to the Editor at the time the request for a translation or fuller abstract is forwarded to him. Whetstone. 19 centre of a condensed field of force. Each individual atom in any given molecule possesses a certain amount of free affinity, which must be accompanied by the existence of lines of force in its immediate neighbourhood. Inasmuch as there exist two types of this affinity, acid and basic, it follows that the independent existence of these lines of force in a molecule must be a metastable condition, and that the various force lines must condense together with the escape of free energy. The chemical reactivity of the resulting condensed system will be very much reduced, and in some cases may fall to zero. It has been shown how these systems can be unlocked by the action of light, and how the reactivity thereby may be increased. In many cases the closed system can partly be opened by the influence of a solvent, and under the influence of light they may still further be opened. A quantitative measure of the amount of light absorbed by substances at various concentrations in suitable solvents has been carried out. As a result of this theory it would be expected, in the case when a substance is opened up by a solvent, that the amount of light absorbed should increase with the dilution until a maximum is reached. Further dilution should then cause a decrease in the amount of light absorbed, and finally the solution should become diactinic. This result has experimentally been found. *309. "Studies in the Camphane Series. Part XXXIII. Orientation of Tiemann's iso Aminocamphor." By MARTIN ONSLOW FORSTER and HUBERT ARTHUR HARRY HOWARD. Tiemann's isoaminocamphor, produced by the action of hydriodic acid on camphoroxime, was found to have the amino-group in the position occupied by the substituent in 8-chlorocamphor, 3-bromocamphor, and Reychler's camphorsulphonic acid. It is therefore re-named B-aminocamphor, and by hydrolysing the hydroxycamphor semicarbazone, CH1902N3, which arises by exchange of the amino-group for hydroxyl when semicarbazide acetate acts on 3-aminocamphor, B-hydroxycamphor, C10H1602, has been prepared; the substance is short-lived, rapidly changing into the isomeric dihydrocampholenolactone. 310. "A Study of some Organic Derivatives of Tin as regards their Relation to the Corresponding Silicon Compounds." By THOMAS ALFRED SMITH and FREDERIC STANLEY KIPPING. Certificates were read for the first time in favour of Of the following papers those marked were read :- In two previous papers (Trans., 1912, ci., 1469, 1475) it was pointed out that every chemical molecule must be the As the results of a comparison of optically active derivatives of tin with the corresponding silicon compounds might lead to important conclusions, attempts have been made to synthesise dl-dibenzylethylpropylstannanesulphonic acid, SnEt Pr(CH2 C6H5) CH2 C6H4 SO3H, by methods analogous to those employed in the preparation of dibenzylethylpropylsilicanesulphonic acid (Challenger and Kipping, Trans., 1910, xcvii., 142, 755). These experiments were successful only up to a certain point, for although dibenzylethylpropylstannane was, in fact, obtained, the dl-monosulphonic derivative of this compound could not be prepared. The following benzyl and benzylalkyl derivatives of stannic chloride were described: Dibenzylstannic chloride, bromide, iodide, and acetate; tetrabenzylstannane, tridibenzyldiethylstannane, and diEthylpropylstannic chloride 311. "Contributions to the Chemistry of the Terpenes. Part XV. Synthesis of a Menthadiene from Carvacrol." By GEORGE GERALD HENDERSON and SCHACHNO PEISACH SCHOTZ. Carvomenthol, C10H19 OH, prepared by hydrogenating carvacrol according to the method of Sabatier and Senderens, yields A1-menthene, CroH18, when heated with anhydrous oxalic acid. The hydrocarbon forms an oily dibromide, C10H18Br2, which, when heated with alcoholic potassium hydroxide or with anhydrous sodium acetate and acetic acid, is converted into a menthadiene, C10H16, a colourless liquid with a pleasant odour, which boils at 172-174°. It was expected that the product of these reactions would be either a- or 8-phellandrere, but this was not the case; at least, it could not be converted into a nitrite. On the other hand, the menthadiene obtained in this way from carvacrol has considerable resemblance to the corresponding hydrocarbon formerly obtained from thymol by a similar process, although it has not been proved that they are identical. 