arrived at the points where they left the earth and appeared on the surface. These points were previously unknown by the spring finders. M. Edmond Perrier, when presenting these experiments to the Academy of Sciences, added that neither he nor M. Armand Viré take upon themselves the responsibility of these observations. They offer no explanations, but simply give the mere facts. THE MAP OF The World to a SCALE OF ONE MILLIONTH. M. Charles Lallemand, Director of the Service and Organisation of the General Levelling of France, has given some information concerning the last conference of the international map of a millionth scale. At the first conference, which was held at London in 1909, only seventeen countries were represented. At the present time thirty-one states have joined the convention. M. Lallemand also announced that the Prince of Monaco was The PRESIDENT referred to the meeting of the International Association of Chemical Societies which had been held in Brussels during September, 1913, and drew the attention of Fellows to the abbreviated report of the meeting which the Council have ordered to be printed in the Proceedings. Of the following papers, those marked were read :*286. "Investigations on the Dependence of Rotatory Power on Chemical Constitution. Part V. The Simpler Esters of the Carbinols, CH, CH(OH) R." BY ROBERT HowSON PICKARD and JOSEPH Kenyon. The following homologous series of esters of normal aliphatic acids have been prepared and examined polarimetrically under various conditions:-(i.) The esters of d-methylethylcarbinol; (ii) the esters of d-methyl-npropylcarbinol; (iii.) the esters of d-methyl-n-butylcarbinol taking upon himself the expense of several oceanic pages. of d-methyl-n-hexylcarbinol; (vi.) the esters of d-methyl-n(iv.) the esters of d-methyl-n-amylcarbinol; (v.) the esters nonylcarbinol [these six series range from the acetates to the stearates]; (vii.) the acetates and (viii.) the n-dodecoates of the d-carbinols [methylethylcarbinol to methyl-nundecylcarbinol). MICROBIAN Life. Microbian cultures are often very difficult. M. Adrien Lucet, Member of the Academy of Medicine, has just shown that a regular agitation or shaking of the liquid mediums used in bacteriology, contrary to the opinion that is generally admitted, acts favourably on these infinitely little creatures. By making these bouillons undergo a slow and continuous movement he has, in fact, been able to obtain cultures as many as eight times more abundant of the microbes of cholera, typhus fever, carbuncle, diphtheria, the glanders, dysentery, and even of lock-jaw, the microbe of which can only be cultivated without the penetration of any air. It was M. Chauveau who communicated M. Lucet's study to the Academy. PROCEEDINGS OF SOCIETIES. CHEMICAL SOCIETY. Prof. W. H. PERKIN, LL.D., F.R.S., President, in the Chair. MESSRS. R. E. Slade and S. C. Sastry were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Albert Frederick Calvert Royston, Eton Avenue, N.W.; Behari Lal Das, 107/2/1, Manaharpukur Road, Kalighah, Calcutta; Eric Russell Harrap, Maisemore, Ebury Road, Rickmansworth, Herts; Oswald Ryle Horwood, M.A., M.R.C.S., L.R.C.P., Tunstall Rectory, Suffolk; Dan Ivor James, M.A., B Sc., Frondeg, Llandilo, Carmarthenshire; Alexander Williamson McLaren, 3, Hayfield Terrace, Langside, Glasgow; Harold Edwin Temple, 239, Cashel Street, Christchurch, New Zealand; Robert James Wright, M.A., care of R. Burnett, Esq., 336, Pollokshaws Road, Glasgow. A Certificate has been authorised by the Council for presentation to ballot under By-law I.(3) in favour of Mr. Bertie Mandel Welsh, 80, Hunter Street, Sydney, N.S.W. The PRESIDENT announced:-1. That the bust of the Rt. Hon. Sir Henry Roscoe which was exhibited at the meeting had been presented to the Society by the friends and former students of Sir Henry Roscoe. 2. That by request of the Council Messrs. Vieweg and Sohn have offered to sell the first volume of the "Literatur Register," by R. Stelzner, to Fellows of the Chemical Society at the reduced price of £3 10s. (original price £4 48.), provided that not less than twenty copies are sold to Fellows of the Society. Those Fellows who desire to obtain a copy of the "Literatur Register on these terms are requested to send in their names to the Honorary Secretaries. Many of these esters (all of very simple constitution) metrically at temperatures above 150° or at various conexhibit anomalous dispersion when examined polaricentrations in solvents such as pyridine, benzene, or carbon disulphide. *287. "Co ordination of Rotatory Powers for different Wave-lengths, Temperatures, and Solutions." (Preliminary Note). By ROBERT HOWSON PICKARD and JOSEPH KENYON. The authors have already described the synthesis of thirty optically active carbinols of the general formula RICH(OH) R, and some seventy esters derived from some of them. These compounds have been examined polarimetrically for three wave lengths (a) in the homogeneous state at different temperatures, and (b) in several solvents at various concentrations. It was found (see preceding paper) that many of these under certain conditions exhibited anomalous optically rotatory dispersion. The attention of the present authors was therefore directed to a paper by H. E. Armstrong and E. E. Walker entitled "The Causes of Variation in the Optical Rotatory Power of Organic Compounds and of Anomalous Rotatory Dispersive Power" (Proc. Roy. Soc., 1913, A, lxxxviii., 388). In this paper it is suggested that anomalous dispersion is caused by the presence of two substances (in the actual cases considered of two isodynamic forms) having rotatory powers of opposite sign and different dispersive powers. In the case of esters of such simple constitution as those described in the preceding paper, the suggested explanation of the anomalous dispersion seems feasible, however, only on the assumption of a change in the association of the esters, not only in the homogeneous state on increase of temperature, but also on solution in various solvents. A "characteristic diagram" for d sec.-octyl acetate was therefore coustructed according to the method of Armstrong and Walker (loc. cit.). A reference line with slope of unity was drawn, and on it were plotted the various numbers representing the specific rotatory powers for mercury-green light. The numbers representing the specific rotatory powers for sodium-yellow and mercuryviolet lights were then plotted on the ordinates passing through the points previously located on the reference line. The various points for the latter two lights were found to lie on two straight lines, and the diagram was similar in character to those for the substances of previously known anomalous dispersive power as drawn and described by Armstrong and Walker. It is now found, however, that this same "characteristic diagram" can be used to co ordinate the results of all the determinations of rotatory power of one of the two optically active forms of the hundred synthetical com creased the activity. This is in accordance with the work of Kailan (Monatsh., 1912, xxxiii., 1329). DISCUSSION. pounds previously described by the present authors; thus | 1882, xv., 670). Exposure to radium bromide also in the numerical results (varying from +50 to -25) of the determinations of rotatory power for the three lights in different solvents at all concentrations and in the homogeneous state at different temperatures, not only of one compound, but of many (all of which are of very simple, but closely related constitution), have been plotted on one diagram. In this the various values lie on three straight lines, which intersect above the zero-line, and not all at one point. The dispersions then appear in the diagram as some function varying with the magnitude of the rotatory powers, thus co-ordinating the small, but very definite, differences in the dispersions of the homologous compounds which have been observed experimentally. It cannot yet be said whether this co-ordination is due either (i) to the comparison of a large number of compounds which have very similar dispersive powers, or (ii.) to the closely related constitutions of the substances. This method of plotting appears to afford (in some cases at least) a means by which a derivative differing in sign from that of the optically active parent substance can be properly designated "d" or "1" and also a means of determining whether a change in configuration has taken place in the formation of a derivative. DISCUSSION. Sir W. RAMSAY suggested that the cause of rotation was ultimately in the direction of the circular motion of electrons within the molecule. A dextrorotatory substance, say, might have hydroxy in the molecule, capable of repelling an electron, and causing it to rotate dextrorotatorily. On the other hand, if the hydroxyl be replaced by bromine, the bromine atom might have the property of attracting an electron and of reversing the direction of its rotation. This suggestion was made, not with any conviction of its applicability, but merely for consideration as to whether it was possible to obtain any clue to the fundamental reason of rotation. *288. "The Interaction of Sodium Amalgam and Water." By HERBERT BRERETON BAKER and LESLIE HENRY PARKER. Water distilled under special conditions has a visibly slower rate of action on sodium amalgam than ordinary distilled water. An apparatus was constructed to measure accurately the hydrogen evolved, and various samples of water were tested. The least active specimens of water were obtained by distillation from copper or platinum apparatus, especially on superheating the steam before the latter was condensed. The rate of action was shown to be no