312. "The Action of Halogens on Silver Salts." By HUGH STOTT TAYLOR. Iodine reacts with silver salts in a manner analogous to that observed in reactions with chlorine and bromine, to yield insoluble silver iodide, hypoiodous acid, and another acid. The reaction occurring may be represented by the equation: AgX+12+ H2O = AgI+HIO+HX. Owing to the instability of hypoiodous acid, a second reaction occurs, accelerated by rise of temperature, increase in concentration, or presence of soluble silver salts, in which the hypoiodous acid is converted into iodide and iodate. This secondary reaction may be generally represented thus: 3HIO+3AgX = 2AgI+AgIO3+3HX. The progress of this second reaction has been followed in various concentrations of the reacting solutions. The simple equation of Birnbaum (Annalen, 1869, clii., III) and of Normand and Cumming (Trans., 1912, ci., 1852), 312+ 3H2O +6AgX = 5AgI + 3 + AgIO3+6HX, represents the sum of the two preceding equations. 313. "The Formation of Tetrahydro-oxazoles from a-Hydroxy-B-anilino-B-diphenylethane and its Homologues." By HORACE Leslie CrowtheR and HAMILTON MCCOMBIE. | and more complex, but it still proceds mainly according to the equation 4PbS2O3= PbS+4S +3PbSO4. The authors' results are in conflict with those of Fogh (Ann. Chim. Phys., 1890 [6], xxi., 56), who prepared his thiosulphate from moderately concentrated lead acetate solution, and represented its decomposition on boiling by the equation 2PbS2O3 = PbS + PbS3O6. 315. "Studies on Cyclic Ketones." (Part II.) By SIEGFRIED RUHEMANN and STANLEY ISAAC LEVY. The work on cyclic ketones (Ruhemann, Trans., 1912, ci., 1729) has been continued on the same lines as before; in particular, the authors have examined the hydroxymethylene derivatives of various cyclic ketones. They find that 2-hydroxymethylene-1-hydrindone, — -CH2C6H4CO2 C:CH CH-OH, undergoes the same change at a somewhat higher temperature; but the hydroxymethylene derivatives of I: 3dimethyl-▲-cyclohexen-5-one, CHMe -C(CH•OH)-CO CH2CMe CH, Tetrahydro-oxazoles cannot be prepared from the dihydro-oxazoles described by McCombie and Parkes (Trans., 1912, ci., 1991) by simple reduction. If, however, a-keto-3-anilino-a3-diphenylethane is reduced to the corresponding hydroxy-compound (I) by means of sodium which is a yellow oil, and of 1-methylcyclopentan-3-one,— amalgam in alcohol, this compound then undergoes condensation with carbonyl chloride to yield 3:4:5 triphenyl-2: 34: 5-tetrahydro 2-oxazolone (II.) :— Attempts were also made to condense -hydroxy-3anilino-ad-diphenylethane and its homologues with thionyl chloride and sulphuryl chloride, but these successful. were un 314. "The Precipitation of Lead Thiosulphate and its Behaviour on Boiling with Water." BY WILLIAM HUGHES PERKINS and ALBERT THEODORE KING. The addition of sodium thiosulphate to a solution of lead acetate produces a precipitate the composition of which varies with the dilution of the solutions, and with the proportions in which they are mixed. From concentrated solutions, especially those containing excess of the lead salt, the precipitate consists of the double salt Pb(C2H3O2)2,2PbS203, whilst from dilute solutions or with excess of thiosulphate it has a composition corresponding with PbS203. It is therefore advisable when pure lead thiosulphate is required to obtain it from lead nitrate. The well-known blackening of this salt on warming takes place most readily in the presence of excess of sodium thiosulphate according to the equation PbS2O3+3 Na2S2O3 = PbS+4S+3Na2SO4. Without the sodium salt the reaction is slower CHMe CH2CO which is a very volatile colourless solid, can both be distilled in a vacuum without change. In other respects the hydroxymethylene derivatives of the hydrindone series resemble those already examined by Claisen and his pupils; thus they yield green copper salts, and anilides, and react with semicarbazide, and with phenylhydrazine, in the latter case forming pyrazole derivatives. 316. "Some Hydrogen Ferrocyanides." By Herbert ERNEST WILLIAMS. By treating solutions of the ferrocyanides of the alkali or alkaline earth metals with hydrochloric acid, ferrocyanic acid is liberated. The ferrocyanides of the heavy metals, however, behave differently; thus, when cupric ferrocyanide is boiled with concentrated hydrochloric acid, half of the copper is replaced by hydrogen, and there is obtained a yellow insoluble cupric hydrogen ferrocyanide, CuH2Fe(CN)6,4H2O. In a similar manner, but with slight variation of conditions, such as lower temperature or diluted acid, double hydrogen salts of nickel, cobalt, manganese, zinc, and cadmium can be obtained. By these means the following compounds have been prepared and examined: Cobalt hydrogen ferrocyanide, CoH2Fe(CN)6,4H2O; MnH-Fe(CN)6.5H2O; and nickel hydrogen ferrocyanide, ; manganese hydrogen ferrocyanide, NiH2Fe(CN)6,3 H2O. These acid salts are insoluble in water, and decompose alkali carbonates readily with liberation of carbon dioxide, and when digested in solutions of the chlorides of the alkali metals, hydrochloric acid is liberated. The cupric salt, when digested with solutions of potas sium or ammonium chlorides, liberates two equivalents of |