function of the conductivity of the water used, but was found to depend largely on the pressure at which the reaction was conducted, increase of pressure causing the rate of action to diminish, and vice versa. Various explanations of this phenomenon were put forward and tested, but the only feasible one was the assumption of the presence of some impurity in minute quantity, which was volatile under the conditions of ordinary distillation, but was destroyed on heating to redness. Experimental evidence was adduced which seemed to show that the only impurity which satisfied all the conditions was hydrogen peroxide, and the widely differing activities of various samples of water on sodium amalgam is ascribed to the presence of varying quantities of hydrogen peroxide. *289. "The Action of variously treated Waters on Sodium Amalgam." By LESLIE HENRY PARKER. Further evidence was adduced in support of the explanation of the varying activity of different samples of water on sodium amalgam put forward by Baker and Parker (preceding paper). as Various metals were sealed up with a quantity of the inactive water for definite periods. Metals such copper, mercury, &c., did not have much effect, whilst aluminium increased the activity of the water on sodium amalgam. This was shown to be in harmony with Traube's work on the wet oxidation of metals (Ber., come under the heading of over-voltage phenomena, the Dr. SENTER suggested that the results would probably between pure zinc and sulphuric acid. Over-voltage at best-known example of which was the retarded action the boundary between solid and liquid appeared to be connected with surface tension, and it might be assumed that the active substance, whatever it might be, modified the surface tension. With reference to the author's proof of the presence of hydrogen peroxide in tap water, tests depending on the liberation of iodine from iodides were rather untrustworthy, as in certain circumstances dissolved oxygen gave the reaction in question. The titanium dioxide test was trustworthy, and was extremely sensitive, as it was of water (compare Senter, Trans. Faraday Soc., 1906, capable of detecting I part of peroxide in 50 million parts ii., 142), and the fact that it was not given by the water in question appeared to render further investigation desirable The effect of added hydrogen peroxide might be connected with the fact that this compound was readily decomposed at a mercury surface (Bredig); the evolution of oxygen would presumably disturb the very unstable equilibrium characteristic of over-voltage. Dr. R. E. SLADE agreed that it was to be expected that hydrogen peroxide would disturb the over-voltage at the surface of the amalgam in the manner suggested by Dr. Senter. He believed, however, that a very important factor was the existence of dust particles in the water, and quoted the work of G. N. Lewis on the potential of sodium amalgams in support of this. The experiment which Mr. Parker has just shown rather pointed to this theory, for in the tube of pure water the bubbles of hydrogen came off at a few points which moved about on the surface of the amalgam. Perhaps the superheating of the steam was an efficient way of removing particles of dust by destroying them or by causing them to adhere to the hot tube. Dr. KEANE asked whether the influence of light had been studied in connexion with the experiments described, as this might have considerable effect both in regard to the production and decomposition of hydrogen peroxide. In reply to Dr. Senter, Mr. PARKER said that no comparative experiments had been made as to the relative values of the tests for hydrogen peroxide: further experiments were in progress with the view of obtaining some light on the mechanism of the reaction. In reply to Dr. Keane, he also stated that no experiments had been tried on the influence of light on the reaction. *290. "The Polymerisation of Cyanamide." GEORGE FRANCIS MORRELL and PETER Burgen. By The polymerisation of cyanamide, under various condi tions, both in the solid state and in solution, and also under the influence of catalysts, has been quantitatively studied. With the pure substance itself only about 10 per cent was found to have changed in six months, and in aqueous solution, even at elevated temperatures, the reaction proceeds comparatively slowly, many hours' heating at 100° being required to complete it. In absolute alcoholic solution the reaction-velocity is much further reduced. In all these cases the velocity-constant was not that of a bimolecular reaction, but equal amounts were found to be changed in equal intervals, except at great dilution, in which case a logarithmic curve was obtained. An ionic explanation may be advanced to explain these facts, the ions present in very small and, at first, practically constant concentration alone taking part in the change. The influence of acids and bases, such as sulphuric acid, ammonia, and sodium hydroxide, as catalysts produces an extremely marked acceleration, very small quantities reducing the period of half-change in aqueous solution at 100° from about twelve hours to as many minutes. Increasing quantities of sodium hydroxide pro- | duced increasing acceleration up to a point corresponding with the addition of 0.25 equivalent, but the further addition brought about a slight retardation, so that a solution containing sodium cyanamide, although it polymerised much more rapidly than pure cyanamide (half period at 100°, thirty minutes, compared with twelve hours in the latter case), yet did not do so more quickly than one containing less than 1/30th of the amount of hydroxide. The velocity-constant of these reactions was found to be between that of a unimolecular and of a bimolecular reaction, which latter stage it would only reach, on the authors' hypothesis, at infinite dilution and complete ionisation. DISCUSSION. Dr. MORRELL, in reply to Dr. Forster, stated that the method found most satisfactory for isolating cyanamide centrated aqueous solution of the latter with oxalic acid. The precipitated sodium oxalate was filtered off, and the filtrate evaporated almost to dryness in a vacuum. From this residue the cyanamide was extracted with ether, in which other substances present were insoluble. finally purified by recrystallisation from the same solvent. *291. "Some Derivatives of Oleanol." By FRANK TUTIN and WILLIAM JOHNSON SMITH NAUNTON. from its sodium salt was to neutralise a well-cooled con It was Oleanol, C31H5003, a crystalline substance from olive leaves (Power and Tutin, Trans., 1908, xciii., 896), has been further investigated. On oxidation with potassium permanganate it yields oleanone, C29H44O2(OH)2, which gives a mono- and di acetyl derivative. Oleanone, when heated with dilute acetic acid, undergoes a profound change, the reaction products containing a substance, C50H7607(OH)2. An analogous change occurs when diacetyloleanone is heated with a mixture of acetic and hydrochloric acids. The monoacetyl derivative, C50H7608(OH) CO CH3, thus produced, on hydrolysis with alkali, yields the above-mentioned dihydroxy. compound. On oxidation with chromic acid, oleanone yields a substance, C29H41O3°OH (m. p. 275°), which, when heated for two hours with alcoholic alkali, gives an isomeride, melting at 315°. Both substances yield monoacetyl derivatives. When oleanol itself is oxidised with chromic acid the above-mentioned substance, C29H4204 (m. p. 275°), is formed, together with a mixture of at least three carboxylic acids. 292. "Some Derivatives of Phorone." Part I. By FRANCIS FRANCIS and FRANCIS GEORGE WILLSON. An investigation of some derivatives of phorone has been commenced by the study of a phorone dibromide obtained from the tetrabromide by the action of pyridine. The most characteristic reaction of this dibromide is the ease with which it is converted by concentrated sulphuric acid into a crystalline derivative, a study of the oxidation and reduction products of which has led to the conclusion that it is 4-bromo-2: 2:3: 3-tetramethylbicyclo [0, 1, 2 pentan-1-ol-5-one, conclusion of Friend that iron is slightly porous (Trans., 1912, ci., 50). It is concluded that only very small quantities of the alkalis, and therefore presumably of other salts, are retained under prolonged washing. The quantity of ammonia retained by iron after about fifteen to twenty minutes' washing is probably not more than about o'0000001 grm. per sq. cm. 294. "The Bleaching Action of Hypochlorite Solutions.” By SYDNEY HERBERT HIGGINS. Bleaching powder solution to which an excess of boric acid has been added has very energetic bleaching properties because the boric acid merely liberates hypochlorous acid from the hypochlorite, whereas an excess of hydrochloric acid produces free chlorine and a solution of very weak bleaching properties. If, however, calcium carbonate is added to the latter solution, hypochlorous acid is regenerated, and the bleaching properties are restored. The addition of hydroxides to hypochlorite solutions opposes the hydrolysis of the hypochlorite, and retards the bleaching action, whereas the addition of small quantities of acids assists the hydrolysis and stimulates the bleaching action; the effect on the bleaching properties of the solution is due to the active mass of the free hypochlorous acid present, being in the one case reduced and in the other augmented. Even in the presence of a large excess of hydroxides the solutions have a small bleaching effect, which is probably due to a small amount of hypochlorous acid being still present in solution in spite of the opposition of the hydroxide to the hydrolysis of the metallic hypochlorite. All the experiments point to the conclusion that hypochlorite solutions entirely owe their bleaching properties to the free hypochlorous acid present in solution. Sometimes there is a secondary reaction between the hypochlorous acid and any neutral chloride present, producing nascent chlorine of energetic bleaching properties ((Proc., 1912, xxviii., 130), but the main action is one of direct oxidation by the hypochlorous acid. During the bleaching action chlorides are produced by the reduction of the hypochlorites, but the stimulating effect of chlorides thus produced on the bleaching action is negligible. 295. "Guaiacum Resin as a Reagent for the Detection of Oxydases and of Minute Traces of Copper." By WILLIAM RINGROSE GELSTON ATKINS. In order to ascertain how far traces of metals might vitiate tests for oxydases by guaiacum resin, a series of experiments was carried out to determine the limits of sensitiveness of the reaction towards certain salts. Adopting the methods usual in water analysis, it was found that very minute amounts of copper salts or of potassium permanganate may be detected by this test. Accordingly it is brought forward as a reaction of utility in water analysis. Below are recorded the limits of sensitiveness of the reaction, expressed in gims. per cc. Potassium Copper as sulphate, 2 X 10-9 to 2x 10-. permanganate, 4 × 10 -. Potassium dichromate, 1 x 10—7. Iron, as ferrous sulphate, IX 10", as ferric sulphate, IX I0-6. Lead as acetate, 6x 10-. Nitric acid, 2X-3. Manganese as sulphate. 8 × 10-4. In each case a few drops of hydrogen peroxide were added, as well as a very dilute solution of the reagent. Traces of chlorides were also present, and play an important part. 296. "The Absorption Spectra of various Derivatives of Pyridene, Piperidine, and Piperazine in Solution and as Vapours." By JOHN EDWARD PURVIS. The absorption spectra of a number of the derivatives of pyridine, piperidine, and piperazine, both in solution and in the vaporous condition, have been investigated. The general results show that, besides the nature of the molecule, the type, the number, and the orientation of the sidechains influence the production of the narrow vapour bands; and that, when these bands disappear, the remaining bands are generally comparable with the solu tion bands. 297. "Derivatives of p-Iodoaniline." By FREDERICK DANIEL CHATTAWAY and ALFRED BERTIE CONSTABLE. The ease with which chlorine and bromine substitute arylamines has led to a very complete knowledge of the simpler derivatives which they form, but comparatively few of the corresponding iodine compounds have been pre. pared on account of the difficulty of effecting iodine substitution and the readiness with which the iodoanilines decompose. The conditions necessary to obtain a good yield of p-iodoacetanilide, and from it to prepare biodoaniline, were described. The aniline having been obtained in quantity, a number of its simpler derivatives have been prepared. 298. "The Interaction of Tetranitromethane and Compounds containing Centres of Residual Affinity." (Preliminary Note). By ERNEST MAGOWAN HARPER and ALEXANDER KILLEN MACBETH. The work was undertaken to investigate the colours developed on adding tetranitromethane to various substances. Ostromisslensky (Journ. Prakt. Chem., 1911, [2], lxxxiv., 349) has recorded such effects with aromatic amines, and also with aliphatic compounds containing the ethylenic double linking. Clarke, Macbeth, and Stewart (Proc. Chem. Soc., xxix., 161) have shown that these are only particular cases of a more general phenomenon. Colours have been obtained with organic sulphides, iodides, phosphines, amino-compounds, &c. The method employed was to photograph tetranitromethane in an alcoholic solution of the substance of constant strength. Tetranitromethane itself gives no colour in dry alcohol. With the sulphides a yellow colour is produced on mixing the solutions, but the absorption spectrum does not differ greatly from that of tetranitromethane. The colour deepens on keeping, and after some time the spectrum undergoes a great change. A band is developed in the region I/A 2800-2900; thus tetranitromethane with N/10-pentamethylene sulphide after fourteen hours shows a band the head of which is at 1/A 2850 in the log-thickness 35 of N/100,000 solution. With compounds containing an ethylenic double bond a similar band is obtained; thus tetranitromethane with N/10-amylene after five days gives a band the head of which is at 1/A 2850 in the log-thickness 32 N/100,000solution. Similar bands are obtained with sulphur compounds other than the sulphides (ethyl mercaptan, &c.), and with various aliphatic amino-compounds, the band development being exceptionally rapid in these cases. In most cases the penetration of the band increases with time, thus: Log-thickness Time. 1/λ2850 32 I/A2850 26 N/10-pentamethylene sulphide 1/A2850 33 N/10-pentamethylene sulphide 1/2850 28 5 ΙΟ 2 5 Further, it would appear that there is in this way a means, not only of detecting, but also of comparing, the residual affinities of different substances; thus the different sulphides give bands of different penetrations in equal times, for example : | With regard to the nature of the reaction, nitromethane was substituted for tetranitromethane with negative results. Investigations are being continued with other mononitrocompounds, in which the hydrogen atoms are replaced by chlorine and other electro-negative atoms. Dinitro- and trinitro-compounds are also being substituted. The effect of introducing electro-negative atoms into the molecule containing the centre of residual affinity is also being studied. 299. "The Relative Activities of certain Organic Iodocompounds with Sodium Fhenoxide in Alcoholic Solution. Part III. The Temperature Coefficients." BY DAVID SEGALLER. The velocity coefficients of the following alkyl iodides, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert. butyl, amyl, isoamyl, sec.-amyl, hexyl, sec.-hexyl, heptyl, sec.-heptyl, octyl, sec.-octyl, and cetyl iodides have been measured with sodium phenoxide in alcoholic solution at four different temperatures, and the temperature coefficients determined. It is found that the results obtained are in good agreement with the equation of Arrhenius (Zeit. Phys. Chem., 1889, iv., 226). The results show that the relative activities of the alkyl iodides are approximately independent of the temperature. 300. "Resolution of a-Anilinostearic Acid." By HENRY RONDEL LE SUEUR. salt. a-Anilinostearic acid has been resolved into its optically active components by crystallisation of its l-menthylamine d-a-Anilinostearic acid melts at 129-130°, and has [a] D 19+ 347° in solution in pyridine, and [a]D 40 +18.6° in solution in alcohol. The lavo-acid has also been isolated, and its properties are the same as those of its dextro-isomeride. 301. "The Conversion of d-Glucosamine into d-Mannose." (Preliminary Note). By JAMES COLQUHOUN Irvine and ALEXANDER HYND. In previous communications (Proc., 1912, xxviii., 54; Trans., 1912, ci., 1128), the authors have already described the conversion of d glucosamine into d-glucose. They have now succeeded, by a process which on first inspection seems more direct, in transforming the amino-sugar into d-mannose. Methylglucosamine hydrochloride, when gently warmed with excess of benzaldehyde, passes gradually into solution when the liquid is saturated with dry hydrogen chloride. The product of this reaction is benzylidenemethylglucosamine hydrochloride (m. p. 205° with decomposition; [a] D 20 - 54'4° in methyl alcohol), which is formed by condensation of the aldehyde with two hydroxyl groups of the sugar, and is thus comparable with the benzylidenemethylglucoside described by Alberda van Ekenstein. The compound is exceedingly unstable towards acids, and, when acted on by silver nitrite, loses not only the aminogroup, but also the benzylidene residue and the glucosidic group. Chitose is thus the ultimate product of the reaction. It appears that the solvent plays a very important part amino-group was removed by the addition of excess of Log-thickness N/10-pentamethylene sulphide Head of band 28 5 A similar effect holds in the case of other classes of compounds. D version into crystalline derivatives, such as methyl- when the concentration of the acid is changed. The mannoside and mannoseanilide. The individual steps of the process outlined above appear to proceed practically quantitatively, and are summarised below: d-Glucosamine → methylglucosamine hydrochloride → benzylidenemethylglucosamine hydrochloride → benzylidenemannose →d-mannose. It was shown that the formation of d-mannose as the final product cannot be attributed to the well-known action of alkali in effecting the conversion of closely related reducing sugars. Glucosamine may thus be converted into either d-glucose or d-mannose, and in one of the two processes a change of the nature of a Walden inversion must take place. The evidence at present available indicates that the change in configuration probably occurs during the decomposition of benzylidenemethylglucosamine by nitrous acid, and there seems no necessity to modify the claim made in a previous paper (loc. cit.) that glucosamine is a derivative of d-glucose. 302. "The Mechanism of Denitrification." By WILLIAM HULME. observations are, however, in good agreement with the view that both the non-ionised and ionised forms of the acid take part in the acceleration of the reaction, the actual catalytic effect being additively composed of the effects due to the two components. .n n The activity of the non-ionised acid diminishes rapidl as its tendency to ionise decreases; this is clearly show! by the following numbers, which express the activities i terms of that of the hydrogen ion:-Hydrochloric, 177 dichloroacetic, o'50; 3-dibromopropionic, o 152; chloro i As yet it does not seem acetic, o'056; acetic, 0.0034. possible to say whether these ratios are independent of the nature of the catalysed reaction. 304. "The Configuration of the Doubly linked Nitrogen Atom. Optically Active Salts of the Semicarbazone and Benzoylphenylhydrazone of cyclo-Hexanone-4-Carboxylic Acid." By WILLIAM HOBSON MILLS and ALICE MARY BAIN. The method which the authors used in order to investi gate the configuration of tervalent nitrogen in the oximinogroup (Trans., 1910, xcvii., 1866) has been further emin-ployed for the examination of the configuration of the doubly-linked nitrogen in the hydrazone group, :N.NR,R2. cyclo Hexanone-4-carboxylic acid benzoylphenylhydrazone has been obtained in an optically active form by crystallisation of its quinine salt from dilute methyl alcohol. The sodium salt obtained by treating the quinine salt with sodium hydroxide was strongly dextrorotatory, having [M]D 238-6°. A series of experiments, conducted with a view to vestigate the mechanism of denitrification, showed that this reduction might be divided into two parts, namely, (1) the bacterial reduction, and (2) the enzymatic reduction. The fermentation of similar media, one with and the other without potassium nitrate, under anaerobic conditions, showed the gas evolution to consist of nitrogen (98 per cent) and carbon dioxide from the nitrate-containing medium, and of hydrogen (70 per cent) and carbon dioxide from the nitrate-free medium. A medium containing only a very small percentage of nitrate evolved nitrogen and carbon dioxide as long as nitrate and nitrite obtained in the solution, but hydrogen and carbon dioxide appeared as soon as these had disappeared; thus the chemical agent by which the organism reduces the nitrate is nascent hydrogen. The media were tested for enzyme action by precipita: tion with alcohol, drying, dissolving in water, and Chamberland-filtration, measured quantities of this solution being added to small quantities of a sterilised I per cent solution of potassium nitrate, and the nitrite produced being measured. The results showed a considerable duction with the "product" obtained from the nitrate containing flasks, whilst that obtained from the nitrate-free flasks was devoid of this reducing power. Dextrorotatory salts of cyclohexanone 4-carboxylic acid semicarbazone (W. H. Perkin, Trans., 1904, lxxxv., 427) were obtained similarly with the aid of morphine, the molecular rotations observed varying from [M] 37.8° to 27.9° in different preparations. The active salts of both compounds showed marked autoracemisation on keeping, the loss of activity being much more rapid in the case of the semicarbazone than in that of the benzoylphenylhydrazone. The autoracemisation was checked by the addition of alkali hydroxides, sodium and potassium hydroxides being much more effective than ammonia. On acidification the activity in both cases instantly disappeared. These results can only be satisre-factorily explained by regarding the molecular asymmetry of these compounds as being of the centro-asymmetric type, and due to the fact that when the carbonyl oxygen of the symmetrical keto-acid is replaced by the hydrazone residue, :N NR, R2, the NR,R2 group takes up a position outside the original plane of symmetry of the keto-acid. Accordingly, in these hydrazones, the three valencies of the doubly-linked nitrogen atoms do not lie in one plane, but are directed along the three edges of a trihedral angle. These results were confirmed by a second series of experiments, in which the fermentation took place aerobically. The enzyme solutions in all cases were not affected by boiling. The mechanism of denitrification may be, therefore, represented as follows: 1. C ... + H2O + organism = CO2 + H2+ CH2 where C represents the carbon of the nutrient substance. 2. KNO3 + E = KNO2+EO (Enzyme). EO+2H E+ H2O 2KNO2 + 5H+2CO2 = 2KHCO3 + 4H2O + N2, thus accounting for the large percentage of nitrogen in the gases evolved from the nitrogen-containing flasks. "The Catalytic Activity of Acids. Evaluation of 303. the Activities of the Hydrogen Ion and the Undissociated Acid." By HARRY MEDFORTH DAWSON and FRANK POWIS. The catalytic activity of a series of acids has been examined by measurements of the velocity with which acetone passes from the ketonic to the enolic form in aqueous solutions of determinate acid concentration. The results obtained are entirely at variance with the theory that the catalysing activity of an acid is determined by its hydrogen-ion concentration, for the ratio of the reactionvelocity to the ionic concentration varies to a large extent NOTICES OF BOOKS. Metallography. By CECIL H. DESCH, D.Sc. (Lond.), THE latest results of recent investigations are incorporated |